KR20130034005A - Curable composition, hardened material, and method for using curable composition - Google Patents

Abstract

The present invention provides a curing agent containing (A) a silane compound copolymer having a specific repeating unit, (B) an epoxy compound having an isocyanurate skeleton, (C) an alicyclic acid anhydride having a carboxyl group, and (D) an acid. A curable composition containing a silane coupling agent having an anhydride structure, a cured product obtained by curing the composition, and a method of using the composition as an adhesive for an optical device fixing material and a sealing material for an optical device fixing material. According to the curable composition of this invention, even when high energy light is irradiated or a high temperature state, it does not color and transparency does not fall, it has excellent transparency over a long term, and it has a high adhesive force even at high temperature. You can get the cargo. The curable composition of this invention can be used when forming an optical element fixing material, Especially it can be used suitably as an adhesive agent for optical element fixing materials, and the sealing agent for optical element fixing materials.

Description

Curable composition, hardened | cured material, and usage method of curable composition {CURABLE COMPOSITION, HARDENED MATERIAL, AND METHOD FOR USING CURABLE COMPOSITION}

This invention is excellent in transparency and heat resistance, and also the curable composition from which the hardened | cured material which has high adhesive force is obtained, the hardened | cured material formed by hardening this composition, and the said composition is used as an adhesive for optical element fixing materials, or the sealing agent for optical element fixing materials. It is about how to use.

Conventionally, the curable composition is variously improved according to a use, and has been widely used industrially as a raw material, an adhesive agent, a coating agent, etc. of an optical component or a molded object. For example, the curable composition which forms the hardened | cured material excellent in transparency is a raw material of an optical component, and the curable composition which forms the hardened | cured material which has a high adhesive force as a raw material of the optical component, and is used suitably as an adhesive agent or a coating agent. many.

Moreover, in recent years, when manufacturing an optical element sealing body, curable composition has been used also as composition for optical element fixing materials, such as the adhesive agent for optical element fixing materials, and the sealing agent for optical element fixing materials.

Optical devices include various lasers such as semiconductor lasers (LD) and light emitting devices such as light emitting diodes (LEDs), light receiving devices, composite optical devices, and optical integrated circuits. In recent years, optical devices of blue or white light having a shorter peak wavelength of light emission have been developed and widely used. Such high luminance of a light emitting device having a short peak wavelength of light emission proceeds dramatically, and there is a tendency that the amount of heat generated by the optical device is further increased.

By the way, in recent years with the high brightness of the optical element, the hardened | cured material of the composition for optical element fixing materials is exposed to higher temperature heat | fever which generate | occur | produces from higher energy light or an optical element for a long time, and it cracks or peels off. Problem occurred.

In order to solve this problem, in patent documents 1-3, the composition for optical element fixing materials which has a polysilsesquioxane compound as a main component is proposed.

However, even if it is the hardened | cured material of the composition for optical element fixing materials which has the polysilsesquioxane compound of patent documents 1-3 as a main component, it may be difficult to acquire heat resistance and transparency, maintaining sufficient adhesive force.

Moreover, the epoxy resin composition which contains the polythiol compound in patent document 4 and the epoxy resin composition which uses alicyclic epoxy resin is proposed by patent document 4 as a composition used for optical element sealing.

However, even when using these compositions, sufficient light deterioration resistance with time-dependent change could not be satisfied, or the adhesive force might fall.

Japanese Laid-Open Patent Publication 2004-359933 Japanese Laid-Open Patent Publication 2005-263869 Japanese Laid-Open Patent Publication No. 2006-328231 Japanese Laid-Open Patent Publication No. 7-309927 Japanese Unexamined Patent Publication No. 2009-001752

This invention is made | formed in view of such a situation of the prior art, The curable composition which is excellent in heat resistance and transparency, and also the hardened | cured material which obtains the hardened | cured material which has high adhesive force, the hardened | cured material formed by hardening this composition, and the said composition is an optical element. An object of the present invention is to provide a method for use as an adhesive for a fixing material or a sealant for an optical device fixing material.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched in order to solve the said subject, As a result, (A) the specific silane compound copolymer, (B) the epoxy compound which has isocyanurate frame | skeleton, and (C) alicyclic acid anhydride which has a carboxyl group Cured product of the composition containing the curing agent and (D) silane coupling agent having an acid anhydride structure, while maintaining excellent transparency and heat resistance over a long period of time, and also becomes a cured product having a high adhesion even at high temperatures It was found out and completed this invention.

In this way, according to the 1st of this invention, the curable composition of the following [1]-[9] is provided.

[1] In the molecule (A), the following formulas (i), (ii) and (iii)

[Formula 1]

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, 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 a linking group. R <^2> represents the C1-C20 alkyl group or the phenyl group which may have a substituent.]

It has a repeating unit of (i) and (ii), (i) and (iii), (ii) and (iii) or (i), (ii) and (iii) among the repeating units represented by A silane compound copolymer having a molecular weight of 1,000 to 30,000,

(B) an epoxy compound having an isocyanurate skeleton,

(C) a curing agent containing an alicyclic acid anhydride having a carboxyl group, and

(D) Silane coupling agent having an acid anhydride structure

Curable composition containing.

[2] The amount of groups ([R ¹ -CH (X ^O ) -D]) and R ^{2 in which} the silane compound copolymer of the above (A) is represented by the formula: R ¹ -CH (X ^O ) -D- in a molar ratio of the amount present ^{([R 2]), [} R 1 -CH (X O) -D]: [R 2] = 60: 40 ~ 5: 95 the curable composition according to the silane compound copolymer [1] of .

 [3] The content ratio of the components (A), (B), (C) and (D) is a mass ratio of (A) and [(B) + (C) + (D)], (A): [(B) + (C) + (D)] = 90: 10-50: 50 The curable composition as described in [1] or [2] characterized by the above-mentioned.

[4] (A ') Formula (1): R ¹ -CH (X ^O ) -D-Si (OR ³ ) _p (X ¹ ) _3-p

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, 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 a linking group. R ³ represents an alkyl group having 1 to 6 carbon atoms, X ¹ represents a halogen atom, and p represents an integer of 0 to 3.]

At least one of the silane compounds (1) represented by

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

(In formula, R <^2> represents a C1-C20 alkyl group or the phenyl group which may have a substituent, R <^4> represents a C1-C6 alkyl group, X <^2> represents a halogen atom, q is an integer of 0-3. Indicates)

Silane compound copolymer whose weight average molecular weights obtained by condensing the mixture of the silane compound containing at least 1 sort (s) of the silane compound (2) represented by 1,000-30,000,

(B) an epoxy compound having an isocyanurate skeleton,

(C) a curing agent containing an alicyclic acid anhydride having a carboxyl group, and

(D) Silane coupling agent having an acid anhydride structure

Curable composition containing.

[5] The silane compound copolymer of (A ') contains a silane compound (1) and a silane compound (2) in a molar ratio, [silane compound (1)]: [silane compound (2)] = 60:40 Curable composition as described in [4] obtained by condensing at the ratio of-5:95.

[6] The content ratio of the above-mentioned (A '), (B), (C) and (D) component is a mass ratio of (A') and [(B) + (C) + (D)], (A '): [(B) + (C) + (D)] = 90: 10-50: 50 The curable composition as described in [4] or [5] characterized by the above-mentioned.

[7] The content ratio of the components (B), (C) and (D) is [(B) + (C)] and (D) in the mass ratio of [(B) + (C)]: (D ) = 90:10-10:90, The curable composition as described in [1] or [4] characterized by the above-mentioned.

[8] The curing agent of (C) comprises one or two or more selected from alicyclic acid anhydrides having carboxyl groups and other alicyclic acid anhydrides, and the mass ratio thereof is (alicyclic acid anhydrides having carboxyl groups). : (Other alicyclic acid anhydride) = Curable composition as described in [1] or [4] which is 100: 0-10: 90.

[9] The curable composition according to [1] or [4], which is a composition for an optical device fixing material.

According to the 2nd of this invention, the hardened | cured material of following [10] and [11] is provided.

[10] A cured product obtained by curing the curable composition according to [1] or [4].

[11] The cured product according to [10], which is an optical element fixing material.

According to the 3rd of this invention, the method of using the curable composition of this invention of following [12] and [13] is provided.

[12] A method of using the curable composition according to [1] or [4] as an adhesive for an optical device fixing material.

[13] A method of using the curable composition according to [1] or [4] as a sealant for an optical device fixing material.

According to the curable composition of this invention, even when high energy light is irradiated or a high temperature state, it does not color and transparency does not fall, it has excellent transparency over a long term, and it has a high adhesive force even at high temperature. You can get the cargo.

The curable composition of this invention can be used when forming an optical element fixing material, Especially it can be used suitably as an adhesive agent for optical element fixing materials, and the sealing agent for optical element fixing materials.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is classified into 1 class of curable compositions, 2) hardened | cured material, and 3) the usage method of a curable composition, and it demonstrates in detail.

1) Curable Composition

The curable composition of the present invention comprises

In the molecule (A), the following formulas (i), (ii) and (iii)

[Formula 2]

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, 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 a linking group. R <^2> represents the C1-C20 alkyl group or the phenyl group which may have a substituent.]

In the repeating unit shown by (b), it has a repeating unit of (i) and (ii), (i) and (iii), (ii) and (iii) or (i), (ii) and (iii), and a weight average A silane compound copolymer having a molecular weight of 1,000 to 30,000, an epoxy compound having an isocyanurate skeleton (B), a curing agent containing an alicyclic acid anhydride having a (C) carboxyl group, and a silane having an (D) acid anhydride structure It is characterized by containing a coupling agent.

(A) Silane Compound Copolymer

Curable composition of this invention is (i) and (ii), (i) and (iii), (ii) in the repeating unit represented by said Formula (i), (ii) and (iii) as (A) component. And a silane compound copolymer having a repeating unit of (iii) or (i), (ii) and (iii) and having a weight average molecular weight of 1,000 to 30,000 (hereinafter referred to as "silane compound copolymer (A)"). Sometimes).

The silane compound copolymer (A) may have 1 type, respectively, and may have 2 or more types of repeating units represented by (i), (ii), and (iii).

R <^1> represents a hydrogen atom or a C1-C6 alkyl group in formula (i)-(iii), and a hydrogen atom is preferable.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ are methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, i-butyl group, s-butyl group, n-pen Tyl group, n-hexyl group, etc. are mentioned.

X <^0> is halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; Cyano group; Or formula: group represented by OG; Indicates.

G represents a protecting group of a hydroxyl group. There is no restriction | limiting in particular as a protecting group of a hydroxyl group, The well-known protecting group known as a protecting group of a hydroxyl group is mentioned. For example, acyl-type protecting group; Silyl-based protecting groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group and t-butyldiphenylsilyl group; Acetal type protecting groups, such as a methoxymethyl group, a methoxyethoxymethyl group, 1-ethoxyethyl group, tetrahydropyran-2-yl group, and tetrahydrofuran-2-yl group; alkoxycarbonyl protecting groups such as t-butoxycarbonyl group; Ether-based protecting groups such as methyl group, ethyl group, t-butyl group, octyl group, allyl group, triphenylmethyl group, benzyl group, p-methoxybenzyl group, fluorenyl group, trityl group and benzhydryl group; And the like. Among these, as G, an acyl-type protecting group is preferable.

Acyl-based protecting group, specifically, the formula: -C (= O), a group represented by R ^5. In formula, R <^5> is C1-C6, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, etc. Alkyl group; Or the phenyl group which may have a substituent is shown.

As a substituent of the phenyl group which may have a substituent represented by R <^5> , a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n Alkyl groups such as -pentyl group, n-hexyl group, n-heptyl group, n-octyl group and i-octyl group; Halogen atoms such as fluorine atom, chlorine atom and bromine atom; Alkoxy groups, such as a methoxy group and an ethoxy group; .

Among these, as X ⁰ , a chlorine atom, a group represented by the formula: OG '(in the formula, G' represents an acyl-based protecting group) in terms of availability and a cured product having a high adhesive strength can be obtained, and cyan A group selected from the furnace group is preferable, a group selected from a chlorine atom, an acetoxy group and a cyano group is more preferable, and an acetoxy group is particularly preferable.

D represents a single bond or a linking group.

Examples of the linking group include divalent organic groups which may have a substituent. 1-20 are preferable and, as for carbon number of the said organic group, 1-10 are more preferable.

As a divalent organic group which may have a substituent, for example, the alkylene group which may have a substituent, the alkenylene group which may have a substituent, the alkynylene group which may have a substituent, the arylene group which may have a substituent, and a substituent The divalent group etc. which consist of the combination of the (alkylene group, alkenylene group, or alkynylene group) which may have and arylene group which may have a substituent are mentioned.

As an alkylene group of the alkylene group which may have a substituent, C1-C20, such as methylene group, ethylene group, a propylene group, trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group, Preferably it is C1-C20 10 alkylene groups are mentioned.

As an alkenylene group of the alkenylene group which may have a substituent, C2-C20 alkenylene groups, such as a vinylene group, a propenylene group, butenylene group, and a pentenylene group, Preferably, it is a C2-C10 alkenylene The group can be mentioned.

As an alkynylene group of the alkynylene group which may have a substituent, C2-C20 alkynylene groups, such as an ethynylene group and a propynylene group, Preferably a C2-C10 alkynylene group is mentioned.

As an arylene group of the arylene group which may have a substituent, C6-C20 arylene groups, such as o-phenylene group, m-phenylene group, p-phenylene group, and 2, 6- naphthylene group, Preferably it is C6 The arylene group of -10 is mentioned.

As a substituent of the said alkylene group, alkenylene group, and alkynylene group, Halogen atoms, such as a fluorine atom and a chlorine atom; Alkoxy groups, such as a methoxy group and an ethoxy group; Alkylthio groups such as methylthio group and ethylthio group; An alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group; And the like.

As a substituent of the said arylene group, Cyano group; Nitro group; Halogen atoms such as fluorine atom, chlorine atom and bromine atom; Alkyl groups such as methyl group and ethyl group; Alkoxy groups, such as a methoxy group and an ethoxy group; Alkylthio groups such as methylthio group and ethylthio group; And the like.

These substituents may be couple | bonded in arbitrary positions in groups, such as an alkylene group, an alkenylene group, an alkynylene group, and an arylene group, and two or more may be couple | bonded similarly or differently.

As a bivalent group which consists of the combination of the (alkylene group, alkenylene group, or alkynylene group) which may have a substituent, and the arylene group which may have a substituent, it may have the said substituent (alkylene group, alkenylene group, or The group which combined at least 1 sort (s) of an alkynylene group) and at least 1 sort (s) of the arylene group which may have the said substituent in series is mentioned. Specifically, group represented by a following formula is mentioned.

(3)

Among these, as D, the hardened | cured material which has a high adhesive force is obtained, a C1-C10 alkylene group is preferable, a C1-C6 alkylene group is more preferable, and a methylene group or ethylene group is especially preferable.

R <^2> represents the phenyl group which may have a C1-C20 alkyl group or substituent in formula (i)-(iii).

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group and n-pen A methyl group, n-hexyl group, n-octyl group, i-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, etc. are mentioned.

As a substituent of the phenyl group which may have a substituent represented by R <^2> , a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n Alkyl groups such as -pentyl group, n-hexyl group, n-heptyl group, n-octyl group and i-octyl group; Alkoxy groups, such as a methoxy group and an ethoxy group; Halogen atoms such as a fluorine atom and a chlorine atom, and the like.

As a specific example of the phenyl group which may have a substituent represented by R <^2> , a phenyl group, 2-chlorophenyl group, 4-methylphenyl group, 3-ethylphenyl group, 2, 4- dimethylphenyl group, 2-methoxyphenyl group, etc. are mentioned. .

In the silane compound copolymer (A), the amount of the group represented by the formula: R ¹ -CH (X ^O ) -D- ([R ¹ -CH (X ^O ) -D]) and the amount of R ² ( The molar ratio of [R ² ]) is preferably [R ¹ -CH (X ^O ) -D]: [R ² ] = 60:40 to 5:95, more preferably 50:50 to 5:95, 50: 50-10: 90 are especially preferable. By being in such a range, the hardened | cured material excellent in transparency and adhesiveness and excellent in heat resistance is obtained.

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

The silane compound copolymer (A) may be any copolymer such as a random copolymer, a block copolymer, a graft copolymer, an alternating copolymer, and a random copolymer is particularly preferable.

The weight average molecular weight (Mw) of a silane compound copolymer (A) is the range of 1,000-30,000, Preferably it is the range of 1,500-6,000. By being in the said range, the hardened | cured material excellent in the handleability of a composition and excellent in adhesiveness and heat resistance is obtained. A weight average molecular weight (Mw) can be calculated | required as a standard polystyrene conversion value by the gel permeation chromatography (GPC) which uses tetrahydrofuran (THF) as a solvent, for example.

Although the molecular weight distribution (Mw / Mn) of a silane compound copolymer (A) is not specifically limited, Usually, 1.0-3.0, Preferably it is the range of 1.1-2.0. By being in the said range, the hardened | cured material excellent in adhesiveness and heat resistance is obtained.

A silane compound copolymer (A) can be used individually by 1 type or in combination of 2 or more type.

The silane compound copolymer (A) is a polysilsesquioxane compound having a ladder structure.

That a silane compound copolymer has a ladder structure can be confirmed, for example by performing infrared absorption spectrum measurement, X-ray diffraction measurement, and NMR measurement of a reaction product.

In the curable composition of this invention, the said (A) component,

(A ') Formula (1): R ¹ -CH (X ^O ) -D-Si (OR ³ ) _p (X ¹ ) _3-p

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, 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 a linking group. R ³ represents an alkyl group having 1 to 6 carbon atoms, X ¹ represents a halogen atom, and p represents an integer of 0 to 3.]

At least one of the silane compounds (1) represented by

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

(In formula, R <^2> represents a C1-C20 alkyl group or the phenyl group which may have a substituent, R <^4> represents a C1-C6 alkyl group, X <^2> represents a halogen atom, q is a 0-3 Represents an integer)

Silane compound copolymer (hereinafter referred to as "silane compound copolymer (A ')") having a weight average molecular weight of 1,000 to 30,000 obtained by condensing a mixture of silane compounds containing at least one kind of silane compound (2) represented by It may be sufficient), and it is preferable that a silane compound copolymer (A) is a silane compound copolymer (A ').

[Silane compound (1)]

The silane compound (1) is a compound represented by the formula (1): R ¹ -CH (X ^O ) -D-Si (OR ³ ) _p (X ¹ ) _{3- p} . By using a silane compound (1), the silane compound copolymer which is excellent in transparency and adhesive force even after hardening can be obtained.

In formula (1), R <^1> represents a hydrogen atom or a C1-C6 alkyl group, and a hydrogen atom is preferable. As an example, what was illustrated as R <^1> in a silane compound copolymer (A) is mentioned.

In formula (1), X <^0> represents group represented by halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a cyano group, or a formula: OG (wherein G represents a protecting group of a hydroxyl group), and D Represents a single bond or a linking group. Specific examples of what represented by X ⁰ and D are, respectively, those exemplified as X ⁰ and D of the silane compound copolymer (A).

R ³ is carbon number such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group The alkyl group of -6 is shown.

X <^1> represents halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

p represents the integer of 0-3.

When p is 2 or more, OR <^{3> may be} same or different. Moreover, when (3-p) is 2 or more, X <^{1> may be} same or different.

Specific examples of the silane compound (1) include chloromethyltrimethoxysilane, bromomethyltriethoxysilane, 2-chloroethyltripropoxysilane, 2-bromoethyltributoxysilane, and 3-chloropropyltri Methoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltripropoxysilane, 3-chloropropyltributoxysilane, 3-bromopropyltrimethoxysilane, 3-bromopropyltriethoxysilane , 3-bromopropyltripropoxysilane, 3-bromopropyltributoxysilane, 3-fluoropropyltrimethoxysilane, 3-fluoropropyltriethoxysilane, 3-fluoropropyltripropoxysilane , 3-fluoropropyltributoxysilane, 3-iodinepropyltrimethoxysilane, 2-chloroethyltrimethoxysilane, 3-chloropropyltriethoxysilane, 4-chlorobutyltripropoxysilane, 5-chloro Pentyltripropoxysilane, 2-chloropropyltrimethoxysilane, 3-cle Rho-3-acetylpropyltrimethoxysilane, 3-chloro-3-methoxycarbonylpropyltrimethoxysilane, o- (2-chloroethyl) phenyltripropoxysilane, m- (2-chloroethyl) phenyl Trialkoxysilane compounds in which X ⁰ is a halogen atom such as trimethoxysilane, p- (2-chloroethyl) phenyltriethoxysilane and p- (2-fluoroethyl) phenyltrimethoxysilane;

Chloromethyltrichlorosilane, bromomethylbromodimethoxysilane, 2-chloroethyldichloromethoxysilane, 2-bromoethyldichloroethoxysilane, 3-chloropropyltrichlorosilane, 3-chloropropyltribromosilane, 3-chloropropyldichloromethoxysilane, 3-chloropropyldichloroethoxysilane, 3-chloropropylchlorodimethoxysilane, 3-chloropropylchlorodiethoxysilane, 3-bromopropyldichloroethoxysilane, 3-bromo Propyltribromosilane, 3-bromopropyltrichlorosilane, 3-bromopropylchlorodimethoxysilane, 3-fluoropropyltrichlorosilane, 3-fluoropropylchlorodimethoxysilane, 3-fluoropropyldichlorome Methoxysilane, 3-fluoropropylchlorodiethoxysilane, 3-iodinepropyltrichlorosilane, 4-chlorobutylchlorodiethoxysilane, 3-chloro-n-butylchlorodiethoxysilane, 3-chloro-3-ace Halogenosilane compounds in which X ⁰ is a halogen atom such as propylpropyldichloroethoxysilane and 3-chloro-3-methoxycarbonylpropyltribromosilane;

Cyanomethyltrimethoxysilane, cyanomethyltriethoxysilane, 1-cyanoethyltrimethoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 2-cyano Ethyltripropoxysilane, 3-cyanopropyltrimethoxysilane, 3-cyanopropyltriethoxysilane, 3-cyanopropyltripropoxysilane, 3-cyanopropyltributoxysilane, 4-cyano Butyl trimethoxysilane, 5-cyanopentyl trimethoxysilane, 2-cyanopropyltrimethoxysilane, 2- (cyanomethoxy) ethyltrimethoxysilane, 2- (2-cyanoethoxy) ethyltri Methoxysilane, o- (cyanomethyl) phenyltripropoxysilane, m- (cyanomethyl) phenyltrimethoxysilane, p- (cyanomethyl) phenyltriethoxysilane, p- (2-cyano Trialkoxysilane compounds in which X ⁰ is a cyano group such as ethyl) phenyltrimethoxysilane;

Cyanomethyltrichlorosilane, cyanomethylbromodimethoxysilane, 2-cyanoethyldichloromethoxysilane, 2-cyanoethyldichloroethoxysilane, 3-cyanopropyltrichlorosilane, 3-cyanopropyl Tribromosilane, 3-cyanopropyldichloromethoxysilane, 3-cyanopropyldichloroethoxysilane, 3-cyanopropylchlorodimethoxysilane, 3-cyanopropylchlorodiethoxysilane, 4-cyanobutylchloro Diethoxysilane, 3-cyano-n-butylchlorodiethoxysilane, 2- (2-cyanoethoxy) ethyltrichlorosilane, 2- (2-cyanoethoxy) ethylbromodiethoxysilane, 2 -(2-cyanoethoxy) ethyldichloropropoxysilane, o- (2-cyanoethyl) phenyltrichlorosilane, m- (2-cyanoethyl) phenylmethoxydibromosilane, p- (2-sia Halogenosilane compounds in which X ⁰ is a cyano group, such as noethyl) phenyldimethoxychlorosilane and p- (2-cyanoethyl) phenyltribromosilane ;

3-acetoxypropyltrimethoxysilane, 3-acetoxypropyltriethoxysilane, 3-acetoxypropyltripropoxysilane, 3-acetoxypropyltributoxysilane, 3-propionyloxypropyltrimethoxysilane , 3-propionyloxypropyltriethoxysilane, 3-benzoyloxypropyltrimethoxysilane, 3-benzoyloxypropyltriethoxysilane, 3-benzoyloxypropyltripropoxysilane, 3-benzoyloxypropyltributoxy Silane, 2-trimethylsilyloxyethyltrimethoxysilane, 3-triethylsilyloxypropyltriethoxysilane, 3- (2-tetrahydropyranyloxy) propyltripropoxysilane, 3- (2-tetrahydrofura Nyloxy) propyltributoxysilane, 3-methoxymethyloxypropyltrimethoxysilane, 3-methoxyethoxymethyloxypropyltriethoxysilane, 3- (1-ethoxyethyloxy) propyltripropoxysilane , 3- (t-butoxycarbonyloxy) propyltrimethoxy Is, 3-t- butoxy-trimethoxysilane, 3-benzyloxy, such as the profile triethoxysilane, 3-triphenyl methoxy-ethoxy propyl triethoxysilane, X ⁰ is the formula: trialkoxy group represented by OG Silane compounds;

3-acetoxypropyltrichlorosilane, 3-acetoxypropyltribromosilane, 3-acetoxypropyldichloromethoxysilane, 3-acetoxypropyldichloroethoxysilane, 3-acetoxypropylchlorodimethoxysilane, 3- Acetoxypropylchlorodiethoxysilane, 3-benzoyloxypropyltrichlorosilane, 3-trimethylsilyloxypropylchlorodimethoxysilane, 3-triethylsilyloxypropyldichloromethoxysilane, 3- (2-tetrahydropyranyloxy ) Propylchlorodiethoxysilane, 3- (2-tetrahydrofuranyloxy) propyldichloroethoxysilane, 3-methoxymethyloxypropyltribromosilane, 3-methoxyethoxymethyloxypropyltrichlorosilane, 3- (1-ethoxyethyloxy) propylchlorodimethoxysilane, 3-t-butoxycarbonyloxypropyldichloromethoxysilane, 3-t-butoxypropylchlorodiethoxysilane, 3-triphenylmethoxypropyldichloroe Oxysilane Halogenosilane compounds such as 3-benzyloxypropyltribromosilane, wherein X ⁰ is a group represented by the formula: OG; And the like.

These silane compounds (1) can be used individually by 1 type or in combination of 2 or more type.

Among these, as a silane compound (1), since the hardened | cured material which has more excellent adhesiveness is obtained, the trialkoxysilane compound whose X <^0> is a halogen atom, the trialkoxysilane compound whose X <^0> is a cyano group, or X <^{0> is used.} Trialkoxysilane compounds which are group represented by this said formula: OG are preferable, the trialkoxysilane compound which has 3-chloropropyl group, the trialkoxysilane compound which has 3-acetoxypropyl group, and the tree which has 2-cyanoethyl group More preferred are alkoxysilane compounds or trialkoxysilane compounds having a 3-cyanopropyl group.

[Silane compound (2)]

The silane compound (2) is a compound represented by formula (2): R ² Si (OR ⁴ ) _q (X ² ) _{3- q} .

In formula (2), R <^2> represents the phenyl group which may have a C1-C20 alkyl group or substituent. As an example, what was illustrated as R <^2> in a silane compound copolymer (A) is mentioned.

R <^4> represents the same C1-C6 alkyl group as said R <^3> .

X ² represents the same halogen atom as X ^{1 described} above.

q represents any integer of 0-3.

When q is 2 or more, OR <^{4> may be} same or different. Moreover, when (3-q) is 2 or more, X <^{2> may be} same or different.

Specific examples of the silane compound (2) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-butyltriethoxysilane , i-butyltrimethoxysilane, n-pentyltriethoxysilane, n-hexyltrimethoxysilane, i-octyltriethoxysilane, dodecyltrimethoxysilane, methyldimethoxyethoxysilane, methyldiethoxy Alkyltrialkoxysilane compounds such as methoxysilane;

Alkylhalo such as methylchlorodimethoxysilane, methyldichloromethoxysilane, methylchlorodiethoxysilane, ethylchlorodimethoxysilane, ethyldichloromethoxysilane, n-propylchlorodimethoxysilane, n-propyldichloromethoxysilane and the like Genoalkoxysilane compounds;

Alkyl trihalogenosilane compounds such as methyl trichlorosilane, methyl tribromosilane, ethyl trichlorosilane, ethyl tribromosilane, and n-propyltrichlorosilane;

Phenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 2-chlorophenyltrimethoxysilane, phenyltriethoxysilane, 2-methoxyphenyltriethoxysilane, phenyldimethoxyethoxysilane, phenyl die Phenyl trialkoxysilane compounds which may have substituents, such as methoxy methoxysilane;

Phenyl halogeno alkoxysilane compounds which may have substituents, such as phenyl chloro dimethoxy silane, phenyl dichloro methoxy silane, phenyl chloro methoxy ethoxy silane, phenyl chloro diethoxy silane, and phenyl dichloro ethoxy silane;

Phenyl trihalogenosilane compound which may have substituents, such as phenyl trichlorosilane, phenyl tribromosilane, 4-methoxyphenyl trichlorosilane, 2-chlorophenyl trichlorosilane, and 2-ethoxyphenyl trichlorosilane; Can be mentioned.

These silane compounds (2) can be used individually by 1 type or in combination of 2 or more type.

[Mixture of silane compounds]

As a mixture of the silane compound used at the time of manufacturing a silane compound copolymer (A '), the mixture which consists of a silane compound (1) and a silane compound (2) may be sufficient, and that in the range which does not impair the objective of this invention Although the mixture containing an external silane compound may be sufficient, the mixture which consists of a silane compound (1) and a silane compound (2) is preferable.

The use ratio of the silane compound (1) and the silane compound (2) is preferably in a molar ratio of [silane compound (1)]: [silane compound (2)] = 60:40 to 5:95, and 50 It is more preferable that it is: 50-5: 95, and it is especially preferable that it is 50: 50-10: 90.

The method for condensing the mixture of silane compounds is not particularly limited, but the silane compound (1), the silane compound (2), and other silane compounds may be dissolved in a solvent as desired, and a predetermined amount of catalyst may be added to And a method of stirring at a predetermined temperature.

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

As an acid catalyst, Inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid, phosphoric acid; Organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid and trifluoroacetic acid; And the like.

Examples of the base catalyst include trimethylamine, triethylamine, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, pyridine, 1,8-diazabicyclo [5.4.0] -7-undecene, aniline, picoline Organic bases such as 1,4-diazabicyclo [2.2.2] octane and imidazole; Organic salt hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; Metal alcoholates such as sodium methoxide, sodium ethoxide, sodium t-butoxide and potassium t-butoxide; Metal hydrides such as sodium hydride and calcium hydride; Metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide; Metal carbonates such as sodium carbonate, potassium carbonate and magnesium carbonate; Metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; And the like.

Among these, as a catalyst to be used, an acid catalyst is preferable and an inorganic acid is more preferable.

The amount of the catalyst used is usually 0.1 mol% to 10 mol%, preferably 1 mol% to 5 mol%, based on the total molar amount of the silane compound.

The solvent to be used can be suitably selected according to the kind etc. of a silane compound. For example, water; Aromatic hydrocarbons such as benzene, toluene and xylene; Esters such as methyl acetate, ethyl acetate, propyl acetate and methyl propionate; Ketones such as acetone, methyl ethyl ketone, methyl i-butyl ketone and cyclohexanone; Alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, s-butyl alcohol and t-butyl alcohol; And the like. These solvent can be used individually by 1 type or in mixture of 2 or more types.

Among them, water, aromatic hydrocarbons and mixed solvents thereof are preferable, and mixed solvents of water and toluene are particularly preferable. When using water and toluene, the ratio (volume ratio) of water and toluene becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 7: 3-3: 7.

The amount of the solvent used is an amount such that the total molar amount of the silane compound per liter of the solvent is usually from 0.1 mol to 10 mol, preferably from 0.5 mol to 10 mol.

The temperature at the time of condensation (reaction) of a silane compound is usually in the temperature range from 0 degreeC to the boiling point of the solvent used, Preferably it is the range of 20 degreeC-100 degreeC. When reaction temperature is too low, advancing of a condensation reaction may become inadequate. On the other hand, when reaction temperature becomes high too much, gelatinization suppression will become difficult. The reaction is usually completed in 30 minutes to 20 hours.

After the completion of the reaction, when an acid catalyst is used, neutralization is performed by adding an aqueous alkali solution such as an aqueous sodium hydrogen carbonate solution to the reaction solution, and when a base catalyst is used, an acid such as hydrochloric acid is added to the reaction solution. The salt which generate | occur | produces at the time can be removed by filtration separation, water washing, etc., and the target silane compound copolymer can be obtained.

(B) an epoxy compound having an isocyanurate skeleton

The curable composition of this invention contains the epoxy compound (henceforth called "epoxy compound (B)") which has an isocyanurate skeleton as (B) component.

Since the curable composition of this invention contains an epoxy compound (B), the hardened | cured material excellent in heat resistance and transparency can be obtained also after heat history.

The epoxy compound (B) is not particularly limited as long as it is a compound having an isocyanurate skeleton (following (c), in which-represents a bond) and an epoxy ring in the molecule. In addition, although the tautomer (cyanurate skeleton (c ')-in which-represents a bonding hand) may exist in the isocyanurate skeleton (c) below, the epoxy compound which has this skeleton Moreover, it shall be contained in the epoxy compound (B) used for this invention.

[Formula 4]

Especially, as an epoxy compound (B), at least of the hydrogen atom couple | bonded with the nitrogen atom of the 1, 3, 5 position of an isocyanurate ring as shown to following formula (c-1)-(c-3) The compound which substituted one by the group (E) which has an epoxy ring is preferable.

[Chemical Formula 5]

(In the formula, E represents a group having an epoxy ring, and R represents any group other than a group having an epoxy ring such as a hydrogen atom or an organic group.)

As group (E) which has the said epoxy ring, it is a following formula, for example.

[Formula 6]

The group shown by (in formula, a, b, c represents the integer of 1-20, respectively, and alkyl groups, such as a methyl group and an ethyl group, may be substituted as a methylene group).

Specific examples of the epoxy compound (B) include glycidyl isocyanurate, diglycidyl isocyanurate and tris (2,3-epoxypropyl) isocyte from the viewpoint of obtaining a cured product having a high adhesion. An anurate, a tris (glycidoxy propyl) isocyanurate, a tris ((alpha)-methyl glycidyl) isocyanurate, the mixture containing 2 or more types of these compounds, etc. are mentioned.

Moreover, as an epoxy compound (B), what is marketed as an epoxy compound which has an isocyanurate frame | skeleton (For example, brand name: TEPIC-S, TEPIC-PAS B22, brand name: TEPIC-PAS B26, etc. are all Nissan Chemicals. Industrial company) can also be used as it is.

Although the compounding quantity of an epoxy compound (B) is not specifically limited, From a viewpoint of obtaining the hardened | cured material which has higher adhesive force, 50-300 g / eq is preferable and 100-200 g / eq is especially preferable as an epoxy equivalent. In addition, epoxy equivalent is a value measured according to JISK7236: 2001.

(C) Curing agent

The curable composition of this invention contains the hardening | curing agent (Hereinafter, it may be called "hardening | curing agent (C)") containing alicyclic acid anhydride which has a carboxyl group as (C) component. Since the curable composition of this invention contains a hardening | curing agent (C), the hardened | cured material excellent in heat resistance can be obtained.

The alicyclic acid anhydride having a carboxyl group is an acid anhydride having an alicyclic structure in which at least one carboxyl group is substituted. As an alicyclic structure, a saturated cyclic hydrocarbon (cycloalkane) structure, an unsaturated cyclic hydrocarbon (cycloalkene, cycloalkyne) structure, etc. are mentioned.

As an alicyclic acid anhydride, 3-methyl-1,2,3,6- tetrahydro phthalic anhydride, 4-methyl-1,2,3,6- tetrahydro phthalic anhydride, tetrahydro phthalic anhydride, 3-methyl- Hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2,3-dicar Acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, methyl-norbornane-2,3-dicarboxylic acid 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.

Among them, cyclohexane-1,2,4-tricarboxylic acid-1,2 anhydride and cyclohexane-1,2,3-tricarboxylic acid-1,2 anhydride in which carboxyl group is substituted with hexahydrophthalic anhydride This is preferable and cyclohexane-1,2,4-tricarboxylic acid-1,2 anhydride is especially preferable. The stereoisomer may exist in this compound, but any isomer may be sufficient as it.

The alicyclic acid anhydride which has a carboxyl group can be used individually by 1 type or in combination of 2 or more type.

The curing agent (C) may further contain another curing agent.

As another hardening | curing agent, alicyclic acid anhydride which does not have a carboxyl group (henceforth "other alicyclic acid anhydride"), aliphatic acid anhydrides, such as a polyazelate anhydride, an aliphatic amine-type hardener, an alicyclic amine-type hardener, agent And secondary or tertiary amine curing agents, aromatic amine curing agents, dicyandiamides, boron trifluoride amine complex salts, and imidazole compounds.

Another hardener can be used individually by 1 type or in combination of 2 or more type.

As another hardening | curing agent, since the hardened | cured material which has high adhesive force is obtained even at high temperature, another alicyclic acid anhydride is preferable. As another alicyclic acid anhydride, the thing similar to what was illustrated as an alicyclic acid anhydride of the alicyclic acid anhydride which has the said carboxyl group is mentioned. Especially, 3-methyl- hexahydro phthalic anhydride and 4-methyl- hexahydro phthalic anhydride are preferable, and 4-methyl- hexahydro phthalic anhydride is especially preferable.

It is preferable that a hardening | curing agent (C) consists of 1 type (s) or 2 or more types chosen from the alicyclic acid anhydride which has a carboxyl group, and other alicyclic acid anhydride, The mass ratio is (alicyclic acid anhydride which has a carboxyl group): Outside alicyclic acid anhydride) = 100: 0-10: 90, It is more preferable that it is 50: 50-10: 90.

(D) silane coupling agent

The curable composition of this invention contains the silane coupling agent (henceforth a "silane coupling agent (D)") which has an acid anhydride structure as (D) component. Since the curable composition of this invention contains a silane coupling agent (D), hardened | cured material which is excellent in transparency and has high adhesive force can be obtained, without being phase-separated (cloudy).

The silane coupling agent (D) is an organosilicon compound having both an acid anhydride group (Y) and a hydrolyzable group (OR ^b ) in one molecule. Specifically, it is a compound represented by following formula (d).

[Formula 7]

In the formula, Y represents an acid anhydride structure, R ^a represents an alkyl group having 1 to 6 carbon atoms or a phenyl group which may have a substituent, R ^b represents an alkyl group having 1 to 6 carbon atoms, i represents an integer of 1 to 3 J represents an integer of 0 to 2, k represents an integer of 1 to 3, and i + j + k = 4.

As Y, the following formula

[Formula 8]

The group represented by (in formula, h shows the integer of 0-10) etc. are mentioned, Group represented by (Y1) is especially preferable.

Formula (d) wherein the alkyl group of 1 to 6 carbon atoms represented by R ^a, R ^b is, there may be mentioned the same groups as alkyl groups having 1 to 6 carbon atoms represented by the R ¹ as a first example, the substituent represented by the above R ^a Examples of the phenyl group which may have a group similar to those exemplified above as the phenyl group which may have a substituent represented by the above R ² .

Especially, as a compound represented by Formula (d), it is following formula (d-1)

[Chemical Formula 9]

(Wherein, R ^b , h, i, j, k represent the same meaning as above)

The compound represented by is preferable. In formula, it is preferable that h is 2-8.

Specific examples of the silane coupling agent represented by formula (d-1) include 2-trimethoxysilylethyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, and the like.

A silane coupling agent (D) can be used individually by 1 type or in combination of 2 or more type.

In the curable composition of this invention, the content rate of said (A), (B), (C) and (D) component is the mass ratio of (A) and [(B) + (C) + (D)]. , (A): [(B) + (C) + (D)] is preferably 90:10 to 50:50. Moreover, the content ratio of said (A '), (B), (C) and (D) component is a mass ratio of (A') and [(B) + (C) + (D)], and (A ' ): [(B) + (C) + (D)] = 90:10-50:50 are preferable.

Moreover, the content ratio of said (B), (C), and (D) component is [(B) + (C)]: (D) by the mass ratio of [(B) + (C)] and (D). It is preferable that it is = 90: 10-10: 90.

By using each component in such a ratio, the curable composition which is excellent in transparency and heat resistance over a long term, and has a hardened | cured material which has high adhesive force even in high temperature can be obtained.

The curable composition of this invention may contain another component further in the range which does not impair the objective of this invention.

As another component, a curing catalyst, antioxidant, an ultraviolet absorber, an optical stabilizer, a diluent, etc. are mentioned.

A curing catalyst is added to promote curing. 2-methylimidazole, a triphenyl phosphine, etc. are mentioned as a curing catalyst. These curing catalysts can be used individually by 1 type or in combination of 2 or more type.

Antioxidant is added in order to prevent oxidative deterioration at the time of heating. As antioxidant, phosphorus antioxidant, a phenolic antioxidant, sulfur type antioxidant, etc. are mentioned.

As phosphorus antioxidant, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris (2, 4-di-) t-butylphenyl) phosphite, cyclic neopentane tetrayl bis (octadecyl) phosphite, cyclic neopentane tetrayl bis (2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl Bis (2,4-di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen Phosphites such as phosphite; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9 Oxaphosphaphenanthrene oxides, such as -oxa-10-phosphazanthanthene-10-oxide and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphazanthanth-10-oxide ; .

As a phenolic antioxidant, 2,6-di-t-butyl-p-cresol, dibutylhydroxytoluene, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, ste Monophenols such as aryl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate; 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3- Methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis [1,1-dimethyl-2- {β- ( Bisphenols such as 3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} 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, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3' -Bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ', 5'-di-t-butyl-4'-hydroxy Polymeric phenols such as benzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione and tocophenol; .

Examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and the like. Can be mentioned.

These antioxidants can be used individually by 1 type or in combination of 2 or more type. However, since the curable composition of this invention contains (B) component and (D) component, the oxidation deterioration at the time of heating does not produce easily even if there is no antioxidant especially. When using antioxidant, the usage-amount is 0.01-10 mass parts normally with respect to 100 mass parts of silane compound copolymers (A) or (A ').

A ultraviolet absorber is added for the purpose of improving the light resistance of the hardened | cured material obtained.

As a ultraviolet absorber, For example, Salicylic acids, such as phenyl salicylate, p-t- butylphenyl salicylate, p-octylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2 Benzos such as' -dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and 2-hydroxy-4-methoxy-5-sulfobenzophenone Phenones; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ' , 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'- Hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-amylphenyl) benzotriazole, Benzotria, such as 2-{(2'-hydroxy-3 ', 3' ', 4' ', 5' ', 6' '-tetrahydrophthalimidemethyl) -5'-methylphenyl} benzotriazole Sols; Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1, Hindered amines such as 2,2,6,6-pentamethyl-4-piperidyl) [{3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] butyl malonate; And the like.

These ultraviolet absorbers can be used individually by 1 type or in combination of 2 or more type.

The usage-amount of a ultraviolet absorber is 0.01-10 mass parts normally with respect to 100 mass parts of silane compound copolymers (A) or (A ').

An optical stabilizer is added for the purpose of improving the light resistance of the hardened | cured material obtained.

As an optical stabilizer, for example, poly [{6- (1,1,3,3, -tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2 And hindered amines such as 6,6-tetramethyl-4-piperidine) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidine) imino}]. Can be.

These light stabilizers can be used individually by 1 type or in combination of 2 or more type.

The usage-amount of an optical stabilizer is 0.01-10 mass parts normally with respect to 100 mass parts of silane compound copolymers (A) or (A ').

Diluents are added to adjust the viscosity of the curable composition.

As a diluent, For example, glycerin diglycidyl ether, butanediol diglycidyl ether, diglycidyl aniline, neopentyl glycol glycidyl ether, cyclohexane dimethanol diglycidyl ether, alkylene diglyci Dyl ether, polyglycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, 4-vinylcyclohexene monooxide, vinylcyclohexenedioxide, methylated vinylcyclo Hexene dioxide and the like.

These diluents can be used individually by 1 type or in combination of 2 or more type.

The curable composition of this invention mix | blends the said (A) or (A '), (B), (C), (D) component, and the other component in predetermined ratio as desired, for example, to a well-known method, By mixing and defoaming.

According to the curable composition of this invention obtained as mentioned above, even when high energy light is irradiated or high temperature state, it does not color and transparency falls, it has the outstanding transparency over a long term, and also has high adhesive force The hardened | cured material which has is obtained.

Therefore, the curable composition of this invention is used suitably as a raw material, an adhesive agent, a coating agent, etc. of an optical component or a molded object. In particular, the curable composition of the present invention can be suitably used as a composition for an optical device fixing material in view of solving the problem of deterioration of the optical device fixing material with high brightness of the optical device.

2) cured product

2nd of this invention is hardened | cured material formed by hardening | curing the curable composition of this invention.

Heat hardening is mentioned as a method of hardening | curing the curable composition of this invention. The heating temperature at the time of hardening is 100-200 degreeC normally, and a heating time is 10 minutes-20 hours normally, Preferably it is 30 minutes-10 hours.

Even if high energy light is irradiated or a high temperature state, the hardened | cured material of this invention does not color and transparency falls, it has the outstanding transparency over a long term, and has high adhesive force.

Therefore, the hardened | cured material of this invention is used suitably as an optical component, a molded object, an adhesive layer, a coating layer, etc. In particular, the cured product of the present invention can be suitably used as an optical device fixing material in view of solving the problem of deterioration of the optical device fixing material with high brightness of the optical device.

It can be confirmed that the hardened | cured material of this invention has a high adhesive force by measuring adhesive force as follows, for example. That is, a curable composition is apply | coated to the mirror surface of a silicon chip, a coating surface is mounted on a to-be-adhered body, it crimped | bonded, and it heat-processes and hardens. This is left for 30 seconds on the measurement stage of the bond tester heated to predetermined temperature (for example, 23 degreeC, 100 degreeC) previously, and it is horizontal direction (shear direction) with respect to an adhesive surface from the position of 50 micrometer height in a to-be-adhered body. ) To measure the adhesion between the specimen and the adherend.

It is preferable that the adhesive force of hardened | cured material is 110 N / 2 mmsquare or more in 23 degreeC.

It can be confirmed that the said hardened | cured material is excellent in transparency by measuring light transmittance. As for the light transmittance of hardened | cured material, 80% or more is preferable at the light of wavelength 400 nm, 84% or more is especially preferable, and 87% or more is preferable at the light of wavelength 450 nm.

The said hardened | cured material is excellent in heat resistance over a long term can be confirmed by the point that the change of transparency is small, even after leaving hardened | cured material for a long time at high temperature. After 500 hours of transparency at 150 ° C., the transmittance with a wavelength of 400 nm is preferably 70% or more, and more preferably 80% or more of the initial transmittance.

3) Use of Curable Composition

3rd of this invention is the method of using the curable composition of this invention as an adhesive agent for optical element fixing materials, or the sealing agent for optical element fixing materials.

As an optical element, light emitting elements, such as LED and LD, a light receiving element, a composite optical element, an optical integrated circuit, etc. are mentioned.

〈Glue for optical element fixing material〉

The curable composition of this invention can be used suitably as an adhesive agent for optical element fixing materials.

As a method of using the curable composition of the present invention as an adhesive for an optical device fixing material, after applying the composition to one or both adhesive surfaces of a material (optical device and its substrate) to be subjected to adhesion, and compressing the composition, The method of making it harden | cure by heat-hardening and adhere | attaching the material made into the object of adhesion | attachment is mentioned.

As a main substrate material for bonding an optical element, Glass, such as soda-lime glass and heat resistant hard glass; Ceramics; Metals such as iron, copper, aluminum, gold, silver, platinum, chromium, titanium, alloys of these metals, and stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.); Polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyether ether ketone, polyether sulfone, polyphenylene sulfide, polyetherimide Synthetic resins such as polyimide, polyamide, acrylic resin, norbornene-based resin, cycloolefin resin and glass epoxy resin; And the like.

Although heating temperature at the time of heat-hardening may differ according to the curable composition etc. to be used, it is 100-200 degreeC normally. The heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

<Seal Agent for Optical Device Fixing Material>

The curable composition of this invention can be used suitably as a sealant of an optical element sealing body.

As a method of using the curable composition of the present invention as a sealant for an optical device fixing material, for example, the composition is molded into a desired shape, a molded article containing an optical device is obtained, and the optical device sealant is formed by heating and curing it. The manufacturing method etc. are mentioned.

It does not specifically limit as a method of shape | molding the curable composition of this invention to a desired shape, A well-known mold method, such as a normal transfer molding method and the casting method, can be employ | adopted.

Although heating temperature at the time of heat-hardening may differ according to the curable composition etc. to be used, it is 100-200 degreeC normally. The heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

Since the optical element sealing body obtained uses the curable composition of this invention, even if the peak wavelength of light emission, such as a white and blue light emitting LED, is short-wavelength using 400-490 nm, it coloring by heat and light It is excellent in transparency and heat resistance which do not deteriorate.

Example

Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

(Weight average molecular weight measurement)

The weight average molecular weight (Mw) of the silane compound copolymer obtained by the manufacture example was made into the standard polystyrene conversion value, and it measured on the following apparatuses and conditions.

Device name: HLC-8220 GPC, manufactured by Tosoh Corporation

Column: Serial connection of TSKgel GMHXL, TSKgel GMHXL, and TSKgel 2000HXL

Solvent: tetrahydrofuran

Injection volume: 80 μl

Measurement temperature: 40 ℃

Flow rate: 1 ml / min

Detector: differential refractometer

(Measurement of IR spectrum)

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

Fourier Transform Infrared Spectrophotometer (Spectrum 100, manufactured by Parkin Elmer)

(Production Example 1)

In a 300 ml eggplant flask, 16.7 g (84 mmol) of phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) as the silane compound (2), and 3-acetoxypropyltrimethoxysilane as the silane compound (1) ( 8.0 g (36 mmol) of Azmax Co., Ltd., 60 mL of toluene, and 30 mL of distilled water were injected as a solvent, and 0.15 g (1.5 mmol) of phosphoric acid (Kanto Chemical Co., Ltd.) was added as a catalyst, stirring, Stirring was continued for another 16 hours at room temperature.

After the reaction was completed, 100 ml of ethyl acetate was added to the reaction mixture, and the mixture was neutralized with saturated aqueous sodium hydrogen carbonate solution. After stopping for a while, the organic layer was separated. Subsequently, the organic layer was washed twice with distilled water and then dried over anhydrous magnesium sulfate. After magnesium sulfate was separated by filtration, the filtrate was concentrated to 50 ml with an evaporator, which was dropped into a large amount of n-hexane to precipitate, and the precipitate was separated by decantation. The obtained precipitate was dissolved in methyl ethyl ketone and recovered, and the solvent was distilled off under reduced pressure with an evaporator to obtain 14.7 g of a silane compound copolymer (A1) by vacuum drying.

The weight average molecular weight (Mw) of the silane compound copolymer (A1) was 2,700, and the molecular weight distribution (Mw / Mn) was 1.53.

Moreover, IR spectrum (Fourier Transform Infrared Spectrophotometer (FT-IR)) data of a silane compound copolymer (A1) is shown below.

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

(Production Example 2)

Preparation Example 1, except that the usage-amount of phenyltrimethoxysilane was 14.3 g (72 mmol) and the usage-amount of 3-acetoxypropyltrimethoxysilane was 10.7 g (48 mmol). In the same manner as the above, 15.9 g of a silane compound copolymer (A2) was obtained.

The weight average molecular weight (Mw) of the silane compound copolymer (A2) was 2,600, and the molecular weight distribution (Mw / Mn) was 1.50.

Moreover, IR spectrum (Fourier Transform Infrared Spectrophotometer (FT-IR)) data of a silane compound copolymer (A2) is shown below.

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

(Production Example 3)

Preparation Example 1, except that the usage amount of phenyltrimethoxysilane was 19.0 g (96 mmol), and the usage-amount of 3-acetoxypropyltrimethoxysilane was 5.3 g (24 mmol). In the same manner as the above, 14.9 g of a silane compound copolymer (A3) was obtained.

The weight average molecular weight (Mw) of the silane compound copolymer (A3) was 2,500, and the molecular weight distribution (Mw / Mn) was 1.59.

Moreover, IR spectrum (Fourier Transform Infrared Spectrophotometer (FT-IR)) data of a silane compound copolymer (A3) is shown below.

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

(Production Example 4)

In manufacture example 1, instead of using 16.7 g (84 mmol) of phenyl trimethoxysilane and 8.0 g (36 mmol) of 3-acetoxy propyl trimethoxysilane (Phenyltrimethoxysilane (Tokyo Chemical Co., Ltd.) 14.9 g (60 mmol) and 3-glycidoxypropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) (in the following Tables 1 and 2, "GlyTMS" is described) 14.2 g (60 mmol) 16.3 g of silane compound copolymer (A4) was obtained in the same manner as in Production Example 1, except that was used.

 The weight average molecular weight (Mw) of the silane compound copolymer (A4) was 2,800, and the molecular weight distribution (Mw / Mn) was 1.56.

 Moreover, IR spectrum (Fourier Transform Infrared Spectrophotometer (FT-IR)) data of a silane compound copolymer (A4) is shown below.

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

(Production Example 5)

19.0 g (96 mmol) of phenyl trimethoxysilane (made by Tokyo Kasei Kogyo Co., Ltd.) as a silane compound (2) in a 300 ml eggplant flask, and 3-chloropropyl trimethoxysilane (The Tokyo Chemical Co., Ltd.) as a silane compound (1) 4.77 g (24 mmol) of industrial company), 60 ml of toluene and 30 ml of distilled water are injected as a solvent, and 0.15 g (1.5 mmol) of phosphoric acid (made by Kanto Chemical Co., Ltd.) is added as a catalyst, stirring, and it adds at room temperature. Stirring was continued for 16 hours.

After the reaction was completed, 100 ml of ethyl acetate was added to the reaction mixture, and the mixture was neutralized with saturated aqueous sodium hydrogen carbonate solution. After stopping for a while, the organic layer was separated. Subsequently, the organic layer was washed twice with distilled water and then dried over anhydrous magnesium sulfate. After magnesium sulfate was separated by filtration, the filtrate was added dropwise in a large amount of n-hexane to reprecipitate, and hexane was removed to remove the precipitate. The obtained precipitate was dissolved in methyl ethyl ketone and recovered, and the solvent was distilled off under reduced pressure with an evaporator to obtain 13.6 g of a silane compound copolymer (A5) by vacuum drying.

The weight average molecular weight (Mw) of the silane compound copolymer (A5) was 3,000, and the molecular weight distribution (Mw / Mn) was 1.59.

Moreover, IR spectrum data of a silane compound copolymer (A5) is shown below.

Si-Ph: 700 cm ^-1 , 741 cm ^-1 , Si-O: 1132 cm ^-1 , -Cl: 648 cm ^-1

(Production Example 6)

In Production Example 5, except that the amount of phenyltrimethoxysilane used was 16.7 g (84 mmol), and the amount of 3-chloropropyltrimethoxysilane was used in 7.15 g (36 mmol), In the same manner, 13.4 g of a silane compound copolymer (A6) was obtained.

The weight average molecular weight (Mw) of the silane compound copolymer (A6) was 3,300, and the molecular weight distribution (Mw / Mn) was 1.59.

Moreover, IR spectrum data of a silane compound copolymer (A6) is shown below.

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

(Production Example 7)

In Production Example 5, except that the usage-amount of phenyltrimethoxysilane was 14.3 g (72 mmol), and the usage-amount of 3-chloropropyltrimethoxysilane was 9.54 g (48 mmol), In the same manner, 13.0 g of a silane compound copolymer (A7) was obtained.

The weight average molecular weight (Mw) of the silane compound copolymer (A7) was 3,400, and the molecular weight distribution (Mw / Mn) was 1.61.

Moreover, IR spectrum data of a silane compound copolymer (A7) is shown below.

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

(Preparation Example 8)

In Production Example 5, except that the usage-amount of phenyltrimethoxysilane was 11.9 g (60 mmol), and the usage-amount of 3-chloropropyltrimethoxysilane was 11.9 g (60 mmol), In the same manner, 12.9 g of a silane compound copolymer (A8) was obtained.

The weight average molecular weight (Mw) of the silane compound copolymer (A8) was 3,600, and the molecular weight distribution (Mw / Mn) was 1.63.

Moreover, IR spectrum data of a silane compound copolymer (A8) is shown below.

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

(Preparation Example 9)

In Production Example 5, the same as in Production Example 5 except that 4.21 g (24 mmol) of 2-cyanoethyltrimethoxysilane (manufactured by Azmax) was used instead of 4.77 g of 3-chloropropyltrimethoxysilane. 13.5 g of silane compound copolymers (A9) were obtained.

The weight average molecular weight (Mw) of the silane compound copolymer (A9) was 2,900, and the molecular weight distribution (Mw / Mn) was 1.58.

Moreover, IR spectrum data of a silane compound copolymer (A9) is shown below.

Si-Ph: 700 cm ^-1 , 741 cm ^-1 , Si-O: 1131 cm ^-1 , -CN: 2252 cm ^-1

(Preparation Example 10)

Preparation Example 9, except that the usage amount of phenyltrimethoxysilane was 16.7 g (84 mmol) and the usage amount of 2-cyanoethyltrimethoxysilane was 6.31 g (36 mmol). In the same manner as the above, 13.3 g of a silane compound copolymer (A10) was obtained.

The weight average molecular weight (Mw) of the silane compound copolymer (A10) was 3,200, and the molecular weight distribution (Mw / Mn) was 1.64.

Moreover, IR spectrum data of a silane compound copolymer (A10) is shown below.

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

(Manufacture example 11)

Preparation Example 9, except that the amount of phenyltrimethoxysilane used was 14.3 g (72 mmol) and the amount of 2-cyanoethyltrimethoxysilane was 8.41 g (48 mmol). In the same manner as in the above, 12.8 g of a silane compound copolymer (A11) was obtained.

The weight average molecular weight (Mw) of the silane compound copolymer (A11) was 3,300, and the molecular weight distribution (Mw / Mn) was 1.62.

Moreover, IR spectrum data of a silane compound copolymer (A11) is shown below.

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

(Production Example 12)

Preparation Example 9, except that the usage amount of phenyltrimethoxysilane was 11.9 g (60 mmol) and the usage amount of 2-cyanoethyltrimethoxysilane was 10.5 g (60 mmol). In the same manner as in the above, 12.3 g of a silane compound copolymer (A12) was obtained.

The weight average molecular weight (Mw) of the silane compound copolymer (A12) was 3,500, and the molecular weight distribution (Mw / Mn) was 1.61.

Moreover, IR spectrum data of a silane compound copolymer (A12) is shown below.

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

(Example 1)

Epoxy compound (TEPIC-PAS B26 by Nissan Chemical Industries, Ltd., epoxy equivalent 137 g / eq) which has isocyanurate frame | skeleton as an epoxy compound (B) to 10 g of silane compound copolymers (A1) obtained by the manufacture example 1 (following) In the 1st table | surface and 2nd table | surface, 4-methylcyclohexane- 1, 2- dicarboxylic acid anhydride (made by Tokyo Chemical Industry Co., Ltd.) as 1.5 g and a hardening | curing agent (C) (the 1st table | surface) 0.375 g and cyclohexane-1,2,4-tricarboxylic acid-1,2- anhydride (made by Mitsubishi Gas Chemical Co., Ltd.) (alicyclic acid anhydride which has a carboxyl group) in a 2nd table | surface (In the following 1st table | surface and 2nd table | surface, it describes as "C2.)) 0.75g and 3-triethoxysilylpropyl succinic anhydride (made by Azmax company) as a silane coupling agent (D) (the 1st table | surface) Curable composition by adding 0.375 g of a 2nd table, "it is described as" D1 ", and fully mixing and defoaming whole capacity. (1) was obtained.

(Examples 2-7)

According to the following 1st table | surface, curable compositions (2)-(7) were obtained like Example 1 using the silane compound copolymer, an epoxy compound, a hardening | curing agent, and a silane coupling agent.

In addition, in the following 1st table | surface and 2nd table | surface, "B2" shows the epoxy compound (TEPIC-PAS B22 by Nissan Chemical Industries, Ltd., epoxy equivalent 179g / eq) which has an isocyanurate skeleton.

(Comparative Examples 1 and 2)

According to the following 1st table | surface, curable compositions (8) and (9) were obtained like Example 1 using the silane compound copolymer, an epoxy compound, a hardening | curing agent, and a silane coupling agent.

(Comparative Example 3)

In Example 1, 3, 4- epoxycyclohexane carboxylic acid 3, 4- epoxy cyclohexylmethyl (made by Sigma-Aldrich) instead of an epoxy compound (B) (In the following 1st table | surface, 2nd table | surface, BF1 "), and the curable composition (10) was obtained like Example 1 except having used 1.5 g.

(Comparative Example 4)

In Example 1, except having used the silane compound copolymer (A4) obtained by the manufacture example 4 instead of the silane compound copolymer (A1) obtained by the manufacture example 1, it carried out similarly to Example 1, and the curable composition (11 )

(Comparative Example 5)

In Example 1, 3-glycidoxy propyl trimethoxysilane (made by Tokyo Kasei Kogyo Co., Ltd.) (it describes as "DF1" in the following 1st table | surface and 2nd table | surface) instead of a silane coupling agent (D1) 0.375 Except having used g, it carried out similarly to Example 1, and obtained the curable composition (12).

(Comparative Example 6)

Example 1 except that 0.375 g of orthosilicate tetramethyl (manufactured by Tokyo Chemical Industry Co., Ltd.) (described as "DF2" in the following Tables 1 and 2) was used as the silane coupling agent (D1) of Example 1. In the same manner, the curable composition (13) was obtained.

(Example 8)

1.5 g of epoxy compounds (TEPIC-PAS B26 manufactured by Nissan Chemical Industries, Ltd., epoxy equivalent 137 g / eq) having an isocyanurate skeleton as an epoxy compound (B) in 10 g of the silane compound copolymer (A5) obtained in Production Example 5. As the curing agent (C), 0.38 g of 4-methylcyclohexane-1,2-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride ( Curable composition by adding 0.75 g of Mitsubishi Gas Chemical Co., Ltd. and 0.38 g of 3-triethoxysilylpropyl succinic anhydride (manufactured by Azmax Corporation) as the silane coupling agent (D), and fully mixing and defoaming the entire capacity. (14) was obtained.

(Examples 9-15, Comparative Examples 7-16)

According to the following 2nd table | surface, curable compositions (15)-(31) were obtained like Example 8 using the silane compound copolymer, an epoxy compound, a hardening | curing agent, and a silane coupling agent.

About the hardened | cured material of curable compositions 1-31 obtained in Examples 1-15 and Comparative Examples 1-16, the adhesive force, initial stage transmittance | permeability, and the transmittance | permeability after heating were measured as follows.

The measurement results are shown in the following third table and fourth table.

(Adhesion test)

Each of the curable compositions 1-31 was apply | coated to the mirror surface of the 2 mm square silicon chip so that thickness might be set to about 2 micrometers, and the coated surface was mounted on the to-be-adhered body (silver-plated copper plate), and was crimped | bonded. Then, it heat-processed at 180 degreeC for 2 hours and hardened | cured and obtained the to-be-adhered body with a test piece. This to-be-adhered to-be-adhered body was left to stand on the measurement stage of the bond tester (Series 4000, Daisy company) heated to predetermined temperature (23 degreeC, 100 degreeC) previously, and from a position of 50 micrometer height in a to-be-adhered body, Stress was applied in the horizontal direction (shear direction) to the adhesive surface at a speed of 200 μm / s, and the adhesive force (N / 2 mm □) between the test piece and the adherend at 23 ° C. and 100 ° C. was measured.

(Adhesion heat resistance)

In the adhesive force test, the case where "(circle)" and less than 50% of the case where the adhesive force in 100 degreeC is 50% or more of the adhesive force in 23 degreeC was evaluated as "x".

(Measurement of initial transmittance)

Each of curable compositions 1-31 was poured into the mold so that it might be set to length 25mm, width 20mm, and thickness 1mm, and it heated and hardened | cured at 140 degreeC for 6 hours, and produced the test piece, respectively. About the obtained test piece, the initial stage transmittance | permeability (%) of wavelength 400nm and 450nm was measured with the spectrophotometer (MPC-3100, Shimadzu Corporation make).

(Initial transparency)

In initial stage transmittance | permeability measurement, the transmittance | permeability of 400 nm evaluated "(circle)", 70% or more, and less than 80% of "(circle)", and less than 70% of "(circle)" as "x".

(Measurement of transmittance after heating)

Each test piece which measured the initial transmittance | permeability was thrown into the oven of 150 degreeC for 500 hours, and the transmittance | permeability (%) of wavelength 400nm and 450nm was measured again. This was made into the transmittance | permeability after heating.

[Heat resistance (transparency after heating)]

In the measurement of the transmittance | permeability after heating, when the transmittance | permeability of 400 nm is 80% or more of initial stage transmittance | permeability, it evaluated as "(circle)", 70% or more and less than 80%, it evaluated as "(triangle | delta)" and less than 70% as "x".

From the 3rd table | surface and the 4th table | surface, the hardened | cured material of the curable compositions (1-7, 14-21) of Examples 1-15 has a high adhesive force of 134 N / 2mm @ or more in 23 degreeC, and is high temperature (100 (Degree. C.), the adhesive strength of 58% or more of the adhesive force at 23 ° C. was maintained, and the adhesion heat resistance was excellent. Moreover, the initial transmittance | permeability of wavelength 400nm and 450nm and the transmittance | permeability after heating were all high, and it was excellent in initial stage transparency and heat resistance (transparency after heating).

On the other hand, the hardened | cured material of the curable compositions (8, 12, 13, 22, 25-27, 30, 31) of Comparative Examples 1, 5-7, 10-12, 15, 16 was inferior to initial stage transparency. Hardened | cured material of the curable compositions (9, 23, 28) of Comparative Examples 2, 8 and 13 was inferior in both the adhesive force and the adhesive heat resistance, and the curable compositions (10, 11, 24 and 29) of Comparative Examples 3, 4, 9 and 14 The cured product was markedly inferior in heat resistance (transparency after heating).

Claims (13)

In the molecule (A), the following formulas (i), (ii) and (iii)
[Formula 1]

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, 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 a linking group. R <^2> represents the C1-C20 alkyl group or the phenyl group which may have a substituent.]
In the repeating unit shown by (b), it has a repeating unit of (i) and (ii), (i) and (iii), (ii) and (iii) or (i), (ii) and (iii), and a weight average Silane compound copolymer having a molecular weight of 1,000 to 30,000,
(B) an epoxy compound having an isocyanurate skeleton,
(C) a curing agent containing an alicyclic acid anhydride having a carboxyl group, and
(D) Silane coupling agent having an acid anhydride structure
Curable composition containing. The method of claim 1,
The silane compound in the copolymer (A), formula: R existing amount of the group represented by ^{1 -CH (X O) -D- (} [R 1 -CH (X O) -D]) and the amount present in R ² ([R ^2]) in a molar ^{ratio, [R 1 -CH (X O} ) -D] of: [R ^2] = 60:40 ~ silane compound copolymer composition of the curable 5:95. 3. The method according to claim 1 or 2,
The content ratio of said (A), (B), (C), and (D) component is a mass ratio of (A) and [(B) + (C) + (D)], and (A): [(B ) + (C) + (D)] = 90: 10-50: 50 Curable composition characterized by the above-mentioned. (A ') Formula (1): R ¹ -CH (X ^O ) -D-Si (OR ³ ) _p (X ¹ ) _3-p
[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, 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 a linking group. R ³ represents an alkyl group having 1 to 6 carbon atoms, X ¹ represents a halogen atom, and p represents an integer of 0 to 3.]
At least one of the silane compounds (1) represented by
Formula (2): R ² Si (OR ⁴ ) _q (X ² ) _3-q
(In formula, R <^2> represents a C1-C20 alkyl group or the phenyl group which may have a substituent, R <^4> represents a C1-C6 alkyl group, X <^2> represents a halogen atom, q is an integer of 0-3. Indicates)
Silane compound copolymer with a weight average molecular weight of 1,000-30,000 obtained by condensing the mixture of the silane compound containing at least 1 sort (s) of the silane compound (2) represented by
(B) an epoxy compound having an isocyanurate skeleton,
(C) a curing agent containing an alicyclic acid anhydride having a carboxyl group, and
(D) Silane coupling agent having an acid anhydride structure
Curable composition containing. The method of claim 4, wherein
The silane compound copolymer of the above-mentioned (A ') has a silane compound (1) and a silane compound (2) in a molar ratio, and [silane compound (1)]: [silane compound (2)] = 60: 40-5: 95 Curable composition obtained by condensation at the ratio of. The method according to claim 4 or 5,
The content ratio of the above-mentioned (A '), (B), (C) and (D) component is a mass ratio of (A') and [(B) + (C) + (D)], and (A '): [(B) + (C) + (D)] = 90: 10-50: 50 Curable composition characterized by the above-mentioned. The method according to claim 1 or 4,
The content ratio of the said (B), (C) and (D) component is [(B) + (C)] :( D) = 90 by mass ratio of [(B) + (C)] and (D). Curable composition characterized by the above-mentioned: 10-10: 90. The method according to claim 1 or 4,
The hardening | curing agent of said (C) consists of 1 type (s) or 2 or more types chosen from an alicyclic acid anhydride which has a carboxyl group, and other alicyclic acid anhydrides, and the mass ratio is (alicyclic acid anhydride which has a carboxyl group): (others) Alicyclic acid anhydride) = 100: 0-10:90 curable composition. The method according to claim 1 or 4,
Curable composition which is a composition for optical element fixing materials. Hardened | cured material formed by hardening | curing the curable composition of Claim 1 or 4. 11. The method of claim 10,
Hardened | cured material which is an optical element fixing material. The method of using the curable composition of Claim 1 or 4 as an adhesive agent for optical element fixing materials. The method of using the curable composition of Claim 1 or 4 as a sealing agent for optical element fixing materials.