TW201609976A - Curable composition, cured material, method of using curable composition, and optical device - Google Patents

Abstract

The present invention is: a curable composition having components (A) through (E), the curable composition characterized by containing component (A) and component (B) in a mass ratio of [component (A):component (B)] = 100:0.3-100:20; a cured material; a method of using the curable composition; and an optical device. Component (A): a silane compound copolymer represented by formula (a-1) (where X0 represents a cyano group or the like, D represents a single bond or the like, R1 represents a hydrogen atom or the like, R2 represents a C1-20 alkyl group or the like, Z1-Z4 represent hydroxyl groups or the like, m and n represent positive integers, and o-r represent 0 or positive integers). Component (B): microparticles having an average primary particle diameter of more than 0.04 [mu]m to less than or equal to 8 [mu]m. Component (C): a silane coupling agent having a nitrogen atom. Component (D): a silane coupling agent having an acid anhydride structure. Component (E): a silane coupling agent having a sulfur atom-containing functional group. The present invention provides: a curable composition such that the resultant cured material has excellent peeling resistance and heat resistance, and high adhesive strength; a cured material obtained by curing the composition; a method of using the curable composition as an adhesive or the like for an optical element; and an optical device. (a-1): (CHR1X0-D-SiO3/2)m(R2SiO3/2)n(CHR1X0-D-SiZ1O2/2)o(R2SiZ2O2/2)p(CHR1X0-D-SiZ3 2O1/2)q(R2SiZ4 2O1/2)r.

Description

Curing composition, cured product, method for using curable composition, and optical device

The present invention relates to a curable composition which is excellent in peeling resistance and heat resistance and has a high adhesion, and a cured product obtained by curing the composition, and the composition is used as an adhesive for an optical element. Or a method of packaging materials for optical components, and an optical device.

In recent years, the curable composition has been variously modified in accordance with the use, and has been widely used as a raw material, an adhesive, a coating agent, and the like of the optical member and the molded article.

In addition, the curable composition has been attracting attention as a composition for an optical element fixing material such as an adhesive for an optical element or a sealing material for an optical element.

The optical element includes various types of lasers such as semiconductor lasers (LDs), light-emitting elements such as light-emitting diodes (LEDs), light-receiving elements, composite optical elements, and optical integrated circuits. In recent years, optical elements of blue light and white light having a shorter wavelength of a light-emitting peak have been developed and are gradually being widely used. The high luminance of such a light-emitting element having a short light-emitting peak wavelength is progressing violently, and in this case, the heat generation amount of the optical element tends to gradually increase.

With the recent increase in brightness of optical components, optical component fixing materials have been used. The cured product of the composition is exposed to higher temperature heat generated from higher energy light and light elements for a long period of time, causing problems of deterioration and peeling, followed by low force.

In order to solve this problem, Patent Literatures 1 to 3 propose a composition for an optical element fixing material containing a polysilsesquioxane compound as a main component, and Patent Document 4 proposes a hydrolysis using a decane compound. . A member for a semiconductor light-emitting device of a polycondensate or the like.

However, even in the cured product such as the composition or the member described in Patent Documents 1 to 4, it is difficult to obtain peeling resistance and heat resistance while maintaining sufficient adhesion.

Therefore, it has been desired to develop a curable composition capable of obtaining a cured product excellent in peeling resistance and heat resistance and having high adhesion.

Prior 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 Laid-Open Patent Publication No. 2007-112975 (US2009008673A1)

The present invention has been made in view of the actual circumstances of the prior art, and an object of the present invention is to provide a curable composition which is excellent in peeling resistance (interlayer separation resistance) and heat resistance and has a high adhesion. Hardened The cured product is used as a method for using an adhesive for an optical element or an encapsulant for an optical element, and an optical device.

As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing a specific decane compound copolymer, fine particles, and a decane coupling agent in a specific ratio can be excellent in peeling resistance and heat resistance. The present invention has been completed with a high adhesion hardener.

Thus, according to the present invention, the curable composition of the following [1] to [8], the cured product of [9], [10], the method of using the curable composition of [11], [12], and the like, and [13] Light device.

[1] A hardening composition comprising a curable composition of the following components (A) to (E), characterized in that: (A) component and (B) component, (A) component and ( B) The mass ratio of the component is [(A) component: (B) component] == 100: 0.3 to 100:20, (A) a decane compound copolymer represented by the following formula (a-1), (CHR ¹ X ⁰ -D-SiO _3/2 ) _m (R ² SiO _3/2 ) _n (CHR ¹ X ⁰ -D-SiZ ¹ O _2/2 ) ₀ (R ² SiZ ² O _2/2 ) _p (CHR ¹ X ⁰ -D-SiZ ³ ₂ O _1/2 ) _q (R ² SiZ ⁴ ₂ O _1/2 ) _r ‧‧‧(a-1)

In the formula, X ⁰ represents a halogen atom, a cyano group, or a group represented by the formula: OG (wherein G represents a protective group of a hydroxyl group), and D represents a single bond, or has a substituent or has no substitution. A divalent organic group having 1 to 20 carbon atoms. R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ² represents an alkyl group having 1 to 20 carbon atoms or a phenyl group having a substituent or a substituent. Z ¹ to Z ⁴ each independently represent a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. m and n are each independent and represent a positive integer. o, p, q, r are each independent and represent 0 or a positive integer], (B) fine particles having an average primary particle diameter of more than 0.04 μm and 8 μm or less, (C) a decane coupling agent having a nitrogen atom in the molecule, and (D) a molecule a decane coupling agent having an acid anhydride structure and (E) a decane coupling agent having a functional group containing a sulfur atom in the molecule.

[2] The curable composition according to [1], wherein the component (B) is selected from the group consisting of silica, polysilicon, and a metal oxide coated with a silicone. At least one type of microparticles.

[3] The curable composition according to [1], wherein the component (A) has a mass average molecular weight of 800 to 30,000.

[4] The curable composition according to [1], wherein the (A) component is in the formula (a-1), (m+o+q) and (n+p+r) are (m+o). +q): (n+p+r)=5:95~60:40 ratio of the compound.

[5] The curable composition according to any one of [1] to [4] further comprising a diluent.

[6] The curable composition according to [1], wherein the total amount of the component (A), the component (B), the component (C), the component (D), and the component (E) is relative to The total amount of the components after removing the diluent of the curable composition is 50 to 100% by mass.

[7] The curable composition according to [1], wherein the curable composition has a solid content concentration of 50 to 100% by mass.

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

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

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

[11] A method of using the curable composition according to the above [1] as an adhesive for an optical element fixing material.

[12] A method of using the curable composition according to the above [1] as a packaging material for an optical element fixing material.

[13] An optical device according to the above [1], which is used as an adhesive for an optical element fixing material or a sealing material for an optical element fixing material.

According to the curable composition of the present invention, a cured product excellent in peeling resistance and heat resistance and having high adhesion can be obtained.

The curable composition of the present invention can be used when forming an optical element fixing material, and in particular, it can be suitably used as an adhesive for an optical element and an encapsulating material for an optical element.

The cured product of the present invention is excellent in peeling resistance and heat resistance in terms of fixing of the optical element, and has high adhesion.

Form for implementing the invention

Hereinafter, the present invention will be described in detail with reference to 1) a curable composition, 2) a cured product, 3) a method of using a curable composition, and 4) an optical device.

1) Sturdy composition

The curable composition of the present invention is a curable composition having the following components A) to (E), characterized in that (A) component and (B) component are (A) component and (B) component. The mass ratio is [(A) component: (B) component] = 100: 0.3 to 100: 20 ratio,

(A) a decane compound copolymer represented by the following formula (a-1)

The component (A) used in the present invention is a decane compound copolymer represented by the following formula (a-1).

(CHR ¹ X ⁰ -D-SiO _3/2 ) _m (R ² SiO _3/2 ) _n (CHR ¹ X ⁰ -D-SiZ ¹ O _2/2 ) _o (R ² SiZ ² O _2/2 ) _p (CHR ¹ X ⁰ -D-SiZ ³ ₂ O _1/2 ) _q (R ² SiZ ⁴ ₂ O _1/2 ) _r ‧‧‧(a-1)

(B) Fine particles having an average primary particle diameter of more than 0.04 μm and 8 μm or less

(C) a decane coupling agent having a nitrogen atom in the molecule

(D) a decane coupling agent having an acid anhydride structure in the molecule

(E) a decane coupling agent having a functional group containing a sulfur atom in the molecule

(A) component

The component (A) used in the curable composition of the present invention is a decane compound copolymer represented by the decane compound copolymer (a-1) represented by the above formula (a-1) (hereinafter, referred to as "decane" The case of the compound copolymer (A)").

In the above formula (a-1), X ⁰ represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a cyano group; or a group represented by the formula: OG.

G is a protecting group of a hydroxyl group. The protective group of the hydroxyl group is not particularly limited, and a known protective group which is a protective group of a hydroxyl group can be mentioned. For example, a sulfhydryl-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; a protecting group for an acetal system such as a methoxymethyl group, a methoxyethoxymethyl group, a 1-ethoxyethyl group, a tetrahydrofuran-2-yl group or a tetrahydrofuran-2-yl group; a third butoxycarbonyl group; Alkoxycarbonyl protecting group; methyl, ethyl, tert-butyl, octyl, allyl, triphenylmethyl, benzyl, p-methoxybenzyl, decyl, trityl Ether, such as diphenylmethyl Protection base, etc. Among these, as G, a protecting group based on an anthracene group is preferred.

The protecting group of the indenyl group, specifically, the group represented by -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 having a substituent or having no substituent.

Examples of the substituent of the phenyl group having a substituent represented by R ⁵ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, and 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, as X ⁰ , from the viewpoint of availability, and a cured product having high adhesion, a group selected from a chlorine atom and a formula: OG′ (wherein G′ represents 醯). The protecting group of the base system and the cyano group are preferably a group selected from the group consisting of a chlorine atom, an ethoxy group and a cyano group, and a cyano group is particularly preferred.

D represents a single bond or a divalent organic group having 1 to 20 carbon atoms which has a substituent or has no substituent.

Examples of the divalent organic group having 1 to 20 carbon atoms include an alkylene group having 1 to 20 carbon atoms, an extended alkenyl group having 2 to 20 carbon atoms, an extended alkynyl group having 2 to 20 carbon atoms, and a carbon number of 6 to 20 An extended aryl group, a divalent group having 7 to 20 carbon atoms, which is composed of a combination of an alkyl group, an alkenyl group or an alkynyl group, and an extended aryl group.

Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an exoethyl group, a propyl group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.

Examples of the alkenyl group having 2 to 20 carbon atoms include a vinyl group, a propylene group, a butenyl group, and a pentenyl group.

Examples of the alkynyl group having 2 to 20 carbon atoms include an exetylene group and a propargylene group.

Examples of the extended aryl group having 6 to 20 carbon atoms include an ortho-phenyl group, an exophenyl group, a para-phenyl group, and a 2,6-anthranyl group.

Examples of the substituent which the above-mentioned alkyl group having 1 to 20 carbon atoms, the alkenyl group having 2 to 20 carbon atoms, and the alkynyl group having 2 to 20 carbon atoms may have a fluorine atom or a chlorine atom. A halogen atom; an alkoxy group such as a methoxy group or an ethoxy group; an alkylthio group such as a methylthio group or an ethylthio group; an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group; and the like.

The substituent of the aryl group having 6 to 20 carbon atoms, for example, 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; methoxy group; An alkoxy group such as an oxy group; an alkylthio group such as a methylthio group or an ethylthio group; and the like.

The substituents may be bonded to any of the groups of an alkyl group, an alkenyl group, an alkynyl group, and an extended aryl group, or may be bonded to the same or different plural.

As the divalent group composed of a combination of a (alkyl group, an alkenyl group, or an alkynyl group) having a substituent or having no substituent, and a substituted aryl group having a substituent or a substituent, At least one of the above-mentioned (extended alkyl group, an extended alkenyl group, or an extended alkynyl group) having a substituent or having no substituent, and at least one of the above-mentioned substituted or unsubstituted aryl group is bonded in series The basis of the formation. Specifically, a base or the like represented by the following formula is mentioned.

Among these, as D, since a cured product having a high adhesion is obtained, an alkylene group having 1 to 10 carbon atoms is preferred, and an alkylene group having 1 to 6 carbon atoms is preferred. The base or the ethyl group is particularly preferred.

R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms of R ¹ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a t-butyl group, and a n-pentyl group. Base, n-hexyl, etc.

Among these, as R ¹ , a hydrogen atom is preferred.

R ² represents an alkyl group having 1 to 20 carbon atoms or a phenyl group having a substituent or a substituent.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ² include 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, and a positive alkyl group. Amyl, n-hexyl, n-octyl, isooctyl, n-decyl, n-decyl, n-dodecyl and the like.

Examples of the substituent of the phenyl group having a substituent of R ² include 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, and a positive group. An alkyl group such as a pentyl group, a n-hexyl group, a n-heptyl group, an n-octyl group or an isooctyl group; 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.

Specific examples of the phenyl group having a substituent or having no substituent of R ² include a phenyl group, a 2-chlorophenyl group, a 4-methylphenyl group, a 3-ethylphenyl group, and a 2,4- Dimethylphenyl, 2-methoxyphenyl, and the like.

Among these, R ² is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group having a substituent or a substituent, and particularly preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. .

Z ¹ to Z ⁴ each independently represent a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms or a halogen atom. Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a third butoxy group, a pentyloxy group, a hexyloxy group, and a octyl group. Oxyl and the like. Examples of the halogen atom include a chlorine atom and a bromine atom.

Among these, Z ¹ to Z ⁴ are each independently and preferably have a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms.

m and n are each independent and represent a positive integer. o, p, q, r are independent and represent 0 or a positive integer. Since the effect of the present invention is more easily obtained, (m+o+q) and (n+p+r) are (m+o+q):(n+p+r)=5:95~60:40 Preferably, a positive integer having a ratio of 10:90 to 30:70 is preferred.

The method for producing the decane compound copolymer (A) is not particularly limited, and the decane compound represented by the formula (1): R ¹ -CH(X ⁰ )-D-Si(OR ⁴ ) _v (X ¹ ) _3-v ( 1) and (2): a method of condensing the decane compound (2) represented by R ² Si(OR ⁵ ) _w (X ² ) _3-w is preferred. Here, "condensation" is used in the broad concept including hydrolysis and polycondensation reaction (the same applies hereinafter).

When OR ⁴ or X ^{1 of the} decane compound (1) is not subjected to dehydration or dealcoholization condensation reaction, it remains in the decane compound copolymer (a-1). When one of OR ⁴ or X ¹ in the condensation reaction is carried out, the above formula (a-1) is retained as (CHR ¹ X ⁰ -D-SiZ ¹ O _2/2 ), and the OR ^{4 of the} condensation reaction is not carried out. When X ¹ is two, it remains as (CHR ¹ X ⁰ -D-SiZ ³ ₂ O _1/2 ) in the formula (a-1).

Similarly to the decane compound (2), when the NO ⁵ or X ^{2 is} not subjected to dehydration or dealcoholization condensation reaction, it remains in the decane compound copolymer (a-1). When the number of OR ⁵ or X ² in the condensation reaction is one, the formula (a-1) remains as (R ² SiZ ² O _2/2 ), and the OR ⁵ or X ^{2 which} is not subjected to the condensation reaction is 2 In the case of the formula (a-1), it remains as (R ² SiZ ⁴ 2O _1/2 ).

[decane compound (1)]

In the above formula (1), R ¹ , X ⁰ and D represent the same meaning as described above. R ⁴ represents an alkyl group having 1 to 10 carbon atoms, X ¹ represents a halogen atom, and v represents an integer of 0 to 3.

Examples of the alkyl group having 1 to 10 carbon atoms of R ⁴ include 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, and a n-pentyl group. Base, and hexyl group, etc.

Examples of the halogen atom of X ¹ include a fluorine atom, a chlorine atom, and a bromine atom.

When v is 2 or more, OR ⁴ may be the same or different from each other. Further, when (3-v) is 2 or more, X ¹ may be the same or different.

Specific examples of the decane compound (1) include chloromethyltrimethoxydecane, bromomethyltriethoxydecane, 2-chloroethyltripropoxydecane, and 2-bromoethyltributoxy group. Decane, 3-chloropropyltrimethoxydecane, 3-chloropropyltriethoxydecane, 3-chloropropyltripropoxydecane, 3-chloropropyltributoxydecane, 3-bromopropyl Trimethoxydecane, 3-bromopropyltriethoxydecane, 3-bromopropyltripropoxydecane, 3-bromopropyltributoxydecane, 3-fluoropropyltrimethoxydecane, 3- Fluoropropyltriethoxydecane, 3-fluoropropyltripropoxydecane, 3-fluoropropyltributoxydecane, 3-iodopropyltrimethoxydecane, 2-chloroethyltrimethoxydecane , 3-chloropropyltriethoxydecane, 4-chlorobutyltripropoxydecane, 5-chloropentyltripropoxydecane, 4-chlorobutyldichlorodecane, 2-chloropropane Trimethoxy decane, o-(2-chloroethyl)phenyltripropoxydecane, m-(2-chloroethyl)phenyltrimethoxydecane, p-(2-chloroethyl)phenyltriethoxy a trialkyloxydecane compound in which X ⁰ such as a decane or a p-(2-fluoroethyl)phenyltrimethoxydecane is a halogen atom Species; chloromethyl chlorodimethoxy decane, bromomethyl bromodimethoxy decane, 2-chloroethyl chlorodimethoxy decane, 3-chloropropyl chlorodimethoxy decane, 3-bromo X ⁰ such as propyl chlorodimethoxy decane, 3-fluoropropyl chlorodimethoxy decane, 3-fluoropropyl chlorodiethoxy decane, 3-chloro-n-butyl chlorodiethoxy decane, etc. a halogenated dialkoxy decane compound of a halogen atom; 2-chloroethyldichloromethoxy decane, 2-bromoethyldichloroethoxy decane, 3-chloropropyldichloromethoxy decane, 3 X ⁰ such as -fluoropropyldichloromethoxydecane, 3-chloropropyldichloroethoxysilane, 3-chloropropyl chlorodiethoxy decane, 3-bromopropyldichloroethoxy decane, etc. a dihaloalkoxydecane compound of a halogen atom; chloromethyltrichlorodecane, 3-bromopropyltribromodecane, 3-bromopropyltrichlorodecane, 3-fluoropropyltrichlorodecane, 3-chloro a trihalodecane compound in which X ⁰ such as propyl trichlorodecane, 3-chloropropyltribromodecane or 3-iodopropyltrichloromethane is a halogen atom; cyanomethyltrimethoxydecane, cyanomethyltriethyl Oxydecane, 1-cyanoethyltrimethoxydecane, 2-cyanoethyltrimethoxy Decane, 2-cyanoethyltriethoxydecane, 2-cyanoethyltripropoxydecane, 3-cyanopropyltrimethoxydecane, 3-cyanopropyltriethoxydecane, 3-cyanopropyl Tripropoxydecane, 3-cyanopropyl tributoxydecane, 4-cyanobutyltrimethoxydecane, 5-cyanopentyltrimethoxydecane, 2-cyanopropyltrimethoxydecane, 2-( Cyanomethoxy)ethyltrimethoxydecane, 2-(2-cyanoethoxy)ethyltrimethoxydecane, o-(cyanomethyl)phenyltripropoxydecane, m-(cyanomethyl)benzene trimethoxy Silane, p- (cyanomethyl) phenyl triethoxysilane Silane, p- (2-cyanoethyl) phenyl trimethoxy silane-like X ⁰ trialkoxy Silane compounds of cyano; cyanomethyl Methyl trichlorodecane, cyanomethyl bromodimethoxy decane, 2-cyanoethyl dichloromethoxy decane, 2-cyanoethyl dichloroethoxy decane, 3-cyanopropyl trichloro decane, 3 -Cyanopropyltribromodecane, 3-cyanopropyldichloromethoxydecane, 3-cyanopropyldichloroethoxysilane, 3-cyanopropylchlorodimethoxydecane, 3-cyanopropyl chloride Diethoxydecane, 4-cyanobutyl chloride diethoxy decane, 3-cyano-n-butyl chloride diethoxy decane, 2-(2- Cyanoethoxy)ethyltrichlorodecane, 2-(2-cyanoethoxy)ethylbromodiethoxydecane, 2-(2-cyanoethoxy)ethyldichloropropoxydecane, adjacent (2-cyanoethyl)phenyltrichlorodecane, m-(2-cyanoethyl)phenylmethoxydibromodecane, p-(2-cyanoethyl)phenyldimethoxychlorodecane, p-(2 - cyanoethyl)phenyltribromodecane, etc. X ⁰ is a cyano halodecane compound; 3-ethyloxypropyltrimethoxydecane, 3-ethyloxypropyltriethoxydecane, 3 - ethoxylated propyl tripropoxy decane, 3-ethoxypropyl propyl tributoxy decane, 3-propoxy propyl trimethoxy decane, 3-propoxy propyl triethyl Oxydecane, 3-benzyloxypropyltrimethoxydecane, 3-benzyloxypropyltriethoxydecane, 3-benzylidenepropyltripropoxydecane, 3- Benzomethoxypropyl tributoxy decane, 2-trimethyl decyloxyethyl trimethoxy decane, 3-triethyl decyloxypropyl triethoxy decane, 3-(2 -tetrahydropyranyloxy)propyltripropoxydecane, 3-(2-tetrahydrofuryloxy)propyl tributoxydecane, 3-methoxymethoxypropyl III Methoxy decane, 3-methoxyethoxymethoxypropyl triethoxy decane, 3-(1-ethoxyethoxy)propyl tripropoxy decane, 3-(third butyl Oxycarbonyloxy)propyltrimethoxydecane, 3-tert-butoxypropyltrimethoxydecane, 3-benzyloxypropyltriethoxydecane, 3-triphenylmethoxypropyl X ⁰ such as triethoxysilane or the like is a trialkyloxy decane compound represented by the above formula: OG; 3-ethyloxypropyltrichlorodecane, 3-ethyloxypropyltribromonane, 3-Ethyloxypropyldichloromethoxydecane, 3-ethyloxypropyldichloroethoxysilane, 3-ethyloxypropylchlorodimethoxydecane, 3-ethyloxene Propyl chlorodiethoxy decane, 3-benzylidene propyl trichloro decane, 3-trimethyl decyloxypropyl chlorodimethoxy decane, 3-triethyl decyloxy Propyl dichloromethoxy decane, 3-(2-tetrahydropyranyloxy)propyl chlorodiethoxy decane, 3-(2-tetrahydrofuryloxy)propyl dichloroethoxy decane, 3-methoxymethoxypropyltribromodecane, 3-methoxyethoxymethoxypropyltrichlorodecane, 3-(1-ethoxyethoxy) ) propyl chlorodimethoxy decane, 3-tert-butoxycarbonyloxypropyl dichloromethoxy decane, 3-tert-butoxypropyl chlorodiethoxy decane, 3-triphenyl X ⁰ such as methoxypropyldichloroethoxysilane or 3-benzyloxypropyltribromodecane is a halodecane compound of the above formula: OG.

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

Among these, as the decane compound (1), a cured product having more excellent adhesion can be obtained, and a trialkoxy decane compound is preferred, and a 3-chloropropyl trialkoxy decane compound is preferable. a trialkoxy decane compound having a 3-ethoxymethoxypropyl group, a trialkoxy decane compound having a 2-cyanoethyl group, or a trialkoxy decane compound having a 3-cyanopropyl group. Preferably, it is particularly preferred to use a triacyloxydecane compound having a 2-cyanoethyl group.

[decane compound (2)]

In the above formula (2), R ² represents the same meaning as described above. R ⁵ represents an alkyl group having 1 to 10 carbon atoms similar to the above R ⁴ , X ² represents a halogen atom similar to the above X ¹ , and w represents an integer of 0 to 3.

When w is 2 or more, OR ⁵ may be the same or different from each other based. Further, when (3-w) is 2 or more, X ² may be the same or different.

As a specific example of the decane compound (2), methyltrimethoxy Base 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, methyl dimethoxy ethoxy decane, methyl diethoxy Alkyltrialkoxydecane compounds such as methoxymethoxydecane; methylchlorodimethoxydecane, methyldichloromethoxydecane, methyldichloromethoxydecane, methylchlorodiethoxy Alkyl haloalkoxy decane compounds such as decane, ethyl chlorodimethoxy decane, ethyl dichloromethoxy decane, n-propyl chlorodimethoxy decane, n-propyl dichloromethoxy decane An alkyltrihalothane compound such as methyltrichlorodecane, methyltribromodecane, ethyltrichlorodecane, ethyltribromodecane or n-propyltrichlorodecane; phenyltrimethoxydecane, 4 -methoxyphenyltrimethoxydecane, 2-chlorophenyltrimethoxydecane, phenyltriethoxydecane, 2-methoxyphenyltriethoxy a phenyltrialkoxydecane compound having a substituent or a non-substituent such as decane, phenyldimethoxyethoxy decane or phenyldiethoxymethoxydecane; phenylchlorodimethoxy a substituted or unsubstituted benzene such as decane, phenyldichloromethoxydecane, phenylchloromethoxyethoxydecane, phenylchlorodiethoxydecane or phenyldichloroethoxysilane. Alkyl halooxy decane compounds; phenyl trichlorodecane, phenyl tribromodecane, 4-methoxyphenyl trichlorodecane, phenyl trichlorodecane, 2-ethoxyphenyl trichloromethane, 2 A phenyltrihalothane compound having a substituent or a substituent such as -chlorophenyltrichloromethane.

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

Among these, as the decane compound (2), an alkyltrialkoxydecane compound having 1 to 6 carbon atoms, a phenyltrialkoxydecane compound having a substituent or having no substituent is preferred. .

The ratio of the decane compound (1) to the decane compound (2) is preferably a molar ratio of [decane compound (1)]: [decane compound (2)] = 60:40 to 5:95. 40:60~10:90 is better.

The method of condensing the decane compound is not particularly limited, and examples thereof include a method in which a decane compound (1) and a decane compound (2) are dissolved in a solvent, and a predetermined amount of a catalyst is added and stirred at a predetermined temperature.

The catalyst to be used may be either an acid catalyst or an alkali catalyst.

Further, it is also possible to use an acid catalyst in combination with an alkali catalyst. For example, after the condensation reaction of the decane compound is carried out in the presence of an acid catalyst, the base catalyst is added to the reaction liquid to be alkaline, and the condensation reaction is further carried out under basic conditions.

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.

Examples of the base catalyst include trimethylamine, triethylamine, lithium diisopropylamide, lithium bis(trimethyldecyl)amide, pyridine, and 1,8-diazabicyclo[5.4.0. An organic base such as 7-undecene, aniline, pyridyl, 1,4-diazabicyclo[2.2.2]octane or imidazole; tetramethylammonium hydroxide or tetraethylammonium hydroxide Ammonium salt hydroxide; sodium alkoxide, sodium sulphate, third butyl oxide, sodium alkoxide, potassium, etc.; a metal hydride such as sodium hydride or calcium hydride; sodium hydroxide, a metal hydroxide such as potassium hydroxide or calcium hydroxide; a metal carbonate such as sodium carbonate, potassium carbonate or magnesium carbonate; or a metal hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate.

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

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

The total mole amount of the decane compound is 0.1 to 10 liters, preferably 0.1 to 2 liters per 1 mol of the solvent.

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, and 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 become insufficient. On the other hand, when the reaction temperature is too high, it becomes difficult to suppress the gelation system. The reaction system is usually completed from 30 minutes to 20 hours.

When an acid catalyst is used, an alkali aqueous solution such as sodium hydrogencarbonate or the like is added to the reaction solution, and when an alkali catalyst is used, neutralization is carried out by adding an acid such as hydrochloric acid to the reaction solution, and the mixture is separated by filtration. The salt produced at this time is removed by water washing or the like to obtain a target decane compound copolymer.

The decane compound copolymer (A) can be a random copolymer or a block. Any copolymer such as a copolymer, a graft copolymer or an alternating copolymer is preferably a random copolymer from the viewpoint of easiness of production and the like.

Further, the structure of the decane compound copolymer (A) may be any one of a ladder structure, a two-layer structure structure, a cage structure, a partial crack cage structure, a cyclic structure, and a random structure.

The mass average molecular weight (Mw) of the decane compound copolymer (A) is usually 800 to 30,000, preferably 1,000 to 2,500, more preferably 1,200 to 2,000. Within this range, the handleability of the composition is excellent, and a cured product excellent in adhesion and heat resistance can be obtained.

The mass average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent in the form of standard polystyrene (the same applies hereinafter). ).

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

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

(B) component

The curable composition of the present invention contains fine particles having an average primary particle diameter of more than 0.04 μm and 8 μm or less as the component (B).

The fine particles are not particularly limited, and may be fine particles composed of an inorganic material, or fine particles composed of organic substances. Examples of the constituent components of the fine particles composed of the inorganic material include metals; metal oxides; minerals; metal carbonates such as calcium carbonate and magnesium carbonate; and metal sulfates such as calcium sulfate and barium sulfate. a salt; a metal hydroxide such as aluminum hydroxide; a metal ruthenate such as aluminum citrate, calcium citrate or magnesium ruthenate; ruthenium oxide; polyfluorene oxide; a metal oxide having a surface coated with polyoxane. As a constituent component of the fine particles composed of an organic substance, acrylic resin beads (Acrylic resin Beads) or the like.

These fine particles may be used in combination of two or more types.

Here, the term "metal" refers to the first group (other than H), the second to the eleventh, the twelfth (except Hg), the thirteenth (except B), and the other Elements other than C and Si), Group 15 (other than N, P, As, and Sb), or Group 16 (other than O, S, Se, Te, and Po).

The cerium oxide may be any of dry cerium oxide, wet cerium oxide, and organically modified cerium oxide, or a mixture of two or more of these.

The term "silicone" means an artificial polymer compound having a main skeleton that transmits a siloxane chain. For example, dimethyl polysiloxane, diphenyl polysiloxane, methyl phenyl polyoxyalkylene, etc. are mentioned.

Examples of the metal oxide include titanium oxide, aluminum oxide, boehmite, chromium oxide, nickel oxide, copper oxide, titanium oxide, zirconium oxide, indium oxide, zinc oxide, and the like. . The fine particles of the metal oxide may also contain sol particles composed of the metal oxides.

Examples of the mineral include smectite and bentonite.

Examples of the bentonite include montmorillonite, beidellite, hectorite, saponite, stevensite, nontronite, and sauconite. Wait.

Among these, since the object of the present invention is easily manifested in the present invention, it is preferable to use silica, a silicon oxide, a metal oxide, or a fine particle having a surface coated with a metal oxide of polyoxyn oxide. Preferably, cerium oxide and polyoxyn oxide are preferred.

The shape of the microparticles may be any of a spherical shape, a chain shape, a needle shape, a plate shape, a sheet shape, a rod shape, and a fiber shape, and is preferably a spherical shape. Here, the spherical shape means a substantially spherical shape including a spherical shape and a polyhedral shape of a nearly spherical body such as a spheroid, an oval, a sugar sphere, or a braid.

The average primary particle diameter of the fine particles is more than 0.04 μm and 8 μm or less. When it is more than 0.04 μm, the effect of adding fine particles can be obtained. When it is 8 μm or less, the dispersibility of the obtained curable composition becomes good.

The average primary particle diameter is preferably 0.06 to 7 μm, more preferably 0.3 to 6 μm, and particularly preferably 1 to 4 μm from the viewpoint of having both peeling resistance and dispersibility.

In the present invention, the average primary particle size of the microparticles refers to the use of laser diffraction. A scattering type particle size distribution measuring apparatus (for example, manufactured by Horiba, Ltd., product name "LA-920"), etc., is obtained by measuring the particle size distribution by a laser scattering method.

The amount of use of the component (B) is such that the ratio of use of the component (A) to the component (B) is such that the mass ratio of the component (A) to the component (B) is [100% of the component (B): 0.3~100:20, preferably 100:0.5~100:15, preferably 100:0.8~100:12. When the amount of the component (B) used is less than the above range, the effect of the target peeling resistance is not easily obtained, and when it is larger than the above range, the adhesion is not preferable.

(C) component

The curable composition of the present invention contains a decane coupling agent having a nitrogen atom in the molecule of the C component (hereinafter referred to as "the decane coupling agent (C)").

The decane coupling agent (C) is not particularly limited as long as it has a nitrogen atom in the molecule. For example, a trialkoxy decane compound represented by the following formula (c-1), a dialkoxyalkyl decane compound represented by the formula (c-2), a dialkoxy aryl decane compound, etc. .

(R ^a ) ₃ SiR ^c ‧‧‧(c-1)

(R ^a ) ₂ (R ^b )SiR ^c ‧‧‧(c-1)

In the above formula, R ^a represents an alkoxy group having 1 to 6 carbon atoms such as ^a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group or a third butoxy group. The plurality of R ^a systems may all be the same or different.

R ^b represents an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl or t-butyl; or phenyl, 4-chlorophenyl or 4-methyl An aryl group having a substituent or a substituent without a phenyl group.

R ^c represents an organic group having a nitrogen atom and having 1 to 10 carbon atoms. Further, R ^c may be further bonded to a group containing another ruthenium atom.

Specific examples of the organic group having 1 to 10 carbon atoms of R ^c include N-2-(aminoethyl)-3-aminopropyl group, 3-aminopropyl group, and N-(1,3-dimethyl group). Alkyl-butylene)aminopropyl, 3-ureidopropyltriethoxydecane, N-phenyl-aminopropyl, and the like.

Among the compounds represented by the above formula (c-1) or (c-2), the compound which is an organic group in the case where Rc is bonded to a group containing another ruthenium atom is exemplified by an isocyanurate skeleton. Other helium atom bonded to form an isocyanurate-based decane coupling agent; and a urea-based decane coupling agent bonded to another ruthenium atom through a urea skeleton.

Among these, since it is easy to obtain a cured product having a higher adhesion, it is preferable to use an isocyanurate-based decane coupling agent and a urea-based decane coupling agent as the decane coupling agent (C). It is preferred that there are four or more alkoxy groups bonded to the ruthenium atom in the molecule.

The alkoxy group having four or more bonds to a ruthenium atom means that the total number of alkoxy groups bonded to the same ruthenium atom and the alkoxy group bonded to a different ruthenium atom is 4 or more.

The isocyanurate-based decane coupling agent having four or more alkoxy groups bonded to a ruthenium atom is a compound represented by the following formula (c-3), and has four or more bonds bonded to a ruthenium atom. The urea-based decane coupling agent of the alkoxy group may, for example, be a compound represented by the following formula (c-4).

In the formula, R ^a represents the same meaning as described above.

T1~t5 are independent and represent integers from 1 to 10, preferably 1 to 6 integers, and 3 is particularly preferred.

Specific examples of the compound represented by the formula (c-3) include 1,3,5-N-glucos(3-trimethoxydecylpropyl)isocyanurate, 1,3,5. -N-parameter (3- Triethoxydecylpropyl)isocyanurate, 1,3,5,-N-glucos(3-triisopropoxydecylpropyl)isocyanurate, 1,3,5, 1,3,5-N-para [(tri(carbo-1~6) alkoxy)decyl) (carbon) such as -N-gin (3-tributoxydecylpropyl)isocyanurate a number of 1 to 10) alkyl] isocyanurate; 1,3,5,-N-parade (3-dimethoxymethyldecylpropyl)isocyanurate, 1,3,5, -N-gin (3-dimethoxyethyl decylpropyl) isocyanurate, 1,3,5,-N-parade (3-dimethoxyisopropyl decylpropyl) Cyanurate, 1,3,5,-N-parade (3-dimethoxy-n-propyl-decylpropyl)isocyanurate, 1,3,5,-N-para (3-di Methoxyphenyl decyl propyl) isocyanurate, 1,3,5,-N- cis (3-diethoxymethyl decyl propyl) isocyanurate, 1,3, 5,-N-gin(3-diethoxyethyl-decylpropyl)isocyanurate, 1,3,5,-N-parade (3-diethoxyisopropyl decylpropyl) Isocyanurate, 1,3,5,-N-parade (3-diethoxy-n-propyl-decylpropyl)isocyanurate, 1,3,5,-N-parameter (3) -diethoxyphenyl decyl propyl)isocyanurate, 1,3,5,-N- cis (3-diisopropoxymethyl decylpropyl) isocyanurate Acid ester, 1,3,5,-N-parade (3-diisopropoxyethyl decylpropyl) isocyanurate, 1,3,5,-N-para (3-diisopropyl Oxypropylisopropyl propyl propyl) isocyanurate, 1,3,5,-N- cis (3-diisopropoxy n-propyl decyl propyl) isocyanurate, 1, 3,5,-N-gin(3-diisopropoxyphenyl-decylpropyl)isocyanurate, 1,3,5,-N-parade (3-dibutoxymethyldecyl) Propyl)isocyanurate, 1,3,5,-N-gin (3-dibutoxyethyl decylpropyl) isocyanurate, 1,3,5,-N-para 3-dibutoxyisopropyl decyl propyl) isocyanurate, 1,3,5,-N- cis (3-dibutoxy n-propyl decyl propyl) isocyanurate 1,3,5-N-parameters such as 1,3,5,-N-parade (3-dibutoxyphenyl decylpropyl) isocyanurate [(two (carbon number 1~6) Alkoxy)decylalkyl (carbon number 1 to 10)alkyl]isocyanurate or the like.

Specific examples of the compound represented by the formula (c-4) include N,N'-bis(3-trimethoxydecylpropyl)urea, and N,N'-bis(3-triethoxy). Nonylalkyl)urea, N,N'-bis(3-tripropoxydecylpropyl)urea, N,N'-bis(3-tributoxydecylpropyl)urea, N,N N,N'-bis[(tris(C 1~6) alkoxyalkyl) (carbon 1 to 10) alkyl] urea such as '-bis(2-trimethoxydecylethyl) urea N,N'-bis(3-dimethoxymethyldecylpropyl)urea, N,N'-bis(3-dimethoxyethyl-decylpropyl)urea, N,N'- N,N'-bis[(di(carbo-1~6) alkoxy (carbon number 1~6) alkyl) alkyl (carbon) of bis(3-diethoxymethyldecylpropyl)urea a number of 1 to 10)alkyl)ureas; N,N'-bis(3-dimethoxyphenylphosphonylpropyl)urea, N,N'-bis(3-diethoxyphenylanthracenepropyl N,N'-bis[(di(carbon number 1 to 6) alkoxy (carbon number 6 to 20) aryl decyl (carbon number 1 to 10) alkyl) urea, etc., such as urea.

These can be used alone or in combination of two or more.

Among these, as the component (C) of the present invention, 1,3,5-N-gin(3-trimethoxydecylpropyl)isocyanurate, 1,3,5-N- is used. Ginseng (3-triethoxydecylpropyl)isocyanurate (hereinafter referred to as "isocyanurate compound"), N,N'-bis(3-trimethoxydecylpropyl) Urea, N,N'-bis(3-triethoxydecylpropyl)urea (hereinafter referred to as "urea compound"), and a combination of the aforementioned isocyanurate compound and urea compound are preferred.

When the above isocyanurate compound is used in combination with a urea compound, the ratio of use of the two is based on the mass ratio of (isocyanurate compound) to (urea compound), and is 100:1 to 100:200. It is better.

In addition, the use ratio of the isocyanurate compound is preferably 35 parts by mass or less, and is 25 parts by mass or less based on 100 parts by mass of the component (A). The next is better. When the isocyanurate compound is used alone, it is also the same as when the urea compound is used in combination.

In addition, the use ratio of the urea compound is preferably 20 parts by mass or less, and preferably 15 parts by mass or less, based on 100 parts by mass of the component (A). When the urea compound is used alone, it is also the same as when the isocyanurate compound is used in combination.

The curable composition of the present invention contains the above-mentioned (A) in a ratio of (A) component to (C) component [(A) component: (C) component] in a ratio of 100:0.3 to 100:40. The component (C) is preferably contained in the ratio of 100:1 to 100:30, and the component (C) is preferably contained in a ratio of 100:3 to 100:25, and the component (A) is contained in a ratio of 100:3 to 100:25. And (C) ingredients are better.

By using the component (A) and the component (C) in such a ratio, a curable composition which is excellent in heat resistance and has a high adhesion can be obtained.

(D) component

The curable composition of the present invention contains a decane coupling agent having an acid anhydride structure in the molecule (hereinafter referred to as "the decane coupling agent (D)") as the component (D).

The decane coupling agent (D) is an organic hydrazine compound having both a group (Q) having an acid anhydride structure and a hydrolyzable group (R ^e ) in one molecule. Specifically, it is a compound represented by the following formula (d).

In the formula, Q represents an acid anhydride structure, R ^d represents an alkyl group having 1 to 6 carbon atoms, or a phenyl group having a substituent or a substituent, and R ^e represents an alkoxy group having 1 to 6 carbon atoms or The halogen atom, i and k are integers of 1 to 3, and j is an integer of 0 to 2, and i+j+k=4. When j is 2, R ^d may be the same or different from each other. When k is 2 or 3, the plurality of R ^e may be the same or different from each other. When i is 2 or 3, a plurality of Qs may be the same or different from each other.

Examples of Q include a group represented by the following formula, and the like.

(wherein h is an integer of 0 to 10), and the group represented by (Q1) is particularly preferable.

In the formula (d), examples of the alkoxy group having 1 to 6 carbon atoms of R ^e include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a third butoxy group, and the like. .

Examples of the halogen atom include a chlorine atom and a bromine atom.

The alkyl group having 1 to 6 carbon atoms of R ^{d is} the same as those exemplified as the alkyl group having 1 to 6 carbon atoms represented by the above R ¹ , and is a phenyl group having a substituent or a substituent. The same base as the above-mentioned R ² is exemplified.

In particular, the compound represented by the formula (d) is preferably a compound represented by the following formula (d-1).

(wherein R ^e , h, i, j, and k are the same meanings as described above). In the formula, h is preferably 2-8, 2 or 3 is preferred, and 3 is particularly preferred.

Specific examples of the decane coupling agent represented by the above formula (d-1) include 2-(trimethoxydecyl)ethyl succinic anhydride and 2-(triethoxydecyl)ethyl succinic anhydride. a tri(carbon number 1 to 6) alkoxyalkylene group (carbon number 2 to 8) such as 3-(trimethoxydecyl)propyl succinic anhydride or 3-(triethoxydecyl)propyl succinic anhydride Alkane succinic anhydride; 2-(carbon number 1 to 6) alkoxymethyl fluorenyl (carbon number 2-8) alkyl succinic anhydride; 2-(dimethoxymethyl decyl) ethyl succinic anhydride; 2-(methoxydimethylmethylalkyl)ethyl succinic anhydride or the like (carbon number 1 to 6) alkoxydimethylalkyl (carbon number 2 to 8) alkyl succinic anhydride; 2- (trichloro) a trihaloalkylene group (carbon number 2-8) alkyl succinic anhydride such as a nonyl)ethyl succinic anhydride or a 2-(tribromodecylalkyl)ethyl succinic anhydride; 2-(dichloromethyl decyl) ethyl a dihalomethylalkylalkyl group (carbon number 2-8) alkyl succinic anhydride such as succinic anhydride; a halodimethylalkyl group such as 2-(chlorodimethylalkylalkyl)ethyl succinic anhydride (carbon number 2-8) Alkyl succinic anhydride and the like.

Among these, three (carbon number 1 to 6) alkoxy fluorenyl groups (carbon number 2 to 8) Alkyl succinic anhydride is preferred, and 3-(trimethoxydecyl)propyl succinic anhydride and 3-(triethoxydecyl)propyl succinic anhydride are particularly preferred.

The component (D) can be used singly or in combination of two or more.

The curable composition of the present invention preferably contains the component (A) and the component (D), and the mass ratio of the component (A) to the component (D) [(A) component: (D) component] is 100:0.01~ The ratio of 100:30 is preferably in the ratio of 100:0.1 to 100:10.

By using the component (A) and the component (D) in this ratio, the cured product of the curable composition of the present invention is excellent in heat resistance, adhesion, and peeling resistance.

(E) component

The curable composition of the present invention contains a decane coupling agent having a functional group having a sulfur atom in the molecule (E) (hereinafter referred to as "the decane coupling agent (E)").

As the decane coupling agent (E), as long as it has a thiol group (-SH) in the molecule; a thiol group (-S-CO-R'); a thioether group (-S-); a disulfide group (-SS) The decane coupling agent of the sulfur atom-containing functional group such as a polysulfide group [-(S)n-] such as a tetrasulfide group (-SSSS-) is not particularly limited.

Examples of the decane coupling agent (E) include a decane coupling agent represented by any one of the following formulas (e-1) to (e-4), and another decane coupling agent having a functional group containing a sulfur atom. And such oligomers and the like.

(Y ¹ ) ₃ Si-A ¹ -SH (e-1)

(Y ¹ ) ₃ Si-A ¹ -S-CO-R' (e-2)

(Y ¹ ) ₃ Si-A ¹ -S-Si(Y ² ) ₃ (e-3)

(Y ¹ ) ₃ Si-A ¹ -(S) _v -A ² -Si(Y ² ) ₃ (e-4)

In the formula, Y ¹ and Y ² each independently represent an alkoxy group having 1 to 10 carbon atoms, and A ¹ and A ² each independently represent a carbon number of 1 to 20 having a substituent or having no substituent. The valent hydrocarbon group, R' represents a monovalent organic group having 1 to 20 carbon atoms. v is an integer from 1 to 4. Y ¹ and Y ² may be the same or different from each other].

Examples of the alkoxy group having 1 to 10 carbon atoms of Y ¹ and Y ² include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a second butoxy group, and a different one. Butoxy, tert-butoxy and the like.

As Y ¹ and Y ² , an alkoxy group having 1 to 6 carbon atoms is preferred.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms which have a substituent or a substituent of A ¹ and A ² include an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and carbon. The alkynyl group having 2 to 20, the aryl group having 6 to 20 carbon atoms, the divalent group consisting of a combination of an alkyl group, an alkenyl group or an alkynyl group and an extended aryl group.

Examples of the divalent carbon having 1 to 20 carbon atoms which have a substituent or have no substituent, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, The divalent group consisting of a aryl group having 6 to 20 carbon atoms and a combination of an alkyl group, an alkenyl group or an alkynyl group and an extended aryl group may be exemplified by those exemplified in the above D. The same thing.

Among these, as A ¹ and A ² , an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylidene group, a propyl group, a trimethylene group or a tetramethylene group is preferred.

As R, there is no particular limitation as long as -CO-R' can function as a protecting group. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl An alkyl group having a group, a n-decyl group, a n-decyl group, a n-undecyl group, a n-dodecyl group or the like; a phenyl group having a substituent or a substituent; and the like.

Examples of the substituent of the phenyl group having a substituent of R' include 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, and a positive group. An alkyl group such as a pentyl group or a n-hexyl 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.

R' is preferably an alkyl group having 1 to 20 carbon atoms, and preferably an alkyl group having 1 to 10 carbon atoms.

v is an integer of 1 to 4, preferably 1 or 2 or 4, and preferably 2 or 4.

Examples of the decane coupling agent represented by the formula (e-1) include thiomethylmethyltrimethoxydecane, thiomethylmethyltriethoxydecane, and thiomethylmethyltripropoxydecane. -Hexylthioethyltrimethoxydecane, 2-hydrothioethyltriethoxydecane, 2-hydrothioethyltripropoxydecane, 3-hydrothiopropyltrimethoxydecane, 3 a hydrothioalkyltrialkaloxynonane such as hydrogenthiopropyltriethoxydecane or 3-hydrothiopropyltripropoxydecane.

Examples of the decane coupling agent represented by the formula (e-2) include 2-hexylthioethyltrimethoxydecane, 2-hexylthioethyltriethoxydecane, and 2-octylthioalkyl. Trimethoxy decane, 2-octyl thioethyl triethoxy decane, 2-mercaptothioethyl trimethoxy decane, 2-mercaptothioethyl triethoxy decane, 3- Hexyl propyl propyl trimethoxy decane, 3-hexyl thiopropyl triethoxy decane, 3- octyl thiopropyl trimethoxy decane, 3- octyl thiopropyl triethoxy decane, An alkylsulfonylthioalkyltrialkoxydecane compound such as 3-mercaptothiopropyltrimethoxydecane or 3-mercaptothiopropyltriethoxydecane.

As the decane coupling agent represented by the formula (e-3), 2-trimethoxy Base alkyl ethyl sulfonyl trimethoxy decane, 2-trimethoxy decyl ethyl ethyl sulfonyl triethoxy decane, 2-triethoxy decyl ethyl sulfonyl trimethoxy decane, 2 -triethoxydecylethylethylsulfonyltriethoxydecane, 3-trimethoxydecylpropylsulfonyltrimethoxydecane, 3-trimethoxydecylpropylsulfonyltriethoxy Basear, 3-triethoxydecylpropylsulfonyltrimethoxydecane, 3-triethoxydecylpropylsulfonyltriethoxydecane, and the like.

Examples of the decane coupling agent represented by the formula (e-4) include bis(2-trimethoxydecylethyl)disulfide and bis(2-triethoxydecylethyl)disulfide. Bis(3-trimethoxydecylpropyl)disulfide, bis(3-triethoxydecylpropyl)disulfide, bis(4-trimethoxydecylbutyl)disulfide, double a disulfide compound such as (4-triethoxydecylbutyl)disulfide; bis(2-triethoxydecylethyl)tetrasulfide, bis(3-trimethoxydecylpropyl) a tetrasulfide compound such as tetrasulfide or bis(3-triethoxydecylpropyl)tetrasulfide.

Examples of the other decane coupling agent having a functional group containing a sulfur atom include 3-trimethoxydecylpropyl-N,N-dimethylthiocarbamoyltetrazole, 3-triethoxy. Nonylalkyl-N,N-dimethylthiocarbamoyltetrazole, 2-triethoxydecylethyl-N,N-dimethylthiocarbamoyltetrasulfide, Sulfur-containing amine-alkyl-based decane coupling agent such as 2-trimethoxydecylethyl-N,N-dimethylthioaminocarbazyl tetrasulfide; 3-trimethoxydecylpropylbenzene a benzothiazolyl-containing decane coupling agent such as thiazolyl tetrathioether or 3-triethoxydecylpropylbenzothiazolyl tetrasulfide; 3-triethoxydecylpropyl (meth)acrylic acid a (meth) acrylate-based decane coupling agent such as ester monosulfide or 3-trimethoxydecyl propyl (meth) acrylate monothiolate [so-called "(meth) acrylate" means Acrylate or methacrylate]; bis(3-triethoxydecylpropyl) A polythioether group-containing decane coupling agent such as polysulfide, bis(2-triethoxydecylpropyl)polysulfide or bis(4-triethoxydecylbutyl)polysulfide.

The oligomer is a partially hydrolyzed product of these compounds, and the molecular weight is usually from 300 to 3,000.

Among these, as the component (E), a decane coupling agent represented by the above formula (e-1) or (e-3), and these oligomers are preferred, and 2-hydrogenthio B is used. Trimethoxy decane, 2-hydrothioethyl triethoxy decane, 2-hydrothioethyl tripropoxy decane, 3-hydrothiopropyltrimethoxy decane, 3-hydrothiopropyl In the formula (e-1), such as a triethoxy decane or a 3-hydrothiopropyltripropoxydecane, Y ¹ is a decane coupling agent of an alkoxy group having 1 to 10 carbon atoms; 2-trimethoxy group矽alkylethylsulfonyltrimethoxydecane, 2-trimethoxydecylethylethylsulfonyltriethoxydecane, 2-triethoxydecylethylsulfonyltrimethoxydecane, 2- Triethoxydecylethylethylsulfonyltriethoxydecane, 3-trimethoxydecylpropylsulfonyltrimethoxydecane, 3-trimethoxydecylpropylsulfonyltriethoxy In the formula (e-3), decane, 3-triethoxydecylpropylsulfonyltrimethoxydecane, 3-triethoxydecylpropylsulfonyltriethoxydecane, Y ¹ and Y ² is an alkoxy decane coupling agent having 1 to 10 carbon atoms; and the oligomers are preferably 3-hydrothiopropyl More preferably, methoxytrimethoxydecane, 3-trimethoxydecylpropylsulfonyltriethoxydecane, and such oligomers.

The decane coupling agent (E) can be used alone or in combination of two or more.

The amount of the component (E) used is the hydrogenthio group equivalent of the curable composition [the number of moles of the thiol group per 1 g of the curable composition (or the number of moles of the hydrogenthio group, the same applies hereinafter) It is preferably 0.001 to 1.00 mmol/g, more preferably 0.005 to 0.80 mmol/g, and particularly preferably 0.015 to 0.60 mmol/g. before The thiol group equivalent can be determined by a known method.

The content ratio (mass ratio) of the component (A) to the component (E) is preferably 100:0.1 to 100:50, preferably 100:0.3 to 100:30, more preferably 100:0.4 to 100:25. .

The cured product containing the curable composition of the component (A) and the component (E) in this ratio is excellent in peeling resistance and heat resistance, and has high adhesion. When the content ratio of the component (E) is less than the above range, the object of the present invention cannot be attained. When the content is too large, the obtained cured product is colored, and the strength at the time of high temperature may be lowered.

In the present invention, the total mass of the components (A) to (E) is preferably 60% by mass or more of the total composition, and preferably 70% by mass or more.

(F) thinner

The curable composition of the present invention may further contain a diluent for the purpose of imparting fluidity.

Examples of the diluent include diethylene glycol monobutyl ether acetate, glycerol diepoxypropyl ether, butanediol diepoxypropyl ether, diepoxypropyl aniline, and neopentyl glycol epoxy. Propyl ether, cyclohexane dimethanol diepoxypropyl ether, alkyl diepoxypropyl ether, polyglycol diepoxypropyl ether, polypropylene glycol diepoxypropyl ether, trimethylolpropane Triepoxypropyl ether, glycerol triepoxypropyl ether, 4-vinylcyclohexene oxide, vinyl cyclohexene oxide, methylated ethylene cyclohexene, and the like.

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

The amount of the diluent to be used is preferably from 50 to 100% by mass, more preferably from 60 to 90% by mass, even more preferably from 70 to 85% by mass, based on the solid content of the curable composition of the present invention.

Further, when the curable composition of the present invention contains a diluent, the component (A), the component (B), the component (C), and the component (D) are all contained after the diluent from which the curable composition is removed. The total amount of the component (E) is preferably 50 to 100% by mass, and more preferably 60 to 100% by mass. When the total amount of the component (A), the component (B), the component (C), the component (D), and the component (E) is within the above range, the curable composition of the present invention is more resistant to heat and adhesion. Excellent.

(G) Other ingredients

The curable composition of the present invention may further contain other components in the above components without departing from the object of the present invention.

Examples of other components include an antioxidant, an ultraviolet absorber, and a photostabilizer.

The antioxidant is added to prevent oxidative degradation during heating. Examples of the antioxidant include a phosphorus-based antioxidant, a phenol-based antioxidant, and a sulfur-based antioxidant.

Examples of the phosphorus-based antioxidant include phosphites and oxaphosphorus oxides. Examples of the phenolic antioxidant include monophenols, bisphenols, and polymeric phenols. Examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'. - thiodipropionate and the like.

These antioxidants can be used singly or in combination of two or more. The amount of the antioxidant to be used is usually 10% by mass or less based on the component (A).

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

Examples of the ultraviolet absorber include salicylic acid, diphenylketone, benzotriazole, and hindered amine.

The ultraviolet absorbers can be used singly or in combination of two or more.

The amount of the ultraviolet absorber to be used is usually 10% by mass or less based on the component (A).

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

As the photostabilizer, for example, poly[{6-(1,1,3,3,-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{ (2,2,6,6-tetramethyl-4-piperidine)imido}hexamethylene {(2,2,6,6-tetramethyl-4-piperidine)imido}] Hindered amines, etc.

These light stabilizers can be used singly or in combination of two or more.

The total amount of these other components (excluding the diluent) is usually 20% by mass or less based on the component (A).

The curable composition of the present invention can be prepared by, for example, mixing the components (A) to (E) and the components (F) and (G) as needed, and mixing and defoaming according to a conventional method. And get it.

According to the curable composition of the present invention obtained as described above, a cured product having excellent peeling resistance and heat resistance and having high adhesion can be obtained.

Therefore, the curable composition of the present invention can be suitably used as a raw material, an adhesive, a coating agent, or the like as an optical member and a molded body. In particular, it is possible to solve the problem that the optical element fixing material is deteriorated as the optical element is increased in brightness. Therefore, the curable composition of the present invention can be suitably used as a composition for fixing an optical element.

2) Hardened material

The second invention of the present invention is a cured product obtained by curing the curable composition of the present invention.

As a method of hardening the curable composition of this invention, heat hardening is mentioned. The heating temperature at the time of hardening is usually 100 to 200 ° C, and the heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

The cured product of the present invention has high adhesion, and is excellent in peeling resistance and heat resistance.

Therefore, the cured product of the present invention can be suitably used as an optical element fixing material which can solve the problem of deterioration due to high luminance of the optical element. For example, a raw material, an adhesive, a coating agent, or the like which is an optical member and a molded body can be suitably used.

The cured product obtained by heating the curable composition of the present invention is excellent in peeling resistance, and can be confirmed, for example, as follows.

After the curable composition was applied to the LED lead frame, the sapphire wafer was pressure-bonded and heat-treated at 170 ° C for 2 hours to be hardened, and then the encapsulating material was poured into a cup and heat-treated at 150 ° C for 1 hour to obtain a hardened material test. sheet. After exposing the test piece to an environment of 85 ° C and 85% RH for 168 hours, an IR reflow treatment was performed at a preheating temperature of 160 ° C and a maximum temperature of 260 ° C for 1 minute, followed by a thermal cycle tester. The test in which each of -40 ° C and +100 ° C was allowed to stand for 30 minutes was set to 1 cycle, and 300 cycles were carried out. Subsequently, the encapsulating material was removed and investigation was made as to whether the components were peeled off together at this time. In the cured product of the present invention, the probability of peeling is usually 45% or less, preferably 25% or less.

The cured product obtained by hardening the curable composition of the present invention has High adhesion can be confirmed, for example, as follows. That is, the curable composition is applied onto the mirror surface of the tantalum wafer, and the coated surface is placed on the object to be pressed and pressure-bonded, and heat-treated to be cured. It is placed on a measuring stage of a bond tester which has been preheated to a predetermined temperature (for example, 23 ° C, 100 ° C) for 30 seconds, and is at a height of 50 μm from the object to be pressed. Next, a stress is applied in the horizontal direction (shear direction) to measure the adhesion between the test piece and the object to be pressed.

The adhesion of the cured product is preferably 60 N/2 mm □ or more at 23 ° C, preferably 80 N / 2 mm □ or more, and particularly preferably 100 N / 2 mm □ or more. Further, the adhesion of the cured product is preferably 40 N/2 mm□ or more at 100 °C, preferably 50 N/2 mm□ or more, and particularly preferably 60 N/2 mm□ or more.

3) How to use the curable composition

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

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.

<Battery for optical element>

The curable composition of the present invention can be suitably used as an adhesive for an optical element fixing material.

As a method of using the curable composition of the present invention as an adhesive for an optical element fixing material, there is a method in which the composition is applied to one or both of the target material (optical element, substrate, and the like). After the surface is then pressure-bonded, it is heat-hardened and the method of adhering firmly between the target materials is followed.

As the substrate material for the optical element to be followed, an alkali stone is mentioned Glass such as gray glass or heat-resistant hard glass; ceramics; sapphire; iron, copper, aluminum, gold, silver, platinum, chromium, titanium, alloys of these metals, stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.) Metals; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, Polyfluorene, polyetheretherketone, polyether oxime, polyphenylene sulfide, polyether oximine, polyimine, polyamine, acrylic resin, norbornene resin, cyclic olefin resin, glass ring A synthetic resin such as an oxygen resin.

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

<Packaging material for optical components>

The curable composition of the present invention can be suitably used as a sealing material for an optical element fixing material.

As a method of using the curable composition of the present invention as a sealing material for an optical element fixing material, for example, a method in which the composition is formed into a desired shape to obtain a package containing an optical element is exemplified. After the body, a method of manufacturing the optical element package by heat-hardening itself.

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

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

Since the obtained light element encapsulating system uses the curable composition of the present invention, it is excellent in peeling resistance and heat resistance, and has high adhesion.

4) Optical device

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

In the optical device of the present invention, the curable composition of the present invention is obtained by using an adhesive or an encapsulant for an optical element fixing material and fixing the optical element. Therefore, the optical element is excellent in durability by being fixed by a high adhesion force.

[Examples]

Next, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited by the examples described below. Further, as long as it is not limited, "%" and "parts" are quality standards.

(mass average molecular weight determination)

The mass average molecular weight (Mw) and the number average molecular weight (Mn) of the decane compound polymer obtained in the following production examples were measured under the following apparatus and conditions in terms of standard polystyrene.

Device name: HLC-8220GPC, made by TOSOH

Column: Connect TSKgelGMHXL, TSKgelGMHXL, and TSKgel2000HXL in turn

Solvent: tetrahydrofuran

Injection volume: 80μl

Measuring temperature: 40 ° C

Flow rate: 1ml/min

Detector: Differential Refractometer

(Measurement of IR spectrum)

The IR spectrum of the decane compound polymer obtained in the production example was measured using a Fourier transform infrared spectrophotometer (Spec 100, manufactured by Perkinelmer Co., Ltd.).

(Manufacturing Example 1)

In a 300 ml eggplant type flask, phenyltrimethoxydecane (manufactured by Tokyo Chemical Industry Co., Ltd., the same applies hereinafter), 20.2 g (102 mmol), 2-cyanoethyltrimethoxydecane (manufactured by AZMAX Co., Ltd., the same applies hereinafter), 3.15 g ( After 18 ml of the solvent and 96 ml of acetone as a solvent and 24 ml of distilled water, 0.15 g (1.5 mmol) of phosphoric acid (manufactured by Kanto Chemical Co., Ltd., the following) was added as a catalyst while stirring the contents, and stirring was further continued at 25 ° C for 16 hours.

After completion of the reaction, the reaction mixture was concentrated to 50 ml using an evaporator, and ethyl acetate (100 ml) was added to the concentrate, and the mixture was neutralized with a saturated aqueous sodium hydrogencarbonate solution. After standing for a while, the organic layer was separated. Next, the organic layer was washed twice with distilled water, and then dried using anhydrous magnesium sulfate. After separating the magnesium sulfate by filtration, the filtrate was concentrated to 50 ml using an evaporator, and the obtained concentrate 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 (MEK) and recovered, and the solvent was distilled off under reduced pressure using an evaporator. 13.5 g of a decane compound copolymer (A1) was obtained by vacuum drying the residue.

The mass average molecular weight (Mw) of the decane compound copolymer (A1) is 1,870, molecular weight distribution (Mw / Mn) was 1.42.

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

Si-Ph: 698 cm ^-1 , 740 cm ^-1 , Si-O: 1132 cm ^-1 , -CN: 2259 cm ^-1

(Example 1)

100 parts (parts by mass or less) of the decane compound copolymer (A1) obtained in Production Example 1 was added as a component (B), and the polyfluorinated microparticles having an average primary particle diameter of 0.8 μm (manufactured by Nisshin RICA Co., Ltd., MSP) -SN08, as described in Table 1 below as "(B2)"), as a component (C), 1,3,5-N-gin[3-(trimethoxydecyl)propyl]isocyanuric acid 10 parts of ester (described as "(C1)" in Table 1), 3-(trimethoxydecyl)propyl succinic anhydride as component (D) (described as "(D1)" in Table 1) In the case of the component (E), 3-hydroxythiopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803, referred to as "(E1)" in Table 1), 0.5 parts, and a solid component Diethylene glycol monobutyl ether acetate was added in such a manner that the concentration was 80%, and the entire content was sufficiently mixed and defoamed to obtain a curable composition 1.

(Examples 2 to 27, Comparative Examples 1 to 9)

In the first embodiment, the type (B) of the component (B), the amount of use (C), the amount of the component (D), the type of the component (E), and the amount of use (part) are changed. The curable compositions 2 to 27 of Examples 2 to 27 and the curable compositions 1r to 9r of Comparative Examples 1 to 9 were obtained in the same manner as in Example 1 except as described in the following Table 1.

In the following table, the type of the component (B): B1 to B4, B9, and the component (E): E1 to E3 are as follows.

. B1: Polyfluorene-based fine particles (average primary particle diameter: 0.5 μm), manufactured by Nisshin RICA, MSP-SN05

. B2: Polyfluorene-based fine particles (average primary particle diameter: 0.8 μm), manufactured by Nisshin RICA, MSP-SN08

. B3: Polyoxynene microparticles (average primary particle size: 2 μm), Momentive. Performance. Materials. Japan contract company, TOSPEARL 120

. B4: Polyfluorene-based fine particles (average primary particle diameter: 4.5 μm), Momentive. Performance. Materials. Japan company, TOSPEARL 145

. B9: yttrium oxide microparticles (average primary particle diameter: 0.07 μm), manufactured by Tokuyama Co., Ltd., Silfil NSS-5N

. E1: 3-Hydroxythiopropyltrimethoxydecane [manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803, thiol equivalent (molar number of E1 per 1 g of hydrogenthio group): 5.10 mmol/g]

. E2: 3-trimethoxydecylpropylsulfonyltriethoxydecane [manufactured by Shin-Etsu Chemical Co., Ltd., X-12-1056ES, thiol equivalent (E2 per mole of thiol group of 1g): 2.79mmol/g]

. E3: oligomer [molecular weight: 700, manufactured by Shin-Etsu Chemical Co., Ltd., X-41-1810, hydrogenthio group equivalent (molar number of E3 per 1 g of hydrogenthio group): 2.22 mmol/g]

The cured products of the curable compositions 1 to 27 and 1 r to 9 r obtained in Examples 1 to 27 and Comparative Examples 1 to 9 were measured as follows, and the peel strength was measured and the peeling resistance was evaluated.

The measurement results and evaluations are shown in Table 1 below.

(following the determination of the strength)

The curable compositions 1 to 27 and 1 r to 9 r were applied to the mirror surface of a 2 mm square tantalum wafer so as to have a thickness of about 2 μm, and the coated surface was placed on the substrate (silver-plated copper plate) and pressure-bonded. Subsequently, it was heat-treated at 170 ° C for 2 hours to be hardened to obtain an adherend of the test piece. The adherend of the test piece was placed on a measuring stage of a bonding strength tester (Dage Co., Ltd., Series 4000) heated to a predetermined temperature (23 ° C, 100 ° C) for 30 seconds, and was carried out for 30 seconds. The height of the object was calculated to be 50 μm, and the bonding force was applied to the bonding surface at a speed of 200 μm/s in the horizontal method (shear direction) to measure the bonding strength between the test piece and the substrate at 23 ° C and 100 ° C (N/2 mm □). ).

(resistance test)

The curable composition 1~27, 1r~9r is 0.4mm After coating the LED lead frame (manufactured by Enomoto Co., Ltd., product name: 5050 D/G PKG LEADFRAME), a 0.5 mm square sapphire wafer was pressure-bonded. Subsequently, the mixture was heat-treated at 170 ° C for 2 hours to be hardened, and then a sealing material (manufactured by Shin-Etsu Chemical Co., Ltd., product name: EG6301) was poured into the cup, and heated at 150 ° C for 1 hour to obtain a test piece.

After the test piece was exposed to an environment of 85 ° C and 85% RH for 168 hours, IR reflow was performed for 1 minute at a preheating temperature of 160 ° C and a maximum temperature of 260 ° C (reflow furnace: manufactured by Sagami Mori Co., Ltd., product name) "WL-15-20DNX type") processing. Subsequently, 300 cycles were carried out by a thermal cycle tester and a test in which each of -40 ° C and +100 ° C was allowed to stand for 30 minutes. Subsequently, the operation of removing the encapsulating material was performed and it was investigated whether the elements were peeled off together at this time. The test was carried out 12 times for each of the curable compositions.

In Table 1 below, the number of peeling off of the components was calculated, and the peeling yield was 25%. In the following, the rating is "A". If it is greater than 25% and less than 50%, it is rated as "B". When it is greater than 50%, it is rated as "C".

In the following table, the right column of (E) indicates the thiol group equivalent (the number of moles of the thiol group per gram of the curable composition) (mmol/g) with respect to the curable composition.

As is clear from Table 1, the cured products of the curable compositions 1 to 27 of Examples 1 to 27 were evaluated as A or B in total peeling resistance, and were excellent in peeling resistance. Then, the strength is also 87 N/2 mm □ or more (mostly 95 N/2 mm □ or more) at 23 ° C, and 42 N / 2 mm □ or more at 100 ° C, and the force and heat resistance are excellent.

On the other hand, the cured products of 1 r to 9 r of the curable composition of Comparative Examples 1 to 9 had a total strength of 94 N/2 mm □ or less, and were also less than 42 N / 2 mm □ at 100 ° C, and the strength was inferior. Further, except for Comparative Example 5, the evaluation of all the peeling resistance was poor. The evaluation of the peeling resistance of the curable composition of Comparative Example 5 was B, but the adhesive strength at 100 ° C was 18.85 N / 2 mm □, and the force and heat resistance were inferior.

Claims (13)

A curable composition comprising a curable composition of the following components (A) to (E), a component (A) and a component (B), wherein the mass ratio of the component (A) to the component (B) is [( A) Component: (B) component] = 100: 0.3 to 100: 20 ratio, (A) a decane compound copolymer represented by the following formula (a-1) (CHR ¹ X ⁰ -D-SiO _{3/ 2} ) _m (R ² SiO _3/2 ) _n (CHR ¹ X ⁰ -D-SiZ ¹ O _2/2 ) ₀ (R ² SiZ ² O _2/2 ) _p (CHR ¹ X ⁰ -D-SiZ ³ ₂ O _1/2 ) _q (R ² SiZ ⁴ ₂ O _1/2 ) _r ‧‧‧(a-1) [wherein X ⁰ represents a halogen atom, a cyano group, or a group represented by the formula: OG (formula) Wherein G represents a protecting group of a hydroxyl group), and D represents a single bond or a divalent organic group having a substituent or a substituent having 1 to 20 carbon atoms, and R ¹ represents a hydrogen atom or a carbon number of 1 to 2; 6 alkyl, R ² represents an alkyl group having 1 to 20 carbon atoms, or a phenyl group having a substituent or a substituent, and Z ¹ to Z ⁴ are each independently represented by a hydroxyl group and having a carbon number of 1 to 10. An alkoxy group or a halogen atom, wherein m and n are each independently and represent a positive integer, o, p, q, and r are each independently and represent 0 or a positive integer], and (B) an average primary particle diameter of more than 0.04 μm and 8 μm or less. Microparticle, (C) molecule Silane coupling agents having nitrogen atoms, (D) a silane-coupling agent having a molecular structure of the acid anhydride, a sulfur-containing silicon atoms having a functional group of the silane coupling agent (E) molecule. The sclerosing composition according to claim 1, wherein the component (B) is selected from the group consisting of silica, polysilicon, and metal oxide coated with a silicon oxide. At least one kind of microparticles. The sclerosing composition according to claim 1, wherein the aforementioned (A) The mass average molecular weight of the ingredients is 800 to 30,000. The sclerosing composition according to claim 1, wherein the (A) component of the formula (a-1) is (m+o+q) and (n+p+r) is (m+o+). q): (n+p+r)=5:95~60:40 ratio of the compound. The sclerosing composition of claim 1, which further contains a diluent. The curable composition according to claim 1, wherein the total amount of the component (A), the component (B), the component (C), the component (D), and the component (E) is relative to the removal hardening. The total amount of the components after the diluent of the composition is 50 to 100% by mass. The curable composition according to claim 1, wherein the curable composition has a solid content concentration of 50 to 100% by mass. The curable composition according to claim 1, which is a composition for a fixing member for a light element. A cured product obtained by hardening the curable composition according to the above [1]. A cured product according to claim 9 which is a fixing member for a light element. A method of using the curable composition according to item 1 of the patent application as an adhesive for an optical element fixing material. A method of using a curable composition as described in claim 1 as a packaging material for an optical element fixing material. An optical device according to the first aspect of the invention is used as an adhesive for an optical element fixing material or a sealing material for an optical element fixing material.