CN102906198A

CN102906198A - Curable composition, hardened material, and method for using curable composition

Info

Publication number: CN102906198A
Application number: CN2011800128989A
Authority: CN
Inventors: 樫尾干广
Original assignee: Lintec Corp
Current assignee: Lintec Corp
Priority date: 2010-03-08
Filing date: 2011-03-07
Publication date: 2013-01-30
Anticipated expiration: 2031-03-07
Also published as: JPWO2011111667A1; KR101768246B1; WO2011111667A1; CN102906198B; KR20130034005A; TW201141952A; TWI504681B; JP5725479B2

Abstract

Disclosed is a curable composition that includes (A) a silane compound copolymer having specific repeating units, (B) an epoxy compound having an isocyanurate skeleton, (C) a curing agent that includes an alicyclic acid anhydride having a carboxyl group, and (D) a silane coupling agent having an acid anhydride structure. Also disclosed are a hardened material formed by hardening the composition and a method for using the aforementioned composition as an adhesive for an optical element fixing material and as a sealing material for an optical element fixing material. With the curable composition, a hardened material can be obtained that does not lose transparency with coloring and has excellent transparency over an extended period of time even when irradiated with high-energy light or when in a high temperature state, and that has high adhesive strength even at high temperatures. The curable composition can be used when forming an optical element fixing material, and in particular can be optimally used as an adhesive for an optical element fixing material and as a sealing material for an optical element fixing material.

Description

The using method of solidification compound, cured article and solidification compound

Technical field

The present invention relates to obtain the transparency and excellent heat resistance and have the solidification compound of the cured article of high bonding force, said composition is solidified the cured article that forms and with above-mentioned composition as the optical element immobilization material with caking agent or the optical element immobilization material method with the sealing agent use.

Background technology

In the past, solidification compound had carried out various improvement corresponding to purposes, industrially was widely used as raw material, caking agent, coating agent of optics or molding etc.For example, the solidification compound that forms the excellent cured article of the transparency is preferably used as raw material or its coating agent of optics mostly, and in addition, the solidification compound that forms the cured article with high bonding force is preferably used as caking agent or coating agent mostly.

In addition, in recent years, when making the optical element sealing member, solidification compound also be used as the optical element immobilization material with caking agent or optical element immobilization material with optical element immobilization material compositions such as sealing agents.

Optical element comprises luminous element, photo detector, composite optic element, the optical integrated circuits etc. such as various laser, photodiode (LED) such as semiconductor laser (LD).In recent years, the long optical element for short wavelength's blue light, white light of more luminous spike is developed and is widely used.The high brightnessization of the luminous element that this glow peak wavelength is short develops by leaps and bounds, and there is the tendency that further increases in the thermal value of the optical element that accompanies with it.

Yet, follow in recent years the high brightness of optical element, the optical element immobilization material by under the heat of the more high temperature that is exposed to for a long time more high-octane light or is produced by optical element, has the problems such as occuring deteriorated and cracks or peel off with the cured article of composition.

In order to address this problem, the optical element immobilization material composition take the polysilsesquioxane compound as principal constituent has been proposed in the patent documentation 1～3.

Yet the optical element immobilization material take the polysilsesquioxane compound as principal constituent of record also is difficult to obtain thermotolerance and the transparency sometimes with the cured article of composition in the patent documentation 1～3 when keeping sufficient bonding force.

In addition, as the composition that is used for optical element sealing usefulness, propose to use the composition epoxy resin of alicyclic epoxy resin in the patent documentation 4, proposed to contain the composition epoxy resin of poly-thiol compound in the patent documentation 5.

Yet, when using these compositions, also exist and can't satisfy the situation that the sufficient fast light deterioration of following rheological parameters' change with time or bonding force reduce.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2004-359933 communique

Patent documentation 2: TOHKEMY 2005-263869 communique

Patent documentation 3: TOHKEMY 2006-328231 communique

Patent documentation 4: Japanese kokai publication hei 7-309927 communique

Patent documentation 5: TOHKEMY 2009-001752 communique.

Summary of the invention

The technical problem that invention will solve

The present invention finishes in view of the practical situation of above-mentioned prior art, its problem be to provide can obtain thermotolerance and the transparency excellent and have the cured article of high bonding force solidification compound, said composition is solidified the cured article that forms and the method that above-mentioned composition is used with sealing agent with caking agent or optical element immobilization material as the optical element immobilization material.

The means that are used for the technical solution problem

The inventor conducts in-depth research for solving the problems of the technologies described above repeatedly, found that: contain the cured article of composition that epoxy compounds, (C) that (A) specific silane compound multipolymer, (B) have the chlorinated isocyanurates skeleton contain the solidifying agent of the ester ring type acid anhydrides with carboxyl and (D) have a silane coupling agent of acid anhydride structure and keep for a long time the excellent transparency, thermotolerance, and, at high temperature also formation has the cured article of high bonding force, thereby has finished the present invention.

Like this, according to the 1st aspect of the present invention, provide the solidification compound of following (1)～(9).

(1) solidification compound, it contains:

(A) in molecule, has following formula (i), (ii) and (iii)

[changing 1]

(in the formula, R ¹The alkyl of expression hydrogen atom or carbonatoms 1～6, X ⁰Expression halogen atom, cyano group or formula: the group shown in the OG (in the formula, G represents the protecting group of hydroxyl), D represents singly-bound or linking group.R ²The alkyl of expression carbonatoms 1～20 maybe can have substituent phenyl)

(i) in the shown repeating unit and (ii), (i) and (iii), (ii) and (iii) or repeating unit (i), (ii) and (iii), weight-average molecular weight be 1,000～30,000 silane compound multipolymer,

(B) have the chlorinated isocyanurates skeleton epoxy compounds,

(C) contain the ester ring type acid anhydrides with carboxyl solidifying agent and

(D) has the silane coupling agent of acid anhydride structure.

(2) (1) described solidification compound, wherein, the silane compound multipolymer of above-mentioned (A) is with formula: R ¹-CH(X ⁰The amount ((R of the group shown in the)-D- ¹-CH(X ⁰And R)-D)) ²Amount ((R ²)) molar ratio computing be (R ¹-CH(X ⁰)-D): (R ²The silane compound multipolymer of)=60: 40～5: 95.

(3) (1) or (2) described solidification compound, it is characterized in that above-mentioned (A), (B), (C) and (D) proportionally count (A) with (A) with the mass ratio of ((B)+(C)+(D)) containing of composition: ((B)+(C)+(D))=90: 10～50: 50.

(4) solidification compound, it contains:

(A ') make and contain formula (1): R ¹-CH(X ⁰)-D-Si(OR ³) _p(X ¹) _3-p

(in the formula, R ¹The alkyl of expression hydrogen atom or carbonatoms 1～6, X ⁰Expression halogen atom, cyano group or formula: the group shown in the OG (in the formula, G represents the protecting group of hydroxyl), D represents singly-bound or linking group.R ³The alkyl of expression carbonatoms 1～6, X ¹The expression halogen atom, p represents 0～3 integer)

Shown silane compound (1) at least a and

Formula (2): R ²Si(OR ⁴) _q(X ²) _3-q

(in the formula, R ²The alkyl of expression carbonatoms 1～20 maybe can have substituent phenyl, R ⁴The alkyl of expression carbonatoms 1～6, X ²The expression halogen atom, q represents 0～3 integer)

The mixture condensation of at least a silane compound of shown silane compound (2) and, weight-average molecular weight be 1,000～30,000 silane compound multipolymer,

(B) have the chlorinated isocyanurates skeleton epoxy compounds,

(D) has the silane coupling agent of acid anhydride structure.

(5) (4) described solidification compound, wherein, the silane compound multipolymer of above-mentioned (A ') is to make silane compound (1) and silane compound (2) take molar ratio computing as (silane compound (1)): the ratio of (silane compound (2))=60: 40～5: 95 is carried out the silane compound multipolymer that condensation gets.

(6) (4) or (5) described solidification compound, it is characterized in that above-mentioned (A '), (B), (C) and (D) the containing and proportionally count with the mass ratio of ((B)+(C)+(D)) with (A ') of composition (A '): ((B)+(C)+(D))=90: 10～50: 50.

(7) (1) or (4) described solidification compound, it is characterized in that above-mentioned (B), (C) and (D) proportionally count ((B)+(C)) with ((B)+(C)) and (D) mass ratio containing of composition: (D)=90: 10～10: 90.

(8) (1) or (4) described solidification compound, wherein, the solidifying agent of above-mentioned (C) comprises one or two or more kinds that is selected from ester ring type acid anhydrides with carboxyl and other ester ring type acid anhydrides, and its mass ratio is (the ester ring type acid anhydrides with carboxyl): (other ester ring type acid anhydrides)=100: 0～10: 90.

(9) (1) or (4) described solidification compound, it is optical element immobilization material composition.

According to the 2nd aspect of the present invention, provide the cured article of following (10), (11).

(10) cured article, it forms (1) or (4) described solidification compound curing.

(11) (10) described cured article, it is the optical element immobilization material.

According to the 3rd aspect of the present invention, provide method following (12), (13), that use solidification compound of the present invention.

(12) method of (1) or (4) described solidification compound being used with caking agent as the optical element immobilization material.

(13) method of (1) or (4) described solidification compound being used with sealing agent as the optical element immobilization material.

The invention effect

According to solidification compound of the present invention, even can obtain under illuminated high-octane light time or the condition of high temperature, the cured article of high bonding force can not occur to have under the excellent transparency of having for a long time of painted or transparent reduction and the high temperature yet yet.

Solidification compound of the present invention can use when forming the optical element immobilization material, especially can be aptly as the optical element immobilization material with caking agent and optical element immobilization material sealing agent.

Embodiment

Below, the present invention is divided into 1) solidification compound, 2) cured article and 3) every being elaborated of using method of solidification compound.

1) solidification compound

Solidification compound of the present invention is characterised in that,

It contains: (A) have following formula (i), (ii) and (iii) in molecule

[changing 2]

(i) in the shown repeating unit and (ii), (i) and (iii), (ii) and (iii) or (i), (ii) and (iii) repeating unit, weight-average molecular weight is 1, epoxy compounds, (C) that 000～30,000 silane compound multipolymer, (B) have the chlorinated isocyanurates skeleton contain the solidifying agent of the ester ring type acid anhydrides with carboxyl and the silane coupling agent that (D) has acid anhydride structure.

(A) silane compound multipolymer

Solidification compound of the present invention contains (A) composition: have above-mentioned formula (i), (ii) and (i) in the repeating unit (iii) and (ii), (i) and (iii), (ii) and (iii) or repeating unit (i), (ii) and (iii), weight-average molecular weight is 1,000～30,000 silane compound multipolymer (below, sometimes be called " silane compound multipolymer (A) ").

Silane compound multipolymer (A) can have (i), (ii), each is a kind of for the repeating unit shown in (iii), also can have more than two kinds.

In the formula (i)～(iii), R ¹The alkyl of expression hydrogen atom or carbonatoms 1～6, preferred hydrogen atom.

R ¹The alkyl of shown carbonatoms 1～6 can be enumerated methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, sec-butyl, n-pentyl, n-hexyl etc.

X ⁰The halogen atoms such as expression fluorine atom, chlorine atom, bromine atoms, iodine atom; Cyano group; Or formula: the group shown in the OG.

G represents the protecting group of hydroxyl.The protecting group of hydroxyl is not particularly limited, and can enumerate the known protecting group that is known as hydroxyl protecting group.For example can enumerate: the protecting group of acyl group system; The protecting group of the silicomethane base systems such as trimethyl silyl, triethylsilyl, t-butyldimethylsilyl, t-butyldiphenylsilyl; The protecting group of methoxymethyl, methoxy ethoxy methyl, 1-ethoxyethyl group, tetrahydropyrans-2-base, the tetrahydrofuran (THF)-acetals such as 2-base system; The protecting group of the alkoxy carbonyls such as tert-butoxycarbonyl system; Methyl, ethyl, the tertiary butyl, octyl group, propenyl, trityl group, benzyl, to the protecting group of the ethers such as methoxy-benzyl, fluorenyl, trityl, diphenyl-methyl system etc.Wherein, as G, be preferably the protecting group of acyl group system.

The protecting group of acyl group system is specially formula :-C(=O) R ⁵Shown group.In the formula, R ⁵The alkyl of the carbonatomss 1～6 such as expression methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl; Maybe can have substituent phenyl.

R ⁵The shown substituting group with substituent phenyl can be enumerated: the alkyl of methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl etc.; The halogen atoms such as fluorine atom, chlorine atom, bromine atoms; The alkoxyl group such as methoxyl group, oxyethyl group.

Wherein, as X ⁰From easiness and the cured article that can obtain to have high bonding force of starting with; be preferably chlorine atom, the formula of being selected from: the group shown in the OG ' is (in the formula; the protecting group of G ' expression acyl group system) and the group in the cyano group; more preferably be selected from the group in chlorine atom, acetoxyl group and the cyano group, be particularly preferably acetoxyl group.

D represents singly-bound or linking group.

As linking group, can enumerate the organic group that can have substituent divalent.The carbonatoms of this organic group is preferably 1～20, more preferably 1～10.

As the organic group that can have substituent divalent, can have substituent alkylidene group such as enumerating, can have substituent alkenylene, can have substituent alkynylene, can have substituent arylidene, substituent by having (alkylidene group, alkenylene or alkynylene) and the divalent group that constitutes that can have substituent arylidene etc.

As the alkylidene group that can have substituent alkylidene group, can enumerate the alkylidene group of the carbonatomss 1～20 such as methylene radical, ethylidene, propylidene, trimethylene, tetramethylene, pentamethylene, hexa-methylene, preferred carbonatoms 1～10.

As the alkenylene that can have substituent alkenylene, can enumerate the alkenylene of the carbonatomss 2～20 such as vinylidene, propenylidene, crotonylidene, inferior pentenyl, the alkenylene of preferred carbonatoms 2～10.

As the alkynylene that can have substituent alkynylene, can enumerate the alkynylene of the carbonatomss 2～20 such as ethynylene, inferior proyl, the alkynylene of preferred carbonatoms 2～10.

As the arylidene that can have substituent arylidene, can enumerate adjacent phenylene, metaphenylene, to phenylene, 2, the arylidene of the arylidene of the carbonatomss 6～20 such as 6-naphthylidene, preferred carbonatoms 6～10.

As the substituting group of above-mentioned alkylidene group, alkenylene and alkynylene, can enumerate: the halogen atoms such as fluorine atom, chlorine atom; The alkoxyl group such as methoxyl group, oxyethyl group; The alkylthio such as methylthio group, ethylmercapto group; The alkoxy carbonyl such as methoxycarbonyl, ethoxy carbonyl etc.

As the substituting group of above-mentioned arylidene, can enumerate cyano group; Nitro; The halogen atoms such as fluorine atom, chlorine atom, bromine atoms; The alkyl such as methyl, ethyl; The alkoxyl group such as methoxyl group, oxyethyl group; The alkylthio such as methylthio group, ethylmercapto group etc.

These substituting groups can be bonded to arbitrarily position in the groups such as alkylidene group, alkenylene, alkynylene and arylidene, all right identical or different ground bonding is a plurality of.

As substituent by having (alkylidene group, alkenylene or alkynylene) with can have the divalent group that constitutes of substituent arylidene, can enumerate above-mentioned group at least a, that form with the above-mentioned at least a bonding of connecting with substituent arylidene with substituent (alkylidene group, alkenylene or alkynylene).Particularly, can enumerate the group shown in the following formula.

[changing 3]

Wherein, as D, from obtaining having the cured article of high bonding force, the alkylidene group of preferred carbonatoms 1～10, the more preferably alkylidene group of carbonatoms 1～6, particularly preferably methylene radical or ethylidene.

In the formula (i)～(iii), R ²The alkyl of expression carbonatoms 1～20 maybe can have substituent phenyl.

As R ²The alkyl of shown carbonatoms 1～20 can be enumerated: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-octyl, iso-octyl, n-nonyl, positive decyl, dodecyl etc.

As R ²The shown substituting group with substituent phenyl can be enumerated: the alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl; The alkoxyl group such as methoxyl group, oxyethyl group; The halogen atoms such as fluorine atom, chlorine atom etc.

As R ²The shown concrete example with substituent phenyl can be enumerated: phenyl, 2-chloro-phenyl-, 4-aminomethyl phenyl, 3-ethylphenyl, 2,4-3,5-dimethylphenyl, 2-p-methoxy-phenyl etc.

In the silane compound multipolymer (A), formula: R ¹-CH(X ⁰The amount ((R of the group shown in the)-D- ¹-CH(X ⁰And R)-D)) ²Amount ((R ²)) mol ratio be preferably (R ¹-CH(X ⁰)-D): (R ²)=60: 40～5: 95 more preferably 50: 50～5: 95, are particularly preferably 50: 50～10: 90.By in this scope, can obtain cured article transparent and excellent in adhesion and excellent heat resistance.

Formula: R ¹-CH(X ⁰Group shown in the)-D-and R ²Amount for example can be undertaken quantitatively by the NMR spectrum of measuring silane compound multipolymer (A).

Silane compound multipolymer (A) can be the arbitrarily multipolymer such as random copolymers, segmented copolymer, graft copolymer, alternating copolymer, but random copolymers particularly preferably.

The weight-average molecular weight (Mw) of silane compound multipolymer (A) is 1,000～30,000 scope, is preferably 1,500～6,000 scope.By in this scope, the operability of composition is excellent, and can obtain the cured article of cementability, excellent heat resistance.Weight-average molecular weight (Mw) for example can utilize the gel permeation chromatography (GPC) take tetrahydrofuran (THF) (THF) as solvent to try to achieve with the form of polystyrene standard scaled value.

The molecular weight distribution (Mw/Mn) of silane compound multipolymer (A) is not particularly limited, but is generally 1.0～3.0, preferred 1.1～2.0 scope.By in this scope, can obtain the cured article of cementability, excellent heat resistance.

Silane compound multipolymer (A) can a kind of independent use, perhaps makes up two or more uses.

The polysilsesquioxane compound of silane compound multipolymer (A) for having the notch cuttype structure.

The silane compound multipolymer has that the notch cuttype structure can be measured by the infrared absorption spectrum that carries out reaction product for example, X-ray diffraction is measured, NMR measures to confirm.

In the solidification compound of the present invention, above-mentioned (A) composition can be

(A ') make and contain formula (1): R ¹-CH(X ⁰)-D-Si(OR ³) _p(X ¹) _3-p

Shown silane compound (1) at least a and

Formula (2): R ²Si(OR ⁴) _q(X ²) _3-q

The mixture condensation of at least a silane compound of shown silane compound (2) and, weight-average molecular weight is 1,000～30,000 silane compound multipolymer (below, be sometimes referred to as " silane compound multipolymer (A ') "), preferred silane compound copolymer (A) is silane compound multipolymer (A ').

(silane compound (1))

Silane compound (1) is formula (1): R ¹-CH(X ⁰)-D-Si(OR ³) _p(X ¹) _3-pShown compound.By using silane compound (1), even can obtain also good silane compound multipolymer of after the curing transparency, bonding force.

In the formula (1), R ¹The alkyl of expression hydrogen atom or carbonatoms 1～6, preferred hydrogen atom.As concrete example, can enumerate illustration as the R in the silane compound multipolymer (A) ¹Those.

In the formula (1), X ⁰Halogen atom, cyano group or the formulas such as expression fluorine atom, chlorine atom, bromine atoms, iodine atom: the group shown in the OG (in the formula, G represents the protecting group of hydroxyl), D represent singly-bound or linking group.X ⁰Can enumerate respectively illustration as the X in the silane compound multipolymer (A) with the concrete example of the group shown in the D ⁰With those of D.

R ³The alkyl of the carbonatomss 1～6 such as expression methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl.

X ¹The halogen atoms such as expression fluorine atom, chlorine atom, bromine atoms, iodine atom.

P represents 0～3 integer.

P is 2 when above, OR ³Each other can be identical or different.In addition, be 2 when above (3-p), X ¹Each other can be identical or different.

As the concrete example of silane compound (1), can enumerate: the chloromethyl Trimethoxy silane; the brooethyl triethoxyl silane; 2-chloroethyl tripropoxy silane; 2-bromotrifluoromethane three butoxy silanes; the 3-r-chloropropyl trimethoxyl silane; the 3-chloropropyl triethoxysilane; 3-chloropropyl tripropoxy silane; 3-chloropropyl three butoxy silanes; 3-bromopropyl Trimethoxy silane; 3-bromopropyl triethoxyl silane; 3-bromopropyl tripropoxy silane; 3-bromopropyl three butoxy silanes; 3-fluoropropyl Trimethoxy silane; 3-fluoropropyl triethoxyl silane; 3-fluoropropyl tripropoxy silane; 3-fluoropropyl three butoxy silanes; 3-iodine propyl trimethoxy silicane; 2-chloroethyl Trimethoxy silane; the 3-chloropropyl triethoxysilane; 4-chlorobutyl tripropoxy silane; 5-chlorine amyl group tripropoxy silane; the 2-r-chloropropyl trimethoxyl silane; 3-chloro-3-ethanoyl propyl trimethoxy silicane; 3-chloro-3-methoxycarbonyl propyl trimethoxy silicane; ortho-, meta-or p-(2-chloroethyl) phenyl tripropoxy silane; meta-(2-chloroethyl) phenyltrimethoxysila,e; p-(2-chloroethyl) phenyl triethoxysilane; the X such as p-(2-fluoro ethyl) phenyltrimethoxysila,e ⁰Trialkoxy silane compounds for halogen atom;

Chloromethyltrichlorosilane; brooethyl bromine dimethoxy silane; 2-chloroethyl dichloromethane TMOS; 2-bromotrifluoromethane dichloro Ethoxysilane; the 3-chloropropyl trichloro-silane; 3-chloropropyl tribromosilane; 3-chloropropyl dichloromethane TMOS; 3-chloropropyl dichloro Ethoxysilane; 3-chloropropyl chlorine dimethoxy silane; 3-chloropropyl chlorine diethoxy silane; 3-bromopropyl dichloro Ethoxysilane; 3-bromopropyl tribromosilane; 3-bromopropyl trichlorosilane; 3-bromopropyl chlorine dimethoxy silane; 3-fluoropropyl trichlorosilane; 3-fluoropropyl chlorine dimethoxy silane; 3-fluoropropyl dichloromethane TMOS; 3-fluoropropyl chlorine diethoxy silane; 3-iodine propyltrichlorosilan; 4-chlorobutyl chlorine diethoxy silane; 3-chloro-n-butyl chlorine diethoxy silane; 3-chloro-3-ethanoyl propyl group dichloro Ethoxysilane; the X such as 3-chloro-3-methoxycarbonyl propyl group tribromosilane ⁰Halogenated silanes compounds for halogen atom;

The cyano methyl Trimethoxy silane, the cyano methyl triethoxyl silane, 1-cyano ethyl Trimethoxy silane, 2-cyano ethyl Trimethoxy silane, 2-cyano ethyl triethoxyl silane, 2-cyano ethyl tripropoxy silane, 3-cyanopropyl Trimethoxy silane, 3-cyanopropyl triethoxyl silane, 3-cyanopropyl tripropoxy silane, 3-cyanopropyl three butoxy silanes, 4-cyano group butyl trimethoxy silane, 5-cyano group amyltrimethoxysilane, 2-cyanopropyl Trimethoxy silane, 2-(cyano group methoxyl group) ethyl trimethoxy silane, 2-(2-cyano group oxyethyl group) ethyl trimethoxy silane, ortho-, meta-or p-(cyano methyl) phenyl tripropoxy silane, meta-(cyano methyl) phenyltrimethoxysila,e, p-(cyano methyl) phenyl triethoxysilane, the X such as p-(2-cyano ethyl) phenyltrimethoxysila,e ⁰Trialkoxy silane compounds for cyano group;

The cyano methyl trichlorosilane, cyano methyl bromine dimethoxy silane, 2-cyano ethyl dichloromethane TMOS, 2-cyano ethyl dichloro Ethoxysilane, 3-cyanopropyl trichlorosilane, 3-cyanopropyl tribromosilane, 3-cyanopropyl dichloromethane TMOS, 3-cyanopropyl dichloro Ethoxysilane, 3-cyanopropyl chlorine dimethoxy silane, 3-cyanopropyl chlorine diethoxy silane, 4-cyano group Butyryl Chloride diethoxy silane, 3-cyano group n-butyl chloride diethoxy silane, 2-(2-cyano group oxyethyl group) ethyl trichlorosilane, 2-(2-cyano group oxyethyl group) monobromoethane diethoxy silane, 2-(2-cyano group oxyethyl group) ethyl dichloro propoxy-silane, ortho-, meta-or p-(2-cyano ethyl) phenyl-trichloro-silicane, meta-(2-cyano ethyl) phenyl methoxyl group two bromo-silicanes, p-(2-cyano ethyl) phenyl dimethoxy chlorosilane, the X such as p-(2-cyano ethyl) phenyl tribromosilane ⁰Halogenated silanes compounds for cyano group;

3-acetoxyl group propyl trimethoxy silicane, 3-acetoxyl group propyl-triethoxysilicane, 3-acetoxyl group propyl group tripropoxy silane, 3-acetoxyl group propyl group three butoxy silanes, 3-propionyloxy propyl trimethoxy silicane, 3-propionyloxy propyl-triethoxysilicane, 3-benzoyloxy propyl trimethoxy silicane, 3-benzoyloxy propyl-triethoxysilicane, 3-benzoyloxy propyl group tripropoxy silane, 3-benzoyloxy propyl group three butoxy silanes, 2-trimethylsiloxy ethyl trimethoxy silane, 3-silicoheptane alcoxyl base propyl-triethoxysilicane, the 3-(2-tetrahydro-pyran oxy) propyl group tripropoxy silane, 3-(2-tetrahydrofuran oxygen base) propyl group three butoxy silanes, 3-methoxymethyl oxygen base propyl trimethoxy silicane, 3-methoxy ethoxy methyl oxygen base propyl-triethoxysilicane, 3-(1-ethoxyethyl group oxygen base) propyl group tripropoxy silane, 3-(tert-butoxycarbonyl oxygen base) propyl trimethoxy silicane, 3-tert.-butoxy propyl trimethoxy silicane, 3-benzyloxy propyl-triethoxysilicane, the X such as 3-triphenyl methoxy-propyl triethoxyl silane ⁰Be above-mentioned formula: the trialkoxy silane compounds of the group shown in the OG;

3-acetoxyl group propyltrichlorosilan, 3-acetoxyl group propyl group tribromosilane, 3-acetoxyl group propyl group dichloromethane TMOS, 3-acetoxyl group propyl group dichloro Ethoxysilane, 3-acetoxyl group propyl chloride dimethoxy silane, 3-acetoxyl group propyl chloride diethoxy silane, 3-benzoyloxy propyltrichlorosilan, 3-trimethylsiloxy propyl chloride dimethoxy silane, 3-silicoheptane alcoxyl base propyl group dichloromethane TMOS, the 3-(2-tetrahydro-pyran oxy) propyl chloride diethoxy silane, 3-(2-tetrahydrofuran oxygen base) propyl group dichloro Ethoxysilane, 3-methoxymethyl oxygen base propyl group tribromosilane, 3-methoxy ethoxy methyl oxygen base propyltrichlorosilan, 3-(1-ethoxyethyl group oxygen base) propyl chloride dimethoxy silane, 3-tert-butoxycarbonyl oxygen base propyl group dichloromethane TMOS, 3-tert.-butoxy propyl chloride diethoxy silane, 3-triphenyl methoxy-propyl dichloro Ethoxysilane, the X such as 3-benzyloxy propyl group tribromosilane ⁰Be above-mentioned formula: the halogenated silanes compounds of the group shown in the OG etc.

These silane compounds (1) can a kind of independent use, perhaps makes up two or more uses.

Wherein, as silane compound (1), from obtaining having the more preferably cured article of cementability, preferred X ⁰Trialkoxy silane compounds, X for halogen atom ⁰Trialkoxy silane compounds or X for cyano group ⁰Be above-mentioned formula: the trialkoxy silane compounds of the group shown in the OG, more preferably have the 3-chloropropyl the trialkoxy silane compounds, have 3-acetoxyl group propyl group the trialkoxy silane compounds, have the trialkoxy silane compounds of 2-cyano ethyl or have the trialkoxy silane compounds of 3-cyanopropyl.

(silane compound (2))

Silane compound (2) is formula (2): R ²Si(OR ⁴) _q(X ²) _3-qShown compound.

In the formula (2), R ²The alkyl of expression carbonatoms 1～20 maybe can have substituent phenyl.As concrete example, can enumerate illustration as the R in the silane compound multipolymer (A) ²Those.

R ⁴Expression and above-mentioned R ³The alkyl of identical carbonatoms 1～6.

X ²Expression and above-mentioned X ¹Identical halogen atom.

Q represents arbitrary integer of 0～3.

Q is 2 when above, OR ⁴Each other can be identical or different.In addition, be 2 when above (3-q), X ²Each other can be identical or different.

As the concrete example of silane compound (2), can enumerate: the alkyltrialkoxysilanecompounds compounds classes such as methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl Trimethoxy silane, ne-butyltriethoxysilaneand, isobutyl-Trimethoxy silane, n-pentyl triethoxyl silane, n-hexyl Trimethoxy silane, iso-octyl triethoxyl silane, dodecyltrimethoxysilane, methyl dimethoxy oxygen base oxethyl silane, methyl diethoxy methoxy silane;

The halogenated alkyl alkoxysilane compound containing trialkylsilyl group in molecular structure classes such as methyl chloride dimethoxy silane, methyl dichloro methoxy silane, methyl chloride diethoxy silane, ethyl chloride dimethoxy silane, ethyl dichloromethane TMOS, normal propyl chloride dimethoxy silane, n-propyl dichloromethane TMOS;

The alkyl trihalosilane compounds such as METHYL TRICHLORO SILANE, methyl tribromosilane, ethyl trichlorosilane, ethyl tribromosilane, n-propyltrichlorosilan;

Phenyltrimethoxysila,e, 4-p-methoxy-phenyl Trimethoxy silane, 2-chloro-phenyl-Trimethoxy silane, phenyl triethoxysilane, 2-p-methoxy-phenyl triethoxyl silane, phenyl dimethoxy Ethoxysilane, diethylamino phenyl Oxymethoxy silane etc. can have substituent phenyl trialkoxy silane compounds;

Phenyl-chloride dimethoxy silane, phenyl dichloromethane TMOS, phenyl-chloride methoxy ethoxy silane, phenyl-chloride diethoxy silane, phenyl dichloro Ethoxysilane etc. can have substituent phenyl-halide for the alkoxysilane compound containing trialkylsilyl group in molecular structure class;

Phenyl-trichloro-silicane, phenyl tribromosilane, 4-p-methoxy-phenyl trichlorosilane, 2-chlorophenyl trichlorosilane, 2-ethoxyl phenenyl trichlorosilane etc. can have substituent phenyl trihalosilane compound.

These silane compounds (2) can a kind of independent use, perhaps makes up two or more uses.

(mixture of silane compound)

The mixture of the silane compound that uses when making silane compound multipolymer (A '), the mixture that can be formed by silane compound (1) and silane compound (2), and then can also be not hinder the scope of the object of the invention to contain the mixture of other silane compound, but be preferably the mixture that is formed by silane compound (1) and silane compound (2).

The usage ratio of silane compound (1) and silane compound (2) is preferably (silane compound (1)) with molar ratio computing: the ratio of (silane compound (2))=60: 40～5: 95, more preferably 50: 50～5: 95, be particularly preferably 50: 50～10: 90.

Method as the mixture of the above-mentioned silane compound of condensation, be not particularly limited, can enumerate silane compound (1), silane compound (2) and other silane compound as required are dissolved in solvent, add the catalyzer of specified amount, the method that under specified temperature, stirs.

The catalyzer that uses can be any one of acid catalyst and alkaline catalysts.

As acid catalyst, can enumerate: the mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid; The organic acids such as methylsulfonic acid, trifluoromethanesulfonic acid, Phenylsulfonic acid, tosic acid, acetic acid, trifluoroacetic acid etc.

As alkaline catalysts, can enumerate: Trimethylamine, triethylamine, lithium diisopropylamine, two (trimethyl silyl) Lithamide, pyridine, 1, the organic basess such as 8-diazabicyclo ［ 5.4.0 ］-7-undecylene, aniline, picoline, Isosorbide-5-Nitrae-diazabicyclo ［ 2.2.2 ］ octane, imidazoles; The organic salt such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide oxyhydroxide; The metal alkoxides such as sodium methylate, sodium ethylate, sodium tert-butoxide, potassium tert.-butoxide; The metal hydride such as sodium hydride, hydrolith; The metal hydroxidess such as sodium hydroxide, potassium hydroxide, calcium hydroxide; The metal carbonates such as yellow soda ash, salt of wormwood, magnesiumcarbonate; The alkali metal bicarbonate salt such as sodium bicarbonate, saleratus etc.

Wherein, as the catalyzer that uses, preferred acid catalyzer, more preferably mineral acid.

The usage quantity of catalyzer is with respect to the integral molar quantity of silane compound, is generally 0.1mol%～10mol%, is preferably the scope of 1mol%～5mol%.

The solvent that uses can be corresponding to the selections that suit such as kind of silane compound.For example can enumerate: water; The arenes such as benzene,toluene,xylene; The ester classes such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate; The ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone; The alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol etc.These solvents can a kind of independent use, perhaps mixes two or more uses.

Wherein, be preferably water, arene and their mixed solvent, be particularly preferably the mixed solvent of water and toluene.When making water and toluene, the ratio of water and toluene (volumetric ratio) is preferably 1: 9～and 9: 1, more preferably 7: 3～3: 7.

The usage quantity of solvent is that to make the integral molar quantity with respect to 1 liter of solvent silane compound be the amount of common 0.1mol～10mol, preferred 0.5mol～10mol.

Temperature when making silane compound condensation (reaction) is generally 0 ℃ of temperature range to the boiling point of solvent for use, is preferably 20 ℃～100 ℃ scope.Reaction temperature spend low then sometimes condensation reaction carry out insufficient.Too high then the becoming of temperature of reaction is difficult to suppress gelation.Reaction finished at 30 minutes to 20 hours usually.

After reaction finishes, in the situation of using acid catalyst, neutralize by add the alkali aqueous solutions such as sodium bicarbonate aqueous solution to reaction soln, in the situation of using alkaline catalysts, neutralize by add the acid such as hydrochloric acid to reaction soln, by filtering or washing and remove the salt that produce this moment, can obtain target silane compound multipolymer.

(B) has the epoxy compounds of chlorinated isocyanurates skeleton

Solidification compound of the present invention contains epoxy compounds with chlorinated isocyanurates skeleton (below, be sometimes referred to as " epoxy compounds (B) ") as (B) composition.

Even solidification compound of the present invention is owing to containing epoxy compounds (B), so after the experience thermal process, also can obtain the cured article of thermotolerance, transparency excellence.

As epoxy compounds (B), so long as in molecule, have chlorinated isocyanurates skeleton (following (c), in the formula ,-expression bonding key) and the compound of oxirane ring then is not particularly limited.Should illustrate, in the chlorinated isocyanurates skeleton (c), can have tautomer as follows (cyanurate skeleton (c '), in the formula ,-expression bonding key), the epoxy compounds with this skeleton is also contained in the used epoxy compounds of the present invention (B).

[changing 4]

Wherein, as epoxy compounds (B), be preferably that in the hydrogen atom of 1,3,5 the nitrogen-atoms that will be bonded to like that the chlorinated isocyanurates ring shown in following formula (c-1)～(c-3) at least one replaces with the group (E) with oxirane ring and compound.

[changing 5]

(in the above-mentioned formula, E represents to have the group of oxirane ring, and R represents that hydrogen atom, organic group etc. have group any group in addition of oxirane ring)

As above-mentioned group (E) with oxirane ring, can enumerate for example following formula

[changing 6]

Group shown in (in the formula, a, b, c represent 1～20 integer separately, can replace the alkyl such as methyl, ethyl are arranged on the methylene radical).

Concrete example as epoxy compounds (B), viewpoint from the cured article that can obtain having high bonding force, can enumerate glycidyl chlorinated isocyanurates, Diglycidylisocyanury-ester, three (2,3-epoxypropyl) chlorinated isocyanurates, three (glycidoxypropyl) chlorinated isocyanurates, three (Alpha-Methyl glycidyl) chlorinated isocyanurates and contain two or more mixture of these compounds etc.

In addition, as epoxy compounds (B), can also directly use as the commercially available product of the epoxy compounds with chlorinated isocyanurates skeleton (for example, trade(brand)name: TEPIC-S, TEPIC-PAS B22, trade(brand)name: TEPIC-PAS B26 etc. are daily output chemical industry society system).

The use level of epoxy compounds (B) is not particularly limited, and the viewpoint from the cured article that obtains having higher bonding force as epoxy equivalent (weight), is preferably 50～300g/eq, is particularly preferably 100～200g/eq.Should illustrate that epoxy equivalent (weight) is the value of measuring according to JIS K7236:2001.

(C) solidifying agent

Solidification compound of the present invention contains as the solidifying agent of (C) composition (below, sometimes be called " solidifying agent (C) "), and this solidifying agent contains the ester ring type acid anhydrides with carboxyl.Solidification compound of the present invention is owing to containing solidifying agent (C), so can obtain the cured article of excellent heat resistance.

Ester ring type acid anhydrides with carboxyl is to have the acid anhydrides that replaces the ester ring type structure that at least one carboxyl is arranged.As the ester ring type structure, can enumerate saturated cyclic hydrocarbon (naphthenic hydrocarbon) structure, unsaturated cyclic hydrocarbon (cyclenes, cycloalkyne) structure etc.

As the ester ring type acid anhydrides, can enumerate: 3-methyl isophthalic acid, 2,3,6-Tetra Hydro Phthalic Anhydride, 4-methyl isophthalic acid, 2,3,6-Tetra Hydro Phthalic Anhydride, Tetra Hydro Phthalic Anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl carbic anhydride, 5-norbornylene-2,3-dicarboxylic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride, methyl-5-norbornylene-2,3-dicarboxylic acid anhydride, methyl-norbornane-2,3-dicarboxylic acid anhydride etc.

Carboxyl can replace in the optional position of the ester ring type structure of ester ring type acid anhydrides, and the number of the position of substitution or the carboxyl that replaces is not particularly limited.

Wherein, preferred carboxyl substituted forms in hexahydrophthalic anhydride, hexanaphthene-1,2,4-tricarboxylic acid-1,2 acid anhydrides, hexanaphthene-1,2,3-tricarboxylic acid-1,2 acid anhydrides, hexanaphthene-1,2 particularly preferably, 4-tricarboxylic acid-1,2 acid anhydrides.Can there be steric isomer in this compound, can be isomer arbitrarily.

Ester ring type acid anhydrides with carboxyl can a kind of independent use, perhaps makes up two or more uses.

Solidifying agent (C) can further contain other solidifying agent.

As other solidifying agent, can enumerate aliphatic anhydride, the fatty amines such as ester ring type acid anhydrides with carboxyl (below, be called " other ester ring type acid anhydrides "), poly-nonane diacid acid anhydride is that solidifying agent, ester ring type amine are that solidifying agent, the second month in a season or tertiary amine are that solidifying agent, aromatic amine are solidifying agent, Dyhard RU 100, boron trifluoride amine complex salt, imidazolium compounds etc.

Other solidifying agent can a kind of independent use, perhaps makes up two or more uses.

As other solidifying agent, even under high temperature, also can obtain having the cured article of high bonding force, be preferably other ester ring type acid anhydrides.As other ester ring type acid anhydrides, can enumerate with illustration as identical those of the ester ring type acid anhydrides of above-mentioned ester ring type acid anhydrides with carboxyl.Wherein, preferred 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, particularly preferably 4-methyl-hexahydrophthalic anhydride.

Solidifying agent (C) preferably comprises one or two or more kinds that is selected from ester ring type acid anhydrides with carboxyl and other ester ring type acid anhydrides, its mass ratio is preferably (the ester ring type acid anhydrides with carboxyl): (other ester ring type acid anhydrides)=100: 0～10: 90, more preferably 50: 50～10: 90.

(D) silane coupling agent

Solidification compound of the present invention contains as the silane coupling agent with acid anhydride structure of (D) composition (below, be sometimes referred to as " silane coupling agent (D) ").Solidification compound of the present invention is owing to contain silane coupling agent (D), thereby can not be separated (gonorrhoea), can obtain the cured article that the transparency is excellent, have high bonding force.

Silane coupling agent (D) be in a part, have concurrently group (Y) with acid anhydride structure, with hydrolization group (OR ^b) both radical silicide arranged.Be specially the compound shown in the following formula (d).

[changing 7]

In the formula, Y represents acid anhydride structure, R ^aThe alkyl of expression carbonatoms 1～6 maybe can have substituent phenyl, R ^bThe alkyl of expression carbonatoms 1～6, i represents 1～3 integer, and j represents 0～2 integer, and k represents 1～3 integer, i+j+k=4.

As Y, can enumerate following formula

[changing 8]

Groups shown in (in the formula, h represents 0～10 integer) etc. are particularly preferably the group shown in (Y1).

In the formula (d), as R ^a, R ^bThe alkyl of shown carbonatoms 1～6 can be enumerated with illustration before as above-mentioned R ¹Those identical groups of the alkyl of shown carbonatoms 1～6 are as above-mentioned R ^aShown have a substituent phenyl, can enumerate with illustration before as above-mentioned R ²Shown those identical groups with substituent phenyl.

Wherein, the compound as shown in the formula (d) is preferably following formula (d-1)

[changing 9]

(in the formula, R ^b, h, i, j, k represent implication same as described above)

Shown compound.In the formula, h is preferably 2～8.

As the concrete example of the silane coupling agent shown in the formula (d-1), can enumerate 2-trimethoxysilylethylgroup group succinyl oxide, 3-triethoxysilylpropyltetrasulfide succinyl oxide etc.

Silane coupling agent (D) can a kind of independent use, perhaps makes up two or more uses.

In the solidification compound of the present invention, above-mentioned (A), (B), (C) and (D) composition contain proportionally in (A) mass ratio with ((B)+(C)+(D)), be preferably (A): ((B)+(C)+(D))=90: 10～50: 50.In addition, above-mentioned (A '), (B), (C) and (D) composition contain proportionally in (the A ') mass ratio with ((B)+(C)+(D)), be preferably (A '): ((B)+(C)+(D))=90: 10～50: 50.

And then, above-mentioned (B), (C) and (D) composition contain proportionally in ((B)+(C)) and (D) mass ratio, be preferably ((B)+(C)): (D)=90: 10～10: 90.

By use each composition with aforementioned proportion, can obtain a kind of solidification compound, it is excellent for a long time that this solidification compound can obtain the transparency, thermotolerance, even at high temperature also have the cured article of high bonding force.

In the solidification compound of the present invention, can in the scope of not damaging the object of the invention, further contain other composition.

As other composition, can enumerate curing catalysts, antioxidant, UV light absorber, photostabilizer, thinner etc.

Curing catalysts adds in order to promote to solidify.As curing catalysts, can enumerate glyoxal ethyline, triphenylphosphine etc.These curing catalysts can a kind of independent use, perhaps makes up two or more uses.

The oxidative degradation of antioxidant in order to prevent from heating adds.As antioxidant, can enumerate phosphorous antioxidant, phenol is that antioxidant, sulphur are antioxidant etc.

As phosphorous antioxidant, can enumerate: triphenyl, phenylbenzene isodecyl phosphoric acid ester, phenyl diiso decyl phosphoric acid ester, three (nonyl phenyl) phosphoric acid ester, the diiso decyl pentaerythritol phosphate, three (2, the 4-di-tert-butyl-phenyl) phosphoric acid ester, ring type neopentane four bases (octadecyl) phosphoric acid ester, ring type neopentane four bases (2, the 4-di-tert-butyl-phenyl) phosphoric acid ester, ring type neopentane four bases (2,4-di-t-butyl-4-aminomethyl phenyl) phosphoric acid ester, the phosphoric acid esters such as two ［ the 2-tertiary butyl-6-methyl-4-{ 2-(octadecane oxygen base carbonyl) ethyl } phenyl ］ phosphoric acid hydrogen ester; 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound, 10-(3, the 5-di-tert-butyl-4-hydroxyl benzyl)-the oxa-phospho hetero phenanthrene such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-oxygen in last of the ten Heavenly stems base-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is oxide-based.

Be antioxidant as phenol, can enumerate: 2,6 ditertiary butyl p cresol, butylated hydroxytoluene, butylated hydroxyanisol, 2,6-di-t-butyl p-ethyl phenol, stearyl-β-single phenols such as (3,5-di-tert-butyl-hydroxy phenyl) propionic ester; 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 3,9-two ［ 1,1-dimethyl-2-{ β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy } ethyl ］ 2,4,8, the bisphenols such as 10-four oxaspiros ［ 5,5 ］ undecane; 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, four methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester ］ methane, two ［ 3,3 '-two-(4 '-hydroxyl-3 '-tert-butyl-phenyl) butyric acid ］ glycol ester, 1,3,5-three (3 ', 5 '-di-t-butyl-4 '-hydroxybenzyl)-and S-triazine-2,4,6-(1H, 3H, 5H) the polymer phenols such as triketone, tocopherol.

Be antioxidant as sulphur, can enumerate: dilauryl-3,3 '-thiodipropionate, myristyl-3,3 '-thiodipropionate, distearyl-3,3 '-thiodipropionate etc.

These antioxidants can a kind of independent use, perhaps makes up two or more uses.Wherein, solidification compound of the present invention is owing to contain (B) composition, (D) composition, thereby the oxidative degradation when especially also being difficult to heat even without antioxidant.When using antioxidant, its usage quantity is generally 0.01～10 mass parts with respect to silane compound multipolymer (A) or (A ') 100 mass parts.

UV light absorber is added for the photostabilization that improves the gained cured article.

As UV light absorber, such as enumerating: phenyl salicylic acid esters, to salicylic acids such as tert-butyl-phenyl salicylate, p-octylphenyl salicylate; 2,4-dihydroxy benaophenonel, ESCALOL 567,2-hydroxyl-4-octyloxy benzophenone, 2-hydroxyl-4-dodecyloxy benzophenone, 2,2 '-dihydroxyl-4-methoxy benzophenone, 2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone, the 2-hydroxyl-4-methoxyl group-benzophenones such as 5-diphenylsulfone ketone; UV-P, 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-the 5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-the 5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl) benzotriazole, 2-{ (2 '-hydroxyl-3 ', 3 ' ', 4 ' ', 5 ' ', 6 ' '-and the tetrahydric phthalimide methyl)-5 '-aminomethyl phenyl } benzotriazole category such as benzotriazole; Two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) hindered amines such as ［ { 3,5-two (1,1-dimethyl ethyl)-4-hydroxy phenyls } methyl ］ butyl malonic acid ester etc.

These UV light absorber can a kind of independent use, perhaps makes up two or more uses.

The usage quantity of UV light absorber is generally 0.01～10 mass parts with respect to silane compound multipolymer (A) or (A ') 100 mass parts.

Photostabilizer adds for the photostabilization that improves the gained cured article.

As photostabilizer, for example can enumerate: poly-［ { 6-(1,1,3,3,-tetramethyl butyl) amino-1,3,5-triazines-2,4-two bases } { (2,2,6,6-tetramethyl--4-piperidines) imino-} hexa-methylene { (2,2,6,6-tetramethyl--4-piperidines) imino-} etc. hindered amines etc.

These photostabilizers can a kind of independent use, perhaps makes up two or more uses.

The usage quantity of photostabilizer is generally 0.01～10 mass parts with respect to silane compound multipolymer (A) or (A ') 100 mass parts.

Thinner adds for the viscosity of regulating solidification compound.

As thinner, such as enumerating: glycerin diglycidyl ether, butanediol diglycidyl ether, diglycidylaniline, neopentyl glycol glycidyl ether, cyclohexanedimethanodiglycidyl diglycidyl ether, alkylidene group diglycidylether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, T 55,4 vinyl cyclohexene list oxide compound, vinyl cyclohexene dioxide, the vinyl cyclohexene that methylates dioxide etc.

These thinners can a kind of independent use, perhaps makes up two or more uses.

Solidification compound of the present invention can be by for example, and above-mentioned (A) or (A '), (B), (C), (D) composition and other composition are as required cooperated with the regulation ratio, utilizes that known method is mixed, deaeration obtains.

With the solidification compound of the present invention that gets according to the above, even can obtain under illuminated high-octane light time or the condition of high temperature, the excellent transparency of having for a long time of painted or transparent reduction can not occur yet and have the cured article of high bonding force.

So, the suitable raw material as optics or molding of solidification compound of the present invention, caking agent, coating agent etc.Particularly owing to can solve the deteriorated relevant problem of the optical element immobilization material of the high brightness of following optical element, thereby solidification compound of the present invention can be used as optical element immobilization material composition aptly.

2) cured article

The 2nd aspect of the present invention is that solidification compound of the present invention is solidified the cured article that forms.

As the method that solidification compound of the present invention is solidified, can enumerate and be heating and curing.Heating temperature when being cured be generally 100～200 ℃, heat-up time be generally 10 minutes to 20 hours, preferred 30 minutes to 10 hours.

Even painted or transparent reduction under illuminated high-octane light time or the condition of high temperature, can not occur yet, have an excellent transparency and have high bonding force for a long time in cured article of the present invention.

So cured article of the present invention is used as optics or molding, adhesive linkage, coating layer etc. aptly.Particularly can solve deteriorated relevant problem high brightness, the optical element immobilization material of following optical element, thereby cured article of the present invention can be used as the optical element immobilization material aptly.

Cured article of the present invention has high bonding force and can confirm by for example mensuration bonding force as described below.That is, be coated with solidification compound at the minute surface of silicon, coated face is placed by on the convered structure and pressing, carry out heat treated and make it to solidify.It (for example is being heated to specified temperature in advance, 23 ℃, 100 ℃) the mensuration platform of adhesive test instrument on placed for 30 seconds, from apart from by the position of convered structure 50 μ m height, with respect to the upper stress application of the horizontal direction (blocking direction) of bonding plane, the determination test sheet with by the bonding force of convered structure.

The bonding force of cured article is being preferably more than the 110N/2mm under 23 ℃.

The transparent excellence of above-mentioned cured article can be confirmed by measuring transmittance.The transmittance of cured article is preferably more than 80% under the light of wavelength 400nm, is particularly preferably more than 84%, is preferably more than 87% under the light of wavelength 450nm.

Above-mentioned cured article long-term heat resistance excellence can be confirmed by the variation of the transparency after cured article is at high temperature placed for a long time is also little.For the transparency, after 500 hours, the transmissivity of optimal wavelength 400nm is more than 70% of initial transmission, more preferably more than 80% 150 ℃ of placements.

3) using method of solidification compound

The 3rd aspect of the present invention is the method that solidification compound of the present invention is used with sealing agent with caking agent or optical element immobilization material as the optical element immobilization material.

As optical element, can enumerate the luminous elements such as LED, LD, photo detector, composite optic element, optical integrated circuit etc.

＜optical element immobilization material caking agent 〉

Solidification compound of the present invention can be used as optical element immobilization material caking agent aptly.

As the method that solidification compound of the present invention is used with caking agent as the optical element immobilization material, can enumerate: after as the bonding plane coating said composition of the one or both of the material (optical element and substrate thereof etc.) of adhering object, pressing, make it to be heating and curing, will be as the material of adhering object bonding method securely each other.

As the baseplate material that needs only that is used for bonding optical elements, can enumerate: the category of glass such as soda-lime glass, thermotolerance hard glass; Pottery; The metal species such as the alloy of iron, copper, aluminium, gold and silver, platinum, chromium, titanium and these metals, stainless steel (SUS302, SUS304, SUS304L, SUS309 etc.); The synthetic resins such as polyethylene terephthalate, polybutylene terephthalate, PEN, vinyl-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfones, polyether-ether-ketone, polyethersulfone, polyphenylene sulfide, polyetherimide, polyimide, polymeric amide, acrylic resin, norbornene resin, cyclic olefin resins, glass epoxy resin etc.

Heating temperature when being heating and curing depends on used solidification compound etc., but is generally 100～200 ℃.Be generally 10 minutes to 20 hours heat-up time, be preferably 30 minutes to 10 hours.

＜optical element immobilization material sealing agent 〉

Solidification compound of the present invention can be used as the sealing agent of optical element sealing member aptly.

As the method that solidification compound of the present invention is used with sealing agent as the optical element immobilization material, for example can enumerate: the shape that said composition is configured as expectation, after being surrounded by the molding of optical element in obtaining, being heated curing and making thus method of optical element sealing member etc.

Method as solidification compound of the present invention being configured as the shape of expectation is not particularly limited, and can adopt the known moulding method such as common transmission moulding method or injection moulding.

The optical element sealing member of gained is owing to used solidification compound of the present invention, even thereby optical element use white or cyan emitting led etc., the glow peak wavelength is the short wavelength's of 400～490nm optical element, can be painted not deteriorated because of heat or light yet, the transparency, excellent heat resistance.

Embodiment

Illustrate in greater detail the present invention with comparative example by the following examples, but the present invention is not subjected to the restriction of following embodiment.

(weight-average molecular weight mensuration)

The weight-average molecular weight (Mw) of the silane compound multipolymer of gained is to pass through to measure with lower device and condition with the form of polystyrene standard scaled value in the Production Example.

Device name: HLC-8220GPC, Dong ソー society system

Post: TSKgelGMHXL, TSKgelGMHXL and TSKgel2000HXL are connected in sequence

Solvent: tetrahydrofuran (THF)

Injection rate: 80 μ l

Measure temperature: 40 ℃

Flow velocity: 1ml/ divides

Detector: differential refractometer.

(mensuration of IR spectrum)

The IR spectrum of the silane compound multipolymer of gained is to use with lower device to measure in the Production Example.

Fourier transform infrared spectrophotometer (Spectrum100, パーキ Application エルマー society system).

(Production Example 1)

In the eggplant type flask of 300ml, add phenyltrimethoxysila,e (Tokyo the changes into industrial society system) 16.7g(84mmol as silane compound (2)), as 3-acetoxyl group propyl trimethoxy silicane (the アヅマッ Network ス society system) 8.0g(36mmol of silane compound (1)), as toluene 60ml and the distilled water 30ml of solvent, then add while stirring phosphoric acid (the Northeast chemistry society system) 0.15g(1.5mmol as catalyzer), at room temperature further continue to stir 16 hours.

After reaction finishes, in reaction mixture, add ethyl acetate 100ml, neutralize with saturated sodium bicarbonate aqueous solution.After temporarily leaving standstill, divide and get organic layer.Then, behind organic layer usefulness distilled water wash 2 times, use anhydrous magnesium sulfate drying.After filtering sal epsom, filtrate is concentrated into 50ml with rotatory evaporator, it is dropped to make it precipitation in a large amount of normal hexanes, by the decant sediment separate out.The gained throw out is dissolved in methyl ethyl ketone reclaims, with vaporizer the solvent underpressure distillation is removed, carry out vacuum-drying, obtain thus silane compound multipolymer (A1) 14.7g.

The weight-average molecular weight (Mw) of silane compound multipolymer (A1) is 2,700, and molecular weight distribution (Mw/Mn) is 1.53.

In addition, the IR spectrum of silane compound multipolymer (A1) (Fourier transform infrared spectrophotometer (FT-IR)) data are as follows.

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

(Production Example 2)

In Production Example 1, except the usage quantity that makes phenyltrimethoxysila,e is 14.3g(72mmol), the usage quantity that makes 3-acetoxyl group propyl trimethoxy silicane is 10.7g(48mmol) in addition, carry out in the same manner with Production Example 1, obtain silane compound multipolymer (A2) 15.9g.

The weight-average molecular weight (Mw) of silane compound multipolymer (A2) is 2,600, and molecular weight distribution (Mw/Mn) is 1.50.

In addition, the IR spectrum of silane compound multipolymer (A2) (Fourier transform infrared spectrophotometer (FT-IR)) data are as follows.

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

(Production Example 3)

In Production Example 1, except the usage quantity that makes phenyltrimethoxysila,e is 19.0g(96mmol), the usage quantity that makes 3-acetoxyl group propyl trimethoxy silicane is 5.3g(24mmol) in addition, carry out in the same manner with Production Example 1, obtain silane compound multipolymer (A3) 14.9g.

The weight-average molecular weight (Mw) of silane compound multipolymer (A3) is 2,500, and molecular weight distribution (Mw/Mn) is 1.59.

In addition, the IR spectrum of silane compound multipolymer (A3) (Fourier transform infrared spectrophotometer (FT-IR)) data are as follows.

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

(Production Example 4)

In Production Example 1, except replacing using phenyltrimethoxysila,e 16.7g(84mmol) and 3-acetoxyl group propyl trimethoxy silicane 8.0g(36mmol), and use phenyltrimethoxysila,e (Tokyo changes into industrial society system) 11.9g(60mmol) with 3-glycidoxypropyltrimewasxysilane (Tokyo changes into industrial society system) (in following the 1st table the-1, the 1st table-2, be recited as " GlyTMS ") 14.2g(60mmol) in addition, carry out in the same manner with Production Example 1, obtain silane compound multipolymer (A4) 16.3g.

The weight-average molecular weight (Mw) of silane compound multipolymer (A4) is 2,800, and molecular weight distribution (Mw/Mn) is 1.56.

In addition, the IR spectrum of silane compound multipolymer (A4) (Fourier transform infrared spectrophotometer (FT-IR)) data are as follows.

Si-Ph:700cm ^-1, 742cm ^-1, Si-O:1132cm ^-1, epoxy group(ing): 1254cm ^-1

(Production Example 5)

In the eggplant type flask of 300ml, add phenyltrimethoxysila,e (Tokyo the changes into industrial society system) 19.0g(96mmol as silane compound (2)), as 3-r-chloropropyl trimethoxyl silane (Tokyo the changes into industrial society system) 4.77g(24mmol of silane compound (1)), as toluene 60ml and the distilled water 30ml of solvent, then add while stirring phosphoric acid (the Northeast chemistry society system) 0.15g(1.5mmol as catalyzer), at room temperature further continue to stir 16 hours.

After reaction finishes, in reaction mixture, add ethyl acetate 100ml, neutralize with saturated sodium bicarbonate aqueous solution.After temporarily leaving standstill, divide and get organic layer.Then, behind organic layer usefulness distilled water wash 2 times, use anhydrous magnesium sulfate drying.After filtering sal epsom, filtrate dropped in a large amount of normal hexanes make it redeposition, remove hexane, take out throw out.The gained throw out is dissolved in methyl ethyl ketone reclaims, with vaporizer the solvent underpressure distillation is removed, carry out vacuum-drying, obtain thus silane compound multipolymer (A5) 13.6g.

The weight-average molecular weight (Mw) of silane compound multipolymer (A5) is 3,000, and molecular weight distribution (Mw/Mn) is 1.59.

In addition, the IR spectroscopic data of silane compound multipolymer (A5) is as follows.

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

(Production Example 6)

In Production Example 5, except the usage quantity that makes phenyltrimethoxysila,e is 16.7g(84mmol), the usage quantity that makes the 3-r-chloropropyl trimethoxyl silane is 7.15g(36mmol) in addition, carry out in the same manner with Production Example 5, obtain silane compound multipolymer (A6) 13.4g.

The weight-average molecular weight (Mw) of silane compound multipolymer (A6) is 3,300, and molecular weight distribution (Mw/Mn) is 1.59.

In addition, the IR spectroscopic data of silane compound multipolymer (A6) is as follows.

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

(Production Example 7)

In Production Example 5, except the usage quantity that makes phenyltrimethoxysila,e is 14.3g(72mmol), the usage quantity that makes the 3-r-chloropropyl trimethoxyl silane is 9.54g(48mmol) in addition, carry out in the same manner with Production Example 5, obtain silane compound multipolymer (A7) 13.0g.

The weight-average molecular weight (Mw) of silane compound multipolymer (A7) is 3,400, and molecular weight distribution (Mw/Mn) is 1.61.

In addition, the IR spectroscopic data of silane compound multipolymer (A7) is as follows.

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

(Production Example 8)

In Production Example 5, except the usage quantity that makes phenyltrimethoxysila,e is 11.9g(60mmol), the usage quantity that makes the 3-r-chloropropyl trimethoxyl silane is 11.9g(60mmol) in addition, carry out in the same manner with Production Example 5, obtain silane compound multipolymer (A8) 12.9g.

The weight-average molecular weight (Mw) of silane compound multipolymer (A8) is 3,600, and molecular weight distribution (Mw/Mn) is 1.63.

In addition, the IR spectroscopic data of silane compound multipolymer (A8) is as follows.

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

(Production Example 9)

In Production Example 5, except replacing 3-r-chloropropyl trimethoxyl silane 4.77g, and use 2-cyano ethyl Trimethoxy silane (アヅマッ Network ス society system) 4.21g(24mmol) in addition, carry out in the same manner with Production Example 5, obtain silane compound multipolymer (A8) 13.5g.

The weight-average molecular weight (Mw) of silane compound multipolymer (A9) is 2,900, and molecular weight distribution (Mw/Mn) is 1.58.

In addition, the IR spectroscopic data of silane compound multipolymer (A9) is as follows.

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

(Production Example 10)

In Production Example 9, except the usage quantity that makes phenyltrimethoxysila,e is 16.7g(84mmol), the usage quantity that makes 2-cyano ethyl Trimethoxy silane is 6.31g(36mmol) in addition, carry out in the same manner with Production Example 9, obtain silane compound multipolymer (A10) 13.3g.

The weight-average molecular weight (Mw) of silane compound multipolymer (A10) is 3,200, and molecular weight distribution (Mw/Mn) is 1.64.

In addition, the IR spectroscopic data of silane compound multipolymer (A10) is as follows.

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

(Production Example 11)

In Production Example 9, except the usage quantity that makes phenyltrimethoxysila,e is 14.3g(72mmol), the usage quantity that makes 2-cyano ethyl Trimethoxy silane is 8.41g(48mmol) in addition, carry out in the same manner with Production Example 9, obtain silane compound multipolymer (A11) 12.8g.

The weight-average molecular weight (Mw) of silane compound multipolymer (A11) is 3,300, and molecular weight distribution (Mw/Mn) is 1.62.

In addition, the IR spectroscopic data of silane compound multipolymer (A11) is as follows.

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

(Production Example 12)

In Production Example 9, except the usage quantity that makes phenyltrimethoxysila,e is 11.9g(60mmol), the usage quantity that makes 2-cyano ethyl Trimethoxy silane is 10.5g(60mmol) in addition, carry out in the same manner with Production Example 9, obtain silane compound multipolymer (A12) 12.3g.

The weight-average molecular weight (Mw) of silane compound multipolymer (A12) is 3,500, and molecular weight distribution (Mw/Mn) is 1.61.

In addition, the IR spectroscopic data of silane compound multipolymer (A12) is as follows.

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

(embodiment 1)

Among silane compound multipolymer (A1) 10g that obtains in the Production Example 1, adding is as (the daily output chemical industry TEPIC-PAS B26 processed of society of the epoxy compounds with chlorinated isocyanurates skeleton of epoxy compounds (B), epoxy equivalent (weight) 137g/eq) (following the 1st table-1, be recited as " B1 " in the 1st table-2) 1.5g, 4-methylcyclohexane-1 as solidifying agent (C), 2-dicarboxylic acid anhydride (Tokyo changes into industrial society system) (following the 1st table-1, be recited as " C1 " in the 1st table-2) 0.375g and hexanaphthene-1,2,4-tricarboxylic acid-1,2-acid anhydride (the ガス of Mitsubishi chemistry society system) (the ester ring type acid anhydrides with carboxyl) (following the 1st table-1, be recited as " C2 " in the 1st table-2) 0.75g, and as the 3-triethoxysilylpropyltetrasulfide succinyl oxide (アヅマッ Network ス society system) of silane coupling agent (D) (following the 1st table-1, be recited as " D1 " in the 1st table-2) 0.375g, entire contents is fully mixed, deaeration obtains solidification compound (1) thus.

(embodiment 2～7)

According to following the 1st table-1, use silane compound multipolymer, epoxy compounds, solidifying agent and silane coupling agent, carry out in the same manner with embodiment 1, obtain solidification compound (2)～(7).

Should illustrate that in following the 1st table the-1, the 1st table-2, " B2 " expression has the epoxy compounds (the daily output chemical industry TEPIC-PAS B22 processed of society, epoxy equivalent (weight) 179g/eq) of chlorinated isocyanurates skeleton.

(comparative example 1,2)

According to following the 1st table-1, use silane compound multipolymer, epoxy compounds, solidifying agent and silane coupling agent, carry out in the same manner with embodiment 1, obtain solidification compound (8), (9).

(comparative example 3)

In embodiment 1, use 3 except replacing epoxy compounds (B), 4-epoxy cyclohexane formic acid 3, outside 4-epoxycyclohexyl methyl esters (シグマア Le De リッチ society system) (being recited as " BF1 " in following the 1st table the-1, the 1st table-2) 1.5g, carry out in the same manner with embodiment 1, obtain solidification compound (10).

(comparative example 4)

In embodiment 1, the silane compound multipolymer (A1) that obtains in replacing Production Example 1 and using the silane compound multipolymer (A4) that obtains in the Production Example 4 carries out in the same manner with embodiment 1, obtains solidification compound (11).

(comparative example 5)

In embodiment 1, use except replacing silane coupling agent (D1) 3-glycidoxypropyltrimewasxysilane (Tokyo changes into industrial society system) (being recited as " DF1 " in following the 1st table the-1, the 1st table-2) 0.375g, carry out in the same manner with embodiment 1, obtain solidification compound (12).

(comparative example 6)

Except using original quanmethyl silicate (Tokyo changes into industrial society system) (being recited as " DF2 " in following the 1st table the-1, the 1st table-2) 0.375g to be used as the silane coupling agent (D1) of embodiment 1, carry out in the same manner with embodiment 1, obtain solidification compound (13).

(embodiment 8)

Among silane compound multipolymer (A5) 10g that obtains in the Production Example 5, adding is as (the daily output chemical industry TEPIC-PAS B26 processed of society of the epoxy compounds with chlorinated isocyanurates skeleton of epoxy compounds (B), epoxy equivalent (weight) 137g/eq) 1.5g, 4-methylcyclohexane-1 as solidifying agent (C), 2-dicarboxylic acid anhydride (Tokyo changes into industrial society system) 0.38g and hexanaphthene-1,2,4-tricarboxylic acid-1,2-acid anhydride (the ガス of Mitsubishi chemistry society system) 0.75g, and as 3-triethoxysilylpropyltetrasulfide succinyl oxide (the アヅマッ Network ス society system) 0.38g of silane coupling agent (D), entire contents is fully mixed, deaeration obtains solidification compound (14) thus.

(embodiment 9～15, comparative example 7～16)

According to following the 1st table-2, use silane compound multipolymer, epoxy compounds, solidifying agent and silane coupling agent, carry out in the same manner with embodiment 8, obtain solidification compound (15)～(31).

[table 1]

[table 2]

For the cured article of the solidification compound 1～31 of embodiment 1～15 and comparative example 1～16 gained, the transmissivity after mensuration bonding force as described below, initial transmission and the heating.

Measurement result is shown in following the 2nd table the-1, the 2nd table-2.

(bonding force test)

At the minute surface of the square silicon of 2mm coating solidification compound 1～31 so that separately thickness be about 2 μ m, place coated face upper by convered structure (sheffield plate) and carry out pressing.Then, be cured in 2 hours 180 ℃ of lower heat treated, obtain with test film by convered structure.This is being heated to adhesive test instrument (シリーズ 4000, the デイジ society system of specified temperature (23 ℃, 100 ℃) with test film in advance by convered structure) the mensuration platform placed for 30 seconds, from apart from by the position of convered structure 50 μ m height with the speed of 200 μ m/s with respect to the upper stress application of the horizontal direction (blocking direction) of bonding plane, the test film under measuring 23 ℃ and 100 ℃ and by the bonding force of convered structure (N/2mm).

(bonding thermotolerance)

In bonding force test, be that the situation more than 50% of the bonding force under 23 ℃ is evaluated as " zero ", situation less than 50% is evaluated as " * " with the bonding force under 100 ℃.

(mensuration of initial transmission)

Solidification compound 1～31 is injected mold according to the mode of length 25mm, width 20mm, thickness 1mm separately, be cured in 6 hours 140 ℃ of lower heating, make respectively test film.For the gained test film, use spectrophotometer (MPC-3100, Island Tianjin makes society of institute system), measure the initial transmission (%) of wavelength 400nm, 450nm.

(the initial transparency)

In initial transmission is measured, with the transmissivity of 400nm be evaluated as " zero " more than 80%, more than 70% and less than 80% being evaluated as " △ ", being evaluated as " * " less than 70%.

(mensuration of the transmissivity after the heating)

Each test film of having measured initial transmission is put into 150 ℃ baking oven 500 hours, again measure the transmissivity (%) of wavelength 400nm, 450nm.With its as the heating after transmissivity.

(thermotolerance (transparency after the heating))

During transmissivity is measured after heating, if the transmissivity of 400nm is then being evaluated as " zero " more than 80%, being evaluated as " △ ", being evaluated as " * " less than 70% more than 70% and less than 80% of initial transmission.

[table 3]

[table 4]

By the 2nd table the-1, the 2nd table-2 as can be known, the cured article of the solidification compound of embodiment 1～15 (1～7,14～21) is at the high bonding force that has under 23 ℃ more than the 134N/2mm, the bonding force more than 58% that under high temperature (100 ℃), also keeps the bonding force under 23 ℃, bonding excellent heat resistance.In addition, transmissivity is all high after the initial transmission of wavelength 400nm, 450nm, the heating, the initial transparency, thermotolerance (transparency after the heating) excellence.

On the other hand, the initial transparency of the cured article of comparative example 1,5～7,10～12,15,16 solidification compound (8,12,13,22,25～27,30,31) is poor.Bonding force, the bonding thermotolerance inequality of the cured article of comparative example 2,8,13 solidification compound (9,23,28), the thermotolerance (transparency after the heating) of the cured article of comparative example 3,4,9,14 solidification compound (10,11,24,29) is variation significantly.

Claims

1. solidification compound, it contains:

(A) in molecule, have following formula (i), (ii) and (i) in the repeating unit (iii) and (ii), (i) and (iii), (ii) and (iii) or repeating unit (i), (ii) and (iii), weight-average molecular weight be 1,000～30,000 silane compound multipolymer

[changing 1]

In the formula, R ¹The alkyl of expression hydrogen atom or carbonatoms 1～6, X ⁰Expression halogen atom, cyano group or formula: the group shown in the OG, wherein, G represents the blocking group of hydroxyl, D represents singly-bound or linking group, R ²The alkyl of expression carbonatoms 1～20 maybe can have substituent phenyl,

(B) have the epoxy compounds of chlorinated isocyanurates skeleton,

(C) contain the solidifying agent of the ester ring type acid anhydrides with carboxyl, and

(D) has the silane coupling agent of acid anhydride structure.

2. solidification compound claimed in claim 1, wherein, the silane compound multipolymer of above-mentioned (A) is with formula: R ¹-CH(X ⁰The amount ((R of the group shown in the)-D- ¹-CH(X ⁰And R)-D)) ²Amount ((R ²)) molar ratio computing be (R ¹-CH(X ⁰)-D): (R ²The silane compound multipolymer of)=60: 40～5: 95.

3. claim 1 or 2 described solidification compounds, it is characterized in that above-mentioned (A), (B), (C) and (D) proportionally count (A) with (A) with the mass ratio of ((B)+(C)+(D)) containing of composition: ((B)+(C)+(D))=90: 10～50: 50.

4. solidification compound, it contains:

(A ') make and contain formula (1): R ¹-CH(X ⁰)-D-Si(OR ³) _p(X ¹) _3-pAt least a and the formula (2) of shown silane compound (1): R ²Si(OR ⁴) _q(X ²) _3-qThe mixture of at least a silane compound of shown silane compound (2) carry out condensation and, weight-average molecular weight is 1,000～30,000 silane compound multipolymer

In the formula (1), R ¹The alkyl of expression hydrogen atom or carbonatoms 1～6, X ⁰Expression halogen atom, cyano group or formula: the group shown in the OG, wherein, G represents the blocking group of hydroxyl, D represents singly-bound or linking group, R ³The alkyl of expression carbonatoms 1～6, X ¹The expression halogen atom, p represents 0～3 integer,

In the formula (2), R ²The alkyl of expression carbonatoms 1～20 maybe can have substituent phenyl, R ⁴The alkyl of expression carbonatoms 1～6, X ²The expression halogen atom, q represents 0～3 integer,

(B) have the epoxy compounds of chlorinated isocyanurates skeleton,

(D) has the silane coupling agent of acid anhydride structure.

5. solidification compound claimed in claim 4, wherein, the silane compound multipolymer of above-mentioned (A ') is for making silane compound (1) and silane compound (2) in take molar ratio computing as (silane compound (1)): the ratio of (silane compound (2))=60: 40～5: 95 carries out that condensation gets.

6. claim 4 or 5 described solidification compounds, it is characterized in that above-mentioned (A '), (B), (C) and (D) the containing and proportionally count with the mass ratio of ((B)+(C)+(D)) with (A ') of composition (A '): ((B)+(C)+(D))=90: 10～50: 50.

7. claim 1 or 4 described solidification compounds, it is characterized in that above-mentioned (B), (C) and (D) proportionally count ((B)+(C)) with ((B)+(C)) and (D) mass ratio containing of composition: (D)=90: 10～10: 90.

8. claim 1 or 4 described solidification compounds, wherein, the solidifying agent of above-mentioned (C) comprises ester ring type acid anhydrides with carboxyl and is selected from other ester ring type acid anhydrides one or more, and its mass ratio is (the ester ring type acid anhydrides with carboxyl): (other ester ring type acid anhydrides)=100: 0～10: 90.

9. claim 1 or 4 described solidification compounds, it is optical element immobilization material composition.

10. cured article, it forms for claim 1 or 4 described solidification compounds are solidified.

11. cured article claimed in claim 10, it is the optical element immobilization material.

12. the method that claim 1 or 4 described solidification compounds are used with caking agent as the optical element immobilization material.

13. the method that claim 1 or 4 described solidification compounds are used with sealing agent as the optical element immobilization material.