CN102906198B - Curable composition, hardened material, and method for using curable composition - Google Patents

Curable composition, hardened material, and method for using curable composition Download PDF

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CN102906198B
CN102906198B CN201180012898.9A CN201180012898A CN102906198B CN 102906198 B CN102906198 B CN 102906198B CN 201180012898 A CN201180012898 A CN 201180012898A CN 102906198 B CN102906198 B CN 102906198B
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silane
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silane compound
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compound
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CN102906198A (en
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樫尾干广
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Lintec Corp
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Lintec Corp
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/06—Triglycidylisocyanurates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
    • H01L2924/097—Glass-ceramics, e.g. devitrified glass
    • H01L2924/09701—Low temperature co-fired ceramic [LTCC]

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  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Silicon Polymers (AREA)

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 there is the solidification compound of the cured article of high bonding force, said composition solidified to the cured article that forms and using above-mentioned composition as optical element immobilization material caking agent or the method for optical element immobilization material sealing agent use.
Background technology
In the past, solidification compound had carried out various improvement corresponding to purposes, was industrially widely used as raw material, caking agent, coating agent of optics or molding etc.For example, the solidification compound that forms the cured article that the transparency is excellent 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, in the time manufacturing optical element sealing member, solidification compound is also used as optical element immobilization material caking agent or optical element optical element immobilization material compositions such as sealing agent for immobilization material.
Optical element comprises luminous element, photo detector, composite optic element, the optical integrated circuit etc. such as the various laser such as semiconductor laser (LD), photodiode (LED).In recent years, the long blue light for short wavelength of more luminous spike, the optical element of white light are developed and are widely used.The high brightnessization of the short luminous element of this glow peak wavelength develops by leaps and bounds, and the thermal value of the optical element accompanying with it exists the tendency further increasing.
But, follow in recent years the high brightness of optical element, under the heat of the more high temperature that optical element immobilization material is exposed to more high-octane light or produced by optical element for a long time with the cured article of composition, have and occur deteriorated and the problem such as crack or peel off.
In order to address this problem, the optical element immobilization material composition taking polysilsesquioxane compound as principal constituent is proposed in patent documentation 1～3.
But the cured article of the composition of the optical element immobilization material taking polysilsesquioxane compound as principal constituent of recording in patent documentation 1～3, is also difficult to obtain thermotolerance and the transparency sometimes in keeping sufficient bonding force.
In addition, as the composition for optical element sealing use, in patent documentation 4, propose to use the composition epoxy resin of alicyclic epoxy resin, in patent documentation 5, proposed the composition epoxy resin that contains poly-thiol compound.
But, while using these compositions, also exist to meet and follow the sufficient fast light deterioration of rheological parameters' change with time or the situation that bonding force reduces.
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 completes in view of the practical situation of above-mentioned prior art, its problem be to provide can obtain thermotolerance and the transparency excellent and there is the solidification compound of the cured article of high bonding force, said composition solidified to the cured article that forms and using above-mentioned composition as optical element immobilization material caking agent or the method that uses of optical element immobilization material sealing agent.
For the means of technical solution problem
The inventor conducts in-depth research for solving the problems of the technologies described above repeatedly, found that: contain the solidifying agent that epoxy compounds, (C) that (A) specific silane compound multipolymer, (B) have chlorinated isocyanurates skeleton contain the ester ring type acid anhydrides with carboxyl and the cured article (D) with the composition of the silane coupling agent of acid anhydride structure and keep for a long time the excellent transparency, thermotolerance, and, at high temperature also form and there is the cured article of high bonding force, thereby completed 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, there is following formula (i), (ii) and (iii)
[changing 1]
(in formula, R 1represent the alkyl of hydrogen atom or carbonatoms 1～6, X 0represent halogen atom, cyano group or formula: the group shown in OG (in formula, G represents the protecting group of hydroxyl), D represents singly-bound or linking group.R 2the alkyl that represents carbonatoms 1～20 maybe can have substituent phenyl)
Repeating unit (i) and (ii), (i) and (iii), (ii) and (iii) or (i), (ii) and (iii) in shown repeating unit, weight-average molecular weight be 1,000～30,000 silane compound multipolymer,
(B) have chlorinated isocyanurates skeleton epoxy compounds,
(C) solidifying agent that contains the ester ring type acid anhydrides with carboxyl and
(D) there is 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)-D- 1-CH(X 0)-D)) and R 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) composition count (A) with (A) with the mass ratio of ((B)+(C)+(D)) containing proportional: ((B)+(C)+(D))=90: 10～50: 50.
(4) solidification compound, it contains:
(A ') makes to contain formula (1): R 1-CH(X 0)-D-Si(OR 3) p(X 1) 3-p
(in formula, R 1represent the alkyl of hydrogen atom or carbonatoms 1～6, X 0represent halogen atom, cyano group or formula: the group shown in OG (in formula, G represents the protecting group of hydroxyl), D represents singly-bound or linking group.R 3represent the alkyl of carbonatoms 1～6, X 1represent halogen atom, p represents 0～3 integer)
At least one of shown silane compound (1) and
Formula (2): R 2si(OR 4) q(X 2) 3-q
(in formula, R 2the alkyl that represents carbonatoms 1～20 maybe can have substituent phenyl, R 4represent the alkyl of carbonatoms 1～6, X 2represent halogen atom, q represents 0～3 integer)
The mixture condensation of the silane compound of at least one of shown silane compound (2) and, weight-average molecular weight be 1,000～30,000 silane compound multipolymer,
(B) have chlorinated isocyanurates skeleton epoxy compounds,
(C) solidifying agent that contains the ester ring type acid anhydrides with carboxyl and
(D) there is the silane coupling agent of acid anhydride structure.
(5) (4) described solidification compound, wherein, the silane compound multipolymer of above-mentioned (A ') be make silane compound (1) with silane compound (2) taking 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 obtains.
(6) (4) or (5) described solidification compound, it is characterized in that, above-mentioned (A '), (B), (C) and (D) composition containing proportionally counting with the mass ratio of ((B)+(C)+(D)) with (A ') (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) composition count ((B)+(C)) containing proportional with ((B)+(C)) and mass ratio (D): (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 being selected from ester ring type acid anhydrides and other ester ring type acid anhydrides with carboxyl, and its mass ratio is (having the ester ring type acid anhydrides of 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 is that the solidification compound (1) or (4) Suo Shu is solidified and formed.
(11) (10) described cured article, it is 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 solidification compound (1) or (4) Suo Shu being used with caking agent as optical element immobilization material.
(13) method solidification compound (1) or (4) Suo Shu being used with sealing agent as optical element immobilization material.
Invention effect
According to solidification compound of the present invention, even if can obtain under illuminated high-octane light time or the condition of high temperature, what painted or transparent reduction can not occur yet has the cured article also under the excellent transparency and high temperature with high bonding force for a long time.
Solidification compound of the present invention can use in the time forming optical element immobilization material, especially can be aptly as caking agent and optical element immobilization material sealing agent for optical element immobilization material.
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) in molecule, have following formula (i), (ii) and (iii)
[changing 2]
(in formula, R 1represent the alkyl of hydrogen atom or carbonatoms 1～6, X 0represent halogen atom, cyano group or formula: the group shown in OG (in formula, G represents the protecting group of hydroxyl), D represents singly-bound or linking group.R 2the alkyl that represents carbonatoms 1～20 maybe can have substituent phenyl)
(i) and (ii), (i) and (iii), (ii) and (iii) or (i), (ii) and (iii) repeating unit in shown repeating unit, weight-average molecular weight is 1, the solidifying agent that 000～30,000 silane compound multipolymer, epoxy compounds, (C) that (B) has chlorinated isocyanurates skeleton contain the ester ring type acid anhydrides with carboxyl and the silane coupling agent (D) with acid anhydride structure.
(A) silane compound multipolymer
Solidification compound of the present invention contains (A) composition: have the repeating unit (i) and (ii), (i) and (iii), (ii) and (iii) or (i), (ii) and (iii) in the repeating unit of above-mentioned formula (i), (ii) and (iii), weight-average molecular weight is 1,000～30,000 silane compound multipolymer (following, to be sometimes called " silane compound multipolymer (A) ").
Silane compound multipolymer (A) can have (i), (ii), the each one of repeating unit shown in (iii), also can have more than two kinds.
Formula (i)～(iii) in, R 1represent the alkyl of hydrogen atom or carbonatoms 1～6, preferably 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 0represent the halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atom; Cyano group; Or formula: the group shown in 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 the acetal systems such as methoxymethyl, methoxy ethoxy methyl, 1-ethoxyethyl group, tetrahydropyrans-2-base, tetrahydrofuran (THF)-2-base; The protecting group of the alkoxy carbonyl systems such as tert-butoxycarbonyl; Methyl, ethyl, the tertiary butyl, octyl group, propenyl, trityl group, benzyl, protecting group to ether systems such as methoxy-benzyl, fluorenyl, trityl, diphenyl-methyls 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 formula, R 5represent the alkyl of the carbonatomss 1～6 such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl; Maybe can there is 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 starting with easiness and can obtain the cured article with high bonding force; be preferably chlorine atom, the formula of being selected from: the group shown in OG ' is (in formula; G ' represents the protecting group of acyl group system) and cyano group in group; more preferably be selected from the group in chlorine atom, acetoxyl group and cyano group, be particularly preferably acetoxyl group.
D represents singly-bound or linking group.
As linking group, can enumerate the organic group can with substituent divalent.The carbonatoms of this organic group is preferably 1～20, more preferably 1～10.
As the organic group can with substituent divalent, for example can enumerate can there is substituent alkylidene group, can there is substituent alkenylene, can there is substituent alkynylene, can there is substituent arylidene, substituent by having (alkylidene group, alkenylene or alkynylene) and the divalent group constituting etc. can with substituent arylidene.
As the alkylidene group can with 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 can with 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 can with substituent alkynylene, can enumerate the alkynylene of the carbonatoms such as ethynylene, sub-proyl 2～20, the alkynylene of preferred carbonatoms 2～10.
As the arylidene can with substituent arylidene, can enumerate adjacent phenylene, metaphenylene, to phenylene, 2, the arylidene of the carbonatomss 6～20 such as 6-naphthylidene, the preferred arylidene of 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 position arbitrarily in the groups such as alkylidene group, alkenylene, alkynylene and arylidene, and all right identical or different ground bonding is multiple.
As substituent by having (alkylidene group, alkenylene or alkynylene) with can there is the divalent group constituting of substituent arylidene, can enumerate above-mentionedly there is at least one of substituent (alkylidene group, alkenylene or alkynylene), group that the bonding of connecting with above-mentioned at least one with substituent arylidene forms.Particularly, can enumerate the group shown in following formula.
[changing 3]
Wherein, as D, from obtaining having the cured article of high bonding force, the preferably alkylidene group of carbonatoms 1～10, the more preferably alkylidene group of carbonatoms 1～6, particularly preferably methylene radical or ethylidene.
Formula (i)～(iii) in, R 2the alkyl that represents carbonatoms 1～20 maybe can have substituent phenyl.
As R 2the alkyl of shown carbonatoms 1～20, can enumerate: 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 enumerate: 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 enumerate: phenyl, 2-chloro-phenyl-, 4-aminomethyl phenyl, 3-ethylphenyl, 2,4-3,5-dimethylphenyl, 2-p-methoxy-phenyl etc.
In silane compound multipolymer (A), formula: R 1-CH(X 0the amount ((R of the group shown in)-D- 1-CH(X 0)-D)) and R 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 within the scope of this, can obtain cured article transparent and excellent in adhesion and excellent heat resistance.
Formula: R 1-CH(X 0group shown in)-D-and R 2amount for example can by measure silane compound multipolymer (A) NMR spectrum carry out quantitatively.
Silane compound multipolymer (A) can be the multipolymer arbitrarily 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 within the scope of this, the operability excellence of composition, 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) taking 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, preferably 1.1～2.0 scope.By within the scope of this, can obtain the cured article of cementability, excellent heat resistance.
Silane compound multipolymer (A) can a kind ofly use separately, or combines two or more uses.
Silane compound multipolymer (A) is for having the polysilsesquioxane compound of notch cuttype structure.
Silane compound multipolymer has notch cuttype structure and can measure to confirm by the infrared absorption spectrum mensuration, X-ray diffraction mensuration, the NMR that carry out for example reaction product.
In solidification compound of the present invention, above-mentioned (A) composition can be
(A ') makes to contain formula (1): R 1-CH(X 0)-D-Si(OR 3) p(X 1) 3-p
(in formula, R 1represent the alkyl of hydrogen atom or carbonatoms 1～6, X 0represent halogen atom, cyano group or formula: the group shown in OG (in formula, G represents the protecting group of hydroxyl), D represents singly-bound or linking group.R 3represent the alkyl of carbonatoms 1～6, X 1represent halogen atom, p represents 0～3 integer)
At least one of shown silane compound (1) and
Formula (2): R 2si(OR 4) q(X 2) 3-q
(in formula, R 2the alkyl that represents carbonatoms 1～20 maybe can have substituent phenyl, R 4represent the alkyl of carbonatoms 1～6, X 2represent halogen atom, q represents 0～3 integer)
The mixture condensation of the silane compound of at least one of shown silane compound (2) and, weight-average molecular weight is 1,000～30,000 silane compound multipolymer is (following, 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 if can obtain also good silane compound multipolymer of the transparency, bonding force after solidifying.
In formula (1), R 1represent the alkyl of hydrogen atom or carbonatoms 1～6, preferably hydrogen atom.As concrete example, can enumerate exemplified as the R in silane compound multipolymer (A) 1those.
In formula (1), X 0represent halogen atom, cyano group or the formulas such as fluorine atom, chlorine atom, bromine atoms, iodine atom: the group shown in OG (in formula, G represents the protecting group of hydroxyl), D represents singly-bound or linking group.X 0can enumerate respectively exemplified as the X in silane compound multipolymer (A) with the concrete example of the group shown in D 0with those of D.
R 3represent the alkyl of the carbonatomss 1～6 such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl.
X 1represent the halogen atoms such as 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 (3-p) 2 when above, X 1each other can be identical or different.
As the concrete example of silane compound (1), can enumerate: chloromethyl Trimethoxy silane, brooethyl triethoxyl silane, 2-chloroethyl tripropoxy silane, 2-bromotrifluoromethane three butoxy silanes, 3-r-chloropropyl trimethoxyl silane, 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, 3-chloropropyl triethoxysilane, 4-chlorobutyl tripropoxy silane, 5-chlorine amyl group tripropoxy silane, 2-r-chloropropyl trimethoxyl silane, the chloro-3-ethanoyl of 3-propyl trimethoxy silicane, the chloro-3-methoxycarbonyl of 3-propyl trimethoxy silicane, o-(2-chloroethyl) phenyl tripropoxy silane, m-(2-chloroethyl) phenyltrimethoxysila,e, p-(2-chloroethyl) phenyl triethoxysilane, the X such as p-(2-fluoro ethyl) phenyltrimethoxysila,e 0for the trialkoxy silane compounds of halogen atom,
Chloromethyltrichlorosilane, brooethyl bromine dimethoxy silane, 2-chloroethyl dichloromethane TMOS, 2-bromotrifluoromethane dichloro Ethoxysilane, 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, the chloro-3-ethanoyl of 3-propyl group dichloro Ethoxysilane, the X such as the chloro-3-methoxycarbonyl of 3-propyl group tribromosilane 0for the halogenated silanes compounds of halogen atom,
Cyano methyl Trimethoxy silane, 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, o-(cyano methyl) phenyl tripropoxy silane, m-(cyano methyl) phenyltrimethoxysila,e, p-(cyano methyl) phenyl triethoxysilane, the X such as p-(2-cyano ethyl) phenyltrimethoxysila,e 0for the trialkoxy silane compounds of cyano group,
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, o-(2-cyano ethyl) phenyl-trichloro-silicane, m-(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 0for the halogenated silanes compounds of 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, 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 0for above-mentioned formula: the trialkoxy silane compounds of the group shown in 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, 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 0for above-mentioned formula: the halogenated silanes compounds of the group shown in OG etc.
These silane compounds (1) can a kind ofly use separately, or combine two or more uses.
Wherein, as silane compound (1), from obtaining having the more preferably cured article of cementability, preferably X 0for trialkoxy silane compounds, the X of halogen atom 0for trialkoxy silane compounds or the X of cyano group 0for above-mentioned formula: the trialkoxy silane compounds of the group shown in OG, more preferably have 3-chloropropyl trialkoxy silane compounds, have 3-acetoxyl group propyl group trialkoxy silane compounds, there is the trialkoxy silane compounds of 2-cyano ethyl or there is 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 formula (2), R 2the alkyl that represents carbonatoms 1～20 maybe can have substituent phenyl.As concrete example, can enumerate exemplified as the R in silane compound multipolymer (A) 2those.
R 4represent and above-mentioned R 3the alkyl of identical carbonatoms 1～6.
X 2represent 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 (3-q) 2 when above, 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 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 ofly use separately, or combine two or more uses.
(mixture of silane compound)
The mixture of the silane compound using when manufacturing silane compound multipolymer (A '), the mixture that can be formed by silane compound (1) and silane compound (2), and then can also be the mixture that does not hinder the scope of the object of the invention to contain other silane compound, but be preferably the mixture being 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.
As the method for 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 are as required dissolved in to solvent, add the catalyzer of specified amount, the method stirring under specified temperature.
The catalyzer using 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 sodium carbonate, salt of wormwood, magnesiumcarbonate; The alkali metal bicarbonate salt such as sodium bicarbonate, saleratus etc.
Wherein, as the catalyzer using, 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 using can carry out suitable selection corresponding to the kind of silane compound etc.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 ofly use separately, or mix two or more uses.
Wherein, be preferably water, arene and their mixed solvent, be particularly preferably the mixed solvent of water and toluene.While 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 making with respect to the integral molar quantity of 1 liter of solvent silane compound is common 0.1mol～10mol, the preferred amount of 0.5mol～10mol.
Temperature while making silane compound condensation (reaction) is generally 0 DEG C of temperature range to the boiling point of solvent for use, is preferably the scope of 20 DEG C～100 DEG C.Carrying out of the too low condensation reaction sometimes of temperature of reaction is insufficient.Too high the becoming of temperature of reaction is difficult to suppress gelation.Reaction finishes at 30 points to 20 hours conventionally.
After reaction finishes, in the situation of use acid catalyst, neutralize by add the alkali aqueous solutions such as sodium bicarbonate aqueous solution to reaction soln, in the situation of use alkaline catalysts, neutralize by add the acid such as hydrochloric acid to reaction soln, remove by filtering or washing the salt now producing, can obtain target silane compound multipolymer.
(B) there is the epoxy compounds of chlorinated isocyanurates skeleton
Solidification compound of the present invention contains the epoxy compounds (following, to be sometimes referred to as " epoxy compounds (B) ") with chlorinated isocyanurates skeleton as (B) composition.
Solidification compound of the present invention is owing to containing epoxy compounds (B), therefore even after experience thermal process, also can obtain the cured article of thermotolerance, transparency excellence.
As epoxy compounds (B), as long as in molecule, have chlorinated isocyanurates skeleton (following (c), in formula ,-represent bonding key) and the compound of oxirane ring be not particularly limited.Should illustrate, in chlorinated isocyanurates skeleton (c), can have tautomer as follows (cyanurate skeleton (c '), in formula ,-represent bonding key), the epoxy compounds with this skeleton is also contained in the present invention's epoxy compounds used (B).
[changing 4]
Wherein, as epoxy compounds (B), be preferably as shown in following formula (c-1)～(c-3) will be bonded to that at least one in the hydrogen atom of the nitrogen-atoms of 1,3,5 of chlorinated isocyanurates ring replaces with the group (E) with oxirane ring and compound.
[changing 5]
(in above-mentioned formula, E represents to have the group of oxirane ring, and R represents that hydrogen atom, organic group etc. have any group beyond the group of oxirane ring)
As the above-mentioned group (E) with oxirane ring, can enumerate for example following formula
[changing 6]
Group shown in (in formula, a, b, c represent 1～20 integer separately, can replace and have the alkyl such as methyl, ethyl on methylene radical).
As the concrete example of epoxy compounds (B), from obtaining the viewpoint of the cured article with high bonding force, the two or more mixture that 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 these compounds etc.
In addition, as epoxy compounds (B), can also directly be used as the commercially available product (for example, trade(brand)name: TEPIC-S, TEPIC-PAS B22, trade(brand)name: TEPIC-PAS B26 etc., are daily output chemical industry society system) of epoxy compounds with chlorinated isocyanurates skeleton.
The use level of epoxy compounds (B) is not particularly limited, and from obtaining the viewpoint of the cured article with higher bonding force, as epoxy equivalent (weight), is preferably 50～300g/eq, is particularly preferably 100～200g/eq.Should illustrate, 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 (following, to be sometimes 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), therefore can obtain the cured article of excellent heat resistance.
The ester ring type acid anhydrides with carboxyl is to have the acid anhydrides that replaces the ester ring type structure that has at least one carboxyl.As ester ring type structure, can enumerate saturated cyclic hydrocarbon (naphthenic hydrocarbon) structure, unsaturated cyclic hydrocarbon (cyclenes, cycloalkyne) structure etc.
As 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, particularly preferably hexanaphthene-1,2,4-tricarboxylic acid-1,2 acid anhydrides.Can there is steric isomer in this compound, can be isomer arbitrarily.
The ester ring type acid anhydrides with carboxyl can a kind ofly use separately, or combines two or more uses.
Solidifying agent (C) can further contain other solidifying agent.
As other solidifying agent, can enumerate aliphatic anhydride, fatty amines such as not having the ester ring type acid anhydrides (following, to be called " other ester ring type acid anhydrides ") of carboxyl, 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 ofly use separately, or combines two or more uses.
As other solidifying agent, even if also can obtain having the cured article of high bonding force from high temperature, be preferably other ester ring type acid anhydrides.As other ester ring type acid anhydrides, can enumerate those identical with ester ring type acid anhydrides exemplified as the 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 being selected from ester ring type acid anhydrides and other ester ring type acid anhydrides with carboxyl, 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 (following, to be sometimes referred to as " silane coupling agent (D) ").Solidification compound of the present invention is owing to containing 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 have acid anhydride structure group (Y), with hydrolization group (OR b) both have a radical silicide.Be specially the compound shown in following formula (d).
[changing 7]
In formula, Y represents acid anhydride structure, R athe alkyl that represents carbonatoms 1～6 maybe can have substituent phenyl, R bthe alkyl that represents 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 formula, h represents 0～10 integer) etc., are particularly preferably the group shown in (Y1).
In formula (d), as R a, R bthe alkyl of shown carbonatoms 1～6, can enumerate with before exemplified as above-mentioned R 1those identical groups of the alkyl of shown carbonatoms 1～6, as above-mentioned R ashown have a substituent phenyl, can enumerate with before exemplified as above-mentioned R 2shown those identical groups with substituent phenyl.
Wherein, as the compound shown in formula (d), be preferably following formula (d-1)
[changing 9]
(in formula, R b, h, i, j, k represent implication same as described above)
Shown compound.In formula, h is preferably 2～8.
As the concrete example of the silane coupling agent shown in formula (d-1), can enumerate 2-trimethoxysilylethylgroup group succinyl oxide, 3-triethoxysilylpropyltetrasulfide succinyl oxide etc.
Silane coupling agent (D) can a kind ofly use separately, or combines two or more uses.
In solidification compound of the present invention, above-mentioned (A), (B), (C) and (D) composition containing proportional 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 containing proportional in (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 containing proportional in ((B)+(C)) and mass ratio (D), 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 if at high temperature also have the cured article of high bonding force.
In 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 ofly use separately, or combine two or more uses.
The oxidative degradation of antioxidant when preventing 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, diiso decyl pentaerythritol phosphate, three (2, 4-di-tert-butyl-phenyl) phosphoric acid ester, ring type neopentane four bases (octadecyl) phosphoric acid ester, ring type neopentane four bases (2, 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, mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy, 10-(3,5-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-tetra-oxaspiros ［ 5,5 ］ undecane; 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-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 '-bis--(4 '-hydroxyl-3 '-tert-butyl-phenyl) butyric acid ］ glycol ester, 1,3,5-tri-(3 ', 5 '-di-t-butyl-4 '-hydroxybenzyl)-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 ofly use separately, or combine two or more uses.Wherein, solidification compound of the present invention is owing to containing (B) composition, (D) composition, thereby oxidative degradation while especially being also difficult to heating occurs even without antioxidant.Use when 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 gained cured article.
As UV light absorber, for example, can enumerate: 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, the benzophenones such as 4 '-dimethoxy-benzophenone, 2-hydroxyl-4-methoxyl group-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-3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl) benzotriazole, 2-{ (2 '-hydroxyl-3 ', 3 ' ', 4 ' ', 5 ' ', 6 ' '-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 ofly be used separately, or combine 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 gained cured article.
As photostabilizer, for example, can enumerate: poly-［ { 6-(1,1,3,3,-tetramethyl butyl) amino-1,3,5-triazines-2,4-bis-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 ofly use separately, or combine 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 that regulates solidification compound.
As thinner, for example, can enumerate: 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 ofly use separately, or combine 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 coordinated with regulation ratio, utilizes that known method is mixed, deaeration obtains.
With the solidification compound of the present invention obtaining according to the above, even if can obtain under illuminated high-octane light time or the condition of high temperature, what painted or transparent reduction can not occur yet has for a long time the excellent transparency and has 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 solving the deteriorated relevant problem of 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 to the cured article forming.
As by method curing solidification compound of the present invention, can enumerate and be heating and curing.Heating temperature while being cured be generally 100～200 DEG C, heat-up time be generally 10 minutes to 20 hours, preferably 30 minutes to 10 hours.
Even if under illuminated high-octane light time or the condition of high temperature, can there is not painted or transparent reduction yet, there is the excellent transparency and there is 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, optical element immobilization material of following optical element, thereby cured article of the present invention can be used as 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, on the minute surface of silicon, be coated with solidification compound, coated face is placed in by also pressing on convered structure, carry out heat treated and make it curing.It (is for example being heated to specified temperature in advance, 23 DEG C, 100 DEG C) 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, at the upper stress application of the horizontal direction with respect to bonding plane (blocking direction), determination test sheet with by the bonding force of convered structure.
More than the bonding force of cured article is preferably 110N/2mm at 23 DEG C.
The transparency 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%, under the light of wavelength 450nm, is preferably more than 87%.
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 is for a long time also little.For the transparency, to place after 500 hours at 150 DEG C, the transmissivity of optimal wavelength 400nm is initial transmission more than 70%, more preferably more than 80%.
3) using method of solidification compound
The 3rd aspect of the present invention is using solidification compound of the present invention as optical element immobilization material caking agent or the method for optical element immobilization material sealing agent use.
As optical element, can enumerate the luminous element 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 using with caking agent solidification compound of the present invention as optical element immobilization material, can enumerate: after the bonding plane coating said composition of the one or both of the material as adhering object (optical element and substrate thereof etc.), pressing, make it to be heating and curing, using as the material of adhering object bonding method securely each other.
As the baseplate material needing only for bonding optical elements, can enumerate: the category of glass such as soda-lime glass, thermotolerance hard glass; Pottery; The metal species such as alloy, stainless steel (SUS302, SUS304, SUS304L, SUS309 etc.) of iron, copper, aluminium, gold and silver, platinum, chromium, titanium and these metals; 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 while being heating and curing depends on solidification compound used etc., but is generally 100～200 DEG C.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 using with sealing agent solidification compound of the present invention as optical element immobilization material, for example can enumerate: the shape that said composition is configured as to expectation, in obtaining, be surrounded by after the molding of optical element, be heated the curing method of manufacturing thus optical element sealing member etc.
As the method that solidification compound of the present invention is configured as to the shape of expectation, be not particularly limited, can adopt the known moulding method such as common transmission moulding method or injection moulding.
Heating temperature while being heating and curing depends on solidification compound used etc., but is generally 100～200 DEG C.Be generally 10 minutes to 20 hours heat-up time, be preferably 30 minutes to 10 hours.
The optical element sealing member of gained is owing to having used solidification compound of the present invention, even thereby optical element use white or cyan emitting led etc., short wavelength's that glow peak wavelength is 400～490nm optical element, also not can because of heat or light painted deteriorated, 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 subject to the restriction of following embodiment.
(weight-average molecular weight mensuration)
In Production Example, 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.
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 DEG C
Flow velocity: 1ml/ divides
Detector: differential refractometer.
(mensuration of IR spectrum)
In Production Example, the IR spectrum of the silane compound multipolymer of gained is to use with lower device to measure.
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 temporary transient leaving standstill, divide and get organic layer.Then, organic layer, with after distilled water wash 2 times, is used to anhydrous magnesium sulfate drying.Filter after magnesium sulfate, filtrate is concentrated into 50ml with rotatory evaporator, dropped in a large amount of normal hexanes and make it precipitation, by decant sediment separate out.Gained throw out is dissolved in to methyl ethyl ketone and reclaims, with vaporizer, 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, be 14.3g(72mmol except making the usage quantity of phenyltrimethoxysila,e), 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, be 19.0g(96mmol except making the usage quantity of phenyltrimethoxysila,e), 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, use phenyltrimethoxysila,e 16.7g(84mmol except replacing) 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 temporary transient leaving standstill, divide and get organic layer.Then, organic layer, with after distilled water wash 2 times, is used to anhydrous magnesium sulfate drying.Filter after magnesium sulfate, filtrate is dropped in a large amount of normal hexanes and makes it redeposition, remove hexane, take out throw out.Gained throw out is dissolved in to methyl ethyl ketone and reclaims, with vaporizer, 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, be 16.7g(84mmol except making the usage quantity of phenyltrimethoxysila,e), the usage quantity that makes 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, be 14.3g(72mmol except making the usage quantity of phenyltrimethoxysila,e), the usage quantity that makes 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, be 11.9g(60mmol except making the usage quantity of phenyltrimethoxysila,e), the usage quantity that makes 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, be 16.7g(84mmol except making the usage quantity of phenyltrimethoxysila,e), 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, be 14.3g(72mmol except making the usage quantity of phenyltrimethoxysila,e), 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, be 11.9g(60mmol except making the usage quantity of phenyltrimethoxysila,e), 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)
In silane compound multipolymer (A1) 10g obtaining in Production Example 1, add (the daily output TEPIC-PAS B26 processed of chemical industry society of the epoxy compounds with chlorinated isocyanurates skeleton as epoxy compounds (B), epoxy equivalent (weight) 137g/eq) (following the 1st table-1, in the 1st table-2, be recited as " B1 ") 1.5g, as 4-methylcyclohexane-1 of solidifying agent (C), 2-dicarboxylic acid anhydride (Tokyo changes into industrial society system) (following the 1st table-1, in the 1st table-2, be recited as " C1 ") 0.375g and hexanaphthene-1, 2, 4-tricarboxylic acid-1, 2-acid anhydride (the ガ ス of Mitsubishi chemistry society system) (thering is the ester ring type acid anhydrides of carboxyl) (following the 1st table-1, in the 1st table-2, be recited as " C2 ") 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, in the 1st table-2, be recited as " D1 ") 0.375g, entire contents is fully mixed, deaeration, obtain thus solidification compound (1).
(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, in following the 1st table the-1, the 1st table-2, " B2 " represents to have the epoxy compounds (daily output the TEPIC-PAS B22 processed of chemical industry 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, use the silane compound multipolymer (A4) obtaining in Production Example 4 except replacing the silane compound multipolymer (A1) obtaining in Production Example 1, carry out in the same manner with embodiment 1, obtain 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)
In silane compound multipolymer (A5) 10g obtaining in Production Example 5, add (the daily output TEPIC-PAS B26 processed of chemical industry society of the epoxy compounds with chlorinated isocyanurates skeleton as epoxy compounds (B), epoxy equivalent (weight) 137g/eq) 1.5g, as 4-methylcyclohexane-1 of 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, obtain thus solidification compound (14).
(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 heating.
Measurement result is shown in following the 2nd table the-1, the 2nd table-2.
(bonding force test)
At the minute surface coating solidification compound 1～31 of the square silicon of 2mm so that separately thickness be approximately 2 μ m, coated face is placed in and is gone up by convered structure (sheffield plate) and carry out pressing.Then, at 180 DEG C, heat treated is cured for 2 hours, 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 DEG C, 100 DEG C) with test film in advance by convered structure) mensuration platform on placed for 30 seconds, from apart from the speed stress application on the horizontal direction with respect to bonding plane (blocking direction) with 200 μ m/s by the position of convered structure 50 μ m height, the test film at measuring 23 DEG C and 100 DEG C and by the bonding force of convered structure (N/2mm).
(bonding thermotolerance)
In bonding force test, more than 50% situation that is the bonding force at 23 DEG C by the bonding force at 100 DEG C is evaluated as "○", be less than 50% situation is evaluated as "×".
(mensuration of initial transmission)
Solidification compound 1～31 is injected to mold according to the mode of length 25mm, width 20mm, thickness 1mm separately, at 140 DEG C, heat and be cured for 6 hours, make respectively test film.For gained test film, use spectrophotometer (MPC-3100, Island Tianjin makes society of institute system), measure the initial transmission (%) of wavelength 400nm, 450nm.
(the initially transparency)
In initial transmission is measured, by the transmissivity of 400nm be more than 80% be evaluated as "○", more than 70% and be less than and 80% be evaluated as " △ ", be less than 70% and be evaluated as "×".
(mensuration of the transmissivity after heating)
Each test film of having measured initial transmission is put into the baking oven 500 hours of 150 DEG C, again measured the transmissivity (%) of wavelength 400nm, 450nm.Set it as the rear transmissivity of heating.
(thermotolerance (transparency after heating))
During after heating, transmissivity is measured, if the transmissivity of 400nm is initial transmission more than 80% is evaluated as "○", more than 70% and be less than 80% and be evaluated as " △ ", be less than 70% and be evaluated as "×".
[table 3]
[table 4]
From the 2nd table the-1, the 2nd table-2, the cured article of the solidification compound (1～7,14～21) of embodiment 1～15 has high bonding force more than 134N/2mm at 23 DEG C, under high temperature (100 DEG C), also keep more than 58% bonding force of the bonding force at 23 DEG C, bonding excellent heat resistance.In addition, after the initial transmission of wavelength 400nm, 450nm, heating, transmissivity is all high, the initial transparency, thermotolerance (transparency after heating) excellence.
On the other hand, the initial transparency of the cured article of the solidification compound of comparative example 1,5～7,10～12,15,16 (8,12,13,22,25～27,30,31) is poor.Bonding force, the bonding thermotolerance inequality of the cured article of the solidification compound (9,23,28) of comparative example 2,8,13, the significantly variation of thermotolerance (transparency after heating) of the cured article of the solidification compound (10,11,24,29) of comparative example 3,4,9,14.

Claims (13)

1. solidification compound, it contains:
(A) repeating unit (i) and (ii), (i) and (iii), (ii) and (iii) or (i), (ii) and (iii), the weight-average molecular weight that in molecule, have in the repeating unit of following formula (i), (ii) and are (iii) 1,000～30,000 silane compound multipolymer
[changing 1]
In formula, R 1represent the alkyl of hydrogen atom or carbonatoms 1～6, X 0represent halogen atom, cyano group or formula: the group shown in OG, wherein, G represents the blocking group of hydroxyl, D represents singly-bound or linking group, R 2the alkyl that represents carbonatoms 1～20 maybe can have substituent phenyl,
(B) there is the epoxy compounds of chlorinated isocyanurates skeleton,
(C) solidifying agent that contains the ester ring type acid anhydrides with carboxyl, and
(D) there is 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)-D 1-CH(X 0)-D)) and R 2amount ((R 2)) molar ratio computing be (R 1-CH(X 0)-D): (R 2the silane compound multipolymer of)=60: 40～5: 95.
3. the solidification compound described in claim 1 or 2, it is characterized in that, above-mentioned (A), (B), (C) and (D) composition count (A) with (A) with the mass ratio of ((B)+(C)+(D)) containing proportional: ((B)+(C)+(D))=90: 10～50: 50.
4. solidification compound, it contains:
(A ') makes to contain formula (1): R 1-CH(X 0)-D-Si(OR 3) p(X 1) 3-pat least one of shown silane compound (1) and formula (2): R 2si(OR 4) q(X 2) 3-qthe mixture of the silane compound of at least one of shown silane compound (2) carry out condensation and, weight-average molecular weight is 1,000～30,000 silane compound multipolymer
In formula (1), R 1represent the alkyl of hydrogen atom or carbonatoms 1～6, X 0represent halogen atom, cyano group or formula: the group shown in OG, wherein, G represents the blocking group of hydroxyl, D represents singly-bound or linking group, R 3represent the alkyl of carbonatoms 1～6, X 1represent halogen atom, p represents 0～3 integer,
In formula (2), R 2the alkyl that represents carbonatoms 1～20 maybe can have substituent phenyl, R 4represent the alkyl of carbonatoms 1～6, X 2represent halogen atom, q represents 0～3 integer,
(B) there is the epoxy compounds of chlorinated isocyanurates skeleton,
(C) solidifying agent that contains the ester ring type acid anhydrides with carboxyl, and
(D) there is 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 taking molar ratio computing as (silane compound (1)): the ratio of (silane compound (2))=60: 40～5: 95 carries out that condensation obtains.
6. the solidification compound described in claim 4 or 5, it is characterized in that, above-mentioned (A '), (B), (C) and (D) composition containing proportionally counting with the mass ratio of ((B)+(C)+(D)) with (A ') (A '): ((B)+(C)+(D))=90: 10～50: 50.
7. the solidification compound described in claim 1 or 4, is characterized in that, above-mentioned (B), (C) and (D) composition count ((B)+(C)) containing proportional with ((B)+(C)) and mass ratio (D): (D)=90: 10～10: 90.
8. the solidification compound described in claim 1 or 4, wherein, the solidifying agent of above-mentioned (C) comprises and has the ester ring type acid anhydrides of carboxyl and be selected from one or more in other ester ring type acid anhydrides, and its mass ratio is (having the ester ring type acid anhydrides of carboxyl): (other ester ring type acid anhydrides)=100: 0～10: 90.
9. the solidification compound described in claim 1 or 4, it is optical element immobilization material composition.
10. cured article, it is that the solidification compound described in claim 1 or 4 is solidified and formed.
11. cured articles claimed in claim 10, it is optical element immobilization material.
12. methods that use with caking agent the solidification compound described in claim 1 or 4 as optical element immobilization material.
13. methods that use with sealing agent the solidification compound described in claim 1 or 4 as optical element immobilization material.
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