CN102076734A - Modified resin composition, method for producing the same, and curable resin composition containing the same - Google Patents
Modified resin composition, method for producing the same, and curable resin composition containing the same Download PDFInfo
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- CN102076734A CN102076734A CN2009801247757A CN200980124775A CN102076734A CN 102076734 A CN102076734 A CN 102076734A CN 2009801247757 A CN2009801247757 A CN 2009801247757A CN 200980124775 A CN200980124775 A CN 200980124775A CN 102076734 A CN102076734 A CN 102076734A
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- alkoxysilane compound
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- 0 *=C(*CC1CC2OC2CC1)C1CC2O*2CC1 Chemical compound *=C(*CC1CC2OC2CC1)C1CC2O*2CC1 0.000 description 15
- NTKLXRHUZITRKJ-UHFFFAOYSA-N CC(C)(COC(C(C1)C2=CC1C1OC21)=O)COC(C1CC(C2)C3OC3C2C1)=O Chemical compound CC(C)(COC(C(C1)C2=CC1C1OC21)=O)COC(C1CC(C2)C3OC3C2C1)=O NTKLXRHUZITRKJ-UHFFFAOYSA-N 0.000 description 1
- HFTFIZVHAUEHLI-UHFFFAOYSA-N CC(C)(COC(C1(C)CC2OC2CC1)=O)COC(C1(C)CC2OC2CC1)=O Chemical compound CC(C)(COC(C1(C)CC2OC2CC1)=O)COC(C1(C)CC2OC2CC1)=O HFTFIZVHAUEHLI-UHFFFAOYSA-N 0.000 description 1
- DVSSIIIETKQRTN-UHFFFAOYSA-N CC(C)(COC(C1CC=C2OC2C1)O)COC(C1CC2OC2CC1)=O Chemical compound CC(C)(COC(C1CC=C2OC2C1)O)COC(C1CC2OC2CC1)=O DVSSIIIETKQRTN-UHFFFAOYSA-N 0.000 description 1
- BQRFGQSTJCZGBK-UHFFFAOYSA-N CC(C)c(cc1)ccc1[IH]c1ccc(C)cc1 Chemical compound CC(C)c(cc1)ccc1[IH]c1ccc(C)cc1 BQRFGQSTJCZGBK-UHFFFAOYSA-N 0.000 description 1
- DIHBGDSIKPUIFX-UHFFFAOYSA-N CC1NC(C2)OC1C2C(OCC(C)(C)COC(C1=C(C2O3)OC3=C2C=C1)=O)=O Chemical compound CC1NC(C2)OC1C2C(OCC(C)(C)COC(C1=C(C2O3)OC3=C2C=C1)=O)=O DIHBGDSIKPUIFX-UHFFFAOYSA-N 0.000 description 1
- LITDYBHCSKWWRF-UYRXBGFRSA-N CCCCC(CC1OC1)C(C)/[O]=C/C(/C1=CN1)=C/OC(C1COC(C)(C)CC1)=O Chemical compound CCCCC(CC1OC1)C(C)/[O]=C/C(/C1=CN1)=C/OC(C1COC(C)(C)CC1)=O LITDYBHCSKWWRF-UYRXBGFRSA-N 0.000 description 1
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- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
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- 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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
Abstract
Disclosed is a modified resin composition obtained by reacting an epoxy resin (A) and an alkoxysilane compound represented by the following general formula (1): (R1)n-Si-(OR2)4-n. The alkoxysilane compound contains (B) at least one kind of an alkoxysilane compound wherein n is 1 or 2 and at least one cyclic ether group is contained as R1 and (C) at least one kind of an alkoxysilane compound wherein n is 1 or 2 and at least one aromatic organic group is contained as R1. The mixing index a of the alkoxysilane compound, which is represented by the following general formula (2): mixing index alpha = (alpha*c)/( alpha*b), is not less than 0.001 but not more than 19, and the amount of remaining alkoxy groups in the modified resin composition is not more than 5%.
Description
Technical field
The modified resin composition and the manufacture method thereof that the present invention relates to Resins, epoxy and alkoxysilane compound containing trialkylsilyl group in molecular structure are reacted and obtain, and curable resin composition and its purposes of containing this modified resin composition.
Background technology
All the time, having used acid anhydrides is that the composition epoxy resin of solidifying agent is owing to can provide transparent cured article and have higher thermotolerance and cementability, thereby be suitable as the sealing resin that optoelectronic semiconductors such as photodiode (below, abbreviate LED as), photorectifier are used.Yet, in recent years, the high performance of optoelectronic semiconductor constantly develops, as the LED sealing resin, except the desired good transparency, high heat resistance and the cementability in the past, anti-crackle excellence when also expecting heat-resisting discolouration, photostabilization, thermal cycling and the cured article that does not have surface viscosity (タ ッ Network), practical situation are that employed in the past is that Resins, epoxy, Bisphenol F are that the compositions that Resins, epoxy constituted such as Resins, epoxy can't obtain hot fully gradually by dihydroxyphenyl propane.
As encapsulating luminescent element material resin, the stable siloxane backbone of heat or light has been carried out big quantity research as the silicone resin of repeating unit for having.Yet practical situation are, though described silicone resin photostabilization, excellent heat resistance, cementability is lower, produce with base material and peel off, and according to circumstances the hardness of cured article is lower, has surface viscosity etc., and performance is not satisfactory as yet, requires a lot of improvement.
On the other hand, for also having carried out big quantity research as the modified resin composition compound that has epoxy group(ing) in repeating unit, the organic group with siloxane backbone.Modified resin composition has the transparency, the thermotolerance of the excellence that Resins, epoxy has, and the cured article of no surface viscosity not only can be provided, and this cured article can also expect to have concurrently photostabilization, scale resistance and the flexibility that silicone has.
For example, following scheme has been proposed: a kind of modified resin composition in the patent documentation 1, it contains the T structure as necessary repeating unit, and with respect in 1 molecule with the whole organic groups of Siliciumatom bonded, contain the epoxy group(ing) organic group with the scope of 0.1～40 mole of %.
Patent documentation 2 has been put down in writing and has been comprised composition and the application in the optoelectronic semiconductor sealing material thereof that has the silicone compounds of 2 epoxy group(ing) in molecular weight with specified range and 1 molecule at least.
Patent documentation 3～5 discloses a kind of resin combination, and this resin combination mixes Resins, epoxy and the silicone resin that is condensed in advance and obtains.
Patent documentation 6～11 discloses a kind of resin combination, and this resin combination is by with Resins, epoxy and alkoxyl silicone alkanes or the mixing of its partial condensate, then carries out dealcoholization and obtains.
The prior art document
Patent documentation
Patent documentation 1: No. 3263177 communique of Japanese Patent
Patent documentation 2: TOHKEMY 2005-171021 communique
Patent documentation 3: TOHKEMY 2006-225515 communique
Patent documentation 4: TOHKEMY 2006-241230 communique
Patent documentation 5: TOHKEMY 2008-120843 communique
Patent documentation 6: TOHKEMY 2001-059011 communique
Patent documentation 7: TOHKEMY 2001-059013 communique
Patent documentation 8: TOHKEMY 2002-179762 communique
Patent documentation 9: TOHKEMY 2002-249539 communique
Patent documentation 10: TOHKEMY 2003-246838 communique
Patent documentation 11: TOHKEMY 2005-179401 communique
Patent documentation 12: TOHKEMY 2007-321130 communique
Summary of the invention
The problem that invention will solve
Yet the photostabilization of the resin combination described in the patent documentation 1 and 2 is insufficient, and anti-crackle, cementability are not able to gratifying level as yet yet.In addition, above-mentioned modified resin composition according to circumstances storage stability is lower, has the tendency that the viscosity of resin in preservation significantly increases, and not talkative have a sufficient practicality.
In addition, the composition of record is to obtain by under the condition that does not have Resins, epoxy the silicone resin of condensation in advance being mixed with Resins, epoxy in the patent documentation 3～5, the said composition storage stability is lower, has the remarkable tendency that increases of viscosity of resin in preservation.In addition, according to circumstances Resins, epoxy and silicone resin can't uniform mixing etc., and not talkative have a sufficient practicality.
In addition, making by dealcoholization under the situation of silicone, have alkoxyl group and residue in tendency in the silicone, cured article as patent documentation 6～12 records obtains the resin combination curing that contains the organoalkoxysilane residue, this cured article because of through the time hydrolysis produce alcohol, gasification simultaneously, thereby the tendency that the anti-crackle when having thermal cycling, cementability reduce.
In view of the foregoing, the object of the present invention is to provide a kind of modified resin composition, described modified resin composition can form the cured article that has the good transparency, has the anti-crackle in excellent thermotolerance, heat-resisting discolouration, photostabilization, the thermal cycling simultaneously, and described modified resin composition has good storage stability.
In addition, the object of the present invention is to provide a kind of luminous components such as LED of excellence, the adaptation excellence of luminous component such as this LED and element or packaged material, do not crack, the reduction of long-term brightness is less; A kind of optics lens, this optics with lens can injection molding, solidify the hard and excellent in dimensional stability of back quality and have photostabilization; And a kind of semiconductor device, this semiconductor device has used described luminous component and/or optics lens.
In addition, the object of the present invention is to provide and a kind ofly can suppress inhibition that oxygen produces and photosensitive composite excellent in adhesion, contain the coating agent of said composition and make this coating agent solidify filming of forming.
In addition, the object of the present invention is to provide a kind of fluor the dispersion stabilization excellence the fluorescence resin composition and used the light-storing material of this fluorescence resin composition.
In addition, the object of the present invention is to provide a kind of flowability, electroconductibility and excellent in adhesion and do not produce the conductive resin composition of hole (void).
In addition, the object of the present invention is to provide a kind of flowability, insulativity and excellent in adhesion and do not produce the insulating resin composition of hole.
The scheme that is used to deal with problems
The inventor furthers investigate in order to solve above-mentioned problem, found that a kind of modified resin composition that Resins, epoxy and specific alkoxysilane compound containing trialkylsilyl group in molecular structure are obtained with specific ratio reaction, by the residual alcoxyl base unit weight in the resin combination is adjusted to specified range, can solve above-mentioned problem, finish the present invention thus.
That is, the present invention is as described below.
[1]
A kind of modified resin composition, its modified resin composition for Resins, epoxy (A) and the alkoxysilane compound containing trialkylsilyl group in molecular structure reaction shown in the following general formula (1) are obtained,
(R
1)
n-Si-(OR
2)
4-n (1)
(wherein, n represents more than 0 and 3 following integers; In addition, R
1Respectively independently expression be selected from by hydrogen atom, following a), following b), following c) organic group more than at least a kind in the group formed, on the other hand, R
2Expression is selected from by hydrogen atom and following d independently respectively) organic group more than a kind in the group formed,
A) organic group, this organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and this organic group contains carbonatoms be more than 4 and 24 following and oxygen atomicities be 1 or more and 5 below the ring-type ethers
B) 1 valency aliphatics organic group, this 1 valency aliphatics organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aliphatics organic group is more than 1 and 24 following and oxygen atomicities are more than 0 and below 5
C) 1 valency aromatic series organic group, this 1 valency aromatic series organic group is the aromatic hydrocarbons unit of non-replacement or replacement, have in case of necessity non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aromatic series organic group is more than 6 and 24 following and oxygen atomicities are more than 0 and below 5
D) 1 valency organic group, this 1 valency organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and the carbonatoms of this 1 valency organic group is more than 1 and below 8.)
Described alkoxysilane compound containing trialkylsilyl group in molecular structure comprises:
(B) n=1 or 2 and have at least 1 ring-type ether as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure and
(C) n=1 or 2 and have at least 1 aromatic series organic group as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure,
The mixing index α of the described alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the following general formula (2) is more than 0.001 and below 19,
Mixing index α=(α c)/(α b) ... (2)
(wherein, in the formula (2), α b represents the content (mol%) of described (B) composition in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), and α c represents the content (mol%) of described (C) composition in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1).)
And the residual alcoxyl base unit weight in the described modified resin composition is below 5%.
[2]
As above-mentioned [1] described modified resin composition, the viscosity of described modified resin composition under 25 ℃ is below the 1000Pas.
[3]
As above-mentioned [1] or [2] described modified resin composition, the epoxy equivalent (weight) of wherein said modified resin composition is more than the 100g/eq and below the 700g/eq.
[4]
As each described modified resin composition in above-mentioned [1]～[3], the condensation rate of wherein said alkoxysilane compound containing trialkylsilyl group in molecular structure is more than 80%.
[5]
As each described modified resin composition in above-mentioned [1]～[4], the viscosity of wherein said Resins, epoxy (A) under 25 ℃ is below the 500Pas.
[6]
As each described modified resin composition in above-mentioned [1]～[5], the epoxy equivalent (weight) of wherein said Resins, epoxy (A) is more than the 100g/eq and below the 300g/eq.
[7]
As each described modified resin composition in above-mentioned [1]～[6], the polyfunctional epoxy resin that wherein said Resins, epoxy (A) constitutes for the glycidyl ether thing by polyphenolic substance.
[8]
As each described modified resin composition in above-mentioned [1]～[7], wherein said Resins, epoxy (A) is bisphenol A type epoxy resin.
[9]
As each described modified resin composition in above-mentioned [1]～[8], the mixing index β of the described alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the wherein following general formula (3) is more than 0.01 and below 1.4.
Mixing index β={ (β n2)/(β n0+ β n1) } (3)
(wherein, in the formula (3), β n2 represents the content (mol%) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=2, β n0 represents the content (mol%) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=0, β n1 represents the content (mol%) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=1, and β n2, β n0, β n1 are for satisfying the value of 0≤{ (β n0)/(β n0+ β n1+ β n2) }≤0.1.)
[10]
As each described modified resin composition in above-mentioned [1]～[9], the described Resins, epoxy (A) shown in the wherein following general formula (4) is 0.02～15 with the mixing index γ of described alkoxysilane compound containing trialkylsilyl group in molecular structure.
Mixing index γ=(γ a)/(γ s) (4)
(wherein, in the formula (4), the quality (g) of γ a representative ring epoxy resins (A), γ s represents the quality (g) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=0～2.)
[11]
A kind of manufacture method of modified resin composition, it comprises at least that for making (B) shown in the following general formula (1) reaches the manufacture method of each described modified resin composition in that (C) alkoxysilane compound containing trialkylsilyl group in molecular structure reacts, above-mentioned [1]～[10] under Resins, epoxy (A), this method comprises following operation (a) and operation (b):
Operation (a): in the presence of Resins, epoxy (A), will comprise (B) shown in the general formula (1) and alkoxysilane compound containing trialkylsilyl group in molecular structure cohydrolysis (C) at least, thereby make the operation of intermediate by the reflow process of not following dehydration;
Operation (b): the operation of the intermediate dehydration condensation that will make by operation (a).
(R
1)
n-Si-(OR
2)
4-n (1)
(wherein, n represents more than 0 and 3 following integers; In addition, R
1Respectively independently expression be selected from by hydrogen atom, following a), following b), following c) organic group more than at least a kind in the group formed, on the other hand, R
2Expression is selected from by hydrogen atom and following d independently respectively) organic group more than a kind in the group formed,
A) organic group, this organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and this organic group contains carbonatoms be more than 4 and 24 following and oxygen atomicities be 1 or more and 5 below the ring-type ethers
B) 1 valency aliphatics organic group, this 1 valency aliphatics organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aliphatics organic group is more than 1 and 24 following and oxygen atomicities are more than 0 and below 5
C) 1 valency aromatic series organic group, this 1 valency aromatic series organic group is the aromatic hydrocarbons unit of non-replacement or replacement, have in case of necessity non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aromatic series organic group is more than 6 and 24 following and oxygen atomicities are more than 0 and below 5
D) 1 valency organic group, this 1 valency organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and the carbonatoms of this 1 valency organic group is more than 1 and below 8.)
(B) n=1 or 2 and have at least 1 ring-type ether as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure.
(C) n=1 or 2 and have at least 1 aromatic series organic group as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure.
And the mixing index α of the described alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the following general formula (2) is more than 0.001 and below 19.
Mixing index α=(α c)/(α b) ... (2)
(wherein, in the formula (2), α b represents the content (mol%) of described (B) composition, and α c represents the content (mol%) of described (C) composition.)
[12]
A kind of manufacture method of modified resin composition, it comprises at least that for making (B) shown in the following general formula (1) reaches the manufacture method of each described modified resin composition in that (C) alkoxysilane compound containing trialkylsilyl group in molecular structure reacts, above-mentioned [1]～[10] under Resins, epoxy (A), this method comprises following operation (c) and operation (d):
Operation (c): will comprise (B) shown in the general formula (1) and alkoxysilane compound containing trialkylsilyl group in molecular structure cohydrolysis (C) at least by the reflow process of not following dehydration, thereby make the operation of intermediate.
Operation (d): make the intermediate and Resins, epoxy (A) coexistence of making by operation (c), and the operation of dehydration condensation.
(R
1)
n-Si-(OR
2)
4-n (1)
(wherein, n represents more than 0 and 3 following integers; In addition, R
1Respectively independently expression be selected from by hydrogen atom, following a), following b), following c) organic group more than at least a kind in the group formed, on the other hand, R
2Expression is selected from by hydrogen atom and following d independently respectively) organic group more than a kind in the group formed,
A) organic group, this organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and this organic group contains carbonatoms be more than 4 and 24 following and oxygen atomicities be 1 or more and 5 below the ring-type ethers
B) 1 valency aliphatics organic group, this 1 valency aliphatics organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aliphatics organic group is more than 1 and 24 following and oxygen atomicities are more than 0 and below 5
C) 1 valency aromatic series organic group, this 1 valency aromatic series organic group is the aromatic hydrocarbons unit of non-replacement or replacement, have in case of necessity non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aromatic series organic group is more than 6 and 24 following and oxygen atomicities are more than 0 and below 5
D) 1 valency organic group, this 1 valency organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and the carbonatoms of this 1 valency organic group is more than 1 and below 8.)
(B) n=1 or 2 and have at least 1 ring-type ether as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure.
(C) n=1 or 2 and have at least 1 aromatic series organic group as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure.
And the mixing index α of the described alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the following general formula (2) is more than 0.001 and below 19.
Mixing index α=(α c)/(α b) ... (2)
(wherein, in the formula (2), α b represents the content (mol%) of described (B) composition, and α c represents the content (mol%) of described (C) composition.)
[13]
As the manufacture method of above-mentioned [11] or [12] described modified resin composition, the mixing index β of the described alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the wherein following general formula (3) is 0.01～1.4.
Mixing index β={ (β n2)/(β n0+ β n1) } (3)
(wherein, in the formula (3), β n2 represents the content (mol%) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=2, β n0 represents the content (mol%) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=0, β n1 represents the content (mol%) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=1, and β n2, β n0, β n1 are for satisfying the value of 0≤{ (β n0)/(β n0+ β n1+ β n2) }≤0.1.)
[14]
As the manufacture method of each described modified resin composition in above-mentioned [11]～[13], the Resins, epoxy (A) shown in the wherein following general formula (4) is 0.02～15 with the mixing index γ of described alkoxysilane compound containing trialkylsilyl group in molecular structure.
Mixing index γ=(γ a)/(γ s) (4)
(wherein, in the formula (4), the quality (g) of γ a representative ring epoxy resins (A), γ s represents the quality (g) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=0～2.)
[15]
As the manufacture method of each described modified resin composition in above-mentioned [11]～[14], wherein not following the temperature in the reflow process of dehydration is 50～100 ℃.
[16]
As the manufacture method of each described modified resin composition in above-mentioned [11]～[15], wherein the condensation rate of the intermediate that obtains by the reflow process cohydrolysis of not following dehydration is more than 78%.
[17]
As the manufacture method of each described modified resin composition in above-mentioned [11]～[16], wherein when described cohydrolysis, using alkoxide is that organotin is as catalyzer.
[18]
A kind of resin combination, it forms by further add oxetane compound (D) in above-mentioned [1] described modified resin composition.
[19]
A kind of fluorescence resin combination, it forms by further add fluor (E) in above-mentioned [1] described modified resin composition.
[20]
A kind of conductive resin composition, it forms by further add conductive metal powder (F) in above-mentioned [1] described modified resin composition.
[21]
A kind of insulating resin composition, it forms by further add insulativity powder (G) in above-mentioned [1] described modified resin composition.
[22]
A kind of resin combination, it forms by further add Resins, epoxy (A ') in above-mentioned [1] described modified resin composition.
[23]
A kind of curable resin composition, it forms by further adding solidifying agent (H) in each described resin combination in above-mentioned [1], [18], [19].
[24]
A kind of curable resin composition, it forms by further add curing catalyst (I) in above-mentioned [23] described resin combination.
[25]
A kind of photosensitive polymer combination, it forms by further adding light acid producing agent (J) in each described resin combination in above-mentioned [1], [18], [19].
[26]
A kind of luminous component, its use above-mentioned [24] or [25] described resin combination and make.
[27]
A kind of optics lens, its use above-mentioned [24] or [25] described resin combination and make.
[28]
A kind of light-storing material, its use above-mentioned [24] or [25] described resin combination and make.
[29]
A kind of semiconductor device, it comprises above-mentioned [26] described luminous component and/or above-mentioned [27] described optics lens.
[30]
A kind of curable resin composition, it forms by further adding curing catalyst (I) in each described resin combination in above-mentioned [20]～[22].
[31]
A kind of photosensitive polymer combination, it forms by further adding light acid producing agent (J) in each described resin combination in above-mentioned [20]～[22].
[32]
A kind of coating agent, it contains each described resin combination in above-mentioned [24], [25], [30], [31].
[33]
A kind of filming, its use above-mentioned [32] described coating agent and making.
The effect of invention
The present invention can provide a kind of modified resin composition, described modified resin composition can form has excellent photostabilization, the cured article of cold-resistant thermal shocking (the anti-crackle in the thermal cycling), and described modified resin composition has good storage stability.
Description of drawings
Figure 1 shows that the sectional view of bullet cut LED.
Figure 2 shows that the sectional view of SMD type LED.
Description of reference numerals
10,20: photodiode (LED)
10a, 20a:LED chip
10A, 20A: anode electrode
10C, 20C: cathode electrode
12,22: sealing material
14,24: bonding wire
16: outermost resin
18: lead frame
26: base plate for packaging
28: reflector
Embodiment
Below, to the specific embodiment of the present invention (below, be called " present embodiment ".) be elaborated.The invention is not restricted to mode shown below.
The modified resin composition of modified resin composition in the present embodiment for Resins, epoxy (A) and the alkoxysilane compound containing trialkylsilyl group in molecular structure reaction shown in the following general formula (1) are obtained,
(R
1)
n-Si-(OR
2)
4-n (1)
(wherein, n represents more than 0 and 3 following integers.In addition, R
1Respectively independently expression be selected from by hydrogen atom, following a), following b), following c) organic group more than at least a kind in the group formed: a) organic group, this organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and this organic group to contain carbonatoms be 4 or more and 24 following and oxygen atomicities are more than 1 and 5 below the ring-type ethers; B) 1 valency aliphatics organic group, this 1 valency aliphatics organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aliphatics organic group is 1 or more and 24 following to reach oxygen atomicity be more than 0 and below 5; C) 1 valency aromatic series organic group, this 1 valency aromatic series organic group is the aromatic hydrocarbons unit of non-replacement or replacement, have in case of necessity non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aromatic series organic group is 6 or more and 24 following to reach oxygen atomicity be more than 0 and below 5.On the other hand, R
2Expression is selected from by hydrogen atom and following d independently respectively) organic group more than a kind in the group formed: d) 1 valency organic group, this 1 valency organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and the carbonatoms of this 1 valency organic group is more than 1 and below 8.)
Described alkoxysilane compound containing trialkylsilyl group in molecular structure comprises:
(B) n=1 or 2 and have at least 1 ring-type ether as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure and
(C) n=1 or 2 and have at least 1 aromatic series organic group as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure,
The mixing index α of the described alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the following general formula (2) is more than 0.001 and below 19,
Mixing index α=(α c)/(α b) ... (2)
(wherein, in the formula (2), α b represents the content (mol%) of described (B) composition in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), and α c represents the content (mol%) of described (C) composition in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1).)
And the residual alcoxyl base unit weight in the described modified resin composition is below 5%.
The Resins, epoxy that uses in the present embodiment (A) is not particularly limited, for example, can list alicyclic epoxy resin, fatty family Resins, epoxy, by the polyfunctional epoxy resin that the glycidyl ether thing constituted of polyphenolic substance, as the polyfunctional epoxy resin of the glycidyl ether thing of novolac resin, aromatic epoxy resin add hydride (nuclear water elementization thing), hetero ring type Resins, epoxy, glycidyl ester be Resins, epoxy, glycidyl amine be Resins, epoxy, with the Resins, epoxy of halogenation phenols glycidylization etc.These Resins, epoxy may be used alone, and can also use a variety of combinations.
As the alicyclic epoxy resin that can use in the present embodiment, so long as have the Resins, epoxy of ester ring type epoxy group(ing), then be not particularly limited, for example, can list have the epoxy cyclohexane base, the Resins, epoxy of epoxy tristane base, cyclopentane epoxide base etc.As the object lesson of alicyclic epoxy resin, simple function alicyclic epoxy compound can list 4 vinyl epoxy cyclohexane, epoxy di-2-ethylhexyl hexahy-, epoxy di-2-ethylhexyl.As 2 officials energy alicyclic epoxy compound, can list 3,4-epoxycyclohexyl methyl-3, the 4-epoxycyclohexane carboxylate, 3,4-epoxycyclohexyl octyl group-3, the 4-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiral shell-3, the 4-epoxy) hexanaphthene-1, the 3-diox, two (3,4-epoxycyclohexyl methyl) adipic acid ester, the vinyl cyclohexene diepoxide, two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipic acid ester, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylic acid ester, methylene-bis (3, the 4-epoxy cyclohexane), bicyclopentadiene dioxide, ethylene glycol bisthioglycolate (3,4-epoxycyclohexyl methyl) ether, ethylenebis (3, the 4-epoxycyclohexane carboxylate), 1,2,8,9-two epoxy limonenes.As multifunctional alicyclic epoxy compound, can list 2,1 of two (the hydroxymethyl)-1-butanols of 2-, 2-epoxy-4-(2-Oxyranyle) tetrahydrobenzene affixture etc.In addition, as the commercially available product of multifunctional alicyclic epoxy compound, can list EPOLEAD GT401, EHPE3150 (Daicel Chemical Industries, Ltd. system) etc.
The representative example of alicyclic epoxy resin below is shown.
Chemical formula 1
As the fatty family Resins, epoxy that can use in the present embodiment, be not particularly limited, particularly, can list 1,4-butyleneglycol, 1, the Racemic glycidol ethers of polyvalent alcohols such as 6-hexylene glycol, polyoxyethylene glycol, polypropylene glycol, tetramethylolmethane, xylyl alcohol derivative.
The representative example of fatty family Resins, epoxy below is shown.
Chemical formula 2
The polyfunctional epoxy resin that constitutes as the glycidyl ether thing by polyphenolic substance that can use in the present embodiment, be not particularly limited, particularly, can list dihydroxyphenyl propane, Bisphenol F, bisphenol S, 4,4 '-xenol, the tetramethyl-dihydroxyphenyl propane, the dimethyl dihydroxyphenyl propane, the tetramethyl-Bisphenol F, the dimethyl Bisphenol F, the tetramethyl-bisphenol S, the dimethyl bisphenol S, tetramethyl--4,4 '-xenol, dimethyl-4,4 '-xenyl phenol, 1-(4-hydroxy phenyl)-2-[4-(1,1-pair-(4-hydroxy phenyl) ethyl) phenyl] propane, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 4,4 '-butylidene-two (3 methy 6 tert butyl phenol), the trihydroxybenzene methylmethane, Resorcinol, Resorcinol, 2,6-two (tertiary butyl) Resorcinol, pyrogallol, phenol with diisopropylidene skeleton, 1,1-two (4-hydroxy phenyl) fluorenes etc. has the phenol of fluorene skeleton, as polyfunctional epoxy resin of the glycidyl ether thing of the polyphenolic substance of phenol polyhutadiene etc.
The representative example of polyfunctional epoxy resin as the glycidyl ether thing of the phenol with bis-phenol skeleton below is shown.
Chemical formula 3
Under situation about using as the polyfunctional epoxy resin of the glycidyl ether thing of polyphenolic substance, these repeating units (representing the n in the chemical formula of above-mentioned representative example) are not particularly limited, and are preferably more than 0 and are lower than 50 scope.If repeating unit is more than 50, then mobile the reduction may go wrong in the practical application.From the reactive viewpoint of raising with the alkoxysilane compound containing trialkylsilyl group in molecular structure class, and then from the viewpoint of the flowability that improves resulting modified resin composition, the scope of repeating unit is preferably more than 0.001 and 10 following scopes, more preferably 0.01 or more and the scopes below 2.
Polyfunctional epoxy resin as the glycidyl ether thing of novolac resin, be not particularly limited, for example, can list with various phenol such as phenol, cresols class, ethylbenzene phenols, butylbenzene phenols, octyl phenol class, dihydroxyphenyl propane, Bisphenol F, bisphenol S, aphthols as the novolac resin of raw material, contain the xylylene skeleton novolac resin, contain the Dicyclopentadiene (DCPD) skeleton novolac resin, contain the xenyl skeleton novolac resin, contain the glycidyl ether thing etc. of the various novolac resins such as novolac resin of fluorene skeleton.
Representative example as the polyfunctional epoxy resin of the glycidyl ether thing of novolac resin below is shown.
Chemical formula 4
Add hydride (nuclear water elementization thing) as the aromatic epoxy resin that can use in the present embodiment, be not particularly limited, for example, can list the glycidyl ether thing of oxybenzene compound (dihydroxyphenyl propane, Bisphenol F, bisphenol S, 4,4 '-xenol etc.) or various phenol (phenol, cresols class, ethylbenzene phenols, butylbenzene phenols, octyl phenol class, dihydroxyphenyl propane, Bisphenol F, bisphenol S, aphthols etc.) aromatic nucleus the glycidyl ether thing that adds hydride, novolac resin add hydride etc.
As hetero ring type Resins, epoxy, be not particularly limited, for example, can list have isocyanurate ring, heterocyclic hetero ring type Resins, epoxy such as glycolylurea ring etc.
As glycidyl ester is Resins, epoxy, is not particularly limited, and for example, can list Resins, epoxy that hexahydro-phthalic acid 2-glycidyl ester, tetrahydrophthalic acid 2-glycidyl ester etc. are made of carboxylic-acid etc.
As glycidyl amine is Resins, epoxy, be not particularly limited, for example, can list Resins, epoxy that amine glycidylizations such as aniline, Tolylamine, Ursol D, mphenylenediamine, diaminodiphenyl-methane derivative, diamino methylbenzene derivative are obtained etc.
As Resins, epoxy with benzene halide phenols glycidylization, be not particularly limited, for example, can list Resins, epoxy that benzene halide phenols glycidyl ethers such as brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenols Novolac, bromination cresols phenolic varnish, chlorination bisphenol S, chlorination dihydroxyphenyl propane are obtained etc.
Among above-mentioned, owing to can obtain easily, and solidify and the cured article that obtains exists and has the excellent transparency as the modified resin composition of the present embodiment of target, thermotolerance, heat-resisting discolouration, photostabilization, the tendency of the anti-crackle during thermal cycling, thereby preferred alicyclic epoxy resin, fat family Resins, epoxy, the polyfunctional epoxy resin that constitutes by the glycidyl ether thing of polyphenolic substance, more preferably alicyclic epoxy resin, the polyfunctional epoxy resin that constitutes by the glycidyl ether thing of polyphenolic substance, the further preferred polyfunctional epoxy resin that constitutes by the glycidyl ether thing of polyphenolic substance, especially preferred bisphenol A type epoxy resin.
For the viscosity of the Resins, epoxy that uses in the present embodiment (A) under 25 ℃, be not particularly limited, but owing to have the flowability to guarantee as liquid, can improve the tendency with the consistency of alkoxysilane compound containing trialkylsilyl group in molecular structure, be preferably the following liquid of 1000Pas, more preferably below the 500Pas, more preferably below the 300Pas, especially be preferably below the 100Pas.
The epoxy equivalent (weight) (WPE) of the Resins, epoxy that uses in the present embodiment (A) is not particularly limited, viewpoint from the storage stability of the modified resin composition that improves present embodiment, be preferably more than the 100g/eq, from improving that modified resin composition with present embodiment solidifies and the viewpoint of the anti-crackle of the cured article that obtains, be preferably below the 700g/eq, the more preferably scope that 100g/eq is above and 500g/eq is following, the more preferably scope that 100g/eq is above and 300g/eq is following.
The alkoxysilane compound containing trialkylsilyl group in molecular structure that can use in the present embodiment represents to have the silicon compound of 1～4 alkoxyl group, is represented by following general formula (1).
(R
1)
n-Si-(OR
2)
4-n (1)
(wherein, n represents more than 0 and 3 following integers.In addition, R
1Respectively independently expression be selected from by hydrogen atom, following a), following b), following c) organic group more than at least a kind in the group formed: a) organic group, this organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and this organic group to contain carbonatoms be 4 or more and 24 following and oxygen atomicities are more than 1 and 5 below the ring-type ethers; B) 1 valency aliphatics organic group, this 1 valency aliphatics organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aliphatics organic group is 1 or more and 24 following to reach oxygen atomicity be more than 0 and below 5; C) 1 valency aromatic series organic group, this 1 valency aromatic series organic group is the aromatic hydrocarbons unit of non-replacement or replacement, have in case of necessity non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aromatic series organic group is 6 or more and 24 following to reach oxygen atomicity be more than 0 and below 5.On the other hand, R
2Expression is selected from by hydrogen atom and following d independently respectively) organic group more than a kind in the group formed, d) 1 valency organic group, this 1 valency organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and the carbonatoms of this 1 valency organic group is more than 1 and below 8.)
Wherein, the ring-type ether in the present embodiment is described.Ring-type ether in the present embodiment is meant, has the carbon of cyclic hydrocarbon is replaced the organic group of the ether that forms with oxygen, is often referred to the ring-type ether of the structure with 3～6 yuan of rings.Wherein, be preferably 3 yuan of big, the reactive higher rings of ring strain energy or the ring-type ether of 4 yuan of rings, especially be preferably the ring-type ether of 3 yuan of rings.
Then, to the R in the present embodiment
1Describe.The R of present embodiment
1Respectively independently expression be selected from by hydrogen atom, following a), following b), following c) organic group more than at least a kind in the group formed: a) organic group, this organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and this organic group to contain carbonatoms be 4 or more and 24 following and oxygen atomicities are more than 1 and 5 below the ring-type ethers; B) 1 valency aliphatics organic group, this 1 valency aliphatics organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aliphatics organic group is 1 or more and 24 following to reach oxygen atomicity be more than 0 and below 5; C) 1 valency aromatic series organic group, this 1 valency aromatic series organic group is the aromatic hydrocarbons unit of non-replacement or replacement, have in case of necessity non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aromatic series organic group is 6 or more and 24 following to reach oxygen atomicity be more than 0 and below 5.
Above-mentioned a) organic group has non-replacement or replacement, comprise and be selected from by chain, prop up chain, the aliphatic hydrocarbon unit of structure more than a kind in the structural group that ring-type constituted, and this organic group contains carbonatoms be more than 4 and 24 following and oxygen atomicities be 1 or more and 5 below the ring-type ethers, as above-mentioned a) organic group, for example, can list beta epoxide propoxy-ethyl, γ-glycidoxy propyl group, γ-bondings such as glycidoxy butyl have the glycidoxyalkyl of the oxo glycidyl of carbonatoms below 4, glycidyl, β-(3, the 4-epoxycyclohexyl) ethyl, γ-(3, the 4-epoxycyclohexyl) propyl group, β-(3,4-oxirane ring heptyl) ethyl, β-(3,4 epoxycyclohexyls) propyl group, β-(3, the 4-epoxycyclohexyl) butyl, β-usefulness such as (3, the 4-epoxycyclohexyl) amyl group have alkyl that the cycloalkyl substituted of the carbonatoms 5～8 of Oxyranyle forms etc.
Above-mentioned b) 1 valency aliphatics organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aliphatics organic group is more than 1 and 24 following and oxygen atomicities are more than 0 and below 5, as above-mentioned b) 1 valency aliphatics organic group, for example, can list:
(b-1) methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, sec-butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, n-heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl etc. are by catenate organic group that aliphatic hydrocarbon constituted
(b-2) cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, norcamphyl etc. are by the organic group that hydrocarbon constituted that comprises annular unit,
(b-3) methoxy ethyl, ethoxyethyl group, propoxy-ethyl, methoxy-propyl, ethoxycarbonyl propyl, propoxy-propyl group etc. comprise the organic group of ehter bond,
(b-4) vinyl, allyl group, pseudoallyl, butenyl, isobutenyl, pentenyl, hexenyl, etc.
Above-mentioned c) 1 valency aromatic series organic group is the aromatic hydrocarbons unit of non-replacement or replacement, have in case of necessity non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aromatic series organic group is 6 or more and 24 following to reach oxygen atomicity be more than 0 and below 5.As above-mentioned c) 1 valency aromatic series organic group, for example, can list phenyl, tolyl, xylyl, benzyl, alpha-methyl styrene base, 3-vinyl toluene base, 4-vinyl toluene base etc.
Alkoxysilane compound containing trialkylsilyl group in molecular structure can be the above-mentioned different mixture more than 2 kinds of a)～c) organic group.
In addition; as long as in the scope of above-mentioned carbonatoms and oxygen atomicity, then can comprise as organic group halogen atom such as hydroxyl unit, oxyalkyl units, acyl group unit, carboxyl unit, alkene oxygen base unit, acyloxy unit, fluorine or chlorine or, heteroatomss such as ester bond and the nitrogen except that Sauerstoffatom or Siliciumatom, phosphorus, sulphur.In addition, above-mentioned a)～c) can be to mix the organic group that exists more than a kind or 2 kinds.
As organic group R
1Good owing to existing modified resin composition with present embodiment to solidify the photostabilization of the cured article that obtains; or the stability-enhanced tendency when preserving; thereby with respect to the unitary total mole number of whole Si; bonding has the total mole number of the Siliciumatom of following organic group to be preferably below 10%; more preferably below 1%; more preferably do not contain fully, described organic group comprises the hydroxyl unit; oxyalkyl units; the acyl group unit; the carboxyl unit; alkene oxygen base unit; the acyloxy unit; halogen atoms such as fluorine or chlorine; or; ester bond; and the nitrogen except that Sauerstoffatom or Siliciumatom; phosphorus; heteroatomss such as sulphur.
On the other hand, when the modified resin composition that uses present embodiment is made cured article, because existing can be stably, reproducibility makes its solidified tendency well, thereby with respect to the unitary total mole number of whole Si, (b-4) total mole number of the aliphatics organic group of 1 valencys such as vinyl, allyl group, pseudoallyl, butenyl, isobutenyl, pentenyl, hexenyl is preferably below 10%, more preferably below 5%, more preferably below 1%, especially be preferably fully and do not contain.
Because there is the tendency that photostabilization is good and heat-resisting discolouration improves in the modified resin composition of present embodiment, thereby as the organic group R of the general formula in the present embodiment (1)
1Be preferably be selected from by above-mentioned a), b-1), b-2), c) in the group of being formed, as a), more preferably be selected from by beta epoxide propoxy-ethyl, γ-glycidoxy propyl group, γ-bondings such as glycidoxy butyl have the glycidoxyalkyl of the oxo glycidyl of carbonatoms below 4, glycidyl, β-(3, the 4-epoxycyclohexyl) ethyl, γ-(3, the 4-epoxycyclohexyl) propyl group, β-(3,4-oxirane ring heptyl) ethyl, β-(3,4 epoxycyclohexyls) propyl group, β-(3, the 4-epoxycyclohexyl) butyl, β-(3, the 4-epoxycyclohexyl) amyl group, with be selected from b-1) and b-2) in carbonatoms be more than 1 and below 8, oxygen atomicity is the organic group in 0 group of being formed, and phenyl, in the group that benzyl is formed; As a), especially being preferably to be selected from by beta epoxide propoxy-ethyl, γ-glycidoxy propyl group, γ-bondings such as glycidoxy butyl has glycidoxyalkyl, glycidyl, β-(3, the 4-epoxycyclohexyl) ethyl of the oxo glycidyl of carbonatoms below 4 and is selected from b-1) and b-2) in carbonatoms be more than 1 and 3 following, oxygen atomicity is in the group formed of organic group in 0 group of being formed and phenyl.
Then, to the R in the present embodiment
2Describe.The R of present embodiment
2Expression is selected from by hydrogen atom and following d independently respectively) organic group more than a kind in the group formed: d) 1 valency organic group, this 1 valency organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and the carbonatoms of this 1 valency organic group is more than 1 and below 8.As d) organic group, for example, can list methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, sec-butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, n-heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl etc. by catenate organic group that aliphatic hydrocarbon constituted; Cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, norcamphyl etc. are by organic group that the hydrocarbon that comprises annular unit constituted etc.
Alkoxysilane compound containing trialkylsilyl group in molecular structure can be above-mentioned d) the different mixture more than 2 kinds of organic group.In addition, they can be to mix the organic group that exists more than a kind or 2 kinds.
In these organic groups, owing to the tendency of the reactivity raising that has alkoxysilane compound containing trialkylsilyl group in molecular structure, thereby be preferably methyl, ethyl, n-propyl, sec.-propyl, more preferably methyl, ethyl.
In the present embodiment,, in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the described general formula (1), contain at least following (B) and (C): (B) n=1 or 2 and have at least 1 ring-type ether as R as alkoxysilane compound containing trialkylsilyl group in molecular structure
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure; (C) n=1 or 2 and have at least 1 aromatic series organic group as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure.Do not containing (B) n=1 or 2 and have at least 1 ring-type ether as R
1The situation of at least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure under, the modified resin composition of present embodiment solidified and anti-crackle, the cementability of the cured article that obtains are insufficient.On the other hand, do not containing (C) n=1 or 2 and have at least 1 aromatic series organic group as R
1The situation of at least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure under, modified resin composition is separated, and can't obtain to have cold-resistant thermal shocking, the cementability of reproducibility.
Object lesson as (B) composition that uses in the present embodiment, for example, can list 3-glycidoxy propyl group (methyl) dimethoxy silane, 3-glycidoxy propyl group (methyl) diethoxy silane, 3-glycidoxy propyl group (methyl) dibutoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl (methyl) dimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl (phenyl) diethoxy silane, 2,3-epoxypropyl (methyl) dimethoxy silane, 2,3-epoxypropyl (phenyl) dimethoxy silane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group three butoxy silanes, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, 2,3-epoxypropyl Trimethoxy silane, 2,3-epoxypropyl triethoxyl silane etc.They can use a kind or use as the mixture more than 2 kinds.
Object lesson as (C) composition that uses in the present embodiment, for example, can list dimethoxy-methyl phenyl silane, diethoxymethyl phenyl silane, phenyl triethoxysilane, trimethoxy [3-(phenyl amino) propyl group] silane, dimethoxy diphenyl silane, phenylbenzene diethoxy silane, phenyltrimethoxysila,e etc.They can use a kind or use as the mixture more than 2 kinds.
In addition, the modified resin composition in the present embodiment can also use expression R in the above-mentioned general formula (1) as other compositions except above-mentioned (A)～(C) composition
1Number n=0, particularly bonding has 4 (OR
2) alkoxysilane compound containing trialkylsilyl group in molecular structure.As such alkoxysilane compound containing trialkylsilyl group in molecular structure, for example, can list tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane etc.They can be used as a kind or use as the mixture more than 2 kinds.
Wherein, the mixing index α that uses in the present embodiment is described.
With in the organoalkoxysilane that uses in the present embodiment, " (B) in the general formula (1), n=1 or 2 and have at least 1 ring-type ether as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure " and " (C) in the general formula (1), n=1 or 2 and have at least 1 aromatic series organic group as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure " mixture ratio be defined as the mixing index α that is calculated by following formula (2).
Mixing index α=(α c)/(α b) (2)
(wherein, in the formula (2), α b represents the content (mol%) of (B) composition in the organoalkoxysilane shown in the general formula (1), and α c represents the content (mol%) of (C) composition in the organoalkoxysilane shown in the general formula (1).)
In the present embodiment, aspect the flowability of guaranteeing modified resin composition and storage stability, above-mentioned mixing index α need be for more than 0.001, on the other hand, aspect the anti-crackle of guaranteeing the flowability of modified resin composition, cured article, above-mentioned mixing index α need be the scope below 19.The value of described α is more preferably more than 0.2 and 5 following scopes, more preferably more than 0.3 and below 2.
About the modified resin composition of present embodiment, the residual alcoxyl base unit weight in the said composition is below 5%.Surpass under 5% the situation at residual alkoxyl group, anti-crackle, the cementability of the cured article that composition curing is obtained when thermal cycling is insufficient.As the residual alcoxyl base unit weight in the modified resin composition, more preferably below 3%, more preferably below 1%, further be preferably below 0.5%, especially be preferably fully and do not contain.
In addition, about the quantitative values of residual alcoxyl base unit weight, by using 1,1,2, the 2-tetrabromoethane calculates the area ratio of marking peak and residual alcoxyl base peak in resulting as the H-NMR mensuration of internal standard substance, thereby can obtain the quantitative values of residual alcoxyl base unit weight.
Particularly, can try to achieve by the method and the analytical procedure of the following stated.
＜H-NMR measures 〉
(1) with modified resin composition 10mg, internal standard substance (1,1,2, the 2-tetrabromoethane; Tokyo changes into industry) 20mg and deuterochloroform 970mg uniform mixing, measure solution as H-NMR.
(2) solution of above-mentioned (1) is measured under the following conditions the H-NMR spectrum.
Device: Jeol Ltd.'s system " α-400 type "
Nuclear species: H
Cumulative frequency: 200 times
The analysis of＜measurement result 〉
(3) peak area value of the residual alcoxyl base peak in the calculating H-NMR spectrum.
(4) peak area value at the internal standard substance peak in the calculating H-NMR spectrum.
(5) with the area value substitution following formula separately that obtains in above-mentioned (3), (4), resulting result is defined as residual alcoxyl base unit weight (%).
Residual alcoxyl base unit weight (%)=(peak area value of residual alcoxyl base peak)/(peak area value at internal standard substance peak) * 100
The viscosity of modified resin composition under 25 ℃ about present embodiment, be not particularly limited, but owing to have the flowability that to guarantee as liquid, the tendency that operability improves, and there is easily a tendency with the additives mixed of being added as required, thereby being preferably 1, the liquid that 000Pas is following is more preferably below the 500Pas, more preferably below the 300Pas, especially be preferably below the 100Pas.
Epoxy equivalent (weight) (WPE) about the modified resin composition of present embodiment, be not particularly limited, viewpoint from the storage stability that improves modified resin composition, preferably select functional group in the mode that reaches more than the 100g/eq, in addition, from the viewpoint of the anti-crackle that improves the cured article that modified resin composition is solidified and obtain, preferably select functional group in the mode that reaches below the 700g/eq.Preferred scope is the scope that 100g/eq is above and 500g/eq is following, and further preferred range is the scope that 100g/eq is above and 300g/eq is following.
Then, the mixing index β that uses in the present embodiment is described.
Mixture ratio in the alkoxysilane compound containing trialkylsilyl group in molecular structure that uses in the present embodiment, that " alkoxysilane compound containing trialkylsilyl group in molecular structure of n=2 ", " alkoxysilane compound containing trialkylsilyl group in molecular structure of n=1 " reach " alkoxysilane compound containing trialkylsilyl group in molecular structure of n=0 " is defined as the mixing index β that is calculated by following formula (3).
Mixing index β={ (β n2)/(β n0+ β n1) } (3)
(wherein, in the formula (3), β n2 represents the content (mol%) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=2, β n0 represents the content (mol%) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=0, β n1 represents the content (mol%) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=1, and β n2, β n0, β n1 are for satisfying the value of 0≤{ (β n0)/(β n0+ β n1+ β n2) }≤0.1.)
In the present embodiment, owing to there is the tendency that flowability improves, operability improves of modified resin composition, thereby above-mentioned mixing index β is preferably more than 0.01, on the other hand, owing to there being the tendency of modified resin composition being solidified the anti-crackle raising of the cured article that obtains, thereby above-mentioned mixing index β is preferably below 1.4, more preferably more than 0.03 and 1.2 following scopes, more preferably 0.05 or more and the scopes below 1.0.
Then, the mixing index γ that uses in the present embodiment is described.
The mixture ratio of " alkoxysilane compound containing trialkylsilyl group in molecular structure of n=0～2 " that use in the present embodiment, in Resins, epoxy (A) and the alkoxysilane compound containing trialkylsilyl group in molecular structure is defined as the mixing index γ that is calculated by following formula (4).
Mixing index γ=(γ a)/(γ s) (4)
(wherein, in the formula (4), the quality (g) of γ a representative ring epoxy resins (A), γ s represents the quality (g) of the alkoxysilane compound containing trialkylsilyl group in molecular structure of n=0～2 in the organoalkoxysilane shown in the general formula (1).)
In the present embodiment, modified resin composition is solidified the tendency of the anti-crackle raising of cured article when thermal cycling that obtains owing to existence, thereby mixing index γ is preferably more than 0.02, on the other hand, owing to there being the tendency of modified resin composition being solidified the photostabilization raising of the cured article that obtains, thereby mixing index γ is preferably the scope below 15, more preferably more than 0.04 and 7 following scopes, more preferably 0.08 or more and the scopes below 5.
In the modified resin composition of present embodiment, the viscosity of the resin from the storage stability of modified resin composition promptly suppresses to preserve, the viewpoint of operability of improving, the condensation rate of alkoxysilane compound containing trialkylsilyl group in molecular structure is preferably more than 80%, more preferably more than 82%, more preferably more than 85%, especially be preferably more than 88%.
In addition, about the condensation rate of the alkoxysilane compound containing trialkylsilyl group in molecular structure of present embodiment, utilize with respect to contained (OR in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1)
2) (OR in silicone composition mole number (U), that exist in the modified resin composition of base
2) basic mole number (V), represent with the molar percentage shown in the following formula (5).
The condensation rate (%) of alkoxysilane compound containing trialkylsilyl group in molecular structure=[(U-V)/U] * 100 (5)
Below, the example of the concrete manufacture method of the modified resin composition of present embodiment is described.
The modified resin composition of present embodiment, by the method for utilizing following [manufacturing process 1] or [manufacturing process 2] in the presence of Resins, epoxy (A), make comprise at least (B) shown in the following general formula (1) and (C) and the mixing index α of the described alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the following general formula (2) be that alkoxysilane compound containing trialkylsilyl group in molecular structure 0.001 or more and below 19 reacts, thereby can make.
(R
1)
n-Si-(OR
2)
4-n (1)
(wherein, n represents more than 0 and 3 following integers.In addition, R
1Respectively independently expression be selected from by hydrogen atom, following a), following b), following c) organic group more than at least a kind in the group formed: a) organic group, this organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and this organic group to contain carbonatoms be 4 or more and 24 following and oxygen atomicities are more than 1 and 5 below the ring-type ethers; B) 1 valency aliphatics organic group, this 1 valency aliphatics organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aliphatics organic group is 1 or more and 24 following to reach oxygen atomicity be more than 0 and below 5; C) 1 valency aromatic series organic group, this 1 valency aromatic series organic group is the aromatic hydrocarbons unit of non-replacement or replacement, have in case of necessity non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aromatic series organic group is 6 or more and 24 following to reach oxygen atomicity be more than 0 and below 5.On the other hand, R
2Expression is selected from by hydrogen atom and following d independently respectively) organic group more than a kind in the group formed; D) 1 valency organic group, this 1 valency organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and the carbonatoms of this 1 valency organic group is more than 1 and below 8.)
(B) n=1 or 2 and have at least 1 ring-type ether as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure.
(C) n=1 or 2 and have at least 1 aromatic series organic group as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure.
And the mixing index α of the described alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the following general formula (2) is more than 0.001 and below 19.
Mixing index α=(α c)/(α b) ... (2)
(wherein, in the formula (2), α b represents the content (mol%) of described (B) composition, and α c represents the content (mol%) of described (C) composition.)
[manufacturing process 1] is to comprise that following two operations are the manufacture method of the modified resin composition of operation (a) and operation (b).
Operation (a): in the presence of Resins, epoxy (A), will comprise (B) shown in the general formula (1) and alkoxysilane compound containing trialkylsilyl group in molecular structure cohydrolysis (C) at least, thereby make the operation of intermediate by the reflow process of not following dehydration.
Operation (b): the operation of the intermediate dehydration condensation that will make by operation (a).
[manufacturing process 2] is to comprise that following two operations are the manufacture method of the modified resin composition of operation (c) and operation (d).
Operation (c): will comprise (B) shown in the general formula (1) and alkoxysilane compound containing trialkylsilyl group in molecular structure cohydrolysis (C) at least by the reflow process of not following dehydration, thereby make the operation of intermediate.
Operation (d): make the intermediate and Resins, epoxy (A) coexistence of making by operation (c), and the operation of dehydration condensation.
Wherein, describe for the operation of intermediate " thereby make " and " operation of dehydration condensation " by the reflow process cohydrolysis of not following dehydration.
Thereby " making the operation of intermediate by the reflow process cohydrolysis of not following dehydration " is meant, to be used for cohydrolysis and water or solvent from alkoxysilane compound containing trialkylsilyl group in molecular structure that blended water or solvent and reaction produce return reaction soln on one side, Yi Bian the operation of reacting.Reactive mode is not particularly limited, can by a kind in the various reactive modes such as intermittent type, semibatch or continous way or with more than 2 kinds the combination implement.As object lesson, for example, can list following method: cooling tube is installed on reaction vessel top, Yi Bian make water or the solvent refluxing that is generated, Yi Bian the method for reacting; Perhaps, in airtight container, stir on one side and/or circulating reaction solution, Yi Bian the method for reacting; Or the like.
On the other hand, " operation of dehydration condensation " be meant, water or solvent of in the water that added or solvent and above-mentioned " do not follow the reflow process of dehydration " generating removed the on one side operation of carrying out condensation reaction on one side.For example, can make up as a kind in the lower device or with 2 kinds with on carry out: while rotatory evaporator, possess the vertical steel basin that distillates pipe, Surface Renewal type steel basin, thin film evaporation unit, Surface Renewal type twin-screw mixer device, twin screw horizontal agitator, wet wall type reactor, free-falling type porous template reactor, distill the reactor of removing volatile component etc. along the supporter compound that lands.
The modified resin composition of present embodiment can be made by the arbitrary method in above-mentioned [manufacturing process 1] and [manufacturing process 2].The reaction method of the alkoxysilane compound containing trialkylsilyl group in molecular structure when making the modified resin composition of present embodiment is not particularly limited, can disposable in the early stage interpolation and make its reaction, and also can one by one or be added continuously in addition and make its reaction in the reaction system.
In addition,, under the arbitrary situation in [manufacturing process 1] and [manufacturing process 2], both can disposablely add, and also can divide for several times and add one by one about Resins, epoxy (A).
In addition, under situation, can carry out operation (a), operation (b) continuously, carry out operation (b) again after reaction mixture separation that also can in operation (a), obtain or the recovery according to [manufacturing process 1].
On the other hand, under the situation according to [manufacturing process 2], can carry out operation (c), operation (d) continuously, the reaction mixture that also can obtain in operation (c) carries out operation (d) after reclaiming again.
Wherein, Resins, epoxy (A) and alkoxysilane compound containing trialkylsilyl group in molecular structure as using in [manufacturing process 1] and [manufacturing process 2] can list and above-mentioned Resins, epoxy of enumerating (A) and the identical material of alkoxysilane compound containing trialkylsilyl group in molecular structure.
In addition, the preferable range of the mixing index α～γ of the alkoxysilane compound containing trialkylsilyl group in molecular structure in [manufacturing process 1] and [manufacturing process 2] is same as described above.
In [manufacturing process 1] or [manufacturing process 2] of present embodiment, thereby the condensation rate of the intermediate when finishing by the operation that the reflow process cohydrolysis of not following dehydration is made intermediate is preferably more than 78%, more preferably more than 80%, more preferably more than 83%.If the condensation rate of intermediate is lower than 78%, even then through dehydrating condensation operation afterwards, the OH base that derives from silicone in the resin combination of manufacturing also can be more residual, because residual OH base condensation in preservation, can cause the remarkable tackify or the gelation of resin combination, have the tendency that storage stability worsens.
In addition, the condensation rate of the intermediate the when operation of making intermediate about the cohydrolysis in the present embodiment finishes is utilized with respect to contained (OR in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1)
2) (OR in silicone composition mole number (R), that exist in the modified resin composition of base
2) basic mole number (S), represent with the molar percentage shown in the following formula (6).
The condensation rate (%) of alkoxysilane compound containing trialkylsilyl group in molecular structure=[(R-S)/R] * 100 (6)
In the manufacture method of the modified resin composition of present embodiment, the viscosity of the resin from the storage stability of modified resin composition promptly suppresses to preserve, the viewpoint of operability of improving, the condensation rate of alkoxysilane compound containing trialkylsilyl group in molecular structure is preferably more than 80%, more preferably more than 82%, more preferably more than 85%, especially be preferably more than 88%.
In addition, about the condensation rate of the alkoxysilane compound containing trialkylsilyl group in molecular structure of present embodiment, utilize with respect to contained (OR in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1)
2) (OR in silicone composition mole number (U), that exist in the modified resin composition of base
2) basic mole number (V), represent with the molar percentage shown in the following formula (5).
The condensation rate (%) of alkoxysilane compound containing trialkylsilyl group in molecular structure=[(U-V)/U] * 100 (5)
In the manufacture method of the modified resin composition of present embodiment, making the residual alcoxyl base unit weight in the resulting modified resin composition is below 5%.Above under 5% the situation, anti-crackle, cementability during the thermal cycling of the cured article that composition curing is obtained may be insufficient in residual alcoxyl base unit weight.Residual alcoxyl base unit weight in the resulting modified resin composition is preferably below 3%, more preferably below 1%, more preferably below 0.5%, especially is preferably and does not contain residual alkoxyl group fully.
In operation of present embodiment (a) or the operation (c), in order to make the alkoxysilane compound containing trialkylsilyl group in molecular structure hydrolysis, water coexists in reaction system.For adding water, alkoxysilane compound containing trialkylsilyl group in molecular structure be hydrolyzed to main purpose.The interpolation water time is not particularly limited,, can use in the method for reaction disposable interpolation of beginning initial stage, the method for in reaction, adding one by one or the arbitrary method in the continuous method of adding in reaction as long as add between till when thereby the operation to cohydrolysis manufacturing intermediate finishes.Wherein, the preferred method of using in the disposable interpolation of initial reaction stage.
Wherein, the amount to the water that added describes.(OR in amount of the water that is added (mole number) and the above-mentioned formula (1)
2) the ratio of amount (mole number) be defined as the mixing index ε shown in the following formula (7).
Mixing index ε=(ε w)/(ε s) ... (7)
(wherein, in the formula (7), ε w represents the addition (mol number) of water, and on the other hand, ε s represents the (OR in the general formula (1)
2) amount (mol number).)
In the present embodiment, mixing index ε is preferably more than 0.1 and 5 following scopes, more preferably 0.2 or more and 3 following scopes, more preferably more than 0.3 and the scopes below 1.5.If mixing index ε is lower than 0.1, then hydrolysis reaction may not can carry out, if surpass 5, then the storage stability of modified resin composition may reduce.
Above-mentioned operation (a) or operation (c) can be carried out under solvent-free, perhaps also can carry out in solvent.Using under the situation of solvent, so long as can dissolved epoxy and alkoxysilane compound containing trialkylsilyl group in molecular structure and be organic solvent inert with respect to them, then can use known solvent.
As employed solvent, can list dme, diethyl ether, diisopropyl ether, 1,4-diox, 1, ether series solvents such as 3-diox, tetrahydrofuran (THF), glycol dimethyl ether, ethylene glycol diethyl ether, Propylene Glycol Dimethyl Ether, propylene glycol monomethyl ether, methyl-phenoxide; Ketone series solvents such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK); Aliphatic hydrocarbon series solvents such as hexane, hexanaphthene, heptane, octane, octane-iso; Aromatic hydrocarbons series solvents such as toluene, o-Xylol, m-xylene, p-Xylol, ethylbenzene; Ester such as ethyl acetate, butylacetate series solvent; Pure series solvents such as methyl alcohol, ethanol, butanols, Virahol, propyl carbinol, ethylene glycol butyl ether, diethylene glycol monobutyl ether etc.These solvents can use a kind or use as the mixture more than 2 kinds.Wherein, the viewpoint of the open loop of the epoxy group(ing) from inhibited reaction, be preferably ether series solvent, ketone series solvent, aliphatic hydrocarbon series solvent, aromatic hydrocarbons series solvent, the solvent that more preferably contains the above ether series solvent of 50 quality %, more preferably be selected from by 1, the mixed solvent more than at least a kind or 2 kinds in the group that 4-diox, tetrahydrofuran (THF), glycol dimethyl ether, Propylene Glycol Dimethyl Ether are formed especially is preferably 1,4-diox, tetrahydrofuran (THF).
Addition about solvent, under the situation of operation (a), thereby the Resins, epoxy (A) that is added till when finishing and the total mass of alkoxysilane compound containing trialkylsilyl group in molecular structure to the operation of making intermediate by the reflow process cohydrolysis of not following dehydration, on the other hand, under the situation of operation (c), thereby the total mass of the alkoxysilane compound containing trialkylsilyl group in molecular structure that is added till when finishing to the operation of making intermediate by the reflow process cohydrolysis of not following dehydration, be preferably 0.01～20 times of amount, more preferably 0.02～15 times of amount, more preferably 0.03～10 times of amount.By the addition of solvent, can control the molecular weight of the resin combination of present embodiment, thereby be above-mentioned scope by the addition that makes solvent, have the tendency of the resin combination that obtains the molecular weight that is fit to and then proper viscosity.
Temperature of reaction in operation (a) or the operation (c) is generally more than 0 ℃ and the scope below 200 ℃.If temperature of reaction is lower than 0 ℃, then water may solidify.On the other hand, if surpass 200 ℃, then resin combination may be painted.From improving speed of response, suppressing the viewpoint of modification of the resins such as open loop of epoxy group(ing), temperature of reaction is preferably more than 20 ℃ and the scope below 150 ℃, more preferably more than 40 ℃ and the scope below 120 ℃, more preferably more than 50 ℃ and the scope below 100 ℃.Temperature of reaction needn't be steady state value as long as in above-mentioned scope, can change in the reaction.
Reaction times about operation (a) or operation (c) is not particularly limited, but (the OR from improve above-mentioned formula (1)
2) reactivity and the viewpoint that suppresses the modification of resin set out, be preferably more than 0.1 hour and be lower than 100 hours scope, more preferably more than 1 hour and be lower than 80 hours scope, more preferably more than 3 hours and be lower than 60 hours scope, especially be preferably more than 5 hours and be lower than 50 hours scope.
On the other hand, the temperature of reaction of operation (b) or operation (d) is generally more than 0 ℃ and the scope below 200 ℃.If temperature of reaction is lower than 0 ℃, the situation that speed of response reduces, the reaction times increases then may appear, if surpass 200 ℃, then resin combination may be painted.From improving speed of response, suppressing the viewpoint of modification of the resins such as open loop of epoxy group(ing), temperature of reaction is preferably more than 20 ℃ and the scope below 150 ℃, more preferably more than 40 ℃ and the scope below 120 ℃, more preferably more than 50 ℃ and the scope below 100 ℃.Temperature of reaction needn't be steady state value as long as in above-mentioned scope, can change in initial reaction stage or reaction way.
About the reaction times of operation (b) or operation (d), be not particularly limited, but from improving reactivity and suppressing the viewpoint of the modification of resin, be preferably more than 0.1 hour and be lower than 100 hours scope, more preferably more than 0.5 hour and be lower than 80 hours scope, more preferably more than 1 hour and be lower than 50 hours scope, especially be preferably more than 3 hours and be lower than 50 hours scope.
The modified resin composition of present embodiment can be made in rare gas elementes such as nitrogen, helium, neon, argon gas, krypton gas, xenon, carbonic acid gas or rudimentary stable hydrocarbon or air.In these gases, viewpoint from the modification that suppresses resin, be preferably rare gas elementes such as nitrogen, helium, neon, argon gas, krypton gas, xenon, carbonic acid gas or rudimentary stable hydrocarbon, more preferably nitrogen, helium, neon, argon gas, krypton gas, xenon, carbonic acid gas, more preferably nitrogen, helium especially are preferably nitrogen.
Make operation (a)～operation (d) of the modified resin composition of present embodiment, can under the circulation under the atmosphere of above-mentioned gas, at above-mentioned gas, under the decompression, add depress or their combination under carry out.In addition, pressure needn't be steady state value, can change in the reaction.
Wherein, operation (a) and operation (c) blended water or solvent and reaction generate owing to need to be used for cohydrolysis water or solvent from alkoxysilane compound containing trialkylsilyl group in molecular structure turn back in the reaction soln, react on one side in industrial easy mode on one side, thereby preferred under the normal atmosphere atmosphere of above-mentioned gas and/or add to depress and carry out.
On the other hand, operation (b) and operation (d) are owing to need on one side the water or the solvent that generate in operation (a) or the middle water that adds of operation (c) or solvent and above-mentioned " not following the reflow process of dehydration " to be removed, carry out condensation reaction on one side, thereby preferably carrying out under the rare gas element circulation and/or under the decompression.
In the present embodiment, when the cohydrolysis of above-mentioned (A) Resins, epoxy and alkoxysilane compound containing trialkylsilyl group in molecular structure, can add the hydrolytic condensation catalyzer and carry out.
The hydrolytic condensation catalyzer is so long as the catalyzer of known in the past promotion hydrolysis-condensation reaction, then be not particularly limited, for example, can list metal (lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, barium, strontium, zinc, aluminium, titanium, cobalt, germanium, tin, plumbous, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth etc.), organo-metallic (lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, barium, strontium, zinc, aluminium, titanium, cobalt, germanium, tin, plumbous, antimony, arsenic, cerium, boron, cadmium, manganese, the organic oxygen compound of bismuth etc., organic acid salt, Organohalogen compounds, alkoxide etc.), mineral alkali (magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus etc.), organic bases (ammonia, Tetramethylammonium hydroxide etc.) etc.
In the above-mentioned organo-metallic, be preferably organotin.Organotin is meant that bonding on the tin atom has the material of at least one organic group, as structure, can list single organotin, two organotins, three organotins, four organotins etc.As organotin, for example, can list tin tetrachloride, monobutyl-tin-trichloride, Mono-n-butyltin, single octyl group tin trichloride, four n-octyl tin, tetra-n-butyl tin, Dibutyltin oxide, dibutyltin diacetate, two sad dibutyl tins, two tertiary monocarboxylic acid dibutyl tins, dibutyl tin laurate, the oxidation dibutyl tin laurate, the stearic acid dibutyl tin, two oleic acid dibutyl tins, dibutyl tin ethyl silicon (the plain エ チ of ケ イ Le) reactant, the compound of dibutyl pink salt and silicate, the compound of dioctyl pink salt and silicate, two (acetopyruvic acid) dibutyl tin, two (ethyl toxilic acid) dibutyl tin, two (butyl toxilic acid) dibutyl tin, two (2-ethylhexyl toxilic acid) dibutyl tin, two (benzyl toxilic acid) dibutyl tin, two (stearyl toxilic acid) dibutyl tin, two (oleyl toxilic acid) dibutyl tin, the toxilic acid dibutyl tin, two (O-phenyl phenoxy group) dibutyl tin, two (2-ethylhexyl Thiovanic acid) dibutyl tin, two (2-ethylhexyl thiohydracrylic acid) dibutyl tin, two (different nonyl 3-thiohydracrylic acid) dibutyl tin, two (iso-octyl Thiovanic acid) dibutyl tin, two (3-thiohydracrylic acid) dibutyl tin, dioctyl tin oxide, two lauric acid dioctyl tins, the oxalic acid dioctyl tin, two sad dioctyl tins, dilauryl sulfydryl dioctyl tin, the tertiary monocarboxylic acid dioctyl tin, distearyl acid dioctyl tin, two (ethyl toxilic acid) dioctyl tin, two (octyl group toxilic acid) dioctyl tin, dioctyl tin maleate, two (iso-octyl Thiovanic acid) dioctyl tin, two (2-ethylhexyl Thiovanic acid) dioctyl tin, dibutyl dimethoxy tin, dibutyl diethoxy tin, dibutyl dipropoxy tin, dioctyl dimethoxy tin, dioctyl diethoxy tin, dioctyl dipropoxy tin, stannous octoate, stearic acid tin etc.
In addition, in the above-mentioned organo-metallic, the alkali that is shown as alkalescence under part free situation is that organo-metallic is fit to.By use alkali be organo-metallic as the hydrolytic condensation catalyzer, the tendency that exists the storage stability of the modified resin composition of present embodiment to become good.In addition, be organo-metallic by using alkali, there is the tendency that accelerates of condensation reaction, thereby is to be very useful under the situation of the resin combination more than 78% in the condensation rate that obtains intermediate.
Alkali is in the organo-metallic, and being preferably alkali is organotin, and especially being preferably alkoxide is organotin.As alkoxide is organotin, for example, can list dibutyl dimethoxy tin, dibutyl diethoxy tin, dibutyl dipropoxy tin, dioctyl dimethoxy tin, dioctyl diethoxy tin, dioctyl dipropoxy tin etc.
Relative therewith, if use under part free situation, be shown as tart acid be organo-metallic as the hydrolytic condensation catalyzer, then hydrolysis reaction carries out rapidly, but exists condensation reaction to be difficult to the tendency of carrying out, thereby not preferred in actual applications.
The said hydrolyzed condensation catalyst may be used alone, or two or more kinds may be used in combination.For example, can be that organotin is used in combination with organic acid tin and alkali, also can make its reaction with organic acid salts such as tin after, handle with mineral alkali.As the mineral alkali under this situation, be preferably the oxyhydroxide of polyvalent cations such as magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta.
The addition of said hydrolyzed condensation catalyst is not particularly limited, and preferred addition is by with respect to (the OR in the above-mentioned formula (1)
2) ratio be that following mixing index δ tries to achieve.
Mixing index δ is represented by following formula (8).
Mixing index δ=(δ e)/(δ s) ... (8)
(wherein, in the formula (8), δ e represents the addition (mol number) of hydrolytic condensation catalyzer, and δ s represents the (OR in the above-mentioned formula (1)
2) amount (mol number).)
Mixing index δ is preferably more than 0.0005 and 5 following scopes, more preferably 0.001 or more and 1 following scope, more preferably more than 0.005 and the scope below 0.5.
According to the composition of modified resin composition, if mixing index δ is lower than 0.0005, then may be difficult to obtain the facilitation effect of hydrolytic condensation, if surpass 5, the open loop that the ring-type ether then may occur is promoted or is caused the situation of the deterioration of storage stability.
The modified resin composition of present embodiment has good storage stability, and for forming the modified resin composition of cured article with the anti-crackle in the excellent transparency, thermotolerance, heat-resisting discolouration, photostabilization, the thermal cycling, owing to form cured article by heat or energy-ray, thereby can be suitable as material resin compositions uses such as encapsulating luminescent element material, optics lens, photoresist, fluorescence resin, electroconductive resin, insulative resin.
In addition, can also mix oxetane compound (D), fluor (E), conductive metal powder (F), insulativity powder (G), Resins, epoxy (A '), solidifying agent (H), curing catalyst (I), light acid producing agent (J) and cationic polymerisation catalyst as required, properties-correcting agent, vinyl ether compound, organic resin, silane coupling agent except that Resins, epoxy (A ') in the modified resin composition of present embodiment.
The resin combination that further adding oxetane compound (D) in the modified resin composition of present embodiment is formed describes.
Oxetane compound (D) is so long as contain the compound of trimethylene oxide ring, then be not particularly limited, for example, can list 3-ethyl-3-hydroxymethyl trimethylene oxide, 3-ethyl-3-(2-ethyl hexyl oxy methyl) trimethylene oxide, two (3-ethyl-3-trimethylene oxide ylmethyl) ether, 3-ethyl-3-(phenoxymethyl) trimethylene oxide, 3-ethyl-3-(2,3-glycidoxy methyl) trimethylene oxide etc.By mixing these oxetane compounds, have the tendency that polymerization velocity increases, have the tendency of the viscosity reduction of composition in addition.
The representative example of oxetane compound below is shown.
Chemical formula 5
The combined amount of above-mentioned oxetane compound is not particularly limited, and preferably with resin combination: the mass ratio of oxetane compound=20: 80～95: 5 (adding up to 100) mixes.More preferably 40: 60～80: 20.If the mixture ratio of resin combination is lower than 20, then curing reaction possibly can't normally carry out, if surpass 95, then the cementability of cured article may variation.
In addition, in order to improve the consistency of resin combination and oxetane compound, what carry out usually is, select suitable combination, for example, for Resins, epoxy with bis-phenol skeleton resin combination as raw material, combination has the oxetane compound of aromatic nucleus, or the like.
The fluorescence resin combination that further adding fluor (E) in the modified resin composition of present embodiment is formed describes.
Fluor in the present embodiment (E) so long as send the material of fluorescence, promptly absorb the energy of electron rays, X ray, ultraviolet ray, electric field etc. and with the part of the energy that absorbed than the material of emitting (luminous) in higher efficiency as visible rays, then be not particularly limited, no matter inorganic system, organic system all can adopt.Wherein, be preferably demonstrate usually excellent luminiferous inorganic be fluor.
Can use in the present embodiment inorganic be that the size of fluor is not particularly limited, usually, use the powder of particle diameter 1～tens of μ m.In addition, be the performance of fluor in order to manifest inorganic, use the material that in being called as the compd A of parent, has imported the element B that is called as activator (luminescence center) usually, be designated as " parent A: activator B " usually.
Especially, using under the situation of fluorescence resin combination as the sealing material of LED, owing to reason described later, the preferred use by cerium activatory yttrium aluminate fluor (YAG:Ce fluor), as under the situation of light-storing material, preferably use light storing phosphor.They may be used alone, or two or more kinds may be used in combination.
About the combined amount of fluor, by quality ratio, be preferably resin combination: fluor=30: 70～95: 5, more preferably 50: 50～80: 20 (adding up to 100).If the combined amount of fluor is more than resin combination: fluor=30: 70, then the flowability as the fluorescence resin combination may worsen, if be less than 95: 5, then may be insufficient as the function of fluor.
Above-mentioned parent A and activator B are not particularly limited, and for example, as parent A, can list oxide phosphor or nitride phosphor.As activator B, for example, can list europium (Eu), cerium rare earth elements such as (Ce) in addition.
As above-mentioned oxide phosphor, for example, be well known that parent A is that yttrium aluminate (Y3Al5O12: below, be called YAG), activator B are " the YAG:Ce fluor " of cerium (Ce).If it is carried out near blue light irradiation (460nm), then produces Yellow luminous efficiently.This fluor passes through to substitute with other Gd or Tb etc. the part of the Y of " Y3Al5O12 ", or with the part of substitute for Al such as Ga, thereby change the structure of parent A, can make the glow peak position displacement to long wavelength side or short wavelength side thus, thereby be very useful.
That is, " YAG:Ce fluor " thereby so long as described parent A be YAG or with other a Gd or the part of alternative Y such as Tb or be the fluor of Ce with structure and activator B that the part of substitute for Al such as Ga has changed parent A, then be not particularly limited.As its object lesson, for example, can list " Y3Al5O12:Ce3+ " or " (Y3, Gd0.9) Al5O12:Ce3+ " etc.
In addition, as the example of oxide phosphor, known " (Sr, Ba) 2SiO4:Eu fluor ", the parent A of this fluor is strontium silicate barium (Sr, Ba) 2SiO4, and imported europium (Eu) as activator B.In this system,, illuminant colour can be adjusted to green～orange by changing the ratio of components of Sr and Ba.
As above-mentioned nitride phosphor, for example, can following fluor be shown example.
α-SiAlON fluor: the crystallization that parent A forms for metal ion, aluminium and oxygen such as solid solution Ca in the alpha-form si nitride crystallization, by " (Mp (Si, and Al) 12 (O, N) 16 " expression.Wherein, M represents metal ion, and p represents solid solution capacity.Particularly can list " Cap (Si, Al) 12 (O, N) 16:Eu " etc.
β-SiAlON fluor: parent A by solid solution aluminium and oxygen in β type crystalline silicon nitride form form " Si6-qALqOqN8-q " expression.Wherein, q represents solid solution capacity.Particularly can list " Si6-qALqOqN8-q:Eu " etc.
The CaAlSiN3 fluor: parent A makes CaCl2, aluminium nitride and silicon nitride react the crystal of nitride that obtains under 1800 ℃ high temperature, particularly can list " CaAlSiN3:Eu " etc.
As inorganic be the object lesson of fluor, for example, fluor as illuminant colour with red colour system, can list " 6MgOAs2O5:Mn4+; Y (PV) O4:Eu ", " CaLa0.1Eu0.9Ga3O7 ", " BaY0.9Sm0.1Ga3O7 ", " Ca (Y0.5Eu0.5) is 3O7 (Ga0.5In0.5) ", " Y3O3:Eu, YVO4:Eu ", " Y2O2:Eu ", " 3.5MgO0.5MgF2GeO2:Mn4+ ", " (YCd) BO2:Eu " etc.
Fluor as illuminant colour with blue system, for example, can list " (Ba; Ca; Mg) 5 (PO4) 3Cl:Eu2+ ", " (Ba; Mg) 2Al16O27:Eu2+ ", " Ba3MgSi2O8:Eu2+ ", " BaMg2Al16O27:Eu2+ ", " (Sr; Ca) 10 (PO4) 6Cl2:Eu2+ ", " (Sr; Ca) 10 (PO4) 6Cl2nB2O3:Eu2+ ", " Sr10 (PO4) 6Cl2:Eu2+ ", " (Sr; Ba; Ca) 5 (PO4) 3Cl:Eu2+ ", " Sr2P2O7:Eu ", " Sr5 (PO4) 3Cl:Eu ", " (Sr; Ca; Ba) 3 (PO4) 6Cl:Eu ", " SrOP2O5B2O5:Eu ", " (BaCa) 5 (PO4) 3Cl:Eu ", " SrLa0.95Tm0.05Ga3O7 ", " ZnS:Ag ", " GaWO4 ", " Y2SiO6:Ce ", " ZnS:Ag; Ga; Cl ", " Ca2B4OCl:Eu2+ ", " BaMgAl4O3:Eu2+ ", " (M1, Eu) 10 (PO4) 6Cl2 (M1 is for being selected from by Mg; Ca; Sr; reach at least a kind of element in the group that Ba formed) " etc.
Fluor as illuminant colour with green system, for example, can list " Y3Al5O12:Ce3+ (YAG) ", " Y2SiO5:Ce3+; Tb3+ ", " Sr2Si3O82SrCl2:Eu ", " BaMg2Al16O27:Eu2+; Mn2+ ", " ZnSiO4:Mn ", " Zn2SiO4:Mn ", " LaPO4:Tb ", " SrAl2O4:Eu ", " SrLa0.2Tb0.8Ga3O7 ", " CaY0.9Pr0.1Ga3O7 ", " ZnGd0.8Ho0.2Ga3O7 ", " SrLa0.6Tb0.4Al3O7 ", " ZnS:Cu; Al ", " (Zn; Cd) S:Cu; Al ", " ZnS:Cu; Au; Al ", " Zn2SiO4:Mn ", " ZnSiO4:Mn ", " ZnS:Ag; Cu ", " (ZnCd) S:Cu ", " ZnS:Cu ", " GdOS:Tb ", " LaOS:Tb ", " YSiO4:CeTb ", " ZnGeO4:Mn ", " GeMgAlO:Tb ", " SrGaS:Eu2+ ", " ZnS:CuCo ", " MgOnB2O3:Ge; Tb ", " LaOBr:Tb, Tm ", " La2O2S:Tb " etc.
In addition, also can list " YVO4:Dy " of illuminant colour or have " CaLu0.5Dy0.5Ga3O7 " etc. of the illuminant colour of yellow system with white color system.
Object lesson as above-mentioned organic system fluor, for example, can list and have 1 of the blue illuminant colour that is, two (2-methyl styrene base) benzene (Bis-MSB), trans-4 of 4-, 4 '-phenylbenzene stilbene stilbenes such as (DPS) is a pigment, 7-hydroxy-4-methylcoumarin coumarin series pigments such as (tonka bean camphors 4) etc.
As the fluor of the fluorescence color with yellow system～green system, commercially available product for example can list Brilliant sulfoflavine FF, Basic yellow HG, SINLOIHI COLOR FZ-5005 (SINLOIHI corporate system) etc.
As the fluor of the fluorescence color with yellow system～red colour system, commercially available product for example can list Eosine, Rhodamine6G, RhodamineB etc.
Common fluor is if blocking irradiation excitaton source is light or electron rays etc., then luminously decays immediately and disappears.Yet by way of exception, have after excitaton source blocking, demonstrate the several seconds～tens of hours the fluor of twilight sunset, it is called light storing phosphor.So long as demonstrate the fluor of this character, then its kind is not particularly limited, particularly, for example, can list " CaS:Eu; Tm ", " CaS:Bi ", " CaAl2O4:Eu; Nd ", " CaSrS:Bi ", " Sr2MgSi2O7:Eu, Dy ", " Sr4Al14O25:Eu, Dy ", " SrAl2O4:Eu; Dy ", " SrAl2O4:Eu ", " ZnS:Cu ", " ZnS:Cu; Co ", " Y2O2S:Eu, Mg, Ti ", " CaS:Eu; Tm " etc., wherein, be preferably " Sr2MgSi2O7:Eu, the Dy " that demonstrates steady persistence, " Sr4Al14O25:Eu; Dy ", " SrAl2O4:Eu, Dy ", " SrAl2O4:Eu ".
The manufacture method of the fluorescence resin combination of present embodiment is not particularly limited, for example, can following method be shown example: with modified resin composition and fluor heating on one side as required at the same time or separately, Yi Bian utilize mixing device stirring described later, mixing, dispersive method; Perhaps, then preceding method further under reduced pressure carries out the method for deaeration processing etc. as required.Solidifying agent described later in addition, curing catalyst, polymerization starter, additive etc. can suitably add in above-mentioned arbitrary operation.
Above-mentioned mixing device is not particularly limited, and for example, can list mixing and kneading machine, triple-roller mill, ball mill, planetary stirring machine, pipeline stirrer, homogenizer, homogeneous dispersion machine etc.
The conductive resin composition that further adding conductive metal powder (F) in the modified resin composition of present embodiment is formed describes.
The conductive metal powder (F) that can use in the present embodiment so long as contain silver metal powder, then be not particularly limited, be not limited only to silver powder, also can be surface attachment or be coated with silver metal powder.Metal powder described here for example can list the powder of metallic element aluminium, silicon, boron, carbon, magnesium, nickel, copper, graphite, gold, palladium and metal oxide thereof or metal nitride etc.Among above-mentioned,, be preferably aluminium, nickel, gold, palladium from the viewpoint of electroconductibility.
As above-mentioned metal oxide, and the object lesson of metal nitride, can list the oxide compound etc. of composition metal of oxide compound, aluminium and the magnesium of the composition metal of aluminum oxide, magnesium oxide, aluminium nitride, boron nitride, silicon nitride, fused silica, crystalline silica, Magnesium Silicate q-agent, aluminium and silicon.
The conductive metal powder can be to have carried out surface coated conductive metal powder with polymine, Polyvinylpyrolidone (PVP), polyacrylic acid, carboxymethyl cellulose, polyvinyl alcohol, polymers such as multipolymer with polyethyleneimine: amine moiety and polyethylene oxide part.By coating, has the tendency that the dispersiveness in resin combination becomes good with these polymers.
Because silver is the element with lower volume specific resistance, and the electroconductibility of metal powder with compare more low its condition of surface etc. that depends on as the carrier of its nuclear, even if thereby the particle integral body of conductive metal powder be not silver, its surface attachment or be coated with silver metal powder also can use.
The shape of above-mentioned silver powder is not particularly limited, and for example, can list flakey, spherical, tree-shaped etc.
About lepidiod silver powder, more, the excellent electric conductivity in the contact of silver powder because its orientation demonstrates thixotropy when making conductive resin composition, thereby has the tendency of operability excellence.On the contrary, when being used for accurate member, may produce the bad problem that is electrically connected owing to its orientation.In addition, its size is not particularly limited, and as the median size of trying to achieve by laser diffraction formula particle size distribution device, is preferably below the 50 μ m, more preferably 1～20 μ m.By adopting described median size, even also can reduce to produce being electrically connected bad possibility, thereby be preferred under the situation of accurate electronic unit class etc. being used for.
Globular silver powder is not owing to have an orientation basically, thereby is difficult to produce the problem of electrical connection, but owing to be the some contact between the particle, thereby have the relatively poor tendency of electroconductibility.In addition, its size is not particularly limited, and as above-mentioned median size, is preferably below the 20 μ m, more preferably below the 5 μ m.If median size surpasses 20 μ m, the tendency that then exists electroconductibility to reduce.In addition, fill up this hole, thereby realize electroconductibility, under the situation about using, also preferably select the following silver powder of 5 μ m with this purpose by share with lepidiod silver powder.
The specific surface area of tree-shaped silver powder is big, excellent electric conductivity, but the instability quality situation may occur owing to its special shape.Its size is not particularly limited, and as above-mentioned median size, is preferably below the 30 μ m, more preferably below the 5 μ m.By adopting described median size, have the excellent tendency of processing (Ha Application De リ Application グ), thereby be preferred.
In the present embodiment,, preferably share difform silver powder in view of these character according to purpose or purposes.
In addition, the conductive metal powder is 60～85 quality % with respect to the preferred combined amount of resin combination, more preferably 70～80 quality %.By making combined amount is more than the 60 quality %, has the excellent more tendency of electroconductibility, is below the 85 quality % by making combined amount, has the tendency that can prevent the seepage phenomenon.
The insulating resin composition that further adding insulativity powder (G) in the modified resin composition of present embodiment is formed describes.
Object lesson as the insulativity powder (G) that can use in the present embodiment can list non-oxide ceramics powder such as charcoal, norbide, boron nitride, aluminium nitride, titanium nitride; The powder of the oxide compound of beryllium, magnesium, aluminium, titanium etc.; Silicon oxide, silicon nitride, fused silica, crystalline silica, other siliceous fillers; The oxide compound of the composition metal of the oxide compound of the composition metal of Magnesium Silicate q-agent, aluminium and silicon, aluminium and magnesium; The powder of white mica, phlogopite, micanite, saponite, aluminum oxide, soda glass, borosilicate glass, silica glass, timber etc.; The toners of silicon rubber, Teflon (registered trademark) etc. etc., they can use separately or multiple mixing is used.Among above-mentioned, the viewpoint from the easiness of insulativity and acquisition is preferably silicon oxide, silicon nitride, fused silica, crystalline silica, other siliceous fillers.
The insulativity powder can be to have carried out surface coated insulativity powder with silane compound or polymine, Polyvinylpyrolidone (PVP), polyacrylic acid, carboxymethyl cellulose, polyvinyl alcohol, polymers such as multipolymer with polyethyleneimine: amine moiety and polyethylene oxide part.By coating, has the tendency that the dispersiveness in resin combination becomes good with these polymers.
In addition, the insulativity powder is 5～50 quality % with respect to the preferred combined amount of resin combination, more preferably 10～30 quality %.By making combined amount is more than the 5 quality %, has the excellent more tendency of insulativity, is below the 50 quality % by making combined amount, utilizes the stress relaxation effect and has the tendency that the reliability of semiconductor device improves.
In the modified resin composition of present embodiment, certainly also can further mix Resins, epoxy the Resins, epoxy contained in the modified resin composition of present embodiment (A) (A ').In addition, the organic resin as except that Resins, epoxy (A ') can also mix organic resins such as silicone resin, acrylic resin, urea resin, imide resin.
Can also further add solidifying agent (H) and/or curing catalyst (I) in the modified resin composition of present embodiment and make curable resin composition.
Solidifying agent (H) then is not particularly limited so long as be used to make the resin combination solidified material.
As solidifying agent, for example, can use acid anhydrides based compound, amine compound, acid amides based compound, phenol based compound etc., especially be preferably acid anhydrides based compounds such as aromatic anhydride, annular aliphatic acid anhydrides, aliphatic anhydride, more elect carboxylic acid anhydride as.
In addition, comprise the ester ring type acid anhydrides in the acid anhydrides based compound, in carboxylic acid anhydride, be preferably the ester ring type carboxylic acid anhydride.These cured articles may be used alone, or two or more kinds may be used in combination.
Object lesson as solidifying agent, can list Tetra hydro Phthalic anhydride, succinyl oxide, trimellitic acid 1,2-anhydride, pyromellitic acid anhydride, maleic anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, the methyl carbic anhydride, hexahydro phthalic anhydride, methyl hexahydro phthalic anhydride, norcamphane-2, the 3-dicarboxylic anhydride, methyl norcamphane-2, the 3-dicarboxylic anhydride, diaminodiphenyl-methane, diethylenetriamine, Triethylenetetramine (TETA), diamino diphenyl sulfone, isophorone diamine, the dicyano diamide, tetren, dimethyl benzyl amine, ketimine compound, by linolenic 2 aggressiveness and quadrol synthetic polyamide resin, bisphenols, phenol (phenol, alkyl substituted phenol, naphthols, alkyl-substituted naphthaline phenol, dihydroxy-benzene, dihydroxy naphthlene etc.) and the polycondensate of various aldehyde, the polymkeric substance of phenol and various diolefins, the polycondensate of phenol and aromatic series dihydroxymethyl compound, or the condenses of bi-methoxy methyl diphenyl and aphthols or phenol etc., biphenyl phenols and their modifier, imidazoles, boron trifluoride-amine inner complex, guanidine derivative etc.
Object lesson as the ester ring type carboxylic acid anhydride, can list 1,2,3,6-Tetra Hydro Phthalic Anhydride, 3,4,5,6-Tetra Hydro Phthalic Anhydride, hexahydro phthalic anhydride, " 4-methyl hexahydro phthalic anhydride/hexahydro phthalic anhydride=70/30 ", 4-methyl hexahydro phthalic anhydride, " methyl bicycle [2.2.1] heptane-2,3-dicarboxylic anhydride/dicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride " etc.
In these solidifying agent (H), owing to there being the tendency of the modified resin composition of present embodiment being solidified the photostabilization raising of the cured article that obtains, thereby more preferably the ester ring type anhydrides, in 1 molecule, have contain acid anhydrides more than 2 functional group as substituent silicone, more preferably methyl hexahydro phthalic anhydride, hexahydro phthalic anhydride, norcamphane-2,3-dicarboxylic anhydride, methyl norcamphane-2, the 3-dicarboxylic anhydride.These solidifying agent can use a kind or use as the mixture more than 2 kinds.
The addition of solidifying agent (H) by with respect to above-mentioned Resins, epoxy, and alkoxysilane compound containing trialkylsilyl group in molecular structure in the ratio of contained ring-type ether be that mixing index ζ tries to achieve.Mixing index ζ is represented by following formula (9).
Mixing index ζ=(ζ f/ (ζ k) ... (9)
(wherein, in the formula (9), ζ f represents the addition (mol number) of solidifying agent (H), ζ k representative ring epoxy resins, and alkoxysilane compound containing trialkylsilyl group in molecular structure in the amount (mol number) of contained ring-type ether.)
Mixing index ζ is preferably more than 0.1 and 1.5 following scopes, more preferably 0.2 or more and 1.3 following scopes, more preferably more than 0.3 and the scopes below 1.3.If mixing index ζ is lower than 0.1, then curing speed may reduce, if surpass 1.5, then the wet fastness as cured article may worsen.
Curing catalyst (I) is meant the curing catalysts that is used to promote curing reaction.As curing catalyst, be preferably tertiary amines and salt thereof.As the object lesson of curing catalyst, can list following material.
Tertiary amines: benzyl dimethyl amine, 2,4,6-three (dimethylaminomethyl) phenol, cyclohexyl dimethyl amine, trolamine etc.
Imidazoles: glyoxal ethyline, 2-n-heptyl imidazoles, 2-n-undecane base imidazoles, the 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-benzyl-2-phenylimidazole, 1, the 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyano ethyl)-glyoxal ethyline, 1-(2-cyano ethyl)-2-n-undecane base imidazoles, 1-(2-cyano ethyl)-2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazoles, 2-phenyl-4,5-two (hydroxymethyl) imidazoles, 1-(2-cyano ethyl)-2-phenyl-4,5-two ((2 '-cyano group oxyethyl group) methyl) imidazoles, 1-(2-cyano ethyl)-2-n-undecane base imidazoles trimellitate, 1-(2-cyano ethyl)-2-phenylimidazole trimellitate, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole trimellitate, 2,4-diamino-6-(2 '-methylimidazolyl-(1 ')) ethyl-s-triazine, 2,4-diamino-6-(2 '-n-undecane base imidazolyl) ethyl-s-triazine, 2,4-diamino-6-(2 '-ethyl-4 '-methylimidazolyl-(1 ')) ethyl-s-triazine, the isocyanuric acid affixture of glyoxal ethyline, the isocyanuric acid affixture of 2-phenylimidazole etc.
Organophosphorus based compound: diphenylphosphine, triphenylphosphine, triphenyl phosphite etc.
Quaternary phosphine salt: benzyl base triphenyl phosphonium chloride, four-normal-butyl bromination Phosphonium, first base three phenyl phosphonium bromides, ethyl triphenyl phosphonium bromide, normal-butyl three phenyl phosphonium bromides, 4-phenyl phosphonium bromide, ethyl triphenyl phosphonium iodide, second base triphenyl phosphonium acetate, four-positive fourth base Phosphonium-o, o-diethyl phosphorothioate, four-positive fourth base Phosphonium benzotriazole, four-positive fourth base Phosphonium a tetrafluoro borate, four-positive fourth base Phosphonium tetraphenyl borate salts, tetraphenylphosphoniphenolate tetraphenyl borate salts etc.
The Diazabicycloalkene class: 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene and organic acid salt thereof etc.
Organometallic compound: zinc octoate, stannous octoate (ア Network チ Le acid Tin), methyl ethyl diketone aluminum chelate etc.
Quaternary ammonium salt: tetraethylammonium bromide, tetra-n-butyl ammonium bromide etc.
Metal halide: boron compounds such as boron trifluoride, triphenyl borate; Zinc chloride, tin tetrachloride etc.
The addition of curing catalyst (I) by with respect to above-mentioned Resins, epoxy, and the ratio of the quality of alkoxysilane compound containing trialkylsilyl group in molecular structure be that following mixing index η tries to achieve.Mixing index η is represented by following formula (10).
Mixing index η=(η g)/(η k) ... (10)
(wherein, in the formula (10), η g represents the quality (g) of curing catalyst (I), the quality (g) of η k representative ring epoxy resins and alkoxysilane compound containing trialkylsilyl group in molecular structure.)
Mixing index η is preferably more than 0.01 and 5 following scopes, more preferably 0.05 or more and 3 following scopes, more preferably more than 0.1 and the scope below 1.If mixing index η is lower than 0.01, then solidify and may well carry out, as surpassing 5, then cured article may be painted.
The photosensitive polymer combination that further adding light acid producing agent (J) in the modified resin composition of present embodiment is formed describes.
As the light acid producing agent that can use in the present embodiment (J), so long as emit the compound of acid and initiated polymerization during irradiates light, then be not particularly limited, wherein be preferably salt.As object lesson, for example, can list diazonium salt, salt compounded of iodine, sulfosalt etc., they be cationic moiety by aromatic series diazonium, aromatic series iodine, aromatic series sulphur, anionicsite by BF4
-, PF6
-, SbF6
-, [BX4]
-(wherein, X serve as reasons the phenyl that at least 2 above fluorine or trifluoromethyl replace) waits the salt of formation.The representative example of light acid producing agent below is shown.
Chemical formula 6
Wherein, R, R ', R " represent substituting group arbitrarily.
As example more specifically, can list the aryl diazonium salts of tetrafluoride boron, the triaryl sulfonium salts of phosphorus hexafluoride, the diaryl group iodized salt of phosphorus hexafluoride, three fragrant basic phosphonium salts of antimony hexafluoride, the diaryl group iodized salt of antimony hexafluoride, three-4-aminomethyl phenyl sulfosalt of arsenic hexafluoride, three-4-aminomethyl phenyl sulfosalt of tetrafluoride antimony, four (pentafluorophenyl group) boric acid triaryl sulfonium salts, four (pentafluorophenyl group) boric acid diaryl group iodized salt, aluminium acetylacetonate salt and adjacent nitrobenzyl silyl ether mixture, phenyl thiopyridines salt, phosphorus hexafluoride propadiene-iron chelate etc.As commercially available product, can list CD-1012 (SARTOMER corporate system), PCI-019, PCI-021 (Nippon Kayaku K. K's system), Optomer SP-150, Optomer SP-170 (ADEKA CORPORATION system), UVI-6990, UVI-6974 (Dow Chemical corporate system), CPI-100P, CPI-100A, CPI-100L (San-Apro Ltd. system), TEPBI-S (Nippon Shokubai Co., Ltd's system), Rhodorsil2074 (Rhodia corporate system) etc.They may be used alone, or two or more kinds may be used in combination.Among above-mentioned, the painted less viewpoint from cured article is preferably sulfosalt and salt compounded of iodine, and then considers solidified nature, especially is preferably sulfosalt.
In addition, as required can also mixed ethylene base ether compound class in the above-mentioned photosensitive polymer combination.As these compounds, for example, can list the not vinyl ether compound of hydroxyl.Particularly, for example, can list ethylene glycol bisthioglycolate vinyl ether, butyleneglycol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanediol divinyl ether, trimethylolpropane tris vinyl ether, tetramethylolmethane tetrem alkene ether, glycerol trivinyl ether, triethylene glycol divinyl ether, Diethylene Glycol divinyl ether etc.
In addition, can also mix known in the past cationic polymerisation catalyst in the modified resin composition of present embodiment.As the cationic polymerisation catalyst that can use, can list with BF
3Amine inner complex, PF
5, BF
3, AsF
5, SbF
5Deng being the Lewis acid series catalysts of representative; With phosphonium salt or quaternary ammonium salt, sulfosalt, benzyl ammonium salt, benzyl-pyridine salt, benzyl sulfosalt, hydrazonium salt, carboxylicesters, sulphonate, amine imide is the Thermocurable cationic polymerisation catalyst of representative; It with two (dodecylphenyl) iodine of diaryl iodine hexafluorophosphate, hexafluoro-antimonic acid etc. the ultra-violet curing cationic polymerisation catalyst etc. of representative.Among above-mentioned since have obtain that second-order transition temperature is higher, the tendency of the painted less transparent cured thing of welding thermotolerance or adaptation excellence, thereby preferably use the Thermocurable cationic polymerisation catalyst.Commercially available product as such Thermocurable cationic polymerisation catalyst, for example, can list SI-100L, SI-60L as the cationic polymerization initiators of sulfosalt system (more than, three new chemical industry systems), CP-66, CP-77 (more than, rising sun electrochemical industry system) etc.
From giving the viewpoint that cured article is flexible, improve peeling adhesion force, can contain properties-correcting agent as required in the modified resin composition that obtains by present embodiment.As employed properties-correcting agent, can example be illustrated in the polyalcohols that contains 2 above hydroxyls in 1 molecule, for example, preferably make spent glycol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, 1,2-propylene glycol, 1, ammediol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,2-butyleneglycol, 1,4-butyleneglycol, neopentyl glycol, glycerine, red moss alcohol, TriMethylolPropane(TMP), 1,2, fatty family polyalcohols such as 4-trihydroxybutane or polycarbonate diol, end have the silicone of silanol group.These properties-correcting agent can use a kind or use as the mixture more than 2 kinds.
In order to improve rerum naturas such as adaptation, the modified resin composition of present embodiment can use various silane coupling agents.Under this situation, the residual alkoxyl group in the modified resin composition need be for below 5%.Surpass under 5% the situation at residual alkoxyl group, anti-crackle, the cementability of the cured article that composition curing is obtained when thermal cycling is insufficient.
Silane coupling agent as the modified resin composition that is suitable for present embodiment, can list the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl-dimethyl methoxy silane, 3-glycidoxy propyl-dimethyl Ethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 3-aminopropyl methyldiethoxysilane, 3-aminopropyl dimethylethoxysilane, N-(2-amino-ethyl) amino methyl Trimethoxy silane, N-(2-amino-ethyl) (3-aminopropyl) Trimethoxy silane, N-(2-amino-ethyl) (3-aminopropyl) triethoxyl silane, N-(2-amino-ethyl) (3-aminopropyl) methyl dimethoxysilane, N-[N '-(2-amino-ethyl) (2-amino-ethyl)] (3-aminopropyl) Trimethoxy silane, 2-(2-amino-ethyl) thio-ethyl triethoxyl silane, 2-(2-amino-ethyl) thio-ethyl methyldiethoxysilane, 3-(N-phenyl amino) propyl trimethoxy silicane, 3-(N-cyclohexyl amino) propyl trimethoxy silicane, (N-phenyl amino methyl) Trimethoxy silane, (N-phenyl amino methyl) methyl dimethoxysilane, (N-cyclohexyl amino methyl) triethoxyl silane, (N-cyclohexyl amino methyl) methyldiethoxysilane, the piperazinyl methyltrimethoxy silane, the piperazinyl Union carbide A-162,3-piperazinyl propyl trimethoxy silicane, 3-piperazinyl propyl group methyl dimethoxysilane, 3-urea groups propyl-triethoxysilicane, the mercapto methyl Trimethoxy silane, the mercapto methyl triethoxyl silane, the mercapto methyl methyl dimethoxysilane, the mercapto methyl methyldiethoxysilane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, 3-sulfydryl propyl group methyl dimethoxysilane, 3-sulfydryl propyl group methyldiethoxysilane, 3-(trimethoxysilyl) propyl group succinyl oxide, 3-(triethoxysilyl) propyl group succinyl oxide, tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, propyl-triethoxysilicane, vinyltrimethoxy silane, vinyltriethoxysilane, cyclohexyl trimethoxy silane, the cyclohexyl triethoxyl silane, the cyclopentyl Trimethoxy silane, the cyclopentyl triethoxyl silane, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl ethylene dimethoxy silane, the methyl ethylene diethoxy silane, aminomethyl phenyl dimethoxy silane, the aminomethyl phenyl diethoxy silane, methylcyclohexyl dimethoxy silane, the methylcyclohexyl diethoxy silane, methylcyclopentyl dimethoxy silane, the methylcyclopentyl diethoxy silane, 3-methacryloxypropyl methyl dimethoxysilane, the 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxyl silane etc.Also can use the partial condensate of these silane coupling agents in addition.
In addition, in the modified resin composition of present embodiment, in the scope of not damaging these functions, can also suitably add inorganic filling agent except that above-mentioned, tinting material, flow agent, lubricant, tensio-active agent, antioxidant, photostabilizer etc. according to purpose.In addition, in addition, can also mix softening agent that the additive usually used as resin uses, fire retardant, stablizer, static inhibitor, shock-resistant reinforcer, whipping agent, antibacterial mildew inhibitor, electroconductive stuffing, antifogging agent, linking agent etc.
As inorganic filling agent, for example, can list silica-based (silicon-dioxide is pulverized in fusion, silicon-dioxide, spherical silicon dioxide, aerosil, colloid silica, precipitation threshold silicon-dioxide etc. are pulverized in crystallization), silicon carbide, silicon nitride, boron nitride, lime carbonate, magnesiumcarbonate, barium sulfate, calcium sulfate, mica, talcum, clay, aluminum oxide, magnesium oxide, zirconium white, aluminium hydroxide, magnesium hydroxide, Calucium Silicate powder, pure aluminium silicate, lithium aluminium silicate, zirconium silicate, barium titanate, glass fibre, carbon fiber, molybdenumdisulphide etc.Especially be preferably silica-based, lime carbonate, aluminum oxide, aluminium hydroxide, Calucium Silicate powder etc., and then consider the rerum natura of cured article, more preferably silica-based.These inorganic filling agents may be used alone, or two or more kinds may be used in combination.
As tinting material, so long as use to such an extent that material then is not particularly limited to be colored as purpose, for example, can list the various organic system pigments of phthalocyanine, azo, tetrazo, quinacridone, anthraquinone, flavanthrone, purple cyclic ketones (perinone), perylene, dioxazine, condensation azo, azomethine system; Mineral dyes such as titanium oxide, lead sulfate, chrome yellow, zinc yellow, chrome vermilion (chrome vermilion), colcother, cobalt violet, Prussian blue, ultramarine, carbon black, chrome green, chromic oxide, cobalt green etc.These tinting materials may be used alone, or two or more kinds may be used in combination.
As flow agent, be not particularly limited, for example, oligopolymer class, epoxidised soybean fatty acid, epoxidation rosin alcohol, hydrogenated castor oil, the titanium that can list the molecular weight 4000～12000 that is made of esters of acrylic acids such as ethyl propenoate, butyl acrylate, 2-EHAs is coupling agent etc.These flow agents may be used alone, or two or more kinds may be used in combination.
As lubricant, be not particularly limited, for example, can list hydrocarbon system lubricants such as paraffin, Microcrystalline Wax, polyethylene wax; Senior fatty acid series lubricants such as lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid, mountain Yu acid; Senior fatty acid amide base lubricants such as stearylamide, palmitic amide, amine hydroxybenzene, methylene-bis stearylamide, ethylenebisstearamide; Solidify Viscotrol C, stearic acid butyl ester, ethylene glycol monostearate, tetramethylolmethane (single-, two-, three-, or four-) senior fatty acid ester base lubricant such as stearate; Pure base lubricants such as hexadecanol, stearyl alcohol, polyoxyethylene glycol, Polyglycerine; Metallic soap class as the metal-salt of the magnesium of lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid, mountain Yu acid, ricinoleic acid, naphthenic acid etc., calcium, cadmium, barium, zinc, lead etc.; Natural waxes such as carnauba wax, gama wax, beeswax, montanin wax etc.These lubricants may be used alone, or two or more kinds may be used in combination.
Tensio-active agent is meant to exist in its molecule that solvent is not had the hydrophobic group of affinity and solvent had the amphiphilic species of the solvophilic base (being generally hydrophilic group) of affinity.The kind of tensio-active agent is not particularly limited, and for example, can list the silicone-based tensio-active agent, fluorine is a tensio-active agent etc.Tensio-active agent may be used alone, or two or more kinds may be used in combination.
As antioxidant, be not particularly limited, for example, can list organic phosphorous antioxidants such as triphenylphosphate, phosphorous acid phenyl isodecyl ester; 3, organosulfurs such as the two octadecyl esters of 3`-thio-2 acid are antioxidant; 2, phenol such as 6-two-Butylated Hydroxytoluene are antioxidant etc.
As photostabilizer, be not particularly limited, for example, can list UV light absorber such as benzotriazole system, benzophenone series, salicylate system, cyanoacrylate system, nickel system, triazine system or hindered amine is photostabilizer etc.
The modified resin composition of present embodiment can form cured article by known method; Perhaps in the modified resin composition of present embodiment, mix oxetane compound (D), fluor (E), conductive metal powder (F), insulativity powder (G), Resins, epoxy (A '), solidifying agent (H) and curing catalyst (I), or light acid producing agent (J), mixed-cation polymerizing catalyst as required also, properties-correcting agent, vinyl ether compound, organic resin except that Resins, epoxy (A '), the curable resin composition that silane coupling agent forms can form cured article by known method.Wherein, by heating the solidified method or by irradiates light the solidified method is usually as the method for the curing of Resins, epoxy, can be used as preferable methods in the present embodiment and illustration.Temperature when solidifying by heating depends on employed Resins, epoxy or solidifying agent etc., thereby is not particularly limited, but is generally 20～200 ℃ scope.
On the other hand, employed light when solidifying by irradiates light is preferably ultraviolet ray or visible light, more preferably ultraviolet ray.Generation source as light, for example, can list various light sources such as low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, UV lamp, xenon lamp, carbon arc lamp, metal halide lamp, luminescent lamp, tungsten lamp, Argon ion laser, helium cadmium laser, helium-neon laser, krypton ion laser, various semiconductor laser, YAG laser apparatus, excimer laser, photodiode, CRT light source, plasma source etc.
Above-mentioned curing reaction as required, can also carry out under inert gas atmospheres such as nitrogen, helium, argon gas except carrying out in air.
The modified resin composition of present embodiment for example is a) modified resin composition of present embodiment, b) in the modified resin composition of present embodiment, further add the resin combination that oxetane compound (D) forms, c) in the modified resin composition of present embodiment, further add the fluorescence resin composition that fluor (E) forms, or, further add the resin combination that solidifying agent (H) forms above-mentioned in a)～c).The modified resin composition of present embodiment as be used to make and the adaptation excellence of element or packaged material, do not crack, less, the excellent encapsulating luminescent element material of reduction of brightness is very useful down between long-term; Perhaps as can injection molding, solidify the hard and excellent in dimensional stability of back quality and have sunproof optics very useful with the curable resin composition of lens with raw material.In addition, to further add resin combination that solidifying agent (H) forms in a)～c) and further add curable resin composition that curing catalyst (I) forms or further add photosensitive polymer combination that light acid producing agent (J) forms in a)～c) as being used to make above-mentioned encapsulating luminescent element material or optics is very useful with the curable resin composition or the photosensitive polymer combination of lens above-mentioned above-mentioned.
The curable resin composition that contains the modified resin composition of present embodiment by use seals luminous element, can make luminous components such as photodiode.In addition, above-mentioned photodiode and/or above-mentioned optics can be suitable as the semiconductor device with the light source of measuring instrument light source, signal lamp, pilot lamp, display unit, planar twinkler, indicating meter, decoration, various lamps etc. such as the light source, vehicle of (back light) backlight, the illumination of liquid-crystal display for example etc., various transmitter, printer, duplicating machine etc. with lens etc.
Use is sealed with sealing material by the luminous element that curable resin composition constituted of the modified resin composition that contains present embodiment and obtains luminous element, the emission wavelength of this luminous element can use in a wider range from infrared extremely redness, green, blueness, purple, ultraviolet, in actual applications, even can under the light of 250nm～550nm wavelength, use, sealing material in the past produces deterioration owing to photostabilization under the light of 250nm～550nm wavelength is not enough.Thus, can obtain the white light-emitting diode that the life-span is long, energy efficiency is higher, colorrendering quality is higher.Wherein, emission wavelength is meant the main glow peak wavelength.
As the object lesson of employed luminous element, for example, can example be illustrated in lamination semiconductor material on the substrate and the luminous element that forms.Under this situation,, for example, can list GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, SiC etc. as semiconductor material.
As substrate, for example, can list sapphire, spinel, SiC, Si, ZnO, GaN monocrystalline etc.As required, also can between substrate and semiconductor material, form buffer layer.As these buffer layers, can list GaN, AlN etc.
Method as lamination semiconductor material on substrate is not particularly limited, and for example, can use mocvd method, HDVPE method, liquid-phase growth method etc.
The structure example of luminous element has the homogeneity joint that MIS engages, PN engages, PIN engages, heterogeneous joint, double-heterostructure etc. as listing.In addition, can also form single or multi-quantum pit structure.
By using the encapsulating luminescent element material that curable resin composition constituted that luminous element is sealed, can make photodiode by the modified resin composition that contains present embodiment.Sealing under this situation can be only to utilize the encapsulating luminescent element material with encapsulating luminescent element, also can share other sealing materials and seals.Share under the situation of other sealing materials, can use the modified resin composition that obtains by present embodiment, after sealing, will seal around it with other sealing materials with thus obtained encapsulating luminescent element material; Perhaps also can after sealing, use the modified resin composition that obtains by present embodiment, use the encapsulating luminescent element material that obtains by this modified resin composition sealing around it with other sealing materials.As other sealing materials, for example, can list Resins, epoxy, silicone resin, acrylic resin, urea resin, imide resin, glass etc.
The method that the encapsulating luminescent element material that obtains as the modified resin composition by the use present embodiment seals luminous element, for example, can list following method: in mold formwork (モ one Le De type frame), inject the encapsulating luminescent element material in advance, carry out the solidified method after impregnated in lead frame of being fixed with luminous element etc. wherein; In the formwork that has inserted luminous element (type frame), inject the encapsulating luminescent element material and carry out solidified method etc.At this moment, as the method for injecting the encapsulating luminescent element material, can list the injection that utilizes divider (dispenser), transfer mould shaping, injection molding etc.As other sealing methods, can list following method in addition: the encapsulating luminescent element droplets of material is fallen on the luminous element, carried out porous printing, silk screen printing or Jie and be coated with and make its solidified method by mask; Utilize divider etc. to dispose injection encapsulating luminescent element material in the cup etc. of luminous element, and make its solidified method etc. to lower curtate.
The curable resin composition that contains the modified resin composition of present embodiment also can use as the tube core welding material, the passive film on the luminous element, the base plate for packaging that luminous element are fixed in lead terminal or the encapsulation (パ ッ ケ one ジ).The shape of hermetic unit for example can list the lens shape of bullet cut, tabular, film like etc.
The photodiode that uses the modified resin composition of present embodiment and obtain can be realized the raising of performance by known method in the past.Method as improving performance for example, can list following method: the method that reflection of light layer or light collecting layer are set at the luminous element back side; Form the method for the painted portion of complementary color in the bottom; The more method of the layer of short wavelength's light of specific absorption main glow peak is set on luminous element; After with encapsulating luminescent element, further use the method for mechanically resistant material mold pressing; Photodiode is inserted communicating pores and fixed method; The method etc. that luminous element and lead member etc. is connected and takes out light by flip-chip connection etc. from orientation substrate.
The photodiode that uses the modified resin composition of present embodiment and obtain is useful as the light source of (back light) backlight, the illumination of liquid-crystal display etc., various transmitter, printer, duplicating machine etc., vehicle with the luminous component of the light source of measuring instrument light source, signal lamp, pilot lamp, display unit, planar twinkler, indicating meter, decoration, various lamps etc. for example.
On the other hand, by solidifying, can make the light-storing material of luminous excellence in the modified resin composition of present embodiment, further adding further to add the curable resin composition that solidifying agent (H) forms in the fluorescence resin combination that fluor (E) forms or in the modified resin composition of present embodiment, further add the photosensitive polymer combination that light acid producing agent (J) forms.
Then, light-storing material is described.Usually, light-storing material is meant because of light stimulus such as sunlight, luminescent lamp, ultraviolet ray excite, and carries out energy transformation and emits light, and slowly emit light after exciting of producing of above-mentioned light stimulus stops, and continues luminous material for a long time simultaneously.
Used the purposes of light-storing material of the modified resin composition of present embodiment to be not particularly limited, fishing gear, sports requsites class, adornment, toys etc. such as the reflector of the demonstration class in the time of for example, can routine electricity failure at night being shown, the secure ID of taking precautions against natural calamities, clock and watch, wallpaper, electric switch, signboard, clothing, footwear, bicycle motorcycle etc., adhesive tape, crochet hook buoy.
In addition, for example, d) conductive resin composition that further adding conductive metal powder (F) forms in the modified resin composition of present embodiment has excellent flowability, electroconductibility and cementability, and the conductive resin composition as the solidified nature that can suppress the hole generation is very useful with raw material, on the other hand, e) in the modified resin composition of present embodiment, further add the insulating resin composition that insulativity powder (G) forms, f) in the modified resin composition of present embodiment, add the insulating resin composition that Resins, epoxy (A ') and insulativity powder (G) form, or at above-mentioned d)～further add the resin combination that solidifying agent (H) forms in f) and have excellent insulativity and cementability, and very useful as the insulating resin composition raw material that can suppress the solidified nature that hole produces.In addition, for at above-mentioned d)～further add in f) further add the curable resin composition of curing catalyst (I) in the resin combination that solidifying agent (H) forms or at described d)～further add the photosensitive polymer combination of light acid producing agent (J) in f), very useful as the insulating resin composition of the conductive resin composition of above-mentioned various solidified nature or solidified nature.
Purposes as the conductive resin composition of the modified resin composition that has used present embodiment is not particularly limited, and for example, bonding, the conductor wirings that semiconductor element and surrounding member can example be shown forms, the scolder replacement during surface mounting; The caking agent or the tube core welding compound that use in electronic units such as the transparency carrier of the rotary machine coil of the encapsulation of the casting of insulator class, quartz crystal unit, AC transformer, switch etc. and circuit unit, various parts, ICLED semi-conductor etc., electric organ, motor etc., coil dipping, tellite, replacement glass, medium-sized insulator class, coil class, junctor, terminal stud and the distribution class thereof; Conductive coating paint, electrode, printed wiring, electroconductive resin etc.
Used the purposes of insulating resin composition of the modified resin composition of present embodiment to be not particularly limited, for example, the assembling (mounting) of the semi-conductor chip in the semiconductor device can example be shown; Be used for tube core welding compound that semi-conductor chip (IC, LSI etc.) is engaged with ceramic case, lead frame, substrate etc. or caking agent etc.In addition, can be applicable to that the media layer (interposer) of semiconductor packages or tellite, indicating meter, solar cell, generator electric motor require with substrate etc. with substrate, automobile in the purposes of insulating material of high exothermicity.
In addition, for example, by the following curable resin composition that adds solidifying agent (H) and curing catalyst (I) in a)～c), perhaps can use as the coating agent that is difficult to be subjected to inhibition that oxygen produces and influences: a) modified resin composition of present embodiment at the above-mentioned photosensitive polymer combination that further adds light acid producing agent (J) in a)～c) with producing effect, b) in the modified resin composition of present embodiment, further add the resin combination that oxetane compound (D) forms, c) in the modified resin composition of present embodiment, further add the fluorescence resin composition that fluor (E) forms; In addition, for example, by following d)～add the curable resin composition of solidifying agent (H) and curing catalyst (I) in f), perhaps at above-mentioned d)～photosensitive polymer combination that further adds light acid producing agent (J) in f) can be very useful as the coating agent that is difficult to be subjected to the inhibition influence that oxygen produces: d) the further conductive resin composition that forms of adding conductive metal powder (F) in the modified resin composition of present embodiment, e) in the modified resin composition of present embodiment, further add the insulating resin composition that insulativity powder (G) forms, f) in the modified resin composition of present embodiment, add the insulating resin composition that Resins, epoxy (A ') and insulativity powder (G) form.
The material that coating agent in the present embodiment so long as be used for forms on the surface of material, lining is filmed, then be not particularly limited, its main application target is as described below, as required, can also be in above-mentioned coating agent hybrid pigment or pigment etc., use as coating or printing ink.
(1) coating or protection, the weather resistance of base material give, attractive in appearance keeping (protection is in order to avoid be subjected to the injury of ultraviolet ray, infrared rays, oxidation, burn into flaw, dust, dirt, temperature, humidity etc.)
(2) coating or give glossiness to base material
(3) be coated with or the hydrophobic of base material is processed
(4) the anti-skidding processing of flooring material etc.
(5) sealing of electronic unit class, insulation
Usually, epoxy compounds is considered to polymerization to be caused comparatively fast, but polyreaction afterwards and unhappy.Yet the inventor etc. are unexpected to be found, by mix oxetane compound in having the described resin combination of epoxy group(ing), can quicken polymerization velocity, obtains light solidified and photosensitive polymer combination excellent in adhesion.In addition, by the selection of oxetane compound, can also reduce the viscosity of resin combination.
About the viscosity of the photosensitive polymer combination of present embodiment, its flowability is preferably below the 1000Pas, more preferably more than 0.05 and the following scope of 50Pas, more preferably 0.2 or more and the scope below the 30Pas.If the viscosity of photosensitive polymer combination surpasses 1000Pas, and is then mobile impaired, may be unsuitable for practical application.
By utilizing the coating agent of the present embodiment of known method coating in the past, then make its curing, can form and film.At this moment, method as coating, preferred use that brushing, roller coating, spraying, rod are coated with, coating techniques such as roller coat, baking vanish, dip-coating, galvanic deposit coating, electrostatic applications, powder coated, evaporation, plating, printing technologies such as ink-jet, laser printer, cycle type printing, intaglio printing, silk screen printing, on the other hand, the method of filming as formation is preferably used by heating the solidified method or by irradiates light and the solidified method.
The coating agent of present embodiment, and the purposes of filming is not particularly limited, for example, can be used as coating agent (coating, resin, plastics, metal, steel pipe, automobile, buildings, optical fiber purposes etc.), laser disc (DVD, CD, Blu-ray Disc etc.) coating or bonding, printing ink (ink-jet printer, intaglio printing, flexographic printing, the use in printed circuit board resist, UV printing purposes etc.), printing plate material (PS flat board, light-sensitive resin relief printing plate, the silk screen version is with sensitive materials etc.), photo-resist (semi-conductor resist, the use in printed circuit board resist, photo-fabrication (Photo-fabrication) is with resist etc.), with printed circuit board (PCB), IC, the pattern of the various electronic units headed by the LSI forms, the colour filter that liquid crystal or PDP indicating meter are used forms material, the sealing material that liquid crystal or organic EL use, semiconductor LED periphery material (sealing material, lens material, baseplate material, the tube core welding material, the chip coating material, laminated board, optical fiber, optical waveguides, spectral filter, the caking agent of electronic component-use, coating material, sealing material, insulating material, photo-resist, packaged material, mould material, the photic zone of laser disc or interlayer insulating film, printed circuit board (PCB), laminated board, light guiding plate, antireflection film etc.) etc., coating (anticorrosive coating, safeguard, the boats and ships coating, corrosion-resistant coating (lining), vehicle appliance goods priming paint, the beverage beer can, the outside surface japanning, the extruding pipe coating, general protection against corrosion coating, safeguard coating, carpenter work is with painting, automobile electrical deposition priming paint, other commercial power deposition coatings, the japanning of beverage beer can internal surface, the coiled material coating, tube jar internal surface coating, the carpenter uses coating, acidproof coating, wire enamel, insulation compound, automobile priming paint, the double protection against corrosion coating of U.S.'s dress of various metal productss, outside coating in the pipe, electricity parts insulation coating etc.), (chemical device is with managing a jar class for matrix material, the flyer material, automobile component, various sporting goodss, carbon-fibre composite, aramid fiber composites etc.), civil construction material (flooring material, pavement material, film, anti-skidding double thin layer is mated formation, concrete construction joint is increased, anchor is imbedded bonding, the pre-cast concrete engages, ceramic tile is bonding, the be full of cracks of concrete structure is studied for a second time courses one has flunked, the grouting leveling of base, the protection against corrosion waterproof coating of upper and lower water course facility, the corrosion-resistant lamination coating of jar class, the protection against corrosion coating of iron construction thing, thick slurry (mastic) coating of buildings outer wall etc.), caking agent (the caking agent of the of the same race or xenogenesis material of metallic glass ceramic ware cement concrete wood plastic etc., the assembling caking agent of automobile rail truck flyer etc., the prefabricated house with the composition board manufacturing with caking agent etc.: comprise single-liquid type, binary liquid shape, slice-type.), the anchor clamps that are shaped of flyer automobile plastic (resin molds such as pressing mold, stretch-draw dies, extrusion mould, vacuum forming blow molding with mould, master mold, foundry goods with pattern, lamination anchor clamps, various inspection with anchor clamps etc.), properties-correcting agent stablizer (additive in the resin treatment of fiber, polyvinyl-chloride use stablizer, the synthetic rubber etc.) etc.Wherein, useful in coating agent, coating, caking agent, light chisel resin purposes.
Embodiment
Following example illustrates the embodiment that specifies present embodiment, as long as but be no more than its purport then present embodiment be not subjected to the qualification of following examples.
The evaluation of the rerum natura in embodiment 1～26 and the comparative example 1～9 is following to be carried out.
＜epoxy equivalent (weight) (WPE) 〉
Measure according to " JIS K 7236:2001 (epoxy equivalent (weight) of Resins, epoxy ask calculation method) ".
＜viscosity 〉
Measure under the following conditions.
Rotary E shape viscometer: Toki Sangyo Co., Ltd.'s system, " TV-22 shape "
Rotor: (as required, can select other rotors for 3 ° * R14.)
Measure temperature: 25 ℃
Sample size: 0.4mL
The calculating of＜mixing index α 〉
Mixing index α is calculated by following general formula (2).
Mixing index α=(α c)/(α b) (2)
Wherein,
α b:(B) in the general formula (1), n=1 or 2 and have at least a kind of ring-type ether as R
1The mol% of alkoxysilane compound containing trialkylsilyl group in molecular structure,
α c:(C) in the general formula (1), n=1 or 2 and have at least a kind of aromatic series organic group as R
1The mol% of alkoxysilane compound containing trialkylsilyl group in molecular structure.
The calculating of＜mixing index β 〉
Mixing index β is calculated by following general formula (3).
Mixing index β={ (β n2)/(β n0+ β n1) } (3)
Wherein,
β n2: in the general formula (1), the mol% of the alkoxysilane compound containing trialkylsilyl group in molecular structure of n=2,
β n0: in the general formula (1), the mol% of the alkoxysilane compound containing trialkylsilyl group in molecular structure of n=0,
β n1: in the general formula (1), the mol% of the alkoxysilane compound containing trialkylsilyl group in molecular structure of n=1,
Wherein, 0≤{ (β n0)/(β n0+ β n1+ β n2) }≤0.1.
The calculating of＜mixing index γ 〉
Mixing index γ is calculated by following general formula (4).
Mixing index γ=(γ a)/(γ s) (4)
Wherein,
γ a: the quality of Resins, epoxy (g),
γ s: in the general formula (1), the quality of the alkoxysilane compound containing trialkylsilyl group in molecular structure of n=0～2 (g).
The calculating of＜mixing index δ 〉
Mixing index δ is calculated by following general formula (5).
Mixing index δ=(δ e)/(δ s) (5)
Wherein,
δ e: the addition of hydrolytic condensation catalyzer (mol number),
δ the s: (OR in the general formula (1)
2) amount (mol number).
The calculating of＜mixing index ε 〉
Mixing index ε is calculated by following general formula (6).
Mixing index ε=(ε w)/(ε s) (6)
Wherein,
ε w: the addition of water (mol number),
ε the s: (OR in the general formula (1)
2) amount (mol number).
The calculating of＜mixing index ζ 〉
Mixing index ζ is calculated by following general formula (7).
Mixing index ζ=(ζ f)/(ζ k) (7)
Wherein,
ζ f: the addition of solidifying agent (mol number),
ζ k: the amount of contained ring-type ether (mol number) in Resins, epoxy and the alkoxysilane compound containing trialkylsilyl group in molecular structure.
The calculating of＜mixing index η 〉
Mixing index η is calculated by following general formula (8).
Mixing index η=(η g)/(η k) * 100 (8)
Wherein,
η g: the quality of curing catalyst (g),
η k: the quality of Resins, epoxy and alkoxysilane compound containing trialkylsilyl group in molecular structure (g).
The calculating of＜storage stability index θ and the storage stability of resin combination 〉
Storage stability in the resin combination is estimated by the storage stability index θ shown in the following general formula (9).
Storage stability index θ=(preservation viscosity)/(initial viscosity) (9)
To the container sealing of the resin combination after the firm manufacturing be housed, the viscosity under carrying out under 25 ℃ after temperature adjusts 2 hours, measuring 25 ℃, with this as " initial viscosity ".
And then, will the container sealing of resin combination be housed, in 25 ℃ Constant Temperature Incubators, preserved for 2 weeks.After the preservation, the viscosity under measuring 25 ℃, with this as " preservation viscosity ".
Having flowability (viscosity is below the 1000Pas) and storage stability index θ at resin combination is under the situation below 4, is judged as to have storage stability.
The H-NMR of＜intermediate measures 〉
The condensation rate of intermediate is tried to achieve by the H-NMR measurement result of the sample solution of being gathered (intermediate) after reflow process finishes in the following order.
(1) sample solution after the reflow process of weighing 30mg finishes in sample bottle adds chloroform-d (Wako Pure Chemical Industries, Ltd.'s system), is adjusted to 1g.
(2) solution with above-mentioned (1) moves to diameter
The NMR pipe in, measure H-NMR under the following conditions.
Fourier transform nuclear magnetic resonance device: Jeol Ltd.'s system " α-400 type "
Nuclear species: H
Cumulative frequency: 200 times
The calculating of the residual alcoxyl base unit weight the in＜modified resin composition: H-NMR measures 〉
The mensuration of H-NMR is carried out in the following order.
(1) in sample bottle weighing modified resin composition 10mg and internal standard substance (1,1,2, the 2-tetrabromoethane; Tokyo changes into industry) 20mg, add chloroform-d (with the pure medicine of light) 970mg and dissolve modulation.
(2) solution with above-mentioned (1) moves to diameter
The NMR pipe in, measure H-NMR under the following conditions.
Fourier transform nuclear magnetic resonance device: Jeol Ltd.'s system " α-400 type "
Nuclear species: H
Cumulative frequency: 200 times
Calculate residual alcoxyl base unit weight (%) by the said determination result in the following order.
(3) calculate the peak area value of residual alcoxyl base peak by H-NMR figure.
(4) calculate the peak area value at internal standard substance peak by H-NMR figure.
(5) with the area value substitution following formula that reads in above-mentioned (3) and (4), try to achieve residual alcoxyl base unit weight (%).
Residual alcoxyl base unit weight (%)=(peak area value of residual alcoxyl base peak)/(peak area value at internal standard substance peak) * 100
Wherein, the peak area value of residual alcoxyl base peak is calculated by the following method.
The peak of＜residual alkoxyl group is unimodal situation 〉
The area of the part that will be surrounded by baseline and this peak is as the peak area value of residual alcoxyl base peak.
According to the difference of the kind of residual alkoxyl group, the peak of this residual alkoxyl group may exist a plurality of.Under this situation, the peak area value of the residual alcoxyl base peak in the present embodiment is the summation of area at the peak of described a plurality of residual alkoxyl groups.
The peak of＜residual alkoxyl group is the situation of complex spike 〉
From the peak of residual alkoxyl group and the slope that surrounds between the peak of described group except that residual alkoxyl group is 0 light, so that the mode of the area minimum at the peak of residual alkoxyl group is made tangent line, the area of the part that will be surrounded by the peak of this tangent line and residual alkoxyl group is as the peak area value of residual alcoxyl base peak.
In addition, wherein, be the main component at this peak at the peak of residual alkoxyl group, not having slope between the peak of the peak of residual alkoxyl group and the group except that residual alkoxyl group is under the situation of 0 point, will not be considered as the peak except that the peak of the group the residual alkoxyl group, this peak all is the peak of residual alkoxyl group.In addition, be the main component at this peak at the peak of the group except that residual alkoxyl group, not having slope between the peak of the peak of residual alkoxyl group and the group except that residual alkoxyl group is that the peak with residual alkoxyl group is not considered as the peak under the situation of 0 point.
The light fastness test of＜cured article 〉
The photostabilization of evaluate cure thing by the following method.
(1) cured article of preparing by the aftermentioned method is solidified with solution, make the cured article of 20mm * 10mm * thickness 3mm.
(2) black masks of above-mentioned cured article with the 25mm * 15mm * thickness 1.2mm in the hole that has diameter 5.5mm covered, as the light fastness test sample.
(3) preparation device makes that UV illumination can be mapped to constant temperature via optical fiber from UV irradiating unit (Ushio Inc. system, " Spot Cure SP7-250DB ") is above-mentioned sample in 50 ℃ the Constant Temperature Incubators.
(4) be that top state is arranged in 50 ℃ the Constant Temperature Incubators with above-mentioned sample with black masks.
(5) in the mode in the hole that UV illumination can be mapped to diameter 5.5mm, from the top irradiation 2W/cm of black masks
2UV light 96 hours.
(6) utilize the spectral photometric colour measuring meter (Japanese electric look Industrial Co., Ltd system, " SD5000 ") that the integrating sphere peristome is transform as diameter 10mm, measure the postradiation sample of UV.
(7) try to achieve yellow chromaticity (YI) according to " ASTM D1925-70 (1988): Test Method for Yellowness Index of Plastics (plastics yellowness index test method) ".Under this YI is situation below 13, is judged as and has photostabilization.
The cold shock testing of＜cured article 〉
The thermal shock of evaluate cure thing by the following method.
(1) prepares substrate and silicon shown below.
(1-1) substrate: Solvay Advanced Polymers K.K. system, " AMODEL A-4122NL WH 905 " (depression that has diameter 10mm * degree of depth 1.2mm in the dull and stereotyped central authorities of 15mm * 15mm * thickness 2mm)
(1-2) silicon
(2) will flow into aforesaid substrate with solution by the cured article that the aftermentioned method is prepared, prepare 10 samples that wherein are placed with 1 piece of silicon respectively, make its curing, as the cold shock testing sample.
(3) above-mentioned sample is arranged in the thermal shock device (ESPEC CORP. system, " TSE-11-A "), carries out thermal cycling with the condition of " (40 ℃～120 ℃)/circulation: 14 minutes exposure durations, 1 minute heating and cooling time ".
(4) take out above-mentioned sample through 50 thermal cyclings the time, jet penetration liquid (KOHZAI CORPORATION system, " MICRO CHECK ") observes unusual (peeling off or crackle) whether occur, writes down its number.
(5) do not put into device once more with confirming unusual sample in above-mentioned (4), through 50 thermal cyclings the time, estimate, carry out 100 thermal cyclings then, estimate with same method with same operation.Repeat these operations, estimate.
(6) in 10 samples, observe 2 samples and occur interrupting when unusual estimating, obtain " cold-resistant thermal shocking number of times=(times of thermal cycle of interruption)-(50 times) ".Under this cold-resistant thermal shocking number of times is situation more than 50 times, be judged as and have cold-resistant thermal shocking, as described belowly judge.
More than 50 times and be lower than 100 times; Zero
More than 100 times; ◎
Starting material about using in embodiment 1～26 and the comparative example 1～9 are shown in following (1)～(9).
(1) Resins, epoxy
(1-1) Resins, epoxy A1: poly-(dihydroxyphenyl propane-2-hydroxypropyl ether) (below, be called Bis-A1 Resins, epoxy)
Trade(brand)name: Asahi Kasei Epoxy Co., Ltd system, " AER2600 "
In addition, as described below by the epoxy equivalent (weight) (WPE) and the viscosity of aforesaid method mensuration.
Epoxy equivalent (weight) (WPE): 187g/eq
Viscosity (25 ℃): 14.3Pas
(1-2) Resins, epoxy A2: poly-(dihydroxyphenyl propane-2-hydroxypropyl ether) (below, be called Bis-A2 Resins, epoxy)
Trade(brand)name: Asahi Kasei Epoxy Co., Ltd system, " AER2500 "
In addition, as described below by the epoxy equivalent (weight) (WPE) and the viscosity of aforesaid method mensuration.
Epoxy equivalent (weight) (WPE): 186g/eq
Viscosity (25 ℃): 10.2Pas
(1-3) Resins, epoxy A3: poly-(dihydroxyphenyl propane-2-hydroxypropyl ether) (below, be called Bis-A3 Resins, epoxy)
Trade(brand)name: Asahi Kasei Epoxy Co., Ltd system, " AER6071 "
In addition, as described below by the epoxy equivalent (weight) (WPE) of aforesaid method mensuration.Wherein, this Resins, epoxy A3 is down solid-state at 25 ℃, thereby can't measure viscosity.
Epoxy equivalent (weight) (WPE): 470g/eq
(1-4) Resins, epoxy B:3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexyl carboxylicesters (below, be called alicyclic epoxy resin)
Trade(brand)name: Daicel Chemical Industries, Ltd. system, " CEL 2021P "
In addition, as described below by the epoxy equivalent (weight) (WPE) and the viscosity of aforesaid method mensuration.
Epoxy equivalent (weight) (WPE): 131g/eq
Viscosity (25 ℃): 227mPas
(2) alkoxysilane compound containing trialkylsilyl group in molecular structure
(2-1) alkoxysilane compound containing trialkylsilyl group in molecular structure H:3-glycidoxypropyltrime,hoxysilane (below, be called GPTMS)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-403 "
(2-2) alkoxysilane compound containing trialkylsilyl group in molecular structure I: phenyltrimethoxysila,e (below, be called PTMS)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-103 "
(2-3) alkoxysilane compound containing trialkylsilyl group in molecular structure J: dimethyldimethoxysil,ne (below, be called DMDMS)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-22 "
(2-4) alkoxysilane compound containing trialkylsilyl group in molecular structure K: tetraethoxysilane (below, be called TEOS)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBE-04 "
(2-5) alkoxysilane compound containing trialkylsilyl group in molecular structure L:2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane (below, be called ECETMS)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-303 "
(3) silane moiety condenses
(3-1) tetramethoxy-silicane partial condensate (another name: the polymethoxy siloxanes) (below, be called P-MS)
Trade(brand)name: Fukawa Chemical Industries Co., Ltd.'s system, " methyl silicate 51 "
(3-2) methyltrimethoxy silane partial condensate (another name: poly-(methyltrimethoxy silane) (below, be called P-MTMS)
Trade(brand)name: Tama Chemicals Co., Ltd.'s system, " MTMS-A "
(4) solvent
(4-1) tetrahydrofuran (THF): Wako Pure Chemical Industries, Ltd.'s system does not contain stabilizer type (below, be called THF)
(4-2) ethanol: Wako Pure Chemical Industries, Ltd.'s system (below, be called EtOH)
(4-3) Virahol: Wako Pure Chemical Industries, Ltd.'s system (below, be called i-PrOH)
(5) hydrolytic condensation catalyzer
(5-1) dibutyl tin laurate: Wako Pure Chemical Industries, Ltd.'s system (below, be called DBTDL)
(5-2) dibutyltin diacetate: Tokyo HuaCheng Industry Co., Ltd's system (below, be called DBTDA)
(5-3) oxalic acid dioctyl tin: Nitto Kasei Co., Ltd's system, " Neostann U-820 " (below, be called DOTDA)
(6) solidifying agent: " 4-methyl hexahydro phthalic anhydride/hexahydro phthalic anhydride=70/30 "
Trade(brand)name: New Japan Chem Co., Ltd's system, " RIKACID MH-700G "
(7) curing catalyst: amine is solidifying agent
Trade(brand)name: San-Apro Ltd. system, " U-CAT 18X "
(8) silicone resin: Shin-Etsu Chemial Co., Ltd's system, " SCR-1012 (A liquid and B liquid) "
(9) inorganic filler: colloid silica
Trade(brand)name: Nissan Chemical Ind Ltd's system, " methyl alcohol silicon dioxide gel " (SiO2:30%, particle diameter: 10～20nm)
(10) internal standard substance
1,1,2, the 2-tetrabromoethane: Tokyo changes into industrial's system
[embodiment 1]
Make resin combination in the following order, and estimate.
(1) prepares: the circulation Water Tank with Temp.-controlled is set at 5 ℃, and cooling tube is refluxed.And then, on magnetic stirring apparatus, place 80 ℃ oil bath.
(2) according to the proportion of composing of table 1, under 25 ℃ atmosphere, with Bis-A1 Resins, epoxy, alkoxysilane compound containing trialkylsilyl group in molecular structure and THF pack into drop in the flask that stirrer is arranged and mix stir after, and then add water and hydrolytic condensation catalyzer, and mix and stir.
(3) then, cooling tube is set on flask, is impregnated in 80 ℃ the oil bath rapidly and begins to stir, react 7 hours (reflow process) while reflux.
(4) after reaction finishes, be cooled to 25 ℃, take off cooling tube from flask then, finish described reflow process after, collected specimens solution (intermediate).
(5) after reflow process finished, the H-NMR of working sample solution (intermediate) confirmed (OR of following formula (1)
2) be hydrolyzed, generate (OH).
Chemical formula 7
(R
1)
n-Si-(OR
2)
4-n (1)
(6) use vaporizer, under 400Pa, 50 ℃, remove the solution after reflow process finishes with distillation in 1 hour after, and then 80 ℃ down distillation removed 5 hours, carry out dehydration condensation (dehydrating condensation operation) simultaneously.
(7) after reaction finishes, be cooled to 25 ℃, obtain resin combination.The H-NMR of this resin combination is measured and calculates with internal standard substance, and the residual alcoxyl base unit weight of result is 0%≤5%.
(8) the mixing index α 1～ε 1 in this resin combination is shown in table 3.
(9) and then, according to aforesaid method, measure the epoxy equivalent (weight) (WPE), initial viscosity of the resin combination that obtains in above-mentioned (6) and preserve viscosity.In addition, try to achieve storage stability index θ 1, they are shown in table 3.
The epoxy equivalent (weight) of the resin combination of the foregoing description 1 (WPE)=230g/eq is shown as suitable value.In addition, initial viscosity=32.7Pas＜1000Pas, and preserve viscosity=46.4Pas＜1000Pas, both are has mobile liquid.In addition, the resin combination with storage stability is confirmed as in storage stability index θ 1=1.42≤4.
Then, use the above-mentioned resin combination of under 25 ℃, preserving for 2 weeks, make cured article in the following order, and estimate.
(10) under 25 ℃ atmosphere, stir above-mentioned resin combination, solidifying agent and curing catalyst according to the proportion of composing mixing of table 2, under vacuum, outgas, as cured article solution.
(11) with being coated with 2 pieces of stainless steel plate clamping thickness 3mm of releasing agent, the silicon rubber of コ word shape, make shaping jig.
(12) the above-mentioned cured article solution of injection in the substrate at this shaping jig and above-mentioned 10 cold shock testings, and then in each substrate, drop into 1 piece of silicon respectively.
(13) above-mentioned shaping jig and cold shock testing are put into stove with substrate, implemented solidification treatment 1 hour down, and then implemented solidification treatment 1 hour down, make cured article at 150 ℃ at 120 ℃.
(14) temperature drop is low to moderate back below 30 ℃ and takes out cured article in the stove, and according to aforesaid method, the preparation light fastness test is with sample and cold shock testing sample.
(15) use above-mentioned sample, carry out light fastness test and cold shock testing, the results are shown in table 3 by aforesaid method.As YI=10.1≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 450 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 1 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 2]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 2～ε 2, the storage stability index θ 2 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 2 (WPE)=231g/eq is shown as suitable value.In addition, initial viscosity=11.8Pas＜1000Pas, and preserve viscosity=17.0Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 2=1.44≤4 are judged as the resin combination with storage stability.
In addition, as YI=8.3≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is more than 500 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 2 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 3]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 3～ε 3, the storage stability index θ 3 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 3 (WPE)=253g/eq is shown as suitable value.In addition, initial viscosity=27.3Pas＜1000Pas, and preserve viscosity=39.6Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 3=1.45≤4 are judged as the resin combination with storage stability.
In addition, as YI=9.2≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is more than 500 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 3 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 4]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 4～ε 4, the storage stability index θ 4 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 4 (WPE)=208g/eq is shown as suitable value.In addition, initial viscosity=11.7Pas＜1000Pas, and preserve viscosity=16.7Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 4=1.43≤4 are judged as the resin combination with storage stability.
In addition, as YI=8.7≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 450 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 4 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 5]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 5～ε 5, the storage stability index θ 5 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of this resin combination (WPE)=245g/eq is shown as suitable value.In addition, initial viscosity=13.2Pas＜1000Pas, and preserve viscosity=18.7Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 5=1.42≤4 are judged as the resin combination with storage stability.
In addition, as YI=8.5≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 250 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 5 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 6]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 6～ε 6, the storage stability index θ 6 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 6 (WPE)=221g/eq is shown as suitable value.In addition, initial viscosity=18.2Pas＜1000Pas, and preserve viscosity=26.6Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 6=1.46≤4 are judged as the resin combination with storage stability.
In addition, as YI=8.1≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 350 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 6 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 7]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 7～ε 7, the storage stability index θ 7 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 7 (WPE)=217g/eq is shown as suitable value.In addition, initial viscosity=10.3Pas＜1000Pas, and preserve viscosity=14.5Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 7=1.41≤4 are judged as the resin combination with storage stability.
In addition, as YI=8.3≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 450 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 7 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 8]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 8～ε 8, the storage stability index θ 8 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 8 (WPE)=213g/eq is shown as suitable value.In addition, initial viscosity=10.6Pas＜1000Pas, and preserve viscosity=15.3Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 8=1.45≤4 are judged as the resin combination with storage stability.
In addition, as YI=7.6≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 150 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 8 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 9]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 9～ε 9, the storage stability index θ 9 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 9 (WPE)=235g/eq is shown as suitable value.In addition, initial viscosity=27.8Pas＜1000Pas, and preserve viscosity=28.6Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 9=1.03≤4 are judged as the resin combination with storage stability.
In addition, as YI=8.0≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 350 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 9 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 10]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 10～ε 10, the storage stability index θ 10 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 10 (WPE)=214g/eq is shown as suitable value.In addition, initial viscosity=13.2Pas＜1000Pas, and preserve viscosity=13.7Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 10=1.04≤4 are judged as the resin combination with storage stability.
In addition, as YI=7.8≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 450 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 10 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 11]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 11～ε 11, the storage stability index θ 11 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 11 (WPE)=228g/eq is shown as suitable value.In addition, initial viscosity=41.1Pas＜1000Pas, and preserve viscosity=65.8Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 11=1.60≤4 are judged as the resin combination with storage stability.
In addition, as YI=7.5≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 450 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 11 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 12]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 12～ε 12, the storage stability index θ 12 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 12 (WPE)=230g/eq is shown as suitable value.In addition, initial viscosity=33.7Pas＜1000Pas, and preserve viscosity=48.5Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 12=1.44≤4 are judged as the resin combination with storage stability.
In addition, as YI=9.8≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 450 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 12 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 13]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 13～ε 13, the storage stability index θ 13 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 13 (WPE)=253g/eq is shown as suitable value.In addition, initial viscosity=27.5Pas＜1000Pas, and preserve viscosity=40.8Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 13=1.48≤4 are judged as the resin combination with storage stability.
In addition, as YI=9.9≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 450 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 13 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 14]
With the solidification treatment temperature of embodiment 1 (12) change to 110 ℃ following 4 hours, and then 150 ℃ following 1 hour, in addition, utilize method similarly to Example 1, make resin combination and cured articles according to table 1 and 2.To utilize result and mixing index α 14～ε 14, the storage stability index θ 14 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 14 (WPE)=192g/eq is shown as suitable value.In addition, initial viscosity=1.77Pas＜1000Pas, and preserve viscosity=3.08Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 14=1.74≤4 are judged as the resin combination with storage stability.
In addition, as YI=5.2≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 150 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 14 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 15]
With the solidification treatment temperature of embodiment 1 (13) change to 110 ℃ following 4 hours, in addition, utilize method similarly to Example 1, make resin combination and cured articles according to table 1 and 2.To utilize result and mixing index α 15～ε 15, the storage stability index θ 15 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 15 (WPE)=214g/eq is shown as suitable value.In addition, initial viscosity=4.80Pas＜1000Pas, and preserve viscosity=9.23Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 15=1.92≤4 are judged as the resin combination with storage stability.
In addition, as YI=8.8≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 250 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 15 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 16]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 16～ε 16, the storage stability index θ 16 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 16 (WPE)=214g/eq is shown as suitable value.In addition, initial viscosity=12.7Pas＜1000Pas, and preserve viscosity=15.4Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 16=1.21≤4 are judged as the resin combination with storage stability.
In addition, as YI=12.4≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 450 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 16 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 17]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 17～ε 17, the storage stability index θ 22 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 17 (WPE)=238g/eq is shown as suitable value.In addition, initial viscosity=18.9Pas＜1000Pas, and preserve viscosity=28.9Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 17=1.53≤4 are judged as the resin combination with storage stability.
In addition, as YI=7.2≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 150 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 17 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 18]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 18～ε 18, the storage stability index θ 18 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 18 (WPE)=245g/eq is shown as suitable value.In addition, initial viscosity=18.2Pas＜1000Pas, and preserve viscosity=30.5Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 23=1.68≤4 are judged as the resin combination with storage stability.
In addition, as YI=7.9≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 150 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 18 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 19]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 19～ε 19, the storage stability index θ 19 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 19 (WPE)=235g/eq is shown as suitable value.In addition, initial viscosity=16.2Pas＜1000Pas, and preserve viscosity=24.3Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 24=1.50≤4 are judged as the resin combination with storage stability.
In addition, as YI=7.3≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 150 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 19 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 20]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 20～ε 20, the storage stability index θ 20 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 20 (WPE)=296g/eq is shown as suitable value.In addition, initial viscosity=25.2Pas＜1000Pas, and preserve viscosity=100.8Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 20=4≤4 are judged as the resin combination with storage stability.
In addition, as YI=7.8≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 50 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 20 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 21]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 21～ε 21, the storage stability index θ 21 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 21 (WPE)=270g/eq is shown as suitable value.In addition, initial viscosity=20.3Pas＜1000Pas, and preserve viscosity=75.1Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 21=3.7≤4 are judged as the resin combination with storage stability.
In addition, as YI=8.4≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 50 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 21 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 22]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 22～ε 22, the storage stability index θ 22 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 22 (WPE)=208g/eq is shown as suitable value.In addition, initial viscosity=21.9Pas＜1000Pas, and preserve viscosity=87.6Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 22=4≤4 are judged as the resin combination with storage stability.
In addition, as YI=8.2≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 50 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 22 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 23]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.To utilize result and mixing index α 23～ε 23, the storage stability index θ 23 of method evaluation similarly to Example 1 to be shown in table 3.Confirm (the OR in the above-mentioned formula (1) of intermediate in addition
2) be hydrolyzed, generate (OH).
The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of embodiment 23 (WPE)=190g/eq is shown as suitable value.In addition, initial viscosity=14.4Pas＜1000Pas, and preserve viscosity=100.8Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 23=1.2≤4 are judged as the resin combination with storage stability.
In addition, as YI=13.0≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is more than 500 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 23 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 24]
Make resin combination in the following order, and estimate.
(1) prepares: the circulation Water Tank with Temp.-controlled is set at 5 ℃, and cooling tube is refluxed.And then, on magnetic stirring apparatus, place 80 ℃ oil bath.
(2) according to the proportion of composing of table 1, under 25 ℃ atmosphere, with alkoxysilane compound containing trialkylsilyl group in molecular structure and THF pack into drop in the flask that stirrer is arranged and mix stir after, and then add water and hydrolytic condensation catalyzer, and mix and stir.
(3) then, cooling tube is set on flask, is impregnated in 80 ℃ the oil bath rapidly and begins to stir, react 7 hours (reflow process) while reflux.
(4) after reaction finishes, be cooled to 25 ℃, take off cooling tube from flask then, finish described reflow process after, collected specimens solution (intermediate).
(5) after reflow process finished, the H-NMR of working sample solution (intermediate) confirmed (OR of following formula (1)
2) be hydrolyzed, generate (OH).
(6) the Bis-A Resins, epoxy of adding table 1 and mixing to evenly in intermediate, be arranged on the vaporizer then, after 400Pa, 50 ℃ of following distillations are removed 1 hour, and then distillation was removed 5 hours under 80 ℃, carried out dehydration condensation (dehydrating condensation operation) simultaneously.
(7) after reaction finishes, be cooled to 25 ℃, obtain resin combination.The residual alcoxyl base unit weight of being calculated by this resin combination and internal standard substance is 0%≤5%.
(8) the mixing index α 24～ε 24 in this resin combination is shown in table 3.
(9) and then, according to aforesaid method, measure the epoxy equivalent (weight) (WPE), initial viscosity of the resin combination that obtains in above-mentioned (6) and preserve viscosity.In addition, try to achieve storage stability index θ 24, they are shown in table 3.
The epoxy equivalent (weight) of the resin combination of the foregoing description 24 (WPE)=233g/eq is shown as suitable value.In addition, initial viscosity=11.8Pas＜1000Pas, and preserve viscosity=16.8Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 24=1.42≤4 are judged as the resin combination with storage stability.
Utilize method similarly to Example 1, make resin combination and cured article according to table 2.The result who utilizes method similarly to Example 1 to estimate is as shown in table 3, as YI=8.3≤13 of the index of the light fastness test of this cured article, is judged as and has photostabilization.In addition, the cold shock testing number of times is more than 500 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 24 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 25]
Make resin combination in the following order, and estimate.
(1) prepares: the circulation Water Tank with Temp.-controlled is set at 5 ℃, and cooling tube is refluxed.And then, on magnetic stirring apparatus, place 80 ℃ oil bath.
(2) according to the proportion of composing of table 1, under 25 ℃ atmosphere, to equal half Bis-A1 Resins, epoxy, alkoxysilane compound containing trialkylsilyl group in molecular structure and the THF of quality of total amount pack into drop in the flask that stirrer is arranged and mix stir after, and then add water and hydrolytic condensation catalyzer, and mix and stir.
(3) then, cooling tube is set on flask, is impregnated in 80 ℃ the oil bath rapidly and begins to stir, react 7 hours (reflow process) while reflux.
(4) after reaction finishes, be cooled to 25 ℃, take off cooling tube from flask then, finish described reflow process after, collected specimens solution (intermediate).
(5) after reflow process finished, the H-NMR of working sample solution (intermediate) confirmed (OR of following formula (1)
2) be hydrolyzed, generate (OH).
(6) in intermediate, add the Bis-A Resins, epoxy of remaining half amount equal table 1 and mixing to evenly, be arranged on the vaporizer then, after 400Pa, 50 ℃ of following distillations are removed 1 hour, and then distillation was removed 5 hours under 80 ℃, carried out dehydration condensation (dehydrating condensation operation) simultaneously.
(7) after reaction finishes, be cooled to 25 ℃, obtain resin combination.The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 0%≤5%.
(8) the mixing index α 25～ε 25 in this resin combination is shown in table 3.
(9) and then, according to aforesaid method, measure the epoxy equivalent (weight) (WPE), initial viscosity of the resin combination that obtains in above-mentioned (6) and preserve viscosity.In addition, try to achieve storage stability index θ 25, they are shown in table 3.
The epoxy equivalent (weight) of the resin combination of the foregoing description 25 (WPE)=232g/eq is shown as suitable value.In addition, initial viscosity=11.8Pas＜1000Pas, and preserve viscosity=16.7Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 25=1.42≤4 are judged as the resin combination with storage stability.
Utilize method similarly to Example 1, make resin combination and cured article according to table 2.The result who utilizes method similarly to Example 1 to estimate is as shown in table 3, as YI=8.3≤13 of the index of the light fastness test of this cured article, is judged as and has photostabilization.In addition, the cold shock testing number of times is more than 500 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 25 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[embodiment 26]
Make resin combination in the following order, and estimate.
(1) prepares: the circulation Water Tank with Temp.-controlled is set at 5 ℃, and cooling tube is refluxed.And then, on magnetic stirring apparatus, place 80 ℃ oil bath.
(2) except the P-MS composition, according to the proportion of composing of table 1, under 25 ℃ atmosphere, with Bis-A1 Resins, epoxy, alkoxysilane compound containing trialkylsilyl group in molecular structure and THF pack into drop in the flask that stirrer is arranged and mix stir after, and then add water and hydrolytic condensation catalyzer, and mix and stir.
(3) then, cooling tube is set on flask, is impregnated in 80 ℃ the oil bath rapidly and begins to stir, react 7 hours (reflow process) while reflux.
(4) after reaction finishes, be cooled to 25 ℃, take off cooling tube from flask then, finish described reflow process after, collected specimens solution (intermediate).
(5) after reflow process finished, the H-NMR of working sample solution (intermediate) confirmed (OR of following formula (1)
2) be hydrolyzed, generate (OH).
(6) use vaporizer, under 400Pa, 50 ℃, remove the solution after reflow process finishes with distillation in 1 hour after, and then 80 ℃ down distillation removed 5 hours, carry out dehydration condensation (dehydrating condensation operation) simultaneously.
(7) after reaction finishes, be cooled to 25 ℃, add the quality of the whole amounts that equal P-MS and mix to evenly, obtain resin combination according to the proportion of composing of table 1.The residual alcoxyl base unit weight of being calculated by resin combination and internal standard substance is 4.5%≤5%.
(8) the mixing index α 26～ε 26 in this resin combination is shown in table 3.
(9) and then, according to aforesaid method, measure the epoxy equivalent (weight) (WPE), initial viscosity of the resin combination that obtains in above-mentioned (7) and preserve viscosity.In addition, try to achieve storage stability index θ 26, they are shown in table 3.
The epoxy equivalent (weight) of the resin combination of the foregoing description 26 (WPE)=230g/eq is shown as suitable value.In addition, initial viscosity=14.5Pas＜1000Pas, and preserve viscosity=49.3Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 26=3.4≤4 are judged as the resin combination with storage stability.
Utilize method similarly to Example 1, make resin combination and cured article according to table 2.The result who utilizes method similarly to Example 1 to estimate is as shown in table 3, as YI=10.6≤13 of the index of the light fastness test of this cured article, is judged as and has photostabilization.In addition, the cold shock testing number of times is 50 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can be judged that by above result the resin combination of embodiment 26 has flowability and storage stability, the cured article of this resin combination has photostabilization and cold-resistant thermal shocking in addition, and synthetic determination is qualified thus.
[comparative example 1]
Utilize method similarly to Example 1, make resin combination according to table 1.The residual alcoxyl base unit weight of being calculated by this resin combination and internal standard substance is 17%＞5%.
Utilize result and mixing index α 27～ε 27, the storage stability index θ 27 of method evaluation similarly to Example 1 to be shown in table 3.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of comparative example 1 (WPE)=368g/eq is shown as suitable value.In addition, initial viscosity＞1000Pas, and preserve viscosity＞1000Pas, and both all do not demonstrate flowability, and storage stability index θ 27 can't calculate.
In addition, the preservation viscosity＞1000Pas of above-mentioned resin combination does not have flowability, thereby can't make cured article.
Can be judged that by above result the resin combination of comparative example 1 does not have flowability, storage stability can't calculate, and can't make cured article in addition, and synthetic determination is defective thus.
[comparative example 2]
Utilize method similarly to Example 1, make resin combination and cured article according to table 1 and 2.The residual alcoxyl base unit weight of being calculated by this resin combination and internal standard substance is 8%＞5%.
Utilize result and mixing index α 28～ε 28, the storage stability index θ 28 of method evaluation similarly to Example 1 to be shown in table 3.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of comparative example 2 (WPE)=295g/eq is shown as suitable value.In addition, initial viscosity=30.5Pas＜1000Pas, and preserve viscosity=45.1Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 13=1.48≤4 are judged as the resin combination with storage stability.
In addition, as YI=8.4≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 0 time＜50 times, is judged as not have cold-resistant thermal shocking.
Can be judged though the resin combination of comparative example 2 has flowability and storage stability, though the cured article of being made by this resin combination has photostabilization, not have cold-resistant thermal shocking by above result, synthetic determination is defective.
[comparative example 3]
Utilize method similarly to Example 1, make resin combination according to table 1.Utilize method evaluation similarly to Example 1 the result, and mixing index α 29～ε 29, storage stability index θ 29 be shown in table 3.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of comparative example 3 (WPE)=233g/eq is shown as suitable value.In addition, initial viscosity 3.8Pas＜1000Pas, and preserve viscosity＞1000Pas, do not demonstrate flowability.In addition, storage stability index θ 28=263 is above＞4, is judged as not have storage stability.
In addition, the preservation viscosity＞1000Pas of above-mentioned resin combination does not have flowability, thereby can't make cured article.
Can be judged that by above result the resin combination of comparative example 3 does not have flowability or storage stability, can't make cured article in addition, synthetic determination is defective thus.
[comparative example 4]
Utilize method similarly to Example 1, make resin combination according to table 1.Utilize method evaluation similarly to Example 1 the result, and mixing index α 30～ε 30, storage stability index θ 30 be shown in table 3.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of comparative example 4 (WPE)=184g/eq is shown as suitable value.In addition, initial viscosity 10.5Pas＜1000Pas, and preserve viscosity＞1000Pas, do not demonstrate flowability.In addition, storage stability index θ 30=95 is above＞4, is judged as not have storage stability.
In addition, the preservation viscosity＞1000Pas of above-mentioned resin combination does not have flowability, thereby can't make cured article.
Can be judged that by above result the resin combination of comparative example 4 does not have flowability or storage stability, can't make cured article in addition, synthetic determination is defective thus.
[comparative example 5]
Utilize method similarly to Example 1, make resin combination according to table 1.Utilize method evaluation similarly to Example 1 the result, and mixing index α 31～ε 31, storage stability index θ 31 be shown in table 3.
As shown in table 3, the epoxy equivalent (weight) of the resin combination of comparative example 5 (WPE) can't be measured.In addition, initial viscosity 24.0Pas＜1000Pas, and preserve viscosity＞1000Pas, do not demonstrate flowability.In addition, storage stability index θ 30=41 is above＞4, is judged as not have storage stability.
In addition, the preservation viscosity＞1000Pas of above-mentioned resin combination does not have flowability, thereby can't make cured article.
Can judge that by above result the resin combination of comparative example 5 does not have flowability or storage stability, can't make cured article in addition, thereby synthetic determination is defective.
[comparative example 6]
Utilize method similarly to Example 1, make cured article according to table 2.Utilize the table 3 that the results are shown in of similarly to Example 1 method evaluation.
As YI=16.9＞13 of the index of the light fastness test of cured article, be judged as and do not have photostabilization.In addition, the cold shock testing number of times is more than 500 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can judge, not have photostabilization by above result, thereby synthetic determination is defective though the cured article of comparative example 6 has cold-resistant thermal shocking.
[comparative example 7]
The A liquid of above-mentioned silicone resin and B liquid are mixed stirring with 1: 1 mass ratio, utilize method similarly to Example 1 resulting mixture to be made into cured article solution according to table 2.
For above-mentioned curing solution, utilize method similarly to Example 1, the above-mentioned cured article solution of injection in the substrate at shaping jig and above-mentioned 10 cold shock testings, and then in each substrate, drop into 1 piece of silicon respectively.
Above-mentioned shaping jig and cold shock testing are put into stove with substrate, implemented solidification treatment 1 hour down, and then implemented solidification treatment 5 hours down, make cured article at 150 ℃ at 70 ℃.
Utilize the table 3 that the results are shown in of similarly to Example 1 method evaluation.
As YI=2.0≤13 of the index of the light fastness test of cured article, be judged as and have photostabilization.Yet the cold shock testing number of times is 0 time＜50 times, is judged as not have cold-resistant thermal shocking.
Can be judged though the cured article of comparative example 7 has photostabilization, not have cold-resistant thermal shocking by above result, synthetic determination is defective thus.
[comparative example 8]
According to table 1, in reaction vessel, add Resins, epoxy A2 and Resins, epoxy A3, be impregnated in 85 ℃ the oil bath and stirring and dissolving, and then add P-MTMS and DBTDL and mix.
In addition, Yi Bian carry out nitrogen purging,, carried out dealcoholization 8 hours Yi Bian the temperature of oil bath is increased to 105 ℃.
Then, be cooled to 60 ℃ after, be decompressed to 12000Pa, remove dissolving alcohol, obtain resin combination.The residual alcoxyl base unit weight of being calculated by this resin combination and internal standard substance is 11%＞5%.
Utilize the result and the storage stability index θ 32 of method evaluation similarly to Example 1 to be shown in table 3.
The epoxy equivalent (weight) of the resin combination of comparative example 8 (WPE)=282g/eq is shown as suitable value.In addition, initial viscosity 0.15Pas＜1000Pas, and preserve viscosity=0.27Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 32=1.80≤4 are judged as the resin combination with storage stability.
In addition, according to the proportioning of table 2, utilize method similarly to Example 1 to make cured article, and estimate, the cold shock testing number of times of the cured article of comparative example 8 is 0 time＜50 times as a result, is judged as not have cold-resistant thermal shocking.In addition, be used for light fastness test and manufactured samples has produced small crackle, can't measure.
Can judge that by above result the cured article synthetic determination of comparative example 8 is defective.
[comparative example 9]
Utilize method similarly to Example 1, make resin combination according to table 1.Utilize the result and the mixing index α 33～ε 33 of method evaluation similarly to Example 1 to be shown in table 3.In addition, (the OR in the above-mentioned formula (1) of intermediate
2) more not being hydrolyzed and have residually, hydrolysis reaction does not normally carry out.Therefore, can't obtain normal resin combination, be judged as defective.The residual alcoxyl base unit weight of being calculated by this resin combination and internal standard substance is more than 100%＞5%.
By the result of table 1～3 as can be known, by the resin combination (embodiment 1～26) that obtains with specific ratio blending epoxy and specific alkoxysilane compound containing trialkylsilyl group in molecular structure and cohydrolysis condensation, its flowability and excellent storage stability.In addition, the photostabilization and the cold-resistant thermal shocking excellence of the cured article of these resin combinations have been used.
Table 2
Unit: quality %
Below, for the condensation rate of the organoalkoxysilane of modified resin composition and the condensation rate of intermediate, enumerate embodiment and comparative example is specifically described.
The evaluation method of the rerum natura in embodiment 27～35 and the comparative example 10～14 at first, below is shown.
About residual alcoxyl base unit weight, epoxy equivalent (weight) (WPE), viscosity, the mixing index α～η of modified resin composition, utilize with above-mentioned same method and try to achieve.
The calculating of the condensation rate of＜intermediate 〉
The condensation rate of intermediate is tried to achieve by the Si-NMR measurement result of the sample solution of being gathered (intermediate) after reflow process finishes in the following order.
(1) modulation of Cr solution: in the chromium acetylacetonate (Sigma-Aldrich corporate system) of 6.3 quality %, add chloroform-d (Wako Pure Chemical Industries, Ltd.'s system), and dissolving.
(2) sample solution after the reflow process of weighing 200mg finishes in sample bottle adds above-mentioned Cr solution, is adjusted to 1g.
(3) solution with above-mentioned (2) moves to diameter
The NMR pipe in, measure Si-NMR under the following conditions.
The Fourier transform nuclear magnetic resonance device: Jeol Ltd.'s system " α-400 type ",
Nuclear species: Si,
Cumulative frequency: 4000 times
(4), try to achieve the condensation rate K of intermediate according to following formula.
Condensation rate (%)=(D1 * 1+D2 * 2+T1 * 1+T2 * 2+T3 * 3)/
{(D0+D1+D2)×2+(T0+T1+T2+T3)×3}×100…(10)
Wherein,
D0: the total of the integrated value of the signal that produces from the D0 structure alkoxysilane compound containing trialkylsilyl group in molecular structure of n=1 in the formula (1), shown in the following formula (11).
D1: the total of the integrated value of the signal that produces from the D1 structure alkoxysilane compound containing trialkylsilyl group in molecular structure of n=1 in the formula (1), shown in the following formula (12).
D2: the total of the integrated value of the signal that produces from the D2 structure alkoxysilane compound containing trialkylsilyl group in molecular structure of n=1 in the formula (1), shown in the following formula (12).
T0: the total of the integrated value of the signal that produces from the T0 structure alkoxysilane compound containing trialkylsilyl group in molecular structure of n=2 in the formula (1), shown in the following formula (13).
T1: the total of the integrated value of the signal that produces from the T1 structure alkoxysilane compound containing trialkylsilyl group in molecular structure of n=2 in the formula (1), shown in the following formula (14).
T2: the total of the integrated value of the signal that produces from the T2 structure alkoxysilane compound containing trialkylsilyl group in molecular structure of n=2 in the formula (1), shown in the following formula (14).
T3: the total of the integrated value of the signal that produces from the T3 structure alkoxysilane compound containing trialkylsilyl group in molecular structure of n=2 in the formula (1), shown in the following formula (14).
Chemical formula 8
The D0 structure
In the described formula (11), R is organic group or H arbitrarily.
Chemical formula 9
D1 structure D2 structure
In the described formula (12), R is organic group or H arbitrarily.
The T0 structure
In the described formula (13), R is organic group or H arbitrarily.
Chemical formula 11
T1 structure T3 structure T2 structure
In the described formula (14), R is organic group or H arbitrarily.
The calculating of the condensation rate of the alkoxysilane compound containing trialkylsilyl group in molecular structure of＜modified resin composition 〉
About the condensation rate of the alkoxysilane compound containing trialkylsilyl group in molecular structure of modified resin composition, utilize the same method of condensation rate method of calculation with intermediate, finish the Si-NMR measurement result of the sample solution gathered the back by the dehydrating condensation operation and try to achieve as condensation rate L (%).
The calculating of＜storage stability index θ and the storage stability of resin combination 〉
Storage stability in the resin combination is estimated by the storage stability index θ shown in the following formula (9).
Storage stability index θ=(preservation viscosity)/(initial viscosity) ... (9)
To the container sealing of the resin combination after the firm manufacturing be housed, the viscosity under carrying out under 25 ℃ after temperature adjusts 2 hours, measuring 25 ℃, with this as " initial viscosity ".
And then, will the container sealing of resin combination be housed, in 60 ℃ Constant Temperature Incubators, preserved 16.5 days.After the preservation, the viscosity under measuring 25 ℃, with this as " preservation viscosity ".
Having flowability (viscosity is below the 1000Pas) and storage stability index θ at resin combination is under the situation below 6, is judged as to have storage stability, and followingly judges.
0≤θ≤4 ◎
4＜θ≤6 ○
The light fastness test of＜cured article 〉
The photostabilization of the cured article by following method evaluating resin composition.
(1) cured article of preparing by the aftermentioned method is solidified with solution, make the cured article of 20mm * 10mm * thickness 3mm.
(2) black masks of above-mentioned cured article with the 25mm * 15mm * thickness 1.2mm in the hole that has diameter 5.5mm covered, as the light fastness test sample.
(3) preparation device makes that UV illumination can be mapped to constant temperature via optical fiber from UV irradiating unit (Ushio Inc. system, " Spot Cure SP7-250DB ") is above-mentioned sample in 50 ℃ the Constant Temperature Incubators.
(4) be that top state is arranged in 50 ℃ the Constant Temperature Incubators with above-mentioned sample with black masks.
(5) in the mode in the hole that UV illumination can be mapped to diameter 5.5mm, from the top irradiation 2W/cm of black masks
2UV light 96 hours.
(6) utilize the spectral photometric colour measuring meter (Japanese electric look Industrial Co., Ltd system, " SD5000 ") that the integrating sphere peristome is transform as diameter 10mm, measure the postradiation sample of UV.
(7) try to achieve yellow chromaticity (YI) according to " ASTM D1925-70 (1988): Test Method for Yellowness Index of Plastics (plastics yellowness index test method) ".Under this YI is situation below 13, is judged as and has photostabilization.
The cold shock testing of＜cured article 〉
The thermal shock of the cured article of evaluating resin composition by the following method.
(1) prepares following substrate and silicon.
(1-1) substrate: Solvay Advanced Polymers K.K. system, " AMODEL A-4122NL WH 905 " (depression that has diameter 10mm * degree of depth 1.2mm in the dull and stereotyped central authorities of 15mm * 15mm * thickness 2mm)
(1-2) silicon (: commercially available Silicon Wafer is cut into 5mm * 5mm * thickness 200 μ m)
(2) will flow into aforesaid substrate with solution by the cured article that the aftermentioned method is made, make 10 substrates that wherein are placed with 1 piece of described silicon, make its curing, thus as the cold shock testing sample.
(3) above-mentioned sample is arranged in the thermal shock device (ESPEC CORP. system, " TSE-11-A "), carries out thermal cycling with the condition of " (40 ℃～120 ℃)/circulation: 14 minutes exposure durations, 1 minute heating and cooling time ".
(4) take out above-mentioned sample through 50 thermal cyclings the time, jet penetration liquid (KOHZAI CORPORATION system, " MICRO CHECK "), writes down its number at the having or not of visual observation unusual (peeling off or crackle) under magnifying glass.
(5) do not put into device once more with confirming unusual sample in above-mentioned (4), through 50 thermal cyclings the time, estimate, carry out 100 thermal cyclings then, estimate with same method with same operation.Repeat these operations, estimate.
(6) in 10 samples, observe 2 samples and occur interrupting when unusual estimating, obtain " cold-resistant thermal shocking number of times=(times of thermal cycle of interruption)-(50 times) ".
Under this cold-resistant thermal shocking number of times is situation more than 50 times, is judged as and has sufficient cold-resistant thermal shocking in actual applications.
Then, the starting material about using in embodiment 27～35 and the comparative example 10～14 are shown in following (1)～(10).
(1) Resins, epoxy
(1-1) Resins, epoxy A: poly-(dihydroxyphenyl propane-2-hydroxypropyl ether) (below, be called Bis-A Resins, epoxy)
Trade(brand)name: Asahi Kasei Epoxy Co., Ltd system, " AER2600 "
In addition, as described below by the epoxy equivalent (weight) (WPE) and the viscosity of aforesaid method mensuration.
Epoxy equivalent (weight) (WPE): 187g/eq
Viscosity (25 ℃): 14.3Pas
(1-2) Resins, epoxy B:3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexyl carboxylicesters (below, be called alicyclic epoxy resin)
Trade(brand)name: Daicel Chemical Industries, Ltd. system, " CEL 2021P "
In addition, as described below by the epoxy equivalent (weight) (WPE) and the viscosity of aforesaid method mensuration.
Epoxy equivalent (weight) (WPE): 131g/eq
Viscosity (25 ℃): 227mPas
(2) alkoxysilane compound containing trialkylsilyl group in molecular structure H:3-glycidoxypropyltrime,hoxysilane (below, be called GPTMS)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-403 "
(3) alkoxysilane compound containing trialkylsilyl group in molecular structure I: phenyltrimethoxysila,e (below, be called PTMS)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-103 "
(4) alkoxysilane compound containing trialkylsilyl group in molecular structure J: dimethyldimethoxysil,ne (below, be called DMDMS)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-22 "
(5) alkoxysilane compound containing trialkylsilyl group in molecular structure K: tetraethoxysilane (below, be called TEOS)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBE-04 "
(6) solvent
(6-1) tetrahydrofuran (THF): Wako Pure Chemical Industries, Ltd.'s system does not contain stabilizer type (below, be called THF)
(6-2) trimethyl carbinol: Wako Pure Chemical Industries, Ltd.'s system (below, be called t-BuOH)
(7) hydrolytic condensation catalyzer
(7-1) dibutyl dimethoxy tin (below, be called DBTDM): Sigma-Aldrich corporate system
(7-2) oxalic acid dioctyl tin (below, be called DOTDA): Nitto Kasei Co., Ltd's system, " NeostannU-820 "
(7-3) dibutyl tin laurate (below, be called DBTDL): Wako Pure Chemical Industries, Ltd.'s system
(8) solidifying agent: " 4-methyl hexahydro phthalic anhydride/hexahydro phthalic anhydride=70/30 "
Trade(brand)name: New Japan Chem Co., Ltd's system, " RIKACID MH-700G "
(9) curing catalyst: amine compound
Trade(brand)name: San-Apro Ltd. system, " U-CAT 18X "
(10) silicone resin: Shin-Etsu Chemial Co., Ltd's system, " SCR-1012 (A liquid and B liquid) "
(11) internal standard substance
1,1,2, the 2-tetrabromoethane: Tokyo changes into industrial's system
[embodiment 27]
Make resin combination by following operation.
(1) prepares: the circulation Water Tank with Temp.-controlled is set at 5 ℃, and cooling tube is refluxed.And then, on magnetic stirring apparatus, place 80 ℃ oil bath.
(2) according to the proportion of composing shown in the following table 4, under 25 ℃ atmosphere, with above-mentioned Bis-A Resins, epoxy, alkoxysilane compound containing trialkylsilyl group in molecular structure and THF pack into drop in the flask that stirrer is arranged and mix stir after, and then add water and hydrolytic condensation catalyzer, and mix and stir.
(3) then, cooling tube is set on flask, is impregnated in 80 ℃ the oil bath rapidly and begins to stir, react 25 hours (reflow process) while reflux.
(4) after reaction finishes, be cooled to 25 ℃, take off cooling tube from flask then, finish described reflow process after, collected specimens solution (intermediate).
(5) after reflow process finished, the Si-NMR of working sample solution tried to achieve the condensation rate K1 of intermediate according to above-mentioned formula (10).The condensation rate K1 (%)=80.1% 〉=78% of intermediate.
(6) use vaporizer, under 400Pa, 50 ℃, remove the solution after reflow process finishes with distillation in 1 hour after, and then 80 ℃ down distillation removed 10 hours, carry out dehydration condensation (dehydrating condensation operation) simultaneously.
(7) after described dehydration condensation finishes, be cooled to 25 ℃, obtain resin combination, and collected specimens solution.
(8) after the dehydrating condensation operation finished, the Si-NMR of working sample solution tried to achieve the condensation rate L1 of modified resin composition according to above-mentioned formula (10).The condensation rate L1 (%)=86.6% 〉=80% of modified resin composition.The residual alcoxyl base unit weight of modified resin composition is 0%≤5% in addition.
(9) the above-mentioned mixing index α 34～ε 34 of this resin combination is shown in following table 6 respectively.
(10) and then, according to aforesaid method, measure the epoxy equivalent (weight) (WPE), initial viscosity of the resin combination that obtains in above-mentioned (6) and preserve viscosity.In addition, obtain storage stability index θ 34, they are shown in table 6.
The epoxy equivalent (weight) of the resin combination of the foregoing description 27 (WPE)=220g/eq is shown as suitable value.In addition, initial viscosity=12.7Pas＜1000Pas, and preserve viscosity=32.5Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 34=2.6≤4, mobile excellent, be judged as storage stability and obtain the improved resins composition.
Then, use above-mentioned resin combination, make cured article in the following order, and estimate.
(11) under 25 ℃ atmosphere, mix stirring above-mentioned resin combination, solidifying agent and curing catalyst according to the proportion of composing shown in the following table 5, under vacuum, outgas, as cured article solution.
(12) with being coated with 2 pieces of stainless steel plate clamping thickness 3mm of releasing agent, the silicon rubber of コ word shape, make shaping jig, make that the cured article of being made by this shaping jig is about 50mm * about 20mm * thickness 3mm.
(13) the above-mentioned cured article solution of injection in the substrate at this shaping jig and above-mentioned 10 cold shock testings, and then in each substrate, drop into 1 piece of above-mentioned silicon respectively.
(14) above-mentioned shaping jig and cold shock testing are put into stove with substrate, implemented solidification treatment 1 hour down, and then implemented solidification treatment 1 hour down, make cured article at 150 ℃ at 120 ℃.
(15) temperature drop is low to moderate back below 30 ℃ and takes out cured article in the stove, and according to aforesaid method, the preparation light fastness test is with sample and cold shock testing sample.
(16) use above-mentioned sample, carry out light fastness test and cold shock testing, the results are shown in following table 6 by aforesaid method.The index of the light fastness test of this cured article is YI=11.9≤13, is judged as to have sufficient photostabilization in actual applications.In addition, the cold shock testing number of times is 350 times 〉=50 times, is judged as to have sufficient cold-resistant thermal shocking in actual applications.
By above result as can be known, the resin combination of embodiment 27 has good flowability and excellent storage stability, and the cured article of resin combination has sufficient photostabilization and cold-resistant thermal shocking in actual applications, and synthetic determination is qualified.
[embodiment 28]
Utilize the method same,, make resin combination and its cured article according to following table 4 and table 5 with the foregoing description 27.
About this resin combination and its cured article, utilize with the same method of the foregoing description 27 and estimate.Evaluation result, mixing index α 35～ε 35, storage stability index θ 35 are shown in following table 6.
The condensation rate K2 (%)=78.2% 〉=78% of intermediate.
The condensation rate L2 (%)=81.8% 〉=80% of modified resin composition.
The residual alcoxyl base unit weight of modified resin composition is 0%≤5%.
Shown in following table 6, the epoxy equivalent (weight) of the resin combination of embodiment 28 (WPE)=233g/eq is shown as suitable value.
In addition, initial viscosity=15.9Pas＜1000Pas, and preserve viscosity=53.8Pas＜1000Pas, have good flowability.In addition, storage stability index θ 35=3.4≤4, mobile excellent, obtain the improved resins composition for storage stability as can be known.
In addition, as YI=8.1≤13 of the index of the light fastness test of this cured article, be judged as and have sufficient photostabilization in the practical application.The cold shock testing number of times is 250 times 〉=50 times, is judged as to have sufficient cold-resistant thermal shocking in the practical application.
Can judge by above result, the mobile excellence of the resin combination of embodiment 28, storage stability obtains improvement, and the cured article of its resin combination has sufficient photostabilization and cold-resistant thermal shocking in actual applications in addition, and synthetic determination is qualified thus.
[embodiment 29]
Utilize the method same,, make resin combination and its cured article according to following table 4 and table 5 with the foregoing description 27.
About this resin combination and its cured article, utilize with the same method of the foregoing description 26 and estimate.Evaluation result, mixing index α 36～ε 36, storage stability index θ 36 are shown in table 6.
The condensation rate K3 (%)=85.3% 〉=78% of intermediate.
The condensation rate L3 (%)=86.8% 〉=80% of modified resin composition.
The residual alcoxyl base unit weight of modified resin composition is 0%≤5%.
Shown in following table 6, the epoxy equivalent (weight) of the resin combination of embodiment 29 (WPE)=242g/eq is shown as suitable value.
In addition, initial viscosity=14.3Pas＜1000Pas preserves viscosity=41.0Pas＜1000Pas, and both are has mobile liquid.In addition, storage stability index θ 36=2.9≤4, mobile excellent, obtain the improved resins composition for storage stability as can be known.
As YI=8.9≤13 of the index of the light fastness test of this cured article, be judged as and have sufficient photostabilization in the practical application.
The cold shock testing number of times is 250 times 〉=50 times, is judged as to have sufficient cold-resistant thermal shocking in the practical application.
Can judge by above result, the mobile excellence of the resin combination of embodiment 29, storage stability obtains improvement, and the cured article of its resin combination has sufficient photostabilization and cold-resistant thermal shocking in actual applications in addition, and synthetic determination is qualified thus.
[embodiment 30]
Utilize the method same,, make resin combination and its cured article according to following table 4 and table 5 with the foregoing description 27.
About this resin combination and its cured article, utilize with the same method of the foregoing description 27 and estimate.Evaluation result, mixing index α 37～ε 37, storage stability index θ 37 are shown in table 6.
The condensation rate K4 (%)=87.4% 〉=78% of intermediate.
The condensation rate L4 (%)=88.8% 〉=80% of modified resin composition.
The residual alcoxyl base unit weight of modified resin composition is 0%≤5%.
Shown in following table 6, the epoxy equivalent (weight) of the resin combination of embodiment 30 (WPE)=238g/eq is shown as suitable value.
In addition, initial viscosity=15.6Pas＜1000Pas, and preserve viscosity=24.9Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 37=1.6≤4, mobile excellent, obtain the improved resins composition for storage stability as can be known.
As YI=8.8≤13 of the index of the light fastness test of this cured article, be judged as and have sufficient photostabilization in the practical application.
The cold shock testing number of times is 150 times 〉=50 times, is judged as to have sufficient cold-resistant thermal shocking in the practical application.
Can judge by above result, the mobile excellence of the resin combination of embodiment 30, storage stability obtains improvement, and the cured article of its resin combination has sufficient photostabilization and cold-resistant thermal shocking in actual applications in addition, and synthetic determination is qualified thus.
[embodiment 31]
Utilize the method same,, make resin combination and its cured article according to following table 4 and table 5 with the foregoing description 27.
About this resin combination and its cured article, utilize with the same method of the foregoing description 27 and estimate.Evaluation result, mixing index α 38～ε 38, storage stability index θ 38 are shown in following table 6.
The condensation rate K5 (%)=82.6% 〉=78% of intermediate.
The condensation rate L5 (%)=87.2% 〉=80% of modified resin composition.
The residual alcoxyl base unit weight of modified resin composition is 0%≤5%.
Shown in following table 6, the epoxy equivalent (weight) of the resin combination of embodiment 31 (WPE)=245g/eq is shown as suitable value.
In addition, initial viscosity=17.3Pas＜1000Pas, and preserve viscosity=50.2Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 38=2.9≤4, mobile excellent, obtain the improved resins composition for storage stability as can be known.
As YI=8.2≤13 of the index of the light fastness test of this cured article, be judged as and have sufficient photostabilization in the practical application.
The cold shock testing number of times is 150 times 〉=50 times, is judged as to have sufficient cold-resistant thermal shocking in the practical application.
Can judge by above result, the mobile excellence of the resin combination of embodiment 31, storage stability obtains improvement, and the cured article of its resin combination has sufficient photostabilization and cold-resistant thermal shocking in actual applications in addition, and synthetic determination is qualified thus.
[embodiment 32]
Utilize the method same,, make resin combination and its cured article according to following table 4 and table 5 with the foregoing description 27.
About this resin combination and its cured article, utilize with the same method of the foregoing description 27 and estimate.Evaluation result, mixing index α 39～ε 39, storage stability index θ 39 are shown in following table 6.
The condensation rate K6 (%)=82.8% 〉=78% of intermediate.
The condensation rate L6 (%)=83.2% 〉=80% of modified resin composition.
The residual alcoxyl base unit weight of modified resin composition is 0%≤5%.
Shown in following table 6, the epoxy equivalent (weight) of the resin combination of embodiment 32 (WPE)=253g/eq is shown as suitable value.
In addition, initial viscosity=24.3Pas＜1000Pas, and preserve viscosity=86.3Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 39=3.6≤4, mobile excellent, obtain the improved resins composition for storage stability as can be known.
As YI=9.7≤13 of the index of the light fastness test of this cured article, be judged as and have sufficient photostabilization in the practical application.In addition, the cold shock testing number of times is 250 times 〉=50 times, is judged as to have sufficient cold-resistant thermal shocking in the practical application.
Can judge by above result, the mobile excellence of the resin combination of embodiment 32, storage stability obtains improvement, and the cured article of its resin combination has sufficient photostabilization and cold-resistant thermal shocking in actual applications in addition, and synthetic determination is qualified thus.
[embodiment 33]
Utilize the method same,, make resin combination and its cured article according to following table 4 and table 5 with the foregoing description 27.
About this resin combination and its cured article, utilize with the same method of the foregoing description 27 and estimate.Evaluation result, mixing index α 40～ε 40, storage stability index θ 40 are shown in following table 6.
The condensation rate K7 (%)=83.5% 〉=78% of intermediate.
The condensation rate L7 (%)=84.4% 〉=80% of modified resin composition.
The residual alcoxyl base unit weight of modified resin composition is 0%≤5%.
Shown in following table 6, the epoxy equivalent (weight) of the resin combination of embodiment 33 (WPE)=210g/eq is shown as suitable value.
In addition, initial viscosity=12.8Pas＜1000Pas, and preserve viscosity=39.8Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 33=3.1≤4, mobile excellent, obtain the improved resins composition for storage stability as can be known.
As YI=7.5≤13 of the index of the light fastness test of this cured article, be judged as and have sufficient photostabilization in the practical application.In addition, the cold shock testing number of times is 350 times 〉=50 times, is judged as to have sufficient cold-resistant thermal shocking in the practical application.
Can judge by above result, the mobile excellence of the resin combination of embodiment 33, storage stability obtains improvement, and the cured article of its resin combination has sufficient photostabilization and cold-resistant thermal shocking in actual applications in addition, and synthetic determination is qualified thus.
[embodiment 34]
Utilize the method same,, make resin combination and its cured article according to following table 4 and table 5 with the foregoing description 27.
About this resin combination and its cured article, utilize with the same method of the foregoing description 27 and estimate, evaluation result, mixing index α 41～ε 41, storage stability index θ 41 are shown in following table 6.
The condensation rate K8 (%)=84.2% 〉=78% of intermediate.
The condensation rate L8 (%)=84.4% 〉=80% of modified resin composition.
The residual alcoxyl base unit weight of modified resin composition is 0%≤5%.
Shown in following table 6, the epoxy equivalent (weight) of the resin combination of embodiment 33 (WPE)=233g/eq is shown as suitable value.
In addition, initial viscosity=13.2Pas＜1000Pas, and preserve viscosity=46.8Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 41=3.5≤4, mobile excellent, obtain the improved resins composition for storage stability as can be known.
As YI=7.3≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 150 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can judge by above result, the mobile excellence of the resin combination of embodiment 34, storage stability obtains improvement, and the cured article of its resin combination has sufficient photostabilization and cold-resistant thermal shocking in actual applications in addition, and synthetic determination is qualified thus.
[embodiment 35]
It is 2.5 hours that time change is removed in 80 ℃ of following distillations of 5 hours of dehydrating condensation operation.Other conditions are made resin combination according to table 4 similarly to Example 27, utilize method similarly to Example 27 to estimate.
Evaluation result, mixing index α 42～ε 42, storage stability index θ 42 are shown in following table 6.
The condensation rate K9 (%)=78.2% 〉=78% of intermediate.
The condensation rate L9 (%)=79.0%＜80% of modified resin composition.
The residual alcoxyl base unit weight of modified resin composition is 4%≤5%.
Shown in following table 6, the epoxy equivalent (weight) of the resin combination of embodiment 35 (WPE)=230g/eq is shown as suitable value.In addition, initial viscosity=15.1Pas＜1000Pas, and preserve viscosity=68.0Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 42=4.5≤6, the condensation rate of modified resin is lower than 80%, and is mobile excellent, obtains the improved resins composition for storage stability as can be known.
As YI=8.1≤13 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, the cold shock testing number of times is 250 times 〉=50 times, is judged as to have cold-resistant thermal shocking.
Can judge by above result, the mobile excellence of the resin combination of embodiment 35, storage stability obtains improvement, and the cured article of its resin combination has sufficient photostabilization and cold-resistant thermal shocking in actual applications in addition, and synthetic determination is qualified thus.
[comparative example 10]
It is following 1 hour that the solidification treatment temperature of (14) shown in the foregoing description 27 is changed to 110 ℃ of following 4 hours and then 150 ℃.Other conditions according to following table 4 and table 5, are made resin combination and cured article similarly to Example 27, utilize method similarly to Example 27 to estimate.
Evaluation result, mixing index α 43～ε 43, storage stability index θ 43 are shown in following table 6.
The condensation rate K10 (%)=71.1%＜78% of intermediate.
Condensation rate L10 (%)=75.4.0%＜80% of modified resin composition.
The residual alcoxyl base unit weight of modified resin composition is 21%＞5%.
Shown in following table 6, the epoxy equivalent (weight) of the resin combination of comparative example 10 (WPE)=200g/eq is shown as suitable value.
In addition, initial viscosity=11.7Pas＜1000Pas.Yet, preserve viscosity＞1000Pas, not shown flowability, storage stability index θ 43＞85, storage stability is bad.
As shown in table 6, can judge that used the photostabilization and the cold-resistant thermal shocking of cured article of resin combination of comparative example 10 good, but the storage stability of resin combination is bad, synthetic determination is defective.
[comparative example 11]
Utilize the method same, make cured article according to table 5 with the foregoing description 27.About this cured article, utilize method similarly to Example 27 to estimate.Evaluation result is shown in following table 6.
As YI=16.9＞13 of the index of the light fastness test of cured article, be judged as and do not have sufficient photostabilization in the practical application.In addition, the cold shock testing number of times is more than 500 times 〉=50 times, is judged as to have sufficient cold-resistant thermal shocking in the practical application.
Can be judged though the cured article of comparative example 11 has cold-resistant thermal shocking, not have photostabilization by above result, synthetic determination is defective thus.
[comparative example 12]
With silicone resin (Shin-Etsu Chemial Co., Ltd's system, " SCR-1012 (A liquid and B liquid) ") A liquid and B liquid mix stirring with 1: 1 mass ratio, use thus obtained mixture,, utilize method similarly to Example 26 to make cured article solution according to following table 5.
For this curing solution, utilize method similarly to Example 27, the above-mentioned cured article solution of injection in the substrate at shaping jig and above-mentioned 10 cold shock testings, and then in each substrate, drop into 1 piece of silicon respectively.
Above-mentioned shaping jig and cold shock testing are put into stove with substrate, implemented solidification treatment 1 hour down, and then implemented solidification treatment 5 hours down, make cured article at 150 ℃ at 70 ℃.
About this cured article, utilize method similarly to Example 27 to estimate.Evaluation result is shown in following table 6.
As YI=2.0≤13 of the index of the light fastness test of cured article, be judged as and have sufficient photostabilization in the practical application.Yet the cold shock testing number of times is 0 time＜50 times, is judged as not have sufficient cold-resistant thermal shocking in the practical application.
Can be judged though the cured article of comparative example 12 has photostabilization, not have cold-resistant thermal shocking by above result, synthetic determination is defective thus.
[comparative example 13]
Reflow process was changed to 7 hours, carried out the dehydrating condensation operation 25 hours.Other conditions are made resin combination according to table 4 similarly to Example 27, utilize method similarly to Example 27 to estimate.
Evaluation result, mixing index α 44～ε 44, storage stability index θ 44 are shown in following table 6.
The condensation rate K11 (%)=64.8%＜78% of intermediate.
The condensation rate L11 (%)=68.0%＜80% of modified resin composition.
The residual alcoxyl base unit weight of modified resin composition is 7%＞5%.
Shown in following table 6, the epoxy equivalent (weight) of the resin combination of comparative example 13 (WPE)=233g/eq is shown as suitable value.In addition, initial viscosity=15.2Pas＜1000Pas.Yet, preserve viscosity＞1000Pas, do not demonstrate flowability, storage stability index θ 44＞66, storage stability is bad, and synthetic determination is defective.
As shown in the above, even prolong the time of carrying out the dehydrating condensation operation, the storage stability of resin combination is the no show acceptance line also, and the characteristic of resin combination significantly depends on the condensation rate (chemical structure) of the intermediate in the reflow process.
[comparative example 14]
The temperature of the oil bath of reflow process is changed to 60 ℃.Other conditions are made resin combination according to table 4 similarly to Example 27, utilize method similarly to Example 27 to estimate.
Evaluation result, mixing index α 45～ε 45, storage stability index θ 45 are shown in following table 6.
The condensation rate K12 (%)=63.6%＜78% of intermediate.
The condensation rate L12 (%)=65.4%＜80% of modified resin composition.
The residual alcoxyl base unit weight of modified resin composition is 12%＞5%.
Shown in following table 6, the epoxy equivalent (weight) of the resin combination of comparative example 14 (WPE)=238g/eq is shown as suitable value.In addition, initial viscosity=16.4Pas＜1000Pas.Yet, preserve viscosity＞1000Pas, do not demonstrate flowability, storage stability index θ 44＞61, storage stability is bad, and synthetic determination is defective.
Shown in table 4～table 6 as can be known, with specific ratio blending epoxy and specific alkoxysilane compound containing trialkylsilyl group in molecular structure, the condensation rate of the intermediate in the reflow process of special stipulation cohydrolysis condensation, carry out dehydrating condensation then, and the condensation rate of special stipulation modified resin composition, the resin combination of the embodiment 27～35 of Zhi Zuoing has excellent flowability and storage stability thus, and the cured article of these resin combinations all has excellent photostabilization and cold-resistant thermal shocking.
Table 5
Unit: quality %
Then, in the modified resin composition of present embodiment, adding the resin combination that oxetane compound forms, enumerate embodiment and comparative example is specifically described.
About epoxy equivalent (weight) (WPE), viscosity, mixing index α～η, according to trying to achieve with above-mentioned same method.
The evaluation of the rerum natura in embodiment 36～38 and the comparative example 15～16 is following to be carried out.
The viscosimetric analysis of＜composition 〉
To the container sealing of the resin combination after the firm manufacturing be housed, the viscosity under carrying out under 25 ℃ after temperature adjusts 2 hours, measuring 25 ℃.
Viscosity is under the following situation of 1000Pas, is judged as to have flowability.
The light fastness test of＜cured article 〉
The photostabilization of evaluate cure thing by the following method.
(1) cured article of preparing by the aftermentioned method is solidified with solution, make the cured article of 20mm * 10mm * thickness 3mm.
(2) black masks of above-mentioned cured article with the 25mm * 15mm * thickness 1.2mm in the hole that has diameter 5.5mm covered, as the light fastness test sample.
(3) preparation device makes that UV illumination can be mapped to constant temperature via optical fiber from UV irradiating unit (Ushio Inc. system, " Spot Cure SP7-250DB ") is above-mentioned sample in 50 ℃ the Constant Temperature Incubators.
(4) be that top state is arranged in 50 ℃ the Constant Temperature Incubators with above-mentioned sample with black masks.
(5) in the mode in the hole that UV illumination can be mapped to diameter 5.5mm, from the top irradiation 2W/cm of black masks
2UV light 96 hours.
(6) utilize the spectral photometric colour measuring meter (Japanese electric look Industrial Co., Ltd system, " SD5000 ") that the integrating sphere peristome is transform as diameter 10mm, measure the postradiation sample of UV.
(7) try to achieve yellow chromaticity (YI) according to " ASTM D1925-70 (1988): Test Method for Yellowness Index of Plastics (plastics yellowness index test method) ".Under this YI is situation below 11, is judged as and has photostabilization.
The crack test of＜cured article 〉
The crackle of evaluate cure thing has or not by the following method.
(1) prepares substrate shown below.
Substrate: Solvay Advanced Polymers K.K. system, " AMODEL A-4122NL WH 905 " (depression that has diameter 10mm * degree of depth 1.2mm in the dull and stereotyped central authorities of 15mm * 15mm * thickness 2mm)
(2) make 5 and will flow into the sample that aforesaid substrate forms with solution, and make its curing, thus as the crack test sample by the cured article that the aftermentioned method is prepared.
(3), the having or not of visual observation crackle under magnifying glass, write down its number to above-mentioned sample jet penetration liquid (KOHZAI CORPORATION system, " MICRO CHECK ").
(4) 4 samples are not observed under the situation of crackle in 5 samples, are judged as to have anti-crackle.
The surface viscosity test of＜cured article 〉
The surface viscosity of evaluate cure thing by the following method.
(1) cured article of preparing by the aftermentioned method is solidified with solution, make the cured article of 20mm * 10mm * thickness 3mm.
(2) push the surface of resulting cured article gently with the thumb that wears latex glove, do not confirming under the situation about being clamminess, it is good to be judged as surface viscosity.
Starting material about using in embodiment 36～38 and the comparative example 15～16 are shown in following (1)～(12).
(1) Resins, epoxy
(1-1) Resins, epoxy A: poly-(dihydroxyphenyl propane-2-hydroxypropyl ether) (below, be called Bis-A Resins, epoxy)
Trade(brand)name: Asahi Kasei Epoxy Co., Ltd system, " AER "
In addition, epoxy equivalent (weight) (WPE) and the viscosity of utilizing aforesaid method to measure is as described below.
Epoxy equivalent (weight) (WPE): 187g/eq
Viscosity (25 ℃): 14.3Pas
(1-2) Resins, epoxy B:3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexyl carboxylicesters (below, be called alicyclic epoxy resin)
Trade(brand)name: Daicel Chemical Industries, Ltd. system, " CEL 2021P "
In addition, epoxy equivalent (weight) (WPE) and the viscosity of utilizing aforesaid method to measure is as described below.
Epoxy equivalent (weight) (WPE): 131g/eq
Viscosity (25 ℃): 227mPas
(2) alkoxysilane compound containing trialkylsilyl group in molecular structure H:3-glycidoxypropyltrime,hoxysilane (below, be called GPTMS)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-403 "
(3) alkoxysilane compound containing trialkylsilyl group in molecular structure I: phenyltrimethoxysila,e (below, be called PTMS)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-103 "
(4) alkoxysilane compound containing trialkylsilyl group in molecular structure J: dimethyldimethoxysil,ne (below, be called DMDMS)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-22 "
(5) alkoxysilane compound containing trialkylsilyl group in molecular structure K: tetraethoxysilane (below, be called TEOS)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBE-04 "
(6) solvent
(6-1) tetrahydrofuran (THF): Wako Pure Chemical Industries, Ltd.'s system does not contain stabilizer type (below, be called THF)
(7) hydrolytic condensation catalyzer: dibutyl tin laurate (Wako Pure Chemical Industries, Ltd.'s system, below, be called DBTDL)
(8) oxetane compound: methoxyl group 3-ethyl-3{[(3-ethyl trimethylene oxide-3-yl)] methyl } trimethylene oxide (Toagosei Co., Ltd's system, " ARON OXETANE OXT-221 ")
(9) cationic polymerization initiators
Trade(brand)name: three new chemical industry Co., Ltd. systems, " San-Aid SI-100L "
(10) solidifying agent: " 4-methyl hexahydro phthalic anhydride/hexahydro phthalic anhydride=70/30 "
Trade(brand)name: New Japan Chem Co., Ltd's system, " RIKACID MH-700G "
(11) curing catalyst: amine compound
Trade(brand)name: San-Apro Ltd. system, " U-CAT 18X "
(12) silicone resin
Trade(brand)name: Dow Corning Toray Co., Ltd. system, " EG6301 (A liquid/B liquid) "
[synthesis example 1]
Resin combination A: make resin combination A in the following order, and estimate.
(1) prepares: the circulation Water Tank with Temp.-controlled is set at 5 ℃, and cooling tube is refluxed.And then, on magnetic stirring apparatus, place 80 ℃ oil bath.
(2) according to the proportion of composing of table 7, under 25 ℃ atmosphere, with alicyclic epoxy resin, alkoxysilane compound containing trialkylsilyl group in molecular structure and THF pack into drop in the flask that stirrer is arranged and mix stir after, and then add water and hydrolytic condensation catalyzer, and mix and stir.
(3) then, cooling tube is set on flask, is impregnated in 80 ℃ the oil bath rapidly and begins to stir, react 8 hours while reflux.
(4) after reaction finishes, be cooled to 25 ℃, take off cooling tube from flask then, collected specimens solution after the end reflow process.
(5) use vaporizer, under 400Pa, 50 ℃, remove the solution after reflow process finishes with distillation in 1 hour after, and then 80 ℃ down distillation removed 5 hours, carry out dehydration condensation simultaneously.
(6) after reaction finishes, be cooled to 25 ℃, obtain resin combination A.
(7) the mixing index α 46～ε 46 in this resin combination is shown in table 9.
(8) in addition, measure the epoxy equivalent (weight) (WPE) of the resin combination A that obtains in above-mentioned (6) according to aforesaid method.
The epoxy equivalent (weight) of above-mentioned resin combination (WPE)=158g/eq is shown as suitable value.
[synthesis example 2]
Resin combination B:, utilize the method compound resin composition B same, and estimate with synthesis example 1 according to the proportion of composing of table 7.Mixing index α 47～ε 47 is shown in table 9.
The epoxy equivalent (weight) of above-mentioned resin combination B (WPE)=163g/eq is shown as suitable value.
[synthesis example 3]
Resin combination C:, utilize the method compound resin composition C same, and estimate with synthesis example 1 according to the proportion of composing of table 7.Mixing index α 48～ε 48 is shown in table 9.
The epoxy equivalent (weight) of above-mentioned resin combination C (WPE)=160g/eq is shown as suitable value.
[embodiment 36]
Make composition 1 in the following order, and estimate.
(1) oxetane compound of the resin combination A of the above-mentioned synthesis example 1 of 75 quality % and 25 quality % mixed stir, and then under vacuum, outgas, with the mixture after the degassing as composition 1.The viscosity of composition 1 is 1.82Pas, is mobile excellent liquid.
(2) in the composition 1 of 99.2 quality %, add the cationic polymerization initiators of 0.8 quality % and mixing, with (1) same condition under processings that outgas, modulate cured article solution.
(3) with being coated with 2 pieces of stainless steel plate clamping thickness 3mm of releasing agent, the silicon rubber of コ word shape, make shaping jig, make that the cured article of being made by this shaping jig is about 50mm * about 20mm * thickness 30mm.
(4) prepare this shaping jig and above-mentioned 5 crack tests with substrate in the sample that forms with solution of the above-mentioned cured article of injection.
(5) above-mentioned shaping jig and crack test are put into stove with substrate, implemented solidification treatment 1 hour down, and then implemented solidification treatment 3 hours down, make cured article at 150 ℃ at 85 ℃.
(6) use above-mentioned sample, carry out light fastness test, anti-crackle test, reach the surface viscosity test, the results are shown in table 9 by aforesaid method.As YI=6.8≤11 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, 5 samples in 5 samples all do not crack, and are judged as to have anti-crackle.In addition, also do not confirm and be clamminess, surface viscosity is also good.
Can be judged that by above result the composition 1 of embodiment 36 has flowability, the cured article of its composition has photostabilization, anti-crackle in addition, and surface viscosity is also good, and synthetic determination is qualified thus.
[embodiment 37]
Make composition 2 in the following order, and estimate.
(1) oxetane compound of the resin combination B of the above-mentioned synthesis example 2 of 70 quality % and 30 quality % is mixed stir, and utilization and the embodiment 36 same method degassings handle, with the mixture after outgasing as composition 2.The viscosity of composition 2 is 2.78Pas, is mobile excellent liquid.
(2) in the composition 2 of 99.4 quality %, add the cationic polymerization initiators of 0.6 quality % and mixing, with (1) same condition under processings that outgas, modulate cured article solution.
(3) use above-mentioned cured article solution, utilize with the same method of embodiment 36 and implement solidification treatment, the making cured article.
As YI=7.9≤11 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, 5 samples in 5 samples all do not crack, and are judged as to have anti-crackle.In addition, also do not confirm and be clamminess, surface viscosity is also good.
Can be judged that by above result the composition 2 of embodiment 35 has flowability, the cured article of its composition has photostabilization, anti-crackle in addition, and surface viscosity is also good, and synthetic determination is qualified thus.
[embodiment 38]
Make composition 3 in the following order, and estimate.
(1) oxetane compound of the resin combination C of the above-mentioned synthesis example 3 of 80 quality % and 20 quality % is mixed stir, and utilization and the embodiment 36 same method degassings handle, with the mixture after outgasing as composition 3.The viscosity of composition 3 is 2.27Pas, is mobile excellent liquid.
Add the cationic polymerization initiators of 0.7 quality % in the composition 3 of (2) 99.3 quality % and mix, with (1) same condition under processings that outgas, modulate cured article solution.
(3) use above-mentioned cured article solution, utilize with the same method of embodiment 36 and implement solidification treatment, the making cured article.
As YI=8.8≤11 of the index of the light fastness test of this cured article, be judged as and have photostabilization.In addition, 4 samples in 5 samples all do not crack, and are judged as to have anti-crackle.In addition, also do not confirm and be clamminess, surface viscosity is also good.
Can be judged that by above result the composition 3 of embodiment 38 has flowability, the cured article of its composition has photostabilization, anti-crackle in addition, and surface viscosity is also good, and synthetic determination is qualified thus.
[comparative example 15]
In above-mentioned Bis-A Resins, epoxy and alicyclic epoxy resin, replace cationic polymerization initiators, stir and add solidifying agent and curing catalyst and mix according to the proportion of composing of table 8, under vacuum, outgas, with this as cured article solution.Then, utilize the method same, with injecting above-mentioned cured article solution in the substrate, implemented solidification treatment 4 hours down at 110 ℃, the making cured article in shaping jig and above-mentioned 5 crack tests with embodiment 36.
Utilize the table 9 that the results are shown in the same method evaluation of embodiment 36.
As YI=13.9＞11 of the index of the light fastness test of cured article, be judged as and do not have photostabilization.In addition, 4 samples in 5 samples all do not confirm crackle, have anti-crackle.In addition, also do not confirm and be clamminess, surface viscosity is good.
Can be judged that by above result the cured article of comparative example 15 does not have photostabilization, synthetic determination is defective thus.
[comparative example 16]
Use with the mixture that 1: 1 mass ratio mixes, mixes the A liquid of above-mentioned silicone resin and B liquid to stir, under vacuum, outgas, with the mixture after the degassing as cured article solution.
Then, utilize the method same, with injecting above-mentioned cured article solution in the substrate, implemented solidification treatment 1 hour down at 150 ℃, the making cured article in shaping jig and above-mentioned 5 crack tests with embodiment 36.
Utilize the table 9 that the results are shown in the same method evaluation of embodiment 36.
As YI=2.3≤11 of the index of the light fastness test of cured article, be judged as and have photostabilization.In addition, 5 samples all do not confirm crackle in 5 samples, have anti-crackle.Yet, to observe and be clamminess, surface viscosity is bad.Can be judged that by above result though the cured article of comparative example 16 has photostabilization and anti-crackle, surface viscosity is bad, synthetic determination is defective.
Shown in table 7～table 9, resin combination that obtains with specific ratio blending epoxy and specific alkoxysilane compound containing trialkylsilyl group in molecular structure and cohydrolysis condensation and the resin combination that contains oxetane compound mobile excellent.In addition, use the cured article of these resin combinations to have excellent photostabilization, anti-crackle, reached surface viscosity.
Then, in the modified resin composition of present embodiment, adding the photosensitive polymer combination that light acid producing agent forms, enumerate embodiment and comparative example is specifically described.
About epoxy equivalent (weight) (WPE), viscosity, mixing index α～η, by trying to achieve with above-mentioned same method.
The evaluation of the rerum natura in embodiment 39～41 and the comparative example 17～19 is following to be carried out.
The viscosimetric analysis of＜photosensitive polymer combination 〉
To the container sealing of the composition after the firm manufacturing be housed, the viscosity under carrying out under 25 ℃ after temperature adjusts 1 hour, measuring 25 ℃.
Viscosity is under the following situation of 1000Pas, is judged as to have flowability.
＜making method a that films 〉
According to following order, in air, under the condition of 23 ℃ of temperature, humidity 55%RH, make and film.
(1) prepares to use ethanol (Wako Pure Chemical Industries, Ltd.'s system, 99.5%) to clean the surface and make its drying respectively with hypocoxa.
Substrate: pet resin (below, PET be called.)
Polycarbonate resin (below, be called PC.)
Plexiglass (below, be called PMMA.)
(2) use rod to be coated with machine (#3), the photosensitive composite of coating embodiment or the composition of comparative example on aforesaid substrate.
(3) aforesaid substrate is arranged in the UV solidification equipment (Fusion UV Systems Japan K.K. system), repeats 3 times following condition, make its curing.
Light source and light quantity: high voltage mercury lamp (120W/cm2)
Belt conveying motor speed: 10m/ minute
(4) and then, aforesaid substrate 100 ℃ of following heat treated 1 hour, is made its after fixing.
＜making method the b that films 〉
According to following order, in air, under the condition of 23 ℃ of temperature, humidity 55%RH, make and film.
(1) prepares to use ethanol (Wako Pure Chemical Industries, Ltd.'s system, 99.5%) to clean the surface and make its drying respectively with hypocoxa.
Substrate: PET
(2) use rod to be coated with machine (#3), the photosensitive composite of coating embodiment or the composition of comparative example on aforesaid substrate.
(3) aforesaid substrate is arranged in the UV solidification equipment (Fusion UV Systems Japan K.K. system), repeats 5 times following condition, make its curing.
Light source and light quantity: high voltage mercury lamp (120W/cm2)
Belt conveying motor speed: 5m/ minute
＜the light solidified of filming 〉
According to " JIS K5600-5-4:1999 coating ordinary test method-Di 5 parts: mechanical properties-Di of filming 4 joints: scratch intensity (pencil method) ", above-mentioned filming to be measured, under the situation for 3B～6H, it is good to be judged as light solidified.
＜the cementability of filming 〉
According to " JIS K5600-5-6:1999 coating ordinary test method-Di 5 parts: mechanical properties-Di 6 joints of filming: tack (cross-hatching) ", above-mentioned filming measured.
The result estimates with following 3 ranks: zero: do not observe basically peel off, △: the part peel off, *: peel off basically.Under the situation that demonstrates the result better than benchmark, it is good to be judged as cementability.
＜comprehensive judgement 〉
Above-mentioned photosensitive polymer combination has under the good situation of flowability and the light solidified of filming and cementability, and synthetic determination is qualified.
Starting material about using in embodiment 39～41 and the comparative example 17～19 are shown in following (1)～(9).
(1) Resins, epoxy
(1-1) Resins, epoxy A: poly-(dihydroxyphenyl propane-2-hydroxypropyl ether) (below, Bis-A Resins, epoxy be called.)
Trade(brand)name: Asahi Kasei Epoxy Co., Ltd system, " AER "
In addition, epoxy equivalent (weight) (WPE) and the viscosity of utilizing aforesaid method to measure is as described below.
Epoxy equivalent (weight) (WPE): 187g/eq
Viscosity (25 ℃): 14.3Pas
(1-2) Resins, epoxy B:3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexyl carboxylicesters (below, be called alicyclic epoxy resin.)
Trade(brand)name: Daicel Chemical Industries, Ltd. system, " CEL 2021P "
In addition, epoxy equivalent (weight) (WPE) and the viscosity of utilizing aforesaid method to measure is as described below.
Epoxy equivalent (weight) (WPE): 131g/eq
Viscosity (25 ℃): 227mPas
(2) alkoxysilane compound containing trialkylsilyl group in molecular structure H:3-glycidoxypropyltrime,hoxysilane (below, be called GPTMS.)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-403 "
(3) alkoxysilane compound containing trialkylsilyl group in molecular structure I: phenyltrimethoxysila,e (below, PTMS be called.)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-103 "
(4) alkoxysilane compound containing trialkylsilyl group in molecular structure J: dimethyldimethoxysil,ne (below, DMDMS be called.)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-22 "
(5) alkoxysilane compound containing trialkylsilyl group in molecular structure K: tetraethoxysilane (below, TEOS be called.)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBE-04 "
(6) solvent
(6-1) tetrahydrofuran (THF): Wako Pure Chemical Industries, Ltd.'s system, do not contain stabilizer type (below, be called THF.)
(7) hydrolytic condensation catalyzer: dibutyl tin laurate (Wako Pure Chemical Industries, Ltd.'s system, below, DBTDL be called.)
(8) light acid producing agent
(8-1) the phosphofluoric acid salt mixture of triaryl matte
Trade(brand)name: Union Carbide Corporation system, " UVI-6990 " (below, be called UVI-6900.)
(8-2) hexafluoro antimonate of aromatic matte
Trade(brand)name: three new chemical industry Co., Ltd. systems, " San-Aid SI-80L " (below, be called SI-80L.)
(9) oxetane compound
(9-1) 3-ethyl-3-(phenoxymethyl) trimethylene oxide
Trade(brand)name: Toagosei Co., Ltd's system, " OXT-211 " (below, be called POX.)
[synthesis example 4]
Resin combination D: make resin combination D in the following order, and estimate.
(1) prepares: the circulation Water Tank with Temp.-controlled is set at 5 ℃, and cooling tube is refluxed.And then, on magnetic stirring apparatus, place 80 ℃ oil bath.
(2) according to the proportion of composing of table 10, under 25 ℃ atmosphere, with alicyclic epoxy resin, alkoxysilane compound containing trialkylsilyl group in molecular structure and THF pack into drop in the flask that stirrer is arranged and mix stir after, and then add water and hydrolytic condensation catalyzer, and mix and stir.
(3) then, cooling tube is set on flask, is impregnated in 80 ℃ the oil bath rapidly and begins to stir, react 8 hours while reflux.
(4) after reaction finishes, be cooled to 25 ℃, take off cooling tube from flask then, gather solution.
(5) use vaporizer, under 400Pa, 50 ℃, remove above-mentioned solution with distillation in 1 hour after, and then 80 ℃ down distillation removed 5 hours, carry out dehydration condensation simultaneously.
(6) after reaction finishes, be cooled to 25 ℃, obtain resin combination D.
(7) the mixing index α 49～ε 49 in this resin combination is shown in table 12.
(8) in addition, according to aforesaid method, measure the epoxy equivalent (weight) (WPE) of the resin combination D that obtains in above-mentioned (6).
The epoxy equivalent (weight) of above-mentioned resin combination (WPE)=193g/eq is shown as suitable value.Viscosity is 12.7Pas＜1000Pas in addition, demonstrates good flowability.
[synthesis example 5]
Resin combination E:, utilize the method compound resin composition E same, and estimate with synthesis example 4 according to the proportion of composing of table 10.Mixing index α 50～ε 50 is shown in table 12.
The epoxy equivalent (weight) of above-mentioned resin combination E (WPE)=152g/eq is shown as suitable value.In addition, viscosity is 0.93Pas＜1000Pas, demonstrates good flowability.
[embodiment 39]
Make photosensitive polymer combination 1 in the following order and film, and estimate.
(1) use the resin combination D of above-mentioned synthesis example 4, mix according to the proportioning of table 11 and stir, and then under vacuum, outgas, with the mixture after the degassing as photosensitive polymer combination 1.The viscosity of photosensitive polymer combination 1 is 12.6Pas＜1000Pas, is mobile excellent liquid.
(2) according to above-mentioned " the making method a that films ", go up the above-mentioned photosensitive polymer combination 1 of coating at above-mentioned 3 kinds of substrates (PET, PC, PMMA), use the UV solidification equipment to make and film.
(3) according to " JIS K5600-5-4:1999 coating ordinary test method-Di 5 parts: mechanical properties-Di 4 joints of filming: scratch intensity (pencil method) ", above-mentioned filming measured, be the results are shown in table 12.
(4) according to " JIS K5600-5-6:1999 coating ordinary test method-Di 5 parts: mechanical properties-Di 6 joints of filming: tack (cross-hatching) ", above-mentioned filming measured, be the results are shown in table 12.
As mentioned above, photosensitive polymer combination 1 mobile excellent, the light solidified of filming is good, and with to compare cementability as the comparative example 17 of benchmark better, synthetic determination is qualified thus.
[embodiment 40]
According to the proportioning of table 11, utilize with the same method of embodiment 39 and make photosensitive polymer combination 2.Wherein, the endless belt conveyor speed setting with the UV solidification equipment is 10m/ minute.Evaluation result is shown in table 12.
The viscosity of photosensitive polymer combination 2 is 3.2Pas＜1000Pas, is mobile excellent liquid.
As mentioned above, photosensitive polymer combination 2 mobile excellent, the light solidified of filming is good, and with to compare cementability as the comparative example 17 of benchmark better, synthetic determination is qualified thus.
[embodiment 41]
Make photosensitive polymer combination 3 according to the proportioning of table 11, utilize with the same method of embodiment 39 and estimate.The viscosity of photosensitive polymer combination 3 is 1.0Pas＜1000Pas, is mobile excellent liquid.
Then, use above-mentioned photosensitive polymer combination 3, PET as substrate, is filmed according to above-mentioned " the making method b that films " manufacturing.The results are shown in table 12.
As mentioned above, photosensitive polymer combination 3 mobile excellent, the light solidified of filming is good, and with to compare cementability as the comparative example 19 of benchmark better, synthetic determination is qualified thus.
[comparative example 17]
According to the proportioning of table 11, utilize with the same method of embodiment 39 and make photosensitive polymer combination 4.Evaluation result is shown in table 12.
The viscosity of photosensitive polymer combination 4 is 13.8Pas＜1000Pas, is mobile excellent liquid.
Yet as shown in table 12, though photosensitive polymer combination 4 is mobile excellent, the cementability of filming is bad, and synthetic determination is defective thus.
[comparative example 18]
According to the proportioning of table 11, utilize with the same method of embodiment 39 and make photosensitive polymer combination 5.As silane coupling agent, use GPTMS.Evaluation result is shown in table 12.
The viscosity of photosensitive polymer combination 5 is 12.1Pas＜1000Pas, is mobile excellent liquid.
Yet, as shown in table 12, though photosensitive polymer combination 5 is mobile excellent, do not observe the improved in adhesion effect of filming, synthetic determination is defective thus.
[comparative example 19]
According to the proportioning of table 11, utilize with the same method of embodiment 39 and make photosensitive polymer combination 6.Evaluation result is shown in table 12.
The viscosity of photosensitive polymer combination 6 is 0.3Pas＜1000Pas, is mobile excellent liquid.
Yet as shown in table 12, though photosensitive polymer combination 6 is mobile excellent, the cementability of filming is bad, and synthetic determination is defective thus.
By the result of table 10～12 as can be known, if photosensitive polymer combination contains light acid producing agent and the resin combination by Resins, epoxy and specific alkoxysilane compound containing trialkylsilyl group in molecular structure cohydrolysis condensation are obtained, then photosensitive polymer combination is mobile excellent, and has used the coating agent of these photosensitive polymer combinations and filmed and have excellent light solidified and cementability.
Then, in the modified resin composition of present embodiment, adding the fluorescence resin combination that fluor forms, enumerate embodiment and comparative example is specifically described.
The evaluation of the rerum natura in embodiment 42～44 and the comparative example 20～23 is following to be carried out.
About epoxy equivalent (weight) (WPE), viscosity, mixing index α～η, by trying to achieve with above-mentioned same method.
The calculating of＜storage stability index θ and the storage stability of resin combination 〉
Storage stability in the resin combination is estimated by the storage stability index θ shown in the following general formula (9).
Storage stability index θ=(preservation viscosity)/(initial viscosity) (9)
To the container sealing of the resin combination after the firm manufacturing be housed, the viscosity under carrying out under 25 ℃ after temperature adjusts 2 hours, measuring 25 ℃, with this as " initial viscosity ".
And then, will the container sealing of resin combination be housed, in 25 ℃ Constant Temperature Incubators, preserved for 2 weeks.After the preservation, the viscosity under measuring 25 ℃, with this as " preservation viscosity ".
Having flowability (viscosity is below the 1000Pas) and storage stability index θ at resin combination is under the situation below 4, is judged as to have storage stability.
The dispersion stabilization test of＜fluorescence resin composition 〉
After making the fluorescence resin composition, also sealing was preserved 5 hours in 25 ℃ Constant Temperature Incubators in the 50mL vial of packing into.After the preservation, observe outward appearance, by the precipitation or the homogeneity of Visual Confirmation fluor.Do not observing under the precipitation of fluor, the homodisperse situation of fluor, it is qualified to be judged as dispersion stabilization.
The light fastness test of＜cured article (cured article of resin combination) 〉
About being dispersed with the cured article of solid substance (fluor), the deviation of its yellow chromaticity (YI) is bigger.Therefore, utilize following method to make cured article by the resin combination that does not add fluor, and estimate, the result is as the photostabilization evaluation.
(1) cured article of preparing by the aftermentioned method is solidified with solution, make the cured article of 20mm * 10mm * thickness 3mm.
(2) black masks of above-mentioned cured article with the 25mm * 15mm * thickness 1.2mm in the hole that has diameter 5.5mm covered, as the light fastness test sample.
(3) preparation device makes that UV illumination can be mapped to constant temperature via optical fiber from UV irradiating unit (Ushio Inc. system, " Spot Cure SP7-250DB ") is above-mentioned sample in 50 ℃ the Constant Temperature Incubators.
(4) be that top state is arranged in 50 ℃ the Constant Temperature Incubators with above-mentioned sample with black masks.
(5) in the mode in the hole that UV illumination can be mapped to diameter 5.5mm, from the top irradiation 2W/cm of black masks
2UV light 96 hours.
(6) utilize the spectral photometric colour measuring meter (Japanese electric look Industrial Co., Ltd system, " SD5000 ") that the integrating sphere peristome is transform as diameter 10mm, measure the postradiation sample of UV.
(7) try to achieve yellow chromaticity (YI) according to " ASTM D1925-70 (1988): Test Method for Yellowness Index of Plastics (plastics yellowness index test method) ".Under this YI was situation below 13, it was qualified to be judged as.
The luminous test of＜LED 〉
LED is lighted, by its tone of Visual Confirmation, for the LED of unmixed fluor, be changed to by blueness at tone under the situation of white, luminous is qualified.
The luminous test (mensuration time of persistence) of＜light-storing material 〉
With 200 Luxs irradiations to the light source luminescent lamp D65 commonly used of regulation in the sample " classification, performance reference and the test method of JIS Z9107:2008 secure ID-performance " 20 minutes.After the irradiation, measure after-glow brightness, will reach 0.3mcd/m with luminance meter
2Below till time as time of persistence.Be more than 120 minutes the time time of persistence, and it is qualified to be judged as luminous.
The reliability test of＜LED (1) (continuous working test: below, be called " L test ") 〉
With 10 LED according to the method 1026.5 (steady state operation life) of " MIL-STD-750E (test method of semiconductor device) ", and the method 1005.8 (steady-state life) of " MIL-STD-883G (microcircuit) " estimate under the following conditions.
Mode with " IF=20mA, Ta=25 ℃, 960 hours " is lighted, and measures the total light flux (lm) before and after lighting.And then, obtain " total light flux sustainment rate (%)=(total light flux after lighting)/(light before total light flux) * 100 " for each LED, under whole Schwellenwerts of the total light flux sustainment rate (%) of LED was situation more than 90%, it was qualified to be judged as.
The reliability test of＜LED (2) (thermal shock test: below, be called " TS test ") 〉
10 LED are estimated under the following conditions according to the test method 307 (thermal shock test) of " EIAJ ED-4701/300 (environment of semiconductor device and durability test method (strength trial I) ".
As 1 circulation, carry out confirming lighting of LED after 100 round-robin thermal shockings that under 10 situations about all lighting, it is qualified to be judged as with " 10 ℃ (5 minutes)～100 ℃ (5 minutes) ".
The reliability test of＜LED (3) (temperature cycling test: below, be called " TC " test) 〉
10 LED are estimated under the following conditions according to the test method 105 (temperature cycling test) of " EIAJ ED-4701/100 (environment of semiconductor device and durability test method (longevity test I) ".
As 1 circulation, carry out confirming lighting of LED after 100 round-robin temperature cycle that under 10 situations about all lighting, it is qualified to be judged as with " 40 ℃ (30 minutes)～85 ℃ (5 minutes)～100 ℃ (30 minutes)～25 ℃ (5 minutes) ".
In the evaluation of above-mentioned LED, under the whole qualified situations in photostabilization and reliability test (1)～(3), synthetic determination is qualified.
Starting material about using in embodiment 42～44 and the comparative example 20～23 are shown in following (1)～(10).
(1) Resins, epoxy
(1-1) Resins, epoxy A: poly-(dihydroxyphenyl propane-2-hydroxypropyl ether) (below, be called " Bis-A Resins, epoxy ")
Trade(brand)name: Asahi Kasei Epoxy Co., Ltd system, " AER "
In addition, epoxy equivalent (weight) (WPE) and the viscosity of utilizing aforesaid method to measure is as described below.
Epoxy equivalent (weight) (WPE): 188g/eq
Viscosity (25 ℃): 14.8Pas
(1-2) Resins, epoxy B:3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexyl carboxylicesters (below, be called " alicyclic epoxy resin ".)
Trade(brand)name: Daicel Chemical Industries, Ltd. system, " CEL 2021P "
In addition, epoxy equivalent (weight) (WPE) and the viscosity of utilizing aforesaid method to measure is as described below.
Epoxy equivalent (weight) (WPE): 131g/eq
Viscosity (25 ℃): 227mPas
(2) alkoxysilane compound containing trialkylsilyl group in molecular structure
(2-1) alkoxysilane compound containing trialkylsilyl group in molecular structure H:3-glycidoxypropyltrime,hoxysilane (below, be called " GPTMS ")
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-403 "
(2-2) alkoxysilane compound containing trialkylsilyl group in molecular structure I: phenyltrimethoxysila,e (below, be called " PTMS ")
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-103 "
(2-3) alkoxysilane compound containing trialkylsilyl group in molecular structure J: dimethyldimethoxysil,ne (below, be called " DMDMS ")
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-22 "
(2-4) alkoxysilane compound containing trialkylsilyl group in molecular structure K: tetraethoxysilane (below, be called " TEOS ")
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBE-04 "
(3) solvent: tetrahydrofuran (THF) (Wako Pure Chemical Industries, Ltd.'s system does not contain stabilizer type) (below, be called " THF ")
(4) hydrolytic condensation catalyzer: dibutyl tin laurate (Wako Pure Chemical Industries, Ltd.'s system, below, be called " DBTDL ")
(5) solidifying agent: " 4-methyl hexahydro phthalic anhydride/hexahydro phthalic anhydride=70/30 "
Trade(brand)name: New Japan Chem Co., Ltd's system, " RIKACID MH-700G "
(6) curing catalyst: amine compound
Trade(brand)name: San-Apro Ltd. system, " U-CAT 18X "
(7) reactive diluent: " 1,2:8,9 diepoxy terpadienes "
Trade(brand)name: Daicel Chemical Industries, Ltd. system, " CEL 3000 "
(8) polymerization starter: aromatic series sulfosalt
Trade(brand)name: three new chemical industry Co., Ltd. systems, " San-Aid SI-100L "
(9) fluor
(9-1) fluor A: " YAG:Ce3+ fluor " (Kasei Optonix, LTD. system)
(9-2) fluor B (light storing phosphor): " SrAl2O4:Eu, Dy fluor " (Nemoto ﹠ Co., Ltd's system)
(10) silicone resin
Trade(brand)name: Dow Corning Toray Co., Ltd. system, " EG6301 (A liquid/B liquid) "
[synthesis example 6]
Make resin combination by following operation.
(1) prepares: the circulation Water Tank with Temp.-controlled is set at 5 ℃, and cooling tube is refluxed.And then, on magnetic stirring apparatus, place 80 ℃ oil bath.
(2) according to the proportion of composing shown in the following table 13, under 25 ℃ atmosphere, with above-mentioned Bis-A1 Resins, epoxy, alkoxysilane compound containing trialkylsilyl group in molecular structure and THF pack into drop in the flask that stirrer is arranged and mix stir after, and then add water and hydrolytic condensation catalyzer, and mix and stir.
(3) then, cooling tube is set on flask, is impregnated in 80 ℃ the oil bath rapidly and begins to stir, react 20 hours (reflow process) while reflux.
(4) after reaction finishes, be cooled to 25 ℃, take off cooling tube from flask then.
(5) use vaporizer, under 400Pa, 50 ℃, remove the solution after reflow process finishes with distillation in 1 hour after, and then 80 ℃ down distillation removed 10 hours, carry out dehydration condensation (dehydrating condensation operation) simultaneously.
(6) after described dehydration condensation finishes, be cooled to 25 ℃, obtain resin combination.
(7) the above-mentioned mixing index α 51～ε 51 of this resin combination is shown in following table 16 respectively.
(8) in addition, according to aforesaid method, measure epoxy equivalent (weight) (WPE), the initial viscosity of the resin combination that obtains in above-mentioned (6) and preserve viscosity.And then, obtain storage stability index θ 51, they are shown in table 16.
The epoxy equivalent (weight) of the resin combination of above-mentioned synthesis example 6 (WPE)=228g/eq is shown as suitable value.In addition, initial viscosity=38.2Pas＜1000Pas, and preserve viscosity=61.1Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 51=1.6≤4 are judged as the resin combination with storage stability.
[synthesis example 7]
Making reflow process is 6 hours, in addition utilizes the method same with synthesis example 6, makes resin combinations according to table 13 and 14.Utilize with the result of the same method evaluation of synthesis example 6, and mixing index α 52～ε 52, storage stability index θ 52 be shown in table 16.
Shown in table 16, the epoxy equivalent (weight) of the resin combination of synthesis example 7 (WPE)=158g/eq is shown as suitable value.In addition, initial viscosity=1.8Pas＜1000Pas, and preserve viscosity=3.1Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 52=1.72≤4 are judged as the resin combination with storage stability.
[embodiment 42]
Use is made cured article, and is carried out light fastness test at 25 ℃ of resin combinations of preserving the above-mentioned synthesis example 6 in 2 weeks down.The results are shown in table 16.
(1) under 25 ℃ atmosphere, according to the proportion of composing of table 14 above-mentioned resin combination, solidifying agent and curing catalyst are mixed and to stir, and under vacuum, outgas, as cured article solution.
(2) with being coated with 2 pieces of stainless steel plate clamping thickness 3mm of releasing agent, the silicon rubber of コ word shape, make shaping jig.
(3) in this shaping jig, inject above-mentioned cured article solution, implemented solidification treatment 1 hour down, and then implemented solidification treatment 1 hour down, make cured article at 150 ℃ at 120 ℃.
(4) temperature drop is low to moderate the taking-up of back below 30 ℃ cured article in the stove, according to aforesaid method, and preparation light fastness test sample.
(5) use above-mentioned sample, carry out light fastness test, the results are shown in table 16 by aforesaid method.As YI=7.5≤13 of the index of the light fastness test of this cured article, it is qualified to be judged as photostabilization.
(6) then, the fluor A that in the resin combination of the synthesis example 6 of 90 quality %, mixes 10 quality %, utilize planetary stirring machine (Inoue MFG. Inc.'s system) mix to stir after 10 minutes, deaeration is handled under vacuum, with this as the fluorescence resin combination.
(7) with the sample bottle of above-mentioned fluorescence resin combination injection 50mL, preserved 5 hours down at 25 ℃.
(8) after the preservation, by Visual Confirmation side and bottom surface, the result is precipitation not, the fluor homodisperse, and the dispersion stabilization that is judged as the fluorescence resin combination is qualified.Evaluation result is shown in table 16.
And then, use at 25 ℃ and preserve the above-mentioned fluorescence resin combination in 2 weeks down, in the following order, make bullet cut LED, and carry out reliability test (1)～(3).The results are shown in table 16.
The structure of this bullet cut LED is for having 2 lead frames, and wherein one upper end is formed with the cup portion that is used to place led chip.
(9) and then, mix according to the proportion of composing of table 15 and to stir above-mentioned fluorescence resin combination, solidifying agent and curing catalyst, and under vacuum, outgas, as the LED sealing material.
(10) in the cup portion of the casting mold frame of the bullet cut of diameter 5mm, inject the LED sealing material of (9).
(11) utilize silver to stick with paste the led chip of tube core welding emission wavelength 400nm thereon, and dipping has connected the lead frame of bonding wire (copper cash).
(12) in a vacuum after the deaeration, 90 ℃ of following solidification treatment 1 hour, and then 110 ℃ of following solidification treatment 5 hours.
(13) in addition, as outermost resin, adding the solidifying agent of 46.6 quality % and curing catalyst and the mixing of 0.2 quality % in the Bis-A Resins, epoxy of 53.2 quality % stirs, under vacuum, outgas, the material that obtains is injected the casting mold frame, 130 ℃ of following solidification treatment 1 hour, and then, obtain bullet cut LED 150 ℃ of following solidification treatment 6 hours.Evaluation result is shown in table 16.
The result who carries out above-mentioned " luminous test " is, sends blue light as the LED of the comparative example 20 of benchmark, and the LED of embodiment 42 sends the light of white relatively therewith, and it is qualified to be judged as.
The result who carries out above-mentioned " reliability test (1) (L test) " is, all the Schwellenwert of LED is total light flux sustainment rate (%)=94% 〉=90%, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, even after having carried out 100 round-robin thermal shockings, all LED all light, and it is qualified to be judged as.
In addition, the result who carries out above-mentioned " reliability test (3) (TC test) " is, even after having carried out 100 round-robin temperature cycle, all LED all light, and it is qualified to be judged as.
Can judge by above result, the dispersion stabilization test of the fluorescence resin composition of embodiment 42, light fastness test, luminous test, and reliability test (1)～(3) all qualified, synthetic determination is qualified.
[embodiment 43]
Replace the resin combination of synthesis example 6 and use the resin combination of synthesis example 7, with the solidification treatment temperature of embodiment 41 (3), (12) change to 110 ℃ following 4 hours, and then 150 ℃ following 1 hour, in addition utilize the method same with embodiment 40, make resin combinations, cured article, fluorescence resin composition, and LED according to table 13～15, evaluation the results are shown in table 16.
As YI=6.8≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
In addition, 25 ℃ of fluorescence resin compositions precipitations not of preserving down 5 hours, the fluor homodisperse, it is qualified to be judged as dispersion stabilization.
Then, the result who carries out LED " luminous test " is, sends the light of white, and it is qualified to be judged as.
In addition, the result who carries out " reliability test (1) (L test) " is, all the Schwellenwert of LED is total light flux sustainment rate (%)=95% 〉=90%, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, even after having carried out 100 round-robin thermal shockings, all LED all light, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (3) (TC test) " is, even after having carried out 100 round-robin temperature cycle, all LED all light, and it is qualified to be judged as.
Can judge by above result, the dispersion stabilization test of the fluorescence resin composition of embodiment 43, light fastness test, luminous test, and reliability test (1)～(3) all qualified, synthetic determination is qualified.
[embodiment 44]
Utilize with the same method of embodiment 42 and in the resin combination of the synthesis example 7 of 60 quality %, mix the fluor B of 40 quality % and make the fluorescence resin composition, and estimate.Implemented the dispersion stabilization test of the fluorescence resin composition of embodiment 44, the result does not observe precipitation, and is more even, and it is qualified to be judged as.
And, with the ratio shown in the table 17 fluorescence resin composition, reaction diluent and polymerization starter being mixed, deaeration under vacuum, and then according to following order is made light-storing material (filming) in air, under the condition of 23 ℃ of temperature, humidity 55%RH.
(1) slide glass of preparation 5cm * 5cm size is cleaned the surface and is made its drying with ethanol (Wako Pure Chemical Industries, Ltd.'s system, 99.5%).
(2) use rod to be coated with machine (#3), the above-mentioned fluorescence resin composition of coating on above-mentioned slide glass.
(3) above-mentioned slide glass was solidified 10 minutes, film thereby form.
Luminous test as above-mentioned light-storing material (filming) utilizes aforesaid method to measure time of persistence, and the result is more than 600 minutes, and it is qualified to be judged as.
Can be judged that by above result the dispersion stabilization test and the luminous test of the fluorescence resin composition of embodiment 44 are qualified, synthetic determination is qualified.It the results are shown in table 18.
[reference example]
Replace the fluorescence resin composition of embodiment 42 and use the resin combination of synthesis example 6, make resin combinations, cured article, and LED according to table 13～15, evaluation the results are shown in table 16.
As YI=7.5≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
Then, the result who carries out LED " luminous test " is, sends blue light, and it is defective to be judged as luminous.
And then the result who carries out " reliability test (1) (L test) " is, all the Schwellenwert of LED is total light flux sustainment rate (%)=95% 〉=90%, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, even after having carried out 100 round-robin thermal shockings, all LED all light, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (3) (TC test) " is, even after having carried out 100 round-robin temperature cycle, all LED all light, and it is qualified to be judged as.
[comparative example 20]
Replace the resin combination of synthesis example 6 and use alicyclic epoxy resin, make the fluorescence resin combination, evaluation the results are shown in table 16.
The fluorescence resin combination of comparative example 20 is if preserved 5 hours down at 25 ℃, and then the fluor precipitation is inhomogeneous, and it is defective to be judged as dispersion stabilization.And, owing to can't make normal fluorescence resin composition, thereby be not cured making, the evaluation of thing and LED, synthetic determination is defective.
[comparative example 21]
Replace the resin combination of synthesis example 6 and use Bis-A Resins, epoxy, utilize the method same, make resin combinations, cured article, fluorescence resin composition, and LED according to table 13～15 with embodiment 42, evaluation the results are shown in table 16.
As YI=17.2＞13 of the index of light fastness test, it is defective to be judged as photostabilization.
In addition, 25 ℃ of fluorescence resin compositions precipitations not of preserving down 5 hours, the fluor homodisperse, it is qualified to be judged as dispersion stabilization.
Then, the result who carries out LED " luminous test " is, sends the light of white, and it is qualified to be judged as.
And then the result who carries out " reliability test (1) (L test) " is, all the Schwellenwert of LED is total light flux sustainment rate (%)=97% 〉=90%, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, even after having carried out 100 round-robin thermal shockings, all LED all light, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (3) (TC test) " is, even after having carried out 100 round-robin temperature cycle, all LED all light, and it is qualified to be judged as.
Can be judged that by above result the test of the dispersion stabilization of the fluorescence resin composition of comparative example 21, luminous test, and reliability test (1)～(3) are all qualified, but photostabilization is bad, synthetic determination is defective.
[comparative example 22]
The resin combination that replaces synthesis example 6, and use the above-mentioned silicone resin that A liquid and B liquid is mixed together with 1: 1 mass ratio.It is following 5 hours that the solidification treatment temperature of the sealing material of cured article and LED is changed to 70 ℃ of following 1 hour and then 150 ℃, in addition utilize the method same with embodiment 42, make resin combinations, cured article, fluorescence resin composition, and LED according to table 13～15, evaluation the results are shown in table 16.
As YI=2.0≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
Then, the result who carries out LED " luminous test " is, sends the light of white, and it is qualified to be judged as.
The result who carries out above-mentioned " reliability test (1) (L test) " is, 3 LED points in 10 do not work, and total light flux sustainment rate (%) can't be measured, and is judged as defective.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, after having carried out 100 round-robin thermal shockings, only 4 LED in 10 light, and are judged as defective.
And then the result who carries out above-mentioned " reliability test (3) (TC test) " is, after having carried out 100 round-robin temperature cycle, only 6 LED in 10 light, and are judged as defective.
Can judge by above result, the dispersion stabilization test of the fluorescence resin composition of comparative example 22, light fastness test, and luminous stand the test, but the result of reliability test (1)～(3) is defective, and synthetic determination is defective.
[comparative example 23]
Replace the resin combination of synthesis example 7 and use alicyclic epoxy resin, in addition utilize the method same, make fluorescence resin composition and light-storing material (filming), carry out dispersion stabilization test and luminous test according to the proportioning of table 17 with embodiment 44.The results are shown in table 18.
Implemented the dispersion stabilization test of the fluorescence resin composition of comparative example 23, the result has produced precipitation, and is inhomogeneous, is judged as defective.
Luminous test as above-mentioned light-storing material (filming) utilizes aforesaid method to measure time of persistence, and the result is more than 600 minutes, and it is qualified to be judged as.
Can be judged that by above result the luminous test of the fluorescence resin composition of comparative example 23 is qualified, but dispersion stabilization is defective, synthetic determination is defective.
By the result of table 13～18 as can be known, the dispersion stabilization excellence of embodiment 42 and 43 fluorescence resin combination, the photostabilization excellence of its cured article.In addition, LED uses the fluorescence resin composition of embodiment 42 and 43 as sealing material, and then its luminous test is good, and reliability test is also excellent.In addition, the dispersion stabilization excellence of the fluorescence resin combination of embodiment 44, the luminous test of light-storing material is good.On the other hand, the dispersion stabilization of comparative example 20 and 23 fluorescence resin composition is bad.At least one of the luminous test of photostabilization when in addition, making cured article, the LED that uses as sealing material and reliability test is bad.
Above content shows, the dispersion stabilization excellence of the fluorescence resin combination of present embodiment is used the reliability excellence of its sealing material, the luminous excellence of light-storing material.
Table 14
Unit: quality %
Table 17
Unit: quality %
Then, in the modified resin composition of present embodiment, adding the insulating resin composition that the insulativity powder forms, enumerate embodiment and comparative example is specifically described.
The evaluation of the rerum natura in embodiment 45～48 and the comparative example 24～25 is following to be carried out.
About epoxy equivalent (weight) (WPE), viscosity, mixing index α～η, by trying to achieve with above-mentioned same method.
The median size of＜fused silica is measured 〉
Use laser diffraction formula particle size distribution device (SYMPATEC corporate system, " HELOS system "), under the dry type pattern, measure median size.
The viscosimetric analysis of＜resin combination 〉
To the container sealing of the composition after the firm manufacturing be housed, the viscosity under carrying out under 25 ℃ after temperature adjusts 1 hour, measuring 25 ℃.
Viscosity is under the following situation of 1000Pas, is judged as to have flowability.
The volume specific resistance of＜insulating resin composition is measured 〉
Utilize rod to be coated with machine and be coated with insulating resin composition on slide glass, making thickness is 40 μ m, and it was heated 60 minutes down at 200 ℃, and formation is filmed.
Utilizing resistrivity meter (DIA INSTRUMENTS CO., LTD., system, " Loresta ") to measure this and film, is 1 * 10 at volume specific resistance
10Under the above situation of Ω cm, it is good to be judged as insulativity.
The determining bonding strength of＜insulating resin composition and cementability evaluation 〉
In the following order, measure the bonding strength that front and back are handled in moisture absorption.
(1) at chip bonding pad (die pad) portion of copper lead frame (the coating insulating resin composition of 9mm * 9mm).
(2) then, in chip bonding pad portion silicon (8mm * 16mm), heat with stove with 200 ℃ * 1 hour condition is installed.(preceding sample is handled in moisture absorption)
(3) with the moisture absorption 72 hours in the constant temperature and humidity machine that is set at 85 ℃ of temperature, humidity 85% of manufactured samples in (2).(the back sample is handled in moisture absorption)
(4) make silicon down, on 250 ℃ hot plate, above-mentioned " sample before the moisture absorption processing " and " the back sample is handled in moisture absorption " were heated 20 seconds, the lead-in wire of mentioning lead frame then, bonding strength when using pull and push dynamometer (push-pull gauge) (IMADA Co., Ltd. system) mensuration silicon and chip bonding pad to peel off.
(5) under the bonding strength survival rate shown in the following formula is situation more than 80%, it is good to be judged as cementability.
Bonding strength survival rate (%)=(bonding strength after moisture absorption is handled)/(bonding strength before moisture absorption is handled) * 100
The hole evaluation of＜insulating resin composition 〉
At the chip bonding pad portion coating insulating resin composition of above-mentioned copper lead frame, and glass-chip (8mm * 8mm), heat with stove with 200 ℃ * 1 hour condition is installed.This sample of Visual Confirmation has the imporosity under magnifying glass.
About the insulating resin composition of embodiment and comparative example, good and do not confirm under the situation that produces hole at insulativity and cementability, synthetic determination is qualified.
About the starting material that use in embodiment and the comparative example, be shown in following (1)～(10).
(1) Resins, epoxy
(1-1) Resins, epoxy A: bisphenol A type epoxy resin (below, be called Bis-A Resins, epoxy)
Trade(brand)name: Asahi Kasei Epoxy Co., Ltd system, " AER "
In addition, epoxy equivalent (weight) (WPE) and the viscosity of utilizing aforesaid method to measure is as described below.
Epoxy equivalent (weight) (WPE): 187g/eq
Viscosity (25 ℃): 14.3Pas
(1-2) Resins, epoxy F: bisphenol f type epoxy resin (below, be called " Bis-F Resins, epoxy ")
Trade(brand)name: Japan Epoxy Resins Co., Ltd. system, " jER807 "
In addition, epoxy equivalent (weight) (WPE) and the viscosity of utilizing aforesaid method to measure is as described below.
Epoxy equivalent (weight) (WPE): 169g/eq
Viscosity (25 ℃): 3.2Pas
(2) alkoxysilane compound containing trialkylsilyl group in molecular structure H:3-glycidoxypropyltrime,hoxysilane (below, be called " GPTMS ")
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-403 "
(3) alkoxysilane compound containing trialkylsilyl group in molecular structure I: phenyltrimethoxysila,e (below, be called " PTMS ")
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-103 "
(4) alkoxysilane compound containing trialkylsilyl group in molecular structure J: dimethyldimethoxysil,ne (below, be called " DMDMS ")
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-22 "
(5) alkoxysilane compound containing trialkylsilyl group in molecular structure K: tetraethoxysilane (below, be called " TEOS ")
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBE-04 "
(6) solvent
(6-1) tetrahydrofuran (THF): Wako Pure Chemical Industries, Ltd.'s system does not contain stabilizer type (below, be called " THF ")
(7) hydrolytic condensation catalyzer: dibutyl tin laurate (Wako Pure Chemical Industries, Ltd.'s system, below, be called " DBTDL ")
(8) solidifying agent: Dyhard RU 100 (ball is apt to medicine Industry Co., Ltd)
(9) thinner: adjacent toluene glycidyl ether (this pharmaceutical industries of slope Co., Ltd.) system, trade(brand)name " SY-OCG ") (epoxy equivalent (weight) 181g/eq, viscosity 8mPas)
(10) insulativity powder
(10-1) fused silica (east newly changes into Co., Ltd.'s system, median size 6.1 μ m)
(10-2) hydrophobic silica (Wacker Asahikasei Silicone Co., LTD. system, " H18 ")
[synthesis example 8]
Resin combination F: make resin combination F in the following order, and estimate.
(1) prepares: the circulation Water Tank with Temp.-controlled is set at 5 ℃, and cooling tube is refluxed.And then, on magnetic stirring apparatus, place 80 ℃ oil bath.
(2) according to the proportion of composing of table 19, under 25 ℃ atmosphere, with Resins, epoxy, alkoxysilane compound containing trialkylsilyl group in molecular structure and THF pack into drop in the flask that stirrer is arranged and mix stir after, and then add water and hydrolytic condensation catalyzer, and mix and stir.
(3) then, cooling tube is set on flask, is impregnated in 80 ℃ the oil bath rapidly and begins to stir, react 10 hours while reflux.
(4) after reaction finishes, be cooled to 25 ℃, take off cooling tube from flask then, after the end reflow process, collected specimens solution.
(5) use vaporizer, under 400Pa, 50 ℃, remove the solution after reflow process finishes with distillation in 1 hour after, and then 80 ℃ down distillation removed 10 hours, carry out dehydration condensation simultaneously.
(6) after reaction finishes, be cooled to 25 ℃, obtain resin combination F.
(7) the mixing index α 54～ε 54 in this resin combination is shown in table 21.
(8) in addition, according to aforesaid method, measure the epoxy equivalent (weight) (WPE) of the resin combination F that obtains in above-mentioned (6).
The epoxy equivalent (weight) of above-mentioned resin combination (WPE)=195g/eq is shown as suitable value.Viscosity is 12.7Pas in addition, for having mobile liquid.
[synthesis example 9]
Resin combination G:, utilize the method compound resin composition G same, and estimate with synthesis example 8 according to the proportion of composing of table 19.Mixing index α 55～ε 55 is shown in table 21.
The epoxy equivalent (weight) of above-mentioned resin combination (WPE)=228g/eq is shown as suitable value.Viscosity is 13.8Pas in addition, for having mobile liquid.
[synthesis example 10]
Resin combination H:, utilize the method compound resin composition H same, and estimate with synthesis example 8 according to the proportion of composing of table 19.Mixing index α 56～ε 56 is shown in table 21.
The epoxy equivalent (weight) of above-mentioned resin combination (WPE)=206g/eq is shown as suitable value.Viscosity is 18.2Pas in addition, for having mobile liquid.
[synthesis example 11]
Resin combination I:, utilize the method compound resin composition I same, and estimate with synthesis example 8 according to the proportion of composing of table 19.Mixing index α 57～ε 57 is shown in table 21.
The epoxy equivalent (weight) of above-mentioned resin combination (WPE)=208g/eq is shown as suitable value.Viscosity is 10.2Pas, for having mobile liquid.
[embodiment 45]
Make insulating resin composition 1 in the following order, and estimate.Evaluation result, and mixing index α 54～ε 54 be shown in table 21.
Use the resin combination F of above-mentioned synthesis example 8, according to the composition mixing raw material of table 20, and evenly mixing by triple-roller mill (Inoue MFG. Inc.'s system).And then the use vacuum chamber, deaeration is 30 minutes under 400Pa, with this as insulativity composition 1.
Utilize rod to be coated with machine and be coated with insulating resin composition 1 on slide glass, making thickness is 40 μ m, and the slide glass after the coating was heated 60 minutes down at 200 ℃, and formation is filmed.Utilize resistrivity meter (DIA INSTRUMENTS CO., LTD., system, " Loresta ") to measure the volume specific resistance that this is filmed, the result is 1 * 10
10More than the Ω cm, it is good to be judged as insulativity.
Obtain the bonding strength survival rate of insulating resin composition 1 in the following order.
(1) (the coating insulating resin composition 1 of 9mm * 9mm) is made 4 above-mentioned samples in the chip bonding pad portion of copper lead frame.
(2) then, in chip bonding pad portion silicon (8mm * 16mm), heat with stove with 200 ℃ * 1 hour condition is installed.
(3) with 2 conducts in the manufactured samples in (2) " preceding sample is handled in moisture absorption ".
(4) with the moisture absorption 72 hours in the constant temperature and humidity machine that is set at 85 ℃ of temperature, humidity 85% of 2 of the residues of manufactured samples in (2), with this as " sample is afterwards handled in moisture absorption ".
(5) use above-mentioned " preceding sample is handled in moisture absorption " and " the back sample is handled in moisture absorption ", make silicon down, heating is 20 seconds on 250 ℃ hot plate, mentions the lead-in wire of lead frame then, bonding strength when using pull and push dynamometer (IMADA Co., Ltd. system) mensuration silicon and chip bonding pad to peel off.Measure and carry out with n=2 respectively, obtain mean value.
(6) with the mean value substitution following formula of the bonding strength of above-mentioned " moisture absorption handle before sample " of trying to achieve and " the back sample is handled in moisture absorption ", obtain the bonding strength survival rate, and the evaluation cementability.
Bonding strength survival rate (%)=(bonding strength after moisture absorption is handled)/(bonding strength before moisture absorption is handled) * 100=95% 〉=80%, the cementability that is judged as insulating resin composition 1 is good.
Then, at the chip bonding pad portion coating insulating resin composition 1 of copper lead frame, and glass-chip (8mm * 8mm), heat with stove with 200 ℃ * 1 hour condition is installed.This sample of Visual Confirmation does not produce hole under magnifying glass.
Can judge by The above results, the insulativity of insulating resin composition 1 and excellent in adhesion, and do not produce hole, synthetic determination is qualified thus.
[embodiment 46]
According to the composition of table 20, use above-mentioned resin combination G by making insulating resin composition 2, and estimate with the same method of embodiment 45.Evaluation result, and mixing index α 55～ε 55 be shown in table 21.
The volume specific resistance of insulating resin composition 2 is 1 * 10
10More than the Ω cm, it is good to be judged as insulativity.
With the mean value substitution following formula of the bonding strength of " moisture absorption handle before sample " and " the back sample is handled in moisture absorption " of insulating resin composition 2, obtain the bonding strength survival rate, and the evaluation cementability.
Bonding strength survival rate (%)=(bonding strength after moisture absorption is handled)/(bonding strength before moisture absorption is handled) * 100=92% 〉=80%, the cementability that is judged as insulating resin composition 2 is good.
Then, at the chip bonding pad portion coating insulating resin composition 2 of copper lead frame, and glass-chip (8mm * 8mm), heat with stove with 200 ℃ * 1 hour condition is installed.This sample of Visual Confirmation does not produce hole under magnifying glass.
Can judge by The above results, the insulativity of insulating resin composition 2 and excellent in adhesion, and do not produce hole, synthetic determination is qualified thus.
[embodiment 47]
According to the composition of table 20, use above-mentioned resin combination H by making insulating resin composition 3, and estimate with the same method of embodiment 45.Evaluation result, and mixing index α 56～ε 56 be shown in table 21.
The volume specific resistance of insulating resin composition 3 is 1 * 10
10More than the Ω cm, it is good to be judged as insulativity.
With the mean value substitution following formula of the bonding strength of " moisture absorption handle before sample " and " the back sample is handled in moisture absorption " of insulating resin composition 3, obtain the bonding strength survival rate, and the evaluation cementability.
Bonding strength survival rate (%)=(bonding strength after moisture absorption is handled)/(bonding strength before moisture absorption is handled) * 100=89% 〉=80%, the cementability that is judged as insulating resin composition 3 is good.
Then, at the chip bonding pad portion coating insulating resin composition 3 of copper lead frame, and glass-chip (8mm * 8mm), heat with stove with 200 ℃ * 1 hour condition is installed.This sample of Visual Confirmation does not produce hole under magnifying glass.
Can judge by The above results, the insulativity of insulating resin composition 3 and excellent in adhesion, and do not produce hole, synthetic determination is qualified thus.
[embodiment 48]
According to the composition of table 20, use above-mentioned resin combination I by making insulating resin composition 4, and estimate with the same method of embodiment 43.Evaluation result, and mixing index α 57～ε 57 be shown in table 21.
The volume specific resistance of insulating resin composition 4 is 1 * 10
10More than the Ω cm, it is good to be judged as insulativity.
With the mean value substitution following formula of the bonding strength of " moisture absorption handle before sample " and " the back sample is handled in moisture absorption " of insulating resin composition 4, obtain the bonding strength survival rate, and the evaluation cementability.
Bonding strength survival rate (%)=(bonding strength after moisture absorption is handled)/(bonding strength before moisture absorption is handled) * 100=86% 〉=80%, the cementability that is judged as insulating resin composition 4 is good.
Then, at the chip bonding pad portion coating insulating resin composition 4 of copper lead frame, and glass-chip (8mm * 8mm), heat with stove with 200 ℃ * 1 hour condition is installed.This sample of Visual Confirmation does not produce hole under magnifying glass.
Can judge by The above results, the insulativity of insulating resin composition 4 and excellent in adhesion, and do not produce hole, synthetic determination is qualified thus.
[comparative example 24]
According to the composition of table 20, replace resin combination F and use Bis-A Resins, epoxy and Bis-F Resins, epoxy, by making insulating resin composition 5, and estimate with the same method of embodiment 45.The results are shown in table 21.
The volume specific resistance of insulating resin composition 5 is 1 * 10
10More than the Ω cm, it is good to be judged as insulativity.
With the mean value substitution following formula of the bonding strength of " moisture absorption handle before sample " and " the back sample is handled in moisture absorption " of insulating resin composition 5, obtain the bonding strength survival rate, and the evaluation cementability.
Bonding strength survival rate (%)=(bonding strength after moisture absorption is handled)/(bonding strength before moisture absorption is handled) * 100=63%＜80%, the cementability that is judged as insulating resin composition 5 is bad.
Then, at the chip bonding pad portion coating insulating resin composition 5 of copper lead frame, and glass-chip (8mm * 8mm), heat with stove with 200 ℃ * 1 hour condition is installed.This sample of Visual Confirmation does not produce hole under magnifying glass.
Can be judged that by The above results the insulativity of insulating resin composition 5 is good, do not produce hole, but cementability be bad, synthetic determination is defective thus.
[comparative example 25]
According to the composition of table 20, replace resin combination F and use Bis-A Resins, epoxy, GPTMS, PTMS, by making insulating resin composition 6, and estimate with the same method of embodiment 43.The results are shown in table 21.
The volume specific resistance of insulating resin composition 6 is 1 * 10
10More than the Ω cm, it is good to be judged as insulativity.
With the mean value substitution following formula of the bonding strength of " moisture absorption handle before sample " and " the back sample is handled in moisture absorption " of insulating resin composition 6, obtain the bonding strength survival rate, and the evaluation cementability.
Bonding strength survival rate (%)=(bonding strength after moisture absorption is handled)/(bonding strength before moisture absorption is handled) * 100=89% 〉=80%, the cementability that is judged as insulating resin composition 6 is good.
Then, at the chip bonding pad portion coating insulating resin composition 6 of copper lead frame, and glass-chip (8mm * 8mm), heat with stove with 200 ℃ * 1 hour condition is installed.This sample of Visual Confirmation under magnifying glass, results verification is to the generation of hole.
Can be judged that by The above results the insulativity and the cementability of insulating resin composition 6 are good, but confirm the generation of hole, synthetic determination is defective thus.
Shown in table 19～table 21, if insulating resin composition contains by with specific ratio blending epoxy and specific alkoxysilane compound containing trialkylsilyl group in molecular structure and carry out resin combination and insulativity powder and the solidifying agent that the cohydrolysis condensation obtains, the insulativity of this insulating resin composition and excellent in adhesion then, and do not produce hole yet.
Then, for the semiconductor device of the modified resin composition that has used present embodiment, enumerate embodiment and comparative example is specifically described.
The evaluation of the rerum natura in embodiment 49～58 and the comparative example 26～30 is following to be carried out.
About epoxy equivalent (weight) (WPE), viscosity, mixing index α～η, by trying to achieve with above-mentioned same method.
The calculating of＜storage stability index θ and the storage stability of resin combination 〉
Storage stability in the resin combination is estimated by the storage stability index θ shown in the following general formula (9).
Storage stability index θ=(preservation viscosity)/(initial viscosity) (9)
To the container sealing of the resin combination after the firm manufacturing be housed, the viscosity under carrying out under 25 ℃ after temperature adjusts 2 hours, measuring 25 ℃, with this as " initial viscosity ".
The container sealing of resin combination will be housed again, in 25 ℃ Constant Temperature Incubators, preserve for 2 weeks.After the preservation, the viscosity under measuring 25 ℃, with this as " preservation viscosity ".
Having flowability (viscosity is below the 1000Pas) and storage stability index θ at resin combination is under the situation below 4, is judged as to have storage stability.
The light fastness test of＜LED (cured article) 〉
LED is difficult to cutting sample after making.Therefore, utilize following method to make cured article, the result of evaluation substitutes as the photostabilization evaluation of LED.
(1) cured article of preparing by the aftermentioned method is solidified with solution, make the cured article of 20mm * 10mm * thickness 3mm.
(2) black masks of above-mentioned cured article with the 25mm * 15mm * thickness 1.2mm in the hole that has diameter 5.5mm covered, as the light fastness test sample.
(3) preparation device makes that UV illumination can be mapped to constant temperature via optical fiber from UV irradiating unit (Ushio Inc. system, " Spot Cure SP7-250DB ") is above-mentioned sample in 50 ℃ the Constant Temperature Incubators.
(4) be that top state is arranged in 50 ℃ the Constant Temperature Incubators with above-mentioned sample with black masks.
(5) in the mode in the hole that UV illumination can be mapped to diameter 5.5mm, from the top irradiation 2W/cm of black masks
2UV light 96 hours.
(6) utilize the spectral photometric colour measuring meter (Japanese electric look Industrial Co., Ltd system, " SD5000 ") that the integrating sphere peristome is transform as diameter 10mm, measure the postradiation sample of UV.
(7) try to achieve yellow chromaticity (YI) according to " ASTM D1925-70 (1988): Test Method for Yellowness Index of Plastics (plastics yellowness index test method) ".Under this YI was situation below 13, it was qualified to be judged as.
The reliability test of＜LED (1) (continuous working test: below, be called " L test ") 〉
With 10 LED according to the method 1026.5 (steady state operation life) of " MIL-STD-750E (test method of semiconductor device) ", and the method 1005.8 (steady-state life) of " MIL-STD-883G (microcircuit) " estimate under the following conditions.
Under forward current IF=20mA, envrionment temperature Ta=25 ℃, 960 hours condition, light, measure the total light flux (lm) before and after lighting.And then, obtain " total light flux sustainment rate (%)=(total light flux after lighting)/(light before total light flux) * 100 " for each LED, under whole Schwellenwerts of the total light flux sustainment rate (%) of LED was situation more than 90%, it was qualified to be judged as.
The reliability test of＜LED (2) (thermal shock test: below, be called " TS test ") 〉
10 LED are estimated under the following conditions according to the test method 307 (thermal shock test) of " EIAJ ED-4701/300 (environment of semiconductor device and durability test method (strength trial I) ".
As 1 circulation, carry out confirming lighting of LED after 100 round-robin thermal shockings that under 10 situations about all lighting, it is qualified to be judged as with " 10 ℃ (5 minutes)～100 ℃ (5 minutes) ".
The reliability test of＜LED (3) (temperature cycling test: below, be called " TC " test) 〉
10 LED are estimated under the following conditions according to the test method 105 (temperature cycling test) of " EIAJ ED-4701/100 (environment of semiconductor device and durability test method (longevity test I) ".
As 1 circulation, carry out confirming lighting of LED after 100 round-robin temperature cycle that under 10 situations about all lighting, it is qualified to be judged as with " 40 ℃ (30 minutes)～85 ℃ (5 minutes)～100 ℃ (30 minutes)～25 ℃ (5 minutes) ".
In the evaluation of above-mentioned LED, under the whole qualified situations in photostabilization and reliability test (1)～(3), synthetic determination is qualified.
Starting material about using in embodiment 49～59 and the comparative example 26～30 are shown in following (1)～(12).
(1) Resins, epoxy
(1-1) Resins, epoxy A1: poly-(dihydroxyphenyl propane-2-hydroxypropyl ether) (below, be called " Bis-A1 Resins, epoxy ")
Trade(brand)name: Asahi Kasei Epoxy Co., Ltd system, " AER2600 "
In addition, epoxy equivalent (weight) (WPE) and the viscosity of utilizing aforesaid method to measure is as described below.
Epoxy equivalent (weight) (WPE): 188g/eq
Viscosity (25 ℃): 14.8Pas
(1-2) Resins, epoxy A2: poly-(dihydroxyphenyl propane-2-hydroxypropyl ether) (below, be called " Bis-A2 Resins, epoxy ")
Trade(brand)name: Asahi Kasei Epoxy Co., Ltd system, " AER2500 "
In addition, epoxy equivalent (weight) (WPE) and the viscosity of utilizing aforesaid method to measure is as described below.
Epoxy equivalent (weight) (WPE): 186g/eq
Viscosity (25 ℃): 10.2Pas
(1-3) Resins, epoxy A3: poly-(dihydroxyphenyl propane-2-hydroxypropyl ether) (below, be called " Bis-A3 Resins, epoxy ")
Trade(brand)name: Asahi Kasei Epoxy Co., Ltd system, " AER6071 "
In addition, as described below by the epoxy equivalent (weight) (WPE) of aforesaid method mensuration.Wherein, this Resins, epoxy A3 is down solid-state at 25 ℃, thereby can't measure viscosity.
Epoxy equivalent (weight) (WPE): 470g/eq
(2) alkoxysilane compound containing trialkylsilyl group in molecular structure H:3-glycidoxypropyltrime,hoxysilane (below, be called " GPTMS ")
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-403 "
(3) alkoxysilane compound containing trialkylsilyl group in molecular structure L:2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane (below, be called " ECETMS ")
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-303 "
(4) alkoxysilane compound containing trialkylsilyl group in molecular structure I: phenyltrimethoxysila,e (below, be called " PTMS ")
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-103 "
(5) alkoxysilane compound containing trialkylsilyl group in molecular structure J: dimethyldimethoxysil,ne (below, be called " DMDMS ")
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-22 "
(6) alkoxysilane compound containing trialkylsilyl group in molecular structure K: tetraethoxysilane (below, be called " TEOS ")
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBE-04 "
(7) solvent
(7-1) tetrahydrofuran (THF): Wako Pure Chemical Industries, Ltd.'s system does not contain stabilizer type (below, be called " THF ")
(7-2) trimethyl carbinol:: Wako Pure Chemical Industries, Ltd.'s system does not contain stabilizer type (below, be called " t-BuOH ")
(8) hydrolytic condensation catalyzer
(8-1) dibutyl tin laurate (Wako Pure Chemical Industries, Ltd.'s system, below, be called " DBTDL ")
(8-2) dibutyl dimethoxy tin (Sigma-Aldrich corporate system, below, be called " DBTDM ")
(9) solidifying agent: " 4-methyl hexahydro phthalic anhydride/hexahydro phthalic anhydride=70/30 "
Trade(brand)name: New Japan Chem Co., Ltd's system, " RIKACID MH-700G "
(10) curing catalyst: amine compound
Trade(brand)name: San-Apro Ltd. system, " U-CAT 18X "
(11) silicone resin
Trade(brand)name: Dow Corning Toray Co., Ltd. system, " EG6301 (A liquid/B liquid) "
[synthesis example 12]
Make resin combination by following operation.
(1) prepares: the circulation Water Tank with Temp.-controlled is set at 5 ℃, and cooling tube is refluxed.And then, on magnetic stirring apparatus, place 80 ℃ oil bath.
(2) according to the proportion of composing shown in the following table 22, under 25 ℃ atmosphere, with above-mentioned Bis-A1 Resins, epoxy, alkoxysilane compound containing trialkylsilyl group in molecular structure and THF pack into drop in the flask that stirrer is arranged and mix stir after, and then add water and hydrolytic condensation catalyzer, and mix and stir.
(3) then, cooling tube is set on flask, is impregnated in 80 ℃ the oil bath rapidly and begins to stir, react 20 hours (reflow process) while reflux.
(4) after reaction finishes, be cooled to 25 ℃, take off cooling tube from flask then.
(5) use vaporizer, under 400Pa, 50 ℃, remove the solution after reflow process finishes with distillation in 1 hour after, and then 80 ℃ down distillation removed 10 hours, carry out dehydration condensation (dehydrating condensation operation) simultaneously.
(6) after described dehydration condensation finishes, be cooled to 25 ℃, obtain resin combination.
(7) the above-mentioned mixing index α 58～ε 58 in this resin combination is shown in following table 24 respectively.
(8) in addition, according to aforesaid method, measure epoxy equivalent (weight) (WPE), the initial viscosity of the resin combination that obtains in above-mentioned (6) and preserve viscosity.And then, obtain storage stability index θ 58, they are shown in table 24.
The epoxy equivalent (weight) of the resin combination of above-mentioned synthesis example 12 (WPE)=230g/eq is shown as suitable value.In addition, initial viscosity=33.7Pas＜1000Pas, and preserve viscosity=47.0Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 58=1.39≤4 are judged as the resin combination with storage stability.
[synthesis example 13]
According to table 22 and 23, utilize with the same method of synthesis example 12 and make resin combination.Utilize with the result of the same method evaluation of synthesis example 12, and mixing index α 59～ε 59, storage stability index θ 59 be shown in table 24.
Shown in table 24, the epoxy equivalent (weight) of the resin combination of synthesis example 13 (WPE)=231g/eq is shown as suitable value.In addition, initial viscosity=13.2Pas＜1000Pas, and preserve viscosity=19.1Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 59=1.45≤4 are judged as the resin combination with storage stability.
[synthesis example 14]
According to table 22 and 23, utilize with the same method of synthesis example 12 and make resin combination.Utilize with the result of the same method evaluation of synthesis example 12, and mixing index α 60～ε 60, storage stability index θ 60 be shown in table 24.
Shown in table 24, the epoxy equivalent (weight) of the resin combination of synthesis example 14 (WPE)=242g/eq is shown as suitable value.In addition, initial viscosity=14.5Pas＜1000Pas, and preserve viscosity=16.2Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 60=1.12≤4 are judged as the resin combination with storage stability.
[synthesis example 15]
According to table 22 and 23, utilize with the same method of synthesis example 12 and make resin combination.Utilize with the result of the same method evaluation of synthesis example 12, and mixing index α 61～ε 61, storage stability index θ 61 be shown in table 24.
Shown in table 24, the epoxy equivalent (weight) of the resin combination of synthesis example 15 (WPE)=245g/eq is shown as suitable value.In addition, initial viscosity=14.8Pas＜1000Pas, and preserve viscosity=21.0Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 61=1.42≤4 are judged as the resin combination with storage stability.
[synthesis example 16]
According to table 22 and 23, utilize with the same method of synthesis example 12 and make resin combination.Utilize with the result of the same method evaluation of synthesis example 12, and mixing index α 62～ε 62, storage stability index θ 62 be shown in table 24.
Shown in table 24, the epoxy equivalent (weight) of the resin combination of synthesis example 16 (WPE)=228g/eq is shown as suitable value.In addition, initial viscosity=44.0Pas＜1000Pas, and preserve viscosity=61.1Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 62=1.39≤4 are judged as the resin combination with storage stability.
[synthesis example 17]
The time that makes reflow process is 7 hours, in addition utilizes the method same with synthesis example 12, makes resin combinations according to table 22 and 23.Utilize with the result of the same method evaluation of synthesis example 12, and mixing index α 63～ε 63, storage stability index θ 63 be shown in table 24.
Shown in table 24, the epoxy equivalent (weight) of the resin combination of synthesis example 17 (WPE)=214g/eq is shown as suitable value.In addition, initial viscosity=4.9Pas＜1000Pas, and preserve viscosity=9.4Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 63=1.91≤4 are judged as the resin combination with storage stability.
[synthesis example 18]
According to table 22 and 23, utilize with the same method of synthesis example 12 and make resin combination.Utilize with the result of the same method evaluation of synthesis example 12, and mixing index α 64～ε 64, storage stability index θ 64 be shown in table 24.
Shown in table 24, the epoxy equivalent (weight) of the resin combination of synthesis example 18 (WPE)=214g/eq is shown as suitable value.In addition, initial viscosity=13.1Pas＜1000Pas, and preserve viscosity=15.9Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 7=1.21≤4 are judged as the resin combination with storage stability.
[synthesis example 19]
According to table 22 and 23, utilize with the same method of synthesis example 12 and make resin combination.Utilize with the result of the same method evaluation of synthesis example 12, and mixing index α 65～ε 65, storage stability index θ 65 be shown in table 24.
Shown in table 24, the epoxy equivalent (weight) of the resin combination of synthesis example 19 (WPE)=238g/eq is shown as suitable value.In addition, initial viscosity=18.9Pas＜1000Pas, and preserve viscosity=28.7Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 65=1.52≤4 are judged as the resin combination with storage stability.
[synthesis example 20]
According to table 22 and 23, utilize with the same method of synthesis example 12 and make resin combination.Utilize with the result of the same method evaluation of synthesis example 12, and mixing index α 66～ε 66, storage stability index θ 66 be shown in table 24.
Shown in table 24, the epoxy equivalent (weight) of the resin combination of synthesis example 20 (WPE)=213g/eq is shown as suitable value.In addition, initial viscosity=11.2Pas＜1000Pas, and preserve viscosity=16.1Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 66=1.44≤4 are judged as the resin combination with storage stability.
[synthesis example 21]
According to table 22 and 23, utilize with the same method of synthesis example 12 and make resin combination.Utilize with the result of the same method evaluation of synthesis example 12, and mixing index α 67～ε 67, storage stability index θ 67 be shown in table 24.
Shown in table 24, the epoxy equivalent (weight) of the resin combination of synthesis example 21 (WPE)=253g/eq is shown as suitable value.In addition, initial viscosity=26.8Pas＜1000Pas, and preserve viscosity=39.1Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 67=1.46≤4 are judged as the resin combination with storage stability.
[relatively synthesis example 1]
According to table 22 and 23, utilize with the same method of synthesis example 12 and make resin combination.Utilize with the result of the same method evaluation of synthesis example 12, and mixing index α 68～ε 68, storage stability index θ 68 be shown in table 24.
Shown in table 24, relatively epoxy equivalent (weight) (the WPE)=295g/eq of the resin combination of synthesis example 1 is shown as suitable value.In addition, initial viscosity=33.4Pas＜1000Pas, and preserve viscosity=48.2Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 68=1.44≤4 are judged as the resin combination with storage stability.
[relatively synthesis example 2]
According to table 22 and 23, utilize with the same method of synthesis example 12 and make resin combination.Utilize with the result of the same method evaluation of synthesis example 12, and mixing index α 69～ε 69, storage stability index θ 69 be shown in table 24.
Shown in table 24, relatively epoxy equivalent (weight) (the WPE)=295g/eq of the resin combination of synthesis example 2 is shown as suitable value.In addition, initial viscosity=29.0Pas＜1000Pas is for having mobile liquid.Yet, preserve viscosity＞1000Pas, there is not flowability, storage stability index θ 69＞35, relatively the storage stability of the resin combination of synthesis example 2 is bad, can't make LED evaluation sample.
[relatively synthesis example 3]
According to table 22, in reaction vessel, add Resins, epoxy A2 and Resins, epoxy A3, be impregnated in 85 ℃ the oil bath and stir, dissolving, add P-MS and DBTDL again and mix.
And then, Yi Bian carry out nitrogen purging, Yi Bian the temperature of oil bath is increased to 105 ℃ and carried out dealcoholization 8 hours.
Then, be cooled to 60 ℃ after, be decompressed to 12000Pa, and remove dissolving alcohol, obtain resin combination.Utilize result, storage stability index θ 70 with the same method evaluation of synthesis example 12 to be shown in table 24.
Relatively epoxy equivalent (weight) (the WPE)=282g/eq of the resin combination of synthesis example 3 is shown as suitable value.In addition, initial viscosity 1.89Pas＜1000Pas, and preserve viscosity=2.03Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 70=1.07≤4 are judged as the resin combination with storage stability.
[embodiment 49]
Use is made cured article, and is carried out light fastness test at 25 ℃ of resin combinations of preserving the above-mentioned synthesis example 12 in 2 weeks down.The results are shown in table 24.
(1) under 25 ℃ atmosphere, according to the proportion of composing of table 23 above-mentioned resin combination, solidifying agent and curing catalyst are mixed and to stir, and under vacuum, outgas, as cured article solution.
(2) with being coated with 2 pieces of stainless steel plate clamping thickness 3mm of releasing agent, the silicon rubber of コ word shape, make shaping jig.
(3) in this shaping jig, inject above-mentioned cured article solution, implemented solidification treatment 1 hour down, and then implemented solidification treatment 1 hour down, make cured article at 150 ℃ at 120 ℃.
(4) temperature drop is low to moderate the taking-up of back below 30 ℃ cured article in the stove, according to aforesaid method, and preparation light fastness test sample.
(5) use above-mentioned sample, carry out light fastness test, the results are shown in table 24 by aforesaid method.
As YI=10.1≤13 of the index of the light fastness test of this cured article, it is qualified to be judged as photostabilization.
Then, use the resin combination of synthesis example 12, make bullet cut LED in the following order, carry out reliability test (1)～(3) with structure shown in Figure 1.The results are shown in table 24.
(6) inject cured article solution in the cup portion of the casting mold frame of the bullet cut of diameter 5mm as (1) of sealing resin.
(7) utilize silver to stick with paste the led chip of tube core welding emission wavelength 400nm thereon, and dipping has connected the lead frame of bonding wire (gold thread).
(8) in a vacuum after the deaeration, 90 ℃ of following solidification treatment 1 hour, and then 110 ℃ of following solidification treatment 5 hours.
(9) in addition, as outermost resin, adding the solidifying agent of 46.6 quality % and curing catalyst and the mixing of 0.2 quality % in the Bis-A Resins, epoxy of 53.2 quality % stirs, under vacuum, outgas, mixture after the degassing is injected the casting mold frame, 130 ℃ of following solidification treatment 1 hour, and then, obtain bullet cut LED 150 ℃ of following solidification treatment 6 hours.
The result who carries out above-mentioned " reliability test (1) (L test) " is, all the Schwellenwert of LED is total light flux sustainment rate (%)=94% 〉=90%, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, even after having carried out 100 round-robin thermal shockings, all LED all light, and it is qualified to be judged as.
And then the result who carries out above-mentioned " reliability test (3) (TC test) " is, even after having carried out 100 round-robin temperature cycle, all LED all light, and it is qualified to be judged as.
Can be judged that by above result the light fastness test of the LED of embodiment 49 and reliability test (1)～(3) are all qualified, synthetic determination is qualified.
[embodiment 50]
Replace the resin combination of synthesis example 12 and use the resin combination of synthesis example 13, utilize with the same method of embodiment 49 and make cured article and LED, carry out light fastness test and reliability test (1)～(3).The results are shown in table 24.
As YI=8.1≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
The result who carries out above-mentioned " reliability test (1) (L test) " is, all the Schwellenwert of LED is total light flux sustainment rate (%)=96% 〉=90%, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, even after having carried out 100 round-robin thermal shockings, all LED all light, and it is qualified to be judged as.
And then the result who carries out above-mentioned " reliability test (3) (TC test) " is, even after having carried out 100 round-robin temperature cycle, all LED all light, and it is qualified to be judged as.
Can be judged that by above result the light fastness test of the LED of embodiment 50 and reliability test (1)～(3) are all qualified, synthetic determination is qualified.
[embodiment 51]
Replace the resin combination of synthesis example 12 and use the resin combination of synthesis example 14, utilize with the same method of embodiment 49 and make cured article and LED, carry out light fastness test and reliability test (1)～(3).The results are shown in table 24.
As YI=8.9≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
The result who carries out above-mentioned " reliability test (1) (L test) " is, all the Schwellenwert of LED is total light flux sustainment rate (%)=95% 〉=90%, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, even after having carried out 100 round-robin thermal shockings, all LED all light, and it is qualified to be judged as.
And then the result who carries out above-mentioned " reliability test (3) (TC test) " is, even after having carried out 100 round-robin temperature cycle, all LED all light, and it is qualified to be judged as.
Can be judged that by above result the light fastness test of the LED of embodiment 51 and reliability test (1)～(3) are all qualified, synthetic determination is qualified.
[embodiment 52]
Replace the resin combination of synthesis example 12 and use the resin combination of synthesis example 15, utilize with the same method of embodiment 49 and make cured article and LED, carry out light fastness test and reliability test (1)～(3).The results are shown in table 24.
As YI=8.3≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
The result who carries out above-mentioned " reliability test (1) (L test) " is, all the Schwellenwert of LED is total light flux sustainment rate (%)=92% 〉=90%, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, even after having carried out 100 round-robin thermal shockings, all LED all light, and it is qualified to be judged as.
And then the result who carries out above-mentioned " reliability test (3) (TC test) " is, even after having carried out 100 round-robin temperature cycle, all LED all light, and it is qualified to be judged as.
Can be judged that by above result the light fastness test of the LED of embodiment 52 and reliability test (1)～(3) are all qualified, synthetic determination is qualified.
[embodiment 53]
Replace the resin combination of synthesis example 12 and use the resin combination of synthesis example 16, utilize with the same method of embodiment 49 and make cured article and LED, carry out light fastness test and reliability test (1)～(3).The results are shown in table 24.
As YI=7.5≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
The result who carries out above-mentioned " reliability test (1) (L test) " is, all the Schwellenwert of LED is total light flux sustainment rate (%)=96% 〉=90%, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, even after having carried out 100 round-robin thermal shockings, all LED all light, and it is qualified to be judged as.
And then the result who carries out above-mentioned " reliability test (3) (TC test) " is, even after having carried out 100 round-robin temperature cycle, all LED all light, and it is qualified to be judged as.
Can be judged that by above result the light fastness test of the LED of embodiment 53 and reliability test (1)～(3) are all qualified, synthetic determination is qualified.
[embodiment 54]
Replace the resin combination of synthesis example 12 and use the resin combination of synthesis example 17, with the solidification treatment temperature of the sealing resin of cured article and LED change to 110 ℃ following 4 hours, in addition utilize with the same method of embodiment 49 and make cured article and LED, carry out light fastness test and reliability test (1)～(3).The results are shown in table 24.
As YI=8.8≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
The result who carries out above-mentioned " reliability test (1) (L test) " is, all the Schwellenwert of LED is total light flux sustainment rate (%)=96% 〉=90%, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, even after having carried out 100 round-robin thermal shockings, all LED all light, and it is qualified to be judged as.
And then the result who carries out above-mentioned " reliability test (3) (TC test) " is, even after having carried out 100 round-robin temperature cycle, all LED all light, and it is qualified to be judged as.
Can be judged that by above result the light fastness test of the LED of embodiment 54 and reliability test (1)～(3) are all qualified, synthetic determination is qualified.
[embodiment 55]
Replace the resin combination of synthesis example 12 and use the resin combination of synthesis example 18, utilize with the same method of embodiment 49 and make cured article and LED, carry out light fastness test and reliability test (1)～(3).The results are shown in table 24.
As YI=12.4≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
The result who carries out above-mentioned " reliability test (1) (L test) " is, all the Schwellenwert of LED is total light flux sustainment rate (%)=97% 〉=90%, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, even after having carried out 100 round-robin thermal shockings, all LED all light, and it is qualified to be judged as.
And then the result who carries out above-mentioned " reliability test (3) (TC test) " is, even after having carried out 100 round-robin temperature cycle, all LED all light, and it is qualified to be judged as.
Can be judged that by above result the light fastness test of the LED of embodiment 55 and reliability test (1)～(3) are all qualified, synthetic determination is qualified.
[embodiment 56]
Replace the resin combination of synthesis example 12 and use the resin combination of synthesis example 19, utilize with the same method of embodiment 49 and make cured article and LED, carry out light fastness test and reliability test (1)～(3).The results are shown in table 24.
As YI=7.2≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
The result who carries out above-mentioned " reliability test (1) (L test) " is, all the Schwellenwert of LED is total light flux sustainment rate (%)=92% 〉=90%, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, even after having carried out 100 round-robin thermal shockings, all LED all light, and it is qualified to be judged as.
And then the result who carries out above-mentioned " reliability test (3) (TC test) " is, even after having carried out 100 round-robin temperature cycle, all LED all light, and it is qualified to be judged as.
Can be judged that by above result the light fastness test of the LED of embodiment 56 and reliability test (1)～(3) are all qualified, synthetic determination is qualified.
[embodiment 57]
Replace the resin combination of synthesis example 12 and use the resin combination of synthesis example 20, utilize with the same method of embodiment 49 and make cured article and LED, carry out light fastness test and reliability test (1)～(3).The results are shown in table 24.
As YI=7.8≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
The result who carries out above-mentioned " reliability test (1) (L test) " is, all the Schwellenwert of LED is total light flux sustainment rate (%)=93% 〉=90%, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, even after having carried out 100 round-robin thermal shockings, all LED all light, and it is qualified to be judged as.
And then the result who carries out above-mentioned " reliability test (3) (TC test) " is, even after having carried out 100 round-robin temperature cycle, all LED all light, and it is qualified to be judged as.
Can be judged that by above result the light fastness test of the LED of embodiment 57 and reliability test (1)～(3) are all qualified, synthetic determination is qualified.
[embodiment 58]
Replace the resin combination of synthesis example 12 and use the resin combination of synthesis example 21, utilize with the same method of embodiment 49 and make cured article and LED, carry out light fastness test and reliability test (1)～(3).The results are shown in table 24.
As YI=9.2≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
The result who carries out above-mentioned " reliability test (1) (L test) " is, all the Schwellenwert of LED is total light flux sustainment rate (%)=92% 〉=90%, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, even after having carried out 100 round-robin thermal shockings, all LED all light, and it is qualified to be judged as.
And then the result who carries out above-mentioned " reliability test (3) (TC test) " is, even after having carried out 100 round-robin temperature cycle, all LED all light, and it is qualified to be judged as.
Can be judged that by above result the light fastness test of the LED of embodiment 58 and reliability test (1)～(3) are all qualified, synthetic determination is qualified.
[embodiment 59]
Use the resin combination of synthesis example 13, make the SMD type LED with structure shown in Figure 2 of 2.5mm * 2.5mm size in the following order, confirm LED for lighting.
(1) be formed with silver coating paste on the glass-epoxy substrate of metal pattern, and tube core welding led chip.
(2) aforesaid substrate is put into electric furnace and made its curing.
(3) at welded joint line (gold thread) on the led chip of tube core welding, form circuit.
(4) substrate is set in model, and then injects the resin combination of synthesis example 13,90 ℃ of following solidification treatment 1 hour, and then 110 ℃ of following solidification treatment 5 hours.
(5) sever LED on the substrate singly, make SMD type LED.
Can judge by above result, the photostabilization of the LED of embodiment 49～59 and reliability excellence, synthetic determination is qualified.
[comparative example 26]
Replace the resin combination of synthesis example 12 and use the resin combination of comparison synthesis example 1, utilize with the same method of embodiment 49 and make cured article and LED, carry out light fastness test and reliability test (1)～(3).The results are shown in table 24.
As YI=8.4≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
The result who carries out above-mentioned " reliability test (1) (L test) " is, 2 LED among 10 LED do not light, and can't measure total light flux sustainment rate (%), are judged as defective.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, after having carried out 100 round-robin thermal shockings, among 10 LED only 6 LED light, be judged as defective.
And then the result who carries out above-mentioned " reliability test (3) (TC test) " is, after having carried out 100 round-robin temperature cycle, among 10 LED only 6 LED light, be judged as defective.
Can be judged that by above result the photostabilization of the LED of comparative example 26 is good, but reliability test (1)～(3) are all defective, synthetic determination is defective.
[comparative example 27]
Replace the resin combination of synthesis example 12 and use the resin combination of comparison synthesis example 2, utilize with the same method of embodiment 49 and attempt making cured article and LED, and enforcement light fastness test and reliability test (1)～(3), but the storage stability of resin combination is bad, can't make cured article and LED.Therefore, synthetic determination is defective.
[comparative example 28]
Replace the resin combination of synthesis example 12 and use Bis-A1 Resins, epoxy, utilize with the same method of embodiment 49 and make cured article and LED, carry out light fastness test and reliability test (1)～(3).The results are shown in table 24.
As YI=17.2＞13 of the index of light fastness test, it is defective to be judged as photostabilization.
The result who carries out above-mentioned " reliability test (1) (L test) " is, all the Schwellenwert of LED is total light flux sustainment rate (%)=97% 〉=90%, and it is qualified to be judged as.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, even after having carried out 100 round-robin thermal shockings, all LED all light, and it is qualified to be judged as.
And then the result who carries out above-mentioned " reliability test (3) (TC test) " is, even after having carried out 100 round-robin temperature cycle, all LED all light, and it is qualified to be judged as.
Can judge by above result, the reliability excellence of the LED of comparative example 28, but photostabilization is bad, and synthetic determination is defective.
[comparative example 29]
The resin combination that replaces synthesis example 12, and use the above-mentioned silicone resin that A liquid and B liquid is mixed together with 1: 1 mass ratio.The solidification treatment temperature of the sealing resin of cured article and LED is changed to 70 ℃ of following 1 hour and then 150 ℃ following 5 hours, in addition utilize with the same method of embodiment 49 and make cured article and LED, carry out light fastness test and reliability test (1)～(3).The results are shown in table 24.
As YI=2.0≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
The result who carries out above-mentioned " reliability test (1) (L test) " is, 3 LED points among 10 LED do not work, and total light flux sustainment rate (%) can't be measured, and is judged as defective.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, after having carried out 100 round-robin thermal shockings, among 10 LED only 4 LED light, be judged as defective.
And then the result who carries out above-mentioned " reliability test (3) (TC test) " is, after having carried out 100 round-robin temperature cycle, among 10 LED only 6 LED light, be judged as defective.
Can be judged that by above result the photostabilization of the LED of comparative example 29 is good, but reliability test (1)～(3) are all defective, synthetic determination is defective.
[comparative example 30]
Replace the resin combination of synthesis example 12 and use the resin combination of comparison synthesis example 3, utilize with the same method of embodiment 49 and make cured article and LED, carry out light fastness test and reliability test (1)～(3).The results are shown in table 24.
Though made the cured article that light fastness test is used, produced crackle, can't measure, thereby it is defective to be judged as photostabilization.
The result who carries out above-mentioned " reliability test (1) (L test) " is, 4 LED points among 10 LED do not work, and total light flux sustainment rate (%) can't be measured, and is judged as defective.
Then, the result who carries out above-mentioned " reliability test (2) (TS test) " is, after having carried out 100 round-robin thermal shockings, among 10 LED only 5 LED light, be judged as defective.
And then the result who carries out above-mentioned " reliability test (3) (TC test) " is, after having carried out 100 round-robin temperature cycle, among 10 LED only 7 LED light, be judged as defective.
Can be judged that by above result the photostabilization of the LED of comparative example 32, reliability test (1)～(3) are all defective, synthetic determination is defective.
By the result of table 22～24 as can be known, the result of the photostabilization of the LED of embodiment 49～59, L test, TS test and TC test is all excellent.On the other hand, at least one in the storage stability of comparative example 26～30, photostabilization, L test, TS test and the TC test is bad.
Above content shows, photostabilization and the reliability excellence of the LED that the modified resin composition of use present embodiment is made.
Table 23
Unit: quality %
Then, for the optics lens that the modified resin composition that uses present embodiment is made, enumerate embodiment and comparative example is specifically described.
The evaluation of the rerum natura in embodiment 60～63 and the comparative example 31～35 is following to be carried out.
The calculating of＜storage stability index θ and the storage stability of resin combination 〉
Storage stability in the resin combination is estimated by the storage stability index θ shown in the following general formula (9).
Storage stability index θ=(preservation viscosity)/(initial viscosity) (9)
To the container sealing of the resin combination after the firm manufacturing be housed, the viscosity under carrying out under 25 ℃ after temperature adjusts 2 hours, measuring 25 ℃, with this as " initial viscosity ".
And then, will the container sealing of resin combination be housed, in 25 ℃ Constant Temperature Incubators, preserved for 2 weeks.After the preservation, the viscosity under measuring 25 ℃, with this as " preservation viscosity ".
Having flowability (viscosity is below the 1000Pas) and storage stability index θ at resin combination is under the situation below 4, is judged as to have storage stability.
＜optics the light fastness test of lens (cured article) 〉
Because optics is difficult to cutting sample after with the lens manufacturing, therefore utilize following method to make cured article, the photostabilization evaluation with lens substitutes as optics with the result of its evaluation.
(1) cured article of preparing by the aftermentioned method is solidified with solution, make the cured article of 20mm * 10mm * thickness 3mm.
(2) black masks of above-mentioned cured article with the 25mm * 15mm * thickness 1.2mm in the hole that has diameter 5.5mm covered, as the light fastness test sample.
(3) preparation device makes that UV illumination can be mapped to constant temperature via optical fiber from UV irradiating unit (Ushio Inc. system, " Spot Cure SP7-250DB ") is above-mentioned sample in 50 ℃ the Constant Temperature Incubators.
(4) be that top state is arranged in 50 ℃ the Constant Temperature Incubators with above-mentioned sample with black masks.
(5) in the mode in the hole that UV illumination can be mapped to diameter 5.5mm, from the top irradiation 2W/cm of black masks
2UV light 96 hours.
(6) utilize the spectral photometric colour measuring meter (Japanese electric look Industrial Co., Ltd system, " SD5000 ") that the integrating sphere peristome is transform as diameter 10mm, measure the postradiation sample of UV.
(7) try to achieve yellow chromaticity (YI) according to " ASTM D1925-70 (1988): Test Method for Yellowness Index of Plastics (plastics yellowness index test method) ".Under this YI was situation below 13, it was qualified to be judged as.
＜optics the cold shock testing of lens 〉
(1) will be arranged at thermal shock device (ESPEC CORP. system with lens by 10 optics of aftermentioned method manufacturing, " TSE-11-A ") in, condition with " (40 ℃～120 ℃)/circulation: 14 minutes exposure durations, 1 minute heating and cooling time " is carried out thermal cycling.
(2) take out above-mentioned sample through 100 thermal cyclings the time, jet penetration liquid (KOHZAI CORPORATION system, " MICRO CHECK "), writes down its number at the having or not of visual observation unusual (peeling off or crackle) under magnifying glass.
(3) do not put into device once more with confirming unusual sample in above-mentioned (4), further carry out 100 times thermal cycling and estimate by same method.Repeat these operations, estimate.
(4) 1 sample is observed and is interrupted estimating when unusual in 10 samples, obtains " cold-resistant thermal shocking number of times=(times of thermal cycle of interruption)-(100 times) ".
Under this cold-resistant thermal shocking number of times was situation more than 200 times, it was qualified to be judged as cold-resistant thermal shocking.
＜optics is tested with the surface viscosity of lens 〉
Be pressed through optics that the aftermentioned method the makes surface with lens gently with the thumb that wears latex glove, do not confirming under the situation about being clamminess, it is qualified to be judged as surface viscosity.
＜optics is tested with the hole of lens 〉
Visual Confirmation utilizes 10 optics lens that the aftermentioned method is made under magnifying glass, and under 10 situations that all do not have a hole, it is qualified to be judged as.
Under above-mentioned light fastness test, cold-resistant thermal shocking test, surface viscosity test, the whole qualified situations of hole test, synthetic determination is qualified.
Starting material about using in embodiment 60～63 and the comparative example 31～35 are shown in following (1)～(7).
(1) Resins, epoxy
(1-1) Resins, epoxy A: poly-(dihydroxyphenyl propane-2-hydroxypropyl ether) (below, be called Bis-A Resins, epoxy)
Trade(brand)name: Asahi Kasei Epoxy Co., Ltd system, " AER "
In addition, epoxy equivalent (weight) (WPE) and the viscosity of utilizing aforesaid method to measure is as described below.
Epoxy equivalent (weight) (WPE): 187g/eq
Viscosity (25 ℃): 14.3Pas
(1-2) Resins, epoxy B:3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexyl carboxylicesters (below, be called alicyclic epoxy resin)
Trade(brand)name: Daicel Chemical Industries, Ltd. system, " CEL 2021P "
In addition, epoxy equivalent (weight) (WPE) and the viscosity of utilizing aforesaid method to measure is as described below.
Epoxy equivalent (weight) (WPE): 131g/eq
Viscosity (25 ℃): 227mPas
(2) alkoxysilane compound containing trialkylsilyl group in molecular structure
(2-1) alkoxysilane compound containing trialkylsilyl group in molecular structure H:3-glycidoxypropyltrime,hoxysilane (below, be called GPTMS)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-403 "
(2-2) alkoxysilane compound containing trialkylsilyl group in molecular structure I: phenyltrimethoxysila,e (below, be called PTMS)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-103 "
(2-3) alkoxysilane compound containing trialkylsilyl group in molecular structure J: dimethyldimethoxysil,ne (below, be called DMDMS)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-22 "
(2-4) alkoxysilane compound containing trialkylsilyl group in molecular structure K: tetraethoxysilane (below, be called TEOS)
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBE-04 "
(3) solvent: tetrahydrofuran (THF) (Wako Pure Chemical Industries, Ltd.'s system does not contain stabilizer type) (below, be called THF)
(4) hydrolytic condensation catalyzer
(4-1) dibutyl tin laurate (Wako Pure Chemical Industries, Ltd.'s system, below, be called DBTDL)
(4-2) dibutyl dimethoxy tin (Sigma-Aldrich corporate system, below, be called DBTDM)
(5) solidifying agent: " 4-methyl hexahydro phthalic anhydride/hexahydro phthalic anhydride=70/30 "
Trade(brand)name: New Japan Chem Co., Ltd's system, " RIKACID MH-700G "
(6) curing catalyst: amine compound
Trade(brand)name: San-Apro Ltd. system, " U-CAT 18X "
(7) silicone resin
Trade(brand)name: Dow Corning Toray Co., Ltd. system, " EG6301 (A liquid/B liquid) "
[synthesis example 22]
Make resin combination by following operation.
(1) prepares: the circulation Water Tank with Temp.-controlled is set at 5 ℃, and cooling tube is refluxed.And then, on magnetic stirring apparatus, place 80 ℃ oil bath.
(2) according to the proportion of composing shown in the following table 25, under 25 ℃ atmosphere, with above-mentioned Bis-A1 Resins, epoxy, alkoxysilane compound containing trialkylsilyl group in molecular structure and THF pack into drop in the flask that stirrer is arranged and mix stir after, and then add water and hydrolytic condensation catalyzer, and mix and stir.
(3) then, cooling tube is set on flask, is impregnated in 80 ℃ the oil bath rapidly and begins to stir, react 20 hours (reflow process) while reflux.
(4) after reaction finishes, be cooled to 25 ℃, take off cooling tube from flask then.
(5) use vaporizer, under 400Pa, 50 ℃, remove the solution after reflow process finishes with distillation in 1 hour after, and then 80 ℃ down distillation removed 10 hours, carry out dehydration condensation (dehydrating condensation operation) simultaneously.
(6) after described dehydration condensation finishes, be cooled to 25 ℃, obtain resin combination.
(7) the mixing index α 71～ε 71 with resulting resin combination is shown in following table 27 respectively.
(8) in addition, according to aforesaid method, measure epoxy equivalent (weight) (WPE), the initial viscosity of the resin combination that obtains in above-mentioned (6) and preserve viscosity.And then, obtain storage stability index θ 71, they are shown in table 27.
Shown in table 27, the epoxy equivalent (weight) of the resin combination of above-mentioned synthesis example 22 (WPE)=230g/eq is shown as suitable value.In addition, initial viscosity=33.7Pas＜1000Pas, and preserve viscosity=47.0Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 71=1.39≤4 are judged as the resin combination with storage stability.
[synthesis example 23]
The time that makes reflow process is 25 hours, in addition utilizes with the same method of synthesis example 22 and makes resin combinations according to table 25 and 26.By estimating with the same method of synthesis example 22, its evaluation result, and mixing index α 72～ε 72, storage stability index θ 72 be shown in 27.
Shown in table 27, the epoxy equivalent (weight) of the resin combination of synthesis example 23 (WPE)=238g/eq is shown as suitable value.In addition, initial viscosity=15.2Pas＜1000Pas, and preserve viscosity=20.3Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 72=1.33≤4 are judged as the resin combination with storage stability.
[synthesis example 24]
Utilize with the same method of synthesis example 22 and make resin combinations according to table 25 and 26.Utilize with the same method of synthesis example 22 and estimate, its evaluation result, and mixing index α 73～ε 73, storage stability index θ 73 be shown in table 27.
Shown in table 27, the epoxy equivalent (weight) of the resin combination of synthesis example 24 (WPE)=228g/eq is shown as suitable value.In addition, initial viscosity=38.2Pas＜1000Pas, and preserve viscosity=61.1Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 73=1.60≤4 are judged as the resin combination with storage stability.
[synthesis example 25]
The time that makes reflow process is 7 hours, in addition utilizes with the same method of synthesis example 22 and makes resin combinations according to table 25 and 26.Utilize with the same method of synthesis example 22 and estimate, its evaluation result, and mixing index α 74～ε 74, storage stability index θ 74 be shown in table 27.
Shown in table 27, the epoxy equivalent (weight) of the resin combination of synthesis example 25 (WPE)=214g/eq is shown as suitable value.In addition, initial viscosity=4.9Pas＜1000Pas, and preserve viscosity=9.4Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 74=1.91≤4 are judged as the resin combination with storage stability.
[relatively synthesis example 4]
Utilize the method same, make resin combinations according to table 25 and 26 with synthesis example 22.Utilize with the same method of synthesis example 22 and estimate, its evaluation result, and mixing index α 75～ε 75, storage stability index θ 75 be shown in table 27.
Shown in table 27, relatively epoxy equivalent (weight) (the WPE)=295g/eq of the resin combination of synthesis example 4 is shown as suitable value.In addition, initial viscosity=33.4Pas＜1000Pas, and preserve viscosity=48.2Pas＜1000Pas, both are has mobile liquid.In addition, storage stability index θ 75=1.44≤4 are judged as the resin combination with storage stability.
[relatively synthesis example 5]
Utilize the method same, make resin combinations according to table 25 and 26 with synthesis example 22.Utilize with the same method of synthesis example 22 and estimate, its evaluation result, and mixing index α 76～ε 76, storage stability index θ 76 be shown in table 27.
Shown in table 27, relatively epoxy equivalent (weight) (the WPE)=295g/eq of the resin combination of synthesis example 5 is shown as suitable value.In addition, initial viscosity=29.0Pas＜1000Pas is for having mobile liquid.Yet, preserve viscosity＞1000Pas, there is not flowability, storage stability index θ 76＞35 in addition, storage stability is bad, can't make optics with lens evaluation sample.
[embodiment 60]
Use is made cured article by following operation, and is carried out light fastness test at 25 ℃ of resin combinations of preserving the above-mentioned synthesis example 22 in 2 weeks down.The results are shown in table 27.
(1) under 25 ℃ atmosphere, according to the proportion of composing of table 26 resin combination, solidifying agent and curing catalyst are mixed and to stir, and under vacuum, outgas, make cured article solution.
(2) with being coated with 2 pieces of stainless steel plate clamping thickness 3mm of releasing agent, the silicon rubber of コ word shape, make shaping jig.
(3) in this shaping jig, inject above-mentioned cured article solution, implemented solidification treatment 1 hour down, and then implemented solidification treatment 1 hour down, make cured article at 150 ℃ at 120 ℃.
(4) temperature drop is low to moderate the taking-up of back below 30 ℃ cured article in the stove, according to aforesaid method, and preparation light fastness test sample.
(5) use above-mentioned sample, carry out light fastness test by aforesaid method, test-results is shown in table 27.As YI=10.1≤13 of the index of the light fastness test of this cured article, it is qualified to be judged as photostabilization.
Then, use the resin combination of synthesis example 22, make the optics lens, carry out thermal shock test, surface viscosity test, hole test by following operation.The results are shown in table 27.
(6) according to the proportioning mixing raw material of table 26, after the deaeration, be arranged in the injection moulding machine (Sodick Co., Ltd. system) in a vacuum.
(7) and then, solidified 15 minutes down at 140 ℃, be cooled to the demoulding after the room temperature, obtain the optics lens of the about 1cm of diameter.
The result who carries out the thermal shock test by aforesaid method is, the cold shock testing number of times is 400 times 〉=200 times, and it is qualified to be judged as cold-resistant thermal shocking.
The result who carries out surface viscosity test by aforesaid method is, do not confirm and is clamminess, and it is qualified to be judged as.
The result who carries out porosity test by aforesaid method is, do not confirm hole, and it is qualified to be judged as.
Can be judged that by above result the optics of embodiment 60 is all qualified with light fastness test, cold shock testing, surface viscosity test, the hole test of lens, synthetic determination is qualified.
[embodiment 61]
Replace the resin combination of synthesis example 22 and use the resin combination of synthesis example 23, utilize with the same method of embodiment 60 and make cured article and optics lens, carry out light fastness test, cold shock testing, surface viscosity test, hole and test.The results are shown in table 27.
As YI=8.1≤13 of the index of light fastness test, photostabilization is judged as qualified.
The result who carries out the thermal shock test by aforesaid method is, the cold shock testing number of times is 300 times 〉=200 times, and it is qualified to be judged as cold-resistant thermal shocking.
The result who carries out surface viscosity test by aforesaid method is, do not confirm and is clamminess, and it is qualified to be judged as.
The result who carries out porosity test by aforesaid method is, do not confirm hole, and it is qualified to be judged as.
Can be judged that by above result the optics of embodiment 61 is all qualified with light fastness test, cold shock testing, surface viscosity test, the hole test of lens, synthetic determination is qualified.
[embodiment 62]
Replace the resin combination of synthesis example 22 and use the resin combination of synthesis example 24, utilize with the same method of embodiment 60 and make cured article and optics lens, carry out light fastness test, cold shock testing, surface viscosity test, hole and test.The results are shown in table 27.
As YI=8.9≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
The above-mentioned result who carries out the thermal shock test is, the cold shock testing number of times is more than 500 times 〉=200 times, and it is qualified to be judged as cold-resistant thermal shocking.
The result who carries out surface viscosity test by aforesaid method is, do not confirm and is clamminess, and it is qualified to be judged as.
The result who carries out porosity test by aforesaid method is, do not confirm hole, and it is qualified to be judged as.
Can be judged that by above result the optics of embodiment 62 is all qualified with light fastness test, cold shock testing, surface viscosity test, the hole test of lens, synthetic determination is qualified.
[embodiment 63]
Replace the resin combination of synthesis example 22 and use the resin combination of synthesis example 25, utilize with the same method of embodiment 60 and make cured article and optics lens, carry out light fastness test, cold shock testing, surface viscosity test, hole and test.The results are shown in table 27.
As YI=8.3≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
The result who carries out the thermal shock test by aforesaid method is, the cold shock testing number of times is 300 times 〉=200 times, and it is qualified to be judged as cold-resistant thermal shocking.
The result who carries out surface viscosity test by aforesaid method is, do not confirm and is clamminess, and it is qualified to be judged as.
The result who carries out porosity test by aforesaid method is, do not confirm hole, and it is qualified to be judged as.
Can be judged that by above result the optics of embodiment 63 is all qualified with light fastness test, cold shock testing, surface viscosity test, the hole test of lens, synthetic determination is qualified.
[comparative example 31]
Replace the resin combination of synthesis example 22 and use the resin combination of comparison synthesis example 4, utilize with the same method of embodiment 60 and make cured article and optics lens, carry out light fastness test, cold shock testing, surface viscosity test, hole and test.The results are shown in table 27.
As YI=8.4≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
The result who carries out the thermal shock test by aforesaid method is, the cold shock testing number of times is 100 times＜200 times, and it is defective to be judged as cold-resistant thermal shocking.
The result who carries out surface viscosity test by aforesaid method is, do not confirm and is clamminess, and it is qualified to be judged as.
The result who carries out porosity test by aforesaid method is, do not confirm hole, and it is qualified to be judged as.
Can judge by above result, the optics of comparative example 31 light fastness test, surface viscosity test, the hole stand the test of lens, but cold shock testing is defective, thereby synthetic determination is defective.
[comparative example 32]
Replace the resin combination of synthesis example 22 and use the resin combination of comparison synthesis example 5, utilize with the same method of embodiment 60 and attempt making cured article and optics lens, and implement light fastness test, cold shock testing, surface viscosity test, hole test, but the storage stability of resin combination is bad, can't make cured article and optics lens.Therefore, synthetic determination is defective.
[comparative example 33]
Replace the resin combination of synthesis example 22 and use Bis-A Resins, epoxy, utilize with the same method of embodiment 60 and make cured article and optics lens, carry out light fastness test, surface viscosity test, hole and test.The results are shown in table 27.
As YI=17.2＞13 of the index of light fastness test, it is defective to be judged as photostabilization.
The result who carries out the thermal shock test by aforesaid method is, the cold shock testing number of times is more than 500 times 〉=200 times, and it is qualified to be judged as cold-resistant thermal shocking.
The result who carries out surface viscosity test by aforesaid method is, do not confirm and is clamminess, and it is qualified to be judged as.
The result who carries out porosity test by aforesaid method is, do not confirm hole, and it is qualified to be judged as.
Can judge by above result, the optics of comparative example 35 cold shock testing, surface viscosity test, the hole stand the test of lens, but photostabilization is defective, so synthetic determination is defective.
[comparative example 34]
Replace the resin combination of synthesis example 22 and use the above-mentioned silicone resin that A liquid and B liquid is mixed together with 1: 1 mass ratio, utilize with the same method of embodiment 60 and make cured article and optics lens, carry out light fastness test, surface viscosity test, hole and test.The results are shown in table 27.
As YI=2.0≤13 of the index of light fastness test, it is qualified to be judged as photostabilization.
The result who carries out the thermal shock test by aforesaid method is, the cold shock testing number of times is 100 times＜200 times, and it is defective to be judged as cold-resistant thermal shocking.
The result who carries out surface viscosity test by aforesaid method is, do not confirm and is clamminess, and it is qualified to be judged as.
The result who carries out porosity test by aforesaid method is, do not confirm hole, and it is qualified to be judged as.
Can judge by above result, the optics of comparative example 34 light fastness test, surface viscosity test, the hole stand the test of lens, but cold shock testing is defective, so synthetic determination is defective.
[comparative example 35]
The composition that replaces the resin combination of synthesis example 22 and use the proportioning according to table 25 that Bis-A Resins, epoxy, GPTMS, PTMS are mixed, utilize with the same method of embodiment 60 and make cured article and optics lens, carry out light fastness test, surface viscosity test, hole and test.The results are shown in table 27.
In the light fastness test, test has produced a plurality of holes with sample, can't measure photostabilization.
The result who carries out the thermal shock test by aforesaid method is, the cold shock testing number of times is 200 times 〉=200 times, and it is qualified to be judged as cold-resistant thermal shocking.
The result who carries out surface viscosity test by aforesaid method is, confirms and is clamminess, and is judged as defective.
The result who carries out porosity test by aforesaid method is, 8 samples in 10 samples confirm hole, are judged as defective.
Can judge that by above result the optics of comparative example 35 is qualified with the cold shock testing of lens, but light fastness test, surface viscosity test, hole test are defective, thereby synthetic determination is defective.
Table 26
Unit: quality %
Then, in the modified resin composition of present embodiment, adding the conductive resin composition that the conductive metal powder forms, enumerate embodiment and comparative example is specifically described.
The evaluation of the rerum natura in embodiment 64～67 and the comparative example 36～38 is following to be carried out.
About epoxy equivalent (weight) (WPE), viscosity, mixing index α～η, by trying to achieve with above-mentioned same method.
The median size of＜conductive metal powder is measured 〉
Use laser diffraction formula particle size distribution device (SYMPATEC corporate system, " HELOS system "), under the dry type pattern, measure median size.
The viscosimetric analysis of＜conductive resin composition 〉
To the container sealing of the composition after the firm manufacturing be housed, the viscosity under carrying out under 25 ℃ after temperature adjusts 1 hour, measuring 25 ℃.
Viscosity is under the following situation of 1000Pas, is judged as to have flowability.
The softening point measurement of＜phenolic varnish type resol 〉
Measure for 5.8 according to " JIS K6910:2007 (resol test method) ".
The hydroxyl equivalent of＜phenolic varnish type resol is measured 〉
Measure hydroxyl value according to " JIS K0070:1002 (test method of the acid number of chemical preparations, saponification value, ester value, iodine number, hydroxyl value and unsaponifiables) ", and be scaled hydroxyl equivalent.
The volume specific resistance of＜conductive resin composition is measured 〉
Utilize rod to be coated with machine and be coated with conductive resin composition on slide glass, making thickness is 40 μ m, and it was heated 60 minutes down at 200 ℃, and formation is filmed.
Utilize resistrivity meter (DIA INSTRUMENTS CO., LTD., system, " Loresta ") to measure this and film, volume specific resistance is 9 * 10
-4Under the following situation of Ω cm, it is good to be judged as electroconductibility.
The determining bonding strength of＜conductive resin composition and cementability evaluation 〉
Measure moisture absorption in the following order and handle the bonding strength of front and back.
(1) at the chip bonding pad portion of copper lead frame (the coating conductive resin composition of 9mm * 9mm).
(2) then, in chip bonding pad portion silicon (8mm * 16mm), heat with stove with 200 ℃ * 1 hour condition is installed.(preceding sample is handled in moisture absorption)
(3) with the moisture absorption 72 hours in the constant temperature and humidity machine that is set at 85 ℃ of temperature, humidity 85% of manufactured samples in (2).(the back sample is handled in moisture absorption)
(4) make silicon down, on 250 ℃ hot plate, above-mentioned " sample before the moisture absorption processing " and " the back sample is handled in moisture absorption " were heated 20 seconds, the lead-in wire of mentioning lead frame then, the bonding strength when using pull and push dynamometer (IMADA Co., Ltd. system) mensuration silicon and chip bonding pad to peel off.
(5) under the bonding strength survival rate shown in the following formula is situation more than 80%, it is good to be judged as cementability.
Bonding strength survival rate (%)=(bonding strength after moisture absorption is handled)/(bonding strength before moisture absorption is handled) * 100
The hole evaluation of＜conductive resin composition 〉
At the chip bonding pad portion coating conductive resin composition of above-mentioned copper lead frame, and glass-chip (8mm * 8mm), heat with stove with 200 ℃ * 1 hour condition is installed.This sample of Visual Confirmation has the imporosity under magnifying glass.
About the resin combination of embodiment and comparative example, good and do not confirm under the situation of generation of hole at mobile, electroconductibility and cementability, synthetic determination is qualified.
About the starting material that use in embodiment and the comparative example, be shown in following (1)～(10).
(1) Resins, epoxy
(1-1) Resins, epoxy A: bisphenol A type epoxy resin (below, be called " Bis-A Resins, epoxy ")
Trade(brand)name: Asahi Kasei Epoxy Co., Ltd system, " AER "
In addition, epoxy equivalent (weight) (WPE) and the viscosity of utilizing aforesaid method to measure is as described below.
Epoxy equivalent (weight) (WPE): 187g/eq
Viscosity (25 ℃): 14.3Pas
(1-2) Resins, epoxy F: bisphenol f type epoxy resin (below, be called " Bis-F Resins, epoxy ")
Trade(brand)name: Japan Epoxy Resins Co., Ltd. system, " jER807 "
In addition, epoxy equivalent (weight) (WPE) and the viscosity of utilizing aforesaid method to measure is as described below.
Epoxy equivalent (weight) (WPE): 169g/eq
Viscosity (25 ℃): 3.2Pas
(2) alkoxysilane compound containing trialkylsilyl group in molecular structure H:3-glycidoxypropyltrime,hoxysilane (below, be called " GPTMS ")
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-403 "
(3) alkoxysilane compound containing trialkylsilyl group in molecular structure I: phenyltrimethoxysila,e (below, be called " PTMS ")
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-103 "
(4) alkoxysilane compound containing trialkylsilyl group in molecular structure J: dimethyldimethoxysil,ne (below, be called " DMDMS ")
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBM-22 "
(5) alkoxysilane compound containing trialkylsilyl group in molecular structure K: tetraethoxysilane (below, be called " TEOS ")
Trade(brand)name: Shin-Etsu Chemial Co., Ltd's system, " KBE-04 "
(6) solvent
(6-1) tetrahydrofuran (THF): Wako Pure Chemical Industries, Ltd.'s system does not contain stabilizer type (below, be called " THF ")
(7) hydrolytic condensation catalyzer: dibutyl tin laurate (Wako Pure Chemical Industries, Ltd.'s system, below, be called " DBTDL ")
(8) solidifying agent
(8-1) solidifying agent A: phenolic varnish type resol (Dainippon Ink Chemicals's system, trade(brand)name " PHENOLITE "; Hydroxyl equivalent 104g/eq, 100 ℃ of softening temperatures) (below, be called " NP resin ")
(8-2) solidifying agent B:1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene (San-Apro Ltd. system, trade(brand)name " DBU ") (below, be called " DBU ")
(9) thinner: adjacent toluene glycidyl ether (this pharmaceutical industries of slope Co., Ltd. system, trade(brand)name " SY-OCG "; Epoxy equivalent (weight) 181g/eq, viscosity 8mPas)
(10) silver powder
(10-1) flakey silver powder (median size 6.3 μ m)
(10-2) spherical silver powder (median size 1.2 μ m)
[synthesis example 26]
Resin combination J: make resin combination J in the following order, and estimate.
(1) prepares: the circulation Water Tank with Temp.-controlled is set at 5 ℃, and cooling tube is refluxed.And then, on magnetic stirring apparatus, place 80 ℃ oil bath.
(2) according to the proportion of composing of table 28, under 25 ℃ atmosphere, with Resins, epoxy, alkoxysilane compound containing trialkylsilyl group in molecular structure and THF pack into drop in the flask that stirrer is arranged and mix stir after, and then add water and hydrolytic condensation catalyzer, and mix and stir.
(3) then, cooling tube is set on flask, is impregnated in 80 ℃ the oil bath rapidly and begins to stir, react 10 hours while reflux.
(4) after reaction finishes, be cooled to 25 ℃, take off cooling tube from flask then, gather the sample solution after reflow process finishes.
(5) use vaporizer, under 400Pa, 50 ℃, remove the solution after reflow process finishes with distillation in 1 hour after, and then 80 ℃ down distillation removed 5 hours, carry out dehydration condensation simultaneously.
(6) after reaction finishes, be cooled to 25 ℃, obtain resin combination J.
(7) the mixing index α 77～ε 77 in this resin combination is shown in table 30.
(8) in addition, according to aforesaid method, measure the epoxy equivalent (weight) (WPE) of the resin combination J that obtains in above-mentioned (6).
The epoxy equivalent (weight) of above-mentioned resin combination (WPE)=195g/eq is shown as suitable value.In addition, viscosity is 12.7Pas, for having mobile liquid.
[synthesis example 27]
Resin combination K:, utilize the method compound resin composition K same, and estimate with synthesis example 26 according to the proportion of composing of table 28.Mixing index α 78～ε 78 is shown in table 30.
The epoxy equivalent (weight) of above-mentioned resin combination (WPE)=228g/eq is shown as suitable value.In addition, viscosity is 13.8Pas, for having mobile liquid.
[synthesis example 28]
Resin combination L:, utilize the method compound resin composition L same, and estimate with synthesis example 26 according to the proportion of composing of table 28.Mixing index α 79～ε 79 is shown in table 30.
The epoxy equivalent (weight) of above-mentioned resin combination (WPE)=206g/eq is shown as suitable value.In addition, viscosity is 18.2Pas, for having mobile liquid.
[synthesis example 29]
Resin combination M:, utilize the method compound resin composition M same, and estimate with synthesis example 26 according to the proportion of composing of table 28.Mixing index α 80～ε 80 is shown in table 30.
The epoxy equivalent (weight) of above-mentioned resin combination (WPE)=208g/eq is shown as suitable value.Viscosity is 10.2Pas, for having mobile liquid.
[embodiment 64]
Make conductive resin composition 1 in the following order, and estimate.Evaluation result, and mixing index α 77～ε 77 be shown in table 30.
Use the resin combination J of above-mentioned synthesis example 26, according to the composition mixing raw material of table 29, and evenly mixing with triple-roller mill (Inoue MFG. Inc.'s system).And then the use vacuum chamber, deaeration is 30 minutes under 400Pa, with this as conductive resin composition 1.The viscosity of conductive resin composition 1 is 21.5Pas, is mobile excellent liquid.
Utilize rod to be coated with machine and be coated with conductive resin composition 1 on slide glass, making thickness is 40 μ m, and the slide glass after the coating was heated 60 minutes down at 200 ℃, and formation is filmed.Utilize resistrivity meter (DIA INSTRUMENTS CO., LTD., system, " Loresta ") to measure the volume specific resistance that this is filmed, the result is 2 * 10
-4Ω cm, it is good to be judged as electroconductibility.
Obtain the bonding strength survival rate of conductive resin composition 1 in the following order.
(1) (the coating conductive resin composition 1 of 9mm * 9mm) is made 4 above-mentioned samples in the chip bonding pad portion of copper lead frame.
(2) then, in chip bonding pad portion silicon (8mm * 16mm), heat with stove with 200 ℃ * 1 hour condition is installed.
(3) with 2 conducts in the manufactured samples in (2) " preceding sample is handled in moisture absorption ".
(4) with the moisture absorption 72 hours in the constant temperature and humidity machine that is set at 85 ℃ of temperature, humidity 85% of 2 of the residues of manufactured samples in (2), with this as " sample is afterwards handled in moisture absorption ".
(5) use above-mentioned " preceding sample is handled in moisture absorption " and " the back sample is handled in moisture absorption ", make silicon down, heating is 20 seconds on 250 ℃ hot plate, mentions the lead-in wire of lead frame then, bonding strength when using pull and push dynamometer (IMADA Co., Ltd. system) mensuration silicon and chip bonding pad to peel off.Measure and carry out with n=2 respectively, obtain mean value.
(6) with the mean value substitution following formula of the bonding strength of above-mentioned " moisture absorption handle before sample " of trying to achieve and " the back sample is handled in moisture absorption ", obtain the bonding strength survival rate, and the evaluation cementability.
Bonding strength survival rate (%)=(bonding strength after moisture absorption is handled)/(bonding strength before moisture absorption is handled) * 100=(148mN)/(151mN) * 100=98% 〉=80%, the cementability that is judged as conductive resin composition 1 is good.
Then, at the chip bonding pad portion coating conductive resin composition 1 of copper lead frame, and glass-chip (8mm * 8mm), heat with stove with 200 ℃ * 1 hour condition is installed.This sample of Visual Confirmation does not produce hole under magnifying glass.
Can be judged that by The above results the flowability of conductive resin composition 1, electroconductibility, and excellent in adhesion do not produce hole in addition yet, synthetic determination is qualified thus.
[embodiment 65]
Composition according to table 29 uses above-mentioned resin combination K, utilizes with the same method of embodiment 64 and makes conductive resin composition 2, and estimate.Evaluation result, and mixing index α 78～ε 78 be shown in table 30.
The viscosity of conductive resin composition 2 is 23.7Pas, is mobile excellent liquid.
The volume specific resistance of conductive resin composition 2 is 3 * 10
-4Ω cm, it is good to be judged as electroconductibility.
With the mean value substitution following formula of the bonding strength of " moisture absorption handle before sample " and " the back sample is handled in moisture absorption " of conductive resin composition 2, obtain the bonding strength survival rate, and the evaluation cementability.
Bonding strength survival rate (%)=(bonding strength after moisture absorption is handled)/(bonding strength before moisture absorption is handled) * 100=(138mN)/(145mN) * 100=95% 〉=80%, the cementability that is judged as conductive resin composition 2 is good.
Then, at the chip bonding pad portion coating conductive resin composition 2 of copper lead frame, and glass-chip (8mm * 8mm), heat with stove with 200 ℃ * 1 hour condition is installed.This sample of Visual Confirmation does not produce hole under magnifying glass.
Can judge that by The above results the flowability of conductive resin composition 2, electroconductibility, and excellent in adhesion also do not produce hole in addition, thereby synthetic determination are qualified.
[embodiment 66]
Composition according to table 29 uses above-mentioned resin combination L, utilizes with the same method of embodiment 64 and makes conductive resin composition 3, and estimate.Evaluation result, and mixing index α 79～ε 79 be shown in table 30.
The viscosity of conductive resin composition 3 is 28.2Pas, is mobile excellent liquid.
The volume specific resistance of conductive resin composition 3 is 3 * 10
-4Ω cm, it is good to be judged as electroconductibility.
With the mean value substitution following formula of the bonding strength of " moisture absorption handle before sample " and " the back sample is handled in moisture absorption " of conductive resin composition 3, obtain the bonding strength survival rate, and the evaluation cementability.
Bonding strength survival rate (%)=(bonding strength after moisture absorption is handled)/(bonding strength before moisture absorption is handled) * 100=(124mN)/(136mN) * 100=91% 〉=80%, the cementability that is judged as conductive resin composition 3 is good.In addition,, demonstrate more excellent cementability, infer thus by share 2 kinds of solidifying agent to show multiplier effect with except the ratio that changes NP resin and DBU, compare with the conductive resin composition 4 of the embodiment 65 of same composition manufacturing.
Then, at the chip bonding pad portion coating conductive resin composition 3 of copper lead frame, and glass-chip (8mm * 8mm), heat with stove with 200 ℃ * 1 hour condition is installed.This sample of Visual Confirmation does not produce hole under magnifying glass.
Can judge that by The above results the flowability of conductive resin composition 3, electroconductibility, and excellent in adhesion also do not produce hole in addition, thereby synthetic determination are qualified.
[embodiment 67]
Composition according to table 29 uses above-mentioned resin combination M, utilizes with the same method of embodiment 64 and makes conductive resin composition 4, and estimate.Evaluation result, and mixing index α 80～ε 80 be shown in table 30.
The viscosity of conductive resin composition 4 is 19.1Pas, is mobile excellent liquid.
The volume specific resistance of conductive resin composition 4 is 3 * 10
-4Ω cm, it is good to be judged as electroconductibility.
With the mean value substitution following formula of the bonding strength of " moisture absorption handle before sample " and " the back sample is handled in moisture absorption " of conductive resin composition 4, obtain the bonding strength survival rate, and the evaluation cementability.
Bonding strength survival rate (%)=(bonding strength after moisture absorption is handled)/(bonding strength before moisture absorption is handled) * 100=(108mN)/(128mN) * 100=84% 〉=80%, the cementability that is judged as conductive resin composition 4 is good.
Then, at the chip bonding pad portion coating conductive resin composition 4 of copper lead frame, and glass-chip (8mm * 8mm), heat with stove with 200 ℃ * 1 hour condition is installed.This sample of Visual Confirmation does not produce hole under magnifying glass.
Can judge that by The above results the flowability of conductive resin composition 4, electroconductibility, and excellent in adhesion also do not produce hole in addition, thereby synthetic determination are qualified.
[comparative example 36]
According to the composition of table 29, replace resin combination J and use Bis-A Resins, epoxy and Bis-F Resins, epoxy, utilize with the same method of embodiment 64 and make conductive resin composition 5, and estimate.The results are shown in table 30.
The viscosity of conductive resin composition 5 is 26.4Pas, is mobile excellent liquid.
The volume specific resistance of conductive resin composition 5 is 3 * 10
-4Ω cm, it is good to be judged as electroconductibility.
With the mean value substitution following formula of the bonding strength of " moisture absorption handle before sample " and " the back sample is handled in moisture absorption " of conductive resin composition 5, obtain the bonding strength survival rate, and the evaluation cementability.
Bonding strength survival rate (%)=(bonding strength after moisture absorption is handled)/(bonding strength before moisture absorption is handled) * 100=(81mN)/(132mN) * 100=61%＜80%, the cementability of conductive resin composition 5 is bad.
Then, at the chip bonding pad portion coating conductive resin composition 5 of copper lead frame, and glass-chip (8mm * 8mm), heat with stove with 200 ℃ * 1 hour condition is installed.This sample of Visual Confirmation does not produce hole under magnifying glass.
Can be judged that by The above results the flowability and the electroconductibility of conductive resin composition 5 are good, also do not produce hole, but cementability be bad, synthetic determination is defective thus.
[comparative example 37]
According to the composition of table 29, replace resin combination J and use Bis-A Resins, epoxy, GPTMS, PTMS, utilize method similarly to Example 1 to make conductive resin composition 6, and estimate.The results are shown in table 30.
The viscosity of conductive resin composition 6 is 18.2Pas, is mobile excellent liquid.
The volume specific resistance of conductive resin composition 6 is 42 * 10
-4Ω cm, it is bad to be judged as electroconductibility.
With the mean value substitution following formula of the bonding strength of " moisture absorption handle before sample " and " the back sample is handled in moisture absorption " of conductive resin composition 6, obtain the bonding strength survival rate, and the evaluation cementability.
Bonding strength survival rate (%)=(bonding strength after moisture absorption is handled)/(bonding strength before moisture absorption is handled) * 100=(120mN)/(134mN) * 100=89% 〉=80%, the cementability of conductive resin composition 6 is good.
Then, at the chip bonding pad portion coating conductive resin composition 6 of copper lead frame, and glass-chip (8mm * 8mm), heat with stove with 200 ℃ * 1 hour condition is installed.This sample of Visual Confirmation under magnifying glass, results verification is to the generation of hole.
Can be judged that by The above results flowability, the cementability of conductive resin composition 6 are good, but electroconductibility is bad, also confirms the generation of hole, synthetic determination is defective thus.
[comparative example 38]
According to the composition of table 29, replace resin combination J and use Bis-A Resins, epoxy and Bis-F Resins, epoxy, TEOS, utilize with the same method of embodiment 62 and make conductive resin composition 7, and estimate.The results are shown in table 30.
The viscosity of conductive resin composition 7 is 16.3Pas, is mobile excellent liquid.
The volume specific resistance of conductive resin composition 7 is 3 * 10
-4Ω cm, it is good to be judged as electroconductibility.
With the mean value substitution following formula of the bonding strength of " moisture absorption handle before sample " and " the back sample is handled in moisture absorption " of conductive resin composition 7, obtain the bonding strength survival rate, and the evaluation cementability.
Bonding strength survival rate (%)=(bonding strength after moisture absorption is handled)/(bonding strength before moisture absorption is handled) * 100=(131mN)/(140mN) * 100=94% 〉=80%, the cementability of conductive resin composition 7 is good.
Then, at the chip bonding pad portion coating conductive resin composition 7 of copper lead frame, and glass-chip (8mm * 8mm), heat with stove with 200 ℃ * 1 hour condition is installed.This sample of Visual Confirmation under magnifying glass, results verification is to the generation of hole.
Can be judged that by The above results the flowability of conductive resin composition 7, electroconductibility, cementability are good, but confirm the generation of hole, synthetic determination is defective thus.
Shown in table 28～table 30, if conductive resin composition contains resin combination, conductive metal powder and the solidifying agent that obtains by with the specific ratio blending epoxy in the present embodiment and specific alkoxysilane compound containing trialkylsilyl group in molecular structure and cohydrolysis condensation, then conductive resin composition is mobile excellent.
In addition, the electroconductibility of the conductive resin composition of present embodiment and excellent in adhesion, and do not produce hole yet.
The Japanese patent application (Japanese Patent Application 2008-175096) that the application submitted to the Japan special permission Room based on July 3rd, 2008, on December 10th, 2008 be to the Japanese patent application (Japanese Patent Application 2008-314273) of Japan's special permission Room application, and its content is incorporated herein as a reference.
Utilizability on the industry
According to the present invention, a kind of modified resin composition can be provided, it can form the solidfied material that has the good transparency, has simultaneously excellent heat resistance, heat-resisting discolouration, light resistance, cold-hot impact, and this modified resin composition has good storage stability.
In addition, the modified resin composition of the application of the invention can provide:<a>The excellent luminous components such as LED, the adaptation of the luminous component such as this LED and element or encapsulating material is excellent and do not crack, the reduction of for a long time brightness is littler; With the optics lens, this optics with lens can injection moulding, solidify after the hard and excellent in dimensional stability of quality and have light resistance; And, used described luminous component and/or the optics semiconductor device of lens. The modified resin composition of the application of the invention can also provide:<b>Can suppress the inhibition of oxygen generation, photosensitive composite excellent in adhesion, contain the smears of said composition, and make this smears solidify filming of forming;<c>The fluorescence resin composition of the dispersion stabilization excellence of fluorophor has used the light-storing material of this fluorescence resin composition;<d>Mobile, electric conductivity and excellent in adhesion and do not produce the conductive resin composition of hole;<e>Mobile, insulating properties and excellent in adhesion and do not produce the insulating resin composition etc. of hole.
Claims (33)
1. modified resin composition, its modified resin composition for Resins, epoxy (A) and the alkoxysilane compound containing trialkylsilyl group in molecular structure reaction shown in the following general formula (1) are obtained,
(R
1)
n-Si-(OR
2)
4-n (1)
Wherein, n represents more than 0 and 3 following integers; In addition, R
1Respectively independently expression be selected from by hydrogen atom, following a), following b), following c) organic group more than at least a kind in the group formed, on the other hand, R
2Expression is selected from by hydrogen atom and following d independently respectively) organic group more than a kind in the group formed,
A) organic group, this organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and this organic group contains carbonatoms be more than 4 and 24 following and oxygen atomicities be 1 or more and 5 below the ring-type ethers
B) 1 valency aliphatics organic group, this 1 valency aliphatics organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aliphatics organic group is more than 1 and 24 following and oxygen atomicities are more than 0 and below 5
C) 1 valency aromatic series organic group, this 1 valency aromatic series organic group is the aromatic hydrocarbons unit of non-replacement or replacement, have in case of necessity non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aromatic series organic group is more than 6 and 24 following and oxygen atomicities are more than 0 and below 5
D) 1 valency organic group, this 1 valency organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and the carbonatoms of this 1 valency organic group is more than 1 and below 8;
Described alkoxysilane compound containing trialkylsilyl group in molecular structure comprises:
(B) n=1 or 2 and have at least 1 ring-type ether as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure and
(C) n=1 or 2 and have at least 1 aromatic series organic group as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure,
The mixing index α of the described alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the following general formula (2) is more than 0.001 and below 19,
Mixing index α=(α c)/(α b) ... (2)
Wherein, in the formula (2), α b represents the content (mol%) of described (B) composition in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), and α c represents the content (mol%) of described (C) composition in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1);
And the residual alcoxyl base unit weight in the described modified resin composition is below 5%.
2. modified resin composition as claimed in claim 1, the viscosity of described modified resin composition under 25 ℃ is below the 1000Pas.
3. modified resin composition as claimed in claim 1 or 2, the epoxy equivalent (weight) of wherein said modified resin composition are more than the 100g/eq and below the 700g/eq.
4. as each described modified resin composition in the claim 1～3, the condensation rate of wherein said alkoxysilane compound containing trialkylsilyl group in molecular structure is more than 80%.
5. as each described modified resin composition in the claim 1～4, the viscosity of wherein said Resins, epoxy (A) under 25 ℃ is below the 500Pas.
6. as each described modified resin composition in the claim 1～5, the epoxy equivalent (weight) of wherein said Resins, epoxy (A) is more than the 100g/eq and below the 300g/eq.
7. as each described modified resin composition in the claim 1～6, the polyfunctional epoxy resin that wherein said Resins, epoxy (A) constitutes for the glycidyl ether thing by polyphenolic substance.
8. as each described modified resin composition in the claim 1～7, wherein said Resins, epoxy (A) is bisphenol A type epoxy resin.
9. as each described modified resin composition in the claim 1～8, the mixing index β of the described alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the wherein following general formula (3) is more than 0.01 and below 1.4,
Mixing index β={ (β n2)/(β nO+ β n1) } (3)
Wherein, in the formula (3), β n2 represents the content (mol%) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=2, β n0 represents the content (mol%) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=0, β n1 represents the content (mol%) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=1, and β n2, β n0, β n1 are for satisfying the value of 0≤{ (β n0)/(β n0+ β n1+ β n2) }≤0.1.
10. as each described modified resin composition in the claim 1～9, the described Resins, epoxy (A) shown in the wherein following general formula (4) is 0.02～15 with the mixing index γ of described alkoxysilane compound containing trialkylsilyl group in molecular structure,
Mixing index γ=(γ a)/(γ s) (4)
Wherein, in the formula (4), the quality (g) of γ a representative ring epoxy resins (A), γ s represents the quality (g) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=0～2.
11. the manufacture method of a modified resin composition, it comprises at least that for making (B) shown in the following general formula (1) reaches the manufacture method of each described modified resin composition in that (C) alkoxysilane compound containing trialkylsilyl group in molecular structure reacts, the claim 1～10 under Resins, epoxy (A), this method comprises following operation (a) and operation (b):
Operation (a): in the presence of Resins, epoxy (A), will comprise (B) shown in the general formula (1) and alkoxysilane compound containing trialkylsilyl group in molecular structure cohydrolysis (C) at least, thereby make the operation of intermediate by the reflow process of not following dehydration;
Operation (b): make the intermediate of making by operation (a) carry out the operation of dehydration condensation;
(R
1)
n-Si-(OR
2)
4-n (1)
Wherein, n represents more than 0 and 3 following integers; In addition, R
1Respectively independently expression be selected from by hydrogen atom, following a), following b), following c) organic group more than at least a kind in the group formed, on the other hand, R
2Expression is selected from by hydrogen atom and following d independently respectively) organic group more than a kind in the group formed,
A) organic group, this organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and this organic group contains carbonatoms be more than 4 and 24 following and oxygen atomicities be 1 or more and 5 below the ring-type ethers
B) 1 valency aliphatics organic group, this 1 valency aliphatics organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aliphatics organic group is more than 1 and 24 following and oxygen atomicities are more than 0 and below 5
C) 1 valency aromatic series organic group, this 1 valency aromatic series organic group is the aromatic hydrocarbons unit of non-replacement or replacement, have in case of necessity non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aromatic series organic group is more than 6 and 24 following and oxygen atomicities are more than 0 and below 5
D) 1 valency organic group, this 1 valency organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and the carbonatoms of this 1 valency organic group is more than 1 and below 8;
(B) n=1 or 2 and have at least 1 ring-type ether as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure,
(C) n=1 or 2 and have at least 1 aromatic series organic group as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure,
And the mixing index α of the described alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the following general formula (2) is more than 0.001 and below 19,
Mixing index α=(α c)/(α b) ... (2)
Wherein, in the formula (2), α b represents the content (mol%) of described (B) composition, and α c represents the content (mol%) of described (C) composition.
12. the manufacture method of a modified resin composition, it comprises at least that for making (B) shown in the following general formula (1) reaches the manufacture method of each described modified resin composition in that (C) alkoxysilane compound containing trialkylsilyl group in molecular structure reacts, the claim 1～10 under Resins, epoxy (A), this method comprises following operation (c) and operation (d):
Operation (c): will comprise (B) shown in the general formula (1) and alkoxysilane compound containing trialkylsilyl group in molecular structure cohydrolysis (C) at least by the reflow process of not following dehydration, thereby make the operation of intermediate;
Operation (d): make operation by the intermediate and Resins, epoxy (A) coexistence the carrying out dehydration condensation of operation (c) manufacturing;
(R
1)
n-Si-(OR
2)
4-n (1)
Wherein, n represents more than 0 and 3 following integers; In addition, R
1Respectively independently expression be selected from by hydrogen atom, following a), following b), following c) organic group more than at least a kind in the group formed, on the other hand, R
2Expression is selected from by hydrogen atom and following d independently respectively) organic group more than a kind in the group formed,
A) organic group, this organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and this organic group contains carbonatoms be more than 4 and 24 following and oxygen atomicities be 1 or more and 5 below the ring-type ethers
B) 1 valency aliphatics organic group, this 1 valency aliphatics organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aliphatics organic group is more than 1 and 24 following and oxygen atomicities are more than 0 and below 5
C) 1 valency aromatic series organic group, this 1 valency aromatic series organic group is the aromatic hydrocarbons unit of non-replacement or replacement, have in case of necessity non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain and the structural group that ring-type constituted, and the carbonatoms of this 1 valency aromatic series organic group is more than 6 and 24 following and oxygen atomicities are more than 0 and below 5
D) 1 valency organic group, this 1 valency organic group have non-replacement or replacement, comprise the aliphatic hydrocarbon unit of structure more than a kind that is selected from by in chain, chain, the structural group that ring-type constituted, and the carbonatoms of this 1 valency organic group is more than 1 and below 8;
(B) n=1 or 2 and have at least 1 ring-type ether as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure,
(C) n=1 or 2 and have at least 1 aromatic series organic group as R
1At least a kind of alkoxysilane compound containing trialkylsilyl group in molecular structure,
And the mixing index α of the described alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the following general formula (2) is more than 0.001 and below 19,
Mixing index α=(α c)/(α b) ... (2)
Wherein, in the formula (2), α b represents the content (mol%) of described (B) composition, and α c represents the content (mol%) of described (C) composition.
13. as the manufacture method of claim 11 or 12 described modified resin compositions, the mixing index β of the described alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the wherein following general formula (3) is 0.01～1.4,
Mixing index β={ (β n2)/(β n0+ β n1) } (3)
Wherein, in the formula (3), β n2 represents the content (mol%) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=2, β n0 represents the content (mol%) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=0, β n1 represents the content (mol%) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=1, and β n2, β n0, β n1 are for satisfying the value of 0≤{ (β n0)/(β n0+ β n1+ β n2) }≤0.1.
14. as the manufacture method of each described modified resin composition in the claim 11～13, the Resins, epoxy (A) shown in the wherein following general formula (4) is 0.02～15 with the mixing index γ of described alkoxysilane compound containing trialkylsilyl group in molecular structure,
Mixing index γ=(γ a)/(γ s) (4)
Wherein, in the formula (4), the quality (g) of γ a representative ring epoxy resins (A), γ s represents the quality (g) of alkoxysilane compound containing trialkylsilyl group in molecular structure in the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the general formula (1), n=0～2.
15. as the manufacture method of each described modified resin composition in the claim 11～14, wherein not following the temperature in the reflow process of dehydration is 50～100 ℃.
16. as the manufacture method of each described modified resin composition in the claim 11～15, wherein the condensation rate of the intermediate that obtains by the reflow process cohydrolysis of not following dehydration is more than 78%.
17. as the manufacture method of each described modified resin composition in the claim 11～16, wherein when described cohydrolysis, using alkoxide is that organotin is as catalyzer.
18. a resin combination, it forms by further add oxetane compound (D) in the described modified resin composition of claim 1.
19. a fluorescence resin combination, it forms by further add fluor (E) in the described modified resin composition of claim 1.
20. a conductive resin composition, it forms by further add conductive metal powder (F) in the described modified resin composition of claim 1.
21. an insulating resin composition, it forms by further add insulativity powder (G) in the described modified resin composition of claim 1.
22. a resin combination, it forms by further add Resins, epoxy (A ') in the described modified resin composition of claim 1.
23. a curable resin composition, it forms by further adding solidifying agent (H) in each described resin combination in claim 1,18,19.
24. a curable resin composition, it forms by further add curing catalyst (I) in the described resin combination of claim 23.
25. a photosensitive polymer combination, it forms by further adding light acid producing agent (J) in each described resin combination in claim 1,18,19.
26. a luminous component, it uses claim 24 or 25 described resin combinations and makes.
27. optics lens, it uses claim 24 or 25 described resin combinations and makes.
28. a light-storing material, it uses claim 24 or 25 described resin combinations and makes.
29. a semiconductor device, it comprises described luminous component of claim 26 and/or the described optics lens of claim 27.
30. a curable resin composition, it forms by further adding curing catalyst (I) in each described resin combination in claim 20～22.
31. a photosensitive polymer combination, it forms by further adding light acid producing agent (J) in each described resin combination in claim 20～22.
32. a coating agent, it comprises each described resin combination in the claim 24,25,30,31.
33. film for one kind, it uses the described coating agent of claim 32 and makes.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| JP2008-175096 | 2008-07-03 | ||
| JP2008175096 | 2008-07-03 | ||
| JP2008-314273 | 2008-12-10 | ||
| JP2008314273 | 2008-12-10 | ||
| PCT/JP2009/062201 WO2010001992A1 (en) | 2008-07-03 | 2009-07-03 | Modified resin composition, method for producing the same, and curable resin composition containing the same |
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| CN102076734A true CN102076734A (en) | 2011-05-25 |
| CN102076734B CN102076734B (en) | 2013-02-27 |
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| Country | Link |
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| CN (1) | CN102076734B (en) |
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| JPS59174658A (en) * | 1983-03-23 | 1984-10-03 | Toray Silicone Co Ltd | Primer composition |
| JP3077695B1 (en) * | 1999-06-17 | 2000-08-14 | 荒川化学工業株式会社 | Method for producing alkoxy group-containing silane-modified epoxy resin |
| JP4639054B2 (en) * | 2004-04-02 | 2011-02-23 | 旭化成株式会社 | Transparent hybrid sheet |
| JP4723272B2 (en) * | 2004-04-02 | 2011-07-13 | 大阪瓦斯株式会社 | Photopolymerizable resin composition and cured product thereof |
| JP4979963B2 (en) * | 2006-03-10 | 2012-07-18 | 株式会社Ａｄｅｋａ | Curable composition for optical material and optical waveguide |
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2009
- 2009-07-02 TW TW098122385A patent/TWI440647B/en active
- 2009-07-03 WO PCT/JP2009/062201 patent/WO2010001992A1/en active Application Filing
- 2009-07-03 CN CN2009801247757A patent/CN102076734B/en active Active
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| CN109874702A (en) * | 2019-04-12 | 2019-06-14 | 云南农业大学 | A kind of epoxy resin lair model production method demoulded using temperature |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2010001992A1 (en) | 2010-01-07 |
| TWI440647B (en) | 2014-06-11 |
| TW201004993A (en) | 2010-02-01 |
| CN102076734B (en) | 2013-02-27 |
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