CN1154124A - Organopolysiloxane derivative - Google Patents
Organopolysiloxane derivative Download PDFInfo
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- CN1154124A CN1154124A CN 96190505 CN96190505A CN1154124A CN 1154124 A CN1154124 A CN 1154124A CN 96190505 CN96190505 CN 96190505 CN 96190505 A CN96190505 A CN 96190505A CN 1154124 A CN1154124 A CN 1154124A
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Abstract
Disclosed is an organo-polysiloxane derivative useful as a dispersing agent for homogeneously dispersing a silicone gel in a curable resin such as an epoxy resin, and preparation process thereof. The organo-polysiloxane derivative is prepared by a first reaction step for reacting an organo-polysiloxane compound A having an active hydrogen-containing group in each of its both terminals and having from 5 to 70 siloxane bonds with a bifunctional organic compound B having two functional groups reactable with active hydrogen; and a second reaction step for reacting a reaction mixture obtained in the first reaction step with a mixture of a bifunctional organic compound C having two active hydrogens with a bifunctional organic compound D having two functional groups reactable with the active hydrogen.
Description
Technical field
The present invention relates to organopolysiloxane derivative, its manufacture method, be used for the curable resin composition that makes silica gel be scattered in the dispersion agent of curable resin and contain this dispersion agent and silica gel.
Background technology
Resins, epoxy is owing to excellent thermal characteristics, mechanical property and electrical property, and the past is widely used as always and is tackiness agent, coating, electrical/electronic part insulating material, electrical/electronic part sealing material etc.
Yet, use under the occasion of this Resins, epoxy, exist the problem that produces internal stress in the cured article that obtains in its curing, produce various uncomfortable situations thus.For example, sealing with Resins, epoxy under the occasion of electronic component, the internal stress of epoxy resin cured product makes and produces uncomfortable situations such as fault or breakage in this resin-sealed electrical/electronic part.
On the other hand, in order to reduce the internal stress of epoxy resin cured product, once proposed to add the scheme (spy opens clear 61-185527 number) of silica gel.
But the Combination of this silica gel and Resins, epoxy is poor, exists the problem that is difficult to evenly spread in the Resins, epoxy.
And generally speaking, curable resin singly is not above-mentioned Resins, epoxy, all produces internal stress in its cured article.By adding silica gel in the curable resin beyond Resins, epoxy, can reduce the internal stress of this cured article.But, be difficult to make silica gel to evenly spread in the Resins, epoxy curable resin in addition.
Problem of the present invention is as follows.
(1) provide a kind of being used as to make silica gel be dispersed in very useful organopolysiloxane derivative and the manufacture method thereof of dispersion agent in the curable resin.
(2) provide a kind of silica gel that makes to be dispersed in silica gel dispersion agent in the curable resin.
(3) provide a kind of curable resin composition that contains silica gel and silica gel usefulness dispersion agent.
Other problem of the present invention can further be understood by following narration.
Disclosure of the Invention
The inventor has carried out deep research repeatedly for solving above-mentioned problem, so far finishes the present invention.
The invention provides following invention.
(1) a kind of organopolysiloxane derivative is characterized in that, has the represented structure of following general formula (1) in the molecule.
(2) has the manufacture method of the organopolysiloxane derivative of structure shown in the following general formula (1) in a kind of molecule, it is characterized in that, this method be by the organopolysiloxane compound A that two ends is had contain active hydrogen group with 5～70 siloxane bonds with have 2 can with the 1st reaction process of the difunctionality organic compound B reaction of the functional group of active hydrogen reaction, and, make the resultant of reaction that obtains in the 1st reaction process with have 2 contain the difunctionality organic compound C of active hydrogen group and have 2 can with the mixture reaction of the difunctionality organic compound D of the functional group of active hydrogen reaction (the 2nd reaction process).
(3) a kind of silica gel that makes is scattered in dispersion agent in the curable resin, it is characterized in that, it is to be made of the organopolysiloxane derivative that has the represented structure of following general formula (1) in the molecule.
(4) a kind of curable resin composition is characterized in that, it contains the organopolysiloxane derivative that has the represented structure of following general formula (1) in silica gel and the molecule.
In the above-mentioned general formula (1),
A represents above-mentioned organopolysiloxane compound.
B represents above-mentioned difunctionality organic compound B.
C represents above-mentioned difunctionality organic compound C.
D represents above-mentioned difunctionality organic compound D.
N is 1～20, preferred 1～1 4 number.
D is 1～20, preferred 1～1 7 number.
Above-mentioned difunctionality organic compound B can be identical compound with difunctionality organic compound D.Under this occasion, above-mentioned general formula (1) can be rewritten into following general formula (2).
Organopolysiloxane derivative with the represented structure of above-mentioned general formula of the present invention (1) adopts 2 represented reaction process of following reaction formula to make.
(the 1st reaction process)
A+2B→B-A-B????(3)
(the 2nd reaction process)
p(B-A-B)+n(C+D)?(4)
In the above-mentioned formula, A, B, C, D, n and p have implication same as described above.
Among the present invention, be used as among the organopolysiloxane compound A of reaction raw materials, two terminal upward bonded contains the group of reactive hydrogen, can be hydroxyl (OH), carboxyl (COOH), sulfydryl (SH), amino [NH
2,-NHR (R: substituting group)], amide group (CONH
2) etc.These groups that contain reactive hydrogen are that media is attached on the Siliciumatom (Si) with the linking group.Linking group under this occasion comprises aliphatic group, aromatic group or the heterocyclic group of divalence.And, also can contain heteroatomss such as aerobic, nitrogen, sulphur in the carbochain of aliphatic group.
In the aliphatic divalent group, comprise chain or cyclic alkylidene group.As the chain alkylidene group, can enumerate the alkylidene group of carbonatoms 1～20, for example methylene radical, ethylidene, propylidene, butylidene, hexylidene, octylene, inferior dodecyl, inferior hexadecyl, inferior octadecyl etc.And, as cyclic alkylidene (ring alkylidene group), can enumerate ring propylidene, ring butylidene, ring pentylidene, cyclohexylene, cycloethylene thiazolinyl (cyclo hexenylene) etc.These chains or cyclic alkylidene group also can contain two keys.Have again, in the aliphatic divalent group, comprise with formula-(RO)
sThe alkylidene group oxygen base or the polyoxy base alkylidene group of-(in the formula, R represents low-grade alkylidenes such as ethylidene, propylidene, butylidene, and s represents 1～20, preferred 2～10 numeral) expression.
As the divalence aromatic group, can enumerate the derivative of aromatics such as benzene,toluene,xylene, ethylbenzene, anisole, methoxyl biphenyl, cyano group benzene, oil of mirbane, isopropyl benzene, ditan, diphenyl propane, biphenyl, naphthalene, phenanthrene.As divalent heterocyclic group, can enumerate the derivative of the replacement body of furans, tetrahydrofuran (THF), pyrroles, thiophene, cumarone, carbazole, pyridine, piperidines, pyrans, quinoline or their core.
Above-mentioned polysiloxane key can be represented with following general formula (5).
In the above-mentioned formula, X and Y represent alkyl or halo alkyl, and one of them also can be a hydrogen.T represents 5～90, preferred 20～50 number, more preferably 35～40 number.F represents 0 or 1, is generally 0.
As above-mentioned alkyl, can enumerate the low alkyl group of carbonatomss 1～6 such as methyl, ethyl, propyl group, butyl, hexyl; Aromatic base such as phenyl, tolyl; Low-grade alkenyls such as vinyl, allyl group, propenyl; Aralkyl such as benzyl, styroyl; Cycloalkyl such as cyclopentyl, cyclohexyl.As the halo alkyl, can enumerate tetrafluoro ethyl, perfluorovinyl sulfide, dichlorophenyl, trifluoromethyl etc.
In the above-mentioned general formula (5), X and Y are preferably methyl or phenyl.T can stipulate in the above range, if be higher than above-mentioned scope, operability when then being used as dispersion agent owing to organopolysiloxane derivative is damaged, be disadvantageous, on the other hand, if be lower than above-mentioned scope,, also be disadvantageous then because the dispersiveness of silica gel in curable resin is damaged.
The object lesson of above-mentioned organopolysiloxane compound is as follows.
In the formula, R
1The expression methyl or phenyl, Z represents-OH ,-COOH ,-NH
2Or-SH, R
2The expression low-grade alkylidene, t represents 5～90, and is preferred 20～50, more preferably 35～40 number.
In the above-mentioned formula, Z represents-COOH ,-NH
2Or-SH, R
1, R
2Same as described above with the implication of t.
In the above-mentioned formula, Z represents-COOH ,-NH
2Or-SH, R
3Expression ethylidene or propylidene, q represents 1～20, preferred 2～10 number, R
1Same as described above with the implication of t.
Have the organopolysiloxane compound that contains active hydrogen group for above-mentioned two ends, all cpds all has commercially available, the example that can enumerate has, for example " BY16-853 " of East レ ダ ウ コ-two Application グ シ リ コ-Application (strain) system (two end are amino, amino equivalent: 650), " BY16-853B " (two ends are amino, amino equivalent: 2200), " BY16-752 " (two ends are hydroxyphenyl, OH equivalent: 1574), " BY16-150B " (two ends are hydroxyphenyl, OH equivalent: 4500), " BY16-150C " (two ends are hydroxyphenyl, OH equivalent: 10000), " BY16-750 " (two ends are carboxyl, carboxyl equivalent: 700); (two ends are amino to " TSL9346 " of the シ リ of Toshiba コ-Application (strain) system, 250), " TSL9386 " (two ends are amino amino equivalent:, 400), " TSL9836 " (two ends are sulfydryl amino equivalent:, 260), " TSL9876 " (two ends are sulfydryl SH equivalent:, 410), " TSL9846 " (two ends are sulfydryl SH equivalent:, 290), " TSL9886 " (two ends are sulfydryl, SH equivalent: 440) SH equivalent:; (two ends are amino to " X-22-161AS " of the Rui リ of SHIN-ETSU HANTOTAI コ-Application (strain) system, amino equivalent: 450), " X-22-161A " (two ends are amino, amino equivalent: 840), " X-22-161B " (two ends are amino, amino equivalent: 1500), " X-22-161C " (two ends are amino, amino equivalent: 2300), " X-22-162A " (two ends are carboxyl, carboxyl equivalent: 920), " X-22-162C " (two ends are carboxyl, carboxyl equivalent: 2330), " X-22-167B " (two ends are sulfydryl, SH equivalent: 1670), " X-22-165B " (two ends are hydroxyphenyl, OH equivalent: 2000); 1000), " F-204-52 " (two ends are amino, amino equivalent: 3700) etc. (two end be amino to " F-204-51 " of Japan ュ ニ カ-(strain) system, amino equivalent:.
Have 2 can with the difunctionality organic compound B of the functional group of active hydrogen reaction in, comprise fatty compounds, aromatics and heterogeneous ring compound.This difunctionality organic compound B can represent with following general formula.
L-R
4-L(9)
In the above-mentioned formula, R
4The expression divalent organic group, L represent can with the functional group of active hydrogen reaction.And, R
4In can have the various substituting groups of no reactive hydrogens such as alkoxyl group or alkoxy carbonyl, acyl group, nitro, cyano group, halogen.
Above-mentioned divalent organic group R
4In, comprise aliphatic divalent group, divalence aromatic group and divalent heterocyclic group.
In the aliphatic divalent group, comprise chain or cyclic alkylidene group.As the chain alkylidene group, can enumerate carbonatoms 1～20, preferred 1～10 alkylidene group.As cyclic alkylidene (ring alkylidene group), can enumerate ring propylidene, ring butylidene, ring pentylidene, cyclohexylene, cycloethylene thiazolinyl etc.These chains or cyclic alkylidene group also can contain two keys.Have again, in the aliphatic divalent group, also can comprise heteroatomss such as oxygen, nitrogen, sulphur in its carbochain.
As the divalence aromatic group, can enumerate the group of representing with following formula by various aromatics deutero-.
(i)-Ar-
In the formula, Ar represents by aromatics deutero-divalence aromatic groups such as benzene,toluene,xylene, ethylbenzene, anisole, methoxyl biphenyl, cyano group benzene, oil of mirbane, isopropyl benzene, ditan, diphenyl propane, biphenyl, naphthalene, phenanthrene.
(ii)-R-Ar-R-
In the formula, Ar represents the divalence aromatic group, and R represents the low-grade alkylidene of carbonatoms 1～6.
(iii)-RO-Ar-OR-
In the formula, Ar represents the divalence aromatic group, and R represents low-grade alkylidene.
(iv)-CH
2-[OArOCH
2OHCH
2]
m-1-OArOCH
2-
In the formula, Ar represents the divalence aromatic group, and m represents 1 or 2 integer.
As divalent heterocyclic group, can enumerate the derivative of the replacement body of furans, tetrahydrofuran (THF), pyrroles, thiophene, cumarone, carbazole, pyridine, piperidines, pyrans, quinoline or their core.
As the L of functional group in the above-mentioned general formula (9), can enumerate oxyethyl group, isocyanate group (NCO), carboxyl, ester group, hydroxyl, halogen etc.
The object lesson of above-mentioned difunctionality organic compound B is as follows.
In the formula, R represents divalence aromatic group, aliphatic divalent group or divalent heterocyclic group, and m represents 1 or 2 integer.
(ii)OCN-R
4-NCO
In the formula, R
4Expression divalence aromatic group, aliphatic divalent group or divalent heterocyclic group.
(iii)HOOC-R-COOH
In the formula, R
4Expression divalence aromatic group, aliphatic divalent group or divalent heterocyclic group.
In the formula, R represents aromatic group or low alkyl groups such as methyl, ethyl such as phenyl, tolyl.
(v)ROOC-R
4-COOR
In the formula, R
4Expression divalence aromatic group, aliphatic divalent group or divalent heterocyclic group, R represents low alkyl group.
Have among 2 difunctionality organic compound C that contain active hydrogen group, comprise fatty compounds, aromatics and heterogeneous ring compound.This difunctionality organic compound C can represent with following general formula.
H-R
5-H(10)
In the above-mentioned formula, R
5The expression divalent organic group, the reactive hydrogen that H represents to contain in the active hydrogen group and contained.As R
5Object lesson, can enumerate above-mentioned R
4Shown in relevant group.
Have 2 can with the difunctionality organic compound D of the functional group of active hydrogen reaction in, comprise fatty compounds, aromatics and heterogeneous ring compound.As the object lesson of this difunctionality organic compound D, can enumerate the relevant group shown in the above-mentioned difunctionality organic compound B.
The preferred organopolysiloxane derivative of the present invention can use two ends to have to contain the organopolysiloxane compound A with 5～90 siloxane bonds (SiO), difunctionality aromatic epoxy compound B and the bivalent phenol compound C of active hydrogen group to make as reaction raw materials.As above-mentioned organopolysiloxane compound A, can use the compound shown in above-mentioned general formula (6), (7) or (8).
As above-mentioned difunctionality aromatic epoxy compound B, can use the compound shown in the following general formula.
(in the formula, Ar
1Expression divalence aromatic group, m is 1 or 2 integer)
As above-mentioned bivalent phenol compound, can use the compound shown in the following general formula.
HO-Ar
2-OH????……(12)
(in the formula, Ar
2Expression divalence aromatic group)
In the above-mentioned general formula (11) of expression difunctionality aromatic epoxy compound B, Ar
1Expression divalence aromatic group.Ar under this occasion
1, especially preferably by polycyclc aromatic compound deutero-divalence aromatic groups such as two (phenyl) methane, two (phenyl) propane, two (phenyl) ethane, naphthalene, biphenyl, tetrabromo biphenyl.The preferred difunctionality aromatic epoxy compound B that uses is the diglycidylether of divalent phenol among the present invention, and its object lesson is as follows.
Two (4-hydroxyphenyl) propane diglycidylether, two (4-hydroxyl-3, the 5-dibromo phenyl) propane diglycidylether, two (4-hydroxyphenyl) methane diglycidylether, two (4-hydroxyphenyl) ethane diglycidylether, resorcinol diglycidyl ether, two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) methane diglycidylether, two (4-hydroxy-3-methyl phenyl) propane diglycidylether, two (4-hydroxyphenyl) HFC-236fa diglycidylether, 2,6-naphthalene glycol diglycidylether, tetrabromo biphenylene glycol diglycidylether etc.
In the above-mentioned general formula (12) of expression bivalent phenol compound, Ar
2Expression divalence aromatic group.As the Ar under this occasion
2, preferred above-mentioned Ar
1Shown in by the relevant divalence aromatic group of polycyclc aromatic compound deutero-.The object lesson of used bivalent phenol compound is as follows among the present invention.
Two (4-hydroxyphenyl) propane, two (4-hydroxyl-3, the 5-dibromo phenyl) propane, two (4-hydroxyphenyl) methane, two (4-hydroxyphenyl) ethane, Resorcinol, two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) methane, two (4-hydroxy-3-methyl phenyl) propane, two (4-hydroxyphenyl) HFC-236fa, 2,6-naphthalene glycol, tetrabromo biphenylene glycol etc.
When making organopolysiloxane derivative with above-mentioned reaction raw materials, at first, in the 1st reaction process, two ends are had can react with difunctionality aromatic epoxy compound B (being designated hereinafter simply as compd B) with the organopolysiloxane compound A (being designated hereinafter simply as compd A) with 5～70 siloxane bonds that contains active hydrogen group of epoxy reaction.Reaction under this occasion, (still, the reaction formula under occasion Z=-OH) is expressed as follows to use the compound shown in the above-mentioned formula (6) as compd A.
In the above-mentioned formula, R
1, R
2, Ar
1, m and t implication same as described above, B ' represents with following formula.
The tetraalkylammonium salt as catalyzer is preferably used in above-mentioned reaction, and for example, Tetramethylammonium chloride, etamon chloride, tetramethylammonium bromide, iodate tetramethyl-ammonium, chlorination phenyltrimethyammonium wait and carry out.Catalyst consumption for Resins, epoxy, is 0.01～1 mole of %, preferred 0.05～0.1 mole of %.Above-mentioned reaction is carried out with liquid state, and temperature of reaction can be the temperature that reaction mixture is in a liquid state, and is generally 80～140 ℃, preferred 100～120 ℃, temperature of reaction is slowly risen along with the carrying out of reaction.Reaction pressure can adopt normal pressure, pressurization and decompression any, be preferably normal pressure.Difunctionality aromatic epoxy compound B, for organopolysiloxane compound A1 mole, can be more than 2 moles, preferably more than 2.1 moles.
Then, after above-mentioned the 1st reaction process finishes, in the resultant of reaction that obtains, add the mixture of Compound C and compd B, react.Reaction under this occasion is represented with following formula.
+HO-Ar
2-OH
In the above-mentioned formula, R
1, R
2, Ar
1, Ar
2, B ', m and t implication same as described above, A, B and C represent with following formula.And in the above-mentioned formula, n is 1～14, and preferred 8～12 number, p are 1～17, preferred 2～5 number.
C：-O-Ar
2-O-(18)
Above-mentioned reaction can be carried out under the situation that has or do not exist catalyzer.As the catalyzer under this occasion, can use any of the catalyzer that can not promote alcoholic extract hydroxyl group and epoxy reaction especially, preferably can use the catalyzer shown in above-mentioned the 1st reaction process.Use in the 1st reaction process under the occasion of catalyzer, in its 2nd reaction process with regard to unnecessary interpolation catalyzer.Temperature of reaction can be the temperature that reaction mixture is in a liquid state, and is generally 130～170 ℃, preferred 140～150 ℃, preferably heats up along with the carrying out of reaction.Reaction can be implemented under decompression, pressurization or normal pressure, preferably carries out under decompression or nitrogen gas stream.
The end structure of organopolysiloxane derivative of the present invention, have can with compd B or any structure of Compound C bonded (that is, above-mentioned B ' or-O-Ar
2-OH), this depends primarily on the compd B in the said mixture and the ratio of Compound C, and the compound that accounts for the big side of this ratio is attached on the end.Under the occasion of the present invention, preferably Compound C is attached on the end, thereby obtains the organopolysiloxane derivative that two ends have phenolic hydroxyl group.
Other preferred organopolysiloxane derivatives of the present invention can use two ends to have to contain the organopolysiloxane compound A with 5～90 siloxane bonds (SiO), diisocyanate cpd B and the diol compound C of active hydrogen group to make as reaction raw materials.
As above-mentioned organopolysiloxane compound A, can use the compound shown in above-mentioned general formula (6), (7) or (8).
As above-mentioned diisocyanate cpd B, can use the compound shown in the following general formula.
OCN-R
6-NCO????……(19)
(in the formula, R
6Expression divalence aromatic group or aliphatic divalent group)
As above-mentioned glycol compound C, can use the compound shown in the following general formula.
HO-R
7-OH??????……(20)
(in the formula, R
7The expression aliphatic divalent group)
In the above-mentioned diisocyanate cpd, comprise aromatic diisocyanate compounds and aliphatic diisocyanate compound.As the object lesson of diisocyanate cpd, can enumerate phenylene vulcabond, inferior cresyl vulcabond, 4,4 '-phenylbenzene between vulcabond, naphthalene diisocyanate, hexamethylene diisocyanate etc.
As above-mentioned diol compound, can enumerate ethylene glycol, propylene glycol, butyleneglycol, hexamethylene glycol, polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol etc.
When using above-mentioned reaction raw materials to make organopolysiloxane derivative of the present invention, at first, in the 1st reaction process, make diisocyanate cpd B and organopolysiloxane compound A reaction.(still, Z=-OH) under the occasion as compd A, the reaction of this occasion is represented with following reaction formula to use compound shown in the above-mentioned formula (6).
+OCN-R
6-NCO(21)
In the above-mentioned formula, R
1, R
2, R
6, m and t implication same as described above, B ' represents with following formula.
OCN-R
6-NHCO-????……(22)
Then, after above-mentioned the 1st reaction process finishes, in the resultant of reaction that obtains, add the mixture of Compound C and compd B, react.Reaction under this occasion is represented with following formula.
+HO-R
7-OH(23)
+OCN-R
6-NCO
In the above-mentioned formula, R
1, R
2, R
6, R
7, B ', m and t implication same as described above, A, B and C represent with following formula.And in the above-mentioned formula, n is 1～14, and preferred 8～12 number, p are 1～17, preferred 2～5 number.
B：-OCHN-R
6-NHCO-????(25)
C：-O-R
7-O-??????????(26)
Other preferred organopolysiloxane derivatives of the present invention can use two ends to have to contain the organopolysiloxane compound A with 5～90 siloxane bonds (SiO), dicarboxylic acid compound B and the diamino compounds C of active hydrogen group to make as reaction raw materials.
As above-mentioned organopolysiloxane compound A, can use the compound shown in above-mentioned general formula (6), (7) or (8).
As above-mentioned dicarboxylic acid compound B, can use the compound shown in the following general formula.
MOC-R
8-COM????……(27)
(in the formula, R
8Expression divalence aromatic group or aliphatic divalent group, M represents OH or halogen)
As above-mentioned diamino compounds C, can use the compound shown in the following general formula.
H
2N-R
9-NH
2????……(28)
(in the formula, R
9Expression divalence aromatic group or aliphatic divalent group)
As above-mentioned dicarboxylic acid compound B, can enumerate terephthalic acid, naphthalene dicarboxylic acids, toxilic acid, succsinic acid, hexanodioic acid, sebacic acid etc.
As above-mentioned diamino compounds C, can enumerate phenylenediamine, tolylene diamine, 1,4-butanediamine, 1,6-hexanediamine etc.
When using above-mentioned reaction raw materials to make organopolysiloxane derivative of the present invention, at first, in the 1st reaction process, make dicarboxylic acid compound B and organopolysiloxane compound A reaction.Use compound (still, Z=-NH shown in the above-mentioned formula (6)
2) under the occasion as compd A, the reaction of this occasion is represented with following reaction formula.
+MOC-R
8-COM????(29)
In the above-mentioned formula, R
1, R
2, R
8, M, m and t implication same as described above, B represents with following formula.
MOC-R
8-CO-????(30)
Then, after above-mentioned the 1st reaction process finishes, in the resultant of reaction that obtains, add the mixture of Compound C and compd B, react.Reaction under this occasion is represented with following formula.
+H
2N-R
9-NH
2???(31)
+MOC-R
8-COM
In the above-mentioned formula, R
1, R
2, R
8, R
9, M, B ', m and t implication same as described above, A, B and C represent with following formula.And in the above-mentioned formula, n is 1～14, and preferred 8～12 number, p are 1～17, preferred 2～5 number.
B：-OC-R
8-CO-????(33)
C：-HN-R
9-NH-????(34)
Other preferred organopolysiloxane derivatives of the present invention can have the organopolysiloxane compound A with 5～90 siloxane bonds (SiO), carbonic diester compd B and the dihydroxy compound C that contain active hydrogen group with two ends and make as reaction raw materials.
As above-mentioned organopolysiloxane compound A, can use the compound shown in above-mentioned general formula (6), (7) or (8).
As above-mentioned carbonic diester compd B, can use the compound shown in the following general formula.
(in the formula, R
10Expression aliphatic group or aromatic group)
As above-mentioned dihydroxy compound C, can use the compound shown in the following general formula.
HO-R
11-OH????(36)
(in the formula, R
11Expression aliphatic divalent group or divalence aromatic group)
As above-mentioned carbonic diester B, can enumerate methylcarbonate, diethyl carbonate, diphenyl carbonate, carboxylol ester etc.
As above-mentioned dihydroxy compound C, can enumerate ethylene glycol, propylene glycol, butyleneglycol, pyrocatechol, dihydroxyphenyl propane etc.
When using above-mentioned reaction raw materials to make organopolysiloxane derivative of the present invention, at first, in the 1st reaction process, make carbonic diester compd B and organopolysiloxane compound A reaction.(still, Z=-OH) under the occasion as compd A, the reaction of this occasion is represented with following reaction formula to use compound shown in the above-mentioned formula (6).
In the above-mentioned formula, R
1, R
2, R
10, m and t implication same as described above, B ' represents with following formula.
Then, after above-mentioned the 1st reaction process finishes, in the resultant of reaction that obtains, add the mixture of Compound C and compd B, react.Reaction under this occasion is represented with following formula.
+HO-R
11-OH????(39)
In the above-mentioned formula, R
1, R
2, R
10, R
11, B ', m and t implication same as described above, A, B and C represent with following formula.And in the above-mentioned formula, n is 1～14, and preferred 8～12 number, p are 1～17, preferred 2～5 number.
B：
C：
-O-R
11-O-????????????(42)
Other preferred organopolysiloxane derivatives of the present invention can use two ends to have to contain the organopolysiloxane compound A with 5～90 siloxane bonds (SiO), dicarboxylic diester compd B and the dihydroxy compound C of active hydrogen group to make as reaction raw materials.
As above-mentioned organopolysiloxane compound A, can use the compound shown in above-mentioned general formula (6), (7) or (8).
As above-mentioned dicarboxylic diester compd B, can use the compound shown in the following general formula.
R
13OOC-R
12-COOR
13????(43)
(in the formula, R
12Expression aliphatic divalent group or divalence aromatic group, R
13The expression low alkyl group)
As above-mentioned dihydroxy compound C, can use the compound shown in the following general formula.
HO-R
14-OH????????????(44)
(in the formula, R
14Expression aliphatic divalent group or divalence aromatic group)
As above-mentioned dicarboxylic diester (compound) B, can enumerate dimethyl malonate, diethyl malonate, dimethyl adipate, dimethyl sebacate, terephthalic acid dimethyl ester, terephthalic acid diethyl ester etc.
As above-mentioned dihydroxy compound C, can enumerate ethylene glycol, propylene glycol, butyleneglycol, pyrocatechol, dihydroxyphenyl propane etc.
When using above-mentioned reaction raw materials to make organopolysiloxane derivative of the present invention, at first, in the 1st reaction process, make dicarboxylic diester compd B and organopolysiloxane compound A reaction.(still, Z=-OH) under the occasion as compd A, the reaction of this occasion is represented with following reaction formula to use the compound shown in the above-mentioned formula (6).
+R
13OOC-R
12-COOR
13????(45)
In the above-mentioned formula, R
1, R
2, R
12, R
13, m and t implication same as described above, B ' represents with following formula.
R
13OOC-R
12-CO-????????(46)
Then, after above-mentioned the 1st reaction process finishes, in the resultant of reaction that obtains, add the mixture of Compound C and compd B, react.Reaction under this occasion is represented with following formula.
+HO-R
14-OH???????????(47)
+R
13OOC-R
12-COOR
13
In the above-mentioned formula, R
1, R
2, R
12, R
13, R
14, B ', m and t implication same as described above, A, B and C represent with following formula.And in the above-mentioned formula, n is 1～14, and preferred 8～12 number, p are 1～17, preferred 2～5 number.
B：
-OC-R
12-CO-????(49)C：
-O-R
14-O-??????(50)
The organopolysiloxane derivative (being designated hereinafter simply as compound S) that has structure shown in the above-mentioned general formula (1) in the molecule of the present invention, it is characterized in that, contain the organopolysiloxane long-chain in this molecule and contain aromatic ring long-chain or fatty clan elder's chain, this organopolysiloxane derivative demonstrates good effect as making silica gel be dispersed in dispersion agent in the curable resin.
Make silica gel and compound S be dispersed in curable resin composition in the curable resin, the internal stress of its cured article becomes extremely low by the effect that is dispersed in these silica gel in the cured article.
Silica gel is known those silica gel in the past, and as its manufacture method, known have condensation reaction method and an additive reaction method, and the silica gel that is used for curable resin composition of the present invention can adopt any method manufacturing.
Silica gel is owing to have a polysiloxane structure, can be by for example with 0.3～0.8 ratio, and in the presence of as the platinum compounds of catalyzer, the organopolysiloxane and the SiH radical reaction that contain vinyl are obtained.The manufacture method of silica gel for example spy open clear 54-48720 number, the spy opens clear 48-17847 number and each communique such as special public clear 45-9476 number in be described in detail.
The adding proportion of silica gel in curable resin for curable resin 100 weight parts, is 1～100 weight part, the ratio of preferred 5～50 weight parts.Silica gel is below the 1mm, and preferred 200 μ m are following, the more preferably micropartical of 2～0.5 μ m.And, as the method for in curable resin, adding silica gel, have and above-mentioned silica gel added with particle state and be distributed to method in the liquid curing resin, in addition, also has the method for adding the mixed uniformly in advance mixture of curable resins such as silica gel and Resins, epoxy in the curable resin method and in curable resin, reacting generation silica gel etc.About in curable resin, cooperating the composition of silica gel, open in the clear 61-185527 communique for example spy and be described in detail.
Comprise thermosetting resin and photo-curable resin in the curable resin.As this curable resin, can enumerate Resins, epoxy, unsaturated polyester resin, cyanate ester resin, melmac, urea resin, resol, urethane resin, diallyl phthalate resin, BT resin (dimaleimide/cyanate resin) etc.In these curable resins, Resins, epoxy is the most frequently used in the electric and electronic field.Below, be described in detail with regard to Resins, epoxy.
As Resins, epoxy, just can use so long as have the Resins, epoxy of 2 above epoxy group(ing) in the molecule, can use to be in a liquid state under the normal temperature or solid-state known various Resins, epoxy of past.As this Resins, epoxy, can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, dihydroxyphenyl propane D type Resins, epoxy, bisphenol-s epoxy resin, ring type aliphatics type Resins, epoxy, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic-type epoxy resin, polyolefin-type Resins, epoxy, brominated epoxy resin, four hydroxyphenyl ethane type Resins, epoxy, soluble phenolic resin type Resins, epoxy, cresols soluble phenolic resin type Resins, epoxy, dihydroxy naphthlene type Resins, epoxy, silicone modified epoxy etc.
The ratio that cooperates of compound S and Resins, epoxy for Resins, epoxy 100 weight parts, is 10～100 weight parts, the ratio of preferred 30～50 weight parts.And the ratio of compound S and silica gel for silica gel 100 weight parts, is 10～50 weight parts, is preferably the scope of 15～30 weight parts.
In Resins, epoxy, cooperate in the composition epoxy resin of silica gel and compound S,, can form solidification compound by cooperating solidifying agent.
As the solidifying agent under this occasion, can use over known various solidifying agent.In this solidifying agent, comprise amine curing agent, acid anhydride type curing agent, imidazole curing agent, polyamide-based solidifying agent, resol class solidifying agent, polyvinyl phenols curing agent etc., in addition, also comprise the potentiality solidifying agent, for example, boron trifluoride-amine complex class solidifying agent, Dyhard RU 100 class solidifying agent, organic acid hydrazides class solidifying agent, diaminomaleonitrile class solidifying agent, the melamine class solidifying agent, amide imide class solidifying agent, polyamine salt solidifying agent, molecular sieve solidifying agent etc., have again, also comprise ultraviolet curing agent (aromatic series diazonium salt, diallyl iodine, three aromatic base sulfoniums, three aromatic base selenium salt etc.) and light curing agent (polythiol, the polysulfide resin) etc.About these solidifying agent,, be described in detail in the 164th～254 page at " the new エ Port キ シ resin " of for example (strain) clear rolling hall distribution.
Among the present invention, especially preferably use amine curing agent and acid anhydride type curing agent.As amine curing agent, can enumerate for example aliphatic polyamines such as diethylenetriamine, Triethylenetetramine (TETA), tetren, diethyl amino propylamine; Alicyclic polyamines such as alkene diamines, isophorone diamine, N-aminoethyl piperazine, two (4-amino-3-methylcyclohexyl) methane, two (4-aminocyclohexyl) methane; In addition aromatic polyamines such as m-xylene diamine, diaminodiphenyl-methane, diamino diphenyl sulfone, mphenylenediamine, can also enumerate polymeric amide polyamines, Dyhard RU 100, adipic dihydrazide etc.And, as acid anhydride type curing agent, can enumerate, for example, simple function acid anhydrides such as Tetra hydro Phthalic anhydride, tetrahydroxy Tetra hydro Phthalic anhydride, hexahydroxy-Tetra hydro Phthalic anhydride, methyl tetrahydroxy Tetra hydro Phthalic anhydride, methyl hexahydroxy-Tetra hydro Phthalic anhydride, methyl Na ジ ッ Network acid anhydrides, dodecyl succinic anhydride, succinyl oxide, chlorine bacterium (Network mouth レ Application デ イ ッ Network) acid anhydrides; PMA, benzophenone tetracarboxylic anhydride, ethylene glycol bisthioglycolate (difunctionality acid anhydrides such as anhydrous ト リ メ-ト), methyl cyclohexylene tetracarboxylic anhydride; Trimellitic acid 1,2-anhydride, poly-nonane diacid acid anhydride etc. contain the acid anhydrides of free carboxy etc.
In the acid anhydride type curing agent, generally also use alkaline curing catalyst,, can enumerate for example fatty amines such as テ ト ラ ト リ ア Le キ Le ア ミ Application, tetramethyl guanidine, trolamine as this curing catalyst; Piperidines, N, cycloaliphatic amines such as N '-lupetazin, triethylenediamine; Pyridine, picoline, 1,8-diazabicyclo [5.4.0]-heterocycle family amine such as 7-undecylene; Benzyldimethylamine, 2-(dimethylaminomethyl) phenol, 2,4, aromatic amines such as 6-three (diamino methyl) phenol etc.
And, identical with the composition epoxy resin in past, can cooperate ancillary component commonly used in the above-mentioned composition epoxy resin, for example, curing catalyst, curing catalysts, weighting agent, fire retardant, coupler, thinner, tinting material, laser marking agent etc.
Composition epoxy resin of the present invention can be liquid state or powdered, can solidify under normal temperature or high temperature.
Organopolysiloxane derivative of the present invention because contain the organopolysiloxane chain and contain aromatic series loop chain or aliphatic long-chain the two, can be advantageously used for to making silica gel be scattered in dispersion agent in the curable resin equably.Promptly, in the organopolysiloxane derivative of the present invention, its organopolysiloxane chain has affinity to silica gel, it contains the aromatic series loop chain or aliphatic chain has affinity to curable resin, for keeping liquid curable resin, silica gel is mixed with organopolysiloxane derivative of the present invention, can obtain the homodisperse curable resin composition of silica gel thus.
The curable resin composition that contains silica gel and organopolysiloxane derivative of the present invention solidifies by making it, can obtain the very little cured article of internal stress.Curable resin composition of the present invention, the internal stress of its cured article is very little, utilizes this point, can be with it particularly advantageously as the sealing material electric, that electronic component is used.
Curable resin composition of the present invention can be to be liquid composition under the normal temperature, in addition, also can be to be the powdered composition under the normal temperature.When making normal temperature down for the powdered composition, with the fusion of powdered curable resin, after adding silica gel and organopolysiloxane derivative of the present invention also mixed in this fused solution, cooling was solidified it, with the cured article pulverizing of acquisition.
Identical with the occasion of the curable resin composition in past, curable resin composition of the present invention can be advantageously used for and be binding agent, coating, electrical/electronic part insulating material, electrical/electronic part sealing material, formed material etc.
Simple declaration to accompanying drawing
The orthographic plan of Fig. 1 used sample when measuring the internal stress of cured article with the steel loop method.
Fig. 2 is A-A ' sectional view of Fig. 1.
Among Fig. 1 and Fig. 2,1 is resin cured matter, and 2 is steel loop, and 3 is the strain gauge circuit connecting wire.
Embodiment
Illustrate in greater detail the present invention with embodiment below.Embodiment 1 (synthesizing of dispersant A)
In the flask that stirrer is housed, add the terminal silicone oil BY16-752 of phenol (molecular weight=3148, siloxanes bond number t=39; East レ ダ ウ コ-ニ Application グ シ リ コ-Application (strain) system) 100.0g, bisphenol A diglycidyl ether EXA-850CRP (epoxy equivalent (weight) 171, big Japanese イ Application キ (strain) system) 28.70g, as the Tetramethylammonium chloride 0.03g of catalyzer, in oil bath, under 100 ℃/5 hours+120 ℃/4 hours+130 ℃/1 hour condition, make its reaction while stir.Then, stop to stir, will in bisphenol A diglycidyl ether EXA-850CRP, in the mixture 71.3g adding flask of dissolving with weight dihydroxyphenyl propane (molecular weight=228), stir 1 hour down in advance at 130 ℃.Then, make decompression in the flask, under 140 ℃/1 hour+150 ℃/1 hour condition, stir, obtain the purpose product, with it as dispersant A.
This dispersant A is the oily matter that is in a liquid state under the normal temperature, and its viscosity (25 ℃) is 20,000 pools.And in this dispersant A, the mean polymerisation degree of its bisphenol A diglycidyl ether and dihydroxyphenyl propane is 4.9, and its weight-average molecular weight is 31,000.In addition, this dispersant A confirms to have polyether structure by proton N MR, has epoxy group(ing) on an one end or two ends.Embodiment 2 (synthesizing of dispersant B)
In the flask that stirrer is housed, add the terminal silicone oil BY16-752 of phenol 100.0g, naphthalene matrix type diglycidylether HP-4032D (epoxy equivalent (weight)=142, big Japanese イ Application キ (strain) system) 19.0g, as the Tetramethylammonium chloride 0.03g of catalyzer, in oil bath, under 100 ℃/5 hours+120 ℃/4 hours+130 ℃/1 hour condition, make its reaction while stir.Then, stop to stir, will in bisphenol A diglycidyl ether HP-4032D, in the mixture 81.0g adding flask of dissolving with the weight dihydroxyphenyl propane, stir 1 hour down in advance at 130 ℃.Then, make decompression in the flask, under 140 ℃/1 hour+150 ℃/1 hour condition, stir, obtain the purpose product, with it as dispersant B.
This dispersant B is the oily matter that is in a liquid state under the normal temperature, and its viscosity (25 ℃) is 12,000 pools.And in this dispersant A, the mean polymerisation degree of its bisphenol A diglycidyl ether and dihydroxyphenyl propane is 5.6, and its weight-average molecular weight is 25,000.In addition, this dispersant A confirms to have polyether structure by proton N MR, has epoxy group(ing) on an one end or two ends.Reference example 1 (dispersing method of silica gel in Resins, epoxy)
In the flask that homogenizer is housed, add substrate Resins, epoxy 120.0g and above-mentioned dispersant A or B40.0g, Yi Bian in oil bath, remain on 100 ℃, Yi Bian about 1 hour of high-speed stirring.Then, adding contains the silicone of vinyl and the title complex TSE3062A that the Pt series catalysts constitutes (シ of Toshiba リ-コ Application (strain) system) 100.0g, on one side high-speed stirring, make dispersive silicone gelization in resin on one side.Continue stir about 3 hours, gelation is finished fully, prepare silica gel decentralized Resins, epoxy thus.Embodiment 3
In the reference example 1, use the bisphenol A type epoxy resin RE-310S (Japanese chemical drug (strain) system) of substrate Resins, epoxy, and use as the dispersant A of dispersion agent and prepare silica gel decentralized Resins, epoxy, in silica gel decentralized Resins, epoxy 100 weight parts, be mixed into methyl hexahydroxy-Tetra hydro Phthalic anhydride HN5500 (Hitachi changes into (strain) system) 30 weight parts as solidifying agent, and, obtain the Resins, epoxy title complex as benzyldimethylamine (BDMA) 1 weight part of curing catalyst.The characteristic of its cured article is shown in table 1.Embodiment 4
In the reference example 1, use is as the bisphenol f type epoxy resin EPC-830LVP (big Japanese イ Application キ (strain) system) of substrate Resins, epoxy, and use as the dispersant A of dispersion agent and prepare silica gel decentralized Resins, epoxy, in these silica gel decentralized Resins, epoxy 100 weight parts, be mixed into HN5500 33 weight parts and BDMA1 weight part, obtain the Resins, epoxy title complex as solidifying agent.The characteristic of its cured article is shown in table 1.Embodiment 5
Use is as the naphthalene matrix type Resins, epoxy HP-4032D (big Japanese イ Application キ (strain) system) of substrate Resins, epoxy, and use as the dispersant B of dispersion agent and prepare silica gel decentralized Resins, epoxy, in these silica gel decentralized Resins, epoxy 100 weight parts, be mixed into HN5500 39 weight parts and BDMA1 weight part, obtain the Resins, epoxy title complex.The characteristic of its cured article is shown in table 1.Embodiment 6
In the reference example 1, use is as the alicyclic epoxy resin CY179 (チ バ ガ イ ギ-(strain) system) of substrate Resins, epoxy, and use as the dispersant B of dispersion agent and prepare silica gel decentralized Resins, epoxy, in these silica gel decentralized Resins, epoxy 100 weight parts, be mixed into HN5500 40 weight parts and BDMA1 weight part, obtain the Resins, epoxy title complex.The characteristic of its cured article is shown in table 1.Embodiment 7
Use is as the 3 functionality glycidyl amine ELM-100 (Sumitomo Chemical (strain) system) of substrate Resins, epoxy, and use as the dispersant B of dispersion agent and prepare silica gel decentralized Resins, epoxy, in these silica gel decentralized Resins, epoxy 100 weight parts, be mixed into HN5500 52 weight parts and BDMA1 weight part, obtain the Resins, epoxy title complex.The characteristic of its cured article is shown in table 1.Comparative example 1
Use is as the EPC-830LVP of substrate Resins, epoxy, and use commercially available polyether modified silicone TSF4452 (few リ コ-Application (strain) system of Toshiba) to prepare silica gel decentralized Resins, epoxy as dispersion agent, in these silica gel decentralized Resins, epoxy 100 weight parts, be mixed into HN5500 33 weight parts and BDMA1 weight part, obtain the Resins, epoxy title complex.The characteristic of its cured article is shown in table 2.Comparative example 2
In the reference example 1, make 1 molecular reaction of the EXA-850CRP and the terminal silicone oil BY16-752 of phenol of 2 molecules, preparation epoxy/silicone adducts, this adducts is used as dispersion agent, use EPC-830LVP to attempt to prepare silica gel decentralized Resins, epoxy as substrate Resins, epoxy, in case stop to stir it is left standstill, then silica gel and resinous principle are slowly separated.Therefore, stop to carry out thereafter evaluating characteristics.Comparative example 3
In the reference example 1, do not use dispersion agent, EPC-830LVP is used as substrate Resins, epoxy, attempt to prepare silica gel decentralized Resins, epoxy, silica gel directly separates with resinous principle.Therefore, stop to carry out thereafter evaluating characteristics.
In epoxy resin C-830LVP100 weight part, be mixed into HN5500 104 weight parts and BDMA1 weight part, obtain the Resins, epoxy title complex.The characteristic of its cured article is shown in table 3.Comparative example 5
In Resins, epoxy HP-4032D100 weight part, be mixed into HN5500 118 weight parts and BDMA1 weight part, obtain the Resins, epoxy title complex.The characteristic of its cured article is shown in table 3.Comparative example 6
In commercially available silicone modified resin A-20NCL (Japanese grease (strain) system) 100 weight parts that with naphthalene matrix type Resins, epoxy are substrate, be mixed into HN5500 95 weight parts and BDMA 1 weight part, obtain the Resins, epoxy title complex.The characteristic of its cured article is shown in table 3.Comparative example 7
In HP-4032D 80 weight parts, polyether modified silicon oil FZ3736 (Japanese コ ニ カ-(strain) system) 6 weight parts that add silicone oil FZ3720 (Japanese コ ニ カ-(strain) system) 14 weight parts that contain epoxide group and contain epoxide group, be mixed into HN5 500 97 weight parts and BDMA1 weight part, obtain the Resins, epoxy title complex.The characteristic of its cured article is shown in table 3.Comparative example 8
In commercially available silicone modified resin EPC-40NCL (Japanese grease (strain) system) 100 weight parts that with the bisphenol f type epoxy resin are substrate, be mixed into HN5500 63 weight parts and BDMA1 weight part, obtain the Resins, epoxy title complex.The characteristic of its cured article is shown in table 3.(evaluation method)
Above-mentioned Resins, epoxy title complex is solidified under 100 ℃/1 hour+180 ℃/1 hour condition, make cured article thus, carry out evaluating characteristics by following project.
(Tg): adopt the DSC method to measure, with Tg as the thermotolerance index.
(internal stress): adopt steel loop method *, under the occasion of steel loop being imbedded in the resin cured matter, obtain by measuring the stress that produces.Inner-stress value shown in the table under-70 ℃.
* steel loop method:
As Fig. 1, steel rings is imbedded the resin center make resin cured matter, be cooled to-70 ℃ from 180 ℃ of speed with 1 ℃/minute.At this moment, with the deformation quantity of the ring that is produced by resin shrinkage stress when the inboard strain transducer that sticks of ring reads each temperature in advance, the substitution following formula is obtained the stress value σ under the arbitrary temp.
E wherein: the Young mould of steel is heavy
D: the thickness of ring
R: the inside radius of ring
ε: ring is at the deformation quantity (wet fastness) of circumferential direction
To be shaped to the resin cured matter of 50mm * 50mm * 2mm, at pressure kettle test (Pressure Cooker Test, PCT) (121 ℃, 2 normal atmosphere, saturation testing) handle after 100 hours down, at room temperature measure the volume intrinsic resistance under specific inductivity, dielectric dissipation factor and the 500V of 10kHz, will add electrical property after the wet treatment as the wet fastness index.
In addition, before and after the pressure kettle test, obtain water-intake rate by the changes in weight of identical test sheet.
Table 1
Annotate) condition of cure: 100 ℃/1 hour+180 ℃/1 hour
| Embodiment | ||||||||
| ?????????3 | ?????????4 | ??????????5 | ????????6 | ????????7 | ||||
| Silica gel decentralized Resins, epoxy resin (weight part) | Base resin | RE-310s????????120 | EPC-830LVP???????120 | HP-4032D?????????120 | CY179????????120 | ELM-100????????120 | ||
| Dispersion agent | A???????????????40 | A?????????????????40 | B?????????????????40 | B?????????????40 | B???????????????40 | |||
| Silica gel | TSE3062????????200 | TSE3062??????????200 | TSE3062??????????200 | TSE3062??????200 | TSE3062????????200 | |||
| Evaluating characteristics title complex (weight part) | Resin | Above-mentioned resin 100 | Above-mentioned resin 100 | Above-mentioned resin 100 | Above-mentioned resin 100 | Above-mentioned resin 100 | ||
| Solidifying agent | HN5500??????????30 | HN5500????????????33 | HN5500????????????39 | HN5500????????40 | HN5500??????????52 | |||
| Curing catalyst | BDMA?????????????1 | ?BDMA??????????????1 | ?BDMA??????????????1 | BDMA???????????1 | BDMA?????????????1 | |||
| The characteristic of cured article | ????????????Tg(℃) | ???????150 | ????????140 | ?????????160 | ???????180 | ???????190 | ||
| Internal stress (kg/mm under-70 ℃ 2) | ???????0.33 | ????????0.25 | ????????0.24 | ???????0.77 | ???????0.45 | |||
| PCT handles the characteristic after 100 hours | Specific inductivity (10kHz) | ????????3.1 | ????????3.3 | ?????????3.2 | ???????3.7 | Undetermined | ||
| Dielectric dissipation factor (10KHz) | ??????0.009 | ???????0.010 | ????????0.008 | ?????0.015 | ????????＂ | |||
| The volume intrinsic resistance (Ω-cm, 500V) | ????5.1×10 14 | ?????4.8×10 14 | ??????1.2×10 15 | ????2.3×10 14 | ????????＂ | |||
| Specific absorption (%) | ???????1.64 | ????????1.72 | ????????1.36 | ??????4.83 | ????????＂ | |||
Table 2
Annotate) condition of cure: 100 ℃/1 hour+180 ℃/1 hour
Table 3
Annotate) condition of cure: 100 ℃/1 hour+180 ℃/1 hour
| Comparative example | ||||||||
| ????????4 | ?????????5 | ????????6 | ????????7 | ????????8 | ||||
| Evaluating characteristics title complex (weight part) | Resin | EPC-830LVP????100 | ?HP-4032D??????100 | ?A-20NCL?????100 | Epoxy composite 100 | EPC-40NCL??????100 | ||
| Solidifying agent | HN5500?????????30 | ?HN5500????????118 | ?HN5500???????95 | HN5500??????????97 | HN5500??????????63 | |||
| Curing catalyst | BDMA | ?BDMA????????????1 | ?BDMA | BDMA?????????????1 | BDMA | |||
| The characteristic of cured article | ???????????Tg(℃) | ???????140 | ???????160 | ??????155 | ???????150 | ???????135 | ||
| Internal stress (kg/mm under-70 ℃ 2) | ???????1.39 | ???????1.52 | ?????1.26 | ??????1.10 | ???????0.82 | |||
| PCT handles the characteristic after 100 hours | Specific inductivity (10kHz) | ????????3.3 | ???????3.4 | ??????3.6 | ???????3.7 | Can not measure | ||
| Dielectric dissipation factor (10KHz) | ???????0.011 | ???????0.013 | ????0.031 | ??????0.038 | ????????＂ | |||
| The volume intrinsic resistance (Ω-cm, 500V) | ?????3.4×10 15 | ?????2.3×10 16 | ????1.3×10 16 | ?????1.3×10 15 | ?????5.2×10 9 | |||
| Specific absorption (%) | ???????1.02 | ???????1.24 | ??????1.49 | ???????1.53 | Stripping | |||
* composition epoxy resin: HP-4032D:80 weight part+FZ3720:14 part+FZ3736:6 part
(FZ3720: Japanese ュ ニ カ-society's system, epoxide modified silicone oil)
(FZ3736: Japanese ュ ニ カ-society's system, epoxidized polyether modified silicon oil) embodiment 8
To unsaturated polyester resin (Port リ ラ イ ト TE-100, big Japanese イ Application キ society system) in 100 weight part, fit into its organo-peroxide class solidifying agent (パ-メ ッ Network N, Japan grease society system) silica gel decentralized Resins, epoxy 50 weight parts, fused silica 351 weight parts of 1 weight part, embodiment 3, contain vinyl silanes coupler (S210, チ ッ ソ society system) 2.2 weight parts and benzyldimethylamine (hardener for epoxy resin) 1 weight part, with the title complex that obtains 60 ℃ of heating after 1 hour down, again 100 ℃ down heating made its curing in 1 hour.The internal stress of cured article under-50 ℃ that obtains is 0.28kg/mm
2, very little.Embodiment 9
To cyanate ester resin (Arocy L-10, rising sun チ バ society system) in 100 weight part, silane coupling agent (A-187, Japanese ュ ニ カ-society's system) 2.2 weight parts that fit into silica gel decentralized Resins, epoxy 50 weight parts, fused silica 251 weight parts of manganese octoate (cyanate ester resin solidifying agent) 0.14 weight part, embodiment 3 and contain epoxy group(ing).This title complex, was heated 1 hour down at 130 ℃ after 1 hour in heating under 100 ℃, heated 3 hours down at 180 ℃ again, obtain cured article.The internal stress of this cured article under-40 ℃ is 0.4kg/mm
2, very little.Embodiment 10 (synthesizing of dispersing agent C)
In the flask that stirrer is housed, add the terminal silicone oil BY16-752 of phenol 100.0g, 4,4 '-diphenylmethanediisocyanate (MDI) 15.9g, made its reaction in 5 hours while in oil bath, under 60 ℃, stir.Then, stop to stir, in flask, add propylene glycol (PG) 22.0g and MDI62.6g, stirred 5 hours down at 60 ℃.Then,, stirred 1 hour down, obtain the purpose product at 80 ℃ with flask decompression, with it as dispersing agent C.
This dispersing agent C is the oily matter that is in a liquid state under the normal temperature, and its viscosity (25 ℃) is 10,000 pools.And in this dispersing agent C, its polymerization degree is 9.2, and its weight-average molecular weight is 20,000.In addition, this dispersing agent C confirms to have polyurethane structural by proton N MR, has the OH group on an one end or two ends.Embodiment 11 (dispersing method of silica gel in Resins, epoxy)
In the flask that homogenizer is housed, add substrate Resins, epoxy 120.0g and above-mentioned dispersing agent C 40.0g, Yi Bian in oil bath, remain on 80 ℃, Yi Bian about 1 hour of high-speed stirring.Then, adding contains the silicone of vinyl and title complex TSE3062A (Toshiba's シ リ コ one Application (strain) system) 100.0g that the Pt series catalysts constitutes, on one side high-speed stirring, make the silicone gelization that is scattered in the resin on one side.Continue stir about 3 hours, gelation is stopped fully, prepare silica gel decentralized Resins, epoxy thus.Confirm act in the Resins, epoxy homodisperse of silica gel by dispersing agent C.
Claims (9)
1. an organopolysiloxane derivative is characterized in that, has the structure shown in the following general formula in its molecule,
[in the above-mentioned general formula,
A represents that two ends have the organopolysiloxane compound with 5～90 siloxane bonds that contains active hydrogen group,
B represent to have 2 can with the difunctionality organic compound of the functional group of active hydrogen reaction,
C represents to have 2 difunctionality organic compound that contain active hydrogen group,
D represent to have 2 can with the difunctionality organic compound of the functional group of active hydrogen reaction,
N is 1～20 number,
P is 1～20 number].
2. the organopolysiloxane derivative of claim 1, in general formula (1), B is identical with C.
3. an organopolysiloxane derivative is characterized in that, has the structure shown in the following general formula in its molecule,
[in the above-mentioned general formula,
A represents that two ends have the organopolysiloxane compound residue with 5～90 siloxane bonds that contains active hydrogen group,
B represents the residue of the difunctionality aromatic epoxy compound shown in the following general formula,
(in the formula, Ar
1Expression divalence aromatic group, m is 1 or 2 integer)
C represents the residue of the bivalent phenol compound shown in the following general formula,
-O-Ar
2-O-
(in the formula, Ar
2Expression divalence aromatic group)
N is 1～20 number,
P is 1～20 number].
4. manufacture method with organopolysiloxane derivative of structure shown in the following general formula, it is characterized in that, this method be by the organopolysiloxane compound A that two ends is had contain active hydrogen group with 5～90 siloxane bonds with have can with the 1st reaction process of the difunctionality organic compound B reaction of 2 functional groups of active hydrogen reaction, and, make the resultant that obtains in the 1st reaction process and have 2 and contain the difunctionality organic compound C of active hydrogen group and have and to constitute with the 2nd reaction process of the mixture reaction of the difunctionality organic compound D of 2 functional groups of active hydrogen reaction
General formula:
[in the above-mentioned general formula,
A represents that two ends have the organopolysiloxane compound with 5～90 siloxane bonds that contains active hydrogen group,
B represent to have 2 can with the difunctionality organic compound of the functional group of active hydrogen reaction,
C represents to have 2 difunctionality organic compound that contain active hydrogen group,
D represent to have 2 can with the difunctionality organic compound of the functional group of active hydrogen reaction,
N is 1～20 number
P is 1～20 number].
5. the preparation method of the organopolysiloxane derivative of claim 4, in general formula (1), B is identical with C.
6. the manufacture method that has the organopolysiloxane derivative of structure shown in the following general formula in the molecule, it is characterized in that, this method be by the organopolysiloxane compound A that two ends is had contain active hydrogen group with 5～90 siloxane bonds with have 2 can with the 1st reaction process of the difunctionality aromatic epoxy compound B reaction of the functional group of active hydrogen reaction, and, make the resultant that obtains in the 1st reaction process and have 2 and can constitute with the 2nd reaction process of the mixture reaction of the difunctionality aromatic epoxy compound B of the functional group of active hydrogen reaction and bivalent phenol compound C
[in the above-mentioned general formula,
A represents that two ends have the organopolysiloxane compound residue with 5～90 siloxane bonds that contains active hydrogen group,
B represents the residue of the difunctionality aromatic epoxy compound shown in the following general formula
(in the formula, Ar
1Expression divalence aromatic group, m is 1 or 2 number)
C represents the residue of the bivalent phenol compound shown in the following general formula,
-O-Ar
2-O-
(in the formula, Ar
2Expression divalence aromatic group)
N is 1～20 number,
P is 1～20 number]
7. one kind makes silica gel be distributed to dispersion agent in the curable resin composition, it is characterized in that, it is to be made of each organopolysiloxane derivative of claim 1～3.
8. a curable resin composition is characterized in that, it contains each organopolysiloxane derivative and silica gel of claim 1～3.
9. a composition epoxy resin is characterized in that, it contains each organopolysiloxane derivative and silica gel of claim 1～3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96190505 CN1154124A (en) | 1995-03-14 | 1996-03-14 | Organopolysiloxane derivative |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP81678/95 | 1995-03-14 | ||
| CN 96190505 CN1154124A (en) | 1995-03-14 | 1996-03-14 | Organopolysiloxane derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1154124A true CN1154124A (en) | 1997-07-09 |
Family
ID=5128060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96190505 Pending CN1154124A (en) | 1995-03-14 | 1996-03-14 | Organopolysiloxane derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1154124A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106283662A (en) * | 2016-08-17 | 2017-01-04 | 浙江盛发纺织印染有限公司 | A kind of application process of pollen-proof attachment finishing agent |
| CN112513146A (en) * | 2018-08-10 | 2021-03-16 | 东丽株式会社 | Polysiloxane-polyalkylene glycol block copolymer and method for producing same |
| CN114409875A (en) * | 2022-02-28 | 2022-04-29 | 万华化学集团股份有限公司 | Reactive ultraviolet absorbent and preparation method and application thereof |
-
1996
- 1996-03-14 CN CN 96190505 patent/CN1154124A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106283662A (en) * | 2016-08-17 | 2017-01-04 | 浙江盛发纺织印染有限公司 | A kind of application process of pollen-proof attachment finishing agent |
| CN112513146A (en) * | 2018-08-10 | 2021-03-16 | 东丽株式会社 | Polysiloxane-polyalkylene glycol block copolymer and method for producing same |
| CN114409875A (en) * | 2022-02-28 | 2022-04-29 | 万华化学集团股份有限公司 | Reactive ultraviolet absorbent and preparation method and application thereof |
| CN114409875B (en) * | 2022-02-28 | 2023-10-20 | 万华化学集团股份有限公司 | Reactive ultraviolet absorber, preparation method and application thereof |
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