CN102850803A - Addition curing type silicone composition and optical element - Google Patents
Addition curing type silicone composition and optical element Download PDFInfo
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- CN102850803A CN102850803A CN2012101948498A CN201210194849A CN102850803A CN 102850803 A CN102850803 A CN 102850803A CN 2012101948498 A CN2012101948498 A CN 2012101948498A CN 201210194849 A CN201210194849 A CN 201210194849A CN 102850803 A CN102850803 A CN 102850803A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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Abstract
The present invention provides an addition curing type silicone composition capable of obtaining a cured substance having a very high transparency, a good strength characteristic, and excellent optical element properties such as light extraction efficiency and so on. The present invention also provides an optical element which is sealed by using the cured substance of the composition. The addition curing type silicone composition of the present invention at least comprises: (A) 100 parts by mass of linear chain shaped organopolysiloxane; (B) 1-100 parts by mass of organopolysiloxane having a branched chain structure, wherein the branched chain structure contains a siloxane unit represented by SiO4/2 and/or RSiO3/2; (C) organosilicon compound of which one molecule has more than two hydrogen atoms bonded to a silicon atom, wherein a molar ratio between a total aliphatic series unsaturated group of the (A) composition and the (B) composition and a SiH group of the (C) composition is 0.2 <= SiH group/aliphatic series unsaturated group <= 5.0; and (D) effective dose of platinum group metal catalyst.
Description
Technical field
The present invention relates to a kind of addition curable silicon-ketone composition and optical element, relate in particular to a kind of addition curable silicon-ketone composition and optical element, it is good and have the cured article of low-refraction that described addition curable silicon-ketone composition can obtain rubber property and strength characteristics, and described optical element is to utilize the cured article of described composition to seal.
Background technology
The addition curable silicon-ketone composition comprises the organopolysiloxane that contains the aliphatics unsaturated groups such as thiazolinyl, and can solidify by hydrosilylation reactions (hydrosilylation reaction) and obtain cured article.The cured article that obtains like this because thermotolerance, winter hardiness and electrical insulating property are excellent, and transparent, thereby is used to the sealing material of various optical applications.
Employed organopolysiloxane composition in the optical applications, and the sealing material for optical component that consisted of by described composition, be required to have high transparent and high refractive index, in order to reach this requirement, generally take a kind of method, described method is to use dimethyl siloxane-diphenyl siloxane multipolymer or PSI at main framing.
But, described polysiloxane difficulty relatively on synthetic, it is cured article more than 1.54 that described polysiloxane is believed to obtain specific refractory power.In addition, polysiloxane is become prop up chain and import the polysiloxane that phenyl forms, the specific refractory power of its cured article can be made as about 1.53～1.54, but the cured article that obtains is harder arborescens, and does not have elasticity.Therefore, a kind of composition is also proposed, it is that combination chain organopolysiloxane and straight chain shape organopolysiloxane (organopolysiloxane) form, but the transparency of described composition, specific refractory power and elasticity etc. can not fully satisfactory (patent documentation 1 be to patent documentation 7).
Therefore, in patent documentation 8, a kind of addition curable silicon-ketone composition and sealing material for optical component are proposed, described addition curable silicon-ketone composition can obtain to have the good cured article of high transparent and high refractive index and strength characteristics, described sealing material for optical component is made of described composition, but the optical element performance that obtains can not be fully satisfactory.
And previous, being 400nm at 25 ℃ of lower wavelength especially, transmittance is relatively poor.
[prior art document]
(patent documentation)
Patent documentation 1: TOHKEMY 2005-307015 communique
Patent documentation 2: TOHKEMY 2004-143361 communique
Patent documentation 3: TOHKEMY 2004-186168 communique
Patent documentation 4: TOHKEMY 2004-292807 communique
Patent documentation 5: TOHKEMY 2004-359756 communique
Patent documentation 6: TOHKEMY 2005-076003 communique
Patent documentation 7: TOHKEMY 2005-105217 communique
Patent documentation 8: TOHKEMY 2010-132795 communique
Summary of the invention
The present invention finishes in view of described situation, the object of the present invention is to provide a kind of addition curable silicon-ketone composition, described addition curable silicon-ketone composition is by utilizing specific composition to reduce the specific refractory power of cured article, thus can obtain a kind of have the very high transparency, light take out efficient (light extraction efficiency) also very excellent and strength characteristics well, the cured article of optical element performance excellence especially.And, the object of the present invention is to provide a kind of addition curable silicon-ketone composition, to satisfy originally required photodiode (light-emitting diode, LED) etc. optical element performance, described addition curable silicon-ketone composition has improved the transmittance that is 400nm at 25 ℃ of lower wavelength especially.
In order to solve described problem, the invention provides a kind of addition curable silicon-ketone composition, described addition curable silicon-ketone composition is characterised in that, comprises at least:
(A) organopolysiloxane of straight chain shape has the aliphatics unsaturated group that is binding on Siliciumatom more than two and the CF that is binding on Siliciumatom more than one in its a part
3-(CF
2)
m-(CH
2)
n-Ji, and in the formula, m is the integer more than 0, n is the integer more than 1: 100 mass parts;
(B) have the organopolysiloxane of branched structure, have the aliphatics unsaturated group that is binding on Siliciumatom more than two and the CF that is binding on Siliciumatom more than one in its a part
3-(CF
2)
m-(CH
2)
n-Ji, and described branched structure comprises by SiO
4/2And/or RSiO
3/2Represented siloxane unit, and in the formula, m is the integer more than 0, and n is the integer more than 1, and R replaces or unsubstituted monovalence alkyl: 1～100 mass parts;
(C) silicoorganic compound have the hydrogen atom that is binding on Siliciumatom more than two in its a part: the total aliphatics unsaturated group of described (A), described (B) composition and (C) mol ratio of the SiH base of composition become the amount of 0.2≤SiH base/aliphatics unsaturated group≤5.0; And,
(D) platinum metals series catalysts: effective dose.
Addition curable silicon-ketone composition of the present invention like this, can obtain a kind of specific refractory power lower, have all good cured articles of high transparent and rubber property and strength characteristics, when using as the LED sealing material, light taking-up efficient is also very excellent, therefore is fit to optical applications.
And being 400nm at 25 ℃ of lower wavelength especially, transmittance is also very excellent.
In addition, the silicoorganic compound of described (C) composition also can be and then have a CF that is binding on Siliciumatom more than in a part
3-(CF
2)
m-(CH
2)
nThe silicoorganic compound of-Ji, and in the formula, m is the integer more than 0, n is the integer more than 1.
So, if in (C) composition, also import CF
3-(CF
2)
m-(CH
2)
n-Ji just can seek further to reduce specific refractory power.
In addition, when composition of the present invention is applied to optical element sealing material, described addition curable silicon-ketone composition is preferably: can obtain a kind of cured article after the curing, described cured article is to be more than 80% under the layer state of 2mm at thickness at the transmittance that 25 ℃ of lower wavelength are 300～800nm.
In addition, same, described addition curable silicon-ketone composition is preferably: can obtain a kind of cured article after the curing, described cured article is below 1.40 in the specific refractory power of the visible light that 25 ℃ of lower wavelength are 589nm.
So, if the specific refractory power of cured article is below 1.40, the transmittance that can to make at 25 ℃ of lower wavelength be 400nm is more excellent, and simultaneously, it is more excellent also can to make light take out efficient.
In order to satisfy such characteristic, any composition of the eliminating interpolation meeting reduction light transmission of need to trying one's best etc.
And, the invention provides a kind of optical element, it is to utilize the cured article of described composition to seal.
Optical element of the present invention, reliability are very excellent.
As mentioned above, addition curable silicon-ketone composition of the present invention is solidified and the cured article that obtains, its height is transparent, low-refraction and strength characteristics are good.Especially, by being used for the sealing material for optical component such as LED, can making as optical element performance and required be 400nm at 25 ℃ of lower wavelength transmittance is more excellent.That is to say, by addition curable silicon-ketone composition of the present invention is used as sealing material for optical component, the light that optical element sends, its total reflection meeting are subject to high described cured article surface transparent, low-refraction and suppress the brightness that therefore especially improves LED.
Embodiment
Below, further describe the present invention.
As mentioned above, once propose employed organopolysiloxane composition in the various previous optical applications, but anyly all can not obtain abundant gratifying optical element performance.
The present inventors make great efforts research repeatedly, found that, and by seeking to reduce the specific refractory power of addition curable silicon-ketone composition, and be not the previous known specific refractory power of seeking to improve the addition curable silicon-ketone composition, can obtain the composition of excellent in optical properties.
Specifically, we find: have the CF that is binding on silicon in a part
3-(CF
2)
m-(CH
2)
n-Ji (wherein, m is the integer more than 0, n is the integer more than 1) organopolysiloxane in, by also using straight chain shape organopolysiloxane and a chain organopolysiloxane, reduce the specific refractory power of addition curable silicon-ketone composition, the transmittance that is 300～800nm at 25 ℃ of lower wavelength is improved, especially the transmittance that is 400nm at 25 ℃ of lower wavelength is improved, and find to obtain the addition curable silicone cure thing that height is transparent and strength characteristics is good, thereby reached the present invention.
Therefore, the first, the invention provides a kind of addition curable silicon-ketone composition, it is the addition curable silicon-ketone composition, it is characterized in that, comprises at least:
(A) organopolysiloxane of straight chain shape has the aliphatics unsaturated group that is binding on Siliciumatom more than two and the CF that is binding on Siliciumatom more than one in its a part
3-(CF
2)
m-(CH
2)
n-Ji (wherein, m is the integer more than 0, and n is the integer more than 1): 100 mass parts;
(B) have the organopolysiloxane of branched structure, have the aliphatics unsaturated group that is binding on Siliciumatom more than two and the CF that is binding on Siliciumatom more than one in its a part
3-(CF
2)
m-(CH
2)
n-Ji, and described branched structure comprises by SiO
4/2And/or RSiO
3/2Represented siloxane unit (wherein, m is the integer more than 0, and n is the integer more than 1, and R replaces or unsubstituted monovalence alkyl): 1～100 mass parts;
(C) silicoorganic compound have the hydrogen atom that is binding on Siliciumatom more than two in its a part: the total aliphatics unsaturated group of described (A), described (B) composition and (C) mol ratio of the SiH base of composition become the amount of 0.2≤SiH base/aliphatics unsaturated group≤5.0; And,
(D) platinum metals series catalysts: effective dose.
In addition, the second, the invention provides a kind of optical element, it is to utilize the cured article of addition curable silicon-ketone composition of the present invention to seal.
Below, describe the present invention in detail.
[addition curable silicon-ketone composition]
＜(A) composition 〉
(A) composition is the organopolysiloxane of straight chain shape, has the aliphatics unsaturated group that is binding on Siliciumatom more than two and the CF that is binding on Siliciumatom more than one in its a part
3-(CF
2)
m-(CH
2)
n-Ji (wherein, m is the integer more than 0, and n is the integer more than 1).
(A) organopolysiloxane of composition is base polymer (base polymer), is preferably for example by the represented organopolysiloxane of following general formula (1).
(in the formula, R
1The aliphatics unsaturated group, R
2Can be identical or different and be that carbon number beyond the aliphatics unsaturated group is 1～8 replacement or unsubstituted monovalence alkyl, Rf
1CF
3-(CF
2)
m-(CH
2)
n-Ji (wherein, m is the integer more than 0, and n is the integer more than 1), a is 1～3 integer, x, y, z are respectively the integers of x 〉=0, y 〉=1, z 〉=0).
In described general formula (1), R
1The aliphatics unsaturated group be preferably thiazolinyl, be preferably the carbon numbers such as vinyl, allyl group and ethynyl and be 2～10, especially 2～6 thiazolinyl, especially be preferably vinyl.
As R
2The aliphatics unsaturated group beyond carbon number be 1～8 replacement or unsubstituted monovalence alkyl, can illustration: the alkyl such as methyl, ethyl, propyl group and butyl; The cycloalkyl such as cyclohexyl, cyclopentyl; The aryl such as phenyl, tolyl and xylyl; The aralkyl such as benzyl, styroyl; And, the halogenation alkyl such as chloromethyl, chloropropyl and chlorine cyclohexyl (chlorocyclohexyl) etc.Preferably unsubstituted carbon number is 1～6 monovalence alkyl, especially is preferably methyl.
Rf
1To be defined as CF
3-(CF
2)
m-(CH
2)
n-(m is the integer more than 0, and n is the integer more than 1), m is preferably the integer that satisfies 0≤m≤9, and n is preferably the integer that satisfies 1≤n≤10.When a plurality of Rf are arranged
1The time (when y is 2 when above), can be identical group respectively, also can be different groups.
As the present invention, with regard to synthetic aspect, especially be preferably CF
3-(CH
2)
2-, CF
3-(CF
2)
3-(CH
2)
2-and CF
3-(CF
2)
5-(CH
2)
2-Ji.
In addition, in described general formula (1), x is the integer more than 0, is preferably 0～50 integer; Y is the integer more than 1, is preferably 2～5,000 integer, more preferably 5～1,000 integer.Z is the integer more than 0, is preferably 0～10,000 integer, more preferably 0～5,000 integer.X+y+z is preferably 5～10, and 000, more preferably 10～3,000, especially be preferably 20～500.In addition, the value of y/ (x+y+z) is preferably 1/50～1/1, and more preferably 1/10～1/1,1/5～1/1 the scope of especially being preferably is comparatively suitable.
(A) organopolysiloxane of composition, the viscosity under 25 ℃ be 100～10,000,000mPas, and especially 200～500, comparatively suitable in the scope of 000mPas, these organopolysiloxanes can be used alone, and also can make up two or more uses.In addition, viscosity is to use the viscosity of rotary viscosity design determining.
(A) organopolysiloxane of composition can utilize itself known method to make.Can utilize following methods to obtain, for example: in the situation that has alkalescence or an acidic catalyst, make by the represented cyclotrisiloxane of following general formula (i) with by the represented cyclotrisiloxane of following general formula (ii) with by the represented organopolysiloxane of following general formula (iii), and as required carry out copolymerization by the represented cyclotrisiloxane of following general formula (iv).
(in the formula, R
1, R
2, Rf
1And a as mentioned above).
＜(B) composition 〉
(B) composition is the organopolysiloxane with branched structure, has the aliphatics unsaturated group that is binding on Siliciumatom more than two and the CF that is binding on Siliciumatom more than one in its a part
3-(CF
2)
m-(CH
2)
n-Ji, and described branched structure comprises by SiO
4/2And/or RSiO
3/2(wherein, m is the integer more than 0 to represented siloxane unit, and n is the integer more than 1, and R replaces or unsubstituted monovalence alkyl, can the described R of illustration
1And R
2).When the siloxane unit of a plurality of R of having was arranged, R can be identical group respectively, also can be different groups.
As the aliphatics unsaturated group that is binding on Siliciumatom, the aliphatics unsaturated group that is binding on Siliciumatom that the aliphatics unsaturated group that is binding on Siliciumatom of putting down in writing in illustration and (A) composition is identical.
(B) organopolysiloxane of composition has branched structure.(B) organopolysiloxane of composition must be made as by SiO
4/2Unit and/or RSiO
3/2The branched structure that the unit consists of also may further include: the R such as methyl ethylene siloxy (methylvinylsiloxy) unit, dimethylsilyl bis (dimethylsiloxy) unit
2SiO
2/2The R such as dimethyl vinyl siloxy (dimethylvinylsiloxy) unit and trimethylsiloxy group (trimethylsiloxy) unit
3SiO1/2 unit (in the formula, R as mentioned above).SiO
4/2Unit and/or RSiO
3/2The content of unit is preferably in the organopolysiloxane resins of (B) composition all more than 5 % by mole of siloxane unit, more preferably 10 moles～95 % by mole, especially is preferably 25～80 % by mole.
In addition, with regard to the aspect of segregation, the weight average molecular weight of this organopolysiloxane is preferably 500～100,000 scope.
And, since (B) composition also have in described (A) composition by CF
3-(CF
2)
m-(CH
2)
nTherefore the substituting group of-(m is the integer more than 0, and n is the integer more than 1) definition can seek further to reduce specific refractory power.As the present invention, synthetic aspect just especially preferably is similarly CF with (A) composition
3-(CH
2)
2-, CF
3-(CF
2)
3-(CH
2)
2-and CF
3-(CF
2)
5-(CH
2)
2-Ji.
Can be by with each compound as the source, unit, the ratio required in generation unit makes up, and for example in the situation that has acid (together) be hydrolyzed, thereby easily carry out organopolysiloxane synthetic of such resin structure.
And with the organopolysiloxane with branched structure of this (B) composition, can make hardness and the physical strength of cured article of acquisition more excellent, and can not improve specific refractory power.This (B) composition is 1～100 mass parts with respect to described (A) composition 100 mass parts, is preferably 2～50 mass parts.(B) if allotment amount less than 1 mass parts of composition may cause the hardness of cured article and intensity insufficient, if surpass 100 mass parts, it is fragile that cured article may become, and sealing property reduces.
＜(C) composition 〉
(C) composition is silicoorganic compound (silicoorganic compound that contain the SiH base), has the hydrogen atom (namely SiH yl) that is binding on Siliciumatom more than two in its a part, preferably do not have the aliphatics unsaturated group, (C) become branch with (A), (B) composition carries out hydrosilylation reactions, plays the effect as linking agent.(C) composition can be used alone, and also may be used two or more.
As (C) composition, get final product so long as have the silicoorganic compound that are binding on the hydrogen atom of Siliciumatom more than two in a part, can use known any compound, can enumerate such as: in organic hydrogen polysiloxanes, organohydrogensilicon alkanes, organic oligomer or the organic polymer etc., each molecule has the silicoorganic compound of at least two SiH bases, wherein is preferably the organic hydrogen polysiloxanes that has at least two SiH bases in each molecule.
(C) in the composition, be binding on the organic radical of silicon, preferably do not have the aliphatics unsaturated group, the monovalence alkyl of can the unsubstituted monovalence alkyl of illustration or being replaced by substituting group, described substituting group can not cause detrimentally affect to package stability and the curing of addition curable silicon-ketone composition of the present invention, and described substituting group is: halogen atom (chlorine atom for example, bromine atoms and fluorine atom), group (the epoxy group(ing) for example that contains epoxy group(ing), epoxypropyl (glycidyl) and glycidoxy), and alkoxyl group (methoxyl group for example, oxyethyl group, propoxy-and butoxy) etc.Such replacement or unsubstituted monovalence alkyl can be enumerated carbon number and be 1～6 alkyl, carbon number and be 6～10 aryl, more preferably methyl or ethyl; Perhaps can enumerate these groups by group that described illustrative substituting group replaced.In addition, when having the group that contains epoxy group(ing) and/or alkoxyl group as the substituting group of described monovalence alkyl, can give tackyness to the cured article of addition curable silicon-ketone composition of the present invention.
And, just seek further to reduce specific refractory power, more preferably with in described (A), (B) composition by CF
3-(CF
2)
m-(CH
2)
nThe defined substituting group of-(m is the integer more than 0, and n is the integer more than 1) is directed in (C) composition.As the present invention, with regard to synthetic aspect, more preferably CF
3-(CH
2)
2-, CF
3-(CF
2)
3-(CH
2)
2-and CF
3-(CF
2)
5-(CH
2)
2-Ji.
(C) composition is so long as have the silicoorganic compound of at least two SiH bases and get final product in each molecule, there is no particular restriction for the molecular structure of described silicoorganic compound, can use the various silicoorganic compound such as the previous manufacturing of: straight chain shape, ring-type, a chain and tridimensional network (arborescens) etc.
(C) silicoorganic compound of composition have at least two (being generally about 2～300), the preferred SiH base that (is generally 3～200, preferred about 4～100) more than 3 in a part.When the silicoorganic compound of (C) composition have straight chain structure or prop up the chain structure, these SiH bases can only be arranged on arbitrary part of molecule chain end and the non-terminal portions of molecular chain, also can be positioned on the non-terminal portions two portions of molecule chain end and molecular chain.
(C) number (polymerization degree) of the Siliciumatom in a part of the silicoorganic compound of composition is preferably 2～1,000, more preferably 3～200, further more preferably about 4～100.And, (C) silicoorganic compound of composition preferably 25 ℃ lower to aqueous, utilize the viscosity under 25 ℃ of rotary viscosity design determining, be preferably 1～1,000mPas, more preferably about 10～100mPas.
(C) silicoorganic compound of composition can use for example by the represented silicoorganic compound of a following average group accepted way of doing sth (2).
R
4 a’H
bSiO
(4-a’-b)/2 (2)
(in the formula, R
4The kind that is same to each other or different to each other and be replacement or the unsubstituted monovalence alkyl that is binding on Siliciumatom beyond the aliphatics unsaturated group, a ' and b are the positive numbers that satisfies 0.7≤a '≤2.1,0.001≤b≤1.0 and 0.8≤a '+b≤3.0, preferably satisfy the positive number of 1.0≤a '≤2.0,0.01≤b≤1.0 and 1.5≤a '+b≤2.5).
As R
4The aliphatics unsaturated group beyond replacement or unsubstituted, as to be binding on Siliciumatom monovalence alkyl, can enumerate: as the 1 valency alkyl that is not substituted or replaces beyond the described aliphatics unsaturated group and the carbon number of particular instantiation be 1～6 alkyl or haloalkyl, and carbon number be that 6～10 aryl etc. replaces or unsubstituted group.R
4Preferably carbon number is 1～6 alkyl or haloalkyl.
As by the represented organohydrogensiloxanes of a described average group accepted way of doing sth (2), for example can enumerate: comprise at least 4 by formula: R
4The ring compound of the organohydrogensiloxanes unit that HSiO is represented; By formula: R
4 3SiO (HR
4SiO)
cSiR
4 3Represented compound; By formula: HR
4 2SiO (HR
4SiO)
cSiR
4 2The compound that H is represented; And, by formula: HR
4 2SiO (HR
4SiO)
c(R
4 2SiO)
dSiR
4 2The compound that H is represented etc.In described formula, R
4As mentioned above, c and d are at least 1.
Perhaps, by the represented organohydrogensiloxanes of a described average group accepted way of doing sth (2), also can comprise by formula: H
3SiO
1/2Represented siloxane unit, by formula: R
4The siloxane unit that HSiO is represented and/or by formula: R
4 2HSiO
1/2Represented siloxane unit.Described organohydrogensiloxanes also can comprise: the single organo-siloxane unit, two organo-siloxane unit, three organo-siloxane unit and/or the SiO that do not contain the SiH base
4/2The unit.R in the described formula
4As mentioned above.
Preferably in the whole organo-siloxanes unit that is comprised by the represented organohydrogensiloxanes of a described average group accepted way of doing sth (2), 30～100 % by mole is the methyl hydrogen siloxane unit.
When (C) composition is when having the organic hydrogen polysiloxanes of at least two SiH bases in each molecule, its concrete example can be enumerated: 1,1,3, the 3-tetramethyl disiloxane, 1,3,5,7-tetramethyl-ring tetrasiloxane, three (hydrogen dimethylamino base siloxy) methyl-monosilane, three (hydrogen dimethylamino base siloxy) phenyl silane, the methyl hydrogen cyclopolysiloxane, methyl hydrogen siloxane-dimethyl siloxane cyclocopolymer, molecular chain two ends are by the methylhydrogenpolysi,oxane of trimethylsiloxy group sealing, molecular chain two ends are by the dimethyl siloxane-methylhydrogensiloxacopolymer copolymer of trimethylsiloxy group sealing, molecular chain two ends are by the diphenyl siloxane-methylhydrogensiloxacopolymer copolymer of trimethylsiloxy group sealing, molecular chain two ends are by the methylphenyl siloxane-methylhydrogensiloxacopolymer copolymer of trimethylsiloxy group sealing, dimethyl siloxane-methyl hydrogen siloxane that molecular chain two ends are sealed by trimethylsiloxy group-methylphenyl siloxane multipolymer, dimethyl siloxane-methyl hydrogen siloxane that molecular chain two ends are sealed by trimethylsiloxy group-diphenyl siloxane multipolymer, molecular chain two ends are by the methylhydrogenpolysi,oxane of dimethyl hydrogen siloxy sealing, molecular chain two ends are by the dimethyl polysiloxane of dimethyl hydrogen siloxy sealing, molecular chain two ends are by the dimethyl siloxane-methylhydrogensiloxacopolymer copolymer of dimethyl hydrogen siloxy sealing, the dimethyl siloxane that molecular chain two ends are sealed by the dimethyl hydrogen siloxy-methylphenyl siloxane multipolymer, the dimethyl siloxane that molecular chain two ends are sealed by the dimethyl hydrogen siloxy-diphenyl siloxane multipolymer, molecular chain two ends are by the methyl phenyl silicone of dimethyl hydrogen siloxy sealing, molecular chain two ends are by the phenylbenzene polysiloxane of dimethyl hydrogen siloxy sealing, molecular chain two ends are by the diphenyl siloxane-methylhydrogensiloxacopolymer copolymer of dimethyl hydrogen siloxy sealing; In these each exemplary compounds, part or all of methyl is by organic hydrogen polysiloxanes that other alkyl replaced such as ethyl, propyl group; By by formula: R
4 3SiO
1/2Represented siloxane unit, by formula: R
4 2HSiO
1/2Represented siloxane unit reaches by formula: SiO
4/2The organosiloxane copolymer that represented siloxane unit consists of; By by formula: R
4 2HSiO
1/2Represented siloxane unit reaches by formula: SiO
4/2The organosiloxane copolymer that represented siloxane unit consists of; By by formula: R
4HSiO
2/2Represented siloxane unit, by formula: R
4SiO
3/2Represented siloxane unit reaches by formula: H
3SiO
1/2Any one or two kinds of organosiloxane copolymers that consist of in the represented siloxane unit; And, by the two or more mixtures that consist of of these organopolysiloxanes.R in the described formula
4, have implication same as described above.
(C) the allotment amount of composition is, (C) the SiH base in the composition becomes the amount of 0.2≤SiH base/aliphatics unsaturated group≤5.0, preferred 0.5≤SiH base/aliphatics unsaturated group≤2.0 with respect to the mol ratio of the aliphatics unsaturated group in (A), (B) composition.
＜(D) composition 〉
(D) composition is the platinum metals series catalysts, and described platinum metals series catalysts can promote (A), (B) composition and (C) the hydrosilylation addition reaction of composition.
(D) the platinum metals series catalysts of composition, as long as can promote the hydrosilylation addition reaction of the SiH base in the aliphatics unsaturated group that is binding on Siliciumatom and (C) composition in (A), (B) composition, can use any catalyzer.(D) composition can be used alone, and also may be used two or more.(D) composition can be enumerated such as platinum metals such as platinum, palladium and rhodiums; Platinic chloride; Alcohols modification Platinic chloride; The coordination compound of Platinic chloride and olefines, vinylsiloxane or acetylide; And, the platinum group metal compounds such as tetrakis triphenylphosphine palladium, three (triphenylphosphine) rhodium chloride; Especially be preferably platinic compound.
(D) the allotment amount of composition is, effective dose as hydrosilylation catalysts gets final product, preferably with respect to (A), (B) and (C) the total quality of composition, be scaled the scope of 0.1～1000ppm, the more preferably scope of 1～500ppm with the quality of platinum group.
＜other compositions 〉
In addition curable silicon-ketone composition of the present invention, except described (A)～(D) composition, also can allocate other any compositions.As the concrete example of other compositions, can be listed below.These other compositions can be used alone respectively, also may be used two or more.
" (A), the compound that contains the aliphatics unsaturated group beyond (B) composition "
In addition curable silicon-ketone composition of the present invention, except (A), (B) composition, also can allocate can and (C) composition compound that contains the aliphatics unsaturated group of carrying out addition reaction.Such compound that contains the aliphatics unsaturated group as beyond (A), (B) composition is preferably the compound relevant with forming cured article, has at least two aliphatics unsaturated groups in therefore preferred each molecule.As the molecular structure of the such organopolysiloxane beyond (A), (B) composition, can enumerate for example ring texture.
As the concrete example of the compound that contains the aliphatics unsaturated group beyond (A), (B) composition, can enumerate: divinyl, the monomers such as diacrylate that derived by multi-functional alcohols; Polyethylene, polypropylene or vinylbenzene and other ethene unsaturated compounds (for example, vinyl cyanide or divinyl) carry out the polyolefine such as multipolymer that copolymerization forms; And, the oligopolymer or the polymkeric substance that are derived by the functionality substituted organic compounds such as ester of vinylformic acid, methacrylic acid or maleic acid.As the compound that contains the aliphatics unsaturated group beyond (A), (B) composition, at room temperature can be liquid, also can be solid.
" addition reaction control agent "
In order to ensure working life (pot life), can in addition curable silicon-ketone composition of the present invention, allocate the addition reaction control agent.The addition reaction control agent is not particularly limited, and get final product so long as the hydrosilylation catalysts of described (D) composition is had the compound that solidifies inhibition, also can use before since known compound.As the concrete example of addition reaction control agent, can enumerate: the P contained compounds such as triphenylphosphine; The nitrogenous compounds such as Tributylamine, Tetramethyl Ethylene Diamine, benzotriazole; Sulfocompound; The acetylene based compounds such as acetylene alcohols (for example, 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexin-3-alcohol); The compound that contains two above thiazolinyls; Hydroperoxide compound; And, maleic acid derivative etc.
The degree of the curing inhibition that is obtained by the addition reaction control agent, because of the chemical structure of described addition reaction control agent different.Therefore, for employed various addition reaction control agents, preferably its addition is adjusted to only consumption.By adding the addition reaction control agent of optimum consumption, composition long term storage stability and being heating and curing property at room temperature will become excellent.
" other any compositions "
In order to suppress cured article painted, gonorrhoea and oxidative degradation etc. occuring, can allocate the previous known antioxidants such as 2,6 di tert butyl 4 methyl phenol in addition curable silicon-ketone composition of the present invention.And in order to give its patience deteriorated to light, can also allocate hindered amine (hindered amine) in addition curable silicon-ketone composition of the present invention is the photostabilizers such as stablizer.And, in order to improve intensity, also can in addition curable silicon-ketone composition of the present invention, allocate the inanimate matter weighting agents such as aerosil (fumed silica), also can as required, in addition curable silicon-ketone composition of the present invention, allocate dyestuff, pigment and fire retardant etc.
[cured article]
Can under known condition of cure, utilize known curing, addition curable silicon-ketone composition of the present invention is solidified.Specifically, generally can by with room temperature～200 ℃, preferred 80～160 ℃ of heating, described composition be solidified.Be about 0.5 minute～5 hours heat-up time, especially preferred about 1 minute～3 hours, in the situation of the precision prescribeies such as LED seal applications, preferably prolongs set time.There is no particular restriction for the form of the cured article that obtains, and can be in example gel cured article, elastomerics cured article and the resin cured matter any.When being used for optical element sealed, described cured article especially is preferably: water white transparency and specific refractory power lower (being generally below about 1.41) are to be more than 80% under the layer state of 2mm at thickness at the transmittance that 25 ℃ of lower wavelength are 300～800nm.
In order to improve the optical element performance of originally required LED etc., especially for transmittance that to improve at 25 ℃ of lower wavelength be 400nm, specific refractory power under the visible light of cured article (589nm) (25 ℃) is preferably below 1.40, especially is preferably 1.30～1.39.
Addition curable silicon-ketone composition of the present invention solidifies and the cured article that obtains, and same with the cured article of general addition curable silicon-ketone composition, thermotolerance, winter hardiness and electrical insulating property are also very excellent.
[optical element sealing material]
As mentioned above, this composition solidifies and the cured article of acquisition, can be the elastomerics shape, and the rubber-like of example gel shape or softness is until have elastic arborescens.
Addition curable silicon-ketone composition of the present invention like this, especially the transmittance of cured article is higher, and when optical element was sealed, light taking-up efficient was also very excellent, therefore was best suited for optical applications, wherein was suitable as most optical element sealing material.
[optical element]
In addition, a kind of optical element is provided in the present invention, it is by addition curable silicon-ketone composition of the present invention being coated on for example LED, semiconductor laser, photorectifier, phototransistor, solar cell and charge coupled cell (Charge-coupled Device, CCD) etc. on, and under known condition of cure, utilize known curing, be specially and make as described above the sealing material curing that is coated with, thus sealing.
[embodiment]
Below, preparation example, embodiment and comparative example are shown, specifically describe the present invention, but the present invention is not limited to following embodiment.
In addition, in following example, viscosity refers to use rotational viscosimeter 23 ℃ of lower values of measuring.
Specific refractory power refer to use Japan to like to delay digital refractometer RX-5000 that company (ATAGO CO., LTD.) makes, in the specific refractory power of 25 ℃ of lower 589nm that measure, elongation and tensile strength are to measure take JIS-K6249 as benchmark when hardness, fracture.
Transmittance is that measuring wavelength with spectrophotometer under 25 ℃ is the optical transmission rate of 400nm for to make composition form thickness be the lamellar of 2mm and make its curing and the cured article that obtains.
In addition, in following example, expression straight chain shape organopolysiloxane or have the symbol of average composition of the organopolysiloxane of branched structure is the unit that is expressed as follows.
And each straight chain shape or have the organopolysiloxane of branched structure, the mole number of organic hydrogen polysiloxanes represents the average mol of vinyl contained in each composition or SiH base.
M
Vi：(CH
2=CH)(CH
3)
2SiO
1/2
M
ФVi：(CH
2=CH)(C
6H
5)(CH
3)SiO
1/2
D：(CH
3)
2SiO
2/2
D
Vi：(CH
2=CH)(CH
3)SiO
2/2
D
F1：(CF
3-CH
2-CH
2)(CH
3)SiO
2/2
T
F1：(CF
3-CH
2-CH
2)SiO
3/2
D
F2：[CF
3-(CF
2)
5-(CH
2)
2](CH
3)SiO
2/2
T
F2：[CF
3-(CF
2)
5-(CH
2)
2]SiO
3/2
D
Ф：(C
6H
5)
2SiO
2/2
The preparation of [preparation example 1] platinum catalyst (catalyst A)
With the reaction product that toluene dilutes Platinic chloride and sym-tetramethyl divinyl disiloxane, make platinum content become 1.0 quality %, thus employed platinum catalyst (catalyst A) in preparation present embodiment and the comparative example.
[preparation example 2] is synthetic by D
Vi/ T
F1The organopolysiloxane of=2/8 represented branched structure
In the flask of 2L, add 160g hexafluoro m-xylene (hexafluoro-m-xylene), 290g water and 323g concentrated hydrochloric acid, be warming up to 70 ℃ while stir.After the intensification, splash into 175g (0.8 mole) trifluoro propyl Trimethoxy silane, 26g (0.2 mole) methyl ethylene dimethoxy silane and 40g hexafluoro m-xylene.After splashing into, 75 ℃ of lower slakings 2 hours.After the slaking, remove the hydrochloric acid water on upper strata, then water cleans organic layer, repeatedly cleans, until the water after cleaning is neutral.Add 0.1g potassium hydroxide in the organic layer after cleaning, be warming up to 120 ℃, and carry out dehydration condensation.After reaction finishes, add 1g Potassium ethanoate and 0.23g trimethylchlorosilane, carry out neutralization reaction.Filter after the neutralization, and concentrate 1 hour with 100 ℃/5mmHg, thereby obtain water white by D
Vi/ T
F1The organopolysiloxane of=2/8 represented branched structure.
[preparation example 3] is synthetic by D
Vi/ T
F2The organopolysiloxane of=2/8 represented branched structure
In the flask of 2L, add 160g hexafluoro m-xylene, 290g water and 323g concentrated hydrochloric acid, be warming up to 70 ℃ while stir.After the intensification, splash into 375g (0.8 mole) perfluoro capryl Trimethoxy silane, 26g (0.2 mole) methyl ethylene dimethoxy silane and 40g hexafluoro m-xylene.After splashing into, 75 ℃ of lower slakings 2 hours.After the slaking, remove the hydrochloric acid water on upper strata, then water cleans organic layer, repeatedly cleans, until the water after cleaning is neutral.Add 0.1g potassium hydroxide in the organic layer after cleaning, be warming up to 120 ℃, and carry out dehydration condensation.After reaction finishes, add 1g Potassium ethanoate and 0.23g trimethylchlorosilane, carry out neutralization reaction.Filter after the neutralization, and concentrate 1 hour with 100 ℃/5mmHg, thereby obtain by D
Vi/ T
F2The organopolysiloxane of=2/8 represented branched structure.
[preparation example 4] synthesizes an average group accepted way of doing sth: M
Vi 2D
Ф 2.8Organopolysiloxane
In the flask of 2L, add 1000g water and 585g toluene, heat to 75 ℃, splash into therein the 500g diphenyl dichlorosilane, 80 ℃ of lower stirring 5 hours that continue.After being cooled to room temperature, water phase separated.Use the 50g anhydrous sodium sulphate that organic phase is dry, and leach, thus the toluene solution of acquisition diphenyl dichlorosilane hydrolyzed oligomers.Add 357g dimethyl vinyl chlorosilane, 300g triethylamine and 650g toluene in the 5L flask, be cooled to 10 ℃, the toluene solution of the diphenyl dichlorosilane hydrolyzed oligomers that obtains before splashing into is afterwards 80 ℃ of lower lasting stirrings 5 hours.After being cooled to room temperature, mix 2250g dilute hydrochloric acid, and water phase separated.Clean organic phase with sodium bicarbonate water and water, remove toluene by concentrating under reduced pressure afterwards.Carry out activated carbon treatment, thereby obtain a water white average group accepted way of doing sth: M
Vi 2D
Ф 2.8Silicone oil.
[preparation example 5] synthesizes an average group accepted way of doing sth: M
Ф Vi 2D
Ф 3.6Organopolysiloxane
In the flask of 500mL, add 200g water and 117g toluene, heat to 75 ℃, splash into therein the 100g diphenyl dichlorosilane, 80 ℃ of lower stirring 3 hours that continue.After being cooled to room temperature, water phase separated.Use the 10g anhydrous sodium sulphate that organic phase is dry, and leach, thus the toluene solution of acquisition diphenyl dichlorosilane hydrolyzed oligomers.Remove toluene by concentrating under reduced pressure, add 30.6g dimethyl diphenyl divinyl disiloxane (dimethyldiphenyldivinyldisiloxane) and mixing.And add the 5.0g vitriol oil, under the condition of 50 ℃/15mmHg, carry out condensation reaction in 5 hours.After adding the 10 % by weight saltcake water (mirabilite) and mixing of 100g toluene, 100g, water phase separated.Clean organic phase with sodium bicarbonate water and water, remove toluene by concentrating under reduced pressure afterwards.Filter the gonorrhoea liquid that obtains, thereby obtain a water white average group accepted way of doing sth: M
Ф Vi 2D
Ф 3.6Silicone oil.
[comparative example 1]
The viscosity of utilizing acid balance to adjust is 5.0Pas, an average group accepted way of doing sth: M
Vi 2D
F1 161D
69Straight chain shape organopolysiloxane 100.0g(0.0057 mole), and following formula (v)
0.74g(0.0063 mixture mole), with as the ethynylcyclohexanol 0.075g of control agent, and catalyst A 0.15g mixes, thereby the acquisition silicon-ketone composition.Under 150 ℃, to this composition heating it is solidified, measure the elastomeric physical property that obtains.Each measurement result is shown in table 1.
[comparative example 2]
The viscosity of utilizing acid balance to adjust is 2.0Pas, an average group accepted way of doing sth: M
Vi 2D
F1 27.3Straight chain shape organopolysiloxane 100.0g(0.037 mole), and by the represented organic hydrogen polysiloxanes 4.7g(0.040 mole of described formula (v)) mixture, with as the ethynylcyclohexanol 0.075g of control agent, and catalyst A 0.15g mixes, thereby the acquisition silicon-ketone composition.Under 150 ℃, to this composition heating it is solidified, measure the elastomeric physical property that obtains.Each measurement result is shown in table 1.
[embodiment 1]
The viscosity of utilizing acid balance to adjust is 2.0Pas, an average group accepted way of doing sth: M
Vi 2D
F1 27.3Straight chain shape organopolysiloxane 95.0g(0.035 mole), by D
Vi/ T
F1The organopolysiloxane of=2/8 represented branched structure (synthetic in preparation example 2) 5.0g(0.002 mole), and by the represented organic hydrogen polysiloxanes 4.7g(0.040 mole of described formula (v)) mixture, with as the ethynylcyclohexanol 0.075g of control agent, and catalyst A 0.15g mixes, thereby the acquisition silicon-ketone composition.Under 150 ℃, to this composition heating it is solidified, measure the elastomeric physical property that obtains.Each measurement result is shown in table 1.
[embodiment 2]
The viscosity of utilizing acid balance to adjust is 5.2Pas, an average group accepted way of doing sth: M
Vi 2D
F2 27.3Straight chain shape organopolysiloxane 95.0g(0.018 mole), by D
Vi/ T
F2The organopolysiloxane of=2/8 represented branched structure (synthetic in preparation example 3) 5.0g(0.001 mole), and by the represented organic hydrogen polysiloxanes 2.5g(0.021 mole of described formula (v)) mixture, with as the ethynylcyclohexanol 0.075g of control agent, and catalyst A 0.15g mixes, thereby the acquisition silicon-ketone composition.Under 150 ℃, to this composition heating it is solidified, measure the elastomeric physical property that obtains.Each measurement result is shown in table 1.
[comparative example 3]
The viscosity of utilizing soda balance to adjust is 0.4Pas, an average group accepted way of doing sth: M
Vi 2D
146Straight chain shape organopolysiloxane 100.0g(0.019 mole), and by the represented organic hydrogen polysiloxanes 2.5g(0.021 mole of described formula (v)), with as the ethynylcyclohexanol 0.075g of control agent, and catalyst A 0.15g mixes, thereby the acquisition silicon-ketone composition.Under 150 ℃, to this composition heating it is solidified, measure the elastomeric physical property that obtains.Each measurement result is shown in table 1.
[comparative example 4]
Be 0.4Pas, an average group accepted way of doing sth: M with viscosity
Vi 2D Ф
2.8Straight chain shape organopolysiloxane (in preparation example 4 synthetic) 100.0g(0.22 mole), and by the represented organic hydrogen polysiloxanes 28.5g(0.24 mole of described formula (v)) mixture, with as the ethynylcyclohexanol 0.075g of control agent, and catalyst A 0.15g mixes, thereby the acquisition silicon-ketone composition.Under 150 ℃, to this composition heating it is solidified, measure the elastomeric physical property that obtains.Each measurement result is shown in table 1.
[comparative example 5]
Be 3.1Pas, an average group accepted way of doing sth: M with viscosity
Ф Vi 2D
Ф 3.6Straight chain shape organopolysiloxane (in preparation example 5 synthetic) 100.0g(0.20 mole), and by the represented organic hydrogen polysiloxanes 25.9g(0.22 mole of described formula (v)) mixture, with as the ethynylcyclohexanol 0.075g of control agent, and catalyst A 0.15g mixes, thereby the acquisition silicon-ketone composition.Under 150 ℃, to this composition heating it is solidified, measure the elastomeric physical property that obtains.Each measurement result is shown in table 1.
Table 1
As shown in table 1, confirmed following item: addition curable silicon-ketone composition of the present invention, the transparency of its cured article is higher, has the organopolysiloxane of branched structure by further use, and as elastomerics, strength characteristics is good.
In addition, also confirmed following item: specific refractory power is lower, the transmittance that more can to improve at 25 ℃ of lower wavelength be 400nm.
In addition, the present invention is not limited to described embodiment.Described embodiment is illustration, have with claims of the present invention in the identical in fact formation of the technological thought put down in writing and play the technical scheme of same action effect, no matter which kind of is, all be included in the technical scope of the present invention.
Claims (5)
1. addition curable silicon-ketone composition, described addition curable silicon-ketone composition is characterised in that, comprises at least:
(A) organopolysiloxane of straight chain shape has the aliphatics unsaturated group that is binding on Siliciumatom more than two and the CF that is binding on Siliciumatom more than one in its a part
3-(CF
2)
m-(CH
2)
n-Ji, and in the formula, m is the integer more than 0, n is the integer more than 1: 100 mass parts;
(B) have the organopolysiloxane of branched structure, have the aliphatics unsaturated group that is binding on Siliciumatom more than two and the CF that is binding on Siliciumatom more than one in its a part
3-(CF
2)
m-(CH
2)
n-Ji, and described branched structure comprises by SiO
4/2And/or RSiO
3/2Represented siloxane unit, and in the formula, m is the integer more than 0, and n is the integer more than 1, and R replaces or unsubstituted monovalence alkyl: 1～100 mass parts;
(C) silicoorganic compound have the hydrogen atom that is binding on Siliciumatom more than two in its a part: the total aliphatics unsaturated group of described (A) composition, described (B) composition and (C) mol ratio of the SiH base of composition become the amount of 0.2≤SiH base/aliphatics unsaturated group≤5.0; And,
(D) platinum metals series catalysts: effective dose.
2. addition curable silicon-ketone composition as claimed in claim 1, wherein, the silicoorganic compound of described (C) composition are also to have the CF that is binding on Siliciumatom more than in a part
3-(CF
2)
m-(CH
2)
nThe silicoorganic compound of-Ji, and in the formula, m is the integer more than 0, n is the integer more than 1.
3. addition curable silicon-ketone composition as claimed in claim 1, wherein, described addition curable silicon-ketone composition can obtain a kind of cured article after the curing, and described cured article is to be more than 80% under the layer state of 2mm at thickness at the transmittance that 25 ℃ of lower wavelength are 300～800nm.
4. such as each described addition curable silicon-ketone composition in the claims 1 to 3, wherein, described addition curable silicon-ketone composition can obtain a kind of cured article after the curing, and described cured article is below 1.40 in the specific refractory power of the visible light that 25 ℃ of lower wavelength are 589nm.
5. optical element, it is to utilize cured article to seal, described cured article is the cured article of each described addition curable silicon-ketone composition in the claims 1 to 3.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1781991A (en) * | 2004-11-18 | 2006-06-07 | 瓦克化学有限公司 | Crosslinkable silicone compositions having long pot life and storage stability |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5082706A (en) * | 1988-11-23 | 1992-01-21 | Dow Corning Corporation | Pressure sensitive adhesive/release liner laminate |
| JPH0662769B2 (en) * | 1991-06-24 | 1994-08-17 | 信越化学工業株式会社 | Fluoroalkyl group-containing silicone oil |
| JPH10158401A (en) * | 1996-12-03 | 1998-06-16 | Toshiba Silicone Co Ltd | Production of fluroalkylated siloxane |
| JPH115902A (en) * | 1997-06-17 | 1999-01-12 | Shin Etsu Chem Co Ltd | Curable silicone rubber composition |
| JP2001040215A (en) * | 1999-07-28 | 2001-02-13 | Dow Corning Asia Ltd | Optical material |
| JP4409160B2 (en) * | 2002-10-28 | 2010-02-03 | 東レ・ダウコーニング株式会社 | Curable organopolysiloxane composition and semiconductor device |
| JP4908736B2 (en) * | 2003-10-01 | 2012-04-04 | 東レ・ダウコーニング株式会社 | Curable organopolysiloxane composition and semiconductor device |
| US7696295B2 (en) * | 2006-02-03 | 2010-04-13 | Panasonic Electric Works Co., Ltd. | Condensation products of silicic acid derivatives and optical waveguide devices using the same |
| JP5060074B2 (en) * | 2006-05-11 | 2012-10-31 | 東レ・ダウコーニング株式会社 | Adhesion promoter, curable organopolysiloxane composition, and semiconductor device |
| JP2010123769A (en) * | 2008-11-20 | 2010-06-03 | Shin-Etsu Chemical Co Ltd | Light emitting device and method of manufacturing the same |
-
2011
- 2011-06-30 JP JP2011145085A patent/JP5603837B2/en active Active
-
2012
- 2012-06-13 CN CN2012101948498A patent/CN102850803A/en active Pending
- 2012-06-29 KR KR1020120070673A patent/KR20130009621A/en not_active Application Discontinuation
- 2012-06-29 TW TW101123491A patent/TWI554571B/en active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1781991A (en) * | 2004-11-18 | 2006-06-07 | 瓦克化学有限公司 | Crosslinkable silicone compositions having long pot life and storage stability |
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| TWI582169B (en) * | 2013-03-07 | 2017-05-11 | Jsr股份有限公司 | Curable composition, cured product and optical semiconductor device |
| CN104893301B (en) * | 2014-03-05 | 2017-12-08 | 信越化学工业株式会社 | Addition curable silicon-ketone composition and optical element |
| CN104893301A (en) * | 2014-03-05 | 2015-09-09 | 信越化学工业株式会社 | Addition-curable silicone composition and optical device |
| CN106795288A (en) * | 2014-10-03 | 2017-05-31 | 住友化学株式会社 | Silicone resin, UV LED Encapulant compositions, solidfied material and UV LED encapsulants |
| CN107532002B (en) * | 2015-04-10 | 2020-11-13 | 陶氏东丽株式会社 | Fluoroalkyl group-containing curable organopolysiloxane composition, cured product thereof, and electronic component or display device provided with cured product |
| TWI735436B (en) * | 2015-04-10 | 2021-08-11 | 日商陶氏東麗股份有限公司 | Curable organopolysiloxane composition having fluoroalkyl group, cured body thereof, electronic device or display device having the cured body |
| CN107532002A (en) * | 2015-04-10 | 2018-01-02 | 道康宁东丽株式会社 | Curable organopolysiloxane composition containing fluoroalkyl, its solidfied material and the electronic unit or display device that possess the solidfied material |
| CN105238061B (en) * | 2015-11-25 | 2018-06-15 | 泸州北方化学工业有限公司 | Foamed silastic sizing material, low-density silicone sponge and preparation method thereof |
| CN105238061A (en) * | 2015-11-25 | 2016-01-13 | 泸州北方化学工业有限公司 | Foaming silicone rubber compound, low-density silicone rubber sponge and preparing method of low-density silicone rubber sponge |
| CN110268019A (en) * | 2016-12-30 | 2019-09-20 | 埃肯有机硅（上海）有限公司 | Curable silicon-ketone composition |
| CN111073297A (en) * | 2018-10-22 | 2020-04-28 | 信越化学工业株式会社 | Addition-curable silicone composition, silicone cured product, and optical element |
| CN111574839A (en) * | 2019-02-19 | 2020-08-25 | 信越化学工业株式会社 | Silicone resin composition for die bonding, cured product, and optical semiconductor device |
| CN111574839B (en) * | 2019-02-19 | 2022-06-17 | 信越化学工业株式会社 | Silicone resin composition for die bonding, cured product, and optical semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI554571B (en) | 2016-10-21 |
| JP2013010881A (en) | 2013-01-17 |
| KR20130009621A (en) | 2013-01-23 |
| JP5603837B2 (en) | 2014-10-08 |
| TW201319168A (en) | 2013-05-16 |
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