CN103571209A - Addition-curable silicone composition and semiconductor device - Google Patents
Addition-curable silicone composition and semiconductor device Download PDFInfo
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- CN103571209A CN103571209A CN201310331667.5A CN201310331667A CN103571209A CN 103571209 A CN103571209 A CN 103571209A CN 201310331667 A CN201310331667 A CN 201310331667A CN 103571209 A CN103571209 A CN 103571209A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
- H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
Abstract
The invention aims to provide an addition-curable silicone composition and a semiconductor device which is formed through covering a semiconductor element by the condensate and has good reliability. The addition-curable silicone composition is low in adhesiveness, good in filling and condensation, large in refractive rate, high in light transmittance, high in substrate sealing, good in cracking resistance, and low in air permeability. The addition-curable silicone composition comprises (A) 100 mass part of organopolysiloxane; (B) 1-500 mass part of organopolysiloxane expressed by a unit formula (2); (C) organic hydrogen polysiloxane which is expressed by a formula (3) and has at least two Si-H keys in one molecule; and (D) catalyst which is used for the hydrosilylation reaction to promote composition condensation.
Description
Technical field
The present invention relates to a kind of addition curable silicon-ketone composition and use the semiconductor device of this addition curable silicon-ketone composition.
Background technology
The curing addition curable silicon-ketone composition by hydrosilylation reactions, at optics such as photoelectrical coupler, photodiode and solid-state imaging elements with in the semiconductor element in semiconductor device, as supercoat agent.Can be luminous or receive light due to aforementioned components, the supercoat agent that therefore requires this semiconductor element is absorb light or scattered light not.
As solidifying by hydrosilylation reactions, and the addition curable silicon-ketone composition of the cured article that formation specific refractory power is large, light transmission is high for example can be enumerated: comprise and contain the phenyl being binding on Siliciumatom and be binding on the curable organopolysiloxane composition (with reference to patent documentation 1) of catalyzer for the organopolysiloxane of the thiazolinyl on Siliciumatom, organic hydrogen cyclosiloxane and hydrosilylation reactions; Comprising and containing the phenyl being binding on Siliciumatom and the viscosity that is binding on the thiazolinyl on Siliciumatom is in the above liquid or solid organopolysiloxane of 10,000cp (25 ℃), 1 molecule, to have at least 2 to be binding on the organic hydrogen polysiloxanes of the hydrogen atom on Siliciumatom and the curable organopolysiloxane composition (with reference to patent documentation 2) that hydrosilylation reactions is used catalyzer; Comprise and in 1 molecule, there are at least 2 and be binding on the thiazolinyl on Siliciumatom and have and in the organopolysiloxane, 1 molecule that is binding on the aryl on Siliciumatom, there is at least 2 organopolysiloxanes that are binding on the hydrogen atom on Siliciumatom and platinum and containing the curable organopolysiloxane composition (with reference to patent documentation 3) of the complex compound of the organo-siloxane oligopolymer of aryl; And, molecular chain two ends by siloxane bond by being binding on organopolysiloxane composition (with reference to patent documentation 4) of the hydrogen atom end-blocking on Siliciumatom etc.
Yet these curable organopolysiloxane compositions may be difficult to make solidify and transparency maintenance balance, or peel off because a small amount of catalyzer poison produces.
And, also there is following problem: viscosity is compared with high and cause lacking fillibility, cured article lacks adhesion and easily from base material, peels off, when being difficult to control solidified nature and causing manufacturing at the scene, easily break down, (crack resistance) is poor for splitting resistance, and ventilation property is compared with high and easily corrode substrate.
And, a kind of addition curable silicon-ketone composition (with reference to patent documentation 5) that uses straight chain shape silicone oil (silicone oil) simultaneously and have the silicone resin of branched structure is also proposed, but insufficient to the adhesion of base material and splitting resistance.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 8-176447 communique
Patent documentation 2: Japanese kokai publication hei 11-1619 communique
Patent documentation 3: TOHKEMY 2003-128922 communique
Patent documentation 4: TOHKEMY 2005-105217 communique
Patent documentation 5: TOHKEMY 2004-143361 communique
Summary of the invention
The present invention completes in view of above-mentioned condition, its object is, a kind of addition curable silicon-ketone composition is provided and with the cured article of said composition, semiconductor element is covered to the semiconductor device of the reliability excellence forming, described addition curable silicon-ketone composition, viscosity is low and fillibility is good, solidified nature is good, solidifies and form the cured article that specific refractory power is large, transmittance is high, high to the adhesion of base material, splitting resistance is excellent, ventilation property is low.
In order to address the above problem, the invention provides a kind of addition curable silicon-ketone composition, it is characterized in that, it contains: by represented organopolysiloxane 100 mass parts of following averaged unit formula (1):
(R
1SiO
3/2)
a1(R
1 2SiO
2/2)b
1(R
1 3SiO
1/2)
c1(X
1O
1/ 2)
d1 (1)
In formula, R
1can be identical or different, and for replace or unsubstituted monovalence alkyl (wherein, 0.1～50 % by mole of R1 is thiazolinyl, R
110 % by mole be above aryl), X
1for hydrogen atom or alkyl; A1 is that 0.25～1, b1 is that 0～0.75, c1 is that 0～0.3, d1 is 0～0.1, and a1+b1+c1+d1=1};
(B) by represented organopolysiloxane 1～500 mass parts of following averaged unit formula (2):
(R
2SiO
3/2）
a2(R
2 2SiO
2/2)
b2(R
2 3SiO
1/2)
c2X
2O
1/ 2)
d2 (2)
In formula, R
2can be identical or different, and for replacing or unsubstituted monovalence alkyl (wherein, R
20.001～20 % by mole be thiazolinyl, R
210 % by mole be above aryl), X
2for hydrogen atom or alkyl; A2 is that 0～0.1, b2 is that 0.5～0.995, c2 is that 0.005～0.5, d2 is 0～0.1, and a2+b2+c2+d2=1};
(C) in represented 1 molecule of following general formula (3), having the organic hydrogen polysiloxanes of at least 2 Si-H keys, with respect to (A)+(B) become subtotaling 100 mass parts, is the amount of 1～200 mass parts:
(in formula, R
3for any in hydrogen atom, alkyl, aryl and haloalkyl, each R between repeating unit and in repeating unit
3can be identical or different; M is more than 0 integer); And,
(D) promote the hydrosilylation reactions catalyzer of the curing amount of this composition.
This addition curable silicon-ketone composition of the present invention, viscosity is low and fillibility is good, and solidified nature is also good.And, when solidified, will become the cured article that specific refractory power is large, transmittance is high, high to the adhesion of base material, splitting resistance is excellent, ventilation property is low.
And be preferably, in aforementioned (A) composition, the R in aforementioned averaged unit formula (1)
1aryl containing rate be more than 30 % by mole.
So, if form in the averaged unit formula (1) of (A) composition to be binding on aryl on silicon be more than 30 % by mole with respect to what be binding on organic group on Siliciumatom containing rate, specific refractory power, light transmission are excellent so, and splitting resistance is also more excellent.
And be preferably, in aforementioned (B) composition, the R in aforementioned averaged unit formula (2)
2aryl containing rate be more than 20 % by mole.
So, if form in the averaged unit formula (2) of (B) composition to be binding on aryl on silicon be more than 20 % by mole with respect to what be binding on organic group on Siliciumatom containing rate, specific refractory power, light transmission are excellent so, and splitting resistance is also more excellent.
And be preferably, in aforementioned (C) composition, in aforementioned formula (3), be binding on the R on Siliciumatom
3with 30 % by mole of the total of H be phenyl below.
So, if be binding on the R on Siliciumatom in aforementioned formula (3)
3with 30 % by mole of the total of H be phenyl below, so from (A), the intermiscibility of (B) composition, the viewpoints such as physical property of cured article, can use preferably.
And be preferably, in aforementioned (C) composition, the m in aforementioned formula (3) is the integer below 20.
So,, if the m in aforementioned formula (3) is below 20, just can reduce viscosity and the ventilation property of composition.
And be preferably, aforementioned addition curable silicon-ketone composition solidifies and is formed on specific refractory power (25 ℃) in visible ray (589 nm) is that more than 1.5 cured article and/or transmittance (25 ℃) is more than 80% cured article.
This composition if, will be particularly useful for having the semiconductor device of the optical semiconductor that the cured article of thing covers that is combined, and can give sufficient reliability.
And, the invention provides a kind of semiconductor device, it is characterized in that, with the cured article of aforementioned addition curable silicon-ketone composition, semiconductor element is covered.
This semiconductor device of the present invention is owing to being that the cured article that is refracted the addition curable silicon-ketone composition of the present invention that rate is large, transmittance is high, high to the adhesion of base material, splitting resistance is excellent, ventilation property is low covers, and therefore, reliability is excellent.
As described above, addition curable silicon-ketone composition of the present invention, viscosity is low and fillibility is good, and solidified nature is good, after solidifying, can form the cured article that specific refractory power is large, transmittance is high, adhesion is high, splitting resistance is excellent, ventilation property is low.And because semiconductor element is covered by the cured article of above-mentioned composition, therefore, the reliability of semiconductor device of the present invention is excellent.
Accompanying drawing explanation
Fig. 1 means the summary sectional view of an example of semiconductor device of the present invention.
Wherein, description of reference numerals is as follows:
1 semiconductor device; 2 silver-plated substrates; 3 packagies; 4 semi-conductor chips; 5 bonding wires; 6 curing silicon-ketone compositions (cured article).
Embodiment
Below, illustrate in greater detail the present invention.
As mentioned above, addition curable silicon-ketone composition in the past may be difficult to obtain curing and transparent balance, or because producing, peels off a small amount of catalyzer poison, and there is following problem: viscosity is compared with high and cause lacking fillibility, cured article lacks adhesion and easily from base material, peels off, when being difficult to control solidified nature and causing manufacturing at the scene, easily break down, splitting resistance is poor.
Therefore, the inventor makes great efforts to study in order to address the above problem a little, found that: by using end to there is the organopolysiloxane through the SiH base of ethene bond (ethylenic linkage) in composition, make the part that contains organic bond in this composition, especially can reduce ventilation property, or the weather resistance while improving thermal shock test etc., and, utilize the structure of each composition that forms composition etc., can keep under the good state of specific refractory power and light transmission, improve solidified nature, splitting resistance, the various characteristicses such as adhesion, can deal with problems a little, thereby complete the present invention.
That is to say, addition curable silicon-ketone composition of the present invention, is characterized in that, it contains: (A) by represented organopolysiloxane 100 mass parts of following averaged unit formula (1):
(R
1SiO
O/2)
a1(R
1 2SiO
2/2)
b1(R
1 3SiO
1/2)
c1(X
1O
1/ 2)
d1 (1)
In formula, R
1can be identical or different, and for replacing or unsubstituted monovalence alkyl (wherein, R
10.1～50 % by mole be thiazolinyl, R
110 % by mole be above aryl), X
1for hydrogen atom or alkyl; A1 is that 0.25～1, b1 is that 0～0.75, c1 is that 0～0.3, d1 is 0～0.1, and a1+b1+c1+d1=1};
(B) by represented organopolysiloxane 1～500 mass parts of following averaged unit formula (2):
(R
2SiO
3/2)
a2(R
2 2SiO
2/2)
b2(R
2 3SiO
1/2)
c2(X
2O
1/2)
d2 (2)
In formula, R
2can be identical or different, and for replacing or unsubstituted monovalence alkyl (wherein, R
20.001～20 % by mole be thiazolinyl, R
210 % by mole be above aryl), X
2for hydrogen atom or alkyl; A2 is that 0～0.1, b2 is that 0.5～0.995, c2 is that 0.005～0.5, d2 is 0～0.1, and a2+b2+c2+d2=1};
(C) in represented 1 molecule of following general formula (3), having the organic hydrogen polysiloxanes of at least 2 Si-H keys, with respect to (A)+(B) become subtotaling 100 mass parts, is the amount of 1～200 mass parts:
(in formula, R
3for any in hydrogen atom, alkyl, aryl and haloalkyl, each R between repeating unit and in repeating unit
3can be identical or different; M is more than 0 integer); And,
(D) promote the hydrosilylation reactions catalyzer of the curing amount of this composition.
Below, explain each composition of composition of the present invention.
< (A) composition >
(A) composition is by the represented organopolysiloxane of following averaged unit formula (1):
(R
1SiO
3/2)
a1(R
1 2SiO
2/2)
b1(R
1 3SiO
1/2)
c1(x1o
1/ 2)
d1 (1)
In formula, R
1can be identical or different, and for replacing or unsubstituted monovalence alkyl (wherein, R
10.1～50 % by mole be thiazolinyl, R
110 % by mole be above aryl), X
1for hydrogen atom or alkyl; A1 is that 0.25～1, b1 is that 0～0.75, c1 is that 0～0.3, d1 is 0～0.1, and a1+b1+c1+d1=1}.
As R
1in thiazolinyl, exemplify vinyl, allyl group, butenyl, pentenyl and hexenyl, be especially preferably vinyl.R
1in thiazolinyl containing rate be 0.1～50 % by mole, be preferably 1～40 % by mole, be especially preferably 5～30 % by mole.If 0.1 % by mole of less than, the solidified nature of composition is just insufficient; And if over 50 % by mole, cured article will become fragile, splitting resistance reduces.
And, as R
1in aryl, exemplify phenyl, tolyl, xylyl and naphthyl, be especially preferably phenyl.R
1in aryl containing rate be more than 10 % by mole, be preferably more than 30 % by mole, more preferably 40～99.9 % by mole, be especially preferably 45～95 % by mole.If 10 % by mole of less thaies, the light transmission of cured article will reduce.And if more than 30 % by mole, specific refractory power, light transmission are excellent, and splitting resistance is also more excellent.
And, as R
1in except thiazolinyl and aryl, be binding on the monovalence alkyl on Siliciumatom, exemplify: the alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl and heptyl; The aralkyl such as benzyl, styroyl; And the haloalkyls such as chloromethyl, 3-chloropropyl and 3,3,3-trifluoro propyl etc. replace or unsubstituted monovalence alkyl; Especially be preferably methyl.
And, in above-mentioned averaged unit formula (1), X
1for hydrogen atom or alkyl, as this alkyl, exemplify with as R
1the group that illustrated group is identical, is especially preferably methyl, ethyl.
And a1 is 0.25～1, be preferably 0.5～1, being especially preferably 0.6～1, b1 is 0～0.75, is preferably 0～0.5, and being especially preferably 0～0.4, c1 is 0～0.3, and being preferably 0～0.2, d1 is 0～0.1, is preferably 0～0.05, and a1+b1+c1+d1=1.
If a1 deficiency 0.25((R
1siO
3/2) unit containing 25 % by mole of rate less thaies), splitting resistances etc. are just insufficient.
Molecular weight the indefinite of this (A) composition, but be preferably to utilize and use tetrahydrofuran (THF) (Tetrahydrofuran, THF) gel permeation chromatography of solvent (Gel Permeation Chromatography, GPC) weight-average molecular weight (Mw) of measuring (polystyrene standard conversion) is 500～10,000, more preferably 700～5,000, especially be preferably 1,000～3,000.
< (B) composition >
(B) composition is by the represented organopolysiloxane of following averaged unit formula (2):
(R
2SiO
3/2）
a2（R
2 2SiO
2/2)
b2R
2 3SiO
1/2)
c2(X
2O
1/ 2)
d2 (2)
In formula, R
2can be identical or different, and for replacing or unsubstituted monovalence alkyl (wherein, R
20.001～20 % by mole be thiazolinyl, R
210 % by mole be above aryl), X
2for hydrogen atom or alkyl; A2 is that 0～0.1, b2 is that 0.5～0.995, c2 is that 0.005～0.5, d2 is 0～0.1, and a2+b2+c2+d2=1}.
As R
2in thiazolinyl, exemplify vinyl, allyl group, butenyl, pentenyl and hexenyl, be especially preferably vinyl.R
2in thiazolinyl containing rate be 0.001～20 % by mole, be preferably 0.003～10 % by mole, be especially preferably 0.01～5 % by mole.If 0.001 % by mole of less than, the solidified nature of composition is just insufficient; And if over 20 % by mole, cured article will become fragile, splitting resistance reduces.
And, as R
2in aryl, exemplify phenyl, tolyl, xylyl and naphthyl, be especially preferably phenyl.R
2in aryl containing rate be more than 10 % by mole, be preferably 15～80 % by mole, be especially preferably 20～70 % by mole.If 10 % by mole of less thaies, the light transmission of cured article will reduce.And if more than 20 % by mole, specific refractory power, light transmission are excellent, and splitting resistance is also more excellent.
And, as R
2in except thiazolinyl and aryl, be binding on the monovalence alkyl on Siliciumatom, exemplify: the alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl and heptyl; The aralkyl such as benzyl, styroyl; And the haloalkyls such as chloromethyl, 3-chloropropyl and 3,3,3-trifluoro propyl etc. replace or unsubstituted monovalence alkyl; Especially be preferably methyl.
And, in above-mentioned averaged unit formula (2), X
2for hydrogen atom or alkyl, as this alkyl, exemplify with as R
2the group that illustrated group is identical, is especially preferably methyl, ethyl.
And a2 is 0～0.1, be preferably 0～0.05, be especially preferably less than 0.05, b2 is 0.5～0.995, and being preferably 0.6～0.9, c2 is 0.005～0.5, and being preferably 0.01～0.1, d2 is 0～0.1, is preferably 0～0.05, and a2+b2+c2+d2=1.
And be preferably, composition of the present invention, especially (B) composition comprise by the represented modular construction of following formula:
Be preferably (R
2 2siO
2/2) 10 % by mole of unit above, especially 25 % by mole be said units structure above.
If contain said units structure, just can obtain splitting resistance and the more excellent cured article of the transparency.
Molecular weight the indefinite of this (B) composition, but the weight-average molecular weight (Mw) that utilization is used the GPC of THF solvent to measure (polystyrene standard conversion) is preferably 1,000～30,000, more preferably 2,000～20,000, especially be preferably 4,000～15,000.
And (B) viscosity of the organopolysiloxane of composition is preferably 0.5～10,000mPa.s at 25 ℃, more preferably 10～6,000mPa.s.
And the viscosity described in this specification sheets is the value of using rotational viscosimeter to measure at 25 ℃.
Be preferably by the represented organopolysiloxane of following formula:
(in formula, A is methyl or phenyl; B2', b2'' are more than 0 positive number, and b2'+b2''=b2; C2' is for surpassing 0 positive number, and c2'' is more than 0 positive number, and c2'+c2''=c2).
As the allotment amount of the organopolysiloxane of above-mentioned (B) composition, with respect to aforementioned (A) composition 100 mass parts, be 1～500 mass parts.
< (C) composition >
(C) composition is by the represented straight chain shape organic hydrogen polysiloxanes of following general formula (3), in 1 molecule, have at least 2 with the Si-H key of ethene bond (namely, be binding on the hydrogen atom on Siliciumatom), the viscosity being preferably at 25 ℃ is 1, below 000mPa.s, be generally 0.5～1,000mPa.s, more preferably 1～500 mPa.s:
(in formula, R
3for any in hydrogen atom, alkyl, aryl and haloalkyl, each R between repeating unit and in repeating unit
3can be identical or different; M is more than 0 integer).
At this, R
3for any in hydrogen atom, alkyl, aryl and haloalkyl, each R between repeating unit and in repeating unit
3can be identical or different.As this R
3, can enumerate specifically: the alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl and hexyl; The aryl such as phenyl, tolyl; And, the haloalkyls such as 3,3,3-trifluoro propyl etc.
And the m in aforementioned formula (3) is preferably the integer below 20, more preferably the integer below 10.If the value of m, will be excellent compared with the low fillibility that makes due to the viscosity of composition within the scope of this.And, because the ratio of the silicon alkylene base key in composition increases, therefore, can reduce ventilation property.
(C) the concrete structure of composition is shown in following.
With respect to (A)+(B), become subtotaling 100 mass parts, the allotment amount of the organic hydrogen polysiloxanes of above-mentioned (C) composition is 1～200 mass parts, be preferably 5～80 mass parts, if allotment quantity not sufficient 1 mass parts, solidified nature is just insufficient, if and over 200 mass parts, just cannot obtain sufficient hardness, intensity.
And, the organic hydrogen polysiloxanes of this (C) composition is more preferably allocated by following amount: (C) hydrogen atom (namely SiH yl) on Siliciumatom of being binding in composition is 0.5～5 moles/mole with respect to the mol ratio of the thiazolinyl in (A)+(B) composition, especially 1～3 moles/mole.
< (D) composition >
(D) the hydrosilylation reactions catalyzer of composition is for promoting (A) composition and (B) catalyzer of the hydrosilylation reactions that is binding on the hydrogen atom on Siliciumatom in thiazolinyl and (C) composition of composition.As this (D) composition, exemplify platinum group catalyst, rhodium series catalysts and palladium series catalyst, from promoting significantly the curing aspect of this composition, be preferably platinum group catalyst.As this platinum group catalyst, exemplify alcoholic solution, platinum/alkenyl siloxane complex compound, platinum/alkene complex and the platinum/carbonylcomplex of platinum micro mist, Platinic chloride, Platinic chloride, be especially preferably platinum/alkenyl siloxane complex compound.As this alkenyl siloxane, exemplify 1,3-divinyl-1,1,3,3-tetramethyl disiloxane, 1,3,5,7-tetramethyl--1,3,5,7-tetrem thiazolinyl cyclotetrasiloxane, the alkenyl siloxane part methyl replacement of these alkenyl siloxane being formed with groups such as ethyl, phenyl and the alkenyl siloxane vinyl substituted of these alkenyl siloxane being formed with groups such as allyl group, hexenyls.Especially from making the aspect having good stability of platinum/alkenyl siloxane complex compound, alkenyl siloxane is preferably 1,3-divinyl-1,1,3,3-tetramethyl disiloxane.
And, from improving the aspect of the stability of this platinum/alkenyl siloxane complex compound, be preferably in this complex compound and add 1, 3-divinyl-1, 1, 3, 3-tetramethyl disiloxane, 1, 3-diallyl-1, 1, 3, 3-tetramethyl disiloxane, 1, 3-divinyl-1, 3-dimethyl-1, 3-phenylbenzene sily oxide, 1, 3-divinyl-1, 1, 3, 3-tetraphenyl sily oxide, 1, 3, 5, 7-tetramethyl--1, 3, 5, the organo-siloxane oligopolymer such as the alkenyl siloxane such as 7-tetrem thiazolinyl cyclotetrasiloxane or dimethyl siloxane oligopolymer, especially be preferably interpolation alkenyl siloxane.
(D) content of composition indefinite, so long as promote the amount (catalytic amount) of solidifying (hydrosilylation reactions) of this composition, specifically, be preferably with respect to (A) composition of this composition and (B) total of composition, atoms metal in this composition is expressed as the amount in the scope of 0.01～500ppm with mass unit, the amount in the scope of 0.05～100ppm more preferably, is especially preferably the amount in the scope of 0.05～50 ppm.This is that this composition will be fully curing because if (D) content of composition is above-mentioned scope, and can produce the problems such as painted without the cured article of worrying gained, and both economical.
Any composition > of <
As other any compositions, in this composition, can contain: 2-methyl-3-butyne-2-alcohol, 3, the alkynes alcohol such as 5-dimethyl-1-hexin-3-alcohol and 2-phenyl-3-butyne-2-alcohol; 3-methyl-pirylene, 3, the eneyne compounds such as 5-dimethyl-3-hexene-1-alkynes; And, 1,3,5,7-tetramethyl--1,3,5,7-tetrem thiazolinyl cyclotetrasiloxane, 1,3,5,7-tetramethyl--1, the reaction suppressors such as 3,5,7-, tetra-hexenyl cyclotetrasiloxanes, benzotriazole.The content of this reaction suppressor indefinite, become subtotaling 100 mass parts with (B) with respect to (A) composition, be preferably in the scope of 0.0001～5 mass parts.
And, can also be containing being useful on the close-burning tackifier that improve it in this composition.As these tackifier, be preferably and in 1 molecule, there is at least 1, be preferably 2 above silicoorganic compound that are binding on the alkoxyl group on Siliciumatom.As this alkoxyl group, exemplify methoxyl group, oxyethyl group, propoxy-, butoxy and methoxy ethoxy, be especially preferably methoxyl group.And the group (atom) the alkoxyl group on Siliciumatom that is binding on as except these silicoorganic compound, exemplifies: as R
1etc. illustrated aforesaid alkyl, aforementioned thiazolinyl, aforementioned aryl, aforementioned aralkyl and aforementioned haloalkyl etc., replace or unsubstituted monovalence alkyl; Glycidoxyalkyl, the 2-(3 such as 3-glycidoxy propyl group and 4-glycidoxy butyl, 4-epoxy group(ing) cyclohexyl) any monovalent organic radical group that epoxy alkyl alkyl such as epoxy group(ing) cyclohexyl alkyl, 4-epoxy alkyl butyl and 8-epoxy alkyl octyl group such as ethyl and 3-(3,4-epoxy group(ing) cyclohexyl) propyl group etc. contain epoxy group(ing); Any monovalent organic radical group that 3-methacryloxypropyl etc. contains acryl (acryl group); And, hydrogen atom.Exemplify specifically the silane coupling agent that contains epoxy group(ing), the silane coupling agents such as silane coupling agent that contain methacryloyl (methacryl group) and its partial hydrolysis condenses (oligopolymer of silane coupling agent) etc.
More particularly, exemplify: the silane compounds such as 3-glycidoxypropyltrime,hoxysilane, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, 3-methacryloxypropyl trimethoxy silane; In 1 molecule, having respectively 1 above is binding on thiazolinyl on Siliciumatom, is binding on the hydrogen atom on Siliciumatom and is binding on the silicone compounds of the alkoxyl group on Siliciumatom; There is at least 1 silane compound that is binding on the alkoxyl group on Siliciumatom; In 1 molecule, having respectively at least 1 is binding on the hydroxyl on Siliciumatom and is binding on the silicone compounds of the thiazolinyl on Siliciumatom and the mixture of above-mentioned silicone compounds; And, poly-methyl silicate, ethyl polysilicate and the ethyl polysilicate that contains epoxy group(ing).
These tackifier are preferably low viscous liquid, its viscosity indefinite, but be preferably at 25 ℃ in the scope of 1～500mPa.s.Can also add the tackifier that are shown below.
And, in this composition, the content of these tackifier indefinite, but with respect to (A) composition, become subtotaling 100 mass parts with (B), be preferably 0.01～10 mass parts.
And, in this composition, as other compositions arbitrarily, can also contain following composition: the inorganic fillers such as silicon-dioxide, glass, aluminum oxide, zinc oxide; The resin micropowders such as polymethacrylate resin, silicone resin, silicone powder; And, heat-resistant agent, dyestuff, pigment, flame retardant resistance imparting agent, solvent etc.
And, the viscosity of this composition, being preferably at 25 ℃ is 50～100,000mPa.s, more preferably 100～7,000mPa.s.
And, be preferably, this composition solidify and form the hardness stipulated in Japanese JIS with Shore D be expressed as more than 20,30～90 cured article especially.
So, when solidified, if form, for example with Shore D, be expressed as the composition of more than 20 cured articles, when for semiconductor device etc., be just not easy to be subject to the impact of external stress, and dust etc. extremely difficulty adhere to.
And, this composition for to have semiconductor element that the cured article of the thing that is combined covers particularly the semiconductor device of optical semiconductor give sufficient reliability, be preferably, the specific refractory power (25 ℃) of the cured article of the curing gained of this composition in visible ray (589nm) is more than 1.5, and the transmittance of cured article (25 ℃) is more than 80%.
And this specific refractory power can utilize for example Abbe formula (Abbe-type) refractometer to measure.Now, can, by changing the wavelength of the light source in Abbe formula refractometer, measure the specific refractory power under any wavelength.And this transmittance can be by for example utilizing the cured article that spectrophotometric determination path length is 2.0mm to try to achieve.
And be preferably, this composition is solidified and the wavelength of 200nm～250nm of cured article under ultraviolet ray transmissivity (25 ℃) be below 10%.This is because the cured article of this composition of serving as reasons covers semiconductor device that semiconductor element forms when receiving short wavelength ultraviolet of 200nm～250nm, can prevent from forming material deteriorated of this semiconductor device.For example can, by utilizing the cured article of spectrophotometric determination path length 2.0mm, obtain this ultraviolet ray transmissivity.
This composition is at room temperature or utilizes heating to be cured, but for it is solidified rapidly, is preferably heating.As this Heating temperature, be preferably in the scope of 50～200 ℃.
The cured article that this composition is solidified and obtain, can obtain the rubber-like of synthetic chloroprene rubber shape, example gel shape or softness and have elastic arborescens.This composition can be as binding agent, embedding agent (potting agent), supercoat agent and underfilling (under filler) for electrical/electronic; because transmittance is higher, be therefore especially suitable as binding agent, embedding agent, supercoat agent and the underfilling of semiconductor element for optics.
The present invention also provides a kind of semiconductor device, and it is that cured article with this addition curable silicon-ketone composition of the present invention covers semiconductor element.
Below, with reference to the accompanying drawings of semiconductor device of the present invention, but the present invention is not limited to these.
Fig. 1 means the summary sectional view of an example (being now LED) of semiconductor device of the present invention.
The covering of semi-conductor chip 4 is to carry out by the following method: be coated with above-mentioned addition curable silicon-ketone composition 6 of the present invention, and utilize heating that addition curable silicon-ketone composition 6 is solidified.And, can certainly, under other known conditions of cure, utilize known curing that it is solidified.
And now, from being not easy to be subject to the impact of external stress and doing one's utmost to suppress the viewpoint of adhering to of dust etc., be preferably, addition curable silicon-ketone composition 6 utilizes and solidifies, and forms the hardness of stipulating in Japanese JIS and is expressed as more than 20 cured articles with Shore D.
Due to addition curable silicon-ketone composition of the present invention, can form the cured article that specific refractory power is large, transmittance is high, high to the adhesion of base material, splitting resistance is excellent, ventilation property is low, therefore, use the semiconductor device of the present invention of this composition of the present invention, reliability is excellent, especially be suitable as diode, photodiode (light emitting diode, LED) etc.
[embodiment]
Below, embodiment and comparative example are shown, specifically describe the present invention, but the present invention are not restricted to following embodiment etc.
And the characteristic of addition curable silicon-ketone composition and its cured article is to be measured by following mode.
And the viscosity described in this specification sheets is the value of using rotational viscosimeter to measure at 25 ℃.
[hardness of cured article]
By addition curable silicon-ketone composition is heated and within 3 hours, makes cured article in the Hotaircirculatingoven (circulating hot air oven) of 150 ℃.Use Shore D sclerometer to measure the hardness of this cured article.
[specific refractory power of cured article]
Addition curable silicon-ketone composition is heated 3 hours in the Hotaircirculatingoven of 150 ℃, it is solidified, and the specific refractory power of the cured article that uses Abbe formula refractometer to measure to be made at 25 ℃.And, use visible ray (589 nm) as measuring the light source using.
[transmittance of cured article]
Addition curable silicon-ketone composition is heated 3 hours in the Hotaircirculatingoven of 150 ℃, it is solidified, and measure the transmittance of the wavelength of the cured article (path length 2.0mm) that the is made 400nm at 25 ℃.
[thermotolerance of cured article]
Making the result of gained in above-mentioned [transmittance of cured article] is 100, and this cured article is heated in the Hotaircirculatingoven of 150 ℃ after 500 hours, takes out cured article, measures transmittance and compares to have declined how many with 100.
[crackle after cured article life-time service]
To as Fig. 1, make and with the package that is heating and curing and forms of 150 ℃, 4 hours, be loaded to and take { 40 ℃ (30 minutes), 100 ℃ (30 minutes) } in the heat impact tester in 1 cycle, through 100 all after dates, with zoom microscope, observe package, when cured article exists crackle, be designated as *, during flawless, be designated as 〇, the uncertain △ that is designated as while whether there is crackle.
[permeability of cured article]
Addition curable silicon-ketone composition is heated 3 hours in the Hotaircirculatingoven of 150 ℃, it is solidified, and use oxygen to see through device, the permeability of the cured article that the thickness that mensuration is made is 1mm.
(embodiment 1)
Following composition is mixed equably to the addition curable silicon-ketone composition that preparation viscosity is 3,700mPa.s:
By represented chain organopolysiloxane 50 mass parts of following averaged unit formula:
(C
6H
5S1O
3/2)
0.75[CH
2=CH)(CH
3)SiO]
0.25
{ proterties=solid state (25 ℃), be binding in vinyl on the Siliciumatom all organic groups on being binding on Siliciumatom containing rate=20 % by mole, be binding in phenyl on the Siliciumatom all organic groups on being binding on Siliciumatom containing rate=60 % by mole, weight-average molecular weight=2400} that polystyrene standard converts;
Viscosity is 4,000mPa.s, phenyl methyl polysiloxane 25 mass parts by the represented molecule chain end of following averaged unit formula by dimethyl vinyl silanes oxygen base end-blocking:
((C
6H
5)
2SiO
2/2)
0.3((CH
3)
2SiO
2/2)
0.68((CH
2=CH(CH
3)
2SiO
1/2)0.
02 (2)
(be binding on vinyl on Siliciumatom containing rate=1 % by mole, be binding in phenyl on the Siliciumatom all organic groups on being binding on Siliciumatom containing rate=30 % by mole);
Silicoorganic compound 15 mass parts by represented molecular chain two ends of following general formula by dimethyl hydrogen silyl ethyl capping:
Platinum and 1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex compound (in this composition, the platinum in this complex compound is expressed as the amount of 10ppm with mass unit); And,
As tackifier, by the represented compound that contains SiH 1.0 mass parts of following structural formula:
Measure the characteristic of this addition curable silicon-ketone composition and its cured article.These be the results are shown in to table 1.And, with this addition curable silicon-ketone composition, make LED.The evaluation result of the reliability of these semiconductor devices is shown in to table 1.
(embodiment 2)
Following composition is mixed equably to the addition curable silicon-ketone composition that preparation viscosity is 1,000mPa.s:
By represented chain organopolysiloxane 55 mass parts of following averaged unit formula: (C
6h
5siO
3/2)
0.8[(CH
2=CH) (CH
3)
2siO
1/2]
0.2
{ proterties=solid state (25 ℃), be binding in vinyl on the Siliciumatom all organic groups on being binding on Siliciumatom containing rate=14 % by mole, be binding in phenyl on the Siliciumatom all organic groups on being binding on Siliciumatom containing rate=57 % by mole, weight-average molecular weight=1 that polystyrene standard converts, 600};
Viscosity is 700mPa.s, phenylbenzene dimethyl polysiloxane 25 mass parts by the represented molecule chain end of following averaged unit formula by dimethyl vinyl silanes oxygen base end-blocking:
(C
6H
5)
2SiO
2/2)
0.3((CH
3)
2SiO
2/2)
0.63((CH
3=CH)(CH
3)
2SiO
1/2)
0.07
(be binding on vinyl on Siliciumatom containing rate=3 % by mole, be binding in phenyl on the Siliciumatom all organic groups on being binding on Siliciumatom containing rate=29 % by mole);
Silicoorganic compound 22 mass parts by represented molecular chain two ends of following general formula by dimethyl hydrogen silyl ethyl capping:
Platinum and 1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex compound (in this composition, the platinum in this complex compound is expressed as the amount of 2.5ppm with mass unit); And,
As tackifier, by represented silane compound 2.0 mass parts of following structural formula:
Measure the characteristic of this addition curable silicon-ketone composition and its cured article.These be the results are shown in to table 1.And, with this addition curable silicon-ketone composition, make LED.The evaluation result of the reliability of these semiconductor devices is shown in to table 1.
(comparative example 1)
Following composition is mixed equably to the addition curable silicon-ketone composition that preparation viscosity is 2,460mPa.s:
By represented chain organopolysiloxane 50 mass parts of following averaged unit formula: (C
6h
5siO
3/2)
0.75[(CH
2=CH) (CH
3) SiO]
0.25
{ proterties=solid state (25 ℃), be binding in vinyl on the Siliciumatom all organic groups on being binding on Siliciumatom containing rate=20 % by mole, be binding in phenyl on the Siliciumatom all organic groups on being binding on Siliciumatom containing rate=60 % by mole, weight-average molecular weight=2400} that polystyrene standard converts;
Viscosity is 4,000mPa.s, phenyl methyl polysiloxane 25 mass parts by the represented molecule chain end of following averaged unit formula by dimethyl vinyl silanes oxygen base end-blocking:
((C
6H
5)
2.siO
2/2)
0.3((CH
3)
2SiO
2/2)
0.68((CH
2=CH(CH
3)
2SiO
1/2)
0.02 (2)
(be binding on vinyl on Siliciumatom containing rate=1 % by mole, be binding in phenyl on the Siliciumatom all organic groups on being binding on Siliciumatom containing rate=30 % by mole);
By represented molecular chain two ends of following formula by alkoxy end-capped silicoorganic compound 15 mass parts of dimethyl hydrogen silicon:
H (CH
3)
2siO (C
6h
5)
2siOSi (CH
3)
2h; And,
Platinum and 1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex compound (in this composition, the platinum in this complex compound is expressed as the amount of 30ppm with mass unit).
Measure the characteristic of this addition curable silicon-ketone composition and its cured article.These be the results are shown in to table 1.And, with this addition curable silicon-ketone composition, make LED.The evaluation result of the reliability of these semiconductor devices is shown in to table 1.
(comparative example 2)
Following composition is mixed equably to the addition curable silicon-ketone composition that preparation viscosity is 3,500mPa.s:
By represented chain organopolysiloxane 55 mass parts of following averaged unit formula:
(C
6H
5SiO
3/2)
0.75[(CH
2=CH)(CH
3)
2SiO
1/2]
0.25
{ proterties=solid state (25 ℃), be binding in vinyl on the Siliciumatom all organic groups on being binding on Siliciumatom containing rate=17 % by mole, be binding in phenyl on the Siliciumatom all organic groups on being binding on Siliciumatom containing rate=50 % by mole, weight-average molecular weight=1 that polystyrene standard converts, 600};
Viscosity is 950mPa.s, by represented chain organopolysiloxane 12 mass parts of averaged unit formula:
(C
6H
5SiO
3/2)
0.60[(CH
3)
2HSiO
1/2]
0.40
(be binding in hydrogen atom on the Siliciumatom all groups on being binding on Siliciumatom containing rate=22 % by mole, be binding in phenyl on the Siliciumatom all groups on being binding on Siliciumatom containing rate=33 % by mole, weight-average molecular weight=1 that polystyrene standard converts, 100);
Viscosity is 3, molecular chain two ends of the straight chain shape of 500mPa.s by methyl phenyl silicone 50 mass parts of dimethyl vinyl silanes oxygen base end-blocking (be binding on vinyl on Siliciumatom containing rate=0.20 % by mole, be binding in phenyl on the Siliciumatom all organic groups on being binding on Siliciumatom containing rate=49 % by mole); And,
Platinum and 1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex compound (in this composition, the platinum in this complex compound is expressed as the amount of 2.5ppm with mass unit).
Measure the characteristic of this addition curable silicon-ketone composition and its cured article.These be the results are shown in to table 1.And, with this addition curable silicon-ketone composition, make LED.The evaluation result of the reliability of these semiconductor devices is shown in to table 1.
(comparative example 3)
Following composition is mixed equably to the addition curable silicon-ketone composition that preparation viscosity is 1,700mPa.s:
By represented chain organopolysiloxane 45 mass parts of following averaged unit formula:
(C
6H
5SiO
3/2)
0.75[(CH
2=CH)(CH
3)
2SiO
1/2]
0.25
{ proterties=solid state (25 ℃), be binding in vinyl on the Siliciumatom all organic groups on being binding on Siliciumatom containing rate=17 % by mole, be binding in phenyl on the Siliciumatom all organic groups on being binding on Siliciumatom containing rate=50 % by mole, weight-average molecular weight=1 that polystyrene standard converts, 600};
Viscosity is 3,500mPa.s, straight chain shape molecular chain two ends by methyl phenyl silicone 55 mass parts of dimethyl vinyl silanes oxygen base end-blocking (be binding on vinyl on Siliciumatom containing rate=0.20 % by mole, be binding in phenyl on the Siliciumatom all organic groups on being binding on Siliciumatom containing rate=49 % by mole);
By represented molecular chain two ends of following formula by alkoxy end-capped methyl phenyl silicone 24 mass parts of dimethyl hydrogen silicon:
H (CH
3)
2siO[CH
3(C
6h
5) SiO]
4si (CLI
3)
2h; And,
Platinum and 1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex compound (in this composition, the platinum in this complex compound is expressed as the amount of 2.5ppm with mass unit).
Measure the characteristic of this addition curable silicon-ketone composition and its cured article.These be the results are shown in to table 1.And, with this addition curable silicon-ketone composition, make LED.The evaluation result of the reliability of these semiconductor devices is shown in to table 1.
(comparative example 4)
Make the averaged unit formula of a chain organopolysiloxane of embodiment 1 be:
(C
6H
5SiO
3/2)
0.25(CN
3SiO
3/2)
0.70[(CH
2=CH)(CH
3)
2SiO
l/2]
0.25
{ proterties=solid state (25 ℃), be binding in vinyl on the Siliciumatom all organic groups on being binding on Siliciumatom containing rate=16.7 % by mole, be binding in phenyl on the Siliciumatom all organic groups on being binding on Siliciumatom containing rate=3.3 % by mole, the weight-average molecular weight 2 that polystyrene standard converts, 100}, in addition, prepare similarly to Example 1 the addition curable silicon-ketone composition that viscosity is 2,300mPa.s.
Measure the characteristic of this addition curable silicon-ketone composition and its cured article.These be the results are shown in to table 1.And, with this addition curable silicon-ketone composition, make LED.The evaluation result of the reliability of these semiconductor devices is shown in to table 1.
Table 1
As shown in table 1, the hardness of the cured article of embodiment 1,2 is all abundant, and the specific refractory power of cured article, transmittance and thermotolerance are also good, does not find to crack in cured article.And gas barrier property (gas barrier property) is also excellent.And, because producing, do not peel off catalyzer poison, and higher to the adhesion of substrate.
On the other hand, in comparative example 2～4, although hardness is abundant, find to crack; And in the uncertain comparative example 1 that whether has a crackle, thermotolerance is also poor.And the ventilation property of the arbitrary example in comparative example 1～4 is all higher, easily corrode substrate.And, because catalyzer poison produces, peel off.
And, the composition of (C) of the present invention as being equivalent to composition, comparative example 1 contains and does not comprise 2 compositions with the Si-H key of ethene bond; The allotment amount that comparative example 2 contains each unit does not all meet (A) of the present invention composition and (B) composition of any definition in composition, replaces (B) composition; Comparative example 3 does not comprise the composition that is equivalent to (B) of the present invention composition, and as being equivalent to the composition of (C) composition, containing not comprise 2 compositions with the Si-H key of ethene bond; And, the composition of (A) of the present invention as being equivalent to composition, comparative example 4 contain phenyl (aryl) containing rate lower than the composition of 10 % by mole, and as the composition that is equivalent to (C) composition, contain and do not comprise 2 compositions with the Si-H key of ethene bond.
According to above situation, can confirm following item: if addition curable silicon-ketone composition of the present invention, owing to forming the cured article that specific refractory power is large, transmittance is high, high to the adhesion of base material, splitting resistance is excellent, ventilation property is low, be therefore suitable for various optical applications etc.
In the above-described embodiments; to use addition curable silicon-ketone composition of the present invention as the embedding agent of semiconductor element; but addition curable silicon-ketone composition of the present invention is because transmittance is high; therefore; especially be suitable as in addition binding agent, supercoat agent and the underfilling etc. of semiconductor element for optics; and, binding agent, embedding agent, supercoat agent and the underfilling etc. that can certainly use as electrical/electronic.
In addition, the present invention is not limited to above-mentioned embodiment.Above-mentioned embodiment is illustration, has the structure identical with technological thought essence described in claims of the present invention and brings into play the technical scheme of same function effect, is all included in technical scope of the present invention.
Claims (12)
1. an addition curable silicon-ketone composition, is characterized in that, it contains:
(A) by represented organopolysiloxane 100 mass parts of following averaged unit formula (1):
(R
1SiO
3/2)
a1(R
1 2SiO
2/2)
b1(R
1 3SiO
1/2)
c1(X
1O
1/ 2)
d1 (1)
In formula (1), R
1can be identical or different, and for replacing or unsubstituted monovalence alkyl, and, R
10.1～50 % by mole be thiazolinyl, R
110 % by mole be above aryl; X
1for hydrogen atom or alkyl; A1 is that 0.25～1, b1 is that 0～0.75, c1 is that 0～0.3, d1 is 0～0.1, and a1+b1+c1+d1=1,
(B) by represented organopolysiloxane 1～500 mass parts of following averaged unit formula (2):
(R
2SiO
3/2）
a2)(R
2 2SiO
2/2)
b2(R
2 3SiO
1/2)
c2(X
2O
1/ 2)
d2 (2),
In formula (2), R
2can be identical or different, and for replacing or unsubstituted monovalence alkyl, and, R
20.001～20 % by mole be thiazolinyl, R
210 % by mole be above aryl; X
2for hydrogen atom or alkyl; A2 is that 0～0.1, b2 is that 0.5～0.995, c2 is that 0.005～0.5, d2 is 0～0.1, and a2+b2+c2+d2=1,
(C) in represented 1 molecule of following general formula (3), having the organic hydrogen polysiloxanes of at least 2 Si-H keys, with respect to (A)+(B) become subtotaling 100 mass parts, is the amount of 1～200 mass parts:
In formula (3), R
3for any in hydrogen atom, alkyl, aryl and haloalkyl, each R between repeating unit and in repeating unit
3can be identical or different; M is more than 0 integer,
And, (D) promote the hydrosilylation reactions catalyzer of the curing amount of this composition.
2. addition curable silicon-ketone composition as claimed in claim 1, wherein, in aforementioned (A) composition, the R in aforementioned averaged unit formula (1)
1aryl containing rate be more than 30 % by mole.
3. addition curable silicon-ketone composition as claimed in claim 1, wherein, in aforementioned (B) composition, the R in aforementioned averaged unit formula (2)
2aryl containing rate be more than 20 % by mole.
4. addition curable silicon-ketone composition as claimed in claim 2, wherein, in aforementioned (B) composition, the R in aforementioned averaged unit formula (2)
2aryl containing rate be more than 20 % by mole.
5. addition curable silicon-ketone composition as claimed in claim 1, wherein, in aforementioned (C) composition, is binding on the R on Siliciumatom in aforementioned formula (3)
3with 30 % by mole of the total of H be phenyl below.
6. addition curable silicon-ketone composition as claimed in claim 2, wherein, in aforementioned (C) composition, is binding on the R on Siliciumatom in aforementioned formula (3)
3with 30 % by mole of the total of H be phenyl below.
7. addition curable silicon-ketone composition as claimed in claim 3, wherein, in aforementioned (C) composition, is binding on the R on Siliciumatom in aforementioned formula (3)
3with 30 % by mole of the total of H be phenyl below.
8. addition curable silicon-ketone composition as claimed in claim 4, wherein, in aforementioned (C) composition, is binding on the R on Siliciumatom in aforementioned formula (3)
3with 30 % by mole of the total of H be phenyl below.
9. the addition curable silicon-ketone composition as described in any one in claim 1 to 8, wherein, in aforementioned (C) composition, the m in aforementioned formula (3) is the integer below 20.
10. the addition curable silicon-ketone composition as described in any one in claim 1 to 8, wherein, solidifies and the specific refractory power that is formed at 25 ℃ in the visible ray of 589nm is more than 1.5 cured article.
11. addition curable silicon-ketone compositions as described in any one in claim 1 to 8, wherein, solidify and the transmittance that is formed at 25 ℃ is more than 80% cured article.
12. 1 kinds of semiconductor devices, is characterized in that, its cured article by the addition curable silicon-ketone composition described in any one in claim 1 to 8 covers semiconductor element.
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|---|---|---|---|
| JP2012170903A JP2014031394A (en) | 2012-08-01 | 2012-08-01 | Addition curable silicone composition, and semiconductor apparatus comprising semiconductor element coated with cured material of said composition |
| JP2012-170903 | 2012-08-01 |
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|---|---|
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| CN104875496A (en) * | 2014-02-27 | 2015-09-02 | 精工爱普生株式会社 | Joining body, joining method and manufacturing apparatusof, ink jet head unit, and ink jet type recording apparatus |
| WO2015192654A1 (en) * | 2014-06-17 | 2015-12-23 | 广州慧谷化学有限公司 | Curable organopolysiloxane composition and semiconductor device |
| CN107001769A (en) * | 2014-12-08 | 2017-08-01 | 信越化学工业株式会社 | The optical semiconductor device of the die bond material that heat-curing type silica composition, said composition are constituted and the solidfied material with the die bond material |
| CN110272627A (en) * | 2019-07-24 | 2019-09-24 | 杭州之江新材料有限公司 | A kind of silicon gel of high refractive index and preparation method thereof |
| CN110862802A (en) * | 2018-08-28 | 2020-03-06 | 信越化学工业株式会社 | Addition-curable silicone composition and semiconductor device |
| CN111117256A (en) * | 2018-10-30 | 2020-05-08 | 信越化学工业株式会社 | Addition-curable silicone resin composition, cured product thereof, and optical semiconductor device |
| CN112480681A (en) * | 2019-09-12 | 2021-03-12 | 信越化学工业株式会社 | Addition-curable silicone composition, cured product thereof, light-reflecting material, and optical semiconductor device |
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| CN107001769A (en) * | 2014-12-08 | 2017-08-01 | 信越化学工业株式会社 | The optical semiconductor device of the die bond material that heat-curing type silica composition, said composition are constituted and the solidfied material with the die bond material |
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| CN110862802B (en) * | 2018-08-28 | 2023-04-07 | 信越化学工业株式会社 | Addition-curable silicone composition and semiconductor device |
| CN111117256A (en) * | 2018-10-30 | 2020-05-08 | 信越化学工业株式会社 | Addition-curable silicone resin composition, cured product thereof, and optical semiconductor device |
| CN110272627A (en) * | 2019-07-24 | 2019-09-24 | 杭州之江新材料有限公司 | A kind of silicon gel of high refractive index and preparation method thereof |
| CN112480681A (en) * | 2019-09-12 | 2021-03-12 | 信越化学工业株式会社 | Addition-curable silicone composition, cured product thereof, light-reflecting material, and optical semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20140017447A (en) | 2014-02-11 |
| JP2014031394A (en) | 2014-02-20 |
| TW201412878A (en) | 2014-04-01 |
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Application publication date: 20140212 |