CN106947258A - Addition curing organosilicon resin composition and semiconductor device - Google Patents
Addition curing organosilicon resin composition and semiconductor device Download PDFInfo
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- CN106947258A CN106947258A CN201611196873.XA CN201611196873A CN106947258A CN 106947258 A CN106947258 A CN 106947258A CN 201611196873 A CN201611196873 A CN 201611196873A CN 106947258 A CN106947258 A CN 106947258A
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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
- C08G77/06—Preparatory processes
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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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The present invention relates to addition curing organosilicon resin composition and semiconductor device, it is therefore an objective to provides that low-temperature characteristics is good, can form the semiconductor device with high reliability of the addition curable silicon composition of the excellent solidfied material of temperature change patience and the solidfied material packaging semiconductor with said composition.The addition curing organosilicon resin composition is contained with specified quantitative respectively（A）Following formula（1）Shown branched organopolysiloxanes,（B）Following formula（2）Shown organopolysiloxane,（C）Intramolecular have at least two hydrosilyl organopolysiloxane and（D）Hydrosilylation catalysts.Formula（1）In formula, R1、R2, a, b, c etc. definition it is identical with specification, formula（2）（R2 3SiO1/2）r（R2 2SiO2/2）S（R2SiO3/2）T（SiO4/2）U （2）In formula, R2, r, s, t, u etc. definition it is identical with specification.
Description
Technical field
The present invention relates to addition curable silicon composition, more particularly to containing the siloxane branches with long chain length
The branched organopolysiloxanes containing alkenyl（Difference shape オ Le ガ ノ Port リ シ ロ キ サ Application）Addition curable organosilicon combination
Thing and the semiconductor device that semiconductor is encapsulated using its solidfied material.
Background technology
Addition curable organic siliconresin is excellent due to heat-resisting, light resistance, fast solidity etc., therefore conduct is used for all the time
The encapsulating material of the semiconductor elements such as encapsulation LED is used.For example, in patent document 1, describing for the heat with PPA etc.
The LED packagings that plastic resin makes show the addition curable organic siliconresin of high bonding force.In addition, in patent document 2,
Describe the method for optical-semiconductor element encapsulation by the compression forming of addition curable organosilicon resin composition.
So, addition curable organic siliconresin is used extensively, in general manner as semiconductor sealing material, but it is special
Property is still unsatisfactory.Especially, LED encapsulation material is not disposed only on temperature caused by the ON/OFF by optical semiconductor device
Under the internal pressure of change, but also it is placed under the external pressure of the change of gas epidemic disaster etc., therefore except heat-resisting, light resistance
In addition, cold resistance is also important.However, conventional addition curable organic siliconresin is not abundant in terms of low-temperature characteristics
, the problem of cracking such with the pressure for being unable to bearing temperature change.
As for improving a means of low-temperature characteristics, it is known that make the silicone chains of straight-chain（シ リ コ ー ン Lock）Middle tool
It is effective to have branched structure, and various researchs are completed for its manufacture method（Patent document 1,2 and 3）.But, using acid
Catalyst, base catalyst will contain such R3SiO1/2Unit ［ M units ］ and RSiO3/2The hydrolysable silanes of unit ［ T unit ］
Be condensed/method of equilibrating in, it is impossible to independently control the chain length of main chain and side chain, therefore, it is difficult to obtain required structure
Siloxanes.
【Prior art literature】
【Patent document】
【Patent document 1】Japanese Unexamined Patent Publication 2006-256603 publications
【Patent document 2】Japanese Unexamined Patent Publication 2006-93354 publications
【Patent document 3】Japanese Unexamined Patent Publication 2002-348377 publications
【Patent document 4】Japanese Unexamined Patent Publication 2001-163981 publications
【Patent document 5】Japanese Unexamined Patent Publication 2000-351949 publications.
The content of the invention
The present invention is in view of above-mentioned problem and the invention made, its object is to provide, low-temperature characteristics is good, can form temperature
Degree changes the addition curable silicon composition of the excellent solidfied material of patience and encapsulates half using the solidfied material of said composition
The semiconductor device with high reliability of conductor element.
That is, the present invention is provided containing following（A）~（D）The addition curable silicon composition of composition.
Addition curing organosilicon resin composition, it contains：
（A）Following formula（1）Shown branched organopolysiloxanes
（In formula, R1Independently of one another it is selected from the substituted or unsubstituted saturated hydrocarbyl or carbon number 6 of carbon number 1~12
Group in~12 substituted or unsubstituted aromatic hydrocarbyl, R2Independently of one another it is selected from the substitution of carbon number 1~12
Or substituted or unsubstituted aromatic hydrocarbyl, the alkene of carbon number 2~10 of unsubstituted saturated hydrocarbyl or carbon number 6~12
Group in base, each R1、R2Can be with identical, can also be different, wherein R2In at least two be alkenyl, a for 2~100 it is whole
Number, b be 5~100 integer, c be 5~100 integer, 0.03≤a/ (a+b) ＜ 1.0,（R1 2R2SiO1/2）The quantity of unit/
（R2SiO3/2）The arrangement of the siloxane chain of quantity≤2, a of unit, b and c can be random, or block）；
（B）Following formula（2）Shown organopolysiloxane
（R2 3SiO1/2）r（R2 2SiO2/2）s（R2SiO3/2）t（SiO4/2）u （2）
（In formula, R2Definition it is same as described above, R2In at least two be alkenyl, r is 0~100 integer, and s is 0~300
Integer, t is 0~200 integer, and u is 0~200 integer, 1≤t+u≤400,2≤r+s+t+u≤800）,
Should（B）The amount of composition relative to（A）The mass parts of composition 100 are 5~900 mass parts；
（C）There is at least two hydrosilyl in intramolecular（ヒ De ロ シ リ Le bases）Organopolysiloxane,
Should（C）The amount of composition is to make（C）The quantity of hydrosilyl in composition relative to（A）Composition and（B）In composition
The sum of alkenyl is 0.4~4.0 amount；With
（D）Hydrosilylation catalysts（ヒ De ロ シ リ Le catalyst）
Should（D）The amount of composition is for making hydrosilylation reactions enter the enough amounts of behavior.
According to the present invention, by make volume contain compared with the siloxanes chain length of main chain it is fully long it is side chain, containing alkenyl
Branched organopolysiloxanes with it is specific other into subassembly, the straight chain of the chain length with having used the main chain with same degree
The situation of shape organopolysiloxane is compared, the reduction of the glass transition temperature of solidfied material, resistance to anti-thread breakage etc. to be enhanced.
The simple declaration of accompanying drawing
The storage elastic modulus of the solidfied material of [Fig. 1] embodiment 1 (solid line) and comparative example 1 (dotted line)（Zhu KURA spring rates）Curve
The curve map of figure and Tan δ.
Embodiment
The present invention explained in detail below.
（A）Side chain polysiloxane
One of feature as the present invention（A）Side chain polysiloxane is as shown in following formula.
（A）Following formula（1）Shown branched organopolysiloxanes
（In formula, R1Independently of one another it is selected from the substituted or unsubstituted saturated hydrocarbyl or carbon number 6 of carbon number 1~12
Group in~12 substituted or unsubstituted aromatic hydrocarbyl, R2Independently of one another it is selected from the substitution of carbon number 1~12
Or substituted or unsubstituted aromatic hydrocarbyl, the alkene of carbon number 2~10 of unsubstituted saturated hydrocarbyl or carbon number 6~12
Group in base, each R1、R2Can be with identical, can also be different, wherein R2In at least two be alkenyl, a for 2~100 it is whole
Number, b be 5~100 integer, c be 5~100 integer, 0.03≤a/ (a+b) ＜ 1.0,（R1 2R2SiO1/2）The quantity of unit/
（R2SiO3/2）The arrangement of the siloxane chain of quantity≤2, a of unit, b and c can be random, or block）.
A be 2~100 integer, preferably 2~75 integer, more preferably 2~50 integer, b for 5~100 it is whole
Number, preferably 5~75 integer, more preferably 10~50 integer, c be 5~100 integer, preferably 5~75 integer,
More preferably 10~50 integer.（R1 2R2SiO1/2）The quantity of unit/（R2SiO3/2）Quantity≤2, a of unit, b siloxanes
Chain（A, b シ ロ キ サ ン Lock）Arrangement can be random, or block.
In formula（1）In, 0.03≤a/（A+b）＜ 1.0, preferably 0.09≤a/（A+b）≤0.9.
R1Independently of one another selected from carbon number 1~12 substituted or unsubstituted saturated hydrocarbyl or carbon number 6~
Group in 12 substituted or unsubstituted aromatic hydrocarbyl, as the example of saturated hydrocarbyl, can specifically enumerate methyl, second
The alkyl of base, propyl group, butyl, octyl group etc.；The cycloalkyl of cyclopenta, cyclohexyl etc.；Part or all and carbon of these groups
The hydrogen atom of atomistic binding replaced by the halogen atoms such as fluorine, bromine, chlorine or cyano group obtained from group, such as trifluoro propyl, chlorine third
The halo monovalent hydrocarbon of base etc.；The cyanoalkyl of beta-cyano ethyl, γ-cyanopropyl etc., 3- methacryloxypropyls, 3-
Glycidyl epoxide propyl group, 3- mercaptopropyis, 3- aminopropyls.Wherein, preferably methyl, cyclohexyl etc., particularly preferred methyl.
In addition, as the example of aromatic hydrocarbyl, the aryl of phenyl, tolyl, naphthyl etc., benzyl, phenethyl, phenylpropyl can be enumerated
Deng aralkyl etc..Can also be part or all of hydrogen atom with carbon atom bonding of these groups by halogen such as fluorine, bromine, chlorine
Group obtained from plain atom or cyano group substitution.Wherein, preferably phenyl, tolyl, particularly preferred phenyl.R1In at least one
The preferably aromatic hydrocarbyl of carbon number 6~12.
R2It is former selected from carbon number 1~12, preferably 1~8 substituted or unsubstituted saturated hydrocarbyl, carbon independently of each other
Subnumber 6~12, preferably 6~10 substituted or unsubstituted aromatic hydrocarbyl and carbon number 2~10, preferably 2~8 alkenyl
In group.Saturated hydrocarbyl and aromatic hydrocarbyl can be enumerated and for above-mentioned R1Illustrated group is identical group.Make
For alkenyl, vinyl, pi-allyl, acrylic, hexenyl and styryl etc., preferably vinyl and allyl can be enumerated
Base, particularly preferably vinyl.
It should illustrate,（A）In composition, in the sum with whole substituents of silicon atom bonding, 1 valency aromatic hydrocarbyl
Quantity ratio preferably more than 3%, particularly preferred more than 5%, preferably less than 90%, particularly preferred less than 80%.If
In the range of being somebody's turn to do, then（A）The branched organopolysiloxanes of composition are high index of refraction, and gas permeability is low, therefore said composition can be suitable
Ground is used for encapsulation purposes of semiconductor device etc..
（A）Branched organopolysiloxanes can be by making following formula（4）Shown organopolysiloxane and type siloxane, example
Such as following formula（5）It is shown, there is alkoxysilyl or hydroxyl silicyl in two ends（Silanol group）Organic poly- silicon
Oxygen alkane cocondensation, then passes through silane, such as following formula（6）The shown silane compound containing hydrolization group carries out end-capped
To manufacture,
（In formula, R1、R2, c it is same as described above, R3For hydrogen atom or the saturated hydrocarbyl of carbon number 1~6）
（In formula, R2、R3Same as described above, b ' is more than 1 and below b, and b is same as described above）
（In formula, R1、R2Same as described above, X is halogen atom or R3O- ［ R3It is same as described above ］ shown in group）.
In formula（4）In, R3For the group in the saturated hydrocarbyl selected from hydrogen atom or carbon number 1~6, first can be enumerated
Base, ethyl, propyl group, butyl, isopropyl, hexyl, cyclohexyl.Wherein, preferably methyl, ethyl etc., particularly preferably methyl.
Above-mentioned formula（4）As long as shown, to have dialkoxy in single end organopolysiloxane is closed with known method
Into.For example there are following methods：As Japanese Unexamined Patent Application 59-78236 publications, metal silanolate is regard as initiation
Agent, ring-opening polymerisation is carried out by ring-type silicon compound, after making end with acid termination, the method for making it be reacted with trialkoxy silane,
Or as Japanese Unexamined Patent Publication 7-224168 publications, using silanol compound as initiator, using pentacoordinate silicon as
Catalyst, ring-type silicon compound is polymerize, and makes the method etc. of end and trialkoxy silane reaction.
（B）Organosiloxane
（B）Organosiloxane is by following formula（2）It is shown.
（R2 3SiO1/2）r（R2 2SiO2/2）s（R2SiO3/2）t（SiO4/2）u （2）
（In formula, R2Definition it is same as described above, R2In at least two be alkenyl, r is 0~100 integer, and s is 0~300
Integer, t is 0~200 integer, and u is 0~200 integer, 1≤t+u≤400,2≤r+s+t+u≤800）
Wherein, r is 0~100 integer, preferably 0~75 integer, and then preferably 0~50 integer, s for 0~300 it is whole
Number, preferably 0~200 integer, and then preferably 0~100 integer, t is 0~200 integer, preferably 0~100 it is whole
Number, and then preferably 0~50 integer, u is 0~200 integer, preferably 0~100 integer, and then preferably 0~50
Integer, 1≤t+u≤400, preferably 1≤t+u≤200, more preferably 1≤t+u≤100,2≤r+s+t+u≤800, preferably
2≤r+s+t+u≤400, more preferably 2≤r+s+t+u≤200.
R2Example be such as above-mentioned（A）R in composition2Example as illustrated.
It should illustrate,（B）In composition, in the sum with whole substituents of silicon atom bonding, 1 valency aromatic hydrocarbyl
Quantity ratio preferably more than 3%, particularly preferred more than 5%, preferably less than 90%, particularly preferred less than 80%.If
In the range of being somebody's turn to do, then（B）The branched organopolysiloxanes of composition are high index of refraction, and gas permeability is low, and with（A）Composition phase well
Hold, the solidfied material transparency of the composition containing it is excellent, and with excellent mechanical strength.Therefore, said composition can be closed
Suitablely for encapsulation purposes of semiconductor device etc..
（B）The compounding amount of composition relative to（A）The mass parts of composition 100 are 5~900 mass parts, are preferably 10~800 mass
Part and then preferably 20~600 mass parts.Contained with the amount for forming above range（B）During composition, the solidification of rubber-like can obtain
Thing, therefore preferably.
（C）There is the organopolysiloxane of at least two hydrosilyl in intramolecular
（C）The organopolysiloxane for having at least two hydrosilyl in intramolecular is not particularly limited, but preferably following formula
（3）Shown material.
（R3 3SiO1/2）r’（R3 2SiO2/2）s’（R3SiO3/2）t’（SiO4/2）u’ （3）
（In formula, R3For hydrogen atom, the substituted or unsubstituted saturated hydrocarbyl of carbon number 1~12 or taking for carbon number 6~12
Generation or unsubstituted aromatic hydrocarbyl, but R3In at least two be hydrogen atom, r ' be 0~100 integer, s ' be 0~300 it is whole
Number, t ' is 0~200 integer, and u ' is 0~200 integer, 2≤r '+s '+t '+u '≤800）.
Wherein, the substitution of the substituted or unsubstituted saturated hydrocarbyl or carbon number 6~12 of carbon number 1~12 or do not take
The aromatic hydrocarbyl in generation can be for R1Illustrated group.In R3In, at least two is hydrogen atom, it is other be preferably methyl or
Phenyl.R ' is 0~100 integer, preferably 0~75 integer, and then preferably 0~50 integer, and s ' is 0~300 integer, excellent
Elect as 0~200 integer, and then preferably 0~100 integer, t ' is 0~200 integer, preferably 0~100 integer,
And then preferably 0~50 integer, u ' be 0~200 integer, preferably 0~100 integer, so preferably 0~50 it is whole
Number, the preferably scope of the scope of 2≤r '+s '+t '+u '≤800, more preferably 2≤r '+s '+t '+u '≤400, Jin Eryou
Select the scope of 2≤r '+s '+t '+u '≤200.
In addition,（C）The ratio of the quantity of the 1 valency aromatic hydrocarbyl with silicon atom bonding in whole substituents of composition is excellent
Elect more than 3%, and then preferably more than 5%, less than 80% as.If in the range of this, then（C）The organopolysiloxane of composition
It is not only that high index of refraction or gas permeability are low, Er Qieyu（A）Composition,（B）Composition is compatible well, therefore forms the saturating of solidfied material
Bright property also excellent composition.It therefore, it can be suitably used for encapsulation purposes of semiconductor device etc..
As（C）Composition in intramolecular there is the addition of the organopolysiloxane of at least two hydrosilyl to be
Relative to（A）Composition and（B）The sum of the alkenyl of composition, make（C）The quantity of the hydrosilyl of composition is 0.4~4.0
Amount, preferably 0.6~2.0 amount, and then preferably 0.8~1.6 amount.During less than 0.4, SiH bases are not enough, therefore become solidification
It is bad, from without preferred, if it exceeds 4.0, then it is easy to produce the side reaction by dehydrogenation caused by residual Si H bases etc., therefore not
It is preferred that.
（D）Hydrosilylation catalysts
As long as catalyst of the catalyst with the ability that can make hydrosilylation reactions progress, is not particularly limited.Its
In, it is preferably selected from the catalyst of platinum group metal monomer and platinum group metal compounds.Such as platinum can be enumerated（Contain platinum black）, chlorine
Change platinum-olefin complex, the platinum-carbonyl ligand compound of platinum, chloroplatinic acid, platinum-divinylsiloxanes complex etc.
Platinum catalyst, palladium catalyst, rhodium catalyst of thing etc. etc..These catalyst can be used alone, and can also combine two or more
Use.Wherein it is particularly preferably platinum-olefin complex of chloroplatinic acid and platinum-divinylsiloxanes complex etc..
（D）The compounding amount of composition is preferably catalytic amount.As long as catalytic amount can promote the amount of hydrosilylation reactions
, suitably adjusted according to desired curing rate.For example, platinum metal catalysts when, examined from the angle of reaction speed
Consider, to be scaled in terms of the quality criteria of platinum group metal atom, preferably relative to above-mentioned（A）~（C）The mass of total 100 of composition
Part is 1.0 × 10-4The amount of~1.0 mass parts, and then more preferably relative to above-mentioned（A）~（C）The mass parts of total 100 of composition
For 1.0 × 10-3~1.0 × 10-1The amount of mass parts.
Any condition
The solidification compound of the present invention is except above-mentioned（A）~（D）Beyond composition, can also as needed containing it is other into
Divide, such as fluorophor, inorganic filling material, bonding agent, curing inhibitors.Hereinafter, illustrated for each composition.
［ fluorophor ］
Fluorophor is not particularly limited, as long as using known fluorophor.For example, it is preferable to be to absorb semiconductor element
Part, the light that particularly semiconductor light-emitting-diode using nitride semiconductor as luminescent layer is sent, wavelength convert is different
The material of the light of wavelength.As such fluorophor, such as being preferably selected from by the nitrogen of the lanthanide series primary activation Eu, Ce
The element primary activation of compound system fluorophor/oxynitride system fluorophor, the group of the lanthanides using Eu etc., Mn etc. transition metal system
Alkaline-earth metal halogen apatite fluorescent body, alkaline-earth metal boric acid halogen fluorophor, alkali earth metal aluminate fluorophor, alkaline-earth metal
Silicate phosphor, alkaline earth sulfide fluorophor, alkaline earth metal thiogallate fluorophor, alkaline-earth metal nitridation luminescence from silicon
Body, germanate fluorophor or by the terres rares chlorate MClO 3 fluorescent substance of Ce etc. lanthanide series primary activation, terres rares silicate
Fluorophor or by the organic and organic coordination compounds fluorophor of Eu etc. lanthanide series primary activation, Ca-Al-Si-O-N systems
More than a kind in oxynitride glass fluorophor etc..
As by the nitride fluorophor of Eu, Ce etc. lanthanide series primary activation, M can be enumerated2Si5N8：Eu（M is
It is at least one kind of in Sr, Ca, Ba, Mg, Zn）.Furthermore it is possible to enumerate MSi7N10：Eu、M1.8Si5O0.2N8：Eu and
M0.9Si7O0.1N10：Eu（M is at least one kind of in Sr, Ca, Ba, Mg, Zn）Deng.
As by the oxynitride system fluorophor of Eu, Ce etc. lanthanide series primary activation, MSi can be enumerated2O2N2：Eu
（M is at least one kind of in Sr, Ca, Ba, Mg, Zn）.
It is used as the alkaline-earth metal halogen apatite of the element primary activation of group of the lanthanides, the Mn using Eu etc. etc. transition metal system
Fluorophor, can enumerate M5（PO4）3X：R（M is at least one kind of in Sr, Ca, Ba, Mg, Zn.X is selected from F, Cl, Br, I
In it is at least one kind of.R is any more than a kind of Eu, Mn, Eu and Mn）.
As alkaline-earth metal boric acid halogen fluorophor, M can be enumerated2B5O9X：R（M is in Sr, Ca, Ba, Mg, Zn
It is at least one kind of.X is at least one kind of in F, Cl, Br, I.R is any more than a kind of Eu, Mn, Eu and Mn）.
As alkali earth metal aluminate fluorophor, SrAl can be enumerated2O4：R、Sr4Al14O25：R、CaAl2O4：R、
BaMg2Al16O27：R、BaMg2Al16O12：R and BaMgAl10O17：R（R is any more than a kind of Eu, Mn, Eu and Mn）.
As alkaline earth sulfide fluorophor, La can be enumerated2O2S：Eu、Y2O2S：Eu and Gd2O2S：Eu etc..
As by the terres rares chlorate MClO 3 fluorescent substance of Ce etc. lanthanide series primary activation, it can enumerate by Y3Al5O12：
Ce、（Y0.8Gd0.2）3Al5O12：Ce、Y3（Al0.8Ga0.2）5O12：Ce and（Y, Gd）3（Al, Ga）5O12The YAG that represents of composition formula
It is fluorophor.In addition, also having Y part or all of Tb that substituted for Tb, Lu etc.3Al5O12：Ce、Lu3Al5O12：Ce etc..
In other fluorophor, ZnS can be enumerated：Eu、Zn2GeO4：Mn、MGa2S4：Eu（M be selected from Sr, Ca, Ba, Mg,
It is at least one kind of in Zn.X is at least one kind of in F, Cl, Br, I）Deng.
Above-mentioned fluorophor can replace Eu and contain and be selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, Ti needed for
In more than a kind or can except Eu, also containing a kind in Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, Ti with
On.
Ca-Al-Si-O-N systems oxynitride glass fluorophor is the fluorophor using oxynitride glass as fertile material,
In the oxynitride glass, represented with a mole %, by CaCO3It is 20~50 moles of %, Al to be converted into CaO2O3Rubbed for 0~30
Your %, SiO is that 25~60 moles of %, AlN are that 5~50 moles of %, rare-earth oxide or transition metal oxide are 0.1~20 to rub
Your %, 5 kinds of compositions add up to 100 moles of %.It should illustrate, in using oxynitride glass as the fluorophor of fertile material,
It is preferred that nitrogen content is below 15wt%, preferably in addition to rare-earth oxide ion, to form other terres rares of sensitizer
Element ion is as rare-earth oxide, and the content using 0.1~10 mole of % scope in fluorescent glass contains as coactivator
Have.
Alternatively, it is also possible to use the fluorophor beyond above-mentioned fluorophor, i.e., the fluorophor with same performance, effect.
The compounding amount of fluorophor relative to the composition beyond fluorophor, for example（A）~（D）The mass parts of composition 100, be preferably
0.1~2000 mass parts, more preferably 0.1~100 mass parts.It regard the solidfied material of the present invention as the wavelength convert containing fluorophor
During film, the content for preferably making fluorophor is 10~2000 mass parts.In addition, fluorophor preferably has more than 10nm average grain
Footpath, more preferably 10nm~10 μm, and then preferably 10nm~1 μm.Above-mentioned average grain diameter can be measured with particle size distribution, institute
Particle size distribution is stated to make use of using シ ー ラ ス（CIRRUS）The laser diffractometry of laser determination device etc..
［ inorganic filling material ］
As inorganic filling material, can enumerate for example silica, fume colloidal silica, fumed titanium dioxide, aluminum oxide,
Calcium carbonate, calcium silicates, titanium dioxide, di-iron trioxide and zinc oxide etc..They can be used alone, or can be by 2 kinds
Share above.The compounding amount of inorganic filling material is not particularly limited, with（A）~（D）Every 100 mass parts of total of composition are 20
Below mass parts, the scopes of preferably 0.1~10 mass parts is suitably compounded.
［ bonding agent ］
The solidification compound of the present invention is preferred containing bonding agent as needed in order to assign cohesive.As bonding agent,
Can enumerate for example in a molecule has that at least two kinds of, preferably 3 kinds selected from hydrogen atom, alkenyl, alcoxyl with silicon atom bonding
The organosiloxane oligomers of functional group in base, epoxy radicals.The preferred silicon atom number of the organosiloxane oligomers is 4~50
It is individual, more preferably 4~20.In addition, as bonding agent, following formulas can be used（7）Shown organic epoxide silicyl
Modified isocyanurate compound and its hydrolytic condensate（Organic siloxane modified isocyanurate compound）.
Above-mentioned formula（7）In, R4It is independently of one another following（8）Shown organic group contains aliphatic unsaturated bond
Monovalent hydrocarbon.
R5For hydrogen atom or the monovalent hydrocarbon of carbon number 1~6, k is 1~6 integer, preferably 1~4 integer.
The compounding amount of bonding agent relative to（A）~（D）The mass parts of total 100 of composition are preferably below 10 mass parts,
More preferably 0.1~8 mass parts, particularly preferably 0.2~5 mass parts.If compounding amount is below above-mentioned higher limit, solidify
Thing hardness is uprised, and can also suppress surface viscosity.
［ curing inhibitors ］
The solidification compound of the present invention is preferred to control reactivity, improve storage stability containing curing inhibitors.As
Curing inhibitors, can enumerate selected from Triallyl isocyanurate, alkyl maleates, acetylene alcohols and its is silane-modified
Compound in thing and silicone-modified thing, hydrogen peroxide, tetramethylethylenediamine, BTA and their mixture.Solidification
The compounding amount of inhibitor relative to（A）~（D）Every 100 mass parts of total of composition, preferably 0.001~1.0 mass parts are more excellent
Elect 0.005~0.5 mass parts as.
［ other additives ］
In the solidification compound of the present invention, in addition to mentioned component, other additives can be compounded.It is used as other additions
Agent, can enumerate such as antiaging agent, free radical inhibitors（ラ ジ カ Le forbids agent）, fire retardant, surfactant, ozone-resistant
Degradation, light stabilizer, thickener, plasticizer, antioxidant, heat stabilizer, conductivity-imparting agent, antistatic agent, radioactive ray
Interdict agent, nucleator, phosphorus system peroxide decomposer, lubricant, pigment, matal deactivator, physical property conditioning agent, organic solvent
Deng.These any conditions can be used alone one kind, can also be used in combination two or more.
The present invention solidification compound simplest embodiment be by（A）Composition,（B）Composition,（C）Composition and
（D）The composition of composition composition.Preferably by（A）Composition,（B）Composition,（C）Composition,（D）The group of composition and fluorophor composition
Compound.Especially, in order to obtain, with high transparent solidfied material, not containing the inorganic fill of silica filler material etc.
Material is suitable.The example of the inorganic filling material is as described above.
The preparation method of the solidification compound of the present invention is not particularly limited, as long as being prepared according to known method
.For example, it is possible to use arbitrary method will（A）Composition,（B）Composition,（C）Composition and（D）Composition is mixed to make
It is standby.Or, will using arbitrary method（A）、（B）、（C）、（D）Composition and fluorophor or（A）、（B）、（C）、（D）Composition and
It is prepared by any condition mixing.For example can be by being put into commercially available mixer（THINKY CONDITIONING
MIXER（（Strain）シ ン キ ー systems）Deng）In, with 1~5 minute or so, equably mixed and to be prepared.
The method of the solidification compound solidification of the present invention is not particularly limited, as long as entering according to known method
Row.For example, can solidify 1~12 hour or so at 60~180 DEG C.In particular it is preferred at 60~150 DEG C by progressively solid
Change（ステップキュア）Solidified.More preferably in progressively solidifying, by following 2 stages.First, by curability group
Compound is heated 0.5~2 hour at a temperature of 60~100 DEG C, fully makes its deaeration.Then, make solidification compound 120~
It is heating and curing at a temperature of 180 DEG C 1~10 hour.By passing through these stages, in the case that solidfied material is thick, it can also fill
Divide solidification, do not have alveolate generation, there can be water white transparency.In the present invention, the solidfied material of water white transparency refers to thick for 1mm
, 450nm when light transmission for more than 80%, preferably more than 85%, particularly preferred more than 90% material.
The solidification compound of the present invention can form the solidfied material with high optical transmissibility.Therefore, it is of the invention to consolidate
It is useful that the property changed composition encapsulates use, particularly blue led as LED element, the component encapsulation of ultraviolet LED is used.Sent out with this
As long as the method for bright solidification compound encapsulation LED element etc. is according to known method.It can for example utilize and divide
With method（デ ィ ス ペ Application ス methods）, compression moulding etc. carries out.
The solidification compound and solidfied material of the present invention formed in addition, also its have it is excellent resistance to anti-thread breakage, heat-resisting
The solidfied material of the characteristic such as property, light resistance, the transparency, thus display material, optical recording medium material, optical instrument material,
In the purposes of light component materials, fiber optics material, optical electrical subfunction organic material, semiconductor integrated circuit adjacent material etc.
It is useful.
Embodiment
Embodiment described below and comparative example, are described in more detail the present invention, but the invention is not restricted to following embodiments.
Weight average molecular weight shown in following embodiments（Mw）It is to be oozed by the use of using the gel of polystyrene as standard substance
Saturating chromatography（GPC）The value being measured.Condition determination described below.
[GPC condition determinations]
Developing solvent：Tetrahydrofuran
Flow velocity：0.6mL/min
Pillar：TSK guard columns SuperH-L
TSKgel SuperH4000（6.0mmI.D. × 15cm × 1）
TSKgel SuperH3000（6.0mmI.D. × 15cm × 1）
TSKgel SuperH2000（6.0mmI.D. × 15cm × 2）
（Jun Wei East ソ ー company systems）
Column temperature：40℃
Sample injection rate：20μL （Sample solution concentration：0.5wt%- tetrahydrofuran solutions）
Detector：Differential refraction rate meter（RI）
Vi values shown in following embodiments（Vi value）（mol/100g）With SiH values（SiH value）（mol/100g）It is by measureization
The 400MHz's of compound1The value that H-NMR spectrum, the integrated value of the hydrogen atom obtained using dimethyl sulfoxide as internal standard are calculated.1H-NMR
Measure uses ULTRASHIELDTM400PLUS（BRUKER company systems）Carry out,29Si-NMR is determined and is used RESONANCE500
（JEOL company systems）Carry out.
Used in embodiment（A）The synthesis example of composition and comparing is illustrated in following.In the following, Me represents methyl,
Ph represents phenyl.
［ synthesis example 1 ］
（a-1）
Lithium trimethylsilanolate 96.3g, hexamethyl cyclotrisiloxane 1560g, hexaphenyl cyclotrisiloxane are added in toluene solvant
4160g, is stirred 12 hours at 100 DEG C.Then, add acetic acid 90.0g to be neutralized, the product of gained is filtered.Then, add
MTMS 408g, Sr（OH）2・8H2O 8.10g, are stirred 3 hours at 60 DEG C.Then, acetic acid 12.2g is added to carry out
Neutralize, the product of gained filtered, methanol and toluene vacuum distillation are removed, thus synthesize it is following, there are 2 in single end
The organopolysiloxane of alkoxy（a-1）.Understand Mw=6000.
（In formula, c=c '=20）.
（A-1）
Add（a-1）The organopolysiloxane 600g of middle synthesis, PSI-alpha, omega-diol（Mw=530）
140g、Sr（OH）2・8H2O 0.810g, are stirred 18 hours at 60 DEG C.Then, add acetic acid 1.22g to be neutralized, add chlorine two
Ethylene methacrylic base silane 17.1g, is stirred 8 hours at 60 DEG C.The product of gained is filtered, washing, azeotropic dehydration carries out decompression steaming
Distillation is gone, and thus synthesizes following branched chain silicones.Understand to be with Mw=27000, Vi value=7.41 × 10-3Mol/100g, by29Si-NMR spectrum draw a=4, b=40, c=20, c '=20 organopolysiloxane（A-1）.
［ synthesis example 2 ］
（a-2）
Lithium trimethylsilanolate 96.3g, hexamethyl cyclotrisiloxane 222g, hexaphenyl cyclotrisiloxane are added in toluene solvant
595g, is stirred 3 hours at 100 DEG C.Then, add acetic acid 90.0g to be neutralized, the product of gained is filtered.Then, first is added
Base trimethoxy silane 408g, Sr（OH）2・8H2O 8.10g, are stirred 3 hours at 60 DEG C.Then, add in acetic acid 12.2g progress
With the product of gained is filtered, methanol and toluene vacuum distillation are removed, following single end dialkoxies are thus synthesized organic poly-
Siloxanes（a-2）.Understand Mw=1000.
（In formula, c=c '=3）.
（A-2）
Add（a-2）The organopolysiloxane 100g of middle synthesis, PSI-alpha, omega-diol（Mw=530）
27.9g、Sr（OH）2・8H2O 0.640g, are stirred 3 hours at 60 DEG C.Then, add acetic acid 0.960g to be neutralized, add chlorine two
Ethylene methacrylic base silane 24.4g, is stirred 8 hours at 60 DEG C.The product of gained is filtered, washing, azeotropic dehydration carries out decompression steaming
Distillation is gone, and thus synthesizes following branched chain silicones.Understand to be with Mw=3300, Vi value=6.06 × 10-2Mol/100g, by29Si-NMR spectrum draw a=3, b=6, c=3, c '=3 organopolysiloxane.
［ synthesis example 3 ］
（a-3）
Trimethyl silicane alkanol 90.1g, hexamethyl cyclotrisiloxane 6660g, two catechol phenyl first are added in acetonitrile solvent
Siloxy sodium（ジカテコールフェニルシロキシナトリウム）121g, is stirred 12 hours at 60 DEG C.By gained
Product is filtered, and adds MTMS 408g, Sr（OH）2・8H2O 8.10g, are stirred 3 hours at 60 DEG C.Then, add
Acetic acid 12.2g is neutralized, and the product of gained is filtered, and methanol and toluene vacuum distillation are removed, and thus synthesizes following single ends
Hold dialkoxy organopolysiloxane.Understand Mw=6800.
（In formula, c=90）.
（A-3）
Add（a-3）The organopolysiloxane 680g of middle synthesis, dimethyl silicone polymer-alpha, omega-diol（Mw=280）72.0g、
Sr（OH）2・8H2O 3.76g, are stirred 18 hours at 60 DEG C.Then, add acetic acid 5.64g to be neutralized, add Chlorodimethyl second
Alkenyl silanes 13.0g, is stirred 8 hours at 60 DEG C.The product of gained is filtered, washing, azeotropic dehydration, vacuum distillation is removed, by
This synthesizes following branched chain silicones.Understand to be with Mw=73000, Vi value=2.74 × 10-3Mol/100g, by29Si-NMR spectrum
Draw a=10, b=90, c=90 organopolysiloxane.
［ synthesis example 4 ］
（a-4）
Trimethyl silicane alkanol 90.1g, hexamethyl cyclotrisiloxane 890g, two catechol phenyl first silicon are added in acetonitrile solvent
Epoxide sodium 121g, is stirred 6 hours at 60 DEG C.The product of gained is filtered, MTMS 408g, Sr is added（OH）2・
8H2O 8.10g, are stirred 3 hours at 60 DEG C.Then, add acetic acid 12.2g to be neutralized, the product of gained is filtered, by methanol
Vacuum distillation removing is carried out with toluene, following single end dialkoxy organopolysiloxanes are thus synthesized.Understand Mw=1000.
（In formula, c=12）.
（A-4）
Add（a-4）The organopolysiloxane 1000g of middle synthesis, dimethyl silicone polymer-alpha, omega-diol（Mw=280）
12.0g、Sr（OH）2・8H2O 5.06g, are stirred 18 hours at 60 DEG C.Then, add acetic acid 7.59g to be neutralized, add chlorine two
Ethylene methacrylic base silane 340g, is stirred 8 hours at 60 DEG C.The product of gained is filtered, washing, azeotropic dehydration, vacuum distillation is removed
Go, thus synthesize following branched chain silicones.Understand to be with Mw=81000, Vi value=2.47 × 10-3Mol/100g, by29Si-
NMR spectra draws a=80, b=12, c=12 organopolysiloxane.
［ comparative example 1 ］
（A-1’）
Two terminal ethylenyl groups phenyl methyl silicone oils shown in following formula（Shin-Etsu Chemial Co., Ltd's system, Vi value=3.81 × 10-2mol/100g）.
［ comparative example 2 ］
（A-2’）
Two terminal ethylenyl groups dimethicones shown in following formula（Shin-Etsu Chemial Co., Ltd's system, Vi value=1.33 × 10- 2mol/100g）
N=200（Average value）.
［ comparative example 3 ］
（A-3’）
By 1,1- diphenyl -1,3- dimethyl -3,3- dimethoxy disiloxane 63.7g, PSI-α, ω -
Glycol（Mw=530）1200g and dimethylvinylmethoxysiiane 48.8g stirrings, are adjusted to 60 DEG C.Then, Sr is added
（OH）2・8H2O 3.15g, in the reaction of 60 DEG C of progress 3 hours.Catalyst is removed in filtering the product obtained by, by methanol
Removed with water vacuum distillation, thus synthesize following branched chain silicones.Understand to be with Mw=5700, Vi value=3.51 × 10-2mol/
100g, by29Si-NMR spectrum draw n=37, m=1 organopolysiloxane.
（B）Composition,（C）Composition and（D）Composition
Hereinafter, show what is used in embodiment（B）Composition,（C）Composition and（D）Composition.
（B-1）Phenyl system organic siliconresin shown in following formula（Shin-Etsu Chemial Co., Ltd's system, Vi values=
0.147mol/100g）
N=3, m=10, molecular weight=1600.
（B-2）Methyl system organic siliconresin shown in following formula（Shin-Etsu Chemial Co., Ltd's system, Vi value=9.12 ×
10-2mol/100g）
N=5, m=30, j=48, molecular weight=5800.
（C-1）It is shown in following formula, there is the silicone oil of hydrosilyl in two ends（Shin-Etsu Chemial Co., Ltd
System, SiH values=0.600mol/100g）.
（C-2）Silicone oil shown in following formula, that there is hydrosilyl in side chain（Shin-Etsu Chemial Co., Ltd's system,
SiH values=1.63mol/100g）
N=average 38.
（D）The Permethyl 99A solution of the divinylsiloxanes complex of chloroplatinic acid（The mass % of platinum content 0.5）
［ embodiment 1 ］
Will（A-1）100 mass parts and（B-1）300 mass parts,（C-1）81 mass parts are mixed, and are added as the chlorine that platinum amount is 5ppm
The divinylsiloxanes complex of platinic acid, is mixed, prepares solidification compound.
［ embodiment 2~4 and comparative example 1~3 ］
In addition to the compounding amount of each composition is changed as described in table 1, the behaviour of other repetitions similarly to Example 1
Make, prepare solidification compound.
For the solidification compound prepared in above-described embodiment 1~4 and comparative example 1~3, examination as shown below is carried out
Test.
［ viscosity of solidification compound ］
According to JIS Z 8803：2011, the viscosity of the solidification compound at 23 DEG C is determined using Brookfield viscometer.As a result remember
It is loaded in table 1.
［ hardness of solidfied material ］
In the aluminium dish that the solidification compound of preparation is poured into diameter 50mm × thickness 10mm, with 60 DEG C × 1 hour, 100 DEG C × 1
Hour, the order of 150 DEG C × 4 hours are progressively solidified, and obtain solidfied material.According to JIS K 6253-3：2012 determine solidification
The hardness of thing（Hardometer ShoreA or ShoreD）.As a result it is recorded in table 1.
［ light transmission of solidfied material ］
The 1mm thickness テ Off ロ Application of matrix is clamped between the thick slides of 2 50mm × 20mm × 1mm（Teflon
）（Registration mark）Pad, after they are fixed, pours into solidification compound, with 60 DEG C × 1 hour, 100 DEG C × 1 hour,
The order of 150 DEG C × 4 hours is progressively solidified, and makes transmissivity determination sample.Utilize spectrophotometer U-4100（Strain formula meeting
Community day founds Ha イ テ Network ノ ロ ジ ー ズ systems）The light transmission during 450nm of the sample obtained by measure.As a result it is recorded in table 1.
［ the elongation when tensile strength of solidfied material and cut-out ］
In the thick matrix テ Off ロ Application of 150mm × 200mm × 2mm（Registration mark）The curability group of preparation is poured into metal die
Compound, the order with 60 DEG C × 1 hour, 100 DEG C × 1 hour, 150 DEG C × 4 hours is progressively solidified, and makes sample.According to
JIS K 6251：2010, use EZ TEST（EZ-L, Shimadzu Scisakusho Ltd's system）, in test speed 500mm/min, folder
Between tool between 80mm, metering punctuate under conditions of 40mm the tensile strength of determination sample and elongation during cut-out（Cut-out
Time stretches び）.
As a result it is recorded in table 1.
［ glass transition temperature of solidfied material ］
Utilize DMA Q800（TA イ Application ス Star Le メ Application ト Co. Ltd. systems）- 140 DEG C~150 DEG C scopes determine as described above
The elongation when tensile strength of solidfied material and cut-out ］ storage elastic modulus of solidfied material sample that is made as described in item
（MPa）, the value of Tan δ derived from the storage elastic modulus and the value of loss elastic modulus as gained is drawn and song is obtained
Line chart, glass transition temperature (Tg) is set to by the temperature of the summit obtained by the curve map.
Condition determination is in sample wide × thick 1mm 20mm length × 5mm, 5 DEG C/min of programming rate, multiple-frequency-mode（マ
Le チ cycle モ ー De）, stretch mode, carry out under conditions of 15 μm of amplitude.As a result it is recorded in table 1.Embodiment 1 (solid line)
With the curve map and Tan δ curve map of the storage elastic modulus of the solidfied material of comparative example 1 (dotted line).Fig. 1 represents that embodiment 1 is (real
Line) and comparative example 1 (dotted line) solidfied material storage elastic modulus curve map and Tan δ curve map.
［ temperature cycling test ］
In Tiger3528 packagings（パッケージ）（KCC of SHIN-ETSU HANTOTAI system）Upper distribution solidification compound, with 60 DEG C ×
1 hour, 100 DEG C × 1 hour, the order of 150 DEG C × 4 hours progressively solidified, manufacture encapsulates the examination packed with solidfied material
Test thing.For 20 triers, -50 DEG C~140 DEG C, the thermal cycling test of 1000 times are carried out（TCT）, measure on encapsulant
The quantity of the trier cracked.As a result it is recorded in table 1.
【Table 1】
H/Vi=（The mol of SiH bases in composition）/（The mol of Vi bases in composition）
The quantity of the trier of NG quantity=generated on encapsulant crackle.
As shown in table 1, the curable silicone resin group of the branched organopolysiloxanes of the present invention has been used
Compound, with replacing the present invention's（A）Composition and used the composition of the organopolysiloxane of straight-chain to compare, formed vitrifying
Transition temperature is low, resistance to anti-thread breakage excellent solidfied material.In addition, the viscosity of resin combination is sufficiently low, operating efficiency is good.
Industry utilizability
Present invention offer low-temperature characteristics is good, can form the addition curable organosilicon group of the excellent solidfied material of temperature change patience
Compound and encapsulate the semiconductor device with high reliability of semiconductor element using the solidfied material of said composition.
Claims (10)
1. addition curing organosilicon resin composition, it contains
（A）Following formula（1）Shown branched organopolysiloxanes
（In formula, R1Independently of one another selected from carbon number 1~12 substituted or unsubstituted saturated hydrocarbyl or carbon number 6~
Group in 12 substituted or unsubstituted aromatic hydrocarbyl, R2Independently of one another selected from carbon number 1~12 substitution or
The substituted or unsubstituted aromatic hydrocarbyl of unsubstituted saturated hydrocarbyl or carbon number 6~12, the alkenyl of carbon number 2~10
In group, each R1、R2Can with it is identical, can also be different, wherein, R2In at least two be alkenyl, a be 2~100 integer, b
For 5~100 integer, c is 5~100 integer, 0.03≤a/ (a+b) ＜ 1.0,（R1 2R2SiO1/2）The quantity of unit/
（R2SiO3/2）The arrangement of the siloxane chain of quantity≤2, a of unit, b and c can be random, or block）、
（B）Following formula（2）Shown organopolysiloxane
（R2 3SiO1/2）r（R2 2SiO2/2）s（R2SiO3/2）t（SiO4/2）u （2）
（In formula, R2Definition it is same as described above, R2In at least two be alkenyl, r be 0~100 integer, s for 0~300 it is whole
Number, t is 0~200 integer, and u is 0~200 integer, 1≤t+u≤400,2≤r+s+t+u≤800）、
（C）Intramolecular have at least two hydrosilyl organopolysiloxane and
（D）Hydrosilylation catalysts,
It is described（B）The amount of composition relative to（A）The mass parts of composition 100 are 5~900 mass parts, described（C）The amount of composition is to make
（C）The quantity of hydrosilyl in composition is relative to described（A）Composition and（B）The sum of alkenyl in composition be 0.4~
4.0 amount, it is described（D）The amount of composition is for making hydrosilylation reactions enter the enough amounts of behavior.
2. addition curing organosilicon resin composition according to claim 1, wherein, in formula（1）In, 0.09≤a/（a
+ b）≤0.9.
3. according to addition curing organosilicon resin composition according to any one of claims 1 to 2, wherein, in formula（1）
In, R1In at least one be carbon number 6~12 aromatic hydrocarbyl.
4. according to addition curing organosilicon resin composition according to any one of claims 1 to 3, it is characterised in that
（A）In composition, with the quantity of whole substituents of silicon atom bonding, the ratio of the quantity of 1 valency aromatic hydrocarbyl for 3% with
It is upper and less than 90%.
5. according to addition curing organosilicon resin composition according to any one of claims 1 to 4, wherein,（C）Composition is
Following formula（3）Shown composition,
（R3 3SiO1/2）r’（R3 2SiO2/2）s’（R3SiO3/2）t’（SiO4/2）u’ （3）
In formula, R3The independently of one another substituted or unsubstituted saturated hydrocarbyl or carbon number 6 of hydrogen atom, carbon number 1~12
~12 substituted or unsubstituted aromatic hydrocarbyl, and R3In at least two be hydrogen atom, r ' be 0~100 integer, s ' be 0~
300 integer, t ' is 0~200 integer, and u ' is 0~200 integer, 2≤r '+s '+t '+u '≤800.
6. semiconductor device, it is characterised in that utilize the addition curing organosilicon tree any one of Claims 1 to 55
The solidfied material packaging semiconductor of oil/fat composition.
7. semiconductor device according to claim 6, it is characterised in that semiconductor element is light-emitting component.
8. the manufacture method of addition curing organosilicon resin composition, it includes will be following（A）Composition,（B）Composition,（C）Into
Point and（D）Composition is mixed,
（A）Composition：By making following formula（4）Shown organopolysiloxane and following formula（5）It is shown, there is alcoxyl in two ends
Base silicyl or hydroxyl silicyl（Silanol group）Organopolysiloxane cocondensation, followed by following formula（6）Shown
The reaction product that silane compound containing hydrolization group carries out end-capped and manufactured,
（In formula, R1Independently of one another selected from carbon number 1~12 substituted or unsubstituted saturated hydrocarbyl or carbon number 6~
Group in 12 substituted or unsubstituted aromatic hydrocarbyl, R2Independently of one another selected from carbon number 1~12 substitution or
The substituted or unsubstituted aromatic hydrocarbyl of unsubstituted saturated hydrocarbyl or carbon number 6~12, the alkenyl of carbon number 2~10
In group, each R1、R2Can with it is identical, can also be different, wherein, R2In at least two be alkenyl, c be 5~100 integer,
R3For hydrogen atom or the saturated hydrocarbyl of carbon number 1~6）
（In formula, R2、R3Same as described above, b ' is more than 1 and below b, and b is 5~100 integer）,
（In formula, R1、R2Same as described above, X is halogen atom or R3O- ［ R3It is same as described above ］ shown in group）；
（B）Composition：Following formula（2）Shown organopolysiloxane
（R2 3SiO1/2）r（R2 2SiO2/2）s（R2SiO3/2）t（SiO4/2）u （2）
（In formula, R2Definition it is same as described above, R2In at least two be alkenyl, r be 0~100 integer, s for 0~300 it is whole
Number, t is 0~200 integer, and u is 0~200 integer, 1≤t+u≤400,2≤r+s+t+u≤800）,
Should（B）The amount of composition relative to（A）The mass parts of composition 100 are 5~900 mass parts；
（C）Composition：There is the organopolysiloxane of at least two hydrosilyl in intramolecular,
Should（C）The amount of composition is to make（C）The quantity of hydrosilyl in composition relative to（A）Composition and（B）In composition
The sum of alkenyl is 0.4~4.0 amount；With
（D）Composition：Hydrosilylation catalysts,
Should（D）The amount of composition is for making hydrosilylation reactions enter the enough amounts of behavior.
9. the manufacture method of addition curing organopolysiloxane composition according to claim 8, it is characterised in that
（A）In reaction product, with the quantity of whole substituents of silicon atom bonding, the ratio of the quantity of 1 valency aromatic hydrocarbyl is
More than 3% and less than 90%.
10. the manufacture method of the addition curing organosilicon resin composition according to any one of claim 8~9, its
In,
（C）Composition is following formula（3）Shown composition,
（R3 3SiO1/2）r’（R3 2SiO2/2）s’（R3SiO3/2）t’（SiO4/2）u’ （3）
In formula, R3The independently of one another substituted or unsubstituted saturated hydrocarbyl or carbon number 6 of hydrogen atom, carbon number 1~12
~12 substituted or unsubstituted aromatic hydrocarbyl, and R3In at least two be hydrogen atom, r ' be 0~100 integer, s ' be 0~
300 integer, t ' is 0~200 integer, and u ' is 0~200 integer, 2≤r '+s '+t '+u '≤800.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109661418A (en) * | 2016-09-07 | 2019-04-19 | 住友化学株式会社 | Solidfied material, wavelength convert sheet material, light emitting device, sealing component and semiconductor light-emitting apparatus |
| CN110603283A (en) * | 2017-05-05 | 2019-12-20 | 美国陶氏有机硅公司 | Hydrosilylation curable silicone resins |
| CN110776744A (en) * | 2018-07-31 | 2020-02-11 | 信越化学工业株式会社 | Addition-curable silicone resin composition and semiconductor device |
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| US20210246337A1 (en) * | 2018-06-29 | 2021-08-12 | Dow Silicones Corporation | Solventless silicone pressure sensitive adhesive and methods for making and using same |
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Also Published As
| Publication number | Publication date |
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| CN106947258B (en) | 2021-06-25 |
| JP6657037B2 (en) | 2020-03-04 |
| JP2017115116A (en) | 2017-06-29 |
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