CN108070261A - Heat-curing type silica composition, die bond material and optical semiconductor device - Google Patents

Heat-curing type silica composition, die bond material and optical semiconductor device Download PDF

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CN108070261A
CN108070261A CN201711092143.XA CN201711092143A CN108070261A CN 108070261 A CN108070261 A CN 108070261A CN 201711092143 A CN201711092143 A CN 201711092143A CN 108070261 A CN108070261 A CN 108070261A
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organic
heat
siloxanes
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ingredient
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CN108070261B (en
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平野大辅
小材利之
小内谕
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Shin Etsu Chemical Co Ltd
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • 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
    • C08L83/14—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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    • C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
    • C09J183/14—Adhesives based on 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; Adhesives based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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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    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
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    • 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
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector 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
    • H01L2224/32221—Disposition the layer connector 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
    • H01L2224/32245—Disposition the layer connector 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 metallic
    • 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
    • H01L2224/48245—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 metallic
    • H01L2224/48247—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 metallic connecting the wire to a bond pad of the item
    • 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
    • H01L2224/48245—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 metallic
    • H01L2224/48257—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 metallic connecting the wire to a die pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
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  • Led Device Packages (AREA)
  • Silicon Polymers (AREA)
  • Die Bonding (AREA)

Abstract

Problem to be solved by this invention is to provide a kind of heat-curing type silicon-ketone composition, and can obtain a kind of solidfied material, the solidfied material is overcome since oxygen inhibition causes the uncured situation of surface portion.The technical solution for solving described problem is a kind of heat-curing type silicon-ketone composition, which is characterized in that contains following component：(A) organic (poly-) siloxanes of 100 mass parts, organic (poly-) siloxanes have the structure that at least one is represented by the following general formula (1) in the molecule,(B) organic peroxide of 0.1~30 mass parts, the organic peroxide include diacyl peroxide or peroxy esters；(C) organic hydrogen polysiloxanes of 0.1~20 mass parts, the organic hydrogen polysiloxanes are bonded to the hydrogen atom on silicon atom in a molecule containing at least two；And (D) becomes the platinum group catalyst of the amount of 0.01~1000ppm.

Description

Heat-curing type silica composition, die bond material and optical semiconductor device
Technical field
It a kind of formed the present invention relates to heat-curing type silica composition, by said composition die bond material and uses The optical semiconductor device that the solidfied material of the die bond material forms.
Background technology
Since the optical semiconductors such as light emitting diode (Light Emitting Diode, LED) are few with power consumption Such excellent specific property gradually increases for the application of the luminescent semiconductor device (device) of lighting use outside room or mobile applications Add.Such luminescent semiconductor device will usually send the photosemiconductor light-emitting component institute of blue light, near ultraviolet ray or ultraviolet light The light sent, the light-emitting device that wavelength conversion is carried out can obtain similar to white light by wavelength shifter, that is, fluorophor.This In the luminescent semiconductor device of sample, optical semiconductor is bonded with frame, fixed using die bond material.
It is that use includes tool excellent adhesiveness and machine mostly in the past as optical semiconductor die bond material compositions The bisphenol A type epoxy resin of tool intensity etc., the epoxy resin for not absorbing ultraviolet light, the composition of curing agent and curing catalysts, Wherein, the epoxy resin for not absorbing ultraviolet light (UV) is, for example, bisphenol-A epoxy resin or alicyclic epoxy resin.So And become higher with the brightness and output of LED element, because of ultraviolet light, heat etc. caused by LED element, the change of adhesive layer can be triggered The problem of color and fragmentation.
Therefore, motion uses silicone resin, as the optical semiconductor replacement of the epoxy resin in die bond material Product (patent document 1,2).The species of the curing mechanism of silicone resin is various, but the main addition reaction using SiH bases and alkenyl, The addition reaction is carried out using platinum catalyst.At this point, in order to improve the adhesiveness with base material, can add mostly has The adhesiveness enhancer of (methyl) acryloyl group or epoxy group etc..If the additive amount of adhesiveness enhancer is few, lack bonding Property, but if additive amount is excessive, then become larger after curing for material properties affect, such as hardness is caused to reduce etc., therefore can not be a large amount of It uses.
On the other hand, there is the example using peroxide cure, the peroxide cure has used adhesiveness function Base i.e. methylpropionyl etc. (patent document 3,4), but hinder to cure due to oxygen, there are the curability variation on surface The problem of.In addition, cured situation is hindered being irradiated with ultraviolet light (UV) also causing when curing methylpropionyl due to oxygen, Therefore motion is a kind of solves the method for the influence (patent document 5) using addition curing, but this method actually needs UV cures and heat cure both sides, the position for it is dfficult to apply to carry out UV irradiations complicated device so being needed to design.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2004-186168 publications；
Patent document 2：Japanese Unexamined Patent Publication 2006-342200 publications；
Patent document 3：Japanese Unexamined Patent Publication 2008-074982 publications；
Patent document 4：Japanese Unexamined Patent Publication 2016-108456 publications；
Patent document 5：Japanese Unexamined Patent Publication 2013-203794 publications.
The content of the invention
The present invention has been made in view of the above-described circumstances, and an object thereof is to provide a kind of heat-curing type silicon-ketone composition, It can obtain a kind of solidfied material, and the solidfied material is overcome since oxygen inhibition causes the uncured situation of surface portion.In addition, It is an object of the invention to provide a kind of die bond materials, are made of said composition.Further, it is an object of the invention to carry For a kind of optical semiconductor device, the solidfied material with the die bond material.
To solve the above-mentioned problems, according to the present invention, a kind of heat-curing type silicon-ketone composition is provided, which is characterized in that Contain following component：
(A) organic (poly-) siloxanes of 100 mass parts, organic (poly-) siloxanes in the molecule have at least one by The structure that the following general formula (1) represents,
In formula (1), m is any one in 0,1,2, R1It is hydrogen atom, phenyl or halogenated phenyl, R2It is hydrogen atom or methyl, R3Be be substituted or it is unsubstituted and can be identical or different carbon number 1~12 1 valency organic group, Z1It is-R4-、-R4- O-、-R4(CH3)2Any one of Si-O-, Z2It is oxygen atom or is substituted or unsubstituted and can be identical or different The divalent organic group of carbon number 1~10, wherein, R4It is to be substituted or unsubstituted and can be identical or different carbon atom The divalent organic group of number 1~10；
(B) organic peroxide of 0.1~30 mass parts, the organic peroxide are included selected from diacyl peroxidating One or more of object, peroxy esters；
(C) organic hydrogen polysiloxanes of 0.1~20 mass parts, the organic hydrogen polysiloxanes are in a molecule containing at least 2 hydrogen atoms being bonded on silicon atom；And
(D) platinum group catalyst, the content of the platinum group catalyst compared with (A) ingredient, make matter with the platinum in (D) ingredient Amount is scaled the amount of 0.01~1000ppm.
The heat-curing type silicon-ketone composition of the present invention, by the consolidating based on peroxide for carrying out (methyl) acryloyl group Change and the curing of the addition reaction both sides of SiH bases and unsaturated group, can obtain a kind of solidfied material, the solidfied material overcome by Cause the uncured situation of surface portion in oxygen inhibition.
In addition, it is preferably the Z of organic (poly-) siloxanes of foregoing (A) ingredient at this time1It is-R4-, Z2It is oxygen atom.
In addition, it is preferably the Z of organic (poly-) siloxanes of foregoing (A) ingredient at this time1It is-R4- O- or-R4(CH3)2Si- O-, Z2Be be substituted or it is unsubstituted and can be identical or different carbon number 1~10 divalent organic group.
If include such Z1、Z2Combination (A) ingredient heat-curing type silicon-ketone composition, then (B) ingredient exist Reaction can be effectively performed with (A) ingredient in generated free radical during decomposition, thus can obtain a kind of solidfied material, and bonding is strong Degree and operability are excellent, and heat resistance, light resistance and crumpling resistance are excellent.
In addition, organic (poly-) siloxanes of foregoing (A) ingredient is preferably the whole silica for forming organic (poly-) siloxanes In alkane unit, there is (the SiO of more than 0.1mol%2) unit.
If including the heat-curing type silicon-ketone composition of this (A) ingredient, then (B) ingredient is generated when decomposing Free radical is effectively further reacted with (A) into branch, thus can obtain a kind of solidfied material, the bonding of the solidfied material Intensity and operability are further excellent, and heat resistance, light resistance and crumpling resistance are excellent.
In addition, the present invention provides a kind of die bond material, which is characterized in that is by foregoing heat-curing type silicon-ketone composition structure Into.
The heat-curing type silicon-ketone composition of the present invention can obtain adhesive strength and operability is excellent, and heat resistance, resistance to Photosensitiveness and the excellent solidfied material of crumpling resistance, therefore die bond material can be suitable as.
In addition, the present invention provides a kind of optical semiconductor device, which is characterized in that has and cures foregoing die bond material Obtained by solidfied material.
Optical semiconductor device with this solidfied material can become the high optical semiconductor device of reliability, the curing Object is to cure the die bond material being made of the heat-curing type silicon-ketone composition of the present invention and obtained.
The heat-curing type silicon-ketone composition of the present invention, by the consolidating based on peroxide for carrying out (methyl) acryloyl group Change and the curing of the addition reaction both sides of SiH bases and unsaturated group, can obtain a kind of solidfied material, the solidfied material overcome by Cause the uncured situation of surface portion in oxygen inhibition, and adhesive strength and operability are excellent, and heat resistance, light resistance and resistance to Fragmentation is excellent.Optical semiconductor device with this solidfied material can become the high optical semiconductor device of reliability, described solid Compound is to cure the die bond material being made of the heat-curing type silicon-ketone composition of the present invention and obtained.
Description of the drawings
Fig. 1 is the sectional view for an example for representing the optical semiconductor device of the present invention.
Wherein, the reference numerals are as follows：
1 frame；
2 optical semiconductors；
3 the 1st lead electrodes；
4 the 2nd lead electrodes；
5 die bond materials (solidfied material)；
6th, 7 gold thread；
8 sealing resins；
10 optical semiconductor devices.
Specific embodiment
The present inventor is studied in order to achieve the above objectives and attentively, it turns out that a kind of heat-curing type silicone combination Object, which is characterized in that containing following (A)~(D) ingredients, if the heat-curing type silicon-ketone composition, then pass through progress The curing based on peroxide of (methyl) acryloyl group and the curing of the addition curing both sides of SiH bases and unsaturated group, even if It is irradiated without UV, can also obtain a kind of solidfied material, the solidfied material is overcome since oxygen inhibition causes surface portion not solid The situation of change, thereby completing the present invention.Hereinafter, explain in detail the present invention heat-curing type silicon-ketone composition, die bond material, And optical semiconductor device.
That is, the present invention provides a kind of heat-curing type silicon-ketone composition, which is characterized in that contains following component：
(A) organic (poly-) siloxanes of 100 mass parts, organic (poly-) siloxanes in the molecule have at least one by The structure that the following general formula (1) represents,
In formula (1), m is any one in 0,1,2, R1It is hydrogen atom, phenyl or halogenated phenyl, R2It is hydrogen atom or methyl, R3Be be substituted or it is unsubstituted and can be identical or different carbon number 1~12 1 valency organic group, Z1It is-R4-、-R4- O-、-R4(CH3)2Any one of Si-O-, Z2It is oxygen atom or is substituted or unsubstituted and can be identical or different The divalent organic group of carbon number 1~10, wherein, R4It is to be substituted or unsubstituted and can be identical or different carbon atom The divalent organic group of number 1~10；
(B) organic peroxide of 0.1~30 mass parts, the organic peroxide are included selected from diacyl peroxidating One or more of object, peroxy esters；
(C) organic hydrogen polysiloxanes of 0.1~20 mass parts, the organic hydrogen polysiloxanes are in a molecule containing at least 2 hydrogen atoms being bonded on silicon atom；And
(D) platinum group catalyst, the content of the platinum group catalyst compared with (A) ingredient, make matter with the platinum in (D) ingredient Amount is scaled the amount of 0.01~1000ppm.
＜ (A) ingredient：Organic (poly-) siloxanes ＞
(A) organic (poly-) siloxanes of ingredient is that have the structure that at least one is represented by the following general formula (1) in the molecule Organic (poly-) siloxanes.In addition, in the present invention, organic (poly-) siloxanes, refer in a molecule siloxanes bond (- Si-O-Si-) it is the organosiloxane of 1, and/or organic poly- silica of 2 or more siloxanes bonds is included in a molecule Alkane.
In formula (1), m is any one in 0,1,2, R1It is hydrogen atom, phenyl or halogenated phenyl, R2It is hydrogen atom or methyl, R3Be be substituted or it is unsubstituted and can be identical or different carbon number 1~12 1 valency organic group, Z1It is-R4-、-R4- O-、-R4(CH3)2Si-O-(R4Be be substituted or it is unsubstituted and can be identical or different carbon number 1~10 divalent it is organic Any one of group), Z2Oxygen atom or be substituted or it is unsubstituted and can be identical or different carbon number 1~ 10 divalent organic group.
(A) in organic (poly-) siloxanes of ingredient, as Z1With Z2Combination, be preferably, Z1It is-R4-、Z2It is oxygen atom Combination or Z1It is-R4- O- or-R4(CH3)2Si-O-、Z2It is to be substituted or unsubstituted and can be identical or different carbon is former The combination of the divalent organic group of subnumber 1~10.If the heat-curing type silicon-ketone composition of this (A) ingredient is included, then (B) reaction can be effectively performed with (A) ingredient in ingredient generated free radical when decomposing, thus can obtain a kind of curing Object, the adhesive strength and operability of the solidfied material are excellent, and heat resistance, light resistance and crumpling resistance are excellent.
Furthermore it is preferred that being, in the whole siloxane units for organic (poly-) siloxanes for forming (A) ingredient, have (the SiO of more than 0.1mol%2) unit.If including the heat-curing type silicon-ketone composition of this (A) ingredient, then (B) into The generated free radical when decomposing is divided effectively further to be reacted into branch with (A), thus a kind of curing can be obtained Object, the adhesive strength and operability of the solidfied material are further excellent, and heat resistance, light resistance and crumpling resistance are excellent.
Further, it is preferable to be, organic (poly-) siloxanes of (A) ingredient has at least one by the following general formula in the molecule (2) structure represented.If including the heat-curing type silicon-ketone composition of this (A) ingredient, then (B) ingredient is decomposing when institute The free radical of generation is more effectively carried out reacting with (A) into branch, thus can obtain a kind of solidfied material, and the solidfied material glues It closes intensity and operability is excellent, and heat resistance, light resistance and crumpling resistance are excellent.
In formula (2), m, R1、R2、R3、R4It is same as described above.
(A) organic (poly-) siloxanes of ingredient is preferably that viscosity at 25 DEG C is the liquid or solid of more than 5mPas Branched or space network organopolysiloxane.
In above-mentioned general formula (1), as by R3It is represented to be incorporated into being substituted on silicon atom or unsubstituted and be with 1 valency organic group of identical or different carbon number 1~12 is preferably, carbon number 1~8 or so, specifically, can be with It enumerates：Methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tertiary butyl, amyl, neopentyl, hexyl, cyclohexyl, octyl group, nonyl The alkyl such as base, decyl；The aryl such as phenyl, tolyl, xylyl, naphthalene；The aralkyl such as benzyl, phenethyl, phenylpropyl；Second The alkenyls such as alkenyl, pi-allyl, acrylic, isopropenyl, cyclobutenyl, hexenyl, cyclohexenyl group, octenyl；And these groups Some or all of hydrogen atom obtained by the substitutions such as the halogen atoms such as fluorine, bromine, chlorine, cyano group, such as chloromethyl, chlorine The halogen-substituted alkyls such as propyl, bromoethyl, trifluoro propyl and cyanoethyl etc..
Organic (poly-) siloxanes of (A) ingredient illustrated below.
In addition, organic (poly-) siloxanes as (A) ingredient, may be exemplified：Organopolysiloxane represented by following formula, It is with MA：M：Q=1：4：6 ratio includes MA units, M units, Q unit, and molecular weight is 5000, the molecular weight be with The weight average molecular weight of polystyrene conversion；
Organopolysiloxane represented by following formula, MA-D units, D units, T unit are MA-D：D：T=2：6：7 Ratio, and molecular weight is 3500, and the molecular weight is the weight average molecular weight to be converted with polystyrene.
In addition, organic (poly-) siloxanes as (A) ingredient, may be exemplified with the organic of following represented structures (poly-) siloxanes etc..
In above-mentioned formula, p=18, q=180.
In above-mentioned formula, t=18, u=180.
As the synthetic method of this (A) ingredient, as long as such as in the presence of platinum catalyst, making following compound and bag Organic (poly-) silica of fatty race's unsaturated group (it can be cited for example that ethylene unsaturated group and acetylene unsaturated group) Alkane carries out hydrosilylation (hydrosilylation) and reacts：Organohydrogensilicon alkane represented by following formula,
In above-mentioned formula, m, R1、R2、R3、Z1It is same as described above；
Preferably, the compound represented by following formula,
In above-mentioned formula, m, R1、R2、R3、Z1、Z2It is same as described above；
More particularly, (3- methacryloxypropyls) -1,1,3,3- tetramethyl disiloxane, be by by 1, Double (3- methacryloxypropyls) tetramethyl disiloxanes and 1 of 3-, 1,3,3- tetramethyl disiloxane are deposited in acid catalyst Being balanced is reacted and obtained under；It can be produced using the method and be suitable for the compound of the present invention, but before being not limited to The synthetic method stated.In addition, organic (poly-) siloxanes comprising aliphatic unsaturated group, can utilize comprising with aliphatic not Method well known to (common) hydrolytic condensation of the alkoxy silane of the organopolysiloxane of saturation base etc. manufactures, and can also use city Sell product.
These (A) ingredients can be single kind, can also be two kinds or more.
In addition, in (A) ingredient, the purpose of in order to adjust the hardness of the viscosity of composition or solidfied material, can add such as with The reactive diluent comprising silicone shown in lower or the reactive diluent without silicone.
As the reactive diluent comprising silicone, the organopolysiloxane with following structures can be enumerated.
This reactive diluent comprising silicone can be single kind, can also be two kinds or more.
As the reactive diluent without silicone, just like H2C=CGCO2R5Represented (methyl) esters of acrylic acid, on It states in formula, G is the alkyl of hydrogen, halogen or 1~about 4 carbon atom, R5It is to be selected from alkyl, ring with 1~about 16 carbon atom Alkyl, alkenyl, cycloalkenyl group, alkaryl, aralkyl or aryl；Any one of these groups, can be as needed, with silane, Silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, carbamate, amine, amide, sulphur, sulphonic acid ester, sulfo group etc. are come Substituted or closed.
As in reactive diluent, particularly preferred further details of (methyl) esters of acrylic acid, there are：Poly- second It is glycol two (methyl) acrylate, double as ethoxylated bisphenol A (methyl) acrylate (" EBIPA " or " EBIPMA ") Phenol-A two (methyl) acrylate, tetrahydrofuran (methyl) acrylate and two (methyl) acrylate, acrylic acid citronellyl acrylate and Methacrylic acid citronellyl acrylate, (methyl) hydroxypropyl acrylate, hexylene glycol two (methyl) acrylate (" HDDA " or " HDDMA "), Trimethylolpropane tris (methyl) acrylate, (methyl) acrylic acid tetrahydrochysene bicyclopentadiene ester, ethoxyquin trimethylolpropane Triacrylate (" ETTA "), triethylene glycol diacrylate and triethylene glycol dimethacrylate (" TRIEGMA "), propylene Sour isobornyl thiocyanoacetate and isobornyl methacrylate；And with these corresponding acrylate.Certainly, these (methyl) third The combination of olefin(e) acid esters can also be used as reactive diluent use.
As addition reactive diluent when additive amount, compared with the present invention heat-curing type silicone combination object amount, The scope of the preferably scope of 0.01~40 mass %, more preferably 0.05~20 mass %.＜ (B) is included selected from diacyl mistake The organic peroxide ＞ of one or more of oxide, peroxy esters
(B) organic peroxide included selected from diacyl peroxide, one or more of peroxy esters of ingredient, be for After the heat-curing type silicon-ketone composition of the present invention is shaped to desired shape, heated and to pass through crosslinking anti- The silicon-ketone composition should be made to cure blended ingredient, and it is possible to according to the connection temperature of purpose, Connection Time, make It is properly selected with time limit etc..
Organic peroxide for the viewpoint by having both high response and long life, is preferably that half-life period is small for 10 When temperature be 40 DEG C or more, and half-life period is that the temperature of 1 minute is less than 200 DEG C, more preferably, when half-life period is 10 small Temperature is 60 DEG C or more, and the temperature that half-life period is 1 minute is less than 180 DEG C.
As diacyl peroxide, it can be cited for example that, peroxidating isobutyl group, peroxidating 2,4- dichloro-benzoyls, mistake Aoxidize 3,5,5- trimethyl acetyls, caprylyl peroxide, lauroyl peroxide, stearoyl, succinyl peroxide (succinic peroxide), benzoylperoxy toluene and benzoyl peroxide.
As peroxy esters, it can be cited for example that, the withered ester of peroxide neodecanoic acid, 1,1,3,3- tetramethyl butyl ester of peroxide neodecanoic acid, Peroxide neodecanoic acid 1- cyclohexyl -1- Methylethyls, the tertiary own ester of peroxide neodecanoic acid, the peroxide trimethylace tonitric tert-butyl ester, peroxide -2- second Base caproic acid -1,1,3,3- tetramethyls butyl ester, 2,5- dimethyl -2,5- double (2- ethylhexanoylperoxies) hexane, peroxide -2- second Base caproic acid -1- cyclohexyl -1- Methylethyls, the tertiary own ester of peroxide -2 ethyl hexanoic acid, the peroxide -2 ethyl hexanoic acid tert-butyl ester, peroxide are different Tert-butyl acetate, 1,1-bis(t-butylperoxy)cyclohexane, the tertiary own ester of peroxy isopropyl base single carbon acid, peroxide -3,5,5- front threes Base hecanoic acid t-butyl ester, the peroxide lauric acid/dodecanoic acid tert-butyl ester, 2,5- dimethyl -2,5- double (toluyl groups peroxy) hexane, peroxides Isopropyl single carbon tert-butyl acrylate, peroxide -2- ethylhexyl single carbons tert-butyl acrylate, the tertiary own ester of benzoper acid, Peracetic acid uncle Butyl ester and bis(t-butylperoxy) hexahydro terephthalic acid ester.
These peroxy esters can be used alone a kind, can also combine two or more use.
As other organic peroxides, can enumerate, dialkyl peroxide, peroxydicarbonate, peroxy ketal, Hydroperoxides, silyl peroxides etc..Also these organic peroxides can be selected from diacyl peroxide, mistake with above-mentioned The combination of one or more of oxygen ester, the organic peroxide as (B) ingredient use.
As dialkyl peroxide, it can be cited for example that, α, α ' it is-bis(t-butylperoxy) diisopropyl benzene, two withered Base peroxide, 2,5- dimethyl -2,5- bis(t-butylperoxy)s hexane and tert-butyl cumyl peroxide.
As peroxydicarbonate, it can be cited for example that, two carbonic acid di-n-propyl ester of peroxide, diisopropyl peroxydicarbonate, Two carbonic acid of peroxide double (4- tert-butylcyclohexyls) ester, two carbonic acid of peroxide, two -2- ethyoxyls methoxyethoxy ester, double (2- ethylhexyl peroxides Base) two carbonic esters, two carbonic acid dimethoxy butyl ester of peroxide and double (3- methyl -3- methoxybutyls peroxies) two carbonic esters.
As peroxy ketal, it can be cited for example that, 1,1- double (tertiary hexyl peroxies) -3,3,5- trimethyl-cyclohexanes, 1, 1- double (tertiary hexyl peroxy) hexamethylene, 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes, 1,1- (tertiary butyls Peroxy) cyclododecane and 2,2- bis(t-butylperoxy) decane.
As hydroperoxides, it can be cited for example that, diisopropyl benzene hydroperoxides and cumene hydroperoxide.
As silyl peroxides, it can be cited for example that, tertiary butyl trimethylsilyl peroxide, two (tertiary butyls) Dimethylsilyl peroxide, tertiary butyl trivinyl silyl peroxides, two (tertiary butyl) divinyl silylation mistakes Oxide, three (tertiary butyl) vinyl silanes base peroxide, tertiary butyl triallyl silyl peroxides, two (tertiary butyls) Diallylsilane base peroxide and three (tertiary butyl) allyl silicane base peroxide.
Compared with organic 100 mass parts of (poly-) siloxanes total amount of (A) ingredient, the additive amount of (B) ingredient is 0.1~30 Mass parts are preferably 0.5~20 mass parts.(B) when the additive amount of ingredient is less than 0.1 mass parts, it can so that reaction can not be abundant Ground carries out, and solidfied material as a purpose is possible to that hardness can not be obtained.(B) when the additive amount of ingredient is more than 30 mass parts, except It is possible that the physical property after desired curing can not be obtained, be possible to that sufficient heat resistance, light resistance, chip resistance can not be obtained Outside property, it is also possible to the reason for colouring, becoming discoloration.In addition, when the additive amount of (B) ingredient is more than 30 mass parts, glue Degree is substantially reduced, and can not be used sometimes as die bond material
＜ (C) is bonded to the organic hydrogen polysiloxanes ＞ of the hydrogen atom on silicon atom in a molecule containing at least two
(C) organic hydrogen polysiloxanes of ingredient are the ingredients to play a role as crosslinking agent, hydrogen can occur with (A) ingredient SiClx alkylation reaction contributes to the curing of this composition.The organic hydrogen polysiloxanes have at least two and silicon original in a molecule The hydrogen atom (i.e. SiH yls) of sub-key knot, it is however preferred to have 3~500 hydrogen atoms being bonded with silicon atom, more preferably 3~200 It is a, particularly preferably 3~150.Silicon atom number (or degree of polymerization) in a molecule, it is preferable to use 2~200, more excellent It elects as and uses 3~150.Foregoing SiH bases can be located at any one in the non-end of molecule chain end and strand, can also Positioned at this both sides.
As the specific example of the group being bonded on silicon atom in this organic hydrogen polysiloxanes, it can be cited for example that with Do not have aliphatic unsaturated bond and 1 valency alkyl that is unsubstituted or being substituted down：Methyl, ethyl, propyl, isopropyl, butyl, The alkyl such as amyl, hexyl；The cycloalkyl such as cyclopenta, cyclohexyl；The aryl such as phenyl, tolyl, xylyl；Benzyl, benzene second The aralkyl such as base；Halogenated alkyls such as 3,3,3- trifluoro propyls, 3- chloropropyls etc.；Alkyl and aryl can be preferably enumerated, it can be with Particularly preferably enumerate methyl and phenyl.
(C) viscosity of the ingredient at 23 DEG C is preferably 0.5~100000mPas, particularly preferably 10~5000mPa s.The molecular structure of this organic hydrogen polysiloxanes does not limit, it can be cited for example that, straight-chain, branched have a part The straight-chain of branch, ring-type, solid netted etc..The organic hydrogen polysiloxanes can be made of single kind of siloxane unit Homopolymer (homopolymer) or the copolymer that is made of two or more siloxane unit or these is mixed Close object.
As the organic hydrogen polysiloxanes, it can be cited for example that, 1,1,3,3- tetramethyl disiloxane, 1,3,5,7- tetramethyls Basic ring tetrasiloxane, methylhydrogensiloxane cyclic polymer, methyl hydrogen siloxane-dimethyl siloxane cyclocopolymer, molecule Two terminal dimethyl group hydrogen siloxy of chain closing dimethyl polysiloxane, two end trimethylsiloxy group closing methyl hydrogen of strand are gathered Siloxanes, two end trimethylsiloxy group closing dimethyl siloxane-methyl hydrogen siloxane copolymer of strand, two end of strand Hold dimethyl hydrogen siloxy closing dimethyl siloxane-methyl hydrogen siloxane copolymer, two end trimethylsiloxy group closing first Base hydrogen siloxane-diphenylsiloxane copolymer, two end trimethylsiloxy group closing methyl hydrogen siloxane-diphenyl silica Alkane-dimethylsiloxane copolymer, two terminal dimethyl group hydrogen siloxies closing methyl hydrogen siloxane-dimethyl siloxane-hexichol Radical siloxane copolymer, by (CH3)2HSiO1/2Unit, (CH3)3SiO1/2Unit and SiO4/2Unit form copolymer, by (CH3)2HSiO1/2Unit and SiO4/2Unit form copolymer, by (CH3)2HSiO1/2Unit, SiO4/2Unit and (C6H5)3SiO1/2Copolymer that unit is formed etc..Wherein, more than the 1mol% preferably containing the siloxane unit entirety in (C) ingredient Dimethyl siloxane units, more preferably dimethyl siloxane units containing 1~100mol%.
In the present compositions, compared with 100 mass parts of (A) ingredient, the content of (C) ingredient is 0.1~20 mass parts, more excellent Elect 0.5~20 mass parts as, particularly preferably 1~10 mass parts.
If the content of (C) ingredient is less than 0.1 mass parts, this composition is not easy fully to cure, it may occur that solidfied material table The situation that face is not hardened.If it exceeds 20 mass parts, then this composition becomes by (B) ingredient not cured, and is based on The curing performance of oxide becomes weak.In addition, for the above reasons, the blended amount of this (C) ingredient also can be in (C) ingredient With silicon atom bond hydrogen atom (i.e. SiH yls) compared in this composition all containing in organic (poly-) siloxanes of alkenyl with (ingredient beyond (A) ingredient is in (B) ingredient when not having foregoing alkenyl to the molar ratio of the total amount of the alkenyl of silicon atom bond With the hydrogen atom of silicon atom bond compared with the molar ratio with the alkenyl of silicon atom bond in (A) ingredient) become 0.01~ The mode of 4.0mol/mol is blended, and is preferably 0.05~2.5mol/mol, particularly preferably 0.1~1.0mol/mol.
＜ (D) platinum group catalysts ＞
(D) platinum group catalyst of ingredient is for promoting the cured catalyst of this composition, it can be cited for example that platinum and platinum Compound as specific example, can be enumerated, chloroplatinic acid, the alcohol solution of chloroplatinic acid, the alkene complex of platinum, the alkenyl of platinum The carbonyl complex etc. of silicone complex, platinum.The content of (D) ingredient in this composition can be effective quantity, specifically, Compared with (A) ingredient, the palladium metal component in (D) ingredient is converted into platinum, and the amount of 0.01~1000ppm is calculated as with quality criteria, The preferably amount of 0.1~500ppm.
＜ other compositions ＞
The heat-curing type silicon-ketone composition of the present invention, under specific purposes, can also change containing other compositions Desired curing or uncured characteristic.For example, it can include to picture (methyl) acryloxy third of the amount of about 20 mass % Base trimethoxy silane, three alkyl ester of fulminuric acid or fulminuric acid triallyl, glycidoxypropyl group trimethoxy silicon Adhesion promotor as alkane, vinyltrimethoxysilane etc..As other any ingredients, can include to about 30 matter Measure non-(methyl) the acrylic acid silicone diluent of amount of % or plasticizer (plasticizer).As non-(methyl) silicon Acrylote Ketone can enumerate the trimethylsilyl end carburetion and silicone rubber of the viscosity with 100~500csp.Non- (methyl) third Olefin(e) acid silicone can include the co-curing base as vinyl.
In addition, in order to improve the intensity of the heat-curing type silicon-ketone composition of the present invention, adjustment viscosity, assign thixotropy (thixotropy) etc., it is further possible to which it is inorganic to blend aerosil (fumed silica), nano aluminium oxide etc. Matter filler.As needed, in heat-curing type silicon-ketone composition of the invention, dyestuff, pigment, fire retardant can also be blended Deng.
In addition, in order to improve the purpose of operability, can also add and using solvent etc..The species of solvent has no special limit System, can use can it is dissolving cured before heat-curing type silicon-ketone composition, aforementioned inorganic matter filler etc. is made to divide well It dissipates, and the solvent of uniform die bond material or adhesive etc. can be provided.As long as the blending ratio of the solvent is according to using die bond material Operating condition, environment, usage time etc. of material etc. is suitably adjusted.The solvent that can also be used together by two or more types.Make It for this solvent, can enumerate, fourth carbitol acetate, carbitol acetate, methyl ethyl ketone, α-abienol and cellosolve Acetic acid esters etc..
In addition, in the composition of the present invention, adhesiveness enhancer can also be blended.It, can example as adhesiveness enhancer Show silane coupling agent or its oligomer, have and the same silicone of reactive base etc. of silane coupling agent.
As adhesiveness enhancer, preferably there is silane compound or silicon that 1 or more epoxy contains base in the molecule Siloxane compound.It may be exemplified for example, containing the silane coupling agent of epoxy group or its hydrolytic condensate etc..As containing epoxy group Silane coupling agent or its hydrolytic condensate, can enumerate, glycidoxypropyltrime,hoxysilane, glycidoxypropyl group The silane compounds such as triethoxysilane or its hydrolytic condensate etc..
Adhesiveness enhancer is to improve the heat-curing type silicon-ketone composition of the present invention and its solidfied material for base material Adhesiveness and blend any ingredient in said composition.Herein, base material refers to the metal materials such as gold, silver, copper, nickel；Oxidation The ceramic materials such as aluminium, aluminium nitride, titanium oxide；The high molecular materials such as silicone resin, epoxy resin.Adhesiveness enhancer can individually make With a kind, two or more use can be also combined.
Compared with 100 mass parts of total amount of above-mentioned (A) ingredient and (B) ingredient, the blended amount of adhesiveness enhancer is preferred For 1~30 mass parts, more preferably 5~20 mass parts.If the blended amount is 5~20 mass parts, make the heating of the present invention Curing type silicon-ketone composition and its solidfied material are effectively improved for the adhesiveness of base material, and not easy coloring.
As the suitable specific example of adhesiveness enhancer, following examples can be enumerated, but are not limited to these examples.
A, r is 0~50 integer, and b, s, t are 1~50 integers.
In addition, in order to ensure service life, 3- methyl-1s-dodecyne -3- alcohol, 1- ethynylcyclohexanols, 3 can be blended, The addition reactions controlling agents such as 5- dimethyl -1- hexin -3- alcohol.
In order to inhibit to generate coloring, oxidative degradation etc. of solidfied material, can by 2,6- di-t-butyl -4- sylvans etc. with It is blended toward well known antioxidant in the heat-curing type silicon-ketone composition of the present invention.In addition, in order to assign to light deterioration Repellence, the light stabilizers such as amine system stabilizer that can also will be obstructed are blended in the heat-curing type silicon-ketone composition of the present invention.
The heat-curing type silicon-ketone composition of the present invention, can be by by mentioned component, using well known mixed method, example Such as mixed to manufacture using mixer, roller.In addition, the heat-curing type silicon-ketone composition of the present invention, using rotary Viscosimeter, such as E type viscosimeters, measured viscosity is 10~1000000mPas in the state of 23 DEG C, in particular, it is preferred that For 100~1000000mPas.
The heat-curing type silicon-ketone composition of the present invention, can pass through well known curing side under well known condition of cure Method is cured.Specifically, typically with 80~200 DEG C, be preferably heated with 100~160 DEG C, this can be made as a result, Composition cures.When heating time can be 0.5 minute~5 small or so, in particular, when can be 1 minute~3 small or so.It can be with Condition of cure is suitably selected by the balance between operating condition, productivity, light-emitting component and frame heat resistance.
The consolidating based on peroxide that the heat-curing type silicon-ketone composition of the present invention passes through progress (methyl) acryloyl group Change and the curing of the addition reaction both sides of SiH bases and unsaturated group, can obtain a kind of solidfied material, the solidfied material overcome by Cause the uncured situation of surface portion in oxygen inhibition.In addition, the heat-curing type silicon-ketone composition of the present invention can obtain one Kind solidfied material, the adhesive strength and operability of the solidfied material are excellent, and heat resistance, light resistance and crumpling resistance are excellent.
In addition, the present invention provides a kind of die bond material, it is made of the heat-curing type silicon-ketone composition of the invention described above. In particular, a kind of die bond material can be enumerated, can be used for semiconductor element being connected to wiring board.
The heat-curing type silicon-ketone composition of the present invention, can be adapted to LED chip being fixed on packaging body.This Outside, organic electroluminescent device (organic EL), laser diode and light emitting diode matrix (LED can also be suitable for Other optical semiconductors such as array).
The heat-curing type silicon-ketone composition of the present invention can obtain a kind of solidfied material, and the transparency of the solidfied material is high, Adhesive strength and operability are excellent, and heat resistance, light resistance and crumpling resistance are excellent.Therefore, if being heating and curing by above-mentioned The die bond material that type silicon-ketone composition is formed can be adapted to as LED chip to be carried on to the die bond on wiring board Material.
There is no particular restriction for the method for coating die bond material, it can be cited for example that, rotary coating, printing and compression forming Deng.The thickness of die bond material is typically 5~50 μm, especially 10~30 μm as long as properly selecting.Divide for example, using Dispensing device, temperature be 23 DEG C, pressure is 0.5~5kgf/cm2Under conditions of sent out, thus, it is possible to be applied easily Cloth.In addition, by using punching press (stamping) device, it can also be easily by the die bond material transferring of defined amount to base Plate.
There is no particular restriction for the bearing method of semiconductor element, it can be cited for example that bonder.Determine die bond material thickness An important factor for, it in addition to the viscosity of foregoing die bond material, can enumerate, when the crimping loading of optical semiconductor, crimping Between, crimping temperature.These conditions, as long as the outer shape according to optical semiconductor, die bond material thickness as a purpose come It properly selects.In general it is more than 1gf and below 1kgf to crimp loading.Preferably more than 10gf and below 100gf. If the crimping loading of more than 1gf, then die bond material can fully be crimped.In addition, if the crimping using below 1kgf Loading then will not cause to damage to the luminescent layer on optical semiconductor surface.As long as the time is crimped according to the productivity with step Between balance properly select, be in general more than 0 millisecond and less than 1 second.Preferably 1 millisecond or more and 30 millis Below second.If less than 1 second, in productive viewpoint preferably.Crimping temperature is not particularly limited, as long as according to die bond material The use temperature range of material, but in general, it is preferred to be 15 DEG C or more and less than 100 DEG C.If the crimping stations of bonder On when there is no warming-up device, as long as the use within the temperature range of room temperature.If 15 DEG C or more, die bond material Viscosity will not become excessively high, therefore can fully crimp.If less than 100 DEG C, die bond material will not start to cure, therefore, The thickness for the die bond material that can be achieved the goal.
Further, the present invention provides a kind of optical semiconductor device, is carried out with the above-mentioned die bond material by the present invention Solidfied material obtained by curing.
The optical semiconductor device of the present invention is consolidated due to having by what is be made of the heat-curing type silicon-ketone composition of the present invention Solidfied material obtained by brilliant material is cured, therefore a kind of optical semiconductor device can be become, have and overcome surface portion Uncured situation and heat resistance, light resistance and the excellent solidfied material of crumpling resistance.
The optical semiconductor device of the present invention, can manufacture in the following manner：In the adding by the present invention of coating on substrate After the die bond material that thermohardening type silicon-ketone composition is formed, according to previous known method, optical semiconductor is subjected to die bond.
Hereinafter, for one of embodiment of optical semiconductor device of the invention, illustrated with reference to diagram.Fig. 1 It is the sectional view for an example for representing optical semiconductor device, wherein, the optical semiconductor device had adding by the present invention Solidfied material obtained by the die bond material that thermohardening type silicon-ketone composition is formed is cured.Optical semiconductor device 10 shown in FIG. 1 It is on the 1st lead electrode 3 of the frame 1 of package substrate, having will be made of the heat-curing type silicon-ketone composition of the present invention Die bond material cured obtained by solidfied material 5, and in bearing semiconductor element 2 on this solidfied material 5.This optical semiconductor 2 electrode is to be electrically connected by gold thread 6 with the 1st lead electrode 3.In addition, the electrode of this optical semiconductor 2, is logical Gold thread 7 is crossed to be electrically connected with the 2nd lead electrode 4.In addition, this optical semiconductor 2, is carried out using sealing resin 8 Sealing.
The manufacturing method of optical semiconductor device 10 as Fig. 1, may be exemplified following methods.
First, on the 1st lead electrode 3 of the frame 1 of package substrate, quantitative transfer is by heat-curing type silicon of the invention The die bond material that one compositions are formed, and in carrying optical semiconductor 2 on the die bond material.Next, to die bond material It is heating and curing that solidfied material 5 is made.Next, using gold thread 6 by the electrode of optical semiconductor 2 and the 1st lead electrode 3 It is electrically connected, and is electrically connected the electrode of semiconductor element 2 and the 2nd lead electrode 4 using gold thread 7, to be carried There is the package substrate of optical semiconductor 2.Then, sealing resin 8 is quantitatively coated with, and by the sealing resin after coating well known Under condition of cure, cured according to well known curing, thus, it is possible to be sealed to package substrate.As with general The luminescent semiconductor device of solidfied material obtained by the die bond material of the present invention is cured, it can be cited for example that, LED, semiconductor swash Light, optical diode, photistor (phototransistor), solar cell, charge coupling device (charge Coupled device, CCD) etc..
[embodiment]
Hereinafter, embodiment and comparative example are shown, specifically describe the present invention, but the present invention is not limited to following embodiments.
(Examples 1 to 8, comparative example 1~5)
Prepare following component, and prepare the silicon-ketone composition of the composition shown in table 1,2.
(A-1)
Organopolysiloxane is made of following siloxane units, and MA：M：Q=1：4：6 ratio, molecular weight are 5000, and be solid at 25 DEG C, the molecular weight is according to gel permeation chromatography (GPC) and with the weight of polystyrene conversion Average molecular weight.
(A-2)
The organosiloxane represented by following structural formula, the viscosity at 25 DEG C are 7mPas.
(B-1)
As diacyl peroxide, peroxidating two (3- methyl benzoyls) (Di- (3- are directly used Methylbenzoyl) peroxide), benzoyl (3- methyl benzoyls) peroxide (Benzoyl- (3- Methylbenzoyl) peroxide) and dibenzoyl peroxide (Dibenzol peroxide) 40% xylene solution (trade name：Niper BMT-K40, Japanese grease limited company manufacture).
(B-2)
As peroxy esters, the benzoper acid tert-butyl ester (t-Butyl peroxybenzoate) (trade name is directly used： Perbutyl Z, Japanese grease limited company manufacture).
(C) crosslinking agent
Straight-chain organopolysiloxane is made of following siloxane units,
M：(CH3)3SiO1/2、
D：(CH3)2SiO2/2、
DH：(CH3)SiHO2/2,
And by M：D：DH=2：32：66 represent, the viscosity at 25 DEG C is 150mPas.
(D) platinum group catalyst：
Platinum 1,3- divinyl -1,1, the toluene solution of 3,3- tetramethyl disiloxane complex compounds, platinum content are 0.5 matter Measure %.
Any other ingredient
Viscosity modifier：Aerosil (trade name：REOLOSIL DM-30S, moral mountain (TOKUYAMA) company system It makes)
Adhesiveness enhancer：Contain the ring shape silicone oil (trade name of epoxy group in side chain：X-40-2670, SHIN-ETSU HANTOTAI's chemistry work Industry limited company manufactures)
Reaction controlling agent：3- methyl-1s-laurylene -3- alcohol
[table 1]
[table 2]
[measurement of hardness]
The composition obtained is poured into the grid (cell) of 2mm thickness, is cured with 150 DEG C × 2 condition when small, is come Prepare solidfied material.Then, manufactured hardometer D types are made using upper island to measure hardness.
[evaluation of surface viscosity]
The composition obtained is poured into aluminium dish, is cured with 150 DEG C × 2 condition when small under air, to prepare Solidfied material.The surface viscosity of obtained solidfied material is evaluated with finger touch.
[making of optical semiconductor package]
[(one annotates precision to SMD5050 to the LED package substrates with recess portion for having prepared respectively as LED package substrates Industries, Inc (I-CHIUN PRECISION INDUSTRY CO., LTD.) manufactures, and resin portion is poly- adjacent benzene two Formamide (PPA；Polyphthalamide)), the limited public affairs of Puri photoelectricity (Bridgelux) share as optical semiconductor The BXCD33 of manufacture is taken charge of, wherein the recess portion is for loading optical semiconductor, and is equipped with and has plated in the bottom of the recess portion The 1st lead electrode and the 2nd lead electrode of silver.
Using bonder (ASM limited companies manufacture, AD-830), by each composition shown in table 1,2, pass through punching press Mode, be quantitatively needed on the 1st silver-plated lead electrode of package substrate, and in carrying photosemiconductor member on the composition Part.The carrying condition of optical semiconductor at this time is 13 milliseconds of the time of crimping, crimps loading 60gf, without using heating apparatus simultaneously It is carried out in the environment of 25 DEG C of room temperature.Next, package substrate is put into baking oven, various die bond materials is made to be heating and curing (real Apply example 1~8, comparative example 2 and comparative example 4 be 150 DEG C, 4 it is small when, when comparative example 1 is 170 DEG C, 1 is small).Next, use gold thread (Tanaka's electronics industry limited company manufacture, 25 μm of line footpath (FA)) is by the electrode of optical semiconductor and the 1st lead electrode It is electrically connected, using gold thread (Tanaka's electronics industry limited company manufacture, 25 μm of line footpath (FA)) by semiconductor element Electrode is electrically connected with the 2nd lead electrode.Each a piece of LED package substrates for carrying optical semiconductor are obtained as a result, (with to encapsulate for number be 120).
Manner described above makes the different optical semiconductor package of die bond material, and uses it for tests below.
[chip shear test (Die shear test)]
It 10 in the optical semiconductor package that will be obtained using the above method, 25 DEG C of interior, is surveyed using pulling force Test-run a machine (bond tester) (Dage companies manufacture, Series 4000) carries out the measurement of Chip Adhesion Strength, and will be obtained The average value of the measured value obtained is represented with MPa.
[evaluation that the situation of surface cure is hindered due to oxygen]
In the optical semiconductor package obtained using the above method, 25 DEG C of interior, the pin that front end is tapering is utilized It scrapes around chip, confirmation whether there is due to oxygen and hinders the situation of surface cure.
The result of acquisition is shown in table 3,4.
[table 3]
[table 4]
As shown in table 3, Examples 1 to 8 has used the heat-curing type silicon-ketone composition for meeting the scope of the invention as solid Brilliant material, can obtain high rigidity and the solidfied material without surface viscosity, and the solidfied material is overcome since oxygen inhibition causes table The uncured situation in face part.Further, the result measured from Die shear, can manufacture bonding force height and reliability is high Luminescent semiconductor device.
On the other hand, comparative example 1,2 does not include C, D ingredient, although being all high rigidity and observing high Die shear, has Surface viscosity, and confirm due to oxygen and hinder the situation of surface cure.In addition, from comparative example 2, that is, substantially increase peroxide The amount of compound can not also prevent hindering here the situation of surface cure.During the amount surplus of B component (comparative example 3), viscosity significantly drops It is low, become that punching press can not be carried out.In addition, during C ingredient surpluses (comparative example 4), although can prevent from due to oxygen and surface being hindered to consolidate The situation of change, but result Die shear reduces.Comparative example 5 is free of B component, is cured merely with platinum catalyst, wherein, hardness It significantly decreases, and punching press can not be carried out since viscosity rises.
In addition, the present invention is not limited to above-mentioned embodiments.The above embodiment is to illustrate, as long as have and this hair The substantially identical composition of bright technological thought described in claim simultaneously plays the technical solution of same effect, all It is included in the technical scope of the present invention.

Claims (8)

1. a kind of heat-curing type silicon-ketone composition, which is characterized in that contain following component：
(A) organic (poly-) siloxanes of 100 mass parts, organic (poly-) siloxanes have at least one by following in the molecule The structure that general formula (1) represents,
In formula (1), m is any one in 0,1,2, R1It is hydrogen atom, phenyl or halogenated phenyl, R2It is hydrogen atom or methyl, R3It is Be substituted or it is unsubstituted and can be identical or different carbon number 1~12 1 valency organic group, Z1It is-R4-、-R4-O-、- R4(CH3)2Any one of Si-O-, Z2It is oxygen atom or is substituted or unsubstituted and can be identical or different carbon is former The divalent organic group of subnumber 1~10, R4Be be substituted or it is unsubstituted and can be identical or different carbon number 1~10 2 Valency organic group；
(B) organic peroxide of 0.1~30 mass parts, the organic peroxide are included selected from diacyl peroxide, mistake One or more of oxygen ester；
(C) organic hydrogen polysiloxanes of 0.1~20 mass parts, the organic hydrogen polysiloxanes contain at least two in a molecule The hydrogen atom being bonded on silicon atom；And
(D) platinum group catalyst, the content of the platinum group catalyst compared with (A) ingredient, are changed with the platinum in (D) ingredient as quality Calculate the amount for 0.01~1000ppm.
2. heat-curing type silicon-ketone composition as described in claim 1, wherein, organic (poly-) siloxanes of (A) ingredient Z1It is-R4-, Z2It is oxygen atom.
3. heat-curing type silicon-ketone composition as described in claim 1, wherein, organic (poly-) siloxanes of (A) ingredient Z1It is-R4- O- or-R4(CH3)2Si-O-, Z2Be be substituted or it is unsubstituted and can be identical or different carbon number 1~ 10 divalent organic group.
4. heat-curing type silicon-ketone composition as described in claim 1, wherein, organic (poly-) siloxanes of (A) ingredient, In the whole siloxane units for forming organic (poly-) siloxanes, there is (the SiO of more than 0.1mol%2) unit.
5. heat-curing type silicon-ketone composition as claimed in claim 2, wherein, organic (poly-) siloxanes of (A) ingredient, In the whole siloxane units for forming organic (poly-) siloxanes, there is (the SiO of more than 0.1mol%2) unit.
6. heat-curing type silicon-ketone composition as claimed in claim 3, wherein, organic (poly-) siloxanes of (A) ingredient, In the whole siloxane units for forming organic (poly-) siloxanes, there is (the SiO of more than 0.1mol%2) unit.
7. a kind of die bond material, which is characterized in that be by heat-curing type silicone group according to any one of claims 1 to 6 Object is closed to form.
8. a kind of optical semiconductor device, which is characterized in that have obtained by the die bond material described in claim 7 is cured Solidfied material.
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