CN107001769B - The optical semiconductor device of heat-curing type silicon oxygen composition, the die bond material that the composition is constituted and the solidfied material with the die bond material - Google Patents

The optical semiconductor device of heat-curing type silicon oxygen composition, the die bond material that the composition is constituted and the solidfied material with the die bond material Download PDF

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CN107001769B
CN107001769B CN201580065668.7A CN201580065668A CN107001769B CN 107001769 B CN107001769 B CN 107001769B CN 201580065668 A CN201580065668 A CN 201580065668A CN 107001769 B CN107001769 B CN 107001769B
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ingredient
heat
curing type
type silicon
aforementioned
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CN107001769A (en
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小内谕
小材利之
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Shin Etsu Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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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
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
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    • H01—ELECTRIC ELEMENTS
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    • 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
    • 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
    • H01L2224/73—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

Abstract

The present invention is a kind of heat-curing type silicon-ketone composition, contains following component: the organopolysiloxane for the structure that (A) is indicated at least one by the following general formula (1) in the molecule: 100 mass parts；(B) comprising the organic peroxide selected from one or more of diacyl peroxide, peroxy esters: 100 mass parts of total amount relative to aforementioned (A) ingredient are 0.1~20 mass parts；And the silane compound of (C) containing epoxy group or the silicone compounds containing epoxy group: 100 mass parts of total amount relative to aforementioned (A) ingredient are 0.1~20 mass parts.Accordingly, a kind of heat-curing type silicon-ketone composition can be provided, transparency height, adhesive strength and operability are excellent, and can obtain the solidfied material with heat resistance, light resistance and crumpling resistance,

Description

The die bond material and consolidated with this that heat-curing type silicon oxygen composition, the composition are constituted The optical semiconductor device of the solidfied material of brilliant material
Technical field
The present invention relates to a kind of heat-curing type silicon oxygen composition, the die bond material being made of the composition and uses should The optical semiconductor device of the solidfied material of die bond material.
Background technique
Since the optical semiconductors such as light emitting diode (Light Emitting Diode, LED) have power consumption Few such excellent characteristics gradually increases outside room on lighting use or mobile applications using luminescent semiconductor device (device).This The luminescent semiconductor device of sample is usually issued the photosemiconductor light-emitting component for issuing blue light, near ultraviolet ray or ultraviolet light Light, wavelength conversion is carried out by wavelength shifter, that is, fluorophor, and obtain the light emitting device of similar white light.Such light In semiconductor devices, optical semiconductor is bonded with frame using die bond material, is fixed.
It is using comprising 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, the epoxy resin for not absorbing ultraviolet light, curing agent and curing catalysts composition, In, the epoxy resin for not absorbing ultraviolet light (UV) is such as bisphenol-A epoxy resin or alicyclic epoxy resin.However, As the brightness and output of LED element are got higher, because of ultraviolet light, heat caused by LED element etc., can cause adhesive layer discoloration and The problem of fragmentation.
As the substance solved these problems, known is a kind of resin that epoxy group is imported in silicone resin, And the resin can provide do not absorb ultraviolet light and have can be flexible solidfied material, for example, proposing in report: one kind having 1 The cyclic ethers such as above glycidyl, epoxycyclohexyl contain the silicone resin (patent document 1) of base；It is a kind of that there is intramolecular Silicone copolymer resin that 1 or more ester ring type epoxy contains base, intramolecular contain base with 1 or more glycidyl Resin (patent document 2) obtained by 2 function silicone resins and use；Further, by ester ring type epoxy modified silicone resin and alicyclic ring Resin (patent document 3) obtained by formula epoxy resin and use etc..However, these resins are come using acid anhydrides or amine compound As curing agent, in general, when using this curing agent, it is necessary to cooperate epoxide equivalent to add the allotment number of curing agent. Therefore, as a result make in resin cured matter, become to have remained many organic functionals for being originated from cross-linked structure and there is light absorption Base leads to chipping or discoloration etc., at this due to being exposed under the light than previous more efficient LED element, heat for a long time These resins of aspect are simultaneously unable to satisfy required, it is desirable that are improved.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2008-45088 bulletin；
Patent document 2: Japanese Unexamined Patent Publication 2008-202036 bulletin；
Patent document 3: Japanese Unexamined Patent Publication 2011-109058 report.
Summary of the invention
Problem to be solved by the invention
The present invention considers above-described problem and completes that its purpose is to provide a kind of heat-curing type silicone combinations Object, transparency height, adhesive strength and operability are excellent, and can obtain consolidating with heat resistance, light resistance and crumpling resistance Compound.In addition, other objects of the present invention are to provide a kind of die bond material being made of the composition.Further, of the invention Another object be to provide a kind of optical semiconductor device, be that optical semiconductor is subjected to die bond using the die bond material.
The technical solution solved the problems, such as
In order to achieve the above objectives, the present invention provides a kind of heat-curing type silicon-ketone composition, which is characterized in that containing with Lower ingredient:
(A) organopolysiloxane of the structure indicated in the molecule at least one by the following general formula (1): 100 mass Part；
In formula (1), m is any of 0,1,2, R1It is hydrogen atom, phenyl or halogenated phenyl, R2It is hydrogen atom or methyl, R3Be substituted or unsubstituted and can be identical or different carbon number 1~12 1 valence 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 number 1~10 divalent organic group, wherein R4Be substituted or unsubstituted and can be identical or different carbon number 1~ 10 divalent organic group；
(B) comprising the organic peroxide selected from one or more of diacyl peroxide, peroxy esters: relative to aforementioned (A) 100 mass parts of total amount of ingredient are 0.1~20 mass parts；And
(C) silane compound containing epoxy group or the silicone compounds containing epoxy group: relative to aforementioned (A) ingredient 100 mass parts of total amount be 0.1~20 mass parts.
If it is this heat-curing type silicon-ketone composition, the transparency is high, adhesive strength and operability are excellent, and can be with Obtain heat resistance, light resistance and the excellent solidfied material of crumpling resistance.
Furthermore it is preferred that being the Z of the organopolysiloxane of aforementioned (A) ingredient1It is-R4, aforementioned Z2It is oxygen atom.
Furthermore it is preferred that being the Z of the organopolysiloxane of aforementioned (A) ingredient1It is-R4- O- or-R4(CH3)2Si-O-, it is aforementioned Z2Be substituted or unsubstituted and can be identical or different carbon number 1~10 divalent organic group.
If it is this heat-curing type silicon-ketone composition, then generated free radical and (A) ingredient when (B) ingredient breakdown Reaction can be effectively performed, thus adhesive strength and operability are excellent, and it is excellent to obtain heat resistance, light resistance and crumpling resistance Different solidfied material.
Furthermore it is preferred that being the organopolysiloxane of aforementioned (A) ingredient, have at least one by the following general formula in the molecule (2) structure indicated:
In formula (2), m, R1、R2、R3、R4It is same as described above.
If it is this heat-curing type silicon-ketone composition, then generated free radical and (A) ingredient when (B) ingredient breakdown It can be more effectively carried out reaction, thus adhesive strength and operability are excellent, and can obtain heat resistance, light resistance and crumpling resistance Excellent solidfied material.
Furthermore it is preferred that be, in the organopolysiloxane of aforementioned (A) ingredient, (the SiO with 0.1mol% or more2) single Member.
If it is this heat-curing type silicon-ketone composition, then generated free radical and (A) ingredient when (B) ingredient breakdown It can effectively further be reacted, further, the epoxy group of the organic acid and (C) ingredients that generated by (B) ingredient can be effective Ground is reacted, thus adhesive strength and operability are excellent, and can obtain heat resistance, light resistance and crumpling resistance is excellent consolidates Compound.
Furthermore it is preferred that be the solidfied material of thickness 2mm obtained by being solidified aforementioned heat-curing type silicon-ketone composition, Its full light transmittance is 80% or more, and haze value is 20% or less.
If it is this heat-curing type silicon-ketone composition, the transparency of the solidfied material of the composition can change height.
Further, the present invention provides a kind of die bond material, which is characterized in that is the heat-curing type by aforementioned present invention Silicon-ketone composition is constituted.
If it is this die bond material, the die bond material for being equipped on LED chip on wiring board can be suitable as Material.
Further, the present invention provides a kind of optical semiconductor device, which is characterized in that has the die bond of aforementioned present invention Solidfied material obtained by material is solidified.
Heat-curing type silicon-ketone composition of the invention, transparency height, adhesive strength and operability are excellent, and can obtain Heat resistance, light resistance and the excellent solidfied material of crumpling resistance.Therefore, optical semiconductor device use of the invention is by die bond material Solidfied material obtained by being solidified, and the die bond material be made of the heat-curing type silicon-ketone composition, thus the present invention Optical semiconductor device become with heat resistance, light resistance and crumpling resistance.
Invention effect
Heat-curing type silicon-ketone composition of the invention can obtain a kind of solidfied material (transparent cured object), the solidification The transparency of object, adhesive strength and operability are excellent, and have heat resistance, light resistance, crumpling resistance and discoloration-resistant.Therefore, The die bond material being made of heat-curing type silicon-ketone composition of the invention can be suitably used for as being used to LED chip The die bond material being carried on wiring board.In addition, used the die bond material is solidified obtained by the light of solidfied material partly lead Body device then becomes with heat resistance, light resistance and crumpling resistance.
Detailed description of the invention
Fig. 1 is the sectional view for indicating an example of optical semiconductor device of the invention, wherein the optical semiconductor device Solidfied material obtained by being solidified die bond material is used, the die bond material is by heat-curing type silicone group of the invention Object is closed to constitute.
Specific embodiment
Hereinafter, the present invention is described in more detail.
As described above, needing a kind of heat-curing type silicon-ketone composition, transparency height, adhesive strength and operability are excellent It is different, and the solidfied material with heat resistance, light resistance and crumpling resistance can be obtained.
The present inventor studies in order to achieve the above objectives and attentively.Finally, it is found that a kind of heat-curing type silicone Composition, transparency height, adhesive strength and operability are excellent, and it is excellent to obtain heat resistance, light resistance and crumpling resistance Solidfied material, and be capable of providing the optical semiconductor device of high reliablity, thereby completing the present invention, wherein the heat-curing type Silicon-ketone composition is characterized in that, contains following component:
(A) organopolysiloxane of the structure indicated in the molecule at least one by the following general formula (1): 100 mass Part；
In formula (1), m is any one of 0,1,2, R1It is hydrogen atom, phenyl or halogenated phenyl, R2It is hydrogen atom or methyl, R3Be substituted or unsubstituted and can be identical or different carbon number 1~12 1 valence organic group, Z1It is-R4-、-R4- O-、-R4(CH3)2Si-O-(R4Be substituted or unsubstituted and can be identical or different carbon number 1~10 divalent organic group Any one of group), Z2Oxygen atom or substituted or unsubstituted and can be identical or different carbon number 1~10 2 Valence organic group；
(B) comprising the organic peroxide selected from one or more of diacyl peroxide, peroxy esters: relative to aforementioned (A) 100 mass parts of total amount of ingredient are 0.1~20 mass parts；And
(C) silane compound containing epoxy group or the silicone compounds containing epoxy group: relative to aforementioned (A) ingredient 100 mass parts of total amount be 0.1~20 mass parts.
Hereinafter, further illustrating the present invention, but the present invention is not limited to this.
[(A) organopolysiloxane]
(A) organopolysiloxane of ingredient is the structure indicated in the molecule at least one by the following general formula (1) Organopolysiloxane.
In formula (1), m is any of 0,1,2, R1It is hydrogen atom, phenyl or halogenated phenyl, R2It is hydrogen atom or methyl, R3Be substituted or unsubstituted and can be identical or different carbon number 1~12 1 valence organic group, Z1It is-R4-、-R4- O-、-R4(CH3)2Si-O-(R4Be substituted or unsubstituted and can be identical or different carbon number 1~10 divalent organic group Any one of group), Z2Oxygen atom or substituted or unsubstituted and can be identical or different carbon number 1~10 2 Valence organic group.
(A) in the organopolysiloxane of ingredient, as Z1With Z2Combination, preferably, Z1It is-R4-、Z2It is the group of oxygen atom Conjunction or Z1It is-R4- O- or-R4(CH3)2Si-O-、Z2Be substituted or unsubstituted and can be identical or different carbon number 1 The combination of~10 divalent organic group.If it is the heat-curing type silicon-ketone composition comprising this (A) ingredient, then (B) ingredient Generated free radical can be effectively performed with (A) ingredient and react when decomposition, thus adhesive strength and operability are excellent, and can be with Obtain heat resistance, light resistance and the excellent solidfied material of crumpling resistance.
In addition, in the organopolysiloxane of (A) ingredient, preferably, (the SiO with 0.1mol% or more2) unit.If The heat-curing type silicon-ketone composition comprising this (A) ingredient, then when (B) ingredient breakdown generated free radical and (A) at Branch is effectively further reacted, and further, the epoxy group of the organic acid and (C) ingredient that are generated by (B) ingredient has Reacted to effect, thus adhesive strength and operability are excellent, and it is excellent to obtain heat resistance, light resistance and crumpling resistance Solidfied material.
Further, the organopolysiloxane of (A) ingredient preferably has at least one by the following general formula in the molecule (2) structure indicated.If it is the heat-curing type silicon-ketone composition comprising this (A) ingredient, then produced when (B) ingredient breakdown Raw free radical, which is more effectively carried out with (A) at branch, to react, thus adhesive strength and operability are excellent, and can obtain heat-resisting Property, light resistance and the excellent solidfied material of crumpling resistance.
In formula (2), m, R1、R2、R3、R4It is same as described above.
Furthermore it is preferred that being the solidification of thickness 2mm obtained by being solidified heat-curing type silicon-ketone composition of the invention Object, full light transmittance are 80% or more, and haze value is 20% or less.If it is such heat-curing type silicone combination The transparency of object, the solidfied material of the composition can change height.In addition, haze value is to define in the following manner: (haze value (%))=(diffusion light transmittance)/(full light transmittance) × 100.
(A) organopolysiloxane of ingredient, preferably, the liquid or solid that viscosity at 25 DEG C is 10mPas or more Branched or space network organopolysiloxane.
In above-mentioned general formula (1), as by R3It is represented to be incorporated into being substituted or unsubstituted on silicon atom and With 1 identical or different valence organic group, the alkyl that carbon number is 1~12, preferably, carbon number 1~8 or so can be usually enumerated Alkyl can specifically be enumerated: methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, amyl, neopentyl, The alkyl such as hexyl, cyclohexyl, octyl, nonyl, decyl；The aryl such as phenyl, tolyl, xylyl, naphthalene；Benzyl, benzene second The aralkyl such as base, phenylpropyl；Vinyl, allyl, acrylic, isopropenyl, cyclobutenyl, hexenyl, cyclohexenyl group, octenyl Equal alkenyls；And some or all of hydrogen atom of these groups is replaced and obtained by the halogen atoms such as fluorine, bromine, chlorine, cyano etc. The halogen-substituted alkyls and cyanoethyl etc. such as group, such as chloromethyl, chloropropyl, bromoethyl, trifluoro propyl.
In above-mentioned general formula (1), as by R4The represented divalent for being substituted or unsubstituted and can be identical or different Organic group can specifically be enumerated, the alkylene that the carbon atom numbers such as methylene, ethylidene, propylidene, butylidene are 1~10 The divalent alkyls such as base；Preferably, the alkylidene that carbon atom number is 1~3.
The example of the organopolysiloxane of (A) ingredient described below (in following formula, Me indicates methyl).The ingredient can be Single component can also be used in combination with other compositions.In addition, in following formula, the R that is equivalent in above-mentioned formula (1)3Group, be with The case where methyl as example, but can also be altered to other groups (substituted or unsubstituted and can it is identical or 1 valence organic group of different carbon numbers 1~12).
Organopolysiloxane represented by following formula, be with the ratio of MA:M:Q=1:4:6 come include MA unit, M unit, Q unit, and molecular weight is 5000, the molecular weight is the weight average molecular weight to be converted with polystyrene.
Organic polysiloxane represented by following formula is with the ratio of MA-D:D:T=2:6:7 including MA-D unit, D Unit, T unit, and molecular weight is 3500, and the molecular weight is the weight average molecular weight to be converted with polystyrene.
(A) in ingredient, in order to adjust composition viscosity or solidfied material hardness the purpose of, can add following represented The reactive diluent comprising silicone or the reactive diluent without silicone.
As the specific example of the reactive diluent comprising silicone, can enumerate is had by what following formula (3)~(7) indicated Machine polysiloxanes (in following formula, Me indicates methyl).The ingredient can be single component, can also be used in combination with other compositions.
In formula (5), p is that 18, q is 180.
In formula (6), p ' is that 20, q is 180.
In formula (7), p is that 18, q is 180.
As the synthetic method of this (A) ingredient, as long as such as in the presence of chloroplatinic acid catalyst, making following compound With having comprising unsaturated group of aliphatic series (it can be cited for example that ethylenic unsaturated group and acetylene unsaturated group) Machine polysiloxanes carries out hydrosilylation (hydrosilylation) reaction: organohydrogensilicon alkane represented by following formula,
In above-mentioned formula, m, R1、R2、R3、Z1It is same as described above；
Preferably, compound represented by following formula,
In above-mentioned formula, m, R1、R2、R3、Z1、Z2It is same as described above；
More specifically, (3- methacryloxypropyl) -1,1,3,3- tetramethyl disiloxane, be by by 1, Bis- (3- methacryloxypropyl) tetramethyl disiloxanes of 3- and 1,1,3,3- tetramethyl disiloxane, in acid catalyst In the presence of being balanced reaction obtained；It can be produced using this method and be suitable for the compound of the present invention, but is unlimited In synthetic method above-mentioned.In addition, the organopolysiloxane comprising unsaturated group of aliphatic series, can use comprising having fat Method well known to (total) hydrolytic condensation of the alkoxy silane of the organopolysiloxane of race's unsaturated group etc. manufactures, can also be with Use commercially available product.
As the reactive diluent for being free of silicone, just like H2C=CGCO2R5Represented (methyl) esters of acrylic acid, on It states in formula, G is any one of hydrogen, halogen, the alkyl of carbon atom number 1~4, R5It is selected from the alkane with 1~16 carbon atom Any one of base, naphthenic base, alkenyl, cycloalkenyl, alkaryl, aralkyl, aryl.Any one of these groups, Ke Yigen According to needs, with silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, carbamate, amine, amide, sulphur, sulphonic acid ester, Sulfo group etc. replaces.
As (methyl) particularly preferred in reactive diluent esters of acrylic acid, have for example with the following acrylic acid being consistent Ester: polyethylene glycol two (methyl) acrylate, as ethoxylated bisphenol A (methyl) acrylate (" EBIPA " or " EBIPMA ") this Bisphenol-A two (methyl) acrylate of sample, tetrahydrofuran (methyl) acrylate and two (methyl) acrylate, propylene sour Thatch ester and methacrylic acid citronellyl acrylate, (methyl) hydroxypropyl acrylate, hexylene glycol two (methyl) acrylate (" HDDA " or " HDDMA "), trimethylolpropane tris (methyl) acrylate, (methyl) acrylic acid tetrahydro bicyclopentadiene ester, three hydroxyl of ethoxyquin Propane tri (" ETTA "), triethylene glycol diacrylate and triethylene glycol dimethacrylate (" TRIEGMA "), isobornyl acrylate and isobornyl methacrylate.Certainly, the group of these (methyl) esters of acrylic acid Conjunction can also be used as reactive diluent use.
Additive amount when addition reactive diluent, the preferably range of 0.01~30 mass %, more preferably 0.05~ The range of 10 mass %.
Heat-curing type silicon-ketone composition of the invention can also change under specific purposes containing other compositions Desired solidification or uncured characteristic.For example, may include as (methyl) acryloyloxypropyltrimethoxysilane, different three Adhesion promotor as paracyanogen acid three alkyl esters or fulminuric acid triallyl, vinyl front three oxosilane etc., preferably, packet Containing the amount to about 20 mass %.Other any ingredients can enumerate non-(methyl) acrylic acid silicone diluent or plasticizer (plasticizer), preferably, comprising the amount to about 30 mass %.As non-(methyl) silicon Acrylote ketone, tool can be enumerated There are the trimethylsilyl end carburetion and silicone rubber of the viscosity of 100~500mPas.Non- (methyl) silicon Acrylote ketone, can To include the co-curing base as vinyl.
[(B) organic peroxide]
(B) ingredient comprising selected from one or more of diacyl peroxide, peroxy esters organic peroxide, be for After heat-curing type silicon-ketone composition of the invention is configured to desired shape, heat and by being crosslinked instead The silicon-ketone composition should be made to solidify blended ingredient, and it is possible to according to the connection temperature of purpose, Connection Time, use Time limit etc. properly selects.
Organic peroxide, for the viewpoint by having both high response and long life, preferably, half-life period is 10 small When temperature be 40 DEG C or more, and it is 200 DEG C hereinafter, more preferably, half-life period is 10 hours that half-life period, which is 1 minute temperature, Temperature is 60 DEG C or more, and the temperature that half-life period is 1 minute is 180 DEG C or less.
At this point, above-mentioned (A) can be made by free radical caused by the thermal decomposition because of the organic peroxide of (B) ingredient It is generated between the alkenyls such as vinyl, allyl between the alkyl being bonded on silicon atom in ingredient or in above-mentioned (A) ingredient Bonding reaction, and crosslinking curing object is made.Further, a part as the decomposition product of (B) ingredient, can generate has The organic acid of carboxyl, thus the organic acid as the epoxy reaction with aftermentioned (C) ingredient crosslinking agent and play a role, energy Enough form more robust cross-linked structure.
As diacyl peroxide, it can be cited for example that, isobutyl peroxide, 2,4- dichloro-benzoyl base peroxidating Object, 3,5,5- trimethyl acetyl base peroxide, sim peroxides, dodecane acyl peroxide, stearyl peroxide Compound, succinic peroxide compound (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- Methylethyl, the tertiary own ester of peroxide neodecanoic acid, the peroxide trimethylace tonitric tert-butyl ester, peroxide -2- second Bis- (2- ethylhexanoylperoxy) hexanes of base caproic acid -1,1,3,3- tetramethyl butyl ester, 2,5- dimethyl -2,5-, peroxide -2- second Base caproic acid -1- cyclohexyl -1- Methylethyl, 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 three Base hecanoic acid t-butyl ester, the peroxide lauric acid/dodecanoic acid tert-butyl ester, 2,5- dimethyl -2,5- bis- (toluyl groups peroxy) hexanes, peroxide Isopropyl single carbon tert-butyl acrylate, peroxide -2- ethylhexyl single carbon 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 2 kinds with Upper use.
As other organic peroxides, it can be cited for example that, dialkyl peroxide, peroxydicarbonate, peroxide Ketal, hydroperoxides, silyl peroxides etc..Also these organic peroxides and above-mentioned (B) ingredient can namely be wrapped It is applied in combination containing the organic peroxide selected from one or more of diacyl peroxide, peroxy esters.
As dialkyl peroxide, it can be cited for example that, it is α, α '-bis(t-butylperoxy) diisopropyl benzene, two withered Base peroxide, 2,5- dimethyl -2,5- bis(t-butylperoxy) 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, Bis- (4- tert-butylcyclohexyl) esters of two carbonic acid of peroxide, two carbonic acid of peroxide, two -2- ethyoxyl methoxyethoxy ester, bis- (2- ethylhexyl peroxides Base) two carbonic esters, two carbonic acid dimethoxy butyl ester of peroxide and bis- (3- methyl -3- methoxybutyl peroxies) two carbonic esters.
As peroxy ketal, it can be cited for example that, 1,1- bis- (tertiary hexyl peroxies) -3,3,5- trimethyl-cyclohexanes, 1, Bis- (the tertiary hexyl peroxy) hexamethylenes of 1-, 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexane, 1,1- (tert-butyl 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, tert-butyl trimethylsilyl peroxide, two (tert-butyls) Dimethylsilyl peroxide, tert-butyl trivinyl silyl peroxides, two (tert-butyl) divinyl silylation mistakes Oxide, three (tert-butyl) vinyl silanes base peroxide, tert-butyl triallyl silyl peroxides, two (tert-butyls) Diallylsilane base peroxide and three (tert-butyl) allyl silicane base peroxide.
Relative to 100 mass parts of organopolysiloxane total amount of (A) ingredient, the additive amount of (B) ingredient is 0.1~20 matter Measure part, preferably 0.5~10 mass parts.(B) when the additive amount of ingredient is less than 0.1 mass parts, reaction can be made to be unable to fully ground It carries out, solidfied material as a purpose is possible to that hardness can not be obtained.(B) when the additive amount of ingredient is more than 20 mass parts, in addition to having Possibly can not obtain the physical property after desired solidification, be possible to that sufficient heat resistance, light resistance, crumpling resistance can not be obtained Except, it is also possible to it colours, the reason of full light transmittance for becoming solidfied material is low, discoloration.
[silane compound of (C) containing epoxy group or the silicone compounds containing epoxy group]
Heat-curing type silicon-ketone composition of the invention contains the silane compound containing epoxy group as (C) ingredient Or the silicone compounds containing epoxy group.These compounds, as long as in the molecule containing 1 or more epoxy group.This In specification, refer to containing epoxy group, includes epoxy group at least part of group, for example, alkyl, alkane can be contained The others functional group such as ether and epoxy group.
In the present invention, as mentioned earlier, as a part of the decomposition product of (B) ingredient, can generate having with carboxyl Machine acid, therefore the purpose for adding (C) ingredient is that the organic acid can be as the crosslinking reacted with the epoxy group of (C) ingredient Agent plays a role, and forms further firm cross-linked structure, thus (C) ingredient be important component.
(C) it in ingredient, is not particularly limited as epoxy group, it can be cited for example that, glycidyl, epoxycyclohexyl etc.. More specifically, it can be cited for example that, 2,3- glycidyl, 3,4- epoxybutyl, 4,5- epoxypentyl, 2- glycidoxy second Base, 3- glycidoxypropyl group, 4- glycidoxy butyl etc..
As (C) ingredient, as long as the silane compound or siliconization that there is intramolecular 1 or more epoxy to contain base Object is closed, then is not particularly limited.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, it can be cited for example that, glycidoxypropyltrime,hoxysilane, glycidoxy The silane compounds such as propyl-triethoxysilicane or its hydrolytic condensate etc..
(C) in ingredient, as the silicone compounds containing epoxy group, can enumerate it is following shown in silicone compound Object, but can be not limited to using these silicone compounds.
A, r is 0~50 integer, and b, s, t are 1~50 integers.
By containing (C) ingredient, heat-curing type silicon-ketone composition of the invention, the penetrability after solidification is high, for light The fever of semiconductor element or luminous heat resistance and excellent in light-resistance, and remain to obtain by force even for thermal shock repeatedly Tough characteristic, i.e. crumpling resistance.
Relative to 100 mass parts of total amount of aforementioned (A) ingredient, the additive amount of (C) ingredient is 0.1~20 mass parts, excellent It is selected as 0.5~15 mass parts.(C) when the additive amount of ingredient is less than 0.1 mass parts, it is possible to after desired solidification can not be obtained Physical property, i.e. be possible to can not obtain sufficient heat resistance, light resistance, crumpling resistance.(C) additive amount of ingredient is more than 20 mass When part, reaction is unable to fully carry out, and unreacted epoxy group remains in solidfied material, and it is therefore possible to become discoloration.
[(D) other compositions]
In order to further maintain the transparency of composition, inhibit coloring, the oxidative degradation etc. that generate solidfied material, can by 2, The known antioxidant such as 6- di-t-butyl -4- sylvan blends in heat-curing type silicon-ketone composition of the invention. In addition, the light stabilizers such as amine system stabilizer that can also will be obstructed are blended in of the invention in order to assign the repellence to light deterioration In heat-curing type silicon-ketone composition.
In order to improve the intensity of heat-curing type silicon-ketone composition of the invention, adjustment viscosity, assign thixotropy (thixotropy) etc., it is further possible to which it is inorganic to blend fumed silica (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, can also add to improve the purpose of operability using solvent etc..The type of solvent has no special limit System, can be used can it is dissolving cured before heat-curing type silicon-ketone composition, divide aforementioned inorganic matter filler etc. well The solvent for dissipating, and uniform die bond material or adhesive capable of being provided etc..As long as the blending ratio of the solvent is according to using die bond material The operating condition of material etc., is suitably adjusted using time etc. environment.Also the solvent that two or more kinds may be used.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, heat-curing type silicon-ketone composition of the invention, can also assign containing the bonding to improve its adhesiveness Give agent.As the silane coupling agent or its hydrolytic condensate etc. other than the bonding imparting agent, such as above-mentioned (C) ingredient.As (C) Silane coupling agent other than ingredient, such as the silane coupling agent containing (methyl) acryloyl group, the silane containing isocyanate group are even Mixture, the silane coupling agent containing fulminuric acid base, the silane coupling agent containing amino, silane coupling agent containing sulfydryl etc. 0.1~20 mass can be preferably used relative to 100 mass parts of total amount of aforementioned (A) ingredient in well known silane coupling agent Part, 0.3~10 mass parts can more preferably be preferably used.
Heat-curing type silicon-ketone composition of the invention can use well known mixed method, example by by mentioned component It is such as mixed using blender, roller to manufacture.In addition, heat-curing type silicon-ketone composition of the invention, using rotary Viscosimeter, such as E type viscosimeter, measured viscosity is 10~1000000mPas in the state of 23 DEG C, in particular, it is preferred that For 100~1000000mPas.
Heat-curing type silicon-ketone composition of the invention can pass through well known solidification side under well known condition of cure Method is solidified.Specifically, usually with 80~200 DEG C, preferably heated with 100~160 DEG C, this can be made as a result, Composition solidification.Heating time is 0.5 minute~5 hours or so, in particular, preferably 1 minute~3 hours or so.It can be by grasping Make the balance between condition, productivity, light-emitting component and frame heat resistance suitably to select condition of cure.
Heat-curing type silicon-ketone composition of the invention, can suitably use and LED chip is fixed on packaging body. In addition it is also possible to suitably be used in organic electroluminescent device (organic EL), laser diode and light emitting diode matrix The others such as (LED array) optical semiconductor.
Further, the present invention provides a kind of die bond material, is the heat-curing type silicone combination by aforementioned present invention Object is constituted, and can be used to semiconductor element being connected to wiring board.
Heat-curing type silicon-ketone composition of the invention, transparency height, adhesive strength and operability are excellent, and can obtain Heat resistance, light resistance and the excellent solidfied material of crumpling resistance.Therefore, if it is by above-mentioned heat-curing type silicon-ketone composition The die bond material of composition can suitably be used as the die bond material LED chip to be carried on to wiring board.
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 molding Deng.The thickness of die bond material, as long as properly selecting, usually 5~50 μm, especially 10~30 μm.For example, using dividing Dispensing device, temperature is 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 other than the viscosity of aforementioned die bond material, can enumerate, when the crimping loading of optical semiconductor, crimping Between, crimping temperature.These conditions, as long as die bond material thickness according to the outer shape of optical semiconductor, as a purpose comes It properly selects.In general crimping loading is 1gf or more and 1kgf or less.Preferably 10gf or more and 100gf or less. If it is the crimping loading of 1gf or more, then die bond material can fully be crimped.In addition, if using 1kgf crimping below Loading then will not cause to damage to the luminescent layer on optical semiconductor surface.As long as crimping the time according to the productivity with step Between balance properly select, be in general more than 0 millisecond and 1 second or less.Preferably 1 millisecond or more and 30 millis Second or less.If it is 1 second hereinafter, 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 100 DEG C or less.If the crimping stations of bonder On when there is no warming-up device, as long as use within the temperature range of room temperature.If it is 15 DEG C or more, die bond material Viscosity will not become excessively high, therefore can fully crimp.If it is 100 DEG C hereinafter, die bond material will not start to solidify, 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, carries out die bond material of the invention with above-mentioned Solidfied material obtained by solidification.
Optical semiconductor device of the invention has the die bond that will be made of heat-curing type silicon-ketone composition of the invention Solidfied material obtained by material is solidified, therefore there is heat resistance, light resistance and crumpling resistance.
Optical semiconductor device of the invention can manufacture in the following manner: being coated on substrate and added by of the invention After the die bond material that thermohardening type silicon-ketone composition is constituted, according to previous known method, optical semiconductor is subjected to die bond.
Hereinafter, being directed to one of embodiment of optical semiconductor device of the invention, it is illustrated referring to diagram.Fig. 1 It is the sectional view for indicating an example of optical semiconductor device of the invention, wherein the optical semiconductor device has will be by this Solidfied material obtained by the die bond material that the heat-curing type silicon-ketone composition of invention is constituted is solidified.Light shown in FIG. 1 is partly led Body device is in the 1st lead electrode 3 of the frame 1 of package substrate, and having will be by heat-curing type silicone combination of the invention Solidfied material obtained by the die bond material 5 that object is constituted is solidified, and the bearing semiconductor element 2 on the solidfied material.The light is partly led The electrode of volume elements part 2 is to be electrically connected by gold thread 6 with the 1st lead electrode 3.In addition, the electricity of the optical semiconductor 2 Pole is to be electrically connected by gold thread 7 with the 2nd lead electrode 4.In addition, the optical semiconductor 2, is to utilize sealing resin 8 To be sealed.
The manufacturing method of optical semiconductor device as Fig. 1 can be exemplified as following methods.
Firstly, quantitative transfer is by heat-curing type silicon of the invention in the 1st lead electrode 3 of the frame 1 of package substrate The die bond material 5 that one compositions are constituted, and optical semiconductor 2 is carried on the die bond material 5.Next, to die bond material Material 5 is heating and curing.Next, the electrode of optical semiconductor 2 and the 1st lead electrode 3 are electrically connected using gold thread 6 It connects, the electrode of semiconductor element 2 and the 2nd lead electrode 4 is electrically connected using gold thread 7, carry photosemiconductor to obtain The package substrate of element 2.Then, it is quantitatively coated with sealing resin 8, by the sealing resin being coated under well known condition of cure, Solidified according to well known curing method, thus, it is possible to be sealed to package substrate.As having die bond of the invention The luminescent semiconductor device of solidfied material obtained by material is solidified, it can be cited for example that, LED, semiconductor laser, optical diode, Photistor (phototransistor), solar battery, charge-coupled device (charge coupled device, CCD) etc..
[embodiment]
Hereinafter, providing Examples and Comparative Examples, the present invention is specifically described, but the present invention is not limited to following embodiments. (in following formula, Me indicates methyl.)
[preparation example]
(preparation example 1~3)
Following component is stirred, the silicon-ketone composition of composition shown in table 1 is prepared.
[(A) ingredient]
(A-1)
Organopolysiloxane represented by following formula, be with the ratio of MA:M:Q=1:4:6 come include MA unit, M unit, Q unit, and molecular weight is 5000, the molecular weight is the weight average molecular weight to be converted with polystyrene.
(A-2)
Organopolysiloxane represented by following formula.(in following formula, Me indicates methyl.)
(A-3)
Organopolysiloxane represented by following formula is with the ratio of MA-D:D:T=2:6:7 including MA-D unit, D Unit, T unit, and molecular weight is 3500, the molecular weight is the weight average molecular weight to be converted with polystyrene.(in following formula, Me Indicate methyl.)
The blended amount of (A) ingredient of preparation example 1~3, as shown in table 1.
[table 1]
Preparation example 1 Preparation example 2 Preparation example 3
(A-1) 80 70
(A-2) 20 30 40
(A-3) 60
[(B) ingredient]
(B-1)
As diacyl peroxide, two (3- methyl benzoyl) peroxide (Di- (3- can be directly used Methylbenzoyl) peroxide), benzoyl (3- methyl benzoyl) peroxide (Benzoyl- (3- Methylbenzoyl) peroxide) and dibenzoyl peroxide (Dibenzol peroxide) (trade name: Niper BMT-K40, Japanese grease limited liability company manufacture).
(B-2)
As peroxy esters, the peroxide -2 ethyl hexanoic acid tert-butyl ester (t-Butyl peroxy-2- can be directly used Ethylhexanoate) (trade name: Perbutyl O, Japanese grease limited liability company manufacture).
(B-3)
As dialkyl peroxide, tert-butyl cumyl peroxide (t-Butyl cumyl can be directly used Peroxide) (trade name: Perbutyl C, Japanese grease limited liability company manufacture).
[(C) ingredient]
(C-1)
It can be used directly for the reactive silicone oil (trade name: X-22-343, SHIN-ETSU HANTOTAI's chemical industry that branch contains epoxy group Limited liability company's manufacture).
(C-2)
As the silane compound containing epoxy group, glycidoxypropyltrime,hoxysilane (quotient can be directly used The name of an article: KBM-403, Shin-Estu Chemical Co., Ltd's manufacture).
(C-3)
It, can be directly using 2,4,6,8- tetramethyls represented by following formula as the silicone compounds containing epoxy group Base -2,4,6,8- tetra- [β-(3,4- expoxycyclohexyl) ethyl] cyclotetrasiloxane (trade names: X-40-2670, SHIN-ETSU HANTOTAI's chemistry work Industry limited liability company manufacture).
(C-4)
As the silane compound for not containing epoxy group, 3- methacryloxypropyl trimethoxy can be directly used Silane (trade name: KBM-503, Shin-Estu Chemical Co., Ltd's manufacture).
[Examples 1 to 6]
(embodiment 1)
Will as 100 mass parts of silicon-ketone composition obtained of preparation example 1 of (A) ingredient, as (B-1) of (B) ingredient 10 mass parts, (C-1) 4 mass parts as (C) ingredient, the 7 mass parts (product of aerosol silica as supporting material Name: REOLOSIL DM-30S, TOKUYAMA limited liability company manufacture) mixing, kneading processing further is carried out with three rollers, And decompression de-bubble is carried out to manufacture resin combination.
(embodiment 2)
Will as 100 mass parts of silicon-ketone composition obtained of preparation example 2 of (A) ingredient, as (B-1) of (B) ingredient 10 mass parts, (C-1) 4 mass parts as (C) ingredient, the 7 mass parts (product of aerosol silica as supporting material Name: REOLOSIL DM-30S, TOKUYAMA limited liability company manufacture) mixing, kneading processing further is carried out with three rollers, And decompression de-bubble is carried out to manufacture resin combination.
(embodiment 3)
Will as 100 mass parts of silicon-ketone composition obtained of preparation example 3 of (A) ingredient, as (B-1) of (B) ingredient 10 mass parts, (C-1) 4 mass parts as (C) ingredient, the 7 mass parts (product of aerosol silica as supporting material Name: REOLOSIL DM-30S, TOKUYAMA limited liability company manufacture) mixing, kneading processing further is carried out with three rollers, And decompression de-bubble is carried out to manufacture resin combination.
(embodiment 4)
Will as 100 mass parts of silicon-ketone composition obtained of preparation example 1 of (A) ingredient, as (B-2) 5 of (B) ingredient Mass parts, (C-1) 4 mass parts as (C) ingredient, 7 mass parts of aerosol silica as supporting material (ProductName: The manufacture of REOLOSIL DM-30S, TOKUYAMA limited liability company) mixing, kneading processing further is carried out with three rollers, is gone forward side by side Row depressurizes de-bubble to manufacture resin combination.
(embodiment 5)
Will as 100 mass parts of silicon-ketone composition obtained of preparation example 1 of (A) ingredient, as (B-2) 5 of (B) ingredient Mass parts, (C-2) 4 mass parts as (C) ingredient, 7 mass parts of aerosol silica as supporting material (ProductName: The manufacture of REOLOSIL DM-30S, TOKUYAMA limited liability company) mixing, kneading processing further is carried out with three rollers, is gone forward side by side Row depressurizes de-bubble to manufacture resin combination.
(embodiment 6)
Will as 100 mass parts of silicon-ketone composition obtained of preparation example 1 of (A) ingredient, as (B-1) of (B) ingredient 10 mass parts, (C-3) 5 mass parts as (C) ingredient, the 7 mass parts (product of aerosol silica as supporting material Name: REOLOSIL DM-30S, TOKUYAMA limited liability company manufacture) mixing, kneading processing further is carried out with three rollers, And decompression de-bubble is carried out to manufacture resin combination.
[comparative example 1~4]
(comparative example 1)
Will as 100 mass parts of silicon-ketone composition obtained of preparation example 1 of (A) ingredient, as (B-3) 5 of (B) ingredient Mass parts, (C-1) 4 mass parts as (C) ingredient, 7 mass parts of aerosol silica as supporting material (ProductName: The manufacture of REOLOSIL DM-30S, TOKUYAMA limited liability company) mixing, kneading processing further is carried out with three rollers, is gone forward side by side Row depressurizes de-bubble to manufacture resin combination.
(comparative example 2)
Will as 100 mass parts of silicon-ketone composition obtained of preparation example 1 of (A) ingredient, as (B-1) 5 of (B) ingredient Mass parts, (C-4) 4 mass parts as (C) ingredient, 7 mass parts of aerosol silica as supporting material (ProductName: The manufacture of REOLOSIL DM-30S, TOKUYAMA limited liability company) mixing, kneading processing further is carried out with three rollers, is gone forward side by side Row depressurizes de-bubble to manufacture resin combination.
(comparative example 3)
Will as 100 mass parts of silicon-ketone composition obtained of preparation example 1 of (A) ingredient, as (B-1) 5 of (B) ingredient Mass parts do not add (C) ingredient, 7 mass parts of the aerosol silica (ProductName: REOLOSIL DM- as supporting material The manufacture of 30S, TOKUYAMA limited liability company) mixing, kneading processing further is carried out with three rollers, and is carried out decompression de-bubble and come Manufacture resin combination.
(comparative example 4)
Following component is mixed:
35 mass parts of silicone oil, average composition formula are MViD300MVi；
65 mass parts of silicone resin are by M unit, MViUnit and Q unit are constituted, and relative to MViUnit, M unit Molar ratio be 6.25, relative to Q unit, M unit and MViTotal molar ratio of unit is 0.8；
8 mass parts of methyl hydrogen siloxane, average formula are by MDH 80M is indicated；
0.06 mass parts of toluene solution containing chloroplatinic acid/1,3- divinyl tetramethyl disiloxane complex compound, and institute The pt atom content for stating toluene solution is 1 mass %；
Acetylene basic ring 0.05 mass parts of alcohol；
3 mass parts of γ-glycidoxypropyltrime,hoxysilane；And
7 mass parts of aerosol silica (ProductName: REOLOSIL DM-30S, TOKUYAMA strand as supporting material Part Co., Ltd manufacture)；
Kneading processing further is carried out with three rollers, and carries out decompression de-bubble to prepare silicone die bond material.
In addition, in above-mentioned silicone die bond material, to indicate that the mark of average composition of each composition is indicated with lower unit.
M:(CH3)3SiO1/2
MVi: (CH2=CH) (CH3)2SiO1/2
DH: (CH3)HSiO2/2
D:(CH3)2SiO2/2
Q:SiO4/2
For the composition of embodiment, comparative example, following various characteristics are measured.It the results are shown in Table 2.
[measurement of haze measurement and full light transmittance]
Mist degree and full light are carried out using the haze meter NDH-5000SP that Japanese electricity Se Industries, Inc manufactures The measurement of penetrance.Mixed sample will be carried out with above-mentioned condition, and the sample cell (cell) of 2mm thickness be poured into, with defined item Part (Examples 1 to 6, comparative example 2~4 are 150 DEG C, 4 hours, and comparative example 1 is 170 DEG C, 1 hour) Lai Jinhang is heating and curing, obtains The solidfied material that surface is clean and 2mm is thick is obtained, the solidfied material is installed on measurement portion to measure.Measurement 3 times, acquires mist degree The average value of value, full light transmittance.
[production of optical semiconductor package]
Package substrate [SMD5050 (the I-CHIUN of the LED with recess portion as LED package substrate is prepared respectively The manufacture of PRECISION limited liability company, resin portion are polyphthalamide (PPA；Polyphthalamide))], make For the BXCD33 that the Bridgelux limited liability company of optical semiconductor manufactures, wherein the recess portion is for loading light half Conductor element, and silver-plated the 1st lead electrode and the 2nd lead electrode are equipped in the bottom of the recess portion.
Using bonder (ASM limited liability company manufactures, AD-830), by various die bonds shown in Examples and Comparative Examples Material is quantitatively needed on the 1st silver-plated lead electrode of package substrate, and in the die bond material by way of punching press Upper carrying optical semiconductor.The carrying condition of optical semiconductor at this time is 13 milliseconds of the time of crimping, crimps loading 60gf, It is carried out without using heating apparatus and in the environment of 25 DEG C of room temperature.Next, package substrate is put into baking oven, make various die bonds Material is heating and curing (Examples 1 to 6, comparative example 2~4 are 150 DEG C, 4 hours, and comparative example 1 is 170 DEG C, 1 hour).Next, Using gold thread (Tanaka's electronics industry limited liability company manufacture, 25 μm of line footpath (FA)) by the electrode of optical semiconductor and the 1st Lead electrode is electrically connected, and will partly be led using gold thread (Tanaka's electronics industry limited liability company manufactures, 25 μm of line footpath (FA)) The electrode of volume elements part is electrically connected with the 2nd lead electrode.Each a piece of LED for carrying optical semiconductor is obtained as a result, to use Package substrate (with to encapsulate for number be 120).
Then, the above-mentioned LED package substrate obtained for carrying photosemiconductor of half is taken (to encapsulate for number It is 60), using dispenser (Musashi high-tech limited liability company manufactures, Super Σ CM II), it is close to be quantitatively coated with silicone Closure material (ProductName: KER2500, Shin-Estu Chemical Co., Ltd manufacture), and with the condition of 150 DEG C, 4 hours come into Row sealing material is heating and curing.
Manner described above, the different optical semiconductor package of production die bond material, and it is used for following tests.
[temperature cycling test]
By using the above method 10 be filled in the optical semiconductor package of sealing material obtained, it to be used for temperature Cyclic test (- 40 DEG C~125 DEG C, each 20 minutes, carry out 1000 circulations), utilizes the photosemiconductor after the test of micro- sem observation Whether there is or not fragmentations in the jointing material portion of packaging body, and calculate the quantity of chipping optical semiconductor package.
[high temperature dot lantern test]
By using the above method 10 be filled in the optical semiconductor package of sealing material obtained, at high temperature (85 DEG C), energization 150mA after lighting 1000 hours, utilize micro- sem observation optical semiconductor and carrying optical semiconductor Recess portion bottom between the case where whether there is or not the Poor cohesions such as removing, whether there is or not fragmentation occur and optical semiconductor around it is viscous Closing layer, whether there is or not discolorations, and calculate the quantity that the optical semiconductor package of abnormal appearance occurs.
[chip shear test (Die shear test)]
By using 10 in the above method unfilled optical semiconductor package for having sealing material obtained, at 25 DEG C Interior, use measurer for pulling force (bond tester) (Dage limited liability company manufacture, Series 4000) Lai Jinhang core The measurement of piece shear strength, and the average value of measured value obtained is indicated with MPa.
The result of acquisition is shown in table 2.
[table 2]
As shown in table 2, Examples 1 to 6 is to use the heat-curing type silicon-ketone composition for meeting the scope of the invention as admittedly Brilliant material, wherein by full light transmittance, mist degree result it is found that the Examples 1 to 6 can obtain consolidating for high transparency Compound, will not be chipping after temperature cycling test, and whole packaging bodies can carry out lighting.In addition, even if carrying out High temperature dot lantern test, composition is in appearance and unchanged, and whole packaging bodies can carry out lighting.Further, by The result of Die shear measurement is it is found that the luminescent semiconductor device of bonding force height and high reliablity can be manufactured.
On the other hand, comparative example 1 is the silicone resin component for not meeting the scope of the invention using (B) ingredient, wherein by Full light transmittance, mist degree result it is found that its transparency is good, but in the heat-curing step of die bond material and can not It is sufficiently carried out solidification, good solidfied material can not be obtained.Therefore, there is generation in temperature cycling test, high temperature dot lantern test The case where fragmentation, can not also obtain sufficient adhesive strength in Die shear measurement test.
Comparative example 2 is the silicone resin component for not meeting the scope of the invention using (C) ingredient, wherein is worn by full light Saturating rate, the result of mist degree it is found that its transparency is good, but in the heat-curing step of die bond material and can not fully into Row solidification, can not obtain good solidfied material.Therefore, there are chipping feelings in temperature cycling test, high temperature dot lantern test Condition can not also obtain sufficient adhesive strength in Die shear measurement test.
The formula of comparative example 3 is not added with (C) composition, wherein by full light transmittance, mist degree result it is found that its is transparent Property be it is good, in the heat-curing step of die bond material, although being sufficiently carried out solidification, be easy to happen fragmentation, therefore, In temperature cycling test, high temperature dot lantern test, there is very low probability chipping, and in Die shear measurement test, Sufficient adhesive strength can not be obtained.
Comparative example 4 is to use general silicone resin as die bond material, can by the result of full light transmittance, mist degree Know, can not be the solidfied material of high transparency.Not chipping after temperature cycling test, whole packaging bodies can carry out Lighting, in addition, resin combination is in appearance and unchanged even if carrying out high temperature dot lantern test, and whole packaging bodies can Enough carry out lighting.On the other hand, Die shear measurement as a result, be compared to object of the invention, the bonding force of comparative example 4 compared with It is low.
In addition, the present invention is not limited to above-mentioned embodiments.Above embodiment is example, as long as having and this hair The substantially identical composition of the technical idea recorded in bright claims and the technical solution for playing same function and effect, all It is included in technical scope of the invention.

Claims (10)

1. a kind of heat-curing type silicon-ketone composition, which is characterized in that contain following component:
(A) organopolysiloxane of the structure indicated in the molecule at least one by the following general formula (1): 100 mass parts；
In formula (1), m is any of 0,1,2, R1It is hydrogen atom, phenyl or halogenated phenyl, R2It is hydrogen atom or methyl, R3It is Substituted or unsubstituted and can be identical or different carbon number 1~12 1 valence organic group, Z1It is-R4-、-R4-O-、-R4 (CH3)2Any one of Si-O-, Z2Oxygen atom or substituted or unsubstituted and can be identical or different carbon number 1 ~10 divalent organic group, wherein R4Be substituted or unsubstituted and can be identical or different carbon number 1~10 divalent Organic group；
(B) comprising selected from one or more of diacyl peroxide, peroxy esters organic peroxide: relative to aforementioned (A) at 100 mass parts of total amount divided are 0.1~20 mass parts；And
(C) containing the silicone compounds of epoxy group: 100 mass parts of total amount relative to aforementioned (A) ingredient are 0.1~20 matter Measure part.
2. heat-curing type silicon-ketone composition as described in claim 1, wherein the Z of the organopolysiloxane of aforementioned (A) ingredient1 It is-R4, aforementioned Z2It is oxygen atom.
3. heat-curing type silicon-ketone composition as described in claim 1, wherein the Z of the organopolysiloxane of aforementioned (A) ingredient1 It is-R4- O- or-R4(CH3)2Si-O-, aforementioned Z2Be substituted or 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 the organopolysiloxane of aforementioned (A) ingredient, The structure indicated at least one by the following general formula (2) in molecule:
In formula (2), m, R1、R2、R3、R4It is same as described above.
5. heat-curing type silicon-ketone composition as claimed in claim 2, wherein the organopolysiloxane of aforementioned (A) ingredient, The structure indicated at least one by the following general formula (2) in molecule:
In formula (2), m, R1、R2、R3、R4It is same as described above.
6. heat-curing type silicon-ketone composition as claimed in claim 3, wherein the organopolysiloxane of aforementioned (A) ingredient, The structure indicated at least one by the following general formula (2) in molecule:
In formula (2), m, R1、R2、R3、R4It is same as described above.
7. such as heat-curing type silicon-ketone composition described in any one of claims 1 to 6, wherein in having for aforementioned (A) ingredient In machine polysiloxanes, (the SiO with 0.1mol% or more2) unit.
8. such as heat-curing type silicon-ketone composition described in any one of claims 1 to 6, wherein by aforementioned heat-curing type The solidfied material of thickness 2mm obtained by silicon-ketone composition is solidified, full light transmittance is 80% or more, and haze value is 20% or less.
9. a kind of die bond material, which is characterized in that be by heat-curing type silicone group described in any one of claims 1 to 6 Object is closed to constitute.
10. a kind of optical semiconductor device, which is characterized in that have and solidify die bond material as claimed in claim 9 and obtained Solidfied material.
CN201580065668.7A 2014-12-08 2015-10-19 The optical semiconductor device of heat-curing type silicon oxygen composition, the die bond material that the composition is constituted and the solidfied material with the die bond material Active CN107001769B (en)

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