CN108070261B - Heat-curable silicon-oxygen composition, die-bonding material, and optical semiconductor device - Google Patents

Heat-curable silicon-oxygen composition, die-bonding material, and optical semiconductor device Download PDF

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CN108070261B
CN108070261B CN201711092143.XA CN201711092143A CN108070261B CN 108070261 B CN108070261 B CN 108070261B CN 201711092143 A CN201711092143 A CN 201711092143A CN 108070261 B CN108070261 B CN 108070261B
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silicone composition
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CN108070261A (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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Abstract

The problem to be solved by the present invention is to provide a heat-curable silicone composition that can give a cured product that overcomes the problem of surface partial non-curing due to oxygen inhibition. The technical scheme for solving the problems is that the heating curing type silicone composition is characterized by comprising the following components: (A)100 parts by mass of an organo (poly) siloxane having at least 1 structure represented by the following general formula (1) in a molecule,
Figure DDA0001461469200000011
(B) 0.1-30 parts by mass of an organic peroxide, wherein the organic peroxide comprises a diacyl peroxide or a peroxyester; (C)0.1 to 20 parts by mass of an organohydrogenpolysiloxane containing at least 2 hydrogen atoms bonded to silicon atoms in one molecule; and (D) a platinum-based catalyst in an amount of 0.01 to 1000 ppm.

Description

Heat-curable silicon-oxygen composition, die-bonding material, and optical semiconductor device
Technical Field
The present invention relates to a heat-curable silicon oxygen composition, a die bonding material composed of the composition, and an optical semiconductor device using a cured product of the die bonding material.
Background
Since optical semiconductor elements such as Light Emitting Diodes (LEDs) have excellent characteristics such as low power consumption, they are increasingly used for optical semiconductor devices (devices) for outdoor lighting and automotive applications. Such an optical semiconductor device is generally a light emitting device in which light emitted from an optical semiconductor light emitting element that emits blue light, near ultraviolet light, or ultraviolet light is wavelength-converted by a phosphor that is a wavelength conversion material to obtain white light. In such an optical semiconductor device, the optical semiconductor element is bonded and fixed to the frame using a die bonding material.
As a die bond material composition for an optical semiconductor element, conventionally, a composition containing a bisphenol a type epoxy resin having excellent adhesiveness, mechanical strength and the like, an ultraviolet-non-absorbing epoxy resin such as a hydrogenated bisphenol a type epoxy resin or an alicyclic epoxy resin, a curing agent and a curing catalyst has been used in many cases. However, as the luminance and output of the LED element become higher, the problem of discoloration and chipping of the adhesive layer is caused by ultraviolet rays, heat, and the like generated from the LED element.
Therefore, it has been proposed to use a silicone resin as a substitute for an epoxy resin in a die attach material for an optical semiconductor element (patent documents 1 and 2). The curing mechanism of silicone resins is various, but an addition reaction of SiH groups and alkenyl groups, which is carried out using a platinum catalyst, is mainly used. In this case, an adhesion improver having a (meth) acryloyl group, an epoxy group, or the like is often added to improve adhesion to the substrate. If the amount of the adhesion improver added is small, the adhesion is poor, but if the amount is too large, the effect on the physical properties after curing becomes large, for example, the hardness is lowered, and thus the adhesion improver cannot be used in a large amount.
On the other hand, there is an example of curing with a peroxide using a methacryloyl group or the like which is an adhesive functional group (patent documents 3 and 4), but there is a problem that curability of the surface is deteriorated because curing is inhibited by oxygen. Further, since the inhibition of curing by oxygen is caused even when the methylpropionyl group is cured by Ultraviolet (UV) irradiation, a method of solving the influence by addition curing has been proposed (patent document 5), but this method actually requires both UV curing and thermal curing, and thus is difficult to apply to a site where complicated device design is required, such as UV irradiation cannot be performed.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2004-186168;
patent document 2: japanese patent laid-open publication No. 2006-342200;
patent document 3: japanese patent laid-open No. 2008-074982;
patent document 4: japanese patent laid-open publication No. 2016-108456;
patent document 5: japanese patent laid-open publication No. 2013-203794.
Disclosure of Invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a heat-curable silicone composition which can give a cured product that overcomes the problem of surface partial non-curing due to oxygen inhibition. The present invention also provides a die bond material comprising the composition. Further, an object of the present invention is to provide an optical semiconductor device having a cured product of the die attach material.
In order to solve the above problems, the present invention provides a heat-curable silicone composition comprising:
(A)100 parts by mass of an organo (poly) siloxane having at least 1 structure represented by the following general formula (1) in a molecule,
Figure BDA0001461469180000021
in the formula (1), m is any one of 0, 1 and 2, R1Is a hydrogen atom, a phenyl group or a halogenated phenyl group, R2Is a hydrogen atom or a methyl group, R3Is a substituted or unsubstituted 1-valent organic group having 1 to 12 carbon atoms, Z1is-R4-、-R4-O-、-R4(CH3)2Any one of Si-O-, Z2Is an oxygen atom or a substituted or unsubstituted 2-valent organic group having 1 to 10 carbon atoms, wherein R is4Is a substituted or unsubstituted 2-valent organic group having 1 to 10 carbon atoms which may be the same or different;
(B) 0.1-30 parts by mass of an organic peroxide, wherein the organic peroxide comprises more than 1 selected from diacyl peroxides and peroxyesters;
(C)0.1 to 20 parts by mass of an organohydrogenpolysiloxane containing at least 2 hydrogen atoms bonded to silicon atoms in one molecule; and the number of the first and second groups,
(D) a platinum-based catalyst in an amount of 0.01 to 1000ppm in terms of platinum in the component (D) based on the component (A).
The heat-curable silicone composition of the present invention can provide a cured product that overcomes the problem of the surface portion being uncured due to oxygen inhibition by performing both the peroxide-based curing of a (meth) acryloyl group and the addition reaction of an SiH group and an unsaturated group.
In this case, Z of the organo (poly) siloxane of the component (A) is preferably Z1is-R4-，Z2Is an oxygen atom.
In this case, Z of the organo (poly) siloxane of the component (A) is preferably Z1is-R4-O-or-R4(CH3)2Si-O-，Z2Is a substituted or unsubstituted 2-valent organic group having 1 to 10 carbon atoms which may be the same or different.
If it is Z containing1、Z2The heat-curable silicone composition containing the component (a) in combination of (a) can give a cured product excellent in adhesive strength and workability, and excellent in heat resistance, light resistance and chipping resistance, because radicals generated during decomposition of the component (B) react with the component (a) effectively.
The organo (poly) siloxane of the component (A) preferably has 0.1 mol% or more of (SiO) in all siloxane units constituting the organo (poly) siloxane2) And (4) units.
In the case of a heat-curable silicone composition containing component (a), radicals generated during decomposition of component (B) react with component (a) more efficiently, and thus a cured product having further excellent adhesive strength and handling properties, and excellent heat resistance, light resistance, and chipping resistance can be obtained.
The present invention also provides a die bonding material comprising the heat-curable silicone composition.
The heat-curable silicone composition of the present invention can provide a cured product that is excellent in adhesive strength and workability, and is excellent in heat resistance, light resistance, and chipping resistance, and therefore can be suitably used as a die bonding material.
The present invention also provides an optical semiconductor device comprising a cured product obtained by curing the die attach material.
An optical semiconductor device having a cured product obtained by curing a crystal-fixing material composed of the heat-curable silicone composition of the present invention can be highly reliable.
The heat-curable silicone composition of the present invention can provide a cured product that overcomes the problem of the surface portion being uncured due to oxygen inhibition, has excellent adhesive strength and handling properties, and has excellent heat resistance, light resistance, and chipping resistance, by performing both of (meth) acryloyl group-based peroxide curing and SiH group-and unsaturated group-based addition reaction curing. An optical semiconductor device having a cured product obtained by curing a crystal-fixing material composed of the heat-curable silicone composition of the present invention can be highly reliable.
Drawings
Fig. 1 is a cross-sectional view showing an example of an optical semiconductor device of the present invention.
Wherein the reference numerals are as follows:
1, a frame;
2 an optical semiconductor element;
3 1 st lead electrode;
4, 2 nd lead electrode;
5 a die bond material (cured product);
6. 7, gold wire;
8 sealing resin;
10 optical semiconductor device.
Detailed Description
The present inventors have intensively studied to achieve the above object, and as a result, have found that a heat-curable silicone composition containing the following components (a) to (D) can obtain a cured product which overcomes the problem that a surface portion is not cured due to oxygen inhibition by curing both of a (meth) acryloyl group-based peroxide and an SiH group and an unsaturated group without UV irradiation, by curing the composition. The heat-curable silicone composition, the die attach material, and the optical semiconductor device of the present invention will be described in detail below.
That is, the present invention provides a heat-curable silicone composition characterized by containing the following components:
(A)100 parts by mass of an organo (poly) siloxane having at least 1 structure represented by the following general formula (1) in a molecule,
Figure BDA0001461469180000051
in the formula (1), m is any one of 0, 1 and 2, R1Is a hydrogen atom, a phenyl group or a halogenated phenyl group, R2Is a hydrogen atom or a methyl group, R3Is a substituted or unsubstituted 1-valent organic group having 1 to 12 carbon atoms, Z1is-R4-、-R4-O-、-R4(CH3)2Any one of Si-O-, Z2Is an oxygen atom or a substituted or unsubstituted 2-valent organic group having 1 to 10 carbon atoms, wherein R is4Is a substituted or unsubstituted 2-valent organic group having 1 to 10 carbon atoms which may be the same or different;
(B) 0.1-30 parts by mass of an organic peroxide, wherein the organic peroxide comprises more than 1 selected from diacyl peroxides and peroxyesters;
(C)0.1 to 20 parts by mass of an organohydrogenpolysiloxane containing at least 2 hydrogen atoms bonded to silicon atoms in one molecule; and the number of the first and second groups,
(D) a platinum-based catalyst in an amount of 0.01 to 1000ppm in terms of platinum in the component (D) based on the component (A).
< (A) component: organo (poly) siloxanes
(A) The organo (poly) siloxane of component (a) is an organo (poly) siloxane having at least 1 structure represented by the following general formula (1) in a molecule. In the present invention, the organo (poly) siloxane means an organosiloxane in which 1 siloxane bond (-Si-O-Si-) is present in one molecule and/or an organopolysiloxane containing 2 or more siloxane bonds in one molecule.
Figure BDA0001461469180000052
In the formula (1), m is any one of 0, 1 and 2, R1Is a hydrogen atom, a phenyl group or a halogenated phenyl group, R2Is a hydrogen atom or a methyl group, R3Is a substituted or unsubstituted 1-valent organic group having 1 to 12 carbon atoms, Z1is-R4-、-R4-O-、-R4(CH3)2Si-O-(R4Is any of substituted or unsubstituted and may be the same or different, a 2-valent organic group having 1 to 10 carbon atoms), Z2Is an oxygen atom or a substituted or unsubstituted 2-valent organic group having 1 to 10 carbon atoms which may be the same or different.
(A) In the organo (poly) siloxanes of component (B), as Z1And Z2Preferably, Z1is-R4-、Z2Is a combination of oxygen atoms, or Z1is-R4-O-or-R4(CH3)2Si-O-、Z2Is a combination of substituted or unsubstituted 2-valent organic groups having 1 to 10 carbon atoms, which may be the same or different. Heating if containing the component (A)The curable silicone composition can provide a cured product that is excellent in adhesive strength and workability, and is excellent in heat resistance, light resistance, and chipping resistance, because radicals generated when the component (B) is decomposed react with the component (a) efficiently.
Further, it is preferable that the organic (poly) siloxane constituting the component (A) has 0.1 mol% or more of (SiO) units in the whole siloxane units2) And (4) units. In the case of a heat-curable silicone composition containing component (a), radicals generated during decomposition of component (B) react with component (a) more efficiently, and thus a cured product having further excellent adhesive strength and handling properties, and excellent heat resistance, light resistance, and chipping resistance can be obtained.
Further, it is preferable that the organo (poly) siloxane of the component (a) has at least 1 structure represented by the following general formula (2) in the molecule. In the case of a heat-curable silicone composition containing component (A), radicals generated during decomposition of component (B) react with component (A) more efficiently, and thus a cured product having excellent adhesive strength and workability, and excellent heat resistance, light resistance, and chipping resistance can be obtained.
Figure BDA0001461469180000061
In the formula (2), m and R1、R2、R3、R4As described above.
(A) The organo (poly) siloxane as the component (B) is preferably a liquid or solid branched or three-dimensional network-structured organopolysiloxane having a viscosity of 5 mPas or more at 25 ℃.
In the above general formula (1), as represented by R3The 1-valent organic group having 1 to 12 carbon atoms, which may be the same or different and is substituted or unsubstituted, bonded to a silicon atom, is preferably about 1 to 8 carbon atoms, and specifically, there may be mentioned: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentylAlkyl groups such as hexyl, cyclohexyl, octyl, nonyl, decyl and the like; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl, phenethyl, and phenylpropyl; alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, and octenyl; and those in which some or all of the hydrogen atoms are substituted with a halogen atom such as fluorine, bromine or chlorine, a cyano group or the like, for example, a halogen-substituted alkyl group such as chloromethyl, chloropropyl, bromoethyl or trifluoropropyl, a cyanoethyl group or the like.
The following exemplifies the organo (poly) siloxane of the component (a).
Figure BDA0001461469180000071
Further, examples of the organic (poly) siloxane as the component (a) include: an organopolysiloxane represented by the following formula, which is MA: m: q is 1: 4: 6 MA unit, M unit, Q unit, and a molecular weight of 5000, the molecular weight being a weight average molecular weight in terms of polystyrene;
Figure BDA0001461469180000072
an organopolysiloxane represented by the following formula, wherein the MA-D units, and T units are MA-D: d: t is 2: 6: 7, and the molecular weight is 3500, and the molecular weight is a weight average molecular weight in terms of polystyrene.
Figure BDA0001461469180000081
Examples of the organo (poly) siloxane as the component (a) include organo (poly) siloxanes having the structures shown below.
Figure BDA0001461469180000082
In the above formula, p is 18 and q is 180.
Figure BDA0001461469180000091
In the above formula, t is 18 and u is 180.
As a method for synthesizing the component (a), for example, the following compounds may be used in the hydrosilylation reaction with an organic (poly) siloxane containing an aliphatic unsaturated group (for example, an ethylenic unsaturated group and an acetylenic unsaturated group) in the presence of a platinum catalyst: an organohydrogensilane represented by the following formula,
Figure BDA0001461469180000092
in the above formula, m and R1、R2、R3、Z1The same as above;
preferably, the compound represented by the following formula,
Figure BDA0001461469180000093
in the above formula, m and R1、R2、R3、Z1、Z2The same as above;
more specifically, (3-methacryloxypropyl) -1,1,3, 3-tetramethyldisiloxane, which is obtained by an equilibration reaction of 1, 3-bis (3-methacryloxypropyl) tetramethyldisiloxane with 1,1,3, 3-tetramethyldisiloxane in the presence of an acid catalyst; the compounds suitable for the present invention can be produced by this method, but are not limited to the aforementioned synthetic methods. The organic (poly) siloxane containing an aliphatic unsaturated group can be produced by a known method such as (co) hydrolytic condensation of an alkoxysilane containing an organopolysiloxane having an aliphatic unsaturated group, or a commercially available product can be used.
These (A) components may be used singly or in combination of 2 or more.
In the component (a), a reactive diluent containing silicone or a reactive diluent not containing silicone as shown below may be added for the purpose of adjusting the viscosity of the composition, the hardness of the cured product, and the like.
As the reactive diluent containing silicone, an organopolysiloxane having the following structure can be exemplified.
Figure BDA0001461469180000101
The reactive diluent containing silicone may be a single one, or 2 or more kinds may be used in combination.
As reactive diluents which are silicone-free, there are, for example, H2C＝CGCO2R5(meth) acrylates of the formula wherein G is hydrogen, halogen or alkyl of 1 to about 4 carbon atoms and R5Is selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl, or aryl groups having from 1 to about 16 carbon atoms; any of these groups may be substituted or blocked with silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, carbamate, amine, amide, sulfur, sulfonate, sulfo, or the like, as necessary.
Among the reactive diluents, particularly preferred are more detailed (meth) acrylates, which include: polyethylene glycol di (meth) acrylate, bisphenol-a di (meth) acrylate such as ethoxylated bisphenol a (meth) acrylate ("EBIPA" or "EBIPMA"), tetrahydrofuran (meth) acrylate and di (meth) acrylate, citronellyl acrylate and methacrylate, hydroxypropyl (meth) acrylate, hexanediol di (meth) acrylate ("HDDA" or "HDDMA"), trimethylolpropane tri (meth) acrylate, tetrahydrodicyclopentadienyl (meth) acrylate, ethoxylated trimethylolpropane triacrylate ("ETTA"), triethylene glycol diacrylate and triethylene glycol dimethacrylate ("TRIEGMA"), isobornyl acrylate and isobornyl methacrylate; and the corresponding acrylates. Of course, combinations of these (meth) acrylates may also be used as reactive diluents.
The amount of the reactive diluent added is preferably in the range of 0.01 to 40% by mass, more preferably 0.05 to 20% by mass, based on the amount of the heat-curable silicone composition of the present invention. < (B) an organic peroxide containing 1 or more species selected from diacyl peroxides and peroxyesters
(B) The component (b) contains 1 or more organic peroxides selected from diacyl peroxides and peroxy esters, and is a component blended for the purpose of molding the heat-curable silicone composition of the present invention into a desired shape, and then curing the silicone composition by heat treatment and a crosslinking reaction, and may be appropriately selected depending on the intended bonding temperature, bonding time, service life, and the like.
From the viewpoint of achieving both high reactivity and long life, the organic peroxide preferably has a half-life of 10 hours at a temperature of 40 ℃ or more and a half-life of 1 minute at a temperature of 200 ℃ or less, and more preferably has a half-life of 10 hours at a temperature of 60 ℃ or more and a half-life of 1 minute at a temperature of 180 ℃ or less.
Examples of the diacyl peroxide include isobutyl peroxide, 2, 4-dichlorobenzoyl peroxide, 3,5, 5-trimethylhexanoyl peroxide, octanoyl peroxide, dodecanoyl peroxide, stearoyl peroxide, succinyl peroxide (succinic peroxide), benzoyl peroxide toluene and benzoyl peroxide.
Examples of the peroxy ester include cumyl peroxyneodecanoate, 1,3, 3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxypivalate, 1,3, 3-tetramethylbutyl peroxy-2-ethylhexanoate, 2, 5-dimethyl-2, 5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, 1-bis (t-butylperoxy) cyclohexane, isopropyl peroxymonocarbonate, t-hexyl peroxypivalate, t-butyl peroxypivalate, and the like, T-butyl peroxy-3, 5, 5-trimethylhexanoate, t-butyl peroxydodecanoate, 2, 5-dimethyl-2, 5-bis (m-toluoylperoxy) hexane, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, t-butyl peroxyacetate, and bis (t-butylperoxy) hexahydroterephthalate.
These peroxyesters can be used alone in 1 kind, and can also be used in combination with 2 or more kinds.
Examples of the other organic peroxide include dialkyl peroxides, peroxydicarbonates, peroxyketals, hydroperoxides, and silane-based peroxides. These organic peroxides can be used as the organic peroxide of the component (B) in combination with 1 or more species selected from the group consisting of diacyl peroxides and peroxyesters.
Examples of the dialkyl peroxide include α, α' -bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, and t-butylcumyl peroxide.
Examples of the peroxydicarbonate include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxymethoxy peroxydicarbonate, bis (2-ethylhexyl peroxy) dicarbonate, dimethoxybutyl peroxydicarbonate, and bis (3-methyl-3-methoxybutyl peroxy) dicarbonate.
Examples of the peroxyketal include 1, 1-bis (t-hexylperoxy) -3,3, 5-trimethylcyclohexane, 1, 1-bis (t-hexylperoxy) cyclohexane, 1, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 1,1- (t-butylperoxy) cyclododecane, and 2, 2-bis (t-butylperoxy) decane.
Examples of the hydroperoxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide.
Examples of the silyl peroxide include tert-butyltrimethylsilyl peroxide, di (tert-butyl) dimethylsilyl peroxide, tert-butyltrivinylsilyl peroxide, di (tert-butyl) divinylsilyl peroxide, tri (tert-butyl) vinylsilyl peroxide, tert-butyltriallylsilyl peroxide, di (tert-butyl) diallylsilyl peroxide, and tri (tert-butyl) allylsilyl peroxide.
The amount of the component (B) is 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the total amount of the organo (poly) siloxane of the component (A). (B) If the amount of the component (b) is less than 0.1 part by mass, the reaction may not proceed sufficiently, and the desired cured product may not have a hardness. (B) If the amount of the component (b) exceeds 30 parts by mass, the desired physical properties after curing may not be obtained, that is, sufficient heat resistance, light resistance and chipping resistance may not be obtained, and coloring may occur to cause discoloration. When the amount of the component (B) exceeds 30 parts by mass, the viscosity is remarkably lowered, and the composition may not be used as a die bonding material
< (C) an organohydrogenpolysiloxane containing at least 2 hydrogen atoms bonded to silicon atoms in one molecule
(C) The organohydrogenpolysiloxane of component (a) is a component that functions as a crosslinking agent, and can undergo a hydrosilylation reaction with component (a), contributing to curing of the present composition. The organohydrogenpolysiloxane has at least 2 hydrogen atoms (i.e., SiH groups) bonded to silicon atoms in one molecule, preferably 3 to 500 hydrogen atoms bonded to silicon atoms, more preferably 3 to 200 hydrogen atoms, and particularly preferably 3 to 150 hydrogen atoms. The number of silicon atoms (or polymerization degree) in one molecule is preferably 2 to 200, more preferably 3 to 150. The SiH group may be located at either or both of the molecular chain end and the non-end of the molecular chain.
Specific examples of the group bonded to the silicon atom in the organohydrogenpolysiloxane include, for example, the following unsubstituted or substituted 1-valent hydrocarbon groups having no aliphatic unsaturated bond: alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl, tolyl, and xylyl; aralkyl groups such as benzyl and phenethyl; halogenated alkyl groups such as 3,3, 3-trifluoropropyl and 3-chloropropyl; alkyl groups and aryl groups are preferably mentioned, and methyl groups and phenyl groups are particularly preferably mentioned.
(C) The viscosity of the component (A) at 23 ℃ is preferably 0.5 to 100000 mPas, particularly preferably 10 to 5000 mPas. The molecular structure of such an organohydrogenpolysiloxane is not limited, and examples thereof include linear, branched, partially branched linear, cyclic, and three-dimensional networks. The organohydrogenpolysiloxane may be a homopolymer (homopolymer) composed of a single kind of siloxane unit, a copolymer composed of 2 or more kinds of siloxane units, or a mixture thereof.
Examples of the organohydrogenpolysiloxane include 1,1,3, 3-tetramethyldisiloxane, 1,3,5, 7-tetramethylcyclotetrasiloxane, methylhydrogensiloxane cyclic polymer, methylhydrogensiloxane-dimethylsiloxane cyclic copolymer, dimethylhydrogensiloxane-blocked dimethylpolysiloxane at both molecular chain terminals, trimethylsiloxy-blocked methylhydrogensiloxane at both molecular chain terminals, trimethylsiloxy-blocked dimethylsiloxane-methylhydrogensiloxane copolymer at both molecular chain terminals, dimethylhydrogensiloxane-methylhydrogensiloxane copolymer at both molecular chain terminals, trimethylsiloxy-blocked methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane copolymer at both molecular chain terminals, and the like, (CH) Dimethylhydrogensiloxane-dimethylsiloxane-diphenylsiloxane copolymer having both terminal dimethylhydrogensiloxy groups3)2HSiO1/2Unit, (CH)3)3SiO1/2 bit and SiO4/2Copolymer of units of (CH)3)2HSiO1/2Units and SiO4/2Copolymer of units of (CH)3)2HSiO1/2Unit, SiO4/2Unit and (C)6H5)3SiO1/2Copolymers composed of units, and the like. Among these, the siloxane unit in the component (C) is preferably contained as a wholeMore preferably 1 to 100 mol% of the dimethylsiloxane unit(s).
The content of the component (C) in the present composition is 0.1 to 20 parts by mass, more preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 10 parts by mass, relative to 100 parts by mass of the component (A).
If the content of the component (C) is less than 0.1 part by mass, the present composition is not easily cured sufficiently, and the surface of the cured product may not be hardened. If the amount exceeds 20 parts by mass, the composition cannot be cured by the component (B), and the curability by a peroxide is impaired. For the above reasons, the amount of the component (C) to be blended may be such that the molar ratio of the silicon atom-bonded hydrogen atoms (i.e., SiH groups) in the component (C) to the total amount of silicon atom-bonded alkenyl groups in the entire alkenyl group-containing organo (poly) siloxane in the present composition (the molar ratio of the silicon atom-bonded hydrogen atoms in the component (B) to the silicon atom-bonded alkenyl groups in the component (A) when the component other than the component (A) does not have the alkenyl groups) is 0.01 to 4.0mol/mol, preferably 0.05 to 2.5mol/mol, and particularly preferably 0.1 to 1.0 mol/mol.
(D) platinum group catalyst
(D) The platinum-based catalyst of the component (a) is a catalyst for accelerating the curing of the present composition, and examples thereof include platinum and platinum compounds, and specific examples thereof include chloroplatinic acid, alcohol solutions of chloroplatinic acid, olefin complexes of platinum, alkenylsiloxane complexes of platinum, and carbonyl complexes of platinum. The content of the component (D) in the present composition may be an effective amount, specifically an amount of 0.01 to 1000ppm, preferably 0.1 to 500ppm, in terms of platinum, based on the mass of the platinum metal component in the component (D) relative to the component (A).
< other ingredients >
The heat-curable silicone composition of the present invention may contain other components to change desired cured or uncured properties in a specific application. For example, an adhesion promoter such as (meth) acryloxypropyltrimethoxysilane, trialkyl or triallyl isocyanurate, glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, or the like may be included in an amount of up to about 20 mass%. As other optional components, a non- (meth) acrylic silicone diluent or plasticizer (plastisizer) may be included in an amount of up to about 30 mass%. Examples of the non- (meth) acrylic silicone include trimethylsilyl-terminated oils having a viscosity of 100 to 500csp, and silicone rubbers. The non- (meth) acrylic silicone may contain a co-curable group such as a vinyl group.
In addition, in order to improve the strength, adjust the viscosity, provide thixotropy (thixotropy), and the like of the heat-curable silicone composition of the present invention, an inorganic filler such as fumed silica (fumed silica) or nano alumina may be further blended. If necessary, dyes, pigments, flame retardants, and the like may be blended in the heat-curable silicone composition of the present invention.
In addition, a solvent or the like may be added and used for the purpose of improving the workability. The type of the solvent is not particularly limited, and a solvent capable of dissolving the heat-curable silicone composition before curing, well dispersing the inorganic filler and the like, and providing a uniform crystal-fixing material, binder and the like can be used. The blending ratio of the solvent may be appropriately adjusted depending on the operation conditions, environment, use time, and the like of the die bonding material. More than 2 kinds of solvents may be used in combination. Examples of such solvents include butyl carbitol acetate, methyl ethyl ketone, α -abietyl alcohol, and cellosolve acetate.
In addition, the composition of the present invention may contain an adhesion improver. Examples of the adhesion improver include a silane coupling agent or an oligomer thereof, and silicone having the same reactive group as the silane coupling agent.
The adhesion improver is preferably a silane compound or a siloxane compound having 1 or more epoxy-containing groups in the molecule. Examples thereof include, for example, epoxy group-containing silane coupling agents and hydrolysis condensates thereof. Examples of the epoxy group-containing silane coupling agent or a hydrolysis condensate thereof include silane compounds such as glycidoxypropyltrimethoxysilane and glycidoxypropyltriethoxysilane, and hydrolysis condensates thereof.
The adhesion improver is an optional component to be blended in the heat-curable silicone composition of the present invention for the purpose of improving the adhesion of the composition and the cured product thereof to a substrate. Here, the base material refers to a metal material such as gold, silver, copper, nickel, or the like; ceramic materials such as alumina, aluminum nitride, and titanium oxide; high polymer materials such as silicone resin and epoxy resin. The adhesion improver may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
The blending amount of the adhesion improver is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass, based on 100 parts by mass of the total amount of the component (A) and the component (B). When the amount of the silicone composition is 5 to 20 parts by mass, the adhesion of the heat-curable silicone composition and the cured product thereof of the present invention to a substrate is effectively improved, and the composition is less likely to be colored.
Specific examples of the adhesion improver which are suitable include, but are not limited to, the following.
Figure BDA0001461469180000161
Figure BDA0001461469180000171
Figure BDA0001461469180000181
a. r is an integer of 0 to 50, and b, s, and t are integers of 1 to 50.
In addition, in order to secure the life span, an addition reaction control agent such as 3-methyl-1-dodecyn-3-ol, 1-ethynylcyclohexanol, 3, 5-dimethyl-1-hexyn-3-ol, or the like may be blended.
In order to suppress the occurrence of coloring, oxidative deterioration, and the like of a cured product, a conventionally known antioxidant such as 2, 6-di-tert-butyl-4-methylphenol may be blended in the heat-curable silicone composition of the present invention. In addition, in order to impart resistance to light deterioration, a light stabilizer such as a hindered amine stabilizer may be incorporated in the heat-curable silicone composition of the present invention.
The heat-curable silicone composition of the present invention can be produced by mixing the above components by a known mixing method, for example, by using a stirrer, a roll, or the like. The heat-curable silicone composition of the present invention has a viscosity of 10 to 1000000 mPas, particularly preferably 100 to 1000000 mPas, as measured at 23 ℃ with a rotary viscometer, for example, an E-type viscometer.
The heat-curable silicone composition of the present invention can be cured by a known curing method under known curing conditions. Specifically, the composition can be cured by heating at a temperature of usually 80 to 200 ℃ and preferably 100 to 160 ℃. The heating time may be about 0.5 minutes to 5 hours, and particularly about 1 minute to 3 hours. The curing conditions can be appropriately selected in accordance with the balance among the operating conditions, productivity, light-emitting element, and heat resistance of the frame.
The heat-curable silicone composition of the present invention can obtain a cured product that overcomes the problem of the surface portion being uncured due to oxygen inhibition by performing both the peroxide-based curing of a (meth) acryloyl group and the curing of an SiH group and unsaturated group addition reaction. Further, the heat-curable silicone composition of the present invention can provide a cured product that is excellent in adhesive strength and workability, and that is excellent in heat resistance, light resistance, and chipping resistance.
The present invention also provides a die bonding material comprising the heat-curable silicone composition of the present invention. In particular, a die bond material can be used to connect a semiconductor element to a wiring board.
The heat-curable silicone composition of the present invention can be suitably used for fixing an LED chip to a package. In addition, the present invention can be suitably used for other optical semiconductor devices such as an organic electroluminescence device (organic EL), a laser diode, and a light emitting diode array (LED array).
The heat-curable silicone composition of the present invention can provide a cured product that has high transparency, excellent adhesive strength and workability, and excellent heat resistance, light resistance, and chipping resistance. Therefore, if the die bonding material is composed of the heat-curable silicone composition, the die bonding material can be suitably used as a die bonding material for mounting an LED chip on a wiring board.
The method of applying the die bonding material is not particularly limited, and examples thereof include spin coating, printing, and compression molding. The thickness of the die bonding material may be selected as appropriate, and is usually 5 to 50 μm, particularly 10 to 30 μm. For example, a dispensing device is used, and the temperature is 23 ℃ and the pressure is 0.5 to 5kgf/cm2The coating can be easily performed by carrying out the feeding under the condition of (1). Further, by using a pressing (holding) device, a predetermined amount of the die bonding material can be easily transferred to the substrate.
The method of mounting the semiconductor element is not particularly limited, and a die bonder, for example, may be used. The important factors for determining the thickness of the die bond material include the pressure bonding load, the pressure bonding time, and the pressure bonding temperature of the optical semiconductor element, in addition to the viscosity of the die bond material. These conditions may be appropriately selected depending on the outer shape of the optical semiconductor element and the thickness of the intended die bond material. The pressure bonding load is generally 1gf to 1 kgf. Preferably 10gf to 100 gf. When the pressure contact load is 1gf or more, the die bonding material can be sufficiently pressure contacted. Further, if a pressure bonding load of 1kgf or less is used, the light-emitting layer on the surface of the optical semiconductor element is not damaged. The crimping time may be appropriately selected in accordance with the balance with the productivity of the step, and is generally more than 0 msec and 1 sec or less. Preferably 1 millisecond or more and 30 milliseconds or less. If it is 1 second or less, it is preferable from the viewpoint of productivity. The pressure bonding temperature is not particularly limited as long as it is in accordance with the use temperature range of the die attach material, but is generally preferably 15 ℃ or higher and 100 ℃ or lower. If no heating device is arranged on the crimping table of the die bonder, the die bonder can be used within a temperature range around room temperature. If the temperature is 15 ℃ or higher, the viscosity of the die bond material does not become too high, and thus the die bond material can be sufficiently pressure bonded. If the temperature is 100 ℃ or lower, the solidification of the die bond material does not start, and therefore, the thickness of the die bond material can be achieved.
Further, the present invention provides an optical semiconductor device having a cured product obtained by curing the above-described die bond material of the present invention.
The optical semiconductor device of the present invention has a cured product obtained by curing a crystal-fixing material composed of the heat-curable silicone composition of the present invention, and therefore can be an optical semiconductor device having a cured product which overcomes the problem that the surface portion is not cured and has excellent heat resistance, light resistance, and chipping resistance.
The optical semiconductor device of the present invention can be manufactured by: after a die bonding material comprising the heat-curable silicone composition of the present invention is applied to a substrate, an optical semiconductor element is die bonded by a conventionally known method.
Hereinafter, one embodiment of the optical semiconductor device of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view showing an example of an optical semiconductor device having a cured product obtained by curing a crystal fixing material composed of a heat-curable silicone composition of the present invention. The optical semiconductor device 10 shown in fig. 1 has a cured product 5 obtained by curing a die-bonding material made of the heat-curable silicone composition of the present invention on the 1 st lead electrode 3 of the frame 1 of the package substrate, and the semiconductor element 2 is mounted on the cured product 5. The electrode of the optical semiconductor element 2 is electrically connected to the 1 st lead electrode 3 by a gold wire 6. The electrodes of the optical semiconductor element 2 are electrically connected to the 2 nd lead electrode 4 by gold wires 7. The optical semiconductor element 2 is sealed with a sealing resin 8.
As a method for manufacturing the optical semiconductor device 10 of fig. 1, the following method can be exemplified.
First, a die bond material made of the heat-curable silicone composition of the present invention is quantitatively transferred onto the 1 st lead electrode 3 of the frame 1 of the package substrate, and the optical semiconductor element 2 is mounted on the die bond material. Next, the die bond material is cured by heating to obtain a cured product 5. Next, the electrodes of the optical semiconductor element 2 and the 1 st lead electrode 3 were electrically connected using the gold wires 6, and the electrodes of the semiconductor element 2 and the 2 nd lead electrode 4 were electrically connected using the gold wires 7, to obtain a package substrate on which the optical semiconductor element 2 was mounted. Next, the sealing resin 8 is applied in a fixed amount, and the applied sealing resin is cured under a known curing condition by a known curing method, whereby the package substrate can be sealed. Examples of the optical semiconductor device having a cured product obtained by curing the die attach material of the present invention include an LED, a semiconductor laser, a photodiode, a phototransistor (phototransistor), a solar cell, a Charge Coupled Device (CCD), and the like.
[ examples ]
The present invention will be described specifically below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
(examples 1 to 8, comparative examples 1 to 5)
The following ingredients were prepared, and silicone compositions having the compositions shown in tables 1 and 2 were prepared.
(A-1)
An organopolysiloxane which is composed of the following siloxane units, and MA: m: q is 1: 4: a ratio of 6, a molecular weight of 5000, which is a weight average molecular weight in terms of polystyrene according to Gel Permeation Chromatography (GPC), and which is a solid at 25 ℃.
Figure BDA0001461469180000211
(A-2)
An organosiloxane represented by the following structural formula, having a viscosity of 7 mPas at 25 ℃.
Figure BDA0001461469180000212
(B-1)
As the diacyl peroxide, a 40% xylene solution of bis (3-methylbenzoyl) peroxide (Di- (3-methylbenzoyl) peroxide), Benzoyl (3-methylbenzoyl) peroxide (Benzoyl- (3-methylbenzoyl) peroxide), and dibenzoyl peroxide (Dibenzol peroxide) (trade name: Niper BMT-K40, manufactured by Nippon fat Co., Ltd.) was used as it was.
(B-2)
As the peroxy ester, t-Butyl peroxybenzoate (t-Butyl peroxybenzoate) (trade name: Perbutyl Z, manufactured by Nippon fat Co., Ltd.) was used as it is.
(C) Crosslinking agent
A linear organopolysiloxane composed of the following siloxane units,
M：(CH3)3SiO1/2、
D：(CH3)2SiO2/2、
DH：(CH3)SiHO2/2，
and is represented by M: d: DH 2: 32: 66 denotes a viscosity of 150 mPas at 25 ℃.
(D) A platinum-based catalyst:
a toluene solution of platinum 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex, the platinum content of which was 0.5 mass%.
Other optional ingredients
Viscosity modifier: fumed silica (trade name: REOLOSIL DM-30S, manufactured by Tokuyama, Inc.)
Adhesion improver: cyclic silicone oil having epoxy group in side chain (trade name: X-40-2670, manufactured by shin-Etsu chemical Co., Ltd.)
Reaction control agent: 3-methyl-1-dodecen-3-ol
[ Table 1]
Figure BDA0001461469180000221
[ Table 2]
Figure BDA0001461469180000231
[ measurement of hardness ]
The obtained composition was poured into a 2mm thick cell (cell) and cured at 150 ℃ for 2 hours to prepare a cured product. Then, the hardness was measured using a durometer type D manufactured by upper island manufacturing.
[ evaluation of surface tackiness ]
The obtained composition was poured into an aluminum pan and cured at 150 ℃ for 2 hours under atmospheric conditions to prepare a cured product. The surface tackiness of the obtained cured product was evaluated by touching with a finger.
[ production of optical semiconductor Package ]
An LED package substrate having a concave portion for mounting an optical semiconductor element, and a 1 st lead electrode and a 2 nd lead electrode which are silver plated on the bottom of the concave portion, which is manufactured by SMD5050 (which is manufactured by I-chinese preliminary INDUSTRY co., LTD.) and has a resin Portion of Polyphthalamide (PPA) and BXCD33 manufactured by bridge optoelectronics (Bridgelux) as an optical semiconductor element, is prepared.
Each of the compositions shown in tables 1 and 2 was quantitatively transferred to the silver-plated 1 st lead electrode of the package substrate by pressing using a die bonder (AD-830, manufactured by ASM corporation), and an optical semiconductor element was mounted on the composition. The supporting conditions of the optical semiconductor element at this time were a pressure bonding time of 13 milliseconds and a pressure bonding load of 60gf, and the process was carried out at room temperature and 25 ℃ without using a heating apparatus. Next, the package substrate was placed in an oven to heat-cure the various die attach materials (150 ℃ C. for examples 1 to 8, comparative example 2, and comparative example 4, and 170 ℃ C. for comparative example 1, and 1 hour). Then, the electrode of the optical semiconductor element and the 1 st lead electrode were electrically connected using a gold wire (with a wire diameter (FA) of 25 μm, manufactured by electronics, inc.) and the electrode of the semiconductor element and the 2 nd lead electrode were electrically connected using a gold wire (with a wire diameter (FA) of 25 μm, manufactured by electronics, inc.). Thus, each of the LED package substrates (120 packages in terms of the number of packages) on which the optical semiconductor element is mounted was obtained.
In the above manner, optical semiconductor packages having different die attach materials were produced and used in the following tests.
[ Die shear test ]
10 of the optical semiconductor packages obtained by the above-described method were subjected to measurement of the shear strength of the chip using a tensile tester (manufactured by Dage corporation, Series 4000) in a room at 25 ℃, and the average value of the obtained measurement values was expressed in MPa.
[ evaluation of inhibition of surface curing by oxygen ]
In the optical semiconductor package obtained by the above method, the periphery of the chip was scratched by a sharp-pointed needle in a room at 25 ℃, and it was confirmed whether or not the surface curing was inhibited by oxygen.
The results obtained are shown in tables 3 and 4.
[ Table 3]
Figure BDA0001461469180000241
[ Table 4]
Figure BDA0001461469180000242
As shown in table 3, in examples 1 to 8, when the heat-curable silicone composition satisfying the scope of the present invention was used as the die bond material, a cured product having high hardness and no surface tackiness, which was free from the problem of partial uncured surface due to oxygen inhibition, was obtained. Further, from the results of the die-cut measurement, it was found that an optical semiconductor device having high adhesion and high reliability could be manufactured.
On the other hand, comparative examples 1 and 2 did not contain C, D component, and both had high hardness and high die shear, but had surface tackiness, and it was confirmed that surface curing was inhibited by oxygen. Further, as is clear from comparative example 2, even if the amount of the peroxide is increased, it is impossible to prevent the inhibition of the surface curing. When the amount of the component B is excessive (comparative example 3), the viscosity is significantly reduced, and pressing becomes impossible. In addition, when the component C is excessive (comparative example 4), the surface curing can be prevented from being inhibited by oxygen, but as a result, the die shear is reduced. Comparative example 5, which contained no component B and was cured only with a platinum catalyst, was remarkably reduced in hardness and could not be pressed due to an increase in viscosity.
The present invention is not limited to the above-described embodiments. The above-described embodiments are illustrative, and any embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same operational effects are included in the technical scope of the present invention.

Claims (8)

1. A heat-curable silicone composition characterized by containing the following components:
(A)100 parts by mass of an organo (poly) siloxane having at least 1 structure represented by the following general formula (1) in a molecule,
Figure FDA0001461469170000011
in the formula (1), m is any one of 0, 1 and 2, R1Is a hydrogen atom, a phenyl group or a halogenated phenyl group, R2Is a hydrogen atom or a methyl group, R3Is a substituted or unsubstituted 1-valent organic group having 1 to 12 carbon atoms, Z1is-R4-、-R4-O-、-R4(CH3)2Any one of Si-O-, Z2Is an oxygen atom or a substituted or unsubstituted carbon atom which may be the same or differentA number of 1 to 10 of a 2-valent organic group, R4Is a substituted or unsubstituted 2-valent organic group having 1 to 10 carbon atoms which may be the same or different;
(B) 0.1-30 parts by mass of an organic peroxide, wherein the organic peroxide comprises more than 1 selected from diacyl peroxides and peroxyesters;
(C)0.1 to 20 parts by mass of an organohydrogenpolysiloxane containing at least 2 hydrogen atoms bonded to silicon atoms in one molecule; and the number of the first and second groups,
(D) a platinum-based catalyst in an amount of 0.01 to 1000ppm in terms of platinum in the component (D) based on the component (A).
2. The heat-curable silicone composition according to claim 1, wherein component (A) is component (Z) of an organo (poly) siloxane1is-R4-，Z2Is an oxygen atom.
3. The heat-curable silicone composition according to claim 1, wherein component (A) is component (Z) of an organo (poly) siloxane1is-R4-O-or-R4(CH3)2Si-O-，Z2Is a substituted or unsubstituted 2-valent organic group having 1 to 10 carbon atoms which may be the same or different.
4. The heat-curable silicone composition according to claim 1, wherein the organo (poly) siloxane of component (A) has 0.1 mol% or more of (SiO) in all siloxane units constituting the organo (poly) siloxane2) And (4) units.
5. The heat-curable silicone composition according to claim 2, wherein the organo (poly) siloxane of component (A) has 0.1 mol% or more of (SiO) in all siloxane units constituting the organo (poly) siloxane2) And (4) units.
6. The heat-curable resin composition according to claim 3The silicone composition, wherein the organic (poly) siloxane of the component (A) has 0.1 mol% or more of (SiO) in all siloxane units constituting the organic (poly) siloxane2) And (4) units.
7. A die bond material comprising the heat-curable silicone composition according to any one of claims 1 to 6.
8. An optical semiconductor device, comprising a cured product obtained by curing the die-bonding material according to claim 7.
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