CN111978736A - Silicone composition for die bonding, cured product thereof, and optical semiconductor device - Google Patents
Silicone composition for die bonding, cured product thereof, and optical semiconductor device Download PDFInfo
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Abstract
The invention provides a silicone composition for die bonding, which gives a cured product with excellent hardness and chip shear strength and inhibits metal pad contamination in an optical semiconductor device. The organosilicon composition for solid crystal comprises the following components in a specific blending ratio: (A) an organopolysiloxane containing 2 or more alkenyl groups in 1 molecule and having a viscosity of 100 mPas or less at 25 ℃, (B) a specific three-dimensional network organopolysiloxane that is waxy or solid at 23 ℃, (C) a specific organohydrogenpolysiloxane having at least 2 silicon atom-bonded hydrogen atoms in 1 molecule, (D) a specific polysiloxane containing an epoxy group, and (E) a platinum group metal-based catalyst.
Description
Technical Field
The present invention relates to a silicone composition for die bonding, a cured product thereof, and an optical semiconductor device using the cured product.
Background
Recently, since the luminance of LED elements is increased and the heat generation of the elements is increased, silicone resins having excellent durability have been used as sealing materials and die bond (die bond) materials for light emitting diode (hereinafter referred to as "LED") elements (patent documents 1 and 2). In particular, if the resin is too soft, a defect that bonding cannot be performed in a wire bonding step performed after the die bonding step occurs, and thus a die bonding material having high hardness is required.
In recent years, the LED devices have been miniaturized, and a die bonding material having higher adhesiveness is required. If the adhesive force of the die attach material is insufficient, a fatal problem in manufacturing such as chip detachment occurs in a wire bonding step in the production of an LED. Conventional silicone die attach materials have excellent durability, but have insufficient adhesion, and thus a material having a higher shear strength of a chip is required.
In addition to the high die shear strength, low molecular components generated when the die attach material is heat cured may contaminate metal pads (metal pads) of the die, which is a cause of a failure in the wire bonding process. Among silicones, silane coupling agents having an adhesive functional group are used for improving the adhesiveness, but a general silane coupling agent has a low molecular weight and causes volatilization under heat (100 to 180 ℃) in a curing step of die bonding, generation of voids, reduction in shear strength of chips, and contamination of metal pads. That is, a die bonding material that does not contaminate the metal pad while improving the shear strength of the chip is required.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2006-342200
Patent document 2: japanese laid-open patent application No. 2010-285571
Disclosure of Invention
Technical problem to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a silicone composition for die bonding which gives a cured product excellent in hardness and chip shear strength and suppresses metal pad contamination in an optical semiconductor device.
Means for solving the problems
In order to achieve the above object, the present invention provides a silicone composition for die bonding, which contains the following components (a) to (E):
(A) an organopolysiloxane that contains 2 or more alkenyl groups in 1 molecule and has a viscosity of 100 mPas or less at 25 ℃;
(B) a three-dimensional network organopolysiloxane represented by the following formula (1) which is waxy or solid at 23 ℃, which is 70 to 95 parts by mass relative to 100 parts by mass of the total of the components (A) and (B),
(R1 3SiO1/2)a(R2 3SiO1/2)b(R2R1 2SiO1/2)c(R2R1SiO)d(R1 2SiO)e(R2SiO3/2)f(R1SiO3/2)g(SiO4/2)h (1)
in the formula, R1Is a substituted or unsubstituted monovalent hydrocarbon radical which is optionally identical or different, respectively, and which does not contain alkenyl groups, R2A, b, c, d, e, f, g and h are each a number satisfying a.gtoreq.0, b.gtoreq.0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0, f.gtoreq.0, g.gtoreq.0 and h.gtoreq.0, and b + c>0、f+g+h>0 and a + b + c + d + e + f + g + h is a number of 1;
(C) an organohydrogenpolysiloxane represented by the following average composition formula (2) and having at least 2 silicon atom-bonded hydrogen atoms in 1 molecule, in which the number of silicon atom-bonded hydrogen atoms in component (C) is 0.5 to 5.0 times the total number of all silicon atom-bonded alkenyl groups in components (A) and (B),
R1 iHjSiO(4-i-j)/2 (2)
in the formula, R1And said R1I and j are numbers satisfying 0.7. ltoreq. i.ltoreq.2.1, 0.001. ltoreq. j.ltoreq.1.0, and 0.8. ltoreq. i + j.ltoreq.3.0;
(D) an epoxy group-containing polysiloxane represented by the following formula (3), wherein the epoxy group-containing polysiloxane is 1 to 25 parts by mass relative to 100 parts by mass of the total of the component (A), the component (B) and the component (C),
(R3SiO3/2)k(R1SiO3/2)m(R4O1/2)n (3)
in the formula, R1And said R1Same as R3Are optionally identical or different epoxy-containing radicals, R4Is an optionally identical or different, respectively, alkenyl-free, substituted or unsubstituted, monovalent hydrocarbon radical, k and m are each independently of the other k>0. m is more than or equal to 0, k + m is a number equal to 1, and n is a number which satisfies that n is more than or equal to 0 and less than or equal to 2;
(E) the platinum group metal catalyst is 1 to 500ppm by mass in terms of the mass of the platinum group metal element relative to the total mass of the component (A), the component (B), the component (C) and the component (D).
The silicone composition for die bonding of the present invention can give a cured product which is excellent in hardness and chip shear strength and which is suppressed in metal pad contamination in an optical semiconductor device.
The component (a) is preferably an organopolysiloxane represented by the following formula (4).
(R1 3SiO1/2)q(R2R1 2SiO1/2)r(R2SiO3/2)o(R1SiO3/2)p (4)
In the formula, R1And R2And said R1And R2Similarly, o, p, q, r are numbers satisfying q.gtoreq.0, r.gtoreq.0, o.gtoreq.0, and p.gtoreq.0, respectively, and q + r>0、r+o>0、o+p>0 and o + p + q + r is a number of 1.
When the component (a) is the specific organopolysiloxane, the silicone composition for die bonding can give a cured product which is more excellent in hardness and die shear strength and further suppresses metal pad contamination in an optical semiconductor device.
In said formula (1), b >0 and h >0 are preferred.
In the formula (1), b >0 and h >0 give a cured product which is more excellent in hardness and shear strength of a die, particularly in adhesive strength, and further suppresses metal pad contamination in an optical semiconductor device.
The component (C) preferably has a mass loss of 1 mass% or less when heated at 150 ℃ for 30 minutes under 1 standard atmosphere.
If the component (C) is the above-mentioned component, the silicone composition for die bonding can further suppress metal pad contamination in the optical semiconductor device.
The component (D) preferably has a mass loss of 5 mass% or less when heated at 150 ℃ for 30 minutes under 1 standard atmosphere.
If the component ((D) is the above-mentioned component, the silicone composition for die bonding can further suppress metal pad contamination in the optical semiconductor device.
Among the above-mentioned (D) components, R is preferable3Is a group represented by the following formula (5).
[ chemical formula 1]
Wherein s is an integer of 1 to 6, and the dotted line represents a bond.
If R is3The specific functional group gives a cured product which is more excellent in hardness and shear strength of a die and which further suppresses contamination of a metal pad in an optical semiconductor device.
Preferably all R in the composition1Wherein 80 mol% or more of the total amount of the compounds are methyl groups.
If all R in the composition1When 80 mol% or more of the total amount of the silicone composition is methyl, a cured product having excellent heat resistance, light resistance (ultraviolet resistance), and resistance to deterioration such as discoloration due to stimulation with heat, ultraviolet light, or the like can be provided.
The composition preferably contains (F) a BET specific surface area of 100 to 400m2Fumed silica per gram.
If the composition contains the fumed silica, the composition is excellent in thixotropy and handling properties.
The present invention also provides a cured silicone material which is a cured product of the above-described silicone composition for die bonding.
Such a silicone cured product is excellent in hardness and chip shear strength, has high adhesion to a substrate, an LED chip, or the like, and is particularly useful as a die bonding material for die bonding of an LED device or the like.
Further, the present invention provides an optical semiconductor device obtained by die bonding an optical semiconductor element using the silicone cured product.
In such an optical semiconductor device, the silicone cured product is used as a die bonding material having excellent hardness and chip shear strength and high adhesion to a substrate, an LED chip, or the like, and thus has high reliability.
Effects of the invention
As described above, the silicone composition for die bonding of the present invention can provide a silicone cured product having excellent hardness and chip shear strength, and can suppress metal pad contamination in an optical semiconductor device, and therefore is particularly useful as a die bonding material for die bonding of LED elements and the like. In addition, in the wire bonding step performed after the die bonding step, defects such as chip detachment and failure in bonding are less likely to occur, and an optical semiconductor device in which an optical semiconductor element is die bonded using the cured silicone material has high reliability and improved productivity.
Drawings
Fig. 1 is a photograph showing the appearance of the metal gasket of example 1 after the stain test.
Fig. 2 is a photograph showing the appearance of the metal gasket of comparative example 7 after the stain test.
Detailed Description
As described above, there is a need for development of a silicone composition for die bonding which is a die bonding material for die bonding of LED devices and the like with less metal pad contamination and which can give a silicone cured product excellent in hardness and chip shear strength.
The present inventors have conducted extensive studies on the above-mentioned problems, and as a result, have found that the above-mentioned problems can be achieved by a silicone composition for die bonding containing the components (a), (B), (C), (D), and (E) described below, and have completed the present invention.
That is, the present invention is a silicone composition for die bonding, which contains the following components (a) to (E).
(A) An organopolysiloxane that contains 2 or more alkenyl groups in 1 molecule and has a viscosity of 100 mPas or less at 25 ℃;
(B) a three-dimensional network organopolysiloxane represented by the following formula (1) which is waxy or solid at 23 ℃, which is 70 to 95 parts by mass relative to 100 parts by mass of the total of the components (A) and (B),
(R1 3SiO1/2)a(R2 3SiO1/2)b(R2R1 2SiO1/2)c(R2R1SiO)d(R1 2SiO)e(R2SiO3/2)f(R1SiO3/2)g(SiO4/2)h (1)
in the formula, R1Is a substituted or unsubstituted monovalent hydrocarbon radical which is optionally identical or different, respectively, and which does not contain alkenyl groups, R2A, b, c, d, e, f, g and h are each a number satisfying a.gtoreq.0, b.gtoreq.0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0, f.gtoreq.0, g.gtoreq.0 and h.gtoreq.0, and b + c>0、f+g+h>0 and a + b + c + d + e + f + g + h is a number of 1;
(C) an organohydrogenpolysiloxane represented by the following average composition formula (2) and having at least 2 silicon atom-bonded hydrogen atoms in 1 molecule, in which the number of silicon atom-bonded hydrogen atoms in component (C) is 0.5 to 5.0 times the total number of all silicon atom-bonded alkenyl groups in components (A) and (B),
R1 iHjSiO(4-i-j)/2 (2)
in the formula, R1And said R1I and j are numbers satisfying 0.7. ltoreq. i.ltoreq.2.1, 0.001. ltoreq. j.ltoreq.1.0, and 0.8. ltoreq. i + j.ltoreq.3.0;
(D) an epoxy group-containing polysiloxane represented by the following formula (3), wherein the epoxy group-containing polysiloxane is 1 to 25 parts by mass relative to 100 parts by mass of the total of the component (A), the component (B) and the component (C),
(R3SiO3/2)k(R1SiO3/2)m(R4O1/2)n (3)
in the formula, R1And said R1Same as R3Are optionally identical or different epoxy-containing radicals, R4Is an optionally identical or different, respectively, alkenyl-free, substituted or unsubstituted, monovalent hydrocarbon radical, k and m are each independently of the other k>0. m is more than or equal to 0, k + m is a number equal to 1, and n is a number which satisfies that n is more than or equal to 0 and less than or equal to 2;
(E) the platinum group metal catalyst is 1 to 500ppm by mass in terms of the mass of the platinum group metal element relative to the total mass of the component (A), the component (B), the component (C) and the component (D).
The present invention will be described in detail below, but the present invention is not limited thereto.
[ Silicone composition for die bonding ]
The silicone composition for die bonding of the present invention contains the components (a) to (E) described below.
Hereinafter, each component will be described in detail.
< ingredient (A) >
(A) The component (A) is an organopolysiloxane which contains 2 or more alkenyl groups in 1 molecule and has a viscosity of 100 mPas or less at 25 ℃.
(A) The viscosity of the component (A) is 100 mPas or less, preferably 30 mPas or less, as measured at 25 ℃ with a rotational viscometer. When the viscosity exceeds 100mPa · s, the viscosity of the silicone composition for die bonding increases, and therefore handling is difficult in the step of applying the composition onto the LED substrate using a die bonder. In addition, unless otherwise specified below, the viscosity is a measured value measured at 25 ℃ using a rotational viscometer.
The alkenyl group contained in the component (A) is not particularly limited, but is preferably an alkenyl group having 2 to 10 carbon atoms such as a vinyl group, allyl group, or ethynyl group, more preferably an alkenyl group having 2 to 6 carbon atoms, and further preferably a vinyl group.
(A) The component (C) may contain a substituted or unsubstituted monovalent hydrocarbon group having no alkenyl group, and examples thereof are not particularly limited as long as they have no alkenyl group, and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms is preferable. Examples of the monovalent hydrocarbon include alkyl groups such as methyl, ethyl, propyl and butyl, cycloalkyl groups such as cyclohexyl and cyclopentyl, aryl groups such as phenyl, tolyl and xylyl, aralkyl groups such as benzyl and phenylethyl, and halogenated hydrocarbon groups such as chloromethyl, chloropropyl and chlorocyclohexyl. Preferably an alkyl group, more preferably a methyl group.
Examples of the component (A) include branched organopolysiloxanes represented by the following average composition formula (4).
(R1 3SiO1/2)q(R2R1 2SiO1/2)r(R2SiO3/2)o(R1SiO3/2)p (4)
In the formula, R1Is optionally identical or different, respectively, substituted or unsubstituted, monovalent hydrocarbon radicals which are free of alkenyl radicals, R2Is optionally identical or different alkenyl, o, p, q, r are each a number satisfying q.gtoreq.0, r.gtoreq.0, o.gtoreq.0, p.gtoreq.0, and q + r>0、r+o>0、o+p>0 and o + p + q + r is a number of 1.
As R1The substituted or unsubstituted monovalent hydrocarbon group not containing an alkenyl group is not particularly limited as long as it does not contain an alkenyl group, but is preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Examples of the monovalent hydrocarbon include alkyl groups such as methyl, ethyl, propyl and butyl, cycloalkyl groups such as cyclohexyl and cyclopentyl, aryl groups such as phenyl, tolyl and xylyl, aralkyl groups such as benzyl and phenylethyl, and halogenated hydrocarbon groups such as chloromethyl, chloropropyl and chlorocyclohexyl. Preferably an alkyl group, more preferably a methyl group.
As R2Alkenyl radicals representedThe alkenyl group is not particularly limited, but is preferably an alkenyl group having 2 to 10 carbon atoms such as a vinyl group, allyl group, or ethynyl group, more preferably an alkenyl group having 2 to 6 carbon atoms, and still more preferably a vinyl group.
Specific examples of the branched organopolysiloxane include branched organopolysiloxanes represented by the following formulae.
((CH2＝CH)(CH3)2SiO1/2)0.5((CH3)SiO3/2)0.5；
((CH2＝CH)(CH3)2SiO1/2)0.5((CH2＝CH)SiO3/2)0.5；
((CH2＝CH)(CH3)2SiO1/2)0.5((CH3)SiO3/2)0.3((CH2＝CH)SiO3/2)0.2；
((CH3)3SiO1/2)0.4((CH2＝CH)SiO3/2)0.6；
((CH3)3SiO1/2)0.4((CH3)SiO3/2)0.3((CH2＝CH)SiO3/2)0.3。
(A) The component (C) may be an organopolysiloxane having a linear molecular structure.
Specific examples of the linear organopolysiloxane include linear organopolysiloxanes represented by the following formulae.
[ chemical formula 2]
In the above formula, the order of arrangement of the siloxane units in parentheses may be arbitrary.
(A) The components can be used singly or in combination.
< ingredient (B) >
(B) The component (A) is a three-dimensional network organopolysiloxane which is represented by the average composition formula (1) and is waxy or solid at 23 ℃. (B) The component (A) is a component for obtaining reinforcement (reinforcement) while maintaining the transparency of the cured product, and contains an alkenyl group bonded to a silicon atom and SiO in the molecule3/2Units or SiO4/2A three-dimensional network organopolysiloxane resin of at least one of the units. The term "wax-like" as used herein means a rubber-like (raw rubber-like) material which has a viscosity of 10,000,000 mPas or more, particularly 100,000,000 mPas or more at 23 ℃ and shows little self-fluidity.
(R1 3SiO1/2)a(R2 3SiO1/2)b(R2R1 2SiO1/2)c(R2R1SiO)d(R1 2SiO)e(R2SiO3/2)f(R1SiO3/2)g(SiO4/2)h (1)
In the formula, R1And R2And said R1And R2Similarly, a, b, c, d, e, f, g and h are numbers satisfying a.gtoreq.0, b.gtoreq.0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0, f.gtoreq.0, g.gtoreq.0 and h.gtoreq.0, respectively, and b + c>0、f+g+h>0 and a + b + c + d + e + f + g + h is a number of 1.
As R1Examples thereof include the compounds represented by the formula R in the component (A)1The same group is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
As R2Examples thereof include the compounds represented by the formula R in the component (A)2The same group is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, and still more preferably a vinyl group.
a is preferably a number of 0 to 0.65, b is preferably a number of 0.1 to 0.65, c is preferably a number of 0 to 0.65, d is preferably a number of 0 to 0.5, e is preferably a number of 0 to 0.5, f is preferably a number of 0 to 0.8, g is preferably a number of 0 to 0.8, and h is preferably a number of 0 to 0.6. f + g + h is preferably a number of 0.05 or more, more preferably a number of 0.1 to 0.9, and still more preferably a number of 0.2 to 0.6.
(B) In the component (B), the content of the alkenyl group bonded to the silicon atom is preferably in the range of 0.01 to 1mol, more preferably in the range of 0.1 to 0.6mol, per 100g of the component (B). When the content is in the range of 0.01 to 1mol, the crosslinking reaction proceeds sufficiently, and a cured product having a higher hardness can be obtained.
(B) Component (C) preferably has R2 3SiO1/2Unit and SiO4/2Unit (i.e., b)>0 and h>0) In this case, the adhesive strength of the cured product obtained from the composition can be imparted. Furthermore, the component (B) must have a composition consisting of SiO4/2Unit and/or SiO3/2The branched structure of the unit may further contain SiO such as methylvinylsiloxy unit, dimethylsiloxy unit and the like2/2SiO such as (SiO) unit, dimethylvinylsiloxy unit, trimethylsiloxy unit1/2And (4) units. SiO 24/2Unit and/or SiO3/2The content of the unit is preferably 5 mol% or more, more preferably 10 to 90 mol%, and particularly preferably 20 to 60 mol% of all siloxane units in the organopolysiloxane resin of component (B).
The content of the component (B) is 70 to 95 parts by mass, preferably 75 to 95 parts by mass, and more preferably 80 to 90 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). When the blending amount of the component (B) is less than 70 parts by mass, the adhesiveness is poor, and a cured product with high hardness cannot be obtained, and when it exceeds 95 parts by mass, the viscosity of the composition becomes remarkably high, and transfer becomes difficult, and handling becomes difficult when the composition is used for a solid crystal material.
Specific examples of the three-dimensional network-like organopolysiloxane as the component (B) include the following organopolysiloxanes.
((CH2＝CH)3SiO1/2)0.1((CH2＝CH)(CH3)2SiO1/2)0.2((CH3)3SiO1/2)0.35(SiO4/2)0.35；
((CH2＝CH)3SiO1/2)0.2((CH3)3SiO1/2)0.1(SiO4/2)0.7；
((CH2＝CH)3SiO1/2)0.07((CH3)3SiO1/2)0.4(SiO4/2)0.53；
((CH2＝CH)3SiO1/2)0.14((CH3)3SiO1/2)0.32(SiO4/2)0.54；
((CH2＝CH)3SiO1/2)0.07((CH3)3SiO1/2)0.33(SiO4/2)0.6；
((CH2＝CH)3SiO1/2)0.1((CH3)3SiO1/2)0.1((CH3)2SiO)0.2((CH3)SiO3/2)0.6；
((CH2＝CH)3SiO1/2)0.07((CH3)3SiO1/2)0.13((CH3)2SiO)0.2(SiO4/2)0.6；
((CH2＝CH)3SiO1/2)0.3(SiO4/2)0.7；
((CH2＝CH)3SiO1/2)0.2((CH3)SiO3/2)0.8；
((CH2＝CH)3SiO1/2)0.2((CH3)SiO3/2)0.6(SiO4/2)0.2。
(B) The components can be used singly or in combination.
< ingredient (C) >
(C) Component (B) functions as a crosslinking agent which crosslinks the alkenyl groups contained in component (a) and component (B) by a hydrosilylation reaction. (C) The component (A) is an organohydrogenpolysiloxane represented by the following average composition formula (2) and having at least 2 silicon atom-bonded hydrogen atoms (i.e., Si-H groups) in 1 molecule.
R1 iHjSiO(4-i-j)/2 (2)
In the formula, R1And said R1Similarly, i and j are numbers satisfying 0.7. ltoreq. i.ltoreq.2.1, 0.001. ltoreq. j.ltoreq.1.0, and 0.8. ltoreq. i + j.ltoreq.3.0.
As R1Examples thereof include the compounds represented by the formula R in the component (A)1The same group is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
In addition, in the compositions of the present invention, the methyl group is at R1The proportion of the total number of all monovalent hydrocarbon groups bonded to a silicon atom other than the alkenyl group is preferably 80 mol% or more (that is, the R is1In the case where the methyl group accounts for at least 80 mol% of the total amount of the organic solvent, methyl groups are preferred, particularly when the methyl group accounts for at least 90 mol%, since the organic solvent is excellent in heat resistance, light resistance (ultraviolet resistance), and resistance to deterioration such as discoloration caused by stimulus such as heat or ultraviolet light.
(C) The component (A) has at least 2 hydrogen atoms (Si-H groups) bonded to silicon atoms in 1 molecule, preferably 2 to 200, more preferably 3 to 100, and still more preferably 4 to 50.
The amount of the component (C) to be blended is an amount of 0.5 to 5.0 times, preferably 0.7 to 3.0 times, the number of silicon atom-bonded hydrogen atoms (Si-H groups) in the component (C) relative to the total number of all silicon atom-bonded alkenyl groups in the components (A) and (B), from the viewpoint of crosslinking balance. If the number of hydrogen atoms is less than 0.5 times the total number of alkenyl groups, crosslinking may not sufficiently proceed, and a cured product having excellent hardness may not be obtained. If the number of hydrogen atoms is more than 5.0 times the total number of alkenyl groups, flexibility of the silicone cured product is lost, and the silicone cured product becomes brittle.
(C) The viscosity of the component (C) at 25 ℃ is not particularly limited, but is preferably 100 mPas or less, more preferably 5 to 100 mPas.
Further, the mass loss after heating the component (C) at 150 ℃ for 30 minutes under 1 standard atmosphere is preferably 1 mass% or less with respect to the mass before heating. Within this range, metal pad contamination can be further reduced.
(C) The molecular structure of the organohydrogenpolysiloxane of component (a) may be any of linear, cyclic, branched and three-dimensional network structures, and the number of silicon atoms in 1 molecule is preferably 10 to 300, more preferably 50 to 200. With such a component (C), a composition having a low volatile content during curing and less staining of the metal pad can be obtained.
Examples of the organohydrogenpolysiloxane of component (C) include 1,1,3, 3-tetramethyldisiloxane, 1,3,5, 7-tetramethylcyclotetrasiloxane, tris (hydrogendimethylsiloxy) methylsilane, tris (hydrogendimethylsiloxy) phenylsilane, methylhydrocyclopolysiloxane, methylhydrogensiloxane-dimethylsiloxane cyclic copolymer, trimethylsiloxy-terminated methylhydrogensiloxane at both ends, trimethylsiloxy-terminated dimethylsiloxane-methylhydrogensiloxane copolymer at both ends, dimethylsiloxy-terminated dimethylpolysiloxane at both ends, dimethylsiloxy-terminated methylhydrogensiloxane-methylhydrogensiloxane copolymer at both ends, dimethylsiloxy-terminated dimethylsiloxy-dimethylsiloxane copolymer at both ends, dimethylsiloxy-terminated methylhydrogensiloxane-diphenylsiloxane copolymer at both ends, and the like, Both-terminal trimethylsiloxy-terminated methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane copolymer, both-terminal trimethylsiloxy-terminated methylhydrogensiloxane-methylphenylsiloxane-dimethylsiloxane copolymer, both-terminal dimethylhydrogensiloxy-terminated methylhydrogensiloxane-dimethylsiloxane-diphenylsiloxane copolymer, both-terminal dimethylhydrogensiloxy-terminated methylhydrogensiloxane-dimethylsiloxane-methylphenylsiloxane copolymer, block Copolymer of (CH) and (C) are used as3)2HSiO1/2Unit and (CH)3)3SiO1/2Units and SiO4/2Copolymer of units of (CH)3)2HSiO1/2Units and SiO4/2Copolymers of unitsIs Composed of (CH)3)2HSiO1/2Units and SiO4/2Unit and (C)6H5)3SiO1/2Examples of the copolymer having a unit structure include a copolymer represented by the following general formula (6) or (7) in addition to the above copolymers.
R1 3SiO[SiR1(H)O]tSiR1 3 (6)
Cyclic [ SiR1(H)O]u (7)
In the formula, R1And said R1Similarly, t is an integer of 2 to 40, preferably an integer of 8 to 35, and u is an integer of 6 to 8.
Specific examples of the component (C) include a component represented by the following formula (8), a component represented by the following formula, and the like.
Me3SiO[SiMe(H)O]tSiMe3 (8)
Wherein t is the same as t, and Me is methyl.
[ chemical formula 3]
In the above formula, the order of arrangement of the siloxane units in parentheses is arbitrary.
(C) The organohydrogenpolysiloxane of component (a) may be used alone or in combination of two or more.
< ingredient (D) >
(D) The component (A) is an epoxy group-containing polysiloxane represented by the following formula (3).
(R3SiO3/2)k(R1SiO3/2)m(R4O1/2)n (3)
In the formula, R1And said R1Same as R3Are optionally identical or different epoxy-containing radicals, R4Is an optionally identical or different, respectively, alkenyl-free, substituted or unsubstituted, monovalent hydrocarbon radical, k and m are each independently of the other k>0. m is not less than 0, k + m is 1, n isN is a number of 0 to 2.
Since the component (D) of the present invention is composed of SiO3/2The polymer having a repeating unit structure can provide a composition having a reduced low-molecular weight component, improved adhesion, and no metal pad contamination.
As R3Examples of the epoxy group-containing group include groups bonded to a silicon atom via a carbon atom such as an alicyclic epoxy group or a glycidyl group, and preferably have a glycidyl group. More preferably, the group represented by the following formula (5) such as γ -glycidoxypropyl group, and β - (3, 4-epoxycyclohexyl) ethyl group are mentioned.
[ chemical formula 4]
Wherein s is an integer of 1 to 6, and the dotted line represents a bond.
As R1Examples thereof include the compounds represented by the formula R in the component (A)1The same group is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
As R4The substituted or unsubstituted monovalent hydrocarbon group not containing an alkenyl group is not particularly limited as long as it has no alkenyl group, but is preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Examples of the monovalent hydrocarbon include alkyl groups such as methyl, ethyl, propyl and butyl, cycloalkyl groups such as cyclohexyl and cyclopentyl, aryl groups such as phenyl, tolyl and xylyl, aralkyl groups such as benzyl and phenylethyl, and halogenated hydrocarbon groups such as chloromethyl, chloropropyl and chlorocyclohexyl. Preferably an alkyl group, more preferably a methyl group and an ethyl group.
The mass loss after heating component (D) at 150 ℃ for 30 minutes under 1 standard atmosphere is preferably 5 mass% or less with respect to the mass before heating. Within this range, metal pad contamination can be further reduced.
(D) The component (B) is preferably in a liquid state, and the molecular weight is preferably in the range of 500 to 10,000 from the viewpoint of handling and prevention of contamination of the metal gasket.
In formula (3), k and m are preferably numbers that satisfy 0< k.ltoreq.0.9, 0< m.ltoreq.0.9, and k + m is 1. When the component (D) is within the above range, the compatibility with the components (A), (B) and (C) is excellent, and the obtained cured product is excellent in adhesiveness and chip shear strength.
From the viewpoint of the storage stability of the composition and the prevention of contamination of the metal gasket, n is preferably a number of 0 to 1, more preferably a number of 0 to 0.1, and still more preferably 0.
The amount of the component (D) is 1 to 25 parts by mass, preferably 3 to 10 parts by mass, per 100 parts by mass of the components (A), (B) and (C). If the amount is less than the lower limit, the target chip shear strength may not be obtained. If the amount exceeds the upper limit, the components may be separated from the composition, and the strength of the resulting cured product may be reduced.
< ingredient (E) >
(E) The platinum group metal catalyst of component (a) is a component for promoting the hydrosilylation reaction of components (a) to (C).
The platinum group metal catalyst is not particularly limited, and examples thereof include platinum group metals such as platinum, palladium, and rhodium; platinum compounds such as chloroplatinic acid, alcohol-modified chloroplatinic acid, and coordination compounds of chloroplatinic acid with olefins, vinylsiloxanes, and acetylene compounds; platinum group metal compounds such as tetrakis (triphenylphosphine) palladium and tris (triphenylphosphine) rhodium chloride are preferably organosilicon-modified with platinic chloride, because they have good compatibility with components (a) to (C) and contain almost no chlorine impurities.
(E) The components can be used singly or in combination.
The amount of component (E) is 1 to 500ppm, preferably 3 to 100ppm, more preferably 5 to 40ppm, in terms of the mass of the platinum group metal element, relative to the total mass of components (A) to (D). If the blending amount of the component (E) is less than the lower limit, the obtained silicone composition for solid crystal cannot be cured sufficiently, while if the blending amount is more than the upper limit of the above range, the curing rate of the obtained silicone composition for solid crystal cannot be further improved.
< ingredient (F) >
The silicone composition for die bonding of the present invention may contain fumed silica as the component (F). (F) The component (b) is a component which imparts appropriate thixotropy to the composition for the purpose of stably applying the silicone composition for die bonding of the present invention.
The BET specific surface area of the component (F) is preferably 100 to 400m from the viewpoint of thixotropy and workability2In the range of/g.
From the viewpoint of thixotropy and workability, the amount of component (F) is preferably 3 to 10 parts per 100 parts by mass of components (A) to (E).
As a specific example of the component (F), there can be mentioned REOLOSIL DM-30 (manufactured by Tokuyama Corporation, BET specific surface area 300 m)2,/g), etc.
< other ingredients >
In addition to the components (a) to (F), the composition of the present invention may further contain other components shown below.
(reaction inhibitor)
In the silicone composition for die bonding of the present invention, a known reaction inhibitor (reaction inhibitor) having a curing inhibitory effect on the addition reaction catalyst of the component (D) may be used as necessary. Examples of the reaction inhibitor include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine and benzotriazole; a sulfur-containing compound; acetylene compounds; a hydroperoxide compound; maleic acid derivatives, and the like.
The degree of the curing inhibition effect by the reaction inhibitor varies greatly depending on the chemical structure of the reaction inhibitor, and therefore, it is preferable to adjust the blending amount of the reaction inhibitor to the most suitable amount for each reaction inhibitor used. In general, it is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of the component (A), the component (B), the component (C) and the component (D).
(Filler)
The silicone composition for solid crystals of the present invention may be filled with an inorganic filler such as a crystalline silica hollow filler or silsesquioxane, in addition to the fumed silica of the component (F); fillers obtained by subjecting these fillers to surface hydrophobization treatment using an organic silicon compound such as an organoalkoxysilane compound, an organochlorosilane compound, an organoazane compound, or a low-molecular-weight siloxane compound; silicone rubber powder; silicone resin powder, and the like. As the component, a filler capable of imparting thixotropy is particularly preferably used in view of handling properties.
These other components may be used alone or in combination of two or more.
In addition, all R in the silicone composition for die bonding of the present invention is preferable1Wherein 80 mol% or more of the total amount of the compounds are methyl groups. In addition, the viscosity of the silicone composition for die bonding of the present invention is preferably 5 to 100 pas, more preferably 20 to 50 pas at 25 ℃ in order to improve the workability of die bonding (transfer method).
[ cured product ]
Further, the present invention provides a cured product of the silicone composition for die bonding (silicone cured product).
The curing of the silicone composition for die bonding of the present invention may be carried out under known conditions, and for example, it may be carried out at 100 to 180 ℃ for 10 minutes to 5 hours.
The cured product of the silicone composition for die bonding of the present invention has high adhesion to a substrate, an LED chip, and the like, and is particularly useful as a die bonding material for die bonding of an LED device and the like. As described above, the silicone cured product of the present invention can provide an adhesive having high adhesion to a substrate, an LED chip, or the like.
[ optical semiconductor device ]
Further, the present invention provides an optical semiconductor device in which the optical semiconductor element is die-bonded using the cured product.
As an example of a method for die bonding an optical semiconductor element using the silicone composition for die bonding of the present invention, the following method can be mentioned: the silicone composition for die bonding of the present invention is filled in a syringe, applied to a substrate such as a package by using a dispenser (dispenser) so as to be 1 to 100 μm thick in a dry state, and then an optical semiconductor element (for example, a light emitting diode) is disposed on the applied composition, and the composition is cured, thereby die bonding the optical semiconductor element on the substrate. Further, the following method may be used: the composition is placed on a doctor blade (squeegee dish), and is applied to a substrate by dispensing (holding) while scraping the composition so that the thickness of the composition in a dry state is 1 to 100 [ mu ] m, and then an optical semiconductor element is arranged on the applied composition, and the composition is cured, whereby the optical semiconductor element is fixed to the substrate. The curing conditions of the composition may be set as described above. Thus, an optical semiconductor device having high reliability and having an optical semiconductor element bonded with a crystal using the cured silicone of the present invention can be obtained.
Examples
The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The molecular weight is a weight average molecular weight in terms of standard polystyrene in Gel Permeation Chromatography (GPC). The viscosity at 25 ℃ is a measured value measured using a rotational viscometer. The volatile matter was mass loss (mass%) when heated at 150 ℃ for 30 minutes under 1 standard atmosphere.
Further, the abbreviations for the respective siloxane units have the following meanings.
M：(CH3)3SiO1/2
MVi：(CH2＝CH)(CH3)2SiO1/2
MVi3：(CH2＝CH)3SiO1/2
D：(CH3)2SiO2/2
DH：H(CH3)SiO2/2
T：(CH3)SiO3/2
T1：
[ chemical formula 5]
T2：
[ chemical formula 6]
T3：
[ chemical formula 7]
T4：
[ chemical formula 8]
T5：
[ chemical formula 9]
Q：SiO4/2
[ Synthesis example 1]
352.5g of [ (CH) was charged into a 3,000mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer3O)3SiO1/2]2[(CH3O)2SiO]2The organopolysiloxane represented by (1), 45.6g of hexavinyldisiloxane, 182.3g of hexamethyldisiloxane, and 58g of isopropanol were added dropwise with stirring 6.7g of methanesulfonic acid. Then, 90g of water was added dropwise thereto, and the mixture was mixed at 65 ℃ for 2 hours to effect a reaction. 700g of hexene and 10.9g of a 50% aqueous potassium hydroxide solution were added thereto, and the mixture was heated to remove the low boiling point component by distillationThe reaction was carried out at 120 ℃ for 5 hours. 3.5g of methanesulfonic acid was added as an additive, and neutralization treatment was performed at 120 ℃ for 2 hours. Cooling and filtering to obtain the composition ratio of MVi3 0.07M0.4Q0.53A three-dimensional network organopolysiloxane (B-1: molecular weight 3,350, solid at 23 ℃, amount of vinyl group relative to solid component 0.287mol/100g) was represented.
[ Synthesis example 2]
A1,000 mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer was charged with 234g of 3-glycidoxypropyltrimethoxysilane, 136g of methyltrimethoxysilane and 37.8g of methanol, and a mixture of 29g of 0.04N hydrochloric acid and 70.3g of methanol was added dropwise with stirring. After the reaction was carried out at 25 ℃ for 3 hours while stirring, 10% sodium acetate/methanol solution was added dropwise to neutralize the reaction solution, and the reaction mixture was stirred at 65 ℃ for 2 hours. Further, after cooling, filtration was performed, and then the low molecular weight was removed by repeating 3 times the washing operation of adding 500g of a methanol/water (mass ratio 50:50) mixed solution, mixing the mixture for 20 minutes and standing the mixture for 30 minutes, and separating and removing the methanol solvent layer, and further, the residual methanol was removed by performing concentration under reduced pressure at 100 ℃ for 1 hour. After cooling to 25 ℃ filtration is carried out to obtain a structural unit ratio T1 0.49T0.51The epoxy group-containing silicone (D-1: molecular weight 2,780, viscosity 313 mPas). The volatile matter was 1.7 mass%.
[ Synthesis example 3]
Into a 1,000mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer were charged 304g of 8-glycidoxyoctyltrimethoxysilane, 136g of methyltrimethoxysilane and 37.8g of methanol, and a mixture of 29g of 0.04N hydrochloric acid and 70.3g of methanol was added dropwise with stirring. After the reaction was carried out at 25 ℃ for 3 hours while stirring, 10% sodium acetate/methanol solution was added dropwise to neutralize the reaction solution, and the reaction mixture was stirred at 65 ℃ for 2 hours. Further, after cooling to 25 ℃, filtration was performed, and then the methanol solution was removed by repeating 3 times the addition of 500g of a methanol/water (mass ratio 50:50) mixed solution, mixing for 20 minutes and standing for 30 minutes, and separationThe agent layer was washed to remove low molecules, and further concentrated at 100 ℃ for 1 hour under reduced pressure to remove residual methanol. After cooling to 25 ℃ filtration is carried out to obtain a structural unit ratio T2 0.47T0.53The epoxy group-containing silicone (D-2: molecular weight 2,570, viscosity 138 mPas). The volatile matter was 1.5 mass%.
[ Synthesis example 4]
Into a 1,000mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer were charged 246g of 2- (3, 4-epoxycyclohexyl) trimethoxysilane, 136g of methyltrimethoxysilane and 37.8g of methanol, and a mixture of 29g of 0.04N hydrochloric acid and 70.3g of methanol was added dropwise with stirring. After the reaction was carried out at 25 ℃ for 3 hours while stirring, 10% sodium acetate/methanol solution was added dropwise to neutralize the reaction solution, and the reaction mixture was stirred at 65 ℃ for 2 hours. Further, after cooling to 25 ℃, filtration was performed, and then the low molecular weight was removed by repeating 3 times the washing operation of adding 500g of a methanol/water (mass ratio 50:50) mixed solution, mixing the mixture for 20 minutes, standing the mixture for 30 minutes, and separating and removing the methanol solvent layer, and further, the residual methanol was removed by performing concentration under reduced pressure at 100 ℃ for 1 hour. After cooling to 25 ℃ filtration is carried out to obtain a structural unit ratio T3 0.57T0.43The epoxy group-containing silicone (D-3: molecular weight 1890, viscosity 137 mPas). The volatile matter (30 minutes at 150 ℃) was 4.7% by mass.
[ comparative Synthesis example 1]
Into a 1,000mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer were charged 248g of 3-methacryloxypropyltrimethoxysilane, 136g of methyltrimethoxysilane and 37.8g of methanol, and a mixture of 29g of 0.04N hydrochloric acid and 70.3g of methanol was added dropwise with stirring. After the reaction was carried out at 25 ℃ for 3 hours while stirring, 10% sodium acetate/methanol solution was added dropwise to neutralize the reaction solution, and the reaction mixture was stirred at 65 ℃ for 2 hours. Further, after cooling to 25 ℃, filtration was performed, and then the methanol solvent layer was removed by repeating 3 times the addition of 500g of a methanol/water (mass ratio 50:50) mixed solution, mixing for 20 minutes and standing for 30 minutes, and separationRemoving low molecules, and further performing concentration under reduced pressure at 100 ℃ for 1 hour to remove residual methanol. After cooling to 25 ℃ filtration is carried out to obtain a structural unit ratio T4 0.52T0.48Has a molecular weight of 2,900 and a viscosity of 261 mPas. The volatile matter was 2.7 mass%.
[ comparative Synthesis example 2]
Into a 1,000mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer were charged 248g of 3-acryloxypropyltrimethoxysilane, 136g of methyltrimethoxysilane and 37.8g of methanol, and a mixture of 29g of 0.04N hydrochloric acid and 70.3g of methanol was added dropwise with stirring. After the reaction was carried out at 25 ℃ for 3 hours while stirring, 10% sodium acetate/methanol solution was added dropwise to neutralize the reaction solution, and the reaction mixture was stirred at 65 ℃ for 2 hours. Further, after cooling to 25 ℃, filtration was performed, and then the low molecular weight was removed by repeating 3 times the washing operation of adding 500g of a methanol/water (mass ratio 50:50) mixed solution, mixing the mixture for 20 minutes, standing the mixture for 30 minutes, and separating and removing the methanol solvent layer, and further, the residual methanol was removed by performing concentration under reduced pressure at 100 ℃ for 1 hour. After cooling to 25 ℃ filtration is carried out to obtain the structural unit ratio T5 0.49T0.51The organopolysiloxane (D-5: molecular weight 3,350, viscosity 387 mPas) was represented. The volatile matter was 0.9 mass%.
[ Synthesis example 5]
M was used so that the platinum content was 0.004 mass%Vi 2D40The platinum catalyst (E) was prepared by diluting the reaction product of hexachloroplatinic acid and 1, 3-divinyltetramethyldisiloxane with a linear dimethylpolysiloxane (viscosity: 60mPa · s).
Examples 1 to 4 and comparative examples 1 to 7
The following components were mixed in the blending amounts shown in table 1 to prepare a silicone composition for die bonding.
In table 1, the numerical values of the respective components represent parts by mass. [ Si-H ]/[ Si-Vi ] represents the ratio (molar ratio) of the number of silicon atom-bonded hydrogen atoms (Si-H groups) in component (C) to the total number of all silicon atom-bonded alkenyl groups in components (A) and (B).
(A) The components:
(A-1) structural Unit ratio MVi 0.47T0.53The organopolysiloxane (viscosity at 25 ℃ C. is 17 mPas)
(A-2) average structure consisting of MVi 2D15The straight-chain dimethylpolysiloxane (viscosity at 25 ℃ C. is 8.8 mPas)
(A-3) average structure consisting of MVi 2D204Dimethylpolysiloxane (viscosity at 25 ℃ C. is 600 mPas)
(B) The components:
(B-1) three-dimensional network organopolysiloxane obtained in Synthesis example 1
(B-2) average structure consisting of MVi 1.2M7.4Q10The amount of vinyl groups represented as a solid at 23 ℃ was 0.085mol/100g of a three-dimensional network organopolysiloxane
(C) The components: average structure is formed by M2D14.5DH 38The organohydrogenpolysiloxane (volatile component content: 0.2% by mass) was represented
(D) The components:
(D-1) organopolysiloxane obtained in Synthesis example 2 (volatile component amount 1.7% by mass)
(D-2) organopolysiloxane obtained in Synthesis example 3 (volatile component amount 1.5% by mass)
(D-3) organopolysiloxane obtained in Synthesis example 4 (volatile component content 4.7% by mass)
(D-4) organopolysiloxane obtained in comparative Synthesis example 1 (volatile component amount: 2.7% by mass)
(D-5) organopolysiloxane obtained in comparative Synthesis example 2 (volatile component content 0.9% by mass)
(D-6) 3-glycidoxypropyltrimethoxysilane (volatile component content: 97% by mass)
As for the volatile matter of the component (D), 1.5g of each component (D) was coated on an aluminum dish having a diameter of 60mm, and heated in an oven at 150 ℃ for 30 minutes in an open system, and the mass ratio decreased after heating was calculated.
(E) The components: synthesis of platinum catalyst obtained in example 5
(F) The components: fumed silica [ REOLOSIL DM30 (manufactured by Tokuyama Corporation, BET specific surface area 300 m)2/g)]
(G) Reaction inhibitors: 1-ethynylcyclohexanol
The following evaluations were made with respect to the silicone compositions for die bonding obtained in examples 1 to 4 and comparative examples 1 to 7, and the results are shown in table 1.
[ hardness ]
The composition was poured into a mold so that the thickness thereof became 2mm, and cured at 150 ℃ for 4 hours. The TypeD hardness of the cured product was measured in accordance with JIS K6253-3: 2012.
[ chip shear Strength ]
The composition was quantitatively transferred to a silver-plated electrode portion of an SMD5730 package (I-child previous manufacturing input co., ltd., manufactured by polyphthalamide) by dispensing using a die bonder (AD-830, manufactured by ASM inc.). The case where the resin could not be transferred or the case where the stringiness occurred during dispensing was evaluated as "x", and the case where the resin could be transferred without any problem was evaluated as "o". Further, an optical semiconductor element (manufactured by Semleds Corporation, EV-B35A, 35mil) was mounted thereon. The resulting package was heated in an oven at 150 ℃ for 4 hours to cure the composition, and then the shear strength of the chip was measured using a bond tester (manufactured by Dage corporation, Series 4000).
[ contamination of Metal gasket ]
PKG mounted with an optical semiconductor element (manufactured by Semleds Corporation, EV-B35A, 35mil) was set on an aluminum dish of Φ 105mm, and 2g of a resin was coated around the PKG. Then, after curing at 150 ℃ for 4 hours, the metal pad of the semiconductor element was observed with a microscope, and the metal pad was evaluated as "x" when a siloxane component was adhered to the metal pad and as "o" when a siloxane component was not adhered to the metal pad.
[ Table 1]
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | |
| A-1 | 20 | 20 | 20 | - | 20 | 20 | 20 | - | 20 | 20 | 20 |
| A-2 | - | - | - | 30 | - | - | - | - | - | - | - |
| A-3 | - | - | - | - | - | - | - | 20 | - | - | - |
| B-1 | 80 | 80 | 80 | - | 80 | 80 | 80 | 80 | 80 | 80 | 80 |
| B-2 | - | - | - | 70 | - | - | - | - | - | - | - |
| C | 21.7 | 21.7 | 21.7 | 9.6 | 21.7 | 21.7 | 21.7 | 17.2 | 21.7 | 21.7 | 21.7 |
| D-1 | 6 | - | - | 6 | - | - | - | 6 | 0.5 | 32 | - |
| D-2 | - | 6 | - | - | - | - | - | - | - | - | - |
| D-3 | - | - | 6 | - | - | - | - | - | - | - | - |
| D-4 | - | - | - | - | - | 6 | - | - | - | - | - |
| D-5 | - | - | - | - | - | - | 6 | - | - | - | - |
| D-6 | - | - | - | - | - | - | - | - | - | - | 6 |
| E | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| F | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| G | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| [S-H]/[Si-Vi](mols) Than) | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Hardness of | 65 | 64 | 65 | 67 | 65 | 63 | 64 | 51 | 67 | 58 | 62 |
| Chip shear strength (23 ℃ C.) | 13.3 | 15.9 | 1.7 | 14.1 | 6.1 | 9.6 | 9.1 | - | 9.8 | 7.1 | 10.4 |
| Chip shear strength (150 ℃ C.) | 9.6 | 10.3 | 10.3 | 9.9 | 3.8 | 6.5 | 5.6 | - | 5.5 | 4.1 | 8.5 |
| Property of preventing contamination of metal gasket Can be used for | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × |
| Operability (transferability) | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | ○ | × | ○ |
As shown in table 1, it is understood that in each of examples 1 to 4, there was no problem in dispensing, and the cured product was excellent in hardness and chip shear strength, and was an excellent die bonding material without metal pad contamination. Fig. 1 shows the results of the metal pad contamination test of example 1.
On the other hand, comparative example 1 did not contain the component (D), and the shear strength of the chip was insufficient. In comparative examples 2 to 3, since the component (D) does not contain an epoxy group, the shear strength of the chip is poor.
The component (A) in comparative example 4 had a high viscosity, and the resulting die bond material could not be dispensed, resulting in poor handling properties, while the component (D) in comparative example 5 had a small amount and low die shear strength. In comparative example 6, since the amount of component (D) was too large, the cured product had sufficient hardness, but the composition separated, and the composition did not have storage stability as a solid crystal material and had poor reliability. In comparative example 7, the shear strength of the chip was slightly improved by the epoxy group-containing silane coupling agent, but as shown in fig. 2, metal pad contamination occurred and the reliability was poor.
As described above, the silicone composition for die bonding of the present invention can give a silicone cured product excellent in hardness and chip shear strength, and can effectively suppress metal pad contamination during curing, and is particularly useful as a die bonding material for die bonding used for optical semiconductor devices and the like. In particular, due to this feature, in the wire bonding step performed after the die bonding step, since defects such as chip detachment and failure in bonding are not likely to occur, the reliability of an optical semiconductor device in which the optical semiconductor element is die bonded using the silicone cured product is improved, and the productivity of the device is also improved. Therefore, the silicone composition for die bonding and the cured product thereof of the present invention have high utility values in the technical field of optical semiconductor devices.
The present invention is not limited to the above embodiments. The above embodiments are merely exemplary, and any embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same operation and effect are included in the scope of the present invention.
Claims (17)
1. A silicone composition for die bonding, characterized by comprising the following components (A) to (E):
(A) an organopolysiloxane that contains 2 or more alkenyl groups in 1 molecule and has a viscosity of 100 mPas or less at 25 ℃;
(B) a three-dimensional network organopolysiloxane represented by the following formula (1) which is waxy or solid at 23 ℃, which is 70 to 95 parts by mass relative to 100 parts by mass of the total of the components (A) and (B),
(R1 3SiO1/2)a(R2 3SiO1/2)b(R2R1 2SiO1/2)c(R2R1SiO)d(R1 2SiO)e(R2SiO3/2)f(R1SiO3/2)g(SiO4/2)h (1)
in the formula, R1Is a substituted or unsubstituted monovalent hydrocarbon radical which is optionally identical or different, respectively, and which does not contain alkenyl groups, R2A, b, c, d, e, f, g and h are each a number satisfying a.gtoreq.0, b.gtoreq.0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0, f.gtoreq.0, g.gtoreq.0 and h.gtoreq.0, and b + c>0、f+g+h>0 and a + b + c + d + e + f + g + h is a number of 1;
(C) an organohydrogenpolysiloxane represented by the following average composition formula (2) and having at least 2 silicon atom-bonded hydrogen atoms in 1 molecule, wherein the number of silicon atom-bonded hydrogen atoms in component (C) is 0.5 to 5.0 times the total number of all silicon atom-bonded alkenyl groups in components (A) and (B),
R1 iHjSiO(4-i-j)/2 (2)
in the formula, R1And said R1I and j are numbers satisfying 0.7. ltoreq. i.ltoreq.2.1, 0.001. ltoreq. j.ltoreq.1.0, and 0.8. ltoreq. i + j.ltoreq.3.0;
(D) an epoxy group-containing polysiloxane represented by the following formula (3), wherein the epoxy group-containing polysiloxane is 1 to 25 parts by mass relative to 100 parts by mass of the total of the component (A), the component (B) and the component (C),
(R3SiO3/2)k(R1SiO3/2)m(R4O1/2)n (3)
in the formula, R1And said R1Same as R3Are optionally identical or different epoxy-containing radicals, R4Is a substituted or unsubstituted monovalent hydrocarbon group optionally the same or different and having no alkenyl group, and k and m are each k>0. m is more than or equal to 0, k + m is a number equal to 1, and n is a number which satisfies that n is more than or equal to 0 and less than or equal to 2; and
(E) the platinum group metal catalyst is 1 to 500ppm by mass in terms of the mass of the platinum group metal element relative to the total mass of the component (A), the component (B), the component (C) and the component (D).
2. The silicone composition for die bonding according to claim 1, wherein the component (A) is an organopolysiloxane represented by the following formula (4),
(R1 3SiO1/2)q(R2R1 2SiO1/2)r(R2SiO3/2)o(R1SiO3/2)p (4)
in the formula, R1And R2And said R1And R2Similarly, o, p, q, r are numbers satisfying q.gtoreq.0, r.gtoreq.0, o.gtoreq.0, and p.gtoreq.0, respectively, and q + r>0、r+o>0、o+p>0 and o + p + q + r is a number of 1.
3. The silicon composition for die bonding according to claim 1, wherein in the formula (1), b >0 and h > 0.
4. The silicon composition for die bonding according to claim 2, wherein in the formula (1), b >0 and h > 0.
5. The silicon composition for die bonding according to claim 1, wherein the mass loss of the component (C) when heated at 150 ℃ for 30 minutes under 1 standard atmosphere is 1 mass% or less.
6. The silicon composition for die bonding according to claim 2, wherein the mass loss of the component (C) when heated at 150 ℃ for 30 minutes under 1 standard atmosphere is 1 mass% or less.
7. The silicon composition for die bonding according to claim 3, wherein the mass loss of the component (C) when heated at 150 ℃ for 30 minutes under 1 standard atmosphere is 1 mass% or less.
8. The silicon composition for die bonding according to claim 4, wherein the mass loss of the component (C) when heated at 150 ℃ for 30 minutes under 1 standard atmosphere is 1 mass% or less.
9. The silicon composition for die bonding according to claim 1, wherein the mass loss of the component (D) when heated at 150 ℃ for 30 minutes under 1 atm is 5 mass% or less.
10. The silicon composition for die bonding according to claim 2, wherein the mass loss of the component (D) when heated at 150 ℃ for 30 minutes under 1 atm is 5 mass% or less.
11. The silicon composition for die bonding according to claim 3, wherein the mass loss of the component (D) when heated at 150 ℃ for 30 minutes under 1 atm is 5% by mass or less.
12. The silicon composition for die bonding according to claim 4, wherein the mass loss of the component (D) when heated at 150 ℃ for 30 minutes under 1 atm is 5% by mass or less.
13. According to the claimsThe silicone composition for die bonding as set forth in any one of claims 1 to 12, wherein R in the component (D)3Is a group represented by the following formula (5),
[ chemical formula 1]
Wherein s is an integer of 1 to 6, and the dotted line represents a bond.
14. The silicon composition for die bonding according to any one of claims 1 to 12, wherein all R in the composition1Wherein 80 mol% or more of the total amount of the compounds are methyl groups.
15. The silicone composition for die bonding according to any one of claims 1 to 12, further comprising (F) a BET specific surface area of 100 to 400m2Fumed silica per gram.
16. A cured silicone material characterized by being a cured product of the silicone composition for die bonding according to any one of claims 1 to 12.
17. An optical semiconductor device, which is characterized by using the cured silicone according to claim 16 for die bonding of an optical semiconductor element.
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| JP2019095074A JP7041094B6 (en) | 2019-05-21 | 2019-05-21 | Silicone composition for die bonding, cured product thereof, and optical semiconductor device |
| JP2019-095074 | 2019-05-21 |
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Cited By (2)
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|---|---|---|---|---|
| CN117089318A (en) * | 2023-07-25 | 2023-11-21 | 北京康美特科技股份有限公司 | Organic silicon die-bonding adhesive and preparation method and application thereof |
| CN117165236A (en) * | 2023-10-30 | 2023-12-05 | 空净视界智能科技有限公司 | Insulating die bond adhesive for LED and preparation method thereof |
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| JPWO2022138341A1 (en) * | 2020-12-25 | 2022-06-30 |
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| KR20200134162A (en) | 2020-12-01 |
| JP2020189908A (en) | 2020-11-26 |
| JP7041094B2 (en) | 2022-03-23 |
| TW202111072A (en) | 2021-03-16 |
| JP7041094B6 (en) | 2023-12-18 |
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