CN111138860A

CN111138860A - Addition-curable silicone resin composition, cured product thereof, and optical semiconductor device

Info

Publication number: CN111138860A
Application number: CN201911046191.4A
Authority: CN
Inventors: 小林之人
Original assignee: Shin Etsu Chemical Co Ltd
Current assignee: Shin Etsu Chemical Co Ltd
Priority date: 2018-11-02
Filing date: 2019-10-30
Publication date: 2020-05-12
Anticipated expiration: 2039-10-30
Also published as: JP6966411B2; TW202024239A; CN111138860B; KR20200050875A; TWI831858B; JP2020070402A

Abstract

本发明提供一种加成固化型硅酮树脂组合物，其给与硬度及芯片剪切强度优异的固化物，其含有：(A)下述式表示的有机聚硅氧烷，(R¹ ₃SiO_1/2)_a(R²R¹ ₂SiO_1/2)_b(R²R¹SiO)_c(R¹ ₂SiO)_d(R²SiO_3/2)_e(R¹SiO_3/2)_f(SiO_4/2)_g；(B)下述式表示的支链状有机聚硅氧烷，(R¹ ₃SiO_1/2)_h(R² ₃SiO_1/2)_i(R²R¹ ₂SiO_1/2)_j(R²R¹SiO)_k(R¹ ₂SiO)_l(R²SiO_3/2)_m(R¹SiO_3/2)_n(SiO_4/2)_o；(C)下述式表示的有机氢聚硅氧烷，R³ _pH_qSiO_{(4‑p‑q)/2}，式中，R¹、R³为不含烯基的一价烃基，R²为烯基；及(D)铂族金属类催化剂。The present invention provides an addition-curable silicone resin composition which provides a cured product excellent in hardness and chip shear strength, comprising: (A) an organopolysiloxane represented by the following formula, (R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² R ¹ SiO) _c (R ¹ ₂ SiO) _d (R ² SiO _3/2 ) _e (R ¹ SiO _3/2 ) _f (SiO _4/2 ) _g ; (B) branched organopolysiloxane represented by the following formula, (R ¹ ₃ SiO _1/2 ) _h (R ² ₃ SiO _1/2 ) _i (R ² R ¹ ₂ SiO _1/2 ) _j (R ² R ¹ SiO) _k (R ¹ ₂ SiO) _l (R ² SiO _3/2 ) _m (R ¹ SiO _3/2 ) _n (SiO _4/2 ) _o ; ( C) Organohydrogenpolysiloxane represented by the following formula, R ³ _p H _q SiO _(4-p-q)/2 , wherein R ¹ and R ³ are monovalent hydrocarbon groups without alkenyl groups, and R ² is an alkenyl group; and (D) a platinum group metal-based catalyst.

Description

Addition-curable silicone resin composition, cured product thereof, and optical semiconductor device

Technical Field

The present invention relates to an addition-curable silicone resin composition, a cured product thereof, and an optical semiconductor device using the same.

Background

Recently, since the luminance of LED elements is increased and the heat generation of the elements is increased, silicone resins having excellent durability are used as sealing materials and die bonding materials for light emitting diode (hereinafter referred to as "LED") elements (patent documents 1 and 2). In particular, if the resin is too soft in the die bonding material, a problem occurs that bonding cannot be performed in the wire bonding step performed after the die bonding step, and thus a die bonding material having high hardness is required.

In recent years, the miniaturization of LED devices has been advanced, and a die bonding agent having higher adhesiveness is required. If the die bonding agent has insufficient adhesive strength, chip detachment and the like occur in the wire bonding step in the LED production, which is a fatal problem in the production. Conventional silicone die bonding materials have been excellent in durability, but insufficient in adhesion, and materials having higher shear strength of the chip have been desired.

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 an addition-curable silicone resin composition that gives a cured product having excellent hardness and chip shear strength.

Means for solving the problems

In order to solve the above-mentioned problems, the present invention provides an addition-curable silicone resin composition comprising:

(A) an organopolysiloxane having a viscosity at 25 ℃ of 500 mPas or less, represented by the average compositional formula (1),

(R¹ ₃SiO_1/2)_a(R²R¹ ₂SiO_1/2)_b(R²R¹SiO)_c(R¹ ₂SiO)_d(R²SiO_3/2)_e(R¹SiO_3/2)_f(SiO_4/2)_g(1)

in the formula, R¹Is a substituted or unsubstituted monovalent hydrocarbon radical which may be identical or different, each free of alkenyl groups, R²A, b, c, d, e, f and g are each a number satisfying a.gtoreq.0, b.gtoreq.0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0, f.gtoreq.0 and g.gtoreq.0, and a number satisfying b + c + e > 0 and a + b + c + d + e + f + g ═ 1;

(B) a branched organopolysiloxane represented by the average composition formula (2), wherein the amount of the branched organopolysiloxane is 70 to 95 parts by mass per 100 parts by mass of the total of the components (A) and (B),

(R¹ ₃SiO_1/2)_h(R² ₃SiO_1/2)_i(R²R¹ ₂SiO_1/2)_j(R²R¹SiO)_k(R¹ ₂SiO)_l(R²SiO_3/2)_m(R¹SiO_3/2)_n(SiO_4/2)_o(2)

in the formula, R¹And R²And the above-mentioned R¹And R²Similarly, h, i, j, k, l, m, n, and o are numbers satisfying h ≥ 0, i > 0, j ≥ 0, k ≥ 0, l ≥ 0, m ≥ 0, n ≥ 0, and o ≥ 0, respectively, and are numbers satisfying m + n + o > 0 and h + i + j + k + l + m + n + o ═ 1;

(C) an organohydrogenpolysiloxane represented by the following average composition formula (3) and having at least 2 hydrogen atoms bonded to silicon atoms in 1 molecule,

R³ _pH_qSiO_(4-p-q)/2(3)

in the formula, R³Are respectively the same or different, notA substituted or unsubstituted monovalent hydrocarbon group containing an alkenyl group, p and q being numbers satisfying 0.7. ltoreq. p.ltoreq.2.1, 0.001. ltoreq. q.ltoreq.1.0, and 0.8. ltoreq. p + q.ltoreq.3.0; and

(D) a platinum group metal catalyst.

The addition-curable silicone resin composition of the present invention can provide a cured product having excellent hardness and chip shear strength.

In the present invention, it is preferable that the component (A) is a branched organopolysiloxane represented by the average composition formula (1a),

(R¹ ₃SiO_1/2)_a(R²R¹ ₂SiO_1/2)_b(R²SiO_3/2)_e(R¹SiO_3/2)_f(1a)

wherein a, b, e, and f are numbers satisfying a + b > 0, b + e > 0, e + f > 0, and a + b + e + f is 1.

Such an addition-curable silicone resin composition can provide a cured product having further excellent hardness and chip shear strength.

In the present invention, it is preferable that 80 mol% or more of all monovalent hydrocarbon groups bonded to silicon atoms other than alkenyl groups in the composition be methyl groups.

Such an addition-curable silicone resin composition can provide a cured product having excellent resistance to deterioration such as discoloration due to heat and ultraviolet radiation, as well as heat resistance and light resistance (ultraviolet resistance).

The present invention preferably further contains an organic peroxide.

Such an addition-curable silicone resin composition can provide a cured product having further improved strength.

In this case, the organic peroxide is more preferably 1, 6-bis (t-butylperoxycarbonyloxy) hexane.

The present invention also provides a silicone cured product characterized by being a cured product of the addition-curable silicone resin composition.

Such a silicone cured product is useful as a composition having excellent hardness and chip shear strength and high adhesive strength to a substrate, an LED chip, or the like, and is particularly useful as a die bonding material for die bonding of an LED element or the like.

Further, the present invention provides an optical semiconductor device obtained by die bonding an optical semiconductor element using the cured silicone material.

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 addition-curable silicone resin composition of the present invention can give a silicone cured product excellent in hardness and chip shear strength, and is particularly useful as a die-bonding material for die-bonding of LED elements and the like. Further, in the wire bonding step performed after the die bonding step, since defects such as peeling of the chip or failure in bonding are unlikely to occur, the optical semiconductor device obtained by die bonding the optical semiconductor element using the cured silicone material has high reliability and productivity is improved.

Detailed Description

As described above, there has been a demand for development of a silicone composition that gives a cured product having excellent hardness and chip shear strength and gives a silicone cured product as a die bonding material for die bonding of LED elements and the like.

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 solved by an addition-curable silicone composition containing the components (a), (B), (C), and (D) described below, and have completed the present invention.

That is, the present invention is an addition-curable silicone resin composition containing:

(C) an organohydrogenpolysiloxane having at least 2 hydrogen atoms bonded to silicon atoms in 1 molecule, represented by the following average composition formula (3),

R³ _pH_qSiO_(4-p-q)/2(3)

in the formula, R³Is a substituted or unsubstituted mono-or mono-which may be the same or different, respectively, and which does not contain an alkenyl groupA divalent hydrocarbon group, p and q being numbers satisfying 0.7. ltoreq. p.ltoreq.2.1, 0.001. ltoreq. q.ltoreq.1.0, and 0.8. ltoreq. p + q.ltoreq.3.0;

(D) a platinum group metal catalyst.

The present invention will be described in detail below, but the present invention is not limited to these contents.

[ addition-curable Silicone composition ]

The addition-curable silicone composition of the present invention contains the components (a) to (D) described below.

The components are described in detail below.

< ingredient (A) >

(A) The component (A) is an organopolysiloxane represented by the following average composition formula (1),

in the formula, R¹Is a substituted or unsubstituted monovalent hydrocarbon radical which may be identical or different, each free of alkenyl groups, R²A, b, c, d, e, f and g are each a number satisfying a.gtoreq.0, b.gtoreq.0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0, f.gtoreq.0 and g.gtoreq.0, and a number satisfying b + c + e > 0 and a + b + c + d + e + f + g ═ 1.

(A) The viscosity of the component (A) is 500 mPas or less, preferably 100 mPas or less, as measured at 25 ℃ with a rotary viscometer. When the viscosity exceeds 500mPa · s, the viscosity of the composition increases, and therefore, handling in a step of coating the composition on an LED substrate using a die bonder is difficult. The viscosity is a value measured at 25 ℃ with a rotational viscometer unless otherwise specified below.

As R¹The substituted or unsubstituted monovalent hydrocarbon group not having an alkenyl group is not particularly limited as long as it has no alkenyl group, and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms is preferable. Examples of the monovalent hydrocarbon group includeAlkyl 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 phenethyl; halogenated hydrocarbon groups such as chloromethyl, chloropropyl, and chlorocyclohexyl. Alkyl groups are preferred, and methyl groups are particularly preferred.

As R²The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms such as a vinyl group, allyl group, or ethynyl group, particularly preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably a vinyl group.

(A) The component (b) is preferably a branched organopolysiloxane represented by the average composition formula (1 a).

(R¹ ₃SiO_1/2)_a(R²R¹ ₂SiO_1/2)_b(R²SiO_3/2)_e(R¹SiO_3/2)_f(1a)

Specific examples of the branched organopolysiloxane include branched organopolysiloxanes represented by the following formulae.

((CH₂＝CH)(CH₃)₂SiO_1/2)_0.5((CH₃)SiO_3/2)_0.5、

((CH₂＝CH)(CH₃)₂SiO_1/2)_0.5((CH₂＝CH)SiO_3/2)_0.5、

((CH₂＝CH)(CH₃)₂SiO_1/2)_0.5((CH₃)SiO_3/2)_0.3((CH₂＝CH)SiO_3/2)_0.2、

((CH₃)₃SiO_1/2)_0.4((CH₂＝CH)SiO_3/2)_0.6、

((CH₃)₃SiO_1/2)_0.4((CH₃)SiO_3/2)_0.3((CH₂＝CH)SiO_3/2)_0.3

(A) As the component (C), an organopolysiloxane having a linear molecular structure can be used.

Specific examples of the linear organopolysiloxane of the component (a) include diphenylsiloxanes terminated with methylphenylvinyl groups at both ends, diphenylsiloxanes terminated with methylphenylvinyl groups at one end and diphenylvinyl groups at one end, diphenylsiloxanes terminated with diphenylvinyl groups at both ends, diphenylvinyl group-terminated diphenylsiloxane-methylphenylsiloxane copolymers terminated with diphenylvinyl groups at both ends, diphenylsiloxanes terminated with dimethylvinyl groups at one end and methylphenylvinyl groups at one end, methylphenylsiloxanes terminated with dimethylvinyl groups at both ends, and methylphenylsiloxanes terminated with dimethylvinyl groups at one end and methylphenylvinyl groups at one end. The organopolysiloxane may be used alone or in combination of two or more.

Other specific examples of the linear organopolysiloxane include compounds represented by the following formulae.

[ chemical formula 1]

[ chemical formula 2]

[ chemical formula 3]

In the above formula, the order of arrangement of the siloxane units in parentheses is arbitrary.

(A) The components can be used singly or in combination.

< ingredient (B) >

(B) The component (A) is a branched organopolysiloxane represented by the average composition formula (2).

In the formula, R¹And R²And the above-mentioned R¹And R²Similarly, h, i, j, k, l, m, n, and o are numbers satisfying h ≧ 0, i > 0, j ≧ 0, k ≧ 0, l ≧ 0, m ≧ 0, n ≧ 0, and o ≧ 0, respectively, and are numbers satisfying m + n + o > 0 and h + i + j + k + l + m + n + o ═ 1.

R¹Examples thereof include the same groups as those exemplified for the component (A), preferably alkyl groups, and particularly preferably methyl groups.

R²Examples thereof include the same groups as those exemplified for the component (A), preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably a vinyl group.

In the average composition formula (2), h is preferably a number of 0 to 0.65, i is preferably a number of 0.1 to 0.65, j is preferably a number of 0 to 0.65, k is preferably a number of 0 to 0.5, l is preferably a number of 0 to 0.5, m is preferably a number of 0 to 0.8, n is preferably a number of 0 to 0.8, and o is preferably a number of 0 to 0.6. m + n + o is preferably a number of 0.05 or more, more preferably a number of 0.1 to 0.9, and particularly 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.

The weight average molecular weight of the organopolysiloxane of component (B) is preferably in the range of 500 to 100,000 in view of ease of separation.

By making the component (B) have R² ₃SiO_1/2Units (i.e., i > 0) capable of combining the units of the present inventionThe resulting cured product was provided with adhesive strength. Furthermore, the component (B) must have a composition consisting of SiO_4/2Unit and/or SiO_3/2The branched structure of the units may further contain SiO such as methylvinylsiloxy units, dimethylsiloxy units and the like_2/2SiO such as (SiO) unit, dimethylvinylsiloxy unit, trimethylsiloxy unit_1/2And (4) units. SiO 2_4/2Unit and/or SiO_3/2The 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 amount of the component (B) to be blended 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). (B) When the amount of the component (b) is less than 70 parts by mass, the adhesiveness is poor or a cured product having 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 die bonding material or the like.

Specific examples of the branched organopolysiloxane of the component (B) include the following branched organopolysiloxanes.

((CH₂＝CH)₃SiO_1/2)_0.1((CH₂＝CH)(CH₃)₂SiO_1/2)_0.2((CH₃)₃SiO_1/2)_0.35(SiO_4/2)_0.35、

((CH₂＝CH)₃SiO_1/2)_0.2((CH₃)₃SiO_1/2)_0.1(SiO_4/2)_0.7、

((CH₂＝CH)₃SiO_1/2)_0.07((CH₃)₃SiO_1/2)_0.4(SiO_4/2)_0.53、

((CH₂＝CH)₃SiO_1/2)_0.14((CH₃)₃SiO_1/2)_0.32(SiO_4/2)_0.54、

((CH₂＝CH)₃SiO_1/2)_0.07((CH₃)₃SiO_1/2)_0.33(SiO_4/2)_0.6、

((CH₂＝CH)₃SiO_1/2)_0.1((CH₃)₃SiO_1/2)_0.1((CH₃)₂SiO)_0.2((CH₃)SiO_3/2)_0.6、

((CH₂＝CH)₃SiO_1/2)_0.07((CH₃)₃SiO_1/2)_0.13((CH₃)₂SiO)_0.2(SiO_4/2)_0.6、

((CH₂＝CH)₃SiO_1/2)_0.3(SiO_4/2)_0.7、

((CH₂＝CH)₃SiO_1/2)_0.2((CH₃)SiO_3/2)_0.8、

((CH₂＝CH)₃SiO_1/2)_0.2((CH₃)SiO_3/2)_0.6(SiO_4/2)_0.2。

(B) The components can be used singly or in combination.

< ingredient (C) >

(C) Component (B) functions as a crosslinking agent that crosslinks the alkenyl groups contained in component (a) and component (B) by a hydrosilylation reaction. (C) Component (c) is represented by the following average composition formula (3), and is an organohydrogenpolysiloxane having at least 2 hydrogen atoms (i.e., Si — H groups) bonded to silicon atoms in 1 molecule.

R³ _pH_qSiO_(4-p-q)/2(3)

In the formula, R³And p and q are numbers satisfying 0.7. ltoreq. p.ltoreq.2.1, 0.001. ltoreq. q.ltoreq.1.0, and 0.8. ltoreq. p + q.ltoreq.3.0, preferably numbers satisfying 1.0. ltoreq. p.ltoreq.2.0, 0.01. ltoreq. q.ltoreq.1.0, and 1.5. ltoreq. p + q.ltoreq.2.5.

(C) The viscosity of the component (A) at 25 ℃ is preferably 100 mPas or less, more preferably 5 to 100 mPas.

R³Examples thereof include the compounds represented by the formula R in the component (A)¹The same groups as those exemplified above are preferably alkyl groups, and particularly preferably methyl groups.

In addition, methyl groups represent R in the compositions of the invention¹And R³The 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 (80 mol% or more of all monovalent hydrocarbon groups are methyl groups), particularly preferably 90 mol% or more, and is preferable because it is excellent in resistance to deterioration such as discoloration due to load such as heat and ultraviolet rays, light resistance (ultraviolet ray resistance), and resistance to heat and ultraviolet rays.

(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 particularly preferably 4 to 50.

(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 one molecule is preferably 2 to 300, and more preferably 3 to 200.

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, methylhydrosiloxane-dimethylsiloxane cyclic copolymer, trimethylsiloxy-terminated methylhydropolysiloxane at both ends, trimethylsiloxy-terminated dimethylsiloxane-methylhydrosiloxane copolymer at both ends, dimethylhydrogensiloxy-terminated dimethylpolysiloxane at both ends, dimethylhydrogensiloxy-terminated methylhydropolysiloxane at both ends, dimethylhydrogensiloxane-methylhydrosiloxane copolymer at both ends, trimethylsiloxy-terminated methylhydrosiloxane-diphenylsiloxane copolymer at both ends, tetramethyldisiloxane-diphenylsiloxane copolymer at both ends, and the like, Double-end trimethylsiloxy end-blocked methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane copolymer, and double-end trimethylsiloxy end-blocked copolymerTerminal methyl hydrogen siloxane-methyl phenyl siloxane-dimethyl siloxane copolymer, two-terminal dimethyl hydrogen siloxy end-blocked methyl hydrogen siloxane-dimethyl siloxane-diphenyl siloxane copolymer, two-terminal dimethyl hydrogen siloxy end-blocked methyl hydrogen siloxane-dimethyl siloxane-methyl phenyl siloxane copolymer, Copolymer of (CH) and (C) are used as raw materials₃)₂HSiO_1/2Unit, (CH)₃)₃SiO_1/2Unit and SiO_4/2Copolymer of units of (CH)₃)₂HSiO_1/2Units and SiO_4/2Copolymer of units of (CH)₃)₂HSiO_1/2Unit, SiO_4/2Unit and (C)₆H₅)₃SiO_1/2Examples of the copolymer having a unit structure include those represented by the following general formula (4) or (5) in addition to the copolymer having a unit structure.

R³ ₃SiO[SiR³(H)O]_rSiR³ ₃(4)

Cyclic [ SiR³(H)O]_s(5)

In the formula, R³As mentioned above, r is an integer of 2 to 40, preferably 8 to 35, and s is an integer of 6 to 8.

Specific examples of the component (C) include a substance represented by the following general formula (6), a substance represented by the following chemical formula, and the like,

Me₃SiO[SiMe(H)O]_rSiMe₃(6)

wherein r is as defined above and Me is methyl.

[ chemical formula 4]

[ chemical formula 5]

[ chemical formula 6]

(C) The organohydrogenpolysiloxane of component (a) may be used alone or in combination of two or more.

From the viewpoint of the balance of crosslinking, the amount of the component (C) to be blended is preferably 0.5 to 5.0 times, more preferably 0.7 to 3.0 times the number of (Si-H groups) of the silicon atom-bonded hydrogen atoms in the component (C) relative to the total number of all silicon atom-bonded alkenyl groups in the components (A) and (B). When the amount is in the above range, crosslinking proceeds sufficiently, and a cured product having excellent hardness can be obtained.

< ingredient (D) >

(D) The platinum group metal catalyst of component (a) is a component for promoting and accelerating 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; a platinum compound such as chloroplatinic acid, alcohol-modified chloroplatinic acid, or a complex of chloroplatinic acid with olefins, vinylsiloxanes or acetylene compounds, or a platinum group metal compound such as tetrakis (triphenylphosphine) palladium or chlorotris (triphenylphosphine) rhodium, is preferable because the catalyst obtained by silicone-modifying chloroplatinic acid has good compatibility with the components (a) to (C) and contains almost no chlorine impurities.

(D) The components can be used singly or in combination.

(D) The amount of the component (C) is preferably 1 to 500ppm, more preferably 3 to 100ppm, and still more preferably 5 to 40ppm, in terms of the mass of the platinum group metal element, based on the total amount of the components (A) to (C). If the amount of the compound is set to an appropriate amount, the hydrosilylation reaction can be more effectively promoted.

< other ingredients >

In addition to the components (a) to (D), the composition of the present invention may contain other components as exemplified below.

Organic peroxide:

in the present invention, the resin strength can be further improved by adding an organic peroxide.

Examples of the organic peroxide include 1, 6-bis (t-butylperoxycarbonyloxy) hexane, benzoyl peroxide, t-butyl peroxybenzoate, o-methylbenzoyl peroxide, p-methylbenzoyl peroxide, dicumyl peroxide, 1-bis (t-butylperoxy) -3,3, 3-trimethylcyclohexane, bis (4-methylbenzoylperoxy) hexamethylene dicarbonate, etc., and 1, 6-bis (t-butylperoxycarbonyloxy) hexane is preferable. The amount of the organopolysiloxane to be added is only required to be an effective amount, and is usually 0.01 to 5 parts by mass, particularly preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the total amount of the organopolysiloxane of the component (A) · (B). These organic peroxides may be used alone or in combination of two or more.

Reaction inhibitors:

in the composition of the present invention, a conventionally known reaction inhibitor (reaction regulator) which is a compound having a curing-inhibiting 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-inhibiting effect by the reaction inhibitor varies significantly depending on the chemical structure of the reaction inhibitor, and therefore the blending amount of the reaction inhibitor is preferably adjusted to the most appropriate amount for each reaction inhibitor used. In general, it is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total of the component (A), the component (B), the component (C) and the component (D).

Adhesion improver:

in order to improve the adhesion to the resin, an adhesion improver may be added to the present composition. From the viewpoint of imparting self-adhesiveness to the composition of the present invention which is of addition reaction curing type, an organic silicon compound such as silane or siloxane, a non-silicone organic compound, or the like containing a functional group imparting adhesiveness can be used as the adhesiveness-improving agent.

Specific examples of the functional group for imparting adhesiveness include an alkenyl group such as a vinyl group or an allyl group bonded to a silicon atom, a hydrogen atom, an epoxy group (e.g., γ -glycidoxypropyl group, β - (3, 4-epoxycyclohexyl) ethyl group, etc.) bonded to a silicon atom via a carbon atom, an acryloyloxy group (e.g., γ -acryloyloxypropyl group, etc.) or a methacryloyloxy group (e.g., γ -methacryloyloxypropyl group, etc.), an alkoxysilyl group (e.g., an alkoxysilyl group such as a trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group, etc. bonded to a silicon atom via an alkylene group which may have 1 to 2 ester structures, urethane structures, or ether structures), and the like.

Examples of the organic silicon compound having a functional group for imparting adhesiveness include a silane coupling agent, a siloxane having an alkoxysilyl group and an organic functional group, and a compound obtained by introducing an alkoxysilyl group into an organic compound having a reactive organic group.

Examples of the non-silicone organic compound include allyl organosilicate, epoxy ring-opening catalysts, organotitanium compounds, organozirconium compounds, organoaluminum compounds, and the like.

Filling agent:

the composition of the present invention may be filled with inorganic fillers such as crystalline silica, hollow fillers, and silsesquioxanes, and fillers obtained by subjecting the fillers to surface hydrophobization treatment with an organic silicon compound such as an organoalkoxysilane compound, an organochlorosilane compound, an organosilazane 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, and by imparting thixotropy, a cured product excellent in handling property and chip shear strength can be obtained.

These other components may be used alone or in combination of two or more.

In addition, the viscosity of the addition-curable silicone resin composition 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 an addition-curable silicone composition (silicone cured product).

The addition-curable silicone composition of the present invention may be cured under known conditions, and for example, may be cured at 100 to 180 ℃ for 10 minutes to 5 hours.

The cured product of the addition curing silicone composition of the present invention is useful as a composition having high adhesive strength to a substrate, an LED chip, or the like, and particularly useful as a die bonding material used for die bonding of an LED element or 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 obtained by die bonding an optical semiconductor element using the cured product.

An example of a method for die bonding an optical semiconductor element using the composition of the present invention includes the following methods: the composition of the present invention is filled in a syringe, applied to a substrate such as a package by a dispenser in a dry state so as to have a thickness of 5 to 100 μm, and then an optical semiconductor element (for example, a light emitting diode) is disposed on the applied composition and the composition is cured, thereby bonding the optical semiconductor element die to 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 in a dry state by a method of pressing while applying the composition so that the thickness is 5 to 100 [ mu ] m, and then a photo-semiconductor element is disposed on the applied composition, and the composition is cured, thereby bonding the photo-semiconductor element die to the substrate. The curing conditions of the composition may be as described above. Thus, an optical semiconductor device having high reliability and die bonding an optical semiconductor element using the cured silicone material of the present invention can be obtained.

Examples

The present invention will be specifically described below with reference to 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 for Gel Permeation Chromatography (GPC). The viscosity at 25 ℃ is a measured value measured using a rotary viscometer.

Further, the abbreviations of the respective siloxane units are as follows.

M：(CH₃)₃SiO_1/2

M^Vi：(CH₂＝CH)(CH₃)₂SiO_1/2

M^Vi3：(CH₂＝CH)₃SiO_1/2

D：(CH₃)₂SiO_2/2

D^H：H(CH₃)SiO_2/2

D^Vi：(CH＝CH₂)(CH₃)SiO

T：(CH₃)SiO_3/2

Q：SiO_4/2

[ Synthesis example 1]

352.5g of [ (CH) was charged into a 3,000mL four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer₃O)₃SiO_1/2]₂[(CH₃O)₂SiO]₂The organopolysiloxane represented by (1), 45.6g of hexavinyldisiloxane, 182.3g of hexamethyldisiloxane, and 58g of isopropanol were added dropwise to 6.7g of methanesulfonic acid while stirring. Then, 90g of water was added dropwise thereto, and the mixture was mixed at 65 ℃ for 2 hours to effect a reaction. 700g of xylene was added thereto, 10.9g of 50% potassium hydroxide solution was then added thereto, the temperature was raised, the low boiling point component was distilled off, and the 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. After cooling, filtration is carried out to obtain the average structure M^Vi3 _0.07M_0.4Q_0.53Branched organopolysiloxane (B-1: molecular weight 3,350, phase)The amount of vinyl groups in the solid content was 0.287mol/100 g).

[ Synthesis example 2]

A3,000 mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer was charged with 353.5g of [ (CH)₃O)₃SiO_1/2]₂[(CH₃O)₂SiO]₂The organopolysiloxane, 94.8g of hexavinyldisiloxane, 145.8g of hexamethyldisiloxane, and 59g of isopropanol were added dropwise to 7.5g of methanesulfonic acid while stirring. Then, 90g of water was added dropwise thereto, and the mixture was mixed at 65 ℃ for 2 hours to effect a reaction. 800g of xylene was added thereto, and then 12.3g of 50% potassium hydroxide solution was added thereto, and the mixture was heated, distilled to remove low boiling components, and reacted at 120 ℃ for 5 hours. 3.9g of methanesulfonic acid was added as an additive, and neutralization treatment was performed at 120 ℃ for 2 hours. After cooling, filtration is carried out to obtain the average structure M^Vi3 _0.14M_0.32Q_0.54The branched organopolysiloxane (B-2: molecular weight 3,630, vinyl content based on solid content 0.567mol/100 g).

[ Synthesis example 3]

352.5g of [ (CH) was charged into a 3,000mL four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer₃O)₃SiO_1/2]₂[(CH₃O)₂SiO]₂The organopolysiloxane, hexavinyldisiloxane (38.6 g), hexamethyldisiloxane (133.7 g), and isopropanol (52 g) was added dropwise to the mixture, and while stirring, methanesulfonic acid (7.1 g) was added dropwise. Then, 90g of water was added dropwise thereto, and the mixture was mixed at 65 ℃ for 2 hours to effect a reaction. 600g of xylene was added thereto, and then 13.3g of 50% potassium hydroxide solution was added thereto, and the mixture was heated, distilled to remove low boiling components, and reacted at 120 ℃ for 5 hours. 4.3g of methanesulfonic acid was added as an additive, and neutralization treatment was performed at 120 ℃ for 2 hours. After cooling, filtration is carried out to obtain the average structure M^Vi3 _0.07M_0.33Q_0.60The branched organopolysiloxane (B-3: molecular weight 7,890, vinyl amount based on solid content 0.263mol/100 g).

[ Synthesis example 4]

A3,000 mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer was charged with 408.0g of methyltrimethoxysilane, 70.2g of hexavinyldisiloxane, 63.0g of dimethyldimethoxysilane and 54g of isopropanol, and 6.8g of methanesulfonic acid was added dropwise with stirring. Then, 90g of water was added dropwise thereto, and the mixture was mixed at 65 ℃ for 2 hours to effect a reaction. 600g of xylene was added thereto, and then 11.1g of 50% potassium hydroxide solution was added thereto, and the mixture was heated, distilled to remove low boiling components, and reacted 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. After cooling, filtration is carried out to obtain the average structure M^Vi3 _0.14D_0.14T_0.72The branched organopolysiloxane (B-4: molecular weight 2,890, vinyl amount based on solid content 0.586mol/100 g).

[ comparative Synthesis example 1]

352.5g of [ (CH) was charged into a 3,000mL four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer₃O)₃SiO_1/2]₂[(CH₃O)₂SiO]₂The organopolysiloxane represented by (1), 3-divinyltetramethyldisiloxane (111.6 g), hexamethyldisiloxane (89.2 g), and isopropanol (55 g) was added dropwise to the mixture under stirring, to thereby prepare methanesulfonic acid (7.0 g). Then, 90g of water was added dropwise thereto, and the mixture was mixed at 65 ℃ for 2 hours to effect a reaction. 550g of xylene was added thereto, and then 11.4g of 50% potassium hydroxide solution was added thereto, and the mixture was heated, distilled to remove low boiling components, and reacted at 120 ℃ for 5 hours. 3.7g of methanesulfonic acid was added as an additive, and neutralization treatment was performed at 120 ℃ for 2 hours. After cooling, filtration is carried out to obtain the average structure M^Vi _0.21M_0.23Q_0.56The branched organopolysiloxane (B-6: molecular weight 7,890) of (a).

[ Synthesis example 5]

Viscosity of 60 mPas, M was adjusted to 0.004 mass% using platinum^Vi ₂D₄₀The reaction product of hexachloroplatinic acid and 1, 3-divinyltetramethyldisiloxane was diluted with the linear dimethylpolysiloxane represented by the formula to prepare a platinum catalyst (D).

Examples 1 to 5 and comparative examples 1 to 3

The following components were mixed in the blending amounts shown in table 1 to prepare addition curable silicone compositions.

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 silicon atom-bonded alkenyl groups in all of components (A) and (B).

(A) The components:

(A-1)M^Vi _0.47T_0.53a branched organopolysiloxane (viscosity at 25 ℃ C. of 17 mPas)

(A-2)M^Vi _0.0097D_0.9903(M^Vi ₂D₂₀₄) Represented by a straight-chain dimethylpolysiloxane having both ends blocked with vinyl groups (viscosity at 25 ℃ C. is 600 mPas)

(B) The components:

(B-1) branched organopolysiloxane obtained in Synthesis example 1

(B-2) branched organopolysiloxane obtained in Synthesis example 2

(B-3) branched organopolysiloxane obtained in Synthesis example 3

(B-4) branched organopolysiloxane obtained in Synthesis example 4

(comparative ingredients):

(B-5)M^Vi _0.064M_0.398Q_0.538(M^Vi _1.2M_7.4Q₁₀) Branched organopolysiloxane (vinyl amount per solid 0.085mol/100g)

(B-6) branched organopolysiloxane obtained in comparative Synthesis example 1

(C) The components:

(C)M_0.037D_0.266D^H _0.697(M₂D_14.5D^H ₃₈) Methylhydrogensiloxane as shown

(D) The components:

(D) synthesis of platinum catalyst obtained in example 5

Other components:

(E) reaction inhibitors: 1-ethynylcyclohexanol

(F-1) adhesion improving agent: d^Vi ₄Cyclic organopolysiloxane represented by

(F-2) adhesion improving agent: triallylisocyanurate

(F-3) adhesion improving agent: a compound represented by the following formula

[ chemical formula 7]

(G) Organic peroxide: 1, 6-bis (tert-butylperoxycarbonyloxy) hexane

The following evaluations were performed on the addition-curable silicone resin compositions obtained in examples 1 to 5 and comparative examples 1 to 3, and the results are shown in table 2.

[ hardness ]

The composition was poured into a mold so as to have a thickness of 2mm, and the TypeD hardness of a cured product obtained by curing the composition at 150 ℃ for 4 hours was measured in accordance with JIS K6253.

[ chip shear Strength ]

The composition was quantitatively transferred onto a silver-plated electrode portion of an SMD5050 package (I-CHIUN PRECISION INDUSTRY CO., manufactured by Semleds Corporation, EV-B35A, 35mil) by pressing using a die bonder (AD-830, manufactured by Advanced software materials Inc.), and an optical semiconductor element (Semleds Corporation) was mounted thereon. The resultant package was heated in an oven at 150 ℃ for 2 hours, and after the composition was cured, a chip shear strength was measured using a weld strength tester (manufactured by Dage corporation, Series 4000).

The case where the viscosity of the composition exceeded 100 mPas and transfer by pressing was not possible was regarded as "transfer failed".

[ Table 1]

[ Table 2]

	Example 1	Example 2	Example 3	Example 4	Example 5	Comparative example 1	Comparative example 2	Comparative example 3
									Hardness (Type D)	67	69	73	69	69	59	69	65
Chip shear strength (MPa)	24.8	25.9	29.7	25.5	23.4	17.1	5.9	Fail to transfer

As shown in Table 2, the cured products of examples 1 to 5 were excellent in both hardness and chip shear strength and excellent as die bonding agents.

On the other hand, in comparative examples 1 and 2, since the component (B) does not have a trialkenylsilyl group (R)² ₃SiO_1/2Unit), the cured product has poor chip shear strength and is insufficient as a die bonding agent.

In comparative example 3, although the component (B) contained a branched organopolysiloxane containing a trialkenylsilyl group, the component (a) had a high viscosity, and therefore had poor transferability, and no die bonding could be performed.

As described above, the addition-curable silicone resin composition of the present invention gives a silicone cured product excellent in hardness and chip shear strength, and is particularly useful as a die-bonding material for die-bonding of optical semiconductor devices and the like. In particular, due to this feature, in the step of wire bonding after the die bonding step, such defects as chip peeling or failure to bond are less likely to occur, and therefore, the reliability of an optical semiconductor device in which the optical semiconductor element is die bonded using the cured silicone material is improved, and the productivity of the device is also improved. Therefore, the addition-curable silicone resin composition 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-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

1. an addition curing type silicone resin composition is characterized in that, it contains:

(A) an organopolysiloxane having a viscosity at 25°C of 500 mPa·s or less represented by the following average composition formula (1),

(R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² R ¹ SiO) _c (R ¹ ₂ SiO) _d (R ² SiO _3/2 ) _e (R ¹ SiO _3/2 ) _f (SiO _4/2 ) _g (1)

In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group that may be the same or different, and does not contain an alkenyl group, R ² is an alkenyl group that may be the same or different, respectively, a, b, c, d, e, f and g are numbers satisfying a≥0, b≥0, c≥0, d≥0, e≥0, f≥0, and g≥0, respectively, and are numbers satisfying b+c+e>0 and a+b+ The number of c+d+e+f+g=1;

(B) The branched organopolysiloxane represented by the following average composition formula (2), which is 70 to 95 parts by mass relative to 100 parts by mass of the total of the (A) component and (B) component,

(R ¹ ₃ SiO _1/2 ) _h (R ² ₃ SiO _1/2 ) _i (R ² R ¹ ₂ SiO _1/2 ) _j (R ² R ¹ SiO ) _k (R ¹ ₂ SiO ) _l (R ² SiO _3/2 ) _m (R ¹ SiO _3/2 ) _n (SiO _4/2 ) _o (2)

In the formula, R ¹ and R ² are the same as R ¹ and R ² above, and h, i, j, k, l, m, n, and o satisfy h≥0, i>0, j≥0, and k≥0, respectively. , l≥0, m≥0, n≥0, and o≥0, and are numbers that satisfy m+n+o>0 and h+i+j+k+l+m+n+o=1;

(C) an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule, represented by the following average composition formula (3),

R ³ _p H _q SiO _(4-pq)/2 (3)

In the formula, R ³ is a substituted or unsubstituted monovalent hydrocarbon group that may be the same or different, and does not contain an alkenyl group, and p and q satisfy 0.7≤p≤2.1, 0.001≤q≤1.0, and 0.8≤p+q A number ≤ 3.0; and

(D) Platinum group metal-based catalyst.

2 . The addition-curing silicone resin composition according to claim 1 , wherein the component (A) is a branched organopolysiloxane represented by the following average composition formula (1a), 3 .

(R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² SiO _3/2 ) _e (R ¹ SiO _3/2 ) _f (1a)

In the formula, a, b, e, and f are numbers satisfying a+b>0, b+e>0, e+f>0, and a+b+e+f=1.

3 . The addition-curable silicone resin composition according to claim 1 , wherein 80 mol % or more of all monovalent hydrocarbon groups bonded to silicon atoms other than alkenyl groups in the composition are methyl groups. 4 . base.

4 . The addition-curable silicone resin composition according to claim 2 , wherein 80 mol % or more of all monovalent hydrocarbon groups bonded to silicon atoms other than alkenyl groups in the composition are methyl groups. 5 . base.

5 . The addition-curing silicone resin composition according to claim 1 , further comprising an organic peroxide. 6 .

6 . The addition-curing silicone resin composition according to claim 2 , further comprising an organic peroxide. 7 .

7 . The addition-curing silicone resin composition according to claim 3 , further comprising an organic peroxide. 8 .

8 . The addition-curing silicone resin composition according to claim 4 , further comprising an organic peroxide. 9 .

9 . The addition-curable silicone resin composition according to claim 5 , wherein the organic peroxide is 1,6-bis(tert-butylperoxycarbonyloxy)hexane. 10 .

10 . The addition-curable silicone resin composition according to claim 6 , wherein the organic peroxide is 1,6-bis(tert-butylperoxycarbonyloxy)hexane. 11 .

11 . The addition-curable silicone resin composition according to claim 7 , wherein the organic peroxide is 1,6-bis(tert-butylperoxycarbonyloxy)hexane. 12 .

12 . The addition-curable silicone resin composition according to claim 8 , wherein the organic peroxide is 1,6-bis(tert-butylperoxycarbonyloxy)hexane. 13 .

13 . A cured silicone product, which is a cured product of the addition-curable silicone resin composition according to claim 1 .

14. An optical semiconductor device obtained by die-bonding an optical semiconductor element using the cured silicone product according to claim 13.