JP7084343B2 - Additive-curable silicone composition, cured product thereof, and opto-semiconductor device - Google Patents

Description

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

As the encapsulant for the light emitting diode (hereinafter referred to as "LED") element, a silicone resin having good durability is used because the heat generated by the element has increased due to the improvement in the brightness of the LED element (Patent Document 1). ..
However, peeling easily occurs between the LED substrate and the sealing material made of a silicone resin, and improvement in adhesiveness is further required.

Japanese Patent No. 4648099

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an addition-curable silicone composition that gives a cured product having excellent adhesiveness to an optical semiconductor substrate.

（式中、Ｒ^１は独立に、炭素原子数２～１０のアルケニル基であり、Ｒ^２は独立に、脂肪族不飽和結合を有しない置換又は非置換の炭素原子数１～１２の一価炭化水素基であり、Ｒ^３は独立に、炭素原子数１～８のアルキル基であり、Ｒ^４は独立に、炭素原子数６～１０のアリール基である。ａは０～１００の整数であり、ｂは１～５０の整数である。各シロキサン単位の配列順は任意であってよい。）
（Ｂ）下記平均単位式（２）で表される分岐状オルガノポリシロキサン：（Ａ）成分と（Ｂ）成分との合計１００質量部に対して１０～９０質量部、
（Ｒ^５ _３ＳｉＯ_１／２）_ｃ（Ｒ^１Ｒ^５ _２ＳｉＯ_１／２）_ｄ（Ｒ^１Ｒ^５ＳｉＯ）_ｅ（Ｒ^５ _２ＳｉＯ）_ｆ（Ｒ^１ＳｉＯ_３／２）_ｇ（Ｒ^５ＳｉＯ_３／２）_ｈ（ＳｉＯ_４／２）_ｉ （２）
(式中、Ｒ^１は前記と同じである。Ｒ^５は独立に、脂肪族不飽和結合を有しない置換又は非置換の炭素原子数１～１２の一価炭化水素基であり、但し、全Ｒ^５の少なくとも５０モル％は炭素原子数６～１２のアリール基である。ｃ、ｄ、ｅ、ｆ、ｇ、ｈ、及びｉは、それぞれｃ≧０、ｄ≧０、ｅ≧０、ｆ≧０、ｇ≧０、ｈ≧０、ｉ≧０、ｄ＋ｅ＋ｇ＞０、ｇ＋ｈ＋ｉ＞０、かつｃ＋ｄ＋ｅ＋ｆ＋ｇ＋ｈ＋ｉ＝１を満たす数である。)
（Ｃ）１分子あたり少なくとも２つのケイ素原子に結合した水素原子を有し、かつ、エポキシ基を有しないオルガノハイドロジェンポリシロキサン：（Ａ）成分および（Ｂ）成分中のケイ素原子結合アルケニル基１個に対して、ケイ素原子に結合した水素原子が０．２～５．０個となる量、
（Ｄ）酸無水物基を有する化合物：（Ａ）成分と（Ｂ）成分との合計１００質量部に対して０．００５～５質量部、
（Ｅ）白金族金属触媒：（Ａ）成分と（Ｂ）成分との合計質量に対して白金族金属の質量換算で０．１～１，０００ｐｐｍ、
（Ｆ）エポキシ基を有する化合物：（Ａ）成分と（Ｂ）成分との合計１００質量部に対して０．１～１０質量部
を含有する付加硬化型シリコーン組成物を提供する。 The present invention
(A) A linear organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule represented by the following formula (1).

(In the formula, R ¹ is independently an alkenyl group having 2 to 10 carbon atoms, and R ² is independently a substituted or unsubstituted monovalent with 1 to 12 carbon atoms having no aliphatic unsaturated bond. It is a hydrocarbon group, R ³ is an independently alkyl group having 1 to 8 carbon atoms, R ⁴ is an independent aryl group having 6 to 10 carbon atoms, and a is an integer of 0 to 100. Yes, b is an integer from 1 to 50. The order of arrangement of each siloxane unit may be arbitrary.)
(B) Branched organopolysiloxane represented by the following average unit formula (2): 10 to 90 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).
(R ⁵ ₃ SiO _1/2 ) _c (R ¹ R ⁵ ₂ SiO _1/2 ) _d (R ¹ R ⁵ SiO) _e (R ⁵ ₂ SiO) _f (R ¹ SiO _3/2 ) _g (R ⁵ SiO) _3/2 ) _h (SiO _4/2 ) _i (2)
(In the formula, R ¹ is the same as above. R ⁵ is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms having no aliphatic unsaturated bond, except that all of them are used. At least 50 mol% of R ⁵ is an aryl group having 6 to 12 carbon atoms. C, d, e, f, g, h, and i are c ≧ 0, d ≧ 0, e ≧ 0, f, respectively. ≧ 0, g ≧ 0, h ≧ 0, i ≧ 0, d + e + g> 0, g + h + i> 0, and c + d + e + f + g + h + i = 1.
(C) Organohydrogenpolysiloxane having a hydrogen atom bonded to at least two silicon atoms per molecule and having no epoxy group: Silicon atom-bonded alkenyl group 1 in the components (A) and (B) The amount of hydrogen atoms bonded to silicon atoms is 0.2 to 5.0 per atom,
(D) Compound having an acid anhydride group: 0.005 to 5 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).
(E) Platinum group metal catalyst: 0.1 to 1,000 ppm in terms of mass of platinum group metal with respect to the total mass of the component (A) and the component (B).
(F) Compound having an epoxy group: Provided is an addition-curable silicone composition containing 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).

This addition-curable silicone composition provides a cured product having excellent adhesiveness to an optical semiconductor substrate.

In the above formula (1), it is preferable that R ² is a phenyl group or a methyl group and R ⁴ is a phenyl group.
When R ² and R ⁴ are the above-mentioned specific functional groups, the addition-curable silicone composition gives a cured product having better adhesiveness to the optical semiconductor substrate.

The component (D) is preferably a compound represented by the following formula (3).

When the component (D) is the specific compound, the addition-curable silicone composition gives a cured product having better adhesiveness to the optical semiconductor substrate.

The component (F) is preferably a cyclic organohydrogenpolysiloxane containing an epoxy group.
When the component (F) is the specific polysiloxane, the addition-curable silicone composition surely gives a cured product having excellent adhesiveness to the optical semiconductor substrate.

The present invention provides a cured silicone composition obtained by curing the above-mentioned addition-curable silicone composition.
This silicone cured product has excellent adhesiveness to an optical semiconductor substrate.

The present invention also provides an optical semiconductor device sealed with the cured silicone product.

Further, the present invention provides an optical semiconductor device die-bonded with the cured silicone material.
These opto-semiconductor devices are highly reliable because they have high adhesiveness to the cured silicone material.

Since the addition-curable silicone composition of the present invention provides a cured product having excellent adhesiveness to an optical semiconductor substrate, it is useful as a sealing material and a die bonding material for an optical semiconductor.

It is a perspective view of the shear adhesion test body used for the shear adhesion test in an Example and a comparative example.

As described above, there has been a demand for the development of an additive-curable silicone composition that gives a cured product having excellent adhesiveness to an optical semiconductor substrate.

As a result of diligent studies to achieve the above object, the present inventors have added a compound containing an acid anhydride group and a compound containing an epoxy group to the addition-curable silicone composition to bond them. The present invention has been completed by finding that a cured product having excellent properties can be obtained.

（式中、Ｒ^１は独立に、炭素原子数２～１０のアルケニル基であり、Ｒ^２は独立に、脂肪族不飽和結合を有しない置換又は非置換の炭素原子数１～１２の一価炭化水素基であり、Ｒ^３は独立に、炭素原子数１～８のアルキル基であり、Ｒ^４は独立に、炭素原子数６～１０のアリール基である。ａは０～１００の整数であり、ｂは１～５０の整数である。各シロキサン単位の配列順は任意であってよい。）
（Ｂ）下記平均単位式（２）で表される分岐状オルガノポリシロキサン：（Ａ）成分と（Ｂ）成分との合計１００質量部に対して１０～９０質量部、
（Ｒ^５ _３ＳｉＯ_１／２）_ｃ（Ｒ^１Ｒ^５ _２ＳｉＯ_１／２）_ｄ（Ｒ^１Ｒ^５ＳｉＯ）_ｅ（Ｒ^５ _２ＳｉＯ）_ｆ（Ｒ^１ＳｉＯ_３／２）_ｇ（Ｒ^５ＳｉＯ_３／２）_ｈ（ＳｉＯ_４／２）_ｉ （２）
(式中、Ｒ^１は前記と同じである。Ｒ^５は独立に、脂肪族不飽和結合を有しない置換又は非置換の炭素原子数１～１２の一価炭化水素基であり、但し、全Ｒ^５の少なくとも５０モル％は炭素原子数６～１２のアリール基である。ｃ、ｄ、ｅ、ｆ、ｇ、ｈ、及びｉは、それぞれｃ≧０、ｄ≧０、ｅ≧０、ｆ≧０、ｇ≧０、ｈ≧０、ｉ≧０、ｄ＋ｅ＋ｇ＞０、ｇ＋ｈ＋ｉ＞０、かつｃ＋ｄ＋ｅ＋ｆ＋ｇ＋ｈ＋ｉ＝１を満たす数である。)
（Ｃ）１分子あたり少なくとも２つのケイ素原子に結合した水素原子を有し、かつ、エポキシ基を有しないオルガノハイドロジェンポリシロキサン：（Ａ）成分および（Ｂ）成分中のケイ素原子結合アルケニル基１個に対して、ケイ素原子に結合した水素原子が０．２～５．０個となる量、
（Ｄ）酸無水物基を有する化合物：（Ａ）成分と（Ｂ）成分との合計１００質量部に対して０．００５～５質量部、
（Ｅ）白金族金属触媒：（Ａ）成分と（Ｂ）成分との合計質量に対して白金族金属の質量換算で０．１～１，０００ｐｐｍ、
（Ｆ）エポキシ基を有する化合物：（Ａ）成分と（Ｂ）成分との合計１００質量部に対して０．１～１０質量部
を含有する付加硬化型シリコーン組成物である。 That is, the present invention
(A) A linear organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule represented by the following formula (1).

(In the formula, R ¹ is independently an alkenyl group having 2 to 10 carbon atoms, and R ² is independently a substituted or unsubstituted monovalent with 1 to 12 carbon atoms having no aliphatic unsaturated bond. It is a hydrocarbon group, R ³ is an independently alkyl group having 1 to 8 carbon atoms, R ⁴ is an independent aryl group having 6 to 10 carbon atoms, and a is an integer of 0 to 100. Yes, b is an integer from 1 to 50. The order of arrangement of each siloxane unit may be arbitrary.)
(B) Branched organopolysiloxane represented by the following average unit formula (2): 10 to 90 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).
(R ⁵ ₃ SiO _1/2 ) _c (R ¹ R ⁵ ₂ SiO _1/2 ) _d (R ¹ R ⁵ SiO) _e (R ⁵ ₂ SiO) _f (R ¹ SiO _3/2 ) _g (R ⁵ SiO) _3/2 ) _h (SiO _4/2 ) _i (2)
(In the formula, R ¹ is the same as above. R ⁵ is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms having no aliphatic unsaturated bond, except that all of them are used. At least 50 mol% of R ⁵ is an aryl group having 6 to 12 carbon atoms. C, d, e, f, g, h, and i are c ≧ 0, d ≧ 0, e ≧ 0, f, respectively. ≧ 0, g ≧ 0, h ≧ 0, i ≧ 0, d + e + g> 0, g + h + i> 0, and c + d + e + f + g + h + i = 1.
(C) Organohydrogenpolysiloxane having a hydrogen atom bonded to at least two silicon atoms per molecule and having no epoxy group: Silicon atom-bonded alkenyl group 1 in the components (A) and (B) The amount of hydrogen atoms bonded to silicon atoms is 0.2 to 5.0 per atom,
(D) Compound having an acid anhydride group: 0.005 to 5 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).
(E) Platinum group metal catalyst: 0.1 to 1,000 ppm in terms of mass of platinum group metal with respect to the total mass of the component (A) and the component (B).
(F) Compound having an epoxy group: An addition-curable silicone composition containing 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).

（式中、Ｒ^１は独立に、炭素原子数２～１０のアルケニル基であり、Ｒ^２は独立に、脂肪族不飽和結合を有しない置換又は非置換の炭素原子数１～１２の一価炭化水素基であり、Ｒ^３は独立に、炭素原子数１～８のアルキル基であり、Ｒ^４は独立に、炭素原子数６～１０のアリール基である。ａは０～１００の整数であり、ｂは１～５０の整数である。各シロキサン単位の配列順は任意であってよい。） Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
[(A) component]
The component (A) is a linear organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule, which is represented by the following formula (1).

(In the formula, R ¹ is independently an alkenyl group having 2 to 10 carbon atoms, and R ² is independently a substituted or unsubstituted monovalent with 1 to 12 carbon atoms having no aliphatic unsaturated bond. It is a hydrocarbon group, R ³ is an independently alkyl group having 1 to 8 carbon atoms, R ⁴ is an independent aryl group having 6 to 10 carbon atoms, and a is an integer of 0 to 100. Yes, b is an integer from 1 to 50. The order of arrangement of each siloxane unit may be arbitrary.)

The viscosity of the component (A) is preferably in the range of 10 to 100,000,000 mPa · s at a value of 23 ° C. by a rotational viscometer, and more preferably in the range of 200 to 10,000 mPs · s. When it is 100,000,000 mPa · s or less, the hardness of the cured product does not decrease and the workability is excellent, which is preferable.

The alkenyl group represented by R ¹ is an alkenyl group having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms such as a vinyl group, an allyl group and an ethynyl group, and a vinyl group is particularly preferable.
The monovalent hydrocarbon group represented by ^R2 is not particularly limited as long as it is a monovalent hydrocarbon group having 1 to 12 carbon atoms and does not have an aliphatic unsaturated bond, and is, for example, a methyl group or an ethyl group. Alkyl groups such as propyl group, butyl group, pentyl group, hexyl group and heptyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, trill group, xylyl group and naphthyl group; benzyl group and phenethyl An aralkyl group such as a group; an alkyl halide group such as a chloromethyl group or a 3-chloropropyl group is used, and an unsubstituted or halogen group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms is preferable. Examples thereof include a substituted monovalent hydrocarbon group, and a methyl group and a phenyl group are particularly preferable.

R ³ is an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group and an octyl group. It is preferably an alkyl group having 1 to 4 carbon atoms, and a methyl group is more preferable.

^R4 is an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group, and a phenyl group is more preferable.

Specific examples of the component (A) include methylphenylvinyl syroxy group-blocked polydiphenylsiloxane at both ends of the molecular chain, diphenylvinyl syroxy group-blocked polydiphenylsiloxane at both ends of the molecular chain, and methylphenylvinyl syroxy group-blocked polymethylphenyl at both ends of the molecular chain. Examples thereof include siloxane, diphenylvinylsiloxy group-blocking polymethylphenylsiloxane at both ends of the molecular chain.
The component (A) may be used alone or in combination of two or more.

[(B) component]
The component (B) is a branched organopolysiloxane represented by the following average composition formula (2).
(R ⁵ ₃ SiO _1/2 ) _c (R ¹ R ⁵ ₂ SiO _1/2 ) _d (R ¹ R ⁵ SiO) _e (R ⁵ ₂ SiO) _f (R ¹ SiO _3/2 ) _g (R ⁵ SiO) _3/2 ) _h (SiO _4/2 ) _i (2)
(In the formula, R ¹ is the same as above. R ⁵ is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms having no aliphatic unsaturated bond, except that all of them are used. At least 50 mol% of R ⁵ is an aryl group having 6 to 12 carbon atoms. C, d, e, f, g, h, and i are c ≧ 0, d ≧ 0, e ≧ 0, f, respectively. ≧ 0, g ≧ 0, h ≧ 0, i ≧ 0, d + e + g> 0, g + h + i> 0, and c + d + e + f + g + h + i = 1.

The component (B) is preferably a wax-like or solid three-dimensional network-like organopolysiloxane resin at 23 ° C. "Wax-like" means a gum-like (raw rubber-like) having almost no self-fluidity at 23 ° C. of 10,000,000 mPa · s or more, particularly 100,000,000 mPa · s or more. ..
In the formula (2), R ¹ may be the same as that exemplified for the component (A), and a vinyl group is particularly preferable.

The monovalent hydrocarbon group represented by ^R5 is not particularly limited as long as it does not have an aliphatic unsaturated bond, and is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. , Heptyl group and other alkyl groups; cyclopentyl group, cyclohexyl group and other cycloalkyl groups; phenyl group, trill group, xylyl group, naphthyl group and other aryl groups; benzyl group, phenethyl group and other aralkyl groups; chloromethyl group, 3 -Unsubstituted alkyl groups such as chloropropyl groups, 3,3,3-trifluoropropyl groups and the like, usually having 1 to 12, preferably 1 to 10, more preferably 1 to 8 carbon atoms. Alternatively, a halogen-substituted monovalent hydrocarbon group is mentioned, and a methyl group and a phenyl group are particularly preferable.
Further, it is preferable that at least 50 mol% of R ⁵ is an aryl group having 6 to 12 carbon atoms, and 70 mol% or more of R ⁵ is an aryl group having 6 to 12 carbon atoms. As a result, it is possible to improve the refractive index, improve the light extraction efficiency in the LED package, and impart sulfurization resistance for suppressing blackening of the silver substrate. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like, and a phenyl group is particularly preferable.

The branched organopolysiloxane of the component (B) has a branched structure. The content of the branched organopolysiloxane of the component (B) is _4/2 units of SiO and / or the content of R ¹ SiO _3/2 and R ⁵ SiO _3/2 units is preferably the branched organopolysiloxane of the component (B). It is 5 mol% or more, more preferably 10 mol to 95 mol%, particularly preferably 20 to 60 mol% of the total siloxane unit in it. Further, the branched organopolysiloxane preferably has a weight average molecular weight in the range of 500 to 100,000 from the viewpoint of isolation. The weight molecular weight is a value in terms of standard polystyrene in gel permeation chromatography (GPC).

（Ｂ）成分は一種単独でも二種以上併用してもよい。 Specific examples of the component (B) include branched organopolysiloxane represented by the following formula.

The component (B) may be used alone or in combination of two or more.

The blending amount of the component (B) is 10 to 90 parts by mass, preferably 20 to 60 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). When the blending amount of the component (B) is less than 10 parts by mass, the adhesiveness and the mechanical properties of the cured product are inferior, and when it exceeds 90 parts by mass, the viscosity of the composition becomes extremely high and handling becomes difficult. Become.

[(C) component]
The component (C) is an organohydrogenpolysiloxane having a hydrogen atom bonded to at least two silicon atoms per molecule and having no epoxy group, and is hydrosilylated with the components (A) and (B). It reacts and acts as a cross-linking agent. Further, the component (C) is distinguished from the component (F) described later in that it does not have an epoxy group.
The molecular structure of the organohydrogenpolysiloxane as a component (C) may be linear, cyclic, branched, or three-dimensional network structure, but the number of silicon atoms in one molecule is preferably 2 to 300. The number is, more preferably 3 to 200.

The component (C) is preferably liquid at 25 ° C., and the viscosity at 23 ° C. measured by a rotational viscometer is preferably 1 to 1,000 mPa · s, more preferably 5 to 200 mPa · s.
The component (C) is a hydrogen atom (SiH group) bonded to at least two (usually about 2 to 300), preferably three or more (usually about 3 to 200) silicon atoms in one molecule. Have. When the component (C) has a linear structure or a branched structure, these SiH groups are located at either the end of the molecular chain or the non-end of the molecular chain, even if they are located at both of them. May be.

As the organic silicon compound of the component (C), for example, a compound represented by the following average composition formula (3') can be used.
R ⁶ _j H _k SiO _{(4-j-k) / 2} (3')
(In the formula, R ⁶ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms having no aliphatic unsaturated bond, and j and k are 0.7 ≦ j ≦ 2. .1, 0.001 ≦ k ≦ 1.0 and 0.8 ≦ j + k ≦ 3.0, preferably 1.0 ≦ j ≦ 2.0, 0.01 ≦ k ≦ 1.0 and 1.5 ≦ It is a number that satisfies j + k ≦ 2.5.)

Examples of the monovalent hydrocarbon group represented by R ⁶ include the same groups as those exemplified as R ⁵ , but even if they have an acrylic polymerizable functional group such as an acryloyl group or a methacryloyl group. good. Examples of R ⁶ include an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably a methyl group and a phenyl group.

Specific examples of the component (C) include, for example, a cyclic polysiloxane composed of an organohydrogensiloxane unit represented by (HR ⁶ SiO _2/2 ), represented by R ⁶ ₃ SiO ₍ HR ⁶ SiO) _l SiR ⁶³ . Organohydrogensiloxane, HR ⁶ ₂ SiO (HR ⁶ SiO) _l SiR ⁶ ₂ H Organohydrogen siloxane, HR ⁶ ₂ SiO (HR ⁶ SiO) _l (R ⁶ ₂ SiO) _m SiR ⁶ ₂ Examples thereof include organohydrogensiloxane represented by H (in the above ^formula , R6 is as described above, and l and m are integers of 1 or more).

The component (C) is represented by a siloxane unit represented by (H ₃ SiO _1/2 ), a siloxane unit represented by (HR ⁶ SiO _2/2 ), and / or (R ⁶ ₂ HSiO _1/2 ). It may contain a monoorganosiloxane unit, a diorganosiloxane unit, a triorganosiloxane unit and / or a SiO _4/2 unit that does not contain a SiH group (R in the above formula). ⁶ is as described above).

Specific examples of the component (C) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (hydrogendimethylsiloxane) methylsilane, and tris (hydrogen). Dimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends of the molecular chain, trimethylsiloxy group-blocked diphenylsiloxane at both ends of the molecular chain Methylhydrogensiloxane copolymer, trimethylsiloxy group-blocked methylphenylsiloxane / methylhydrogensiloxane copolymer at both ends of the molecular chain, trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane / methylphenylsiloxane copolymer at both ends of the molecular chain , Molecular chain double-ended trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane / diphenylsiloxane copolymer, Molecular chain double-ended dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane, Molecular chain double-ended dimethylhydrogensiloxy group-blocked dimethyl Polysiloxane, dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer at both ends of the molecular chain, dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer at both ends of the molecular chain, dimethylhydro at both ends of the molecular chain Genciloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer, molecular chain double-ended dimethylhydrogensiloxy group-blocked methylphenylpolysiloxane, molecular chain double-ended dimethylhydrogensiloxy group-blocked diphenylpolysiloxane, molecular chain double-ended dimethylhydrogensiloxy A base-blocking diphenylsiloxane / methylhydrogensiloxane copolymer, an organohydrogenpolysiloxane in which some or all of the methyl groups are substituted with other alkyl groups such as ethyl groups and propyl groups in each of these exemplary compounds, ( Organosiloxane co-weight consisting of a siloxane unit represented by R ⁶ ₃ SiO _1/2 ), a siloxane unit represented by (R ⁶ ₂ HSiO _1/2 ), and a siloxane unit represented by (SiO _4/2 ). Combined, represented by (R _{62 HSiO 1/2} ⁾ siloxane unit and ( _{SiO 4/2 )} An organosiloxane copolymer composed of a siloxane unit to be formed, a siloxane unit represented by (R ⁶ HSiO _2/2 ), a siloxane unit represented by (R ⁶ SiO _3/2 ), and (H ₃ SiO). Organosiloxane copolymer composed of one or both of the siloxane units represented by _1/2 ) (R6 in the above ^formula is as described above. ) And a mixture of two or more of these organopolysiloxanes.

The blending amount of the component (C) is such that the number of hydrogen atoms bonded to the silicon atom is 0.2 to 5.0 with respect to one silicon atom-bonded alkenyl group in the component (A) and the component (B). The amount is preferably 0.5 to 2.0.

[(D) component]
The component (D) is a compound having an acid anhydride group, which contributes to improving the adhesiveness of the addition-curable silicone composition of the present invention.

The component (D) is not particularly limited as long as it has an acid anhydride group, and is, for example, acetic anhydride, succinic anhydride, phthalic anhydride, maleic anhydride, benzoic acid anhydride, allylsuccinic anhydride, and allylsuccinic anhydride. Examples thereof include those having a trimethoxysilicon group added thereto, propionic anhydride, oxalic anhydride, and 4,4'-oxydiphthalic anhydride, and the compound represented by the following formula (3) is preferable.

（Ｄ）成分は一種単独で用いても二種以上を併用してもよい。
（Ｄ）成分の配合量は、（Ａ）成分と（Ｂ）成分との合計１００質量部に対して０．００５～５質量部であり、好ましくは０．０１～１質量部である。

The component (D) may be used alone or in combination of two or more.
The blending amount of the component (D) is 0.005 to 5 parts by mass, preferably 0.01 to 1 part by mass with respect to 100 parts by mass in total of the component (A) and the component (B).

[(E) component]
The platinum group metal-based catalyst of the component (E) is a component for advancing and promoting the hydrosilylation reaction of the components (A) to (C).
The platinum group metal catalyst is not particularly limited, and is, for example, a platinum group metal such as platinum, palladium, rhodium; a combination of platinum chloride acid, alcohol-modified platinum chloride acid, platinum chloride acid and olefins, vinylsiloxane or acetylene compound. Examples thereof include platinum compounds such as position compounds, platinum group metal compounds such as tetrakis (triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium, and the compatibility with the components (A) to (C) is good. Since it contains almost no chlor impurities, it is preferably a silicone-modified rhodium chloride.
The component (E) may be used alone or in combination of two or more.

The blending amount of the component (E) may be an effective amount as a hydrosilylation catalyst, but is usually 0.1 in terms of the mass of the platinum group metal with respect to the total mass of the component (A) and the component (B). It is in the range of about 1,000 ppm, more preferably in the range of 1 to 500 ppm.

[(F) component]
The component (F) is a compound having an epoxy group, which contributes to improving the adhesiveness of the addition-curable silicone composition of the present invention.
The component (F) is not particularly limited as long as it has an epoxy group, and is, for example, allylglycidyl ether, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane. , 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, dimethylethoxy-3-glycidoxypropylsilane, etc., and cyclic representations of the following formulas (5) to (8). Examples thereof include organohydrogenpolysiloxane and compounds represented by the following formula (9). It is preferably a cyclic organohydrogenpolysiloxane containing an epoxy group of the following formulas (5), (6) and (8).

The component (F) may be used alone or in combination of two or more.
The blending amount of the component (F) is 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B).

[Other ingredients]
In the present invention, an inorganic filler can be further added for the purpose of improving strength, adjusting viscosity, imparting thixotropic properties, and the like. The inorganic filler is not particularly limited, but the specific surface area by the BET method is preferably 50 m ² / g or more, more preferably 80 m ² / g, still more preferably 100 m ² / g or more. Oxides can be mentioned. The specific surface area is preferably 300 m ² / g or less, more preferably 250 m ² / g or less. If the specific surface area is 50 m ² / g or more, the effect of adding an inorganic filler such as silica fine particles is sufficiently recognized, and if it is 300 m ² / g or less, the dispersion treatment in the resin may not be difficult. Is preferable. As the inorganic filler, silica fine particles are preferable, and as the silica fine particles, for example, a silica fine particle whose surface is made hydrophobic by reacting a silanol group existing on the surface of the hydrophilic silica fine particles with a surface modifier may be used. good. Examples of the surface modifier include compounds of alkylsilanes, and specific examples thereof include dimethyldichlorosilane, hexamethyldisilazane, octylsilane, and dimethylsilicone oil.

Examples of the silica fine particles include fumed silica. Fused silica is produced by oxidizing and hydrolyzing _SiCl4 gas with a flame at 1,100 to 1,400 ° C. in which a mixed gas of H ₂ and O ₂ is burned. The primary particles of fumed silica are spherical ultrafine particles mainly composed of amorphous silicon dioxide (SiO ₂ ) having an average particle size of about 5 to 50 nm, and the primary particles are aggregated to have a particle size. It forms secondary particles that are several hundred nm. Since fumed silica is ultrafine particles and is produced by quenching, the surface structure is chemically active.

Specifically, for example, "Aerosil" (registered trademark) manufactured by Nippon Aerosil Co., Ltd. is mentioned, and examples of hydrophilic silica include "90", "130", "150", "200", "300", etc. Examples of hydrophobic silica are "R8200", "R972", "R972V", "R972CF", "R974", "R202", "R805", "R812", "R812S", "RY200", "RY200S". , "RX200". In addition, examples of "Leoloseal" (registered trademark) manufactured by Tokuyama Corporation include "DM-10", "DM-20", and "DM-30".

Other ingredients include 1-ethylnylcyclohexanol, 3,5-dimethyl-1-hexin-3-ol, ethynylmethyldecylcarbinol, 1,3,5,7-tetramethyl to ensure pot life. Addition reaction control agents such as -1,3,5,7-tetravinylcyclotetrasiloxane can be blended. Further, if necessary, a dye, a pigment, a flame retardant or the like may be blended, or an adhesive auxiliary agent (silane coupling agent or the like) other than the above may be blended in order to improve the adhesive strength. These components may be used alone or in combination of two or more.

When the component (C) has an acrylic polymerizable functional group such as an acryloyl group or a methacryloyl group, it acts as a curing agent (catalyst) by adding an organic peroxide to promote the polymerization of the acryloyl group or the methacryloyl group. It gives a highly adhesive silicone composition. Examples of the organic peroxide include benzoyl peroxide, t-butyl perbenzoate, o-methylbenzoyl peroxide, p-methylbenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 1,1-. Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,5-dimethyl-2,5-di (t-butylperoxy) Hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin, 1,6-bis (p-toluoil peroxycarbonyloxy) hexane, di (4-methylbenzoylperoxy) hexamethylene Examples thereof include biscarbonate, dibenzoyl-peroxide, and benzoyl- (m-methylbenzoyl peroxide, m-toluole peroxide, etc.), which may be used alone or in combination of two or more. The addition amount of is an effective amount (that is, a so-called catalyst amount), which is 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B), and is 0.05 to 0.05. It is preferable to mix 3 parts by mass.

[Cursed product]
The present invention also provides a cured product of the addition-curable silicone composition.
The addition-curable silicone composition of the present invention can be cured under known curing conditions by a known curing method, but it is preferably heated at 60 to 180 ° C. for 1 to 5 hours.

[Optical semiconductor device]
Furthermore, the present invention provides an optical semiconductor device that is sealed or die-bonded with the cured product. Examples of the optical semiconductor element include LEDs, semiconductor lasers, photodiodes, phototransistors, solar cells, CCDs and the like.
When the cured product of the present invention is used as a sealing material, the addition-curable silicone composition of the present invention may be applied to an optical semiconductor device and cured by the above-mentioned known methods and conditions.

As an example of a method of die-bonding an optical semiconductor device using the composition of the present invention, the composition of the present invention is filled in a syringe, and the thickness is 5 to 100 μm in a dry state on a substrate such as a package using the dispenser. A method of die-bonding an optical semiconductor element onto a substrate by arranging an optical semiconductor element (for example, a light emitting diode) on the applied composition and curing the composition can be mentioned. .. Further, the composition is placed on a squeegee dish, and while squeezing, the composition is applied onto the substrate in a dry state to a thickness of 5 to 100 μm by a stamping method, and then an optical semiconductor element is arranged on the applied composition. A method of die-bonding an optical element onto a substrate by curing an object may also be used. The curing conditions of the composition may be as described above. In this way, it is possible to obtain a highly reliable opto-semiconductor device die-bonded with the cured product of the addition-curable silicone composition of the present invention.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. Each component used in Examples and Comparative Examples is shown below.

(A) Component: A linear organopolysiloxane having a viscosity of 2,000 mPa · s at 23 ° C. by a rotational viscometer, which is represented by the following average composition formula (10).

Component (B): Branched organopolysiloxane represented by the following unit formula (11)

(C) Ingredient:
(C-1) Organohydrogenpolysiloxane represented by the following formula (12)

(C-2) Organohydrogenpolysiloxane represented by the following formula (13)

Component (D): Acid anhydride group-containing compound represented by the above formula (3)

Component (E): A complex of platinum hexachloride and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is represented by the following formula (14) so as to have a platinum content of 1% by mass. Organopolysiloxane diluted solution

(F) Ingredient:
(F-1) Adhesive aid represented by the formula (5) (F-2) Adhesive aid represented by the formula (6) (F-3) Adhesive aid represented by the formula (8) Agent

Component (G): Organic peroxide represented by the following formula (15)

[Example 1]
80 parts by mass of (A) and 20 parts by mass of (B) were dissolved in xylene, and 0.1 part by mass of dibutylhydroxytoluene was mixed. A viscous liquid was obtained by distilling xylene from the obtained liquid mixture at 90 ° C. under a reduced pressure condition of 10 mmHg or less. 0.02 parts by mass of ethynylmethyldecylcarbinol and 34.3 parts by mass of the above (C-1) were mixed with 100 parts by mass of this viscous liquid to obtain a transparent liquid mixture. To this liquid mixture, 0.03 part by mass of the above (E) was added, and 2 parts by mass of the above (F-1) was further added, and 3 parts by mass of the above (F-2) and the above (F-3). The silicone composition was prepared by stirring and mixing 1 part by mass, 0.01 part by mass of (D), and 0.8 part by mass of (G).
The molar ratio represented by {total of SiH groups of the component (C)} / {total of Si-vinyl groups in the component (A) and the component (B)} of this composition is 1.1. rice field.

[Example 2]
45 parts by mass of (A) and 55 parts by mass of (B) are dissolved in xylene, and the obtained liquid mixture is distilled off xylene at 150 ° C. under a reduced pressure condition of 10 mmHg or less to obtain a viscous liquid. Obtained. 0.02 parts by mass of ethynylmethyldecylcarbinol and 30.1 parts by mass of the above (C-2) were mixed with 100 parts by mass of this viscous liquid to obtain a transparent liquid mixture. To this liquid mixture, 0.04 part by mass of (E) is added, 3 parts by mass of (F-1) is further added, and 0.2 part by mass of (D) is stirred and mixed to form a silicone composition. I adjusted things.
The molar ratio represented by {total of SiH groups of the component (C-2)} / {total of Si-vinyl groups in the component (A) and the component (B)} of this composition is 1.1. Met.

[Comparative Example 1]
80 parts by mass of (A) and 20 parts by mass of (B) were dissolved in xylene, and 0.1 part by mass of dibutylhydroxytoluene was mixed. A viscous liquid was obtained by distilling xylene from the obtained liquid mixture at 90 ° C. under a reduced pressure condition of 10 mmHg or less. 0.02 parts by mass of ethynylmethyldecylcarbinol and 34.3 parts by mass of the above (C-1) were mixed with 100 parts by mass of this viscous liquid to obtain a transparent liquid mixture. To this liquid mixture, 0.03 part by mass of the above (E) was added, and 2 parts by mass of the above (F-1) was further added, and 3 parts by mass of the above (F-2) and the above (F-3). 1 part by mass and 0.8 part by mass of the above (G) were stirred and mixed to prepare a silicone composition.
The molar ratio represented by {total of SiH groups of the component (C)} / {total of Si-vinyl groups in the component (A) and the component (B)} of this composition is 1.1. rice field.

[Comparative Example 2]
45 parts by mass of (A) and 55 parts by mass of (B) are dissolved in xylene, and the obtained liquid mixture is distilled off xylene at 150 ° C. under a reduced pressure condition of 10 mmHg or less to obtain a viscous liquid. Obtained. 0.02 parts by mass of ethynylmethyldecylcarbinol and 30.1 parts by mass of the above (C-2) were mixed with 100 parts by mass of this viscous liquid to obtain a transparent liquid mixture. To this liquid mixture, 0.04 part by mass of the above (E) was added, and 3 parts by mass of the above (F-1) was further added, and the mixture was stirred and mixed to prepare a silicone composition.
The molar ratio represented by {total of SiH groups of the component (C-2)} / {total of Si-vinyl groups in the component (A) and the component (B)} of this composition is 1.1. Met.

[Comparative Example 3]
80 parts by mass of (A) and 20 parts by mass of (B) were dissolved in xylene, and 0.1 part by mass of dibutylhydroxytoluene was mixed. A viscous liquid was obtained by distilling xylene from the obtained liquid mixture at 90 ° C. under a reduced pressure condition of 10 mmHg or less. 0.02 parts by mass of ethynylmethyldecylcarbinol and 34.3 parts by mass of the above (C-1) were mixed with 100 parts by mass of this viscous liquid to obtain a transparent liquid mixture. To this liquid mixture, 0.03 part by mass of the above (E) is added, and 0.01 part by mass of the above (D) and 0.8 part by mass of the above (G) are stirred and mixed to prepare a silicone composition. did.
The molar ratio represented by {total of SiH groups of the component (C)} / {total of Si-vinyl groups in the component (A) and the component (B)} of this composition is 1.1. rice field.

Table 1 shows the blending amount of each component in the compositions of Examples and Comparative Examples (numerical values represent parts by mass).

The compositions obtained in Examples and Comparative Examples were evaluated as follows, and the results are shown in Table 2.
[Adhesiveness (adhesive strength)]
As shown in FIG. 1, the obtained silicone composition was made to have a thickness of 2 mm so that the ends of the two alumina ceramic substrates 11 and 12 (manufactured by KDS, 25 mm in width × 50 mm in depth × 1 mm in thickness) overlapped by 10 mm. The silicone composition was cured by heating at 150 ° C. for 3 hours so as to be sandwiched, and the two alumina ceramic substrates 11 bonded by the cured product 13 of the silicone composition (adhesion area 25 mm × 5 mm = 125 mm ² ). , A test piece consisting of 12 was produced.

The ends of the alumina ceramic substrates 11 and 12 of this test piece are pulled in opposite directions (in the direction of the arrow in FIG. 1) using a tensile tester (manufactured by Shimadzu Corporation, Autograph) at a tensile speed of 50 mm / min. The adhesive strength (MPa) per area was determined. The measurement was carried out at 23 ° C., and it was evaluated as having sufficient adhesiveness when the adhesive strength was 3 MPa or more.

As shown in Table 2, it can be seen that the cured product made of the addition-curable silicone composition of the present invention has high adhesive strength. On the other hand, in Comparative Examples 1 and 2 containing no acid anhydride group-containing compound and Comparative Example 3 containing no epoxy group-containing compound, the adhesive strength was inferior to that of Examples 1 and 2.

The present invention is not limited to the above embodiment. The above-described embodiment is an example, and any one having substantially the same structure as the technical idea described in the claims of the present invention and having the same effect and effect is the present invention. Is included in the technical scope of.

11, 12 ... Alumina ceramic substrate, 13 ... A cured product of a silicone composition.

Claims (7)

(A) A linear organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule represented by the following formula (1).

(In the formula, R ¹ is independently an alkenyl group having 2 to 10 carbon atoms, and R ² is independently a substituted or unsubstituted monovalent with 1 to 12 carbon atoms having no aliphatic unsaturated bond. It is a hydrocarbon group, R ³ is an independently alkyl group having 1 to 8 carbon atoms, R ⁴ is an independent aryl group having 6 to 10 carbon atoms, and a is an integer of 0 to 100. Yes, b is an integer from 1 to 50. The order of arrangement of each siloxane unit may be arbitrary.)
(B) Branched organopolysiloxane represented by the following average unit formula (2): 10 to 90 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).
(R ⁵ ₃ SiO _1/2 ) _c (R ¹ R ⁵ ₂ SiO _1/2 ) _d (R ¹ R ⁵ SiO) _e (R ⁵ ₂ SiO) _f (R ¹ SiO _3/2 ) _g (R ⁵ SiO) _3/2 ) _h (SiO _4/2 ) _i (2)
(In the formula, R ¹ is the same as above. R ⁵ is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms having no aliphatic unsaturated bond, except that all of them are used. At least 50 mol% of R ⁵ is an aryl group having 6 to 12 carbon atoms. C, d, e, f, g, h, and i are c ≧ 0, d ≧ 0, e ≧ 0, f, respectively. ≧ 0, g ≧ 0, h ≧ 0, i ≧ 0, d + e + g> 0, g + h + i> 0, and c + d + e + f + g + h + i = 1.
(C) Organohydrogenpolysiloxane having a hydrogen atom bonded to at least two silicon atoms per molecule, having an acrylic polymerizable functional group, and having no epoxy group: the component (A) and the above . (B) The amount of hydrogen atoms bonded to silicon atoms is 0.2 to 5.0 for each silicon atom-bonded alkenyl group in the component.
(D) Compound having an acid anhydride group: 0.005 to 5 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).
(E) Platinum group metal catalyst: 0.1 to 1,000 ppm in terms of mass of platinum group metal with respect to the total mass of the component (A) and the component (B).
(F) Compound having an epoxy group: 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B) .
(G) Organic peroxide: 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B).
An addition-curable silicone composition, characterized in that it contains. The addition-curable silicone composition according to claim 1, wherein R ² is a phenyl group or a methyl group, and R ⁴ is a phenyl group. The addition-curable silicone composition according to claim 1 or 2, wherein the component (D) is a compound represented by the following formula (3).

The addition-curable silicone composition according to any one of claims 1 to 3, wherein the component (F) is a cyclic organohydrogenpolysiloxane containing an epoxy group. A silicone cured product obtained by curing the addition-curing silicone composition according to any one of claims 1 to 4. An optical semiconductor device characterized by being sealed with the cured silicone product according to claim 5. An optical semiconductor device characterized by being die-bonded with the cured silicone product according to claim 5.

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