TWI762636B - Silicone resin composition for die bonding, die bonding material and optical semiconductor device - Google Patents

Abstract

An object of the present invention is to provide a silicone resin composition useful for solidification, which can provide a cured product with good adhesion, high hardness, and excellent product reliability. The solution is a silicone resin composition for solid crystal, which is characterized by containing: (A) a waxy or solid three-dimensional network organopolysiloxane resin (R ² ) of the following formula (1) at 23° C. ₃ SiO _1/2 ) _a (R ¹ R ² ₂ SiO _1/2 ) _b (R ¹ R ² SiO) _c (R ² ₂ SiO) _d (R ¹ SiO _3/2 ) _e (R ² SiO _3/2 ) _f (R ³ SiO _3/2 ) _g (SiO _4/2 ) _h (1); (B) 1 molecule has a vinyl group, CH ₂ =CH-COO-(CH ₂ ) _m -group and CH ₂ = Linear organopolysiloxane with one or more C(CH ₃ )-COO-(CH ₂ ) _m -groups; (C) an organosilicon compound having two or more Si-H in one molecule; ( D) organic peroxide; (E) platinum group metal-based catalyst.

Description

Silicone resin composition for die bonding, die bonding material and optical semiconductor device

The present invention relates to a silicone resin composition for die bonding, a die bonding material composed of the composition, and an optical semiconductor device having a cured product of the die bonding material.

Conventionally, epoxy resins have been used as sealing materials and die-bonding materials for light emitting diode (LED) elements (ie, adhesives for bonding chips such as LED elements to substrates such as packages). In particular, if the resin in the die-bonding material is too soft, in the wire-bonding step performed after the die-bonding step, there will be problems such as inability to bond. Therefore, as this die-bonding material, high-hardness adhesives have always been used. epoxy resin.

However, when the sealing material and die-bonding material made of epoxy resin are applied to blue LEDs emitting short-wavelength light or white LEDs using the same, there is a problem in durability, that is, it is easy to be Ultraviolet rays cause the resin to turn yellow, resulting in a decrease in brightness and the like.

In recent years, the requirements for the durability of LED devices have become higher and higher, and the use of epoxy resins for sealing LED components has gradually changed from epoxy resins to silicone resins with good durability. Similarly, the die-bonding material is also required to have durability, and a die-bonding material composition composed of a silicone resin has been proposed (Patent Document 1).

In particular, since most of the used part of the die-bonding material is in direct contact with the LED element, it is further required to improve the adhesion. Specifically, the die-bonding material is required to have high adhesiveness, for example, when the wire is pasted on the LED element, the element does not deviate from the adhesiveness. In addition, miniaturization due to improvement of components is gradually progressing. Therefore, for the die-bonding material, high hardness and high adhesiveness are extremely important. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2006-342200

[The problem to be solved by the invention]

The present invention has been made in view of the above-mentioned facts, and an object of the present invention is to provide a silicone resin composition useful for solidification of semiconductor elements such as LED elements, wherein the silicone resin composition can impart good adhesion and high hardness It is a hardened product with excellent product reliability. Another object is to provide a die-bonding material composed of the composition. Furthermore, it aims at providing an optical semiconductor device which has the hardened|cured material of this die-bonding material. [Means of Solving Problems]

[式(1)中，R¹ 表示碳原子數2～10之烯基，R² 表示不具有脂肪族不飽和鍵之可經鹵素原子取代的碳原子數1～12之一價烴基，R³ 表示CH₂ =CH-COO-(CH₂ )_n -基或 CH₂ =C(CH₃ )-COO-(CH₂ )_n -基；n為0～20之整數；又，a、b、c、d、e、f、g及h分別為滿足a≧0、b≧0、c≧0、d≧0、e≧0、f≧0、g＞0、h≧0的數，惟b+c+e＞0，且為滿足a+b+c+d+e+f+g+h=1的數] 　　(B)1分子中具有乙烯基、CH₂ =CH-COO-(CH₂ )_m -基及CH₂ =C(CH₃ )-COO-(CH₂ )_m -基中的1個以上的直鏈狀有機聚矽氧烷(m為0～20之整數)：相對於(A)成分與(B)成分的合計100質量份為10～40質量份； 　　(C)一分子中具有2個以上鍵結於矽原子之氫原子的有機矽化合物：{(C)成分之SiH基的合計}/{(A)成分及(B)成分中之烯基的合計}所示之莫耳比成為0.2～5.0的量； 　　(D)有機過氧化物：相對於(A)成分之有機聚矽氧烷樹脂及(B)成分之有機聚矽氧烷的合計量100質量份為0.01～5質量份； 　　(E)鉑族金屬系觸媒：相對於(A)～(C)成分的合計質量，以鉑族金屬元素的質量換算為0.1～1,000ppm。In order to solve the above problems, according to the present invention, a silicone resin composition for solid crystal is provided, which is characterized by containing: (A) a waxy or solid substance represented by the following average structural formula (1) at 23° C. Three-dimensional network organopolysiloxane resin: 60 to 90 parts by mass relative to 100 parts by mass of the total of the (A) component and the following (B) component;

[In formula (1), R ¹ represents an alkenyl group having 2 to 10 carbon atoms, R ² represents a halogen atom-substituted monovalent hydrocarbon group that does not have an aliphatic unsaturated bond and has 1 to 12 carbon atoms, and R ³ Represents CH ₂ =CH-COO-(CH ₂ ) _n -group or CH ₂ =C(CH ₃ )-COO-(CH ₂ ) _n -group; n is an integer from 0 to 20; and a, b, c , d, e, f, g and h are numbers satisfying a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, g>0, h≧0, respectively, only b+ c+e>0, and is a number satisfying a+b+c+d+e+f+g+h=1] (B) 1 molecule has a vinyl group, CH ₂ =CH-COO-(CH ₂ ) Linear organopolysiloxane (m is an integer of 0 to 20) in _m -group and at least one of _CH2 =C( _CH3 )-COO-( _CH2 ) _m -group: relative to (A ) component and (B) component total of 100 parts by mass is 10 to 40 parts by mass; (C) an organosilicon compound having two or more hydrogen atoms bonded to silicon atoms in one molecule: {(C) SiH group of component The molar ratio represented by the sum of the alkenyl groups in the component (A) and the alkenyl group in the (B) component} is 0.2 to 5.0; (D) Organic peroxide: the organic The total amount of the polysiloxane resin and the organopolysiloxane of the component (B) is 0.01 to 5 parts by mass in 100 parts by mass; (E) Platinum group metal catalyst: relative to the amount of the components (A) to (C) The total mass is 0.1 to 1,000 ppm in terms of the mass of the platinum group metal element.

The silicone resin composition for die bonding of the present invention can provide a cured product with good adhesion and high hardness and excellent product reliability, and can be used for bonding of semiconductor elements such as LED elements.

In addition, in this case, R ³ of the component (A) is preferably a CH ₂ =C(CH ₃ )-COO-(CH ₂ ) ₃ - group.

If it is the silicone resin composition for die-bonding containing the component (A) having such R ³ , it is possible to provide a cured product with better adhesiveness and higher hardness and better product reliability.

In addition, in this case, the component (B) preferably has one or more CH ₂ =C(CH ₃ )-COO-(CH ₂ ) _m - groups (m is the same as above) in one molecule.

If it is the silicon-oxygen resin composition for die-bonding containing such a component (B), it can provide the hardened|cured material which has more favorable adhesiveness and higher hardness and the reliability of the product is more excellent.

。In this case, the component (D) is preferably an organic peroxide represented by the following formula (2):

.

If it is such a component (D), hardening of the composition of this invention can be accelerated|stimulated reliably.

In addition, in the present invention, a die-bonding material is provided, which is composed of the aforementioned silicon-oxygen resin composition for die-bonding.

Since the silicone resin composition for die bonding of the present invention can provide a cured product with good adhesion and high hardness, it can be suitably used as a die bonding material.

Moreover, in this invention, it is characterized by providing the optical semiconductor device which has the hardened|cured material obtained by hardening the said die-bonding material.

Such an optical semiconductor device having a cured product obtained by curing the die-bonding silicone resin composition for die-bonding of the present invention is a highly reliable optical semiconductor device. [Effect of invention]

The silicone resin composition for die bonding of the present invention can be cured by two kinds of curing, namely, curing by organic peroxide and addition curing, to provide a cured product with excellent adhesion and high hardness, and can be effectively used for LED devices. Solid crystal solid materials such as crystal solid. Such an optical semiconductor device having a cured product obtained by curing the die-bonding silicone resin composition for die-bonding of the present invention is a highly reliable optical semiconductor device.

[Form of implementing the invention]

The inventors of the present invention, as a result of their studies to achieve the above-mentioned object, found that, in the case of a silicone resin composition for die bonding characterized by containing the following components (A) to (E), the organic peroxide can be used to prevent the Two kinds of hardening, namely, induced hardening and addition hardening, are obtained, and a hardened product with excellent adhesion and high hardness is provided, and the present invention is completed. Hereinafter, the silicon-oxygen resin composition for die-bonding, the die-bonding material, and the optical semiconductor device of the present invention will be described in detail.

[式(1)中，R¹ 表示碳原子數2～10之烯基，R² 表示不具有脂肪族不飽和鍵之可經鹵素原子取代的碳原子數1～12之一價烴基，R³ 表示CH₂ =CH-COO-(CH₂ )_n -基或 CH₂ =C(CH₃ )-COO-(CH₂ )_n -基；n為0～20之整數；又，a、b、c、d、e、f、g及h分別為滿足a≧0、b≧0、c≧0、d≧0、e≧0、f≧0、g＞0、h≧0的數，惟b+c+e＞0，且為滿足a+b+c+d+e+f+g+h=1的數] 　　(B)1分子中具有乙烯基、CH₂ =CH-COO-(CH₂ )_m -基及CH₂ =C(CH₃ )-COO-(CH₂ )_m -基中的1個以上的直鏈狀有機聚矽氧烷(m為0～20之整數)：相對於(A)成分與(B)成分的合計100質量份為10～40質量份； 　　(C)一分子中具有2個以上鍵結於矽原子之氫原子的有機矽化合物：{(C)成分之SiH基的合計}/{(A)成分及(B)成分中之烯基的合計}所示之莫耳比成為0.2～5.0的量； 　　(D)有機過氧化物：相對於(A)成分之有機聚矽氧烷樹脂及(B)成分之有機聚矽氧烷的合計量100質量份為0.01～5質量份； 　　(E)鉑族金屬系觸媒：相對於(A)～(C)成分的合計質量，以鉑族金屬元素的質量換算為0.1～1,000ppm。That is, the present invention provides a silicone resin composition for solid crystals, which is characterized by containing: (A) a three-dimensional network organic compound represented by the following average structural formula (1) that is waxy or solid at 23° C. Polysiloxane resin: 60 to 90 parts by mass relative to 100 parts by mass of the total of the (A) component and the following (B) component;

[In formula (1), R ¹ represents an alkenyl group having 2 to 10 carbon atoms, R ² represents a halogen atom-substituted monovalent hydrocarbon group that does not have an aliphatic unsaturated bond and has 1 to 12 carbon atoms, and R ³ Represents CH ₂ =CH-COO-(CH ₂ ) _n -group or CH ₂ =C(CH ₃ )-COO-(CH ₂ ) _n -group; n is an integer from 0 to 20; and a, b, c , d, e, f, g and h are numbers satisfying a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, g>0, h≧0, respectively, only b+ c+e>0, and is a number satisfying a+b+c+d+e+f+g+h=1] (B) 1 molecule has a vinyl group, CH ₂ =CH-COO-(CH ₂ ) Linear organopolysiloxane (m is an integer of 0 to 20) in _m -group and at least one of _CH2 =C( _CH3 )-COO-( _CH2 ) _m -group: relative to (A ) component and (B) component total of 100 parts by mass is 10 to 40 parts by mass; (C) an organosilicon compound having two or more hydrogen atoms bonded to silicon atoms in one molecule: {(C) SiH group of component The molar ratio represented by the sum of the alkenyl groups in the component (A) and the alkenyl group in the (B) component} is 0.2 to 5.0; (D) Organic peroxide: the organic The total amount of the polysiloxane resin and the organopolysiloxane of the component (B) is 0.01 to 5 parts by mass in 100 parts by mass; (E) Platinum group metal catalyst: relative to the amount of the components (A) to (C) The total mass is 0.1 to 1,000 ppm in terms of the mass of the platinum group metal element.

Hereinafter, each component will be described in detail. In addition, in this specification, "Me" represents a methyl group, Ph represents a "phenyl group", and Vi represents a "vinyl group".

[式(1)中，R¹ 表示碳原子數2～10之烯基，R² 表示不具有脂肪族不飽和鍵之可經鹵素原子取代的碳原子數1～12之一價烴基，R³ 表示CH₂ =CH-COO-(CH₂ )_n -基或 CH₂ =C(CH₃ )-COO-(CH₂ )_n -基；n為0～20之整數；又，a、b、c、d、e、f、g及h分別為滿足a≧0、b≧0、c≧0、d≧0、e≧0、f≧0、g＞0、h≧0的數，惟b+c+e＞0，且為滿足a+b+c+d+e+f+g+h=1的數]。[Component (A)] The component (A) is a component for obtaining reinforcement while maintaining the transparency of the cured product. It is a three-dimensional network organopolysiloxane resin which is represented by the following average structural formula (1) and is waxy or solid at 23°C. "Waxy" means jelly-like (raw rubber-like) that hardly exhibits self-fluidity at 23°C at 10,000,000 mPa･s or more, particularly 100,000,000 mPa･s or more.

[In formula (1), R ¹ represents an alkenyl group having 2 to 10 carbon atoms, R ² represents a halogen atom-substituted monovalent hydrocarbon group that does not have an aliphatic unsaturated bond and has 1 to 12 carbon atoms, and R ³ Represents CH ₂ =CH-COO-(CH ₂ ) _n -group or CH ₂ =C(CH ₃ )-COO-(CH ₂ ) _n -group; n is an integer from 0 to 20; and a, b, c , d, e, f, g and h are numbers satisfying a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, g>0, h≧0, respectively, only b+ c+e>0, and is a number satisfying a+b+c+d+e+f+g+h=1].

In the above formula (1), the alkenyl group of R ¹ is an alkenyl group having 2 to 10 carbon atoms such as vinyl group and allyl group, preferably 2-6 alkenyl group, and particularly preferably vinyl group.

In the aforementioned average structural formula (1), the content of the alkenyl group bonded to the silicon atom in the organopolysiloxane resin of the component (A) is preferably in the range of 0.01 to 1 mol per 100 g of the component (A), and more The range of 0.05-0.5 mol is preferable. When it is the range of 0.01-1 mol, crosslinking can fully progress, and the hardened|cured material with higher hardness can be obtained.

R ² is not particularly limited as long as it is a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted by a halogen atom and has no aliphatic unsaturated bond, and examples thereof include methyl, ethyl, propyl, butyl, and pentyl. alkyl, hexyl, heptyl and other alkyl groups; cyclopentyl, cyclohexyl and other cycloalkyl groups; phenyl, tolyl, xylyl, naphthyl and other aryl groups; benzyl, phenethyl and other aralkyl groups; chlorine Halogenated alkyl groups (haloalkyl groups) such as methyl and 3-chloropropyl are preferably alkyl groups having 1 to 10 carbon atoms, and particularly preferably methyl groups.

R ³ is a group represented by CH ₂ =CH-COO-(CH ₂ ) _n - or a group represented by CH ₂ =C(CH ₃ )-COO-(CH ₂ ) _n -. Here, n is an integer of 0-20, Preferably it is an integer of 3-10, Especially preferably, it is an integer of 3-5.

In the above-mentioned average structural formula (1), g>0, and by including a unit (R ³ SiO _3/2 ) having a branched structure and having R ³ in the component (A), high adhesiveness and high hardness can be obtained. hardened material.

The organopolysiloxane resin of the component (A) has a branched structure. The total content of the R ¹ SiO _3/2 unit, the R ² SiO _3/2 unit, the R ³ SiO _3/2 unit and the SiO _4/2 unit is preferably the total in the organopolysiloxane resin of the component (A) 5 mol% or more of the siloxane unit (when a+b+c+d+e+f+g+h=1 in the aforementioned average structural formula (1), e+f+g+h≧0.05 ), more preferably 10 mol% to 95 mol%, particularly preferably 20 to 60 mol%.

In addition, the organopolysiloxane resin of the component (A) is preferably in the range of 500 to 100,000 in terms of the weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) in terms of separation and purification. .

(式中，R¹ 、R² 、R³ 、a,b,c,d,e,f,g及h係與前述平均結構式(1)中的定義相同)。The organopolysiloxane resin of the component (A) is preferably represented by, for example, the following average composition formula:

(In the formula, R ¹ , R ² , R ³ , a, b, c, d, e, f, g and h are the same as defined in the aforementioned average structural formula (1)).

Specific examples of (A) component include:

。In addition, in the above formula, preferably

.

(A) component may be used individually by 1 type, and may use 2 or more types together.

The ratio of (A) component and (B) component is also one of important factors in the present invention. The compounding quantity of (A) component needs to be 60-90 mass parts with respect to the total of 100 mass parts of (A) component and (B) component, Preferably it is 65-85 mass parts, More preferably, it is 70-80 mass parts share. When the blending amount of the component (A) is less than 60 parts, the desired high hardness cannot be obtained; when it exceeds 90 parts by mass, the viscosity of the composition increases significantly, and it becomes difficult to use the composition as a solid for LED elements and the like. crystal material used.

[Component (B)] The organopolysiloxane of the component (B) is a base polymer for the purpose of relaxing the stress of the cured product composed of the silicon resin composition for solid state of the present invention. The component (B) has a vinyl group in one molecule, a group represented by CH ₂ =CH-COO-(CH ₂ ) _m -, and a group represented by CH ₂ =C(CH ₃ )-COO-(CH ₂ ) _m - One or more linear organopolysiloxanes in the group. These groups may be located only at either the terminal of the molecular chain or the non-terminal part of the molecular chain, or may be located at both of them. Here, m is an integer of 0-20, Preferably it is an integer of 3-10, Especially preferably, it is an integer of 3-5.

The component (B) may contain a dimethylsiloxane unit or a diphenylsiloxane unit in the siloxane main chain, and examples thereof include vinyl-terminated polydimethylsiloxane at both ends, vinyl Group-terminated dimethylsiloxane-diphenylsiloxane copolymer, two-end vinyl-terminated polydiphenylsiloxane, two-end methacryloyl-terminated polydimethylsiloxane, Two-end methacryloyl-terminated dimethylsiloxane-diphenylsiloxane copolymer, two-end methacryloyl-terminated polydiphenylsiloxane, one-end methacryloyl-capped Terminated polydimethylsiloxane, single-end methacryloyl-terminated dimethylsiloxane-diphenylsiloxane copolymer, single-end methacryloyl-terminated polydiphenylsiloxane , single-end vinyl-terminated polydimethylsiloxane, single-end vinyl-terminated dimethylsiloxane-diphenylsiloxane copolymer, single-end vinyl-terminated polydiphenylsiloxane Wait.

(式(3)及(4)中，i為2～20之整數，較佳為2～10之整數，更佳為2～5之整數)。Specifically, as the component (B), an organopolysiloxane represented by the following general formula (3) or (4) is preferred:

(In formulae (3) and (4), i is an integer of 2-20, Preferably it is an integer of 2-10, More preferably, it is an integer of 2-5).

(B) component may be used individually by 1 type, and may use 2 or more types together.

The organopolysiloxane of the component (B) is preferably in the range of 1,000 mPa･s or less as measured by a rotational viscometer at 23°C, more preferably in the range of 10 mPa･s to 300 mPa･s. If it is 1,000 mPa･s or less, there is no possibility that the hardness of the hardened product will be lowered by acting as a soft segment unnecessarily, and workability is also excellent, which is preferable.

(B) The compounding quantity of a component is 10-40 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, Preferably it is 15-35 mass parts, More preferably, it is 20-30 mass parts.

[Component (C)] Component (C) is an organosilicon compound having two or more hydrogen atoms (ie, SiH groups) bonded to silicon atoms in one molecule, and is subjected to a hydrosilylation reaction with components (A) and (B) , acts as a crosslinking agent. The structure of the organosilicon compound is not particularly limited as long as it has two or more hydrogen atoms (ie, SiH groups) bonded to silicon atoms in one molecule. For example, linear, cyclic, branched, three-dimensional Various organosilicon compounds that have been conventionally manufactured, such as mesh structure (resin-like). (C) component may be used individually by 1 type, and may use 2 or more types together.

Moreover, (C) component may contain the organic group which couple|bonded with a silicon atom. As the organic group bonded to the silicon atom, an unsubstituted monovalent hydrocarbon group, a halogen atom (eg, a chlorine atom, a bromine atom), an epoxy group-containing group (eg, an epoxy group, a glycidyl group, an epoxy group, etc.) can be exemplified. propoxy), alkoxy (eg, methoxy, ethoxy, propoxy, butoxy) and the like substituted monovalent hydrocarbon groups. Examples of such a substituted or unsubstituted monovalent hydrocarbon group include an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms, and more preferably a methyl group and an ethyl group. Moreover, when having an epoxy group-containing group and/or an alkoxy group as a substituent of the monovalent hydrocarbon group, adhesiveness can be further imparted to the cured product of the silicone resin composition for solid crystal of the present invention.

In (C)component, it is preferable to contain a methacrylate moiety or an acrylate moiety from the viewpoint of compatibility with resin or high adhesiveness, and it may be single or multiple in 1 molecule. Further, the carbon chain to which the ester group is bonded is preferably an alkyl chain having 1 to 10 carbon atoms, and particularly preferably an alkyl chain having 2 to 8 carbon atoms. These may be located only at any one of the molecular chain terminal and the non-terminal part of the molecular chain, or may be located at both.

The organosilicon compound of the component (C) has at least two (usually about 2 to 300), preferably three or more (usually about 3 to 200) SiH groups in one molecule. When the organosilicon compound of the component (C) has a linear structure or a branched structure, these SiH groups may be located only at any one of the molecular chain terminal and the non-terminal part of the molecular chain, or may be located at both of them.

The number of silicon atoms (polymerization degree) in one molecule of the organosilicon compound of the component (C) is preferably 1 to 1,000, more preferably 1 to 200. Furthermore, the organosilicon compound of the component (C) is preferably liquid at 25°C, and the viscosity at 25°C measured by a rotational viscometer is preferably 1-1,000 mPa･s, more preferably 5- About 200mPa･s.

(式中，R⁴ 為彼此相同或不同的取代或未取代之鍵結於矽原子之烴基，j及k為滿足0.7≦j≦2.1、0.001≦k≦1.0，且0.8≦j+k≦3.0，較佳為1.0≦j≦2.0、0.01≦k≦1.0且1.5≦j+k≦2.5的數)。As the organosilicon compound of the component (C), for example, one represented by the following average composition formula (5) can be used:

(wherein, R ⁴ is the same or different substituted or unsubstituted hydrocarbon group bonded to the silicon atom, j and k satisfy 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≦j+k≦2.5).

Specific examples of the substituted or unsubstituted monovalent hydrocarbon group bonded to the silicon atom of R ⁴ include an alkyl group having 1 to 6 carbon atoms, a haloalkyl group, and a carbon A substituted or unsubstituted group such as an aryl group of numbers 6 to 10 and the like. R ⁴ is preferably an aryl group or a haloalkyl group having 1 to 6 carbon atoms. Moreover, R ⁴ may be a methacrylate group or an acrylate group.

Examples of the organohydrosiloxane represented by the above-mentioned average composition formula (5) include cyclic compounds containing at least four organohydrosiloxane units represented by the formula: R ⁴ HSiO, and the formula: R ⁴ ₃ SiO The compound represented by (HR ⁴ SiO) _p SiR ⁴ ₃ , the compound represented by the formula: HR ⁴ ₂ SiO(HR ⁴ SiO) _p SiR ⁴ ₂ H, the compound represented by the formula: HR ⁴ ₂ SiO(HR ⁴ SiO) _p (R ⁴ ₂ SiO) _q SiR ⁴ ₂ H and the like. In the above formula, R ⁴ is the same as described above, and p and q are integers of 1 or more.

Alternatively, the organohydrosiloxane represented by the above average composition formula (5) may also include a siloxane unit represented by the formula: H ₃ SiO _1/2 , a siloxane unit represented by the formula: R ⁴ HSiO and or, formula: siloxane unit represented by R ⁴ ₂ HSiO _1/2 . The organohydrosiloxane may also include a siloxane unit represented by R ⁴ ₃ SiO _1/2 without SiH group, a siloxane unit represented by R ⁴ ₂ SiO, and a siloxane unit represented by R ⁴ SiO _3/2 Siloxane units and/or siloxane units as indicated by SiO _4/2 . In the above formula, R ⁴ is the same as described above.

Specific examples of the component (C) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, siloxane) methyl silane, ginseng (hydrodimethylsiloxy) phenyl silane, methylhydrogen cyclopolysiloxane, methylhydrosiloxane-dimethylsiloxane cyclic copolymer, Trimethylsiloxy-terminated methylhydropolysiloxane at both ends of the molecular chain, trimethylsiloxy-terminated diphenylsiloxane-methylhydrosiloxane copolymer at both ends of the molecular chain, molecular chain Two-terminal trimethylsiloxy-terminated methylphenylsiloxane-methylhydrosiloxane copolymer, two-terminal trimethylsiloxy-terminated dimethylsiloxane-methylhydrosiloxane Oxane-methylphenylsiloxane copolymer, trimethylsiloxy-terminated dimethylsiloxane-methylhydrosiloxane-diphenylsiloxane copolymer at both ends of the molecular chain, molecular chain Dimethylhydrosiloxy-terminated methylhydropolysiloxane at both ends, dimethylhydrogensiloxy-terminated dimethylpolysiloxane at both ends of the molecular chain, dimethylhydrogensiloxane at both ends of the molecular chain Group-terminated dimethylsiloxane-methylhydrosiloxane copolymer, Dimethylhydrosiloxy-terminated dimethylsiloxane-methylphenylsiloxane copolymer at both ends of the molecular chain, molecule Dimethylhydrosiloxy-terminated dimethylsiloxane-diphenylsiloxane copolymer at both ends of the chain, methylphenylpolysiloxane end-capped with dimethylhydrosiloxy at both ends of the molecular chain, Dimethylhydrosiloxy-terminated diphenyl polysiloxane at both ends of the molecular chain, Diphenylsiloxane and methylhydrosiloxane copolymers end-capped with dimethylhydrosiloxy at both ends of the molecular chain, In each of these exemplified compounds, a part or all of the methyl groups are substituted with other alkyl groups such as ethyl, propyl and other organohydrogen polysiloxanes, siloxane units represented by the formula: R ⁴ ₃ SiO _1/2 , the organosiloxane copolymer composed of the siloxane unit represented by R ⁴ ₂ HSiO _1/2 and the siloxane unit represented by the formula: SiO _4/2 , is composed of the formula: R ⁴ ₂ HSiO _1/ The organosiloxane copolymer composed of the siloxane unit represented by ₂ and the siloxane unit represented by the formula: SiO _4/2 , is composed of the siloxane unit represented by the formula: R ⁴ HSiO _2/2 and R ⁴ Siloxane units represented by SiO _3/2 and formula: organosiloxane copolymers composed of either or both of the siloxane units represented by H ₃ SiO _1/2 and/or such organic A mixture of two or more kinds of polysiloxanes. R ⁴ in the above formula has the same meaning as described above.

The blending amount of the component (C) is such that the molar ratio represented by {total of SiH groups in component (C)}/{total of alkenyl groups in component (A) and the aforementioned (B) component} is 0.2 to 5.0 The amount is preferably an amount of 0.5 to 2.0.

[Component (D)] The organic peroxide of the component (D) is a curing agent (catalyst) composed of an organic peroxide, and forms a silicon oxide in order to harden the silicone resin composition for solid crystal of the present invention. rubber or resin. By adding the (D) component, the polymerization of the acryl group or the methacryl group can be accelerated, thereby contributing to the improvement of high hardness and adhesive force.

Examples of organic peroxides include benzyl peroxide, tertiary butyl perbenzoate, o-methyl benzyl peroxide, p-methyl benzyl peroxide, di(tertiary butyl peroxide) ), dicumyl peroxide, 1,1-bis(tertiary butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tertiary butylperoxy) ring Hexane, 2,5-dimethyl-2,5-bis(tertiarybutylperoxy)hexane, 2,5-dimethyl-2,5-bis(tertiarybutylperoxy)hexyne , 1,6-bis(p-toluyl peroxycarbonyloxy) hexane, bis(4-methylbenzyl peroxide) hexamethylene biscarbonate, etc., these can be used alone or Use two or more in combination.

As (D)component, the organic peroxide represented by following formula (2) is preferable. In addition, the tBu series represents a tertiary butyl group.

The addition amount of the (D) component is an effective amount (that is, the so-called catalyst amount), and is 100 parts by mass relative to the total amount of the organopolysiloxane resin of the (A) component and the organopolysiloxane of the (B) component. 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass.

[Component (E)] The component (E) is a platinum group metal-based catalyst for promoting the hydrosilylation reaction of the component (A) and/or the component (B) and the component (C).

Examples of the component (E) include platinum group metals such as platinum, palladium, and rhodium, or coordination of chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid, and olefins, vinylsiloxane, or acetylene compounds. Compounds, platinum group metal compounds such as tetra(triphenylphosphine) palladium and chlorosyn(triphenylphosphine) rhodium, and platinum compounds are particularly preferred. (E) A component may be used individually by 1 type, and may use 2 or more types together.

The blending amount of the component (E) is an effective amount as a hydrosilylation catalyst, and is in the range of 0.1 to 1,000 ppm in terms of the mass of the platinum group metal element relative to the total mass of the components (A) to (C). , preferably in the range of 1 to 500 ppm.

[Other Components] In the present invention, an inorganic filler may be further added for the purpose of improving strength, adjusting viscosity, imparting thixotropy, and the like. The inorganic filler is not particularly limited, and the specific surface area measured by the BET method is preferably 50 m ² /g or more, more preferably 80 m ² /g, and still more preferably 100 m ² /g or more. Inorganic oxides. Further, the specific surface area is preferably 300 m ² /g or less, more preferably 250 m ² /g or less. When the specific surface area is 50 m ² /g or more, the effect of adding inorganic fillers such as silica fine particles can be sufficiently seen; when it is 300 m ² /g or less, it is not difficult to disperse in the resin. Doubt is better. In addition, as the inorganic filler, silica fine particles are preferred, and the silica fine particles can also be hydrophobicized by reacting the silanol groups present on the surface of the hydrophilic silica fine particles with a surface modifier, for example. adult. Examples of the surface modifier include compounds of alkylsilanes, and specific examples thereof include dimethyldichlorosilane, hexamethylsilazane, octylsilane, and dimethylsilicone oil.

As the silica fine particles, for example, fumed silica can be mentioned. Fumed silica is produced by oxidizing and hydrolyzing SiCl ₄ gas with a flame at 1,100-1,400°C generated by burning a mixed gas of H ₂ and O ₂ . The primary particles of fumed silica are spherical ultrafine particles mainly composed of amorphous silicon dioxide (SiO ₂ ) with an average particle size of about 5 to 50 nm. 100 nm secondary particles. Because fumed silica is ultrafine particles and is produced by quenching, its surface structure is in a chemically active state.

Specifically, for example, "AEROSIL" (registered trademark) manufactured by Japan AEROSIL Co., Ltd. can be mentioned, and examples of hydrophilic silica include "90", "130", "150", "200", "300"; as examples of hydrophobic silica, "R8200", "R972", "R972V", "R972CF", "R974", "R202", "R805", "R812", " R812S", "RY200", "RY200S", "RX200". Moreover, as "REOLOSIL" (registered trademark) manufactured by TOKUYAMA CO., LTD., "DM-10", "DM-20", and "DM-30" are mentioned.

The content of the above-mentioned silica fine particles is preferably 1-15 parts by mass, more preferably 2-10 parts by mass, relative to 100 parts by mass of the silicon-oxygen resin composition for solidification of the present invention. When the content is 1 part by mass or more, the effect of adding silica fine particles can be sufficiently seen; when the content is 15 parts by mass or less, there is no concern that the resin viscosity will increase and the workability will be deteriorated, which is preferable.

In addition, as other components, 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, ethynylmethyldecylcarbitol, 1-ethynylcyclohexanol, 1-ethynylmethyldecylcarbitol, ,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and other addition reaction control agents. Dyestuffs, pigments, flame retardants, etc. can also be further blended as required. In order to improve the adhesive force, adhesive additives (silane coupling agents, etc.) can also be blended. These components may be used alone or in combination of two or more.

In addition, the curing conditions of the silicon-oxygen resin composition for die bonding of the present invention are not particularly limited, but generally, heating conditions of 60 to 180° C. for 1 to 5 hours are preferable.

In the cured product of the silicone resin composition for die bonding of the present invention, the Shore D hardness of JIS K6253 is preferably 30 or more, more preferably 50 or more.

In the present invention, a die-bonding material is provided, which is composed of the silicon-oxygen resin composition for die-bonding of the present invention. The silicone resin composition for die bonding of the present invention is particularly useful as a die bonding material for LED elements and the like because it can impart a cured product with excellent adhesiveness and high hardness.

As an example of a method of using the silicone resin composition for die bonding of the present invention to bond an LED element, etc., filling a syringe with the composition of the present invention, and using a dispenser on a substrate such as a package, can be exemplified. A method of arranging LED elements on a composition after coating so as to have a thickness of 5 to 100 μm in a dry state, and curing the composition to solidify the LED elements on a substrate. The hardening of the composition can be carried out, for example, under the above-mentioned hardening conditions.

Furthermore, in the present invention, there is provided an optical semiconductor device characterized by having a cured product obtained by curing a die-bonding material. If it is such an optical semiconductor device, it becomes a highly reliable optical semiconductor device. [Example]

The following examples and comparative examples are given to specifically describe the present invention, but the present invention is not limited by the following examples. In addition, each component used in embodiment and comparative example is as follows:

(A-1) Waxy branched organopolysiloxane resin represented by the following average composition formula (6) at 23°C

(A-2) Branched organopolysiloxane resin that is solid at 23° C. represented by the following average composition formula (7)

(B-1) Linear organopolysiloxane having a viscosity of 1000 mPa･s at 23°C as measured by a rotational viscometer represented by the following formula (8)

(式中，各矽氧烷單元的排列順序為任意)。(B-2) Linear organopolysiloxane having a viscosity of 1000 mPa･s as measured by a rotational viscometer at 23°C represented by the following formula (9)

(In the formula, the arrangement order of each siloxane unit is arbitrary).

(B-3) Linear organopolysiloxane having a viscosity of 60 mPa･s at 23°C as measured by a rotational viscometer represented by the following formula (10)

(C-1) Organohydrogenpolysiloxane represented by the following formula (11)

(式中，各矽氧烷單元的排列順序為任意)。(C-2) Organohydrogenpolysiloxane represented by the following average composition formula (12)

(In the formula, the arrangement order of each siloxane unit is arbitrary).

(D) Organic peroxide represented by the following formula (2)

(E-1) A complex of hexachloroplatinic acid and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is diluted with toluene to obtain a platinum content of 0.5% by mass.

(E-2) The complex of hexachloroplatinic acid and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is diluted with the organopolysiloxane of the above formula (10) The platinum content becomes 0.04 mass %.

(F-1) Adhesive agent represented by the following formula (13)

(F-2) Adhesive agent represented by the following formula (14)

(Example 1) 75 parts by mass of the aforementioned (A-1) was dissolved in xylene, and 25 parts by mass of the aforementioned (B-1) and 0.1 part by mass of dibutylhydroxytoluene were mixed. A viscous liquid was obtained by distilling off xylene under the reduced pressure condition of 90 degreeC and 10 mmHg or less of the obtained liquid mixture. 100 parts by mass of the viscous liquid were mixed with 3.4 parts by mass of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, ethynylmethyldecylcarbitol 1 mass part, and 18.8 mass parts of said (C-1), and the transparent liquid mixture was obtained. To this liquid mixture, the above-mentioned (E-1) was added in an amount of 12 ppm in terms of the mass of platinum relative to the total of (A-1), (B-1) and (C-1), and the above-mentioned (F- 1) 2.4 parts by mass, 1 part by mass of the above (F-2), 12 parts by mass of REOLOSIL DM30S (manufactured by TOKUYAMA), and 0.4 part by mass of the above (D) were further stirred and mixed to prepare a silicone resin composition. The molar ratio represented by {total of SiH groups in component (C-1) above}/{total of Si-vinyl groups in component (A-1) and component (B-1)} of this composition is 1.0.

(Example 2) Except in Example 1, 25 parts by mass of the aforementioned (B-2) was used instead of 25 parts by mass of the aforementioned (B-1), and 12 parts by mass of the aforementioned (C-2) was used instead of the aforementioned (C-2) -1) A silicone resin composition was prepared in the same procedure as in Example 1 except for 18.8 parts by mass. The molar ratio represented by {the sum of SiH groups in the aforementioned (C-2) component}/{the sum of the Si-vinyl groups in the aforementioned (A-1) component and the aforementioned (B-1) component} of this composition is 1.0.

(Comparative Example 1) 75 parts by mass of the aforementioned (A-2) were dissolved in xylene, and 25 parts by mass of the aforementioned (B-3) were mixed. A viscous liquid was obtained by distilling off xylene from the obtained liquid mixture at 90 degreeC and 10 mmHg or less under reduced pressure. 100 parts by mass of the viscous liquid were mixed with 3.4 parts by mass of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, ethynylmethyldecylcarbitol 1 mass part and the said (C-1) 15 mass parts, and the transparent liquid mixture was obtained. To this liquid mixture, 12 ppm of (E-2) was added based on the total of (A-2), (B-3) and (C-1) in terms of the mass of platinum, and the above (F) was further stirred and mixed. -1) 2.4 parts by mass, 1 part by mass of the aforementioned (F-2), 7 parts by mass of REOLOSIL DM30S (manufactured by TOKUYAMA), and 0.4 part by mass of the aforementioned (D) to prepare a silicone resin composition. The molar ratio represented by {the total of SiH groups in the aforementioned (C-1) component}/{the total of Si-vinyl groups in the aforementioned (A-2) component and the aforementioned (B-3) component} of this composition is 1.0.

(Comparative Example 2) A silicone resin composition was prepared in the same procedure as in Example 2, except that the component (D) was not added. The molar ratio represented by {the sum of SiH groups in the aforementioned (C-2) component}/{the sum of the Si-vinyl groups in the aforementioned (A-1) component and the aforementioned (B-1) component} of this composition is 1.0.

(Comparative Example 3) Except in Example 1, 50 parts by mass of the aforementioned (A-1), 50 parts by mass of the aforementioned (B-1) were used, and 9.7 parts by mass of the aforementioned (C-2) were used instead of the aforementioned (C- 1) A silicone resin composition was prepared by the same procedure as in Example 1 other than 18.8 parts by mass. The molar ratio represented by {the sum of SiH groups in the aforementioned (C-2) component}/{the sum of the Si-vinyl groups in the aforementioned (A-1) component and the aforementioned (B-1) component} of this composition is 1.0.

於上述表1中，E-1、E-2以外的單元為質量份。The blending amounts of the respective components of the compositions in Examples and Comparative Examples are shown in Table 1 together.

In Table 1 above, units other than E-1 and E-2 are parts by mass.

The compositions obtained in Examples and Comparative Examples were evaluated as follows, and Table 2 shows the results.

[Hardness] The hardness was measured according to JIS K6253 with a durometer D type manufactured by Ueshima Seisakusho for a cured product with a thickness of 2 mm produced by heating the obtained silicone resin composition in a hot air circulating oven at 150°C for 2 hours.

[Adhesion (Adhesion Strength)] A test piece for an adhesive test as shown in FIG. 1 was produced. That is, two sheets of alumina ceramic substrates 11 and 12 (manufactured by KDS Corporation, width 25 mm × depth 50 mm × thickness 1 mm) overlapped by 5 mm at the ends, sandwiched the obtained silicone resin composition with a thickness of 1 mm, and placed them at 150 mm. The silicone resin composition is hardened by heating at ℃ for 2 hours, and the cured product 13 made of the silicone resin composition is bonded (bonding area 25mm×5mm=125mm ² ) and consists of two alumina ceramic substrates 's test piece.

The ends of the alumina ceramic substrates 11 and 12 of this test piece were stretched in opposite directions (arrow directions in FIG. 1 ) using a tensile tester (Autograph, manufactured by Shimadzu Corporation) at a tensile speed of 50 mm/min. , and obtain the bonding strength (MPa) per unit area.

As shown in Table 2, regarding the silicone resin composition for die bonding of the present invention (Examples 1 and 2), it can be seen that the obtained cured products have high hardness and excellent adhesive force. On the other hand, in Comparative Example 1 in which the component (A) does not have a CH ₂ =CH-COO-(CH ₂ ) _n - group and a CH ₂ =C(CH ₃ )-COO-(CH ₂ ) _n - group, although It is a hard composition, but results in poor adhesion. As for the comparative example 2, it shows that since the organic peroxide of (D) component was not used, both hardness and adhesive force were remarkably reduced, and the reliability as a die-bonding material was low. In Comparative Example 3, as the ratio of the component (A) decreased, the hardness decreased as a result, and CH ₂ =CH-COO-(CH ₂ ) _n -group and CH ₂ =C(CH ₃ )-COO-(CH ₂ ) The content of _n -groups decreases and the adhesive force decreases.

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

11. 12‧‧‧Alumina ceramic substrate 13‧‧‧hardened product of silicone resin composition

FIG. 1 is a view of a test piece for a subsequent test produced using the compositions obtained in Examples and Comparative Examples.

Claims (6)

A silicone resin composition for solid crystal, which is characterized by containing: (A) a three-dimensional network organopolysiloxane resin that is waxy or solid at 23° C. represented by the following average structural formula (1): relatively (R ² ₃ SiO _1/2 ) _a (R ¹ R ² ₂ SiO _1/2 ) _b (R ¹ R ) based on 100 parts by mass of the total of the (A) component and the following (B) component: (R 2 3 SiO 1/2 ) ² SiO) _c (R ² ₂ SiO) _d (R ¹ SiO _3/2 ) _e (R ² SiO _3/2 ) _f (R ³ SiO _3/2 ) _g (SiO _4/2 ) _h (1) [Formula In (1), R ¹ represents an alkenyl group with 2 to 10 carbon atoms, R ² represents a halogen atom-substituted monovalent hydrocarbon group with 1 to 12 carbon atoms, and R ³ represents CH ₂ =CH-COO-(CH ₂ ) _n -base or CH ₂ =C(CH ₃ )-COO-(CH ₂ ) _n -base; n is an integer from 0 to 20; and, a, b, c, d , e, f, g and h are numbers satisfying a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, g>0, h≧0, respectively, only b+c+ e>0, and is a number satisfying a+b+c+d+e+f+g+h=1] (B) 1 molecule has a vinyl group, CH ₂ =CH-COO-(CH ₂ ) _m - Linear organopolysiloxane (m is an integer of 0 to 20) among groups and one or more of CH ₂ =C(CH ₃ )-COO-(CH ₂ ) _m - groups: relative to component (A) 10 to 40 parts by mass in total of 100 parts by mass with (B) component; (C) Organosilicon compound having two or more hydrogen atoms bonded to silicon atoms in one molecule: {(C) The total amount of SiH groups in component The molar ratio shown in }/{the sum of alkenyl groups in (A) component and (B) component} is 0.2 to 5.0; (D) organic peroxide: relative to the organopolysilicon of (A) component The total amount of the oxane resin and the organopolysiloxane of the component (B) is 0.01 to 5 parts by mass in 100 parts by mass; (E) platinum group metal catalyst: relative to the total mass of the components (A) to (C) , 0.1 to 1,000 ppm in terms of the mass of platinum group metal elements. The silicone resin composition for die bonding according to claim 1, wherein R ³ of the component (A) is a CH ₂ =C(CH ₃ )-COO-(CH ₂ ) ₃ - group. The silicone resin composition for die bonding according to claim 1 or claim 2, wherein the component (B) has one or more CH ₂ =C(CH ₃ )-COO-(CH ₂ ) _m − base (m is the same as above). The silicone resin composition for solid crystal according to claim 1 or claim 2, wherein the component (D) is an organic peroxide represented by the following formula (2):

A die-bonding material, which is composed of the silicon-oxygen resin composition for die-bonding according to any one of claim 1 to claim 4. An optical semiconductor device characterized by having a cured product obtained by curing the die-bonding material according to claim 5.

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