TWI798500B - Addition-curing polysiloxane resin composition, cured product thereof, and optical semiconductor device - Google Patents

Abstract

(B)下述式所表示之分枝狀有機聚矽氧烷、

(C)以下述式(3)表示，且1分子中具有至少2個SiH基的有機氫聚矽氧烷、

(上述式中，R¹ 、R³ 為不含烯基的一價烴基，R² 為烯基)、及 (D)鉑族金屬系觸媒。[Problem] To provide an addition-curable silicone resin composition capable of obtaining a cured product excellent in hardness and grain shear strength. [Solution] An addition-curable polysiloxane resin composition containing the following components: (A) a branched organopolysiloxane represented by the following formula,

(B) branched organopolysiloxane represented by the following formula,

(C) An organohydrogenpolysiloxane represented by the following formula (3) and having at least two SiH groups in one molecule,

(In the above formula, R ¹ and R ³ are monovalent hydrocarbon groups not containing alkenyl groups, and R ² is alkenyl groups), and (D) a platinum group metal-based catalyst.

Description

Addition-curing polysiloxane resin composition, cured product thereof, and optical semiconductor device

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

Recently, encapsulants and die-attach materials for light-emitting diode (hereinafter referred to as "LED") elements use polysiloxane resins with good durability because the brightness of LED elements increases and the heat generation of the elements increases (Patent Documents 1 and 2 ). Especially in the die-bonding material, if the resin is too soft, the wire bonding step after the die-bonding step will lead to an undesired situation that bonding cannot be performed, so a high-hardness die-bonding material is required.

In addition, due to the progress in miniaturization of LED devices in recent years, a die-attach material with higher adhesion is required. Insufficient adhesive force of the die-bonding material will lead to fatal problems on the manufacturing side such as chip peeling in the wire bonding step of LED manufacturing. So far, although polysiloxane bonding crystal materials have excellent durability, their adhesion is insufficient, and materials with higher grain shear strength are required. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2006-342200 [Patent Document 2] Japanese Unexamined Patent Publication No. 2010-285571

[Problem to be Solved by the Invention]

The present invention was made in consideration of the above circumstances, and an object of the present invention is to provide an addition-curable silicone resin composition capable of obtaining a cured product excellent in hardness and grain shear strength. [Means to solve the problem]

(式中，R¹ 為各自可相同或相異的不含烯基的取代或未取代之一價烴基，R² 為各自可相同或相異的烯基。a，b，c，d各自為符合a≧0、b≧0，c≧0及d≧0的數，但是，為符合a+b＞0、b+c＞0、c+d＞0，且a+b+c+d=1的數。) (B)以下述平均組成式(2)表示之分枝狀有機聚矽氧烷：相對於(A)成分及(B)成分的合計100質量份為60～90質量份、

(式中，R¹ 及R² 同前述。e，f，g，h，i，j，k各自為符合e≧0、f≧0，g≧0、h≧0、i≧0，j≧0及k≧0的數，但是，符合f+g+i＞0、i+j+k＞0且e+f+g+h+i+j+k=1的數。) (C)以下述平均組成式(3)表示，且1分子中具有至少2個鍵結於矽原子的氫原子的有機氫聚矽氧烷、

(式中，R³ 為各自可相同或相異的不含烯基的取代或未取代之一價烴基，l及m為符合0.7≦l≦2.1、0.001≦m≦1.0且0.8≦l+m≦3.0的數。) 及 (D)鉑族金屬系觸媒 的加成硬化型聚矽氧樹脂組成物。In order to solve the above-mentioned problems, the present invention provides: (A) a branched organopolysiloxane represented by the following average composition formula (1) and having a viscosity at 25°C of 100 mPa·s or less,

(wherein, R ¹ is an alkenyl-free substituted or unsubstituted monovalent hydrocarbon group that may be the same or different, and R ² is an alkenyl that may be the same or different. a, b, c, and d are each Numbers satisfying a≧0, b≧0, c≧0 and d≧0, but satisfying a+b>0, b+c>0, c+d>0, and a+b+c+d= number of 1.) (B) Branched organopolysiloxane represented by the following average composition formula (2): 60 to 90 parts by mass with respect to 100 parts by mass of the total of components (A) and (B),

(In the formula, R ¹ and R ² are the same as above. e, f, g, h, i, j, k each meet e≧0, f≧0, g≧0, h≧0, i≧0, j≧ The number of 0 and k≧0, but the number that meets f+g+i>0, i+j+k>0 and e+f+g+h+i+j+k=1.) (C) Below An organohydrogenpolysiloxane represented by the average composition formula (3) and having at least 2 hydrogen atoms bonded to silicon atoms in one molecule,

(In the formula, ^R3 is a substituted or unsubstituted monovalent hydrocarbon group that does not contain an alkenyl group, which may be the same or different, and l and m meet the requirements of 0.7≦l≦2.1, 0.001≦m≦1.0 and 0.8≦l+m ≦3.0.) and (D) an addition-curable polysiloxane resin composition with a platinum group metal catalyst.

According to the addition-curable polysiloxane resin composition of the present invention, a cured product having excellent hardness and grain shear strength can be obtained.

In the present invention, more than 80 mol% of the aforementioned ^R1 and ^R3 are preferably methyl groups.

Such an addition-curable polysiloxane resin composition can obtain a cured product having excellent hardness and grain shear strength.

Also, in the present invention, it is preferable that a=c=0 in the component (A) in the aforementioned composition.

Such an addition-curable polysiloxane resin composition can obtain a cured product having excellent hardness and grain shear strength.

Also, the present invention provides a cured silicone product of a cured product of the above-mentioned addition-curable silicone resin composition.

Such a polysiloxane cured product can be used as a composition with excellent hardness and grain shear strength, high adhesion to substrates, LED chips, etc., especially as an adhesive material for die bonding of LED elements.

Furthermore, the present invention provides an optical semiconductor device in which an optical semiconductor element is grain-bonded with the above-mentioned cured silicone.

In such an optical semiconductor device, the above-mentioned polysiloxane cured product is used as a die-attach material with excellent hardness and grain shear strength, and high adhesion to substrates and LED chips, so it is highly reliable. [Effect of Invention]

As mentioned above, if it is the addition-curable polysiloxane resin composition of the present invention, a polysiloxane cured product with excellent hardness and grain shear strength can be obtained, and it can be used as a die-bonding material for die bonding of LED elements, etc. . Next, in the wire bonding step performed after the die-bonding step, undesired situations such as peeling of the wafer or inability to bond hardly occur, the optical semiconductor device in which the optical semiconductor element is grain-bonded with the polysiloxane cured product has high reliability, Its productivity is also improved. [Best Mode for Carrying Out the Invention]

As mentioned above, it is necessary to develop a polysiloxane composition capable of obtaining a cured product having excellent hardness and grain shear strength, and a polysiloxane cured product which can be used as a die bonding material for LED devices and the like.

As a result of diligently examining the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using an addition-curable polysiloxane composition containing components (A), (B), (C), and (D) described later. Complete the present invention.

(式中，R¹ 為各自可相同或相異的不含烯基的取代或未取代之一價烴基，R² 為各自可相同或相異的烯基。a，b，c，d各自為符合a≧0、b≧0，c≧0及d≧0的數，但是，為符合a+b＞0、b+c＞0、c+d＞0，且a+b+c+d=1的數。) (B)以下述平均組成式(2)表示之分枝狀有機聚矽氧烷：相對於(A)成分及(B)成分的合計100質量份為60～90質量份、

(式中，R¹ 及R² 同前述。e，f，g，h，i，j，k各自為符合e≧0、f≧0，g≧0、h≧0、i≧0，j≧0及k≧0的數，但是，符合f+g+i＞0、i+j+k＞0且e+f+g+h+i+j+k=1的數。) (C)以下述平均組成式(3)表示，且1分子中具有至少2個鍵結於矽原子的氫原子的有機氫聚矽氧烷、

(式中，R³ 為各自可相同或相異的不含烯基的取代或未取代之一價烴基，l及m為符合0.7≦l≦2.1、0.001≦m≦1.0且0.8≦l+m≦3.0的數。) 及 (D)鉑族金屬系觸媒 的加成硬化型聚矽氧樹脂組成物。That is, the present invention contains: (A) a branched organopolysiloxane represented by the following average composition formula (1) and having a viscosity at 25°C of 100 mPa･s or less,

(wherein, R ¹ is an alkenyl-free substituted or unsubstituted monovalent hydrocarbon group that may be the same or different, and R ² is an alkenyl that may be the same or different. a, b, c, and d are each Numbers satisfying a≧0, b≧0, c≧0 and d≧0, but satisfying a+b>0, b+c>0, c+d>0, and a+b+c+d= number of 1.) (B) Branched organopolysiloxane represented by the following average composition formula (2): 60 to 90 parts by mass with respect to 100 parts by mass of the total of components (A) and (B),

(In the formula, R ¹ and R ² are the same as above. e, f, g, h, i, j, k each meet e≧0, f≧0, g≧0, h≧0, i≧0, j≧ The number of 0 and k≧0, but the number that meets f+g+i>0, i+j+k>0 and e+f+g+h+i+j+k=1.) (C) Below An organohydrogenpolysiloxane represented by the average composition formula (3) and having at least 2 hydrogen atoms bonded to silicon atoms in one molecule,

(In the formula, ^R3 is a substituted or unsubstituted monovalent hydrocarbon group that does not contain an alkenyl group, which may be the same or different, and l and m meet the requirements of 0.7≦l≦2.1, 0.001≦m≦1.0 and 0.8≦l+m ≦3.0.) and (D) an addition-curable polysiloxane resin composition with a platinum group metal catalyst.

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

[Addition hardening polysiloxane composition] The addition-curable polysiloxane composition of the present invention contains components (A) to (D) described later. Each component will be described in detail below.

＜(A)Ingredient＞ Component (A) is a branched organopolysiloxane represented by the following average composition formula (1), which is used to increase the strength of the cured product of the composition and to increase the bonding strength, that is, the grain shear strength.

(式中，R¹ 為各自可相同或相異的不含烯基的取代或未取代之一價烴基，R² 為各自可相同或相異的烯基。a，b，c，d各自為符合a≧0、b≧0，c≧0及d≧0的數，但是，為符合a+b＞0、b+c＞0、c+d＞0，且a+b+c+d=1的數。)

(wherein, R ¹ is an alkenyl-free substituted or unsubstituted monovalent hydrocarbon group that may be the same or different, and R ² is an alkenyl that may be the same or different. a, b, c, and d are each Numbers satisfying a≧0, b≧0, c≧0 and d≧0, but satisfying a+b>0, b+c>0, c+d>0, and a+b+c+d= number of 1.)

The viscosity of component (A) measured by a rotational viscometer at 25°C is 100mPa･s or less, preferably 30mPa･s or less. When it exceeds 100 mPa･s, there is a problem that the viscosity of the composition becomes high, and the stampability deteriorates. In addition, unless there is a particular limitation in the following, the viscosity is a value measured by a rotational viscometer at 25°C.

The substituted or unsubstituted monovalent hydrocarbon group not containing an alkenyl group represented by R ¹ is not particularly limited if it does not have an alkenyl group, but is preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Examples of the monovalent hydrocarbon include alkyl groups such as methyl, ethyl, propyl, and butyl, cycloalkyl groups such as cyclohexyl, and cyclopentyl, and aryl groups such as phenyl, tolyl, and xylyl. , aralkyl groups such as benzyl and phenylethyl groups, halogenated hydrocarbon groups such as chloromethyl groups, chloropropyl groups, and chlorocyclohexyl groups, etc. An alkyl group is preferred, and a methyl group is particularly preferred.

The alkenyl group represented by ^R2 is not particularly limited, but is preferably an alkenyl group having 2 to 10, especially 2 to 6 carbons, such as vinyl, allyl, and ethynyl, especially vinyl.

(A)成分可一種單獨使用亦可二種以上併用。(A) As a specific example of a component, what is represented by the following formula etc. are mentioned, for example.

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

(式中，R¹ 及R² 同前述。e，f，g，h，i，j，k各自為符合e≧0、f≧0，g≧0、h≧0、i≧0，j≧0及k≧0的數，但是，符合f+g+i＞0、i+j+k＞0且e+f+g+h+i+j+k=1的數。)<(B) component> (B) component is a branched organopolysiloxane represented by the following average composition formula (2).

(In the formula, R ¹ and R ² are the same as above. e, f, g, h, i, j, k each meet e≧0, f≧0, g≧0, h≧0, i≧0, j≧ 0 and k ≧ 0, however, the number that meets f+g+i>0, i+j+k>0 and e+f+g+h+i+j+k=1.)

R ¹ may be, for example, the same ones as those exemplified for the above-mentioned (A) component, preferably an alkyl group, particularly preferably a methyl group.

R ² can be, for example, the same ones as those exemplified in the above-mentioned (A) component, preferably an alkenyl group having 2 to 10 carbons, more preferably an alkenyl group having 2 to 6 carbons, particularly preferably a vinyl group.

In the above average composition formula (2), e is 0-0.65, f is 0-0.65, g is 0-0.5, h is 0-0.5, i is 0-0.8, j is 0-0.8, and k is 0-0. The number of 0.6 is better. Also, f+g+i is preferably 0.1 to 0.8, especially preferably 0.2 to 0.65, and i+j+k is preferably 0.05 or more, more preferably 0.1 to 0.9, especially preferably 0.2 to 0.6.

In the component (B), the content of the alkenyl group bonded to the silicon atom is preferably in the range of 0.01 to 1 mol, more preferably in the range of 0.05 to 0.5 mol, per 100 g of the component (B). If it is in the range of 0.01 to 1 mol, the crosslinking reaction will fully proceed, and a cured product with higher hardness can be obtained.

The organopolysiloxane of the component (B) preferably has a weight average molecular weight of 500 to 100,000 from the viewpoint of ease of separation.

The organopolysiloxane of the component (B) is a component for obtaining reinforcement of a cured product, and has a branched structure. The organopolysiloxane of component (B) must have a branched structure composed of SiO _4/2 units and/or SiO _3/2 units, but may further contain methyl vinyl siloxy units, dimethyl siloxy SiO _2/2 (SiO) units, such as SiO 2/2 (SiO) units, SiO _1/2 units such as dimethylvinylsiloxy units, and trimethylsiloxy units. The content of SiO _4/2 unit and/or SiO _3/2 unit is preferably at least 5 mol % of the total siloxane unit in the organopolysiloxane resin of component (B), more preferably 10 mol ～90 mol%, especially preferably 20～60 mol%.

The compounding quantity of (B) component is 60-90 mass parts with respect to the total 100 mass parts of (A) component and (B) component, Preferably it is 65-80 mass parts, More preferably, it is 65-75 mass parts share. When the blending amount of the component (B) is less than 60 parts by mass, the adhesiveness may be poor and a hardened product with high hardness may not be obtained. If it exceeds 90 parts by mass, the viscosity of the composition becomes significantly high and transfer becomes difficult, and the Handling becomes difficult when the composition is used for bonding crystal materials, etc.

(B)成分可一種單獨使用亦可二種以上併用。(B) Specific examples of the branched organopolysiloxane of the component include the following.

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

＜(C)Ingredient＞ (C)component is used as a crosslinking agent which crosslinks the alkenyl group contained in (A) component and (B)component by hydrosilylation reaction. The component (C) is an organohydrogenpolysiloxane represented by the following average composition formula (3) and having at least two hydrogen atoms (Si—H groups) bonded to silicon atoms in one molecule.

(式中，R³ 為各自可相同或相異的不含烯基的取代或未取代之一價烴基，l及m為符合0.7≦l≦2.1、0.001≦m≦1.0且0.8≦l+m≦3.0、較佳為1.0≦l≦2.0、0.01≦m≦1.0且1.5≦l+m≦2.5的數。)

(In the formula, ^R3 is a substituted or unsubstituted monovalent hydrocarbon group that does not contain an alkenyl group, which may be the same or different, and l and m meet the requirements of 0.7≦l≦2.1, 0.001≦m≦1.0 and 0.8≦l+m ≦3.0, preferably 1.0≦l≦2.0, 0.01≦m≦1.0 and 1.5≦l+m≦2.5.)

The viscosity of the component (C) at 25°C is not particularly limited, but is preferably not more than 100 mPa·s, more preferably in the range of 5 to 100 mPa·s.

R ³ can be exemplified by the same ones as R ¹ in the above-mentioned component (A), preferably an alkyl group, particularly preferably a methyl group.

Also, in the composition of the present invention, the number of methyl groups occupied in the total number of all monovalent hydrocarbon groups bonded to silicon atoms other than the alkenyl groups represented by ^R1 and ^R3 is more than 80 mole % (that is, the aforementioned R In ¹ and ^R3 , more than 80 mole % is methyl group), especially if more than 90 mole %, heat resistance, light resistance (ultraviolet resistance), and discoloration caused by heat and ultraviolet stress, etc. are deteriorated Excellent durability.

The component (C) has at least 2 hydrogen atoms (i.e. Si-H groups) bonded to silicon atoms in one molecule, preferably 2 to 200, more preferably 3 to 100, most preferably 4 to 50 indivual.

(C) The molecular structure of the organohydrogen polysiloxane can be linear, cyclic, branched, or three-dimensional network structure, but the number of silicon atoms in one molecule is preferably 2- 300, more preferably 3 to 200.

(式中，R³ 同前述，r為2～40、較佳為8～35的整數，s為6～8的整數。)(C) As for the organohydrogenpolysiloxane of the component, for example, 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, ref. (Hydrodimethylsiloxy)methylsilane, ginseng(hydrogendimethylsiloxy)phenylsilane, methylhydrocyclopolysiloxane, methylhydrogensiloxane･dimethylsiloxane ring Copolymer, two-terminal trimethylsiloxy-blocked chain methylhydrogen polysiloxane, two-terminal trimethylsiloxy-blocked chain dimethylsiloxane・methylhydrogen siloxane copolymer, two-terminal Dimethylhydrogensiloxy-blocked chain dimethyl polysiloxane, two-terminal dimethylhydrogensiloxy-blocked chain methylhydrogenpolysiloxane, two-terminal dimethylhydrogensiloxy-blocked chain dimethyl Siloxane・Methylhydrogensiloxane Copolymer, Both-terminal Trimethylsiloxy-blocked Methylhydrogensiloxane・Diphenylsiloxane Copolymer, Both-terminal Trimethylsiloxy-blocked Chain Hydrogen siloxane・diphenylsiloxane・dimethylsiloxane copolymer, trimethylsiloxy blocked chain methylhydrogensiloxane・methylphenylsiloxane・dimethylsiloxane at both ends Siloxane copolymer, two-terminal dimethylhydrogen siloxy blocked chain methylhydrogen siloxane, dimethyl siloxane, diphenyl siloxane copolymer, two-terminal dimethyl hydrogen siloxy blocked Chain methylhydrogensiloxane・dimethylsiloxane・methylphenylsiloxane copolymer, (CH ₃ ) ₂ HSiO _1/2 unit and (CH ₃ ) ₃ SiO _1/2 unit and SiO _{4/ 2} units of copolymers, (CH ₃ ) ₂ HSiO _1/2 units and SiO _4/2 units of copolymers, (CH ₃ ) ₂ HSiO _1/2 units and SiO _4/2 units and (C ₆ In addition to copolymers composed of H ₅ ) ₃ SiO _1/2 units, those represented by the following general formula (4) or (5) can also be mentioned.

(In the formula, ^R3 is the same as above, r is an integer of 2 to 40, preferably 8 to 35, and s is an integer of 6 to 8.)

(式中，r同前述。Me為甲基。) 下述式所表示者等。

(式中，括弧內的矽氧烷單位的排列順序為任意。) (C)成分的有機氫聚矽氧烷可一種單獨使用或二種以上併用。Specific examples of the component (C) include those represented by the following general formula (6),

(In the formula, r is the same as above. Me is a methyl group.) Those represented by the following formula, etc.

(In the formula, the arrangement order of the siloxane units in parentheses is arbitrary.) The organohydrogenpolysiloxane of the component (C) may be used alone or in combination of two or more.

(C) The blending amount of component From the point of view of crosslinking balance, relative to the total number of alkenyl groups bonded to silicon atoms in (A) and (B) components, the number of alkenyl groups bonded to silicon atoms in (C) component The number of hydrogen atoms (Si—H groups) of silicon atoms is preferably 0.5 to 5.0 times, more preferably 0.7 to 3.0 times. If it is such a range, crosslinking will fully progress, and the hardened|cured material excellent in hardness will be obtained.

＜(D)Ingredient＞ (D) The platinum group metal-based catalyst of the component is a component for performing and promoting the hydrosilylation reaction of the aforementioned (A) to (C) components.

Platinum group metal catalysts are not particularly limited, and examples include platinum group metals such as platinum, palladium, and rhodium; chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefins, and vinyl siloxane Platinum compounds such as coordination compounds of acetylene compounds, platinum group metal compounds such as tetrakis (triphenylphosphine) palladium, chloroquine (triphenylphosphine) rhodium, etc., but because of the combination of (A) ~ (C) It has good compatibility and hardly contains chlorine impurities, preferably chloroplatinic acid modified with polysiloxane. (D) A component may be used individually by 1 type, and may use 2 or more types together.

The blending amount of the component (D) may be an effective amount as a catalyst, but relative to the total of the components (A) to (C), it is preferably 1 to 500 ppm in terms of mass conversion of platinum group metal elements, more preferably 3-100 ppm, more preferably 5-40 ppm. When the blending amount is appropriate, the hydrosilylation reaction can be promoted more effectively.

＜Other ingredients＞ In addition to the above-mentioned (A)-(D) components, the composition of this invention can also mix the other components illustrated below.

Reaction Inhibitors: In the composition of the present invention, a conventionally known reaction inhibitor (reaction control agent) of a compound having a hardening inhibitory effect on the addition reaction catalyst of the component (D) may be used as necessary. As for the reaction inhibitor, phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine or tetramethylethylenediamine, benzotriazole, etc.; sulfur-containing compounds; acetylene compounds; Hydroperoxide compounds; maleic acid derivatives, etc.

The degree of the hardening inhibitory effect by the reaction inhibitor varies greatly depending on the chemical structure of the reaction inhibitor, so it is better to adjust the blending amount of the reaction inhibitor to the optimum amount of each reaction inhibitor used. Usually, 0.001-5 mass parts is preferable with respect to a total of 100 mass parts of (A) component, (B) component, (C) component, and (D)component.

Adherence enhancer: In this composition, in order to improve the adhesiveness to the resin, an adhesiveness improving agent can be added. As for the adhesion improving agent, from the viewpoint of imparting self-adhesiveness to the addition reaction hardening type composition of the present invention, organosilicon compounds such as silane and siloxane containing functional groups imparting adhesiveness, non-polymeric compounds, etc. can be used. Silicone-based organic compounds, etc.

Specific examples of functional groups that impart adhesiveness include alkenyl groups such as vinyl and allyl groups bonded to silicon atoms, and hydrogen atoms; epoxy groups bonded to silicon atoms through carbon atoms (such as γ- Glycidoxypropyl, β-(3,4-epoxycyclohexyl)ethyl, etc.) or acryloxy (such as γ-acryloxypropyl, etc.) or methacryloxy ( For example, γ-methacryloxypropyl group, etc.); alkoxysilyl group (for example, it can contain 1 to 2 ester structures, urethane structures, and ether structures that are bonded to silicon atoms through alkylene groups alkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, methyldimethoxysilyl, etc.) etc.

Organosilicon compounds containing functional groups that impart adhesion, such as silane coupling agents, siloxanes with alkoxysilyl groups and organic functional groups, and alkoxysilyl groups introduced into organic compounds with reactive organic groups compounds etc.

As for the non-polysiloxane-based organic compound, for example, allyl organic acid, epoxy-based ring-opening catalyst, organic titanium compound, organic zirconium compound, organic aluminum compound, and the like.

Organic peroxides: In the present invention, the strength of the resin can be further improved by adding an organic peroxide.

In terms of organic peroxides, for example, benzoyl peroxide, t-butyl perbenzoate, o-methylbenzoyl peroxide, p-methylbenzoyl peroxide, di Cumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,3-trimethylcyclohexane, bis(4-methylbenzoylperoxy) Hexamethylene biscarbonate, etc. An effective amount is sufficient, but usually 0.01 to 5 parts by mass, especially 0.05 to 3 parts by mass, relative to 100 parts by mass of the total organopolysiloxane of components (A)･(B). These can be used individually by 1 type or in combination of 2 or more types.

Filling agent: The composition of the present invention can be filled with inorganic fillers such as crystalline silica, hollow fillers, and silsesquioxane, and these fillers can be filled with organic alkoxysilane compounds, organochlorosilane compounds, organic Silicone compounds such as silazane compounds, low-molecular-weight siloxane compounds, etc., fillers for surface hydrophobization treatment; polysiloxane rubber powder, polysiloxane resin powder, etc. In terms of this component, it is particularly preferable to use a filler that can impart thixotropy. By imparting thixotropy, a cured product that is excellent in workability and grain shear strength can be obtained.

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

Also, since the workability of the die bonding (transfer method) becomes better, the viscosity of the addition-curable polysiloxane resin composition of the present invention is preferably 5 to 100 Pa･s at 25°C, more preferably 20 to 100 Pa·s. 50Pa･s.

[hardened object] Furthermore, the present invention provides a cured product of an addition-curable polysiloxane composition. The curing of the addition-curable polysiloxane composition of the present invention can be carried out under conventional conditions. For example, it can be cured at 100-180° C. for 10 minutes to 5 hours.

The cured product of the addition-curable polysiloxane composition of the present invention can be used as a composition with high adhesion to substrates and LED chips, especially as a die-bonding material for die bonding of LED devices and the like. As mentioned above, according to the cured polysiloxane of the present invention, it can be used as an adhesive with high adhesion to substrates and LED chips.

[Optical semiconductor device] Furthermore, the present invention provides an optical semiconductor device in which an optical semiconductor element is die-bonded with the above-mentioned cured silicone.

As an example of the method of die-bonding optical semiconductor elements using the composition of the present invention, for example, filling a syringe with the composition of the present invention, using a dispenser, and placing it on a substrate such as a package in a dry state to a thickness of 5 to 100 μm After coating in a manner of a certain thickness, arrange an optical semiconductor element (such as a light-emitting diode) on the coated composition, and harden the composition to bond the optical semiconductor element crystal grains to the substrate. It is also possible to load the composition on a spatula pan, and apply it on the substrate so that the thickness of the applied dry state becomes 5 to 100 μm by punching while using the spatula, and arrange it on the coated composition. The optical semiconductor element is a method of bonding the optical semiconductor element crystal grains to the substrate by curing the composition. The hardening conditions of the composition can be the same as above. Thus, a highly reliable optical-semiconductor device in which an optical-semiconductor element is grain-bonded with the polysiloxane cured product of the present invention can be manufactured.

[Example]

The present invention will be specifically described below using examples and comparative examples, but these do not limit the present invention in any way. In addition, molecular weight is the weight average molecular weight of standard polystyrene conversion of the colloid permeation chromatography (GPC). The viscosity at 25°C is the measured value of the rotational viscometer. In addition, the meaning of the abbreviation of each siloxane unit is as follows.

[Synthesis Example 1] In a 1,000 mL 4-necked flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer, [(CH ₃ )(CH ₃ O) ₂ SiO _1/2 ] ₂ [(CH ₃ ) ( 733 g of organopolysiloxane represented by CH ₃ O)SiO] ₂ , 528 g of 1,3-divinyltetramethyldisiloxane, and 170 g of isopropanol were added dropwise to 14.0 g of methanesulfonic acid while stirring. Then, 144 g of water was dripped, and it mixed and reacted at 65 degreeC for 2 hours. Furthermore, 7.0 g of baking soda was thrown in, and it mixed at 65 degreeC for 2 hours, and neutralized reaction was performed. The temperature was further raised to 85° C., and after the alcohol was removed in the process, it was cooled to room temperature. After cooling, wash with water, and concentrate under reduced pressure at 170°C･10mmHg for 1 hour to obtain a branched organopolysiloxane (A-1) with a viscosity of 17mPa･s, an average structure M ^Vi _0.47 T _0.53 , and a molecular weight of 3,500.

[Synthesis Example 2] In a 500 mL 4-neck flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer, 136 g of methyltrimethoxysilane, 93.2 g of 1,3-divinyltetramethyldisiloxane, 61.2 g of isopropanol was added dropwise to 3.0 g of methanesulfonic acid while stirring. Then, 28.9 g of water was dripped, and it mixed and reacted at 65 degreeC for 2 hours. Furthermore, 6.0 g of baking soda was added, and it mixed at 65 degreeC for 2 hours, and neutralization reaction was performed. The temperature was further raised to 85° C., and after the alcohol was removed in the process, it was cooled to room temperature. After cooling, wash with water, and concentrate under reduced pressure at 170°C･10mmHg for 1 hour to obtain a branched organopolysiloxane (A-2) with a viscosity of 17mPa･s, an average structure M ^Vi _0.5 T _0.5 , and a molecular weight of 1,320.

[Synthesis Example 3] In a 500 mL 4-necked flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer, 150.0 g of vinyltrimethoxysilane, 93 g of 1,3-divinyltetramethyldisiloxane, 60.8 g of isopropanol was added dropwise to 2.9 g of methanesulfonic acid while stirring. Then, 30.6 g of water was dripped, and it mixed and reacted at 65 degreeC for 2 hours. Furthermore, 5.8 g of baking soda was added, and it mixed at 65 degreeC for 2 hours, and neutralization reaction was performed. The temperature was further raised to 85° C., and after the alcohol was removed in the process, it was cooled to room temperature. After cooling, wash with water, and concentrate under reduced pressure at 170°C･ _10mmHg ^for 1 hour to obtain a branched organopolysiloxane ( ^A _- 3 ).

[Comparative Synthesis Example 1] In a 500 mL 4-necked flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer, 136 g of methyltrimethoxysilane, 45 g of 1,3-divinyltetramethyldisiloxane, 45.2 g of isopropanol was added dropwise to 2.2 g of methanesulfonic acid while stirring. Then, 28.4 g of water was dripped, and it mixed and reacted at 65 degreeC for 2 hours. Furthermore, 4.4 g of baking soda was added, and it mixed at 65 degreeC for 2 hours, and neutralization reaction was performed. The temperature was further raised to 85° C., and after the alcohol was removed in the process, it was cooled to room temperature. After cooling, wash with water, and concentrate under reduced pressure at 170°C･10mmHg for 1 hour to obtain a branched organopolysiloxane (A-5) with a viscosity of 153mPa･s, an average structure M ^Vi _0.32 T _0.68 , and a molecular weight of 9,730 .

[Synthesis Example 4] The reaction product of hexachloroplatinic acid and 1,3-divinyltetramethyldisiloxane was prepared with a viscosity of 60mPa･s and M ^Vi ₂ D so that the platinum content was 0.004% by mass. The linear dimethyl polysiloxane represented by ₄₀ was diluted to prepare a platinum catalyst (D).

[Examples 1 to 3, Comparative Examples 1 and 2] The following components were mixed in the blending amounts shown in Table 1 to prepare an addition-curable polysiloxane composition. In addition, the numerical value of each component in Table 1 represents a mass part. The [Si-H]/[Si-Vi] value is relative to the total number of alkenyl groups bonded to silicon atoms in (C) component and silicon atom in component (A) and (B) The ratio of the number of hydrogen atoms (Si-H groups) (molar ratio).

(A) Ingredients: (A-1) Branched organopolysiloxane obtained in Synthesis Example 1 (A-2) Branched organopolysiloxane obtained in Synthesis Example 2 (A-3) Branched organopolysiloxane obtained in Synthesis Example 3

Comparative composition: (A-4) M ^Vi _0.167 D _0.833 (M ^Vi ₂ D ₁₀ ) is a linear organopolysiloxane whose both ends are blocked by vinyl groups (viscosity at 25°C: 8.7mPa･s) (A-5) Branched organopolysiloxane obtained in comparative synthesis example 1

(B)～(D) Components: (B) M ^Vi _0.064 M _0.398 Q _0.538 (M ^Vi _1.2 M _7.4 Q ₁₀ ) represents a branched organopolysilicon with a vinyl content of 0.085mol/100g relative to the solid content Oxane (C) M _0.037 D _0.266 D ^H _0.697 (M ₂ D _14.5 D ^H ₃₈ ) Methylhydropolysiloxane (D) The platinum catalyst obtained in Synthesis Example 4

Other ingredients: (E) Reaction inhibitor: 1-ethynyl cyclohexanol (F-1) Adhesion enhancer: Cyclic polysiloxane represented by D ^Vi ₄ (F-2) Adhesion enhancer: three Allyl isocyanurate (F-3) Adhesion enhancer: a compound represented by the following formula

The addition-curable silicone resin compositions obtained in Examples 1-3 and Comparative Examples 1 and 2 were evaluated as follows, and the results are shown in Table 2.

[hardness] The Type D hardness of the cured product obtained by pouring the composition into a mold to have a thickness of 2 mm and curing it at 150° C. for 4 hours was measured in accordance with JIS K6253. [Grain shear strength] Using a crystal bonder (ASM Corporation, AD-830), the composition was placed on the silver-plated electrode part of the SMD5050 package (I-CHIUN PRECSION INDUSTRY CO., resin part: polyphthalamide) to Quantitative transfer was performed by pressing, and an optical semiconductor element (manufactured by SemiLEDs, EV-B35A, 35mil) was mounted thereon. The produced package was heated in an oven at 150° C. for 2 hours to harden the composition, and then the grain shear strength was measured using an adhesion tester (manufactured by Dage, Series 4000).

As shown in Table 2, in Examples 1 to 3, any hardened product has excellent hardness and grain shear strength, and is suitable as a bonding crystal material. On the other hand, in Comparative Example 1, since the component (A) is a straight-chain organopolysiloxane, the crystal grain shear strength of the cured product was poor. Also, in Comparative Example 2, although the component (A) was a branched organopolysiloxane, its transferability was poor because of its high viscosity, and it was impossible to bond the die.

As mentioned above, the addition-curable polysiloxane resin composition of the present invention can obtain a polysiloxane cured product with excellent hardness and grain shear strength, and can be used especially as a die-bonding material for die bonding of optical semiconductor devices and the like. . In particular, due to this feature, in the wire bonding step after the die-bonding step, undesired situations such as chip peeling or non-bonding are less likely to occur, so the optical semiconductor device in which the optical semiconductor element is grain-bonded with the polysiloxane hardened material In addition to increasing the reliability, the productivity of the device is also improved. Therefore, the addition-curable silicone resin composition of the present invention and its cured product have high utility value in the technical field of optical semiconductor devices.

In addition, the present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are examples, and those having substantially the same structure as the technical idea described in the scope of claims of the present invention, and having the same function and effect are all included in the technical scope of the present invention.

Claims (5)

An addition-hardening polysiloxane resin composition is characterized in that it contains: (A) represented by the following average composition formula (1), and has a viscosity of 100mPa at 25°C. Branched organopolysiloxanes below s, (R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² SiO _3/2 ) _c (R ¹ SiO _3/2 ) _d (1) (In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group that does not contain alkenyl, which may be the same or different, R ² is an alkenyl that may be the same or different, a, b, c, d are each a number satisfying a≧0, b≧0, c≧0, and d≧0, however, it is a number satisfying a+b>0, b+c>0, c+d>0, and a+b +c+d=1 number) (B) branched organopolysiloxane represented by the following average composition formula (2): 60~ 90 parts by mass, (R ¹ ₃ SiO _1/2 ) _e (R ² R ¹ ₂ SiO _1/2 ) _f (R ² R ¹ SiO) _g (R ¹ ₂ SiO) _h (R ² SiO _3/2 ) _i (R ¹ SiO _3/2 ) _j (SiO _4/2 ) _k (2) (In the formula, R ¹ and R ² are the same as above, e, f, g, h, i, j, k are each in line with e≧0 , f≧0, g≧0, h≧0, i≧0, j≧0 and k≧0, but satisfy f+g+i>0, i+j+k>0 and e+f+ The number of g+h+i+j+k=1) (C) is represented by the following average composition formula (3), and an organohydrogenpolysiloxane having at least 2 hydrogen atoms bonded to a silicon atom in one molecule , R ³ ₁ H _m SiO _(4-lm)/2 (3) (wherein, R ³ is the same or different substituted or unsubstituted monovalent hydrocarbon groups that do not contain alkenyl, and l and m are in accordance with 0.7≦l≦2.1, 0.001≦m≦1.0 and 0.8≦l+m≦3.0) and (D) a platinum group metal-based catalyst, and, in the aforementioned (B) component, an alkenyl group bonded to a silicon atom The content of the component (B) is in the range of 0.01 to 1 mol per 100 g of the component (B), and the weight average molecular weight of the organopolysiloxane of the component (B) is in the range of 500 to 100,000. The addition-curable polysiloxane resin composition as described in claim 1, wherein more than 80 mol% of the aforementioned R ¹ and R ³ are methyl groups. The addition-curable polysiloxane resin composition according to claim 1 or claim 2, wherein, in the component (A) of the composition, a=c=0. A cured product of polysiloxane, which is a cured product of the addition-curable polysiloxane resin composition described in any one of claim 1 to claim 3. An optical semiconductor device, which is an optical semiconductor element bonded with polysiloxane hardened material as described in Claim 4.