TW202104378A - Silicone resin composition for die-bonding cured product light-emitting diode element and method for producing said composition - Google Patents

Abstract

[Problem] To provide a silicone resin composition for die bonding, which imparts high hardness to a cured product with little change in hardness and mass reduction under high temperature conditions. [Solution] The silicone resin composition for die bonding contains (A) a specific linear organopolysiloxane, (B) a specific branched organopolysiloxane, and (C) in a specific range of content. Specific organohydrogen polysiloxanes, (D) platinum group metal catalysts, and (E) specific polyorganometallic siloxanes containing Si-O-Ce bonds and Si-O-Ti bonds.

Description

Silicone resin composition for die bonding, cured product, light-emitting diode element, and manufacturing method of the composition

The present invention relates to a silicone resin composition for die bonding of light-emitting diode elements, a cured product, a light-emitting diode element, and a method for manufacturing the composition.

Silicone resins are used as packaging materials and die bonding materials for light-emitting diode (LED) elements (Patent Documents 1 and 2). Compared with conventional epoxy resins, silicone resins are superior in heat resistance, weather resistance, and discoloration resistance. In recent years, as the amount of electricity to the LED increases and the temperature around the LED components rises, silicone resins are used. In this case, the packaging material also deteriorates, cracks occur, or the light transmittance decreases due to discoloration. From such a background, in recent years, long-term reliability (ie, heat resistance) in high-temperature environments has been sought for packaging materials and die bonding materials for LED devices.

As an LED encapsulating material for improving heat resistance, it is disclosed that a silicone resin composition containing polyorganometallic siloxane is excellent in transparency, and imparts a cured product with little change in hardness and weight loss under high temperature conditions (Patent Documents 3 and 4) . However, especially in die bonding materials, if the resin is too soft, the wire bonding step performed after the die bonding step may lead to failure of bonding. Therefore, higher hardness die bonding materials are sought. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2004-186168 A [Patent Document 2] JP 2006-342200 A [Patent Document 3] JP 2017-88776 A [Patent Document 4] Japanese Patent Application Publication No. 2018-184579

[The problem to be solved by the invention]

The present invention was made in order to solve the above-mentioned problems, and its object is to provide a silicone resin composition for die bonding, which imparts high hardness and has a hardened product with little change in hardness and mass reduction under high temperature conditions. [Means to solve the problem]

(式中，R¹ 獨立表示烯基，R² 獨立表示不含加成反應性碳-碳雙鍵之無取代或取代之1價烴基，惟，全R² 之至少80莫耳%為甲基，l、m、n、p、q、r及s，分別為滿足l≧0、m≧0、n≧0、p≧0、q≧0、r≧0及s≧0之數，惟，m+n+q＞0、q+r+s＞0，且為滿足l+m+n+p+q+r+s=1之數)； (C)下述平均組成式(2)所表示，1分子中具有至少2個SiH鍵之有機氫聚矽氧烷：相對於1個(A)成分及(B)成分中之鍵結於矽原子之烯基而言(C)成分中之SiH鍵成為0.5~5.0個的量，

(式中，R³ 獨立為不含加成反應性碳-碳雙鍵之無取代或取代的1價烴基，全R³ 之至少50莫耳%為甲基，a及b為0.7≦a≦2.1、0.001≦b≦1.0，且為滿足0.8≦a+b≦3.0之數)； (D)鉑族金屬系觸媒：相對於(A)~(C)成分之合計而言以金屬原子之質量換算成為1~500ppm的量； (E)含有Si-O-Ce鍵及Si-O-Ti鍵，Ce含量為50~ 5,000ppm，Ti含量為50~5,000ppm，且25℃下之黏度為10~ 10,000mPa・s之聚有機金屬矽氧烷：相對於(A)~(D)成分之合計100質量份而言為0.01~5質量份。In order to achieve the above-mentioned problems, the present invention provides a silicone resin composition for die bonding, which contains the following (A), (B), (C), (D) and (E), (A) having At least 2 alkenyl groups bonded to silicon atoms, linear organopolysiloxanes with a viscosity of less than 50mPa·s at 25°C; (B) The following average unit formula (1) is expressed at 25°C Wax-like or solid branched organopolysiloxane: The amount of (B) component is 50 to 90 parts by mass relative to 100 parts by mass of the total of (A) component and (B) component,

(In the formula, R ¹ independently represents an alkenyl group, R ² independently represents an unsubstituted or substituted monovalent hydrocarbon group without addition-reactive carbon-carbon double bonds, but at least 80 mole% of ^{all R 2 is methyl} , L, m, n, p, q, r, and s are the numbers satisfying l≧0, m≧0, n≧0, p≧0, q≧0, r≧0, and s≧0, respectively, but, m+n+q＞0, q+r+s＞0, and it is a number satisfying l+m+n+p+q+r+s=1); (C) The following average composition formula (2) Means that an organohydrogen polysiloxane with at least two SiH bonds in one molecule: In the (C) component, relative to the alkenyl group in the (A) component and the (B) component bonded to the silicon atom The amount of SiH bonds becomes 0.5~5.0,

(In the formula, R ^{3 is} independently an unsubstituted or substituted monovalent hydrocarbon group without an addition-reactive carbon-carbon double bond, ^{at least 50 mol% of all R 3} is a methyl group, and a and b are 0.7≦a≦ 2.1. 0.001≦b≦1.0, and it is a number that satisfies 0.8≦a+b≦3.0); (D) Platinum group metal catalyst: relative to the total of (A) ~ (C) components, the number of metal atoms The mass is converted into an amount of 1~500ppm; (E) Containing Si-O-Ce bonds and Si-O-Ti bonds, the Ce content is 50~5,000ppm, the Ti content is 50~5,000ppm, and the viscosity at 25°C is 10~10,000mPa·s polyorganometallic siloxane: 0.01~5 parts by mass relative to 100 parts by mass of the total of components (A)~(D).

This silicone resin composition for die bonding imparts a hardened product with high hardness and little change in hardness and mass reduction under high temperature conditions, and is particularly useful as a die bonding material for die bonding of LED devices and the like.

In addition, the present invention provides a cured product obtained by curing the aforementioned silicone resin composition for die bonding. This hardened product has high hardness, and the hardness change and quality reduction under high temperature conditions are small.

The hardness change of this hardened product after heating at 250°C for 500 hours is within 20%, and the mass reduction rate is preferably within 5%. The hardness change and mass reduction in a high temperature environment are within the above-mentioned range, and it can be used as a die bonding material for optical semiconductor devices such as LED devices with high long-term reliability.

The present invention provides a light-emitting diode device, which is formed by bonding the above-mentioned hardened substance through die. The long-term reliability of the light-emitting diode device is high, and its productivity is also improved.

(式中，R⁵ 為同種或異種之一價烴基，x為3或4)， (iii)下述一般式(e-2)所示之鈦化合物及/或其部分水解縮合物：鈦之質量相對於前述(i)成分100質量份而言成為0.05~5質量份的質量，

(式中，R⁶ 為同種或異種之一價烴基)。Furthermore, the present invention provides a method of manufacturing the aforementioned silicone resin composition for die bonding, comprising: heat-treating a mixture containing (i), (ii), and (iii) at a temperature of 150° C. or higher to obtain the aforementioned (E) ) The step of ingredients, the step of mixing the aforementioned (A) to (E) ingredients; (i) Organopolysiloxane with a viscosity of 10 to 10,000 mPa·s at 25°C, (ii) Containing the following general formula (e) -1) Rare earth carboxylate of cerium carboxylate: The mass of cerium is 0.05 to 5 parts by mass relative to 100 parts by mass of the aforementioned (i) component,

(In the formula, R ⁵ is a monovalent hydrocarbon group of the same or different species, and x is 3 or 4), (iii) The titanium compound represented by the following general formula (e-2) and/or its partial hydrolysis condensate: Titanium The mass is 0.05 to 5 parts by mass relative to 100 parts by mass of the aforementioned (i) component,

(In the formula, R ⁶ is a monovalent hydrocarbon group of the same or different species).

With this manufacturing method, the above-mentioned (E) component having a specified Ce content and Ti content can be easily synthesized, so the above-mentioned silicone resin composition for die bonding can be easily manufactured. [Effects of the invention]

As described above, the silicone resin composition for die bonding of the present invention imparts a hardened product with high hardness and little change in hardness and mass reduction under high temperature conditions, and is used as die bonding for die bonding of LED elements, etc. The material is particularly useful. Then, in the wire bonding step performed after the die bonding step, it is difficult to peel off the wafer or fail to be bonded. Therefore, the optical semiconductor device is an optical semiconductor device formed by die bonding of the polysilicon cured product. Reliability is high, and its productivity is also improved.

As described above, it is desired to develop a silicone resin composition that imparts a cured product with excellent hardness and heat resistance, and a polysilicon cured product that becomes a die bonding material used for die bonding of LED elements and the like.

As a result of intensive research on the above-mentioned problems, the inventors found that a silicone resin composition for die bonding including the following components (A) to (E) can solve the above-mentioned problems, and completed the present invention.

(式中，R¹ 獨立表示烯基，R² 獨立表示不含加成反應性碳-碳雙鍵之無取代或取代之1價烴基，惟，全R² 之至少80莫耳%為甲基，l、m、n、p、q、r及s，分別為滿足l≧0、m≧0、n≧0、p≧0、q≧0、r≧0及s≧0之數，惟，m+n+q＞0、q+r+s＞0，且為滿足l+m+n+p+q+r+s=1之數)； (C)下述平均組成式(2)所表示，1分子中具有至少2個SiH鍵之有機氫聚矽氧烷：相對於1個(A)成分及(B)成分中之鍵結於矽原子之烯基而言(C)成分中之SiH鍵成為0.5~5.0個的量，

(式中，R³ 獨立為不含加成反應性碳-碳雙鍵之無取代或取代的1價烴基，全R³ 之至少50莫耳%為甲基，a及b為0.7≦a≦2.1、0.001≦b≦1.0，且為滿足0.8≦a+b≦3.0之數)； (D)鉑族金屬系觸媒：相對於(A)~(C)成分之合計而言以金屬原子之質量換算成為1~500ppm的量； (E)含有Si-O-Ce鍵及Si-O-Ti鍵，Ce含量為50~ 5,000ppm，Ti含量為50~5,000ppm，且25℃下之黏度為10~ 10,000mPa・s之聚有機金屬矽氧烷：相對於(A)~(D)成分之合計100質量份而言為0.01~5質量份。That is, the present invention is a silicone resin composition for die bonding, which contains the following (A), (B), (C), (D), and (E), (A) having at least two in one molecule Alkenyl groups bonded to silicon atoms, linear organopolysiloxanes with a viscosity of less than 50mPa·s at 25°C; (B) The following average unit formula (1) is expressed, and it is waxy or waxy at 25°C. Solid branched organopolysiloxane: The amount of (B) component becomes 50 to 90 parts by mass relative to 100 parts by mass of the total of (A) component and (B) component,

(In the formula, R ¹ independently represents an alkenyl group, R ² independently represents an unsubstituted or substituted monovalent hydrocarbon group without addition-reactive carbon-carbon double bonds, but at least 80 mole% of ^{all R 2 is methyl} , L, m, n, p, q, r, and s are the numbers satisfying l≧0, m≧0, n≧0, p≧0, q≧0, r≧0, and s≧0, respectively, but, m+n+q＞0, q+r+s＞0, and it is a number satisfying l+m+n+p+q+r+s=1); (C) The following average composition formula (2) Means that an organohydrogen polysiloxane with at least two SiH bonds in one molecule: In the (C) component, relative to the alkenyl group in the (A) component and the (B) component bonded to the silicon atom The amount of SiH bonds becomes 0.5~5.0,

(In the formula, R ^{3 is} independently an unsubstituted or substituted monovalent hydrocarbon group without an addition-reactive carbon-carbon double bond, ^{at least 50 mol% of all R 3} is a methyl group, and a and b are 0.7≦a≦ 2.1. 0.001≦b≦1.0, and it is a number that satisfies 0.8≦a+b≦3.0); (D) Platinum group metal catalyst: relative to the total of (A) ~ (C) components, the number of metal atoms The mass is converted into an amount of 1~500ppm; (E) Containing Si-O-Ce bonds and Si-O-Ti bonds, the Ce content is 50~5,000ppm, the Ti content is 50~5,000ppm, and the viscosity at 25°C is 10~10,000mPa·s polyorganometallic siloxane: 0.01~5 parts by mass relative to 100 parts by mass of the total of components (A)~(D).

Hereinafter, although the present invention will be described in detail, the present invention is not limited to these. In addition, in this specification, "Me" represents a methyl group, and "Vi" represents a vinyl group.

<Silicone resin composition for die bonding> Hereinafter, each component will be described in further detail. [(A) Ingredient] (A) Component has at least two alkenyl groups bonded to silicon atoms in one molecule, and the viscosity at 25°C is less than 50mPa·s (usually 1mPa·s or more and less than 50mPa·s, preferably 5 ~20mPa·s) linear organopolysiloxane. When the viscosity exceeds 50mPa·s, this component acts as a softer segment that is more than necessary, so it is difficult to obtain the target high hardness.

As the alkenyl group bonded to the silicon atom, a vinyl group, an allyl group, an ethynyl group, etc., having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably a vinyl group. The alkenyl group bonded to the silicon atom and the organopolysiloxane molecule of component (A) may exist in either the end of the molecular chain or the side chain of the molecular chain, or it may exist in both of them. However, it is preferably present at least at both ends of the molecular chain.

The group other than the alkenyl group bonded to the silicon atom is not particularly limited as long as it does not have an addition-reactive carbon-carbon double bond, but examples include methyl, ethyl, propyl, butyl, and pentyl. Alkyl, hexyl, heptyl, etc.; Cycloalkyl, cyclopentyl, cyclohexyl, etc.; Aryl, phenyl, tolyl, xylyl, naphthyl, etc.; Aralane, such as benzyl, phenethyl, etc. Group; Halogenated alkyl groups such as chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, etc. usually have 1 to 12 carbon atoms, preferably 1 to 10, and more preferably 1 ~8 unsubstituted or halogen-substituted monovalent hydrocarbon group, especially methyl is preferred.

(式中，R⁶ 獨立為不具有加成反應性碳-碳雙鍵之無取代或取代的一價烴基，R⁷ 獨立為烯基，d為1.9~2.1之數，e為0.005~1.0之數，惟，d+e滿足1.95~3.0)。The organopolysiloxane of the component (A) is preferably represented by the average composition formula (5), for example.

(In the formula, R ^{6 is} independently an unsubstituted or substituted monovalent hydrocarbon group without an addition-reactive carbon-carbon double bond, R ^{7 is} independently an alkenyl group, d is a number from 1.9 to 2.1, and e is from 0.005 to 1.0. Number, only, d+e satisfies 1.95~3.0).

Examples of the unsubstituted or substituted monovalent hydrocarbon group having no addition-reactive carbon-carbon double bond represented by R ^{6 are the same as those exemplified as the group bonded to the silicon atom other than the aforementioned alkenyl group.} Examples of the alkenyl group represented by R ⁷ are the same as those exemplified as the alkenyl group bonded to the silicon atom. d is preferably a number from 1.95 to 2.00, e is preferably a number from 0.01 to 0.5, and d+e satisfies 1.98 to 2.5.

(式中，R⁸ 獨立表示不含加成反應性碳-碳雙鍵之無取代或取代之1價烴基，f為0~60，較佳為5~40之整數，g為1~10，較佳為1~5之整數，h為0~50，較佳為5~30之整數。f為0~200，較佳為3~120之整數，g為1~10，較佳為1~5之整數，h為0~200，較佳為3~110之整數)。As the linear organopolysiloxane of the component (A), for example, those represented by the following formulas are exemplified.

(In the formula, R ⁸ independently represents an unsubstituted or substituted monovalent hydrocarbon group without an addition-reactive carbon-carbon double bond, f is 0-60, preferably an integer of 5-40, and g is 1-10, Preferably it is an integer of 1 to 5, h is 0 to 50, preferably an integer of 5 to 30. f is 0 to 200, preferably an integer of 3 to 120, and g is 1 to 10, preferably 1 to An integer of 5, h is 0~200, preferably an integer of 3~110).

In the above formula, ^{the unsubstituted or substituted monovalent hydrocarbon group represented by R 8} preferably has 1 to 10 carbon atoms, more preferably 1 to 6. As a specific example, it is preferable to exemplify the same kind as the aryl group and aralkyl group exemplified as the group bonded to the silicon atom other than the alkenyl group, but it is determined by the light resistance and heat resistance of the cured product. From a point of view, it is more preferably an alkyl group, and particularly preferably a methyl group.

(式中，括弧內之矽氧烷單位，可為任意之排列順序)。 (A)成分可一種單獨使用亦可併用二種以上。As a specific example of (A) component, what is represented by the following formula etc. are illustrated.

(In the formula, the siloxane units in parentheses can be arranged in any order). (A) A component may be used individually by 1 type, and may use 2 or more types together.

(式中，R¹ 獨立表示烯基，R² 獨立表示不含加成反應性碳-碳雙鍵之無取代或取代之1價烴基，惟，全R² 之至少80莫耳%為甲基，l、m、n、p、q、r及s，分別為滿足l≧0、m≧0、n≧0、p≧0、q≧0、r≧0及s≧0之數，惟，m+n+q＞0、q+r+s＞0，且為滿足l+m+n+p+q+r+s=1之數)。[Component (B)] The component (B) is a branched organopolysiloxane represented by the following average unit formula (1).

(In the formula, R ¹ independently represents an alkenyl group, R ² independently represents an unsubstituted or substituted monovalent hydrocarbon group without addition-reactive carbon-carbon double bonds, but at least 80 mole% of ^{all R 2 is methyl} , L, m, n, p, q, r, and s are the numbers satisfying l≧0, m≧0, n≧0, p≧0, q≧0, r≧0, and s≧0, respectively, but, m+n+q>0, q+r+s>0, and it is a number satisfying l+m+n+p+q+r+s=1).

In addition, the component (B) is a branched organopolysiloxane having a branched structure such ^{as R 1} SiO _3/2 unit or SiO _{4/2 unit.} In addition, component (B) is waxy or solid at 25°C. The so-called "waxy" refers to 10,000 Pa·s or more at 25°C, especially 100,000 Pa·s or more that hardly exhibits self-fluidity. The meaning of shape (raw rubber shape).

In the above average composition formula (1), ^{the alkenyl group represented by R 1 is of the same kind} as that exemplified as the alkenyl group bonded to the silicon atom in the component (A), but in terms of ease of acquisition and price Vinyl is preferred.

The ^{unsubstituted or substituted monovalent hydrocarbon group that does not contain an addition-reactive carbon-carbon double bond represented by R 2} is the same kind as the group exemplified in the component (A) as the group bonded to the silicon atom other than the alkenyl group However, at least 80 mol% (80-100 mol%) of all R ^{2 are methyl groups.} When the ratio of methyl groups is less than ^{80 mol% of the total R 2} , the composition may become turbid due to poor compatibility with the component (A), and a cured product with the desired high transparency may not be obtained.

l is from 0 to 0.65, m is from 0 to 0.65, n is from 0 to 0.5, p is from 0 to 0.5, q is from 0 to 0.8, r is from 0 to 0.8, and s is preferably from 0 to 0.6. In addition, m+n+q is 0.1 to 0.8, particularly preferably 0.2 to 0.65, and q+r+s is 0.1 to 0.8, particularly 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 per 100 g of the component (B), and more preferably in the range of 0.05 to 0.5 mol. If the content of the alkenyl group satisfies the range of 0.01 to 1 mol, the cross-linking reaction proceeds sufficiently and a hardened product with higher hardness can be obtained.

(式中，R¹ 、R² 、l、m、n、p、q、r及s與前述相同)。As such (B) component, specifically, the organopolysiloxane represented by the following average unit formula is illustrated.

(In the formula, R ¹ , R ² , l, m, n, p, q, r, and s are the same as described above).

As a specific example of the component (B), the organopolysiloxane represented by the following average unit formula can be exemplified.

In the present invention, the ratio of (B) component to (A) component is also important, and the content of (B) component is relative to 100 parts by mass of (A) component and (B) component in total (B) component The amount is 50 to 90 parts by mass, preferably 60 to 80 parts by mass, and more preferably 70 to 80 parts by mass. (B) When the content of the component is less than 50 parts by mass, the target high hardness may not be obtained. When it exceeds 90 parts by mass, the viscosity of the composition becomes significantly higher, and the composition becomes difficult to be used as die bonding of LED elements. Material use. (B) A component may be used individually by 1 type, and may use 2 or more types together.

(式中，R³ 獨立表示不含加成反應性碳-碳雙鍵之無取代或取代之1價烴基，惟，全R³ 之至少50莫耳%為甲基，a及b為0.7≦a≦2.1、0.001≦b≦1.0，且為滿足0.8≦a+b≦3.0之數)。[Component (C)] The component (C) is represented by the following average unit formula (2), an organohydrogen polysiloxane having at least two SiH bonds in one molecule. This component (C) is used as the The alkenyl group contained in the component (A) and the component (B) react by a hydrosilylation reaction to make the crosslinking agent function as a component for crosslinking.

(In the formula, R ³ independently represents an unsubstituted or substituted monovalent hydrocarbon group without an addition-reactive carbon-carbon double bond. However, ^{at least 50 mol% of all R 3} is a methyl group, and a and b are 0.7≦ a≦2.1, 0.001≦b≦1.0, and it is a number that satisfies 0.8≦a+b≦3.0).

From the point of view that component (C) is a component that functions as a crosslinking agent, the viscosity of component (C) at 25°C is preferably 1,000 mPa·s or less, more preferably 0.5 to 1,000 mPa·s, and more preferably It is 2~200mPa·s.

In addition, from the viewpoint of the balance of crosslinking, the content of component (C) is relative to one alkenyl group of component (A) and component (B), and the number of SiH bonds in component (C) becomes The amount of 0.5 to 5.0 is preferably the amount of 0.7 to 3.0.

In addition, in the component (C), one molecule contains 2 or more (usually 2 to 200), preferably 3 or more (for example, 3 to 100), more preferably 4 to 50 SiH The bond can be located at either end of the molecular chain, in the middle of the molecular chain, or both.

In the component (C), the content of the SiH bond is preferably in the range of 0.001 to 0.02 mol per 1 g of the component (C), and more preferably in the range of 0.002 to 0.017 mol.

In addition, the molecular structure of component (C) may be any of linear, cyclic, branched, and three-dimensional network structures. In addition, the number of silicon atoms (or degree of polymerization) in one molecule of the component (C) can usually be 2 to 200, preferably 3 to 100, and more preferably about 4 to 50.

In the above average composition formula (2), R ³ is an unsubstituted or substituted monovalent hydrocarbon group that does not contain an addition-reactive carbon-carbon double bond, although it can be exemplified by being bonded to other than the alkenyl group in the component (A) The organic groups of the silicon atom are the same as those exemplified, but at least 50 mol%, preferably 60-100 mol% of ^{all R 3 are methyl groups.} When the ratio of methyl groups is less than ^{50 mol% of all R 3} , the compatibility with (A) component and (B) component is poor, and the problem of white turbidity or phase separation of the composition may occur. a is 1.0 to 2.0, b is 0.01 to 1.0, and a+b is preferably a number of 1.1 to 2.6.

As the organohydrogen polysiloxane represented by the above average composition formula (2), for example, 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane Silicone, ginseng (hydrodimethylsiloxy) methyl silane, ginseng (hydrodimethyl siloxy) phenyl silane, methyl hydrogen cyclosiloxane, methyl hydrogen siloxane, dimethyl Silicone cyclic copolymer, both ends of trimethylsiloxy-terminated methyl hydrogen polysiloxane, both ends of trimethylsiloxy-terminated dimethylsiloxane, methylhydrosiloxane Copolymer, two-terminal dimethylhydrosiloxy-terminated dimethylpolysiloxane, two-terminal dimethylhydrosiloxane-terminated methylhydropolysiloxane, two-terminal dimethylhydrosiloxane Blocked dimethylsiloxane and methylhydrosiloxane copolymer, both ends of trimethylsiloxy terminated methylhydrosiloxane and diphenylsiloxane copolymer, both ends of trimethylsilicon Oxygen-terminated methylhydrosiloxane, diphenylsiloxane, dimethylsiloxane copolymer, trimethylsiloxy-terminated methylhydrosiloxane, methylphenylsiloxane on both ends Alkyl, dimethylsiloxane copolymer, both ends of dimethylhydrosiloxane terminated methylhydrosiloxane, dimethylsiloxane, diphenylsiloxane copolymer, both ends of dimethylsiloxane Hydrosiloxy terminated methylhydrosiloxane, dimethylsiloxane, methylphenylsiloxane copolymer, containing (CH ₃ ) ₂ HSiO _1/2 unit and (CH ₃ ) ₃ SiO _{1/ Copolymer containing 2} units and SiO _4/2 units, copolymer containing (CH ₃ ) ₂ HSiO _1/2 units and SiO _4/2 units, containing (CH ₃ ) ₂ HSiO _1/2 units and SiO _4/2 units Copolymer with (C ₆ H ₅ ) ₃ SiO _1/2 unit, etc.

(式中，i、j為2~100，較佳為2~20之整數)。As a specific example of the component (C), a linear organohydrogenpolysiloxane or a cyclic organohydrogenpolysiloxane represented by the following formula can be exemplified.

(In the formula, i and j are 2-100, preferably an integer of 2-20).

(式中，括弧內之矽氧烷單位，可為任意之排列順序)。 (C)成分可一種單獨使用亦可併用二種以上。

(In the formula, the siloxane units in parentheses can be arranged in any order). (C) A component may be used individually by 1 type, and may use 2 or more types together.

[Component (D)] The component (D) is a platinum group metal catalyst, and the component (D) is used to promote the reaction between the above-mentioned (A) component and (B) component and (C) component (hydrosilylation reaction) The reaction catalyst functions as a component. As this platinum group metal-based catalyst, any one known as a catalyst for the hydrosilylation reaction can also be used. Examples include platinum group metal monomers such as platinum black, rhodium, and palladium; H ₂ PtCl ₄ ·kH ₂ O, H ₂ PtCl ₆ ·kH ₂ O, NaHPtCl ₆ ·kH ₂ O, KHPtCl ₆ ·kH ₂ O, Na ₂ PtCl ₆ ·kH ₂ O, K ₂ PtCl ₄ ·kH ₂ O, PtCl ₄ ·kH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ ·kH ₂ O (where k is an integer from 0 to 6, preferably 0 or 6) platinum chloride, chloroplatinic acid, and chloroplatinate; alcohol-modified chloroplatinic acid (refer to the specification of U.S. Patent No. 3,220,972); chloroplatinic acid and olefin compound (refer to U.S. Patent No. 3,159,601 Specification No. 3,159,662, and Specification No. 3,775,452); platinum group metals such as platinum black and palladium are supported on carriers such as alumina, silicon dioxide, carbon, etc.; rhodium-olefin composite; chlorine ginseng (Triphenylphosphine) rhodium (Wilkinson catalyst); compound of platinum chloride, chloroplatinic acid or chloroplatinate and vinyl-containing silicone, especially with vinyl-containing cyclic silicone Things etc. Among these, as a better one, from the viewpoint of compatibility and the viewpoint of chlorine impurity, chloroplatinic acid can be modified by polysiloxane. Specifically, for example, chloroplatinic acid can be modified with tetramethyl Platinum catalyst for modification of vinyl disiloxane.

(D) The content of the component, the so-called effective amount, is specifically 1 to 500 ppm, preferably 3 to 100 ppm, in terms of the mass of metal atoms, relative to the total of (A) to (C) components. , More preferably, it becomes an amount of 5-40 ppm.

[(E) Ingredient] (E) component, containing Si-O-Ce bond and Si-O-Ti bond, Ce content is 50~5,000ppm, Ti content is 50~5,000ppm, and viscosity at 25℃ is 10~10,000mPa·s The (E) component is an additive for improving the heat resistance of the silicone resin composition for die bonding of the present invention. In addition, the method for producing the polyorganometallic siloxane of the (E) component will be described later.

(E) The content of the component is 0.01 to 5 parts by mass, preferably 0.1 to 3 parts by mass, and more preferably 0.5 to 3 parts by mass relative to 100 parts by mass of the total of the components (A) to (D). If the content of the component (E) exceeds 5 parts by mass, the obtained silicone resin composition for die bonding may be discolored or the hardness of the cured product may decrease. Moreover, if the content of the component (E) is less than 0.01 parts by mass, sufficient heat resistance cannot be obtained.

[Other ingredients] In the silicone resin composition for die bonding of the present invention, in addition to the above-mentioned components (A) to (E), other components exemplified below may be blended as necessary. As other components, for example, thixotropy control agents such as vapor-phase silica; light scattering agents such as crystalline silica; reinforcing materials such as vapor-phase silica and crystalline silica; phosphors; Viscosity regulators for petroleum solvents, non-reactive silicone oils without reactive functional groups, etc.; with carbon-functional silanes, epoxy groups, alkoxy groups, and hydrogen atoms bonded to silicon atoms (ie, SiH bonds) ) And at least one of vinyl groups bonded to silicon atoms (A)~(E) other than the adhesion promoters of polysiloxane compounds, etc.; conductivity of metal powders such as silver, gold, etc. Donating agent; pigments and dyes for coloring; reaction inhibitors for ethynyl cyclohexanol, tetramethyltetravinyltetracyclosiloxane, etc. These other components may be used alone or in combination of two or more.

＜Hardened material＞ Furthermore, the present invention provides a cured product of the aforementioned silicone resin composition for die bonding. The curing of the silicone resin composition of the present invention can be performed under known conditions, for example, it can be performed by heating at 60 to 180°C for 10 minutes to 3 hours. In particular, it is preferable that the Shore D hardness of the cured product obtained by curing the composition is 60 or more. The curing condition for the Shore D hardness to be 60 or more is usually that the composition of the present invention is set to 120~ It is cured by heating at 180°C for 30 minutes to 3 hours.

In addition, the hardness change of the cured product obtained by curing the silicone resin composition for die bonding of the present invention after heating at 250°C for 500 hours is within 20%, and the mass reduction rate is preferably within 5%. Since the cured product of the silicone resin composition for die bonding of the present invention has high hardness and little change in hardness and mass reduction under high temperature conditions, it is particularly useful as a die for die bonding of LED elements. The bonding material is useful.

＜Light Emitting Diode Components＞ Furthermore, the present invention provides a light-emitting diode device, which is formed by bonding the above-mentioned hardened product through die. As an example of a method of bonding optical element die using the composition of the present invention, the composition of the present invention can be filled into a syringe, and then coated on a substrate such as a package in a dry state using a dispenser to a thickness of 5-100 μm. After mounting, an optical element (for example, a light-emitting diode) is placed on the coated composition, and the composition is hardened, thereby bonding the optical element die on the substrate. Alternatively, the composition is placed on a squeegee plate, and the composition is coated on the substrate in a dry state with a thickness of 5-100 μm by a method of squeegee coating and punching, and then the optical element is placed on the coated composition. It is a method of hardening the composition to bond the die of the optical element on the substrate. The curing conditions of the composition may be carried out as described above. In this way, a light-emitting diode device with high reliability can be obtained by die-bonding the cured product of the polysilicon oxide composition for die bonding of the present invention.

(式中，R⁵ 為同種或異種之一價烴基，x為3或4)， (iii)下述一般式(e-2)所示之鈦化合物及/或其部分水解縮合物：鈦之質量相對於前述(i)成分100質量份而言成為0.05~5質量份的質量，

(式中，R⁶ 為同種或異種之一價烴基)。<Method for manufacturing silicone resin composition for die bonding> The present invention provides a method for manufacturing the silicone resin composition for die bonding of the present invention, which comprises: containing (i), (ii) and (iii) The mixture is heat-treated at a temperature above 150°C to obtain the aforementioned (E) component, and the aforementioned step (A) to (E) is mixed; (i) Organic polymer with a viscosity of 10~10,000mPa·s at 25°C Silicone, (ii) Rare earth carboxylate containing cerium carboxylate represented by the following general formula (e-1): the mass of cerium is 0.05 to 5 relative to 100 parts by mass of the aforementioned component (i) The mass of the mass,

(In the formula, R ⁵ is a monovalent hydrocarbon group of the same or different species, and x is 3 or 4), (iii) The titanium compound represented by the following general formula (e-2) and/or its partial hydrolysis condensate: Titanium The mass is 0.05 to 5 parts by mass relative to 100 parts by mass of the aforementioned (i) component,

(In the formula, R ⁶ is a monovalent hydrocarbon group of the same or different species).

According to such a manufacturing method, since the polyorganometallic siloxane (ie, the above-mentioned (E) component) with the specified Ce content and Ti content can be easily synthesized, the silicone resin composition for die bonding of the present invention can be easily manufactured Things. [Example]

Hereinafter, although the present invention will be specifically described using examples and comparative examples, the present invention is not limited to these. In addition, in the examples, "Me" represents a methyl group, and "Vi" represents a vinyl group. The viscosity is the value at 25°C using a rotary viscometer.

[Synthesis Example 1] (E) Synthesis of component: To 100 parts by mass of trimethylsiloxy-terminated dimethylpolysiloxane at both ends with a viscosity of 100mPa·s at 25°C, add cerium as the main ingredient while fully stirring Composition of 2-ethylhexanoate turpentine solution (rare earth element content 6 mass%) 10 parts by mass (mass of cerium: 0.55 parts by mass) and 2.1 parts by mass of tetra-n-butyl titanate (mass of titanium: 1.65 parts by mass) are pre-mixed to obtain a yellowish-white dispersion. Here, while a small amount of nitrogen was circulated, the turpentine was heated to flow out, and then heated at 300°C for 1 hour to obtain a uniform composition of a thick reddish-brown and transparent polyorganometal siloxane. The thus synthesized polyorganometallic siloxane has a Ce content of 3,400 ppm, a Ti content of 3,700 ppm, and a viscosity of 104 mPa·s at 25°C.

[Synthesis example 2] (D) Synthesis of component: The reaction product of hexachloroplatinic acid and 1,3-divinyltetramethyldisiloxane is averaged so that the platinum content becomes 1.0% by mass: ViMe ₂ SiO (Me ₂ SiO) ₁₈₀ SiMe ₂ Vi shows linear dimethyl polysiloxane (viscosity 600mPa·s) diluted to prepare platinum catalyst.

[Example 1] The average molecular formula: ViMe ₂ SiO (Me ₂ SiO) ₁₀ SiMe ₂ Vi is a linear dimethyl polymer with a viscosity of 10 mPa·s at 25 ℃ and a vinyl end capped at both ends shown by ViMe 2 SiO (Me 2 SiO) 10 SiMe 2 Vi Siloxane (A-1), which is composed of Me ₃ SiO _1/2 , ViMe ₂ SiO _1/2 and SiO _4/2 units, relative to SiO _4/2 , Me ₃ SiO _1/2 and ViMe ₂ SiO _{The mol ratio of 1/2} is 0.8, the amount of vinyl is 0.085 mol/100g relative to the solid content of the xylene solution of silicone resin (B) that is solid at 25°C, calculated as the mass ratio of effective ingredients Mixing in a ratio of 25:75. From this mixture, xylene was removed at 160°C under reduced pressure below 10 mmHg to obtain a mixed liquid of polysiloxane.

(式中，括弧內之矽氧烷單位之排列順序為任意)。Next, in 100 parts by mass of the mixed liquid of polysiloxane, mix the average molecular formula: Me ₃ SiO (MeHSiO) ₄₅ (Me ₂ SiO) ₁₇ SiMe ₃ represented by methylhydrosiloxane (C-1) 14.8 Parts by mass, and 1.2 parts by mass of epoxy-containing organopolysiloxane (F-1) shown in the following formula as other ingredients, and tetramethyltetravinyltetracyclosiloxane as an addition reaction control agent 3 parts by mass of oxane (G) were obtained to obtain a transparent liquid (the molar ratio of the total SiH groups to the total alkenyl groups in the composition was 1.14).

(In the formula, the order of the siloxane units in parentheses is arbitrary).

Furthermore, 1 part by mass of the component (E) obtained in Synthesis Example 1, 0.12 part by mass of the platinum catalyst (D) obtained in Synthesis Example 2, and fumed silica (REOLOSIL DM-30S manufactured by Tokuyama Co., Ltd.) were mixed. H) 8 parts by mass to obtain a transparent silicone resin composition for die bonding with a viscosity of 31 Pa·s at 25°C.

[Example 2] The average molecular formula: ViMe ₂ SiO (Me ₂ SiO) ₁₀ SiMe ₂ Vi is a linear dimethyl polymer with a viscosity of 10 mPa·s at 25 ℃ and a vinyl-terminated end shown in ViMe 2 SiO (Me 2 SiO) 10 SiMe 2 Vi. Siloxane (A-1), which is composed of Me ₃ SiO _1/2 , ViMe ₂ SiO _1/2 and SiO _4/2 units, relative to SiO _4/2 , Me ₃ SiO _1/2 and ViMe ₂ SiO _{The mol ratio of 1/2} is 0.8, and the amount of vinyl is 0.085 mol/100g relative to the solid content of the xylene solution of silicone resin (B). The effective ingredient is converted into a mass ratio of 25:75. . From this mixture, xylene was removed at 160°C under reduced pressure below 10 mmHg to obtain a mixed liquid of polysiloxane.

進而，混合合成例1所得之(E)成分1質量份、合成例2所得之鉑觸媒(D)0.12質量份，及氣相二氧化矽((股)德山製REOLOSIL DM-30S)(H)9質量份而得到25℃下之黏度為44Pa・s之透明的晶粒接合用矽氧樹脂組成物。Next, in 100 parts by mass of the mixed liquid of polysiloxane, mix the average molecular formula: Me ₃ SiO (MeHSiO) ₆₆ (Me ₂ SiO) ₃₂ SiMe ₃ represented by methylhydrosiloxane (C-2) 15.7 Parts by mass, and 2.4 parts by mass of the alkoxysilyl group-containing compound (F-2) represented by the following formula as other components, and tetramethyltetravinyltetracyclosiloxane ( G) 3 parts by mass to obtain a transparent liquid (the molar ratio of the total SiH groups to the total alkenyl groups in the composition is 1.14).

Furthermore, 1 part by mass of the component (E) obtained in Synthesis Example 1, 0.12 part by mass of the platinum catalyst (D) obtained in Synthesis Example 2, and fumed silica (REOLOSIL DM-30S manufactured by Tokuyama Co., Ltd.) were mixed. H) 9 parts by mass to obtain a transparent silicone resin composition for die bonding with a viscosity of 44 Pa·s at 25°C.

[Comparative Example 1] (1) Average molecular formula: ViMe ₂ SiO(Me ₂ SiO) ₄₀ SiMe ₂ Vi shows a linear dimethyl methacrylate with a viscosity of 60 mPa·s at 25°C with both ends blocked by vinyl -Based polysiloxane (A-2), which is composed of Me ₃ SiO _1/2 , ViMe ₂ SiO _1/2 and SiO _4/2 units, relative to SiO _4/2 , Me ₃ SiO _1/2 and ViMe ₂ The molar ratio of SiO _1/2 is 0.8, and the amount of vinyl is 0.085 mol/100g relative to the solid content of the xylene solution of silicone resin (B). The effective component is converted into a mass ratio of 25:75. Proportional mixing. From this mixture, xylene was removed at 160°C under reduced pressure below 10 mmHg to obtain a mixed liquid of polysiloxane.

Next, in 100 parts by mass of the mixed liquid of polysiloxane, mix 10 parts by mass of methylhydrosiloxane (C-3) represented by _{Me 3} SiO(MeHSiO) ₈ SiMe _{3 in average molecular formula, and other} Ingredients: 5 parts by mass of epoxy group-containing compound (F-3) represented by the following formula, and 3 parts by mass of tetramethyltetravinyltetracyclosiloxane (G) as an addition reaction control agent to obtain Transparent liquid (the molar ratio of the total SiH groups to the total alkenyl groups in the composition is 1.65).

進而，混合合成例1所得之(E)成分1質量份、合成例2所得之鉑觸媒(D)0.12質量份，及氣相二氧化矽((股)德山製REOLOSIL DM-30S)(H)5質量份而得到25℃下之黏度為35Pa・s之透明的加成硬化型矽氧樹脂組成物。

Furthermore, 1 part by mass of the component (E) obtained in Synthesis Example 1, 0.12 part by mass of the platinum catalyst (D) obtained in Synthesis Example 2, and fumed silica (REOLOSIL DM-30S manufactured by Tokuyama Co., Ltd.) were mixed. H) 5 parts by mass to obtain a transparent addition-curing silicone resin composition with a viscosity of 35 Pa·s at 25°C.

[Comparative Example 2] The same operation as in Example 1 was performed except that the component (E) was not used to obtain a transparent addition-curing silicone resin composition.

[Comparative Example 3] The same operation as in Example 2 was performed except that the component (E) was not used to obtain a transparent addition-curing silicone resin composition.

With respect to the composition prepared as described above, the following tests were performed. The results of the test are shown in Table 1. (Measurement of Hardness of Hardened Material) Using the composition obtained in each example and each comparative example, the ShoreD hardness of the cured product obtained by heating at 150°C for 3 hours was measured as the initial hardness.

(Measurement of hardness after heat resistance test) After storing the cured product used for the above-mentioned hardness measurement at 250°C for 500 hours, the ShoreD hardness of the re-cured product was measured. The rate of change of hardness is calculated according to the following formula. (Rate of change)=((Hardness after heat resistance test)÷(Initial hardness)×100)-100(%)

(Measurement of mass reduction rate caused by heat resistance test) The initial mass of the cured product used for the measurement of the above-mentioned light transmittance is set as 100, and the mass after storage at 250°C for 500 hours is measured, and the mass% is compared to calculate the mass reduction rate.

As shown in Table 1, in the examples using the silicone resin composition for die bonding of the present invention, the result is that the obtained cured product has a small change in physical properties in a heat resistance test, and is therefore good. On the other hand, the hardness of the cured product obtained in Comparative Example 1 outside the range of the component (A) of the present invention is poor. In Comparative Examples 2 and 3 that do not contain the component (E), the hardness changes due to the heat resistance test. And the quality changes greatly, so the reliability is poor.

In addition, the present invention is not limited to the above-mentioned embodiment. The above-mentioned embodiment is an example, and it has substantially the same structure as the technical idea described in the scope of the patent application of the present invention, and exhibits the same functions and effects, regardless of which is included in the technical scope of the present invention.

Claims (6)

A silicone resin composition for die bonding, which is characterized by containing the following (A), (B), (C), (D) and (E), (A) having at least two bonds in one molecule Alkenyl groups of silicon atoms, linear organopolysiloxanes with a viscosity of less than 50mPa·s at 25°C; (B) The following average unit formula (1) is expressed, and it is a waxy or solid branch at 25°C Form organopolysiloxane: The amount of (B) component becomes 50 to 90 parts by mass relative to 100 parts by mass of the total of (A) component and (B) component,

(In the formula, R ¹ independently represents an alkenyl group, R ² independently represents an unsubstituted or substituted monovalent hydrocarbon group without addition-reactive carbon-carbon double bonds, but at least 80 mole% of ^{all R 2 is methyl} , L, m, n, p, q, r, and s are the numbers satisfying l≧0, m≧0, n≧0, p≧0, q≧0, r≧0, and s≧0, respectively, but, m+n+q＞0, q+r+s＞0, and it is a number satisfying l+m+n+p+q+r+s=1); (C) The following average composition formula (2) Means that an organohydrogen polysiloxane with at least two SiH bonds in one molecule: In the (C) component, relative to the alkenyl group in the (A) component and the (B) component bonded to the silicon atom The amount of SiH bonds becomes 0.5~5.0,

(In the formula, R ^{3 is} independently an unsubstituted or substituted monovalent hydrocarbon group without an addition-reactive carbon-carbon double bond, ^{at least 50 mol% of all R 3} is a methyl group, and a and b are 0.7≦a≦ 2.1. 0.001≦b≦1.0, and it is a number that satisfies 0.8≦a+b≦3.0); (D) Platinum group metal catalyst: relative to the total of (A) ~ (C) components, the number of metal atoms The mass is converted into an amount of 1~500ppm; (E) Containing Si-O-Ce bond and Si-O-Ti bond, Ce content is 50~5,000 ppm, Ti content is 50~5,000ppm, and the viscosity at 25°C is 10~10,000mPa·s polyorganometallic siloxane: 0.01~5 parts by mass relative to 100 parts by mass of the total of components (A)~(D). A hardened product obtained by hardening the silicone resin composition for die bonding as in claim 1. For the hardened product of claim 2, the hardness change after heating at 250°C for 500 hours is within 20%. For the hardened product of claim 2 or 3, the mass reduction rate after heating at 250°C for 500 hours is within 5%. A light-emitting diode device, which is formed by die-bonding the hardened material of claim 2 or 3. A method of manufacturing the silicone resin composition for die bonding as claimed in Claim 1, characterized by comprising: heat-treating a mixture containing (i), (ii) and (iii) at a temperature of 150°C or higher to obtain the aforementioned ( E) The step of component, the step of mixing the aforementioned components (A) to (E); (i) Organopolysiloxane with a viscosity of 10 to 10,000 mPa·s at 25°C, (ii) Containing the following general formula ( e-1) Rare earth carboxylate of cerium carboxylate: The mass of cerium is 0.05 to 5 parts by mass relative to 100 parts by mass of the aforementioned (i) component,

(In the formula, R ⁵ is a monovalent hydrocarbon group of the same or different species, and x is 3 or 4), (iii) The titanium compound represented by the following general formula (e-2) and/or its partial hydrolysis condensate: Titanium The mass is 0.05 to 5 parts by mass relative to 100 parts by mass of the aforementioned (i) component,

(In the formula, R ⁶ is a monovalent hydrocarbon group of the same or different species).