JP2012074416A - Die-bonding material for optical semiconductor device and optical semiconductor device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a die-bonding material for optical semiconductor device which has high heat dissipation and high reflectance of light, and is harder to be discolored into yellow even if exposed to high temperature.SOLUTION: The die-bonding material for optical semiconductor device contains a first silicon resin having a hydrogen atom bonded to a silicon atom, a second silicon resin not having a hydrogen atom bonded to a silicon atom but having an alkenyl group, a catalyst for hydrosilylation reaction, and titanium oxide. The titanium oxide is a rutile type titanium oxide. Thermal conductivity of titanium oxide is 10 W/mK or higher. The titanium oxide is coated with at least one of metal oxides and metal hydroxides.

Description

  The present invention relates to a die bond material for an optical semiconductor device used for die bonding of an optical semiconductor element such as a light emitting diode (LED) element, and an optical semiconductor device using the die bond material for an optical semiconductor device.

  Optical semiconductor elements such as light emitting diode (LED) elements are widely used as light sources for display devices. An optical semiconductor device using an optical semiconductor element has low power consumption and long life. Moreover, the optical semiconductor device can be used even in a harsh environment. Accordingly, optical semiconductor devices are used in a wide range of applications such as mobile phone backlights, liquid crystal television backlights, automobile lamps, lighting fixtures, and signboards.

  In an optical semiconductor device, an LED element is generally bonded to the upper surface of a substrate using a die bond material.

  The following Patent Document 1 discloses an adhesive composition that can be used as the die bond material. Specifically, Patent Document 1 discloses a silicone resin having an alkenyl group bonded to two or more silicon atoms, a silicone resin having three or more SiH groups, a platinum-based catalyst, an adhesion promoter, An adhesive composition containing titanium oxide is disclosed.

  In Patent Document 2 below, a silicone resin having two or more alkenyl groups bonded to a silicon atom, a cyclic siloxane oligomer, a thermally conductive filler, a platinum-based catalyst, and a volatile compound having an aliphatic unsaturated group. A thermally conductive composition containing a reaction modifier and a silicone resin having a hydrogen atom bonded to a silicon atom is disclosed. Examples of the thermally conductive filler include aluminum oxide powder, silicon oxide powder, silicon nitride powder, boron nitride powder, and aluminum nitride powder.

JP 2008-120844 A JP 2008-280395 A

  Silver electrodes and gold electrodes are widely used as electrodes of LCD elements in optical semiconductor devices. When the electrode of the LED element is a silver electrode, the surface of the silver electrode is oxidized and blackened by oxygen or the like that has passed through the sealing material, and the reflectance of light by the electrode tends to decrease. On the other hand, when the electrode of the LCD element is a gold electrode, the electrode itself is inactive, so that the electrode is hardly discolored by the surrounding atmosphere, and the reflectance of light by the electrode is relatively difficult to decrease. However, when a die-bonding material containing a transparent silicone resin is used, there is a problem that light emitted from the LED element reaches the surface of the gold electrode and is absorbed, resulting in poor light extraction efficiency. For these reasons, the die bond material is required to sufficiently reflect light. The higher the light reflectance by the die bond material, the better.

  When an optical semiconductor device is produced using the conventional composition as described in Patent Documents 1 and 2 as a die bond material, the light reflectivity by the die bond material is too low and the optical semiconductor device has sufficient brightness. May not be emitted. Furthermore, the heat dissipation of the die bond material may be low.

  In particular, in the adhesive composition described in Patent Document 1, the use of titanium oxide increases the initial light reflectivity to some extent, but it is difficult to sufficiently increase heat dissipation. In the heat conductive composition described in Patent Document 2, although the heat dissipation is increased to some extent by the heat conductive filler, it is difficult to sufficiently increase the light reflectivity.

  Further, in the above optical semiconductor device, a high amount of heat is generated when light is emitted from the optical semiconductor element. When an optical semiconductor device is manufactured using a conventional composition as described in Patent Documents 1 and 2 as a die bond material, there is also a problem that the die bond material is yellowed by generated heat. When the die bond material turns yellow, the brightness of light extracted from the optical semiconductor device is further reduced.

  An object of the present invention is to provide a die bond material for an optical semiconductor device that has high heat dissipation, high light reflectivity, and hardly yellows even when exposed to high temperatures, and an optical semiconductor using the die bond material for an optical semiconductor device Is to provide a device.

  According to a broad aspect of the present invention, a first silicone resin having a hydrogen atom bonded to a silicon atom, a second silicone resin not having a hydrogen atom bonded to a silicon atom and having an alkenyl group, and hydrosilyl The titanium oxide has a rutile type crystal structure, the titanium oxide has a thermal conductivity of 10 W / m · K or more, and the titanium oxide is oxidized by metal. There is provided a die bond material for an optical semiconductor device, which is coated with at least one of a material and a metal hydroxide.

  The metal element constituting the metal oxide and metal hydroxide is preferably at least one of aluminum and zirconium.

  The titanium oxide is preferably coated with a coating material containing at least one of zirconium oxide and silicon oxide.

  In a specific aspect of the die bond material for an optical semiconductor device according to the present invention, the first silicone resin has a hydrogen atom represented by the following formula (1A) or the following formula (1B) and bonded to a silicon atom. The second silicone resin is a first silicone resin represented by the following formula (51A) or the following formula (51B), which does not have a hydrogen atom bonded to a silicon atom and has an alkenyl group. 2 silicone resin.

  In the above formula (1A), a, b and c are a / (a + b + c) = 0.05 to 0.50, b / (a + b + c) = 0 to 0.40 and c / (a + b + c) = 0.30. 0.81 is satisfied, at least one of R1 to R6 represents a hydrogen atom, and R1 to R6 other than a hydrogen atom represent a hydrocarbon group having 1 to 8 carbon atoms.

  In the formula (1B), a, b, c and d are a / (a + b + c + d) = 0.05 to 0.50, b / (a + b + c + d) = 0 to 0.40, c / (a + b + c + d) = 0. 30 to 0.80 and d / (a + b + c + d) = 0.01 to 0.40, at least one of R1 to R6 represents a hydrogen atom, and R1 to R6 other than a hydrogen atom have 1 to 8 carbon atoms. R7 to R10 each represents a hydrocarbon group having 1 to 8 carbon atoms, and R11 represents a divalent hydrocarbon group having 1 to 8 carbon atoms.

  In the above formula (51A), p, q and r are p / (p + q + r) = 0.05 to 0.50, q / (p + q + r) = 0 to 0.40 and r / (p + q + r) = 0.30. 0.85 is satisfied, and at least one of R51 to R56 represents an alkenyl group, and R51 to R56 other than the alkenyl group represent a hydrocarbon group having 1 to 8 carbon atoms.

  In the above formula (51B), p, q, r and s are p / (p + q + r + s) = 0.05 to 0.50, q / (p + q + r + s) = 0 to 0.40, r / (p + q + r + s) = 0. 30 to 0.80 and s / (p + q + r + s) = 0.01 to 0.40, R51 to R56 each represents at least one alkenyl group, and R51 to R56 other than the alkenyl group have 1 to 8 carbon atoms. R57-60 represents a hydrocarbon group having 1 to 8 carbon atoms, and R61 represents a divalent hydrocarbon group having 1 to 8 carbon atoms.

  In another specific aspect of the die bond material for an optical semiconductor device according to the present invention, the first silicone resin is a first silicone resin having a hydrogen atom bonded to a silicon atom and an alkenyl group.

  An optical semiconductor device according to the present invention includes an optical semiconductor device die-bonding material configured according to the present invention, a connection target member, and an optical semiconductor element connected to the connection target member using the optical semiconductor device die-bonding material. Is provided.

  A die bond material for an optical semiconductor device according to the present invention includes a first silicone resin having a hydrogen atom bonded to a silicon atom, and a second silicone resin not having a hydrogen atom bonded to a silicon atom and having an alkenyl group. , A catalyst for hydrosilylation reaction, and titanium oxide, the crystal structure of the titanium oxide is rutile type, the thermal conductivity of the titanium oxide is 10 W / m · K or more, and the titanium oxide is Since it is coat | covered with at least 1 sort (s) of a metal oxide and a metal hydroxide, heat dissipation can be made high and also the reflectance of light can be made high.

  Furthermore, since the die bond material for optical semiconductor devices according to the present invention has the above composition, the die bond material is yellowed even if a high amount of heat is generated in the optical semiconductor device using the die bond material for optical semiconductor devices according to the present invention. It is hard to do. For this reason, a high light reflectance can be maintained over a long period of time.

FIG. 1 is a front sectional view showing an optical semiconductor device according to an embodiment of the present invention.

  Details of the present invention will be described below.

  The die bond material for an optical semiconductor device according to the present invention includes a first silicone resin having a hydrogen atom bonded to a silicon atom, and a second silicone resin not having a hydrogen atom bonded to a silicon atom and having an alkenyl group. And a hydrosilylation reaction catalyst and titanium oxide. The crystal structure of the titanium oxide is rutile type. The thermal conductivity of the titanium oxide is 10 W / m · K or more. The titanium oxide is coated with at least one of a metal oxide and a metal hydroxide.

  By adopting the above composition, since the thermal conductivity of rutile titanium oxide is 10 W / m · K or more in particular, the heat dissipation of the die bond material can be increased. For this reason, thermal degradation of the optical semiconductor device can be suppressed. Furthermore, since the heat dissipation of the die bond material is high, the amount of heat generated in the optical semiconductor device is effectively dissipated through the die bond material. For this reason, yellowing of the die bond material can be suppressed. Furthermore, the reflectance of the light in a die-bonding material can also be made high by using a specific rutile type titanium oxide. For this reason, in the optical semiconductor device, when light is emitted from the optical semiconductor element, the light is effectively reflected by the die bond material. For this reason, the light extracted from the optical semiconductor device becomes brighter.

  In addition, by adopting the above composition, even if rutile-type titanium oxide is coated with a specific material, a high amount of heat is generated in the optical semiconductor device, and the die bond material is exposed to a high temperature. Is less likely to yellow. As a result, a high light reflectance can be maintained for a long time. For this reason, the brightness of light extracted from the optical semiconductor device is unlikely to decrease.

(First silicone resin)
The 1st silicone resin contained in the die-bonding material for optical semiconductor devices which concerns on this invention has the hydrogen atom couple | bonded with the silicon atom. The hydrogen atom is directly bonded to the silicon atom. From the viewpoint of further improving the gas barrier property of the die bond material, the first silicone resin preferably has a hydrogen atom bonded to a silicon atom and an aryl group. Examples of the aryl group include an unsubstituted phenyl group, a substituted phenyl group, an unsubstituted phenylene group, and a substituted phenylene group.

  From the viewpoint of obtaining a die bond material that is more excellent in gas barrier properties, the first silicone resin preferably has a hydrogen atom bonded to a silicon atom and an alkenyl group.

  From the viewpoint of obtaining a die bond material that is more excellent in gas barrier properties, the first silicone resin is preferably a first silicone resin represented by the following formula (1A) or the following formula (1B). However, as the first silicone resin, a first silicone resin other than the first silicone resin represented by the following formula (1A) or the following formula (1B) may be used. The first silicone resin represented by the following formula (1B) may have a phenylene group or may not have a phenylene group. As for the said 1st silicone resin, only 1 type may be used and 2 or more types may be used together.

In the above formula (1A), a, b and c are a / (a + b + c) = 0.05 to 0.50, b / (a + b + c) = 0 to 0.40 and c / (a + b + c) = 0.30. 0.81 is satisfied, at least one of R1 to R6 represents a hydrogen atom, and R1 to R6 other than a hydrogen atom represent a hydrocarbon group having 1 to 8 carbon atoms. In the above formula (1A), the structural unit represented by (R4R5SiO _2/2 ) and the structural unit represented by (R6SiO _3/2 ) may each have an alkoxy group, and have a hydroxy group. You may have.

In the formula (1B), a, b, c and d are a / (a + b + c + d) = 0.05 to 0.50, b / (a + b + c + d) = 0 to 0.40, c / (a + b + c + d) = 0. 30 to 0.80 and d / (a + b + c + d) = 0.01 to 0.40, at least one of R1 to R6 represents a hydrogen atom, and R1 to R6 other than a hydrogen atom have 1 to 8 carbon atoms. R7 to R10 each represents a hydrocarbon group having 1 to 8 carbon atoms, and R11 represents a divalent hydrocarbon group having 1 to 8 carbon atoms. In the above formula (1B), the structural unit represented by (R4R5SiO _2/2 ), the structural unit represented by (R6SiO _3/2 ), and the structural unit represented by (R7R8R9R10Si ₂ R11O _2/2 ) are Each may have an alkoxy group and may have a hydroxy group.

  From the viewpoint of obtaining a die bond material that is further excellent in gas barrier properties, in the above formula (1A), at least one of R1 to R6 represents a phenyl group, at least one represents a hydrogen atom, a phenyl group, and a hydrogen atom. It is preferable that R1-R6 other than represents a C1-C8 hydrocarbon group.

  From the viewpoint of obtaining a die bond material that is further excellent in gas barrier properties, in the formula (1B), at least one of R1 to R6 represents a phenyl group, at least one represents a hydrogen atom, a phenyl group, and a hydrogen atom. It is preferable that R1-R6 other than represents a C1-C8 hydrocarbon group.

  From the viewpoint of obtaining a die bond material that is further excellent in gas barrier properties, in the formula (1A), at least one of R1 to R6 represents a hydrogen atom, at least one represents an alkenyl group, and a hydrogen atom and an alkenyl group. It is preferable that R1-R6 other than represents a C1-C8 hydrocarbon group.

  From the viewpoint of obtaining a die bond material that is further excellent in gas barrier properties, in the above formula (1B), R1 to R6 represent at least one hydrogen atom, at least one alkenyl group, and a hydrogen atom and an alkenyl group. It is preferable that R1-R6 other than represents a C1-C8 hydrocarbon group.

  From the viewpoint of obtaining a die bond material that is further excellent in gas barrier properties, in the formula (1A), at least one of R1 to R6 represents a phenyl group, at least one represents a hydrogen atom, and at least one represents alkenyl. R1 to R6 other than a phenyl group, a hydrogen atom and an alkenyl group preferably represent a hydrocarbon group having 1 to 8 carbon atoms.

  From the viewpoint of obtaining a die bond material that is further excellent in gas barrier properties, in the above formula (1B), at least one of R1 to R6 represents a phenyl group, at least one represents a hydrogen atom, and at least one represents alkenyl. R1 to R6 other than a phenyl group, a hydrogen atom and an alkenyl group preferably represent a hydrocarbon group having 1 to 8 carbon atoms.

  The above formulas (1A) and (1B) represent average composition formulas. The hydrocarbon group in the above formula (1A) and formula (1B) may be linear or branched. R1 to R6 in the above formulas (1A) and (1B) may be the same or different. R7 to R10 in the above formula (1B) may be the same or different.

In the above formulas (1A) and (1B), an oxygen atom part in the structural unit represented by (R4R5SiO _2/2 ), an oxygen atom part in the structural unit represented by (R6SiO _3/2 ), (R7R8R9R10Si ₂ R11O ₂ The oxygen atom part in the structural unit represented by _{/ 2} ) represents an oxygen atom part forming a siloxane bond, an oxygen atom part of an alkoxy group, or an oxygen atom part of a hydroxy group.

  In general, in each structural unit of the above formulas (1A) and (1B), the content of alkoxy groups is small, and the content of hydroxy groups is also small. In general, when an organosilicon compound such as an alkoxysilane compound is hydrolyzed and polycondensed in order to obtain a first silicone resin, most of the alkoxy groups and hydroxy groups are converted into partial skeletons of siloxane bonds. Because. That is, most of oxygen atoms of the alkoxy group and oxygen atoms of the hydroxy group are converted into oxygen atoms forming a siloxane bond. When each structural unit of the above formula (1A) and formula (1B) has an alkoxy group or a hydroxy group, a slight amount of unreacted alkoxy group or hydroxy group that has not been converted into a partial skeleton of a siloxane bond remains. Indicates that The same applies to the case where each structural unit of formulas (51A) and (51B) described later has an alkoxy group or a hydroxy group.

  It does not specifically limit as a C1-C8 hydrocarbon group in the said Formula (1A) and Formula (1B), For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group, cyclohexyl group, A vinyl group, an allyl group, a phenyl group, etc. are mentioned.

  The divalent hydrocarbon group having 1 to 8 carbon atoms in the formula (1B) is not particularly limited, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a cyclohexylene group, and phenylene. Groups and the like.

  In the above formula (1A) and formula (1B), examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. From the viewpoint of further enhancing gas barrier properties, the alkenyl group in the first silicone resin and the alkenyl group in the above formulas (1A) and (1B) are preferably vinyl groups or allyl groups, and are vinyl groups. It is more preferable.

  It is preferable that the content ratio of the aryl group calculated | required from the following formula (X1) in the said 1st silicone resin is 10 mol% or more and 50 mol% or less. When the content ratio of the aryl group is 10 mol% or more, the gas barrier property is further enhanced. When the content ratio of the aryl group is 50 mol% or less, the die bond material is hardly peeled off. From the viewpoint of further enhancing the gas barrier properties, the content ratio of the aryl group is more preferably 20 mol% or more. From the viewpoint of making the peeling of the die bond material more difficult to occur, the content ratio of the aryl group is more preferably 40 mol% or less.

  Aryl group content ratio (mol%) = (average number of aryl groups contained in one molecule of the first silicone resin × molecular weight of aryl group / number average molecular weight of the first silicone resin) × 100・ Formula (X1)

  When the first silicone resin represented by the above formula (1A) or the above formula (1B) is used as the first silicone resin, in the above formula (X1), the “first silicone resin” "The 1st silicone resin whose average composition formula is represented by the said Formula (1A) or the said Formula (1B)" is shown.

  When the first silicone resin represented by the above formula (1A) and having a phenyl group is used, the aryl group in the above formula (X1) represents a phenyl group, and the content ratio of the aryl group is the content ratio of the phenyl group. Show.

  When the first silicone resin represented by the above formula (1B) and having a phenyl group and a phenylene group is used, the aryl group in the above formula (X1) represents a phenyl group and a phenylene group, and contains an aryl group The ratio indicates the total content ratio of the phenyl group and the phenylene group.

  When the first silicone resin represented by the above formula (1B) and having a phenyl group and not having a phenylene group is used, the aryl group in the above formula (X1) represents a phenyl group, The content ratio indicates the content ratio of the phenyl group.

From the viewpoint of further enhancing the gas barrier properties, in the above formula (1B), the structural unit of (R7R8R9R10Si ₂ R11O _2/2 ) is preferably a structural unit represented by the following formula (1b-1). The structural unit represented by the following formula (1b-1) has a phenylene group, and the phenylene group is a substituted or unsubstituted phenylene group. In the present specification, the term “phenylene group” includes a substituted phenylene group in which a hydrocarbon group having 1 to 8 carbon atoms is substituted on a benzene ring. In the structural unit represented by the following formula (1b-1), the terminal oxygen atom generally forms a siloxane bond with an adjacent silicon atom, and shares an oxygen atom with the adjacent structural unit. Therefore, one oxygen atom at the terminal is defined as “O _1/2 ”.

  In the formula (1b-1), Ra represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R7 to R10 each represents a hydrocarbon group having 1 to 8 carbon atoms. The hydrocarbon group may be linear or branched. In addition, the coupling | bonding site | part of three groups couple | bonded with the benzene ring in the said Formula (1b-1) is not specifically limited.

In the above formula (1B), the structural unit of (R7R8R9R10Si ₂ R11O _2/2 ) is preferably a structural unit represented by the following formula (1b-2). The structural unit represented by the following formula (1b-2) has a phenylene group, and the phenylene group is a substituted or unsubstituted phenylene group. The bonding site of Ra bonded to the benzene ring in the following formula (1b-2) is not particularly limited.

  In said formula (1b-2), Ra represents a hydrogen atom or a C1-C8 hydrocarbon group, R7-R10 represents a C1-C8 hydrocarbon group, respectively.

In the above formula (1B), the structural unit represented by (R7R8R9R10Si ₂ R11O _2/2 ) is more preferably a structural unit represented by the following formula (1b-3). The structural unit represented by the following formula (1b-3) has a phenylene group, and the phenylene group is an unsubstituted phenylene group.

  In said formula (1b-3), R7-R10 represents a C1-C8 hydrocarbon group, respectively.

In the first silicone resin represented by the above formula (1A) or formula (1B), the structural unit represented by (R4R5SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) has the following formula (1- The structure represented by 2), that is, a structure in which one of oxygen atoms bonded to a silicon atom in the bifunctional structural unit constitutes a hydroxy group or an alkoxy group may be included.

(R4R5SiXO _1/2 ) (Formula (1-2))

The structural unit represented by (R4R5SiO _2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (1-b), and is further represented by the following formula (1-2b). A portion surrounded by a broken line of the structural unit may be included. That is, a structural unit having a group represented by R4 and R5 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R4R5SiO _2/2 ). Specifically, when the alkoxy group is converted into a partial skeleton of a siloxane bond, the structural unit represented by (R4R5SiO _2/2 ) is a broken line of the structural unit represented by the following formula (1-b) The part enclosed by is shown. When an unreacted alkoxy group remains, or when the alkoxy group is converted to a hydroxy group, the structural unit represented by (R4R5SiO _2/2 ) having the remaining alkoxy group or hydroxy group has the following formula: The part enclosed with the broken line of the structural unit represented by (1-2-b) is shown.

  In the above formulas (1-2) and (1-2-b), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. R4 and R5 in the above formulas (1-b), (1-2) and (1-2b) are the same groups as R4 and R5 in the above formula (1A) or formula (1B).

In the first silicone resin represented by the above formula (1A) or formula (1B), the structural unit represented by (R6SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) is represented by the following formula (1- 3) or a structure represented by (1-4), that is, a structure in which two oxygen atoms bonded to a silicon atom in a trifunctional structural unit each constitute a hydroxy group or an alkoxy group, or in a trifunctional structural unit One of the oxygen atoms bonded to the silicon atom may include a structure constituting a hydroxy group or an alkoxy group.

(R6SiX ₂ O _1/2 ) Formula (1-3)
(R6SiXO _2/2 ) Formula (1-4)

The structural unit represented by (R6SiO _3/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (1-c), and further includes the following formula (1-3-c) or (1 The part enclosed with the broken line of the structural unit represented by -4-c) may be included. That is, a structural unit having a group represented by R6 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R6SiO _3/2 ).

  In the above formulas (1-3), (1-3-c), (1-4) and (1-4-c), X represents OH or OR, and OR represents a linear or branched group. An alkoxy group having 1 to 4 carbon atoms is represented. R6 in the above formula (1-c), (1-3), (1-3-c), (1-4) and (1-4-c) is in the above formula (1A) or (1B). R6 is the same group as R6.

In the first silicone resin represented by the above formula (1B), the structural unit represented by (R7R8R9R10Si ₂ R11O _2/2 ) is a structure represented by the following formula (1-5), that is, (R7R8R9R10Si ₂ One of the oxygen atoms bonded to the silicon atom in the structural unit of R 11 O _2/2 ) may contain a structure constituting a hydroxy group or an alkoxy group.

(R7R8R9R10Si ₂ R11XO _1/2) ··· formula (1-5)

Structural unit represented by (R7R8R9R10Si ₂ R11O _2/2) includes a portion which is surrounded by dashed lines of a unit represented by the following formula (1-d), further by the following formula (1-5-d) The part enclosed by the broken line of the structural unit represented may be included. That is, a structural unit having a group represented by R7, R8, R9, R10 and R11 and having an alkoxy group or a hydroxy group remaining at the terminal is also a structure represented by (R7R8R9R10Si ₂ R11O _2/2 ). Included in the unit.

  In the above formulas (1-5) and (1-5-d), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. R7 to R11 in the above formulas (1-d), (1-5) and (1-5-d) are the same groups as R7 to R11 in the above formula (1B).

  The above formulas (1-b) to (1-d), formulas (1-2) to (1-5), and formulas (1-2-b), (1-3-c), (1-4- In (c) and (1-5-d), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, and n- Examples include butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group and t-butoxy group.

  In the above formula (1A), the lower limit of a / (a + b + c) is 0.05, and the upper limit is 0.50. When a / (a + b + c) is not less than the above lower limit and not more than the upper limit, the heat resistance of the die bond material can be further enhanced, and peeling of the die bond material can be further suppressed. In the above formula (1A), a preferable lower limit of a / (a + b + c) is 0.10, a more preferable lower limit is 0.15, a preferable upper limit is 0.45, and a more preferable upper limit is 0.40.

In the above formula (1A), the lower limit of b / (a + b + c) is 0, and the upper limit is 0.40. When b / (a + b + c) satisfies the above upper limit, the storage elastic modulus at a high temperature of the die-bonding material can be increased. In addition, when b is 0 and b / (a + b + c) is 0, the structural unit of (R4R5SiO _2/2 ) does not exist in the above formula (1A).

  In the above formula (1A), the lower limit of c / (a + b + c) is 0.30, and the upper limit is 0.80. When c / (a + b + c) satisfies the above lower limit, the storage elastic modulus at a high temperature of the die-bonding material can be increased. When c / (a + b + c) satisfies the above upper limit, the heat resistance of the die bond material becomes high, and the thickness of the cured product of the die bond material is difficult to decrease under a high temperature environment. In said formula (1A), the preferable minimum of c / (a + b + c) is 0.35, the more preferable minimum is 0.40, and a preferable upper limit is 0.75.

  In the above formula (1B), the lower limit of a / (a + b + c + d) is 0.05, and the upper limit is 0.50. When a / (a + b + c + d) satisfies the above lower limit and upper limit, the heat resistance of the die bond material can be further increased, and peeling of the die bond material can be further suppressed. In the above formula (1A), a preferable lower limit of a / (a + b + c + d) is 0.10, a more preferable lower limit is 0.15, a preferable upper limit is 0.45, and a more preferable upper limit is 0.40.

In the above formula (1B), the lower limit of b / (a + b + c + d) is 0, and the upper limit is 0.40. When b / (a + b + c) satisfies the above upper limit, the storage elastic modulus at a high temperature of the die-bonding material can be increased. In addition, when b is 0 and b / (a + b + c + d) is 0, the structural unit of (R4R5SiO _2/2 ) does not exist in the above formula (1B).

  In the above formula (1B), the lower limit of c / (a + b + c + d) is 0.30, and the upper limit is 0.80. When c / (a + b + c + d) satisfies the above lower limit, the storage elastic modulus at a high temperature of the die bond material can be increased. When c / (a + b + c + d) satisfies the above upper limit, the heat resistance of the die bond material becomes high, and the thickness of the cured product of the die bond material is difficult to decrease under a high temperature environment. The preferable lower limit of c / (a + b + c + d) is 0.35, the more preferable lower limit is 0.40, and the preferable upper limit is 0.75.

  In the above formula (1B), the lower limit of d / (a + b + c + d) is 0.01, and the upper limit is 0.40. When d / (a + b + c + d) satisfies the above lower limit and upper limit, a die bond material for an optical semiconductor device that has a high gas barrier property against corrosive gas and hardly cracks or peels even when used in a harsh environment is obtained. be able to. From the viewpoint of obtaining a die bond material for an optical semiconductor device that has a higher gas barrier property against corrosive gas and is less likely to cause cracking or peeling even when used in a harsh environment, in the above formula (1B) The preferable lower limit of d / (a + b + c + d) is 0.03, the more preferable lower limit is 0.05, the preferable upper limit is 0.35, and the more preferable upper limit is 0.30.

When the first silicone resin is subjected to ²⁹ Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) based on tetramethylsilane (hereinafter referred to as TMS), although the above formula shows a slight variation depending on the type of substituent. The peak corresponding to the structural unit represented by (R1R2R3SiO _1/2 ) _a in (1A) and formula (1B) appears in the vicinity of +10 to −5 ppm, and (R4R5SiO in formula (1A) and formula (1B) above _2/2 ) Each peak corresponding to the bifunctional structural unit of _b and (1-2) appears in the vicinity of −10 to −50 ppm, and (R6SiO _3/2 ) _{c in the} above formulas (1A) and (1B). And peaks corresponding to the trifunctional structural units of (1-3) and (1-4) appear in the vicinity of −50 to −80 ppm, and (R7R8R9R10Si ₂ R11O _2/2 ) in the above formula (1B) A peak corresponding to _d appears in the vicinity of 0 to -5 ppm.

Therefore, ²⁹ Si-NMR is measured, and the ratio of each structural unit in the above formulas (1A) and (1B) can be measured by comparing the peak areas of the respective signals.

However, in the case where the structural unit in the formula (1A) and the formula (1B) cannot be distinguished from the ²⁹ Si-NMR measurement based on the TMS, not only the ²⁹ Si-NMR measurement result but also ¹ H The ratio of each structural unit in the above formula (1A) and formula (1B) can be distinguished by using the measurement result of -NMR as necessary.

(Second silicone resin)
The second silicone resin contained in the die bond material for optical semiconductor devices according to the present invention has an alkenyl group. The alkenyl group is directly bonded to the silicon atom. The carbon atom in the carbon-carbon double bond of the alkenyl group may be bonded to the silicon atom, and the carbon atom different from the carbon atom in the carbon-carbon double bond of the alkenyl group is bonded to the silicon atom. It may be.

  From the viewpoint of further enhancing the gas barrier property of the die bond material, the second silicone resin preferably has an alkenyl group and an aryl group. Examples of the aryl group include an unsubstituted phenyl group, a substituted phenyl group, an unsubstituted phenylene group, and a substituted phenylene group.

  From the viewpoint of obtaining a die bond material that is more excellent in gas barrier properties, the second silicone resin is preferably a second silicone resin represented by the following formula (51A) or the following formula (51B). However, as the second silicone resin, a second silicone resin other than the second silicone resin represented by the following formula (51A) or the following formula (51B) may be used. The second silicone resin represented by the following formula (51B) may have a phenylene group or may not have a phenylene group. As for the said 2nd silicone resin, only 1 type may be used and 2 or more types may be used together.

In the above formula (51A), p, q and r are p / (p + q + r) = 0.05 to 0.50, q / (p + q + r) = 0 to 0.40 and r / (p + q + r) = 0.30. 0.85 is satisfied, and at least one of R51 to R56 represents an alkenyl group, and R51 to R56 other than the alkenyl group represent a hydrocarbon group having 1 to 8 carbon atoms. In the formula (51A), the structural unit represented by (R54R55SiO _2/2 ) and the structural unit represented by (R56SiO _3/2 ) may each have an alkoxy group, You may have.

In the above formula (51B), p, q, r and s are p / (p + q + r + s) = 0.05 to 0.50, q / (p + q + r + s) = 0 to 0.40, r / (p + q + r + s) = 0. 30 to 0.80 and s / (p + q + r + s) = 0.01 to 0.40, R51 to R56 each represents at least one alkenyl group, and R51 to R56 other than the alkenyl group have 1 to 8 carbon atoms. R57-60 represents a hydrocarbon group having 1 to 8 carbon atoms, and R61 represents a divalent hydrocarbon group having 1 to 8 carbon atoms. In the above formula (51B), the structural unit represented by (R54R55SiO _2/2 ), the structural unit represented by (R56SiO _3/2 ), and the structural unit represented by (R57R58R59R60Si ₂ R61O _2/2 ) are Each may have an alkoxy group and may have a hydroxy group.

  The above formula (51A) and formula (51B) show the average composition formula. The hydrocarbon group in the above formula (51A) and formula (51B) may be linear or branched. R51 to R56 in the above formula (51A) and formula (51B) may be the same or different. R57 to R60 in the above formula (51B) may be the same or different.

  In the above formula (51A) and formula (51B), examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. From the viewpoint of further enhancing the gas barrier properties, the alkenyl group in the second silicone resin and the alkenyl group in the above formulas (51A) and (51B) are preferably vinyl groups or allyl groups, and are vinyl groups. It is more preferable.

  It does not specifically limit as a C1-C8 hydrocarbon group in the said Formula (51A) and Formula (51B), For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group, cyclohexyl group, A vinyl group, an allyl group, and a phenyl group are mentioned. The divalent hydrocarbon group having 1 to 8 carbon atoms in the formula (51B) is not particularly limited, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a cyclohexylene group, and Examples include a phenylene group.

  From the viewpoint of further enhancing the gas barrier property of the die bond material and further preventing the occurrence of peeling, the second silicone resin is represented by the following formula (51A) or the following formula (51B) and bonded to a silicon atom. It is preferable that the second silicone resin does not have a hydrogen atom and has an alkenyl group and an aryl group.

  From the viewpoint of obtaining a die bond material that is more excellent in gas barrier properties, in the above formula (51A), at least one of R51 to R56 represents a phenyl group, at least one represents an alkenyl group, and other than phenyl group and alkenyl group R51 to R56 preferably represent a hydrocarbon group having 1 to 8 carbon atoms.

  From the viewpoint of obtaining a die bond material that is more excellent in gas barrier properties, in the formula (51B), at least one of R51 to R56 represents a phenyl group, at least one represents an alkenyl group, and other than the phenyl group and the alkenyl group R51 to R56 in the formula represent a hydrocarbon group having 1 to 8 carbon atoms, R57 to 60 represent a hydrocarbon group having 1 to 8 carbon atoms, and R61 represents a divalent hydrocarbon group having 1 to 8 carbon atoms. Is preferably represented.

  It is preferable that the content ratio of the aryl group calculated | required from the following formula (X51) in the said 2nd silicone resin is 10 mol% or more and 50 mol% or less. When the content ratio of the aryl group is 10 mol% or more, the gas barrier property is further enhanced. When the content ratio of the aryl group is 50 mol% or less, the die bond material is hardly peeled off. From the viewpoint of further enhancing the gas barrier properties, the content ratio of the aryl group is more preferably 20 mol% or more. From the viewpoint of making peeling more difficult, the aryl group content is more preferably 40 mol% or less.

Aryl group content ratio (mol%) = (average number of aryl groups contained in one molecule of second silicone resin × molecular weight of aryl group / number average molecular weight of second silicone resin) × 100 Formula (X51)
When the second silicone resin represented by the formula (51A) or the formula (51B) is used as the second silicone resin, in the formula (X51), the “second silicone resin” "The 2nd silicone resin whose average composition formula is represented by said Formula (51A) or said Formula (51B)" is shown.

  When the second silicone resin represented by the above formula (51A) and having a phenyl group is used, the aryl group in the above formula (X51) represents a phenyl group, and the content ratio of the aryl group is the content ratio of the phenyl group. Show.

  In the case of using the second silicone resin represented by the above formula (51B) and having a phenyl group and a phenylene group, the aryl group in the above formula (X51) represents a phenyl group and a phenylene group, and contains an aryl group The ratio indicates the total content ratio of the phenyl group and the phenylene group.

  When the second silicone resin represented by the above formula (51B) and having a phenyl group and not having a phenylene group is used, the aryl group in the above formula (X51) represents a phenyl group, The content ratio indicates the content ratio of the phenyl group.

From the viewpoint of further enhancing gas barrier properties, in the above formula (51B), the structural unit of (R57R58R59R60Si ₂ R61O _2/2 ) is preferably a structural unit represented by the following formula (51b-1). The structural unit represented by the following formula (51b-1) has a phenylene group, and the phenylene group is a substituted or unsubstituted phenylene group.

  In said formula (51b-1), Rb represents a hydrogen atom or a C1-C8 hydrocarbon group, R57-R60 represents a C1-C8 hydrocarbon group, respectively. The hydrocarbon group may be linear or branched. In addition, the coupling | bonding site | part of three groups couple | bonded with the benzene ring in the said Formula (51b-1) is not specifically limited.

In the above formula (51B), the structural unit represented by (R57R58R59R60Si ₂ R61O _2/2 ) is preferably a structural unit represented by the following formula (51b-2). The structural unit represented by the following formula (51b-2) has a phenylene group, and the phenylene group is a substituted or unsubstituted phenylene group. The bonding site of Rb bonded to the benzene ring in the following formula (51b-2) is not particularly limited.

  In said formula (51b-2), Rb represents a hydrogen atom or a C1-C8 hydrocarbon group, R57-R60 represents a C1-C8 hydrocarbon group, respectively.

In the above formula (51B), the structural unit represented by (R57R58R59R60Si ₂ R61O _2/2 ) is more preferably a structural unit represented by the following formula (51b-3). The structural unit represented by the following formula (51b-3) has a phenylene group, and the phenylene group is an unsubstituted phenylene group.

  In said formula (51b-3), R57-R60 represents a C1-C8 hydrocarbon group, respectively.

In the second silicone resin represented by the above formula (51A) or formula (51B), the structural unit represented by (R54R55SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) has the following formula (51- The structure represented by 2), that is, a structure in which one of oxygen atoms bonded to a silicon atom in the bifunctional structural unit constitutes a hydroxy group or an alkoxy group may be included.

(R54R55SiXO _1/2 ) Formula (51-2)

The structural unit represented by (R54R55SiO _2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (51-b), and is further represented by the following formula (51-2-b). A portion surrounded by a broken line of the structural unit may be included. That is, a structural unit having a group represented by R54 and R55 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R54R55SiO _2/2 ).

  In the above formulas (51-2) and (51-2-b), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. R54 and R55 in the above formulas (51-b), (51-2) and (51-2-b) are the same groups as R54 and R55 in the above formula (51A) or formula (51B).

In the second silicone resin represented by the above formula (51A) or formula (51B), the structural unit represented by (R56SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) is represented by the following formula (51- 3) or a structure represented by (51-4), that is, a structure in which two oxygen atoms bonded to a silicon atom in a trifunctional structural unit each constitute a hydroxy group or an alkoxy group, or in a trifunctional structural unit One of the oxygen atoms bonded to the silicon atom may include a structure constituting a hydroxy group or an alkoxy group.

(R56SiX ₂ O _1/2 ) (Formula (51-3)
(R56SiXO _2/2 ) Formula (51-4)

The structural unit represented by (R56SiO _3/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (51-c), and further includes the following formula (51-3-c) or (51 The part enclosed with the broken line of the structural unit represented by -4-c) may be included. That is, a structural unit having a group represented by R56 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R56SiO _3/2 ).

  In the above formulas (51-3), (51-3-c), (51-4) and (51-4-c), X represents OH or OR, and OR represents a linear or branched group. An alkoxy group having 1 to 4 carbon atoms is represented. R56 in the above formulas (51-c), (51-3), (51-3-c), (51-4) and (51-4-c) is in the above formulas (51A) and (51B). R56 is the same group as R56.

In the second silicone resin represented by the above formula (51B), the structural unit represented by (R57R58R59R60Si ₂ R61O _2/2 ) is a structure represented by the following formula (51-5), that is, (R57R58R59R60Si ₂ R61O _2/2 ) may contain a structure in which one of oxygen atoms bonded to a silicon atom in the structural unit constitutes a hydroxy group or an alkoxy group.

(R57R58R59R60Si ₂ XR61O _1/2 ) (Formula (51-5)

The structural unit represented by (R57R58R59R60Si ₂ R61O _2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (51-d), and further represented by the following formula (51-5-d). The part enclosed by the broken line of the structural unit represented may be included. That is, the structural unit having a group represented by R57, R58, R59, R60 and R61 and having an alkoxy group or a hydroxy group remaining at the terminal is also a structure represented by (R57R58R59R60Si ₂ R61O _2/2 ). Included in the unit.

  In the above formulas (51-5) and (51-5-d), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. R57 to R61 in the above formulas (51-d), (51-5) and (51-5-d) are the same groups as R57 to R61 in the above formula (51B).

  The above formulas (51-b) to (51-d), formulas (51-2) to (51-5), and formulas (51-2b), (51-3-c), (51-4-) In (c) and (51-5-d), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include methoxy group, ethoxy group, n-propoxy group, n- Examples include butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group and t-butoxy group.

  In the above formula (51A), the lower limit of p / (p + q + r) is 0.05, and the upper limit is 0.50. When p / (p + q + r) satisfies the above lower limit and upper limit, the heat resistance of the die bond material can be further increased, and peeling of the die bond material can be further suppressed. In the above formula (51A), the preferable lower limit of p / (p + q + r) is 0.10, the more preferable lower limit is 0.15, the preferable upper limit is 0.45, and the more preferable upper limit is 0.40.

In the above formula (51A), the lower limit of q / (p + q + r) is 0, and the upper limit is 0.40. q / (p + q + r) When the above upper limit is satisfied, the storage elastic modulus at a high temperature of the die bond material can be increased. In said formula (51A), the preferable upper limit of q / (p + q + r) is 0.35, and a more preferable upper limit is 0.30. In addition, when q is 0 and q / (p + q + r) is 0, the structural unit of (R54R55SiO _2/2 ) does not exist in the above formula (51A).

  In the above formula (51A), the lower limit of r / (p + q + r) is 0.30, and the upper limit is 0.80. When r / (p + q + r) satisfies the above lower limit, the storage elastic modulus at a high temperature of the die-bonding material can be increased. When r / (p + q + r) satisfies the above upper limit, the heat resistance of the die bond material becomes high, and the thickness of the cured product of the die bond material becomes difficult to decrease under a high temperature environment.

  In the above formula (51B), the lower limit of p / (p + q + r + s) is 0.05, and the upper limit is 0.50. When p / (p + q + r + s) satisfies the above upper limit, the heat resistance of the die bond material can be further increased, and peeling of the die bond material can be further suppressed.

In the above formula (51B), the lower limit of q / (p + q + r + s) is 0, and the upper limit is 0.40. When q / (p + q + r + s) satisfies the above upper limit, the storage elastic modulus at a high temperature of the die bond material can be increased. In addition, when q is 0 and q / (p + q + r + s) is 0, there is no structural unit of (R54R55SiO _2/2 ) in the above formula (51B).

  In the above formula (51B), the lower limit of r / (p + q + r + s) is 0.30, and the upper limit is 0.80. When r / (p + q + r + s) satisfies the above lower limit, the storage elastic modulus at a high temperature of the die-bonding material can be increased. When the above upper limit is satisfied, the heat resistance of the die bond material is increased, and the thickness of the cured product of the die bond material is difficult to decrease under a high temperature environment.

  In the above formula (51B), the lower limit of s / (p + q + r + s) is 0.01, and the upper limit is 0.40. When s / (p + q + r + s) satisfies the above lower limit and upper limit, a die bond material for optical semiconductor devices that has a high gas barrier property against corrosive gas and hardly cracks or peels even when used in harsh environments is obtained. be able to. From the viewpoint of obtaining a die-bonding material for an optical semiconductor device that has a higher gas barrier property against corrosive gas and is less prone to cracking or peeling even when used in a harsh environment, in the above formula (51B) The preferable lower limit of s / (p + q + r + s) is 0.03, the more preferable lower limit is 0.05, the preferable upper limit is 0.35, and the more preferable upper limit is 0.30.

For the second silicone resin, when ²⁹ Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) is performed with reference to tetramethylsilane (hereinafter referred to as TMS), although some variation is observed depending on the type of substituent, the above formula The peak corresponding to the structural unit represented by (R51R52R53SiO _1/2 ) _p in (51A) and formula (51B) appears in the vicinity of +10 to −5 ppm, and (R54R55SiO in the above formula (51A) and formula (51B)) _2/2 ) Each peak corresponding to _q and the bifunctional structural unit of (51-2) appears in the vicinity of −10 to −50 ppm, and (R56SiO _3/2 ) _{r in the} above formulas (51A) and (51B). And peaks corresponding to the trifunctional structural units of (51-3) and (51-4) appear in the vicinity of −50 to −80 ppm, and (R57R5 in the above formula (51B) R59R60Si ₂ R61O _2/2) peak corresponding to _d appears in the vicinity of 0 to-5 ppm.

Therefore, ²⁹ Si-NMR is measured, and the ratio of each structural unit in the above formula (51A) and formula (51B) can be measured by comparing the peak areas of the respective signals.

However, when the structural unit in the formula (51A) and the formula (51B) cannot be distinguished from the ²⁹ Si-NMR measurement based on the TMS, not only the ²⁹ Si-NMR measurement result but also ¹ H The ratio of each structural unit in the above formula (51A) and formula (51B) can be distinguished by using the measurement result of -NMR as necessary.

  The content of the second silicone resin is preferably 10 parts by weight or more and 400 parts by weight or less with respect to 100 parts by weight of the first silicone resin. When the contents of the first and second silicone resins are within this range, it is possible to obtain a die bond material having a higher storage elastic modulus at a high temperature and a more excellent gas barrier property. From the viewpoint of obtaining a die-bonding material having an even higher storage elastic modulus at a high temperature and a further excellent gas barrier property, the content of the second silicone resin is 100% by weight of the first silicone resin. A more preferred lower limit is 30 parts by weight, a still more preferred lower limit is 50 parts by weight, a more preferred upper limit is 300 parts by weight, and a still more preferred upper limit is 200 parts by weight.

  The total content of the first and second silicone resins in 100% by weight of the die bond material for an optical semiconductor device is preferably 20% by weight or more, more preferably 25% by weight or more, and further preferably 30% by weight or more. Especially preferably, it is 40 weight% or more, Preferably it is 80 weight% or less, More preferably, it is 70 weight% or less. When the content of the first and second silicone resins is not less than the above lower limit and not more than the above upper limit, the viscosity of the die bond material can be easily adjusted to an appropriate range, and the curability of the die bond material can be improved.

  From the viewpoint of obtaining a die bond material that is more excellent in gas barrier properties, the die bond material for an optical semiconductor device according to the present invention is represented by the first silicone resin represented by the above formula (1B) and the above formula (51B). It is preferable that at least one of the second silicone resins is included.

(Other properties of the first and second silicone resins and their synthesis methods)
The preferable lower limit of the alkoxy group content of the first and second silicone resins is 0.5 mol%, the more preferable lower limit is 1 mol%, the preferable upper limit is 10 mol%, and the more preferable upper limit is 5 mol%. When the content of the alkoxy group is within the above preferred range, the adhesion of the die bond material can be enhanced.

  When the content of the alkoxy group satisfies the preferable lower limit, the adhesion of the die bond material can be improved. When the content of the alkoxy group satisfies the above preferable upper limit, the storage stability of the first and second silicone resins and the die bond material is increased, and the heat resistance of the die bond material is further increased.

  The content of the alkoxy group means the amount of the alkoxy group contained in the average composition formula of the first and second silicone resins.

  The first and second silicone resins preferably do not contain silanol groups. When the first and second silicone resins do not contain silanol groups, the storage stability of the first and second silicone resins and the die bond material is increased. The silanol group can be reduced by heating under vacuum. The content of silanol groups can be measured using infrared spectroscopy.

  The preferable lower limit of the number average molecular weight (Mn) of the first and second silicone resins is 500, the more preferable lower limit is 800, the still more preferable lower limit is 1000, the preferable upper limit is 50000, and the more preferable upper limit is 15000. When the number average molecular weight satisfies the above preferable lower limit, the volatile components are reduced at the time of thermosetting, and the thickness of the cured product of the die bond material is hardly reduced under a high temperature environment. When the number average molecular weight satisfies the above preferable upper limit, viscosity adjustment is easy.

  The number average molecular weight (Mn) is a value obtained by using polystyrene as a standard substance using gel permeation chromatography (GPC). The number average molecular weight (Mn) was measured using two measuring devices manufactured by Waters (column: Shodex GPC LF-804 (length: 300 mm) manufactured by Showa Denko KK), measuring temperature: 40 ° C., flow rate: 1 mL / min, solvent: Tetrahydrofuran, standard substance: polystyrene) means a value measured.

  The method for synthesizing the first and second silicone resins is not particularly limited, and examples thereof include a method in which an alkoxysilane compound is hydrolyzed and subjected to a condensation reaction, and a method in which a chlorosilane compound is hydrolyzed and condensed. Especially, the method of hydrolyzing an alkoxysilane compound from a viewpoint of control of reaction is preferable.

  Examples of the method for hydrolyzing and condensing the alkoxysilane compound include a method of reacting in the presence of an alkoxysilane compound, water and an acidic catalyst or a basic catalyst. Further, the disiloxane compound may be hydrolyzed and used.

  Examples of the organosilicon compound for introducing a phenyl group into the first and second silicone resins include triphenylmethoxysilane, triphenylethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methyl (phenyl) dimethoxysilane, and Examples thereof include phenyltrimethoxysilane.

As the organosilicon compound for introducing (R57R58R59R60Si ₂ R61O _2/2 ), (R7R8R9R10Si ₂ R11O _2/2 ) into the first and second silicone resins, for example, 1,4-bis (dimethylmethoxysilyl) Benzene, 1,4-bis (diethylmethoxysilyl) benzene, 1,4-bis (ethoxyethylmethylsilyl) benzene, 1,6-bis (dimethylmethoxysilyl) hexane, 1,6-bis (diethylmethoxysilyl) hexane and Examples include 1,6-bis (ethoxyethylmethylsilyl) hexane.

  Examples of organosilicon compounds for introducing alkenyl groups into the first and second silicone resins include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, methoxydimethylvinylsilane, vinyldimethylethoxysilane, and 1,3. -Divinyl-1,1,3,3-tetramethyldisiloxane and the like.

  Examples of the organosilicon compound for introducing a hydrogen atom bonded to a silicon atom into the first silicone resin include trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, and 1,1,3,3. -Tetramethyldisiloxane and the like.

  Examples of other organosilicon compounds that can be used to obtain the first and second silicone resins include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and isopropyl (methyl) dimethoxysilane. Cyclohexyl (methyl) dimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, and octyltrimethoxysilane.

  Examples of the acidic catalyst include inorganic acids, organic acids, acid anhydrides of inorganic acids and derivatives thereof, and acid anhydrides of organic acids and derivatives thereof.

  Examples of the inorganic acid include hydrochloric acid, phosphoric acid, boric acid, and carbonic acid. Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, lactic acid, malic acid, tartaric acid, citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid and oleic acid. Is mentioned.

  Examples of the basic catalyst include alkali metal hydroxides, alkali metal alkoxides, and alkali metal silanol compounds.

  Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, and cesium hydroxide. Examples of the alkali metal alkoxide include sodium-t-butoxide, potassium-t-butoxide, and cesium-t-butoxide.

  Examples of the alkali metal silanol compound include a sodium silanolate compound, a potassium silanolate compound, and a cesium silanolate compound. Of these, a potassium-based catalyst or a cesium-based catalyst is preferable.

(Catalyst for hydrosilylation reaction)
The hydrosilylation reaction catalyst contained in the die bond material for optical semiconductor devices according to the present invention includes a hydrogen atom bonded to a silicon atom in the first silicone resin, and an alkenyl group in the second silicone resin. Is a catalyst for hydrosilylation reaction.

  As the hydrosilylation reaction catalyst, various catalysts that cause the hydrosilylation reaction to proceed can be used. As for the said catalyst for hydrosilylation reaction, only 1 type may be used and 2 or more types may be used together.

  Examples of the hydrosilylation reaction catalyst include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. A platinum-based catalyst is preferable because the transparency of the die-bonding material can be increased.

  Examples of the platinum-based catalyst include platinum powder, chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex. In particular, a platinum-alkenylsiloxane complex or a platinum-olefin complex is preferable.

  Examples of the alkenylsiloxane in the platinum-alkenylsiloxane complex include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,3,5,7-tetramethyl-1,3,5. , 7-tetravinylcyclotetrasiloxane and the like. Examples of the olefin in the platinum-olefin complex include allyl ether and 1,6-heptadiene.

  Since the stability of the platinum-alkenylsiloxane complex and platinum-olefin complex can be improved, alkenylsiloxane, organosiloxane oligomer, allyl ether or olefin is added to the platinum-alkenylsiloxane complex or platinum-olefin complex. Is preferred. The alkenylsiloxane is preferably 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. The organosiloxane oligomer is preferably a dimethylsiloxane oligomer. The olefin is preferably 1,6-heptadiene.

  In 100% by weight of the die bond material, the content of the hydrosilylation catalyst is preferably in the range of 0.01 to 0.5% by weight. When the content of the catalyst for hydrosilylation reaction is not less than the above lower limit, it is easy to sufficiently cure the die bond material, and the gas barrier property of the die bond material can be further enhanced. When the content of the catalyst for hydrosilylation reaction is not more than the above upper limit, the die bond material is more difficult to discolor. The content of the hydrosilylation reaction catalyst is more preferably 0.02% by weight or more, and more preferably 0.3% by weight or less.

(Titanium oxide)
By including titanium oxide in the die bond material for optical semiconductor devices according to the present invention, the light reflectivity of the die bond material is increased. In particular, the use of rutile titanium oxide can further increase the light reflectivity of the die bond material. Moreover, since the thermal conductivity of the titanium oxide is 10 W / m · K or more, the thermal conductivity of the die bond material can be increased. As a result, the heat dissipation of the die bond material is increased.

  Furthermore, in the present invention, the titanium oxide is coated with at least one of a metal oxide and a metal hydroxide. Therefore, not only can the thermal conductivity of the die bond material be significantly increased, but it can also be made difficult to yellow even when the die bond material is exposed to high temperatures.

  The titanium oxide is preferably coated with a basic metal oxide or basic metal hydroxide so that the surface is basic. When the surface of the titanium oxide is basic, yellowing at a high temperature can be further suppressed.

  Examples of the metal oxide and metal hydroxide include compounds of metals such as magnesium, zirconium, cerium, strontium, antimony, barium or calcium. Among these, the compound is appropriately selected and used so that the thermal conductivity of the titanium oxide is 10 W / m · K.

  In order to increase the thermal conductivity of the titanium oxide to 10 W / m · K or more, and further to suppress yellowing due to heat of the die bond material, the metal element constituting the metal oxide and metal hydroxide is aluminum. And at least one of zirconium. Since the yellowing of the die bond material can be further suppressed when exposed to a high temperature, the titanium oxide is preferably coated with a coating material containing at least one of zirconium oxide and silicon oxide. As for a metal oxide and a metal hydroxide, only 1 type may respectively be used and 2 or more types may be used together. A metal oxide and a metal hydroxide may be used in combination.

  As a method of surface-treating titanium oxide with a compound that is a metal oxide or metal hydroxide, (1) pulverizing titanium oxide added with the above compound using a dry pulverizer such as a fluid energy pulverizer or an impact pulverizer. (2) A method of stirring and mixing titanium oxide after dry pulverization with the above compound using a high-speed stirrer such as a Henschel mixer or a super mixer, and (3) adding the compound to an aqueous slurry of titanium oxide. And stirring. Since the pulverization of titanium oxide and the surface treatment with the above compound can be performed simultaneously, the method (1) is preferred. As the dry pulverizer, a fluid energy pulverizer is preferable, and a swirl pulverizer such as a jet mill is more preferable.

  From the viewpoint of improving the dispersibility in the die bond material and obtaining a uniform light reflectance, the number average particle diameter of the titanium oxide is preferably 0.01 μm or more, preferably 1.0 μm or less, more preferably. 0.5 μm or less.

  The content of titanium oxide in 100% by weight of the die bond material for optical semiconductor devices is preferably 3% by weight or more, more preferably 10% by weight or more, preferably 80% by weight or less, more preferably 75% by weight or less. . When the content of the titanium oxide is not less than the above lower limit, the heat dissipation property and light reflectance of the die bond material are further increased. When the content of the titanium oxide is not more than the above upper limit, the dispersibility of the titanium oxide becomes high and die bonding becomes easier.

(Coupling agent)
The die bond material for optical semiconductor devices according to the present invention may further contain a coupling agent in order to impart adhesiveness.

  It does not specifically limit as said coupling agent, For example, a silane coupling agent etc. are mentioned. Examples of the silane coupling agent include vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-methacryloxypropyltrimethoxy. Examples include silane, γ-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. As for a coupling agent, only 1 type may be used and 2 or more types may be used together.

(Other ingredients)
The die bond material for an optical semiconductor device according to the present invention includes an ultraviolet absorber, an antioxidant, a solvent, a colorant, a filler, an antifoaming agent, a surface treatment agent, a flame retardant, a viscosity modifier, and a dispersant as necessary. , A dispersion aid, a surface modifier, a plasticizer, an antifungal agent, a leveling agent, a stabilizer, a coupling agent, an anti-sagging agent, or a phosphor.

(Details and applications of die bond materials for optical semiconductor devices)
The die bond material for optical semiconductor devices according to the present invention may be in the form of a paste or a film. The die bond material for an optical semiconductor device according to the present invention is preferably in a paste form.

  The first silicone resin, the second silicone resin, and the hydrosilylation reaction catalyst are prepared separately in a liquid containing one or more of them, and a plurality of liquids are prepared immediately before use. The die-bonding material for optical semiconductor devices according to the present invention may be prepared by mixing. For example, the liquid A containing the second silicone resin and the hydrosilylation reaction catalyst and the liquid B containing the first silicone resin are prepared separately, and the liquid A and the liquid B are mixed immediately before use. A die bond material may be prepared. In this case, the titanium oxide may be included in the A liquid or may be included in the B liquid. Thus, the storage stability is improved by separately forming the second silicone resin and the hydrosilylation reaction catalyst and the first silicone resin into two liquids of the first liquid and the second liquid. Can be made.

  The method for producing a die bond material for an optical semiconductor device according to the present invention is not particularly limited. For example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a triple roll or a bead mill, Or the method of mixing the said 1st silicone resin, said 2nd silicone resin, the said catalyst for hydrosilylation reaction, the said titanium oxide, and the other component mix | blended as needed under a heating etc. is mentioned.

  The die bond material for an optical semiconductor device according to the present invention is disposed on a connection target member such as a substrate or disposed on the lower surface of the optical semiconductor element, and the connection target member and the optical semiconductor element are connected via the die bond material. Thus, an optical semiconductor device can be obtained.

  The curing temperature of the die bond material for optical semiconductor devices according to the present invention is not particularly limited. The curing temperature of the die bond material for an optical semiconductor device is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° C. or lower. When the curing temperature is equal to or higher than the preferable lower limit, the die bond material is sufficiently cured. When the curing temperature is equal to or lower than the preferable upper limit, thermal deterioration of the die bonding material and the member bonded by the die bonding material hardly occurs.

  Although it does not specifically limit to hardening, It is preferable to use a step cure system. The step cure method is a method in which the resin is temporarily cured at a low temperature and then cured at a high temperature. By using the step cure method, curing shrinkage of the die bond material can be suppressed.

(Optical semiconductor device)
An optical semiconductor device according to the present invention includes a die bond material for an optical semiconductor device, a connection target member, and an optical semiconductor element connected to the connection target member using the die bond material for an optical semiconductor device.

  Specific examples of the optical semiconductor device according to the present invention include a light emitting diode device, a semiconductor laser device, and a photocoupler. Such optical semiconductor devices include, for example, backlights such as liquid crystal displays, illumination, various sensors, light sources such as printers and copiers, vehicle measuring instrument light sources, signal lights, indicator lights, display devices, and light sources for planar light emitters. , Displays, decorations, various lights, switching elements and the like.

  The light-emitting element that is the optical semiconductor element is not particularly limited as long as it is a light-emitting element using a semiconductor. Structure is mentioned. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.

  Examples of the material for the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. Further, a buffer layer may be formed between the substrate and the semiconductor material as necessary. Examples of the material of the buffer layer include GaN and AlN.

  FIG. 1 is a front sectional view showing an optical semiconductor device according to an embodiment of the present invention.

  The optical semiconductor device 1 of the present embodiment includes a housing 2 that is a connection target member and an optical semiconductor element 3. An optical semiconductor element 3 that is an LED element is mounted in the housing 2. The optical semiconductor element 3 is surrounded by an inner surface 2 a having light reflectivity of the housing 2. In the present embodiment, the optical semiconductor element 3 is used as a light emitting element formed of an optical semiconductor.

  The inner surface 2a of the housing 2 is formed so that the diameter of the inner surface 2a increases toward the opening end. Accordingly, among the light emitted from the optical semiconductor element 3, the light B <b> 1 that has reached the inner surface 2 a is reflected by the inner surface 2 a and travels forward of the optical semiconductor element 3.

  The optical semiconductor element 3 is connected to a lead electrode 4 provided in the housing 2 using a die bond material 5. The die bond material 5 is a die bond material for optical semiconductor devices. A bonding pad (not shown) provided on the optical semiconductor element 3 and the lead electrode 4 are electrically connected by a bonding wire 6. A sealing agent 7 is filled in a region surrounded by the inner surface 2 a so as to seal the optical semiconductor element 3 and the bonding wire 6.

  The die bond material 5 may be disposed so as to protrude from the bottom of the optical semiconductor element 3 and surround the periphery thereof, or may be disposed so as not to protrude from the bottom of the optical semiconductor element 3. The thickness of the die bond material 5 is preferably in the range of 2 to 50 μm.

  In the optical semiconductor device 1, when the optical semiconductor element 3 is driven, light is emitted as indicated by a broken line A. In this case, not only the light irradiated from the optical semiconductor element 3 to the side opposite to the upper surface of the lead electrode 4, that is, the upper side, but also the light that reaches the die bond material 5 is reflected as indicated by the arrow B 2.

  The structure shown in FIG. 1 is merely an example of an optical semiconductor device according to the present invention, and can be appropriately modified to the mounting structure of the optical semiconductor element 3.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples.

(First and second silicone resin)
The first and second silicone resins were synthesized as follows.

(Synthesis Example 1) Synthesis of First Silicone Resin In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 120 g of dimethylmethoxysilane, 54 g of methyltrimethoxysilane, and 1,1,3,3-tetra 40 g of methyldisiloxane was added and stirred at 50 ° C. Into this, a solution of 1.2 g of hydrochloric acid and 83 g of water was slowly added dropwise. After the addition, the solution was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (A) was obtained.

The number average molecular weight (Mn) of the obtained polymer (A) was 1500. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (A) had the following average composition formula (A1).

(HMe ₂ SiO _1/2 ) _0.20 (Me ₂ SiO _2/2 ) _0.50 (MeSiO _3/2 ) _0.30 ... Formula (A1)

  In the above formula (A1), Me represents a methyl group.

In addition, the molecular weight of each polymer obtained in Synthesis Example 1 and Synthesis Examples 2 to 3 was measured by GPC measurement by adding 1 mL of tetrahydrofuran to 10 mg, stirring until dissolved. In GPC measurement, a measuring device manufactured by Waters (column: Shodex GPC manufactured by Showa Denko KK)
LF-804 (length: 300 mm) × 2, measurement temperature: 40 ° C., flow rate: 1 mL / min, solvent: tetrahydrofuran, standard substance: polystyrene) were used.

Synthesis Example 2 Synthesis of First Silicone Resin In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 204 g of methyltrimethoxysilane, 40 g of vinylmethyldimethoxysilane, and 1,1,3,3- 80 g of tetramethyldisiloxane was added and stirred at 50 ° C. Into this, a solution of 1.2 g of hydrochloric acid and 102 g of water was slowly added dropwise. After the addition, the solution was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (B) was obtained.

The number average molecular weight (Mn) of the obtained polymer (B) was 1500. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (B) had the following average composition formula (B1).

(HMe ₂ SiO _1/2 ) _0.40 (ViMeSiO _2/2 ) _0.10 (MeSiO _3/2 ) _0.50 ... Formula (B1)

  In the above formula (B1), Me represents a methyl group, and Vi represents a vinyl group.

(Synthesis Example 3) Synthesis of Second Silicone Resin In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 41 g of trimethylmethoxysilane, 72 g of dimethyldimethoxysilane, 81 g of methyltrimethoxysilane, and vinylmethyldimethoxysilane 52 g was added and stirred at 50 ° C. A solution obtained by dissolving 0.8 g of potassium hydroxide in 114 g of water was slowly dropped therein, and after the dropwise addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, 0.9 g of acetic acid was added to the reaction solution, the pressure was reduced to remove volatile components, and potassium acetate was removed by filtration to obtain a polymer (C).

The number average molecular weight (Mn) of the obtained polymer (C) was 2000. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (C) had the following average composition formula (C1).

(Me ₃ SiO _1/2 ) _0.20 (ViMeSiO _2/2 ) _0.20 (Me ₂ SiO _2/2 ) _0.30 (MeSiO _3/2 ) _0.30 ... Formula (C1)

  In the above formula (C1), Me represents a methyl group, and Vi represents a vinyl group.

(Filler)
In Examples and Comparative Examples, fillers shown in Table 1 below were used.

  In Table 1 above, rutile-type titanium oxide No. 1-4 are coat | covered with the basic metal compound or the basic metal hydroxide. When surface-treating rutile titanium oxide, aluminum hydroxide or aluminum oxide is used when the metal species is Al, silicon oxide is used when the metal species is Si, and zirconium oxide is used when the metal species is Zr.

Example 1
Polymer B 5 parts by weight, Polymer C 5 parts by weight, platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum catalyst) 0.02 part by weight, rutile titanium oxide No. 1 4 (D-918) 60 parts by weight were mixed and defoamed to obtain a die bond material for an optical semiconductor device.

(Examples 2-8 and Comparative Examples 1-3)
A die bond material for an optical semiconductor device was obtained in the same manner as in Example 1 except that the type and blending amount of the materials used were changed as shown in Table 2 below.

(Evaluation)
(1) Thermal conductivity Each die-bonding material for optical semiconductor devices obtained in the examples and comparative examples was heated at 150 ° C. for 3 hours and cured to obtain a cured product of 100 mm × 100 mm × thickness 50 μm. This cured product was used as an evaluation sample.

  The thermal conductivity of the obtained evaluation sample was measured using a thermal conductivity meter “rapid thermal conductivity meter QTM-500” manufactured by Kyoto Electronics Industry Co., Ltd. In addition, it is better that the thermal conductivity is high, and the thermal conductivity needs to be 0.3 W / m · K or more.

(2) Reflectance Color colorimeter (product name “CR-400” manufactured by Konica Minolta Co., Ltd.) (1) Light reflectance Y value (%) of the evaluation sample obtained by the above (1) thermal conductivity evaluation Was measured.

(3) Heat resistance The evaluation sample obtained by the evaluation of the above (1) thermal conductivity was put in an oven and heated at 270 ° C. for 5 minutes.

  Using a color / color difference meter (CR-400, manufactured by Konica Minolta Co., Ltd.), L *, a *, and b * of the evaluation sample before heat treatment were measured. Further, L *, a *, and b * of the evaluation sample after the heat treatment were measured, and ΔE * ab was obtained from these two measured values. When ΔE * ab of the evaluation sample after the heat treatment is 0.8 or less, “◯◯” exceeds 0.8, and when it is 1.0 or less, “◯” exceeds 1.0, and 1. A case of 2 or less was judged as “Δ”, a value exceeding 1.2, a case of 1.5 or less being judged as “X”, and a case exceeding 1.5 was judged as “XX”. Note that the greater the ΔE * ab, the greater the degree of yellowing of the die bond material.

(4) Adhesiveness (die shear strength)
A die-bonding material for an optical semiconductor device was applied on an Ag-plated Cu substrate so that the adhesion area was 3 mm × 3 mm, and a 3 mm square Si chip was placed thereon to obtain a test sample.

  The obtained test sample was heated at 150 ° C. for 3 hours to cure the die bond material. Next, the die shear strength at 185 ° C. was evaluated at a speed of 300 μ / sec using a die shear tester (manufactured by Arctech, model number: DAGE 4000).

  The results are shown in Table 2 below.

DESCRIPTION OF SYMBOLS 1 ... Optical semiconductor device 2 ... Housing 2a ... Inner surface 3 ... Optical semiconductor element 4 ... Lead electrode 5 ... Die-bonding material 6 ... Bonding wire 7 ... Sealing agent

Claims (6)

A first silicone resin having hydrogen atoms bonded to silicon atoms;
A second silicone resin not having a hydrogen atom bonded to a silicon atom and having an alkenyl group;
A catalyst for hydrosilylation reaction;
Including titanium oxide,
The crystal structure of the titanium oxide is a rutile type,
The titanium oxide has a thermal conductivity of 10 W / m · K or more, and
A die bond material for an optical semiconductor device, wherein the titanium oxide is coated with at least one of a metal oxide and a metal hydroxide.   2. The die bond material for an optical semiconductor device according to claim 1, wherein the metal element constituting the metal oxide and the metal hydroxide is at least one of aluminum and zirconium.   The die bond material for optical semiconductor devices according to claim 1 or 2, wherein the titanium oxide is coated with a coating material containing at least one of zirconium oxide and silicon oxide. The first silicone resin is a first silicone resin represented by the following formula (1A) or the following formula (1B) and having a hydrogen atom bonded to a silicon atom,
The second silicone resin is a second silicone resin represented by the following formula (51A) or the following formula (51B), having no hydrogen atom bonded to a silicon atom, and having an alkenyl group. Item 4. The die bond material for an optical semiconductor device according to any one of Items 1 to 3.

In the formula (1A), a, b and c are a / (a + b + c) = 0.05 to 0.50, b / (a + b + c) = 0 to 0.40 and c / (a + b + c) = 0.30. 0.81 is satisfied, at least one of R1 to R6 represents a hydrogen atom, and R1 to R6 other than a hydrogen atom represent a hydrocarbon group having 1 to 8 carbon atoms.

In the formula (1B), a, b, c and d are a / (a + b + c + d) = 0.05 to 0.50, b / (a + b + c + d) = 0 to 0.40, c / (a + b + c + d) = 0. 30 to 0.80 and d / (a + b + c + d) = 0.01 to 0.40, at least one of R1 to R6 represents a hydrogen atom, and R1 to R6 other than a hydrogen atom have 1 to 8 carbon atoms. R7 to R10 each represents a hydrocarbon group having 1 to 8 carbon atoms, and R11 represents a divalent hydrocarbon group having 1 to 8 carbon atoms.

In the formula (51A), p, q and r are p / (p + q + r) = 0.05 to 0.50, q / (p + q + r) = 0 to 0.40 and r / (p + q + r) = 0.30. 0.85 is satisfied, and at least one of R51 to R56 represents an alkenyl group, and R51 to R56 other than the alkenyl group represent a hydrocarbon group having 1 to 8 carbon atoms.

In the formula (51B), p, q, r and s are p / (p + q + r + s) = 0.05 to 0.50, q / (p + q + r + s) = 0 to 0.40, r / (p + q + r + s) = 0. 30 to 0.80 and s / (p + q + r + s) = 0.01 to 0.40, R51 to R56 each represents at least one alkenyl group, and R51 to R56 other than the alkenyl group have 1 to 8 carbon atoms. R57-60 represents a hydrocarbon group having 1 to 8 carbon atoms, and R61 represents a divalent hydrocarbon group having 1 to 8 carbon atoms.   5. The die bond material for an optical semiconductor device according to claim 1, wherein the first silicone resin is a first silicone resin having a hydrogen atom bonded to a silicon atom and an alkenyl group. The die-bonding material for optical semiconductor devices according to any one of claims 1 to 5,
A connection target member;
An optical semiconductor device comprising: an optical semiconductor element connected to the connection target member using the die bond material for an optical semiconductor device.

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