JP2011074201A - Reflection type die bonding material for optical semiconductor device and optical semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reflection type die bonding material for an optical semiconductor device which can strongly join an optical semiconductor device, can efficiently reflect light from the optical semiconductor device, can increase the utilization efficiency of light, and is excellent in heat resistance of a cured product. <P>SOLUTION: The reflection type die bonding material for an optical semiconductor device includes a silicone resin having a cyclic ether-containing group in the molecule, titanium oxide having a rutile-type crystal structure, and a thermosetting agent capable of reacting with the cyclic ether-containing group. There is also provided an optical semiconductor device to which an optical semiconductor device is joined using the reflection type die bonding material for a semiconductor device. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

  Conventionally, an optical semiconductor element such as a light emitting diode (LED) element has been widely used as a light source of a display device. Patent Document 1 below discloses an optical semiconductor device in which an LED element is mounted on a substrate. In Patent Document 1, the LED element is bonded to the upper surface of the substrate using a die bond material. The die bond material mainly includes a thermosetting resin made of an alicyclic epoxy resin obtained by hydrogenating a bisphenol A type epoxy resin, is cured by heating, and bonds the LED element to the upper surface of the substrate.

JP 2004-256603 A

  By the way, the die-bonding material may extend not only to the lower surface of the LED element but also to the area around the LED element. On the other hand, light traveling from the LED element also proceeds to the substrate side. Accordingly, if the light reaching the die bonding material extending around the LED element can be reflected, the reflected light can also be used. Therefore, the utilization efficiency of the light generated from the LED element can be increased.

  However, the die-bonding material described in Patent Document 1 does not efficiently reflect the light even if the light generated from the LED element arrives. Therefore, it has been difficult to increase the light utilization efficiency.

  In addition, when exposed to a high temperature environment of 200 ° C. or higher, such as the temperature during solder reflow, yellowing may occur or the adhesive strength with the substrate or lead electrode may be reduced.

  An object of the present invention is to reflect light from an optical semiconductor element, to improve the utilization efficiency of light generated in the optical semiconductor element, and to firmly bond the optical semiconductor element to a substrate or the like. Another object of the present invention is to provide a reflective die-bonding material for optical semiconductor devices that gives a cured product with further excellent heat resistance, and an optical semiconductor device to which an optical semiconductor element is bonded using the reflective die-bonding material for optical semiconductor devices.

  A reflective die-bonding material for an optical semiconductor device according to the present invention comprises a silicone resin having a cyclic ether-containing group in the molecule, a rutile-type titanium oxide crystal structure, and a thermosetting agent capable of reacting with the cyclic ether-containing group. Including.

  In the reflective die-bonding material for an optical semiconductor device according to the present invention, preferably, the titanium oxide is heated until a solution obtained by adding 5 g of the titanium oxide to 100 ml of pure water is boiled for 5 minutes, and then statically maintained until reaching 23 ° C. To obtain a boiling treatment liquid, and to the resulting boiling treatment liquid, an amount of water evaporated by boiling is added to make the water volume 100 ml, and the pH of the liquid is 6.2 or more and 11 or less. Titanium. In this case, yellowing or the like of the reflective die bond material for optical semiconductor devices hardly occurs, and adhesion to the substrate can be further enhanced.

  In another specific aspect of the reflective die-bonding material for an optical semiconductor device according to the present invention, the titanium oxide is coated with at least one of a basic metal oxide and a basic metal hydroxide. In this case, since the surface of the titanium oxide is basic, it is possible to further suppress coloring deterioration due to high temperature.

  Preferably, the metal element constituting the basic metal oxide and the basic metal hydroxide is at least one selected from the group consisting of magnesium, zirconium, cerium, strontium, antimony, barium and calcium. In this case, deterioration due to coloring when exposed to a high temperature can be further suppressed, and adhesion to a substrate or the like can be further enhanced.

  More preferably, the titanium oxide is coated with a coating material containing at least one of zirconium oxide and silicon oxide. In this case, deterioration due to coloring when exposed to a high temperature can be further suppressed, and adhesion to a substrate or the like can be further enhanced.

  In another specific aspect of the reflective die-bonding material for optical semiconductor devices in the present invention, the silicone resin having a cyclic ether-containing group in the molecule contains a resin component whose average composition formula is represented by the following general formula (1). And content of the said cyclic ether containing group exists in the range of 0.1 mol%-50 mol%.

In the general formula (1), a, b, and c are a / (a + b + c) = 0 to 0.3, b / (a + b + c) = 0.3 to 1.0, c / (a + b + c) = 0 to 0, respectively. 0.5, at least one of R ^{1 to} R ⁶ represents a cyclic ether-containing group, and R ^{1 to} R ⁶ other than the cyclic ether-containing group have a linear or branched carbon number of 1 to 8 Or a fluorinated product thereof may be the same as or different from each other.

  When the silicone resin having a cyclic ether-containing group in the molecule is the above-mentioned specific silicone resin, the viscosity at the time of application of the reflective die-bonding material for optical semiconductor devices during production can be lowered, and application is easy. And after hardening, while being able to adhere | attach an optical semiconductor element firmly to a board | substrate, the heat resistance of hardened | cured material can be improved further.

  An optical semiconductor device according to the present invention includes an optical semiconductor element, a substrate or a lead electrode, and a reflective die bond material for an optical semiconductor device according to the present invention in which the optical semiconductor element is bonded to the substrate or the lead electrode. .

  According to the reflective die-bonding material for an optical semiconductor device according to the present invention, a silicone resin having a cyclic ether-containing group in the molecule, a rutile-type titanium oxide crystal structure, and a thermosetting agent capable of reacting with the cyclic ether-containing group. Therefore, when the light from an optical semiconductor element such as an LED element arrives, the cured product is white and reflects the light with high efficiency. Therefore, the light use efficiency of the optical semiconductor element can be increased. In addition, the optical semiconductor element can be firmly bonded to a substrate or the like, and the cured product has excellent heat resistance, so that even when exposed to high temperatures such as during solder reflow, deterioration due to coloring Is less likely to occur and the adhesion to the substrate or the like is less likely to deteriorate.

It is front sectional drawing which shows the optical semiconductor device which concerns on one Embodiment of this invention.

  Details of the present invention will be described below.

[Silicone resin having a cyclic ether-containing group in the molecule]
The silicone resin having a cyclic ether-containing group in the molecule used in the present invention is not particularly limited as long as it has a cyclic ether-containing group. Examples of the cyclic ether-containing group include a glycidyl-containing group, an epoxycyclohexyl-containing group, and an oxetane-containing group.

  The resin whose average composition formula is represented by the general formula (1) is not only a resin in which the die bond material for an optical semiconductor device of the present invention contains only the resin component represented by the formula (1), but also various And a resin represented by the above formula (1) when the average of the composition of the resin component contained is taken.

  It is preferable that the phenyl group content ratio calculated | required from (a) in resin represented by following General formula (1) is 15 mol%-60 mol%.

At least one of R ^{1 to} R ⁶ contained in the silicone resin represented by the general formula (1) is a phenyl group, and the ratio of the phenyl group is 15 to 60 mol%. If the ratio of the phenyl group is less than 15 mol%, the adhesive strength may be insufficient, and if it exceeds 60 mol%, peeling tends to occur. A more preferred lower limit is 20 mol%, and a more preferred upper limit is 55 mol%.

  In addition, in this specification, the ratio of the said phenyl group is a ratio of the said phenyl group contained in the average composition of the said silicone resin component. Specifically, the ratio is obtained using the following formula (a).

Phenyl group content ratio (mol%) = (average number of phenyl groups contained in one molecule of resin represented by general formula (1) × molecular weight of phenyl group / average composition is represented by general formula (1) Average molecular weight of represented resin component) × 100 Formula (a)
In the general formula (1), at least one of R ^{1 to} R ⁶ represents a cyclic ether-containing group.

  It does not specifically limit as said cyclic ether containing group, For example, cyclic ether groups, such as a glycidyl containing group, an epoxy cyclohexyl containing group, or an oxetane containing group, are mentioned. Of these, a glycidyl-containing group and / or an epoxycyclohexyl-containing group is preferable.

  In the present specification, the cyclic ether-containing group is a functional group containing a cyclic ether group in at least a part of the skeleton. The cyclic ether-containing group may be, for example, a functional group that includes a cyclic ether group in the skeleton and also includes another skeleton such as an alkyl group or an alkyl ether group.

  The glycidyl-containing group is not particularly limited. For example, 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxy Examples thereof include a propyl group and a 4-glycidoxybutyl group.

  The epoxycyclohexyl-containing group is not particularly limited, and examples thereof include 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group, and the like.

  In the said silicone resin, the minimum with the preferable content rate of the said cyclic ether containing group is 0.1 mol%, and a preferable upper limit is 50 mol%. When the content ratio of the cyclic ether-containing group is less than 0.1 mol%, the reactivity between the silicone resin and the thermosetting agent described later is remarkably lowered, and the curability of the die bond material for an optical semiconductor device of the present invention is reduced. It may be insufficient. When the content ratio of the cyclic ether-containing group exceeds 50 mol%, the number of cyclic ether-containing groups not involved in the reaction between the silicone resin and the thermosetting agent increases, and the heat resistance of the die bond material for an optical semiconductor device of the present invention decreases. There are things to do. The more preferable lower limit of the content ratio of the cyclic ether-containing group is 1 mol%, the more preferable upper limit is 40 mol%, the still more preferable lower limit is 5 mol%, and the still more preferable upper limit is 30 mol%.

  In addition, in this specification, the ratio of the said cyclic ether containing group is a ratio of the said cyclic ether containing group contained in the average composition of the said silicone resin component. Specifically, the ratio is obtained based on the following formula (b).

Ratio of cyclic ether-containing groups (mol%) = (average number of cyclic ether-containing groups contained in one molecule of resin whose average composition is represented by general formula (1) × molecular weight of cyclic ether-containing groups / average composition Average molecular weight of resin component represented by general formula (1)) × 100 Formula (b)
In the silicone resin represented by the general formula (1), R ^{1 to} R ⁶ other than the cyclic ether-containing group represent a linear or branched hydrocarbon group having 1 to 8 carbon atoms or a fluorinated product thereof. .

  The linear or branched hydrocarbon having 1 to 8 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an 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, or phenyl group Can be mentioned.

In the silicone resin represented by the general formula (1), the structural unit represented by (R ⁴ R ⁵ SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) has the following general formula (1-2): That is, a structure in which one of oxygen atoms bonded to a silicon atom in the bifunctional structural unit constitutes a hydroxyl group or an alkoxy group.

  In the general formula (1-2), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.

In the silicone resin represented by the general formula (1), the structural unit represented by (R ⁶ SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) is represented by the following general 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 hydroxyl group or an alkoxy group, or silicon in a trifunctional structural unit It includes a structure in which one of oxygen atoms bonded to an atom constitutes a hydroxyl group or an alkoxy group.

  In the general formulas (1-3) and (1-4), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.

  In the general formulas (1-2) to (1-4), 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, and an n-propoxy group. , N-butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group or t-butoxy group.

  In the general formula (1), a is a numerical value that satisfies the relationship that the lower limit of a / (a + b + c) is 0 and the upper limit is 0.3. When a / (a + b + c) exceeds 0.3, the heat resistance of the die bond material for optical semiconductor devices of the present invention may be deteriorated or peeling may easily occur. A more preferred upper limit is 0.25, and even more preferred is 0.2.

  In the general formula (1), b is a numerical value that satisfies the relationship that the lower limit of b / (a + b + c) is 0.3 and the upper limit is 1.0. When b / (a + b + c) is less than 0.3, the cured product of the die bond material for an optical semiconductor device of the present invention becomes too hard, and cracks may occur. A more preferred lower limit is 0.4, a more preferred upper limit is 0.95, a still more preferred lower limit is 0.5, and a further preferred upper limit is 0.9.

  In the above general formula (1), c is a numerical value that satisfies the relationship that the lower limit of c / (a + b + c) is 0 and the upper limit is 0.5. If it exceeds 0.5, it may be difficult to maintain an appropriate viscosity as the die bond material for an optical semiconductor device of the present invention, or the adhesion may be lowered. A more preferred lower limit is 0.05, a more preferred upper limit is 0.4, a still more preferred lower limit is 0.1, and a still more preferred upper limit is 0.35.

When the ²⁹ Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) is performed on the silicone resin represented by the general formula (1) based on tetramethylsilane (hereinafter referred to as TMS), there is a slight variation depending on the type of substituent. Although seen, a peak corresponding to the structural unit represented by (R ¹ R ² R ³ SiO _1/2 ) _a in the general formula (1) appears in the vicinity of +10 to 0 ppm, and ( R ⁴ R ⁵ SiO _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 (R ⁶ SiO _{3/2 of the} above general formula (1)). _C ) Each peak corresponding to the trifunctional structural units of (1-3) and (1-4) appears in the vicinity of −50 to −80 ppm.

Therefore, it is possible to measure the ratio of the general formula (1) by measuring ²⁹ Si-NMR and comparing the peak areas of the respective signals.

However, in the case where the functional structural unit of the general formula (1) cannot be distinguished by ²⁹ Si-NMR measurement based on the TMS, not only the ²⁹ Si-NMR measurement result but also ¹ H-NMR or ¹⁹ F- The ratio of structural units can be identified by using the results measured by NMR as necessary.

  It is preferable that the said silicone resin contains 0.5-10 mol% of alkoxy groups. When such an alkoxy group is contained, heat resistance and light resistance are drastically improved. This is thought to be due to the fact that the silicone resin contains an alkoxy group, so that the curing rate can be drastically improved, so that thermal degradation during curing can be prevented.

  In addition, since the curing speed is dramatically increased in this way, when a curing accelerator is added, sufficient curability can be obtained even with a relatively small addition amount.

  When the content of the alkoxy group is less than 0.5 mol%, a sufficient curing rate cannot be obtained and the heat resistance may be deteriorated. When the content exceeds 10 mol%, the storage stability of the silicone resin or the composition is increased. It may worsen or heat resistance may deteriorate. The minimum with more preferable content of an alkoxy group is 1 mol%, and a more preferable upper limit is 5 mol%.

  In the present specification, the content of the alkoxy group means the amount of the alkoxy group contained in the average composition of the silicone resin component.

  The silicone resin preferably does not contain a silanol group. The silanol group is not preferable because the storage stability of the polymer is remarkably deteriorated and the storage stability when the resin composition is obtained is also remarkably deteriorated. Such silanol groups can be reduced by heating in a vacuum, and the amount of silanol groups can be measured using infrared spectroscopy.

  In the die bond material for an optical semiconductor device of the present invention, the preferable lower limit of the number average molecular weight (Mn) of the silicone resin is 1000, and the preferable upper limit is 50,000. When the number average molecular weight (Mn) of the silicone resin is less than 1000, volatile components increase at the time of thermosetting, and film loss after curing increases, which is not preferable. When the number average molecular weight (Mn) of the silicone resin exceeds 50,000, it is not preferable because it becomes difficult to adjust the viscosity. The minimum with a more preferable number average molecular weight (Mn) of the said silicone resin is 1500, and a more preferable upper limit is 15000.

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

  The method for synthesizing the silicone resin is not particularly limited. For example, (1) a method of introducing a substituent by a hydrosilylation reaction between a silicone resin having a SiH group and a vinyl compound having a cyclic ether-containing group, or ( 2) A method in which a siloxane compound and a siloxane compound having a cyclic ether-containing group are subjected to a condensation reaction may be mentioned.

  In the above method (1), the hydrosilylation reaction is a method of reacting a SiH group and a vinyl group in the presence of a catalyst as necessary.

  The silicone resin having a SiH group has a structure represented by the general formula (1) described above after reacting a vinyl compound having a SiH group in the molecule and the cyclic ether-containing group. You can use something.

  The vinyl compound having a cyclic ether-containing group is not particularly limited as long as it is a vinyl compound having one or more cyclic ether-containing groups in the molecule. For example, vinyl glycidyl ether, allyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate Alternatively, an epoxy group-containing compound such as vinylcyclohexene oxide can be used.

  In the said method (2), as a siloxane compound, the alkoxysilane which has a siloxane unit of the following general formula (2), (3), (4), or its partial hydrolyzate is mentioned, for example.

In the general formula ^{(2) ~ (4),} R 22 ~R 27 represents a linear or branched hydrocarbon or a fluorinated compound having 1 to 8 carbon atoms, OR is a linear or branched Represents an alkoxy group having 1 to 4 carbon atoms.

In the general formulas (2) to (4), when R ^{22 to} R ²⁷ are linear or branched hydrocarbons having 1 to 8 carbon atoms, specifically, 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 Group, t-pentyl group, isohexyl group, cyclohexyl group or phenyl group.

  In the general formulas (2) to (4), the linear or branched alkoxy group having 1 to 4 carbon atoms represented by OR is specifically, for example, a methoxy group, an ethoxy group, or n -Propoxy group, n-butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, etc. are mentioned.

  Specific examples of the compound represented by the general formula (2) include trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, and triphenylethoxysilane.

  Specific examples of the compound represented by the general formula (3) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, isopropyl (methyl) dimethoxysilane, and cyclohexyl (methyl) dimethoxy. Examples include silane or methyl (phenyl) dimethoxysilane.

  Specific examples of the compound represented by the general formula (4) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, and the like. An example is phenyltrimethoxysilane.

  Examples of the siloxane compound having a cyclic ether-containing group include an alkoxysilane having a cyclic ether-containing group represented by the following general formula (5), (6) or (7) or a partial hydrolyzate thereof.

In the general formulas (5), (6) and (7), at least one of R ²⁸ , R ²⁹ and R ³⁰ , R ³¹ and / or R ³² and R ³³ is a cyclic ether-containing group and contains a cyclic ether R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² other than the group represent a hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and OR is a linear or branched carbon having 1 to 4 carbon atoms. Represents an alkoxy group.

In general formulas (5), (6) and (7), the cyclic ether-containing group represented by at least one of R ²⁸ , R ²⁹ and R ³⁰ , R ³¹ and / or R ³² and R ³³ is particularly limited. Examples thereof include glycidyl-containing groups, epoxycyclohexyl-containing groups, and oxetane-containing groups. Of these, a glycidyl-containing group and / or an epoxycyclohexyl-containing group is preferable.

  The glycidyl-containing group is not particularly limited. For example, 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxy A propyl group or 4-glycidoxybutyl group is mentioned.

  The epoxycyclohexyl-containing group is not particularly limited, and examples thereof include a 2- (3,4-epoxycyclohexyl) ethyl group or a 3- (3,4-epoxycyclohexyl) propyl group.

In the general formulas (5) and (6), R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , and R ³² other than the cyclic ether-containing group are specifically, for example, a methyl group, an ethyl group, and 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 -A pentyl group, an isohexyl group, a cyclohexyl group, or a phenyl group is mentioned.

  In the general formulas (5), (6) and (7), the linear or branched alkoxy group having 1 to 4 carbon atoms represented by OR is specifically, for example, a methoxy group, An ethoxy group, n-propoxy group, n-butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group or t-butoxy group can be mentioned.

  Specific examples of the compound represented by the general formula (5) include 3-glycidoxypropyl (dimethyl) methylmethoxysilane or 2- (3,4-epoxycyclohexyl) ethyl (dimethyl) methoxysilane. Can be mentioned.

  Specific examples of the compound represented by the general formula (6) include 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, and 3-glycidoxy. Propyl (methyl) dibutoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane or 2- (3,4-epoxycyclohexyl) ethyl (methyl ) Diethoxysilane.

  Specific examples of the compound represented by the general formula (7) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl). Examples include ethyltrimethoxysilane or 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

  In the method (2), as a specific method for the condensation reaction of the siloxane compound and the siloxane compound having a cyclic ether-containing group, for example, the siloxane compound and the compound having a cyclic ether-containing group are mixed with water, and The method of synthesize | combining a silicone resin by making it react in presence of an acid or a basic catalyst is mentioned.

  The amount of the water is not particularly limited as long as it is an amount capable of hydrolyzing an alkoxy group bonded to a silicon atom in the siloxane compound having the siloxane compound and the cyclic ether-containing group.

  The acidic catalyst is a catalyst for reacting the siloxane compound with a siloxane compound having a cyclic ether-containing group, and examples thereof include inorganic acids, organic acids, acid anhydrides or derivatives thereof.

  Examples of the inorganic acid include 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 or oleic acid Is mentioned.

  The basic catalyst is a catalyst for reacting the siloxane compound with a siloxane compound having a cyclic ether-containing group, and examples thereof 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, potassium-based catalysts and cesium-based catalysts are preferred.

  In the die-bonding material for optical semiconductor devices of the present invention, other curable compounds may be contained in the range not impeding the effects of the present invention in addition to the above-described resins. Examples of such a compound include compounds having an amino group, a urethane group, an imide group, a hydroxyl group, a carboxyl group, or an epoxy group. Among these, an epoxy compound is preferable. The epoxy compound is not particularly limited, and various conventionally known epoxy compounds can be used.

  The blending amount of the other curable compound is not particularly limited, but a preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the total silicone resin described above. A more preferred upper limit is 5 parts by weight, a still more preferred upper limit is 3 parts by weight, and a particularly preferred upper limit is 1 part by weight.

[Titanium oxide with a rutile crystal structure]
The reflective die-bonding material for an optical semiconductor device according to the present invention contains titanium oxide whose crystal structure is rutile type in order to enhance reflectivity. Further, since the rutile type titanium oxide is contained, even if the reflective die bond material for optical semiconductor devices is exposed to light, deterioration due to coloring such as yellowing hardly occurs.

  Preferably, for titanium oxide, a liquid obtained by adding 5 g of titanium oxide to 100 ml of pure water is heated, boiled for 5 minutes, and then allowed to stand until it reaches 23 ° C. to obtain a boiling treatment liquid. In addition, it is desirable that the titanium oxide exhibit a pH of 6.2 or more and 11 or less when the amount of water evaporated by boiling is added to bring the amount of water to 100 ml. The pH of the obtained liquid can be measured according to the operation described in 7 of JIS Z8802.

  The pH is more preferably 7.0 or more, further preferably 7.4 or more, and most preferably 8.1 or more. Thereby, deterioration of the reflective die-bonding material for optical semiconductor devices can be further suppressed. The upper limit value of the pH measured by the boiling method is more preferably 10.0 or less, and even more preferably 9.0 or less. Thereby, the pot life of the reflective die-bonding material for optical semiconductor devices can be lengthened.

  It is preferable that at least one kind of titanium oxide is coated with a basic metal oxide or a basic metal hydroxide so that the surface is made basic. It is preferable that the surface of the titanium oxide is basic because yellowing at a high temperature can be further suppressed.

  Examples of the basic metal oxide or basic metal hydroxide include compounds of metals such as magnesium, zirconium, cerium, strontium, antimony, barium, and calcium. Especially, since the possibility of yellowing when exposed to high temperatures can be reduced, it is preferable that zirconium oxide is contained in the material covering titanium oxide.

  Examples of the titanium oxide coating method include a method in which titanium oxide to be coated is dispersed in water or a liquid medium containing water as a main component. At this time, preliminary pulverization may be performed using a wet pulverizer such as a sand mill or a ball mill according to the degree of aggregation of titanium oxide. The pH of the slurry is preferably set as appropriate according to the titanium oxide. For example, in the case of titanium oxide, the pH is preferably 9 or more. Next, a water-soluble salt of the metal to be coated is added to the slurry. Thereafter, neutralization, solid-liquid separation, drying and dry pulverization are carried out, whereby a coated titanium oxide can be obtained.

  The titanium oxide preferably contains a compound capable of reacting with an acidic site of titanium oxide in order to increase the basicity of the titanium oxide surface. Moreover, in order to improve the basicity of titanium oxide, it is preferable that the compound which can react with the acidic site | part of a titanium oxide contains the titanium oxide which exists on the surface. Compounds that can react with the acidic sites of titanium oxide include (1) polymethyl alcohols such as trimethylolpropane, trimethylolethane, ditrimethylolpropane, trimethylolpropane ethoxylate, or pentaerythritol, and (2) monoethanol. Examples thereof include alkanolamines such as amine, monopropanolamine diethanolamine, dipropanolamine, triethanolamine, and tripropanolamine, (3) chlorosilane, and (4) alkoxysilane.

  If the compound which can react with the acidic site | part of a titanium oxide is a basic compound, the basicity of a titanium oxide can be improved more and it is preferable. Examples of such preferable basic compound include alkanolamine.

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

  The content of titanium oxide in 100% by weight of the reflective die-bonding material for optical semiconductor devices is preferably 3% by weight or more and 80% by weight or less. If it is less than 3% by weight, it may be difficult to improve reflectivity, and if it exceeds 80% by weight, die bonding may be difficult. A more preferred lower limit is 10% by weight, and a more preferred upper limit is 75% by weight.

[Thermosetting agent]
The reflective die-bonding material for an optical semiconductor device of the present invention contains a thermosetting agent that reacts with the cyclic ether-containing group (hereinafter also simply referred to as a thermosetting agent).

  The thermosetting agent is not particularly limited as long as it can react with the cyclic ether-containing group of the silicone resin. For example, ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylamino Aliphatic amines such as piperazine and isophoronediamine, metaphenylenediamine, paraphenylenediamine, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenolsulfone, 4,4′-diaminodiphenormethane, 4 Aromatic amines such as 4,4'-diaminodiphenol ether, mercaptans such as mercaptopropionic esters, terminal mercapto compounds of epoxy resins, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol Nord A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, biphenol, dihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) ) Methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol, phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, bromine Phenolic resins such as bisphenol A novolak, polyols obtained by hydrogenating the aromatic rings of these phenolic resins, polyazeline acid anhydride, methyltetrahydrophthalic anhydride, tetrahydro (B) Phthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3 -Dicarboxylic anhydride, methyl-norbornane-2,3-dicarboxylic anhydride, cyclohexane-1,2,3-tricarboxylic acid-1,2 anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2 3-alkylglutaric anhydride having an optionally branched alkyl group having 1 to 8 carbon atoms, such as alicyclic acid anhydride such as anhydride, 3-methylglutaric anhydride, 2-ethyl-3- 2,3-dialkylglutaric anhydride, 2,4-diethylglutenic acid having 1 to 8 carbon atoms which may be branched, such as propylglutaric anhydride Alkyl-substituted glutaric anhydrides such as 2,4-dialkylglutaric anhydrides having an alkyl group having 1 to 8 carbon atoms which may be branched, such as taric anhydride, 2,4-dimethylglutaric anhydride, Aromatic anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and their salts, aliphatic amines, Amine adduct obtained by reaction of aromatic amine and / or imidazole with epoxy resin, hydrazine such as adipic acid dihydrazide, dimethylbenzylamine, third compound such as 1,8-diazabicyclo [5.4.0] undecene-7 Examples include organic phosphines such as secondary amines or triphenylphosphine, and dicyandiamide. It is. These thermosetting agents may be used independently and 2 or more types may be used together.

  Among the above thermosetting agents, acid anhydrides such as alicyclic acid anhydrides, alkyl-substituted glutaric acid anhydrides, and aromatic acid anhydrides are preferable to improve heat resistance, and more preferably, alicyclic Formula acid anhydrides, alkyl-substituted glutaric anhydrides, particularly preferably methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-norbornane-2,3 -Dicarboxylic anhydride, cyclohexane-1,2,3-tricarboxylic acid-1,2 anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2 anhydride, or 2,4-diethylglutaric anhydride It is.

  The blending amount of the thermosetting agent is not particularly limited, but the preferred lower limit is 1 part by weight and the preferred upper limit is 200 parts by weight with respect to 100 parts by weight of the silicone resin. Within this range, the reflective die-bonding material for optical semiconductor devices of the present invention sufficiently undergoes a crosslinking reaction, is excellent in heat resistance and light resistance, and has a sufficiently low moisture permeability. A more preferred lower limit is 5 parts by weight, and a more preferred upper limit is 120 parts by weight.

[Curing accelerator]
The reflective die bond material for optical semiconductor devices of the present invention preferably further contains a curing accelerator.

  The curing accelerator is not particularly limited, and examples thereof include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; and third compounds such as 1,8-diazabicyclo (5,4,0) undecene-7. Phosphines such as triphenylphosphine; phosphonium salts such as triphenylphosphonium bromide; tins such as aminotriazoles, tin octylate and dibutyltin dilaurate, zincs such as zinc octylate, aluminum, And metal catalysts such as acetylacetonate such as chromium, cobalt, and zirconium. These hardening accelerators may be used independently and may use 2 or more types together.

  Although it does not specifically limit as a compounding quantity of the said hardening accelerator, A preferable minimum is 0.01 weight part and a preferable upper limit is 5 weight part with respect to 100 weight part of said silicone resins. If it is less than 0.01 part by weight, the effect of adding the curing accelerator cannot be obtained, and if it exceeds 5 parts by weight, the coloration of the cured product, heat resistance, and light resistance are significantly reduced, which is not preferable. A more preferred lower limit is 0.05 parts by weight, and a more preferred upper limit is 1.5 parts by weight.

[Other ingredients]
The reflective die-bonding material for optical semiconductor devices according to the present invention comprises an ultraviolet absorber, an antioxidant, a solvent, a colorant, a filler, an antifoaming agent, a surface treatment agent, a flame retardant, a viscosity modifier, a dispersant, and a dispersion aid. An agent, a surface modifier, a plasticizer, an antifungal agent, a leveling agent, a stabilizer, a coupling agent, an anti-sagging agent, or a phosphor may be contained.

[Preparation method and usage method]
The reflective die-bonding material for optical semiconductor devices according to the present invention can be prepared by stirring and mixing the above components and then uniformly mixing, for example, using three rolls.

  In use, a reflective die-bonding material for an optical semiconductor device may be applied to a substrate or the like or a bonding surface of the optical semiconductor element, and the optical semiconductor element may be bonded to the substrate and then heated. The heating conditions are not particularly limited, but may be a temperature of 100 ° C. to 170 ° C. and about 5 minutes to 5 hours.

The optical semiconductor element is not particularly limited. For example, when the optical semiconductor element is a light emitting diode, for example, a semiconductor material stacked on a substrate can be used. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.
Examples of the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. In addition, a buffer layer may be formed between the substrate and the semiconductor material as necessary. Examples of the buffer layer include GaN and AlN.

Specific examples of the optical semiconductor device of the present invention include a light emitting diode device, a semiconductor laser device, and a photocoupler. Such an optical semiconductor device of the present invention includes, for example, a backlight such as a liquid crystal display, illumination, various sensors, a light source such as a printer and a copying machine, a measurement light source for a vehicle, a signal light, a display light, a display device, and a planar light emission. It can be suitably used for body light sources, displays, decorations, various lights or switching elements.

[Optical semiconductor device]
The optical semiconductor device according to the present invention has a structure in which a light-emitting element is bonded to a lead electrode via the reflective die bond material for an optical semiconductor device of the present invention. FIG. 1 is a front sectional view showing an embodiment of an optical semiconductor device.

  The optical semiconductor device 1 includes a housing 2 having a tapered opening at a substantially center, and a light emitting element 3. The housing 2 has a pair of lead electrodes 4. One end of each lead electrode 4 is exposed at the bottom of the housing 2, and the other end is provided to extend outside the housing 2.

  The light emitting element 3 is fixed to a lead electrode 4 provided in the housing 2 with a reflective die bond material 5 for an optical semiconductor device, which is a cured product of the present composition. Further, a bonding pad (not shown) provided in the light emitting element 3 and the lead electrode 4 are electrically connected by a bonding wire 6, and an integrated product thereof is sealed with a sealant 7.

  As shown in FIG. 1, the reflective die-bonding material 5 for an optical semiconductor device is applied so as to protrude from the bottom of the light-emitting element 3 and surround the periphery of the light-emitting element 3, or so as not to protrude from the light-emitting element 3. It may be optional. The film thickness of the reflective die bond material 5 for an optical semiconductor device is preferably in the range of 10 to 100 μm.

  In the optical semiconductor device 1, when the light emitting element 3 is driven, light is emitted as indicated by a broken line A. In this case, not only the light irradiated from the light emitting element 3 to the side opposite to the upper surface of the lead electrode 4, that is, the light that has reached the reflective die bond material 5 for an optical semiconductor device is reflected as indicated by an arrow B. There is also light. The reflective die bond material 5 for an optical semiconductor device is white and reflects the light with high efficiency. Therefore, since the reflected light indicated by the arrow B is also used, the light use efficiency of the light emitting element 3 can be increased.

  Hereinafter, the effects of the present invention will be clarified by giving specific examples and comparative examples of the present invention.

(Synthesis Example 1)
750 g of dimethyldimethoxysilane and 150 g of 3-glycidoxypropyl (methyl) dimethoxysilane were put into a separable flask equipped with a 2000 mL thermometer and a dropping device and stirred at 50 ° C. An aqueous solution composed of 1.9 g of potassium hydroxide and 250 g of water was slowly dropped into the solution, and stirred at 50 ° C. for 6 hours after the dropwise addition. The acetic acid 2.1g was put in it, the volatile component was removed under reduced pressure, potassium acetate was filtered, and the polymer was obtained. The obtained polymer was washed with hexane / water, and volatile components were removed under reduced pressure to obtain polymer A.

The molecular weight of the polymer A is Mn = 11000, Mw = 25000, and (Me ₂ SiO _2/2 ) _0.90 (EpMeSiO _2/2 ) _0.10 from 29Si-NMR.
The 3-glycidoxypropyl group content was 14 mol%, and the epoxy equivalent was 760 g / eq. It was confirmed that.

  The molecular weight was stirred until tetrahydrofuran (1 mL) was added and dissolved in polymer A (10 mg), and a measuring device manufactured by Waters (column: Shodex GPC LF-804 (length: 300 mm) x 2 manufactured by Showa Denko KK) Measurement temperature: 40 ° C., flow rate: 1 mL / min, solvent: tetrahydrofuran, standard substance: polystyrene) were used for GPC measurement. Moreover, the epoxy equivalent was calculated | required based on JISK-7236.

(Synthesis Example 2)
In a separable flask equipped with a 2000 mL thermometer and a dropping device, 440 g of dimethyldimethoxysilane and 160 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added and stirred at 50 ° C. An aqueous solution consisting of 1.2 g of potassium hydroxide and 170 g of water was slowly dropped into the solution, and the mixture was stirred at 50 ° C. for 6 hours after the dropping was completed. The acetic acid 1.3g was put in it, the volatile component was removed under pressure reduction, potassium acetate was filtered, and the polymer was obtained. The obtained polymer was washed with hexane / water, and volatile components were removed under reduced pressure to obtain polymer B.

The molecular weight of the polymer B is Mn = 2300, Mw = 4800, and (Me ₂ SiO _2/2 ) _0.84 (EpSiO _3/2 ) _0.16 from 29Si-NMR.
The 2- (3,4-epoxycyclohexyl) ethyl group content was 22 mol%, and the epoxy equivalent was 550 g / eq. It was confirmed that.

  In addition, it calculated | required similarly to the molecular weight and the epoxy equivalent synthesis example 1 of the polymer B.

(Synthesis Example 3)
In a separable flask with a 1000 mL thermometer, dropping device and stirrer, 23 g of trimethylmethoxysilane, 180 g of dimethyldimethoxysilane, 100 g of phenyltrimethoxysilane, 100 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane The mixture was stirred at 50 ° C. An aqueous solution composed of 0.7 g of potassium hydroxide and 107 g of water was slowly dropped into the solution, and the mixture was stirred at 50 ° C. for 6 hours after the addition was completed. The acetic acid 0.8g was put in it, the volatile component was removed under reduced pressure, potassium acetate was filtered, and the polymer C was obtained.

The molecular weight of the polymer C is Mn = 2200. From 29Si-NMR, (Me ₃ SiO _1/2 ) _0.08 (Me ₂ SiO _2/2 ) _0.58 (PhSiO _3/2 ) _0.19 (EpSiO _{3 / 2} ) _0.15
The ratio of 2- (3,4-epoxycyclohexyl) ethyl group is 19 mol%, the ratio of phenyl group is 15 mol%, and the epoxy equivalent is 691 g / eq. It was confirmed that.

  The molecular weight and epoxy equivalent of polymer C were determined in the same manner as in Synthesis Example 1.

(Synthesis Example 4)
In a separable flask with a 1000 mL thermometer, dropping device and stirrer, 25 g of trimethylmethoxysilane, 208 g of dimethyldimethoxysilane, 71 g of diphenyldimethoxysilane, 58 g of phenyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ) 111g of ethyltrimethoxysilane was added and stirred at 50 ° C. An aqueous solution consisting of 0.8 g of potassium hydroxide and 117 g of water was slowly dropped therein, and after the dropping was completed, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid 0.9g was put in it, the volatile component was removed under reduced pressure, potassium acetate was filtered, and the polymer D was obtained.

The molecular weight of the polymer D is Mn = 1800, and from 29Si-NMR, (Me ₃ SiO _1/2 ) _0.08 (Me ₂ SiO _2/2 ) _0.57 (Ph ₂ SiO _2/2 ) _0.10 (PhSiO _3/2 ) _0.10 (EpSiO _3/2 ) _0.15
The ratio of 2- (3,4-epoxycyclohexyl) ethyl group is 17 mol%, the ratio of phenyl group is 21 mol%, and the epoxy equivalent is 723 g / eq. It was confirmed that.

  The molecular weight and epoxy equivalent of polymer D were determined in the same manner as in Synthesis Example 1.

(Synthesis Example 5)
In a separable flask equipped with a 1000 mL thermometer, a dropping device and a stirrer, 254 g of dimethyldimethoxysilane, 106 g of diphenyldimethoxysilane, and 111 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added and stirred at 50 ° C. did. An aqueous solution consisting of 0.8 g of potassium hydroxide and 116 g of water was slowly dropped into the solution, and the mixture was stirred at 50 ° C. for 6 hours after the addition was completed. The acetic acid 0.9g was put in it, the volatile component was removed under reduced pressure, potassium acetate was filtered, and the polymer E was obtained.

The molecular weight of the polymer E is Mn = 1600, and (Me ₂ SiO _2/2 ) _0.70 (Ph ₂ SiO _2/2 ) _0.15 (EpSiO _3/2 ) _0.15 from 29Si-NMR.
The ratio of 2- (3,4-epoxycyclohexyl) ethyl group was 17 mol%, the ratio of phenyl group was 21 mol%, and the epoxy equivalent was 742 g / eq. It was confirmed that.

  The molecular weight and epoxy equivalent of polymer E were determined in the same manner as in Synthesis Example 1.

Example 1
100 g of the polymer C, 20 g of acid anhydride (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, manufactured by Shin Nippon Science Co., Ltd., product number: Ricacid MH-700G), and a curing accelerator (1, 8 -Octylate of diazabicyclo (5.4.0) undecene-7, manufactured by San Apro, product number: U-CAT SA 102), and antioxidant (manufactured by Clariant, product name: Sandstub P-EPQ) 0.1 g and 200 g of titanium oxide (rutile-type titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., product number: CR-90) are put into a mixer, mixed and degassed to obtain a reflective die-bonding material for an optical semiconductor device. It was.

(Example 2)
100 g of the polymer C, 20 g of acid anhydride (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, manufactured by Shin Nippon Science Co., Ltd., product number: Ricacid MH-700G), and a curing accelerator (1, 8 -Octylate of diazabicyclo (5.4.0) undecene-7, manufactured by San Apro, part number: U-CAT SA 102), and antioxidant (manufactured by Clariant, trade name: Sandstub P-EPQ) 0.1 g and 200 g of titanium oxide (rutile type titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., product number: CR-50) are put into a mixer, mixed and degassed to obtain a reflective die bond material for an optical semiconductor device. It was.

(Example 3)
100 g of the polymer C, 20 g of acid anhydride (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, manufactured by Shin Nippon Science Co., Ltd., product number: Ricacid MH-700G), and a curing accelerator (1, 8 -Octylate of diazabicyclo (5.4.0) undecene-7, manufactured by San Apro, product number: U-CAT SA 102), and antioxidant (manufactured by Clariant, product name: Sandstub P-EPQ) 0.1 g and 200 g of titanium oxide (rutile-type titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., product number: CR-97) are put into a mixer, mixed and degassed to obtain a reflective die-bonding material for an optical semiconductor device. It was.

Example 4
100 g of the polymer C, 20 g of acid anhydride (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, manufactured by Shin Nippon Science Co., Ltd., product number: Ricacid MH-700G), and a curing accelerator (1, 8 -Octylate of diazabicyclo (5.4.0) undecene-7, manufactured by San Apro, product number: U-CAT SA 102), and antioxidant (manufactured by Clariant, product name: Sandstub P-EPQ) 0.1 g and 200 g of titanium oxide (rutile-type titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., product number: CR-90-2) are put into a mixer, mixed, degassed, and a reflective die-bonding material for an optical semiconductor device. Got.

(Example 5)
100 g of the polymer C, 20 g of acid anhydride (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, manufactured by Shin Nippon Science Co., Ltd., product number: Ricacid MH-700G), and a curing accelerator (1, 8 -Octylate of diazabicyclo (5.4.0) undecene-7, manufactured by San Apro, part number: U-CAT SA 102), and antioxidant (manufactured by Clariant, trade name: Sandstub P-EPQ) 0.1 g and 200 g of titanium oxide (rutile-type titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., product number: CR-50-2) are put into a mixer, mixed, degassed, and a reflective die-bonding material for an optical semiconductor device. Got.

(Example 6)
100 g of the polymer C, 20 g of acid anhydride (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, manufactured by Shin Nippon Science Co., Ltd., product number: Ricacid MH-700G), and a curing accelerator (1, 8 -Octylate of diazabicyclo (5.4.0) undecene-7, manufactured by San Apro, product number: U-CAT SA 102), and antioxidant (manufactured by Clariant, product name: Sandstub P-EPQ) 0.1 g and 200 g of titanium oxide (rutile type titanium oxide, manufactured by Titanium Industry Co., Ltd., product number: KR-270) are put into a mixer, mixed and degassed to obtain a reflective die bond material for an optical semiconductor device. It was.

(Example 7)
100 g of the above polymer A, 20 g of acid anhydride (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, manufactured by Shin Nippon Science Co., Ltd., product number: Ricacid MH-700G), and a curing accelerator (1, 8 -Octylate of diazabicyclo (5.4.0) undecene-7, manufactured by San Apro, part number: U-CAT SA 102), and antioxidant (manufactured by Clariant, trade name: Sandstub P-EPQ) 0.1 g and 200 g of titanium oxide (rutile-type titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., product number: CR-97) are put into a mixer, mixed and degassed to obtain a reflective die-bonding material for an optical semiconductor device. It was.

(Example 8)
100 g of the above polymer B, 20 g of acid anhydride (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, manufactured by Shin Nippon Science Co., Ltd., product number: Ricacid MH-700G), and a curing accelerator (1, 8 -Octylate of diazabicyclo (5.4.0) undecene-7, manufactured by San Apro, part number: U-CAT SA 102), and antioxidant (manufactured by Clariant, trade name: Sandstub P-EPQ) 0.1 g and 200 g of titanium oxide (rutile-type titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., product number: CR-97) are put into a mixer, mixed and degassed to obtain a reflective die-bonding material for an optical semiconductor device. It was.

Example 9
100 g of the polymer D, 20 g of acid anhydride (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, manufactured by Shin Nippon Science Co., Ltd., product number: Ricacid MH-700G), and a curing accelerator (1, 8 -Octylate of diazabicyclo (5.4.0) undecene-7, manufactured by San Apro, part number: U-CAT SA 102), and antioxidant (manufactured by Clariant, trade name: Sandstub P-EPQ) 0.1 g and 200 g of titanium oxide (rutile-type titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., product number: CR-97) are put into a mixer, mixed and degassed to obtain a reflective die-bonding material for an optical semiconductor device. It was.

(Example 10)
100 g of the above polymer E, 20 g of acid anhydride (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, manufactured by Shin Nippon Science Co., Ltd., product number: Ricacid MH-700G), and a curing accelerator (1, 8 -Octylate of diazabicyclo (5.4.0) undecene-7, manufactured by San Apro, product number: U-CAT SA 102), and antioxidant (manufactured by Clariant, product name: Sandstub P-EPQ) 0.1 g and 200 g of titanium oxide (rutile-type titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., product number: CR-97) are put into a mixer, mixed and degassed to obtain a reflective die-bonding material for an optical semiconductor device. It was.

(Comparative Example 1)
100 g of the polymer C, 20 g of acid anhydride (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, manufactured by Shin Nippon Science Co., Ltd., product number: Ricacid MH-700G), and a curing accelerator (1, 8 -Octylate of diazabicyclo (5.4.0) undecene-7, manufactured by San Apro, part number: U-CAT SA 102), and antioxidant (manufactured by Clariant, trade name: Sandstub P-EPQ) 0.1 g and 200 g of titanium oxide (anatase type, manufactured by Cii Kasei Co., Ltd., product number: NanoTekTiO2) were put into a mixer, mixed and degassed to obtain a reflective die-bonding material for an optical semiconductor device.

(Comparative Example 2)
100 g of epoxy resin (manufactured by Toto Kasei Co., Ltd., product number: YD-127) and acid anhydride (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, manufactured by Shin Nippon Science Co., Ltd., product number: Ricacid MH- 700 g) and 20 g of a curing accelerator (octylate of 1,8-diazabicyclo (5.4.0) undecene-7, manufactured by San Apro, product number: U-CAT SA 102), and an antioxidant (Clariant) Company name, product name: Sandstub P-EPQ (0.1 g) and titanium oxide (rutile-type titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., product number: CR-97) 200 g were introduced into a mixer and mixed to defoam. Thus, a reflective die bond material for an optical semiconductor device was obtained.

(Titanium oxide used)
Table 1 shows the evaluation of titanium oxide used in Examples and Comparative Examples.

(Evaluation of Examples and Comparative Examples)
(1) Initial reflectivity Each of the reflective die-bonding materials for optical semiconductor devices obtained in Examples and Comparative Examples was cured at 150 ° C. for 3 hours to obtain a cured product of 50 mm × 50 mm × 100 μm thick, The cured product was used as an evaluation sample. About this evaluation sample, the Y value was measured using a color / color difference meter (manufactured by Konica Minolta, product number: CR-400).

(2) Heat resistance at 150 ° C. × 1500 hours (1) The evaluation sample obtained with the initial reflectivity is 1500 ° C. at a temperature of 150 ° C. using a blowing constant temperature and humidity chamber (manufactured by YAMATO, product number: DKM-600) A heat treatment was performed to maintain the time. After the heat treatment, (1) the Y value of the evaluation sample was measured using the color / color difference meter used in the evaluation of the initial reflectance. ΔY1 of the evaluation sample obtained by the following formula (8) was obtained. When ΔY1 is 2.0% or less, ◎, more than 2.0%, ○ when 3.0% or less, ○, more than 3.0%, and 4.0% or less Δ, 4.0% A value exceeding x was taken as x. The results are shown in Tables 2 and 3 below.

ΔY1 = (Y of evaluation sample before heat treatment—Y of evaluation sample after heat treatment at 1500 ° C. 1500 h) / (Y of evaluation sample before heat treatment) × 100% (Equation 8)

(3) Heat resistance at 150 ° C. for 3000 hours Above (1) The evaluation sample obtained with the initial reflectivity is 3000 at a temperature of 150 ° C. using a blowing constant temperature and humidity chamber (manufactured by YAMATO, product number: DKM-600). A heat treatment was performed to maintain the time. After the heat treatment, (1) the Y value of the evaluation sample was measured using the color / color difference meter used in the evaluation of the initial reflectance. ΔY2 of the evaluation sample obtained by the following formula (9) was obtained. When ΔY2 is 2.0% or less, ◎, more than 2.0%, ◯ when 3.0% or less, ◯, more than 3.0%, 4.0% or less △, 4.0% A value exceeding x was taken as x. The results are shown in Tables 2 and 3 below.

ΔY2 = (Y of evaluation sample before heat treatment—Y of evaluation sample after heat treatment at 150 ° C. for 3000 h) / (Y of evaluation sample before heat treatment) × 100% (Equation 9)

(4) Shear competitive adhesive strength The reflective die-bonding material for optical semiconductor devices obtained in the examples and comparative examples is a 3 mm × 3 mm silicone wafer and a silver-plated copper plate (TP Giken, product number: C1100P). A laminated body having a thickness of 50 μm was prepared, and the laminated body was heated at 150 ° C. for 3 hours to cure the reflective die-bonding material by heating. Next, using a die shear strength measuring device (Arctech, product number: DAGE 4000), a contact tool is used to apply a force in the lateral direction perpendicular to the stacking direction to the silicone wafer from the silver-plated copper plate. The strength at the time of peeling was measured, and the strength was defined as shear adhesive strength. The results are shown in Tables 2 and 3.

DESCRIPTION OF SYMBOLS 1 ... Optical semiconductor device 2 ... Housing 3 ... Light emitting element 4 ... Lead electrode 5 ... Reflective die-bonding material for optical semiconductor devices 6 ... Bonding wire 7 ... Sealing agent

Claims (7)

  A reflective die-bonding material for an optical semiconductor device, comprising: a silicone resin having a cyclic ether-containing group in the molecule; a titanium oxide having a rutile crystal structure; and a thermosetting agent capable of reacting with the cyclic ether-containing group.   The titanium oxide is heated to a solution obtained by adding 5 g of the titanium oxide to 100 ml of pure water, boiled for 5 minutes, and then allowed to stand until it reaches 23 ° C. to obtain a boiling treatment liquid. In the obtained boiling treatment liquid, The reflective die bond for an optical semiconductor device according to claim 1, wherein the pH of the liquid when the amount of water evaporated by boiling is added to make the amount of water 100 ml is titanium oxide having a value of 6.2 or more and 11 or less. Wood.   The reflective die-bonding material for optical semiconductor devices according to claim 1 or 2, wherein the titanium oxide is coated with at least one of a basic metal oxide and a basic metal hydroxide.   The metal element constituting the basic metal oxide and the basic metal hydroxide is at least one selected from the group consisting of magnesium, zirconium, cerium, strontium, antimony, barium and calcium. A reflective die-bonding material for an optical semiconductor device as described in 1.   The reflective die-bonding 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 silicone resin having a cyclic ether-containing group in the molecule contains a resin component whose average composition formula is represented by the following general formula (1), and the content of the cyclic ether-containing group is 0.1 mol% to 50%. The reflective die-bonding material for optical semiconductor devices according to any one of claims 1 to 5, which is in a range of mol%.

In the general formula (1), a, b, and c are a / (a + b + c) = 0 to 0.3, b / (a + b + c) = 0.3 to 1.0, c / (a + b + c) = 0 to 0, respectively. 0.5, and at least one of R ^{1 to} R ⁶ represents a cyclic ether-containing group, and R ^{1 to} R ⁶ other than the cyclic ether-containing group have a linear or branched carbon number of 1 to 8 hydrocarbons or fluorinated compounds thereof, which may be the same or different from each other.   An optical semiconductor device in which an optical semiconductor element is bonded using the reflective die-bonding material for an optical semiconductor device according to claim 1.

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