JP2008202036A - Thermosetting composition for optical semiconductor, sealant for optical semiconductor device, die bond material for optical semiconductor device, underfill material for optical semiconductor device, and optical semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting composition for an optical semiconductor, a sealant for an optical semiconductor device, a die bond material for an optical semiconductor device, and an underfill material for an optical semiconductor device, all of them are excellent in transparency, heat resistance, light resistance, and adhesiveness to a housing material, hardly generate cracks and exfoliation even when subjected to a rapid thermal change, such as a soldering reflow process or heat cycle, and do not cause problems, such as yellowing, under use conditions; and a semiconductor device using the above-described materials. <P>SOLUTION: The thermosetting composition for an optical semiconductor contains a silicone copolymer resin (A) having, in its molecule, at least one alicyclic epoxy-containing group, structural units represented by general formula (1), and structural units represented by general formula (2), a bifunctional silicone resin (B) having one or more glycidyl-containing groups in the molecule, and a thermosetting agent reactive with the above-described alicyclic epoxy-containing group and glycidyl-containing group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention has excellent transparency, excellent heat resistance, light resistance, and adhesion to a housing material, and is extremely unlikely to crack or peel even during a rapid thermal change such as a solder reflow process or thermal cycle. , A thermosetting composition for optical semiconductors, a sealing compound for optical semiconductor elements, a die bond material for optical semiconductor elements, an underfill material for optical semiconductor elements, and light using them The present invention relates to a semiconductor element.

Light-emitting elements such as light-emitting diodes (LEDs) are usually sealed with a sealant because their light-emitting characteristics rapidly deteriorate due to moisture in the atmosphere or floating dust when they come into direct contact with the atmosphere. It has a structure. As a resin constituting a sealant for sealing such a light emitting element, an epoxy resin such as a bisphenol type epoxy resin or an alicyclic epoxy resin is used because of its high adhesive strength and excellent mechanical durability. (For example, refer to Patent Document 1).

By the way, in recent years, LEDs have come to be used for applications that require high brightness, such as automotive headlights and lighting. Therefore, the sealant that seals the light emitting element has a heat generation during lighting. In addition to high heat resistance that can withstand an increase in the amount of light, high light resistance that prevents light deterioration associated with higher brightness has been required. However, it is difficult to say that a conventional sealant made of an epoxy resin has sufficient heat resistance and light resistance, and is made of an epoxy resin in applications requiring high brightness such as automotive headlights and lighting. There was a problem that the sealant may not be able to cope.

Moreover, although the sealing agent which consists of the conventional epoxy resin has advantages, such as high adhesiveness and low moisture permeability, it has the problem that it has low light resistance with respect to the light of a short wavelength, and will be colored by light degradation. there were.

On the other hand, in place of epoxy resin, a method is known in which a silicone resin having a high transmittance for light having a short wavelength in the blue to ultraviolet region is used as a sealant for sealing a light emitting element of an LED (for example, Patent Document 2). reference).
However, since the silicone resin is generally soft and has surface tackiness, foreign substances are likely to adhere to the surface of the light emitting element, and the light emitting surface may be damaged during sealing. On the other hand, the silicone resin having an increased crosslink density has a problem that the cured product is inferior in mechanical strength and has insufficient adhesion to a housing material enclosing the light emitting element.

Further, for example, Patent Document 3 discloses a thermosetting composition for sealing a light-emitting element, in which a modified polysiloxane having two or more epoxy groups in one molecule and, if necessary, an epoxy resin are blended. Yes. The thermosetting composition for sealing a light-emitting element disclosed in Patent Document 3 can improve adhesion by blending an epoxy resin. However, the composition in which the modified polysiloxane and the epoxy resin are blended has poor compatibility and sufficient transparency cannot be obtained, and the problem of mechanical strength of the cured product is not sufficiently improved, and crack resistance is poor. It left many challenges. For this reason, what provided the outstanding transparency, heat resistance, light resistance, adhesiveness, and crack resistance was calculated | required as resin which can be used for optical semiconductors, especially a sealing use.
JP 2003-277473 A JP 2002-314142 A JP 2004-289102 A

In view of the above-mentioned present situation, the present invention has excellent transparency, heat resistance, light resistance, and adhesion to a housing material, and cracks and delamination even when abrupt thermal changes such as a solder reflow process and a thermal cycle are performed. Is hard to occur and does not cause problems such as yellowing under use conditions, an optical semiconductor element sealant, an optical semiconductor element die bond material, an optical semiconductor element underfill material, and An object of the present invention is to provide an optical semiconductor device using them.

The present invention relates to a silicone copolymer having one or more alicyclic epoxy-containing groups in a molecule, a structural unit represented by the following general formula (1), and a structural unit represented by the following general formula (2). An optical semiconductor comprising a coalesced resin (A), a bifunctional silicone resin (B) having at least one glycidyl-containing group in the molecule, and a thermosetting agent capable of reacting with the alicyclic epoxy-containing group and the glycidyl-containing group Thermosetting composition.

一般式（１）及び（２）中、Ｒ^１、Ｒ^２及びＲ^３は、少なくとも１つが脂環式エポキシ含有基であり、脂環式エポキシ含有基以外のＲ^１、Ｒ^２及びＲ^３は、直鎖状若しくは分岐状の炭素数１〜８の炭化水素或いはそのフッ素化物を表し、これらは、互いに同一であってもよく、異なっていてもよい。
以下、本発明を詳述する。

In the general formula (1) and ^(2), R 1, ^{R 2} and ^{R 3} is at least 1 Tsugaabura cyclic epoxy-containing group, ^R 1, ^{R 2} and ^{R 3} other than alicyclic epoxy-containing group Represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and these may be the same or different from each other.
The present invention is described in detail below.

As a result of intensive studies, the present inventors have a silicone copolymer resin having a specific structural unit having at least one alicyclic epoxy-containing group in the molecule, and at least one glycidyl-containing group in the molecule. The curable composition using a bifunctional silicone resin exhibits excellent transparency in a heat environment, has high transparency to light in the short wavelength range from blue to ultraviolet, and is heat resistant without discoloration due to heat or light. The present invention has been completed by finding that it has excellent properties and light resistance and has extremely excellent crack resistance.

The thermosetting composition for optical semiconductors of the present invention comprises a silicone copolymer resin (A) having at least one alicyclic epoxy-containing group in the molecule, and 2 having at least one glycidyl-containing group in the molecule. A functional silicone resin (B) is contained.
When the silicone copolymer resin (A) has at least one alicyclic epoxy-containing group in the molecule, the thermosetting composition for optical semiconductors of the present invention has an adhesive property to a housing material or the like of the cured product. It is excellent in transparency, can prevent yellowing under thermal conditions, and has excellent transparency.

In the thermosetting composition for optical semiconductors of the present invention, the silicone resin (A) has a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2).

The silicone resin (A) is composed mainly of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), and the total number of structural units included is 1. The lower limit of the content of the structural unit represented by the general formula (1) is 0.5 and the upper limit is 0.95 (molar conversion), and the content of the structural unit represented by the general formula (2) It is preferable that the lower limit of the amount is 0.05 and the upper limit is 0.5 (in terms of mole). By containing the silicone resin (A) having an alicyclic epoxy-containing group and containing the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the above range. The thermosetting composition for optical semiconductors of the present invention, when used as an encapsulant for optical semiconductor elements, is excellent in heat resistance and light resistance without causing heat generation or film loss or discoloration due to light emission of the light emitting elements to be sealed. At the same time, when the light emitting element of the optical semiconductor element such as a light emitting diode is sealed, the optical semiconductor element is more excellent in adhesion to the housing material or the like.
In the present specification, “having as a main component” means that the silicone resin (A) includes only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2). It is preferable that the resin is composed of a resin other than the structural unit represented by the general formula (1) and the structural unit (2), as long as the effects of the present invention are not impaired. It may mean that it may have a structural unit of

In the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), at least one of R ^{1 to} R ³ represents an alicyclic epoxy-containing group. In the present specification, the alicyclic epoxy-containing group only needs to contain an alicyclic epoxy group in at least a part of the group, for example, other skeletons such as an alkyl group and an alkyl ether group, and an alicyclic epoxy group. It means a group which may contain a group.
Specific examples of the alicyclic epoxy-containing group include 2- (3,4-epoxycyclohexyl) ethyl group and 3- (3,4-epoxycyclohexyl) propyl group.
The silicone resin (A) may contain a plurality of different types of R ¹ , R ² and R ³ in the repeating structure in the silicone resin skeleton. As long as both the structural unit represented by the above (1) and the structural unit represented by the above general formula (2) are contained in the skeleton as essential components, a plurality of repeated structural units are not necessarily the same. This means that it may not be a repeating unit.

The silicone resin (A) preferably has a lower limit of the content of the alicyclic epoxy-containing group of 5 mol% and an upper limit of 40 mol%. If it is less than 5 mol%, the reactivity between the silicone resin (A) and the thermosetting agent described later is remarkably lowered, and the curability of the thermosetting composition for optical semiconductors of the present invention becomes insufficient. When it exceeds 40 mol%, the alicyclic epoxy-containing group not involved in the reaction between the silicone resin (A) and the thermosetting agent increases, and the heat resistance of the thermosetting composition for optical semiconductors of the present invention decreases. A more preferred lower limit is 7 mol%, and a preferred upper limit is 30 mol%.
In the present specification, the content of the alicyclic epoxy-containing group means the amount of the alicyclic epoxy-containing group contained in the average composition of the silicone resin (A) component.

In the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), R ^{1 to} R ³ other than the alicyclic epoxy-containing group have 1 to 8 carbon atoms. Or a fluorinated product thereof.

It does not specifically limit as said C1-C8 hydrocarbon, 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, phenyl group and the like.

In the silicone resin (A), the structural unit represented by the general formula (1) (hereinafter also referred to as a bifunctional structural unit) has a structure represented by the following general formula (1-2), that is, a bifunctional It includes a structure in which one of oxygen atoms bonded to a silicon atom in a structural unit constitutes a hydroxyl group or an alkoxy group.
(R ¹ R ² SiXO _1/2 ) (1-2)
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 (A), the structural unit represented by the general formula (2) (hereinafter also referred to as trifunctional structural unit) is represented by the following general formula (2-2) or (2-3). A structure in which two of the oxygen atoms bonded to the silicon atom in the trifunctional structural unit each constitute a hydroxyl group or an alkoxy group, or one of the oxygen atoms bonded to the silicon atom in the trifunctional structural unit One of which constitutes a hydroxyl group or an alkoxy group.
(R ³ SiX ₂ O _1/2 ) (2-2)
(R ³ SiXO _2/2 ) (2-3)
In the general formulas (2-2) and (2-3), 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), (2-2), and (2-3), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited. Group, n-propoxy group, n-butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, t-butoxy group and the like.

When the above-mentioned silicone resin (A) 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-mentioned general variation is observed depending on the type of substituent. Each peak corresponding to the bifunctional structural unit of the formulas (1) and (1-2) appears in the vicinity of −10 to −30 ppm, and 3 in the above general formulas (2), (2-2), and (2-3) Each peak corresponding to the functional structural unit appears in the vicinity of −50 to −70 ppm.
Therefore, it is possible to measure the ratio of the silicone resin (A) by measuring ²⁹ Si-NMR and comparing the peak areas of the respective signals.
However, when the ²⁹ Si-NMR measurement based on the TMS cannot be distinguished from the bifunctional structural unit of the general formula (1), not only the ²⁹ Si-NMR measurement result but also ¹ H-NMR The ratio of structural units can be discriminated by using the results measured by ¹⁹ F-NMR or the like as necessary.

The silicone copolymer resin (A) contains a resin component whose average composition formula is represented by the following general formula (3), (4), (5), (6), (7) or (8). It is preferable.
The silicone copolymer resin (A) is represented by the following general formula (3), (4), (5), (6), (7) or (8): The thermosetting composition for optical semiconductors of the invention is represented by the following general formula (3), (4), (5), (6), (7) or (8) as the silicone copolymer resin (A). When it is a mixture containing not only the resin component but also the resin component having various structures, the following general formulas (3), (4), (5) ), (6), (7) or (8).

In the general formula (3), R ⁶ represents an alicyclic epoxy-containing group, R ⁴ and R ⁵ represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, These may be the same as each other or different. The preferable lower limit of a / (a + b) is 0.5, the preferable upper limit is 0.95, the more preferable lower limit is 0.6, the more preferable upper limit is 0.9, and the preferable lower limit of b / (a + b) is 0.00. 05, a preferable upper limit is 0.5, a more preferable lower limit is 0.1, and a more preferable upper limit is 0.4.

In the general formula (4), R ⁸ and / or R ⁹ is an alicyclic epoxy-containing group, and R ⁷ is a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. To express. When only one of R ^{8 and} R ⁹ is an alicyclic epoxy-containing group, the other represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. The preferable lower limit of c / (c + d) is 0.5, the preferable upper limit is 0.95, the more preferable lower limit is 0.6, the more preferable upper limit is 0.9, and the preferable lower limit of d / (c + d) is 0. 05, a preferable upper limit is 0.5, a more preferable lower limit is 0.1, and a more preferable upper limit is 0.4.

一般式（５）中、ｅ、ｆ、ｇは、（ｅ＋ｆ）／（ｅ＋ｆ＋ｇ）＝０．５〜０．９５、ｇ／（ｅ＋ｆ＋ｇ）＝０．０５〜０．５を満たし、Ｒ^１４は、脂環式エポキシ含有基であり、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３は、直鎖状若しくは分岐状の炭素数１〜８の炭化水素或いはそのフッ素化物を表し、これらは、互いに同一であってもよく、異なっていてもよい。（Ｒ^１０Ｒ^１１ＳｉＯ_２／２）と（Ｒ^１２Ｒ^１３ＳｉＯ_２／２）とは構造が異なるものである。

In the general formula (5), e, f and g satisfy (e + f) / (e + f + g) = 0.5 to 0.95, g / (e + f + g) = 0.05 to 0.5, and R ¹⁴ is It is an alicyclic epoxy-containing group, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and these are the same as each other May be different or different. (R ¹⁰ R ¹¹ SiO _2/2 ) and (R ¹² R ¹³ SiO _2/2 ) have different structures.

In the general formula (6), R ¹⁷ and / or R ¹⁸ is an alicyclic epoxy-containing group, and R ¹⁵ , R ¹⁶ , and R ¹⁹ are linear or branched carbon atoms having 1 to 8 carbon atoms. It represents hydrogen or a fluorinated product thereof, and these may be the same as or different from each other. When only one of R ^{17 and} R ¹⁸ is an alicyclic epoxy-containing group, the other represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. The preferable lower limit of (h + i) / (h + i + j) is 0.5, the preferable upper limit is 0.95, the more preferable lower limit is 0.6, and the more preferable upper limit is 0.9. The preferable lower limit of j / (h + i + j) is 0.05, a preferable upper limit is 0.5, a more preferable lower limit is 0.1, and a more preferable upper limit is 0.4.

In the general formula (7), R ²² is an alicyclic epoxy-containing group, and R ²⁰ , R ²¹ , and R ²³ are linear or branched hydrocarbons having 1 to 8 carbon atoms or a fluorinated product thereof. These may be the same as or different from each other. The preferred lower limit of k / (k + l + m) is 0.5, the preferred upper limit is 0.95, the more preferred lower limit is 0.6, and the more preferred upper limit is 0.9. The preferred lower limit of (l + m) / (k + l + m) is 0.05, a preferable upper limit is 0.5, a more preferable lower limit is 0.1, and a more preferable upper limit is 0.4.

In the general formula (8), n, o and p satisfy n / (n + o + p) = 0.5 to 0.95, (o + p) / (n + o + p) = 0.05 to 0.5, R ²⁴ and / Or R ²⁵ represents an alicyclic epoxy-containing group, and R ²⁶ and R ²⁷ represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and these are the same as each other. It may be different. When only one of R ^{24 and} R ²⁵ is an alicyclic epoxy-containing group, the other represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. (R ²⁶ SiO _3/2 ) and (R ²⁷ SiO _3/2 ) have different structures.

Since the silicone copolymer resin (A) has excellent curability and heat resistance, the resin composition represented by the general formula (3), (5) or (7) is represented by the average composition formula. It is preferable to contain.

If the silicone resin is composed mainly of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), structural units other than these structural units may be used. You may have. In this case, when the total number of structural units contained in the silicone resin is 1, the total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) A preferred lower limit is 0.9 (molar conversion). If it is less than 0.9 (in terms of mole), the effects such as excellent heat resistance, light resistance, and high adhesion of the thermosetting composition for optical semiconductors of the present invention may be significantly impaired. A more preferred lower limit is 0.95 (molar conversion).

The structural unit other than the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) that may be contained in the silicone resin is not particularly limited. The structural unit represented by (9) or chemical formula (10) is mentioned.

一般式（９）中、Ｒ^２８、Ｒ^２９及びＲ^３０は、脂環式エポキシ含有基、又は、炭素数１〜８の炭化水素或いはそのフッ素化物を表し、これらは、互いに同一であってもよく、異なっていてもよい。

In the general formula (9), R ²⁸ , R ²⁹ and R ³⁰ represent an alicyclic epoxy-containing group, a hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, which may be the same as each other. Well, it can be different.

In the case where the silicone resin contains a structural unit represented by the general formula (9) or the chemical formula (10), these contents include the structural unit represented by the general formula (1) and the general formula There is no particular limitation as long as the total content of the structural units represented by (2) falls within the above-described range. For example, when the total number of structural units contained in the silicone resin is 1, The upper limit with preferable content of the structural unit represented by General formula (9) is 0.1 (mol conversion). The upper limit with preferable content of the structural unit represented by the said Chemical formula (10) is 0.1 (mol conversion). When content of the structural unit represented by the said General formula (9) exceeds 0.1 (mol conversion), the heat resistance of the thermosetting composition for optical semiconductors of this invention may fall. Moreover, when the content of the structural unit represented by the chemical formula (10) exceeds 0.1, it may be difficult to maintain an appropriate viscosity as the thermosetting composition for optical semiconductors of the present invention, It may be difficult to maintain adhesion.

The structural unit represented by the general formula (10) (hereinafter also referred to as a tetrafunctional structural unit) is represented by the following general formula (10-2), (10-3), or (10-4). A structure, that is, a structure in which three or two oxygen atoms bonded to a silicon atom in a tetrafunctional structural unit constitute a hydroxyl group or an alkoxy group, or one of oxygen atoms bonded to a silicon atom in a tetrafunctional structural unit One of which constitutes a hydroxyl group or an alkoxy group.
(SiX ₃ O _1/2 ) (10-2)
(SiX ₂ O _2/2 ) (10-3)
(SiXO _3/2 ) (10-4)
In the general formulas (10-2), (10-3) and (10-4), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. To express.

In the general formulas (10-2) to (10-4), 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, t-butoxy group and the like.

It is preferable that the said silicone copolymer resin (A) contains 0.5-10 mol% of alkoxy groups. By containing such an alkoxy group, the heat resistance and light resistance of the cured product of the thermosetting composition for optical semiconductors of the present invention are improved. This is presumably because the curing rate can be drastically improved by containing an alkoxy group in the silicone copolymer resin (A), so that thermal deterioration during curing can be prevented.
In addition, since the curing speed is dramatically improved as described above, sufficient curability can be obtained even with a relatively small addition amount when a curing accelerator is added.

When the content of the alkoxy group is less than 0.5 mol%, the curing rate may not be sufficiently obtained and the heat resistance may be deteriorated. When the content exceeds 10 mol%, the silicone copolymer resin (A) or The storage stability of the thermosetting composition for optical semiconductors of this invention worsens, or heat resistance worsens. A more preferred lower limit is 1 mol%, and a more preferred upper limit is 5 mol%.
In addition, in this specification, content of the said alkoxy group means the quantity of the alkoxy group contained in the average composition of the said silicone copolymer resin (A).

Moreover, it is preferable that the said silicone copolymer resin (A) 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 of the resin composition is remarkably deteriorated. Such silanol groups can be reduced by heating under vacuum, and the amount of silanol groups can be measured using infrared spectroscopy or the like.

In the thermosetting composition for optical semiconductors of the present invention, the preferable lower limit of the number average molecular weight (Mn) of the silicone copolymer resin (A) is 1000, and the preferable upper limit is 50,000. If it is less than 1000, volatile components increase at the time of thermosetting, and film loss increases when used as a sealant, which is not preferable. If it exceeds 50,000, viscosity adjustment becomes difficult, which is not preferable. A more preferred lower limit is 1500, and a more preferred 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 (column: manufactured by Showa Denko KK). It means a value measured using Shodex GPC LF-804 (length: 300 mm) × 2, measurement temperature: 40 ° C., flow rate: 1 mL / min, solvent: tetrahydrofuran, standard substance: polystyrene.

The method for synthesizing the silicone copolymer resin (A) is not particularly limited. For example, (1) a hydroxy resin comprising a silicone resin (a) having a SiH group and a vinyl compound having an alicyclic epoxy-containing group. Examples thereof include a method of introducing a substituent by a relation reaction, and (2) a method of subjecting a siloxane compound and a siloxane compound having an alicyclic epoxy-containing group to a condensation reaction.

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 (a) having the SiH group is a structure represented by the general formula (1) described above after reacting a vinyl compound having an SiH group in the molecule and an alicyclic epoxy-containing group. Examples thereof include a structure having a unit and a structural unit represented by the general formula (2), preferably a structure represented by any one of the above general formulas (3) to (8).

The vinyl compound having an alicyclic epoxy-containing group is not particularly limited as long as it is a vinyl compound having one or more alicyclic epoxy-containing groups in the molecule, and examples thereof include vinylcyclohexene oxide and allylcyclohexene oxide. Can be mentioned.

Examples of the catalyst used as necessary during the hydrosilylation reaction include, for example, a simple substance of Group 8 metal, a metal solid supported on a carrier such as alumina, silica, carbon black, and the like. Examples include salts and complexes. Specifically, as the metal of Group 8 of the periodic table, for example, platinum, rhodium, and ruthenium are preferable, and platinum is particularly preferable.
As the hydrosilation reaction catalyst using platinum, for example, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone complex, platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-phosphite complex, And dicarbonyldichloroplatinum.

Although it does not specifically limit as reaction conditions at the time of the said hydrosilylation reaction, when the reaction temperature and the yield are considered, the preferable minimum is 10 degreeC and a preferable upper limit is 200 degreeC. A more preferred lower limit is 30 ° C., a more preferred upper limit is 150 ° C., a still more preferred lower limit is 50 ° C., and a still more preferred upper limit is 120 ° C.

Moreover, the said hydrosilylation reaction may be performed without a solvent and may be performed using a solvent.
The solvent is not particularly limited, and examples thereof include ether solvents such as dioxane, tetrahydrofuran and propylene glycol monomethyl ether acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; hydrocarbon solvents such as toluene, xylene and cyclohexane; acetic acid Examples include ester solvents such as ethyl and butyl acetate; alcohol solvents such as butyl cellosolve and butyl carbitol. Of these, ether solvents, ester solvents, ketone solvents, and hydrocarbon solvents are preferred. Specifically, dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate are particularly preferred because of the solubility of the raw materials and the solvent recoverability. preferable.

In the above method (2), examples of the siloxane compound include alkoxysilanes having a siloxane unit represented by the following general formulas (11) and (12) or partial hydrolysates thereof.

In the general formulas (11) and (12), R ^{31 to} R ³³ represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and OR represents a linear or branched chain. Represents an alkoxy group having 1 to 4 carbon atoms.

In the general formulas (11) and (12), when R ^{31 to} R ³³ 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, phenyl group and the like.

In the general formulas (11) and (12), 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 and the like.

Specific examples of the compound represented by the general formula (11) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, isopropyl (methyl) dimethoxysilane, and cyclohexyl (methyl). Examples include dimethoxysilane and methyl (phenyl) dimethoxysilane.

Specific examples of the compound represented by the general formula (12) include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, and octyltrimethoxysilane. And phenyltrimethoxysilane.

In the siloxane compound, the compounding ratio of the alkoxysilane having a siloxane unit represented by the general formulas (11) and (12) or a partial hydrolyzate thereof is condensed with a siloxane compound having an alicyclic epoxy-containing group described later. A structure in which the silicone copolymer resin (A) synthesized by reaction has a structural unit represented by the above general formula (1) and a structural unit represented by the general formula (2), preferably the above general It adjusts suitably so that it may become a structure represented by either of Formula (3)-(8).

Examples of the siloxane compound having an alicyclic epoxy-containing group include alkoxysilane having an alicyclic epoxy-containing group or a partial hydrolyzate thereof.
Examples of the alkoxysilane compound having an alicyclic epoxy-containing group include an alkoxysilane having an alicyclic epoxy-containing group represented by the following general formulas (13) and (14) or a partial hydrolyzate thereof. .

In the general formulas (13) and (14), when R ³⁴ and / or R ³⁵ and R ³⁶ are cyclic ether groups, and only one of R ³⁴ or R ³⁵ is a cyclic ether group, The other represents a hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.

The epoxycyclohexyl 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 general formula (13), when either R ³⁴ or R ³⁵ is a hydrocarbon having 1 to 8 carbon atoms, specifically, for example, methyl group, 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, An isohexyl group, a cyclohexyl group, a phenyl group, etc. are mentioned.

Further, in the general formulas (13) and (14), 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, t-butoxy group and the like.

Specific examples of the general formula (13) include 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane and 2- (3,4-epoxycyclohexyl). Examples include ethyl (methyl) diethoxysilane.

Specific examples of the general formula (14) include, for example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri An ethoxysilane etc. are mentioned.

In the method (2), as a specific method for the condensation reaction of the siloxane compound and the siloxane compound having an alicyclic epoxy-containing group, for example, the siloxane compound and the siloxane compound having an alicyclic epoxy-containing group can be used. And a method of synthesizing the silicone copolymer resin (A) by reacting in the presence of water and an acid or basic catalyst.
The siloxane compound may be reacted in advance in the presence of water and an acid or basic catalyst, and then the siloxane compound having an alicyclic epoxy-containing group may be reacted.

In the method (2), when the siloxane compound and the siloxane compound having an alicyclic epoxy-containing group are reacted in the presence of water and an acid or a basic catalyst, the alicyclic epoxy-containing group is included. The compound preferably has a lower limit of 5 mol% and an upper limit of 40 with respect to all organic groups in which the alicyclic epoxy-containing group is bonded to the silicon atom of the siloxane compound and the siloxane compound having the alicyclic epoxy-containing group. It mix | blends so that it may become mol%.

The amount of 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 an alicyclic epoxy-containing group, and is appropriately adjusted.

The acidic catalyst is a catalyst for reacting the siloxane compound with a siloxane compound having an alicyclic epoxy-containing group. For example, inorganic acids such as phosphoric acid, boric acid, and carbonic acid; formic acid, acetic acid, propionic acid, Organic acids such as lactic acid, lactic acid, malic acid, tartaric acid, citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, oleic acid; these acid anhydrides or derivatives, etc. Can be mentioned.

The basic catalyst is a catalyst for reacting the siloxane compound with a siloxane compound having an alicyclic epoxy-containing group. For example, hydroxide of an alkali metal such as sodium hydroxide, potassium hydroxide, or cesium hydroxide is used. Alkali metal alkoxides such as sodium-t-butoxide, potassium-t-butoxide, cesium-t-butoxide; alkali metal silanol compounds such as sodium silanolate compounds, potassium silanolate compounds, cesium silanolate compounds, etc. It is done. Of these, potassium-based catalysts and cesium-based catalysts are preferred.

The addition amount of the acid or basic catalyst is not particularly limited, but the preferable lower limit is 10 ppm and the preferable upper limit is 10,000 ppm with respect to the total amount of the siloxane compound and the siloxane compound having an alicyclic epoxy-containing group. Yes, a more preferred lower limit is 100 ppm, and a more preferred upper limit is 5000 ppm.
The acid or basic catalyst may be added as it is, or may be added after dissolving in a small amount of water or the siloxane compound.

In the condensation reaction of the siloxane compound and the siloxane compound having an alicyclic epoxy-containing group, the silicone copolymer resin (A) to be synthesized can be prevented from being precipitated from the reaction system, and the water and the condensation reaction can be prevented. From the standpoint that free water can be removed azeotropically, an organic solvent may be used.
Examples of the organic solvent include aromatic organic solvents such as toluene and xylene; ketone organic solvents such as acetone and methyl isobutyl ketone; aliphatic organic solvents such as hexane, heptane and octane. Of these, aromatic organic solvents are preferably used.

Although it does not specifically limit as reaction temperature at the time of the said condensation reaction, A preferable minimum is 40 degreeC and a preferable upper limit is 200 degreeC, A more preferable minimum is 50 degreeC and a more preferable upper limit is 150 degreeC. Moreover, when using the said organic solvent, the said condensation reaction can be easily performed at reflux temperature by using what has a boiling point in the range of 40-200 degreeC as this organic solvent.

As a method of synthesizing the silicone copolymer resin (A), the method (2) is preferable from the viewpoint of adjusting the amount of alkoxy groups.
In order to bring the alkoxy group into an appropriate range, the above method (2) can bring the alkoxy group into an appropriate range by adjusting the reaction temperature, reaction time, amount of catalyst and amount of water. is there.

The thermosetting composition for optical semiconductors of the present invention is represented by one or more alicyclic epoxy-containing groups in the molecule, a structural unit represented by the following general formula (1), and the following general formula (2). And a bifunctional silicone resin (B) having one or more glycidyl-containing groups in the molecule.
By blending such a bifunctional silicone resin (B), the crack resistance of the cured product of the thermosetting composition for optical semiconductors of the present invention is significantly improved. This is because in the cured product, the silicone is formed in the gap between the crosslinking points generated by the reaction of the alicyclic epoxy-containing group of the silicone copolymer resin (A) having one or more alicyclic epoxy-containing groups in the molecule. It is presumed that the bifunctional silicone resin (B) having a flexible skeleton enters the copolymer resin (A). Such an inferred structure is that the cycloaliphatic epoxy-containing group has a faster curing speed than the glycidyl-containing group, and therefore the difference in the reactivity between them causes a gap between the crosslinking points of the silicone copolymer resin (A). Furthermore, it is presumed that the bifunctional silicone resin (B) having a flexible skeleton is contained in the silicone copolymer resin (A) efficiently compared to the above.

In the present specification, the glycidyl-containing group only needs to contain a glycidyl group as at least a part of the group. For example, the glycidyl group may contain another skeleton such as an alkyl group or an alkyl ether group and a glycidyl group. Means.
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, 4-glycidoxybutyl group, etc. are mentioned.

The bifunctional silicone resin (B) having one or more such glycidyl-containing groups in the molecule is not particularly limited, but contains a resin component whose average composition formula is represented by the following general formula (15) or (16) It is preferable to do. When the bifunctional silicone resin (B) contains a resin component represented by the following general formula (15) or (16), the thermosetting composition for optical semiconductors of the present invention has a flexible cured product. Therefore, the crack resistance is extremely excellent.
The bifunctional silicone resin (B) has an average composition formula represented by the following general formula (15) or (16). The thermosetting composition for optical semiconductors of the present invention is a bifunctional silicone resin (B). ) Not only containing the resin component represented by the following general formula (15) or (16), but also a mixture containing resin components of various structures, the average of the composition of the resin components contained It also means the case represented by the following general formula (15) or (16).

In the general formula (15), R ³⁹ and / or R ⁴⁰ is a glycidyl-containing group, and R ³⁷ and R ^{38 each} represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. These may be the same as or different from each other. When only one of R ^{39 and} R ⁴⁰ is a glycidyl-containing group, the other represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. The preferred lower limit for q / (q + r) is 0.5, the preferred upper limit is 0.95, the more preferred lower limit is 0.6, the more preferred upper limit is 0.9, and the preferred lower limit for r / (q + r) is 0. 0.05, a preferred upper limit is 0.5, a more preferred lower limit is 0.1, and a more preferred upper limit is 0.4.

一般式（１６）中、Ｒ^４５及び／又はＲ^４６は、グリシジル含有基であり、Ｒ^４１、Ｒ^４２、Ｒ^４３、Ｒ^４４は、直鎖状若しくは分岐状の炭素数１〜８の炭化水素或いはそのフッ素化物を表し、これらは、互いに同一であってもよく、異なっていてもよい。また、Ｒ^４５又はＲ^４６のいずれか一方のみがグリシジル含有基である場合、他方は、直鎖状若しくは分岐状の炭素数１〜８の炭化水素或いはそのフッ素化物を表す。また、ｓ＋ｔ／（ｓ＋ｔ＋ｕ）の好ましい下限は０．５、好ましい上限は０．９５、より好ましい下限は０．６、より好ましい上限は０．９であり、ｕ／（ｓ＋ｔ＋ｕ）の好ましい下限は０．０５、好ましい上限は０．５、より好ましい下限は０．１、より好ましい上限は０．４である。（Ｒ^４１Ｒ^４２ＳｉＯ_２／２）と（Ｒ^４３Ｒ^４４ＳｉＯ_２／２）とは構造が異なるものである。

In the general formula (16), R ⁴⁵ and / or R ⁴⁶ is a glycidyl-containing group, and R ⁴¹ , R ⁴² , R ⁴³ , and R ⁴⁴ are linear or branched hydrocarbons having 1 to 8 carbon atoms. Or the fluoride is represented, and these may be the same as each other or different. When only one of R ^{45 and} R ⁴⁶ is a glycidyl-containing group, the other represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. The preferred lower limit of s + t / (s + t + u) is 0.5, the preferred upper limit is 0.95, the more preferred lower limit is 0.6, the more preferred upper limit is 0.9, and the preferred lower limit of u / (s + t + u) is 0. 0.05, a preferred upper limit is 0.5, a more preferred lower limit is 0.1, and a more preferred upper limit is 0.4. (R ⁴¹ R ⁴² SiO _2/2 ) and (R ⁴³ R ⁴⁴ SiO _2/2 ) have different structures.

In the bifunctional silicone resin (B), the bifunctional structural unit has a structure represented by the following general formula (1-2), that is, one of oxygen atoms bonded to a silicon atom in the bifunctional structural unit is a hydroxyl group. Or the structure which comprises an alkoxy group is included.
(R ¹ R ² SiXO _1/2 ) (1-2)
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 general formula (1-2), 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, an n-butoxy group, An isopropoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, etc. are mentioned.

The bifunctional silicone resin (B) preferably contains an alkoxy group in an amount of 0.5 to 10 mol%, and preferably does not contain a silanol group, like the silicone copolymer resin (A) described above.

The minimum with a preferable number average molecular weight (Mn) of the said bifunctional silicone resin (B) is 1500, and a preferable upper limit is 50,000. When it is less than 1500, the crack resistance of the cured product of the thermosetting composition for optical semiconductors of the present invention may be insufficient, and when it exceeds 50,000, the thermosetting composition for optical semiconductors of the present invention. It may be difficult to adjust the viscosity. A more preferable lower limit is 2000, and a more preferable upper limit is 20,000.

The method for synthesizing such a bifunctional silicone resin (B) is not particularly limited, and examples thereof include the same method as the method for synthesizing the above-described silicone copolymer resin (A). That is, a method (method (3)) for introducing a substituent by a hydrosilylation reaction between a silicone resin (b) having a SiH group and a vinyl compound having a glycidyl-containing group, a siloxane compound and a siloxane compound having a glycidyl-containing group And the like (Method (4)) and the like.

When the bifunctional silicone resin (B) is synthesized by the method (3), the silicone resin (b) having the SiH group includes, for example, a vinyl compound having a SiH group in the molecule and a glycidyl-containing group. After the reaction, those having a structure represented by the general formula (15) or (16) described above are preferable.

The vinyl compound having a glycidyl-containing group is not particularly limited as long as it is a vinyl compound having one or more glycidyl-containing groups in the molecule. For example, vinyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate butadiene mono Examples include oxides.

Further, at the time of the hydroshell relation reaction, a catalyst may be used as necessary, as in the case of synthesizing the above-described silicone copolymer resin (A), or may be carried out without a solvent. May be used.

When synthesizing the bifunctional silicone resin by the method (4), the alkoxysilane compound is not particularly limited, and examples thereof include the same compounds as the dialkoxysilane compound of the general formula (11) described above.
Moreover, as an alkoxysilane compound which has the said glycidyl containing group, the thing similar to the dialkoxysilane compound of General formula (13) mentioned above is mentioned, for example.

Specific examples of the compound represented by the general formula (11) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, isopropyl (methyl) dimethoxysilane, and cyclohexyl (methyl). Examples include dimethoxysilane and methyl (phenyl) dimethoxysilane.

Specific examples of the compound represented by the general formula (13) include 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, and 3-glycidide. Examples include xylpropyl (methyl) dibutoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, and the like.

As a specific method for the condensation reaction of the siloxane compound and the siloxane compound having a glycidyl-containing group, for example, the siloxane compound and the alicyclic epoxy-containing group in the case of synthesizing the silicone copolymer resin (A) described above are used. The same method as the case of making it react with the siloxane compound which has is mentioned.

In the thermosetting composition for optical semiconductors of the present invention, the amount of the bifunctional silicone resin (B) to the silicone copolymer resin (A) described above is not particularly limited, but the silicone copolymer resin (A ) A preferable lower limit is 10 parts by weight and a preferable upper limit is 120 parts by weight with respect to 100 parts by weight. When the amount is less than 10 parts by weight, the crack resistance of the cured product of the thermosetting composition for optical semiconductors of the present invention may not be sufficiently exhibited, and when it exceeds 120 parts by weight, the thermosetting for optical semiconductors of the present invention is performed. The cured product of the curable composition is inferior in heat resistance, and the cured product may be easily yellowed in a thermal environment. A more preferred lower limit is 15 parts by weight, and a more preferred upper limit is 100 parts by weight.

The thermosetting composition for optical semiconductors of the present invention contains a thermosetting agent capable of reacting with the alicyclic epoxy-containing group and the glycidyl-containing group.
The thermosetting agent is not particularly limited as long as it can react with the alicyclic epoxy-containing group of the silicone copolymer resin (A) and the glycidyl-containing group of the bifunctional silicone resin (B). For example, aliphatic amines such as ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylaminopiperazine, isophoronediamine, metaphenylenediamine, paraphenylenediamine, 3,3′-diaminodiphenylsulfone 4,4'-diaminodiphenol sulfone, 4,4'-diaminodiphenol methane, aromatic amines such as 4,4'-diaminodiphenol ether, mercaptopropionic acid esters, terminal mercapto compounds of epoxy resins Such as mercaptans, bisphenol A, bisphe Nord F, Bisphenol AD, Bisphenol S, Tetramethylbisphenol 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 Phenol resins such as bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak, and the like; Polyazelineic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2,3- Dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, methyl-norbornane-2,3-dicarboxylic acid anhydride, cyclohexane-1,2,3-tricarboxylic acid-1,2 anhydride, An alicyclic acid anhydride such as cyclohexane-1,2,4-tricarboxylic acid-1,2 anhydride, or an optionally branched alkyl group having 1 to 8 carbon atoms such as 3-methylglutaric anhydride. Alkyl having 1 to 8 carbon atoms which may be branched such as 3-alkyl glutaric anhydride, 2-ethyl-3-propyl glutaric anhydride, etc. 2,3-dialkyl glutaric acid anhydride having a group, 2,4-diethyl glutaric acid anhydride, 2,4-dimethyl glutaric acid anhydride, etc., which may have a C 1-8 alkyl group Alkyl-substituted glutaric anhydrides such as 2,4-dialkylglutaric anhydride, aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 2-methylimidazole, 2-ethyl- Imidazoles such as 4-methylimidazole and 2-phenylimidazole and their salts, the above aliphatic amines, aromatic amines, and / or amine adducts obtained by reacting imidazoles with epoxy resins, adipic acid dihydrazide, etc. Hydrazines, dimethylbenzylamine, tertiary amines such as 1,8-diazabicyclo [5.4.0] undecene-7 Examples include amines, organic phosphines such as triphenylphosphine, dicyandiamide, and the like. Among these, acid anhydrides such as alicyclic acid anhydrides, alkyl-substituted glutaric acid anhydrides, and aromatic acid anhydrides are preferable, and alicyclic acid anhydrides and alkyl-substituted glutaric acid anhydrides are more preferable. And 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, 2,4-diethylglutaric anhydride. These thermosetting agents may be used independently and 2 or more types may be used together.

Although it does not specifically limit as a compounding quantity of the said thermosetting agent, A preferable minimum is 1 weight part with respect to a total of 100 weight part of the said silicone copolymer resin (A) and bifunctional silicone resin (B), A preferable upper limit is 200 parts by weight. Within this range, the thermosetting composition for optical semiconductors 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.

It is preferable that the thermosetting composition for optical semiconductors of this invention contains a hardening accelerator further.
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.

The blending amount of the curing accelerator is not particularly limited, but a preferred lower limit is preferably 0.01 parts by weight with respect to 100 parts by weight of the total of the silicone copolymer resin (A) and the bifunctional silicone resin (B). The upper limit is 5 parts by weight. 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.

The thermosetting composition for optical semiconductors of the present invention preferably further contains fine particles having a metal element and / or a metalloid element. By containing the fine particles, the refractive index of the thermosetting composition for optical semiconductors of the present invention is increased, and light extraction of an optical semiconductor element such as an LED using the thermosetting composition for optical semiconductors of the present invention is performed. Excellent in properties.

A preferable upper limit of the average primary particle diameter of the fine particles is 20 nm. If it exceeds 20 nm, light scattering due to the fine particles may occur in the thermosetting composition for optical semiconductors of the present invention, and the thermosetting composition for optical semiconductors of the present invention may become cloudy. A more preferred lower limit is 3 nm, and a more preferred upper limit is 15 nm.

The fine particles have a metal element and / or a metalloid element.
The fine particles are preferably at least one selected from the group represented by 80% or more of the metal elements present in the fine particles. If it is less than 80%, the refractive index of the thermosetting composition for optical semiconductors of the present invention is not so high, and the light extraction property of the optical semiconductor element using the thermosetting composition for optical semiconductors of the present invention is high. May be inferior.
Metal elements: Al, In, Ge, Sn, Ti, Zr, Hf

Further, in the fine particles, it is preferable that 80% or more of the semi-metal elements other than Si present in the fine particles are boron. If it is less than 80%, the refractive index of the thermosetting composition for optical semiconductors of the present invention is not so high, and the light extraction property of the optical semiconductor element using the thermosetting composition for optical semiconductors of the present invention is high. May be inferior.

The fine particles are not particularly limited as long as the fine particles have the metal element and / or metalloid element. However, since the thermosetting composition for optical semiconductors of the present invention is excellent in improving the refractive index, zirconium is particularly preferable. It is preferable because the fine particles having an excellent refractive index and excellent light transmittance.

The blending amount of the fine particles is not particularly limited, but the preferred lower limit is 1 part by weight and the preferred upper limit is 100 parts by weight with respect to a total of 100 parts by weight of the silicone copolymer resin (A) and the bifunctional silicone resin (B). Part. When the amount is less than 1 part by weight, the refractive index of the thermosetting composition for optical semiconductors of the present invention may hardly be improved, and when it exceeds 100 parts by weight, it is difficult to adjust the viscosity. A more preferred lower limit is 5 parts by weight, and a more preferred upper limit is 80 parts by weight.

The preferable lower limit of the refractive index of such fine particles is 1.50. If it is less than 1.50, the refractive index of the thermosetting composition for optical semiconductors of the present invention does not increase, and the light extraction property of the optical semiconductor element using the thermosetting composition for optical semiconductors of the present invention is improved. It may be insufficient.
In addition, in this specification, the said refractive index is the value which measured the refractive index with respect to sodium D line | wire (589.3 nm) using the refractometer (Abbe type | formula) at the measurement temperature of 20 degreeC.

The thermosetting composition for optical semiconductors of the present invention may contain a coupling agent for imparting adhesion.
The coupling agent is not particularly limited, and examples thereof include vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, Examples thereof include silane coupling agents such as N-phenyl-3-aminopropyltrimethoxysilane. These coupling agents may be used independently and 2 or more types may be used together.

As a blending ratio of the coupling agent, a preferable lower limit is 0.1 parts by weight and a preferable upper limit is 5 weights with respect to a total of 100 parts by weight of the silicone copolymer resin (A) and the bifunctional silicone resin (B). Part. When the amount is less than 0.1 parts by weight, the effect of the coupling agent may not be sufficiently exhibited. When the amount exceeds 5 parts by weight, the excess coupling agent volatilizes, and the thermosetting composition for optical semiconductors of the present invention. When an object is cured, film loss may occur.

Moreover, the thermosetting composition for optical semiconductors of this invention may contain antioxidant, in order to improve heat resistance.
The antioxidant is not particularly limited. For example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amylhydroquinone, 2,5-di-t-butylhydroquinone, 4 , 4'-butylidenebis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-) Phenolic antioxidants such as butylphenol), triphenyl phosphite, tridecyl phosphite, nonyl diphenyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene, 9,10- Phosphorous antioxidants such as dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dilauryl-3,3′-thiodipropionate, ditridec Sulfur-3,3′-thiodipropionate, [4,4′-thiobis (3-methyl-6-tert-butylphenyl)]-bis (alkylthiopropionate) and other antioxidants, and other oxidations Examples of the inhibitor include metal antioxidants such as fullerene, iron, zinc and nickel. These antioxidants may be used alone or in combination of two or more.

As a blending ratio of the antioxidant, a preferable lower limit is 0.001 part by weight and a preferable upper limit is 2 weights with respect to a total of 100 parts by weight of the silicone copolymer resin (A) and the bifunctional silicone resin (B). Part. When the amount is less than 0.001 part by weight, the blending effect of the antioxidant may not be sufficiently exhibited. When the amount exceeds 2 parts by weight, the antioxidant volatilizes, and the thermosetting composition for optical semiconductors of the present invention. When the product is cured, film loss or the like may occur, or the cured product may become brittle.

Moreover, the thermosetting composition for optical semiconductors of the present invention may contain silica fine powder, high molecular weight silicone resin, and the like in order to adjust the viscosity. In particular, the silica fine powder not only has a thickening action but also acts as a thixotropic agent, so that the fluidity control of the thermosetting composition for optical semiconductors of the present invention and the prevention effects such as sedimentation of the phosphor also occur. Therefore, it is more preferable.

Although it does not specifically limit as an average particle diameter of the said silica fine powder, A preferable upper limit is 100 nm. If it exceeds 100 nm, the transparency of the thermosetting composition for optical semiconductors of the present invention may decrease.

Moreover, the said silica fine powder has a preferable minimum of a BET specific surface area of 30 m < ² > / g, and a preferable upper limit of 500 m < ² > / g on performance. If it is less than 30 m ² / g, the thickening effect and the thixotropy improving effect are insufficient, and if it exceeds 500 m ² / g, the silica fine powder is strongly aggregated and difficult to disperse.

Examples of such silica fine powder include Aerosil 50 (specific surface area: 50 m ² / g), Aerosil 90 (specific surface area: 90 m ² / g), Aerosil 130 (specific surface area: 130 m ² / g), Aerosil 200 ( Specific surface area: 200 m ² / g), Aerosil 300 (specific surface area: 300 m ² / g), Aerosil 380 (specific surface area: 380 m ² / g), Aerosil OX50 (specific surface area: 50 m ² / g), Aerosil TT600 (specific surface area) : 200 m ² / g), Aerosil R972 (specific surface area: 110 m ² / g), Aerosil R974 (specific surface area: 170 m ² / g), Aerosil R202 (specific surface area: 100 m ² / g), Aerosil R812 (specific surface area: 260 m) ² / g) Aerosil R812S (specific surface ^{area: 220m 2 / g), Aerosil} R805 ( specific surface ^{area: 150m 2 / g), RY200} ( specific surface ^{area: 100m 2 / g), RX200} ( specific surface area: 140m ² / g) (both Nippon Aerosil Etc.).

As a compounding ratio of the silica fine powder, a preferable lower limit is 1 part by weight and a preferable upper limit is 50 parts by weight with respect to 100 parts by weight of the silicone copolymer resin (A) and the bifunctional silicone resin. When the amount is less than 1 part by weight, the effect of blending the cured product of the thermosetting composition for optical semiconductors of the present invention may not be sufficiently obtained. When the viscosity of the composition increases, for example, when used as an encapsulant for an optical semiconductor element such as an LED, a foaming problem may occur in the filling process, voids occur, and the transparency of the cured product May decrease. A more preferred lower limit is 5 parts by weight, and a more preferred upper limit is 40 parts by weight.

The thermosetting composition for optical semiconductors of the present invention has additives such as an antifoaming agent, a colorant, a phosphor, a modifying agent, a leveling agent, a light diffusing agent, a thermally conductive filler, and a flame retardant as necessary. It may be blended.

Although it does not specifically limit as a viscosity of the thermosetting composition for optical semiconductors of this invention, A preferable minimum is 500 mPa * s and a preferable upper limit is 50,000 mPa * s. If it is less than 500 mPa · s, liquid dripping may occur when used as a sealing agent for an optical semiconductor element, and the optical semiconductor element may not be sealed. The semiconductor element may not be sealed. A more preferred lower limit is 1000 mPa · s, and a more preferred upper limit is 10,000 mPa · s.
In addition, in this specification, the said viscosity is the value measured on 25 degreeC and 5 rpm conditions using the E-type viscosity meter (the Toki Sangyo company make, TV-22 type | mold).

The thermosetting composition for optical semiconductors of the present invention preferably has an initial light transmittance of 90% or more. If it is less than 90%, the optical characteristics of the optical semiconductor element using the thermosetting composition for optical semiconductors of the present invention will be insufficient. In addition, the said initial light transmittance uses the hardened | cured material of thickness 1mm which hardened | cured the thermosetting composition for optical semiconductors of this invention, and the transmittance | permeability of light with a wavelength of 400 nm made from Hitachi Ltd. "U-4000. It is the value measured using "."

Moreover, it is preferable that the decreasing rate of the light transmittance after a light resistance test is less than 10% in the thermosetting composition for optical semiconductors of this invention. If it is 10% or more, the optical characteristics of the optical semiconductor element using the thermosetting composition for optical semiconductors of the present invention will be insufficient. In addition, the light resistance test is a 100mW filter in which a filter that cuts light having a wavelength of 340nm or less is attached to a cured product having a thickness of 1mm obtained by curing the thermosetting composition for optical semiconductors of the present invention. the examination of irradiating / cm ² at 24 hours, the light transmittance after light resistance test using the above cured product after the light resistance test, manufactured by Hitachi, Ltd. and the transmittance of light having a wavelength of 400nm "U- It is a value measured using "4000".

Moreover, it is preferable that the decreasing rate of the light transmittance after a heat resistance test is less than 10 in the thermosetting composition for optical semiconductors of this invention. If it is 10% or more, the optical characteristics of the optical semiconductor element using the thermosetting composition for optical semiconductors of the present invention will be insufficient. The heat resistance test is a test in which a cured product having a thickness of 1 mm obtained by curing the thermosetting composition for optical semiconductors of the present invention is left in an oven at 150 ° C. for 500 hours. The light transmittance is a value obtained by measuring the transmittance of light having a wavelength of 400 nm using “U-4000” manufactured by Hitachi, Ltd., using the cured product after the heat resistance test.

The thermosetting composition for optical semiconductors of the present invention is represented by one or more alicyclic epoxy-containing groups in the molecule, the structural unit represented by the general formula (1), and the general formula (2). And a bifunctional silicone resin (B) having one or more glycidyl-containing groups in the molecule as described above, and thus having a short wavelength in the blue to ultraviolet region. When used as an encapsulant for optical semiconductor elements, the optical semiconductor has excellent heat resistance and light resistance with no heat generation or discoloration due to light emission when sealed. The device has excellent adhesion to the housing material, etc., and it is extremely resistant to cracks and delamination even during rapid thermal changes such as solder reflow processes and thermal cycles, and the cured product has excellent crack resistance. To do Kill.

The method for producing the thermosetting composition for optical semiconductors of 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 three roll, a bead mill, Examples include a method of mixing predetermined amounts of the above-described silicone copolymer resin (A), bifunctional silicone resin (B), thermosetting agent, fine particles, curing accelerator, additive, and the like at room temperature or under heating. .

Although it does not specifically limit as a use of the thermosetting composition for optical semiconductors of this invention, For example, optical semiconductor elements, such as a sealing agent, a housing material, die bond material for connecting to a lead electrode, a heat sink, etc., a light emitting diode When the light emitting element is flip-chip mounted, it can be used as an underfill material or a passivation film on the light emitting element. Especially, since the optical semiconductor device which can take out the light by the light emission from an optical semiconductor element efficiently can be manufactured, it can use suitably as a sealing agent, an underfill material, and a die-bonding material.
The sealing compound for optical semiconductors which uses the thermosetting composition for optical semiconductors of this invention is also one of this invention.
The die-bonding material for optical semiconductor elements which uses the thermosetting composition for optical semiconductors of this invention is also one of this invention.
The underfill material for optical semiconductor elements using the thermosetting composition for optical semiconductors of the present invention is also one aspect of the present invention.

(Die bond material for optical semiconductor elements)
Since the die-bonding material for optical semiconductor elements of the present invention comprises the thermosetting composition for optical semiconductor elements of the present invention, it has excellent heat resistance, light resistance, adhesiveness, and crack resistance. In addition, since high transparency can be maintained under use conditions, light in the direction of the housing material of the optical semiconductor element is not absorbed and lost, which can contribute to the provision of an optical semiconductor element with high luminous efficiency. .

The die bond material for optical semiconductor elements of the present invention preferably further contains high thermal conductive fine particles. In the present specification, the high thermal conductive fine particles mean fine particles having high thermal conductivity.
By blending fine particles having high thermal conductivity, the die bond material for optical semiconductor elements of the present invention has excellent heat dissipation. For example, a heat sink is provided in a package of an optical semiconductor device, and the optical semiconductor is provided on the heat sink. It is preferable to fix the optical semiconductor by using a die bonding material for use because it is possible to greatly reduce thermal damage to the optical semiconductor.

As a thermal conductivity of the high thermal conductive fine particles to be blended in the die bond material for optical semiconductor elements of the present invention, a preferable lower limit is 60 Kcal / m · hr · ° C. If the thermal conductivity is less than 60 Kcal / m · hr · ° C., sufficient heat dissipation cannot be obtained without increasing the amount added, and viscosity adjustment may be difficult.

The high thermal conductive fine particles are not particularly limited. For example, metal particles such as nickel, tin, aluminum, gold, silver, copper, iron, cobalt, indium and alloys thereof; metal nitride such as boron nitride and aluminum nitride Product: Metal oxide such as aluminum oxide, magnesium oxide, titanium oxide, etc .; Carbon compound particles such as silicon carbide, graphite, diamond, amorphous carbon, carbon black, carbon fiber; Form other metal layer on resin particles and metal particles Metal coated particles and the like are raised.
As the metal-coated particles, for example, particles obtained by applying gold or silver plating to resin particles are preferable.

Moreover, when the particle | grains containing at least 1 type selected from the group which consists of gold | metal | money, silver, and copper are contained, the said die-bonding material will have high electroconductivity with heat conductivity, and is preferable. By using a die bond material having conductivity, when an optical semiconductor element having a structure in which electrode pads are provided on both upper and lower surfaces of the light emitting element, the lead electrode can be electrically connected with the die bond material, which is preferable.

Further, these fine particles having high thermal conductivity are preferably surface-treated so that they can be uniformly mixed at a high blending ratio.

The preferable lower limit of the amount of the high thermal conductive fine particles is 10% by weight, and the preferable upper limit is 95% by weight. If it is less than 10% by weight, sufficient thermal conductivity may not be obtained, and if it exceeds 95% by weight, viscosity adjustment may be difficult.

(Underfill material for optical semiconductor elements)
Since the underfill material for optical semiconductor elements of the present invention is formed using the thermosetting composition for optical semiconductors of the present invention, the original underfill material that relieves stress applied to electrode connection bumps in the case of flip chip mounting. While being suitable for the purpose, it is excellent in light resistance, heat resistance, adhesion and crack resistance, and can be used suitably. As described above, the underfill material for an optical semiconductor element of the present invention may be cured as an underfill material by performing flip chip mounting, and then the sealant may be cured, and the same sealant as the underfill material may be used. If used, they may be combined. The latter method is a more preferable production method because the tact time is shortened.

An optical semiconductor element using at least one of an encapsulant for optical semiconductor elements, a die bond material for optical semiconductor elements, and an underfill material for optical semiconductor elements, comprising the thermosetting composition for optical semiconductors of the present invention. Can be manufactured.

The light emitting 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.

The method for laminating the semiconductor material on the substrate is not particularly limited, and examples thereof include MOCVD, HDVPE, and liquid phase growth.
Examples of the structure of the light emitting element include a homojunction having a MIS junction, a PN junction, and a PIN junction, a heterojunction, and a double heterostructure. Moreover, it can also be set as a single or multiple quantum well structure.

When sealing the said light emitting element using the sealing compound for optical semiconductor elements of this invention, you may use another sealing agent together. In this case, after sealing the light emitting element with the sealant for optical semiconductor elements of the present invention, the periphery thereof may be sealed with the other sealant, and the light emitting element may be sealed with the other sealant. Then, the periphery thereof may be sealed with the optical semiconductor sealing agent of the present invention.
The other sealing agent is not particularly limited, and examples thereof include an epoxy resin, a silicone resin, an acrylic resin, a urea resin, an imide resin, and glass. Moreover, when a surface modifier is contained, a liquid can be applied to provide a protective layer on the surface.

The method for sealing the light emitting element with the encapsulant for optical semiconductor elements of the present invention is not particularly limited. For example, the encapsulant for optical semiconductor elements of the present invention is pre-injected into a mold frame and light is emitted there. Examples include a method of immersing a lead frame or the like to which the element is fixed and then curing, a method of injecting the curing agent for an optical semiconductor element of the present invention into a mold having a light emitting element inserted therein, and the like.
Examples of the method for injecting the sealant for optical semiconductor elements of the present invention include injection by a dispenser, transfer molding, injection molding and the like. Furthermore, as another sealing method, the sealing agent for optical semiconductor elements of the present invention is dropped on the light emitting element, stencil printing, screen printing, or a method of applying and curing through a mask, and the light emitting element is formed at the bottom. The method etc. which inject | pour the sealing agent for optical semiconductor elements of this invention with a dispenser etc. to the arrange | positioned cup etc. and harden | cure.

The thermosetting composition for optical semiconductors of the present invention is represented by one or more alicyclic epoxy-containing groups in the molecule, the structural unit represented by the general formula (1), and the general formula (2). And a bifunctional silicone resin (B) having one or more glycidyl-containing groups in the molecule as described above, and thus having a short wavelength in the blue to ultraviolet region. When used as an encapsulant for optical semiconductor elements, the optical semiconductor has excellent heat resistance and light resistance with no heat generation or discoloration due to light emission when sealed. The device has excellent adhesion to the housing material, etc., and it is extremely resistant to cracks and delamination even during rapid thermal changes such as solder reflow processes and thermal cycles, and the cured product has excellent crack resistance. To do Kill.
The housing material is not particularly limited, and examples thereof include conventionally known materials made of aluminum, polyphthalamide resin (PPA), polybutylene terephthalate resin (PBT), or the like.

Light formed by using the thermosetting composition for optical semiconductors of the present invention, the encapsulant for optical semiconductor elements of the present invention, the die bond material for optical semiconductor elements of the present invention and / or the underfill material for optical semiconductor elements of the present invention. A semiconductor element is also one aspect of the present invention.

1 and 2 are cross-sectional views schematically showing an example of an optical semiconductor element using the encapsulant for optical semiconductor elements and the die bonding material for optical semiconductor elements of the present invention, and FIG. It is sectional drawing which shows typically an example of the optical semiconductor element which uses the sealing agent for optical semiconductors, and the underfill material for optical semiconductor elements.

In the optical semiconductor element shown in FIG. 1, the light emitting element 11 is installed on the heat sink 16 via the die bonding material 10 for optical semiconductor elements of the present invention, and passes through the side surface from the upper surface of the light emitting element 11 and the housing material. Two lead electrodes 14 extended to the bottom surface are electrically connected by gold wires 13, respectively. And the light emitting element 11, the die-bonding material 10 for optical semiconductor elements of this invention, and the gold wire 13 are sealed with the sealing agent 12 for optical semiconductor elements of this invention.

FIG. 2 shows an optical semiconductor element in which the die bond material for an optical semiconductor element of the present invention has high conductivity by containing particles containing at least one selected from the group consisting of the above-mentioned gold, silver, and copper. Indicates.
In the optical semiconductor element shown in FIG. 2, the light emitting element 21 is installed via the die bonding material 20 for optical semiconductor elements of the present invention, and two leads extending from the upper surface of the housing material 25 through the side surface to the bottom surface. The end of one lead electrode 24 among the electrodes 24 is formed between the die bond material 20 for optical semiconductor elements of the present invention and the housing material 25, and the light emitting element is interposed via the die bond material 20 for optical semiconductor elements of the present invention. The other lead electrode 24 is electrically connected to the light emitting element 21 by a gold wire 23. And the light emitting element 21, the die-bonding material 20 for optical semiconductor elements of this invention, and the gold wire 23 are sealed with the sealing agent 22 for optical semiconductor elements of this invention.

In the optical semiconductor element of the present invention shown in FIG. 3, the light emitting element 31 is installed via the bump 33, and the optical semiconductor element underfill material 30 of the present invention is formed between the light emitting element 31 and the housing material 35. Has been. The two lead electrodes 34 extended from the upper surface of the housing material 35 to the bottom surface through the side surfaces are formed between the bumps 33 and the housing material 35 and are electrically connected to the light emitting element 31. ing. And the light emitting element 31 and the underfill material 30 for optical semiconductor elements of this invention are sealed with the sealing agent 32 for optical semiconductor elements of this invention.
In the optical semiconductor element of the present invention shown in FIG. 3, the underfill material 30 for the optical semiconductor element of the present invention is formed below the light emitting element 31 after connecting the light emitting element 31 and the lead electrode 34 with the bump 33. It is formed by filling the space from the lateral gap.

Specific examples of the optical semiconductor element of the present invention include a light emitting diode, a semiconductor laser, and a photocoupler. Such an optical semiconductor element 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 copy machine, a vehicle measuring instrument light source, 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, switching elements and the like.

According to the present invention, it has excellent transparency, excellent heat resistance, light resistance, and adhesion to a housing material, and cracks and delamination are extremely generated even in rapid thermal changes such as solder reflow process and thermal cycle. A thermosetting composition for optical semiconductors, a sealant for optical semiconductor elements, a die-bonding material for optical semiconductor elements, an underfill material for optical semiconductor elements, and the like. An optical semiconductor device can be provided.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited only to these examples.

(Synthesis Example 1)
Dimethyldimethoxysilane (750 g) and 3-glycidoxypropylmethyldimethoxysilane (150 g) were placed in a 2000 mL thermometer and a separable flask equipped with a dropping device, and the mixture was stirred at 50 ° C. Into this, potassium hydroxide (1.9 g) / water (250 g) was slowly added dropwise, and after completion of the addition, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (2.1g) was put in it, the volatile component was removed under reduced pressure, and 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 and Mw = 25000. From ²⁹ Si-NMR, (Me ₂ SiO _2/2 ) _0.90 (EpMeSiO _2/2 ) _0.10
The 3-glycidoxypropyl group content was 14 mol%, and the epoxy equivalent was 760 g / eq. Met.
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)
Dimethyldimethoxysilane (440 g) and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (160 g) were placed in a 2000 mL thermometer and a separable flask equipped with a dropping device, and the mixture was stirred at 50 ° C. To the solution, potassium hydroxide (1.2 g) / water (170 g) was slowly added dropwise, and after completion of the addition, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.3g) was put in it, the volatile component was removed under reduced pressure, and 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 ²⁹ Si-NMR.
The 2- (3,4-epoxycyclohexyl) ethyl group content was 22 mol%, and the epoxy equivalent was 550 g / eq. Met.
The molecular weight and epoxy equivalent of polymer B were determined in the same manner as in Synthesis Example 1.

(Synthesis Example 3)
Dimethyldimethoxysilane (400 g), methoxytrimethylsilane (100 g), and 3-glycidoxypropyltrimethoxysilane (100 g) were placed in a 2000 mL thermometer and a separable flask equipped with a dropping device, and the mixture was stirred at 50 ° C. Into this, potassium hydroxide (1.3 g) / water (180 g) was slowly added dropwise, and after completion of the addition, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.4g) was put in it, the volatile component was removed under reduced pressure, and 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 C. The molecular weight of the polymer C is Mn = 3200, Mw = 5400, and (Me ₂ SiO _2/2 ) _0.71 (MeSiO _3/2 ) _0.18 (EpSiO _3/2 ) _0.11 from ²⁹ Si-NMR.
3-glycidoxypropyl group content is 15 mol%, epoxy equivalent is 780 g / eq. Met.
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 equipped with a 2000 mL thermometer and a dropping device, dimethyldimethoxysilane (350 g), methoxytrimethylsilane (125 g), and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (125 g) are added and stirred at 50 ° C. did. Potassium hydroxide (1.2 g) / water (190 g) was slowly added dropwise thereto, and after completion of the dropwise addition, the mixture was stirred at 50 ° C. for 6 hours. The acetic acid (1.3g) was put in it, the volatile component was removed under reduced pressure, and 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 D. The molecular weight of the polymer D is Mn = 2900, Mw = 4600, and (Me ₂ SiO _2/2 ) _0.65 (MeSiO _3/2 ) _0.22 (EpSiO _3/2 ) _0.13 from ²⁹ Si-NMR.
The 2- (3,4-epoxycyclohexyl) ethyl group content was 19 mol%, and the epoxy equivalent was 660 g / eq. Met.
The molecular weight and epoxy equivalent of polymer D were determined in the same manner as in Synthesis Example 1.

(Example 1)
Polymer A (30 g), Polymer B (70 g), Ricacid MH-700G (acid anhydride, manufactured by Nippon Nippon Chemical Co., Ltd., 25 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g) Mixing and defoaming were performed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Example 2)
Polymer A (5 g), Polymer B (95 g), Ricacid MH-700G (anhydride, manufactured by Nippon Nippon Chemical Co., Ltd., 25 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g) Mixing and defoaming were performed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Example 3)
Polymer A (60 g), Polymer B (40 g), Ricacid MH-700G (anhydride, manufactured by Nippon Nippon Chemical Co., Ltd., 25 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g) Mixing and defoaming were performed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

Example 4
Polymer A (30 g), Polymer D (70 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., 25 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro Co., 0.5 g) Mixing and defoaming were performed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Comparative Example 1)
Polymer A (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 25 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g) are mixed and degassed. The sealing agent for optical semiconductor elements was obtained. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Comparative Example 2)
Polymer B (100 g), Ricacid MH-700G (anhydride, manufactured by Nippon Nippon Chemical Co., Ltd., 30 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g) are mixed and degassed. The sealing agent for optical semiconductor elements was obtained. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Comparative Example 3)
Polymer C (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Rika Co., Ltd., 25 g), U-CAT SA 102 (curing accelerator, San Apro Co., Ltd., 0.5 g) are added and mixed and degassed. The sealing agent for optical semiconductor elements was obtained. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Comparative Example 4)
Polymer B (80 g), YX-8000 (hydrogenated bisphenol A epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd., 20 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., 35 g), U-CAT SA 102 ( A curing accelerator, San Apro, 0.5 g) was added and mixed and degassed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.

(Comparative Example 5)
Polymer B (70 g), ECMS-924 (bifunctional silicone resin having a cycloaliphatic epoxy-containing group [2- (3,4-epoxycyclohexyl) ethyl group], manufactured by Gelest Co., 30 g), Ricacid MH-700G (acid) Anhydride, manufactured by Nippon Nippon Chemical Co., Ltd., 25 g) and U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g) were added and mixed and degassed to obtain an encapsulant for optical semiconductor elements. This sealing agent was filled in a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to obtain a cured product having a thickness of 1 mm.
(Evaluation)
The following evaluation was performed about the sealing agent for optical semiconductor elements obtained by the Example and the comparative example, and its hardened | cured material.

(1) Initial light transmittance A light transmittance of 400 nm was measured using a U-4000 manufactured by Hitachi, Ltd. using a cured product having a thickness of 1 mm.

(2) Light transmittance after light resistance test A cured product with a thickness of 1 mm is attached to a high-pressure mercury lamp with a filter that cuts 340 nm or less, irradiated at 100 mW / cm ² for 24 hours, and has a light transmittance of 400 nm. The measurement was performed using U-4000 manufactured by the company. In Table 1, when the rate of decrease in light transmittance from the initial stage is less than 5%: ◎ less than 10%: ○, less than 10-40%: Δ, 40% or more: x did.

(3) Light transmittance after heat resistance test A cured product having a thickness of 1 mm was left in an oven at 150 ° C. for 1000 hours, and a light transmittance of 400 nm was measured using U-4000 manufactured by Hitachi, Ltd. In Table 1, when the rate of decrease in light transmittance from the initial stage is less than 5%: ◎ less than 10%: ○, less than 10-40%: Δ, 40% or more: x did.

(4) Moisture absorption reflow test, cooling cycle test (production of die bond material for optical semiconductor elements)
Flake silver powder (170 g) having an average particle size of 3 μm and a maximum particle size of 20 μm was added to polymer A (9 g) and polymer B (21 g), and the mixture was stirred and kneaded using a three roll.
Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., 3.75 g) and U-CAT SA 102 (manufactured by Sun Apro Co., Ltd., 0.075 g) were mixed and removed into the flaky silver powder-containing polymer (100 g). Foaming was performed to obtain a die bond material for optical semiconductor elements.

A light emitting element having a main light emission peak of 460 nm was mounted on a housing material with lead electrodes (PPA) using the produced die bonding material for an optical semiconductor element, and cured at 180 ° C. for 15 minutes to fix the light emitting element. Subsequently, the light emitting element and the lead electrode are electrically connected with a gold wire, and the sealing agents prepared in Examples and Comparative Examples are injected and cured at 110 ° C. × 3 hours + 130 ° C. × 3 hours. An optical semiconductor device having the structure shown in FIG.

The produced optical semiconductor elements (20 pieces) were left at 85 ° C. and 85 RH% for 24 hours, and the absorbed optical semiconductor elements were placed in a solder reflow oven (preheat 150 ° C. × 100 seconds + reflow [maximum temperature 260 ° C.]) three times. The number of cracks after passing and peeling from the housing material was confirmed (moisture absorption reflow test).
Further, the optical semiconductor elements (20 pieces) subjected to the moisture absorption reflow test were subjected to 1000 cycles of cooling and heating at −40 ° C. for 30 minutes and 120 ° C. for 30 minutes to confirm the number of cracks and peeling from the housing material (cooling cycle). test).

According to the present invention, it has excellent transparency, excellent heat resistance, light resistance, and adhesion to a housing material, and cracks and delamination are extremely generated even in rapid thermal changes such as solder reflow process and thermal cycle. A thermosetting composition for optical semiconductors, a sealant for optical semiconductor elements, a die-bonding material for optical semiconductor elements, an underfill material for optical semiconductor elements, and the like. An optical semiconductor device can be provided.

It is sectional drawing which shows typically an example of the optical semiconductor element formed using the sealing compound for optical semiconductors of this invention, and the die-bonding material for optical semiconductor elements. It is sectional drawing which shows typically an example of the optical semiconductor element formed using the sealing compound for optical semiconductors of this invention, and the die-bonding material for optical semiconductor elements. It is sectional drawing which shows typically an example of the optical semiconductor element formed using the sealing agent for optical semiconductors of this invention, and the underfill material for optical semiconductor elements.

Explanation of symbols

10, 20 Die bond material for optical semiconductor element 11, 21, 31 Light emitting element 12, 22, 32 Sealant for optical semiconductor 13, 23 Gold wire 14, 24, 34 Lead electrode 15, 25, 35 Housing material 16 Heat sink 30 Underfill material 33 for optical semiconductors Bump

Claims (10)

Silicone copolymer resin (A) having one or more alicyclic epoxy-containing groups in the molecule, a structural unit represented by the following general formula (1), and a structural unit represented by the following general formula (2) ),
A bifunctional silicone resin (B) having one or more glycidyl-containing groups in the molecule, and
A thermosetting composition for an optical semiconductor, comprising a thermosetting agent capable of reacting with the alicyclic epoxy-containing group and the glycidyl-containing group.

In the general formula (1) and ^(2), R 1, ^{R 2} and ^{R 3} is at least 1 Tsugaabura cyclic epoxy-containing group, ^R 1, ^{R 2} and ^{R 3} other than alicyclic epoxy-containing group Represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and these may be the same or different from each other. The silicone resin (A) is composed mainly of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), and the total number of structural units included is 1. The content of the structural unit represented by the general formula (1) is 0.5 to 0.95 (molar conversion), and the content of the structural unit represented by the general formula (2) is 0.05. The thermosetting composition for optical semiconductors according to claim 1, wherein the content of the alicyclic epoxy-containing group is 5 to 40 mol%.

In the general formula (1) and ^(2), R 1, ^{R 2} and ^{R 3} is at least 1 Tsugaabura cyclic epoxy-containing group, ^R 1, ^{R 2} and ^{R 3} other than alicyclic epoxy-containing group Represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and these may be the same or different from each other. The silicone copolymer resin (A) contains a resin component whose average composition formula is represented by the following general formula (3), (4), (5), (6), (7) or (8). The thermosetting composition for optical semiconductors of Claim 1 or 2 characterized by these.

In general formula (3), a and b satisfy a / (a + b) = 0.5 to 0.95, b / (a + b) = 0.05 to 0.5, and R ⁶ represents an alicyclic epoxy. R ⁴ and R ⁵ each represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and these may be the same or different from each other. .

In the general formula (4), c and d satisfy c / (c + d) = 0.5 to 0.95, d / (c + d) = 0.05 to 0.5, and R ⁸ and / or R ⁹ are , An alicyclic epoxy-containing group, and R ⁷ represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. When only one of R ^{8 and} R ⁹ is an alicyclic epoxy-containing group, the other represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof.

In the general formula (5), e, f and g satisfy (e + f) / (e + f + g) = 0.5 to 0.95, g / (e + f + g) = 0.05 to 0.5, and R ¹⁴ is It is an alicyclic epoxy-containing group, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and these are the same as each other May be different or different. (R ¹⁰ R ¹¹ SiO _2/2 ) and (R ¹² R ¹³ SiO _2/2 ) have different structures.

In the general formula (6), h, i, j satisfy (h + i) / (h + i + j) = 0.5 to 0.95, j / (h + i + j) = 0.05 to 0.5, R ¹⁷ and / or Or R ¹⁸ is an alicyclic epoxy-containing group, and R ¹⁵ , R ¹⁶ , and R ¹⁹ represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, They may be the same or different. When only one of R ^{17 and} R ¹⁸ is an alicyclic epoxy-containing group, the other represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof.

In the general formula (7), k, l and m satisfy k / (k + l + m) = 0.5 to 0.95, (l + m) / (k + 1 + m) = 0.05 to 0.5, and R ²² is It is an alicyclic epoxy-containing group, and R ²⁰ , R ²¹ and R ²³ represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and these may be the same as each other Well, it can be different.

In the general formula (8), n, o and p satisfy n / (n + o + p) = 0.5 to 0.95, (o + p) / (n + o + p) = 0.05 to 0.5, R ²⁴ and / Or R ²⁵ represents an alicyclic epoxy-containing group, and R ²⁶ and R ²⁷ represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and these are the same as each other. It may be different. When only one of R ^{24 and} R ²⁵ is an alicyclic epoxy-containing group, the other represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. (R ²⁶ SiO _3/2 ) and (R ²⁷ SiO _3/2 ) have different structures. The bifunctional silicone resin (B) contains a resin component whose average composition formula is represented by the following general formula (15) or (16): The heat for optical semiconductors according to claim 1, 2 or 3 Curable composition.

In the general formula (15), q and r satisfy q / (q + r) = 0.5 to 0.95, r / (q + r) = 0.05 to 0.5, and R ³⁹ and / or R ⁴⁰ are , A glycidyl-containing group, and R ³⁷ and R ³⁸ each represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, which may be the same or different from each other. Also good. When only one of R ^{39 and} R ⁴⁰ is a glycidyl-containing group, the other represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof.

In the general formula (16), s, t, and u satisfy s + t / (s + t + u) = 0.5 to 0.95, u / (s + t + u) = 0.05 to 0.5, and R ⁴⁵ and / or R ⁴⁶ is a glycidyl-containing group, R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and these are the same as each other May be different or different. When only one of R ^{45 and} R ⁴⁶ is a glycidyl-containing group, the other represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. (R ⁴¹ R ⁴² SiO _2/2 ) and (R ⁴³ R ⁴⁴ SiO _2/2 ) have different structures. The thermosetting composition for optical semiconductors according to claim 1, wherein the thermosetting agent is an acid anhydride. An encapsulant for optical semiconductor elements, comprising the thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4 or 5. A die-bonding material for optical semiconductor elements, comprising the thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4 or 5. The die-bonding material for an optical semiconductor element according to claim 7, further comprising high thermal conductive fine particles. An underfill material for optical semiconductor elements, comprising the thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4 or 5. The thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4 or 5, the encapsulant for optical semiconductor elements according to claim 6, the die-bonding material for optical semiconductor elements according to claim 7 or 8, and / or An optical semiconductor element comprising the underfill material for an optical semiconductor element according to claim 9.

Images