JP2008120850A - Thermosetting composition for optical semiconductor, die bond material for optical semiconductor element, underfill material for optical semiconductor element, sealing agent for optical semiconductor element and optical semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermosetting composition for an optical semiconductor, having a high transparency, no discoloration by heat generation and light emission of a light-emitting element, excellent heat resistance, light resistance and adhesivity to housing materials, etc., no reduction in the film of a cured product after curing in a thermal environment and not causing cracks of the cured product by a thermocycle, etc., a sealing agent for an optical semiconductor element and a die bond material for an optical semiconductor element using the same and to provide an optical semiconductor device made by using the thermosetting composition for an optical semiconductor, the sealing agent for an optical semiconductor element, the die bond material for an optical semiconductor element and/or an underfill for an optical semiconductor element. <P>SOLUTION: The thermosetting composition for an optical semiconductor comprises a silicone resin containing one or more cyclic ether-containing groups in the molecule, a thermosetting agent to be reacted with the cyclic ether-containing group and a nonreactive silicone resin having a number-average molecular weight of 1,000-10,000. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention is highly transparent, has no discoloration due to heat generation or light emission of the light emitting element, is excellent in heat resistance, light resistance, and adhesion to a housing material, etc., and the cured product after curing can be reduced in a thermal environment. A thermosetting composition for optical semiconductors that does not occur and does not cause cracks in the cured product due to thermal cycling, etc., a sealing agent for optical semiconductor elements using the same, a die bond material for optical semiconductor elements, and the optical semiconductor The present invention relates to an optical semiconductor device using the thermosetting composition, the optical semiconductor sealing agent, the optical semiconductor element die-bonding material, and / or the optical semiconductor element underfill material.

Light emitting elements of optical semiconductor devices such as light emitting diodes (LEDs) are usually sealed with a sealant because their light emitting characteristics are rapidly degraded by direct contact with the atmosphere due to moisture in the atmosphere or floating dust. It has a structure. As a resin constituting a sealant for sealing such a light emitting element, epoxy resin such as bisphenol type epoxy resin and 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.

In addition, a sealing agent made of a conventional epoxy resin has advantages such as high adhesion and low moisture permeability, but has a problem that it has low light resistance to light of a short wavelength and is colored due to light deterioration. It was. In addition, the heat resistance was not sufficient.

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. In contrast, silicone resins with increased crosslink density are inferior in mechanical strength, have insufficient adhesion to housing materials that enclose light-emitting elements, and have high moisture permeability, resulting in long-term use. There has been a problem in that the light emitting characteristics of the light emitting element are deteriorated.
In addition, silicone resin has a problem that the refractive index is low, there is a problem that the light extraction efficiency is not sufficient when the light-emitting element of the optical semiconductor is sealed, these problems even when used in combination with an epoxy resin It was not possible to achieve sufficient performance to solve the problem.

In recent years, attempts have been made to develop a silicone resin having a cyclic ether group as a sealant for a light emitting element of an LED.
For example, Patent Document 3 discloses a sealing resin for a light-emitting diode whose main component is a siloxane derivative having an epoxy group or an oxetanyl group.
However, as a sealant for a light emitting element of an LED, a cured product is required to have sufficient hardness. However, such a conventional silicone resin having a cyclic ether group does not cause adhesion or scratches on the cured product. Therefore, if the hardness of the cured product is sufficient, there is a problem that the crack resistance is inferior. On the other hand, crack resistance can be improved by reducing the crosslink density of the cured product, but such a cured product has a very soft surface, and the cured product is attached with dust or scratches. The problem arises. Furthermore, when such a cured product having a reduced crosslinking density is placed in a thermal environment, there has been a problem that the thickness of the cured product is reduced, resulting in a reduction in film thickness. That is, the conventional silicone resin having a cyclic ether group cannot be said to have sufficient heat resistance required as a sealant for a light emitting element of an LED.
JP 2003-277473 A JP 2002-314142 A JP 2004-238589 A

In view of the above situation, the present invention is highly transparent, has no discoloration due to heat generation or light emission of the light emitting element, is excellent in heat resistance, light resistance, and adhesion to a housing material, etc., and film loss occurs in a thermal environment. Thermosetting composition for optical semiconductors that does not cause cracks in the cured product due to thermal cycling, etc., encapsulant for optical semiconductor elements using the same, die bonding material for optical semiconductor elements, and heat for optical semiconductors An object of the present invention is to provide an optical semiconductor device using the curable composition, the optical semiconductor sealing agent, the optical semiconductor element die-bonding material, and / or the optical semiconductor element underfill material.

The present invention relates to a silicone resin having at least one cyclic ether-containing group in the molecule, a thermosetting agent capable of reacting with the cyclic ether-containing group, and a non-reactive silicone resin having a number average molecular weight of 1000 to 10,000. It is the thermosetting composition for optical semiconductors to contain.
The present invention is described in detail below.

As a result of intensive studies, the inventors of the present invention contain a silicone resin having one or more cyclic ether-containing groups in the molecule, a thermosetting agent capable of reacting with the silicone resin, and a predetermined non-reactive silicone resin. The sealing agent has a high transmittance for light of short wavelengths in the blue to ultraviolet region, has no heat generation or discoloration due to light emission of the sealing light emitting element, has excellent heat resistance and light resistance, and is sufficient for a cured product that has been cured. It is possible to prevent problems such as film loss in a thermal environment while maintaining hardness, and when used as a sealing agent for sealing a light emitting element of an optical semiconductor element such as a light emitting diode, the light emitting element is sealed. The present inventors have found that it has excellent adhesion to a housing material and the like and does not cause cracks due to thermal cycling or peeling from the housing material, thereby completing the present invention.

The thermosetting composition for optical semiconductors of the present invention contains a silicone resin having one or more cyclic ether-containing groups in the molecule.
In the thermosetting composition for optical semiconductors of the present invention, the silicone resin having one or more cyclic ether-containing groups preferably has a structural unit represented by the following general formula (1) in the resin skeleton.

一般式（１）中、Ｒ^１は、環状エーテル含有基を表す。

In the general formula (1), R ¹ represents a cyclic ether-containing group.

By having the structural unit represented by the above general formula (1), the cured product for optical semiconductor of the present invention has a cured product having an appropriate hardness, and has a short wavelength from blue to ultraviolet region. When used as a sealant for an optical semiconductor element, the light emitting element to be sealed has no heat generation or discoloration due to light emission, and has excellent heat resistance and light resistance. In particular, an optical semiconductor such as a light emitting diode When the light emitting element of the element is sealed, the optical semiconductor element has excellent adhesion to the housing material or the like.

In the general formula (1), R ¹ represents a cyclic ether-containing group.
The cyclic ether-containing group is not particularly limited, and examples thereof include a glycidyl group, an epoxycyclohexyl group, and an oxetane group. Of these, a glycidyl group and / or an epoxycyclohexyl group are preferable.

The glycidyl group is not particularly limited. For example, 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxypropyl Group, 4-glycidoxybutyl group and the like.

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.

When the silicone resin having a cyclic ether-containing group has a structural unit represented by the general formula (1), when the number of repeating units of the structural unit is a and the number of other repeating units is b, a / The preferable lower limit of (a + b) is 0.1, and the preferable upper limit is 0.7. If it is less than 0.1, the hardness of the cured product of the thermosetting composition for optical semiconductors of the present invention may be insufficient, and if it exceeds 0.7, the thermosetting composition for optical semiconductors of the present invention. The hardness of the cured product may be too high and the crack resistance may be inferior. A more preferred lower limit is 0.15, and a more preferred upper limit is 0.4.

The structural unit represented by the general formula (1) (hereinafter also referred to as trifunctional structural unit) is a structure represented by the following general formula (1-2) or (1-3), that is, trifunctional. A structure in which two oxygen atoms bonded to a silicon atom in a structural unit constitute a hydroxyl group or an alkoxy group, respectively, or one oxygen atom bonded to a silicon atom in a trifunctional structural unit constitutes a hydroxyl group or an alkoxy group Including structures to
(R ¹ SiX ₂ O _1/2 ) (1-2)
(R ¹ SiXO _2/2 ) (1-3)
In the general formulas (1-2) and (1-3), 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) and (1-3), 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.

The silicone resin having one or more cyclic ether-containing groups in the molecule preferably has a structural unit represented by the general formula (1) and the following general formula (2). In this case, the number of repeating units of the structural unit represented by the general formula (1) is a ′, the number of repeating units of the structural unit represented by the general formula (2) is b ′, and the number of other repeating units is c ′. The preferable lower limit of (a ′ + b ′) / (a ′ + b ′ + c ′) is 0.1, the preferable upper limit is 0.7, and the preferable lower limit of the content of the cyclic ether-containing group Is 0.1 mol%, and the preferred upper limit is 50 mol%. When the content of the cyclic ether-containing group is less than 0.1 mol%, the reactivity between the silicone resin having one or more cyclic ether-containing groups in the molecule and a thermosetting agent described later is significantly reduced. The curability of the thermosetting composition for optical semiconductors of the invention may be insufficient. When the content of the cyclic ether-containing group exceeds 50 mol%, the number of cyclic ether-containing groups not involved in the reaction between the silicone resin having one or more cyclic ether-containing groups in the molecule and the thermosetting agent increases. The heat resistance of the thermosetting composition for optical semiconductors may decrease. A more preferred lower limit is 5 mol%, and a more preferred upper limit is 30 mol%.
In the present specification, the content of the cyclic ether-containing group means the amount of the cyclic ether-containing group contained in the average composition of the silicone resin component having one or more cyclic ether-containing groups in the molecule. means. The average composition of the resin component is a composition having a structure represented by averaging the composition formulas of various resin components constituting the silicone resin having one or more cyclic ether-containing groups in the molecule. means.

一般式（２）中、Ｒ^２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。

In the general formula (2), R ² represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof.

The silicone resin having one or more cyclic ether-containing groups in the molecule preferably contains a resin component having an average composition formula represented by the following general formula (3).

一般式（３）中、ｃ、ｄは、ｃ／（ｃ＋ｄ）＝０．３〜０．９、ｄ／（ｃ＋ｄ）＝０．１〜０．７を満たし、Ｒ^５は環状エーテル含有基であり、Ｒ^３、Ｒ^４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。
なお、上記「平均組成式」とは、本発明の光半導体用熱硬化性組成物が上記式（３）で表される樹脂成分のみを含有する場合だけでなく、種々の構造の樹脂成分を含有する混合物である場合に、含有する樹脂成分の組成の平均をとると上記式（３）で表される場合も意味する。

In the general formula (3), c and d satisfy c / (c + d) = 0.3 to 0.9, d / (c + d) = 0.1 to 0.7, and R ⁵ is a cyclic ether-containing group. R ³ and R ⁴ each 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.
The “average composition formula” means not only the case where the thermosetting composition for optical semiconductors of the present invention contains only the resin component represented by the formula (3), but also resin components having various structures. In the case of the mixture to be contained, the average of the composition of the resin component to be contained means the case represented by the above formula (3).

In the general formula (3), R ⁵ is a cyclic ether-containing group, and the portion represented by (R ⁵ SiO _3/2 ) _d in the general formula (3) is the above-described general formula (1). It is a part derived from the structural unit (including the case where it is a structure represented by the above general formulas (1-2) and (1-3)).

In the general formula (3), a structural unit represented by (R ³ R ⁴ SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) is represented by the following general formula (3-2). The structure includes a structure in which one of oxygen atoms bonded to a silicon atom in a bifunctional structural unit constitutes a hydroxyl group or an alkoxy group.
(R ³ R ⁴ SiXO _1/2 ) (3-2)
In the general formula (3-2), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.

In the general formula (3), c and d have a lower limit of c / (c + d) of 0.3 and an upper limit of 0.9, a lower limit of d / (c + d) of 0.1, and an upper limit of 0.7. Meet. When outside the above range, that is, when c / (c + d) is less than 0.3 or d / (c + d) exceeds 0.7, the cured product of the thermosetting composition for optical semiconductors of the present invention If the hardness becomes too high and the crack resistance is inferior, and c / (c + d) exceeds 0.9 or d / (c + d) is less than 0.1, the thermosetting for optical semiconductors of the present invention The hardness of the cured product of the adhesive composition may be insufficient.

In the general formula (3), the linear or branched hydrocarbon having 1 to 8 carbon atoms is not particularly limited, and examples thereof include a 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, isohexyl group, etc. Is mentioned.

In the thermosetting composition for optical semiconductors of the present invention, the resin composition whose average composition formula is represented by the above general formula (3) is R ³ R ⁴ SiO _{2 / in} a skeleton of one molecule in an uncured state. A resin having a structural unit of _{2 and} a structural unit of R ⁵ SiO _3/2 may be used, and a resin having a structural unit of only R ³ R ⁴ SiO _{2/2 and} a structure of R ⁵ SiO _3/2 A mixture of resins having units may be used. Of these, a resin having a structural unit of R ³ R ⁴ SiO _{2/2 and} a structural unit of R ⁵ SiO _3/2 in the skeleton of one molecule of the resin is preferable.

The silicone resin having one or more cyclic ether-containing groups in the molecule preferably contains a resin component whose average composition formula is represented by the following general formula (4).

一般式（４）中、ｅ、ｆ、ｇは、ｅ／（ｅ＋ｆ＋ｇ）＝０．３〜０．９、（ｆ＋ｇ）／（ｅ＋ｆ＋ｇ）＝０．１〜０．７を満たし、Ｒ^８は、環状エーテル含有基であり、Ｒ^６、Ｒ^７、Ｒ^９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。

In general formula (4), e, f, and g satisfy e / (e + f + g) = 0.3 to 0.9, (f + g) / (e + f + g) = 0.1 to 0.7, and R ⁸ is A cyclic ether-containing group, wherein R ⁶ , R ⁷ and R ⁹ represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, which may be the same as each other; May be different.

In the general formula (4), R ⁸ is a cyclic ether-containing group, and the portion represented by (R ⁸ SiO _3/2 ) _f in the general formula (4) is the above-described general formula (1). It is a part derived from the structural unit (including the case where it is a structure represented by the above general formulas (1-2) and (1-3)).

In the general formula (4), the structural unit represented by (R ⁹ SiO _3/2 ) is a structure represented by the following general formula (4-2) or (4-3), that is, (R Or a structure represented by (R ⁹ SiO _3/2 ), wherein two oxygen atoms bonded to a silicon atom in the structural unit represented by ⁹ SiO _3/2 ) constitute a hydroxyl group or an alkoxy group, respectively. It includes a structure in which one of oxygen atoms bonded to a silicon atom in a unit constitutes a hydroxyl group or an alkoxy group.
(R ⁹ SiX ₂ O _1/2 ) (4-2)
(R ⁹ SiXO _2/2 ) (4-3)
In the general formulas (4-2) and (4-3), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.

In the general formula (4), a structural unit represented by (R ⁶ R ⁷ SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) is represented by the following general formula (4-4). The structure includes a structure in which one of oxygen atoms bonded to a silicon atom in a bifunctional structural unit constitutes a hydroxyl group or an alkoxy group.
(R ⁶ R ⁷ SiXO _1/2 ) (4-4)
In the general formula (4-4), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms.

In the general formulas (4-2), (4-3), and (4-4), as the linear or branched alkoxy group having 1 to 4 carbon atoms, the general formulas (1-2) and ( The thing similar to what was demonstrated in 1-3) is mentioned.

In the general formula (4), e, f, and g are such that the lower limit of e / (e + f + g) is 0.3 and the upper limit is 0.9, and the lower limit of (f + g) / (e + f + g) is 0.1. Satisfies 0.7. When out of the above range, that is, when e / (e + f + g) is less than 0.3 or (f + g) / (e + f + g) exceeds 0.7, the thermosetting composition for optical semiconductors of the present invention is cured. If the hardness of the product becomes too high and the crack resistance is inferior, e / (e + f + g) exceeds 0.9 or (f + g) / (e + f + g) is less than 0.1, the light of the present invention The hardness of the cured product of the thermosetting composition for semiconductors may be insufficient.

In the general formula (4), the linear or branched hydrocarbon having 1 to 8 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an 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, etc. Is mentioned.

The resin component in which the average composition formula is represented by the general formula (4) is a structural unit of R ⁶ R ⁷ SiO _2/2 in a skeleton of one molecule in an uncured state, and R ⁸ SiO _3/2. structural units and ^may be used a resin having a structural unit of R _{9 SiO ^3/2,} and a resin having structural units of only R ⁶ R _{7 SiO ^2/2,} structural units R _{8 SiO 3/2} of And a mixture of a resin having a structural unit of R ⁹ SiO _3/2 may be used. Among them, a resin having a structural unit of R ⁶ R ⁷ SiO _2/2, a structural unit of R ⁸ SiO _{3/2, and} a structural unit of R ⁹ SiO _3/2 in the skeleton in one molecule of the resin. preferable.

The silicone resin having one or more cyclic ether-containing groups in the molecule contains the resin component in which the average composition formula described above is represented by the general formula (3) or (4). As for the thermosetting composition for use, the cured product has an appropriate hardness as a sealant for an optical semiconductor element such as an LED.

When the silicone resin having the structural unit represented by the general formula (1) is subjected to 29Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) based on tetramethylsilane (hereinafter referred to as TMS), it may be slightly different depending on the type of the substituent. although variations are observed, the general formula (1), (1-2) and trifunctional structural units (1-3), as well as, the general formula (3) ^(R _{5 SiO 3/2) d} A part represented by (R ⁸ SiO _3/2 ) _f of the above general formula (4), a structural unit represented by (R ⁹ SiO _3/2 ), and the above general formulas (4-2) and (4 Each peak corresponding to the structural unit represented by -3) appears in the vicinity of -50 to -70 ppm, and (R ³ R ⁴ SiO _2/2 ) _{b of} the above general formula (3) and the general formula (3-2) bifunctional structural units, as well as, the general formula ^{(4) (R 6 R 7} SiO 2 / ) And peaks corresponding to the respective bifunctional structural units of the general formula (4-4) appears in the vicinity of -10 to-30 ppm.
Therefore, it is possible to measure the ratio of the general formula (1) and the like by measuring 29Si-NMR and comparing the peak areas of the respective signals.
However, when the 29Si-NMR measurement based on the TMS cannot be distinguished from the functional structural unit of the general formula (1), not only the 29Si-NMR measurement result but also 1H-NMR or 19F-NMR The ratio of the structural units can be discriminated by using the results measured by the above as necessary.

The silicone resin having one or more cyclic ether-containing groups in the molecule preferably contains 1 to 10 mol% of alkoxy groups. By containing such an alkoxy group, heat resistance and light resistance are drastically improved. This is because, by containing an alkoxy group in the silicone resin having one or more cyclic ether-containing groups in the molecule, the curing rate can be drastically improved, so that thermal deterioration during curing can be prevented. It is thought that it is because.

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.

If the alkoxy group is less than 1 mol%, the curing rate may not be sufficiently obtained and heat resistance may deteriorate. If it exceeds 10 mol%, a silicone resin having one or more cyclic ether-containing groups in the molecule, The storage stability of the composition is deteriorated and the heat resistance is deteriorated. A more preferred lower limit is 2 mol%, and a more preferred upper limit is 8 mol%.

In addition, in this specification, content of the said alkoxy group means the quantity of the said alkoxy group contained in the average composition of the silicone resin component which has one or more cyclic ether containing groups in the said molecule | numerator.

The silicone resin having one or more cyclic ether-containing groups in the molecule preferably does not contain a hydroxyl group. Hydroxyl groups are not preferable because the storage stability of the polymer is remarkably deteriorated and the storage stability of the resin composition is also remarkably deteriorated. Such hydroxyl groups can be reduced by heating in a 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 resin having one or more cyclic ether-containing groups in the molecule 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 a silicone resin having one or more cyclic ether-containing groups in the molecule is not particularly limited. For example, (1) hydrosilation of a silicone resin having a SiH group and a vinyl compound having a cyclic ether group Examples thereof include a method of introducing a substituent by reaction, and (2) a method of subjecting a siloxane compound and a siloxane compound having a cyclic ether-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.

As the silicone resin having the SiH group, after reacting the vinyl compound having a SiH group in the molecule and the cyclic ether-containing group, the structure represented by the general formula (1) described above, preferably What has the structure represented by any of the above general formulas (3) to (4) may be used.

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

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 method (2), examples of the siloxane compound include alkoxysilanes having a siloxane unit represented by the following general formulas (5), (6), (7), and (8), or partial hydrolysates thereof.

R ¹⁰ R ¹¹ R ¹² Si (OR) (5)
R ¹³ R ¹⁴ Si (OR) ₂ (6)
R ¹⁵ Si (OR) ₃ (7)
Si (OR) ₄ (8)

In the general formulas (5) to (8), R ^{10 to} R ¹⁵ represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and OR is linear or branched. Represents an alkoxy group having 1 to 4 carbon atoms.

In the general formulas (5) to (8), when R ^{10 to} R ¹⁵ 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 and the like.

In the general formulas (5) to (8), 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.

In the siloxane compound, the compounding ratio of the alkoxysilane having a siloxane unit represented by the general formulas (5) to (8) or a partial hydrolyzate thereof is subjected to a condensation reaction with a siloxane compound having a cyclic ether-containing group described later. The silicone resin synthesized in this manner is appropriately adjusted so as to have a structure represented by the above general formula (1), preferably a structure represented by any one of the above general formulas (3) to (4).

As a siloxane compound which has the said cyclic ether containing group, the alkoxysilane which has the cyclic ether containing group represented by following General formula (9), or its partial hydrolyzate is mentioned, for example.

R ¹⁶ R ¹⁷ _d Si (OR ¹⁸ ) _(3-d) (9)

In the general formula (9), R ¹⁶ represents a cyclic ether-containing group, R ¹⁷ represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, and R ¹⁸ represents a linear chain. Alternatively, it represents a branched alkyl group having 1 to 4 carbon atoms, and d is 0 or 1.

In the general formula (9), the cyclic ether-containing group represented by R ¹⁶ is not particularly limited, and examples thereof include a glycidyl group, an epoxycyclohexyl group, and an oxetane group. Of these, a glycidyl group and / or an epoxycyclohexyl group are preferable.

The glycidyl group is not particularly limited. For example, 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxypropyl Group, 4-glycidoxybutyl group and the like.

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 (9), R ¹⁷ represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. As the linear or branched hydrocarbon having 1 to 8 carbon atoms, It is not particularly limited, and examples thereof include the same as those described in the general formula (1). In general formula (9), d is 0 or 1, and when d is 0, the siloxane compound having a cyclic ether-containing group is a trialkoxysilane having a cyclic ether-containing group or a partial hydrolyzate thereof. When d is 1, the siloxane compound having a cyclic ether-containing group is a dialkoxysilane having a cyclic ether-containing group or a partial hydrolyzate thereof.

Specific examples of the trialkoxysilane having a cyclic ether-containing group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2,3-epoxypropyltrimethoxysilane, 2,3-epoxypropyltriethoxysilane, etc. Is mentioned.

Specific examples of the organodialkoxysilane having a cyclic ether-containing group include 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, and 3-glycidide. Examples include xylpropyl (methyl) dibutoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, and 2,3-epoxypropyl (methyl) dimethoxysilane.

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

In the method (2), when the siloxane compound and the compound having a cyclic ether-containing group are reacted in the presence of water and an acid or a basic catalyst, the compound having the cyclic ether-containing group is It mix | blends so that a lower limit may be 0.1 mol% and an upper limit may be 50 mol% with respect to all the organic groups couple | bonded with the silicon atom of the said siloxane compound and the compound which has a cyclic ether containing group.

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

The acidic catalyst is a catalyst for reacting the siloxane compound with a siloxane compound having a cyclic ether-containing group. For example, inorganic acids such as phosphoric acid, boric acid, and carbonic acid; formic acid, acetic acid, propionic acid, and 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 and other organic acids; their acid anhydrides or derivatives .

The basic catalyst is a catalyst for reacting the siloxane compound with a siloxane compound having a cyclic ether-containing group, and examples thereof include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, cesium hydroxide; Examples include alkali metal alkoxides such as sodium-t-butoxide, potassium-t-butoxide, and cesium-t-butoxide; and alkali metal silanol compounds such as sodium silanolate compounds, potassium silanolate compounds, and cesium silanolate compounds. 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 with respect to the total amount of the siloxane compound and the siloxane compound having a cyclic ether-containing group, a preferred lower limit is 10 ppm, and a preferred upper limit is 10,000 ppm. 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 between the siloxane compound and the siloxane compound having a cyclic ether-containing group, the silicone resin to be synthesized can be prevented from precipitating from the reaction system, and the water and free water due to the condensation reaction can be removed azeotropically. Therefore, it is preferable to use an organic solvent.
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.

From the viewpoint of adjusting the amount of alkoxy groups, it is preferable to synthesize a silicone resin by the above method (2).
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. Moreover, you may adjust the quantity of an alkoxy group by making it condense with a compound like the said General formula (7).

The thermosetting composition for optical semiconductors of this invention contains the thermosetting agent which can react with the said cyclic ether containing group.
The thermosetting agent is not particularly limited as long as it can react with the cyclic ether-containing group of the silicone resin having one or more cyclic ether-containing groups in the molecule. For example, ethylenediamine, triethylenepentamine, hexa Aliphatic amines such as methylenediamine, dimer acid-modified ethylenediamine, N-ethylaminopiperazine, isophoronediamine, metaphenylenediamine, paraphenylenediamine, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenolsulfone , Aromatic amines such as 4,4′-diaminodiphenol methane, 4,4′-diaminodiphenol ether, mercaptans such as mercaptopropionic acid ester, terminal mercapto compound of epoxy resin, bisphenol A, bisphenol 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, bisphenol A novolak, bromine Phenolic resins such as brominated phenol novolac and brominated bisphenol A novolak, polyols obtained by hydrogenating aromatic rings of these phenolic resins, polyazeline acid anhydride, Tyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-5 -Cycloaliphatic anhydrides such as norbornene-2,3-dicarboxylic anhydride, methyl-norbornane-2,3-dicarboxylic anhydride, fragrances such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride Aliphatic acid anhydrides, 2-methylimidazole, 2-ethyl-4-methylimidazole, imidazoles such as 2-phenylimidazole and their salts, aliphatic amines, aromatic amines, and / or imidazoles and epoxies Hydrazides such as amine adducts and adipic acid dihydrazide obtained by reaction with resin S, dimethylbenzylamine, 1,8-diazabicyclo [5.4.0] undecene tertiary amines such as -7, organic phosphines such as triphenylphosphine, dicyandiamide, and the like. Among them, acid anhydrides such as alicyclic acid anhydrides and aromatic acid anhydrides are preferable, more preferably alicyclic acid anhydrides, and particularly preferably methylhexahydrophthalic anhydride, Hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-norbornane-2,3-dicarboxylic anhydride. These thermosetting agents may be used independently and 2 or more types may be used together.

The amount of the thermosetting agent is not particularly limited, but the preferred lower limit is 1 part by weight and the preferred upper limit is 200 parts by weight with respect to 100 parts by weight of the silicone resin having one or more cyclic ether-containing groups in the molecule. is there. 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.

The thermosetting composition for optical semiconductors of the present invention contains a nonreactive silicone resin having a number average molecular weight of 1000 to 10,000 (hereinafter also simply referred to as a nonreactive silicone resin).
When the thermosetting composition for optical semiconductors of the present invention contains the non-reactive silicone resin, the cured product of the thermosetting composition for optical semiconductors of the present invention has excellent crack resistance. This is because in the cured product, the non-reactive silicone resin enters the gap between the crosslinking points generated by the reaction of the cyclic ether-containing group of the silicone resin having one or more cyclic ether-containing groups in the molecule. Is considered to be present without being taken into the cured product. Here, the “non-reactive silicone resin” means that when the thermosetting resin composition for optical semiconductors of the present invention is cured, the above-described thermosetting agent does not form a cross-linked structure, and the curing reaction It means a silicone resin that does not contribute to

The lower limit of the number average molecular weight of the non-reactive silicone resin is 1000, and the upper limit is 10,000. If it is less than 1000, the volatility is high and the weight loss during curing increases, causing film slippage. If it exceeds 10,000, the compatibility with other components will deteriorate, and the transparency of the cured product will be insufficient. A preferable upper limit is 5000, and a more preferable upper limit is 4000.

Although it does not specifically limit as said non-reactive silicone resin, The silicone resin which has a repetition of a bifunctional unit as a main component is used suitably. Such a silicone resin is not particularly limited, and examples thereof include dimethyl silicone, phenylmethyl silicone, and diphenyl silicone.

The non-reactive silicone resin may have a non-reactive hydrogen bonding functional group, specifically, a hydrogen bonding functional group other than a carboxylic acid group or an amino group in the structure. When the non-reactive silicone has a hydrogen-bonding functional group other than a carboxylic acid group or amino group in the structure, the non-reactive silicone resin is less likely to volatilize and is difficult to be taken into the gap between the crosslinking points of the cured product. Therefore, the cured product of the thermosetting composition for optical semiconductors of the present invention may become too hard and the crack resistance may be reduced.

It does not specifically limit as a hydrogen bondable functional group other than the said caric acid group or an amino group, For example, a hydroxyl group etc. are mentioned.

The blending amount of the non-reactive silicone resin is not particularly limited, but a preferred lower limit is 0.5% by weight and a preferred upper limit is 15% by weight. If it is less than 0.5% by weight, the hardness of the entire cured product of the thermosetting composition for optical semiconductors of the present invention may increase. For example, the thermosetting composition for optical semiconductors of the present invention When used as a sealing agent for semiconductor elements, problems such as cracks and breakage of the wires of optical semiconductor elements may occur. If it exceeds 15% by weight, the hardness of the cured product of the thermosetting composition for optical semiconductors of the present invention may be insufficient. A more preferred lower limit is 1% by weight, and a more preferred upper limit is 10% 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.

Although it does not specifically limit as a compounding quantity of the said hardening accelerator, A preferable minimum is 0.01 weight part with respect to 100 weight part of silicone resins which has a 1 or more cyclic ether containing group in the said molecule | numerator, A preferable upper limit of 5 weight Part. 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.

It is preferable that the thermosetting composition for optical semiconductors of this invention contains the nanoparticle which has a metal element further.
By containing the nano fine particles, the refractive index of the thermosetting composition for optical semiconductors of the present invention is increased, and the light of an optical semiconductor element such as an LED using the thermosetting composition for optical semiconductors of the present invention. The takeout property is excellent.

A preferable upper limit of the average primary particle diameter of the nanoparticle is 20 nm. When the thickness exceeds 20 nm, light scattering due to the above-mentioned nano 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 nano fine particles contain a metal element.
The nanoparticle is preferably at least one selected from the group represented by the following in which 80% or more of the metal element present in the nanoparticle is present. 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

The nanoparticulate is not particularly limited as long as it contains the metal element, but since it is excellent in the improvement of the refractive index of the thermosetting composition for optical semiconductors of the present invention, among others, the nanoparticulate having zirconium Is preferable because of its improved refractive index and excellent light transmittance.

The compounding amount of the nanoparticles 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 100 parts by weight of the silicone resin having one or more cyclic ether-containing groups in the molecule. . 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 nano-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 part by weight and a preferable upper limit is 5 parts by weight with respect to 100 parts by weight of the silicone resin having one or more cyclic ether-containing groups in the molecule. 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 parts by weight with respect to 100 parts by weight of the silicone resin having one or more cyclic ether-containing groups in the molecule. 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 a 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 this invention may add silica fine powder etc., in order to adjust a 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.).

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 50000 mPa * s. When 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. When the optical semiconductor element exceeds 50000 mPa · s, the optical semiconductor element is uniform and accurate. 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 preferably has a hardness measured in accordance with JIS K6253 type D of the cured product of 50 or more and less than 80. If it is less than 50, the cured product is too soft, and it is not preferable because dust adheres to the surface or is easily damaged. When it exceeds 80, when the thermosetting composition for optical semiconductors of the present invention is used as an encapsulant for optical semiconductor elements, the cured product may crack or damage the wires of the optical semiconductor elements. . A more preferred lower limit is 55, and a more preferred upper limit is 70.

The thermosetting composition for optical semiconductors of the present invention contains a silicone resin having at least one cyclic ether-containing group in the molecule, a thermosetting agent capable of reacting with the cyclic ether-containing group, and a non-reactive silicone resin. Therefore, transparency is high, there is no discoloration due to heat generation or light emission of the light emitting element, it is excellent in heat resistance, light resistance, and adhesion to the housing material, and the cured product after curing is reduced in a thermal environment. There is no cracking of the cured product due to thermal cycling or the like.

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, At room temperature or under heating, each predetermined amount such as a silicone resin having one or more cyclic ether-containing groups in the molecule, a thermosetting agent, a non-reactive silicone resin, nanoparticles, a curing accelerator, and an additive is mixed. Methods and the like.

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 is composed of the thermosetting composition for optical semiconductor elements of the present invention, it has excellent heat resistance, light resistance and adhesiveness, and the cured product after curing has an appropriate hardness. , Film loss does not occur in a thermal environment. 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. When an optical semiconductor device using a light emitting element having a structure in which electrode pads are provided on both upper and lower surfaces of a light emitting element is manufactured by using a conductive die bond material, the lead electrode is electrically connected with the die bonding material. This 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. At the same time it is suitable for the purpose, it is excellent in light resistance, heat resistance and adhesiveness, and the cured product after curing has an appropriate hardness, and it can be suitably used because it does not cause film loss in a thermal environment. is there. 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.
Furthermore, the encapsulant for optical semiconductor elements of the present invention can also be used as a die bond material for fixing the light emitting element to a lead terminal or a package, a passivation film on the light emitting element, and a package substrate.

As described above, the thermosetting composition for optical semiconductors of the present invention includes a silicone resin having at least one cyclic ether-containing group in the molecule, a thermosetting agent capable of reacting with the cyclic ether-containing group, and a non-reactive property. Since it contains a silicone resin, it has high transparency to short-wavelength light in the blue to ultraviolet region, and when used as an encapsulant for optical semiconductor elements, there is no heat generation or discoloration due to light emission of the light-emitting element to be sealed, heat resistance, When the light-emitting element and the light-emitting element of the optical semiconductor element such as a light-emitting diode are sealed, the optical semiconductor element has excellent adhesion to the housing material or the like, and the cured product after curing is appropriate. In addition to having hardness, film loss does not occur in a thermal environment.
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 device is also one aspect of the present invention.

1 and 2 are cross-sectional views schematically showing an example of an optical semiconductor device using the optical semiconductor element sealant and the optical semiconductor element die-bonding material of the present invention, and FIG. It is sectional drawing which shows typically an example of the optical semiconductor device 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 device 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 gold, silver, and copper described above. 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 device of the present invention shown in FIG. 3, the light emitting element 31 is installed via the bump 33, and the underfill material 30 for the optical semiconductor element 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 device of the present invention shown in FIG. 3, the underfill material 30 for an 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 device of the present invention include a light emitting diode, a semiconductor laser, and a photocoupler. Such an optical semiconductor device of the present invention includes, for example, a backlight such as a liquid crystal display, illumination, various sensors, a light source such as a printer and a copying machine, a measurement light source for a vehicle, a signal light, a display light, a display device, and a planar light emission It can be suitably used for body light sources, displays, decorations, various lights, switching elements and the like.

According to the present invention, transparency is high, there is no discoloration due to heat generation or light emission of the light emitting element, heat resistance, light resistance, and adhesion to a housing material, etc., and a cured product after curing is a film in a thermal environment. A thermosetting composition for optical semiconductors that does not cause a decrease and does not cause cracks in a cured product due to thermal cycles, etc., an encapsulant for optical semiconductor elements using the same, a die bond material for optical semiconductor elements, and the light An optical semiconductor device using the thermosetting composition for semiconductor, the encapsulant for optical semiconductor, the die bond material for optical semiconductor element and / or the underfill material for optical semiconductor element 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 (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 A. The molecular weight of the polymer A is Mn = 2300, Mw = 4800, and (Me ₂ SiO _2/2 ) _0.84 (EpSiO _3/2 ) _0.16 from 29Si-NMR.
The 2- (3,4-epoxycyclohexyl) ethyl group content was 22 mol%, and the epoxy equivalent was 550 g / eq. Met.
The molecular weight and epoxy equivalent of polymer A were measured by adding tetrahydrofuran (1 mL) to polymer A (10 mg) until dissolved, and measuring device manufactured by Waters (column: Shodex GPC LF-804 manufactured by Showa Denko KK (length). 300 mm) × 2, measurement temperature: 40 ° C., flow rate: 1 mL / min, solvent: tetrahydrofuran, standard substance: polystyrene), and measurement was performed by GPC measurement. Moreover, the epoxy equivalent was calculated | required based on JISK-7236.

(Synthesis Example 2)
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 B. The molecular weight of the polymer B is Mn = 3200, Mw = 5400, and (Me ₂ SiO _2/2 ) _0.71 (MeSiO _3/2 ) _0.18 (EpSiO _3/2 ) _0.11 from 29Si-NMR.
3-glycidoxypropyl group content is 15 mol%, epoxy equivalent is 780 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)
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 C. The molecular weight of the polymer C is Mn = 2900, Mw = 4600, and (Me ₂ SiO _2/2 ) _0.65 (MeSiO _3/2 ) _0.22 (EpSiO _3/2 ) _0.13 from 29Si-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 C were determined in the same manner as in Synthesis Example 1.

(Example 1)
Polymer A (100 g), Ricacid MH-700G (acid anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 30 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), FM4411 (hydroxyl group-containing silicone resin [ Number average molecular weight: 1000], manufactured by Chisso Corporation, 3 g) was added and mixed and degassed to obtain an encapsulant for optical semiconductor elements.

(Example 2)
Polymer A (100 g), Ricacid MH-700G (anhydride, manufactured by Shin Nippon Chemical Co., Ltd., 30 g), U-CAT SA 102 (curing accelerator, manufactured by San Apro, 0.5 g), FM4421 (hydroxyl group-containing silicone resin [ Number average molecular weight: 5000], manufactured by Chisso Corporation, 3 g) was added and mixed and degassed to obtain an encapsulant for optical semiconductor elements.

(Example 3)
Polymer B (100 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, 0.5 g), FM4411 (hydroxyl group-containing silicone resin [ Number average molecular weight: 1000], manufactured by Chisso Corporation, 3 g) was added and mixed and degassed to obtain an encapsulant for optical semiconductor elements.

Example 4
Polymer C (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), FM4411 (hydroxyl group-containing silicone resin [ Number average molecular weight: 1000], manufactured by Chisso Corporation, 3 g) was added and mixed and degassed to obtain an encapsulant for optical semiconductor elements.

(Comparative Example 1)
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.

(Comparative Example 2)
Polymer A (100 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), FM3311 (amino group-containing silicone resin) [Number average molecular weight: 1000], manufactured by Chisso Co., Ltd., 3 g) was added and mixed and degassed to obtain an encapsulant for optical semiconductor elements.

(Comparative Example 3)
Celoxide 2021 (alicyclic epoxy resin, manufactured by Daicel Chemical Industries, 50 g), YX-8000 (hydrogenated bisphenol A epoxy resin, manufactured by Japan Epoxy Resin, 50 g), Ricacid MH-700G (manufactured by Nippon Nippon Chemical Co., Ltd., 100 g) U-CAT SA 102 (manufactured by Sun Apro, 0.5 g) was added and mixed and degassed to obtain an encapsulant for optical semiconductor elements.

(Comparative Example 4)
VDT-431 (polysiloxane having a vinyl group, manufactured by Gelest, 45 g), HMS-031 (organohydrogenpolysiloxane, manufactured by Gelest, 55 g), octyl alcohol-modified solution of chloroplatinic acid (Pt concentration: 2% by weight, 0.05 g) was added and mixed and defoamed to obtain an encapsulant for optical semiconductor elements.

(Evaluation)
The following evaluation was performed about the sealing agent for optical semiconductor elements obtained in Examples 1-4 and Comparative Examples 1-4. The results are shown in Table 1.

(Initial light transmittance)
The encapsulant for optical semiconductor elements prepared in Examples and Comparative Examples was poured into a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to produce a 1 mm cured product, and a light transmittance of 400 nm was obtained from Hitachi, Ltd. Measurements were made using U-4000 made.

(Adhesion test)
Apply the optical semiconductor sealants prepared in Examples and Comparative Examples to aluminum, polyphthalamide resin (PPA), and polybutylene terephthalate resin (PBT), and cure them at 110 ° C x 3 hours and 130 ° C x 3 hours. A thin film was prepared, and an adhesion test was performed using a grid tape method with a clearance of 1 mm and 100 squares in accordance with JIS K-5400.
In Table 1, when the number of peels was 0: ◯, when the number of peels 1 to 70: Δ, and when the number of peels 71 to 100: x.

(hardness)
The optical semiconductor encapsulant prepared in Examples and Comparative Examples was poured into a mold and cured at 110 ° C. for 3 hours and 130 ° C. for 3 hours to produce a cured product. The hardness of the cured product was changed to Type D of JIS K6253. Measured in conformity.

(High-temperature energization test (heat and light resistance test), cooling cycle test)
(Preparation of die bond material for optical semiconductor elements)
In polymer A (30 g), flaky silver powder (170 g) having an average particle diameter of 3 μm and a maximum particle diameter of 20 μm, FM4411 (hydroxyl group-containing silicone resin [number average molecular weight: 1000], manufactured by Chisso Corporation, 0.45 g) was stirred. Kneading was performed using three rolls.
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., 0.625 g) are 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 device having a main light emission peak of 460 nm was mounted on the housing material with lead electrode (PPA) using the produced die bonding material for an optical semiconductor device, and cured at 180 degrees for 15 minutes to fix the light emitting device. 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 and 130 ° C. × 3 hours. An optical semiconductor device having the structure shown in FIG.

The produced optical semiconductor device was put in an oven at 85 ° C., and a high-temperature energization test was conducted at a current value of 10 mA for 1000 hours. The luminance was measured after 1000 hours, and the luminance reduction rate from the initial stage was calculated. When the luminance reduction rate is less than 10%: ◯, when less than 10-30%: Δ, when 30 or more: x.
In addition, the optical semiconductor device (20 pieces) was subjected to 1000 cycles of a cooling cycle of −40 ° C. for 30 minutes and 120 ° C. for 30 minutes to confirm the number of peeling and cracks from the housing material (cooling cycle test).

According to the present invention, transparency is high, there is no discoloration due to heat generation or light emission of the light emitting element, heat resistance, light resistance, and adhesion to a housing material, etc., and a cured product after curing is a film in a thermal environment. A thermosetting composition for optical semiconductors that does not decrease and does not cause cracking of the cured product or peeling from the housing material due to thermal cycles, etc., a sealing agent for optical semiconductor elements using the same, and a die bond for optical semiconductor elements And an optical semiconductor element using the thermosetting composition for optical semiconductor, the encapsulant for optical semiconductor, the die bond material for optical semiconductor element, and / or the underfill material for optical semiconductor element. it can.

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 (12)

Containing a silicone resin having at least one cyclic ether-containing group in the molecule, a thermosetting agent capable of reacting with the cyclic ether-containing group, and a non-reactive silicone resin having a number average molecular weight of 1,000 to 10,000. A thermosetting composition for optical semiconductors. A silicone resin having one or more cyclic ether-containing groups in the molecule has a structural unit represented by the following general formula (1) in the resin skeleton, and a repeating structural unit represented by the following general formula (1) 2. The thermosetting for optical semiconductor according to claim 1, wherein (a) / (a + b) is 0.1 to 0.7 when the number of units is a and the number of other repeating units is b. Composition.

In the general formula (1), R ¹ represents a cyclic ether-containing group. The silicone resin having one or more cyclic ether-containing groups in the molecule has structural units represented by the following general formulas (1) and (2) in the resin skeleton, and is represented by the general formula (1). When the number of repeating units of the structural unit is a ′, the number of repeating units of the structural unit represented by the general formula (2) is b ′, and the number of other repeating units is c ′, (a ′ + b ′) / 3. (a ′ + b ′ + c ′) is 0.1 to 0.7, and the content of the cyclic ether-containing group is 0.1 to 50 mol%. The thermosetting composition for optical semiconductors.

In the general formula (1), R ¹ represents a cyclic ether-containing group, and in the general formula (2), R ² represents a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof. The silicone resin having one or more cyclic ether-containing groups in the molecule contains a resin component whose average composition formula is represented by the following general formula (3) or (4): 3. The thermosetting composition for optical semiconductors according to 3.

In the general formula (3), c and d satisfy c / (c + d) = 0.3 to 0.9, d / (c + d) = 0.1 to 0.7, and R ⁵ is a cyclic ether-containing group. R ³ and R ⁴ each 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.

In general formula (4), e, f, and g satisfy e / (e + f + g) = 0.3 to 0.9, (f + g) / (e + f + g) = 0.1 to 0.7, and R ⁸ is A cyclic ether-containing group, wherein R ⁶ , R ⁷ and R ⁹ represent a linear or branched hydrocarbon having 1 to 8 carbon atoms or a fluorinated product thereof, which may be the same as each other; May be different. The thermosetting composition for optical semiconductors according to claim 1, wherein the thermosetting agent is an acid anhydride. The thermosetting composition for optical semiconductors according to claim 1, further comprising nanoparticles having a metal element. The thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4, 5 or 6, wherein the hardness of the cured product measured in accordance with JIS K6253 type D is 50 or more and less than 80. object. An encapsulant for optical semiconductor elements, comprising the thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4, 5, 6 or 7. A die-bonding material for optical semiconductor elements, comprising the thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4, 5, 6 or 7. The die bond material for an optical semiconductor according to claim 9, 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, 5, 6 or 7. The thermosetting composition for optical semiconductors according to claim 1, 2, 3, 4, 5, 6 or 7, the encapsulant for optical semiconductor elements according to claim 8, and the optical semiconductor element according to claim 9 or 10. An optical semiconductor device using a die bond material and / or an underfill material for an optical semiconductor element according to claim 11.

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