JP5972747B2 - Semiconductor light-emitting device sealing agent, semiconductor light-emitting device sealing material using the same, and semiconductor light-emitting device - Google Patents

Description

  The present invention relates to a sealing agent for a semiconductor light emitting device, a sealing material for a semiconductor light emitting device using the same, and a semiconductor light emitting device.

  Semiconductor light-emitting devices are expected as next-generation light sources to replace incandescent lamps and fluorescent lamps, and technological developments such as improved output are being actively promoted in Japan and overseas. The range of application is wide-ranging, and its use is expanding not only for indoor lighting but also as a backlight for liquid crystal display devices. In particular, in recent years, attention has been focused on semiconductor light emitting devices with low power consumption in response to increasing awareness of energy saving, and companies and research institutions are accelerating technological development of LED lighting.

  Looking at the types of semiconductor light-emitting devices by structure, there are a shell type, a surface mount type (SMD), a chip on board (COB), and the like. FIG. 1 shows an example of a surface mount type. In this example, the semiconductor light emitting element 1 is mounted in a reflector package substrate 2 molded from ceramic or resin. The semiconductor light emitting device 1 has a structure in which electricity is supplied from the outside via an electrode 4, a conductive adhesive 8 and a bonding wire 6. The cavity (concave space) W is sealed with a resin (sealing material) 3 such as epoxy or silicone in which a phosphor is dispersed. The surface inside the cavity is provided with a function of a reflecting plate so that a lot of light can be extracted.

  As can be seen from the above structure, the semiconductor light emitting device requires a structure and members different from those of conventional incandescent bulbs and fluorescent lamps, and it cannot be said that the development has yet been made sufficiently. The same applies to the sealing material described above, and epoxy or silicone resins are currently the mainstream, but development studies and material searches for further performance improvement are required. For example, Patent Document 1 discloses a resin raw material composition for a semiconductor light emitting device using an alicyclic hydrocarbon compound.

International Publication No. 2006/051803 Pamphlet

The performance required for the sealing resin of the semiconductor light-emitting element is transparent, and further includes heat resistance, gas barrier properties, and adhesion to the package. The simultaneous achievement of these properties is unique to this application. In particular, for package adhesion, the cavity of this type of device has a resin surface and a metal surface (typically, noble metals such as gold, silver, copper, and alloys thereof). It is required to ensure adhesion to Or even if the cavity is comprised with a single material as a device, the versatility applicable to both is calculated | required. In other words, the sealing resin is required to have adhesion to a surface having physical properties that are usually contradictory to each other, that is, an organic material and an inorganic material, and it has not been easy to meet them.
Accordingly, the present invention provides a sealing agent for a semiconductor light emitting device, which is excellent in transparency, heat resistance, gas barrier properties, and adhesion to a package, particularly required for semiconductor light emitting device applications, and sealing a semiconductor light emitting device using the same. An object is to provide a material and a semiconductor light emitting device.

  The above problem has been solved by the following means.

（式中のＲ^４、Ｒ^５、Ｒ^６は、それぞれ独立に、水酸基、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜２４のアリールオキシ基、炭素数６〜２４のアリール基、下記式（Ｉ）で表されるアクリロイルオキシ基、又は下記式（ＩＩ）で表されるアシルオキシ基を表す。Ｌ^ａは炭素数１〜４のアルキレン基を表す。ただし、Ｒ^４、Ｒ^５、及びＲ^６の少なくとも１つはアクリロイルオキシ基である。）

（式中、Ｒ^７は水素原子又は炭素数１〜３のアルキル基を表す。＊は結合手を表す。）

（式中、Ｒ^８は炭素数１〜１０のアルキル基又は炭素数６〜２４のアリール基を表す。＊は結合手を表す。）
〔２〕ジスルフィド化合物が下記式（３）で表される化合物である〔１〕に記載の半導体発光装置用封止剤。

（Ｌ^１、Ｌ^２はそれぞれ連結基である。Ｒｄ、Ｒｆはそれぞれアルキル基を表す。Ｒｅ、Ｒｇはそれぞれアルコキシ基を表す。ｎｄ〜ｎｇは０以上３以下の整数を表す。ただし、ｎｅ、ｎｇの少なくともどちらかは１以上である。ｎｄ＋ｎｅ＝３であり、ｎｆ＋ｎｇ＝３である。）
〔３〕イソシアヌレート化合物を封止剤中の有機硬化成分に対し８０質量％以上含み、且つ前記ジスルフィド化合物をイソシアヌレート化合物１００質量部に対し０．０１〜２０質量部含む〔１〕または〔２〕に記載の半導体発光装置用封止剤。
〔４〕イソシアヌレート化合物が、下記式（４）で表される水酸基含有イソシアヌレート化合物を少なくとも１種含む〔１〕〜〔３〕のいずれか１項に記載の半導体発光装置用封止剤。

（Ｒ^９は、水素原子またはメチル基である。Ｒ^１０は、水酸基、炭素数１〜１０のアルコキシ基、炭素数６〜２４のアリールオキシ基、式（Ｉ）で表されるアクリロイルオキシ基、および式（ＩＩ）で表されるアシルオキシ基のいずれか１種である。）
〔５〕さらに、下記式（５）で表される環状官能基含有イソシアヌレート化合物を、イソシアヌレート化合物１００質量部に対し０．１〜１０質量部含む〔１〕〜〔４〕のいずれか１項に記載の半導体発光装置用封止剤。

（式中、Ｒ^１１、Ｒ^１２、Ｒ^１３は置換基である。ただし、Ｒ^１１〜Ｒ^１３のうち少なくとも１つは環状官能基を含み、かつＲ^１１〜Ｒ^１３のうち少なくとも１つは加水分解性アルコキシシリル基を含む。）
〔６〕さらに、封止剤の有機硬化成分１００質量部に対し蛍光体１〜４０質量部を配合してなる〔１〕〜〔５〕のいずれか１項に記載の半導体発光装置用封止剤。
〔７〕〔１〕〜〔６〕のいずれか１項に記載の半導体発光装置用封止剤を硬化してなる半導体発光装置用封止材。
〔８〕〔７〕に記載の封止材と封止材で封止された半導体発光素子とを具備する半導体発光装置。
〔９〕下記式（２）で表されるイソシアヌレート化合物およびジスルフィド基とアルコキシシリル基とを含むジスルフィド化合物を含む組成物。

（式中のＲ^４、Ｒ^５、Ｒ^６は、それぞれ独立に、水酸基、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜２４のアリールオキシ基、炭素数６〜２４のアリール基、下記式（Ｉ）で表されるアクリロイルオキシ基、又は下記式（ＩＩ）で表されるアシルオキシ基を表す。Ｌ^ａは炭素数１〜４のアルキレン基を表す。ただし、Ｒ^４、Ｒ^５、及びＲ^６の少なくとも１つはアクリロイルオキシ基である。）

（式中、Ｒ^７は水素原子又は炭素数１〜３のアルキル基を表す。＊は結合手を表す。）

（式中、Ｒ^８は炭素数１〜１０のアルキル基又は炭素数６〜２４のアリール基を表す。＊は結合手を表す。）

That is, the present invention provides the following means for solving the above-mentioned problems.
[1] An encapsulant for a semiconductor light emitting device comprising an isocyanurate compound represented by the following formula ( 2 ) and a disulfide compound containing a disulfide group and an alkoxysilyl group.

(In the formula, R ⁴ , R ⁵ and R ⁶ are each independently a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, or a carbon number. aryl group of 6 to 24, .L ^a representative of the acyloxy group represented by acryloyloxy group represented by the following formula (I), or formula (II) represents an alkylene group having 1 to 4 carbon atoms. However , R ⁴ , R ⁵ , and R ⁶ are acryloyloxy groups.)

(In the formula, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. * Represents a bond.)

(In the formula, R ⁸ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms. * Represents a bond.)
[ 2 ] The encapsulant for a semiconductor light-emitting device according to [1 ], wherein the disulfide compound is a compound represented by the following formula (3).

(L ¹ and L ² are each a linking group. Rd and Rf each represents an alkyl group. Re and Rg each represents an alkoxy group. Nd to ng represent an integer of 0 or more and 3 or less, provided that ne, (At least one of ng is equal to or greater than 1. nd + ne = 3 and nc + ng = 3.)
[3] include isocyanurate compound 80 mass% or more with respect to organic cure component in the sealing agent, and the disulfide compound comprises 0.01 to 20 parts by mass with respect isocyanurate compound 100 parts by mass [1] or [2 ] The sealing agent for semiconductor light-emitting devices of description.
[ 4 ] The encapsulant for a semiconductor light-emitting device according to any one of [1] to [ 3 ], wherein the isocyanurate compound includes at least one hydroxyl group-containing isocyanurate compound represented by the following formula (4).

(R ⁹ is a hydrogen atom or a methyl group. R ¹⁰ is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, an acryloyloxy group represented by the formula (I), And any one of acyloxy groups represented by formula (II).)
[ 5 ] Further, any one of [1] to [ 4 ], wherein the cyclic functional group-containing isocyanurate compound represented by the following formula (5) is contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the isocyanurate compound. The sealing agent for semiconductor light-emitting devices of clause.

^{(Wherein, R 11, R 12, R} 13 is a substituent. ^However, at least one of R 11 ^{to R 13} includes an annular functional group and at least one of ^R 11 ^{to R 13} is hydro (Including degradable alkoxysilyl groups)
[ 6 ] Further, 1 to 40 parts by mass of the phosphor is blended with 100 parts by mass of the organic curing component of the encapsulant. [1] to [ 5 ] The semiconductor light-emitting device encapsulation according to any one of [ 5 ] Agent.
[ 7 ] A sealing material for a semiconductor light-emitting device obtained by curing the sealing agent for a semiconductor light-emitting device according to any one of [1] to [ 6 ].
[ 8 ] A semiconductor light-emitting device comprising the sealing material according to [ 7 ] and a semiconductor light-emitting element sealed with the sealing material.
[ 9 ] A composition comprising an isocyanurate compound represented by the following formula ( 2 ) and a disulfide compound containing a disulfide group and an alkoxysilyl group.

(In the formula, R ⁴ , R ⁵ and R ⁶ are each independently a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, or a carbon number. aryl group of 6 to 24, .L ^a representative of the acyloxy group represented by acryloyloxy group represented by the following formula (I), or formula (II) represents an alkylene group having 1 to 4 carbon atoms. However , R ⁴ , R ⁵ , and R ⁶ are acryloyloxy groups.)

(In the formula, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. * Represents a bond.)

(In the formula, R ⁸ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms. * Represents a bond.)

  In this specification, when there are a plurality of substituents or linking groups indicated by a specific symbol, or when a plurality of substituents are specified simultaneously or alternatively, each of the substituents may be the same or different from each other. It may mean. The same applies to the definition of the number of substituents and the like. Further, even if not specifically stated, when a plurality of substituents and the like are close to each other, they may be connected to each other or condensed to form a ring.

  Moreover, the sealing agent of the present invention is excellent in transparency, heat resistance, gas barrier properties, and adhesiveness to a package when used as a sealing material in which a semiconductor light emitting element is sealed or a semiconductor light emitting device having the same. In particular, with respect to the adhesiveness of the package, there is an excellent effect that it can be applied to both the resin surface and the metal surface.

It is sectional drawing which showed typically an example of the semiconductor light-emitting device of this invention.

  The encapsulant for a semiconductor light-emitting device of the present invention includes a specific acrylate compound having an isocyanurate structure (hereinafter sometimes referred to as a specific isocyanurate compound or simply an isocyanurate compound) and a specific disulfide compound (hereinafter referred to as a specific disulfide compound). Or simply a disulfide compound). Hereinafter, the present invention will be described in detail focusing on preferred embodiments thereof.

[Specific isocyanurate compounds]
In the present invention, an isocyanurate compound represented by the following formula (1) is used.

・Ｒ^１、Ｒ^２、Ｒ^３
式中、Ｒ^１、Ｒ^２、Ｒ^３は置換基である。当該置換基としては水酸基又は炭素数１〜２４の有機基が挙げられる。ただし、Ｒ^１〜Ｒ^３のうち少なくとも１つはアクリロイルオキシ基を含む。本明細書においてアクリロイルオキシ基とはα位の炭素に付加した元素が水素原子のもの以外にも、メチル基やエチル基、プロピル基、シアノ基の置換体といったものを含む意味である。アクリロイルオキシ基としては下記式（Ｉ）で表されるものが好ましい。

・ R ¹ , R ² , R ³
In the formula, R ¹ , R ² and R ³ are substituents. Examples of the substituent include a hydroxyl group or an organic group having 1 to 24 carbon atoms. However, at least one of R ^{1 to} R ³ includes an acryloyloxy group. In the present specification, the acryloyloxy group means that the element added to the carbon at the α-position includes not only a hydrogen atom but also a methyl group, an ethyl group, a propyl group, a substituted cyano group, and the like. As the acryloyloxy group, those represented by the following formula (I) are preferable.

The compound represented by formula (1) is Ru der those represented by the following formula (2).

・Ｒ^４、Ｒ^５、Ｒ^６
式中のＲ^４、Ｒ^５、Ｒ^６は、それぞれ独立に、水酸基、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜２４のアリールオキシ基、炭素数６〜２４のアリール基、下記式（Ｉ）で表されるアクリロイルオキシ基、又は下記式（ＩＩ）で表されるアシルオキシ基を表す。ただし、Ｒ^４、Ｒ^５、及びＲ^６の少なくとも１つは前記アクリロイルオキシ基である。

・ R ⁴ , R ⁵ , R ⁶
R ⁴ , R ⁵ and R ⁶ in the formula are each independently a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, or 6 carbon atoms. Represents an aryl group of ˜24, an acryloyloxy group represented by the following formula (I), or an acyloxy group represented by the following formula (II). However, at least one of R ⁴ , R ⁵ , and R ⁶ is the acryloyloxy group.

式中、Ｒ^７は水素原子又は炭素数１〜３のアルキル基を表す。＊は結合手を表す。

Wherein, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. * Represents a bond.

式中、Ｒ^８は炭素数１〜１０のアルキル基又は炭素数６〜２４のアリール基を表す。＊は結合手を表す。

In the formula, R ⁸ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms. * Represents a bond.

In R ^{4 to} R ⁸ , the alkyl group contained therein may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group. When R ^{4 to} R ⁸ include an aryl group, the aryl group may be monocyclic or multicyclic. The alkyl group and aryl group may be further accompanied by a substituent, and examples thereof include the substituent T described later.

L ^a is is an alkylene group having 1 to 4 carbon atoms, among them ethylene group or an isopropylene group _{(N-CH 2 -CH (CH} 3) -R orientation: R is ^R 4, ^{R 5,} or ^R 6) Are preferable, and an ethylene group is more preferable. La may be linear or branched and may be further substituted. Examples of the substituent T include the examples of the substituent T described later. Incidentally, L ^a hetero linking groups when alkylene group (an oxygen atom, a sulfur atom, such as an imino group of 0-3 carbon atoms) may be interposed.

The isocyanurate compound preferably has a hydroxyl group. In this case, in the acrylate compound specifically represented by the formula (1), it is preferable that at least one of R ⁴ , R ⁵ and R ⁶ is a hydroxyl group. Thereby, the bonded structure through the hydrolysis and dehydration condensation can be formed with the alkoxy group of the disulfide compound described later, and a hardened and stable cured product can be obtained.

As the hydroxyl group-containing isocyanurate compound, those represented by the following formula (4) are further preferred.

· ^{R 9, R 10}
R ⁹ is a hydrogen atom or a methyl group. R ¹⁰ is any one of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, an acryloyloxy group represented by formula (I), and an acyloxy group represented by formula (II). Or one. Among them, R ¹⁰ is preferably a hydroxyl group or an acryloyloxy group represented by the formula (I).
From the above viewpoint, among 100% by mass of the isocyanurate compound represented by the formula (1), 5 to 100% by mass is preferably an isocyanurate compound having a hydroxyl group, and is 20 to 100% by mass. Is more preferable.

[Component composition of sealant]
In the sealing agent of this invention, the density | concentration of the compound represented by said Formula (1) is more than 60 mass% with respect to the organic hardening component whole quantity of a sealing agent, and it is preferable that it is 70 mass% or more. 80% by mass or more, and more preferably 85% by mass or more. There is no particular upper limit, preferably 99.99% by mass or less, more preferably 99.95% by mass or less, even more preferably 99% by mass or less, and 97% by mass or less. Most preferred. The organic curing component of the sealant refers to a curing component consisting of a compound containing carbon atoms (a component that contributes directly to curing by polymerization or the like), but even if it contains carbon atoms, phosphors, polymerization initiators and polymerization are prohibited. It does not include organic solvents such as chemicals and toluene. Specifically, in addition to the isocyanurate compound, the meaning includes a disulfide compound described later. In addition, when it is necessary to make a strict comparison, it is meant to exclude trace components such as water and inorganic salts.
In the sealing agent of the present invention, residual solvent such as toluene may be mixed at a ratio of about 0 to 10% by mass, and the presence of such inevitable contaminants is within a range that does not impair the effects of the present invention. Allow. Alternatively, when it is necessary to lower the viscosity of the sealant, a necessary amount of additive may be added. In addition to the essential components, the sealant of the present invention may contain optional components such as a polymerization inhibitor, as necessary, but the solvent amount is preferably 10% or less, and preferably used without a solvent. . Thus, since it has sufficient fluidity | liquidity and suitable viscosity, it is excellent in the moldability of the sealing agent of a semiconductor light-emitting device, although it is a solvent-free or a small amount of solvent. In particular, it can effectively cope with molding by potting, and contributes to a significant improvement in production efficiency as compared with molding.

  The viscosity of the sealant is not particularly limited, but is 0.1 to 100 Pa. From the viewpoint of potting property and stable dispersibility of the phosphor. s is preferable, and 0.5 to 20 Pa.s. s is more preferable, and 1.0 to 10 Pa.s. s is more preferable. In the present invention, the viscosity means a value measured with a vibration viscometer (manufactured by Seconic, VM-100A (trade name)) unless otherwise specified.

(Isocyanurate compound [A])
The specific isocyanurate compound represented by the formula (1) is preferably one represented by the following formula (1-1), (1-2), or (1-3). In this specification, the isocyanurate compound [A] is referred to as a general term for the compounds represented by the formula (1-1), (1-2), or (1-3).

・ R ^{A1 to} R ^A4
In the formula, R ^A1 , R ^A2 and R ^A3 are each independently a hydrogen atom or a methyl group. R ^A4 is at least one of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, and an acyloxy group represented by the formula (II).

· ^{L a}
L ^a is as defined for formula (1), and preferred ranges are also the same synonymous.

The isocyanurate compound [A] is preferably contained in a specific ratio with respect to the compounds of the above formulas. When the isocyanurate compound [A] is 100% by mass, the compound represented by the formula (1-1) is preferably 0% by mass to 55% by mass, and 0% by mass to 45% by mass. More preferably.
The compound represented by the formula (1-2) is preferably 20% by mass to 100% by mass, more preferably 30% by mass to 100% by mass, and 40% by mass to 100% by mass. It is particularly preferred.
The compound represented by the formula (1-3) is preferably 0% by mass to 30% by mass, more preferably 0% by mass to 25% by mass, and 0% by mass to 15% by mass. It is particularly preferred.

  By containing the isocyanurate compound [A] (each in the above ratio), transparency, heat resistance coloring property, heat shock resistance, and gas barrier property can be satisfied at a higher level.

(Isocyanurate compound [B])
In the present invention, the specific isocyanurate compound preferably includes a compound represented by the following formula (1-4). In this specification, the compound represented by the formula (1-4) is referred to as an isocyanurate compound [B].

R ^A1 and R ^A2 are synonymous with those defined in Formula (1-1). R ^A5 has the same ^meaning as R ^{8 in} formula (II). L ^a is as defined for formula (1).

  The addition amount of the isocyanurate compound [B] is not particularly limited, but is preferably 1% by mass or more and less than 50% by mass in the organic curing component of the composition, and is preferably 3% by mass or more and 40% by mass or less. More preferably, it is 5 mass% or more and 30 mass% or less. By applying the isocyanurate compound [B] within the above range, it is possible to reduce the water absorption rate without deteriorating the thermal shock resistance (crack resistance) and heat resistance colorability of the cured product. (For example, moisture absorption reflow cracks generated when reflow treatment is performed in a state of water absorption) can be reduced, and as a result, a highly reliable semiconductor light emitting element can be provided.

(Specific disulfide compounds)
The sealing agent of this invention contains a specific disulfide compound with the said isocyanurate compound. This compound is a compound having a disulfide group and an alkoxysilyl group in the molecule, and is preferably a compound represented by the following formula (3).

・ L ¹ , L ²
L ¹ and L ² each represent a linking group. The linking group is preferably an alkylene group having 1 to 10 carbon atoms. However, this alkylene group may interpose a hetero linking group, and examples of the hetero linking group include an oxygen atom, a sulfur atom, a carbonyl group, and an imino group having 0 to 6 carbon atoms.

・ Rd ~ Rg
Rd and Rf each represents an alkyl group. As an alkyl group, a C1-C6 thing is mentioned, A C1-C3 alkyl group is more preferable. Re and Rg each represents an alkoxy group. As an alkoxy group, a C1-C6 thing is mentioned, A C1-C3 alkyl group is more preferable. The alkyl group here may be accompanied by arbitrary substituents, and examples thereof include the substituent T described later.

-Nd to ng
nd to ng represent an integer of 0 or more and 3 or less. At least one of ne and ng is 1 or more. Here, nd + ne = 3, and nf + ng = 3. When nd to ng are 2 or more, the substituents defined therein may be the same as or different from each other.

  The content of the specific disulfide compound is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more in the organic curing component of the sealant, More preferably, it is at least mass%. As an upper limit, it is preferable that it is 10 mass% or less, and it is more preferable that it is 5.0 mass% or less. When defined with respect to 100 parts by mass of the isocyanurate compound, it is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more. As an upper limit, it is preferable that it is 20 mass parts or less, 10 mass parts or less are more preferable, and it is more preferable that it is 5 mass parts or less. By making this compounding amount equal to or more than the lower limit value, it is possible to improve the adhesion to the package substrate (reflector package resin and (noble) metal electrode), in particular, (noble) metal electrode. On the other hand, it is preferable that the amount is not more than the above upper limit value because it is possible to minimize a decrease in curability, transparency after curing, and heat-resistant colorability.

(Cyclic functional group-containing isocyanurate compound)
The sealing agent of the present invention preferably further contains a cyclic functional group-containing isocyanurate compound represented by the following formula (5).

In the formula, R ¹¹ , R ¹² and R ¹³ are substituents. However, at least one of R ^{11 to} R ¹³ includes a cyclic functional group (preferably an epoxy group or an oxetane group), and at least one of R ^{11 to} R ¹³ includes a hydrolyzable alkoxysilyl group. When R ^{11 to} R ¹³ are groups containing a cyclic functional group, it is preferably -L ^b -R ⁵¹ . Here, R ⁵¹ is an epoxy group or an oxetane group. L ^b is ^a linking group having the same meaning as L ^a . When R ^{11 to} R ¹³ are hydrolyzable alkoxysilyl groups, it is preferably —L ^c —R ⁵² . Here, R ⁵² is preferably a group having the same meaning as -Si (R ^d ) nd (R ^e ) ne. L ^c is ^a linking group having the same meaning as L ^a . However, ne is 1 or more. When nd and ne are 2 or more, R ^d and R ^e may be the same as or different from each other.

  Although the compounding quantity of the said cyclic functional group containing isocyanurate compound is not specifically limited, It is preferable that it is 0.1 mass% or more, and it is more preferable that it is 0.5 mass% or more. As an upper limit, it is preferable that it is 10 mass% or less, and it is more preferable that it is 7.0 mass% or less. When defined with respect to 100 parts by mass of the isocyanurate compound, it is preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more. As an upper limit, it is preferable that it is 10 mass parts or less, and it is more preferable that it is 7.0 mass parts or less. By making this compounding quantity more than the said lower limit, the adhesiveness of a package base material (reflector package resin and (noble) metal electrode), especially reflector package resin can be improved, which is preferable. On the other hand, it is preferable that the amount is not more than the above upper limit value because it is possible to minimize a decrease in curability, transparency after curing, and heat-resistant colorability.

  The acid value of the sealant of the present invention is preferably 0.10 mgKOH / g or less, more preferably 0.05 mgKOH / g or less, and particularly preferably 0.02 mgKOH / g or less. It is preferable that the heat resistance colorability is further improved by setting the amount to the upper limit or less. Although a lower limit is not specifically limited, It is practical that it is 0.001 mgKOH / g or more. The method for adjusting the acid value of the sealant is not particularly limited, but after mixing the adsorbent such as activated carbon and silica with the isocyanurate compound of the present invention and leaving it to stand, the adsorbent is removed by filtration. The acid value of the nurate compound can be lowered.

  In the present specification, when the term “compound” is added at the end, it is used to mean a salt and an ion in addition to the compound itself. Moreover, it is the meaning including the derivative modified with the predetermined form in the range with the desired effect. In addition, in the present specification, a substituent or a linking group for which substitution or non-substitution is not specified means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution. Preferred substituents include the following substituent T.

Examples of the substituent T include the following.
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl A group (preferably an alkenyl group having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.), A cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, Phenyl, 1-naphthyl, 4-methoxyphenyl, -Chlorophenyl, 3-methylphenyl, etc.), heterocyclic groups (preferably heterocyclic groups having 2 to 20 carbon atoms, such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2 -Oxazolyl etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, benzyloxy etc.), an aryloxy group (preferably an aryloxy group having 6 to 26 carbon atoms) , For example, phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), alkoxycarbonyl groups (preferably C2-C20 alkoxycarbonyl groups such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.) ), Amino group (preferably carbon Amino group having 0 to 20 children, such as amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfonamide group (preferably sulfonamide having 0 to 20 carbon atoms) A group such as N, N-dimethylsulfonamide, N-phenylsulfonamide, etc., an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms such as acetyloxy, benzoyloxy, etc.), a carbamoyl group (preferably A carbamoyl group having 1 to 20 carbon atoms, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), an acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino, benzoylamino, etc.) , A cyano group, a hydroxyl group, or a halogen atom (for example, a fluorine atom, A chlorine atom, a bromine atom, an iodine atom, etc., more preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an amino group, an acylamino group, a cyano group, or a halogen An atom, particularly preferably an alkyl group, an alkenyl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group, or a cyano group.

  The specific isocyanurate compound may be synthesized by a conventional method, and the synthesis method is not particularly limited. For information on such commercial products, reference can be made to, for example, Japanese Patent Application Laid-Open No. 2003-213159.

[Polymerization initiator]
The sealing agent of the present invention preferably contains a polymerization initiator.
Among these, a radical polymerization initiator is added.
Examples of thermal radical polymerization initiators that generate initiation radicals by cleavage by heat include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1 Hydroperoxides such as 1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide and t-butyl hydroperoxide; diisobutyryl peroxide, bis-3,5,5-trimethylhexanol peroxide, lauroyl peroxide Diacyl peroxides such as oxide, benzoyl peroxide and m-toluyl benzoyl peroxide; dicumyl peroxide, 2, 5 Dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) hexane, t-butylcumyl peroxide, di-t-butyl peroxide and 2,5-dimethyl- Dialkyl peroxides such as 2,5-di (t-butylperoxy) hexene; 1,1-di (t-butylperoxy-3,5,5-trimethyl) cyclohexane, 1,1-di-t-butylperoxy Peroxyketals such as cyclohexane and 2,2-di (t-butylperoxy) butane; 1,1,3,3-tetramethylbutylperoxyneodicarbonate, α-cumylperoxyneodicarbonate, t-butylperoxyneodicarbonate , T-hexylperoxypivalate, t-butylperoxypivalate 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butyl Peroxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, 1,1,3,3-tetramethylbutylperoxy-3,5,5-trimethylhexanate, t-amylperoxy-3,5,5-trimethyl Alkyl peresters such as hexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate and dibutylperoxytrimethyladipate; di-3-methoxybutylperoxy Dicarbonate, di-2-ethylhexyl Ruperoxydicarbonate, bis (1,1-butylcyclohexaoxydicarbonate), diisopropyloxydicarbonate, t-amyl peroxyisopropyl carbonate, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate and 1, Peroxycarbonates such as 6-bis (t-butylperoxycarboxy) hexane; 1,1-bis (t-hexylperoxy) cyclohexane and (4-t-butylcyclohexyl) peroxydicarbonate.
Specific examples of the azo compound used as an azo-based (AIBN or the like) polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2, 2'-azobis (2,4-dimethylvaleronitrile), 1,1'-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyano Valeric acid, 2,2′-azobis- (2-amidinopropane) dihydrochloride and the like can be mentioned (see JP 2010-189471 A).

As the radical polymerization initiator, in addition to the thermal radical polymerization initiator, a radical polymerization initiator that generates an initiation radical by light, electron beam, or radiation can be used.
Examples of such radical polymerization initiators include benzoin ether, 2,2-dimethoxy-1,2-diphenylethane-1-one [IRGACURE651, manufactured by Ciba Specialty Chemicals Co., Ltd.], 1-hydroxy-cyclohexyl. -Phenyl-ketone [IRGACURE184, manufactured by Ciba Specialty Chemicals Co., Ltd., trademark], 2-hydroxy-2-methyl-1-phenyl-propan-1-one [DAROCUR1173, manufactured by Ciba Specialty Chemicals Co., Ltd., Trademarks], 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one [IRGACURE2959, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.], 2 -Hydroxy-1- [4- [4- (2-H Roxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one [IRGACURE127, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.], 2-methyl-1- (4-methylthiophenyl) ) -2-morpholinopropan-1-one [IRGACURE907, manufactured by Ciba Specialty Chemicals, Inc.], 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 [ IRGACURE 369, manufactured by Ciba Specialty Chemicals, Inc., trademark], 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-monophorinyl) phenyl] -1-butanone [IRGACURE 379, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.] 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [DAROCUR TPO, manufactured by Ciba Specialty Chemicals, Inc.], bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide [IRGACURE819, Ciba Specialty Chemicals, Inc., Trademark], bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) Titanium [IRGACURE784, trade name, manufactured by Ciba Specialty Chemicals, Inc.], 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] [IRGACURE OXE 01, Ciba Specialty Chemicals Co., Ltd., Trademark], D Non, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) [IRGACURE OXE 02, manufactured by Ciba Specialty Chemicals Co., Ltd. , Trademark] and the like.
These radical polymerization initiators can be used singly or in combination of two or more.
Among them, a peroxide compound is preferable, and perbutyl O (t-butylperoxy-2-ethylhexanoate, manufactured by NOF Corporation) and the like can be used.
The content of the polymerization initiator is preferably applied in the amount described above.

  The amount of the polymerization initiator is not particularly limited, but is preferably 0.1 parts by mass or more and 5 parts by mass or less, and 0.5 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the organic curing component. More preferably. By setting it to the above lower limit or more, the polymerization reaction can be favorably started. On the other hand, by setting it to the upper limit value or less, it is preferable because the excellent effect of the sealant due to the application of the specific isocyanurate compound can be sufficiently obtained.

[Polymerization inhibitor]
A polymerization inhibitor may be added to the sealant of the present invention. Examples of the polymerization inhibitor include phenols such as hydroquinone, tert-butylhydroquinone, catechol, and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines; copper and the like.
The content of the polymerization inhibitor is not particularly limited, but it is preferably 0 to 20000 ppm (parts by mass), preferably 100 to 10000 ppm, more preferably 300 to 8000 ppm based on 1 part of the organic curing component.

[Phosphor]
In this invention, it is preferable to mix | blend 1-40 mass parts of fluorescent substance with respect to 100 mass parts of organic hardening components of sealing agent, It is more preferable that they are 2 mass parts or more and 30 mass parts or less, 5 masses It is particularly preferred that the amount is not less than 20 parts by mass. The phosphor is not particularly limited as long as it absorbs light from the semiconductor light emitting element and emits fluorescence to convert the wavelength, and is a nitride-based phosphor mainly activated by a lanthanoid-based element such as Eu or Ce. Oxynitride phosphors, lanthanoids such as Eu, alkaline earth halogen apatite phosphors activated mainly by transition metal elements such as Mn, alkaline earth metal borate halogen phosphors, alkaline earth metals Lanthanoid elements such as aluminate phosphor, alkaline earth silicate phosphor, alkaline earth sulfide phosphor, alkaline earth thiogallate phosphor, alkaline earth silicon nitride phosphor, germanate phosphor, Ce Selected from rare earth aluminate phosphors, rare earth silicate phosphors, or organic or organic complexes mainly activated by lanthanoid elements such as Eu It is preferred that at least 1 or more. More preferably, (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Ca, Sr, Ba) ₂ SiO ₄ : Eu, (Ca, Sr) ₂ Si ₅ N ₈ : Eu, CaAlSiN ₃ : Eu or the like is used.

[Antioxidant]
The sealant of the present invention preferably contains an antioxidant as necessary. Examples of antioxidants include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, thioether antioxidants, vitamin antioxidants, lactone antioxidants, and amine antioxidants. .

  Examples of phenolic antioxidants include Irganox 1010 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Irganox 1076 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Irganox 1330 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Trademark), Irganox 3114 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Irganox 3125 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), ADK STAB AO-20 (ADEKA Corporation, Trademark), ADK STAB AO-50 ( ADEKA Corporation (trademark), ADK STAB AO-60 (ADEKA Corporation), ADK STAB AO-80 (ADEKA Corporation), ADK STAB AO-30 (ADEKA Corporation), Adeka Stub AO-40 (ADEKA, Inc., trademark), BHT (produced by Takeda Pharmaceutical Co., Ltd., trademark), Cyanox 1790 (produced by Cyanamid Co., Ltd.), Sumizer GP (produced by Sumitomo Chemical Co., Ltd., trademark), Sumizer GM (Sumitomo Chemical) Commercial products such as (trademark), Sumilizer GS (trademark, manufactured by Sumitomo Chemical Co., Ltd.), and Sumitizer GA-80 (trademark, manufactured by Sumitomo Chemical Co., Ltd.) can be given.

  Examples of phosphorus compounds include IRAGAFOS 168 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), IRAGAFOS 12 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), IRAGAFOS 38 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), IRAGAFOS P-EPQ (trade name, manufactured by Ciba Specialty Chemicals), IRAGAFOS 126 (trade name, manufactured by Ciba Specialty Chemicals), ADKSTAB 329K (ADEKA, trademark), ADKSTAP PEP-36 (trade name) ADEKA, trademark), ADKSTAP PEP-8 (ADEKA, trademark), ADKSTAB HP-10 (ADEKA, trademark), ADKSTAB 2112 (ADEKA, trademark), DKSTAB 260 (ADEKA Corporation, trademark), ADKSTAB 522A (ADEKA Corporation, trademark), Weston 618 (GE Corporation, trademark), Weston 619G (GE Corporation, trademark), and Weston 624 (GE Corporation, trademark) And other commercial products.

  Examples of sulfur-based antioxidants include DSTP (Yoshitomi) (trademark), DLTP (Yoshitomi) (trademark, produced by Yoshitomi Corporation), DLTOIB (trademark, produced by Yoshitomi Corporation), DMTP (Yoshitomi). ) [Trademark] made by Yoshitomi Co., Ltd., Seenox 412S [trademark made by Sipro Kasei Co., Ltd.], Cyanox 1212 (trademark made by Cyanamid Co., Ltd.) and TP-D, TPS, TPM, TPL-R [Sumitomo Chemical Co., Ltd. ), Trade name, etc.). Examples of vitamin-based antioxidants include tocopherol (trade name, manufactured by Eisai Co., Ltd.) and Irganox E201 (trade name, compound name: 2,5,7,8-tetramethyl-2 (4, manufactured by Ciba Specialty Chemicals Co., Ltd.). Commercial products such as ', 8', 12'-trimethyltridecyl) coumarone-6-ol].

  Examples of the thioether-based antioxidant include commercial products such as ADK STAB AO-412S (trademark manufactured by ADEKA Corporation) and ADK STAB AO-503 (trademark manufactured by ADEKA Corporation). As the lactone antioxidant, those described in JP-A-7-233160 and JP-A-7-247278 can be used. Moreover, HP-136 [Ciba Specialty Chemicals Co., Ltd., trademark, compound name; 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one] And other commercial products.

  Examples of amine-based antioxidants include commercially available products such as Irgastab FS042 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) and GENOX EP (trade name, compound name; dialkyl-N-methylamine oxide, manufactured by Crompton). Can do. These antioxidants can be used singly or in combination of two or more.

  Content of antioxidant is 0.01-10 mass normally with respect to 100 mass parts of total amounts of the said organic hardening component from a viewpoint of suppressing transparency of sealing agent (resin material) and the fall of yellowing. Parts, preferably 0.01 to 5 parts by mass, more preferably 0.02 to 2 parts by mass.

[Light stabilizers, etc.]
In addition to the above antioxidant, the sealant of the present invention includes a lubricant, a light stabilizer, an ultraviolet absorber, a plasticizer, an antistatic agent, an inorganic filler, a colorant, and an antistatic agent as necessary. , Mold release agents, flame retardants, components for the purpose of improving adhesion with inorganic compounds such as titanium oxide and silicon oxide, and the like can be blended. As the lubricant, higher dicarboxylic acid metal salts, higher carboxylic acid esters, and the like can be used.

  Any known light stabilizer can be used, but a hindered amine light stabilizer is preferred. Specific examples of the hindered amine light stabilizer include ADKSTAB LA-77, LA-57, LA-52, LA-62, LA-67, LA-68, LA-63, and LA-94. LA-94, LA-82 and LA-87 (above, manufactured by ADEKA Corporation), Tinuvin 123, 144, 440 and 662, Chimassorb 2020, 119, 944 (above, manufactured by CSC), Examples include Hostavin N30 (manufactured by Hoechst), Cyasorb UV-3346, UV-3526 (manufactured by Cytec), Uval 299 (GLC), and SanduvorPR-31 (Clariant). These light stabilizers can be used singly or in combination of two or more.

The usage-amount of a light stabilizer is 0.005-5 mass parts normally with respect to 100 mass parts of total amounts of the said organic hardening component, Preferably it is 0.02-2 mass parts.
Examples of the component for improving the adhesion with inorganic compounds such as titanium oxide and silicon oxide include silane coupling agents containing a methacryloxy group or an acryloxy group of the silane compound. This may be contained in the sealing agent, and polymerized and molded.

[Semiconductor light-emitting device]
(Sealing method)
As a sealing method of the sealing agent, a method usually used for sealing a semiconductor light emitting element or a method similar to a general thermosetting resin molding can be used. Examples thereof include potting (dispensing), printing, coating, injection molding, compression molding, transfer molding, and insert molding. Potting represents an operation of discharging the sealing agent into a cavity (concave space) of the package to fill the interior. In addition, printing represents an operation of disposing a sealant at a target site using a mask, and a so-called vacuum printing method in which the surrounding pressure is reduced according to the purpose can be employed. Various types of coating methods can be used for coating. For example, a method of preparing a weir called a dam material for holding a sealing agent in advance and coating the sealing agent on the inside thereof can also be used. Moreover, in various mold shaping | molding, the method of filling the sealing agent inside a mold and thermosetting as it is is mentioned. Further, curing after sealing can be performed by heat curing, UV curing, or a combination thereof.
The semiconductor light-emitting device in preferable embodiment of this invention comprises the sealing material produced by hardening said sealing agent. As a curing method, a method similar to the molding of a normal thermosetting resin can be used. For example, the above-mentioned sealing agent (raw material composition) or a prepolymer thereof may be used for polymerization / molding by injection molding, compression molding, transfer molding or insert molding of these liquid resins. Moreover, a molded object can also be obtained by a potting process or a coating process. Furthermore, a molded body can be obtained by a method similar to the molding of a photo-curing resin such as UV curing molding.

  It is preferable that the semiconductor light-emitting device or its member of this embodiment is manufactured by a liquid resin molding method. Liquid resin molding methods include liquid resin injection molding in which a liquid sealant or a prepolymer thereof is injected into a high-temperature mold and cured by heating, and a liquid sealant is placed in a mold and pressed by a press. Examples thereof include compression molding for pressing and curing, transfer molding for curing the sealant by applying pressure to a heated liquid sealant and press-fitting it into a mold.

Since the sealing agent of the present invention has appropriate fluidity or viscosity as described above, it is preferably used for potting.
Here, the potting will be described. Potting represents an operation of discharging the sealing liquid into the cavity (concave space) W (FIG. 1) of the reflector package base material to fill the interior. The curing process can be performed by placing a reflector package filled with sealing liquid after potting (a package containing a reflector package substrate, as well as a device, bonding wires, and electrodes) in a general heating device such as an oven. Requires only a very simple configuration with only a dispenser and a heating device. In addition, since a mold and a mask are not required, it is possible to deal with a change in the shape of the device quickly and inexpensively, which can be said to be a highly versatile sealing method. Furthermore, in mold molding methods such as compression mold molding and transfer mold molding, there are problems such as poor mold releasability, high disposal rate of sealing liquid, and restriction of viscosity. there is no problem.

  Examples of the liquid discharging method include a screw-type mechanical dispensing method, an air pulse type dispensing method, a non-contact jet dispensing method, and the like. As the dispenser which is a potting device, specifically, for example, devices provided by Musashi Engineering Co., Sanei Tech Co., etc. are used.

  The sealing liquid that can be used for potting needs to be liquid at room temperature, and it is preferable to use a liquid having a viscosity of about 1 mPa · s to 1000 Pa · s.

(Semiconductor light emitting device)
As the semiconductor light emitting element, a blue light emitting LED chip made of a gallium nitride (GaN) based semiconductor, an ultraviolet light emitting LED chip, a laser diode, or the like is used. In addition, for example, a substrate in which a nitride semiconductor such as InN, AlN, InGaN, AlGaN, InGaAlN or the like is formed as a light emitting layer on a substrate by MOCVD or the like can be used. Either a semiconductor light-emitting element that is mounted face-up or a semiconductor light-emitting element that is flip-chip mounted can be used. The semiconductor light emitting device is an example of a semiconductor light emitting device having an n-side electrode and a p-side electrode on the same plane, but a semiconductor light-emitting device having an n-side electrode on one surface and a p-side electrode on the opposite surface is also used. be able to.

(package)
As the package, a package in which electrodes are integrally formed, and a package in which electrodes are provided as circuit wiring by plating after the package is molded can be used. As the shape of the package, any shape such as a cylinder, an elliptical column, a cube, a rectangular parallelepiped, a shape between a rectangular parallelepiped and an elliptical column, or a combination thereof can be adopted. As the shape of the inner wall portion, an arbitrary angle can be selected with respect to the bottom portion, and a box shape that is perpendicular to the bottom surface or a mortar shape that is obtuse can be selected. As the shape of the bottom of the concave portion, any shape such as a flat shape or a concave shape can be selected. Moreover, a package corresponding to an arbitrary mounting method such as a top view or a side view can be used as a mounting method.
As a material constituting the package, an electrically insulating material excellent in light resistance and heat resistance is suitably used. For example, a thermoplastic resin such as polyphthalamide (PPA), a thermosetting resin such as an epoxy resin, Glass epoxy, ceramics, etc. can be used. Moreover, in order to reflect the light from a semiconductor light emitting element efficiently, white pigments, such as a titanium oxide, can be mixed with these resins. As a method for molding the package, insert molding, injection molding, extrusion molding, transfer molding, or the like performed by previously setting the electrode in a mold can be used.

(electrode)
The electrode is electrically connected to the semiconductor light emitting element, and may be, for example, a plate-like electrode inserted into a package or a conductive pattern formed on a substrate such as glass epoxy or ceramic. As the material of the electrode, there can be used silver or an alloy containing silver, or a material in which silver or an alloy containing silver is plated on a part of an electrode containing copper or iron as a main component.

(Evaluation method)
The semiconductor light emitting device can be evaluated by a conventional test method. For example, electrical characteristics, optical characteristics, temperature characteristics, thermal characteristics, lifetime, reliability, safety, and the like can be given. As a technique, for example, the technique and standard described in pages 71 to 84 of Chapter 2 of the book “LED Lighting Handbook, LED Lighting Promotion Council Edition” published by Ohm Co., Ltd. can be adopted.

(Use)
The semiconductor light-emitting device can be used for various applications that require maintenance of luminous intensity, for example, a backlight of a liquid crystal display, a mobile phone or an information terminal, an LED display, a flashlight, and indoor / outdoor lighting.

  The composition containing the isocyanurate compound represented by the following formula (1) and a disulfide compound containing a disulfide group and an alkoxysilyl group according to the present invention is also applicable to other than the encapsulant for semiconductor light emitting devices described herein. Has utility. For example, it can be suitably used for a hard coat layer for preventing discoloration of noble metal plating due to corrosive gas.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is limited and interpreted by the following examples.

Compounds M-1 to M-3
Aronix M-215 (trade name, manufactured by Toagosei Co., Ltd.) was purified by column chromatography to obtain Compound M-1, Compound M-2, and Compound M-3, respectively.

Compound M-4
Aronix M-215 (manufactured by Toagosei Co., Ltd.) 80.0 g and triethylamine 51.4 g were dissolved in tetrahydrofuran 1000.0 g. The reaction solution was ice-cooled, and 46.0 g of cyclohexane acid chloride was added dropwise while maintaining the temperature at 10 ° C. or lower. After returning to room temperature, the mixture was stirred for 2 hours. To the reaction solution was added aqueous sodium hydrogen carbonate solution, and the mixture was extracted with ethyl acetate. The organic layer was collected, MgSO ₄ was added, filtered and concentrated, and the concentrate was purified by column chromatography to obtain 24.5 g of Compound M-4.

Compound S-1
7.50 g of 2,2′-dipyridyl disulfide was dissolved in 90 mL of methylene chloride. While maintaining the reaction solution at 30 ° C. or lower, 13.35 g of 3-mercaptopropyltrimethoxysilane was added dropwise and stirred for 72 hours. Subsequently, the reaction solution was concentrated and filtered, and then 200 mL of hexane and 30 g of activated carbon were added to the filtrate and allowed to stand for 2 hours. After removing activated carbon by filtration, the filtrate was concentrated to obtain 5.2 g of Compound S-1.

Compound S-2
6.93 g of 2,2′-dipyridyl disulfide was dissolved in 90 mL of methylene chloride. While maintaining the reaction solution at 30 ° C. or lower, 15.00 g of 3-mercaptopropyltriethoxysilane was added dropwise and stirred for 72 hours. Subsequently, the reaction solution was concentrated and filtered, and then 200 mL of hexane and 30 g of activated carbon were added to the filtrate and allowed to stand for 2 hours. After removing activated carbon by filtration, 9.0 g of compound S-2 was obtained by concentrating the filtrate.

Compound S-3
7.50 g of 2,2′-dipyridyl disulfide was dissolved in 90 mL of methylene chloride. While maintaining the reaction solution at 30 ° C. or lower, 13.35 g of 3-mercaptopropyl (dimethoxy) methylsilane was added dropwise and stirred for 72 hours. Subsequently, the reaction solution was concentrated and filtered, and then 200 mL of hexane and 30 g of activated carbon were added to the filtrate and allowed to stand for 2 hours. After removing activated carbon by filtration, the filtrate was concentrated to obtain 5.4 g of Compound S-3.

Compound P-1
Monoallyl diglycidyl isocyanurate (manufactured by Shikoku Kasei Co., Ltd.) 55 g and platinum vinylsiloxane complex 0.55 mg were dissolved in 400 mL of toluene. While maintaining the reaction solution at 70 ° C., a solution consisting of 36 g of trimethoxysilane and 150 mL of toluene was added dropwise and stirred for 6 hours. The reaction solution was cooled to room temperature and concentrated to obtain 72 g of Compound P-1.

Compound P-2
55 g of diallyl monoglycidyl isocyanurate (manufactured by Shikoku Chemicals) and 0.55 mg of platinum vinylsiloxane complex were dissolved in 400 mL of toluene. While maintaining the reaction solution at 70 ° C., a solution consisting of 64 g of trimethoxysilane and 150 mL of toluene was added dropwise and stirred for 6 hours. The reaction solution was cooled to room temperature and concentrated to obtain 88 g of Compound P-2.

Compound Crypt-1
Dicyclopentanyl methacrylate (trade name: FA-513M) manufactured by Hitachi Chemical Co., Ltd. was used.

Compound 2,2′-azobisisobutyronitrile 2,2′-azobisisobutyronitrile (trade name: V-60) manufactured by Wako Pure Chemical Industries, Ltd. was used.

<150 ° C heat resistance>
The curable resin composition shown in Table 1 was converted into a PPA resin package (trade name: FLASH LED 6PIN BASE (circular package for top view), manufactured by Enomoto Co., Ltd.) ([cavity size: depth 0.65 mm, After potting and sealing an LED package having a width of 4.4 mm and a diameter of 4.4 mm]), heat was applied at 70 ° C. for 30 minutes, 130 ° C. for 30 minutes, and 150 ° C. for 5 hours in the atmosphere, and after thermosetting, An LED package sealed with the curable resin composition was placed in a reflow furnace equipped with an IR heater, and a light emitting diode for evaluation was produced by performing heat treatment at 260 ° C. for 30 seconds three times. Next, by using the external quantum efficiency measuring device C9920-12 manufactured by Hamamatsu Photonics, the emission spectrum of the light emitting diode for evaluation when a constant current of 1 mA was injected at room temperature was measured, and the emission amount at 450 nm was analyzed. The initial light emission amount was measured. (Because this apparatus measures with an integrating sphere, the amount of light emitted does not depend on the angle of light emission can be measured.) Next, after leaving this evaluation sample at a high temperature of 150 ° C. for 300 hours, using HAMAMATSU external quantum efficiency measuring apparatus C9920-12, by measuring the emission spectrum of the evaluation light emitting diode when injected with a constant current of 1mA at room temperature, to analyze the light emission amount at 450 nm, 0.99 The amount of luminescence was measured after aging at 0 ° C.
The amount of luminescence after aging at 150 ° C./initial luminescence amount × 100 = 150 ° C. heat resistance, and ranking was performed according to the following criteria.
A: 150 ° C. heat resistance is 80 or more A: 150 ° C. heat resistance is 75 or more and less than 80 B: 150 ° C. heat resistance is 65 or more and less than 75 C: 150 ° C. heat resistance is less than 65

<Gas barrier properties>
Curable resin composition shown in Table 1, silver package (trade name: KD-LA9R48 (circular package for top view), manufactured by Kyocera Corporation) [cavity size: depth 0.55 mm, diameter 3.04 mm] After potting and sealing the LED package, heat is applied at 70 ° C. for 30 minutes, 130 ° C. for 30 minutes, and 150 ° C. for 5 hours in the atmosphere, and after thermosetting, the semiconductor light emitting device is sealed in a reflow furnace equipped with an IR heater. An LED package sealed with an agent was placed, and a heat treatment at 260 ° C. for 30 seconds was performed three times to produce a light emitting diode for evaluation. Next, a sealed can of about 23 cm × 16 cm × 23 cm was prepared, and five small petri dishes made of PFA each having 0.5 g of sulfur powder placed on the bottom thereof were evenly arranged. A mesh plate with legs attached thereto so that a distance of about 10 cm was left on the plate. The light emitting diodes for evaluation were arranged in such a way that n = 3 so that the package could look downward from the gap of the mesh, and the sealed can was covered in that state. The sealed can was placed in an oven set at 80 ° in advance and allowed to react for 15 hours. At this time, by heating the sulfur powder, a compound in which sulfur atoms are connected is released in a gaseous state. When this sulfur gas permeates the sealing material, the silver of the reflector is sulfided and turned black, and the amount of light emission is reduced. The rate of decrease in luminescence amount = an index of discoloration resistance, and ranking was performed according to the following criteria.
AA: Reduction rate is less than 10% A: Reduction rate is 10% or more and less than 15% B: Reduction rate is 15% or more and less than 30% C: Reduction rate is 30% or more

<Reflow adhesion>
After potting and sealing the curable resin composition shown in Table 1 to an LED package having the PPA resin package (trade name: SMD5050N-TA112, manufactured by I-CHIUN) shown in FIG. The composition was thermally cured by applying heat at 130 ° C. for 30 minutes and 150 ° C. for 5 hours. Next, the LED package sealed with the curable resin composition was allowed to stand in a constant temperature and humidity oven maintained at 30 ° C. and 60% RH for 192 hours to absorb moisture, thereby producing a reflow adhesion evaluation light emitting diode. The LED package made to absorb moisture was put into a reflow furnace equipped with an IR heater, and heat treatment at 260 ° C. for 30 seconds was performed three times. The number of evaluations is 50,
Number of peeled PPA resin / encapsulant after reflow treatment = reflow adhesion (PPA), number of Ag plating / separation occurred after reflow treatment = reflow adhesion (Ag plating), Ranking was done.
In the evaluation of peeling, AA: the number of peeling is 0 A: the number of peeling is 1 or more and less than 5 B: the number of peeling is 5 or more and less than 10 C: the number of peeling is 10 or more

Ｍｅ：メチル基
Ｅｔ：エチル基

Me: methyl group Et: ethyl group

c02: Shin-Etsu Silicone KER2500 (trade name)
c03: Shin-Etsu Silicone KER6110 (trade name)
c04: Shin-Etsu Silicone SCR1011 (trade name)
(All are silicone resins)

  From the results shown in Table 1, the encapsulant of the present invention containing the specific isocyanurate compound and the specific disulfide compound as compared with the comparative example is resistant to heat when used as the encapsulant that encapsulates the semiconductor light emitting device. It can be seen that the gas barrier property is realized at a high level. Moreover, also about reflow adhesiveness, it turns out that favorable performance is exhibited with respect to both a resin (PPA) site | part and a metal (Ag) plating part. In Test 101, when S-1 was 0 parts by mass, the adhesion (particularly silver plating) was lower.

1 Semiconductor Light Emitting Element (Semiconductor Light Emitting Element)
2 Reflector Package Base 3 Sealing Material 4 Electrode 6 Bonding Wire 8 Conductive Adhesive 10 Semiconductor Light-Emitting Device (Semiconductor Light Emitting Device)

Claims (9)

The sealing agent for semiconductor light-emitting devices containing the isocyanurate compound represented by following formula ( 2 ) and the disulfide compound containing a disulfide group and an alkoxy silyl group.

(In the formula, R ⁴ , R ⁵ and R ⁶ are each independently a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, or a carbon number. aryl group of 6 to 24, .L ^a representative of the acyloxy group represented by acryloyloxy group represented by the following formula (I), or formula (II) represents an alkylene group having 1 to 4 carbon atoms. However , R ⁴ , R ⁵ , and R ⁶ are the acryloyloxy group.)

(In the formula, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. * Represents a bond.)

(In the formula, R ⁸ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms. * Represents a bond.) The encapsulant for a semiconductor light-emitting device according to claim 1, wherein the disulfide compound is a compound represented by the following formula (3).

(L ¹ and L ² are each a linking group. Rd and Rf each represents an alkyl group. Re and Rg each represents an alkoxy group. Nd to ng represent an integer of 0 or more and 3 or less, provided that ne, (At least one of ng is equal to or greater than 1. nd + ne = 3 and nc + ng = 3.) Including in organic cure component in the sealing agent 80 mass% or more of the isocyanurate compound, and wherein said disulfide compound in claim 1 or 2 comprising 0.01 to 20 parts by weight based on the isocyanurate compound 100 parts by weight The sealing agent for semiconductor light-emitting devices. The encapsulant for a semiconductor light-emitting device according to any one of claims 1 to 3 , wherein the isocyanurate compound includes at least one hydroxyl group-containing isocyanurate compound represented by the following formula (4).

(R ⁹ is a hydrogen atom or a methyl group. R ¹⁰ is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, an acryloyloxy group represented by the formula (I), And any one of acyloxy groups represented by formula (II).) Furthermore, 0.1-10 mass parts of cyclic functional group containing isocyanurate compounds represented by following formula (5) are contained to 100 mass parts of said isocyanurate compounds, The any one of Claims 1-4 . Sealant for semiconductor light emitting device.

^{(Wherein, R 11, R 12, R} 13 is a substituent. ^However, at least one of R 11 ^{to R 13} includes an annular functional group and at least one of ^R 11 ^{to R 13} is hydro (Including degradable alkoxysilyl groups) Furthermore, the sealing agent for semiconductor light-emitting devices of any one of Claims 1-5 formed by mix | blending 1-40 mass parts of fluorescent substance with respect to 100 mass parts of organic hardening components of sealing agent. The sealing material for semiconductor light-emitting devices formed by hardening | curing the sealing agent for semiconductor light-emitting devices of any one of Claims 1-6 . A semiconductor light emitting device comprising the sealing material according to claim 7 and a semiconductor light emitting element sealed with the sealing material. A composition comprising an isocyanurate compound represented by the following formula ( 2 ) and a disulfide compound comprising a disulfide group and an alkoxysilyl group.

(In the formula, R ⁴ , R ⁵ and R ⁶ are each independently a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, or a carbon number. aryl group of 6 to 24, .L ^a representative of the acyloxy group represented by acryloyloxy group represented by the following formula (I), or formula (II) represents an alkylene group having 1 to 4 carbon atoms. However , R ⁴ , R ⁵ , and R ⁶ are the acryloyloxy group.)

(In the formula, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. * Represents a bond.)

(In the formula, R ⁸ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms. * Represents a bond.)

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