JP2013082648A - Method for producing sealant for semiconductor light-emitting device and method for refining isocyanurate compound, sealant for semiconductor light-emitting device prepared by using the same, and seal material for semiconductor light-emitting device using the same and semiconductor light-emitting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for refining isocyanurate compound capable of efficiently enhancing the concentration of a bifunctional isocyanurate compound useful as a sealant for a semiconductor light-emitting device in particular, to be independent of a complicated operation or time-consuming treatment, and to provide a method for producing sealant for the semiconductor light-emitting device using the method for refining isocyanurate compound, and also to provide a sealant for the semiconductor light-emitting device, a seal material for light semiconductor, and a light semiconductor element.SOLUTION: The method for producing the sealant for semiconductor light-emitting device containing isocyanurate compound includes treatment which enhances the mixing ratio of the compound represented by formula (II) for a raw material mixture containing a compound represented by the formula (II), a compound represented by formula (I) and a compound represented by formula (III) by undergoing at least a specific extraction process.

Description

  The present invention relates to a method for producing a sealing agent for a semiconductor light-emitting device, a method for purifying an isocyanurate compound, a sealing agent for a semiconductor light-emitting device prepared using the same, a sealing material for a semiconductor light-emitting device using the same, and a semiconductor light-emitting device About.

  Semiconductor light-emitting devices are expected as next-generation light sources to replace incandescent lamps and fluorescent lamps, and technological developments such as improving luminous efficiency 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 due to increasing awareness of energy saving, and companies and research institutions are accelerating technological development of semiconductor light-emitting devices.

  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 cavity (concave space) is sealed with a resin (sealing material) 3 such as epoxy resin or silicone. 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

Performance required for the sealing resin of the semiconductor light emitting device is cured while sealing the device in a minute space, and in addition to transparency, there are heat resistance coloring property, heat shock resistance (crack resistance) and the like. Satisfying these characteristics at the same time is a unique requirement for this application, and it is not easy to find one that can be diverted even when other product fields are included.
Based on the recognition of the above problems, the present inventors have searched for a material suitable for a sealant for a semiconductor light emitting device in various substances and blends. As a result, it was felt that a specific isocyanurate compound having a functional group may satisfy the required characteristics. However, it has been found that satisfactory performance cannot be obtained by simply using any isocyanurate compound, and that the required characteristics can be achieved at a high level by using a specific formulation.

  On the other hand, it is not easy to mix isocyanurate compounds having different numbers of functional groups as represented by the following formulas (I), (II) and (III). For example, each compound is isolated and purified once by a column, It is necessary to mix again at a predetermined ratio. In view of manufacturing on an industrial scale, a simpler and more efficient preparation method was desired that was not practical.

  Therefore, the present invention efficiently increases the concentration of a bifunctional isocyanurate compound (see the following formula (II)) that is particularly useful as a sealing agent for semiconductor light-emitting devices, regardless of complicated operations and time-consuming treatments. An object of the present invention is to provide a method for purifying an isocyanurate compound, a method for producing a sealing agent for a semiconductor light emitting device, a sealing agent for a semiconductor light emitting device, a sealing material for a semiconductor light emitting device, and a semiconductor light emitting device. .

That is, the present invention provides the following means for solving the above-mentioned problems.
(1) A method for producing an optical semiconductor encapsulant containing an isocyanurate compound,
At least the following steps a to c with respect to a raw material mixture containing a compound represented by the following formula (I), a compound represented by the following formula (II), and a compound represented by the following formula (III) The manufacturing method of the sealing agent for semiconductor light-emitting devices including the process which raises the mixing ratio of the compound represented by said Formula (II) by passing through.
[A: A step of dissolving the raw material mixture in an organic solvent A having an SP value of 8.9 or less. ]
[B: The raw material mixture solution prepared in step a is brought into contact with an aqueous medium, and the compound represented by the formula (I) and the compound represented by the formula (II) are extracted from the aqueous medium phase. Process. ] [C: A step of bringing the aqueous medium phase of step b into contact with the organic solvent B having an SP value of 9.0 or more and extracting the compound represented by the formula (II) into the phase of the organic solvent B. ]

（Ｒはそれぞれ独立に水素原子、メチル基、フッ素原子、ＣＦ_３、又はヒドロキシメチル基を表す。）
（２）前記工程ａで用いる有機溶媒ＡがＳＰ値７．０以上８．９以下である（１）に記載の封止剤の製造方法。
（３）前記有機溶媒Ａが、トルエン、酢酸ブチル、及びヘキサンのいずれかである（１）又は（２）に記載の封止剤の製造方法。
（４）前記工程ｃで用いる有機溶媒ＢがＳＰ値９．０以上９．５以下である（１）〜（３）のいずれか１項に記載の封止剤の製造方法。
（５）前記有機溶媒Ｂが、酢酸エチル及びメチルエチルケトンのいずれかである（１）〜（４）のいずれか１項に記載の封止剤の製造方法。
（６）工程ｃを経た有機溶媒Ｂの相に含まれる前記式（ＩＩ）で表される化合物の混合比［ｒ^ｆ _II］が、前記式（Ｉ）で表される化合物と式（ＩＩ）で表される化合物と式（ＩＩＩ）で表される化合物との総量１００質量％に対し、６０質量％以上である（１）〜（５）のいずれか１項に記載の封止剤の製造方法。
（７）前記原料混合物に含まれる前記式（ＩＩ）で表される化合物の混合比［ｒ^ｉ _II］が、前記式（Ｉ）で表される化合物と式（ＩＩ）で表される化合物と式（ＩＩＩ）で表される化合物との総量１００質量％に対し、５５質量％以下である（１）〜（６）のいずれか１項に記載の封止剤の製造方法。
（８）前記式（Ｉ）で表される化合物と式（ＩＩ）で表される化合物と式（ＩＩＩ）で表される化合物との総量１００質量％に対する、前記式（ＩＩ）で表される化合物の混合比を、前記原料混合物に対して８０質量％以上高める（１）〜（７）のいずれか１項に記載の封止剤の製造方法。
（９）前記工程ｃで取得した抽出液を濃縮する、あるいは含有成分を粉末化する（１）〜（８）のいずれか１項に記載の封止剤の製造方法。
（１０）下記式（Ｉ）で表される化合物と、下記式（ＩＩ）で表される化合物と、下記式（ＩＩＩ）で表される化合物とを含有する原料混合物に対し、少なくとも下記ａ〜ｃの工程の処理を経ることにより、前記式（ＩＩ）で表される化合物の混合比を高めるイソシアヌレート化合物の精製方法。
［ａ：前記原料混合物をＳＰ値８．９以下の有機溶媒Ａに溶解させる工程。］
［ｂ：工程ａで調製した原料混合物の溶解液と水性媒体とを接触させ、前記水性媒体の相に前記式（Ｉ）で表される化合物及び前記式（ＩＩ）で表される化合物を抽出する工程。］［ｃ：工程ｂの水性媒体相とＳＰ値９．０以上の有機溶媒Ｂと接触させ、前記式（ＩＩ）で表される化合物を前記有機溶媒Ｂの相に抽出する工程。］

(R each independently represents a hydrogen atom, a methyl group, a fluorine atom, CF ₃ , or a hydroxymethyl group.)
(2) The method for producing a sealant according to (1), wherein the organic solvent A used in the step a has an SP value of 7.0 or more and 8.9 or less.
(3) The manufacturing method of the sealing agent as described in (1) or (2) whose said organic solvent A is either toluene, butyl acetate, and hexane.
(4) The manufacturing method of the sealing agent according to any one of (1) to (3), wherein the organic solvent B used in the step c has an SP value of 9.0 or more and 9.5 or less.
(5) The manufacturing method of the sealing agent according to any one of (1) to (4), wherein the organic solvent B is any one of ethyl acetate and methyl ethyl ketone.
(6) The mixing ratio [r ^f _II ] of the compound represented by the formula (II) contained in the phase of the organic solvent B that has undergone step c is the compound represented by the formula (I) and the formula (II). The production of the sealing agent according to any one of (1) to (5), which is 60% by mass or more with respect to 100% by mass of the total amount of the compound represented by formula (III) and the compound represented by formula (III). Method.
(7) The compound [R ⁱ _II ] of the compound represented by the formula (II) contained in the raw material mixture is a compound represented by the formula (I) and the compound represented by the formula (II) The manufacturing method of the sealing agent of any one of (1)-(6) which is 55 mass% or less with respect to 100 mass% of total amounts with the compound represented by Formula (III).
(8) Represented by the formula (II) with respect to a total amount of 100% by mass of the compound represented by the formula (I), the compound represented by the formula (II), and the compound represented by the formula (III) The manufacturing method of the sealing agent of any one of (1)-(7) which raises the mixing ratio of a compound 80 mass% or more with respect to the said raw material mixture.
(9) The method for producing a sealant according to any one of (1) to (8), wherein the extract obtained in the step c is concentrated or the contained components are pulverized.
(10) At least the following a to the raw material mixture containing a compound represented by the following formula (I), a compound represented by the following formula (II), and a compound represented by the following formula (III): A method for purifying an isocyanurate compound that increases the mixing ratio of the compound represented by the formula (II) through the treatment in the step c.
[A: A step of dissolving the raw material mixture in an organic solvent A having an SP value of 8.9 or less. ]
[B: The raw material mixture solution prepared in step a is brought into contact with an aqueous medium, and the compound represented by the formula (I) and the compound represented by the formula (II) are extracted from the aqueous medium phase. Process. ] [C: A step of bringing the aqueous medium phase of step b into contact with the organic solvent B having an SP value of 9.0 or more and extracting the compound represented by the formula (II) into the phase of the organic solvent B. ]

（Ｒはそれぞれ独立に水素原子、メチル基、フッ素原子、ＣＦ_３、又はヒドロキシメチル基を表す。）
（１１）（１０）に記載の精製方法により混合比が高められた前記式（ＩＩ）で表される化合物を含む半導体発光装置用封止剤であって、前記式（Ｉ）で表される化合物と式（ＩＩ）で表される化合物と式（ＩＩＩ）で表される化合物との総量１００質量％に対し、前記式（ＩＩ）で表される化合物を混合比［ｒ^ｆ _II］６０質量％以上で含む半導体発光装置用封止剤。
（１２）（１１）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。（１３）（１２）に記載の封止材を具備する半導体発光装置。

(R each independently represents a hydrogen atom, a methyl group, a fluorine atom, CF ₃ , or a hydroxymethyl group.)
(11) A sealing agent for a semiconductor light-emitting device containing a compound represented by the formula (II) whose mixing ratio has been increased by the purification method according to (10), which is represented by the formula (I) With ^respect to the total amount of the compound, the compound represented by the formula (II) and the compound represented by the formula (III) of 100% by mass, the compound represented by the formula (II) is mixed at a mixing ratio [r ^f _II ] of 60 mass. The sealing agent for semiconductor light-emitting devices containing in% or more.
(12) A sealing material for a semiconductor light emitting device obtained by curing the sealing agent for a semiconductor light emitting device according to (11). (13) A semiconductor light emitting device comprising the sealing material according to (12).

In the present specification, unless otherwise specified, SP values are allan F.V. M.M. Barton “Solubility Parameters” Chemical Reviews, 1975, Vol. 75, no. The values listed in 6,731-753 are assumed. The SP value is shown with the unit omitted, but the unit is cal ^1/2 cm ^−3/2 .

According to the present invention, the concentration of a bifunctional isocyanurate compound (see the following formula (II)) that is particularly useful as a sealant for a semiconductor light-emitting device can be efficiently obtained regardless of complicated operations and time-consuming treatments. Can be increased.
Moreover, the sealing material for semiconductor light-emitting devices using the sealing agent containing the specific isocyanurate compound obtained by the above, and a semiconductor light-emitting device are the heat resistant coloring property, thermal shock resistance (crack-proof property) required for the application. ) Can be achieved at a high level.

It is sectional drawing which showed an example of the semiconductor light-emitting device typically. It is the flowchart which showed the operation procedure in an example of the manufacturing method of this invention.

  The purification method or the production method of the present invention comprises a step of dissolving a raw material mixture containing a specific isocyanurate compound in an organic solvent (step a), and at least two-stage extraction from which the mixing ratio of the isocyanurate compound bifunctional is increased. Comprising steps (steps b and c). Hereinafter, after explaining a specific isocyanurate compound, each of the above steps will be explained in detail.

[Specific isocyanurate compounds]
The raw material mixture used in the present invention includes a compound represented by the following formula (I), a compound represented by the following formula (II), and a compound represented by the following formula (III). In the present specification, each of these compounds and the compound represented by the following formula (IV) are collectively referred to as “specific isocyanurate compounds”.

R each independently represents a hydrogen atom, a methyl group, a fluorine atom, CF ₃ , or a hydroxymethyl group.

[Step a]
In step a, the raw material mixture containing the specific isocyanurate compound is dissolved in the organic solvent A. In the specific isocyanurate compound, the ratio of the compound of each formula is not particularly limited, but the mixing ratio [r ⁱ _II ] of the compound represented by the formula (II) contained in the raw material mixture is the formula (I). The total amount of the compound represented by the compound represented by formula (II) and the compound represented by formula (III) is 100% by mass, preferably 55% by mass or less, and 40% by mass or more and 50% by mass. The following is more preferable. Thus, the mixing ratio [r ⁱ _II] By the use of relatively low, the benefits of applying the present invention is relatively increased preferably.

  The organic solvent A has an SP value of 8.9 or less, preferably 7.0 or more and 8.9 or less, and more preferably 7.3 or more and 8.9 or less. Specific examples of the organic solvent A include toluene, butyl acetate, and hexane. The organic solvent A may be a solvent composed of one kind of compound or a mixed solvent of two or more kinds of compounds satisfying the above SP value.

  The ratio of the organic solvent A and the specific isocyanurate compound is not particularly limited, but the concentration of the specific isocyanurate compound is preferably in the range of 20 to 70% by mass. By setting it to such a concentration range, it is preferable that both the removal of the compound represented by the formula (III) and the extraction efficiency per time are compatible.

  The dissolution conditions in step a are not particularly limited, but can be performed at room temperature (about 28 ° C.) and can be uniformly dissolved using a normal stirring device or the like.

[Step b]
In step b, the solution of the raw material mixture prepared in step a is contacted with an aqueous medium, and the compound represented by formula (I) and the compound represented by formula (II) are extracted from the phase of the aqueous medium. (See FIG. 2).
Here, the aqueous medium refers to an aqueous solution in which water and a solute soluble in water are dissolved. Examples of the solute include alcohol compounds, ether compounds, ketone compounds, alkali metals or salts thereof, alkaline earth metals or salts thereof, organic acids or salts thereof, inorganic acids or salts thereof, and the like. Examples of the alcohol compound include methanol, ethanol, propanol, and butanol. Examples of the ether compound include dimethyl ether, diethyl ether, and methyl ethyl ether. Examples of the ketone compound include acetone, methyl ethyl ketone, and diethyl ketone. Examples of the alkali metal salt include potassium chloride, sodium chloride, sodium alkoxide and the like. Examples of the alkaline earth metal salt include calcium chloride, calcium carbonate, manesium chloride, magnesium carbonate and the like. Examples of the organic acid include acetic acid, propionic acid, succinic acid and the like. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid and the like. The counter ion when the acid forms a salt is not particularly limited, and may be the alkali metal ion, alkaline earth metal ion, organic amine compound ion, or the like.
Some ethers and the like have an SP value of 8.9 or less, but in this case, it is preferable to define that the aqueous medium does not contain this solute.

  The ratio of the solution of the raw material mixture to the aqueous medium is not particularly limited, but the aqueous medium is preferably 50 to 200 parts by mass, and 75 to 150 parts by mass with respect to 100 parts by mass of the solution. Is more preferable. By setting it to the above lower limit or more, emulsification at the time of mixing is avoided, which is preferable. On the other hand, by setting it to the upper limit value or less, it is preferable because both the extraction of the compound represented by the formula (II) and the extraction efficiency per time are compatible.

  Although the contact condition of the two liquids in the step b is not particularly limited, it can be performed at room temperature (about 28 ° C.), and can be mixed using a normal stirring device or the like.

  In the present embodiment, the liquid mixture that has been allowed to stand through the step b is separated into two phases, which can be separated into the organic solvent A phase and the aqueous medium phase, respectively. Separation can be performed using a liquid separator or the like that is usually used for this type of application. The phase of the separated aqueous medium mainly contains a compound represented by the formula (I) or (II), and the phase of the organic solvent A contains a compound represented by the formula (III) (FIG. 2). However, as long as the effect of the present invention is not impaired, the compound represented by the formula (III) is contained in the phase of the aqueous medium, or the phase of the organic solvent A is represented by the formula (I) or (II). The compound represented may be contained.

[Step c]
In step c, the aqueous medium phase in step b is brought into contact with organic solvent B having an SP value of 9.0 or more, and the compound represented by the formula (II) is extracted into the phase of organic solvent B. The organic solvent B used in step c preferably has an SP value of 9.0 or more and 13.0 or less, and more preferably 9.0 or more and 12.0 or less. Specific examples include ethyl acetate and methyl ethyl ketone. The organic solvent B may be a solvent composed of one kind of compound or a mixed solvent of two or more kinds of compounds satisfying the SP value.

  The ratio of the aqueous medium phase to the organic solvent B is not particularly limited, but the organic solvent B is preferably 50 to 200 parts by mass, and 75 to 150 parts by mass with respect to 100 parts by mass of the aqueous medium phase. More preferably. By setting it to the above lower limit or more, emulsification at the time of mixing is avoided, which is preferable. On the other hand, by setting it to the upper limit value or less, it is preferable because both the extraction of the compound represented by the formula (II) and the extraction efficiency per time are compatible.

  The contact condition of the two liquids in step c is not particularly limited, but it can be performed at room temperature (about 28 ° C.) and can be uniformly dissolved using a normal stirring device or the like.

  In the present embodiment, the liquid mixture that has been allowed to stand through the step c is separated into two phases, which can be separated into the organic solvent B phase and the aqueous medium phase, respectively. Separation can be performed using a liquid separator or the like that is usually used for this type of application. The phase of the separated aqueous medium mainly contains a compound represented by the formula (I), and the phase of the organic solvent A contains a compound represented by the formula (II) (see FIG. 2). However, as long as the effect of the present invention is not impaired, the compound represented by the formula (II) is contained in the phase of the aqueous medium, or the compound represented by the formula (I) in the phase of the organic solvent A. May be contained.

According to the present invention, the mixing ratio [r ^f _II ] of the compound represented by the formula (II) after the treatment with respect to the mixing ratio [r ⁱ _II ] of the compound represented by the formula (II) before the treatment. Can be increased. The range of increase in the mixing ratio depends on the initial mixing ratio, but is preferably 20 to 50 in the mixing ratio difference (Δ [r _II ] = [r ^f _II ] − [r ⁱ _II ]). More preferably, it is -50.
The mixing ratio [r ^f _II ] of the compound represented by the formula (II) after purification is not particularly limited, but is preferably 60% by mass or more, and more preferably 80% by mass or more.

  The amount of residual solvent at the time of concentration is preferably 15% by mass or more, more preferably 10% by mass or more, and most preferably 5% by mass or more with respect to the total mass. By controlling the amount of residual solvent in this way, it is possible to prevent bubbles from being mixed due to solvent volatilization during curing. Further, the concern when the amount of residual solvent is lowered is a decrease in operability due to an increase in viscosity. However, if the production method of this embodiment is used, it is finally compatible with the compound represented by the formula (II). A relatively low viscosity can be maintained since a solvent having a high viscosity remains.

[Component composition of sealant]
The sealant in a preferred embodiment of the present invention preferably uses a specific isocyanurate compound after the purification treatment. The sealant may be in any form such as powder, paste, dispersion, solution, and the like. In the present embodiment, when the sealant is used as a solution or dispersion, the concentration of the specific isocyanurate compound is more than 80% by mass, preferably 85% by mass or more, based on the total amount of the sealant, 90 More preferably, it is at least mass%. There is no particular upper limit, and it is particularly preferably about 100% by mass when excluding the polymerization initiator. However, this concentration means that when there is a compound represented by the following formula (IV), this is included. Here, substantially, the residual solvent such as toluene may be mixed at a rate of about 0 to 10% by mass, and such inevitable contaminants are included within a range that does not impair the effects of the present invention. It allows existence. Alternatively, when it is necessary to lower the viscosity of the sealant, a necessary amount of additive may be added. Moreover, although the sealing agent of this invention may contain arbitrary components, such as a postscript polymerization inhibitor, as needed in addition to an essential component, it is preferable to use 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 element, without solvent. In particular, it can effectively cope with molding by potting, and contributes to a significant improvement in production efficiency as compared with molding.

  It is preferable that the sealing agent of this embodiment has a polymerization initiator. The polymerization initiator is not particularly limited as long as it is usually applied to this type of polymerizable compound, and specific examples thereof will be described later. The amount of the polymerization initiator is not particularly limited, but is preferably 0.01% by mass or more and 0.5 or less, and more preferably 0.05% by mass or more and 0.2 or less. 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.

The specific isocyanurate compound is preferably contained in a specific ratio with respect to the compounds of the above formulas. Although depending on the mixing ratio of the product obtained by the purification treatment, considering the performance as a sealant, when the specific isocyanurate compound (I), (II), (III) is 100% by mass, the formula The compound represented by (I) is preferably 0 to 35% by mass, more preferably 0 to 25% by mass, and 0 to 15% by mass. Particularly preferred.
The compound represented by the formula (II) is preferably 65% by mass or more and 100% by mass or less, more preferably 75% by mass or more and 100% by mass or less, and 80% by mass or more and 100% by mass or less. Is particularly preferred.
The compound represented by the formula (III) is preferably 0% by mass or more and 25% by mass or less, more preferably 0% by mass or more and 25% by mass or less, and 0% by mass or more and 15% by mass or less. Is particularly preferred.

  By containing the specific isocyanurate compound in the above ratio, when it is cured and used as a sealing material, transparency, heat resistance coloring property, and heat shock resistance can be satisfied at a higher level. The reason for this is not clear, but it is one of the important technical findings that the present inventors have found that such a composition works favorably in the present invention.

[Compound represented by Formula (IV)]
In the present invention, the specific isocyanurate compound preferably further contains 1% by mass or more and less than 50% by mass of a compound represented by the following formula (IV).

・ R ⁴ , R ⁵ , R ⁶
In the formula, R ⁴ and R ⁵ are each independently hydrogen or a methyl group. In the formula, R ⁶ represents an alkyl group having 3 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms. Examples of the alkyl group include a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and among them, a cyclohexyl group, a cyclopentyl group, a methyl group, a t-butyl group, and a 2-ethylhexyl group are preferable. The aryl group may be monocyclic or multicyclic, but is preferably a phenyl group. The alkyl group and aryl group may be further accompanied by a substituent, and examples thereof include the substituent T described later.

  Although the addition amount of the compound represented by the formula (IV) is not particularly limited, it is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, and more preferably 1% by mass. It is particularly preferably 30% by mass or less. By applying this within the above range, the thermal shock resistance (crack resistance) can be further improved effectively.

  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 0.01 mgKOH / g or less. It is preferable that the amount is not more than the above upper limit value because there is an advantage of improving heat resistant colorability. 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 it can be reduced by alkali cleaning. Another preferable method for adjusting the acid value of the sealant is to mix an adsorbent such as activated carbon or silica with the isocyanurate compound of the present invention, leave it still, and then remove the adsorbent 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 or indicated by a specific name or chemical formula, it is used in the meaning including its salt and its 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 that does not specify substitution / non-substitution 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, or a halogen atom (eg, fluorine atom, chlorine atom, bromine atom) More preferably an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, amino group, acylamino group, cyano group or halogen atom, Particularly preferred are an alkyl group, an alkenyl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group, and 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 the commercial product and the contents related to synthesis, reference can be made to, for example, JP-A No. 2003-213159, JP-A No. 54-162784, and JP-A No. 60-2932.
Specifically, tris (2-hydroxyethyl) isocyanurate (THEI) can be esterified with acrylic acid or methacrylic acid to obtain an isocyanurate compound having a predetermined acryloyl group introduced. The esterification reaction may be performed under known conditions. For example, THEI and acrylic acid are dissolved in isooctane or toluene, sulfuric acid and hydroquinone are added, and the mixture is heated and stirred. Since the product obtained at this time may be unstable, in that case, it is preferable to perform a treatment such as taking water out of the reaction system. The number of acryloyl groups of the isocyanurate compound thus obtained is difficult to control, and is usually a mixture of monofunctional, bifunctional and trifunctional compounds. That is, it is difficult to selectively synthesize only a bifunctional specific isocyanurate compound. On the other hand, if the method of this invention is used, the bifunctional compound represented by Formula (2) can be acquired by making high concentration as mentioned above using the obtained mixture.

  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 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-amylperoxyisopropylcarbonate, t-butylperoxyisopropylcarbonate, t-butylperoxy-2-ethylhexylcarbonate 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.
Although content of a polymerization initiator is not specifically limited, It is preferable to apply at 0.1-5 mass%.

[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, preferably 100 to 10000 ppm, more preferably 300 to 8000 ppm. If the addition amount of the polymerization inhibitor is too small, the polymerization occurs while generating heat abruptly at the time of sealing and curing, so that the adhesiveness with the reflector package substrate is lowered and the sealing material is applied when a thermal shock is applied. / Peeling easily occurs at the substrate interface. On the other hand, when the addition amount of the polymerization inhibitor is too large, when the sealant is cured in the air, the curing rate is remarkably reduced, resulting in poor surface curing.

[Phosphor]
In this invention, it is preferable to mix | blend 1-40 mass parts of fluorescent substance with respect to 100 mass parts of sealing agents, It is more preferable that they are 2 mass parts or more and 30 mass parts or less, 5 mass parts or more and 20 mass parts It is particularly preferred that the amount is not more than parts. As the phosphor, those usually used in this type of device may be applied. For example, as a typical yellow phosphor, a general formula A ₃ B ₅₀ O ₁₂ : M (wherein component A is Y , Gd, Tb, La, Lu, Se, and Sm, the component B includes at least one element of the group consisting of Al, Ga, and In, and the component M includes Ce, It is particularly advantageous to contain phosphor particles comprising the garnet group of at least one element of the group consisting of Pr, Eu, Cr, Nd and Er. Y ₃ A ₁₅ O ₁₂ : Ce phosphor and / or (Y, Gd, Tb) ₃ (Al, Ga) as a phosphor for a light emitting diode element that emits white light with a light emitting diode chip that emits blue light. ) ₅ O ₁₂ : Ce phosphor is suitable. Other phosphors include, for example, CaGa ₂ S ₄ : Ce ³⁺ and SrGa ₂ S ₄ : Ce ³⁺ , YAlO ₃ : Ce ³⁺ , YGaO ₃ : Ce ³⁺ , Y (Al, Ga) O ₃ : Ce ³⁺ , Y ₂ Examples thereof include SiO ₅ : Ce ³⁺ (see JP 2011-144360 A). In addition to these phosphors, aluminate doped with rare earths or orthosilicates doped with rare earths are suitable for producing mixed color light. By blending 1 to 50 parts by mass of this type of phosphor with respect to 100 parts by mass of the curable composition, when an element emitting blue light is used, the emission color can be converted to white.

[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 Co., Ltd. Can do. These antioxidants can be used singly or in combination of two or more.

  The content of the antioxidant is usually relative to 100 parts by mass of the total amount with the derivative A or B from the viewpoint of suppressing the transparency of the resin material (encapsulant) for the semiconductor light emitting device and the reduction in yellowing. It is 0.01-10 mass parts, Preferably it is 0.01-5 mass parts, More preferably, it is 0.02-2 mass parts.

[Light stabilizers, etc.]
In addition to the above-mentioned antioxidant, the raw material composition (sealing agent) of the present invention contains, as necessary, a lubricant, a light stabilizer, an ultraviolet absorber, a plasticizer, an antistatic agent, an inorganic filler, and coloring. Agents, antistatic agents, 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 with the said derivative A or B, 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 raw material composition (sealing agent), polymerized and molded.

(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 raw material composition (sealing agent) or a prepolymer thereof may be used for polymerization / molding by injection molding, compression molding, transfer molding, insert molding and the like 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 clay of the sealant is not particularly limited, but is 0.1 to 100 Pa. From the viewpoint of potting property and phosphor stable dispersibility. 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 is a value measured by the following method unless otherwise specified.
(Measurement method of viscosity)
In the present invention, unless otherwise specified, an average of values obtained by measuring the viscosity 5 times every 100 seconds after the temperature is changed to a predetermined temperature with a variable-temperature rotary viscometer (Physica MCR301 (trade name, manufactured by Anton Paar)). Say. The measurement temperature is 25 ° C.

(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, a thermosetting resin such as an epoxy resin, a glass epoxy, Ceramics or the like 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 optical 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 acrylic sealing material used in the present invention can be used not only for light emitting elements such as LEDs and laser diodes, but also for sealing light emitting elements, semiconductor elements such as LSIs and ICs other than semiconductor light emitting elements. it can

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

(Quantification of ratio of compounds 1 to 3)

  The above compounds 1 to 3 were isolated by column purification of Aronix M-215 (manufactured by Toagosei Co., Ltd.). For each of compounds 1 to 3, 1.0 g / l, 4.0 g / l, and 8.0 g / l acetonitrile solutions were prepared and measured by HPLC (column: TSK-GEL ODS-100Z 5 μm 4.6 mm × 15 cm manufactured by TOSOH). A calibration curve was prepared from the absorption at 254 nm. The mixture of compounds 1 to 3 was also subjected to HPLC measurement to obtain the respective concentrations of compounds 1 to 3 from the absorption at 254 nm and the prepared calibration curve, and the ratio was quantified.

Example 1
400 g of Aronix M-215 (manufactured by Toa Gosei Co., Ltd.) was dissolved in 400 g of toluene and extracted four times with 1000 g of water. To the aqueous phase, 1000 g of ethyl acetate was added, stirred, allowed to stand, and separated. The ethyl acetate phase was dried with magnesium sulfate, filtered and concentrated to obtain 68 g of a purified product (sealing agent 101). From the NMR, the amount of residual ethyl acetate was 6% by mass of the whole. Table 1 shows the mixing ratio of each phase (ratio of each compound when the total of compounds 1, 2, and 3 is 100% by mass) and the extraction concentration (total concentration of compounds 1, 2, and 3 in the solvent). The same applies to Table 2 and later.

(Example 2)
In the purification example 1, it refine | purified by the same method except having used butyl acetate instead of toluene. Table 2 shows the ratio of each phase.

(Example 3)
In purification example 1, instead of toluene, a 7/3 (weight ratio) mixed solvent of toluene / hexane was used, and the amount was changed to 1600 g. Table 3 shows the ratio of each phase.

(Comparative Example 1)
400 g of Aronix M-215 (manufactured by Toa Gosei Co., Ltd.) was dissolved in 400 g of ethyl acetate and washed 4 times with 1000 g of water (sealing agent c11). Table 4 shows the ratio of each phase.

(Comparative Example 2)
Compound 1 in sealant c12 obtained in the same manner as in Example 1 of JP-A-54-162784, except that the equivalent amount of acrylic acid was changed to 2 equivalents relative to isocyanurate The ratio of ~ 3 is shown in Table 5.

Example 4
(Preparation of curable resin composition)
A mixture of the specific isocyanurate compounds shown in Table 6 was mixed so that the total amount was 3.000 g, and 0.030 g of tert-butyl-2-ethylperoxyhexanoate (Nippon Yushi Co., Ltd., Perbutyl O) was added, The mixture was stirred to make it uniform to prepare a curable resin composition.

(Heat resistant colorability)
A 1 mm-thick glass plate is used as a spacer, the prepared composition is sandwiched between two glass plates, and heated at 90 ° C./10 minutes, 100 ° C./10 minutes, 110 ° C./10 minutes, 150 ° C./90 minutes. A button-like cured product was obtained by heat treatment at. The cured product was heated in an oven at 200 ° C. for 16 hours, and a change in transmittance at 400 nm before and after heating (measured with a UV-visible spectrometer (UV-1650PC [trade name] manufactured by Shimadzu Corporation)) was obtained. The smaller the value, the better the heat resistant colorability.

(Implementation)
Hardening which prepared the recessed part (2.0 * 1.5 * 0.75mm) of 3.0 * 2.0 * 1.0mm (Al2O3) package (Kyocera Corporation KD-V93B96-B [brand name]). The resin was filled with a conductive resin composition, cured at 130 ° C. for 30 minutes, and at 150 ° C. for 1 hour and 30 minutes, and the device was sealed (n = 10).

(Crack resistance)
The mounted element was maintained at −40 ° C. for 15 min using a gas phase thermal shock test apparatus manufactured by Enomoto Kasei Co., Ltd., then rapidly heated to 100 ° C. and maintained for 15 min, and then at −40 ° C. for 15 min. The device after 50 cycles of maintenance was observed, and the number of cracks was counted.

  From the above results, according to the present invention, the compound represented by the formula (II) useful as a sealing agent for semiconductor light emitting devices can be obtained at a high mixing ratio without complicated operations. And the specific isocyanurate compound obtained by this has the property suitable as a sealing agent of an optical semiconductor element, and when this is hardened and used as a sealing material, it is excellent in heat-resistant coloring property and crack resistance. I understand.

1 Semiconductor Light Emitting Elememt
2 Reflector Package Base 3 Sealing Material 4 Electrode 6 Bonding Wire 8 Die Bonding Agent 10 Semiconductor Light Emitting Device

Claims (13)

A method for producing an encapsulant for optical semiconductors containing an isocyanurate compound,
At least the following steps a to c with respect to a raw material mixture containing a compound represented by the following formula (I), a compound represented by the following formula (II), and a compound represented by the following formula (III) The manufacturing method of the sealing agent for semiconductor light-emitting devices including the process which raises the mixing ratio of the compound represented by said Formula (II) by passing through.
[A: A step of dissolving the raw material mixture in an organic solvent A having an SP value of 8.9 or less. ]
[B: The raw material mixture solution prepared in step a is brought into contact with an aqueous medium, and the compound represented by the formula (I) and the compound represented by the formula (II) are extracted from the aqueous medium phase. Process. ]
[C: A step of bringing the aqueous medium phase of step b into contact with the organic solvent B having an SP value of 9.0 or more and extracting the compound represented by the formula (II) into the phase of the organic solvent B. ]

(R each independently represents a hydrogen atom, a methyl group, a fluorine atom, CF ₃ , or a hydroxymethyl group.)   The method for producing a sealant according to claim 1, wherein the organic solvent A used in the step a has an SP value of 7.0 or more and 8.9 or less.   The method for producing a sealant according to claim 1, wherein the organic solvent A is any one of toluene, butyl acetate, and hexane.   The organic solvent B used at the said process c is SP value 9.0 or more and 9.5 or less, The manufacturing method of the sealing agent of any one of Claims 1-3.   The said organic solvent B is either ethyl acetate or methyl ethyl ketone, The manufacturing method of the sealing agent of any one of Claims 1-4. The mixing ratio [r ^f _II ] of the compound represented by the formula (II) contained in the phase of the organic solvent B that has undergone the step c is represented by the compound represented by the formula (I) and the formula (II). The manufacturing method of the sealing agent of any one of Claims 1-5 which is 60 mass% or more with respect to 100 mass% of total amounts of the compound and the compound represented by Formula (III). The mixing ratio [r ⁱ _II ] of the compound represented by the formula (II) contained in the raw material mixture is such that the compound represented by the formula (I), the compound represented by the formula (II) and the formula (III) The method for producing a sealant according to any one of claims 1 to 6, wherein the amount is 55% by mass or less based on a total amount of 100% by mass with the compound represented by formula (1).   Mixing of the compound represented by the formula (II) with respect to 100% by mass of the total amount of the compound represented by the formula (I), the compound represented by the formula (II) and the compound represented by the formula (III). The manufacturing method of the sealing agent of any one of Claims 1-7 which raises ratio 80 mass% or more with respect to the said raw material mixture.   The manufacturing method of the sealing agent of any one of Claims 1-8 which concentrate the extract obtained at the said process c, or pulverize a containing component. Steps a to c below for at least the raw material mixture containing the compound represented by the following formula (I), the compound represented by the following formula (II), and the compound represented by the following formula (III) The purification method of the isocyanurate compound which raises the mixing ratio of the compound represented by said Formula (II) by passing through the process of.
[A: A step of dissolving the raw material mixture in an organic solvent A having an SP value of 8.9 or less. ]
[B: The raw material mixture solution prepared in step a is brought into contact with an aqueous medium, and the compound represented by the formula (I) and the compound represented by the formula (II) are extracted from the aqueous medium phase. Process. ]
[C: A step of bringing the aqueous medium phase of step b into contact with the organic solvent B having an SP value of 9.0 or more and extracting the compound represented by the formula (II) into the phase of the organic solvent B. ]

(R each independently represents a hydrogen atom, a methyl group, a fluorine atom, CF ₃ , or a hydroxymethyl group.) A sealing agent for a semiconductor light-emitting device comprising a compound represented by the formula (II) whose mixing ratio is increased by the purification method according to claim 10, wherein the compound and the formula represented by the formula (I) are used. With ^respect to a total amount of 100% by mass of the compound represented by (II) and the compound represented by formula (III), the compound represented by formula (II) is mixed at a mixing ratio [r ^f _II ] of 60% by mass or more. An encapsulant for a semiconductor light emitting device.   The sealing material for semiconductor light-emitting devices formed by hardening | curing the sealing agent for semiconductor light-emitting devices of Claim 11.   A semiconductor light-emitting device comprising the sealing material according to claim 12.

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