JP2015120767A - Sealant composition for light-emitting diode - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealant composition for a light-emitting diode (LED), comprising a fluorescent material and a resin serving as a base for sealing, where the fluorescent material contained in the composition is in a good dispersion state and, when the light-emitting diode is sealed, variations in chromaticity of the light-emitting diode can be reduced.SOLUTION: There is provided a sealant composition for a light-emitting diode, comprising (I) a silsesquioxane derivative, (II) a fluorescent material, and (III) a resin, where an average particle diameter of the (I) silsesquioxane derivative is 0.1 to 50 nm.

Description

  The present invention is a novel encapsulant composition for a light-emitting diode (hereinafter sometimes simply referred to as “LED”) containing a fluorescent material (phosphor), which has good dispersibility of the phosphor. The present invention relates to a novel sealant composition.

  In the sealing agent for sealing the LED chip, a phosphor is mixed for the purpose of converting light from the light emitting element into light having a desired wavelength with high efficiency. As this phosphor, for example, yttria / aluminum / garnet-based inorganic material (hereinafter sometimes simply referred to as “YAG-based inorganic material”) is used.

  Such a phosphor usually has a specific gravity larger than that of the resin component contained in the sealant, and thus has a problem that it sinks downward with the passage of time. In order to solve such a problem, a method of using a translucent resin as a filler for a sealant has been proposed (see Patent Document 1). According to this method, since the translucent resin is well dispersed in the encapsulant, the phosphor is present between the translucent resins, the chromaticity is stable, and the encapsulant itself Cloudiness can be prevented.

  However, since the translucent resin used in the method is polymethyl methacrylate and is an organic polymer, the method has room for improvement in terms of heat resistance.

  On the other hand, a method of blending silica as a filler in the sealant has been proposed, but since the aggregated particle diameter of silica is about 100 nm to several microns, the method scatters light, and the sealant There was a problem of clouding itself.

  Therefore, development of the sealing agent composition which can disperse | distribute fluorescent substance stably, maintaining the transparency of sealing agent is desired.

JP 2009-117831 A

  Accordingly, an object of the present invention is to provide an LED encapsulant composition that eliminates the above-mentioned drawbacks of the prior art, achieves more stable dispersibility of the phosphor, and is excellent in transparency.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have improved the dispersibility of the phosphor by blending the silsesquioxane derivative into the encapsulant containing the phosphor. It discovered that the sealing compound composition for LED was obtained, and came to complete this invention.

That is, the present invention
A sealing composition for a light emitting diode, comprising (I) a silsesquioxane derivative, (II) a phosphor, and (III) a resin.

  Moreover, in the said composition, it is preferable that the average particle diameter of the said (I) silsesquioxane derivative is 0.1-50 nm.

  The present invention is an LED encapsulant composition comprising (I) a silsesquioxane derivative, (II) a fluorescent dye, and (III) a resin. By sealing the LED chip using this composition, it has excellent transparency, further excellent fluorescent dye dispersion stability, and even when used repeatedly for a long period of time, there is little change in luminescent color and durability. An LED having such characteristics as high can be manufactured. The LED can have a very long life.

  The composition for sealing agents of this invention contains (I) silsesquioxane derivative, (II) fluorescent substance, and (III) resin. First, a silsesquioxane derivative (hereinafter sometimes referred to as component (I)) used in the present invention will be described in detail.

((I) Silsesquioxane derivative: Component (I))
In the present invention, the silsesquioxane derivative is a compound having a main chain skeleton composed of Si—O bonds, and is a siloxane-based compound having 1.5 oxygen atoms in a unit composition. And in this invention, following formula (1)

It is preferable that it is a compound shown by these.

In the formula, R ¹ may be the same or different from each other, and is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 carbon atom. ~ 6 halogenated alkyl group, phenyl group, phenyl group substituted with halogen, phenyl group substituted with halogenated alkyl group having 1 to 6 carbon atoms, hydroxyl group, vinyl group, trimethylsiloxy group, or amino group, One or more groups selected from organic groups having any of a cyano group, an epoxy group, an acrylic group, a methacryl group, a maleimide group, a vinyl group, or a cyclohexenyl group;
g represents the degree of polymerization.

In R ¹ , the alkyl group having 1 to 6 carbon atoms includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n -Hexyl group, n-octyl group, isooctyl group, n-decyl group and the like.

  Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclooctyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

  Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, and tert-butoxy group.

  Examples of the halogenated alkyl group having 1 to 6 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a chloromethyl group, a 2-chloroethyl group, and a bromomethyl group.

  Examples of the phenyl group substituted with halogen include 4-chlorophenyl group and 4-bromophenyl group.

  Examples of the phenyl group substituted with a halogenated alkyl group having 1 to 6 carbon atoms include a 4-chloromethylphenyl group.

  Examples of the organic group having any one of an amino group, a cyano group, an epoxy group, an acrylic group, a methacryl group, a maleimide group, a vinyl group, and a cyclohexenyl group include the following organic groups.

  Examples of the organic group having an amino group include an aminopropyl group, an N-methylaminopropyl group, an aminoethylaminopropyl group, and an N-phenylaminopropyl group.

  Examples of the organic group having a cyano group include a cyanopropyl group.

  Examples of the organic group having an epoxy group include an epoxymethyl group, an epoxyethyl group, an epoxypropyl group, an epoxycyclohexylmethyl group, an epoxycyclohexylethyl group, a glycidylpropyl group, and a (glycidylethyl) dimethylsiloxy group.

  Examples of the organic group having an acrylic group include an acryloxymethyl group, an acryloxypropyl group, and a (3-acryloxypropyl) dimethylsiloxy group.

  Examples of the organic group having a methacryl group include a methacryloxymethyl group, a methacryloxypropyl group, and a (3-methacryloxypropyl) dimethylsiloxy group.

  Examples of the organic group having a maleimide group include an N-maleimidopropyl group.

  Examples of the organic group having a vinyl group include an allyl group, a vinylpropyl group, a vinyloctyl group, a vinyldimethylsiloxy group, an allylpropyl group, and an allylpropyldimethylsiloxy group.

  Examples of the organic group having a cyclohexenyl group include a 4-cyclohexenyl) ethyldimethylsiloxy group.

Among the groups as described above, R ¹ is an organic group having a (meth) acryl group and an organic group having an epoxy group can be cured together with the sealing resin component. Is particularly preferable. In addition, the said (meth) acryl group refers to the general term of an acryl group and a methacryl group.

  g represents the degree of polymerization. This g is preferably in the range of 5 to 100 from the viewpoint of the fluorescent dye dispersibility improving effect and the dispersibility in the resin.

  The silsesquioxane compound can take various structures such as a cage shape, a ladder shape, and a random shape, and any of them can be used in the present invention without any limitation. Moreover, the mixture which consists of a some structure can also be used.

  Of these structures, the following formula (2)

(Where
X ^{1 to} X ^h may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 carbon atom. ~ 6 halogenated alkyl group, phenyl group, phenyl group substituted with halogen, phenyl group substituted with halogenated alkyl group having 1 to 6 carbon atoms, hydroxyl group, vinyl group, trimethylsiloxy group, or amino group, One or more groups selected from organic groups having any of a cyano group, an epoxy group, an acrylic group, a methacryl group, a maleimide group, a vinyl group, or a cyclohexenyl group;
The end groups ^Xa and ^Xb are a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms,
The end groups ^Xc and ^Xd are hydrogen atoms or alkoxy groups having 1 to 6 carbon atoms,
h represents the degree of polymerization. )
The ladder-like silsesquioxane compound shown by these is mentioned.

In the above X ^{1 to} X ^h , an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, and a halogen A substituted phenyl group, a phenyl group substituted with a halogenated alkyl group having 1 to 6 carbon atoms, a trimethylsiloxy group, or an amino group, a cyano group, an epoxy group, an acrylic group, a methacryl group, a maleimide group, a vinyl group, or Examples of the organic group having any of the cyclohexenyl groups include the same groups as those described for R ¹ in the formula (1), and preferred groups are also the same.

Examples of the alkoxy group having 1 to 6 carbon atoms in the terminal groups X ^a X ^b , X ^c and X ^d include the same groups as the alkoxy groups described for R ¹ in the formula (1), and preferable groups are also the same. .

  h represents the degree of polymerization. h is preferably in the range of 5 to 100 from the viewpoint of the fluorescent dye dispersibility improving effect and the dispersibility in the resin.

  Moreover, following formula (3)

(Where
Y ^{1 to} Y ⁱ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 carbon atom. ~ 6 halogenated alkyl group, phenyl group, phenyl group substituted with halogen, phenyl group substituted with halogenated alkyl group having 1 to 6 carbon atoms, hydroxyl group, vinyl group, trimethylsiloxy group, or amino group, One or more groups selected from organic groups having any of a cyano group, an epoxy group, an acrylic group, a methacryl group, a maleimide group, a vinyl group, or a cyclohexenyl group;
i represents a polymerization degree and is an integer of 6-12. )
It is also possible to use a silsesquioxane compound having a cage structure represented by

In the above Y ^{1 to} Y ⁱ , substituted with an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, or a halogen Phenyl group substituted with a halogenated alkyl group having 1 to 6 carbon atoms, trimethylsiloxy group, or amino group, cyano group, epoxy group, acrylic group, methacryl group, maleimide group, vinyl group, or cyclo Examples of the organic group having any of the hexenyl groups include the same groups as those described for R ¹ in the formula (1), and preferred groups are also the same.

  i represents the degree of polymerization. This degree of polymerization is preferably an integer of 6-12.

In the present invention, a silsesquioxane compound that can be particularly preferably used is specifically exemplified by cage-shaped T8 (in formula (3), i is 8 and 6 Si atoms are included in the corner. Cone-shaped T10 (in the formula (3), i is 10 and a seven-sided structure having 10 Si atoms at the corners), cage-shaped T12 (the formula (3) ) Where i is 12 and the octahedral structure has 12 Si atoms at the corners)
The thing containing is preferable.

The above silsesquioxane compounds can be produced by known methods. A commercially available product may also be used. As a commercially available product containing a cage silsesquioxane compound,
AC-SQ TA-100: a mixture of polysiloxane compounds containing polyacryloxypropyl polyorganosiloxane (cage-shaped T8) (manufactured by Toagosei Co., Ltd.),
MAC-SQ TM-100: a mixture of polysiloxane compounds containing polymethacryloxypropyl polyorganosiloxane (cage-shaped T8) (manufactured by Toagosei Co., Ltd.),
Q-8: Octa [(3-methacryloxypropyl) dimethylsiloxy] silsesquioxane (manufactured by Toagosei Co., Ltd.)
Q-6: Octa [2- (vinyl) dimethylsiloxy] silsesquioxane (manufactured by Toagosei Co., Ltd.) and the like,
The POSS series manufactured by Hybrid Plastics can be mentioned.

  In this invention, the said component (I) is 0.5-1.1 with respect to the specific gravity of a resin component from a viewpoint of the dispersibility stability in sealing agent resin (component (III) demonstrated below). Double specific gravity is preferred.

  Further, the component (I) preferably has an average particle size of 0.1 to 50 nm from the viewpoint of preventing sedimentation of the phosphor (component (II)). In addition, when component (I) is a mixture, it is preferable that the average particle diameter of the mixture satisfies the said range.

  The component (I) preferably has a weight average molecular weight of 500 to 20,000 from the viewpoint of preventing sedimentation of the phosphor (component (II)). The molecular weight is a value confirmed by GPC (gel permeation chromatography), and in the case of a mixture, it is the weight average molecular weight of the mixture.

(II) Phosphor (component (II))
In the present invention, the phosphor (II) (hereinafter sometimes referred to as component (II)) is not particularly limited, and usually used inorganic substances can be used. Specifically, for example, a phosphor of a YAG inorganic material doped with a rare earth element can be given.

(III) Resin (component (III))
In the present invention, as the (III) resin (hereinafter sometimes referred to as component (III)), those used for LED encapsulants can be used without any limitation. Specifically, epoxy resins, silicone resins (including cured organopolysiloxanes (crosslinked products) such as silicone rubber and silicone gel), urea resins, fluororesins, or polycarbonate resins can be used. Especially, it is preferable to use a silicone resin from a relationship with a component (I).

(Blend ratio of each component Component ratio of component (I), component (II), component (III))
In the present invention, the blending ratio of each component is not particularly limited, and may be appropriately determined according to the size of the LED chip, the shape of the package, and the like.

  Especially, it is preferable that component (I) shall be 0.1-20 mass parts with respect to 100 mass parts of component (III). In addition, when component (I) contains multiple types of silsesquioxane derivatives, let the total amount of multiple types of silsesquioxane derivatives be the compounding amount of component (I).

  Moreover, it is preferable to contain 0.3-60 weight part of component (II) with respect to 100 mass parts of component (III).

  The sealing agent composition of this invention can be manufactured by mixing the said component (I), component (II), and component (III) by a well-known means. Moreover, a publicly known compounding (addition) agent can also be mix | blended (added) to this sealing agent composition in the range which does not impair the effect of this invention.

  Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to the examples.

Example 1
(I) As a silsesquioxane derivative, the following formula (MS0805)

5 parts by mass of a mixture of silsesquioxane derivatives containing T8 in the form of cage (MS0805 manufactured by Hybrid Plastics, average particle diameter of the mixture: 1.5 nm, weight average molecular weight of the mixture: 1322) represented by 3 parts by mass of YAG-based phosphor ZYP550H (manufactured by Beijing Ugoku Technological Development Co., Ltd.) was mixed with silicone resin (100 parts by mass) to produce a composition for sealant. Table 1 summarizes the type and composition of each component.

  The obtained composition for sealants was cured, and the dispersion state of the phosphor and the white turbidity of the cured product were visually evaluated. The results are shown in Table 3.

Examples 2-5
Evaluation similar to Example 1 was performed except having changed the kind and mass ratio of the silsesquioxane derivative in Example 1. The blending ratio of the sealant composition and the types of each component are summarized in Table 1. Moreover, the same evaluation as Example 1 was performed using the obtained sealing agent composition, and the result was put together in Table 3.

  In addition, Example 2 is the same as the silsesquioxane derivative used in Example 1, and the blending amount is 10 parts by mass.

  Example 3 is a silsesquioxane derivative represented by the following formula (MS0830)

5 parts by mass of a cage-like silsesquioxane derivative mixture (MS0830, manufactured by Hybrid Plastics Co., Ltd., average particle diameter of the mixture: 1.0 nm, weight average molecular weight of the mixture: 550) represented by the formula (1) was used.

  Example 4 is a silsesquioxane derivative represented by the following formula (EP0409)

5 parts by mass of a cage-like silsesquioxane derivative mixture (EP0409, manufactured by Hybrid Plastics Co., Ltd., average particle diameter of the mixture: 2.0 nm, weight average molecular weight of the mixture: 1336) represented by the formula (1) was used.

  Example 5 is a silsesquioxane derivative represented by the following formula (MA0735).

5 parts by mass of a cage-like silsesquioxane derivative mixture (MA0735 manufactured by Hybrid Plastic Co., Ltd., average particle diameter of the mixture: 2.0 nm, weight average molecular weight of the mixture: 1434) represented by the formula (1) was used.

Comparative Examples 1 and 2
In Example 1, it carried out like Example 1 except not adding a silsesquioxane derivative (Comparative Example 1 does not add a filler, and Comparative Example 2 adds a silica.). These types and formulations are summarized in Table 2. Moreover, LED was produced like the Example using the obtained sealing agent composition, evaluation similar to Example 1 was performed, and the result was put together in Table 3. FIG.

  From Table 3, in the case of the composition for sealing agents of Examples 1 to 5, the sealed portion is extremely high in transparency, and further, no sedimentation of the phosphor is observed, and a uniform cured product is obtained in a good dispersion state. It was. In Comparative Examples 1 and 2, when no silsesquioxane was added, the phosphor settled and separated into two layers. When silica having a large particle size was added, white turbidity was exhibited. Therefore, according to the present invention, it was confirmed that a uniform cured product with high transparency can be obtained by mixing the silsesquioxane compound.

Claims (2)

  A sealant composition for a light emitting diode, comprising (I) a silsesquioxane derivative, (II) a phosphor, and (III) a resin.   2. The encapsulant composition for a light-emitting diode according to claim 1, wherein the average particle diameter of the (I) silsesquioxane derivative is 0.1 to 50 nm.