JP5965241B2 - Silicone-treated phosphor, silicone-treated phosphor-containing silicone-based curable composition, and light-emitting device sealed with these compositions - Google Patents

Description

  The present invention relates to a silicone-treated phosphor, a silicone-based curable composition containing the phosphor, and a light-emitting device sealed with these compositions.

  A light emitting device using a light emitting diode (LED) has features such as long life, low power consumption, impact resistance, high speed response, lightness, thinness, and the like, such as a liquid crystal display, a mobile phone, an information terminal, etc. Development of various fields such as backlights, in-vehicle lighting, indoor / outdoor advertising, indoor / outdoor lighting, etc. has been progressing dramatically.

  In an LED, in general, blue light or ultraviolet light emitted from a light emitting element by a method such as sealing a light emitting element with a phosphor-containing composition in which one or more kinds of phosphors are dispersed in a curable resin, Arbitrary emission colors including white light are obtained by adding together the light emitted by the phosphors by absorbing them. However, chromaticity variations occurring between individual LEDs have become a problem due to reasons such as uneven dispersion of phosphors, and this is, for example, in order to suppress uneven light emission in the production of displays and illumination using LEDs. Since the need to sort out LEDs is generated, which leads to problems such as a reduction in productivity and yield, suppression of chromaticity variation between LEDs has been desired.

  In order to deal with such problems, Patent Document 1 improves the dispersibility of the phosphor by using a composition in which the phosphor is dispersed in an epoxy resin having a specific viscosity. However, the effect of suppressing the chromaticity variation is not sufficient, and since an epoxy resin is used, light resistance under severe conditions has become a problem.

  Moreover, in patent document 2, the dispersibility of fluorescent substance is improved by mix | blending a specific silane coupling agent with a composition as a dispersing agent. However, the effect of suppressing the chromaticity variation is not sufficient, and further improvement is desired.

  Moreover, in patent document 3, the dispersibility of fluorescent substance is improved by mix | blending the silica which has specific hydroxyl group density | concentration with a composition. However, the effect of suppressing the chromaticity variation is not sufficient, and excessive light scattering due to poor dispersion of silica sometimes causes a decrease in luminous efficiency and a change in chromaticity.

  On the other hand, a composition composed of polysiloxane having a polyhedral structure is known to exhibit excellent heat resistance, light resistance, chemical stability, low dielectric constant, etc. from its specific chemical structure, For example, Patent Document 4 discloses a composition using a polysiloxane-based modified body having a polyhedral structure. This composition is excellent in molding processability, transparency, heat resistance, light resistance, adhesiveness and the like, and can also be used as an LED sealing agent. However, there remains room for studying the suppression of chromaticity variations when LEDs are used in combination with phosphors.

  The present invention has been made to solve such problems, and an object of the present invention is to provide a silicone-treated phosphor that suppresses chromaticity variation among individual LEDs.

JP 2008-198961 A JP 2007-111694 A JP 2008-50593 A WO08 / 133138

  An object of the present invention is to provide a silicone-treated phosphor that suppresses variation in chromaticity among individual LEDs, a silicone-based curable composition containing the silicone-treated phosphor, and a light-emitting device that is sealed with these compositions. .

  As a result of intensive studies to solve the above problems, the present inventors have obtained a silicone-treated phosphor obtained by mixing a phosphor having a weight average molecular weight of 1,000 or more and 200,000 or less and a phosphor, The present inventors have found that the above problems can be solved, and have reached the present invention.

  That is, the present invention has the following configuration.

  1). A silicone-treated phosphor obtained by mixing phosphor (S) having a weight average molecular weight of 1,000 or more and 200,000 or less and a phosphor.

  2). The silicone-treated phosphor according to 1), wherein the silicone (S) component is 0.75 to 500 parts by weight with respect to 100 parts by weight of the phosphor.

  3). The silicone-treated phosphor according to 1), wherein the silicone (S) component is 0.75 to 30 parts by weight with respect to 100 parts by weight of the phosphor.

  4). The silicone-treated phosphor according to any one of 1) to 3), wherein the silicone (S) component is a silicone having an alkenyl group or a hydrosilyl group.

  5). The silicone-treated phosphor according to any one of 1) to 4), wherein the silicone (S) component is a silicone having a polyhedral polysiloxane skeleton.

  6). The polyhedral polysiloxane-based compound (a) in which the silicone having a polyhedral polysiloxane skeleton contains an alkenyl group and / or a hydrosilyl group (a), a compound having a hydrosilyl group or alkenyl group capable of hydrosilylation with the component (a) ( b), and if necessary, a modified polyhedral polysiloxane (A) obtained by hydrosilylation of an organosilicon compound (a ′) having one alkenyl group or hydrosilyl group in one molecule. 5) The silicone-treated phosphor according to 5).

  7). The silicone-treated phosphor according to 6), wherein the component (b) is a cyclic siloxane having a hydrosilyl group or an alkenyl group.

  8). The silicone-treated phosphor according to 6), wherein the component (b) is a linear siloxane having a hydrosilyl group or an alkenyl group at the molecular end.

9). The component (a) is
Formula [AR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group and / or a hydrogen atom provided that at least one is an alkenyl group;. R ¹ is An alkyl group or an aryl group; R ² is a siloxane unit represented by a substituent other than an alkenyl group and a hydrogen atom, an alkyl group, an aryl group, or a group connected to another polyhedral skeleton polysiloxane or siloxane compound) The silicone-treated phosphor according to any one of 6) to 8), which is a polyhedral polysiloxane compound composed of:

10). The component (a) is
Formula [BR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; B is alkenyl and / or hydrogen atom, provided that at least one is hydrogen atom;. R ¹ is An alkyl group or an aryl group; R ² is a siloxane unit represented by a substituent other than an alkenyl group and a hydrogen atom, an alkyl group, an aryl group, or a group connected to another polyhedral skeleton polysiloxane or siloxane compound) The silicone-treated phosphor according to any one of 6) to 8), which is a polyhedral polysiloxane compound composed of:

11). The component (A) is
[XR ³ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
[A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkyl group, an aryl group, an alkenyl group, a hydrogen atom Or a group linked to another polyhedral polysiloxane; X has a structure represented by the following general formula (1) or general formula (2), and when there are a plurality of X, the general formula (1 ) Or the structure of the general formula (2) may be different, or the structure of the general formula (1) or the general formula (2) may be mixed.

{L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. It is a site | part or the structure represented by following General formula (3), and may be the same or different. Z is a site bonded to a polyhedral polysiloxane via a hydrogen atom, an alkenyl group, an alkyl group, an aryl group or an alkylene chain, or a structure represented by the following general formula (3), It may or may not be. In which at least one of Y or Z is a hydrogen atom or an alkenyl group; R is an alkyl group or an aryl group;
-[CH ₂ ] _l -R ⁵ (3)
(L is an integer of 2 or more; R ⁵ is a group containing an organosilicon compound)}]
The silicone-treated phosphor according to any one of 6) to 10), wherein

  12). The silicone-treated phosphor according to any one of 1) to 11), wherein the silicone (S) component has an aryl group.

  13). The silicone-treated phosphor according to any one of 1) to 12), wherein the phosphor is two or more kinds of phosphors having emission peaks different from each other.

  14). A silicone-treated phosphor-containing silicone-based curable composition obtained by blending the silicone-treated phosphor according to any one of 1) to 13) with a silicone-based curable composition.

15). 14. Silicone-treated phosphor-containing silicone-based curable composition according to 14), which contains an inorganic filler 16). 14. A light-emitting device, which is sealed with the silicone-treated phosphor-containing silicone-based curable composition according to 14) or 15).

  17). A method for producing a silicone-treated phosphor, comprising mixing the silicone (S) component according to 1) to 12) with a phosphor.

  The present invention can provide a silicone-treated phosphor that suppresses variation in chromaticity among individual LEDs, a silicone-based curable composition containing the silicone-treated phosphor, and a light-emitting device that is sealed with these compositions.

  Hereinafter, the present invention will be described in detail.

  The silicone-treated phosphor of the present invention can be obtained by mixing phosphor (S) having a weight average molecular weight of 1,000 or more and 200,000 or less, which will be described later, and the phosphor. The phosphor previously mixed with the component (S) is blended into the silicone-based curable composition described below and used for LED sealing, whereby the untreated phosphor is blended into the same silicone-based curable composition. Thus, compared to the case of using the LED for sealing, it is possible to suppress the chromaticity variation among the individual LED obtained.

<Phosphor>
The phosphor used for obtaining the silicone-treated phosphor of the present invention is not particularly limited as long as it absorbs light emitted from the light emitting element and generates light of different wavelengths, and generally known phosphors can be used. In order to obtain the luminescent color required for the light emitting device of the present invention, an arbitrary one can be selected. Specifically, for example, as a yellow phosphor, a YAG phosphor such as (Y, Gd) ₃ Al ₅ O ₁₂ ; Ce, a TAG phosphor such as Tb ₃ Al ₅ O ₁₂ ; Ce, CaGa ₂ S ₄ Sulfide phosphor such as Eu, (Sr, Ca, Ba) ₂ SiO ₄ ; Silicate phosphor such as Eu, Ca-α-Sialon; Oxynitride phosphor such as Eu, green fluorescence As the body, Y ₃ (Al, Ga) ₅ O ₁₂ ; Ce, SrGa ₂ S ₄ ; Eu, (Ba, Sr) ₂ SiO ₄ ; Eu, Ca ₃ Sc ₂ Si ₃ O ₁₂ ; Ce, CaSc ₂ O ₄ Ce, β-Sialon; Eu, (Sr, Ba) Si ₂ O ₂ N ₂ ; Eu, Ba ₃ Si ₆ O ₁₂ N ₂ ; Eu and the like, and (Ca, Sr) ₂ Si as a red phosphor _{5 N 8; Eu, CaAlSiN 3} ; nitride-based phosphor such as Eu, (Sr Ca) S; Eu, (Sr , Ba) 3 SiO 5; Eu, K 2 SiF 6; Mn and the like, and the blue phosphor, (Sr, Ca, Ba, Mg) 10 (PO 4) 6 Cl ₂ ; Eu, (Ba, Sr) MgAl ₁₀ O ₁₇ ; Eu, SrSi ₉ Al ₁₉ ON ₃₁ ; Eu, (Sr, Ba) ₃ MgSi ₂ O ₈ ; Eu and the like, but not limited thereto . These phosphors can be used alone or in combination of two or more in any ratio and combination. From the viewpoint of the luminous efficiency of the LED obtained, it is preferable to use one type in combination, and from the viewpoint of color rendering properties, it is preferable to use two or more types of phosphor in combination.

  The particle size of the phosphor used in the present invention is not particularly limited, but the median particle size (D50) is preferably 0.1 μm or more, more preferably 0.5 μm or more, further preferably 1 μm or more, preferably It is 100 μm or less, more preferably 50 μm or less, and still more preferably 25 μm or less. If the median particle size (D50) is small, the phosphor may not be able to absorb the excitation light sufficiently, or the phosphor may aggregate in the composition. If the median particle size (D50) is large, the phosphor In some cases, uneven dispersion may occur, or the dispenser may be blocked during sealing. Further, the particle size distribution (QD) of the phosphor is preferably small in order to align the dispersed state of the particles in the composition, but in order to reduce the particle size, the classification yield is reduced and the cost is increased. 0.03 or more, more preferably 0.05 or more, further preferably 0.07 or more, preferably 0.4 or less, more preferably 0.3 or less, and still more preferably 0.2 or less. Further, the shape of the phosphor is not particularly limited, and an arbitrary shape can be used.

<Silicone (S) having a weight average molecular weight of 1,000 to 200,000>
The silicone (S) having a weight average molecular weight of 1,000 to 200,000 used in the present invention is not particularly limited as long as it is a silicone having a weight average molecular weight of 1,000 to 200,000, but 1200 or more. 180,000 or less is more preferable, and 1500 or more and 150,000 or less are more preferable. If the weight average molecular weight of the component (S) is small, the effects of the present invention may not be sufficiently obtained. If the molecular weight of the component (S) is large, the viscosity becomes high and it is difficult to uniformly mix the phosphor and silicone. Or the phosphor may aggregate.

  The amount of the component (S) used in the present invention is preferably 0.75 to 500 parts by weight, more preferably 0.75 to 200 parts by weight, based on 100 parts by weight of the phosphor. More preferably, it is 75-100 weight part. If the amount of component (S) used is small, the effects of the present invention may not be sufficiently obtained. If the amount of component (S) used is large, the silicone-based curable composition described below that contains a silicone-treated phosphor is used. It may adversely affect the curability and various physical properties after curing. Furthermore, in consideration of the change over time of the component (S), the amount of the component (S) used is preferably 0.75 to 30 parts by weight, preferably 0.75 to 25 parts by weight with respect to 100 parts by weight of the phosphor. More preferably, it is 0.75 to 20 parts by weight. If the amount used is small, the effects of the present invention may not be sufficiently obtained as described above. If the amount used is large, the (S) component becomes pasty, and the phosphors are formed on the lower and upper portions of the (S) component over time. In some cases, light and shade may be produced, and remixing may be required before blending into the silicone-based curable composition described below.

  The component (S) used in the present invention is preferably a silicone having an alkenyl group or a hydrosilyl group. By having an alkenyl group or a hydrosilyl group, it can react with the silicone-based curable composition described later, and can be incorporated into the resin skeleton, and the bleeding out of the (S) component after sealing can be suppressed. .

  The component (S) used in the present invention is preferably a silicone having a polyhedral polysiloxane skeleton because the effects of the present invention are further enhanced.

<Silicone with polyhedral polysiloxane skeleton>
As the silicone having a polyhedral structure polysiloxane skeleton used in the present invention, known polyhedral structure polysiloxanes can be widely used. The general formula [R ⁶ SiO _3/2 ] _a and the general formula [R ⁶ ₃ SiO— Polyhedral polysiloxane composed of siloxane units represented by SiO _3/2 ] _a (R ⁶ is an arbitrary organic group and may be the same or different; a is an integer of 6 to 24) However, it may be a partially cleaved polyhedral polysiloxane containing [R ⁶ ₂ SiO _2/2 ] units or [R ⁶ ₃ SiO _1/2 ] units in its structure.

  The silicone having a polyhedral polysiloxane skeleton used in the present invention is composed of a polyhedral polysiloxane compound (a) containing an alkenyl group and / or a hydrosilyl group, a hydrosilyl group or an alkenyl group capable of undergoing a hydrosilylation reaction with the component (a). And a polyhedral polysiloxane modified product obtained by hydrosilylation reaction of a compound (b) having a silane, and if necessary, an organosilicon compound (a ′) having one alkenyl group or hydrosilyl group in one molecule ( A) is preferable from the viewpoints of suppression of chromaticity variation, handling properties, heat resistance, light resistance, gas barrier properties, and the like.

<Polyhedral polysiloxane compound (a) containing alkenyl group and / or hydrosilyl group>
The polyhedral polysiloxane compound (a) having an alkenyl group and / or hydrosilyl group used in the present invention is particularly limited as long as it is a polysiloxane having a polyhedral skeleton having an alkenyl group and / or hydrosilyl group in the molecule. There is no. Specifically, for example, the following formula [R ⁷ SiO _3/2 ] _x [R ⁸ SiO _3/2 ] _y
(X + y is an integer of 6 to 24; x is an integer of 1 or more, y is 0 or an integer of 1 or more; R ⁷ is an alkenyl group and / or hydrosilyl group, or a group having an alkenyl group and / or hydrosilyl group; R ⁸ is an alkenyl group and / or hydrosilyl group-containing polyhedral polysiloxane compound composed of siloxane units represented by any organic group or a group linked to another polyhedral skeleton polysiloxane) Can be used.

Examples of the method for synthesizing the polyhedral siloxane compound (a) containing the alkenyl group and / or hydrosilyl group include R ⁹ SiX ^a ₃ (wherein R ⁹ represents R ⁷ and R ⁸ described above, and X ^a represents a hydrolyzable functional group such as a halogen atom or an alkoxy group). Alternatively, after synthesizing a trisilanol compound having three silanol groups in the molecule by hydrolysis condensation reaction of R ⁹ SiX ^a _3, the ring is closed by reacting the same or different trifunctional silane compounds. The method of doing is also known. Furthermore, a partial cleavage polyhedral polysiloxane can be synthesized by reacting the trisilanol compound with a monofunctional silane and / or a bifunctional silane.

  As another method for synthesizing the polyhedral siloxane compound (a), for example, a tetraalkoxysilane such as tetraethoxysilane is replaced with a quaternary ammonium hydroxy such as trimethyl (2-hydroxyethyl) ammonium hydroxide or tetramethylammonium hydroxide. A silicate having a polyhedral structure is obtained by a hydrolysis condensation reaction in the presence of a base such as a hydrogen atom, and the obtained silicate is further reacted with a silylating agent such as a silyl chloride having an alkenyl group and / or a hydrosilyl group. Can be synthesized. Moreover, it is also possible to obtain the same polyhedral polysiloxane from a substance containing silica such as silica or rice husk instead of tetraalkoxylane.

As a preferable example of the polyhedral polysiloxane compound (a) having an alkenyl group used in the present invention, specifically, for example, a polyhedral polysiloxane compound having an alkenyl group represented by the following formula:
[AR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group and / or a hydrogen atom, provided that at least one is an alkenyl group; Group or aryl group; R ² is exemplified by a group other than an alkenyl group and a substituent other than a hydrogen atom, an alkyl group, an aryl group, or other polyhedral polysiloxane or siloxane compound).

  When such a component (a) is used, by using a compound having a hydrosilyl group as the later-described component (b), for example, in the presence of a later-described hydrosilylation catalyst, a modified polyhedral polysiloxane ( A) can be obtained. At this time, all the alkenyl groups of the polyhedral siloxane compound (a) do not need to react and may partially remain. A plurality of polyhedral polysiloxane compounds (a) and a compound (b) having a plurality of hydrosilyl groups may react. Further, if necessary, an organosilicon compound (a ′) having one alkenyl group or hydrosilyl group in one molecule may be reacted.

As a preferable example of the polyhedral polysiloxane compound (a) having a hydrosilyl group in the present invention, specifically, for example,
[BR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; B is alkenyl and / or hydrogen atom, provided that at least one is hydrogen atom;. R ¹ is An alkyl group or an aryl group; R ² is exemplified by a group other than an alkenyl group and a substituent other than a hydrogen atom, an alkyl group, an aryl group, or another polyhedral polysiloxane or siloxane compound).

  When such a component (a) is used, by using a compound having an alkenyl group as the later-described component (b), for example, in the presence of a later-described hydrosilylation catalyst, a modified polyhedral polysiloxane ( A) can be obtained. At this time, all the hydrogen atoms of the polyhedral siloxane compound (a) do not need to react and may partially remain. A plurality of polyhedral polysiloxane compounds (a) and a compound (b) having a plurality of alkenyl groups may react. Further, if necessary, an organosilicon compound (a ′) having one alkenyl group or hydrosilyl group in one molecule may be reacted.

  Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.

R ¹ is an alkyl group or an aryl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a cyclopentyl group. Examples of the aryl group include aryl groups such as a phenyl group and a tolyl group. Is done. R ¹ in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.

R ² is a group connected to a substituent other than an alkenyl group and a hydrogen atom, for example, an alkyl group, an aryl group, or another polyhedral skeleton polysiloxane. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a cyclopentyl group. Examples of the aryl group include aryl groups such as a phenyl group and a tolyl group. Is done. R ² in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.

  a is not particularly limited as long as it is an integer of 1 or more, but is preferably 2 or more, and more preferably 3 or more, from the handleability of the compound and the physical properties of the resulting cured product. Further, b is not particularly limited as long as it is 0 or an integer of 1 or more.

  The sum of a and b (= a + b) is an integer from 6 to 24, but from the viewpoint of the stability of the compound and the stability of the resulting cured product, it should be 6 to 12, and more preferably 6 to 10. preferable.

<Compound (b) having hydrosilyl group or alkenyl group>
The compound (b) having a hydrosilyl group or alkenyl group used in the present invention is a compound having a hydrosilyl group or alkenyl group capable of reacting with the polyhedral polysiloxane compound (a) having an alkenyl group and / or hydrosilyl group. There is no particular limitation as long as it is a component for reacting with the component (a) to obtain a polyhedral polysiloxane modified body (A) excellent in suppression of chromaticity variation, excellent handling properties, and the like.

  As the compound (b) having a hydrosilyl group used in the present invention, specifically, for example, a compound having a hydrosilyl group (hydrogen atom directly connected to Si atom), reacting with the alkenyl group of component (a), Examples include those that form the reactive functional group X represented by the formula (1) or the formula (2) (in this case, at least one of Y or Z is a hydrogen atom).

  As the compound (b) having a hydrosilyl group, a hydrosilyl group-containing siloxane compound, specifically, for example, a linear polysiloxane having a hydrosilyl group at both ends, a cyclic siloxane containing a hydrosilyl group, and the like are preferable. In addition, cyclic siloxanes containing hydrosilyl groups are preferred from the viewpoints of industrial availability and good reactivity when reacted. These compounds having a hydrosilyl group may be used alone or in combination of two or more.

  Specific examples of the linear polysiloxane having hydrosilyl groups at both ends include poly or oligosiloxanes whose ends are blocked with dimethylhydrogensilyl groups, tetramethyldisiloxane, hexamethyltrisiloxane and the like. The

  As cyclic siloxanes containing hydrosilyl groups, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen- 1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydro Gen-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexahydrogen Examples include -1,3,5,7,9,11-hexamethylcyclosiloxane.

  Specific examples of the compound (b) having an alkenyl group used in the present invention include those having an alkenyl group, which react with the hydrosilyl group of the component (a) to give a general formula (1) or a general formula ( Examples thereof include those that form the reactive functional group X represented by any one of the formulas 2) (in this case, at least one of Y or Z is an alkenyl group).

  As the compound (b) having an alkenyl group, an alkenyl group-containing siloxane compound, specifically, for example, a linear polysiloxane having an alkenyl group at both ends, a cyclic siloxane having an alkenyl group, and the like are preferable. Can be mentioned. These compounds having an alkenyl group may be used alone or in combination of two or more.

  Specific examples of the linear polysiloxane having an alkenyl group at both ends include poly or oligosiloxane blocked with dimethylvinylsilyl groups, tetramethyldivinyldisiloxane, hexamethyldivinyltrisiloxane, etc. Is done.

  Examples of the cyclic siloxane containing an alkenyl group include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1,3. , 5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-trimethylcyclosiloxane, , 3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1,3,5,7,9, Examples thereof include 11-hexamethylcyclosiloxane.

<Organic silicon compound (a ′) having one alkenyl group or hydrosilyl group in one molecule>
The organosilicon compound (a ′) having one alkenyl group or hydrosilyl group in one molecule used in the present invention is composed of the polyhedral polysiloxane compound (a) containing the above alkenyl group and / or hydrosilyl group and hydrosilyl group. The compound (b) having a group or an alkenyl group reacts with a hydrosilyl group or an alkenyl group to cap, thereby improving the handling property by controlling the cross-linking density of the polyhedral polysiloxane modified body (A), (A) It is a component for introducing a new group into the component.

  Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.

  The organosilicon compound (a ′) having one alkenyl group used in the present invention is preferably silane or polysiloxane from the viewpoint of heat resistance and light resistance. When the component (a ′) is a silane having one alkenyl group in one molecule, specifically, for example, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, triphenylvinylsilane, triethylvinylsilane, diethylphenyl Examples include vinyl silane, ethyl diphenyl vinyl silane, allyl trimethyl silane, allyl dimethyl phenyl silane, allyl methyl diphenyl silane, allyl triphenyl silane, allyl triethyl silane, allyl diethyl phenyl silane, allyl ethyl diphenyl silane, and the like. Among these, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, and triphenylvinylsilane are preferable examples from the viewpoint of heat resistance and light resistance, and dimethylphenylvinylsilane and methyldiphenylvinylsilane are also preferable from the viewpoint of gas barrier properties and refractive index. Triphenylvinylsilane is a preferred example.

  Further, when the component (a ′) is a polysiloxane, examples include a linear polysiloxane having one alkenyl group, a polysiloxane having one alkenyl group at the molecular end, and a cyclic siloxane having one alkenyl group. The

  When the component (a ′) is a linear polysiloxane having one alkenyl group, specifically, for example, polydimethylsiloxane, dimethyl dimethylvinylsilyl group and trimethylsilyl group, each of which is blocked at one end. Polymethylphenylsiloxane blocked with a vinylsilyl group and a trimethylsilyl group each at one end, polydiphenylsiloxane blocked with a dimethylvinylsilyl group and a trimethylsilyl group respectively, and a dimethylvinylsilyl group and a trimethylsilyl group. A copolymer of a dimethylsiloxane unit and a methylphenylsiloxane unit each having one end blocked, and a dimethylsiloxane unit and a diphenylsiloxane unit each blocked one by one with a dimethylvinylsilyl group and a trimethylsilyl group, And a copolymer of a methylphenylsiloxane unit and a diphenylsiloxane unit each having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group.

In the case of a polysiloxane having one alkenyl group at the molecular end, specifically, for example, polysiloxane having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group as exemplified above, SiO ₂ unit, SiO _{3 /} Examples include at least one siloxane unit selected from the group consisting of ₂ units, SiO units, and SiO _1/2 units, and polysiloxane composed of one dimethylvinylsiloxane unit.

  When the component (a ′) is a cyclic siloxane having one alkenyl group, specifically, for example, 1-vinyl-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1-vinyl Vinyl-3-phenyl-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1-vinyl-3,5-diphenyl-1,3,5,7,7-pentamethylcyclotetrasiloxane, Examples include 1-vinyl-3,5,7-triphenyl-1,3,5,7-tetramethylcyclotetrasiloxane.

  These (a ′) components, which are organosilicon compounds having one alkenyl group in one molecule, may be used alone or in combination of two or more.

  The organosilicon compound (a ′) having one hydrosilyl group used in the present invention is preferably silane or polysiloxane from the viewpoint of heat resistance and light resistance. When such a component (a ′) is a silane having one hydrosilyl group in one molecule, specifically, for example, trimethylsilane, dimethylphenylsilane, methyldiphenylsilane, triphenylsilane, triethylsilane, diethylphenyl Examples include silane and ethyldiphenylsilane. Among them, trimethylsilane, dimethylphenylsilane, methyldiphenylsilane, and triphenylsilane are preferable examples from the viewpoints of heat resistance and light resistance, and dimethylphenylsilane and methyldiphenylsilane from the viewpoint of gas barrier properties and refractive index. Triphenylsilane is a preferred example.

  In addition, when the component (a ′) is a polysiloxane, examples include a linear polysiloxane having one hydrosilyl group, a polysiloxane having one hydrosilyl group at the molecular end, and a cyclic siloxane having one hydrosilyl group. The

  When the component (a ′) is a linear polysiloxane having one hydrosilyl group, specifically, for example, a polydimethylsiloxane having a hydrodimethylsilyl group and a trimethylsilyl group each blocked at one end, Polydimethylphenylsiloxane with one end blocked with dimethylsilyl group and trimethylsilyl group, Polydiphenylsiloxane with one end blocked with hydrodimethylsilyl group and trimethylsilyl group, Hydrodimethylsilyl group and Trimethylsilyl group respectively Copolymers of dimethylsiloxane units and methylphenylsiloxane units each having one end blocked, and dimethylsiloxane units and diphenylsiloxane each having one end blocked with a hydrodimethylsilyl group and a trimethylsilyl group, respectively. Examples thereof include a copolymer with a xanthone unit, and a copolymer of a methylphenylsiloxane unit and a diphenylsiloxane unit each having one end blocked with a hydrodimethylsilyl group and a trimethylsilyl group.

In the case of a polysiloxane having one hydrosilyl group at the molecular end, specifically, for example, polysiloxane having one end blocked with a hydrodimethylsilyl group and a trimethylsilyl group as exemplified above, SiO ₂ unit, SiO _{3 /} Examples include at least one siloxane unit selected from the group consisting of ₂ units, SiO units, and SiO _1/2 units, and polysiloxane composed of one hydrodimethylsiloxane unit.

  When the component (a ′) is a cyclic siloxane having one hydrosilyl group, specifically, for example, 1-hydro-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1- Hydro-3-phenyl-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1-hydro-3,5-diphenyl-1,3,5,7,7-pentamethylcyclotetrasiloxane, Examples include 1-hydro-3,5,7-triphenyl-1,3,5,7-tetramethylcyclotetrasiloxane.

  These (a ′) components, which are organosilicon compounds having one hydrosilyl group per molecule, may be used alone or in combination of two or more.

<Modified polyhedral polysiloxane (A)>
The modified polyhedral polysiloxane (A) used in the present invention reacts with the polyhedral polysiloxane compound (a) having the alkenyl group and / or hydrosilyl group (a) and the component (a) in the presence of a hydrosilylation catalyst described later. It can be obtained by subjecting a compound (b) having a possible hydrosilyl group or alkenyl group and, if necessary, a hydrosilylation reaction with an organosilicon compound (a ′) having one alkenyl group or hydrosilyl group in one molecule.

  The method for obtaining the component (A) is not particularly limited and can be variously set. However, the component (a) and the component (b) may be reacted without using the component (a ′), or (a) After reacting the component and the component (b), the component (a ′) may be reacted, or after reacting the component (a ′) and the component (b) in advance, the component (a) is reacted. Alternatively, the component (a) and the component (a ′) may be reacted in advance, and then the component (b) may be reacted, or the component (a) and the component (a ′) may coexist (b) You may make it react with a component, and you may make (a ') component and (b) component coexist, and make it react with (a) component. After completion of each reaction, for example, volatile unreacted components may be distilled off under reduced pressure and heating conditions, and used as a target product or an intermediate for the next step. In order to suppress the formation of a compound containing only the component (a ′) and the component (b) and not including the component (a), the component (a) and the component (b) are reacted and the unreacted (b The method of reacting the component (a ′) after distilling off the component) is preferred. From the viewpoint of simplicity of reaction, the method of reacting the component (b) with the component (a) and the component (a ′), or the method of reacting the component (a ′) with the component (b) (a The method of reacting with the component) is preferred.

  In the component (A) thus obtained, a part of the alkenyl group and / or hydrosilyl group of the component (a) may remain.

  The amount of component (b) added is such that the number of hydrosilyl groups or alkenyl groups is 2.5 to 20 for one alkenyl group or hydrosilyl group that reacts with component (b) of component (a). It is preferable to use it. When the addition amount is small, gelation may proceed due to a crosslinking reaction, and when the addition amount is large, physical properties such as storage stability of the obtained component (A) may be adversely affected.

  The amount of the component (a ′) added is such that the number of alkenyl groups or hydrosilyl groups is 0.1 per hydrosilyl group or alkenyl group that can react with the component (a ′) of the components (a) and (b). It is preferable to use it so that it becomes 6 or less. The use of the component (a ′) can provide the above-mentioned effects. However, if the amount added is large, the obtained physical properties after curing may be adversely affected.

Although there is no restriction | limiting in particular as the addition amount of the below-mentioned hydrosilylation catalyst used at the time of the synthesis | combination of (A) component, 1 mol of alkenyl groups which (a) component, (b) component, and (a ') component used for reaction have On the other hand, it is preferably used in the range of 10 ^-1 to 10 ^-10 mol. Preferably, it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. If there are many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it will absorb short-wavelength light, which may cause coloring, and if there are few hydrosilylation catalysts, the reaction will not proceed and the target product will There is a risk that it will not be obtained.

  As reaction temperature of hydrosilylation reaction, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC, More preferably, it is 45-140 degreeC. If the temperature is too low, the reaction does not proceed sufficiently, and if the temperature is too high, gelation may occur and handling properties may deteriorate.

  Such component (A) can also be liquefied at a temperature of 20 ° C. It is preferable that the polyhedral polysiloxane modified is in a liquid form because of excellent handling properties.

As a preferable example of the polyhedral polysiloxane modified body (A) used in the present invention, specifically, for example, a formula
[XR ³ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
[A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom, an alkyl group, or an aryl group Or a group linked to another polyhedral skeleton polysiloxane, X has a structure represented by the following general formula (1) or general formula (2), and when there are a plurality of X, the general formula (1 ) Or the structure of the general formula (2) may be different, or the structure of the general formula (1) or the general formula (2) may be mixed.

{L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. It is a site | part or the structure represented by following General formula (3), and may be the same or different. Z is a site bonded to a polyhedral polysiloxane via a hydrogen atom, an alkenyl group, an alkyl group, an aryl group or an alkylene chain, or a structure represented by the following general formula (3), It may or may not be. In which at least one of Y or Z is a hydrogen atom or an alkenyl group; R is an alkyl group or an aryl group;
-[CH ₂ ] _l -R ⁵ (3)
(L is an integer of 2 or more; R ⁵ is a group containing an organosilicon compound)}].

  As a hydrosilylation catalyst used at the time of the synthesis | combination of (A) component used for this invention, a well-known thing can be selected as a hydrosilylation catalyst, and there is no restriction | limiting in particular.

Specifically, a platinum-olefin complex, chloroplatinic acid, a simple substance of platinum, a carrier (alumina, silica, carbon black, etc.) supported by solid platinum; a platinum-vinylsiloxane complex such as Pt _n ( ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ; platinum-phosphine complex such as Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ; platinum-phosphite complex such as Pt [P ( OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer), Pt (acac) _2, also platinum described in U.S. Patent 3,159,601 and in Pat 3159662 of Ashby et al - hydrocarbon complex, and Lamoreaux et al U.S. Pat. Platinum Arcola described in JP 3220972 specification - DOO catalysts may be mentioned.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl ₄ , and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) _{2 and the} like are preferable.

  Moreover, you may use a retarder for (A) component used for this invention. The curing retarder is a component that can be used for adjusting the hydrosilylation reactivity or improving the storage stability of the component (A). In the present invention, a known curing retarder can be used, specifically, a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, an organic peroxide. Thing etc. are mentioned. These may be used alone or in combination of two or more.

  Specific examples of the compound containing an aliphatic unsaturated bond include 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne, and 3,5-dimethyl-1- Examples thereof include propargyl alcohols such as hexyn-3-ol and 1-ethynyl-1-cyclohexanol, ene-yne compounds, maleic acid esters such as maleic anhydride and dimethyl maleate, and the like.

  Specific examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite.

  Specific examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide, and the like.

  Specific examples of nitrogen-containing compounds include N, N, N ′, N′-tetramethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, and N, N-dibutyl. -1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N-dibutyl-1,4-butanediamine, 2,2 Examples include '-bipyridine.

  Specific examples of tin compounds include stannous halide dihydrate, stannous carboxylate, and the like.

  Specific examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate. Of these, dimethyl maleate, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol can be exemplified as particularly preferred curing retarders.

The addition amount of the curing retarder is not particularly limited, but is preferably used in the range of 10 ⁻¹ to 10 ³ mol, more preferably in the range of 1 to 100 mol, with respect to 1 mol of the hydrosilylation catalyst. preferable. Moreover, these hardening retarders may be used independently and may be used in combination of 2 or more types.

<Aryl group contained in silicone (S) having a weight average molecular weight of 1,000 to 200,000>
The silicone (S) having a weight average molecular weight of 1,000 or more and 200,000 or less used in the present invention preferably has an aryl group from the viewpoint of further enhancing the effects of the present invention. If the aryl group content of the component (S) is significantly different from the aryl group content of the silicone-based curable composition containing the silicone-treated phosphor of the present invention, the silicone-treated phosphor may agglomerate. It is preferably close to the aryl group content of the system curable composition, and can take any value. However, if exemplified, it is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol / g, more preferably 2 × 10 ⁻⁵ to 8 × 10 ⁻³ mol / g, more preferably 5 × 10 ^{−5 to} 6 × 10 ⁻³ mol / g.

  The ratio of the aryl group content (mol / g) of the silicone-based curable composition / the aryl group content (mol / g) of the (S) component is 0.01 to 100, preferably 0.1 to 10, and more preferably. Is 0.3-5.

<Silicone-treated phosphor-containing silicone-based curable composition>
The silicone-treated phosphor-containing silicone-based curable composition of the present invention is obtained by blending the silicone-treated phosphor of the present invention with a silicone-based curable composition. By using the silicone-based phosphor-containing silicone-based curable composition of the present invention for sealing a light-emitting device, the resulting light-emitting device can be obtained in comparison with the case of using a silicone-based curable composition containing an untreated phosphor. Chromaticity variation is suppressed.

  Generally known silicone-based curable compositions can be arbitrarily used for the silicone-based curable composition containing the silicone-treated phosphor of the present invention, and the obtained light-emitting device has reliability such as heat resistance and crack resistance. Is required to use a methyl silicone-based curable composition, and when the obtained light emitting device is required to have gas barrier properties, it is preferable to use a phenyl silicone-based curable composition or an epoxy silicone-based curable composition.

  The viscosity of the silicone-based curable composition used in the present invention is not particularly limited, but it is preferably 1 Pa · s to 300 Pa · s, more preferably 2 Pa · s to 200 Pa · s at a temperature of 23 ° C. . If the viscosity is low, the dispersion of the phosphor may be deteriorated after blending the phosphor, and if the viscosity is high, the handleability of the composition is concerned.

  There is no particular limitation on the amount of the silicone-treated phosphor blended in the silicone-based curable composition, and any amount can be used to obtain the luminescent color desired for the light-emitting device. In the composition, the silicone-treated phosphor is preferably 0.1% by weight or more, more preferably 1% by weight or more, still more preferably 2% by weight or more, preferably 50% by weight or less, more preferably 40% by weight. Hereinafter, it is more preferably 30% by weight or less. If the amount is small, wavelength conversion by the phosphor may be insufficient, and the target emission color may not be obtained. If the amount is large, the handling property of the resulting curable composition may be reduced or optical There is a possibility that the utilization efficiency of the phosphor is lowered due to the interference action.

  The method of mixing and dispersing the silicone-treated phosphor in the silicone-based curable composition is not particularly limited as long as it is a method capable of uniformly dispersing the silicone-treated phosphor without damaging the phosphor crystal structure. For example, a conventionally known method such as a planetary stirring deaerator, a planetary mixer, a trimix, a cutter roll, a high speed disper, a homogenizer, a three roll, a two roll, a kneader, or a bead mill can be used. Of these, planetary agitating and degassing devices, such as planetary agitating and defoaming devices, cutter rolls, etc. that generate little heat during dispersion and those with little metal wear particles from the mixer are preferred. This is preferable because it can be mixed and dispersed with little defoaming. These mixing / dispersing methods may be performed alone or in combination of two or more. The mixing / dispersing time is not particularly limited as long as the phosphor is uniformly dispersed in the curable composition and there is no problem in workability. For example, when a planetary stirring mixer is used, it is preferably 10 seconds or more. Within 1 hour, more preferably within 30 seconds and within 30 minutes, and even more preferably within 1 minute and within 20 minutes. When the mixing / dispersing time is short, the phosphor may not be uniformly dispersed in the curable composition, and when the mixing / dispersing time is long, workability deteriorates.

  The silicone-based curable composition containing the silicone-treated phosphor is preferably used for sealing the light-emitting element within 4 hours, more preferably within 3 hours, and even more preferably within 2 hours after mixing and dispersing as described above. It is preferable. Here, the sealing of the light-emitting element means that the phosphor-containing curable composition is injected into the reflector on which the light-emitting element is mounted, or the LED mounted on the substrate is phosphor-containing by a technique such as press molding or transfer molding. Examples include direct sealing with a curable composition. If the time from mixing / dispersing to molding is long, the dispersion of the phosphor in the curable composition may not be uniform, and the chromaticity variation of the light-emitting device obtained may increase.

  When adding a temperature when hardening a silicone processing fluorescent substance containing silicone type curable composition, Preferably it is 30-400 degreeC, More preferably, it is 50-250 degreeC. When the curing temperature is high, the resulting cured product tends to have poor appearance, and when it is low, curing is insufficient. Moreover, you may make it harden | cure combining the temperature conditions of two or more steps. Specifically, for example, by raising the curing temperature stepwise such as 70 ° C., 120 ° C., and 150 ° C., a preferable cured product can be obtained, which is preferable.

  The curing time can be appropriately selected depending on the curing temperature, the amount of hydrosilylation catalyst to be used and the amount of reactive groups, and other combinations of the curable composition. Preferably, a cured product can be obtained by performing for 10 minutes to 8 hours.

In addition, the silicone-treated phosphor-containing silicone-based curable composition of the present invention includes various additives such as an adhesion-imparting agent, a colorant, and a heat resistance improver, a reaction control agent, a release agent, or a filling agent as necessary. A dispersant for the agent can be optionally added. Examples of the filler dispersant include diphenylsilane diol, various alkoxysilanes, carbon functional silane, silanol group-containing low molecular weight siloxane, and the like. In addition, it is preferable to stop these arbitrary components to the minimum addition amount so that the effect of this invention may not be impaired.
<Inorganic filler>
The silicone-treated phosphor-containing silicone-based curable composition of the present invention preferably contains an inorganic filler. By using inorganic filler, the dispersibility of the phosphor is improved, and the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical characteristics, light reflection after sealing the light emitting device Various physical properties such as rate, flame retardancy, fire resistance, and gas barrier properties can be improved.

  The inorganic filler is not particularly limited as long as it is an inorganic substance or a compound containing an inorganic substance. Specifically, for example, quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder amorphous silica, etc. Silica-based inorganic filler, alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, glass flake, alumina fiber, carbon fiber, mica, graphite, carbon black, Examples thereof include ferrite, graphite, diatomaceous earth, white clay, clay, talc, aluminum hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloon, and silver powder. These may be used alone or in combination of two or more.

The inorganic filler may be appropriately subjected to a surface treatment. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a silane coupling agent, and the like, but are not particularly limited. As the shape of the inorganic filler, various types such as a crushed shape, a piece shape, a spherical shape, and a rod shape can be used. The average particle size and particle size distribution of the inorganic filler are not particularly limited, but from the viewpoint of gas barrier properties, the average particle size is preferably 0.005 to 50 μm, more preferably 0.01 to 20 μm. More preferably. Similarly, the BET specific surface area, although not particularly limited, from the viewpoint of gas barrier properties, it is preferably 70m ² / g or more, more preferably 100 m ² / g or more, further 200 meters ² / It is especially preferable that it is g or more.

  The addition amount of the inorganic filler is not particularly limited, but is 0.01 to 100 parts by weight, more preferably 0.3 to 50 parts by weight, still more preferably 0.5 to 100 parts by weight of the curable composition. -30 parts by weight. When the amount of the inorganic filler added is large, the fluidity may be deteriorated, and when the amount of the inorganic filler added is small, desired physical properties may not be obtained.

  The means for mixing the inorganic filler is not particularly limited. Specifically, for example, a two-roll or three-roll, a planetary stirring and defoaming device, a homogenizer, a dissolver, a planetary mixer, or the like, Examples thereof include a melt kneader such as a plast mill. The mixing of the inorganic filler may be performed at normal temperature, may be performed by heating, may be performed under normal pressure, or may be performed under reduced pressure. However, if the temperature during mixing is high, the composition may be cured before molding.

<Light emitting device>
The light emitting device of the present invention is obtained by sealing a light emitting element with the silicone-treated phosphor-containing silicone-based curable composition of the present invention. The method for sealing the light-emitting element with the curable composition is not particularly limited. For example, the light-emitting element may be mounted on a reflector, and the curable composition may be injected and cured to be sealed. You may seal directly the light emitting element mounted in the board | substrate with a curable composition by techniques, such as press molding and transfer molding, without using. Here, as a reflector and a base | substrate, it does not specifically limit and what is used widely can be used. Further, the light emitting element is not particularly limited, and a light emitting element that is widely used as a light emitting element of an LED can be used as long as it can excite a phosphor with emitted light. For example, a blue light emitting element And ultraviolet light emitting elements. In the light emitting device of the present invention, a plurality of the same or different types of light emitting elements may be mounted per light emitting device.

  The light emitting device using the silicone-treated phosphor of the present invention can be used for various known applications. Specifically, for example, backlights for light emitting / receiving devices, liquid crystal display devices, etc., illumination, sensor light sources, vehicle instrument light sources, signal lights, indicator lights, display devices, light sources for planar light emitters, displays, decorations, various lights, etc. Can be mentioned.

  Next, although the fluorescent substance of this invention is demonstrated still in detail based on an Example, this invention is not limited only to these Examples.

<Weight average molecular weight>
The weight average molecular weight of the synthesized silicone was HLC-8220GPC (column: TSKgel SuperHZM-N (4 pieces) + HZ1000 (1 piece) inner diameter 4.6 mm × 15 cm, solvent: toluene, flow rate: 0.35 ml / min, manufactured by Tosoh Corporation. ). In addition, the catalog value was referred about the weight average molecular weight of commercially available silicone.

(Production Example 1)
To 1803 g of a 48% choline aqueous solution (trimethyl-2-hydroxyethylammonium hydroxide aqueous solution), 1459 g of tetraethoxysilane was added and stirred vigorously at room temperature for 2 hours. When the reaction system generated heat and became a homogeneous solution, the stirring was loosened and the reaction was further continued for 12 hours. Next, 1400 mL of methanol was added to the solid produced in the reaction system to obtain a uniform solution.

  While vigorously stirring a solution of 1149 g of dimethylvinylchlorosilane, 830 g of trimethylsilyl chloride and 1400 mL of hexane, the methanol solution was slowly added dropwise. After completion of the dropwise addition, the mixture was reacted for 1 hour, and then the organic layer was extracted and concentrated to obtain a solid. Next, the resulting solid is washed by vigorously stirring in methanol and filtered to obtain a polyhedral polysiloxane compound containing 16 Si atoms and an alkenyl group having 4 vinyl groups. 760 g of tetrakis (vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane (Fw = 1178.2) was obtained as a white solid.

(Production Example 2)
A platinum vinylsiloxane complex obtained by dissolving 10.0 g of tetrakis (vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane, which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 1, in 20.0 g of toluene. 1.27 μL of a xylene solution (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) was added. The solution thus obtained was slowly added dropwise to a solution of 20.36 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 20.36 g of toluene. , And reacted at 105 ° C. for 2 hours. After completion of the reaction, 7.1 μl of ethynylcyclohexanol and 1.65 μl of dimethyl maleate were added, and toluene and unreacted components were distilled off, whereby 17.5 g of a liquid polyhedral polysiloxane modified product (weight average molecular weight: 2400) Got.

(Production Example 3)
10.0 g of tetrakis (vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane, which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 1, is dissolved in 20.0 g of toluene, and vinyldiphenylmethylsilane is dissolved. 6.67 g of a xylene solution of platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) 0.50 μL was added. The solution thus obtained was slowly added dropwise to a solution of 8.17 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 8.17 g of toluene. , And reacted at 105 ° C. for 2 hours. After completion of the reaction, 2.8 μl of ethynylcyclohexanol and 0.65 μl of dimethyl maleate were added, and toluene and unreacted components were distilled off to obtain 24.2 g of a modified polyhedral polysiloxane having a phenyl group (weight average). Molecular weight: 3200) was obtained.

Example 1
Into a 100 ml plaque, 5.00 g of silicate yellow phosphor manufactured by Intematix and 0.263 g of modified polyhedral polysiloxane obtained in Production Example 2 were added in order and mixed. The silicone-treated phosphor of the present invention was obtained by sequentially performing stirring for 3 minutes, defoaming for 3 minutes, and stirring for 3 minutes using ARE-310.

  Separately, in a 100 ml plastic cup, 0.737 g of the obtained silicone-treated phosphor, 0.993 g of A agent of Phenylsilicone OE6630 (A / B = 1/4 (wt / wt)) manufactured by Toray Dow Silicone Co., B agent 971 g was added in order and mixed, and the silicone-based phosphor-containing silicone-based curable composition of the present invention was obtained by sequentially performing 3 minutes of stirring, 3 minutes of defoaming, and 3 minutes of stirring using ARE-310. Obtained.

  Separately, a reflector made by Enomoto (product number: TOP LED 1-IN-1) on which a 12 mil × 13 mil square blue LED chip (product number: B1213AAA0 S46B / C-19 / 20) made by Genelites Co., Ltd. was prepared was obtained. The curable composition thus obtained was injected using a dispenser 1500 series manufactured by Suntech, a 3 cc barrel-piston set (product number: SH09CP-B) manufactured by Suntech, and a chip (product number: SH23-B) manufactured by Suntech. . Then, it hardened | cured by the step cure of the conditions of 80 degreeC * 2 hours, 100 degreeC * 1 hour, and 180 degreeC * 1 hour in a convection oven. The obtained light-emitting device of the present invention was made to emit light when energized at a temperature of 25 ° C., a current of 30 mA, and a standby time of 30 seconds using a total luminous flux (φ300 mm) system (product number: HM-0930) manufactured by Otsuka Electronics. The chromaticity of the luminescent color was measured, and the standard deviation of the chromaticity of the 32 luminescent colors measured was shown in Table 1.

(Example 2)
The same operation and evaluation as in Example 1 were performed except that the polyhedral polysiloxane modified body obtained in Production Example 3 was used as the silicone to be mixed with the phosphor, and the standard deviation of the chromaticity of the 32 samples of emitted colors was evaluated. Are listed in Table 1.

(Example 3)
The same operation and evaluation as in Example 1 were performed except that both terminal vinyl group-containing phenyl silicone PDV-2331 manufactured by Gelest was used as the silicone mixed with the phosphor, and the standard deviation of the chromaticity of 32 samples of emitted colors was evaluated. Are listed in Table 1.

Example 4
As the silicone mixed with the phosphor, the same operation and evaluation as in Example 1 were carried out except that both terminal vinyl group-containing phenyl silicone PDV-2335 manufactured by Gelest Co. was used, and the standard deviation of chromaticity of 32 samples of emitted colors Are listed in Table 1.

(Example 5)
As the silicone mixed with the phosphor, the same operation and evaluation as in Example 1 were carried out except that both terminal vinyl group-containing phenyl silicone PDV-1625 manufactured by Gelest Co. was used, and the standard deviation of the chromaticity of 32 samples of emitted colors Are listed in Table 1.

(Example 6)
The same operation and evaluation as in Example 1 were performed except that both terminals vinyl group-containing phenyl silicone PDV-1641 manufactured by Gelest Co. was used as the silicone mixed with the phosphor, and the standard deviation of the chromaticity of 32 samples of emitted colors Are listed in Table 1.

(Example 7)
The same operation and evaluation as in Example 1 were performed except that both terminal vinyl group-containing phenyl silicone PDV-0525 manufactured by Gelest Co. was used as the silicone mixed with the phosphor, and the standard deviation of chromaticity of 32 samples of emitted colors Are listed in Table 1.

(Example 8)
As the silicone mixed with the phosphor, the same operation and evaluation as in Example 1 were carried out except that both terminal vinyl group-containing phenyl silicone PDV-0325 manufactured by Gelest Co. was used, and the standard deviation of chromaticity of 32 samples of emitted colors Are listed in Table 1.

Example 9
The same operation and evaluation as in Example 1 were performed except that both terminals vinyl group-containing methyl silicone DMS-V22 manufactured by Gelest was used as the silicone mixed with the phosphor, and the standard deviation of the chromaticity of 32 samples of emitted colors Are listed in Table 1.

(Example 10)
The same operation and evaluation as in Example 1 were carried out except that both ends vinyl group-containing methyl silicone DMS-V25 manufactured by Gelest was used as the silicone mixed with the phosphor, and the standard deviation of the chromaticity of the 32 samples of emitted colors was evaluated. Are listed in Table 1.

(Example 11)
EY4750 5.00 g and the polyhedral polysiloxane modified product 1.25 g obtained in Production Example 3 were added in order to a 100 ml plaque and mixed, and the mixture was further stirred using ARE-310 for 3 minutes and degassed for 3 minutes. The silicone-treated phosphor of the present invention was obtained by sequentially performing stirring for 3 minutes.

  Separately, 0.875 g of the obtained silicone-treated phosphor, 0.965 g of OE6630 A agent and 3.860 g of B agent were added in order to a 100 ml plastic cup and mixed, and the mixture was further stirred using ARE-310 for 3 minutes. The silicone-treated phosphor-containing silicone-based curable composition of the present invention was obtained by sequentially performing defoaming for 3 minutes and stirring for 3 minutes.

  Using the obtained curable composition, the same operation and evaluation as in Example 1 were performed, and the standard deviation of chromaticity of the luminescent color of 32 samples is shown in Table 1.

(Example 12)
EY4750 5.00 g and the polyhedral polysiloxane modified product 0.155 g obtained in Production Example 3 were added in order to 100 ml Plakabu and mixed, and the mixture was further stirred with ARE-310 for 3 minutes and degassed for 3 minutes. The silicone-treated phosphor of the present invention was obtained by sequentially performing stirring for 3 minutes.

  Separately, 0.722 g of the obtained silicone-treated phosphor, 0.996 g of OE6630 A agent, and 3983 g of B agent were added in order to a 100 ml plastic cup and mixed, and the mixture was further stirred for 3 minutes using ARE-310. By performing 3 minutes in order and 3 minutes in stirring, the silicone-treated phosphor-containing silicone-based curable composition of the present invention was obtained.

  Using the obtained curable composition, the same operation and evaluation as in Example 1 were performed, and the standard deviation of chromaticity of the luminescent color of 32 samples is shown in Table 1.

(Example 13)
10.00 g of EY4750 and 0.075 g of the modified polyhedral polysiloxane obtained in Production Example 3 were added in order to a 100 ml plaque and mixed, and the mixture was further stirred using ARE-310 for 3 minutes and degassed for 3 minutes. The silicone-treated phosphor of the present invention was obtained by sequentially performing stirring for 3 minutes.

  Separately, in a 100 ml plastic cup, 0.705 g of the obtained silicone-treated phosphor, 0.999 g of OE6630 A agent, and 3.995 g of B agent were added and mixed in that order, and the mixture was further stirred using ARE-310 for 3 minutes. The silicone-treated phosphor-containing silicone-based curable composition of the present invention was obtained by sequentially performing defoaming for 3 minutes and stirring for 3 minutes.

  Using the obtained curable composition, the same operation and evaluation as in Example 1 were performed, and the standard deviation of chromaticity of the luminescent color of 32 samples is shown in Table 1.

(Example 14)
The same operation as in Example 2 was performed to obtain the silicone-treated phosphor of the present invention treated with the polyhedral polysiloxane modified product obtained in Production Example 3.

  Separately, in a 100 ml plastic cup, 0.737 g of the obtained silicone-treated phosphor, 0.100 g of silica R380S manufactured by Nippon Aerosil Co., Ltd., 0.993 g of OE6630, and 3.971 g of B agent were added and mixed in that order. A silicone-treated phosphor-containing silicone-based curable composition containing the inorganic filler of the present invention was obtained by sequentially performing stirring for 3 minutes, defoaming for 3 minutes, and stirring for 3 minutes using ARE-310.

  Using the obtained curable composition, the same operation and evaluation as in Example 1 were performed, and the standard deviation of chromaticity of the luminescent color of 32 samples is shown in Table 1.

(Comparative Example 1)
Into a 100 ml plastic cup, add 0.700 g of EY4750, 1.000 g of OE6630 A agent, and 4.000 g of B agent in order, and continue to stir using ARE-310 for 3 minutes, defoaming 3 minutes, and stirring 3 minutes. The phosphor-containing silicone-based curable composition was obtained by sequentially performing the steps.

  Using the obtained curable composition, the same operation and evaluation as in Example 1 were performed, and the standard deviation of chromaticity of the luminescent color of 32 samples is shown in Table 1.

(Comparative Example 2)
Polyhedron obtained in Production Example 3 with EY4750 5.00 g, 1,1,7,7-tetramethyl-3,3,5,5-tetraphenyl-1,7-divinyltetrasiloxane manufactured by Clariant 0.263 g of the modified structure polysiloxane was added in order and mixed, and the silicone-treated phosphor was obtained by further performing stirring for 3 minutes, defoaming for 3 minutes, and stirring for 3 minutes using ARE-310.

  Using the obtained silicone-treated phosphor, the same operation and evaluation as in Example 1 were performed, and the standard deviation of the chromaticity of the luminescent color of 32 samples is shown in Table 1.

(Reference Example 1)
In 100 ml Plakabu, 10.00 g of EY4750 and 0.050 g of the modified polyhedral polysiloxane obtained in Production Example 3 were added in order and mixed, and the mixture was further stirred using ARE-310 for 3 minutes and degassed for 3 minutes. A silicone-treated phosphor was obtained by sequentially performing stirring for 3 minutes.

  Separately, in a 100 ml plastic cup, 0.704 g of the obtained silicone-treated phosphor, 0.999 g of OE6630 A agent, and 3.995 g of B agent were added in order and mixed, and the mixture was further stirred using ARE-310 for 3 minutes. By performing defoaming 3 minutes and stirring 3 minutes in order, a silicone-treated phosphor-containing silicone-based curable composition was obtained.

  Using the obtained curable composition, the same operation and evaluation as in Example 1 were performed, and the standard deviation of chromaticity of the luminescent color of 32 samples is shown in Table 1.

(Example 15)
The polyhedral polysiloxane modified product 0 obtained in Production Example 3 was prepared by adding 4.00 g of oxynitride green phosphor GR240 manufactured by Denki Kagaku Kogyo Co., Ltd., 100 g of red nitride BR102C manufactured by Mitsubishi Chemical Co., Ltd. 263 g was added in order and mixed, and the silicone-treated phosphor of the present invention was further processed in this order by sequentially performing 3 minutes of stirring, 3 minutes of defoaming, and 3 minutes of stirring using ARE-310 manufactured by Thinky Co., Ltd. Got.

  Separately, 0.632 g of the obtained silicone-treated phosphor, 0.994 g of OE6630 A agent and 3.975 g of B agent were added in order to a 100 ml plastic cup and mixed, and the mixture was further stirred using ARE-310 for 3 minutes. The silicone-treated phosphor-containing silicone-based curable composition of the present invention was obtained by sequentially performing defoaming for 3 minutes and stirring for 3 minutes.

  Using the obtained curable composition, the same operation and evaluation as in Example 1 were performed, and the standard deviation of chromaticity of the luminescent color of 32 samples is shown in Table 1.

(Example 16)
To a 100 ml plaque, add 4.000 g of GR240, 1.00 g of BR102C and 0.263 g of PDV-1625 in this order, and mix them as they are. Further, the mixture is stirred for 3 minutes using Awatori Rentaro ARE-310 manufactured by Thinky, defoaming 3 Minutes and stirring for 3 minutes in order to obtain the silicone-treated phosphor of the present invention.

  Using the obtained silicone-treated phosphor, the same operation and evaluation as in Example 1 were performed, and the standard deviation of the chromaticity of the luminescent color of 32 samples is shown in Table 1.

(Comparative Example 3)
To the 100 ml plastic cup, 0.480 g of GR240 not treated with silicone, 0.120 g of BR102C not treated with silicone, 1.000 g of OE6630 A agent, and 4.000 g of B agent were added in order and mixed. A phosphor-containing silicone-based curable composition was obtained by sequentially performing stirring for 3 minutes, defoaming for 3 minutes, and stirring for 3 minutes using -310.

  Using the obtained curable composition, the same operation and evaluation as in Example 1 were performed, and the standard deviation of chromaticity of the luminescent color of 32 samples is shown in Table 1.

  As shown in Table 1, it is clear that the chromaticity variation of the resulting light emitting device can be suppressed by using the silicone-treated phosphor of the present invention. In addition, when a silicone having a polyhedral polysiloxane skeleton is used as the (S) component (Examples 1, 2, 11 to 13), a silicone having a phenyl group is used as the (S) component (Example 3). 8) and when silica is used (Example 14), it can be seen that a higher effect is obtained. Further, even when a plurality of types of phosphors are used, it is clear that the chromaticity variation of the obtained light emitting device can be suppressed by using the silicone-treated phosphor of the present invention (Examples 15 and 16).

Claims (16)

A silicone-treated phosphor obtained by mixing phosphor (S) having a weight average molecular weight of 1,000 or more and 200,000 or less, and a phosphor ,
The silicone (S) component is
A silicone-treated phosphor, which is a silicone having a polyhedral polysiloxane skeleton . The silicone-treated phosphor according to claim 1, wherein the silicone (S) component is 0.75 to 500 parts by weight with respect to 100 parts by weight of the phosphor. The silicone-treated phosphor according to claim 1, wherein the silicone (S) component is 0.75 to 30 parts by weight with respect to 100 parts by weight of the phosphor. The silicone-treated phosphor according to any one of claims 1 to 3, wherein the silicone (S) component is a silicone having an alkenyl group or a hydrosilyl group. The polyhedral polysiloxane-based compound (a) in which the silicone having a polyhedral polysiloxane skeleton contains an alkenyl group and / or a hydrosilyl group (a), a compound having a hydrosilyl group or alkenyl group capable of hydrosilylation with the component (a) ( b), and if necessary, a modified polyhedral polysiloxane (A) obtained by hydrosilylation of an organosilicon compound (a ′) having one alkenyl group or hydrosilyl group in one molecule. The silicone-treated phosphor according to claim 1, wherein the phosphor is a silicone-treated phosphor. The silicone-treated phosphor according to claim 5 , wherein the component (b) is a cyclic siloxane having a hydrosilyl group or an alkenyl group. 6. The silicone-treated phosphor according to claim 5 , wherein the component (b) is a linear siloxane having a hydrosilyl group or an alkenyl group at the molecular end. The component (a) is
Formula [AR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group and / or a hydrogen atom provided that at least one is an alkenyl group;. ^{R 1} is R ² is a siloxane unit represented by a substituent other than an alkenyl group and a hydrogen atom, an alkyl group, an aryl group, or a group connected to another polyhedral skeleton polysiloxane or siloxane compound) characterized in that it is a composed polyhedral polysiloxane compound from the silicone treated phosphor according to any one of claims 5-7. The component (a) is
Formula [BR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; B is alkenyl and / or hydrogen atom, provided that at least one is hydrogen atom;. ^{R 1} is R ² is a siloxane unit represented by a substituent other than an alkenyl group and a hydrogen atom, an alkyl group, an aryl group, or a group connected to another polyhedral skeleton polysiloxane or siloxane compound) characterized in that it is a composed polyhedral polysiloxane compound from the silicone treated phosphor according to any one of claims 5-7. The modified polyhedral polysiloxane (A ) is
[XR ³ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
[A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkyl group, an aryl group, an alkenyl group, a hydrogen atom Or a group linked to another polyhedral polysiloxane; X has a structure represented by the following general formula (1) or general formula (2), and when there are a plurality of X, the general formula (1 ) Or the structure of the general formula (2) may be different, or the structure of the general formula (1) or the general formula (2) may be mixed.

{L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. It is a site | part or the structure represented by following General formula (3), and may be the same or different. Z is a site bonded to a polyhedral polysiloxane via a hydrogen atom, an alkenyl group, an alkyl group, an aryl group or an alkylene chain, or a structure represented by the following general formula (3), It may or may not be. In which at least one of Y or Z is a hydrogen atom or an alkenyl group; R is an alkyl group or an aryl group;
^{_{- [CH 2] l -R 5}} (3)
(L is an integer of 2 or more; R ⁵ is a group containing an organosilicon compound)}]
The silicone-treated phosphor according to any one of Claims 5 to 9 , wherein is a structural unit. The silicone-treated phosphor according to any one of claims 1 to 10 , wherein the silicone (S) component has an aryl group. The silicone-treated phosphor according to any one of claims 1 to 11 , wherein the phosphor is two or more kinds of phosphors having emission peaks different from each other. A silicone-treated phosphor-containing silicone-based curable composition obtained by blending the silicone-treated phosphor according to any one of claims 1 to 12 with a silicone-based curable composition. The silicone-based curable composition containing a silicone-treated phosphor according to claim 13 , comprising an inorganic filler . A light emitting device, which is sealed with the silicone-based phosphor-containing silicone-based curable composition according to claim 13 or 14 . Method for producing a silicone-treated phosphor characterized by mixing the silicone component (S) and the phosphor of claim 1 to 11.