WO2014017501A1 - Wavelength-conversion component for semiconductor light-emitting device, method for manufacturing wavelength-conversion component for semiconductor light-emitting device, and thermosetting silicone composition - Google Patents

Abstract

The present invention provides a wavelength-conversion component having sufficient hardness to retain its shape, the component having as a polymer binder a silicone with exceptional resistance to light and heat. The present invention relates to a wavelength-conversion component that is a molded article comprising a silicone composition having a fluorescent substance and a filler dispersed in a silicone binder, wherein the filler contains a spherical silicone resin having a particle diameter of at least 1 µm, the spherical silicon resin content being at least 50 weight parts to 100 weight parts of silicone binder.

Description

Wavelength conversion component for semiconductor light emitting device, method for producing the same, and thermosetting silicone composition

The present invention relates to a wavelength conversion component for a semiconductor light emitting device, a manufacturing method thereof, and a thermosetting silicone composition.

A semiconductor light emitting device configured to generate white light by combining a light emitting diode (LED) and a phosphor that converts a part of light (primary light) emitted from the LED into light of different wavelength (secondary light). The device is known. In such semiconductor light emitting devices, attempts have been made to make components responsible for the wavelength conversion function into components. As an example, there is known a wavelength conversion component formed of a composition in which a phosphor is dispersed in an optically transparent polymer binder. For example, Patent Document 1 discloses an “LED package” using a wavelength conversion component called “fluorescent plate”.

Recently, an LED device for illumination called a remote phosphor type LED device in which a large wavelength conversion component is combined with a high output LED has been developed (Patent Document 2). In the remote phosphor type LED device, in order to reduce the cost, it is required to reduce the amount of phosphor used in the wavelength conversion component as much as possible.

Therefore, in order to efficiently use a small amount of phosphor for wavelength conversion, a light diffusing agent is added to the resin composition, which is a material, in addition to the phosphor, and the primary light is converted into phosphor particles inside the wavelength conversion component. A method for increasing the chance of interaction has been proposed (FIG. 12 of Patent Document 2). Moreover, a silicone composition to which silicone particles are added in order to suppress the sedimentation of the phosphor has been proposed (Patent Document 3).

Japanese Laid-Open Patent Publication No. 2001-111117 (US Pat. No. 6,504,301) US Patent Application Publication No. 2012/0087105 International Publication No. 2011/102272

The wavelength conversion component is required to have translucency in the visible wavelength range (380 nm to 780 nm) and to be hard enough to maintain its own shape. On the other hand, from the viewpoint of productivity, it is desirable that the wavelength conversion component can be manufactured by a molding method such as injection molding or transfer molding.

The present invention has been made in view of such circumstances, and its main purpose is to use a wavelength conversion component having a hardness sufficient to maintain its own shape, using silicone having excellent light resistance and heat resistance as a polymer binder. It is to provide.

Another object of the present invention is to provide a suitable method for manufacturing such a wavelength conversion component.

The object of the present invention also includes providing a thermosetting silicone composition that can be suitably used as a material for such a wavelength conversion component.

According to the present invention, the following wavelength conversion component is provided.
(A1) A wavelength conversion component that is a molded product made of a silicone composition in which a phosphor and a filler are dispersed in a silicone binder,
The filler includes a spherical silicone resin having a particle size of 1 μm or more,
The spherical silicone resin content is 50 parts by weight or more with respect to 100 parts by weight of the silicone binder.
Wavelength conversion component.
(A2) The wavelength conversion component according to (a1), wherein the durometer hardness of the silicone composition is HDD25 or more.
(A3) A wavelength conversion component that is a molded product made of a silicone composition in which a phosphor and a filler are dispersed in a silicone binder,
The silicone binder is an elastomer having a durometer hardness of HDD20 or less,
The filler contains a spherical silicone resin having a particle size of 1 μm or more,
The durometer hardness of the silicone composition is HDD25 or more,
Wavelength conversion component.
(A4) The wavelength conversion component according to any one of (a1) to (a3), wherein a difference in refractive index between the silicone binder and the spherical silicone resin is less than 0.05.
(A5) The wavelength conversion component according to any one of (a1) to (a4), wherein each of the silicone binder and the spherical silicone resin has a refractive index lower than that of silica.
(A6) The silicone binder has a structure in which polydimethylsiloxane is crosslinked, and the spherical silicone resin has a polyalkylsilsesquioxane structure, according to any one of the above (a1) to (a5). Wavelength conversion component.
(A7) The wavelength conversion component according to any one of (a1) to (a6), wherein the filler does not contain a spherical silicone resin having a particle diameter of 3 μm or less.
(A8) The wavelength conversion component according to any one of (a1) to (a7), wherein the filler further contains spherical silica.
(A9) The wavelength conversion component according to (a8), wherein the spherical silica includes fused silica.
(A10) The wavelength conversion component according to (a9), wherein the content of the spherical silica is 5 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the silicone binder.
(A11) The wavelength conversion component according to any one of (a1) to (a10), wherein the filler further contains fumed silica.
(A12) The wavelength conversion component according to any one of (a1) to (a11), wherein the silicone composition has a durometer hardness of HDD35 or more.
(A13) The molded body is a molded body of a silicone composition having a shear rate of 120 / s and a viscosity at a temperature of 25 ° C. of 100 Pa · s or more and less than 1000 Pa · s (a1) to (a12) The wavelength conversion component according to any one of the above.
(A14) The wavelength conversion component according to any one of (a1) to (a13), which is a disk having a diameter of 5 to 7 cm and a thickness of 0.5 to 1 mm.
(A15) The wavelength conversion component according to any one of (a1) to (a13), which is a disk having a diameter of 2 to 3 cm and a thickness of 0.2 to 0.5 mm.
(A16) The wavelength conversion component according to any one of (a1) to (a13), which is a hemispherical dome having a diameter and height of 1 to 5 cm and a thickness of 0.5 to 2 mm.
(A17) A part of the first light emitted by the LED having an emission peak wavelength in the range of 440 to 470 nm can be transmitted, and the other part of the first light is transmitted through the first light. The wavelength conversion component according to any one of (a1) to (a16), wherein the wavelength conversion component can be converted into second light having a color complementary to the color.

According to this invention, the thermosetting silicone composition for the following wavelength conversion components is provided.
(B1) a thermosetting silicone composition in which a phosphor and a filler are mixed with addition-curable silicone,
The filler includes a spherical silicone resin having a particle size of 1 μm or more,
The spherical silicone resin content is 50 parts by weight or more with respect to 100 parts by weight of the addition-curable silicone.
Thermosetting silicone composition for wavelength converting component.
(B2) The thermosetting silicone composition according to (b1), wherein the durometer hardness of the cured product of the thermosetting silicone composition is HDD25 or more.
(B3) a thermosetting silicone composition in which a phosphor and a filler are mixed with addition-curable silicone,
The cured product of the addition-curable silicone is an elastomer having a durometer hardness of HDD 20 or less,
The filler contains a spherical silicone resin having a particle size of 1 μm or more,
The thermosetting silicone composition for wavelength conversion components whose durometer hardness of the hardened | cured material of this thermosetting silicone composition is HDD25 or more.
(B4) The thermosetting silicone composition according to any one of (b1) to (b3), wherein a difference in refractive index between the addition-curable silicone and the spherical silicone resin is less than 0.05.
(B5) The thermosetting silicone composition according to any one of (b1) to (b4), wherein each of the addition-curable silicone and the spherical silicone resin has a refractive index lower than that of silica.
(B6) The addition-curable silicone contains polydimethylsiloxane in which a methyl group is partially substituted with a vinyl group, and the spherical silicone resin has a polyalkylsilsesquioxane structure. The thermosetting silicone composition according to any one of b5).
(B7) The thermosetting silicone composition according to any one of (b1) to (b6), wherein the filler does not contain a spherical silicone resin having a particle size of 3 μm or less.
(B8) The thermosetting silicone composition according to any one of (b1) to (b7), wherein the filler further contains spherical silica.
(B9) The thermosetting silicone composition according to (b8), wherein the spherical silica includes fused silica.
(B10) The thermosetting silicone composition according to (b9), wherein the content of the spherical silica is 5 to 80 parts by weight with respect to 100 parts by weight of the addition-curable silicone.
(B11) The thermosetting silicone composition according to any one of (b1) to (b10), which contains a curing retarder.
(B12) The thermosetting silicone composition according to any one of (b1) to (b11), wherein the filler further contains fumed silica.
(B13) The thermosetting silicone composition according to any one of (b1) to (b12), wherein the durometer hardness of the cured product of the thermosetting silicone composition is HDD 35 or more.
(B14) The thermosetting silicone composition according to any one of (b1) to (b13), wherein the viscosity at a shear rate of 120 / s and a temperature of 25 ° C. is 100 Pa · s or more and less than 1000 Pa · s.

According to the present invention, the following wavelength conversion component manufacturing method is provided.
(C1) A method for producing a wavelength conversion component, comprising the steps of curing and molding the thermosetting silicone composition according to any one of (b1) to (b14).
(C2) The manufacturing method according to (c1), wherein in the step of performing the curing and molding, the thermosetting silicone composition is injection-molded or transfer-molded.
(C3) The manufacturing method according to (c1) or (c2), wherein the wavelength conversion component is a disk having a diameter of 5 to 7 cm and a thickness of 0.5 to 1 mm.
(C4) The manufacturing method according to (c1) or (c2), wherein the wavelength conversion component is a disk having a diameter of 2 to 3 cm and a thickness of 0.2 to 0.5 mm.
(C5) The manufacturing method according to (c1) or (c2), wherein the wavelength conversion component is a hemispherical dome having a diameter and height of 1 to 5 cm and a thickness of 0.5 to 2 mm.
(C6) The wavelength converting component can transmit a part of the first light emitted from the LED having the emission peak wavelength in the range of 440 to 470 nm, and transmits the other part of the first light. The production method according to any one of (c1) to (c5), wherein the light can be converted into second light having a color complementary to the color of the first light.

According to the present invention, there is provided a wavelength conversion component that uses silicone as a polymer binder and has a hardness sufficient to maintain its own shape. Moreover, according to this invention, the suitable manufacturing method of this wavelength conversion component is provided. Moreover, according to this invention, the thermosetting silicone composition which can be used conveniently as a material of this wavelength conversion component is provided.

FIG. 1 is a graph showing the relationship between the “whiteness index” and the volume ratio of spherical silica in micron-sized fillers in a silicone composition. FIG. 2 is a graph showing the relationship between the “whiteness index” and the volume ratio of spherical silica in the micron size filler in the silicone composition. FIG. 3 is an xy chromaticity diagram (CIE 1931). FIG. 4 is a cross-sectional view of a remote phosphor type LED device including the wavelength conversion component according to the embodiment.

In the present specification, when referring to the refractive index of a material, unless otherwise specified, the refractive index means a refractive index at 20 ° C. at the wavelength of sodium D-line.

In this specification, when referring to the viscosity of a liquid silicone, a thermosetting silicone composition or the like, it means a viscosity at a shear rate of 120 / s and a temperature of 25 ° C. unless otherwise specified.

Hereinafter, the present invention will be described with reference to embodiments. However, the present invention is not limited to the embodiments described explicitly or implicitly in the present specification, and various modifications can be made without departing from the spirit of the present invention.

1. 1. Material for Wavelength Conversion Component 1.1 Silicone Binder According to the present invention, there is provided a wavelength conversion component formed of a silicone composition using silicone as a binder for dispersing a phosphor and a filler.

Silicone is also called an organopolysiloxane, and has a siloxane bond in the main chain, so that it is a polymer with extremely good heat resistance and light resistance.

The silicone binder is preferably an elastomer. The silicone binder particularly preferably has a durometer hardness of 20 or less, more preferably A50 or less. Wavelength conversion components in which the silicone binder is an elastomer are difficult to crack when subjected to strain or thermal shock. In addition, the durometer hardness of a silicone binder is usually about A10 or more from the point of resistance to scratches and tearing of the wavelength conversion component.

In order to make it possible to mold a silicone composition by a molding method such as injection molding or transfer molding, it is preferable to select an addition-curable silicone that is cured by a hydrosilylation reaction as a raw material for the silicone binder. Since the hydrosilylation reaction is not accompanied by by-products, this type of curable silicone can be cured preferably in the mold.

Addition-curable silicone is usually an organopolysiloxane having two or more hydrosilyl groups in one molecule (first component), an organopolysiloxane having two or more alkenyl groups in one molecule (second component), and Contains a curing catalyst.

Typical examples of the first component are polydiorganosiloxane having hydrosilyl groups at both ends, polymethylhydrosiloxane having both ends blocked with trimethylsilyl groups, methylhydrosiloxane-dimethylsiloxane copolymer, and the like.

A typical example of the second component is an organopolysiloxane having a silicon atom bonded to a vinyl atom at each end. The hardness and heat resistance of the silicone binder can be improved by using all or part of the second component as a silicone having a branched structure introduced using trifunctional silicon (T component) or tetrafunctional silicon (Q component). it can.

In addition, it is also possible to use an organopolysiloxane having both the first component and the second component, that is, an organopolysiloxane having both a hydrosilyl group and an alkenyl group in one molecule.

The curing catalyst is a catalyst for promoting an addition reaction that occurs between the hydrosilyl group in the first component and the alkenyl group in the second component. Examples thereof include platinum black, second platinum chloride, and platinum chloride. Acids, reaction products of chloroplatinic acid and monohydric alcohol, complexes of chloroplatinic acid and olefins, platinum-based catalysts such as platinum bisacetoacetate, platinum-based metal catalysts such as palladium-based catalysts and rhodium-based catalysts It is done.

The addition curable silicone preferably further contains a curing retarder. Preferred curing retarders include 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne, 3- (trimethylsilyloxy) -3-methyl-1-butyne, 1-ethynyl- Examples thereof include compounds having a carbon-carbon triple bond such as 1-cyclohexanol. Organopolysiloxanes having alkynyl groups can also be used as cure retarders.

The curing retarder not only prolongs the pot life of the thermosetting silicone composition, but also plays an important role in suppressing the dispersion of the phosphor and filler that can occur in the mold. By slowing down the curing of the silicone composition, a part of the silicone composition starts to cure before the cavity is filled with the silicone composition, and the dispersion unevenness caused by the mechanically deforming the quickly cured part. It is because it can suppress.

It is particularly preferable to use an addition-curable silicone in which a branched structure is introduced as the second component, since gelation proceeds rapidly.

The silicone binder having a structure in which polydimethylsiloxane (dimethylsilicone) is cross-linked is particularly excellent in heat resistance and light resistance. Such a structure can be obtained by using polydimethylsiloxane having a vinyl group bonded to a terminal silicon atom as the second component of the addition-curable silicone. Furthermore, the use of silicone that does not contain an aromatic group, such as methylhydrosiloxane-dimethylsiloxane copolymer, as the first component further improves the heat resistance and light resistance of the silicone binder.

In addition, addition-curable silicones having a low ratio of aromatic groups to hydrocarbon groups bonded to silicon atoms tend to be low in viscosity even at a temperature below room temperature, so that phosphors and fillers are easily dispersed uniformly. Also from this viewpoint, the addition-curable silicone used as the raw material for the silicone binder preferably does not contain an aromatic group, and even if it contains an aromatic group, the number is the total number of hydrocarbon groups bonded to silicon atoms. Is preferably less than 5%.

1.2 Phosphor The phosphor used in a general white LED can be used without limitation in the wavelength conversion component of the present invention.

A wavelength conversion component for a white light emitting device using a near ultraviolet LED or a violet LED as a light source usually contains a blue phosphor, a green phosphor, and a red phosphor. In addition to the green phosphor or instead of the green phosphor, a yellow phosphor can be used. The color temperature of the output light can be adjusted by changing the ratio of the content of each phosphor.

A wavelength conversion component for a white light emitting device using a blue LED as a light source usually contains a yellow phosphor. In order to generate white light having a low color temperature such as a light bulb color or warm white, a red phosphor is usually contained in addition to a yellow phosphor. The use of the red phosphor also helps to improve the color rendering properties of the light emitting device. In order to obtain better color rendering properties, part or all of the yellow phosphor can be replaced with a green phosphor.

The blue phosphor is a phosphor whose emission color is classified into “PURPULISH BLUE”, “BLUE” or “GREENISH BLUE” in the xy chromaticity diagram (CIE 1931) shown in FIG. A preferred example is a blue phosphor having Eu ²⁺ as an activator and a crystal composed of an alkaline earth aluminate or alkaline earth halophosphate as a base, for example, (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu.

The green phosphor is a phosphor whose emission color is classified into “GREEN” or “YELLOWISH GREEN” in the xy chromaticity diagram (CIE 1931) shown in FIG. Preferred examples include those using Eu ²⁺ as an activator and those using Ce ³⁺ as an activator.

The green phosphor of the Eu ²⁺ and activator, is one that alkaline earth silicates, alkaline earth silicate nitride, sialon and the like as a matrix.

Green phosphors based on alkaline earth silicate crystals include (Ba, Ca, Sr, Mg) ₂ SiO ₄ : Eu, (Ba, Sr, Ca) ₂ (Mg, Zn) Si ₂ O ₇ : Eu etc. Green phosphors based on alkaline earth silicate nitride crystals include (Ba, Ca, Sr) ₃ Si ₆ O ₁₂ N ₂ : Eu, (Ba, Ca, Sr) ₃ Si ₆ O ₉ N ₄ : Eu, (Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu and the like. Examples of green phosphors based on sialon crystals include β sialon: Eu, Sr ₃ Si ₁₃ Al ₃ O ₂ N ₂₁ : Eu, Sr ₅ Al ₅ Si ₂₁ O ₂ N ₃₅ : Eu.

The green phosphor using Ce ³⁺ as an activator includes (Y, Gd) ₃ Al ₅ O ₁₂ : Ce, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, Lu based on a garnet-type oxide crystal. ₃ (Al, Ga) ₅ O ₁₂ : Ce, Ca ₃ (Sc, Mg) ₂ Si ₃ O ₁₂ : Ce, and CaSc ₂ O ₄ : Ce based on alkaline earth metal scandate crystals.

The yellow phosphor is a phosphor whose emission color is classified into “YELLOW GREEN”, “GREENISH YELLOW”, “YELLOW” or “YELLOWISH ORANGE” in the xy chromaticity diagram (CIE 1931) shown in FIG. .

Preferred examples include Ce ³⁺ as an activator and a garnet-type oxide crystal as a base (Y, Gd) ₃ Al ₅ O ₁₂ : Ce, Tb ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce or Ce ³⁺ as an activator and La ₃ Si ₆ N ₁₁ : Ce, Ca _1.5x La _3-x Si ₆ N ₁₁ : Ce based on a lanthanum silicon nitride crystal. Further, as a yellow phosphor using Eu ²⁺ as an activator, (Ba, Sr) ₂ SiO ₄ : Eu (called BOSE or BOS), α sialon: Eu, (Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu etc.

In addition, as a yellow phosphor that can be preferably excited by a near-ultraviolet LED or a purple LED, “Cl_MS phosphor” reported in Nature Communications 3, Article number: 1132 is known.

The red phosphor is a phosphor whose emission color is classified into “RED”, “REDDISH ORANGE” or “ORANGE” in the xy chromaticity diagram (CIE 1931) shown in FIG. Preferable examples include those having Eu ²⁺ as an activator and an alkaline earth silicon nitride, α-sialon or alkaline earth silicate as a base. Red phosphors based on alkaline earth siliconitride crystals include (Ca, Sr, Ba) AlSi (N, O) ₃ : Eu, (CaAlSiN ₃ ) _1-x (Si _{(3n + 2) / 4} N _n O) _x : Eu, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, SrAlSi ₄ N ₇ : Eu, and the like. Examples of red phosphors based on alkaline earth silicate crystals include (Sr, Ba) ₃ SiO ₅ : Eu.

Another preferred example of the red phosphor is a Mn ⁴⁺ activated fluoro complex phosphor. A hexafluoro complex salt type represented by M ₂ XF ₆ : Mn is preferable, but is not limited, and a complex ion in which 5 to 7 fluorine ions are coordinated to a metal element serving as a coordination center. The inclusion can also be used. The most preferred ^{Mn 4+} -activated fluoro complex phosphor, _K 2 _SiF 6 to potassium hexafluorosilicate as a matrix: A Mn. A part of Si in K ₂ SiF ₆ : Mn can be substituted with Al, and a part of K can be substituted with Na.

Other red phosphors include (La, Y) ₂ O ₂ S: Eu, Mg ₄ (F) GeO ₆ : Mn, and the like.

1.3 Spherical Silicone Resin In the silicone composition constituting the wavelength conversion component of the present invention, a spherical silicone resin can be used as a filler for increasing hardness. The spherical silicone resin is usually hard spherical fine particles made of three-dimensionally crosslinked silicone in which 95% or more of the structural units are T units.

The spherical silicone resin is usually 50 parts by weight or more, preferably more than 50 parts by weight, more preferably 55 parts by weight or more, particularly preferably 95 parts by weight or more, most preferably 120 parts by weight or more based on 100 parts by weight of the silicone binder. By using this ratio, it is possible to obtain a thermosetting silicone composition that provides a cured product having sufficient hardness while having fluidity necessary for injection molding or transfer molding.

Another approach to increase the hardness of the cured product is to introduce a trifunctional silicon (T component) or tetrafunctional silicon (Q component) into the silicone binder at a high concentration to increase the crosslink density and harden the silicone binder itself. Although possible, the high-hardness silicone composition obtained by this method tends to break when subjected to strain or thermal shock. On the other hand, a silicone composition whose hardness is increased by using a highly flexible silicone elastomer as a binder and using a spherical silicone resin as a filler is highly resistant to strain and thermal shock.

Spherical silicone resin usually increases the viscosity of the silicone composition before curing. The degree of thickening increases as the particle size of the spherical silicone resin decreases. The viscosity of the thermosetting silicone composition is preferably 100 Pa · s or more and less than 1000 Pa · s at a shear rate of 120 / s and a temperature of 25 ° C. In particular, in order to perform injection molding using a general pumping pump, the viscosity of the silicone composition is preferably low, specifically, for example, preferably less than 500 Pa · s, and less than 400 Pa · s. More preferably, it is particularly preferably less than 300 Pa · s.

Therefore, the amount of the spherical silicone resin contained in the silicone composition is determined in consideration of the viscosity of the silicone binder as the binder raw material and the type and amount of other fillers used at the same time, in addition to the particle size of the resin. The viscosity of the silicone composition is adjusted so as to fall within an appropriate range. A filler that has a particularly high thickening effect on the silicone composition is fumed silica. Since the particle size of the phosphor is usually several μm or more, the thickening effect on the silicone composition before curing is relatively small.

Suitable spherical silicone resins are those having a polyalkylsilsesquioxane structure, especially a polymethylsilsesquioxane structure. Commercially available products include, for example, silicone resin powder (KMP-590 / 701/702 / X-52-854 / X52-1621) from Shin-Etsu Chemical Co., Ltd. and Tospearl from Momentive Performance Materials Japan (same) (Registered trademark).

Since the spherical silicone resin having such a structure has a refractive index close to that of polydimethylsiloxane, the light diffusing action when dispersed in a silicone binder containing polydimethylsiloxane in the basic skeleton is small. In other words, the silicone binder can be used without impairing its light transmittance.

Both the silicone binder and the spherical silicone resin usually have a lower refractive index than silica. The refractive index of silicone is about 1.41 when polydimethylsiloxane is used as a basic skeleton. Since the refractive index of silica is about 1.46, the refractive index of the spherical silicone resin having a polymethylsilsesquioxane structure is between 1.41 and 1.46. Therefore, in the silicone composition according to the present invention, the refractive index difference between the spherical silicone resin and the silicone binder is preferably less than 0.05.

The effective refractive index of a composite in which fumed silica with a primary particle size of several tens of nanometers is dispersed in a silicone binder having a structure in which polydimethylsiloxane is crosslinked is higher than 1.41 (the refractive index of dimethyl silicone and the refractive index of silica. Therefore, the light diffusing action of the spherical silicone resin having a polymethylsilsesquioxane structure when mixed with such a composite is particularly small.

However, even if the refractive index difference from the binder is small, if the particle size of the spherical silicone resin is 3 μm or less, particularly 2 μm or less, a light diffusion action that cannot be ignored depending on the amount of addition occurs. Therefore, when it is intended to control the light diffusibility of the silicone composition using a light diffusing agent, which will be described later, the components having a particle diameter of 3 μm or less contained in the spherical silicone resin are reduced, or the spherical components not containing such components are contained. It is preferable to use a silicone resin.

On the other hand, in one embodiment, it is also possible to use a spherical silicone resin having such a small particle diameter as a light diffusing agent. Accordingly, the particle size of the spherical silicone resin is usually 1 μm or more, preferably 2 μm or more, more preferably more than 3 μm.

In order for the silicone composition before curing to have fluidity suitable for injection molding or transfer molding, it is preferable that the median diameter of the spherical silicone resin is in the range of 2 to 30 μm, particularly in the range of 2 to 20 μm. A mixture of particles having different median diameters can also be used. When the spherical silicone resin has a particle size of 30 μm or less, particularly 20 μm or less, and further 10 μm or less, an effect of stabilizing the dispersion of the phosphor in the silicone composition before curing is also expected. This is because the phosphor particle size is usually about several μm to 20 μm.

1.4 Light Diffusing Agent In the silicone composition constituting the wavelength conversion component of the present invention, a light diffusing agent may be used as a filler. Examples of the light diffusing agent that can be used include acrylic resin, polystyrene, silicone resin, silica, glass beads, diamond, titanium oxide, zinc oxide, barium sulfate, calcium carbonate, magnesium carbonate, magnesium hydroxide, and clay.

When silicone having a structure in which polydimethylsiloxane is crosslinked is used as a binder, spherical silica can be preferably used as a light diffusing agent.

Spherical silica is true spherical silica particles used as a filler for epoxy resin used for semiconductor encapsulation. Among the spherical silicas produced by various production methods, particularly preferred is fused silica produced by a method in which a pulverized raw material meteorite is melted in a high-temperature flame and spheroidized by surface tension.

The refractive index of fused silica is usually 1.46 (1.46 to 1.47 in the near ultraviolet to blue wavelength region), but the refractive index of spherical silica having a larger specific surface area is lower than this.

A transparent light diffusing agent having a large refractive index difference from the silicone binder exhibits a large light diffusing effect in a small amount, but a slight change in the dispersion state may greatly change the characteristics of the wavelength conversion component. On the other hand, spherical silica has a small difference in refractive index from silicone containing polydimethylsiloxane in the basic skeleton, so that the influence of the dispersion state on the characteristics of the wavelength conversion component is small. Such an effect becomes particularly remarkable when the particle diameter of the spherical silica is 3 μm or more.

The amount of spherical silica dispersed in the silicone composition is adjusted so as to obtain a desired light diffusibility. Although it does not limit, spherical silica can be used in the ratio of 5 weight part or more and 80 weight part or less with respect to 100 weight part of silicone binders, for example.

The silicone composition having a small increase in viscosity due to the use of spherical silica is spherical silica having a specific surface area of 1 to 10 m ² / g, particularly 1 to 5 m ² / g, and a particle diameter of 1 μm or more. However, spherical silica having a specific surface area exceeding 30 m ² / g or spherical silica having a particle diameter of less than 1 μm can be used for the purpose of thickening the silicone composition before curing. Two or more kinds of spherical silicas having different specific surface areas may be mixed and used.

When performing injection molding or transfer molding, the particle diameter of the spherical silica used in the thermosetting silicone composition is preferably 1 μm or more, and on the other hand, preferably 30 μm or less, and 20 μm or less. Is more preferable. In the case of an injection mold, the particle diameter is more preferably 15 μm or less. A mixture of particles having different median diameters can also be used. As the spherical silica, particle groups having different particle diameters can be used. In this case, it is preferable that the median diameter of the particle group is within the above preferable range.

1.5 Fumed Silica It is preferable to use fumed silica for the silicone composition constituting the wavelength conversion component of the present invention.

Fumed silica is ultrafine particles having a large specific surface area of ^{50 m} 2 / g or more, those commercially available as Aerosil (registered trademark) of Nippon Aerosil Co., Asahi Kasei Wacker WACKER HDK silicone Co. ( Registered trademark).

By imparting thixotropic properties to the silicone composition before curing using fumed silica, it is possible to prevent the composition from becoming non-uniform due to sedimentation of the phosphor and filler. In particular, when hydrophobic fumed silica whose surface is modified with a trimethylsilyl group, a dimethylsilicone chain or the like is used, thixotropic properties can be imparted to the liquid silicone composition without causing excessive thickening. The fumed silica can be preferably used at a ratio of 10 to 25 parts by weight with respect to 100 parts by weight of the silicone binder.

1.6 Other Additives In addition to the above-described phosphor and filler, the silicone composition constituting the wavelength conversion component of the present invention includes an anti-aging agent, a radical inhibitor, an ultraviolet absorber, an adhesive as necessary. Such as property improvers, flame retardants, surfactants, storage stability improvers, antiozonants, light stabilizers, plasticizers, coupling agents, antioxidants, thermal stabilizers, antistatic agents, mold release agents, etc. Various additives can be added.

1.7 Particle Diameter of Each Material The particle diameter of each material included in the silicone composition constituting the wavelength conversion component of the present invention can be confirmed by microscopic observation. When using a commercially available material, a material having an appropriate particle size may be selected with reference to the particle size described in a catalog or the like.

2. Molding For the production of the wavelength conversion component of the present invention, a compression mold, a liquid transfer mold or a liquid injection mold can be suitably used. Among them, the liquid injection mold (LIM) is advantageous in that secondary processing (deburring) is unnecessary because it is difficult to generate burrs, automation is easy, and a molding cycle is easily shortened.

The cylinder set temperature in the liquid injection mold is usually 100 ° C. or lower, preferably 80 ° C. or lower, more preferably 60 ° C. or lower. The mold temperature is usually 80 ° C. or higher, preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 200 ° C. or lower. The injection time is usually 1 second or less for short cases and several seconds for long cases. The molding time is usually 3 seconds or more, preferably 5 seconds or more, more preferably 10 seconds or more, and on the other hand, it is usually 600 seconds or less, preferably 200 seconds or less, more preferably 60 seconds or less.

In the liquid injection mold, a low temperature raw material resin is fed into a high temperature mold through a heated channel. Since the inside of the flow path is also heated, the resin viscosity increases as it approaches the mold due to a partial thermosetting reaction. If the viscosity when reaching the mold is low, the resin leaks out from the gaps in the mold and becomes burrs. Therefore, in order to prevent the generation of burrs, it is important to control the viscosity of the raw material resin and increase the mold accuracy (narrow the gap). The gap of the mold is usually required to be 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less.

On the other hand, when the viscosity increase of the raw material resin is too fast, unfilling of the mold occurs. In order to suppress the occurrence of burrs and prevent unfilling of the mold, the degree of cure of the resin rises in a S-curve with time on the graph with the horizontal axis representing time and the vertical axis representing the degree of cure. Ideally. The curing rate of the resin can be controlled by material design (selection of catalyst type, catalyst amount, use of curing rate control agent, degree of crosslinking of the resin, etc.) and molding conditions (mold temperature, filling rate, injection pressure, etc.). The time from the injection of the resin into the mold to the end of curing is usually 60 seconds or less, preferably 30 seconds or less, more preferably 10 seconds or less.

Vacuuming the mold during molding is an effective means for promoting the inflow of resin into a narrow cavity, preventing short molding, and preventing air voids from occurring in the molded product. .

In the case of a compression mold, the molding temperature is usually 80 ° C. or higher, preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 200 ° C. or lower. It is. The molding time is usually 3 seconds or longer, preferably 5 seconds or longer, more preferably 10 seconds or longer, and is usually 1200 seconds or shorter, preferably 900 seconds or shorter, more preferably 600 seconds or shorter.

In the case of a liquid transfer mold, the molding temperature is usually 80 ° C. or higher, preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 200 ° C. It is as follows. The molding time is usually 3 seconds or longer, preferably 5 seconds or longer, more preferably 10 seconds or longer, and is usually 1200 seconds or shorter, preferably 900 seconds or shorter, more preferably 600 seconds or shorter.

Regardless of which molding method is used, post-cure can be performed as necessary. The post-cure temperature is, for example, 100 ° C. or higher, preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 200 ° C. or lower. The post-cure time is, for example, 3 minutes or more, preferably 5 minutes or more, more preferably 10 minutes or more, and 24 hours or less, preferably 10 hours or less, more preferably 5 hours or less.

3. Wavelength Conversion Component The shape of the wavelength conversion component is not limited and can be any shape including a plate, a disk, a dome, and the like.

A typical example of a large wavelength conversion component used in a remote phosphor type LED device is a disk having a diameter of 5 to 7 cm and a thickness of 0.5 to 1 mm. As a form of wavelength conversion component used in combination with a chip-on-board (COB) LED module, a disk having a thickness of 2 to 3 cm and a thickness of 0.2 to 0.5 mm, a diameter and a height of 1 to 5 cm, and a thickness of 0 And a hemispherical dome of 5 to 2 mm.

In order to be able to hold these shapes by themselves, the silicone composition constituting the wavelength conversion component preferably has a durometer hardness of HDD25 or higher, more preferably HDD35 or higher. By using a harder silicone composition, larger wavelength conversion components can be made.

Silicone compositions that are highly filled with fillers such as spherical silicone resin, spherical silica, and fumed silica have a low coefficient of thermal expansion, and thus can be suitably used for LED devices for lighting that generate a large amount of heat. .

4). Remote Phosphor LED Device FIG. 4 is a cross-sectional view showing an example of a remote phosphor LED device that can be configured using the wavelength conversion component of the present invention. The remote phosphor type LED device 10 includes a case 1 having a recess 1a, a blue LED 2 disposed on the bottom surface of the recess 1a, and the wavelength conversion of the present invention disposed so as to close the recess 1a. Component 3.

A wiring (not shown) for supplying current to the blue LED 2 is provided on the bottom surface of the recess of the case 1. Although not shown in detail, the blue LED 2 includes an SMD type package and one or more blue LED chips mounted on the package. The number of blue LEDs 2 arranged on the bottom surface of the recess 1a may be one or two or more.

The wavelength conversion component 3 is a disk formed of a composition in which a YAG: Ce phosphor and a spherical silicone resin are dispersed in a silicone binder. The edge of this disk is tapered.

Blue LED 2 emits blue light by supplying current through the wiring. Part of the blue light is converted into yellow light by the YAG: Ce phosphor included in the wavelength conversion component 3, and the other part is transmitted through the wavelength conversion component 3 without being wavelength-converted. White light obtained by mixing the yellow light and the blue light transmitted through the wavelength conversion component 3 is emitted from the surface of the wavelength conversion component 3 to the outside as output light. That is, a part of the first light emitted from the LED having an emission peak wavelength in the range of 440 to 470 nm can be transmitted, and the other part of the first light can be transmitted through the color of the first light. Can be converted into a second light having a complementary color relationship.

In order to lower the color temperature of the output light of the remote phosphor type LED device 10, a red phosphor may be added to the wavelength conversion component 3 in addition to the yellow phosphor. Adding a red phosphor to the wavelength conversion component 3 or replacing part or all of the yellow phosphor with a green phosphor can contribute to improving the color rendering properties of the remote phosphor type LED device 10.

The blue LED 2 can be replaced with a purple LED or a near ultraviolet LED. In this case, a blue phosphor is added to the wavelength conversion component.

Instead of using the blue LED 2, it is also possible to adopt a chip-on-board structure in which the blue LED chip is directly mounted on the wiring provided at the bottom of the recess 1a. In this case, the number of LED chips mounted on the case 1 may be one to several, may be 10 or more, and may be 50 or more.

5. Experimental Results 5.1 Material A commercially available two-component addition-curable silicone was used as a raw material for the silicone binder. This addition-curing type silicone comprises liquid A and liquid B, and the durometer hardness of the cured product obtained by mixing the liquid A and liquid B at a weight ratio of 9: 1 and curing them at 10 minutes / 100 ° C. Is A45 (nominal value by the manufacturer).

Liquid A is mainly composed of dimethylpolysiloxane in which vinyl groups are substituted on both terminal silicon atoms, and a platinum complex catalyst is dispersed (vinyl group content: 0.3 mmol / g, viscosity: 5000 mPa · s). Liquid B is mainly composed of a methylhydrosiloxane-dimethylsiloxane copolymer (hydrosilyl group content: 4.2 mmol / g, viscosity: 40 mPa · s). Therefore, this addition-curable silicone gives a cured product having a structure in which polydimethylsiloxane is crosslinked.

A curing retarder (vinyl group content: 0.2 mmol / g, alkynyl group content: 0.3 mmol / g, viscosity: 1000 mPa · s) made of an alkynyl group-containing silicone was added to the addition-curable silicone. The mixing ratio of liquid A / liquid B / curing retarder was 9: 1: 0.1 by weight. The viscosity of the mixture was 3500 mPa · s.

As the fumed silica, hydrophobic fumed silica (BET specific surface area: 140 ± 25 m ² / g, average primary particle diameter: about 12 nm) surface-treated with a trimethylsilyl group was used. As the spherical silica, a spherical fused silica having a specific surface area of 2.2 m ² / g and a d50 (median diameter) of 4.9 μm was used.

As the spherical silicone resin, true spherical polymethylsilsesquioxane particles having a specific surface area of 20 m ² / g and a d50 (median diameter) of 6.0 μm were used. The phosphors used are all available from Mitsubishi Chemical Corporation.

5.2 Measuring method 5.2.1 “Whiteness index”
The “whiteness index” of the silicone composition sheet to which no phosphor was added was measured using the whiteness index measurement mode of a spectrocolorimeter “SPECTROPHOTOMETER CM-2600d” manufactured by Konica Minolta Optics. That is, the “whiteness index” of the silicone composition sheet was measured when the whiteness index of the standard white plate for calibration was set to 100 in the same manner as when measuring the whiteness index determined by ASTM E313-73. .

During measurement, the back side of the sheet (the side other than the incident side of the evaluation light) is released into the environment so that the evaluation light that has not been reflected by the sheet (evaluation light that has passed through the sheet) is emitted into the environment. did. Strictly speaking, the “whiteness index” of the silicone composition sheet thus measured is different from the whiteness index of ASTM E313-73, which is an index for basically evaluating an opaque object. However, it can be used as a useful index for the purpose of evaluating the light diffusibility of the silicone composition. This is because the higher the light diffusibility of the silicone composition, the greater the amount of light reflected by the sheet formed from the composition, and the higher the “whiteness index”.

5.2.2 Viscosity The viscosity of the thermosetting silicone composition was measured using a capillary rheometer.

5.2.3 Hardness The hardness of the cured product of the thermosetting silicone composition was measured according to JIS K7215 (1986) (plastic durometer hardness test method). The thermosetting silicone composition was cured using a press molding machine under conditions of a pressure of 50 kg / cm ² , a curing temperature of 150 ° C., and a curing time of 3 minutes to produce a disk having a diameter of 13 mm and a thickness of 3 mm. A test piece was prepared by stacking two sheets. A type D durometer was used as the durometer.

5.3 Trial manufacture and evaluation results 5.3.1 Experimental example 1
A disk made of a phosphor-free silicone composition in which fumed silica as an ultrafine filler and spherical silica and spherical silicone resin as micron-sized fillers are dispersed in a silicone binder (addition-curable silicone) is prepared. Light diffusivity was evaluated using the “whiteness index” as an index.

The disk was produced by a method in which the thermosetting silicone composition was molded using a press molding machine. The pressure during molding was 50 kg / cm ² , and the curing conditions were 150 ° C. and 3 minutes. The diameter of the disk was 13 mm and the thickness was 1 mm.

Table 1 below shows the composition of the thermosetting silicone composition used as a raw material and the measurement results of the “whiteness index” for 16 types of samples S01 to S16.

Of the 16 samples, samples S01 to S09 have substantially the same mixing ratio of the silicone binder and fumed silica (13 to 14 parts by weight of fumed silica with respect to 100 parts by weight of silicone), and the volume percentage of the silicone binder is also approximately Constant (43-44%). Therefore, it can be said that the difference in the “whiteness index” between the samples S01 to S09 is due to the difference in the volume ratio of the spherical silica in the micron size filler (spherical silica and spherical silicone resin).

FIG. 1 is a graph plotting the relationship between the “whiteness index” and the volume ratio of spherical silica in the micron-sized filler in the samples S01 to S09. As can be seen from FIG. 1, the “whiteness index” increases linearly as the volume ratio of spherical silica in the micron-size filler increases. This result clearly shows that mainly spherical silica is acting as a light diffusing agent.

Looking at Samples S10 to S15, Samples S10 to S14 have substantially the same mixing ratio of silicone binder and fumed silica (19 parts by weight of fumed silica with respect to 100 parts by weight of silicone), and the volume percentage of silicone binder is approximately It is constant (45 to 46%), and only the volume ratio of spherical silica in the micron size filler (spherical silica and spherical silicone resin) is different.

Samples S15 and S16, on the other hand, have the same silicone binder volume percentage (45-46%) and spherical silica volume ratio (17%) in the micron-sized filler as sample S14, but the silicone binder and fumed silica. (The fumed silica is 19 parts by weight for S14, 22 parts by weight for S15, and 25 parts by weight for S16 with respect to 100 parts by weight of silicone).

FIG. 2 is an additional plot of the results of samples S10 to S16 with respect to the graph of FIG. Also in samples S10 to S16, it can be seen that the relationship between the “whiteness index” and the volume ratio of spherical silica in the micron size filler is substantially the same as that in samples S01 to S09. This result indicates that fumed silica has substantially no effect on the light diffusibility of the silicone composition.

5.3.2 Experimental Example 2
A disk-shaped wavelength conversion component having a thickness of 1 mm and a diameter of 60 mm is pressed using a thermosetting silicone composition to which a phosphor is added based on the composition of sample S05 in Table 1 (“whiteness index” is 18.2). It was produced by a molding method. Then, the wavelength conversion component was combined with a blue LED to produce a remote phosphor type white light emitting device having a correlated color temperature of about 4000K.

The phosphors used are yellow phosphor YAG (YAG: Ce), green phosphor β sialon (β sialon: Eu), and red phosphor SCASN [(Sr, Ca) AlSiN ₃ : Eu]. The amount of each material used in the produced thermosetting silicone composition was as follows: YAG: 1.01 g, β sialon: 2.35 g, SCASN: 0.64 g, addition-curable silicone: 32.5 g, fumed silica: 4. 4 g, spherical silica: 14.8 g, spherical silicone resin: 44.3 g. The phosphor content in this composition is 4.0 wt%.

The color rendering index (Ra) of the obtained white light emitting device was 82.

5.3.3 Experimental Example 3
A disk-shaped wavelength conversion component having a thickness of 1 mm and a diameter of 60 mm was pressed using a thermosetting silicone composition to which a phosphor was added based on the composition of sample S08 in Table 1 (“whiteness index” was 21.4). It was produced by a molding method. Then, the wavelength conversion component was combined with a blue LED to produce a remote phosphor type white light emitting device having a correlated color temperature of about 4000K.

The phosphor used is the same as in Experimental Example 2 above. The amount of each material used in the produced thermosetting silicone composition was as follows: YAG: 0.88 g, β sialon: 2.06 g, SCASN: 0.56 g, addition-curable silicone: 32.0 g, fumed silica: 4. 3 g, spherical silica: 19.8 g, spherical silicone resin: 40.4 g. The phosphor content in this composition is 3.5 wt%.

The color rendering index (Ra) of the obtained white light emitting device was 82. The brightness of this white light emitting device was substantially the same as that obtained in Experimental Example 2.

5.3.4 Experimental Example 4
Addition-curable silicone: 350 g, fumed silica: 67 g, spherical silica: 145 g, and spherical silicone resin: 438 g. Value) phosphor was not produced. The filler content of the produced thermosetting silicone composition is 19 parts by weight of fumed silica, 41 parts by weight of spherical silica, and 125 parts by weight of spherical silicone resin with respect to 100 parts by weight of addition-curable silicone.

The results of viscosity measurement of this thermosetting silicone composition are shown in Table 2 below.

The mold temperature in the liquid injection molding is in the range of 150 to 200 ° C, the filling time into the mold is 0.1 second to 1 second, and the resin curing time in the mold is between 10 seconds to several minutes. The injection pressure was adjusted between 0.5 and 2t.

When two discs were selected from the manufactured discs and the thicknesses were measured at five locations, the thickness was 1.08 to 1.12 mm, and the average value was 1.09 mm. In addition, when three discs were selected from the manufactured discs and the “whiteness index” and the diffuse reflectance at a wavelength of 450 nm were measured, the “whiteness index” was 19.7, 19.4, and 19.3. The diffuse reflectance was 16.9, 16.5, and 16.7.

5.3.5 Experimental Example 5
Addition-curable silicone: 329 g, fumed silica: 72 g, spherical silica: 132 g, spherical silicone resin: 405 g, and YAG phosphor: 62 g. A disk-shaped wavelength conversion component having a thickness of 1 mm (design value) was produced. The content of the filler and phosphor in the prepared wavelength conversion component is 22 parts by weight of fumed silica, 40 parts by weight of spherical silica, 123 parts by weight of spherical silicone resin, and 100 parts by weight of YAG. The phosphor is 19 parts by weight.

The results of viscosity measurement of this curable silicone composition are shown in Table 3 below.

The durometer hardness of the cured product of this curable silicone composition was HDD36. The conditions for liquid injection molding were adjusted in the same manner as in Experimental Example 4 above.

Although there was a variation in thickness between the manufactured wavelength conversion components, the average value of the film thickness measured at three locations within one surface was within the range of 0.97 to 0.99 mm. Looking at the 18 wavelength conversion components, as shown in Table 4 below, the difference between the maximum value and the minimum value of the film thickness at three locations was 3% or less.

Table 4 also shows the correlated color temperature and xy chromaticity coordinate values of each of the 18 wavelength conversion components when a white light emitting device is configured in combination with a blue LED. ing. Parts (including blue LEDs) other than the wavelength conversion component used when configuring the white light emitting device are the same. As shown in Table 4, the correlated color temperature was in the range of 4007 to 4024 K, and the fluctuation range of the chromaticity coordinate value was 0.001 in the x-axis direction and 0.002 in the y-axis direction.

5.3.6 Experimental Example 6
A thermosetting silicone composition containing no phosphor is prepared by dispersing fumed silica, spherical silica and spherical silicone resin in a silicone binder, and the hardness of the cured product of the silicone composition and the silicone composition are prepared. The “whiteness index” of the disc was measured. The disc was produced in the same manner as in Experimental Example 1 above.

Table 5 below shows the composition and viscosity of the silicone composition before curing, the hardness of the cured product, and the "whiteness index".

As shown in Table 5, sample no. The silicone compositions 1 to 4 gave a cured product having a durometer hardness close to that of the HDD 40. In these compositions, the addition amount of the spherical silicone resin with respect to 100 parts by weight of the addition-curable silicone binder is 120 parts by weight or more.

In contrast, Sample No. containing fumed silica and spherical silica but not containing spherical silicone resin. 5 and Sample No. in which the filler is only fumed silica. In the silicone composition of No. 6, the durometer hardness of the cured product was HDD20 or less. Sample No. The silicone composition of No. 7 is sample no. Compared with 1-4, the spherical silicone resin content was small, but a durometer hardness of HDD29 was obtained.

Sample No. The thermosetting silicone compositions 1, 2, 4 and 7 have a viscosity of less than 500 Pa · s at a shear rate of 120 / s and a temperature of 25 ° C., and are suitable for injection molding and transfer molding. It was. On the other hand, sample No. 1 in which only fumed silica was added at a high concentration to the silicone binder. The thermosetting silicone composition No. 6 had a relatively high viscosity of 751 Pa · s.

5.3.7 Experimental Example 7
In this experiment, as the spherical silicone resin, in addition to the d50 (median diameter) of 6.0 μm used in each of the above experiments, true spherical polymethylsilsesquioxane particles having a d50 (median diameter) of 2.0 μm were used. Using these two types of spherical silicone resins, a thermosetting silicone composition containing no phosphor was prepared in the same manner as in Experimental Example 1, and the viscosity at a shear rate of 120 / s and a temperature of 25 ° C. was measured. The “whiteness index” of the disk obtained by curing the silicone composition was measured.

The results are shown in Table 6.

As shown in Table 6, Sample No. containing only a spherical silicone resin having a d50 (median diameter) of 6.0 μm. Compared with the thermosetting silicone compositions of Nos. 1 and 2, sample No. 1 containing only a spherical silicone resin having a d50 (median diameter) of 2.0 μm. The thermosetting silicone compositions of 3 to 5 had a high viscosity, and the “whiteness index” of the cured product was also high.

Sample No. In the thermosetting silicone composition of No. 6, both spherical silicone resins having a d50 (median diameter) of 6.0 μm and 2.0 μm are added, and spherical silica is further added. The “whiteness index” of Sample No. 5 compared to the silicone composition. The total amount of the spherical silicone resin added per 100 parts by weight of the binder was determined as Sample No. Even though the composition of 6 is more. This is sample no. This is probably because the composition of No. 5 had a higher content of spherical silicone resin having a d50 (median diameter) of 2.0 μm.

5.3.8 Experimental Example 8
28 parts by weight of fumed silica, 54 parts by weight of spherical silica, 97 parts by weight of spherical silicone resin (average particle diameter 6.0 μm), phosphor (YAG, β sialon, SCASN) with respect to 100 parts by weight of addition-curable silicone About 3.2 kg of a thermosetting silicone composition was added. The durometer hardness of the cured product of this silicone composition was HDD36.

Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention. The present application includes a Japanese patent application filed on July 27, 2012 (Japanese Patent Application No. 2012-167550), a Japanese patent application filed on September 18, 2012 (Japanese Patent Application No. 2012-204381), and 2013 This is based on a Japanese patent application (Japanese Patent Application No. 2013-017844) filed on May 31, and is incorporated by reference in its entirety.

1 Case 2 Blue LED
3 Wavelength conversion component 10 Remote phosphor type LED device

Claims (17)

1. A wavelength conversion component that is a molded body made of a silicone composition in which a phosphor and a filler are dispersed in a silicone binder,
   The filler includes a spherical silicone resin having a particle size of 1 μm or more,
   The spherical silicone resin content is 50 parts by weight or more with respect to 100 parts by weight of the silicone binder.
   Wavelength conversion component.
2. The wavelength conversion component according to claim 1, wherein the durometer hardness of the silicone composition is HDD25 or more.
3. A wavelength conversion component that is a molded body made of a silicone composition in which a phosphor and a filler are dispersed in a silicone binder,
   The silicone binder is an elastomer having a durometer hardness of HDD20 or less,
   The filler contains a spherical silicone resin having a particle size of 1 μm or more,
   The durometer hardness of the silicone composition is HDD25 or more,
   Wavelength conversion component.
4. The wavelength conversion component according to any one of claims 1 to 3, wherein a difference in refractive index between the silicone binder and the spherical silicone resin is less than 0.05.
5. The wavelength conversion component according to any one of claims 1 to 4, wherein each of the silicone binder and the spherical silicone resin has a refractive index lower than that of silica.
6. The wavelength conversion component according to any one of claims 1 to 5, wherein the silicone binder has a structure in which polydimethylsiloxane is crosslinked, and the spherical silicone resin has a polyalkylsilsesquioxane structure.
7. The wavelength conversion component according to any one of claims 1 to 6, wherein the filler does not contain a spherical silicone resin having a particle diameter of 3 µm or less.
8. The wavelength conversion component according to any one of claims 1 to 7, wherein the filler further contains spherical silica.
9. The wavelength conversion component according to claim 8, wherein the spherical silica includes fused silica.
10. The wavelength conversion component according to claim 8 or 9, wherein the content of the spherical silica is 5 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the silicone binder.
11. The wavelength conversion component according to any one of Claims 1 to 10, wherein the filler further contains fumed silica.
12. The wavelength conversion component according to any one of claims 1 to 11, wherein the durometer hardness of the silicone composition is HDD35 or more.
13. The molded body according to any one of claims 1 to 12, wherein the molded body is a molded body of a silicone composition having a shear rate of 120 / s and a viscosity at a temperature of 25 ° C of 100 Pa · s or more and less than 1000 Pa · s. The described wavelength conversion component.
14. The wavelength conversion component according to any one of claims 1 to 13, which is a disc having a diameter of 5 to 7 cm and a thickness of 0.5 to 1 mm.
15. The wavelength conversion component according to any one of claims 1 to 13, which is a disc having a diameter of 2 to 3 cm and a thickness of 0.2 to 0.5 mm.
16. The wavelength conversion component according to any one of claims 1 to 13, which is a hemispherical dome having a diameter and height of 1 to 5 cm and a thickness of 0.5 to 2 mm.
17. A part of the first light emitted by the LED having an emission peak wavelength in the range of 440 to 470 nm can be transmitted, and the other part of the first light is the color of the first light. The wavelength conversion component according to any one of claims 1 to 16, wherein the wavelength conversion component can be converted into a second light having a complementary color relationship.

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