JP2014055238A - Polysiloxane-based composition for led sealing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polysiloxane-based composition capable of reducing chromaticity shift between individuals of semiconductor light-emitting devices.SOLUTION: A polysiloxane-based composition for LED sealing is a composition containing polysiloxane capable of forming a resin adsorption layer of 0.1 nm to 1000 nm on a phosphor surface and it can converge luminescent color emitted from a semiconductor light-emitting device containing a luminescence element and a phosphor layer to a range of the standard deviation represented by formulae (1) and (2): δ(x)<0.004(1) and δ(y)<0.005(2) when it is used as LED sealing agent.

Description

  The present invention relates to a polysiloxane composition that reduces chromaticity deviation between individual semiconductor light emitting devices.

  A semiconductor light-emitting device (hereinafter sometimes referred to as an LED) has features such as long life, low power consumption, impact resistance, high-speed response, miniaturization, and the like. Development in various fields such as backlights for information terminals, in-vehicle lighting, indoor / outdoor advertising, indoor / outdoor lighting, etc., has been progressing dramatically.

  An LED is usually manufactured by encapsulating a light-emitting element by applying a curable composition containing a phosphor on a light-emitting element made of a semiconductor and curing the composition.

  However, when the LED is sealed as described above, the phosphors cause uneven dispersion, resulting in uneven color in the obtained semiconductor light emitting device and chromaticity deviation for each semiconductor light emitting device, resulting in manufacturing quality. There is a problem in that the production cost is increased due to the influence on the production yield.

  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 1 discloses a composition using a polysiloxane-based modified body having a polyhedral structure. This composition is excellent in moldability, transparency, heat resistance, light resistance and adhesiveness, and can also be used as an LED sealing material.

  However, there is still room for further improvement regarding the chromaticity shift between individual optical semiconductor devices sealed with a polysiloxane-based composition having a polyhedral structure.

WO08 / 010545

  An object of the present invention is to provide a polysiloxane-based composition that reduces the chromaticity shift between individual semiconductor light emitting devices.

  As a result of intensive studies to solve the above problems, the present inventors have found the following and completed the present invention.

That is, the present invention has the following configuration.
1). A composition containing polysiloxane capable of forming a resin adsorbing layer of 0.1 nm to 1000 nm on the phosphor surface, and when the composition is used as an LED sealant, a phosphor element and a phosphor layer The emission color emitted from the semiconductor light emitting device consisting of the following equations (1) and (2):
δ (x) <0.004 (1)
δ (y) <0.005 (2)
(Where δ (x) is the standard deviation of x on the chromaticity coordinates of the xyX color system of the light emitting color of the semiconductor light emitting device, and δ (y) is the chromaticity of the xyY color system of the light emitting color of the semiconductor light emitting device. The standard deviation of y on the coordinates.The number of samples of these standard deviations is 500 at random.) A polysiloxane-based composition for LED encapsulation that can be converged to the standard deviation range represented by:

2). The polysiloxane composition according to 1) is a polyhedral polysiloxane.

3). 2. The polysiloxane composition according to 2), wherein the polyhedral polysiloxane has an average of 3 or more hydrosilyl groups in one molecule.

4). The polyhedral polysiloxane has an alkenyl group, polyhedral polysiloxane compound (a), a hydrosilyl group-containing compound (b), and an organosilicon compound (a ′) having one alkenyl group in one molecule. The polysiloxane composition according to 2) or 3), which is a modified polyhedral polysiloxane (A) obtained by reacting.

5). 4. The polysiloxane composition according to 4), wherein the modified polyhedral polysiloxane (A) is liquid at a temperature of 20 ° C.

6). 4. The polysiloxane composition according to 4) or 5), wherein the organosilicon compound (a ′) having one alkenyl group in one molecule is an organosilicon compound having one or more aryl groups.

7). The polyhedral polysiloxane compound (a) having an alkenyl group has the 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; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom or an alkyl group 4), characterized in that it is a polyhedral polysiloxane compound containing an alkenyl group composed of a siloxane unit represented by: an aryl group or a group linked to another polyhedral skeleton polysiloxane) The polysiloxane composition according to any one of -6).

8). Any of 4) to 7), wherein the compound (b) containing a hydrosilyl group is a cyclic siloxane containing a hydrosilyl group and / or a linear siloxane containing a hydrosilyl group at the molecular end. 2. The polysiloxane composition according to item 1.

9). The polysiloxane composition according to any one of 4) to 7), wherein the compound (b) containing a hydrosilyl group is a cyclic siloxane containing a hydrosilyl group.

10). The compound (b) containing a hydrosilyl group is 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, Siloxane-based composition.

11). The polyhedral polysiloxane has the 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, 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 ( The structure of 1) or general formula (2) may be different, and the structure of general formula (1) or 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. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain And at least one of Y or Z is a hydrogen atom, and at least one has the structure of the following general formula (3).
-[CH ₂ ] _l -R ⁵ (3)
(L is an integer of 2 or more; R ⁵ is a group containing an organosilicon compound); R is an alkyl group or an aryl group}]
The polysiloxane composition according to 2) or 3), which is a modified polyhedral polysiloxane (A) having a structural unit as a structural unit.

12). 11) The polysiloxane composition according to 11), wherein R ⁵ has one or more aryl groups.

13). The polysiloxane composition according to any one of 2) to 12), which comprises a compound (B) having two or more alkenyl groups in one molecule.

14). 13. The polysiloxane composition according to 13), wherein the compound (B) is a polysiloxane (B1) having two or more alkenyl groups in one molecule.

15). The polysiloxane composition according to 14), wherein the polysiloxane (B1) having two or more alkenyl groups in one molecule has one or more aryl groups.

16). Compound (B) is an organic compound represented by the following general formula (4):

(Wherein R ⁶ represents a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and each R ⁶ may be different or the same), and 2 alkenyl groups in one molecule. The polysiloxane composition according to 13), which is an organic compound (B2) having at least one.

17). The polysiloxane composition according to 16), wherein the organic compound (B2) has a number average molecular weight of less than 900.

18). 16) or 17) characterized in that the organic compound (B2) is at least one compound selected from the group consisting of triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoglycidyl isocyanurate. The polysiloxane composition as described.

19). The polysiloxane composition according to 16) or 17), wherein the organic compound (B2) is diallyl monomethyl isocyanurate.

20). The polysiloxane composition according to any one of 1) to 19), further comprising a hydrosilylation catalyst.

21). The polysiloxane composition according to any one of 1) to 20), further comprising a curing retarder.

22). Hardened | cured material obtained by hardening the polysiloxane type composition of any one of 1) -21) containing fluorescent substance.

23). The semiconductor light-emitting device which mounts the hardened | cured material as described in 22).

  By using the polysiloxane composition of the present invention, it is possible to reduce a chromaticity shift between individual semiconductor light emitting devices.

  The present invention will be described in detail below.

<Semiconductor light emitting device>
The curable composition in the present invention is used in combination with a phosphor described later, and is used for sealing a light emitting device made of a semiconductor. 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 in an LED package, and the curable composition may be injected and cured to be sealed. Instead of using the LED package, the LED mounted on the LED substrate may be directly sealed with the curable composition by a technique such as press molding or transfer molding. Here, the LED package and the LED substrate are not particularly limited, and those generally used can be used.

In the semiconductor light emitting device using the curable composition of the present invention, the fluorescent material emitted from the phosphor and the light emitted from the light emitting element pass through the phosphor layer (the layer composed of the curable composition and the phosphor in the LED package). The emitted light is added with the added light, and the added emission color satisfies the range represented by the following formulas (1) and (2).
δ (x) <0.004 (1)
δ (y) <0.005 (2)
(Where δ (x) is the standard deviation of x on the chromaticity coordinates of the xyY color system of the light emitting color of the semiconductor light emitting device, and δ (y) is the chromaticity of the xyY color system of the light emitting color of the semiconductor light emitting device. (The standard deviation of y on the coordinates. The number of samples of these standard deviations is 500 at random.)
Here, δ (x) is more preferably smaller than 0.0035, and further preferably smaller than 0.003. When δ (x) is large, the chromaticity shift for each semiconductor light emitting device is large, which affects the yield in manufacturing and increases the manufacturing cost. Further, δ (y) is more preferably smaller than 0.0045, and further preferably smaller than 0.004. Similarly to δ (x), when δ (y) is large, the chromaticity shift for each semiconductor light emitting device is large, which affects the yield in manufacturing and increases the manufacturing cost. Note that δ (x) and δ (y) are preferably smaller, but the minimum value is zero.

<Light emitting element made of semiconductor>
The light emitting element of the semiconductor light emitting device in which the curable composition of the present invention is used is not particularly limited, and those commonly used as LEDs of the semiconductor light emitting device can be used. For example, a phosphor is excited by emitted light to emit visible light, and examples thereof include a blue light emitting type LED and an ultraviolet light emitting type LED. In the semiconductor light emitting device in which the curable composition of the present invention is used, a plurality of the same or different types of LEDs may be mounted per semiconductor light emitting device.

<Phosphor>
The curable composition in this invention may contain a fluorescent substance, and forms the fluorescent substance layer which consists of a curable composition and a fluorescent substance in the package for LED. The phosphor absorbs light emitted from the light emitting element and generates light of different wavelengths. The phosphor used in the curable composition of the present invention is not particularly limited, and is generally known inorganic. A phosphor or an organic phosphor can be used, and an arbitrary one can be selected in order to obtain a luminescent color required by the semiconductor light emitting device using the curable composition of the present invention. Specifically, for example, YAG phosphors, TAG phosphors, orthosilicate alkaline earth phosphors, α-sialon phosphors, β-sialon phosphors, cousin phosphors, nitrides and oxynitride phosphors However, it is not limited to these. These phosphors can be used alone or in combination of two or more in any ratio and 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 Is 100 μm or less, more preferably 50 μm or less, and even more preferably 25 μm or less. When the median particle size (D50) is small, the phosphor may aggregate in the composition, and when the median particle size (D50) is large, the phosphor may be unevenly coated or the dispenser may be clogged. . 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.

  The amount of the phosphor used in the present invention is not particularly limited, and any amount can be used to obtain the luminescent color required by the semiconductor light-emitting device. Is preferably 0.1% by weight or more, more preferably 1% by weight or more, further preferably 2% by weight or more, preferably 50% by weight or less, more preferably 40% by weight or less, and further preferably 35% by weight or less. It is. If the amount of phosphor used is small, wavelength conversion by the phosphor may be insufficient, and the target emission color may not be obtained. If the amount of phosphor used is large, the handleability of the composition may be reduced. There is a possibility that the utilization efficiency of the phosphor may be lowered due to the optical interference action.

  The polysiloxane of the curable composition of the present invention forms a resin adsorption layer on the surface of the phosphor, so that the dispersibility of the phosphor is improved and the emission color is within the range of the above formulas (1) and (2). Satisfied. As the polysiloxane, polyhedral polysiloxane is preferable from the viewpoints of adsorptivity and the thickness of the formed adsorption layer. The thickness of the adsorption layer is preferably in the range of 0.1 nm to 1000 nm, more preferably in the range of 0.5 nm to 500 nm, and still more preferably in the range of 1.0 nm to 100 nm. When the thickness of the adsorbing layer is less than this range, the dispersibility of the phosphor is lowered and aggregates, whereby the emission color tends not to satisfy the above formulas (1) and (2). Moreover, if it exceeds this range, the adsorption layer affects the emission color of the illuminant, and the emission color may not satisfy the above formulas (1) and (2).

  Examples of the method for measuring the thickness of the resin adsorption layer include observation with a transmission electron microscope (TEM). Specifically, a phosphor sample with a resin adsorption layer formed on the phosphor surface was vapor-deposited with a metal such as aluminum or platinum or carbon, and the phosphor sample coated with tungsten was cut with an ion beam or the like. Then, it is the method of observing with TEM. The confirmation of the resin adsorption layer in the observed TEM image can include elemental analysis by energy dispersive X-ray spectroscopy (EDX).

<Polyhedral polysiloxane>
The curable composition in the present invention preferably contains polyhedral polysiloxane. As the polyhedral polysiloxane used in the present invention, known polyhedral polysiloxanes can be widely used. The general formula [RSiO _3/2 ] _a and the general formula [R ₃ SiO—SiO _3/2 ] _a ( R is an arbitrary organic group, which may be the same or different; a is an integer of 6 to 24), and is exemplified by a polyhedral polysiloxane composed of siloxane units. A partially cleaved polyhedral polysiloxane containing [R ₂ SiO _2/2 ] units and [R ₃ SiO _1/2 ] units therein may also be used.

  In addition, polyhedral polysiloxane averages hydrosilyl groups in one molecule from the viewpoint of strength, heat resistance, light resistance, and gas barrier properties of the resulting cured product when reacted with the component (B) described below. 3 or more are preferable.

  The polyhedral polysiloxane used in the present invention includes a polyhedral polysiloxane compound (a) having an alkenyl group, a compound (b) having a hydrosilyl group, and an organosilicon compound having one alkenyl group in one molecule ( It is a polyhedral polysiloxane modified product (A) obtained by hydrosilylation reaction with a ′), and the resulting curable composition has heat resistance, light resistance, gas barrier properties, and thermal shock resistance. From the viewpoint of handling property (viscosity) and the like, it is more preferable.

<Polyhedral polysiloxane compound (a) having an alkenyl group>
The polyhedral polysiloxane compound (a) having an alkenyl group used in the curable composition of the present invention is not particularly limited as long as it is a polysiloxane having an alkenyl group in the molecule and having a polyhedral skeleton. 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 or a group having an alkenyl group; R ⁸ is any organic group, or An alkenyl group-containing polyhedral polysiloxane compound composed of a siloxane unit represented by a group linked to other polyhedral skeleton polysiloxanes can be preferably used,
[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; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom or an alkyl group An alkenyl group-containing polyhedral polysiloxane compound composed of a siloxane unit represented by an aryl group or a group linked to another polyhedral skeleton polysiloxane) is exemplified.

  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 hydrogen atom, an alkyl group, an aryl group, or a group linked to 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.

The method for synthesizing the component (a) is not particularly limited, and the component can be synthesized using a known method. As a synthesis method, for example, a silane of 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). Obtained by hydrolysis condensation reaction of compounds. 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 further reacting the same or different trifunctional silane compounds, and polyhedral Methods for synthesizing structural polysiloxanes are also known.

  In addition, for example, there is a method of hydrolytic condensation of tetraalkoxysilane such as tetraethoxysilane in the presence of a base such as quaternary ammonium hydroxide. In this synthesis method, a silicate having a polyhedral structure is obtained by a hydrolytic condensation reaction of tetraalkoxysilane, and the obtained silicate is further reacted with a silylating agent such as an alkenyl group-containing silyl chloride. It is possible to obtain a polyhedral polysiloxane in which Si atoms and alkenyl groups forming a polyhedral structure are bonded through a siloxane bond. In the present invention, the same polyhedral polysiloxane can be obtained from a substance containing silica such as silica or rice husk instead of tetraalkoxylane.

<Compound (b) having hydrosilyl group>
The compound (b) having a hydrosilyl group used in the curable composition of the present invention is not particularly limited as long as it has one or more hydrosilyl groups in the molecule, but the obtained polyhedral polysiloxane modified product is not limited. From the viewpoints of transparency, heat resistance, and light resistance, a siloxane compound having a hydrosilyl group is preferable, and a cyclic siloxane or a linear polysiloxane having a hydrosilyl group is more preferable. In particular, from the viewpoint of heat resistance, light resistance, and gas barrier properties, a cyclic siloxane is preferable.

  The linear polysiloxane having a hydrosilyl group includes a copolymer of a dimethylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, and a copolymer of a diphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit. Copolymers, copolymers of methylphenylsiloxane units and methylhydrogensiloxane units and terminal trimethylsiloxy units, polydimethylsiloxane blocked at the end with dimethylhydrogensilyl groups, polyblocked at the ends with dimethylhydrogensilyl groups Examples thereof include diphenylsiloxane and polymethylphenylsiloxane blocked at the end with a dimethylhydrogensilyl group.

  In particular, as a linear polysiloxane having a hydrosilyl group, a polysiloxane having a molecular end blocked with a dimethylhydrogensilyl group from the viewpoints of reactivity during modification, heat resistance of the resulting cured product, light resistance, etc. Furthermore, polydimethylsiloxane having a molecular end blocked with a dimethylhydrogensilyl group can be suitably used. Specific examples thereof include tetramethyldisiloxane and hexamethyltrisiloxane.

  Examples of the cyclic siloxane having a hydrosilyl group include 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-trihydrogen -1,3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7, Examples include 9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane. Specific examples of the cyclic siloxane in the present invention include, for example, 1,3,5,7-tetrahydro, from the viewpoints of industrial availability and reactivity, or heat resistance, light resistance, strength, and the like of the resulting cured product. Gen-1,3,5,7-tetramethylcyclotetrasiloxane can be preferably used.

  These compounds (b), which have a hydrosilyl group, may be used alone or in combination of two or more.

<Organic silicon compound having one alkenyl group in one molecule (a ')>
The organosilicon compound (a ′) having one alkenyl group in one molecule used in the curable composition of the present invention reacts with the hydrosilyl group of the aforementioned compound (b) having a hydrosilyl group. By using the component (a ′), the elastic modulus of the obtained cured product can be reduced, and the thermal shock resistance can be improved. Moreover, it becomes possible to control the viscosity of the resulting composition, and when used as an LED sealing agent, it is possible to suppress aggregation of phosphors and to improve handling properties when used as an LED sealing agent. It becomes possible.

  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 component (a ′) in the present invention is not particularly limited as long as it is an organosilicon compound having one alkenyl group in one molecule, but it contains at least one aryl group in one molecule. From the viewpoints of gas barrier properties and refractive index, it is more preferable that the aryl group is directly bonded to a silicon atom from the viewpoints of heat resistance and light resistance.

  The component (a ′) 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.

<Modified polyhedral polysiloxane (A)>
The modified polyhedral polysiloxane (A) used in the curable composition of the present invention is a polyhedral polysiloxane compound (a) having an alkenyl group and a compound having a hydrosilyl group in the presence of a hydrosilylation catalyst described later ( It can be obtained by hydrosilylation reaction between b) and an organosilicon compound (a ′) having one alkenyl group in one molecule.

  The method for obtaining the modified polyhedral polysiloxane is not particularly limited and can be variously set, but after reacting the component (a) and the component (b) in advance, the component (a ′) may be reacted, The component (a ′) and the component (b) may be reacted in advance, and then the component (a) may be reacted, or the component (a) and the component (a ′) may be allowed to coexist and react with the component (b). May be. 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. Suppression of the formation of a compound containing only the component (a ′) and the component (b) and not containing the component (a) is preferable from the viewpoint of heat resistance.

  In the polyhedral polysiloxane modified product thus obtained, a part of the alkenyl group of the component (a) used for the reaction may remain.

  Component (b) is preferably added so that the number of hydrosilyl groups is 2.5 to 20 with respect to one alkenyl group of component (a). When the addition amount is small, gelation proceeds due to a crosslinking reaction, so that the handleability of the modified polyhedral polysiloxane may be inferior, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  The amount of component (a ′) added is preferably such that the number of alkenyl groups is 0.01 to 0.4 with respect to one hydrosilyl group of component (b). When the addition amount is small, the effect of improving the thermal shock resistance of the resulting cured product may be small. When the addition amount is large, the resulting cured product may be poorly cured.

The addition amount of the hydrosilylation catalyst used in the synthesis of the modified polyhedral polysiloxane is not particularly limited, but it is 10 ⁻¹ to 10 to 1 mol of the alkenyl group of the component (a) and the component (a ′) used in the reaction. ^It is good to use in the range of ^-10 mol. Preferably, it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. When there are many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it absorbs light with a short wavelength, which may cause coloration or decrease the light resistance of the resulting cured product. There is also a risk of foaming. Moreover, when there are few hydrosilylation catalysts, reaction may not progress and there exists a possibility that a target object may 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.

The modified polyhedral polysiloxane (A) used in the curable composition of the present invention has the 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. Which may be the same or different. Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain, which may be the same or different. However, at least one of Y or Z is a hydrogen atom, and at least one has the structure of the following general formula (3).
-[CH ₂ ] _l -R ⁵ (3)
(L is an integer of 2 or more; R ⁵ is a group containing an organosilicon compound); R is an alkyl group or an aryl group}]
A polyhedral polysiloxane compound composed of siloxane units represented by

Here, R ⁵ is not particularly limited as long as it is a group containing a silicon compound, but preferably contains at least one aryl group in one molecule from the viewpoint of gas barrier properties and refractive index. From the viewpoint of heat resistance and light resistance, it is preferable that the aryl group is directly bonded to a silicon atom.

  Such a polyhedral polysiloxane modified body can ensure compatibility with various compounds, specifically, the later-described component (B), and further includes, for example, a hydrosilyl group in the molecule. It is possible to react with compounds having various alkenyl groups. Specifically, a cured product having excellent heat resistance, light resistance, gas barrier properties, and the like is obtained by reacting with polysiloxane (B1) or organic compound (B2) having two or more alkenyl groups in one molecule described later. be able to.

  The modified polyhedral polysiloxane may be liquid at a temperature of 20 ° C. It is preferable that the polyhedral polysiloxane modified is in a liquid form because of excellent handling properties.

<Compound (B) having two or more alkenyl groups in one molecule>
The curable composition of the present invention may contain a compound (B) having two or more alkenyl groups in one molecule. When the curable composition used for this invention contains a compound (B) and polyhedral structure polysiloxane has a hydrosilyl group, it can be set as hardened | cured material by making these hydrosilylate-react. In the hydrosilylation reaction, it is preferable to use a hydrosilylation catalyst. As the hydrosilylation catalyst that can be used in this reaction, those described below can be used.

  The addition amount of the compound (B) can be variously set, but when the polyhedral polysiloxane has a hydrosilyl group, the hydrosilyl group contained in the modified polyhedral polysiloxane is 0.3 per alkenyl group of the compound (B). It is desirable to add in a ratio of ˜5, preferably 0.5-3. When the proportion of alkenyl groups is small, appearance defects due to foaming or the like are likely to occur, and when the proportion of alkenyl groups is large, physical properties after curing may be adversely affected.

  Here, as the compound (B), for example, polysiloxane (B1) having two or more alkenyl groups in one molecule, an organic compound (B2) described later, and the like are preferable. In addition, you may use together (B1) component and (B2) component.

<Polysiloxane (B1) having two or more alkenyl groups in one molecule>
The number of siloxane units of the polysiloxane (B1) having two or more alkenyl groups in one molecule that can be contained in the curable composition of the present invention is not particularly limited, but preferably two or more, more preferably 2 to 10 pieces. When the number of siloxane units in one molecule is small, the composition tends to volatilize, and desired physical properties may not be obtained after curing. Moreover, when there are many siloxane units, the gas barrier property of the obtained hardened | cured material may fall.

  The polysiloxane having two or more alkenyl groups in one molecule preferably has an aryl group from the viewpoint of gas barrier properties. In addition, in the polysiloxane having two or more alkenyl groups in one molecule having an aryl group, the aryl group is preferably bonded directly to the Si atom from the viewpoint of heat resistance and light resistance. In addition, the aryl group may be present at either the side chain or the terminal of the molecule, and the molecular structure of such an aryl group-containing polysiloxane is not limited. In addition to the chain shape, it may have a cyclic structure.

  Examples of such aryl groups include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, and 4-ethylphenyl. Group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 3-isobutylphenyl group, 4-isobutylphenyl group, 3-tbutylphenyl group, 4-tbutylphenyl group, 3-pentylphenyl group, 4-pentylphenyl group, 3-hexylphenyl group, 4-hexylphenyl group, 3-cyclohexylphenyl group, 4-cyclohexylphenyl group, 2,3-dimethylphenyl Group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3-diethylphenyl group, 2,4-diethylphenyl group, 2,5-diethylphenyl group, 2,6-diethylphenyl group, 3,4-diethylphenyl group, 3,5-diethylphenyl group, biphenyl group, 2,3,4-trimethyl Examples include phenyl group, 2,3,5-trimethylphenyl group, 2,4,5-trimethylphenyl group, 3-epoxyphenyl group, 4-epoxyphenyl group, 3-glycidylphenyl group, 4-glycidylphenyl group and the like. . Among these, a phenyl group is a preferred example from the viewpoint of heat resistance and light resistance. These may be used alone or in combination of two or more.

  The polysiloxane having two or more alkenyl groups in one molecule in the present invention is a linear polysiloxane having two or more alkenyl groups from the viewpoint of heat resistance and light resistance, and two or more alkenyl groups at the molecular ends. Preferred examples include polysiloxanes having a cyclic structure and cyclic siloxanes having two or more alkenyl groups.

  Specific examples of the linear polysiloxane having two or more alkenyl groups include copolymers of dimethylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units. Copolymer, methylphenylsiloxane unit, copolymer of methylvinylsiloxane unit and terminal trimethylsiloxy unit, polydimethylsiloxane blocked with dimethylvinylsilyl group, endblocked with dimethylvinylsilyl group Examples thereof include polydiphenylsiloxane and polymethylphenylsiloxane whose ends are blocked with dimethylvinylsilyl groups.

Specific examples of the polysiloxane having two or more alkenyl groups at the molecular terminals include polysiloxanes whose ends are blocked with dimethylvinylsilyl groups exemplified above, two or more dimethylvinylsiloxane units and SiO ₂ units, SiO _{3 /} Examples thereof include polysiloxane composed of at least one siloxane unit selected from the group consisting of ₂ units and SiO units.

Examples of the cyclic siloxane compound having two or more alkenyl groups include 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5,7-vinyl-1-phenyl. -3,5,7-trimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,5 -Diphenyl-3,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3,5-triphenyl-7-methylcyclotetrasiloxane, 1-phenyl-3,5,7-trivinyl- 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-diphenyl-5,7-divinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-tri Nyl-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11 -Hexavinyl-1,3,5,7,9,11-hexamethylcyclosiloxane and the like are exemplified.
These polysiloxanes having two or more alkenyl groups in one molecule may be used alone or in combination of two or more.

<Organic compound (B2)>
The organic compound (B2) that may be contained in the curable composition of the present invention is an organic compound represented by the following general formula (4), and having two or more alkenyl groups in one molecule If it is, it will not be specifically limited.

(Wherein R ⁶ represents a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and each R ⁶ may be different or the same.)
Since the component (B2) contains two or more alkenyl groups on average in one molecule, the strength, gas barrier property, heat resistance, light resistance and the like of the resulting cured product are excellent. Further, from the viewpoint of gas barrier properties, the number average molecular weight is preferably less than 900.

  The skeleton of the component (B2) may have a functional group other than an alkenyl group, but from the viewpoint of compatibility with the polyhedral polysiloxane, a straight chain such as a methyl group, an ethyl group, or a propyl group. A functional group having low polarity such as the above aliphatic hydrocarbon group is preferred, and a methyl group is particularly preferred from the viewpoint of heat resistance and light resistance.

  The component (B2) is represented by the above general formula (4), for example, from the viewpoint of adhesion to the substrate when the composition is cured with the substrate, and two or more alkenyl groups are contained in one molecule. It is preferably an isocyanuric acid derivative to be contained, and from the viewpoint of balance between heat resistance and light resistance, it is more preferable to use triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoglycidyl isocyanurate, particularly From the viewpoint of resistance to thermal shock, diallyl monomethyl isocyanurate is more preferable. These may be used alone or in combination of two or more.

<Hydrosilylation catalyst>
As the hydrosilylation catalyst that can be used in the present invention, a known hydrosilylation catalyst can be usually selected, and there is no particular limitation.

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.

<Curing retarder>
The curing retarder is a component that can be used to improve the storage stability of the curable composition used in the present invention or to adjust the hydrosilylation reactivity during the curing process. In the present invention, as the retarder, known compounds used in addition-type curable compositions with hydrosilylation catalysts can be used. Specifically, compounds containing aliphatic unsaturated bonds, organophosphorus compounds , Organic sulfur compounds, nitrogen-containing compounds, tin compounds, organic peroxides, and the like. 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.

<Curable composition>
The curable composition of the present invention is obtained by adding a phosphor and polysiloxane, and, if necessary, a compound (B) having two or more alkenyl groups in one molecule, a hydrosilylation catalyst, a curing retarder, and the like. Can be obtained.

  The method for mixing and dispersing the phosphor in the curable composition is not particularly limited as long as the phosphor can be uniformly dispersed without damaging the crystal structure of the phosphor. Conventionally known methods such as a disper, a homogenizer, a three roll, a two roll, a kneader, and a bead mill can be used. Of these, planetary agitation mixers, 3 rolls, 2 rolls, etc., which generate less heat during dispersion and those with less metal wear particles from the mixer are preferred. Among them, planetary agitation mixers damage phosphors. It is preferable because it can be mixed and dispersed with little degassing. 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. For example, when a planetary stirring mixer is used, it is preferably 10 seconds or more and 1 hour or less, more preferably 30 seconds. It is within 30 minutes, more preferably within 1 minute and within 20 minutes. If the mixing / dispersing time is short, the phosphor may not be uniformly dispersed in the curable composition. Further, if the mixing / dispersing time is long, the curable composition and / or the phosphor may be altered.

  The curable composition containing the phosphor is preferably used for molding within 2 hours, more preferably within 1 hour, and even more preferably within 30 minutes after mixing and dispersing as described above. Here, molding means sealing the light emitting element with the curable composition, and injecting the curable composition into the LED package on which the light emitting element is mounted, or the LED mounted on the LED base. Examples thereof include direct sealing with a curable composition by a technique such as press molding and transfer molding. When the time from mixing / dispersion to molding is long, the dispersion of the phosphors in the curable composition is not uniform, and the chromaticity shift between the obtained semiconductor light emitting devices may be increased.

  When adding temperature when hardening a 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 80 ° 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.

  An adhesiveness imparting agent can be added to the curable composition of the present invention as necessary.

  The adhesion-imparting agent is used for the purpose of improving the adhesion between the polysiloxane composition and the substrate in the present invention, and is not particularly limited as long as it has such an effect. A coupling agent can be exemplified as a preferred example.

  The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesiveness and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Specific preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldisilane. Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- Alkoxysilanes having an epoxy functional group such as (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysila Alkoxysilanes having a methacrylic group or an acrylic group such as 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Is mentioned. These may be used alone or in combination of two or more.

  The addition amount of the silane coupling agent is preferably 0.05 to 30 parts by weight, and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the curable composition. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the cured product may be adversely affected.

  Moreover, in order to raise the effect of an adhesive provision agent, a well-known adhesive promoter can also be used. Adhesion promoters include, but are not limited to, epoxy-containing compounds, epoxy resins, boronic ester compounds, organoaluminum compounds, and organotitanium compounds.

  An inorganic filler can be added to the curable composition of this invention as needed. By using an inorganic filler, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical characteristics, light reflectance, flame retardancy, fire resistance, gas barrier properties, etc. of the molded product obtained Various physical 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.

  Although the addition amount of an inorganic filler is not specifically limited, It is 1-1000 weight part with respect to 100 weight part of curable compositions, More preferably, it is 3-500 weight part, More preferably, it is 5-300 weight part. . 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. If the temperature during mixing is high, the composition may be cured before molding.

  The curable composition of the present invention may optionally contain various additives such as a colorant and a heat resistance improver, a reaction control agent, a mold release agent, a dispersant for filler, and the like as necessary. it can. 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.

  In the curable composition of the present invention, the above-mentioned components are uniformly mixed using a kneader such as a roll, a Banbury mixer, a kneader, or a planetary stirring deaerator, and subjected to heat treatment as necessary. May be.

  The semiconductor light emitting device using the curable composition of the present invention can be used for various conventionally known applications. Specifically, for example, backlights such as light receiving and emitting device liquid crystal display devices, illumination, sensor light sources, instrument light sources for vehicles, signal lights, indicator lights, display devices, light sources of planar light emitters, displays, decorations, various lights, etc. Can be mentioned.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereby.

(Production Example 1)
To 1262 g of a 48% choline aqueous solution (trimethyl-2hydroxyethylammonium hydroxide aqueous solution), 1083 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, 1000 mL of methanol was added to the solid produced in the reaction system to obtain a uniform solution. The methanol solution was slowly added dropwise while vigorously stirring a solution of 1485 g of dimethylvinylchlorosilane and 1942 mL of hexane. 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 8 vinyl groups. 597 g of octa (vinyldimethylsiloxy) octasilsesquioxane (Fw = 1226.3) was obtained as a white solid.

(Production Example 2)
10.00 g of octa (vinyldimethylsiloxy) octasilsesquioxane, which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 1, is dissolved in 74.89 g of toluene, and 27.45 g of vinyldiphenylmethylsilane is used. Of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane in an amount of 0.37 alkenyl groups relative to one hydrosilyl group), platinum vinylsiloxane complex 2.45 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 added to 19.61 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (tris (vinyldimethylsiloxy) pentakis (trimethyl used). Siloxy) An amount of 4.9 hydrosilyl groups per one alkenyl group of octasilsesquioxane) was slowly added dropwise to a solution of 19.61 g of toluene and reacted at 105 ° C. for 2 hours. After completion of the reaction, 4.67 μl of ethynylcyclohexanol and 1.09 μl of dimethyl maleate were added, and toluene and unreacted components were distilled off to obtain 54.22 g of a liquid polyhedral polysiloxane modified (SiH value 2.03 mol / kg).

Example 1
To 3.00 g of the modified polyhedral polysiloxane obtained in Production Example 2, 3.00 g of a phosphor (product number: EY4750) manufactured by Intematics Co., Ltd. was used. A composition containing polyhedral polysiloxane and a phosphor was prepared by sequentially performing stirring for 3 minutes, defoaming for 3 minutes, and stirring for 3 minutes. 12 hours after preparation of the composition, 3 mL of hexane was added and stirred, and the resin extraction operation for collecting the phosphor by decantation was repeated 5 times. After this extraction operation, the collected phosphor was dried under reduced pressure for 1 hour at room temperature. Aluminum and carbon were vapor-deposited on the obtained phosphor sample. Further, a phosphor sample coated with tungsten in a focused ion beam apparatus was cut to a thickness of 100 nm by an ion beam (Ar ⁺ ). Using the phosphor samples subjected to these processing treatments, observation by a transmission electron microscope (TEM) and analysis by energy dispersive X-ray spectroscopy (EDX) were performed. As a result, it was found that an adsorption layer of about 8 nm formed by the modified polyhedral polysiloxane was present on the phosphor surface.
1.89 g of diallylmethyl isocyanurate was added to 10.00 g of the modified polyhedral polysiloxane obtained in Production Example 2 and stirred. Next, after adding 1.66 g of a phosphor manufactured by Intematics (product number: EY4750) to the composition and stirring, the mixture was further stirred for 5 minutes with dewaxing 5 using Awatori Kentaro AR-250 manufactured by Thinky. Minutes and stirring 5 minutes in order to prepare a curable composition containing polyhedral polysiloxane and phosphor. In this stirring and defoaming, attention was given to heat radiation of the machine so that the curable composition was not heated. Separately, a 12 mil x 13 mil square blue LED chip (product number: B1213AAA0 S46B / C-19 / 20) manufactured by Genelites Co., Ltd., and an LED package manufactured by Enomoto (product number: TOP) using a gold wire and a die bond agent KER-3000 manufactured by Shin-Etsu Chemical Co., Ltd. LED 1-IN-1). Within 15 minutes from the above stirring and defoaming, the composition obtained here was dispensed by Sanei Tech 1500 series, 3cc barrel-piston set by Sanei Tech (product number: 5109CP-B), produced by Sanei Tech. It inject | poured using the chip | tip (product number: 5123-B). Subsequently, step cure under conditions of 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 5 hours was started in a convection oven. Using the total luminous flux measurement (φ300 mm) system (product number: HM-0930) manufactured by Otsuka Electronics Co., Ltd., the obtained evaluation sample was made to emit light when energized under the conditions of a temperature of 25 ° C., a current of 30 mA, and a standby time of 30 seconds. The chromaticity of the luminescent color was measured, and the standard deviation of the chromaticity of the luminescent color of 500 samples measured is shown in Table 1.

(Comparative Example 1)
A phosphor sample for TEM observation and EDX analysis was prepared in the same manner as in Example 1 except that OE6630-B manufactured by Toray Dow Corning, which is a commercially available phenyl silicone-based sealant, was used. And EDX analysis. In this case, no resin layer was seen on the phosphor surface.
OE6630-B8.00g was added and stirred to OE6630-A2.00g by Toray Dow Corning. Next, 1.40 g of a phosphor (product number: EY4750) manufactured by Intematix was added and stirred to prepare a curable composition containing the phosphor. Using the obtained curable composition, an evaluation sample was prepared in the same manner as in Example 2, the chromaticity of the luminescent color was measured under the same conditions as in Example 2, and the standard deviation of the luminescent color of 500 measured samples was measured. Are listed in Table 1.

  As is clear from the examples, it is clear that the semiconductor light emitting device using the polysiloxane composition of the present invention containing polysiloxane capable of forming a resin adsorption layer on the phosphor surface has little chromaticity deviation between individuals. It became.

Claims (23)

A composition containing polysiloxane capable of forming a resin adsorbing layer of 0.1 nm to 1000 nm on the phosphor surface, and when the composition is used as an LED sealant, a phosphor element and a phosphor layer The emission color emitted from the semiconductor light emitting device consisting of the following equations (1) and (2):
δ (x) <0.004 (1)
δ (y) <0.005 (2)
(Where δ (x) is the standard deviation of x on the chromaticity coordinates of the xyX color system of the light emitting color of the semiconductor light emitting device, and δ (y) is the chromaticity of the xyY color system of the light emitting color of the semiconductor light emitting device. The standard deviation of y on the coordinates.The number of samples of these standard deviations is 500 at random.) A polysiloxane-based composition for LED encapsulation that can be converged to the standard deviation range represented by: The polysiloxane according to claim 1 is a polyhedral polysiloxane. 3. The polysiloxane composition according to claim 2, wherein the polyhedral polysiloxane has an average of 3 or more hydrosilyl groups in one molecule. The polyhedral polysiloxane has an alkenyl group, polyhedral polysiloxane compound (a), a hydrosilyl group-containing compound (b), and an organosilicon compound (a ′) having one alkenyl group in one molecule. 4. The polysiloxane composition according to claim 2, which is a modified polyhedral polysiloxane (A) obtained by reaction. 5. 5. The polysiloxane composition according to claim 4, wherein the modified polyhedral polysiloxane (A) is liquid at a temperature of 20 ° C. 6. The polysiloxane composition according to claim 4 or 5, wherein the organosilicon compound (a ') having one alkenyl group in one molecule is an organosilicon compound having one or more aryl groups. The polyhedral polysiloxane compound (a) having an alkenyl group has the 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; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom or an alkyl group And a polyhedral polysiloxane compound containing an alkenyl group composed of a siloxane unit represented by an aryl group or a group linked to another polyhedral skeleton polysiloxane). The polysiloxane composition according to any one of 4 to 6. 8. The compound (b) containing a hydrosilyl group is a cyclic siloxane containing a hydrosilyl group and / or a linear siloxane containing a hydrosilyl group at the molecular end. 2. The polysiloxane composition according to item 1.   The polysiloxane composition according to any one of claims 4 to 7, wherein the compound (b) containing a hydrosilyl group is a cyclic siloxane containing a hydrosilyl group.   The compound (b) containing a hydrosilyl group is 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, according to claim 9. Polysiloxane composition. The polyhedral polysiloxane has the 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, 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 ( The structure of 1) or general formula (2) may be different, and the structure of general formula (1) or 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. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain And at least one of Y or Z is a hydrogen atom, and at least one has the structure of the following general formula (3).
-[CH ₂ ] _l -R ⁵ (3)
(L is an integer of 2 or more; R ⁵ is a group containing an organosilicon compound); R is an alkyl group or an aryl group}]
The polysiloxane composition according to claim 2 or 3, which is a modified polyhedral polysiloxane (A) having a structural unit as a structural unit. The polysiloxane composition according to claim 11, wherein R ⁵ has one or more aryl groups. 13. The polysiloxane composition according to claim 2, comprising a compound (B) having two or more alkenyl groups in one molecule. 14. The polysiloxane composition according to claim 13, wherein the compound (B) is a polysiloxane (B1) having two or more alkenyl groups in one molecule. The polysiloxane composition according to claim 14, wherein the polysiloxane (B1) having two or more alkenyl groups in one molecule has one or more aryl groups. Compound (B) is an organic compound represented by the following general formula (4):

(Wherein R ⁶ represents a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and each R ⁶ may be different or the same), and 2 alkenyl groups in one molecule. The polysiloxane composition according to claim 13, which is an organic compound (B2) having at least one. The polysiloxane composition according to claim 16, wherein the organic compound (B2) has a number average molecular weight of less than 900. 18. The organic compound (B2) is at least one compound selected from the group consisting of triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoglycidyl isocyanurate, The polysiloxane composition as described. 18. The polysiloxane composition according to claim 16, wherein the organic compound (B2) is diallyl monomethyl isocyanurate. The polysiloxane composition according to claim 1, further comprising a hydrosilylation catalyst. The polysiloxane composition according to any one of claims 1 to 20, further comprising a curing retarder. The hardened | cured material obtained by hardening the polysiloxane type composition of any one of Claims 1-21 containing fluorescent substance. The semiconductor light-emitting device carrying the hardened | cured material of Claim 22.