JP2015098540A - Curable composition added with polyhedron structure polysiloxane, cured material, and semiconductor light-emitting device and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a method for manufacturing semiconductor light-emitting device in which the liquid clogging when dispensing a curable composition containing fluophor to LED, can be prevented and which has an excellent productivity; a curable composition used thereto; a cured material; and a semiconductor light-emitting device.SOLUTION: The problem is solved by using a curable composition that comprises (A) an LED sealant not containing polyhedron structure polysiloxane (100 pts.wt) and (B) a polyhedron structure polysiloxane (0.1 to 25 pts.wt) and in which the (B) component polyhedron structure polysiloxane is composed of a polyhedron structure polysiloxane unit comprising alkenyl group or hydro-silyl group.

Description

  The present invention relates to a method for manufacturing a semiconductor light emitting device that prevents liquid clogging when dispensing a curable composition containing a phosphor to an LED and is excellent in productivity.

Semiconductor light-emitting devices have features such as long life, low power consumption, shock resistance, high-speed response, lightness, thinness, and other features, such as backlights for liquid crystal displays, mobile phones, information terminals, in-vehicle lighting, indoor and outdoor Expansion to various fields such as advertisements and indoor / outdoor lighting is progressing dramatically.
A semiconductor light-emitting device is usually manufactured by applying a curable composition containing a phosphor on a light-emitting element made of a semiconductor (hereinafter referred to as LED) and curing the composition to cure the LED. . At this time, the purpose of dispersing the phosphor uniformly in the curable composition, the purpose of preventing the dispersion of the dispense amount of the dispenser to the LED due to the precipitation of the phosphor and clogging of the liquid, and imparting the scattering effect to the cured product Depending on the purpose, the filler may be included in the curable composition together with the phosphor (see Patent Documents 1 and 2).

However, when the LED is sealed using the curable composition containing the phosphor and the filler as described above, the dispersion of the filler contained in the curable composition is insufficiently aggregated. As a result of excessive filler scattering, the luminous efficiency of the optical semiconductor device is reduced, and the phosphors are unevenly dispersed, leading to chromaticity shifts in each of the obtained semiconductor light emitting devices, resulting in manufacturing quality and yield. There is a problem that the manufacturing cost becomes high.
The present invention has been made to solve such problems, and relates to a method for manufacturing a semiconductor light-emitting device that is less prone to clogging when a curable composition containing a phosphor is dispensed onto an LED and has excellent productivity.

JP 2009-102514 A JP 2006-294821 A

  Provided are a method for producing a semiconductor light-emitting device that prevents clogging when a curable composition containing a phosphor is dispensed to an LED and is excellent in productivity, and a curable composition, a cured product, and a semiconductor light-emitting device used therefor. about.

As a result of intensive studies to solve the above problems, the present inventors have
It discovered that the said subject could be solved by the curable composition which consists of LED sealing agent (100 weight part) which does not contain polyhedral polysiloxane, and polyhedral structure polysiloxane (0.1-25 weight part), and found in this invention. It came.
That is, the present invention has the following configuration.

1). A curable composition comprising (A) an LED sealing agent not containing polyhedral polysiloxane (100 parts by weight) and (B) polyhedral polysiloxane (0.1 to 25 parts by weight),
The polyhedral polysiloxane of component (B) is composed of polyhedral polysiloxane units having an alkenyl group or a hydrosilyl group.

  2). (A) Component is methyl silicone resin, The curable composition as described in 1) characterized by the above-mentioned.

  3). (A) A component is phenyl silicone resin, The curable composition as described in 1) characterized by the above-mentioned.

  4). (B) The curable composition according to any one of 1) to 3), wherein the component is liquid at a temperature of 20 ° C.

  5). The polyhedral polysiloxane compound (a) in which the component (B) has an alkenyl group and / or a hydrosilyl group, and a hydrosilyl group or alkenyl that can be hydrosilylated with the component (a) and / or the component (c) as necessary Compound (b) having two or more groups in one molecule and, if necessary, one alkenyl group or hydrosilyl group capable of hydrosilylation with component (a) and / or (b) in one molecule 5. The curable composition according to any one of 1) to 4), which is a polyhedral polysiloxane obtained by hydrosilylation reaction of the compound (c).

  6). The component (B) is a polyhedral polysiloxane compound (a1) having an alkenyl group and a hydrosilyl group, and, if necessary, a hydrosilyl group or alkenyl group capable of hydrosilylation reaction with the component (a1) and / or the component (c). Compound (b) having two or more in one molecule, and compound having one alkenyl group or hydrosilyl group in one molecule that can be hydrosilylated with component (a) and / or (b) as necessary ( 5. The curable composition according to 5), which is a polyhedral polysiloxane obtained by hydrosilylation reaction of c).

  7). The component (B) is a polyhedral polysiloxane compound (a2) having an alkenyl group, a compound (b1) having two or more hydrosilyl groups in one molecule, and a compound (c1) having one alkenyl group in one molecule And a polyhedral polysiloxane obtained by hydrosilylation reaction.) The curable composition according to 5).

  8). The component (B) is a polyhedral polysiloxane obtained by hydrosilylation reaction of a polyhedral polysiloxane compound (a3) having a hydrosilyl group and a compound (c1) having one alkenyl group in one molecule. The curable composition according to any one of 1) to 4).

9). (B) the polyhedral polysiloxane compound (a2) in which the component has an alkenyl group;
Curability according to any one of 1) to 4), which is a polyhedral polysiloxane obtained by hydrosilylation reaction of a compound (b1) having two or more hydrosilyl groups in one molecule. Composition.

10). The polyhedral polysiloxane compound (a2) having an alkenyl group has the formula:
[AR ² ₂ SiO—SiO _3/2 ] _a [R ³ 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 ² is an alkyl group or an aryl group; R ³ is a hydrogen atom or an alkyl group 7), 9) 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 curable composition according to any one of items 1).

11). The polyhedral polysiloxane compound (a3) having a hydrosilyl group has the formula:
[HR ² ₂ SiO—SiO _3/2 ] _a [R ³ 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; H is a hydrosilyl group; R ² is an alkyl group or an aryl group; R ³ is an alkyl group or an aryl group Or a polyhedral polysiloxane compound containing a hydrosilyl group composed of a siloxane unit represented by a group linked to other polyhedral skeleton polysiloxane). Composition.

  12). Any one of 7) and 9), wherein the compound (b1) having two or more hydrosilyl groups in one molecule is a cyclic siloxane or a linear polysiloxane having two or more hydrosilyl groups in one molecule. 2. The curable composition according to item 1.

  13). 12. The curable composition according to 12), wherein the compound (b1) having two or more hydrosilyl groups in one molecule is a cyclic siloxane having two or more hydrosilyl groups in one molecule.

  14). The compound (b1) having two or more hydrosilyl groups in one molecule is 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane 12 ).

  15). (C) The curable composition according to any one of 5) to 8), wherein the component is an organosilicon compound having one alkenyl group and one or more aryl groups in one molecule. .

16). The component (B) has the formula: [XR ⁴ ₂ SiO—SiO _3/2 ] _a [R ⁵ 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 ⁴ is an alkyl group or an aryl group; R ⁵ is an alkenyl group, a hydrogen atom, an alkyl group, 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. 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 6}} (3)
(1 is an integer of 2 or more; R ⁶ is a group containing an organosilicon compound); R ⁶ is a polyhedral polysiloxane having a structural unit of an alkyl group or an aryl group} Curable composition.

17). R ⁶ is The curable composition according to 16), wherein the having at least one aryl group.

  18). (A) In addition to the component (B), the component (D), which is an organic compound represented by the following general formula (1), is included in any one of 1) to 17) Curable composition.

(Wherein R ¹ represents a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and each R ¹ may be different or the same.)

  19). The curable composition according to any one of 1) to 18), which contains a hydrosilylation catalyst.

  20). The curable composition according to any one of 1) to 19), further comprising a curing retardant.

  21). The curable composition according to any one of 1) to 20), further comprising a dispersant.

  22). The curable composition according to any one of 1) to 21), comprising a phosphor.

  23). A cured product obtained from the curable composition of 22).

  24). The semiconductor light-emitting device obtained from the curable composition of 22).

  By using a curable composition to which a small amount of polyhedral polysiloxane is added, a method for producing a semiconductor light-emitting device that prevents clogging when dispensing a curable composition containing a phosphor to an LED and has excellent productivity, A curable composition, a cured product, and a semiconductor light emitting device used therefor can be provided.

  Hereinafter, the present invention will be described in detail.

<Semiconductor light emitting device>
In the semiconductor light emitting device of the present invention, a light emitting element made of a semiconductor includes a phosphor described later, (A) an LED sealing agent not containing polyhedral polysiloxane (100 parts by weight), and (B) polyhedral polysiloxane (0). 0.1 to 25 parts by weight) is obtained by sealing with a phosphor layer made of a curable composition. 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, it does not specifically limit as a package for LED or a board | substrate for LED, What is used widely can be used.

<Light emitting element made of semiconductor>
The light emitting element made of a semiconductor used in the semiconductor light emitting device of the present invention is not particularly limited, and those widely 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 of the present invention, a plurality of the same or different types of LEDs may be mounted per semiconductor light emitting device.

<Phosphor>
The curable composition used for the semiconductor light emitting device of the present invention contains a phosphor and forms a phosphor layer. The phosphor absorbs light emitted from the light-emitting element and generates light of different wavelengths. The phosphor used in the semiconductor light-emitting device of the present invention is not particularly limited, and is generally known inorganic fluorescence. And an organic phosphor can be used, and an arbitrary one can be selected in order to obtain an emission color required by the semiconductor light emitting device of the present invention. Specifically, for example, YAG phosphor, LuAG phosphor, TAG phosphor, BOS phosphor, orthosilicate alkaline earth phosphor, α-sialon phosphor, β-sialon phosphor, CASN -Based phosphors, SCASN-based phosphors, nitrides, oxynitride-based phosphors, and the like, but are not limited thereto. 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 It is 100 μm or less, more preferably 50 μm or less, and still 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.

<LED sealing agent not containing polyhedral polysiloxane>
The main component of the curable composition used in the semiconductor light-emitting device of the present invention is an LED sealing agent that does not contain polyhedral polysiloxane, and an LED sealing agent that does not contain a known polyhedral polysiloxane can be used. Although it does not specifically limit as LED sealing agent, For example, a methyl silicone resin, a phenyl silicone resin, a hybrid resin, an epoxy resin etc. are mentioned.
Examples of the curing reaction of component (A) include a hydrosilylation reaction of a compound having a carbon-carbon double bond group and a compound having a hydrosilyl group, a curing reaction of a compound having an epoxy group and a compound having an acid anhydride group, and the like. It is done.
The curing reaction of component (A) is preferably a hydrosilylation reaction between a compound having a carbon-carbon double bond group and a compound having a hydrosilyl group from the viewpoint of excellent heat resistance and light resistance of the resulting cured product.
Specific examples of the methyl silicone resin include, for example, OE-6351, OE-6336, EG-6301, JCR-6140, JCR-6126, JCR-6122, JCR-6101, JCR-6115, JCR- manufactured by Toray Dow Corning. 6250, JCR-6109, JCR-6110, Shin-Etsu Chemical KER-2500, KER-2600, KER-2700, and the like.
Specific examples of the phenyl silicone resin include, for example, OE-6450, OE-6550, OE-6520, OE-6665, OE-6650, OE-6636, OE-6635, OE-6630, and OE- manufactured by Toray Dow Corning. 6662, OE-6651, OE-7620, OE-7630, OE07640, JCR-6175, LPS-3600 series manufactured by Shin-Etsu Chemical, ASP-1111, ASP-1031, ASP-1120, KER-6000, KER-6100, KER -6110, KER-6150, KER-6200, KER-6075-F, KER-6020-F and the like.
Specific examples of the hybrid resin include SCR-1011, SCR-1012, and SCR-1016 manufactured by Shin-Etsu Chemical.

  Specific examples of the epoxy resin include the CELVENUS series manufactured by Daicel Chemical Industries, the NT series manufactured by Nitto Denko, and the like.

As the component (A), a methyl silicone resin is preferable from the viewpoint of having a good balance of heat resistance, light resistance, and thermal shock resistance.
As the component (A), a phenyl silicone resin is preferable from the viewpoint of having a good balance of heat resistance, light resistance, and gas barrier properties.
The methyl silicone resin is a curable composition mainly composed of a polysiloxane compound having two or more alkenyl groups and / or hydrosilyl groups in one molecule.
Two liquid components are methyl silicone resins composed of two or more main components, a polysiloxane compound having two or more alkenyl groups in one molecule and a polysiloxane compound having two or more hydrosilyl groups in one molecule. It is preferable in terms of good storage stability of the mold curable composition.
Polysiloxane units of the methyl silicone resin include [SiO _4/2 ] _, [(CH ₃ ) SiO _3/2 ] _, [(CH ₃ ) ₂ SiO _2/2 ] _, [(CH ₃ ) ₃ SiO _1/2 ]. Of methylsiloxane units.
Examples of the alkenyl group of the methyl silicone resin 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 phenyl silicone resin is a curable composition mainly composed of a polysiloxane compound having two or more alkenyl groups and / or hydrosilyl groups in one molecule.
Two components of a phenyl silicone resin composed of two or more main components, a polysiloxane compound having two or more alkenyl groups in one molecule and a polysiloxane compound having two or more hydrosilyl groups in one molecule. It is preferable in terms of good storage stability of the mold curable composition.

  The phenyl silicone resin is a curable composition mainly composed of a polysiloxane compound having two or more alkenyl groups and / or hydrosilyl groups in one molecule, which is mainly composed of the following siloxane units. The siloxane unit of the phenyl silicone resin always includes a phenyl siloxane unit.

Two components of a phenyl silicone resin composed of two or more main components, a polysiloxane compound having two or more alkenyl groups in one molecule and a polysiloxane compound having two or more hydrosilyl groups in one molecule. It is preferable in terms of good storage stability of the mold curable composition. (The siloxane unit of the phenyl silicone resin always includes the phenyl siloxane unit.)
Examples of the alkenyl group of the phenyl silicone resin 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.
Moreover, the liquid clogging at the time of dispensing the curable composition containing a fluorescent substance to LED with respect to 100 weight part of (A) component can be prevented by containing 0.1 to 25 weight part of (B) component. .
The content of the component (B) is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, and even more preferably 1.0 parts by weight or more with respect to 100 parts by weight of the component (A). When the amount is less than 0.1 part by weight, the effect of suppressing clogging when dispensing to the LED cannot be obtained. On the other hand, 25 parts by weight or less is preferable, 15 parts by weight or less is more preferable, and 5 parts by weight or less is even more preferable. If it exceeds 25 parts by weight, tackiness will occur in the cured product, and heat resistance, light resistance and gas barrier properties will deteriorate.

<Polyhedral polysiloxane (B)>
The curable composition used for the semiconductor light-emitting device of the present invention contains polyhedral polysiloxane. The polyhedral polysiloxane is a polysiloxane having a polyhedral polysiloxane skeleton.
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, alkenyl group, or hydrogen atom, which may be the same or different; a is an integer of 6 to 24). Illustratively, it may be a partially cleaved polyhedral polysiloxane containing [R ₂ SiO _2/2 ] units or [R ₃ SiO _1/2 ] units in its structure.
The polysiloxane having a polyhedral polysiloxane skeleton used in the present invention comprises a polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group, and (a) component and / or (c) component as necessary. And a compound (b) having two or more hydrosilyl groups or alkenyl groups capable of hydrosilylation in one molecule, and an alkenyl group capable of hydrosilylation reaction with component (a) and / or (b) as necessary, or The polyhedral polysiloxane obtained by hydrosilylation reaction of the compound (c) having one hydrosilyl group per molecule is excellent in the heat resistance, light resistance and gas barrier property of the resulting cured product, and the LED. This is preferable because clogging during liquid dispensing is suppressed.

When the polyhedral polysiloxane (B) is mixed with the above-described component (A) and cured, it is hydrosilylated in one molecule from the viewpoint of the strength, heat resistance, light resistance, gas barrier properties and tack of the resulting cured product. It is preferable to contain one or more groups and / or alkenyl groups on average.

When the LED encapsulant (A) is an LED encapsulant having an organic group such as a phenyl silicone resin, the polyhedral polysiloxane (B) is preferably a polyhedral polysiloxane having an organic group. In the case of polyhedral polysiloxane having an organic group, the adsorptivity with the phosphor is improved and the aggregation of the phosphor is suppressed, so that clogging during dispensing to the LED is suppressed.
Preferred organic groups include alicyclic aliphatic hydrocarbon groups and aryl groups. These preferable organic groups have a higher effect of suppressing liquid clogging when dispensing to the LED as compared with a linear aliphatic hydrocarbon group having a low carbon number such as a methyl group, an ethyl group, or a propyl group.
Preferred alicyclic aliphatic hydrocarbon groups include, for example, cyclohexyl group, isobornyl group, 3,3,5-trimethylcyclohexyl group, dicyclopentenyl group, dicyclopentanyl group, 1-adamantyl group, tricyclopenta Nyl group, tricyclopentenyl group, 2,2-dimethyl-3-methylene-bicyclo [2.2.1] heptyl group, norbornyl group and the like can be mentioned. Preferred aryl groups include, for example, phenyl group, naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 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 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-trimethylphenyl Group, 2,3,5-trimethylphenyl group, 2,4,5-trimethylphenyl 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.
When the component (A) is a methyl silicone resin, the compatibility of the polyhedral polysiloxane having the above preferred organic group may be poor, so that the straight chain having a low carbon number such as a methyl group, an ethyl group, or a propyl group may be used. Polyhedral polysiloxanes having the following aliphatic hydrocarbon groups may be preferred.
When the component (A) is a phenyl silicone resin, the above-described three-dimensional polysiloxane having a preferable organic group improves the adsorptivity with the phosphor and suppresses the aggregation of the phosphor, so that it is dispensed to the LED. In some cases, liquid clogging may be suppressed.

<Polyhedral polysiloxane compound (a) having alkenyl group and / or hydrosilyl group>
The polyhedral polysiloxane compound (a) having an alkenyl group and / or hydrosilyl group used in the semiconductor light emitting device of the present invention is particularly a polyhedral polysiloxane compound having an alkenyl group and / or hydrosilyl group in the molecule. There is no limitation.
Specific examples of the polyhedral polysiloxane compound having an alkenyl group and / or a hydrosilyl group include, 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 an integer of 0 or 1 or more; R ⁷ is an alkenyl group, a hydrogen atom; R ⁸ is any organic group or other polyhedral skeleton poly A polyhedral polysiloxane compound having an alkenyl group and / or a hydrosilyl group composed of a siloxane unit represented by a group linked to siloxane can be suitably used.
[AR ² ₂ SiO—SiO _3/2 ] _a [R ³ 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, a hydrogen atom; R ² is an alkyl group or an aryl group; R ³ is an alkyl group A polyhedral polysiloxane compound having an alkenyl group and / or a hydrosilyl group composed of a siloxane unit represented by the following formulas: an aryl group, or a group linked to another polyhedral skeleton polysiloxane) .

  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 ² 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 ³ is a hydrogen atom, an alkyl group, an aryl group, or a group connected 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 3 or more, and more preferably 6 or more, from the viewpoint of the effect of suppressing aggregation of the phosphor by the obtained polyhedral polysiloxane. 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 or 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 hydrolytic condensation reaction of R ⁹ SiX ^a _3, the ring is closed by 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.

  Moreover, among the polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group, the component (a) having both an alkenyl group and a hydrosilyl group is designated as “polyhedral polysiloxane compound having an alkenyl group and a hydrosilyl group ( a1) ”, having no alkenyl group and having an alkenyl group (a)“ polyhedral polysiloxane compound having alkenyl group (a2) ”, having no alkenyl group and having a hydrosilyl group (a)“ hydrosilyl group May be referred to as a polyhedral polysiloxane compound (a3).

<Compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule>
The compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule used in the semiconductor light emitting device of the present invention is not particularly limited as long as it has two or more hydrosilyl groups or alkenyl groups in the molecule. However, from the viewpoints of transparency, heat resistance, and light resistance of the polyhedral polysiloxane obtained, the polyhedral structure polysiloxane is preferably a compound having two or more hydrosilyl groups in one molecule, and further has one hydrosilyl group in one molecule. It is preferably a cyclic siloxane or a linear polysiloxane having two or more in each. In particular, from the viewpoint of heat resistance, light resistance, and gas barrier properties, a cyclic siloxane is preferable.

  The linear polysiloxane having two or more hydrosilyl groups in one molecule includes a copolymer of a dimethylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, a diphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal. Copolymers with trimethylsiloxy units, copolymers of methylphenylsiloxane units with methylhydrogensiloxane units and terminal trimethylsiloxy units, polydimethylsiloxanes end-capped with dimethylhydrogensilyl groups, dimethylhydrogensilyl groups And polydiphenylsiloxane whose end is blocked with dimethylhydrogensilyl group, and the like.

  In particular, as a linear polysiloxane having two or more hydrosilyl groups in one molecule, from the viewpoints of reactivity when reacting, heat resistance of the obtained cured product, light resistance, etc., molecules with dimethylhydrogensilyl groups Polysiloxanes whose ends are blocked, and polydimethylsiloxanes whose molecular ends are blocked with a dimethylhydrogensilyl group can be suitably used. Specifically, for example, tetramethyldisiloxane, hexamethyltrisiloxane, etc. Illustrated as a preferred example.

  Examples of the cyclic siloxane having two or more hydrosilyl groups in one molecule 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, 3,5,7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane and the like. Specific examples of the cyclic siloxane in the present invention include, for example, 1,3,5,7-tetrahydrogen-, from the viewpoints of industrial availability and reactivity, or the heat resistance and light resistance of the resulting cured product. 1,3,5,7-tetramethylcyclotetrasiloxane can be preferably used.

These compounds (b), which have two or more hydrosilyl groups in one molecule, may be used alone or in combination of two or more.
Of the compounds (b) having two or more hydrosilyl groups or alkenyl groups in one molecule, a compound having no alkenyl group and two or more hydrosilyl groups in one molecule is referred to as “hydrosilyl group in one molecule”. It may be described as “compound (b1) having two or more”.

<Compound (c) having one alkenyl group or hydrosilyl group in one molecule>
The compound (c) having one alkenyl group or hydrosilyl group in one molecule used in the semiconductor light emitting device of the present invention is not particularly limited as long as it has one alkenyl group or hydrosilyl group in one molecule. Hydrosilylation reaction with the compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule, or the polyhedral or multi-branched polysiloxane compound (a) having an alkenyl group and / or hydrosilyl group .

As the component (c), the compound having an organic group improves the adsorptivity of the obtained polyhedral polysiloxane (B) with the phosphor, and the aggregation of the phosphor is suppressed. This is preferable because clogging is suppressed.
Preferred organic groups include the above-described alicyclic aliphatic hydrocarbon groups and aryl groups. These preferable organic groups have a higher effect of suppressing liquid clogging when dispensing to the LED as compared with a linear aliphatic hydrocarbon group having a low carbon number such as a methyl group, an ethyl group, or a propyl group.

  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.

Specific examples of the compound having one alkenyl group in one molecule include, for example, compounds having a low carbon number alkyl group such as trimethylvinylsilane, triethylvinylsilane, allyltrimethylsilane, allyltriethylsilane, dimethylphenylvinylsilane, and methyldiphenyl. Compounds having an aryl group such as vinylsilane, triphenylvinylsilane, diethylphenylvinylsilane, ethyldiphenylvinylsilane, allyldimethylphenylsilane, allylmethyldiphenylsilane, allyltriphenylsilane, allyldiethylphenylsilane, allylethyldiphenylsilane, trimethoxyvinylsilane, Dimethoxymethylvinylsilane, methoxydimethylvinylsilane, triethoxyvinylsilane, diethoxymethylvinylsilane, Compounds having alkoxysilyl groups such as xyldimethylvinylsilane, trimethoxyallylsilane, dimethoxymethylallylsilane, methoxydimethylallylsilane, triethoxyallylsilane, diethoxymethylallylsilane, ethoxydimethylallylsilane, alicyclic rings such as camphene, norbornene, vinylcyclohexene, allylcyclohexene And compounds having an aliphatic hydrocarbon group of the formula.
The component (c) is preferably a group containing a silicon compound having silane or polysiloxane from the viewpoint of heat resistance and light resistance. When the component (c) is a silane having one alkenyl group in one molecule, for example, trimethylvinylsilane, triethylvinylsilane, allyltrimethylsilane, allyltriethylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, triphenyl Vinylsilane, diethylphenylvinylsilane, ethyldiphenylvinylsilane, allyldimethylphenylsilane, allylmethyldiphenylsilane, allyltriphenylsilane, allyldiethylphenylsilane, allylethyldiphenylsilane, trimethoxyvinylsilane, dimethoxymethylvinylsilane, methoxydimethylvinylsilane, triethoxyvinylsilane , Diethoxymethylvinylsilane, ethoxydimethylvinylsilane, trimethoxyallylsil , Dimethoxymethyl allyl silane, methoxy dimethylallyl silane, triethoxy allyl silane, diethoxy methyl allyl silane, ethoxy dimethyl allyl silane, and the like. Among them, liquid clogging when dispensing to the LED is suppressed, and dimethylphenylvinylsilane, methyldiphenylvinylsilane, and triphenylvinylsilane are preferable examples from the viewpoint of heat resistance and light resistance.

  When the component (c) is a polysiloxane having one alkenyl group in one molecule, a polysiloxane having a linear structure having one alkenyl group, a polysiloxane having one alkenyl group at the molecular end, and 1 alkenyl group The cyclic siloxane etc. which have one are illustrated.

  In the case where the component (c) is a polysiloxane having a linear structure having one alkenyl group in one molecule, specifically, for example, polydimethyl having one end each blocked with a dimethylvinylsilyl group and a trimethylsilyl group. Siloxane, polymethylphenylsiloxane blocked with a dimethylvinylsilyl group and a trimethylsilyl group each at one end, polydiphenylsiloxane blocked with a dimethylvinylsilyl group and a trimethylsilyl group, respectively, and a dimethylvinylsilyl group Copolymers of dimethylsiloxane units and methylphenylsiloxane units each end-capped with trimethylsilyl groups, and dimethylsiloxane units and diphenylsiloxy units each end-capped with dimethylvinylsilyl groups and trimethylsilyl groups. Copolymers of emission units, copolymers of terminal and methylphenylsiloxane units and diphenylsiloxane units are blocked one by one, respectively dimethylvinylsilyl group and trimethylsilyl group and the like.

In the case of a polysiloxane having one alkenyl group at the molecular end, specifically, for example, a polysiloxane having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group as exemplified above, [SiO _4/2 ] unit , [SiO _3/2 ] units, [SiO _2/2 ] units, at least one siloxane unit selected from the group consisting of [SiO _1/2 ] units, and polysiloxane composed of one dimethylvinylsiloxane unit. The

When the component (c) is a cyclic siloxane having one alkenyl group in one molecule, specifically, for example, 1-vinyl-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane 1-vinyl-3-phenyl-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1-vinyl-3,5-diphenyl-1,3,5,7,7-pentamethylcyclo Examples thereof include tetrasiloxane and 1-vinyl-3,5,7-triphenyl-1,3,5,7-tetramethylcyclotetrasiloxane.
When the component (c) is a silane having one hydrosilyl group in one molecule, for example, trimethylhydrosilane, dimethylphenylhydrosilane, methyldiphenylhydrosilane, triphenylhydrosilane, triethylhydrosilane, diethylphenylhydrosilane, ethyldiphenylhydrosilane, etc. Illustrated.

When the component (c) is a polysiloxane having one hydrosilyl group in one molecule, a polysiloxane having a linear structure having one hydrosilyl group, a polysiloxane having one hydrosilyl group at the molecular end, and one hydrosilyl group The cyclic siloxane etc. which have one are illustrated.
Examples of the polysiloxane compound having one hydrosilyl group per molecule include polydimethylsiloxane having one end blocked with a dimethylhydrosilyl group and one trimethylsilyl group, and one end each with a dimethylhydrosilyl group and a trimethylsilyl group. Polymethylphenylsiloxane blocked one by one, polydiphenylsiloxane blocked one by one with dimethylhydrosilyl group and trimethylsilyl group, dimethylsiloxane unit and methyl blocked one by one with dimethylhydrosilyl group and trimethylsilyl group, respectively A copolymer of a phenylsiloxane unit, a copolymer of a dimethylsiloxane unit and a diphenylsiloxane unit each having one end blocked with a dimethylhydrosilyl group and a trimethylsilyl group; Copolymers of terminal and methylphenylsiloxane units and diphenylsiloxane units are blocked one by one, respectively Ruhidoroshiriru group and trimethylsilyl group and the like.

In the case of a polysiloxane having one hydrosilyl group at the molecular end, specifically, for example, a polysiloxane having one end blocked with a dimethylhydrosilyl group and a trimethylsilyl group as exemplified above, [SiO _4/2 ] units, Examples include [SiO _3/2 ] units, [SiO _2/2 ] units, at least one siloxane unit selected from the group consisting of [SiO _1/2 ] units, and a polysiloxane consisting of one dimethylhydrogensiloxane unit. The
When the component (c) is a cyclic siloxane having one hydrosilyl group in one molecule, specifically, for example, 1-hydrogen-1,3,3,5,5,7,7-heptamethylcyclotetra Siloxane, 1-hydrogen-3-phenyl-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1-hydrogen-3,5-diphenyl-1,3,5,7,7- Examples thereof include pentamethylcyclotetrasiloxane and 1-hydrogen-3,5,7-triphenyl-1,3,5,7-tetramethylcyclotetrasiloxane.
These (c) components may be used independently and may use 2 or more types together.
Further, among the compounds (c) having one alkenyl group or hydrosilyl group in one molecule, a compound having no hydrosilyl group and one alkenyl group in one molecule is referred to as “one alkenyl group in one molecule”. It may be described as “compound (c1)”.

<Synthesis of polyhedral polysiloxane (B)>
The polyhedral polysiloxane (B) used in the semiconductor light-emitting device of the present invention comprises a polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group in the presence of a hydrosilylation catalyst described later, and if necessary. Compound (b) having two or more hydrosilyl groups or alkenyl groups capable of hydrosilylation reaction with component (a) and / or component (c), and (a) component and / or (b) as necessary ) Component and a compound (c) having one alkenyl group or hydrosilyl group capable of hydrosilylation reaction in one molecule is obtained by hydrosilylation reaction.

  The method for obtaining the polyhedral polysiloxane is not particularly limited and can be variously set. However, after the (a) component and the (b) component are reacted in advance, the (c) component may be reacted, or the (c) After reacting the component and the component (b), the component (a) may be reacted, or the component (a) and the component (c) may be allowed to coexist and react with the component (b). 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 (c) and the component (b) and not including the component (a), the component (a) and the component (b) are reacted, and the unreacted (b) A method in which the component (c) is reacted after the component is distilled off is preferred. It is preferable from the viewpoint of heat resistance that only the component (c) and the component (b) react and the formation of the compound not containing the component (a) is suppressed.

  Moreover, as a method of obtaining polyhedral polysiloxane, (a) component and (b) component may be made to react, and (a) component and (c) component may be made to react.

  In the polyhedral polysiloxane thus obtained, a part of the alkenyl group or hydrosilyl group of the component (a) used in the reaction may remain.

  Component (b) is added in an amount of 2.5 to 20 hydrosilyl groups or alkenyl groups in component (b) that undergoes hydrosilylation reaction with respect to one alkenyl group or hydrosilyl group in component (a). It is preferable to use as described above. When the addition amount is small, gelation proceeds due to a crosslinking reaction, so that the handling property of the 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 (c) added is such that the number of alkenyl groups or hydrosilyl groups in component (c) undergoing hydrosilylation reaction is 0.1 for one hydrosilyl group or alkenyl group in component (a) or component (b). It is preferable to use so that it may become ~ 1 piece. If the amount added is small, the effect of suppressing clogging when dispensing to the LED may be reduced. If the amount added is large, the physical properties of the resulting cured product may be adversely affected.

Although there is no restriction | limiting in particular as addition amount of the hydrosilylation catalyst used at the time of the synthesis | combination of polyhedral structure polysiloxane (B), It is with respect to 1 mol of alkenyl groups of (a) component, (b) component, and (c) component used for reaction. It is good to use in the range of 10 ^{< -1} > ^-10 <^-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. May foam. Moreover, when there are few hydrosilylation catalysts, reaction may not progress and the 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. If the temperature is too high, gelation may occur and handling properties may deteriorate.
The polyhedral polysiloxane (B) used in the semiconductor light emitting device of the present invention has the formula
[XR ⁴ ₂ SiO—SiO _3/2 ] _a [R ⁵ 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 ⁴ is an alkyl group or an aryl group; R ⁵ is an alkenyl group, a hydrogen atom, an alkyl group, 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 6}} (3)
(L is an integer of 2 or more; R ⁶ is a group containing an organosilicon compound); R ⁶ is an alkyl group or an aryl group}]
Polyhedral polysiloxane composed of siloxane units represented by
Here, R ⁶ 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 polyhedral polysiloxanes can ensure compatibility with various compounds, specifically the component (A), and also contain hydrosilyl groups in the molecule, so that they react with compounds having various alkenyl groups. It becomes possible to make it.

  In addition, the polyhedral polysiloxane can be liquefied at a temperature of 20 ° C. It is preferable to make the polyhedral polysiloxane liquid because it is excellent in handling properties.

As the polyhedral polysiloxane (B), from the viewpoint of good compatibility with the component (A) and good heat resistance, the polyhedral polysiloxane compound (a1) having an alkenyl group and a hydrosilyl group, and ( Compound (b) having 2 or more hydrosilyl or alkenyl groups capable of hydrosilylation reaction with component a1) and / or component (c), and optionally component (a) and / or (b) Polyhedral polysiloxane obtained by hydrosilylation reaction of the component and a compound (c) having one alkenyl group or hydrosilyl group capable of hydrosilylation reaction in one molecule is preferable.
The polyhedral polysiloxane (B) is a polyhedral polysiloxane compound having an alkenyl group from the viewpoint of good compatibility with the component (A), good heat resistance, and easy synthesis of the component (B). Polyhedral polysiloxane obtained by hydrosilylation reaction of (a2), compound (b1) having two or more hydrosilyl groups in one molecule and compound (c1) having one alkenyl group in one molecule A polyhedral polysiloxane compound having a hydrosilyl group (a3) and a polyhedral polysiloxane obtained by hydrosilylation reaction of a compound (c1) having one alkenyl group per molecule, and a polyhedral polycrystal having an alkenyl group Hydrolysis of a siloxane compound (a2) and a compound (b1) having two or more hydrosilyl groups in one molecule Polyhedral polysiloxane obtained by reacting Lil reduction is more preferred.

<Organic compound (D)>
The component (D) in the present invention specifically has, for example, reactivity with the component (A) and can provide a cured product having heat resistance, light resistance, and gas barrier properties.
The organic compound (D) in the present invention is not particularly limited as long as it is an organic compound represented by the following general formula (1) or an organic compound shown below as a specific example of the component (D).

(Wherein R ¹ represents a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and each R ¹ may be different or the same.)

The component (D) in the present invention preferably contains two or more alkenyl groups on average in one molecule from the viewpoints of strength, gas barrier properties, heat resistance, light resistance, and the like of the resulting cured product. More preferably, it is preferable to contain two. Further, from the viewpoint of gas barrier properties, the number average molecular weight is preferably less than 900.

  Specific examples of the component (D) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2-tetraallyloxyethane. Diallylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl dimethyl isocyanurate, monoallyl diglycidyl isocyanurate, 1,2, 4-trivinylcyclohexane and the like are exemplified, and these may be used alone or in combination of two or more.

  Among the above specific examples, for example, it is preferable to use an isocyanuric acid derivative from the viewpoint of adhesion to the base material when the composition is cured with the base material. Further, from the viewpoint of a balance between heat resistance and light resistance, It is more preferable to use allyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, or diallyl monoglycidyl isocyanurate. For example, diallyl monomethyl isocyanurate is more preferable from the viewpoint of crack resistance.

<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, per 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 containing an organically modified polyhedral polysiloxane used in the semiconductor light-emitting device of the present invention can be obtained by mixing a phosphor, and if necessary, a hydrosilylation catalyst, a curing retarder, and the like. it can.
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. This is preferable because it can be mixed and dispersed with little defoaming. These mixing / dispersing methods may be performed alone or in combination of two or more.
The viscosity of the curable composition used in the present invention is not particularly limited, but is preferably 0.2 Pa · s to 300 Pa · s, more preferably 0.5 Pa · s to 200 Pa · s at a temperature of 23 ° C. It is. When the viscosity of the curable composition is low, the phosphor may aggregate, and when the viscosity is high, the handling property of the curable composition may be deteriorated.
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 70 ° C., 120 ° C., and 150 ° C., a preferable cured product can be obtained, which is preferable.
The curing time can be appropriately selected depending on the curing temperature, the amount of hydrosilylation catalyst to be used and the amount of reactive groups, and other combinations of the curable composition. Preferably, a cured product can be obtained by performing for 10 minutes to 8 hours.

  An adhesiveness imparting agent can be added to the curable composition used in the semiconductor light emitting device 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 adhesion 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.

<Dispersant>
An inorganic filler can be added as a dispersing agent to the curable composition used in the semiconductor light emitting device of the present invention as necessary. By using an inorganic filler, the fluidity of the curable composition can be improved. In addition, improve the physical properties such as strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical properties, light reflectivity, flame retardancy, fire resistance, and gas barrier properties of the obtained molded body. be able to.

  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 0.1-1000 weight part with respect to 100 weight part of curable compositions, More preferably, it is 0.5-500 weight part, More preferably, it is 1-100. Parts by weight. When the amount of the inorganic filler added is large, the fluidity may be deteriorated, and when the amount of the inorganic filler added is small, desired physical properties may not be obtained.

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

  The curable composition used in the semiconductor light emitting device of the present invention may contain various additives such as a colorant and a heat resistance improver, a reaction control agent, a mold release agent, or a dispersant for a filler as necessary. It can be optionally added. Examples of the filler dispersant include diphenylsilane diol, various alkoxysilanes, carbon functional silane, silanol group-containing low molecular weight siloxane, and the like. In addition, it is preferable to stop these arbitrary components to the minimum addition amount so that the effect of this invention may not be impaired.

The curable composition used in the semiconductor light-emitting device of the present invention mixes the above-mentioned components uniformly using a kneader such as a roll, a Banbury mixer, a kneader, or a planetary stirring deaerator, and if necessary. Vacuum treatment or heat treatment may be performed.
The optical semiconductor device of the present invention can be used for various 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.

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

<Weight average molecular weight>
The weight average molecular weight of the synthesized reaction product was HLC-8220GPC (column: TSKgel SuperHZM-N (4) + HZ1000 (1), inner diameter 4.6 mm × 15 cm, inner diameter 4.6 mm × 15 cm, solvent: toluene, flow rate: 0.35 ml / min), and measured by a standard polystyrene conversion method.

<Analysis of polyhedral polysiloxane units>
Analysis of the polyhedral polysiloxane unit of the component (A) was measured by ²⁹ Si-NMR using INOVA AS600 manufactured by VARIAN. When polyhedral polysiloxane units are contained, sharp peaks are observed.

<Clogging occurrence time>
Prepare a reflector (product number: Top view SMD6721) equipped with a 12 mil × 13 mil square LED chip (product number: B1213AAA0 S46B / C-19 / 20) manufactured by Genelites, and 8 g of the curable composition in a syringe. A desktop robot (SHOTMASTER DS SERIES SM200DSS-3A) equipped with a volumetric digital control dispenser (MPP-1) manufactured by Musashi Engineering, a 10 ml syringe manufactured by Musashi Engineering (part number: PSY-10E), manufactured by Musashi Engineering A 10 ml syringe plunger (product number: FLP-10E) and Musashi Engineering's precision solid nozzle (product number: SHN-0.4N) were used to dispense the LED. The dispense was repeated until the total dispense time was 2 hours. And the time when the liquid clogging in the nozzle occurred was defined as the liquid clogging occurrence time. The description of 2 hours indicates that no clogging occurred even after repeated dispensing for 2 hours.

(Production Example 1)
To 1803 g of a 48% choline aqueous solution (trimethyl-2-hydroxyethylammonium hydroxide aqueous solution), 1459 g of tetraethoxysilane was added and stirred vigorously at room temperature for 2 hours. When the reaction system generated heat and became a homogeneous solution, the stirring was loosened and the reaction was further continued for 12 hours. Next, 1400 mL of methanol was added to the solid produced in the reaction system to obtain a uniform solution.
While vigorously stirring a solution of 1932 g of dimethylvinylchlorosilane and 1400 mL of hexane, the methanol solution was slowly added dropwise. After completion of the dropwise addition, the mixture was reacted for 1 hour, and then the organic layer was extracted and concentrated to obtain a solid. Next, the produced solid is washed by stirring vigorously in methanol, and filtered to separate the octakis (polyhedral polysiloxane containing 16 Si atoms and an alkenyl group having 8 vinyl groups). 842 g of vinyldimethylsiloxy) octasilsesquioxane (Fw = 1226.3) was obtained as a white solid.

(Production Example 2)
To 1803 g of a 48% choline aqueous solution (trimethyl-2-hydroxyethylammonium hydroxide aqueous solution), 1459 g of tetraethoxysilane was added and stirred vigorously at room temperature for 2 hours. When the reaction system generated heat and became a homogeneous solution, the stirring was loosened and the reaction was further continued for 12 hours. Next, 1400 mL of methanol was added to the solid produced in the reaction system to obtain a uniform solution.
While vigorously stirring a solution of 1149 g of dimethylvinylchlorosilane, 830 g of trimethylsilyl chloride and 1400 mL of hexane, the methanol solution was slowly added dropwise. After completion of the dropwise addition, the mixture was reacted for 1 hour, and then the organic layer was extracted and concentrated to obtain a solid. Next, the produced solid is washed by stirring vigorously in methanol and filtered to obtain tetrakis (polyhedral polysiloxane containing 16 alkenyl groups and alkenyl groups having 4 vinyl groups). 760 g of vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane (Fw = 1175.8) was obtained as a white solid.

(Production Example 3)
30.0 g of octakis (vinyldimethylsiloxy) octasilsesquioxane, which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 1, was dissolved in 60.0 g of toluene, and a xylene solution of platinum vinylsiloxane complex (as platinum) 7.34 μL of platinum vinylsiloxane complex containing 3 wt%, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) was added. The solution thus obtained was slowly added dropwise to a solution of 117.7 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 39.2 g of toluene. , And reacted at 105 ° C. for 2 hours. After completion of the reaction, 14.0 μl of ethynylcyclohexanol and 3.3 μl of dimethyl maleate were added, and toluene and unreacted components were distilled off to obtain 69.3 g of a liquid polyhedral polysiloxane.

(Production Example 4)
2.85 g of vinyldiphenylmethylsilane was dissolved in 2.85 g of toluene. To the obtained solution, a solution of 10.0 g of the liquid polyhedral polysiloxane obtained in Production Example 3 and 10.0 g of toluene was slowly dropped and reacted at 105 ° C. for 2 hours. After completion of the reaction, toluene and unreacted components were distilled off to obtain 12.6 g of polyhedral polysiloxane (reaction product 1) having a liquid organic group. From the GPC measurement, the reaction product 1 had a plurality of peaks, and the weight average molecular weight of the peak having the highest molecular weight was 10,300.

(Production Example 5)
30.0 g of tetrakis (vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane, which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 2, is dissolved in 123.0 g of toluene, and vinyldiphenylmethylsilane 31 is obtained. 0.5 g, 1.46 μL of a platinum vinylsiloxane complex xylene solution (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) was added. The solution thus obtained was slowly added dropwise to a solution of 24.6 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 24.6 g of toluene. , And reacted at 105 ° C. for 2 hours. After completion of the reaction, 2.8 μl of ethynylcyclohexanol and 0.65 μl of dimethyl maleate were added, and toluene and unreacted components were distilled off to obtain a polyhedral polysiloxane having a liquid organic group (Reactant 2) of 80. 8 g was obtained. From the GPC measurement, the reaction product 2 had a plurality of peaks, and the weight average molecular weight of the highest molecular weight peak was 12,200.

(Production Example 6)
To 1803 g of a 48% choline aqueous solution (trimethyl-2-hydroxyethylammonium hydroxide aqueous solution), 1459 g of tetraethoxysilane was added and stirred vigorously at room temperature for 2 hours. When the reaction system generated heat and became a homogeneous solution, the stirring was loosened and the reaction was further continued for 12 hours. Next, 1400 mL of methanol was added to the solid produced in the reaction system to obtain a uniform solution.
While vigorously stirring a solution of 1490 g of dimethylchlorosilane and 1400 mL of hexane, the methanol solution was slowly added dropwise. After completion of the dropwise addition, the mixture was reacted for 1 hour, and then the organic layer was extracted and concentrated to obtain a solid. Next, the produced solid is washed by stirring vigorously in acetonitrile, and then filtered off, whereby octakis (dimethylsiloxy) octacyl which is a polyhedral polysiloxane having 16 Si atoms and 8 hydrosilyl groups. 705 g of sesquioxane (Fw = 1226.3) was obtained as a white solid.

(Production Example 7)
5.00 g of octakis (dimethylsiloxy) octasilsesquioxane, which is a polyhedral polysiloxane containing a hydrosilyl group obtained in Production Example 6, was dissolved in 5.00 g of toluene, and a xylene solution of platinum vinylsiloxane complex (as platinum) A platinum vinylsiloxane complex containing 3 wt%, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) 1.01 μL was added. The solution thus obtained was slowly added dropwise to a solution of 5.51 g of vinyldiphenylmethylsilane and 5.51 g of toluene, and reacted at 105 ° C. for 2 hours. After completion of the reaction, 1.94 μl of ethynylcyclohexanol and 0.45 μl of dimethyl maleate are added, toluene and unreacted components are distilled off, and 10.2 g of polyhedral polysiloxane having a liquid organic group (Reaction product 3) is obtained. It was. From the GPC measurement, the reaction product 3 had one peak and the weight average molecular weight was 1700.

(Production Example 8)
30.0 g of tetrakis (vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane, which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 2, was dissolved in 60.0 g of toluene, and a platinum vinylsiloxane complex 3.67 μL of a xylene solution (a platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) was added. The solution thus obtained was slowly added dropwise to a solution of 58.9 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 19.6 g of toluene. , And reacted at 105 ° C. for 2 hours. After completion of the reaction, 7.0 μl of ethynylcyclohexanol and 1.7 μl of dimethyl maleate were added, and toluene and unreacted components were distilled off to obtain 83.0 g of a liquid polyhedral polysiloxane (reactant 4). From the GPC measurement, the reaction product 4 had a plurality of peaks, and the weight average molecular weight of the peak on the highest molecular weight side was 8,100.

(Examples 1-8, Comparative Examples 1-3)
LED encapsulant (manufactured by Toray Dow Corning, Phenylsilicone resin, OE6630A / B: having multiple peaks from GPC measurement, weight average molecular weight of peak on the highest molecular weight side is 3,300, polyhedral structure from ²⁹ Si-NMR measurement Does not contain polysiloxane units, or made by Shin-Etsu Chemical Co., Ltd., methyl silicone resin, KER2600A / B: has multiple peaks from GPC measurement, the weight average molecular weight of the peak on the highest molecular weight side is 84,800, weight average molecular weight 60, The component exceeding 000 is 20% by weight or more and does not contain a polyhedral polysiloxane unit from ²⁹ Si-NMR measurement), and any one of the reactants 1 to 4 in the above production example is uniformly mixed. After adding a phosphor to the mixture and stirring, the mixture was stirred for 3 minutes using Awatori Netaro ARE-310 manufactured by Thinky, and defoamed. A curable composition containing polyhedral polysiloxane and a phosphor was prepared by performing 3 minutes of stirring and 3 minutes of stirring, and further performing vacuum stirring for 3 minutes in order using Awatori Nertaro ARV-310 manufactured by Thinky.
As phosphors of the above examples and comparative examples, green phosphor GR240 manufactured by Denki Kagaku Kogyo, red phosphor BR240 manufactured by Mitsubishi Chemical, and yellow phosphor EY4750 manufactured by Intematix were used.

  Tables 1 to 3 summarize the amount of each component used. Numerical values indicate weight. In addition, attention was given to heat radiation of the machine so that the curable composition was not heated during stirring and defoaming. Separately, a reflector (product number: Top view SMD6721) equipped with a 12 mil × 13 mil blue LED chip (product number: B1213AAA0 S46B / C-19 / 20) manufactured by Genelites was prepared, and the obtained curability was obtained. The composition was poured into a syringe within 15 minutes from the above stirring and defoaming, and a desktop robot (SHOTMASTER DS SERIES SM200DSS-3A) equipped with a volumetric digital control dispenser (MPP-1) manufactured by Musashi Engineering Co., Ltd. 10 ml syringe manufactured by Musashi Engineering Co., Ltd. (product number: PSY-10E), plunger for 10 ml syringe manufactured by Musashi Engineering Co., Ltd. (product number: FLP-10E), precision solid nozzle manufactured by Musashi Engineering Co., Ltd. (product number: SHN-0.4N) Was used to dispense the LED. The dispensing time for one LED was 5 seconds, and dispensing was continued for 2 hours to dispense 1440 LEDs. Within 30 minutes after dispensing, the film was cured in a convection oven at 80 ° C. for 30 minutes, from 80 ° C. to 180 ° C. for 60 minutes, and cured at 180 ° C. for 60 minutes. The first to 32nd LEDs that were dispensed first were energized under the conditions of a temperature of 25 ° C., a current of 30 mA, and a waiting time of 30 seconds using a total luminous flux (φ300 mm) system (part number: HM-0930) manufactured by Otsuka Electronics Co., Ltd. The chromaticity of the emission color was measured, and the average value of the chromaticity of the 32 emission colors measured is shown in Tables 1-3.

In the table, a (x) is the average value of x on the xy chromaticity coordinates of the emission color of the semiconductor light emitting device, and a (y) is the average value of y on the xy chromaticity coordinates of the emission color of the semiconductor light emitting device. The average number of samples is 32.
The values of a (x) and a (y) are preferably desired values, and these values are controlled according to the type and amount of phosphor used. When using the same type and amount of phosphor, the higher the values of a (x) and a (y), the higher the light conversion efficiency of the phosphor, which is preferable. If the light conversion efficiency of the phosphor is high, a (x) and a (y) can be controlled to a desired value with a small amount of phosphor, so that the manufacturing cost is reduced.

In Table 1, the LED sealant (A) is a phenyl silicone resin, and red and green phosphors are used. Examples 1 to 4 to which polyhedral polysiloxane (reactant 1) was added, and examples 5 to which polyhedral polysiloxane (reactant 2) was added, and Comparative Example 1 not including polyhedral polysiloxane, and In Example 6 to which polyhedral polysiloxane (reactant 3) was added, the time until the occurrence of clogging in the nozzle was long, or clogging in the nozzle did not occur. When the phosphor is clogged in the nozzle attached to the syringe tip, it is necessary to stop the dispenser and remove the liquid clog in the nozzle, and the productivity of the LED is reduced. Therefore, it is better that liquid clogging does not occur.
Moreover, the prevention effect of liquid clogging was seen with 1 part (Example 1) of the addition amount of the reaction product 1. Further, when the addition amount of the reaction product 1 was 10 parts (Example 3), there was no tack of the cured product, but when 20 parts (Example 4), tack was observed in the cured product.

In Table 2, the LED sealant (A) is a phenyl silicone resin, and a yellow phosphor is used. The liquid clogging did not occur in Example 7 in which the polyhedral polysiloxane having an organic group (reactant 1) was added to Comparative Example 2 that did not contain the polyhedral polysiloxane.

In Table 3, the LED sealant (A) is a methyl silicone resin, and red and green phosphors are used. In contrast to Comparative Example 3 containing no polyhedral polysiloxane, Example 8 to which polyhedral polysiloxane (reactant 4) was added did not cause clogging.

  Therefore, the curable composition containing 0.1 to 25 parts of the polyhedral polysiloxane of the present invention is excellent in productivity because it takes a long time until occurrence of liquid clogging when dispensing to an LED or no liquid clogging occurs.

Claims (24)

A curable composition comprising (A) an LED sealing agent not containing polyhedral polysiloxane (100 parts by weight) and (B) polyhedral polysiloxane (0.1 to 25 parts by weight),
The polyhedral polysiloxane of component (B) is composed of polyhedral polysiloxane units having an alkenyl group or a hydrosilyl group. The curable composition according to claim 1, wherein the component (A) is a methyl silicone resin. The curable composition according to claim 1, wherein the component (A) is a phenyl silicone resin. The curable composition according to any one of claims 1 to 3, wherein the component (B) is liquid at a temperature of 20 ° C. The polyhedral polysiloxane compound (a) in which the component (B) has an alkenyl group and / or a hydrosilyl group, and a hydrosilyl group or alkenyl that can be hydrosilylated with the component (a) and / or the component (c) as necessary Compound (b) having two or more groups in one molecule and, if necessary, one alkenyl group or hydrosilyl group capable of hydrosilylation with component (a) and / or (b) in one molecule The curable composition according to any one of claims 1 to 4, which is a polyhedral polysiloxane obtained by hydrosilylation reaction of the compound (c). The component (B) is a polyhedral polysiloxane compound (a1) having an alkenyl group and a hydrosilyl group, and, if necessary, a hydrosilyl group or alkenyl group capable of hydrosilylation reaction with the component (a1) and / or the component (c). Compound (b) having two or more in one molecule, and compound having one alkenyl group or hydrosilyl group in one molecule that can be hydrosilylated with component (a) and / or (b) as necessary ( 6. The curable composition according to claim 5, which is a polyhedral polysiloxane obtained by hydrosilylation reaction of c). The component (B) is a polyhedral polysiloxane compound (a2) having an alkenyl group, a compound (b1) having two or more hydrosilyl groups in one molecule, and a compound (c1) having one alkenyl group in one molecule The curable composition according to claim 5, which is a polyhedral polysiloxane obtained by hydrosilylation reaction. The component (B) is a polyhedral polysiloxane obtained by hydrosilylation reaction of a polyhedral polysiloxane compound (a3) having a hydrosilyl group and a compound (c1) having one alkenyl group in one molecule. The curable composition according to any one of claims 1 to 4. (B) the polyhedral polysiloxane compound (a2) in which the component has an alkenyl group;
The curability according to any one of claims 1 to 4, which is a polyhedral polysiloxane obtained by hydrosilylation reaction of a compound (b1) having two or more hydrosilyl groups in one molecule. Composition. The polyhedral polysiloxane compound (a2) having an alkenyl group has the formula:
[AR ² ₂ SiO—SiO _3/2 ] _a [R ³ 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 ² is an alkyl group or an aryl group; R ³ is a hydrogen atom or an alkyl group 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), 10. The curable composition according to any one of 9 above. The polyhedral polysiloxane compound (a3) having a hydrosilyl group has the formula:
[HR ² ₂ SiO—SiO _3/2 ] _a [R ³ 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; H is a hydrosilyl group; R ² is an alkyl group or an aryl group; R ³ is an alkyl group or an aryl group Or a polyhedral polysiloxane compound containing a hydrosilyl group composed of a siloxane unit represented by a group connected to another polyhedral skeleton polysiloxane). Sex composition. 10. The compound (b1) having two or more hydrosilyl groups in one molecule is a cyclic siloxane or a linear polysiloxane having two or more hydrosilyl groups in one molecule. 2. The curable composition according to item 1. The curable composition according to claim 12, wherein the compound (b1) having two or more hydrosilyl groups in one molecule is a cyclic siloxane having two or more hydrosilyl groups in one molecule. The compound (b1) having two or more hydrosilyl groups in one molecule is 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane. Item 13. A curable composition according to Item 12. The curable composition according to any one of claims 5 to 8, wherein the component (c) is an organosilicon compound having one alkenyl group and one or more aryl groups in one molecule. . The component (B) has the formula: [XR ⁴ ₂ SiO—SiO _3/2 ] _a [R ⁵ 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 ⁴ is an alkyl group or an aryl group; R ⁵ is an alkenyl group, a hydrogen atom, an alkyl group, 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. 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 6}} (3)
(1 is an integer of 2 or more; R ⁶ is a group containing an organosilicon compound); R ⁶ is a polyhedral polysiloxane having a structural unit of an alkyl group or an aryl group} The curable composition as described. The curable composition according to claim 16, wherein R ⁶ has one or more aryl groups. In addition to (A) component and (B) component, (D) component which is an organic compound represented by following General formula (1) is included, The any one of Claims 1-17 characterized by the above-mentioned. Curable composition.

(Wherein R ¹ represents a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and each R ¹ may be different or the same.) The curable composition according to claim 1, comprising a hydrosilylation catalyst. The curable composition according to any one of claims 1 to 19, further comprising a curing retarder. 21. The curable composition according to claim 1, further comprising a dispersant. The curable composition according to any one of claims 1 to 21, comprising a phosphor. A cured product obtained from the curable composition of claim 22. A semiconductor light emitting device obtained from the curable composition of claim 22.