JP6329423B2 - Modified body having polyhedral polysiloxane skeleton, curable composition containing the modified body, cured product, and semiconductor light emitting device - Google Patents

Description

  A method of manufacturing a semiconductor light emitting device that is excellent in cold shock resistance and prevents clogging when dispensing a curable composition containing a phosphor to an LED, and is excellent in productivity, the curable composition used in the method, and curing The present invention relates to a light emitting device and a semiconductor light emitting device, and a modified body having a polyhedral polysiloxane skeleton suitable for them.

  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 usually uses a light emitting element made of a semiconductor (hereinafter referred to as LED), and reliability required for a sealant for sealing the LED includes heat resistance, light resistance, and thermal shock resistance. Can be mentioned. The peeling or cracking of the sealant from the package by the thermal shock test is caused by internal stress of the cured product such as residual stress generated during the curing process in addition to thermal stress caused by temperature change. Generally, a sealant made of a material having a high crosslink density is difficult to relieve the stress as described above, and as a result, problems such as peeling and cracking from the package have occurred due to the thermal shock test. . (Patent Document 1)
Moreover, the sealing agent used for LED is normally manufactured by sealing a LED by applying a curable composition containing a phosphor and curing it. 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 2 and 3).

  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 in order to solve such problems, and has excellent cold-heat shock resistance, and less clogging when dispensing a curable composition containing a phosphor to an LED, and is excellent in productivity. The present invention relates to a method for manufacturing a semiconductor light emitting device.

JP 2010-132895 A JP 2009-102514 A JP 2006-294821 A

  A method of manufacturing a semiconductor light emitting device that is excellent in cold shock resistance and prevents clogging when dispensing a curable composition containing a phosphor to an LED, and is excellent in productivity, the curable composition used in the method, and curing It is an object to provide a light emitting device and a semiconductor light emitting device and a modified body having a polyhedral polysiloxane skeleton suitable for them.

As a result of intensive studies to solve the above problems, the present inventors have
The modified product (B) having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more exhibits excellent characteristics, and in addition to (B), the refractive index is 1.38 or more and 1.60 or less, and (B) It discovered that the said subject could be solved by the combination of LED sealing agent (A) which consists of a curable composition lower than the refractive index of a component, and came to this invention.

  That is, the present invention has the following configuration.

  1). (B) A modified product having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more.

2). The component (B) has a polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group, and two or more hydrosilyl groups or alkenyl groups that can be hydrosilylated with the component (a) in one molecule. Modified product (B-1) having a polyhedral polysiloxane skeleton obtained by hydrosilylation reaction of compound (b) and an aryl group-containing compound (c) having one hydrosilyl group or alkenyl group in one molecule Because
Furthermore, when (a) component, (b) component, and (c) component are 100 weight part, (c) component is contained 40 weight part or more, The polyhedral structure polycrystal as described in 1) characterized by the above-mentioned A modified product having a siloxane skeleton.

  3). The (B) component is a polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group, and an aryl having one hydrosilyl group or alkenyl group in one molecule capable of hydrosilylation reaction with the component (a) A modified product (B-2) having a polyhedral polysiloxane skeleton obtained by hydrosilylation reaction of a group-containing compound (c), further comprising 100 parts by weight of component (a) and component (c) The modified product having a polyhedral polysiloxane skeleton according to 1), wherein the component (c) is contained in an amount of 50 parts by weight or more.

  4). (B) The modified body having a polyhedral polysiloxane skeleton according to any one of 1) to 3), wherein the component is liquid at a temperature of 20 ° C.

5). The component (B-1) has the formula: [XR 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; R ¹ is an alkyl group or an aryl group; R ² 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, and 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).

(1 is an integer of 2 or more; R ³ is a group containing an aryl group ))} as a structural unit. The modified product having a polyhedral polysiloxane skeleton according to 2),

6). The component (B-2) has the formula: [WR 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; R ¹ is an alkyl group or an aryl group; R ² is an alkenyl group, a hydrogen atom, an alkyl group, an aryl group Or a group linked to another polyhedral skeleton polysiloxane, W is represented by the following general formula (4)

(L is an integer of 2 or more; R ³ is a group containing an aryl group). } Is a structural unit. The modified body having a polyhedral polysiloxane skeleton according to 3).

7). (A) 100 parts by weight of an LED sealing agent made of a curable composition having a refractive index of 1.38 or more and 1.60 or less and lower than the refractive index of the component (B);
(B) The curable composition according to any one of 1) to 6), comprising 0.1 to 20 parts by weight of a modified body having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more.

  8). (A) The curable composition as described in 7), wherein the component is liquid at a temperature of 20 ° C.

  9). (A) Component is methyl silicone resin, The curable composition as described in 7) or 8) characterized by the above-mentioned.

  10). (A) Component is a phenyl silicone resin, The curable composition as described in 7) or 8) characterized by the above-mentioned.

11). (A) component is
A polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group, and a compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule that can be hydrosilylated with the component (a). A modified product (A-1) having a polyhedral polysiloxane skeleton obtained by hydrosilylation reaction;
Curing agent (A-2),
The curable composition according to 7) or 8), which comprises

12). (A) component is
A polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group, a compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule, capable of hydrosilylation reaction with the component (a), Hydrosilylation reaction of aryl group-containing compound (c) having one hydrosilyl group or alkenyl group in one molecule and / or cyclic olefin compound (d) having one carbon-carbon double bond in one molecule A modified product (A-3) having a polyhedral polysiloxane skeleton obtained by
Furthermore, when the component (A-3) includes 100 parts by weight of the component (a), the component (b), and the component (c), the polyhedral structure includes the component (c) in excess of 0 part by weight and less than 40 parts by weight. The curable composition according to 7) or 8), which comprises a modified product having a polysiloxane skeleton (including component (c)) and a curing agent (A-2).

  13). 12. The polysiloxane composition according to 12), wherein the cyclic olefin compound (d) having one carbon-carbon double bond in one molecule has a molecular weight of 1000 or less.

14). The polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group is represented by the formula: [AR 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; A is an alkenyl group and / or a hydrogen atom; R ⁴ is an alkyl group or an aryl group; R ⁵ is 2) characterized by being a polyhedral polysiloxane compound containing an alkenyl group composed of a siloxane unit represented by an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane) Or a modified product having a polyhedral polysiloxane skeleton described in 3) 15). The polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group is represented by the formula: [AR 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; A is an alkenyl group and / or a hydrogen atom; R ⁴ is an alkyl group or an aryl group; R ⁵ is 11) characterized by being a polyhedral polysiloxane compound containing an alkenyl group composed of a siloxane unit represented by an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane) Or the curable composition as described in 12).

16). The component (A-1) has the formula [XR ⁶ ₂ SiO—SiO _3/2 ] _a [R ⁷ 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 ⁶ is an alkyl group or an aryl group; R ⁷ 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 (5) or general formula (6), and when there are a plurality of X, the general formula (5 ) Or the structure of the general formula (6) may be different, or the structure of the general formula (5) or the general formula (6) may be mixed. X has at least one of general formula (5) and / or general formula (6).

{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 and Z are a polyhedral polysiloxane via a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. It is the site | part which has couple | bonded and may be the same or different. However, at least one of Y or Z has a hydrogen atom structure. }]
11) The curable composition according to 11), which is a modified product having a polyhedral polysiloxane skeleton characterized by comprising a siloxane unit represented by formula (1).

17). The component (A-3) has the formula [XR ⁸ ₂ SiO—SiO _3/2 ] _a [R ⁹ 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 ⁸ is an alkyl group or an aryl group; R ⁹ 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 (7) or general formula (8), and when there are a plurality of X, the general formula (7 ) Or the structure of the general formula (8) may be different, and the structure of the general formula (7) or the general formula (8) may be mixed. X has at least one of general formula (7) and / or general formula (8).

{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 and Z are a polyhedral polysiloxane via a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. The bonded site, the structure of the following general formula (8), or the structure of the following general formula (9) may be the same or different. However, at least one of Y or Z is a hydrogen atom, at least one is a structure of the following general formula (9), and at least one is a structure of the following general formula (10).

(L is an integer of 2 or more; R ³ is a group containing an aryl group) R is an alkyl group or an aryl group. }

(Q is an integer of 0 or more; R ¹⁰ is a cyclic olefin compound),
The curable composition according to 12), which is a modified product having a polyhedral polysiloxane skeleton characterized by comprising a siloxane unit represented by the formula:

  18). The compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule is a cyclic siloxane or linear polysiloxane having two or more hydrosilyl groups or alkenyl groups in one molecule. And a modified product having a polyhedral polysiloxane skeleton according to 2).

  19). The compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule is a cyclic siloxane or linear polysiloxane having two or more hydrosilyl groups or alkenyl groups in one molecule. ) Or 12).

  20). The polyhedral structure according to 18), wherein the compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule is a cyclic siloxane having two or more hydrosilyl groups or alkenyl groups in one molecule. A modified product having a polysiloxane skeleton.

  21). The curability according to 19), wherein the compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule is a cyclic siloxane having two or more hydrosilyl groups or alkenyl groups in one molecule. Composition.

  22). Compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule is 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, or 1,3 , 5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, which is a modified body having a polyhedral polysiloxane skeleton according to 20).

  23). Compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule is 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, or 1,3 , 5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane. 21) The curable composition according to 21).

  24). The curable composition according to 11) or 12), wherein the curing agent (A-2) is an organopolysiloxane (A-2 ′) having two or more alkenyl groups or hydrosilyl groups in one molecule. object.

  25). The curing agent (A-2) is an organic compound (A-2 ″) represented by the following general formula (11)

(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 11) or 12), wherein the curable composition is a polysiloxane composition.

  26). The curing agent (A-2) includes (A-2 ′) and (A-2 ″) described above, 11), 12), 24), 25) Curable composition.

  27). The curable composition according to any one of 1) to 26), comprising a hydrosilylation catalyst.

  28). The curable composition according to any one of 1) to 27), further comprising a curing retarder.

  29). The curable composition according to any one of 1) to 28), further comprising a dispersant.

  30). The curable composition according to any one of 1) to 29), comprising a phosphor.

  31). Hardened | cured material obtained from the curable composition of any one of 1) -30).

  32). The semiconductor light-emitting device obtained from the curable composition of any one of 1) -30).

A method of manufacturing a semiconductor light emitting device that is excellent in cold shock resistance and prevents clogging when dispensing a curable composition containing a phosphor to an LED, and is excellent in productivity, the curable composition used in the method, and curing Articles and semiconductor light emitting devices are provided.

  In the present invention, a modified body (B) having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more is an essential component.

  The modified body (B) having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more is a curable composition having a refractive index of 1.38 or more and 1.60 or less and lower than the refractive index of the component (B). The curable composition mixed with the LED encapsulant (A) at a specific ratio is excellent in thermal shock resistance and prevents liquid clogging when dispensing a curable composition containing a phosphor to an LED. It is possible to provide a semiconductor light emitting device with excellent productivity.

  The refractive index here refers to the refractive index before curing, and the refractive index of the curable composition is a value measured at a temperature of 25 ° C. and a wavelength of 589 nm using a general Abbe refractive index. is there.

  Hereinafter, the present invention will be described in detail.

<Modified (B) having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more>
The curable composition used for the semiconductor light emitting device of the present invention contains a modified body (B) having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more. The polyhedral polysiloxane is a polysiloxane having a polyhedral polysiloxane skeleton.

    The modified product (B) having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more used in the present invention will be described in detail.

  Modified body (B) having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more, and (A) a curable composition having a refractive index of 1.38 to 1.60 and lower than the refractive index of component (B) By mixing an LED sealing agent made of a product, the modified body (B) having a polyhedral polysiloxane skeleton improves the adsorptivity with the phosphor, and dispenses to the LED because aggregation of the phosphor is suppressed. Liquid clogging at the time is suppressed.

  As such (B) component, it divides into the following (B-1) component and (B-2) component, for example.

The component (B-1) is composed of a polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group, and two hydrosilyl groups or alkenyl groups per molecule capable of hydrosilylation with the component (a). A modified product having a polyhedral polysiloxane skeleton obtained by hydrosilylating a compound (b) having the above and an aryl group-containing compound (c) having one hydrosilyl group or alkenyl group in one molecule. Yes,
Furthermore, when the component (a), the component (b), and the component (c) are 100 parts by weight, the heat-resistant thermal resistance of the resulting cured product is that the component (c) is contained in an amount of 40 parts by weight or more. Furthermore, it is preferable from the point that liquid clogging when dispensing to the LED is suppressed.

The component (B-2) includes a polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group, and a hydrosilyl group or alkenyl group in one molecule capable of hydrosilylation reaction with the component (a). It is a modified body having a polyhedral polysiloxane skeleton obtained by hydrosilylation reaction with one aryl group-containing compound (c),
Furthermore, when the component (a) and the component (b) are 100 parts by weight, it is preferable that the component (c) is contained in an amount of 50 parts by weight or more. This is preferable from the viewpoint of suppressing clogging during dispensing.

  When such a modified body (B) having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more is mixed with the aforementioned component (A) and cured, the strength and heat resistance of the resulting cured product, From the viewpoints of light resistance, thermal shock resistance, and tackiness, it is preferable to contain one or more hydrosilyl groups on average in one molecule.

<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 (a) 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”.

<Aryl group-containing compound (c) having one alkenyl group or hydrosilyl group in one molecule>
The component (c) in the present invention is an aryl group-containing compound having one alkenyl group or hydrosilyl group in one molecule,
When the component (c) is an aryl group-containing compound having one alkenyl group in one molecule, a hydrosilylation reaction is performed with the hydrosilyl group of the component (a) and / or the hydrosilyl group of the component (b). A modified polyhedral polysiloxane such as the aforementioned component (B) or the component (A-3) described later can be obtained. In addition, when the component (c) is an aryl group-containing compound having one hydrosilyl group in one molecule, it undergoes a hydrosilylation reaction with the alkenyl group of the component (a) and / or the alkenyl group of the component (b). A polyhedral polysiloxane-modified product such as the aforementioned component (B) or the component (A-3) described later can be obtained.

  In addition, the component (c) in the present invention contains one or more aryl groups in one molecule, which increases the gas barrier property of the resulting cured product, and the refractive index of the modified product before curing. In the case of increasing, it is preferable, and compared with a linear aliphatic hydrocarbon group having a low carbon number such as a methyl group, an ethyl group, or a propyl group, the adsorptivity with the phosphor is improved, and aggregation of the phosphor is suppressed. Therefore, the effect of suppressing liquid clogging when dispensing to the LED is high. Further, by using the component (c), it is possible to lower the elastic modulus of the obtained cured product, and to improve crack resistance and the like.

  Further, it is more preferable that the aryl group is directly bonded to the silicon atom from the viewpoint of heat resistance and light resistance. Examples of such an aryl group include a phenyl group, a benzyl group, a tolyl group, an o-xylyl group, a naphthyl group, and the like, and a phenyl group is preferable from the viewpoint of heat resistance and light resistance of the obtained cured product.

  Examples of the modified body (B) obtained by using the component (c) and having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more include the following (B-1) component and (B-2) component: Is mentioned.

The component (B-1) is composed of a polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group, and two hydrosilyl groups or alkenyl groups per molecule capable of hydrosilylation with the component (a). A modified product having a polyhedral polysiloxane skeleton obtained by hydrosilylating a compound (b) having the above and an aryl group-containing compound (c) having one hydrosilyl group or alkenyl group in one molecule. Yes,
Furthermore, when the component (a), the component (b), and the component (c) are 100 parts by weight, the polyhedral structure having a refractive index of 1.52 or more is contained because the component (c) is 40 parts by weight or more. A modified product (B-1) having a polysiloxane skeleton is obtained. Further, with respect to 100 parts by weight of the LED sealing agent (A) made of a curable composition having a refractive index of 1.38 to 1.60 and lower than the refractive index of the component (B), (B- 1) The cured product added with 0.1 to 20 parts by weight of the component has good thermal shock resistance, and the mixture of the curable composition and phosphor using the component (B-1) is the component (B-1). Since the adsorbability between the phosphor and the phosphor is improved and the aggregation of the phosphor is suppressed, it is preferable from the viewpoint that liquid clogging is suppressed when dispensing to the LED. When the amount of the component (B-1) is less than 0.1, there may be a case where the effect of suppressing the thermal shock resistance or the liquid clogging when dispensing to the LED may not be obtained, and the component (B-1) When the added amount is more than 20 parts by weight, if it exceeds 20 parts by weight, tackiness may occur in the cured product, and heat resistance, light resistance, and adhesiveness may decrease.

The component (B-2) includes a polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group, and a hydrosilyl group or alkenyl group in one molecule capable of hydrosilylation reaction with the component (a). It is a modified body having a polyhedral polysiloxane skeleton obtained by hydrosilylation reaction with one aryl group-containing compound (c),
Furthermore, when the component (a) and the component (b) are 100 parts by weight, the polyhedral skeleton having a polyhedral structure having a refractive index of 1.52 or more is obtained by including 50 parts by weight or more of the component (c). A modified body (B-2) is obtained. Further, with respect to 100 parts by weight of the LED sealing agent (A) made of a curable composition having a refractive index of 1.38 to 1.60 and lower than the refractive index of the component (B), (B- 2) The cured product added with 0.1 to 20 parts by weight of the component has good thermal shock resistance, and the mixture of the curable composition and phosphor using the component (B-2) is (B-2) Since the adsorptivity between the component and the phosphor is improved and the aggregation of the phosphor is suppressed, it is preferable from the viewpoint that liquid clogging is suppressed when dispensing to the LED. When the amount of the component (B-2) is less than 0.1, there may be a case where the effect of suppressing the thermal shock resistance or the liquid clogging when dispensing to the LED may not be obtained, and the component (B-2) When the added amount is more than 20 parts by weight, if it exceeds 20 parts by weight, tackiness may occur in the cured product, and heat resistance, light resistance, and adhesiveness may decrease.

  In particular, as the component (c) has a larger number of aryl groups in one molecule, the modified (B-1) component having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more, or (B -2) It is easy to obtain a component.

The content of the aryl group can be measured by ¹ H-NMR or the like. For example, phenyl value of (c) modified forms include components, the refractive index has a 1.52 or more polyhedral polysiloxane backbone (B) creates a mixture of the component (B) and dibromoethane, ¹ H- Obtained by measuring with NMR. If the phenyl value of the component (B) obtained here is 3.50 mol / kg or more, a modified product (B) having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more is obtained.

In addition, as the modified (A-3) component having a polyhedral structure polysiloxane skeleton having a refractive index of less than 1.52 obtained by using the component (c), a polyhedral structure polysiloxane having an alkenyl group and / or a hydrosilyl group may be used. A siloxane compound (a), a compound (b) having at least two hydrosilyl groups or alkenyl groups in one molecule capable of hydrosilylation with the component (a), and one hydrosilyl group or alkenyl group in one molecule A modified product having a polyhedral polysiloxane skeleton obtained by hydrosilylation reaction of the aryl group-containing compound (c) having
Furthermore, when the component (a), the component (b), and the component (c) are 100 parts by weight, the component (c) is contained in an amount exceeding 0 part by weight and less than 40 parts by weight. A modified product (A-3) having a polyhedral polysiloxane skeleton of less than .52 is obtained. The cured product obtained by adding 0.1 part or more and 20 parts by weight or less of the component (B) to 100 parts by weight of the component (A-3) has good thermal shock resistance and is cured using the component (B). Since the adsorbing property between the component (B) and the phosphor is improved and the aggregation of the phosphor is suppressed, the mixture of the luminescent composition and the phosphor suppresses liquid clogging when dispensing to the LED. To preferred.
When the addition amount of (B) component is less than 0.1, there may be a case where the effect of suppressing thermal shock resistance or clogging when dispensing to LED may not be obtained. When the amount is more than 20 parts by weight, if it exceeds 20 parts by weight, the cured product may be tacked or the heat resistance, light resistance, and adhesiveness may be lowered.

  Examples of the alkenyl group of component (c) 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 aryl group-containing compound (c) having one alkenyl group per molecule include, for example, compounds such as styrene, o-methylstyrene, m-methylstyrene, p-styrene, dimethylphenyl Aryl group such as vinylsilane, methyldiphenylvinylsilane, triphenylvinylsilane, diethylphenylvinylsilane, ethyldiphenylvinylsilane, allyldimethylphenylsilane, allylmethyldiphenylsilane, allyltriphenylsilane, allyldiethylphenylsilane, allylethyldiphenylsilane is directly silicon Examples include compounds bonded to atoms.

  In addition, 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, an alkenyl group And a cyclic siloxane having a single siloxane.

  In the case where the component (c) is a polysiloxane having a linear structure having one alkenyl group in one molecule, specifically, for example, polydiphenyl having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group. Siloxane, a copolymer of a dimethylsiloxane unit and a methylphenylsiloxane unit each having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group, and one end each blocked with a dimethylvinylsilyl group and a trimethylsilyl group Examples thereof include a copolymer of a dimethylsiloxane unit and a diphenylsiloxane unit, and a copolymer of a methylphenylsiloxane unit and a diphenylsiloxane unit each having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group.

  When the component (c) is a cyclic siloxane having one alkenyl group in one molecule, specifically, for example, 1-vinyl-3-phenyl-1,3,5,5,7,7-hexamethylcyclo Tetrasiloxane, 1-vinyl-3,5-diphenyl-1,3,5,7,7-pentamethylcyclotetrasiloxane, 1-vinyl-3,5,7-triphenyl-1,3,5,7- Examples include tetramethylcyclotetrasiloxane.

  The aryl group-containing compound (c) having one alkenyl group per molecule is preferably a group containing a silicon compound having silane or polysiloxane from the viewpoint of heat resistance and light resistance. Among these (c) components, liquid clogging during dispensing to the LED is suppressed, and dimethylphenylvinylsilane, methyldiphenylvinylsilane, and triphenylvinylsilane are preferable examples from the viewpoint of heat resistance and light resistance.

  Specific examples of the aryl group-containing compound (c) in which the component (c) has one hydrosilyl group in one molecule include dimethylphenylhydrosilane, methyldiphenylhydrosilane, triphenylhydrosilane, diethylphenylhydrosilane, and ethyldiphenylhydrosilane. Illustrated.

  In addition, 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, a hydrosilyl group And a cyclic siloxane having a single siloxane.

  Examples of (c) include polymethylphenylsiloxane having one end blocked with a dimethylhydrosilyl group and a trimethylsilyl group, polydiphenylsiloxane blocked with one end each with a dimethylhydrosilyl group and a trimethylsilyl group, and dimethyl Copolymers of dimethylsiloxane units and methylphenylsiloxane units each blocked with a hydrosilyl group and a trimethylsilyl group, and dimethylsiloxane units and diphenyl each blocked with a dimethylhydrosilyl group and a trimethylsilyl group. Examples thereof include copolymers with siloxane units, and copolymers of methylphenylsiloxane units and diphenylsiloxane units each having one end blocked with a dimethylhydrosilyl group and a trimethylsilyl group. .

  When the component (c) is a cyclic siloxane having one hydrosilyl group in one molecule, specifically, for example, 1-hydrogen-3-phenyl-1,3,5,5,7,7-hexamethyl Cyclotetrasiloxane, 1-hydrogen-3,5-diphenyl-1,3,5,7, pentamethylcyclotetrasiloxane, 1-hydrogen-3,5,7-triphenyl-1,3,5 , 7-tetramethylcyclotetrasiloxane and the like.

  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)”.
These (c) components may be used independently and may use 2 or more types together.

<Synthesis of modified body (B) having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more>
The component (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 (a) if necessary. Compound (b) having 2 or more hydrosilyl groups or alkenyl groups capable of hydrosilylation reaction with component and / or component (c), and (a) component and / or (b) component as necessary It can be obtained by subjecting an aryl group-containing compound (c) having one hydrosilyl group or alkenyl group in one molecule to a hydrosilylation reaction.

  The method for obtaining the component (B) is not particularly limited and can be variously set. However, the component (c) may be reacted after the component (a) and the component (b) are reacted in advance. 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 (B) component, (a) component and (b) component may be made to react, and (a) component and (c) component may be made to react.

  In the component (B) thus obtained, a part of the alkenyl group or hydrosilyl group of the component (a) used for 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.

  Component (c) is added in an amount of 40 parts by weight or more when component (a), component (b) and component (c) are 100 parts by weight. When the amount of the component (c) is less than 30 parts by weight, the refractive index of the component (B) to be obtained may not satisfy 1.52, and predetermined physical properties may not be obtained. Moreover, it is preferable from a viewpoint of a predetermined physical property that it is 40 parts or more and less than 70 parts. On the other hand, if it is too much (100 parts or more), heat resistance / light resistance and adhesiveness may be lowered.

  In order to make the refractive index of the component (B) 1.52 or more, the organic group of the component (c) is preferably a phenyl group. Furthermore, as the number of phenyl groups in the component (c) increases, the refractive index of the component (B) can be increased efficiently, and the effect of suppressing the aggregation of the phosphor becomes higher.

  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 the modified body (B) which has a polyhedral structure polysiloxane frame | skeleton with a refractive index of 1.52 or more, (a) component used for reaction, (b) component And it is good to use in the range of 10 ^{< -1} > ^-10-10 mol with respect to 1 mol of alkenyl groups of (c) component. 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 modified body (B) having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more, which is 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).

(L is an integer of 2 or more; R ³ is a group containing an aryl group); R ³ 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 an aryl group, but it is preferable that at least one aryl group is contained 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 component (B) can ensure compatibility with various compounds, specifically, the component (A), and further contains a hydrosilyl group in the molecule, so that it reacts with compounds having various alkenyl groups. It becomes possible to make it.

  Moreover, (B) component can also be made into a liquid state at the temperature of 20 degreeC. It is preferable to make the polyhedral polysiloxane liquid because it is excellent in handling properties.

  In addition, as the component (B), a polyhedral polysiloxane compound (a1) having an alkenyl group and a hydrosilyl group, and (a1) as necessary, in view of good compatibility with the component (A) and good heat resistance. ) Component and / or (c) component (b) having at least two hydrosilyl groups or alkenyl groups capable of hydrosilylation reaction in one molecule, and (a) component and / or (b) component as necessary And a modified polyhedral polysiloxane obtained by hydrosilylation reaction of an aryl group-containing compound (c) having one hydrosilyl group or alkenyl group in one molecule.

  In addition, (B) includes a polyhedral polysiloxane compound (a2) having an alkenyl group, since it has good compatibility with the component (A), good heat resistance, and easy synthesis of the component (B). A polyhedral polysiloxane obtained by hydrosilylation reaction of a compound (b1) having two or more hydrosilyl groups in one molecule and an aryl group-containing compound (c1) having one alkenyl group in one molecule, Polyhedral polysiloxane obtained by hydrosilylation reaction of polyhedral polysiloxane compound (a3) having hydrosilyl group and aryl group-containing compound (c1) having one alkenyl group in one molecule, polyhedral having alkenyl group A structural polysiloxane compound (a2) and a compound (b1) having two or more hydrosilyl groups in one molecule Polyhedral polysiloxane obtained by reacting Roshiriru of more preferred.

<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 Patent 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.

<Semiconductor light emitting device>
The semiconductor light-emitting device of the present invention comprises a light-emitting element made of a semiconductor, a phosphor described later, and (A) an LED sealing agent made of a curable composition having a refractive index of 1.38 or more and 1.60 or less (100 parts by weight). And (B) obtained by sealing with a phosphor layer comprising a curable composition containing a modified body (0.1 to 20 parts by weight) having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more. . 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 (A) comprising a curable composition having a refractive index of 1.38 or more and 1.60 or less and lower than the refractive index of the component (B)>
The main component of the curable composition used in the semiconductor light emitting device of the present invention is an LED sealing agent comprising a curable composition having a refractive index of 1.38 or more and 1.60 or less and lower than the refractive index of the component (B). A known LED sealant can be used. Such an LED sealant is not particularly limited, and examples thereof include a methyl silicone resin, a phenyl silicone resin, a hybrid resin, an epoxy resin, and a curable composition containing a modified body having a polyhedral polysiloxane skeleton. It is done.

  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.

  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.

  Specific examples of the methyl silicone resin include, for example, OE-6250, OE-6351, OE-6336, EG-6301, OE-6370, JCR-6140, JCR-6126, JCR-6122, JCR- manufactured by Toray Dow Corning 6101, JCR-6115, JCR-6250, JCR-6109, JCR-6110, KE-2500, KER-2600, KER-2700, KER-7000 manufactured by Shin-Etsu Chemical, and the like.

  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, mainly composed of siloxane units of the group of the following formula (12). is there. 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.

  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.

Further, as a curable composition containing a modified body having a polyhedral polysiloxane skeleton having a refractive index of 1.38 or more and 1.60 or less, a known polyhedral polysiloxane can be widely used, and 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, and may be the same or different; a is 6 The polyhedral polysiloxane composed of a siloxane skeleton represented by an integer of ~ 24) is exemplified, and the structure contains [R ₂ SiO _2/2 ] units and [R ₃ SiO _1/2 ] units. Partially cleaved polyhedral polysiloxane may be used.

As the curable composition having such a polyhedral polysiloxane compound, a known one can be used as long as the refractive index is 1.38 or more and 1.60 or less. Specific examples include a curable composition composed of components (A-1) and (A-2) described later, and a curable composition composed of components (A-3) and (A-2). .
Such a curable composition comprising the component (A-1) and the component (A-2) includes a polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group, the component (a) and a hydrosilyl group. A modified polyhedral polysiloxane (A-1) obtained by subjecting a compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule to a hydrosilylation reaction, (A-2) A specific example is a curable composition comprising a curing agent).
The curable composition comprising the component (A-3) and the component (A-2) includes a polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group, and the component (a) and hydrosilylation. Reactive compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule, aryl group-containing compound (c) having one hydrosilyl group or alkenyl group in one molecule and / or one molecule A modified polyhedral polysiloxane (A-3) obtained by hydrosilylation reaction of a cyclic olefin compound (d) having one carbon-carbon double bond therein, further comprising the above (A-3) When the component is 100 parts by weight of the component (a), the component (b), and the component (c), the polyhedral polysiloxane containing 0 part by weight to less than 40 parts by weight of the component (c) A modified product having a down skeleton, (A-2) a curing agent, a curable composition comprising may be mentioned as specific examples.

  The components (A-1), (A-2), and (A-3) described here will be described in detail later.

  Specific examples of the hybrid resin include SCR-1011 and SCR-1012 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.

  From the viewpoint of having a good balance of heat resistance, light resistance and thermal shock resistance, the component (A) is preferably a curable composition having a methyl silicone resin or a polyhedral polysiloxane compound.

  From the viewpoint of having a good balance of heat resistance, light resistance and gas barrier properties, the component (A) is preferably a curable composition having a phenyl silicone resin or a polyhedral polysiloxane compound.

In addition, by adding 0.1 to 20 parts by weight of the component (B) described above with respect to 100 parts by weight of the component (A), the heat and light resistance and the thermal shock resistance of the resulting curable composition are improved. In addition, liquid clogging can be prevented when dispensing a curable composition containing a phosphor to an LED.
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, there may be a case where the thermal shock resistance and the effect of suppressing liquid clogging when dispensing to the LED may not be obtained. On the other hand, it is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less. If it exceeds 20 parts by weight, tackiness may occur in the cured product, and heat resistance, light resistance, and adhesiveness may decrease.

<Modified polyhedral polysiloxane (A-1)>
The modified polyhedral polysiloxane (A-1) of the present invention is a polyhedral polysiloxane compound (a) having a refractive index of 1.38 or more and 1.60 or less and having an alkenyl group and / or a hydrosilyl group, If it is a modified body having a polyhedral structure polysiloxane skeleton obtained by hydrosilylation reaction of a component (b) having at least two hydrosilyl groups or alkenyl groups in one molecule with a component a) Well-known polyhedral polysiloxanes can be widely used, and are represented by the general formula [RSiO _3/2 ] _a and the general formula [R ₃ SiO—SiO _3/2 ] _a (R represents an arbitrary organic group, alkenyl group, hydrogen And may be the same or different; a is a polyhedral polysiloxane composed of a siloxane skeleton represented by an integer of 6 to 24) Is but, _{[R 2 SiO 2/2]} units and may be a polyhedral polysiloxane portion cleavable containing _{[R 3 SiO 1/2]} units in their structure.

Such a component (A-1) has the formula
[XR ⁶ ₂ SiO—SiO _3/2 ] _a [R ⁷ 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 ⁶ is an alkyl group or an aryl group; R ⁷ 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 (5) or general formula (6), and when there are a plurality of X, the general formula (5 ) Or the structure of the general formula (6) may be different, or the structure of the general formula (5) or the general formula (6) may be mixed. X has at least one of general formula (5) and / or general formula (6).

{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 and Z are a polyhedral polysiloxane via a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. It is the site | part which has couple | bonded and may be the same or different. However, at least one of Y or Z has a hydrogen atom structure. }]
A modified polyhedral polysiloxane composed of siloxane units represented by the formula:

  Moreover, (A-1) component can also be made into a liquid state at the temperature of 20 degreeC. It is preferable to make the polyhedral polysiloxane liquid because it is excellent in handling properties.

<Modified body having polyhedral polysiloxane skeleton (A-3)>
The modified body (A-3) having a polyhedral polysiloxane skeleton of the present invention is a polyhedral polysiloxane compound (a) having a refractive index of 1.38 or more and 1.60 or less and having an alkenyl group and / or a hydrosilyl group. And (a) a compound having at least two hydrosilyl groups or alkenyl groups in one molecule, which can be hydrosilylated with component (a), and an aryl group-containing compound having one hydrosilyl group or alkenyl group in one molecule (C) and / or a modified product having a polyhedral structure polysiloxane skeleton obtained by hydrosilylation reaction of (c) and / or a cyclic olefin compound (d) having one carbon-carbon double bond in one molecule, Furthermore, when the component (a), the component (b) and the component (c) are 100 parts by weight, the component (c) contains 0 part by weight or more and less than 40 parts by weight. If any, can be widely used known polyhedral polysiloxane of the general formula _{[RSiO 3/2] a} and the general formula _{[R 3 SiO-SiO 3/2]} a (R is any organic group, an alkenyl group And a hydrogen atom, which may be the same or different; a is a polyhedral polysiloxane composed of a siloxane skeleton represented by an integer of 6 to 24, It may be a partially cleaved polyhedral polysiloxane containing [R ₂ SiO _2/2 ] units or [R ₃ SiO _1/2 ] units.
Such component (A-3) has the formula
[XR ⁸ ₂ SiO—SiO _3/2 ] _a [R ⁹ 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 ⁸ is an alkyl group or an aryl group; R ⁹ 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 (7) or general formula (8), and when there are a plurality of X, the general formula (7 ) Or the structure of the general formula (8) may be different, and the structure of the general formula (7) or the general formula (8) may be mixed. X has at least one of general formula (7) and / or general formula (8).

{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 and Z are a polyhedral polysiloxane via a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. The bonded site, the structure of the following general formula (8), or the structure of the following general formula (9) may be the same or different. However, at least one of Y or Z is a hydrogen atom, at least one is a structure of the following general formula (9), and at least one is a structure of the following general formula (10).

(L is an integer of 2 or more; R ³ is a group containing an aryl group-containing compound) R is an alkyl group or an aryl group. }

(Q is an integer of 0 or more; R ¹⁰ is a cyclic olefin compound),
The modified body which has the polyhedral structure polysiloxane frame | skeleton comprised from the siloxane unit represented by these may be sufficient.

  Moreover, (A-3) component can also be made into a liquid state at the temperature of 20 degreeC. It is preferable to make the polyhedral polysiloxane liquid because it is excellent in handling properties.

<Curing agent (A-2)>
(A-2) component in this invention is the LED sealing agent obtained by the combination with the said (A-1) component or (A-3) component.
Such a component (A-2) may be a compound having two or more alkenyl groups or hydrosilyl groups in one molecule, and specific examples include two alkenyl groups or hydrosilyl groups in one molecule. Organopolysiloxane (A-2 ′) having the above,
Or the organic compound (A-2 '') represented by the following general formula (13)

(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).
Is mentioned.

  The component (A-2 ′) in the present invention may contain two or more alkenyl groups or hydrosilyl groups in one molecule, and more preferably 2-10. If the number of alkenyl groups in one molecule is large, a more crosslinked structure is obtained, and the gas barrier property of the cured product using the organopolysiloxane composition is improved. However, if the number is too large, the heat resistance and light resistance may be lowered. is there.

  The number of siloxane units of the component (A-2 ′) in the present invention is not particularly limited, but two or more units are preferable examples. When the number of siloxane units is small, volatilization tends to occur from within the organopolysiloxane composition, and desired physical properties may not be obtained. Moreover, when there are many siloxane units, gas barrier property may become low, such as the water vapor transmission rate of the obtained hardened | cured material becoming high.

  The organopolysiloxane having two or more alkenyl groups or hydrosilyl groups in one molecule as the component (A-2 ′) in the present invention has two or more alkenyl groups or hydrosilyl groups from the viewpoint of heat resistance and light resistance. Preferred examples include linear polysiloxanes, polysiloxanes having two or more alkenyl groups or hydrosilyl groups at the molecular terminals, and cyclic siloxanes having two or more alkenyl groups or hydrosilyl groups. These compounds having two or more alkenyl groups or hydrosilyl groups may be used alone or in combination of two or more.

  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 Polydiphenylsiloxane, polymethylphenylsiloxane end-capped with dimethylvinylsilyl groups, copolymers of dimethylsiloxane units with methylvinylsiloxane units and terminal triethylsiloxy units, diphenylsiloxy Copolymers of emission units and methylvinylsiloxane units and end triethylsiloxy units, and a copolymer of methylphenylsiloxane units and methylvinylsiloxane units and end triethylsiloxy unit is exemplified. Among them, from the viewpoint of heat resistance and light resistance, a copolymer of a dimethylsiloxane unit, a methylvinylsiloxane unit and a terminal trimethylsiloxy unit, a copolymer of a diphenylsiloxane unit, a methylvinylsiloxane unit and a terminal trimethylsiloxy unit, methylphenyl Copolymers of siloxane units with methylvinylsiloxane units and terminal trimethylsiloxy units, polydimethylsiloxanes blocked with dimethylvinylsilyl groups, polydiphenylsiloxanes blocked with dimethylvinylsilyl groups, dimethylvinylsilyl groups A preferable example is polymethylphenylsiloxane whose end is blocked with a polymethylphenylsiloxane.

Specific examples of the polysiloxane having two or more alkenyl groups at the molecular ends include polysiloxanes whose ends are blocked with the dimethylalkenyl groups exemplified above, dimethylalkenylsiloxane units and SiO ₂ units, SiO _3/2 units, SiO 2 In a group consisting of at least one siloxane unit selected from the group consisting of units, a polysiloxane end-capped with a diethyl alkenyl group, a diethyl alkenyl siloxane unit and a SiO ₂ unit, a SiO _3/2 unit, a SiO unit Examples thereof include polysiloxane composed of at least one selected siloxane unit. Among them, from the viewpoint of heat resistance and light resistance, at least one siloxane unit selected from the group consisting of a polysiloxane blocked with a dimethylalkenyl group, a dimethylalkenylsiloxane unit, a SiO ₂ unit, a SiO _3/2 unit, and a SiO unit. A preferred example is polysiloxane consisting of:

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, 1-propyl-3,5,7-trivinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5- Examples include divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane. Among these, from the viewpoint of heat resistance and light resistance, 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 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-trivinyl-1,3,5 -Trimmer Lucyclosiloxane, 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 is a preferred example.
Specific examples of the linear polysiloxane having two or more hydrosilyl groups include copolymers of dimethylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylhydrogensiloxane units and terminal trimethyl. Copolymers with siloxy units, copolymers of methylphenylsiloxane units with methylhydrogensiloxane units and terminal trimethylsiloxy units, polysiloxanes end-capped with dimethylhydrogensilyl groups, dimethylsiloxane units and methylhydrogen Copolymer of siloxane unit and terminal triethylsiloxy unit, copolymer of diphenylsiloxane unit and methylhydrogensiloxane unit and terminal triethylsiloxy unit, methylphenyl Copolymers of Rokisan units and methylhydrogensiloxane units and terminal triethylsiloxy units, such as polysiloxanes terminals blocked with diethyl hydrogen silyl groups. Among them, from the viewpoint of heat resistance and light resistance, a copolymer of a dimethylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, a copolymer of a diphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, Preferred examples include a copolymer of a methylphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, and a polysiloxane whose ends are blocked with dimethylhydrogensilyl groups.

Specific examples of the polysiloxane having two or more hydrosilyl groups at the molecular ends include polysiloxanes whose ends are blocked with dimethylhydrogensilyl groups exemplified above, dimethylhydrogensiloxane units (H (CH ₃ ) ₂ SiO _{1 / 2} units), SiO ₂ units, SiO _3/2 units, polysiloxanes comprising at least one siloxane unit selected from the group consisting of SiO units, polysiloxanes end-capped with diethyl hydrogensilyl groups, diethyl hydrogen Examples thereof include polysiloxanes composed of at least one siloxane unit selected from the group consisting of siloxane units (H (CH ₃ ) ₂ SiO _1/2 units), SiO ₂ units, SiO _3/2 units, and SiO units. Among them, from the viewpoint of heat resistance and light resistance, polysiloxanes whose ends are blocked with dimethylhydrogensilyl groups, dimethylhydrogensiloxane units (H (CH ₃ ) ₂ SiO _1/2 units) and SiO ₂ units, SiO _{3 / A} preferred example is polysiloxane comprising at least one siloxane unit selected from the group consisting of ₂ units and SiO units.

  Examples of cyclic siloxane compounds having two or more hydrosilyl groups include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5,7-tetrahydrogen. -1-phenyl-3,5,7-trimethylcyclotetrasiloxane, 1,3,5,7-tetrahydrogen-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7 -Tetrahydrogen-1,5-diphenyl-3,7-dimethylcyclotetrasiloxane, 1,3,5,7-tetrahydrogen-1,3,5-triphenyl-7-methylcyclotetrasiloxane, 1- Phenyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-diphenyl-5,7 Dihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentahydro Gen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclosiloxane, 1-propyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7- Examples include tetramethylcyclotetrasiloxane. Among these, from the viewpoint of heat resistance and light resistance, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetrahydrogen-1- Phenyl-3,5,7-trimethylcyclotetrasiloxane, 1,3,5,7-tetrahydrogen-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7-tetrahydro Gen-1,5-diphenyl-3,7-dimethylcyclotetrasiloxane, 1,3,5,7-tetrahydrogen-1,3,5-triphenyl-7-methylcyclotetrasiloxane, 1-phenyl-3 , 5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-diphenyl-5,7-dihydrogen-1,3, , 7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7 , 9-pentamethylcyclosiloxane and 1,3,5,7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclosiloxane are preferred examples.

  In the present invention, from the viewpoint of heat resistance and light resistance, the Si atom of the component (A-2 ′) is preferably composed of a hydrogen atom, a vinyl group and a methyl group.

  The amount of the organopolysiloxane having two or more alkenyl groups or hydrosilyl groups in one molecule as the component (B) can be variously set. However, when the component (A-2 ′) has an alkenyl group, Per group, 0.3 to 5 hydrogen atoms directly connected to Si atoms contained in the polyhedral polysiloxane-based modified product (A-1) or (A-3), preferably 0 It is desirable to add at a ratio of 5 to 3. If the ratio of the alkenyl group is too small, appearance defects due to foaming and the like are likely to occur, and if too large, the physical properties of the cured product may be adversely affected. In addition, when the component (A-2 ′) has a hydrosilyl group, it is included in the polyhedral polysiloxane-based modified product that is the component (A-1) or the component (A-3) per hydrosilyl group. It is desirable that the alkenyl group directly bonded to the Si atom is added in a ratio of 0.2 to 3, preferably 0.3 to 2. If the proportion of hydrogen atoms directly connected to Si atoms is too small, the physical properties of the cured product may be adversely affected. If it is too large, poor appearance due to foaming or the like tends to occur.

  In addition, the organic compound (A-2 ″) component in the present invention specifically has, for example, reactivity with the component (A-1), the component (A-3), or the component (B), and is heat resistant. It becomes possible to give the cured | curing material which has a property, light resistance, and gas barrier property.

  The organic compound (A-2 ″) in the present invention is not particularly limited as long as it is an organic compound represented by the following general formula (14).

(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 (A-2 ″) in the present invention contains an average of two or more alkenyl groups in one molecule from the viewpoint of the strength, gas barrier properties, heat resistance, light resistance, etc. of the resulting cured product. It is preferable to contain two, more preferably two. Further, from the viewpoint of gas barrier properties, the number average molecular weight is preferably less than 900.

  Specific examples of the component (A-2 ″) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2- Tetraallyloxyethane, diarylidenepentaerythritol, 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.

<Curable composition>
The curable composition containing a modified product having a polyhedral polysiloxane skeleton used in the semiconductor light-emitting device of the present invention is obtained by mixing a phosphor, and if necessary, a hydrosilylation catalyst, a curing retarder, and the like. Can do.

  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 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.

<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.

<Refractive index measurement>
The refractive index of the curable composition was measured at 589 nm at 25 ° C. using an Abbe refractometer NAR-3T manufactured by ATAGO.

<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 blue 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.

<Evaluation of thermal shock test>
Prepare a reflector (product number: Top view SMD6721) equipped with a 12 mil x 13 mil square LED chip (product number: B1213AAA0 S46B / C-19 / 20) manufactured by Genelites, and inject the composition into this LED package. A sample was prepared by thermosetting for a predetermined time. The sample was subjected to 100 cycles of a high temperature holding at 100 ° C. for 30 minutes and a low temperature holding at −40 ° C. for 30 minutes using a thermal shock tester (TSA-71H-W manufactured by Espec), and then the sample was observed with a microscope. If there was no change after the test, it was rated as ◯, and when cracks occurred or peeling occurred between the packages, it was marked as x.

(Production Example 1) (a) Synthesis of component
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.

  The methanol solution was slowly added dropwise while vigorously stirring a solution of 1700 g of dimethylvinylchlorosilane, 220 g of trimethylchlorosilane and 1400 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 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 7 vinyl groups). 825 g of vinyldimethylsiloxy) octasilsesquioxane (Fw = 14.14.3) was obtained as a white solid.

(Production Example 2) (a) Synthesis of component
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.

  The methanol solution was slowly added dropwise while vigorously stirring a solution of 1700 g of dimethylchlorosilane and 1400 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 produced solid is washed by stirring vigorously in methanol and filtered to obtain a polyhedral polysiloxane octakis (dimethylsiloxy) octacyl having 16 Si atoms and 8 hydrosilyl groups. 735 g of sesquioxane (Fw = 1017.9) was obtained as a white solid.

(Production Example 3) (a) Synthesis of component
1042 g of tetraalkoxysilane was added to 1288 g of 48% choline aqueous solution (trimethyl-2hydroxyethylammonium hydroxide aqueous solution), and the mixture was vigorously stirred at room temperature for 3 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, 750 mL of methanol was added to the solid produced in the reaction system to obtain a uniform solution.

  While stirring a solution of 200 g of dimethylvinylchlorosilane, 1480 g of dimethylchlorosilane, and 750 mL of hexane, the obtained uniform 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, it is a polyhedral polysiloxane having 16 Si atoms, 1 vinyl group, and 7 hydrosilyl groups by washing the produced solid by vigorously stirring in methanol and filtering it off. 601 g of mono (vinyldimethylsiloxy) heptakis (dimethylsiloxy) octasilsesquioxane (Fw = 1044.0) was obtained as a white solid.

(Production Example 4) (a) Synthesis of component
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 = 1178.2) was obtained as a white solid.

Synthesis of component (A-1) (Production Example 5)
Dissolve 30.0 g of tetrakis (vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane (Fw = 1178.2), which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 4, in 60.0 g of toluene. Then, 7.34 μL of a platinum vinylsiloxane complex xylene solution (platinum vinylsiloxane complex containing 3 wt% of platinum, 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 modified product having a liquid polyhedral structure polysiloxane skeleton. The refractive index of the obtained modified product was 1.41.

(A-3) Synthesis of component (Production Example 6)
30 g of tetrakis (vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane, which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 4, 11.4 g of vinyldiphenylmethylsilane, and 10.4 g of camphene. Was dissolved in 102 g of toluene, and 7.63 μL of a platinum vinylsiloxane complex xylene solution (platinum vinylsiloxane complex containing 3 wt% of platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) was added. The solution thus obtained was slowly added dropwise to a solution of 21.4 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 10.7 g of toluene. , And reacted at 105 ° C. for 2 hours. After completion of the reaction, 14.5 μl of ethynylcyclohexanol and 3.38 μl of dimethyl maleate were added, and toluene was distilled off to obtain 72.2 g of a modified product having a liquid polyhedral polysiloxane skeleton. The refractive index of the obtained modified product was 1.45.

(Production Example 7)
30 g of tetrakis (vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane, which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 4, and 45.8 g of vinyldiphenylmethylsilane are dissolved in 150 g of toluene. 7.63 μL of a xylene solution of platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) was added. The solution thus obtained was slowly added dropwise to a solution of 30.6 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 15.3 g of toluene. , And reacted at 105 ° C. for 2 hours. After completion of the reaction, 14.57 μl of ethynylcyclohexanol and 3.38 μl of dimethyl maleate were added, and toluene was distilled off to obtain 105.1 g of a modified product having a liquid polyhedral polysiloxane skeleton. The refractive index of the obtained modified product was 1.50.

Synthesis of component (B) (Production Example 8)
30.0 g of heptakis (vinyldimethylsiloxy) mono (trimethylsiloxy) octasilsesquioxane (component (a)), which is the alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 1, and vinyldiphenylmethylsilane (( c) Component) 77.82 g of toluene was dissolved in 215.0 g of toluene, and a xylene solution of platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, Pt-VTSC-3X, manufactured by Umicore Precious Metals Japan) 48 μL was added. The solution thus obtained was mixed with 41.6 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (component (b)) and 41.6 g of toluene. The solution was slowly dropped into the solution and reacted at 105 ° C. for 2 hours. After completion of the reaction, 12.3 μl of ethynylcyclohexanol and 2.8 μl of dimethyl maleate were added, and toluene and unreacted components were distilled off to obtain 140.2 g of a modified product having a liquid polyhedral structure polysiloxane skeleton ( (When (a) component, (b) component, and (c) component are 100 weight part, 52 weight part of (c) component is contained). The refractive index of the obtained modified product was 1.54. The modified product is referred to as “reactant 1”.

(Production Example 9)
77.82 g of vinyldiphenylmethylsilane (component (c)) was dissolved in 155.0 g of toluene, and a xylene solution of platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt- (VTSC-3X) 6.48 μL was added. The solution thus obtained was mixed with 41.6 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (component (b)) and 41.6 g of toluene. The solution was slowly dropped into the solution and reacted at 105 ° C. for 1 hour. To this reaction solution, 30.0 g of heptakis (vinyldimethylsiloxy) mono (trimethylsiloxy) octasilsesquioxane (component (a)), which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 1, was further added. A solution of 60.0 g of toluene was slowly added dropwise and reacted at 105 ° C. for 2 hours. After completion of the reaction, 12.4 μl of ethynylcyclohexanol and 2.8 μl of dimethyl maleate were added, and toluene and unreacted components were distilled off to obtain 139.6 g of a modified product having a liquid polyhedral polysiloxane skeleton ( (When (a) component, (b) component, and (c) component are 100 weight part, 52 weight part of (c) component is contained).
The refractive index of the obtained modified product was 1.54. This modified product is designated as reactant 2.

(Production Example 10)
30.0 g of heptakis (vinyldimethylsiloxy) mono (trimethylsiloxy) octasilsesquioxane (component (a)), which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 1, was dissolved in 60.0 g of toluene. Then, 7.34 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 112 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 112 g of toluene at 105 ° C. The reaction was performed for 2 hours. After confirming the 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 68.6 g of a modified product having a liquid polyhedral polysiloxane skeleton. It was.
Furthermore, 68.6 g of the obtained liquid polyhedral polysiloxane was redissolved in 68.6 g of toluene, and a solution prepared by dissolving 88.9 g of diphenylvinylsilane (component (c)) in 88.9 g of toluene was added dropwise to this solution. And reacted at 105 ° C. for 2 hours. Toluene was distilled off to obtain 142 g of a modified product having a liquid polyhedral polysiloxane skeleton. (When (a) component, (b) component, and (c) component are 100 weight part, 40 weight part of (c) component is contained). The refractive index of the obtained modified product was 1.54. The modified product is referred to as “reactant 3”.

(Production Example 11)
A solution of 11.6 g of triphenylvinylsilane (component (c)) and 23.2 g of toluene in a xylene solution of a platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC- 3X) 2.16 μL was added. The solution obtained here was mono (vinyldimethylsiloxy) heptakis (dimethylsiloxy) octasilsesquioxane (component (a)), which is a polyhedral polysiloxane containing vinyl groups and hydrosilyl groups obtained in Production Example 3. The solution was slowly added dropwise to a solution of 10.0 g and 20.0 g of toluene, and reacted at 105 ° C. for 2 hours. After completion of the reaction, 3.88 μl of ethynylcyclohexanol and 0.90 μl of dimethyl maleate were added, and toluene and unreacted components were distilled off to obtain 21.2 g of a modified product having a liquid polyhedral polysiloxane skeleton ((a When component (c) and component (c) are 100 parts by weight, the component (c) contains 53 parts by weight.) The refractive index of the obtained modified product was 1.52. The modified product is referred to as “reactant 4”.

(Production Example 12)
A solution of 61.9 g of triphenylvinylsilane (component (c)) and 61.9 g of toluene in a xylene solution of a platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC- 3X) 6.44 μL was added. The solution obtained here was slowly dropped into a solution of 30.0 g of octakis (dimethylsiloxy) octasilsesquioxane and 60.0 g of toluene, which is the hydrohedral group-containing polyhedral polysiloxane compound obtained in Production Example 2. And reacted at 105 ° C. for 2 hours. After completion of the reaction, 11.4 μl of ethynylcyclohexanol and 2.7 μl of dimethyl maleate were added, and toluene and unreacted components were distilled off to obtain 69.3 g of a modified product having a liquid polyhedral polysiloxane skeleton ( (When component (a) and component (c) are 100 parts by weight, component (c) contains 67 parts by weight.) The refractive index of the obtained modified product was 1.58. This modified product is designated as reactant 5.

(Production Example 13)
8.34 g of vinyldiphenylmethylsilane (component (c)) was dissolved in 8.34 g of toluene, and a xylene solution of platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt- 2.16 μL of VTSC-3X) was added. The solution thus obtained was mixed with 15.9 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (component (b)) and 15.9 g of toluene. The solution was slowly dropped into the solution and reacted at 105 ° C. for 1 hour. To this reaction solution, 10.0 g of heptakis (vinyldimethylsiloxy) mono (trimethylsiloxy) octasilsesquioxane ((a) component) which is the alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 1 was further added. A solution of 10.0 g of toluene was slowly added dropwise and reacted at 105 ° C. for 2 hours. After completion of the reaction, 4.1 μl of ethynylcyclohexanol and 0.9 μl of dimethyl maleate were added, and toluene and unreacted components were distilled off to obtain 33.1 g of a modified product having a liquid polyhedral polysiloxane skeleton ( When (a) component, (b) component, and (c) component are 100 parts by weight, (c) component is contained in 24 parts by weight.) The refractive index of the obtained modified product was 1.47. This modified product is designated as reactant 6.

(Examples and comparative examples)
Tables 1 to 6 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. 10ml syringe (product number: PSY-10E) manufactured by Musashi Engineering, 10ml syringe plunger (product number: FLP-10E) manufactured by Musashi Engineering, precision solid nozzle (product number: SHN-0.4N) manufactured by Musashi Engineering It was dispensed to the LED to have. 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 was shown in Tables 1-5.

(Examples 1-5, Comparative Example 1)
76 parts by weight of the polyhedral polysiloxane modified product (A-3) obtained in Production Example 6 as the LED sealant of component (A) and 1,5-divinyl-3, as component (A-2) A sealant comprising a composition of 21 parts by weight of 3-diphenyl-1,1,5,5-tetramethyltrisiloxane (manufactured by Clariant) and 3 parts by weight of diallyl monomethyl isocyanurate (manufactured by Shikoku Kasei) was used.
(B) As a component, the said manufacture example 8 (reactant 1) or manufacture example 9 (reactant 2) is mixed with predetermined amount with respect to 100 weight part of (A) component, phosphor is added to this liquid. After stirring, the mixture was stirred for 3 minutes using Akyori Nertaro ARE-310 manufactured by Thinky, defoamed for 3 minutes, and stirred for 3 minutes, and further stirred for 3 minutes by vacuum using Narataro Awatori manufactured by Thinky. By carrying out in order, the curable composition containing polyhedral polysiloxane and fluorescent substance was produced. Further, a yellow phosphor EY4750 manufactured by Intematix was used. The results are shown in Table 1.

From Table 1, the liquid clogging did not generate | occur | produce in Examples 1-5 which added the reaction material 4 which is (B) component with respect to the comparative example 1 which does not contain (B) component.

(Examples 6 to 9, Comparative Example 2)
As the LED sealing agent of component (A), 77 parts by weight of the modified product (A-3) having a polyhedral polysiloxane skeleton obtained in Production Example 7 and 1,5-divinyl as component (A-2) A sealant comprising a composition of 21 parts by weight of 3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane (manufactured by Clariant) and 2 parts by weight of diallyl monomethyl isocyanurate (manufactured by Shikoku Kasei) used.

  (B) As a component, the said manufacture example 8 (reactant 1) or manufacture example 9 (reactant 2) is mixed with predetermined amount with respect to 100 weight part of (A) component, phosphor is added to this liquid. After stirring, the mixture was stirred for 3 minutes using Akyori Nertaro ARE-310 manufactured by Thinky, defoamed for 3 minutes, and stirred for 3 minutes. By carrying out in order, the curable composition containing polyhedral polysiloxane and fluorescent substance was produced. Further, a yellow phosphor EY4750 manufactured by Intematix was used. The results are shown in Table 2.

  From Table 2, the liquid clogging did not generate | occur | produce in Examples 6-9 which added the reaction material 8 which is (B) component, or the reaction material 9 with respect to the comparative example 2 which does not contain (B) component.

(Examples 10 and 11, Comparative Example 3)
(A) 66 parts by weight of modified poly (A-1) having a polyhedral polysiloxane skeleton obtained in Production Example 7 as an LED sealant and 1,5-divinyl as a component (A-2) A sealing agent comprising a composition of 32 parts by weight of 3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane (manufactured by Clariant) and 2 parts by weight of diallyl monomethyl isocyanurate (manufactured by Shikoku Kasei) used.
As the component (B), the above-mentioned Production Example 11 (reactant 4) is mixed in a predetermined amount with respect to 100 parts by weight of the component (A), and the phosphor is added to this solution and stirred. Stirring for 3 minutes using TaroARE-310, 3 minutes for defoaming, 3 minutes for stirring, and further performing 3 minutes for vacuum stirring for 3 minutes using Awatori Netaro ARV-310 manufactured by Thinky, A curable composition containing a phosphor was prepared. Further, a yellow phosphor EY4750 manufactured by Intematix was used. The results are shown in Table 3.

  From Table 1, the liquid clogging did not generate | occur | produce in Example 10, 11 which added the reaction material 4 which is (B) component with respect to the comparative example 3 which does not contain (B) component. Moreover, the thermal shock test property was also improved by adding (B) component.

(Examples 12 to 14, Comparative Examples 4 and 5)
As the LED sealant for component (A), phenyl silicone OE6630 (manufactured by Toray Dow Corning) was used. The refractive index of this OE6630 was 1.54.
As component (B), the above Production Example 12 (Reactant 5) or Production Example 13 (Reactant 6) is mixed in a predetermined amount with respect to 100 parts by weight of Component (A), and a phosphor is added to this solution. After stirring, the mixture was stirred for 3 minutes using Akyori Nertaro ARE-310 manufactured by Thinky, defoamed for 3 minutes, and stirred for 3 minutes, and further stirred for 3 minutes by vacuum using Narataro Awatori manufactured by Thinky. By carrying out in order, the curable composition containing polyhedral polysiloxane and fluorescent substance was produced. Furthermore, a green phosphor GR240 manufactured by Denki Kagaku Kogyo and a red phosphor BR240 manufactured by Mitsubishi Chemical were used. The results are shown in Table 4.

In Table 4, 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.

(Examples 15 and 16, Comparative Example 6)
(A) Hybrid resin SCR1012 (made by Shin-Etsu Chemical Co., Ltd.) was used as the LED sealant of the component. The refractive index of this SCR 1012 was 1.50.
As the component (B), the above-mentioned Production Example 10 (reactant 3) is mixed in a predetermined amount with respect to 100 parts by weight of the component (A), the phosphor is added to this solution, and the mixture is stirred. Stirring for 3 minutes using TaroARE-310, 3 minutes for defoaming, 3 minutes for stirring, and further performing 3 minutes for vacuum stirring for 3 minutes using Awatori Netaro ARV-310 manufactured by Thinky, A curable composition containing a phosphor was prepared. Further, a yellow phosphor EY4750 manufactured by Intematix was used. The results are shown in Table 5.

From Table 5, the liquid clogging did not generate | occur | produce in Examples 15 and 16 which added the reaction material 3 which is (B) component with respect to the comparative example 6 which does not contain (B) component. Moreover, the thermal shock test property was also improved by adding (B) component.

(Example 17, comparative example 7)
As the LED sealant of the component (A), methyl silicone KER2600 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used. The refractive index of this KER2600 was 1.41.
As the component (B), the above-mentioned Production Example 11 (reactant 4) is mixed in a predetermined amount with respect to 100 parts by weight of the component (A), and the phosphor is added to this solution and stirred. Stirring for 3 minutes using TaroARE-310, 3 minutes for defoaming, 3 minutes for stirring, and further performing 3 minutes for vacuum stirring for 3 minutes using Awatori Netaro ARV-310 manufactured by Thinky, A curable composition containing a phosphor was prepared. Further, a yellow phosphor EY4750 manufactured by Intematix was used. The results are shown in Table 6.

  From Table 6, the liquid clogging did not generate | occur | produce in Example 17 which added the reaction material 3 which is (B) component with respect to the comparative example 7 which does not contain (B) component.

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.

As described above, the curable composition containing 0.1 to 20 parts of the polyhedral polysiloxane (B) component of the present invention with respect to 100 parts by weight of the LED sealant of the component (A) is dispensed to the LED. Long time to clogging or no clogging, resulting in excellent productivity. Further, the thermal shock resistance of the LED sealant is improved, and the LED quality stability is also effective.

Claims (31)

(A) 100 parts by weight of an LED sealing agent made of a curable composition having a refractive index of 1.38 or more and 1.60 or less and lower than the refractive index of the component (B);
(B) A curable composition comprising 0.1 to 20 parts by weight of a modified product having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more ,
The component (B) has a polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group, and two or more hydrosilyl groups or alkenyl groups that can be hydrosilylated with the component (a) in one molecule. A modified polyhedral polysiloxane (B-1) obtained by hydrosilylating a compound (b) and an aryl group-containing compound (c) having one hydrosilyl group or alkenyl group in one molecule, ,
Furthermore, when (a) component, (b) component, and (c) component are 100 weight part, (c) component is contained 40 weight part or more, The curable composition characterized by the above-mentioned . (A) 100 parts by weight of an LED sealing agent made of a curable composition having a refractive index of 1.38 or more and 1.60 or less and lower than the refractive index of the component (B);
(B) A curable composition comprising 0.1 to 20 parts by weight of a modified product having a polyhedral polysiloxane skeleton having a refractive index of 1.52 or more,
The (B) component is a polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group, and an aryl having one hydrosilyl group or alkenyl group in one molecule capable of hydrosilylation reaction with the component (a) A polyhedral polysiloxane modified product (B-2) obtained by subjecting a group-containing compound (c) to a hydrosilylation reaction,
Moreover, is a modified product having (a) When the component and the component (c) 100 parts by weight, polyhedron polysiloxane skeleton you characterized in that it contains the component (c) is 50 parts by weight or more Curable composition . The component (A) is a curable composition including a methyl silicone resin, a phenyl silicone resin, a hybrid resin, an epoxy resin, or a modified body having a polyhedral polysiloxane skeleton. The curable composition as described. 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 component (B-1) has the formula: [XR 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; R ¹ is an alkyl group or an aryl group; R ² 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, and 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).

The curable composition according to claim 1 , wherein (1 is an integer of 2 or more; R ³ is a group containing an aryl group )}}. The component (B-2) has the formula: [WR 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; R ¹ is an alkyl group or an aryl group; R ² is an alkenyl group, a hydrogen atom, an alkyl group, an aryl group Or a group linked to another polyhedral skeleton polysiloxane, W is represented by the following general formula (4)

(L is an integer of 2 or more; R ³ is a group containing an aryl group). } Is a structural unit. The curable composition according to claim 2 . The curable composition according to any one of claims 1 to 6, wherein the component (A) is liquid at a temperature of 20 ° C. (A) A component is methyl silicone resin, The curable composition of any one of Claims 3-7 characterized by the above-mentioned. (A) A component is phenyl silicone resin, The curable composition of any one of Claims 3-7 characterized by the above-mentioned. (A) component is
A polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group, and a compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule that can be hydrosilylated with the component (a). A modified product (A-1) having a polyhedral polysiloxane skeleton obtained by hydrosilylation reaction;
(A-2) curing agent,
It consists of these, The curable composition of any one of Claims 1-7 characterized by the above-mentioned. (A) component is
A polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group, a compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule, capable of hydrosilylation reaction with the component (a), Hydrosilylation reaction of aryl group-containing compound (c) having one hydrosilyl group or alkenyl group in one molecule and / or cyclic olefin compound (d) having one carbon-carbon double bond in one molecule A modified product (A-3) having a polyhedral polysiloxane skeleton obtained by
Further, when the component (A-3) has a refractive index of less than 1.52, and the components (a), (b), and (c) are 100 parts by weight, the component (c) is 0 part by weight. A modified product having a polyhedral polysiloxane skeleton containing more than 30 parts by weight (including component (c)),
(A-2) curing agent,
It consists of these, The curable composition of any one of Claims 1-7 characterized by the above-mentioned. The curable composition according to claim 11 , wherein the molecular weight of the cyclic olefin compound (d) having one carbon-carbon double bond in one molecule is 1000 or less. The polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group has the formula: [AR 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; A is an alkenyl group and / or a hydrogen atom; R ⁴ is an alkyl group or an aryl group; R ⁵ is 6. A polyhedral polysiloxane compound containing an alkenyl group composed of a siloxane unit represented by an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane). The curable composition according to 1 or 2 . The polyhedral polysiloxane compound (a) having an alkenyl group and / or a hydrosilyl group has the formula: [AR 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; A is an alkenyl group and / or a hydrogen atom; R ⁴ is an alkyl group or an aryl group; R ⁵ is 6. A polyhedral polysiloxane compound containing an alkenyl group composed of a siloxane unit represented by an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane). The curable composition according to 10 or 11 . (A-1) component is
Formula : [XR ⁶ ₂ SiO—SiO _3/2 ] _a [R ⁷ 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 ⁶ is an alkyl group or an aryl group; R ⁷ 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 (5) or general formula (6), and when there are a plurality of X, the general formula (5 ) Or the structure of the general formula (6) may be different, or the structure of the general formula (5) or the general formula (6) may be mixed. X has at least one of general formula (5) and / or general formula (6).

{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 and Z are a polyhedral polysiloxane via a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. It is the site | part which has couple | bonded and may be the same or different. However, at least one of Y or Z has a hydrogen atom structure. }]
The curable composition according to claim 10 , wherein the curable composition is a modified product having a polyhedral polysiloxane skeleton characterized by comprising a siloxane unit represented by the formula: (A-3) component is
Formula : [XR ⁸ ₂ SiO—SiO _3/2 ] _a [R ⁹ 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 ⁸ is an alkyl group or an aryl group; R ⁹ 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 (7) or general formula (8), and when there are a plurality of X, the general formula (7 ) Or the structure of the general formula (8) may be different, and the structure of the general formula (7) or the general formula (8) may be mixed. X has at least one of general formula (7) and / or general formula (8).

{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 and Z are a polyhedral polysiloxane via a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. The bonded site, the structure of the following general formula (8), or the structure of the following general formula (9) may be the same or different. However, at least one of Y or Z is a hydrogen atom, at least one is a structure of the following general formula (9), and at least one is a structure of the following general formula (10).

(L is an integer of 2 or more; R ³ is a group containing an aryl group) R is an alkyl group or an aryl group. }

(Q is an integer of 0 or more; R ¹⁰ is a cyclic olefin compound),
The curable composition according to claim 11 , wherein the curable composition is a modified product having a polyhedral polysiloxane skeleton characterized by comprising a siloxane unit represented by the formula: The compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule is a cyclic siloxane or linear polysiloxane having two or more hydrosilyl groups or alkenyl groups in one molecule. Item 2. The curable composition according to Item 1 . The compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule is a cyclic siloxane or linear polysiloxane having two or more hydrosilyl groups or alkenyl groups in one molecule. Item 12. The curable composition according to Item 10 or 11 . 18. The curing according to claim 17 , wherein the compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule is a cyclic siloxane having two or more hydrosilyl groups or alkenyl groups in one molecule. Sex composition . 19. The curing according to claim 18 , wherein the compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule is a cyclic siloxane having two or more hydrosilyl groups or alkenyl groups in one molecule. Sex composition. Compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule is 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, or 1,3 The curable composition according to claim 19 , which is 1,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane. Compound (b) having two or more hydrosilyl groups or alkenyl groups in one molecule is 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, or 1,3 The curable composition according to claim 20 , wherein the curable composition is 5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane. The curable composition according to claim 10 or 11 , wherein the curing agent (A-2) is an organopolysiloxane (A-2 ') having two or more alkenyl groups or hydrosilyl groups in one molecule. object. The curing agent (A-2) is an organic compound (A-2 ″) represented by the following general formula (11)

(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 10 or 11 , wherein the curable composition is a polysiloxane composition. Curing agent (A-2) contains said (A-2 ') and (A-2''), Curability of any one of Claim 10, 11, 23 , 24 characterized by the above-mentioned. Composition. The curable composition according to any one of claims 1 to 25 , further comprising a hydrosilylation catalyst. The curable composition according to any one of claims 1 to 26 , further comprising a curing retarder. The curable composition according to any one of claims 1 to 27 , further comprising a dispersant. The curable composition according to any one of claims 1 to 28, comprising a phosphor. Cured product obtained from the curable composition according to any one of claims 1 to 29. The semiconductor light emitting device obtained from the curable composition according to any one of claims 1 to 29.