JP7042126B2 - A curable composition and an optical semiconductor device using the composition as a sealing agent. - Google Patents

Description

The present invention relates to a curable composition obtained by hydrosilylation and curing, and an optical semiconductor device using the composition as a sealing agent.

Light emitting devices using light emitting diodes (LEDs) have features such as long life, low power consumption, impact resistance, high-speed response, and realization of lightness, thinness, shortness, and miniaturization, such as liquid crystal displays, mobile phones, and information terminals. The development of various fields such as backlights, in-vehicle lighting, indoor / outdoor advertising, indoor / outdoor lighting, etc. is progressing dramatically. In addition, there is a demand for further improvement in reliability as well as a variety of uses.

For example, in order to suppress a decrease in luminous efficiency of an LED due to a corrosive gas, a sealing agent having a high gas barrier property is required, and an attempt is made to improve the gas barrier property by using a hybrid material of silicone and an organic substance (Patent Document 1). On the other hand, in recent years, it has become important to suppress the occurrence of cracks and non-lighting in the liquid tank thermal shock test in order to ensure the long-term reliability of the product. In Patent Document 1, it is proposed to use a compound having at least two hydrosilyl groups in one molecule, and according to a detailed description, it is possible to use a siloxane having at least two hydrosilyl groups in one molecule. It is explained that a modified product having at least two hydrosilyl groups in one molecule is used, but it is described that it is desirable to have three or more hydrosilyl groups in one molecule for siloxane. As for the modified product, only the modified product having substantially 3 or more hydrosilyl groups in one molecule is specifically exemplified. In such a curable composition composed only of a compound having three or more hydrosilyl groups in one molecule, there is room for improvement in the cold impact resistance of the liquid tank.

JP-A-2009-046616

To provide a curable composition having improved cold heat impact resistance in a liquid tank and an optical semiconductor device using the curable composition as a sealing agent.

As a result of intensive research, the present inventors have conducted diligent research.
(A) A compound (α1) having at least two hydrosilyl groups in one molecule, and
A hydrosilylation reaction product of an organic compound (α2) having at least one alkenyl group in one molecule and a heterocyclic skeleton having at least one polar group in the ring skeleton, at least three in one molecule. Hydrosilyl group of compounds,
(B) A compound having an average of 1.5 to 2.5 hydrosilyl groups in one molecule,
(C) A compound having two or more alkenyl groups in one molecule,
(D) It has been found that the resistance of the obtained optical semiconductor device to a liquid bath cold-heat impact test is improved by using a curable composition containing a hydrosilylation catalyst as a sealing agent, and the present invention has been made.
That is, the present invention has the following configuration.
1). (A) It has a compound (α1) having at least two hydrosilyl groups in one molecule, and a heterocyclic skeleton having at least one alkenyl group and at least one polar group in the ring skeleton in one molecule. A compound having at least 3 hydrosilyl groups in one molecule, which is a hydrosilylation reaction product with an organic compound (α2).
(B) A compound having an average of 1.5 to 2.5 hydrosilyl groups in one molecule,
(C) A compound having two or more alkenyl groups in one molecule,
(D) A curable composition containing a hydrosilylation catalyst.

2). The component (A) is a hydrosilylation reaction product of an organic compound (α3) having one epoxy group and / or one oxetanyl group and one alkenyl group in one molecule in addition to (α1) and (α2). The curable composition according to 1), which is a compound having at least three hydrosilyl groups in one molecule.

3). The curable composition according to 1) or 2), wherein the component (B) is a siloxane having an average of 1.5 to 2.5 hydrosilyl groups in one molecule.

4). The curable composition according to 1) or 2), wherein the component (B) is a modified product having an average of 1.5 to 2.5 hydrosilyl groups in one molecule.

5). The curable composition according to any one of 1) to 4), wherein the component (B) contains an organic skeleton.

6). The curable composition according to any one of 1) to 5), wherein the component (B) has two hydrosilyl groups in one molecule.

7). The curable composition according to any one of 1) to 6), wherein the component (C) is a polysiloxane having two hydrosilyl groups in one molecule.

8). The curable composition according to any one of 1) to 7), wherein the component (C) is a chain siloxane having two hydrosilyl groups in one molecule.

9). The curable composition according to any one of 1) to 8), wherein the component (C) is a compound containing an organic skeleton.

10). The curable composition according to any one of 1) to 6) and 9), wherein the component (C) is an organic component and a modified product of siloxane.

11). An optical semiconductor device using the curable composition according to any one of 1) to 10) as a sealing agent.

By using the curable composition of the present invention as a sealing agent, it is possible to provide an optical semiconductor device having improved resistance to thermal shock in a liquid tank.

It is a schematic sectional drawing of the surface mount type light emitting diode (LED) which is an example of the optical semiconductor device of this invention.

Hereinafter, the present invention will be described in detail.

In the present invention, "a carbon-carbon double bond reactive with a hydrosilyl group" is referred to as an alkenyl group.

<Compound (A) having at least 3 hydrosilyl groups in one molecule>
The component (A) of the present invention comprises a compound (α1) having at least two hydrosilyl groups in one molecule and at least one alkenyl group in one molecule in the presence of the hydrosilylation catalyst (α4) described later. It can be obtained by hydrosilylation reaction with an organic compound (α2) having a heterocyclic skeleton having at least one polar group in the ring skeleton.
Further, the component (A) of the present invention contains a compound (α1) having at least two hydrosilyl groups in one molecule, at least one alkenyl group in one molecule, and at least one polar group in the ring skeleton. It can also be obtained by reacting an organic compound (α2) having a heterocyclic skeleton with an organic compound (α3) having one epoxy group and / or one oxetanyl group and one alkenyl group in one molecule. ..

The production conditions for obtaining a compound having at least three hydrosilyl groups in one molecule are not particularly limited, but after the reaction, for example, volatile unreacted components are distilled off under reduced pressure and heating conditions. Can be done. A part of the alkenyl group of the component (α2) used in the reaction may remain in the component (A) thus obtained.

The amount of the component (α1) added is preferably 1.1 to 20 and more preferably 1.3 to 15 hydrosilyl groups of the component (α1) with respect to one alkenyl group of the component (α2). , 1.5 to 10 are even more preferable. If the amount added is small, gelation proceeds due to the crosslinking reaction, so that the handleability of the modified organopolysiloxane may be inferior, and if the amount added is large, the physical properties of the cured product may be adversely affected. The amount of the component (α3) added is preferably 0 to 20, more preferably 0 to 15, and even more preferably 0 to 10 with respect to one alkenyl group of the component (α2). If the amount added is too large, the heat resistance of the cured product may be adversely affected.

The amount of the hydrosilylation catalyst used in the synthesis of the modified organopolysiloxane is not particularly limited, but it is used in the range of ^10-1 to 10-10 mol with respect to ¹ mol of the alkenyl group of the (α2) component used in the reaction. Is good. It is preferably used in the range of 10 ^-4 to ^10-8 mol. If there are many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, they may absorb light of short wavelengths, which may cause coloring or reduce the light resistance of the obtained cured product. There is also a risk of foaming. Further, if the amount of the hydrosilylation catalyst is small, the reaction may not proceed and the desired product may not be obtained.

The reaction temperature of the hydrosilylation reaction is preferably 30 to 400 ° C, more preferably 40 to 250 ° C, and even more preferably 45 to 140 ° C. If the temperature is too low, the reaction does not proceed sufficiently, and if the temperature is too high, gelation may occur and the handleability may be deteriorated.
The amount of the component (A) is preferably 10% by weight or more and 1000% by weight or less, more preferably 25 to 500% by weight, and 50% when the total amount of the component (B) and the component (C) is 100% by weight. -300% by weight is more preferable. When the amount of the component (A) is less than 10% by weight with respect to the total amount of the component (B) and the component (C), the strength of the obtained cured product may decrease and the cold shock testability of the liquid tank may decrease. There is. On the other hand, when the amount of the component (A) in the formulation is more than 1000% by weight based on the total amount of the components (B) and (C), the hardness of the obtained cured product becomes too high, resulting in a liquid. There is a risk that the bath cold shock testability will deteriorate.

<Compound having at least two hydrosilyl groups in one molecule (α1)>
The compound (α1) having at least two hydrosilyl groups in one molecule of the present invention is not particularly limited as long as it has two or more hydrosilyl groups in the molecule. For example, a linear siloxane having a hydrosilyl group, a cyclic siloxane, a branched siloxane, a silphenylene compound and the like can be mentioned.

The linear siloxane having a hydrosilyl group includes a copolymer of a dimethylsiloxane unit and a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, and a copolymer of a diphenylsiloxane unit and a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit. , A copolymer of a methylphenylsiloxane unit with a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, a polydimethylsiloxane whose end is closed with a dimethylhydrogensilyl group, and a polydiphenyl whose end is closed with a dimethylhydrogensilyl group. Examples thereof include siloxane and polymethylphenylsiloxane whose ends are blocked with a dimethylhydrogensilyl group.

In particular, as the linear siloxane having a hydrosilyl group, a polysiloxane having a molecular end sealed with a dimethylhydrogensilyl group is used from the viewpoint of reactivity at the time of modification, heat resistance of the obtained cured product, light resistance, and the like. It can be suitably used, and specifically, for example, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,5,5. -Tetramethyl-3,3-diphenyltrisiloxane and the like are exemplified as preferred examples.

As the cyclic siloxane having at least two hydrosilyl groups in one molecule, cyclotrisiloxane, cyclotetrasiloxane, cyclopentasiloxane or the like can be used. Cyclotetrasiloxane is preferable from the viewpoint of heat resistance, light resistance and the like of the obtained cured product. As the cyclotetrasiloxane, tetraorganotetrahydrogensiloxane, pentowel ganotrihydrogensiloxane, and hexaorganodihydrogensiloxane are preferable from the viewpoint of availability. More specifically, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetrahydrogen-1,3,5 7-Tetraphenylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl- 1,3,5,7-Tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-1,3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydrogen-1 , 3,5,7,9-Pentamethylcyclopentasiloxane, 1,3,5,7,9,11-Hexahydrogen-1,3,5,7,9,11-Hexamethylcyclohexasiloxane, 1, , 1,3,5,7-Pentamethyl-3,5,7-Trihydrogencyclotetrasiloxane 1,1,3,3,5,7-Hexamethyl-5,7-dihydrogencyclotetrasiloxane, 1 , 1,3,5,5,7-hexamethyl-3,7-dihydrogencyclotetrasiloxane, and the like. The cyclic siloxane in the present invention is specifically, for example, 1,3,5,7-tetrahydro from the viewpoint of industrial availability and reactivity, heat resistance, light resistance, strength, etc. of the obtained cured product. Gen-1,3,5,7-Tetramethylcyclotetrasiloxane, 1,1,3,5,7-Pentamethyl-3,5,7-Trihydrogencyclotetrasiloxane 1,1,3,3,5 , 7-Hexamethyl-5,7-dihydrogencyclotetrasiloxane, 1,1,3,5,5,7-hexamethyl-3,7-dihydrogencyclotetrasiloxane, can be preferably used.
Examples of at least two branched siloxanes in one molecule include 3-[(dimethylsilyl) oxy] -1,1,3,5,5-pentamethyltrisiloxane, 3-[(dimethylsilyl) oxy]-. 1,1,5,5-Tetramethyl-3-phenyltrisiloxane, 3,3-bis [(dimethylsilyl) oxy] -1,1,5,5-tetramethyltrisiloxane, 3-[(trimethylsilyl) oxy] ] -1,1,3,5,5-pentamethyltrisiloxane, 3-[(trimethylsilyl) oxy]-1,1,5,5-tetramethyl-3-phenyltrisiloxane, 3,3-bis [((trimethylsilyl) oxy] -1,1,5,5-tetramethyl-3-phenyltrisiloxane, 3,3-bis Trimethylsilyl) oxy]) -1,1,5,5-tetramethyltrisiloxane, and the like.
Examples of the silphenylene compound include 1,4-bis (dimethylsilyl) benzene, 1,4-bis (diphenylsilyl) benzene, and 1,4-bis (methylphenylsilyl) benzene.

The compounds having at least two hydrosilyl groups in one molecule, which are these (α1) components, may be used alone or in combination of two or more.

<Organic compound (α2) having at least one alkenyl group and a heterocyclic skeleton having at least one polar group in the ring skeleton in one molecule>
The organic compound (α2) having at least one alkenyl group and a heterocyclic skeleton having at least one polar group in one molecule of the present invention includes an alkenyl group and an organic compound having a heterocyclic skeleton. However, the organic compound represented by the following general formula (1) or (2) is preferable from the viewpoint of heat resistance and light resistance of the obtained cured product.

(In the formula, R ¹ to R ³ represent monovalent organic groups or hydrogen atoms having 1 to 50 carbon atoms, and R ¹ to R ³ may be different or the same. Further, R ¹ to R ³ may be different. At least one of them is an alkenyl group.)

(In the formula, R ⁴ to R ⁷ represent monovalent organic groups or hydrogen atoms having 1 to 50 carbon atoms, and R ⁴ to R ⁷ may be different or the same. Further, R ⁴ to R ⁷ may be different. At least one of them is an alkenyl group.)

The component (α2) is represented by the above general formula (1) or (2) from the viewpoint of adhesiveness between the substrate and the substrate when the curable composition is cured, and is contained in one molecule. It is preferably a compound containing one or more alkenyl groups, and from the viewpoint of the balance between heat resistance and light resistance, triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl isosia. Nurate, monoallyl dimethyl isocyanurate, monoallyl diglycidyl isocyanurate, tetraallyl glycol uryl, diallyl diglycidyl glycol uryl, triallyl monoglycidyl glycol uryl, monoallyl triglycidyl glycol uryl, diallyl dimethyl glycol uryl, triallyl dimethyl glycol uryl , Monoallyl trimethyl glycol uryl is preferably used. These may be used alone or in combination of two or more.

<Organic compound (α3) having one epoxy group and / or one oxetanyl group and one alkenyl group in one molecule>
The compound (α3) is not particularly limited as long as it is an organic compound having one epoxy group and / or one oxetanyl group and one alkenyl group in one molecule.
As the epoxy group, the following general formula (3)

(However, R ⁸ is a divalent organic group having 1 to 10 carbon atoms and 0 to 2 oxygen numbers, and R ⁹ to R ¹¹ are monovalent organic groups or hydrogen atoms having 1 to 50 carbon atoms. , R ⁹ to R ¹¹ may be different or the same).
The oxetanyl group includes the following general formula (4).

(However, R ¹² is a divalent organic group having 1 to 10 carbon atoms and 0 to 2 oxygen numbers, and R ¹³ to R ¹⁴ are monovalent organic groups or hydrogen atoms having 1 to 50 carbon atoms. , R ¹³ to R ¹⁴ may be different or the same).
As the compound (α3), allyl glycidyl ether and vinylcyclohexene oxide are preferable from the viewpoint of availability. The above-mentioned various compounds (α3) may be used alone or in combination of two or more.

<Hydrosilylation catalyst (α4)>
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, for example, a platinum-olefin complex, a platinum chloride acid, a simple substance of platinum, a carrier (alumina, silica, carbon black, a polymer, etc.) on which solid platinum is supported; a platinum-vinylsiloxane complex, for example, Pt _n (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ; platinum-phosphine complex, eg Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ; platinum-phosphite complex, eg Pt. [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ (In the formula, Me is a methyl group, Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, and n and m are integers. Represented), Pt (acac) ₂ , and the platinum-hydrocarbon complexes described in Ashby et al., U.S. Pat. Nos. 3,159,601 and 3159662, as well as Lamoreaux et al., U.S. Pat. No. 3220972. Also mentioned is a platinum hydrocarbon catalyst.

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, and NiCl ₂ . , TiCl ₄ , etc. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, platinum chloride acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) ₂ and the like are preferable.

<Compound (B) having an average of 1.5 to 2.5 hydrosilyl groups in one molecule>
The compound (B) having an average of 1.5 to 2.5 hydrosilyl groups in one molecule used in the curable composition of the present invention has an average of 1.5 to 2.5 in one molecule. The compound has no particular limitation as long as it has a hydrosilyl group. Here, having an average of 1.5 to 2.5 hydrosilyl groups in one molecule means that the total number of hydrosilyl groups contained in compound (B) is the total number of molecules contained in compound (B). The value divided by the number is 1.5 to 2.5, and the compound (B) contains a structure having 1 or less per molecule and / or 3 or more hydrosilyl groups per molecule. It is not denied that it is. Examples of such a compound (B) include a siloxane compound (B1) having an average of 1.5 to 2.5 hydrosilyl groups in one molecule, and an average of 1. An example is a modified product (B2) having 5 to 2.5 hydrosilyl groups.

As the compound (B) having an average of 1.5 to 2.5 hydrosilyl groups in one molecule, one of B1 and B2 may be used alone, or two or more thereof may be mixed. May be used.

The number of hydrosilyl groups contained in one molecule is not particularly limited as long as it is in the range of 1.5 to 2.5, but the range of 1.7 to 2.3 is more preferable, and 1.9 to 2.1. The range is more preferably two, more preferably just two, and most preferably composed only of compounds having two hydrosilyl groups per molecule. If the average number of hydrosilyl groups contained in one molecule is less than 1.5, the strength of the obtained cured product will be too low, which is not preferable. When the average number of hydrosilyl groups contained in one molecule is more than 2.5, the effect on improving the cold shock testability of the liquid tank is reduced, which is not preferable. As the number of hydrosilyl groups contained in one molecule is closer to two on average, the curability is obtained because it is incorporated into the cured product without changing the total number of cross-linking points contained in the obtained curable composition. It is possible to impart appropriate elasticity to the composition, and as a result, to improve the resistance to the cold shock test of the liquid tank.

The amount of the component (B) is preferably 0.5% by weight or more and 200% by weight or less, more preferably 1 to 150% by weight, and 2 to 100% by weight when the amount of the component (A) is 100% by weight. Is even more preferable. If the amount of the component (B) is too small with respect to the total amount of the component (A), the effect of improving the resistance to the liquid tank cold shock test may not be sufficiently obtained. On the other hand, if the amount of the component (B) added to the compound (B) is too large with respect to the total amount of the component (A), the strength of the obtained cured product may decrease and the resistance to the cold shock test in the liquid tank may decrease. There is.

<siloxane compound (B1) having an average of 1.5 to 2.5 hydrosilyl groups in one molecule>
Examples of the siloxane compound (B1) having an average of 1.5 to 2.5 hydrosilyl groups in one molecule include linear siloxane, cyclic siloxane, branched siloxane, and silphenylene compound.

The linear siloxane having an average of 1.5 to 2.5 hydrosilyl groups in one molecule includes a copolymer of a dimethylsiloxane unit, a methylhydrogensiloxane unit, and a terminal trimethylsiloxy unit, and a diphenylsiloxane unit. A polymer of methylhydrogensiloxane unit and terminal trimethylsiloxy unit, a polymer of methylphenylsiloxane unit and methylhydrogensiloxane unit and terminal trimethylsiloxy unit, poly whose end is closed with a dimethylhydrogensilyl group. Examples thereof include dimethylsiloxane, polydiphenylsiloxane whose end is closed with a dimethylhydrogensilyl group, and polymethylphenylsiloxane whose end is closed with a dimethylhydrogensilyl group.

In particular, as the linear siloxane having a hydrosilyl group, a polysiloxane having a molecular end sealed with a dimethylhydrogensilyl group can be preferably used because of the availability of the compound. Specifically, for example, 1 , 1,3,3-Tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, dimethylhydro Preferred examples include polydimethylsiloxanes whose ends are closed with a gensilyl group, polydiphenylsiloxanes whose ends are closed with a dimethylhydrogensilyl group, and polymethylphenylsiloxanes whose ends are closed with a dimethylhydrogensilyl group. Will be done.

As the cyclic siloxane having a hydrosilyl group, cyclotrisiloxane, cyclotetrasiloxane, cyclopentasiloxane or the like can be used. Cyclotetrasiloxane is preferable from the viewpoint of heat resistance, light resistance and the like of the obtained cured product. Specific examples of the cyclotetrasiloxane having 1.5 to 2.5 hydrosilyl groups in one molecule include 1,3,5,7-tetrahydrogen-1,3,5,7. -Tetramethylcyclotetrasiloxane, 1,3,5,7-Tetrahydrogen-1,3,5,7-Tetraphenylcyclotetrasiloxane, 1-propyl-3,5,7-Trihydrogen-1,3 , 5,7-Tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-1 , 3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9, 11-Hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane, 1,1,3,5,7-pentamethyl-3,5,7-trihydrogencyclotetrasiloxane, 1 1,3,3,5,7-Hexamethyl-5,7-dihydrogencyclotetrasiloxane, 1,1,3,5,5,7-hexamethyl-3,7-dihydrogencyclotetrasiloxane, etc. Can be mentioned.

Examples of the branched siloxane include 3-[(dimethylsilyl) oxy] -1,1,3,5,5-pentamethyltrisiloxane and 3-[(dimethylsilyl) oxy] -1,1,5,5-. Tetramethyl-3-phenyltrisiloxane, 3,3-bis [(dimethylsilyl) oxy] -1,1,5,5-tetramethyltrisiloxane, 3-[(trimethylsilyl) oxy] -1,1,3, 5,5-Pentamethyltrisiloxane, 3-[(trimethylsilyl) oxy] -1,1,5,5-tetramethyl-3-phenyltrisiloxane, 3,3-bis [(trimethylsilyl) oxy])-1, Examples thereof include 1,5,5-tetramethyltrisiloxane.

Examples of the silphenylene compound include 1,4-bis (dimethylsilyl) benzene, 1,4-bis (diphenylsilyl) benzene, and 1,4-bis (methylphenylsilyl) benzene.

<Denatured product (B2) having an average of 1.5 to 2.5 hydrosilyl groups in one molecule>
The modified compound (B2) having an average of 1.5 to 2.5 hydrosilyl groups in one molecule has, for example, at least two hydrosilyl groups in the one molecule in the presence of the hydrosilylation catalyst. It is obtained by hydrosilylating a compound (α1) with a compound (β1) having at least one alkenyl group in one molecule.

<Compound having at least one alkenyl group in one molecule (β1)>
The compound (β1) having at least one alkenyl group in one molecule is not particularly limited as long as it is a compound having at least one alkenyl group in one molecule. From the viewpoint of heat resistance and light resistance of the obtained cured product, an organosilicon compound (β'1) having one alkenyl group in one molecule and a cyclic olefin compound (β'2) having one alkenyl group in one molecule. ), A polysiloxane (β'3) having two or more alkenyl groups in one molecule, and an organic compound (β'4) having two or more alkenyl groups in one molecule are preferable. These β'1 to β'4 may be used alone or in combination of two or more.

<Organosilicon compound (β'1) having one alkenyl group in one molecule>
Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a hexenyl group and the like, but a vinyl group is preferable from the viewpoint of heat resistance and light resistance. The component (β'1) in the present invention is not particularly limited as long as it is an organosilicon compound having one alkenyl group in one molecule, but one molecule may contain at least one aryl group. , It is preferable from the viewpoint of gas barrier property and refractive index, and further, it is more preferable from the viewpoint of heat resistance and light resistance that the aryl group is directly bonded to the silicon atom.

The component (β'1) in the present invention is preferably silane or polysiloxane from the viewpoint of heat resistance and light resistance. When such a (β'1) component is a silane having one alkenyl group in one molecule, specifically, for example, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, triphenylvinylsilane, triethylvinylsilane, diethyl. Examples thereof include phenylvinylsilane, ethyldiphenylvinylsilane, allyltrimethylsilane, allyldimethylphenylsilane, allylmethyldiphenylsilane, allyltriphenylsilane, allyltriethylsilane, allyldiethylphenylsilane, and allylethyldiphenylsilane. Among them, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane and triphenylvinylsilane are preferable examples from the viewpoint of heat resistance and light resistance, and further, dimethylphenylvinylsilane and methyldiphenylvinylsilane are mentioned from the viewpoint of gas barrier property and refractive index. , Triphenylvinylsilane is a preferred example.

When the (β'1) component is a polysiloxane, examples thereof include a linear siloxane having one alkenyl group, a polysiloxane having one alkenyl group at the molecular terminal, and a cyclic siloxane having one alkenyl group. Will be done.

When the component (β'1) is a polysiloxane having a linear structure having one alkenyl group, specifically, for example, a polydimethylsiloxane having one end sealed with a dimethylvinylsilyl group and one trimethylsilyl group. Polymethylphenylsiloxane with one end sealed with a dimethylvinylsilyl group and one trimethylsilyl group, polydiphenylsiloxane with one end each with a dimethylvinylsilyl group and a trimethylsilyl group, a dimethylvinylsilyl group and a trimethylsilyl group. A copolymer of a dimethylsiloxane unit and a methylphenylsiloxane unit with one end each closed, and a dimethylsiloxane unit and a diphenylsiloxane unit with one end each closed with a dimethylvinylsilyl group and a trimethylsilyl group. Examples thereof include a copolymer, a copolymer of a methylphenylsiloxane unit and a diphenylsiloxane unit in which one end is sealed with a dimethylvinylsilyl group and a trimethylsilyl group, respectively.

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

When the component (β'1) is a cyclic siloxane having one alkenyl group, specifically, for example, 1-vinyl-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1 -Vinyl-3-phenyl-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1-vinyl-3,5-diphenyl-1,3,5,7,7-pentamethylcyclotetrasiloxane , 1-vinyl-3,5,7-triphenyl-1,3,5,7-tetramethylcyclotetrasiloxane and the like are exemplified.

<Cyclic olefin compound having one alkenyl group in one molecule (β'2)>
The component (β'2) in the present invention may be any cyclic olefin compound having one carbon-carbon double bond in one molecule, and this carbon-carbon double bond may be a vinylene group, a vinylidene group, or an alkenyl group. It may be any of. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a hexenyl group and the like, but a vinyl group is preferable from the viewpoint of heat resistance and light resistance.

Further, the component (β'2) in the present invention preferably has an average molecular weight of 1000 or less from the viewpoint of reactivity with the component (α1). Examples of such a cyclic olefin compound include an aliphatic cyclic olefin compound and a substituted aliphatic cyclic olefin compound.
Specific examples of the aliphatic cyclic olefin compound include cyclohexene, cycloheptane, cyclooctene, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, allylcyclohexane, allylcycloheptane, allylcyclooctane, methylenecyclohexane and the like. Be done.

Specific examples of the substituted aliphatic cyclic olefin compound include norbornene, 1-methylnorbornene, 2-methylnorbornene, 7-methylnorbornene, z2-vinylnorbornane, 7-vinylnorbornane, 2-allylnorbornane, and 7-allylnorbornane. 2-Methylenenorbornane, 7-methylenenorbornane, camphen, vinylnorbornene, 6-methyl-5-vinyl-bicyclo [2,2,1] -heptane, 3-methyl-2-methylene-bicyclo [2,2,1] ] -Heptane, α-pinene, β-pinene, 6,6-dimethyl-bicyclo [3,1,1] -2-heptane, 2-vinyladamantan, 2-methyleneadamantan and the like.

Among them, cyclohexene, vinylcyclohexane, norbornene, camphene, and pinene are preferable examples from the viewpoint of availability.

<Polysiloxane (β'3) having two or more alkenyl groups in one molecule>
The number of siloxane units of the polysiloxane (β'3) having two or more alkenyl groups in one molecule, which can be contained in the curable composition of the present invention, is not particularly limited, but is preferably two or more, and more preferably two or more. Is 2 to 100 pieces. If the number of siloxane units in one molecule is small, it tends to volatilize from the composition, and the desired physical properties may not be obtained after curing. Further, if the number of siloxane units is large, the gas barrier property of the obtained cured product may decrease.

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

Specific examples of the linear polysiloxane having two or more alkenyl groups include a copolymer of a dimethylsiloxane unit and a methylvinylsiloxane unit and a terminal trimethylsiloxy unit, a diallylsiloxane unit and a methylvinylsiloxane unit, and a terminal trimethylsiloxy unit. Copolymer with, a copolymer of methylarylsiloxane unit and methylvinylsiloxane unit and terminal trimethylsiloxy unit, polydimethylsiloxane whose end was blocked with a dimethylvinylsilyl group, and terminal blocked with a dimethylvinylsilyl group. Examples thereof include polydiarylsiloxane and polymethylarylsiloxane whose ends are closed with a dimethylvinylsilyl group.

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

Specific examples of the polysiloxane having two or more alkenyl groups at the molecular end include polysiloxane whose end is closed with the dimethylvinylsilyl group exemplified above, two or more dimethylvinylsiloxane units and SiO ₂ unit, SiO _{3 /.} Examples thereof include polysiloxane consisting of at least one siloxane unit selected in the group consisting of ₂ units and SiO units.

Cyclic siloxane compounds 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-trivinyl-1, 3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1 , 3, 5, 7, 9, 11-hexamethylcyclosiloxane and the like are exemplified.
Polysiloxane having two or more alkenyl groups in one of these molecules may be used alone or in combination of two or more.

<Organic compound having two or more alkenyl groups in one molecule (β'4)>
(Β'4) is not particularly limited as long as it is an organic compound having two or more alkenyl groups in one molecule, but is, for example, an organic compound represented by the following general formula (5) or (6). Examples thereof include organic compounds having two or more alkenyl groups in one molecule.

(In the formula, R ¹⁵ to R ¹⁷ represent monovalent organic groups or hydrogen atoms having 1 to 50 carbon atoms, and R ¹⁵ to R ¹⁷ may be different or the same. Further, R ¹⁵ to R ¹⁷ may be different. At least two of them are alkenyl groups.)

(In the formula, R ¹⁸ to R ²¹ represent monovalent organic groups or hydrogen atoms having 1 to 50 carbon atoms, and R ¹⁸ to R ²¹ may be different or the same. Further, R ¹⁸ to R ²¹ may be used. At least two of them are alkenyl groups.)
The component (β'4) preferably has a number average molecular weight of less than 900 from the viewpoint of compatibility with the obtained curable composition. Further, the skeleton of the (β'4) component may have a functional group other than the alkenyl group.

The component (β'4) is represented by the above general formula (3) or (4) from the viewpoint of adhesiveness between the base material and the base material when the composition is cured, and is contained in one molecule. It is preferably a compound containing two or more alkenyl groups, and from the viewpoint of the balance between heat resistance and light resistance, triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoglycidyl isocyanurate, tetraallyl glycol. It is preferable to use uryl, diallyl diglycidyl glycol uryl, triallyl monoglycidyl glycol uryl, monoallyl triglycidyl glycol uryl, diallyl dimethyl glycol uryl, triallyl dimethyl glycol uryl, and monoallyl trimethyl glycol uryl. These may be used alone or in combination of two or more.

<Compound (C) having two or more alkenyl groups in one molecule>
The compound (C) used in the present invention is not particularly limited as long as it is a compound having two or more alkenyl groups in one molecule.

The amount of the compound (C) added can be variously set, but the amount of the hydrosilyl group contained in the entire curable composition is 0.3 to 5, preferably 0.5 to 3 per alkenyl group of the compound (C). It is desirable to add the number, more preferably 0.7 to 1.5. If the proportion of alkenyl groups is small, poor appearance due to foaming or the like is likely to occur, and if the proportion of alkenyl groups is large, the physical properties after curing may be adversely affected.

Here, as the compound (C), for example, a polysiloxane (C1) having two or more alkenyl groups in one molecule, or an organic compound (β'4) having two or more alkenyl groups in one molecule described above. Examples thereof include a modified product (C2) having two or more alkenyl groups in one molecule. These compounds having two or more alkenyl groups in one molecule may be used alone or in combination of two or more.

<Polysiloxane (C1) having two or more alkenyl groups in one molecule>
The number of siloxane units of the polysiloxane (C1) having two or more alkenyl groups in one molecule, which can be contained in the curable composition of the present invention, is not particularly limited, but is preferably 2 or more and 1000 or less. More than 100 pieces are more preferable. If the number of siloxane units in one molecule is small, it tends to volatilize from the composition, and the desired physical properties may not be obtained after curing. Further, if the number of siloxane units is large, the tackiness of the obtained cured product may deteriorate and it may be difficult to handle the obtained cured product as an optical semiconductor device.

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

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

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

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

Specific examples of the polysiloxane having two or more alkenyl groups at the molecular end include polysiloxane whose end is closed with the dimethylvinylsilyl group exemplified above, two or more dimethylvinylsiloxane units and SiO ₂ unit, SiO _{3 /.} Examples thereof include polysiloxane consisting of at least one siloxane unit selected in the group consisting of ₂ units and SiO units.

Cyclic siloxane compounds 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-trivinyl-1, 3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1 , 3, 5, 7, 9, 11-hexamethylcyclosiloxane and the like are exemplified.
Polysiloxane having two or more alkenyl groups in one of these molecules may be used alone or in combination of two or more.

<Denatured product (C2) having two or more alkenyl groups in one molecule>
The (C2) is not particularly limited as long as it is a modified product having two or more alkenyl groups in one molecule. It may be any of a modified product obtained by combining an organic component and an organic component, a modified product obtained by combining an organic component and an inorganic component, and a modified product obtained by combining an inorganic component and an inorganic component. From the viewpoint of heat resistance of the obtained cured product, a combination of an organic component and an inorganic component or a combination of an inorganic component and an inorganic component is preferable.

Examples of the combination of the organic component and the inorganic component include a modified product obtained by reacting the (α1) component and the (β'4) component in the presence of a hydrosilylation catalyst (α4). Examples of the combination of the inorganic component and the inorganic component include a modified product obtained by reacting the (α1) component and the (β'3) component in the presence of a hydrosilylation catalyst (α4).
These may be used alone or in combination of two or more.

<Hydrosilylation catalyst (D)>
Any of the hydrosilylation catalysts described in the above-mentioned hydrosilylation catalyst (α4) may be used. One type may be used alone, or two or more types may be used in combination.

<Curable composition>
The polysiloxane-based curable composition used in the semiconductor light emitting device of the present invention can be obtained by mixing a curing retarder, an inorganic filler, or the like, if necessary.
The viscosity of the curable composition used in the present invention is not particularly limited, but is preferably 0.1 Pa · s to 300 Pa · s at a temperature of 23 ° C., and more preferably 0.3 Pa · s to 200 Pa · s. Is. If the viscosity of the curable composition is low, the phosphor may settle and the chromaticity shift between individuals may become large, and if the viscosity is high, the handleability of the curable composition may deteriorate.

When the temperature is applied when the curable composition is cured, the temperature is preferably 30 to 400 ° C, more preferably 50 to 250 ° C. If the curing temperature is high, the obtained cured product tends to have a poor appearance, and if it is low, the curing is insufficient. Further, it may be cured by combining two or more temperature conditions. Specifically, it is preferable to raise the curing temperature stepwise, for example, at 70 ° C., 120 ° C., and 150 ° C., because a good cured product can be obtained.

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

A curing retarder may be used to improve the storage stability of the curable composition used in the present invention or to adjust the hydrosilylation reactivity in the curing process. As the curing retarder, known compounds used in hydrosilylation-catalyzed addition-type curable compositions can be used, specifically, compounds containing an aliphatic unsaturated bond, organic phosphorus compounds, organic sulfur compounds, and the like. Examples thereof include nitrogen-containing compounds, tin-based compounds, and organic peroxides. These may be used alone or in combination of two or more.

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

Specific examples of the organic phosphorus compound include triorganophosphins, diorganophosphins, organophosphons, and triorganophosphytes.

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

Specific examples of the nitrogen-containing compound include N, N, N', N'-tetramethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, 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 '-Bipylene and the like can be exemplified.

Specific examples of the tin-based compound include stannous halogenated dihydrate and stannous carboxylic acid.

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-hexin-3-ol, and 1-ethynyl-1-cyclohexanol can be exemplified as particularly preferable curing retarders.

The amount of the curing retarder added is not particularly limited, but it is preferably used in the range of 10-1 to 103 mol per ¹ mol of the hydrosilylation catalyst, and more preferably in the range of ¹ to 100 mol. preferable. Further, these curing retarders may be used alone or in combination of two or more.

The curable composition used in the semiconductor light emitting device of the present invention may contain a fluorescent substance. The phosphor absorbs the light emitted by the light emitting element to generate light having a different wavelength, and the phosphor used in the semiconductor light emitting device of the present invention is not particularly limited and is generally known inorganic fluorescence. A body, an organic phosphor, or a quantum dot can be used, and any one can be selected in order to obtain the emission color required by the semiconductor light emitting device of the present invention. Specifically, for example, YAG-based phosphors, TAG-based phosphors, orthosilicate alkaline earth-based phosphors, α-sialon-based phosphors, β-sialon-based phosphors, cousin-based phosphors, nitrides and oxynitride-based phosphors. , CdSe-based quantum dots, CdSSe-based quantum dots, CdS-based quantum dots, InP-based quantum dots, PbS-based quantum dots, perovskite-type phosphors, and the like, but are not limited thereto. As these fluorescent substances, one kind or two or more kinds can be used in any ratio and combination.

The amount of the phosphor used in the present invention is not particularly limited, and any amount can be used to obtain the emission color required by the semiconductor light emitting device. It is preferably 0.1% by weight or more, more preferably 1% by weight or more, still more preferably 2% by weight or more, preferably 200% by weight or less, more preferably 150% by weight or less, still more preferably 100% by weight or less. Is. If the amount of the fluorescent substance used is small, the wavelength conversion by the fluorescent substance may be insufficient and the desired emission color may not be obtained. If the amount of the fluorescent substance used is large, the handleability of the composition may be deteriorated. , There is a possibility that the utilization efficiency of the phosphor may be lowered due to the optical interference action.

The particle size and particle size distribution of the phosphor are not particularly limited, and any amount can be used to obtain the emission color required by the semiconductor light emitting device.

An adhesiveness-imparting agent can be added to the curable composition used in the semiconductor light emitting device of the present invention, if necessary.

The adhesiveness-imparting agent is used, for example, for the purpose of improving the adhesiveness between the polysiloxane-based composition and the substrate in the present invention, and is not particularly limited as long as it has such an effect, but silane. A coupling agent can be exemplified as a preferable 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 at least one hydrolyzable silicon group in the molecule. As the group reactive with the organic group, at least one functional group selected from an epoxy group, a methacrylic group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group and a carbamate group is preferable from the viewpoint of handleability, and curing is preferable. From the viewpoint of properties 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-glycidoxypropylmethyldi. Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethylmethyldiethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane , 3-Acryloxypropyltriethoxysilane, Methacryloxymethyltrimethoxysilane, Methacryloxymethyltriethoxysilane, Acryloxymethyltrimethoxysilane, Acryloxymethyltriethoxysilane, and other alkoxysilanes having a methacrylic group or an acrylic group. Can be mentioned. These may be used alone or in combination of two or more.

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

Further, in order to enhance the effect of the adhesiveness-imparting agent, a known adhesiveness promoter can also be used. Examples of the adhesiveness accelerator include, but are not limited to, epoxy-containing compounds, epoxy resins, boronic acid ester compounds, organic aluminum compounds, and organic titanium compounds.

An inorganic filler can be added to the curable composition used in the semiconductor light emitting device of the present invention, if necessary. By using the inorganic filler, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical characteristics, light reflectance, flame retardancy, fire resistance, gas barrier property, etc. of the obtained molded body, etc. It is possible to improve various physical properties of.

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

The inorganic filler may be appropriately surface-treated. Examples of the surface treatment include an alkylation treatment, a trimethylsilylation treatment, a silicone treatment, a treatment with a silane coupling agent, and the like, but the surface treatment is not particularly limited.

As the shape of the inorganic filler, various shapes such as crushed shape, flaky shape, spherical shape, rod shape and the like 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 0.001 to 100 μm, more preferably 0.005 to 70 μm. It is more preferable to have. Similarly, the BET specific surface area is not particularly limited, but is preferably 70 m ² / g or more, more preferably 100 m ² / g or more, and further 200 m ² / g, from the viewpoint of gas barrier properties. It is particularly preferable that it is g or more.

The amount of the inorganic filler added is not particularly limited, but is 0.1 to 1000 parts by weight, more preferably 0.5 to 500 parts by weight, still more preferably 1 to 300 parts by weight with respect to 100 parts by weight of the curable composition. It is a part by weight. If the amount of the inorganic filler added is large, the fluidity may deteriorate, and if the amount of the inorganic filler added is small, the desired physical properties may not be obtained.

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

Further, in the curable composition used in the semiconductor light emitting device of the present invention, various additives such as a colorant and a heat resistance improver, a reaction control agent, a release agent, a dispersant for a filler and the like may be added as necessary. It can be added at will. Examples of the dispersant for a filler include diphenylsilanediol, various alkoxysilanes, carbon functional silanes, silanol group-containing low molecular weight siloxanes, and the like. In addition, it is preferable to keep these optional components in the minimum amount so as not to impair the effect of the present invention.

In the curable composition used in the semiconductor light emitting device of the present invention, the above-mentioned components are uniformly mixed by using a kneader such as a roll, a Banbury mixer or a kneader, or by using a planetary stirring defoaming machine, if necessary. It may be heat-treated.
The optical semiconductor device of the present invention can be used for various conventionally known applications. Specifically, for example, backlights such as light emitting / receiving device liquid crystal display devices, lighting, sensor light sources, vehicle instrument light sources, signal lights, indicator lights, display devices, light sources of planar light emitters, displays, decorations, various lights, etc. Can be mentioned.

<Optical semiconductor device>
The optical semiconductor device of the present invention is not particularly limited, and examples thereof include the structure shown in FIG. FIG. 1 is a schematic cross-sectional view of an optical semiconductor device.

The optical semiconductor element 1 in FIG. 1 of the present invention is not particularly limited, and a general-purpose LED of a semiconductor light emitting device or the like can be used. For example, a fluorescent substance is excited by the emitted light to emit visible light, and examples thereof include a visible light emitting type LED and an ultraviolet emitting type LED. Alternatively, the emitted light is emitted from the optical semiconductor as it is, and examples thereof include an ultraviolet light emitting type, a visible light emitting type, and an infrared light emitting type LED. The optical semiconductor device 1 of the present invention may mount a plurality of the same or different types of LEDs per semiconductor light emitting device.

The reflector 2 in FIG. 1 of the present invention may be used as needed, and is intended to efficiently reflect the optical semiconductor device from the optical semiconductor element 1. As the material, a thermoplastic resin, a thermosetting resin, a glass epoxy, a ceramic, or the like can be used, but the material is not particularly limited.

The cured product 3 of the polysiloxane-based composition in FIG. 1 of the present invention is corrosive, which efficiently permeates the light from the optical semiconductor element 1 to the outside, protects the optical semiconductor element, wires, etc. from external forces and dust. It has the function of preventing gas from entering the device.

The lead 4 in FIG. 1 of the present invention is for ensuring the conductivity at the time of mounting the LED and increasing the reflection efficiency of the LED. In particular, since the reflectance in the visible light region is high, a metal surface plated with silver is often used, but the metal surface is not limited to silver plating.

The wire 5 in FIG. 1 of the present invention electrically connects the optical semiconductor element 1 and the lead 4, and the material is not particularly limited as long as it is conductive, but gold, a gold alloy, copper, or the like is used. Can be mentioned. Further, instead of using the wire 5, an electric connection may be made by using a conductive adhesive or eutectic solder.

The phosphor 6 in FIG. 1 of the present invention may be used as needed, and absorbs the light emitted from the optical semiconductor device 1 and emits light having a different wavelength. The composition of the fluorescent substance used is not particularly limited, but a fluorescent substance that emits visible light of 400 nm to 800 nm is generally used. Further, there is no limitation on whether the fluorescent substance is settled or suspended in the cured product 3.

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

(Hydrosilyl value)
A mixed solution of 0.200 g of the modified product, 0.200 g of dibromoethane and 1.000 g of deuterated chloroform was prepared. The hydrosilyl value of the modified product was calculated by measuring the obtained solution using 400 MHz NMR manufactured by Varian Technologies Japan Limited and using the following formula (1).
Hydrosilyl value (mol / kg) = (integral value of peak attributed to hydrosilyl group of modified product) / (integral value of peak attributed to methyl group of dibromoethane) x 4 x (weight of dibromoethane in mixture) / (Molecular weight of dibromoethane) / (Weight of modified product in the mixture) (1)

(Alkenyl value)
A mixed solution of 0.200 g of the modified product, 0.200 g of dibromoethane and 1.000 g of deuterated chloroform was prepared. The alkenyl value of the modified product was calculated by measuring the obtained solution using 400 MHz NMR manufactured by Varian Technologies Japan Limited and using the following formula (2).

Alkenyl value (mol / kg) = (integrated value of peak attributed to alkenyl group of modified product) / (number of H atoms attached to alkenyl group of modified product) / (assigned to methyl group of dibromoethane) Integrated value of peak) × 4 × (weight of dibromoethane in the mixture) / (molecular weight of dibromoethane) / (weight of modified product in the mixture) (2)

(Manufacturing Example 1)
1,3,5,7-Tetrahydrogen-1,3,5,7-Tetramethylcyclotetrasiloxane 500g (corresponding to (α1)) and 1800g of toluene are uniformly mixed and stirred at 105 ° C. under a nitrogen atmosphere. did. 180 g of triallyl isocyanurate (corresponding to (α2)), 300 g of allyl glycidyl ether (corresponding to (α3)), 350 g of toluene and a xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, Umicoa Precious) A mixed solution of 0.1 g of Pt-VTSC-3X) manufactured by Metals Japan was added dropwise over 40 minutes and reacted at 105 ° C. for 4 hours. By distilling off the unreacted component and toluene under reduced pressure, a reaction product of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, allylglycidyl ether and triallyl isocyanurate can be obtained. 700 g (hydrosilyl valence 3.5 mol / kg: component (A)) was obtained.

(Manufacturing Example 2)
1,3,5,7-Tetrahydrogen-1,3,5,7-Tetramethylcyclotetrasiloxane 626 g and toluene 602 g (corresponding to (α1)) are uniformly mixed and stirred at 105 ° C. under a nitrogen atmosphere. did. 90 g of triallyl isocyanurate (corresponding to (α2)), 90 g of toluene and a xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, manufactured by Yumicoa Precious Metals Japan, Pt-VTSC-3X) 0. 1 g of the mixed solution was added dropwise over 40 minutes, and the mixture was reacted at 105 ° C. for 4 hours. By distilling off the unreacted component and toluene under reduced pressure, 310 g (hydrosilyl valence) of the reaction product of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and triallyl isocyanurate was obtained. Number 8.60 mol / kg: (A component) was obtained.

(Manufacturing Example 3)
Uniformly mix 90 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (corresponding to (α1)) and 40 g of toluene, and stir at 105 ° C. under a nitrogen atmosphere. did. 100 g of diallyl monomethylisocyanurate (corresponding to (α2)), 200 g of toluene and a xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, manufactured by Yumicoa Precious Metals Japan, Pt-VTSC-3X) 0. A 15 g mixture was added dropwise over 40 minutes and reacted at 105 ° C. for 4 hours. By distilling off the unreacted component and toluene under reduced pressure, 120 g of a reaction product of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and diallylmonomethylisocyanurate was obtained (hydrosilyl valence). Number 6.00 mol / kg: ((A) component) was obtained.

(Manufacturing Example 4)
300 g of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (corresponding to (α1)) and 300 g of toluene were uniformly mixed and stirred at 105 ° C. under a nitrogen atmosphere. 100 g of diallyl monomethylisocyanurate (corresponding to (β'4)), 200 g of toluene and a xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, manufactured by Yumicoa Precious Metals Japan, Pt-VTSC-3X) 0.05 g of the mixed solution was added dropwise over 40 minutes, and the mixture was reacted at 105 ° C. for 4 hours. By distilling off the unreacted component and toluene under reduced pressure, 350 g of a reaction product of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane and diallylmonomethylisocyanurate was obtained (hydrosilyl valence 2.03 mol / kg, The average number of hydrosilyls per molecule was 2 (component (B)).

(Manufacturing Example 5)
360 g (corresponding to (α1)) of polymethylphenylsiloxane (number average molecular weight 1000 measured by GPC in terms of polystyrene) with both ends sealed with a dimethylsilyl group and 180 g of toluene are uniformly mixed, and the temperature is 105 ° C. under a nitrogen atmosphere. Was stirred with. 40 g of diallyl monomethylisocyanurate (corresponding to (β'4)), 100 g of toluene and a xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, manufactured by Yumicoa Precious Metals Japan, Pt-VTSC-3X) 0.03 g of the mixed solution was added dropwise over 40 minutes, and the mixture was reacted at 105 ° C. for 4 hours. 350 g of a reaction product of polymethylphenylsiloxane and diallyl monomethylisocyanurate having both ends sealed with a dimethylsilyl group by distilling off the unreacted component and toluene under reduced pressure (hydrosilyl valence: 0.90 mol / kg / molecule). Average number of hydrosilyls 2: component (B)) was obtained.

(Manufacturing Example 6)
330 g (corresponding to (α1)) of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane and 200 g of toluene were uniformly mixed and stirred at 105 ° C. under a nitrogen atmosphere. 35 g of diallyl monomethylisocyanurate (corresponding to (β'4)), 40 g of triallyl isocyanurate (corresponding to (β'4)), 90 g of toluene and a xylene solution of a platinum vinylsiloxane complex (platinum vinylsiloxane containing 3 wt% as platinum). A mixed solution of 0.05 g of the complex, Pt-VTSC-3X, manufactured by Yumicoa Precious Metals Japan, was added dropwise over 40 minutes and reacted at 105 ° C. for 4 hours. By distilling off the unreacted component and toluene under reduced pressure, 230 g of a reaction product of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, diallyl monomethylisocyanurate and triallyl isocyanurate was obtained (hydrosilyl valence 2). .30 mol / kg, average number of hydrosilyls per molecule 2.5: component (B)) was obtained.

(Manufacturing Example 7)
570 g of 1,3,5,7-tetramethylcyclotetrasiloxane (corresponding to (α1)) and toluene 525 were uniformly mixed and stirred at 105 ° C. under a nitrogen atmosphere. A mixed solution of 120 g of diallyl monoglycidyl isocyanurate (corresponding to (α2)), 0.05 g of a xylene solution of a platinum vinyl siloxane complex (containing 3 wt% as platinum) and 120 g of toluene was added dropwise over 40 minutes, and the mixture was added dropwise at 105 ° C. for 4 hours. It was reacted. By distilling off the unreacted component and toluene under reduced pressure, 303 g of the reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane and diallylmonoglycidyl isocyanurate was obtained (hydrosilyl value: 7.70 mmol / g: (A). Ingredients) obtained.

(Manufacturing Example 8)
43 g of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (corresponding to (α1)) and 43 g of toluene were uniformly mixed and stirred at 105 ° C. under a nitrogen atmosphere. 1,5-Dietenyl-1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane 100g (corresponding to (β'3)), xylene solution of platinum vinylsiloxane complex (containing 3wt% as platinum) 0 A mixed solution of .03 g and 200 g of toluene was added dropwise over 40 minutes, and the mixture was reacted at 105 ° C. for 4 hours. By distilling off the unreacted components and toluene under reduced pressure, 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane and 1,5-diethenyl-1,1,5,5-tetramethyl-3 , 3-Diphenyltrisiloxane reaction product was obtained in 100 g (alkenyl value: 1.80 mmol / g: component (C)).

(Manufacturing Example 9)
75 g of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (corresponding to (α1)) and 75 g of toluene were uniformly mixed and stirred at 105 ° C. under a nitrogen atmosphere. A mixed solution of 100 g of diallyl monomethylisocyanurate (corresponding to (β'4)), 0.03 g of a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) and 200 g of toluene was added dropwise over 40 minutes, and 4 at 105 ° C. Reacted for time. By distilling off the unreacted component and toluene under reduced pressure, 140 g of a reaction product of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane and diallylmonomethylisocyanurate was obtained (alkenyl value: 2.40 mmol / g). : (C) component) obtained.

(Example 1)
To 6.63 g of the reaction product obtained in Production Example 1, 2.89 g of diallyl monomethyl isocyanurate, 0.47 g of 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, and xylene of the platinum vinylsiloxane complex. Add 4.0 μL of a solution (platinum vinylsiloxane complex containing 3 wt% as platinum, Pt-VTSC-3X manufactured by Yumicoa Precious Metals Japan), 7.2 μL of ethynylcyclohexanol, and 0.4 μL of dimethyl maleate, and stir and mix uniformly. After that, a curable composition was prepared by further stirring for 3 minutes, defoaming for 3 minutes, and stirring for 3 minutes using Awatori Rentaro AR-250 manufactured by Thinky.

Separately, a 3030 reflector (product number: SDI4G62) manufactured by SDI, which mounts two 20 mil x 40 mil square blue LED chips (part number: B2040CCI4 V31 P45C-31) manufactured by Generites, was prepared. The prepared unsealed LED was irradiated with Ar plasma using a plasma cleaner manufactured by SAMCO (irradiation at 20 Pa, 130 W, 5 SCCM for 10 seconds). The obtained curable composition was injected into an unsealed LED within 30 minutes after the completion of the above stirring and defoaming and within 1 hour from plasma irradiation using a dispenser ML5000-XII manufactured by Musashi Engineering Co., Ltd. Within 30 minutes after the injection, the temperature was raised in the convection oven in the order of 80 ° C. for 120 minutes, 100 ° C. for 60 minutes, and 150 ° C. for 300 minutes and cured to obtain an optical semiconductor device.

(Liquid tank cold shock test)
100 optical semiconductor devices manufactured in the above examples were mounted on a printed circuit board (manufactured by FR4) by reflow at 260 ° C. using a lead-free solder paste manufactured by Matsuo Solder (product number: FLF01-BZ (L)). After mounting, use the ESPEC liquid tank type thermal shock device (model: TSB-21) to cycle the optical semiconductor device at -45 ° C (3 minutes) ⇔ transfer time within 10 seconds ⇔ 125 ° C (3 minutes). The test was conducted as. In the liquid tank type thermal shock test, if at least one of LED non-lighting, peeling at the interface between the sealant and the reflector, and cracks in the sealant occurs, it is judged to be NG, and the number of NG products is tested. The number of cycles exceeding 10% of the number of implementations was defined as the number of life cycles (times) of the sample.

(Examples 2 to 16, Comparative Examples 1 to 10)
The test was carried out in the same procedure as in Example 1 except that the curable composition was prepared according to the compounding ratios shown in Table 1.
The compounding composition and the number of life cycles of Examples and Comparative Examples are shown in Table 1.
As shown in Table 1, in the optical semiconductor device using the curability of the present invention, the number of life cycles was extended and the liquid tank thermal shock resistance was improved as compared with the comparative example.

The abbreviations used in the table are as follows.
(B) Component (B-1): 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (B-2): Dimethylhydrogensilyl terminal-blocking polymethylphenylsiloxane (polystyrene conversion by GPC measurement) Number average molecular weight = 1000)

(C) Component (C-1): Dialyl monomethylisocyanurate (C-2): 1,5-divinyl-1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (C-3): Dimethylvinylsilyl group-terminated blocked polymethylphenylsiloxane (number average molecular weight in terms of polystyrene measured by GPC = 2800)

(D) Component (D-1): Xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, manufactured by Yumicoa Precious Metals Japan, Pt-VTSC-3X)

(Other ingredients)
(Other-1): 3-((trimethylsilyl) oxy) -1,1,5,5-tetramethyl-3-phenyltrisiloxane

1 LED chip 2 Reflector 3 Cured product of polysiloxane-based composition 4 Lead 5 Bonding wire 6 Fluorescent material

Claims (4)

(A) A hydrosilylation reaction product of a polysiloxane (α1) having at least two hydrosilyl groups in one molecule and an organic compound (α2) represented by the following general formula (1) in one molecule. Compounds with at least 3 hydrosilyl groups,
(B) A polysiloxane having an average of 1.5 to 2.5 hydrosilyl groups in one molecule,
(C) An organic compound represented by the following general formula (5) , or a polysiloxane having two or more alkenyl groups in one molecule, and
(D) Contains a hydrosilylation catalyst,
The component (A) is a hydrosilylation reaction product of an organic compound (α3) having one epoxy group and / or one oxetanyl group and one alkenyl group in one molecule in addition to (α1) and (α2). There is a curable composition.

(In the general formula (1), R ¹ to R ³ represent a monovalent organic group or a hydrogen atom having 1 to 50 carbon atoms, and may be different or the same, but R ¹ to R. At least one of the three is an alkenyl group. ⁾

(In the general formula (5), R ¹⁵ to R ¹⁷ represent monovalent organic groups or hydrogen atoms having 1 to 50 carbon atoms, and may be different or the same, but R ¹⁵ to R. At least two of the ¹⁷ are alkenyl groups.) The curable composition according to claim 1, wherein the amount of the component (B) is 2 to 100% by weight with respect to 100% by weight of the component (A). (B) The curable composition according to claim 1 or 2 , wherein the component has two hydrosilyl groups in one molecule. An optical semiconductor device using the curable composition according to any one of claims 1 to 3 as a sealing agent.

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