JP2018184574A - Curable resin composition, sealing resin made from curable resin composition, and light-emitting device using sealing resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition which enables an ultraviolet emitting element to highly combine ultraviolet light resistance with transparency to ultraviolet, a sealing resin made from the curable resin composition, and a light-emitting device using sealing resin.SOLUTION: The curable resin composition is provided which contains a compound (A) containing at least two or more SiH groups in one molecule, a compound (B) containing at least two alkenyl groups in one molecule, a hydrosilylation catalyst (C) and silica (D) having a specific surface area by BET method of 1 m/g-150 m/g, wherein pts.wt. of (D) is 30 pts.wt. to 200 pts.wt. with respect to 100 pts.wt. of (A), (B) and (C), and (D) is surface treated with polydimethylsiloxane. The sealing resin made from the curable resin composition, and a light-emitting device using sealing resin are also provided.SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition, a sealing resin composed of the curable resin composition, and a light emitting device using the sealing resin.

  A light emitting device using a light emitting diode (LED) has features such as long life, low power consumption, impact resistance, high speed response, lightness, thinness, and the like, such as a liquid crystal display, a mobile phone, an information terminal, etc. Development of various fields such as backlights, in-vehicle lighting, indoor / outdoor advertising, indoor / outdoor lighting, etc. has been progressing dramatically. In addition, there is a need for further improvement in reliability along with the variety of uses.

  In particular, ultraviolet light emitting devices having an emission wavelength of less than 400 nm are desired to be developed in medical fields such as phototherapy, industrial fields such as resin curing and adhesion, and consumer fields such as sterilizing lamps. Is an urgent need.

  Since sealing resin for ultraviolet light emitting elements is exposed to high energy ultraviolet light, high durability is required. In addition, since transparency to ultraviolet light is essential, fluorine-based resins (Patent Documents 1 and 2) and silicone resins (Patent Document 3) have been proposed, but it cannot be said that they are still sufficient. .

JP 2007-311707 A WO2014 / 178288 WO2016 / 052495

  In a UV light emitting element, a curable resin composition capable of achieving both high UV resistance and transparency to UV light, a sealing resin comprising the curable resin composition, and a light emitting device using the sealing resin The purpose is to provide.

The gist of the present invention is as follows.
[1] Compound (A) containing at least two SiH groups in one molecule, Compound (B) containing at least two alkenyl groups in one molecule, hydrosilylation catalyst (C), ratio by BET method surface area containing silica (D) of ^{1m 2} / ^g~150m 2 / g,
The weight part of (D) is 30 to 200 parts by weight with respect to (A) + (B) + (C) = 100 parts by weight,
(D) is a curable resin composition characterized in that surface treatment is performed with polydimethylsiloxane.

  [2] The curable resin composition according to [1] 1, wherein the compound (A) containing at least two SiH groups in one molecule has a polysiloxane structure.

  [3] The curable resin composition according to either [1] or [2], wherein the compound (B) containing at least two alkenyl groups in one molecule has a polysiloxane structure. .

  [4] Obtained by curing a compound (A) containing at least two SiH groups in one molecule, a compound (B) containing at least two alkenyl groups in one molecule, and a hydrosilylation catalyst (C). The curable composition according to any one of [1] to [3], wherein the cured product has a refractive index of 1.42 to 1.50.

  [5] A sealing resin comprising the curable composition according to any one of [1] to [4].

  [6] A light emitting device having an emission wavelength of 200 nm to 400 nm, wherein the curable composition according to any one of [1] to [4] is used as a sealing resin.

  ADVANTAGE OF THE INVENTION According to this invention, in an ultraviolet light emitting element, providing the sealing resin which consists of a curable resin composition and the curable resin composition which can make UV resistance and transparency with respect to an ultraviolet-ray highly compatible. it can.

It is a schematic sectional drawing for demonstrating the structure of the ultraviolet-ray light-emitting device 1 which is an example of the light-emitting device of this invention.

  The curable resin composition of the present invention comprises a compound (A) containing at least two SiH groups in one molecule, a compound (B) containing at least two alkenyl groups in one molecule, a hydrosilylation catalyst ( C), containing silica (D) having a specific surface area of 1 m <2> / g to 150 m <2> / g according to the BET method, wherein (D) parts by weight are (A) + (B) + (C) = 100 parts by weight 30 parts by weight to 200 parts by weight, and (D) is characterized in that the surface treatment is performed with polydimethylsiloxane. Hereinafter, it demonstrates in order.

<Compound (A) containing at least two SiH groups in one molecule>
The compound (A) having two or more SiH groups in one molecule used in the curable composition of the present invention is not particularly limited, but preferably has a polysiloxane structure from the viewpoint of ultraviolet resistance. . Examples thereof include, but are not limited to, a silphenylene compound, a linear polysiloxane, a cyclic polysiloxane, and a modified polysiloxane (A-1) containing a hydrosilyl group. Moreover, these may be used independently and may use 2 or more types together.

Examples of the silphenylene compound having a hydrosilyl group include a structure in which aromatic cyclic hydrogen is substituted with a substituent having a SiH group. Specifically, 1,2-bis (dimethylsilyl) benzene, 1,3-bis (dimethylsilyl) benzene, 1,4-bis (dimethylsilyl) benzene, 1,2-bis (dimethylsilyl) naphthalene, , 3-bis (dimethylsilyl) naphthalene, 1,4-bis (dimethylsilyl) naphthalene, 1,5-bis (dimethylsilyl) naphthalene, 1,6-bis (dimethylsilyl) naphthalene, 1,7-bis (dimethyl) And silyl) naphthalene, 1,8-bis (dimethylsilyl) naphthalene, and the like.
The linear polysiloxane having a hydrosilyl group includes a copolymer of a dimethylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, and a copolymer of a diphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit. Copolymers, copolymers of methylphenylsiloxane units and methylhydrogensiloxane units and terminal trimethylsiloxy units, polydimethylsiloxane blocked at the end with dimethylhydrogensilyl groups, polyblocked at the ends with dimethylhydrogensilyl groups Examples thereof include diphenylsiloxane and polymethylphenylsiloxane blocked at the end with a dimethylhydrogensilyl group.

  Examples of the cyclic siloxane having a hydrosilyl group include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1. , 3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen -1,3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7, Examples include 9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane.

<Modified polysiloxane containing hydrosilyl group (A-1)>
The polysiloxane modified body (A-1) containing a hydrosilyl group in the present invention is not particularly limited as long as it is a polysiloxane compound containing a hydrosilyl group in the molecular skeleton, but for example, a polysiloxane compound containing an alkenyl group. On the other hand, it is possible to obtain a compound having a hydrosilyl group capable of hydrosilylation reaction by modification. The modified polysiloxane obtained in the present invention is preferably liquid at a temperature of 20 ° C. from the viewpoints of handling properties and moldability.

The preferable modified polysiloxane (A-1) in the present invention will be specifically described. A preferred modified polysiloxane in the present invention is characterized in that [XR ⁶ ₂ SiO—SiO _3/2 ] is an essential unit as a siloxane unit having a functional group capable of reacting, and the physical properties are adjusted as necessary. any siloxane units as a unit containing _{^{[R 7 3 SiO-SiO 3/2}} ] as constituent units of the following general formula (1),
[XR ⁶ ₂ SiO—SiO _3/2 ] _a [R ⁷ ₃ SiO—SiO _3/2 ] _b (1)
(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; X is the following general formula (2)

Or the following general formula (3)

R ⁶ is an alkyl group, an aryl group, an alkenyl group, a hydrogen atom, or a group connected to another polysiloxane; R ⁷ is an alkyl group, an aryl group, or another poly group Examples thereof include polysiloxane modified products composed of siloxane units represented by a group linked to siloxane. Here, a is an average of 1 or more, preferably 2 or more, and b is 0 or an integer of 1 or more. a + b is an integer of 6 to 24, preferably an integer of 6 to 12.
(L is an integer greater than or equal to 2; m is an integer greater than or equal to 0; n is an integer greater than or equal to 2; Y is bonded to a polysiloxane via 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 polysiloxane via an alkylene chain, Provided that at least one of Y or Z is an alkenyl group or a hydrogen atom; R is an alkyl group or an aryl group; and when there are a plurality of X, the formula (2) or the formula (The structure of (3) may be different, and the structure of formula (2) or formula (3) may be mixed)
Hereinafter, a siloxane unit having a reactive functional group
[XR ⁶ ₂ SiO—SiO _3/2 ]
Will be described in detail.

The siloxane unit having a functional group capable of reacting, for example, causes a crosslinking reaction with a curing agent by a hydrosilylation reaction in the presence of a hydrosilylation catalyst described later, or in the presence of a thermal curing initiator or a photocuring initiator. It is a unit that plays a role of crosslinking and curing.
The modified polysiloxane containing a hydrosilyl group of the present invention is a modified product having a structure of the formula (2) or (3) as the group X having a reactive functional group and containing at least one hydrosilyl group. If there is no particular limitation, m is preferably an integer of 1 to 7, and n is preferably an integer of 2 to 4.

As R ⁶ in the siloxane unit having a reactive functional group, a substituent having substantially no reactivity, specifically, for example, an alkyl group or an aryl group can be used.

  The siloxane unit having a functional group capable of reacting in the present invention preferably contains, on average, two or more siloxane units constituting the polyhedral skeleton. That is, a in the general formula (1) is preferably 2 or more. When there are few siloxane units containing the reactive functional group to contain, sclerosis | hardenability will become inadequate and there exists a possibility that the intensity | strength of the hardened | cured material obtained may fall.

Then any siloxane unit
^{_{[R 7 3 SiO-SiO 3/2}} ]
Will be described.
This siloxane unit is a unit for adjusting the physical properties of the modified polysiloxane in the present invention and the resulting cured product. Since the present siloxane unit does not substantially contain a reactive substituent, it is possible to adjust the crosslinking density, improve the film property, leveling property, improve brittleness, and the like.

As R ⁷ in the present siloxane unit, an alkyl group, an aryl group, or a group linked to another polysiloxane can be suitably used. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. May be replaced. Specific examples of the alkyl group partially substituted with a substituent having substantially no reactivity include, for example, a polysiloxanylalkyl group. Leveling properties and film properties, and a curing agent described later and Compatibility with a curing initiator can be imparted, and the properties of the compound can be made liquid.

  The polysiloxane modified body (A-1) in the present invention is preferably an organically modified polysiloxane modified body (A-1) ′ described later from the viewpoint of gas barrier properties.

<Organic modified polysiloxane modified (A-1) '>
The organically modified polysiloxane modified body (A-1) ′ in the present invention has an alkenyl group-containing polysiloxane compound (a) and one alkenyl group in one molecule in the presence of a hydrosilylation catalyst described later. It can be obtained by hydrosilylating the organosilicon compound (c) and / or the cyclic olefin compound (d) having one alkenyl group in one molecule with the compound (b) having a hydrosilyl group. The method for obtaining the organically modified polysiloxane modified product (A-1) ′ of the present invention is not particularly limited and can be variously set, but after reacting the component (a) and the component (b) in advance, (c ) And / or (d) component, or after reacting (c) and / or (d) component with (b) component in advance, (a) component may be reacted, The component (a) may be allowed to react with the component (b) in the presence of the component (c) and / or the component (d). 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 that does not contain the component (a) in which only the component (c) and / or the component (d) and the component (b) are reacted, the component (a) and the component (b) are reacted, A method of reacting the components (c) and / or (d) after distilling off the unreacted component (b) is preferred.
A part of the alkenyl group of the component (a) used in the reaction may remain in the organically modified polysiloxane modified product (A-1) ′ thus obtained.

Although there is no restriction | limiting in particular as an addition amount of the hydrosilylation catalyst used at the time of the synthesis | combination of the organic modified polysiloxane modified body (A-1) ', (a) component and (c) and / or (d) component used for reaction It is good to use in the range of 10 ^{< -1} > ^-10 < ^-10 > mol with respect to 1 mol of alkenyl groups. Preferably it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. When there are many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it absorbs light with a short wavelength, which may cause coloration or decrease the light resistance of the resulting cured product. There is also a risk of foaming. Moreover, when there are few hydrosilylation catalysts, reaction may not progress and there exists a possibility that a target object may not be obtained.

  As reaction temperature of hydrosilylation reaction, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC, More preferably, it is 45-140 degreeC. If the temperature is too low, the reaction does not proceed sufficiently, and if the temperature is too high, gelation may occur and handling properties may deteriorate.

  The organically modified polysiloxane modified product (A-1) ′ thus obtained can ensure compatibility with various compounds, particularly siloxane compounds, and further has a hydrosilyl group introduced into the molecule. Therefore, it can be reacted with a compound having various alkenyl groups. Specifically, a cured product can be obtained by reacting with a compound (B-3) having two or more alkenyl groups in one molecule described later.

  In addition, the organically modified polysiloxane modified body (A-1) ′ in the present invention can be liquefied at a temperature of 20 ° C. The organically modified polysiloxane-modified product (A-1) ′ is preferably in a liquid form because of excellent handling properties.

The modified organic polysiloxane (A-1) ′ in the present invention is represented by the general formula (4).
[XR ⁶ ₂ SiO—SiO _3/2 ] _a [R ⁷ ₃ SiO—SiO _3/2 ] _b (4)
[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.

{L is an integer greater than or equal to 2; m is an integer greater than or equal to 0; n is an integer greater than or equal to 2; Y is bonded to a polysiloxane via a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain It 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 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 (7).
^{_{- [CH 2] l -R 8}} (7)
(L is an integer greater than or equal to 0; R ⁸ is a group containing an organosilicon compound); R is an alkyl group or an aryl group}]
It is a polysiloxane type compound comprised from the siloxane unit represented by these.
The polysiloxane modified (A-1) ′ thus obtained was organically modified by controlling the addition amount of components (a) to (d), reaction sequence, reaction time, reaction temperature and the like. It is possible to control the viscosity of the modified polysiloxane (A-1) ′. In addition, the viscosity of the polysiloxane composition (B) can be adjusted by controlling the viscosity of the modified polysiloxane (A-1) ′. The viscosity of the modified polysiloxane (A-1) ′ is not particularly limited, but when the modified polysiloxane (A-1) ′ is liquid at a temperature of 20 ° C., the viscosity at 20 ° C. is 0.01 Pa · It is preferably s to 500 Pa · s, more preferably 1 Pa · s to 300 Pa · s. If the viscosity of the modified polysiloxane (A-1) ′ is too low, the viscosity of the polysiloxane composition described later is lowered, and additives such as phosphors may settle without being dispersed. If the viscosity is too high, the handling property may be deteriorated.
Further, the organically modified polysiloxane modified product (A-1) ′ has at least three hydrosilyl groups in the molecule from the viewpoint of the strength and hardness of the obtained cured product, and further, heat resistance and light resistance. It is preferable to have.

<Polysiloxane compound having alkenyl group (a)>
The polysiloxane compound (a) having an alkenyl group in the present invention is not particularly limited as long as it is a polysiloxane having an alkenyl group in the molecule and having a polyhedral skeleton. Specifically, for example, the following general formula (8)
[R ⁹ SiO _3/2 ] _x [R ¹⁰ SiO _3/2 ] _y (8)
(X + y is an integer of 6 to 24; x is an integer of 1 or more, y is 0 or an integer of 1 or more; R ⁹ is an alkenyl group or a group having an alkenyl group; R ¹⁰ is any organic group, or Groups linked to other polyhedral skeleton polysiloxanes)
An alkenyl group-containing polysiloxane compound composed of a siloxane unit represented by the formula (9) can be suitably used.
[AR ⁶ ₂ SiO—SiO _3/2 ] _a [R ⁷ ₃ SiO—SiO _3/2 ] _b (9)
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ⁶ is an alkyl group or an aryl group; R ⁷ is a hydrogen atom or an alkyl group , Aryl groups, or groups linked to other polyhedral skeleton polysiloxanes)
The alkenyl group containing polysiloxane type compound comprised from the siloxane unit represented by this is illustrated as a preferable thing.

  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 ⁶ 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 ⁶ in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.
R ⁷ is a hydrogen atom, an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a cyclopentyl group. Examples of the aryl group include aryl groups such as a phenyl group and a tolyl group. Is done. R ⁷ in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.
a is not particularly limited as long as it is an integer of 1 or more, but is preferably 2 or more, and more preferably 3 or more, from the handleability of the compound and the physical properties of the resulting cured product. Further, b is not particularly limited as long as it is 0 or an integer of 1 or more.
The sum of a and b (= a + b) is an integer from 6 to 24, but from the viewpoint of the stability of the compound and the stability of the resulting cured product, it should be 6 to 12, and more preferably 6 to 10. preferable.

The method for synthesizing the component (a) is not particularly limited, and the component can be synthesized using a known method. As a synthesis method, for example, R ¹¹ SiXa ₃ (wherein R11 represents R ⁶ or R ⁷ described above, and Xa represents a hydrolyzable functional group such as a halogen atom or an alkoxy group) is added to a silane compound. It is obtained by a decomposition condensation reaction. Alternatively, after synthesizing a trisilanol compound having three silanol groups in the molecule by hydrolytic condensation reaction of R ¹¹ SiXa _3, the ring is closed by reacting the same or different trifunctional silane compounds, and polysiloxane A method of synthesizing is 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 the present synthesis method, a silicate having is obtained by 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 polysiloxane in which the Si atom to be formed and the alkenyl group are bonded via a siloxane bond. In the present invention, a similar polysiloxane can be obtained from a substance containing silica such as silica or rice husk instead of tetraalkoxysilane.

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

The linear polysiloxane having a hydrosilyl group includes a copolymer of a dimethylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, and a copolymer of a diphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit. Copolymers, copolymers of methylphenylsiloxane units and methylhydrogensiloxane units and terminal trimethylsiloxy units, polydimethylsiloxane blocked at the end with dimethylhydrogensilyl groups, polyblocked at the ends with dimethylhydrogensilyl groups Examples thereof include diphenylsiloxane and polymethylphenylsiloxane blocked at the end with a dimethylhydrogensilyl group.
In particular, as a linear polysiloxane having a hydrosilyl group, a polysiloxane having a molecular end blocked with a dimethylhydrogensilyl group from the viewpoints of reactivity during modification, heat resistance of the resulting cured product, light resistance, etc. Furthermore, polydimethylsiloxane having a molecular end blocked with a dimethylhydrogensilyl group can be suitably used. Specific examples thereof include tetramethyldisiloxane and hexamethyltrisiloxane.

Examples of the cyclic siloxane having a hydrosilyl group include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1. , 3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen -1,3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7, Examples include 9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane. Specific examples of the cyclic siloxane in the present invention include, for example, 1,3,5,7-tetrahydro, from the viewpoints of industrial availability and reactivity, or heat resistance, light resistance, strength, and the like of the resulting cured product. Gen-1,3,5,7-tetramethylcyclotetrasiloxane can be preferably used.
These compounds (b), which have a hydrosilyl group, may be used alone or in combination of two or more.

<Organic silicon compound (c) having one alkenyl group in one molecule>
In the present invention, the organosilicon compound (c) having one alkenyl group per molecule reacts with the hydrosilyl group of the compound (b) having a hydrosilyl group. By using the component (c), the elastic modulus of the obtained cured product can be reduced, and the thermal shock resistance can be improved.

Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.
The component (c) in the present invention is not particularly limited as long as it is an organosilicon compound having one alkenyl group in one molecule, but it is a gas barrier that at least one aryl group is contained in one molecule. From the viewpoint of heat resistance and refractive index, it is more preferable that the aryl group is directly bonded to the silicon atom from the viewpoint of heat resistance and light resistance.

The component (c) in the present invention is preferably silane or polysiloxane from the viewpoints of heat resistance and light resistance. When the component (c) is a silane having one alkenyl group in one molecule, specifically, for example, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, triphenylvinylsilane, triethylvinylsilane, diethylphenylvinylsilane And ethyldiphenylvinylsilane, allyltrimethylsilane, allyldimethylphenylsilane, allylmethyldiphenylsilane, allyltriphenylsilane, allyltriethylsilane, allyldiethylphenylsilane, allylethyldiphenylsilane, and the like. Among these, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, and triphenylvinylsilane are preferable examples from the viewpoint of heat resistance and light resistance, and dimethylphenylvinylsilane and methyldiphenylvinylsilane are also preferable from the viewpoint of gas barrier properties and refractive index. Triphenylvinylsilane is a preferred example.
In addition, when the component (c) is a polysiloxane, examples include a linear polysiloxane having one alkenyl group, a polysiloxane having one alkenyl group at the molecular end, and a cyclic siloxane having one alkenyl group. .

  When the component (c) is a linear polysiloxane having one alkenyl group, specifically, for example, polydimethylsiloxane, dimethylvinyl each having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group. Polymethylphenylsiloxane blocked with a silyl group and a trimethylsilyl group each at one end, polydiphenylsiloxane blocked with a dimethylvinylsilyl group and a trimethylsilyl group respectively, and terminated with a dimethylvinylsilyl group and a trimethylsilyl group A copolymer of a dimethylsiloxane unit and a methylphenylsiloxane unit, each of which is blocked one by one, a dimethylsiloxane unit and a diphenylsiloxane unit each having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group. Copolymers, copolymers of terminal and methylphenylsiloxane units and diphenylsiloxane units are blocked one by one, respectively dimethylvinylsilyl group and trimethylsilyl group and the like.

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

When the component (c) 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.
These (c) component organosilicon compounds having one alkenyl group per molecule may be used alone or in combination of two or more.

<Cyclic olefin compound (d) having one alkenyl group in one molecule>
(D) component in this invention should just be a cyclic olefin compound which has one carbon-carbon double bond in 1 molecule, and this carbon-carbon double bond is any of a vinylene group, a vinylidene group, and an alkenyl group. It may be. 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.
In addition, the component (d) in the present invention preferably has an average molecular weight of 1000 or less from the viewpoint of reactivity with the component (b). Examples of such cyclic olefin compounds include aliphatic cyclic olefin compounds and substituted aliphatic cyclic olefin compounds.

  Specific examples of the aliphatic cyclic olefin compound include cyclohexene, cycloheptene, cyclooctene, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, allylcyclohexane, allylcycloheptane, allylcyclooctane, and methylenecyclohexane. It is done.

  Specific examples of the substituted aliphatic cyclic olefin compound include norbornene, 1-methylnorbornene, 2-methylnorbornene, 7-methylnorbornene, z2-vinylnorbornane, 7-vinylnorbornane, 2-allylnorbornane, 7-allylnorbornane, 2-methylene norbornane, 7-methylene norbornane, camphene, vinyl norcamphene, 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-heptaene, 2-vinyladamantane, 2-methyleneadamantane and the like.

Among these, cyclohexene, vinylcyclohexane, norbornene, camphene, and pinene are preferable examples from the viewpoint of availability.
These cyclic olefin compounds (d) having one alkenyl group in one molecule may be used alone or in combination of two or more.

  The amount of the cyclic olefin compound (d) having one alkenyl group in one molecule is such that the number of alkenyl groups in the component (d) is 0 per hydrosilyl group of the compound (b) having a hydrosilyl group described later. It is preferable to use so that it may become 0.01-0.5 piece. When the addition amount is small, the thermal shock resistance of the resulting cured product may be lowered, and when the addition amount is large, a curing failure may occur in the resulting cured product.

<Compound (B) containing at least two alkenyl groups in one molecule>
The compound (B) containing at least two alkenyl groups in one molecule used in the present invention is not particularly limited, but preferably has a polysiloxane structure from the viewpoint of ultraviolet resistance. Examples thereof include, but are not limited to, polysiloxane (B1) having two or more alkenyl groups in one molecule.

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

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

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

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

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

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

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

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

<Hydrosilylation catalyst (C)>
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, platinum alone, a carrier (alumina, silica, carbon black, polymer, etc.) supported by solid platinum; a platinum-vinylsiloxane complex, for example, 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 are integers) represented), 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 Country Patent No. 3220972 No. platinum Arcola described in the 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.

<Refractive index>
In order to obtain transparency to ultraviolet rays of the curable resin composition containing compound (A), compound (B), catalyst (C) and silica (D), compound (A), compound (B) and catalyst (C) The refractive index of the cured product obtained by curing is preferably 1.42 or more and 1.50 or less. The refractive index in the present invention refers to the refractive index at a temperature of 23 ° C. and a wavelength of 589 nm determined by the prism coupler method.

  The lower limit of the refractive index is preferably 1.42, more preferably 1.43, and still more preferably 1.44. Further, the upper limit of the refractive index is preferably 1.50, more preferably 1.48, and still more preferably 1.46. When the refractive index is lower than 1.42, transparency to ultraviolet rays of the curable resin composition containing the compound (A), the compound (B), the catalyst (C) and the silica (D) tends to decrease, It is not preferable. Moreover, when refractive index is higher than 1.50, the transparency with respect to the ultraviolet-ray of the curable resin composition containing a compound (A), a compound (B), a catalyst (C), and a silica (D) tends to fall. Yes, not preferred.

<Silica having a specific surface area by the BET method of ^{1m 2 / g~150m 2 / g (} D)>
The Nanorishika that can be used in the present invention, the specific surface area by BET method if ^{1m 2} / ^g~150m 2 / g, not particularly limited. The specific surface area by the BET method is a value measured by a method based on JIS Z8830.

  The curable resin composition of the present invention can improve ultraviolet resistance by adding silica (D).

  Silica (D) is preferably surface-treated with polydimethylsiloxane. By surface-treating with polydimethylsiloxane, the addition amount is improved while suppressing thickening, and the transmittance of the resulting thermosetting resin composition tends to be high.

Specific lower limit of the surface area by the BET method of the silica (D) is preferably from ^{1 m} 2 / g, more preferably ^{10m 2 / g, 20m 2 /} g is more preferable. The upper limit of the BET specific surface area of the silica (D) is preferably from 150 meters ² / g, more preferably 120 m ² / g, ^{80 m} more preferably 2 / g, particularly preferably ^{50 m} 2 / g. When the specific surface area is smaller than 1 m ² / g, silica (D) tends to aggregate in the resin components ((A) and (B)), which is not preferable. On the other hand, when the specific surface area is larger than 150 m ² / g, the resulting curable resin composition tends to be poor in fluidity, and the workability when sealing the LED is unfavorable.

  Examples of the shape of silica (D) include a true sphere, an oblong sphere, a flake shape, a flat plate shape, a needle shape, a fiber shape, an amorphous shape, a hollow shape, and a shape obtained by crushing or mechanically processing fillers of these shapes, etc. However, it is not limited to these.

  The lower limit of the primary particle diameter of silica (D) is preferably 5 nm, more preferably 10 nm, still more preferably 15 nm, and particularly preferably 20 nm. Further, the upper limit is preferably 70 nm, more preferably 60 nm, and particularly preferably 50 nm. When the primary particle diameter is smaller than 5 nm, the resulting curable resin composition tends to be poor in fluidity, and the workability when sealing the LED may be inferior. When the primary particle diameter is larger than 70 nm, the size of the primary particles or the secondary particles is increased, and ultraviolet rays are scattered to reduce the transmittance.

  Silica (D) can be surface-treated as necessary. Examples of the surface treatment include a hydrophobic treatment and a hydrophilic treatment. Hydrophobic treatment is preferable from the viewpoint of improving filler filling amount while suppressing thickening, and hydrophilic treatment is preferable from the viewpoint of thickening. These surface treatments can be selected according to the required properties. Moreover, in order to adjust a viscosity, hydrophobic processing silica and hydrophilic processing silica can be used together.

  The lower limit of the content of silica (D) is preferably 30 parts by weight, more preferably 45 parts by weight, still more preferably 65 parts by weight, and particularly preferably 80 parts by weight. The upper limit of the content of silica (D) is preferably 200 parts by weight, more preferably 150 parts by weight, still more preferably 130 parts by weight, and particularly preferably 120 parts by weight. When the content is less than 30 parts by weight, the ultraviolet resistance tends to be inferior, which is not preferable. Also. When there is more content than 200 weight part, there exists a tendency for fluidity | liquidity to be scarce and it may be inferior to the workability | operativity at the time of sealing LED, and is unpreferable.

There is no restriction | limiting in particular in the kind of silica (D), Quartz, fumed silica, silicic anhydride, fused silica, crystalline silica, amorphous silica, etc. are mentioned.
The means for mixing the silica (D) is not particularly limited, but specifically, for example, a two-roll or three-roll, a planetary stirring deaerator, a homogenizer, a dissolver, a planetary mixer, etc. And a melt kneader such as a plast mill. The mixing of silica (D) 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.

<Curable resin composition>
The curable resin composition in the present invention can be obtained by mixing a phosphor, a curing retarder, and the like as necessary.

  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 organic phosphors can be used. Specifically, for example, YAG phosphor, TAG phosphor, orthosilicate alkaline earth phosphor, α-sialon phosphor, β-sialon phosphor, CASN phosphor, S-CASN phosphor , Nitride and oxynitride phosphors, KSF 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. There is no particular limitation on the amount of phosphor used, and any amount can be used to obtain the light emission color required by the semiconductor light emitting device. However, if exemplified, it is preferable in the curable resin composition. Is 0.1% by weight or more, more preferably 1% by weight or more, still more preferably 2% by weight or more, preferably 150% by weight or less, more preferably 100% by weight or less. If the amount of phosphor used is small, wavelength conversion by the phosphor may be insufficient, and the target emission color may not be obtained. If the amount of phosphor used is large, the handleability of the composition may be reduced. There is a possibility that the utilization efficiency of the phosphor may be lowered due to the optical interference action.

  The method of mixing the phosphor with the curable resin composition is not particularly limited as long as it is a method capable of uniformly mixing the phosphor without damaging the crystal structure of the phosphor. A conventionally known method such as a homogenizer, three rolls, two rolls, a kneader, or a bead mill can be used. Of these, planetary agitation mixers, 3 rolls, 2 rolls, etc., which generate less heat during mixing and those with less metal wear particles from the mixer are preferred. This is preferable because it can be mixed with little degassing. These mixing methods may be performed alone or in combination of two or more.

  The viscosity of the curable resin composition used in the present invention is not particularly limited, but is preferably 0.1 Pa · s to 500 Pa · s, more preferably 0.3 Pa · s to 300 Pa · s at a temperature of 23 ° C. s. When the viscosity of the curable resin composition is lower than 0.1 Pa · s, there is a possibility that the phosphor is settled and chromaticity deviation between individuals increases, which is not preferable. Moreover, when the viscosity is higher than 500 Pa · s, the handling property of the curable resin composition may be deteriorated, which is not preferable.

  When adding temperature when hardening curable resin composition, Preferably it is 30-400 degreeC, More preferably, it is 50-250 degreeC. When the curing temperature is high, the resulting cured product tends to have poor appearance, and when it is low, curing is insufficient. Moreover, you may make it harden | cure combining the temperature conditions of two or more steps. Specifically, for example, by raising the curing temperature stepwise such as 80 ° C., 120 ° C., 150 ° C., 170 ° C., and 220 ° C., a preferable cured product can be obtained.

  The curing time can be appropriately selected depending on the curing temperature, the amount of hydrosilylation catalyst used and the amount of reactive groups, and other combinations of the curable composition. A good cured product can be obtained by performing the treatment for a time, preferably 1 minute to 12 hours.

  In order to improve the storage stability of the curable composition used in the present invention or to adjust the hydrosilylation reactivity during the curing process, a curing retarder may be used. 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, organosulfur compounds, Nitrogen-containing compounds, tin compounds, organic peroxides and the like can be mentioned. 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.

  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 acryl group such as 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Is mentioned. These may be used alone or in combination of two or more.

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

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

  An antioxidant can be used in the curable composition used in the semiconductor light-emitting device of the present invention, if necessary. By using an antioxidant, it is possible to improve the reliability of the obtained optical semiconductor device in various reliability tests such as a heat cycle test, a high-temperature storage test, and an energization test. Examples of the antioxidant include hindered phenol-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants.

  Examples of hindered phenol compounds include 2,6-di-tert-butyl-3-methylphenol (BHT), tetrakis (methylene-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. ) Methane, n-octadecyl 3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl 3- (3′-methyl-5′-t-butyl-4 ′) -Hydroxyphenyl) -propionate, n-tetradecyl 3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6-hexanediol bis [3- (3,5-di -T-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediolbis [3- (3,5-di-t-butyl-4-hydroxyphenyl) -Propionate], 2,2'-methylene-bis (4-methyl-t-butylphenol), triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate], tetrakis [Methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5] -Methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) undecane, N, N′-bis-3- (3 ′, 5′-di) -T-butyl-4'-hydroxyphenyl) propionyl hexamethylenediamine, N, N'-tetramethylene-bis [3- (3'-methyl-5'-t-butyl-4'- Roxyphenyl) propionyl] diamine, N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionyl] hydrazine, N-salicyloyl-N′-salicylidenehydrazine, 3 -(N-salicyloyl) amino-1,2,4-triazole, N, N'-bis [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] oxyamide Etc.

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. You may heat-process.
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.

<Ultraviolet light emitting device having an emission wavelength of 200 nm to 400 nm>
Hereinafter, a mode for carrying out the present invention will be described by taking the semiconductor device shown in FIG. 1 as an example. The present invention is not limited to the illustrated example. FIG. 1 as an example of the present invention is a schematic cross-sectional view for explaining the structure of an ultraviolet light emitting device 1. In the ultraviolet light emitting device 1 of this illustrated example, the surface (bottom) of a substrate 4 having a circuit 5 is provided. The semiconductor light emitting element 2 and a side wall 7 surrounding the element 2 are attached, and a portion surrounded by the side wall 7 is referred to as a cup or cavity 6. The cavity 6 is filled with the sealing resin 3.
The semiconductor light-emitting element used in the light-emitting device of the present invention is not limited to the illustrated example, 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. The light emitting device of the present invention preferably has an emission wavelength of 200 nm to 400 nm. By setting it as the said range, the effect of this invention becomes remarkable. 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.

  Examples of light emitting elements having an emission wavelength of 200 nm to 400 nm include elements using GaN (gallium nitride), InGaN (indium gallium nitride), and AlGaN (aluminum gallium nitride) as a light emitting material.

  As a substrate having a cup or cavity (hereinafter sometimes referred to as a cup or the like) in which a semiconductor light emitting element is disposed, it can be used as long as it is conventionally used as an LED substrate or an LED package, and is not particularly limited. For example, on a substrate in which one or more lead frames provided with cups at the ends and one or more lead frames paired therewith are connected via a joint, or a large-sized insulating substrate A package substrate (surface-mounted LED substrate) or the like in which one or more cavities in which semiconductor light emitting elements are disposed are formed together with an electrode pattern, a reflector (reflector), and the like. Therefore, a bullet-type LED member can be obtained by using a substrate having at least one pair of lead frames, and a surface-mounted LED can be obtained by using a package substrate having one or more cavities on a large insulating substrate. It is done. Moreover, when the reflector part is formed in the said package board | substrate, surface mount type LED which has a reflector part is obtained. The bullet-type LED member becomes a bullet-type LED if the semiconductor light-emitting element disposed in the cup is sealed with a resin and then the periphery thereof is molded with a transparent resin. The transparent resin used at this time is not particularly limited, and the same resin as that used for sealing the semiconductor light emitting device may be used, and a conventionally known transparent resin used for the manufacture of a bullet-type LED is used. May be.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention. In the following, “parts” means “parts by weight” and “%” means “% by weight” unless otherwise specified.

(Creation of cured products for various evaluations)
The cured product used in the examples of the present invention was prepared by weighing a predetermined amount of the compound (A), the compound (B), and the hydrosilylation catalyst (C), and stirring and mixing them uniformly to prepare one liquid. Stirring and mixing were performed by operating for 3 minutes at 1200 rpm under reduced pressure using Awatori Nertaro ARV-300 manufactured by Thinky. The prepared one liquid was poured into a glass container having a space of 2 mm thickness, and cured by heating in the order of 80 ° C. for 60 minutes, 120 ° C. for 120 minutes, and 150 ° C. for 180 minutes in a convection oven.

(Measurement of refractive index)
The 2 mm-thick plate obtained above was used as a sample, and measurement was performed using a prism coupler (manufactured by Metricon Corporation, model 2010 / M). The measurement was performed at three points of 404, 594, and 827 nm, and the refractive index values at the respective wavelengths obtained were calculated by regression using Cauchy's formula to obtain the refractive index of 589 nm at 23 ° C.

(Measurement of transmittance)
Using the 2 mm-thick plate obtained above as a sample, the total light transmittance was measured in the range of 300 nm to 800 nm using a spectrophotometer (manufactured by JASCO Corporation, V-560), and the transmittance at 365 nm was recorded. .

(Evaluation of UV resistance)
A light resistance test was performed using the 2 mm-thick plate obtained above as a sample, and the maintenance ratio of the total light transmittance at 365 nm before and after the test was determined. As a light resistance test, the light irradiation surface was examined for discoloration by a light irradiation treatment under the condition of an integrated irradiation intensity of 100 MJ (black panel temperature = 120 ° C.) with a metalling weather meter. The light resistance test was performed using a metering weather meter M6T manufactured by Suga Test Instruments Co., Ltd.

(Evaluation of workability)
A thermosetting resin composition comprising the compound (A), the compound (B), the hydrosilylation catalyst (C) and the silica (D) is uniformly stirred and mixed in a 100 mL PP disposable cup, and then cleared by Musashi Engineering Co., Ltd. The operation of transferring to a syringe 3 ml (product number: PSY-3E) was performed. The evaluation was ○ when the fluidity could be easily transferred without any problem, Δ when the fluidity was poor but could be transferred, and × when the fluidity was high and could not be transferred.

(Example 1)
60 parts by weight of dimethylsiloxane A1 (terminal SiH group polydimethylsiloxane, manufactured by Gelest, product number: DMS-H11), 10 parts by weight of dimethylsiloxane A2 (internal SiH group polydimethylsiloxane, manufactured by Gelest, product number: HMS-301), phenyl silicone 30 parts by weight of B1 (1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane), a xylene solution of a platinum vinylsiloxane complex (a platinum vinylsiloxane complex containing 3 wt% as platinum, Umicore Precious Metals Japan, Pt-VTSC-3X) 10 ppm was added and stirred and mixed uniformly to create one liquid. Stirring and mixing were performed by operating for 3 minutes at 1200 rpm under reduced pressure using Awatori Nertaro ARV-300 manufactured by Thinky. Next, 100 parts by weight of one liquid obtained above and 35 parts by weight of silica D1 (fumed silica, manufactured by Nippon Aerosil Co., Ltd., product number: RY50, surface treatment: polydimethylsiloxane, specific surface area by BET method 30 m ² / g) are mixed. And it knead | mixed 3 times using the ceramic three rolls, and it was set as the curable resin composition of this invention. Using the composition, the transmittance, refractive index, ultraviolet resistance, and workability were evaluated. The results are shown in Table 1.

(Examples 2-14, Comparative Examples 1-5)
In the same procedure as in Example 1, compound (A), compound (B), platinum vinylsiloxane complex xylene solution, and silica (D) were blended as shown in parts by weight shown in Table 1, and the test was conducted in the same manner. Carried out. In addition to the raw materials used in Example 1, dimethylsiloxane A3 (terminal SiH group polyphenylmethylsiloxane, manufactured by Gelest, PMV-9925), dimethylsiloxane B2 (terminal vinyl group polyvinylsiloxane, manufactured by Gelest, DMS-V22) silica D2 ( Fumed silica, manufactured by Nippon Aerosil Co., Ltd., product number: RY200, surface treatment: polydimethylsiloxane, BET specific surface area of 100 m ² / g), silica D3 (fumed silica, manufactured by Nippon Aerosil Co., Ltd., product number: R974, surface treatment: dimethyldi Chlorosilane, BET specific surface area 170 m ² / g), silica D4 (fumed silica, manufactured by Nippon Aerosil Co., Ltd., product number: 130, surface treatment: none, BET specific surface area 130 m ² / g), silica D5 (fumed silica) Made by Japan Aerosil Part: RX200, surface treatment: hexamethyldisilazane, specific surface area 140 m ² / g) by BET method using. For Comparative Examples 1, 3, and 4, the viscosity of the obtained curable resin composition was extremely high, and thus the cured product could not be prepared, and the transmittance, refractive index, and ultraviolet resistance were evaluated. I couldn't.

From the above results, it was shown that the semiconductor light-emitting device using the curable composition of the present invention is superior in ultraviolet resistance and workability to the comparative example.

DESCRIPTION OF SYMBOLS 1 Ultraviolet light-emitting device 2 Semiconductor light emitting element 3 Sealing resin 4 Board | substrate 5 Circuit 6 Cavity 7 Side wall body

Claims (6)

Compound (A) containing at least two SiH groups in one molecule, compound (B) containing at least two alkenyl groups in one molecule, hydrosilylation catalyst (C), specific surface area by BET method of 1 m ² / g to 150 m ² / g of silica (D),
The weight part of (D) is 30 to 200 parts by weight with respect to (A) + (B) + (C) = 100 parts by weight,
(D) is a curable resin composition characterized in that surface treatment is performed with polydimethylsiloxane. The curable resin composition according to claim 1, wherein the compound (A) containing at least two or more SiH groups in one molecule has a polysiloxane structure. 3. The curable resin composition according to claim 1, wherein the compound (B) containing at least two alkenyl groups in one molecule has a polysiloxane structure. Cured product obtained by curing compound (A) containing at least two SiH groups per molecule, compound (B) containing at least two alkenyl groups per molecule, and hydrosilylation catalyst (C) The refractory composition according to claim 1, wherein the refractive index of the curable composition is 1.42 to 1.50. Sealing resin which consists of a curable composition in any one of Claims 1-4. A light emitting device having an emission wavelength of 200 nm to 400 nm, wherein the curable composition according to any one of claims 1 to 4 is used as a sealing resin.

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