JP6726517B2 - Resin composition for LED sealing agent and LED sealing agent - Google Patents

Description

The present invention relates to a resin composition for LED encapsulant and an LED encapsulant.

An LED (Light Emitting Diode) is a light emitting element formed of a semiconductor material, and basically has a structure in which the LED element is surrounded by an LED encapsulant.

The LED encapsulant is required to have various properties such as heat resistance, light resistance, impact resistance, and transparency, and is an LED encapsulant having such properties and a raw material for the LED encapsulant. Development of a resin composition for an LED encapsulant is in progress.

For example, Patent Document 1 discloses an organopolysiloxane composition comprising a modified polyhedral polysiloxane and a compound containing two or more alkenyl groups.

Patent Document 2 discloses a polyhedral modified polysiloxane, a polysiloxane having two or more alkenyl groups in one molecule, and a hydrosilylation reaction of a compound containing a hydrosilyl group with an organic compound containing an alkenyl group. Disclosed is a composition comprising the compound thus obtained.

Patent Document 3 discloses a curable resin composition comprising a polysiloxane composition, an inorganic filler, an epoxy group-containing compound having an epoxy group equivalent of 300 g/mol or more, and a hydrosilylation catalyst.

Japanese Patent Laid-Open No. 2013-57032 (Published March 28, 2013) JP 2012-162666 A (Published August 30, 2012) Japanese Patent Laid-Open No. 2015-10132 (Published January 19, 2015)

The silver electrode used in the LED element is corroded by a corrosive gas (for example, a sulfide gas such as hydrogen sulfide) in the use environment, which reduces the brightness of the LED. In order to prevent this phenomenon, it is necessary to protect the silver electrode from corrosive gas, and the LED encapsulant encapsulating the silver electrode is required to have high gas barrier properties (in other words, low gas permeability).

However, the conventionally used LED encapsulant has room for improvement in gas barrier properties.

The present invention has been made in view of the above conventional problems, and an object thereof is to provide an LED encapsulant having a high gas barrier property, and a resin composition for an LED encapsulant, which is a raw material of the LED encapsulant. To provide.

As a result of intensive studies in view of the above problems, the present inventors have developed a resin composition for an LED encapsulant, which has a compound having a bisphenol skeleton and having two or more alkenyl groups in one molecule as a vinyl component. It was found that an LED encapsulant having a high gas barrier property can be realized by using it, and the present invention has been completed.

<1> The resin composition for an LED encapsulant of the present invention comprises (A) a compound having a hydrosilyl group, (B) a compound having two or more alkenyl groups in one molecule, and (C) a hydrosilylation catalyst. And at least one component of the component (B) is an organic compound having a bisphenol skeleton (d).

<2> In the resin composition for LED encapsulant of the present invention, the compound (A) having a hydrosilyl group is (a) a polyhedral polysiloxane compound having an alkenyl group, and (b) a compound having a hydrosilyl group. It is preferable that (A') modified polysiloxane having a polyhedral structure, which is a hydrosilylated product of

<3> In the resin composition for an LED encapsulant of the present invention, the compound (A) having a hydrosilyl group is (a) a polyhedral polysiloxane compound having an alkenyl group, and (b) a compound having a hydrosilyl group. It is preferable that (A') is a polyhedral modified polysiloxane, which is a hydrosilylation product of (c) an organosilicon compound having one alkenyl group in one molecule.

<4> In the resin composition for LED encapsulant of the present invention, the polysiloxane compound having an alkenyl group-containing polyhedral structure (a) is composed of siloxane units represented by the following (Formula 1). Preferably:
^{_{[AR 1 2 SiO-SiO 3/2}} ] a [R 2 3 SiO-SiO 3/2] b ··· ( Equation 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; A is an alkenyl group; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom, an alkyl group, an aryl group, or a group linked to another polyhedral polysiloxane compound).

<5> In the resin composition for LED encapsulant of the present invention, the compound (b) having a hydrosilyl group is selected from the group consisting of a cyclic siloxane having a hydrosilyl group and a linear siloxane having a hydrosilyl group at the molecular end. Is preferably at least one.

<6> In the resin composition for LED encapsulant of the present invention, the compound (b) having a hydrosilyl group is preferably a cyclic siloxane having a hydrosilyl group.

<7> In the resin composition for LED encapsulant of the present invention, the compound (b) having a hydrosilyl group is 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetra. It is preferably siloxane.

<8> In the resin composition for LED encapsulant of the present invention, it is preferable that (A′) modified polyhedral polysiloxane is composed of siloxane units represented by the following (formula 2). :
[XR ³ ₂ SiO-SiO _3/2 ] _a [R ⁴ ₃ SiO-SiO _3/2 ] _b ... (Formula 2)
(A+b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom , An alkyl group, an aryl group, or a group linked to another polyhedral polysiloxane compound; X is a structure represented by the following general formula (1) or a general formula (2), When there are a plurality of Xs in the siloxane unit represented by (Formula 2), the specific chemical structural formulas of each X may be different, and in the siloxane unit represented by (Formula 2) The structure of general formula (1) and the structure of general formula (2) may be mixed):

(L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; R is a hydrogen atom, an alkyl group or an aryl group; Y is a hydrogen atom, an alkenyl group, an alkyl A group bonded to the polyhedral polysiloxane compound through a group, an aryl group, or an alkylene chain, and when there are a plurality of Ys in the siloxane unit represented by (Formula 2), the Ys are the same. Z may be different or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane compound through an alkylene chain, and in the formula (2) When there is more than one Z in the represented siloxane unit, Z may be the same or different; at least one of Y or Z is a hydrogen atom).

<9> In the resin composition for an LED encapsulant of the present invention, it is preferable that the modified polyhedral polysiloxane (A′) is composed of a siloxane unit represented by the following (formula 3). :
[XR ³ ₂ SiO-SiO _3/2 ] _a [R ⁴ ₃ SiO-SiO _3/2 ] _b ... (Formula 3)
(A+b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom , An alkyl group, an aryl group, or a group linked to another polyhedral polysiloxane compound; X is a structure represented by the following general formula (1) or a general formula (2), When there are a plurality of Xs in the siloxane unit represented by (Formula 3), the specific chemical structural formula of each X may be different, and in the siloxane unit represented by (Formula 3) The structure of general formula (1) and the structure of general formula (2) may be mixed):

(L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; R is an alkyl group or an aryl group; Y is a hydrogen atom, an alkenyl group, an alkyl group, aryl A group that is bonded to a polyhedral polysiloxane compound through a group or an alkylene chain, and when there are a plurality of Y in the siloxane unit represented by (Formula 3), Y may be the same or different. Z is a site bonded to a polyhedral polysiloxane compound through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain, and is a siloxane unit represented by (formula 3). When there are a plurality of Zs, Z may be the same or different; when two or more Y and Z are contained in total in the siloxane unit represented by (Formula 3), Y or At least one of Z is a hydrogen atom, and at least one of Y and Z has a structure of the following general formula (3)):

(1 is an integer of 2 or more; R ⁵ is a group having an organosilicon compound).

<10> In the resin composition for LED encapsulant of the present invention, the organic compound (d) having a bisphenol skeleton is preferably an organic compound having a number average molecular weight of less than 1,000.

<11> In the resin composition for LED encapsulant of the present invention, the organic compound (d) having a bisphenol skeleton is an organic compound in which hydrogen of two phenolic hydroxyl groups on the bisphenol skeleton is substituted with an alkenyl group. It is preferable to have.
<12> The LED encapsulant of the present invention comprises the LED encapsulant resin composition described in the above items.

The present invention can provide an LED encapsulant having a high gas barrier property, and a resin composition for an LED encapsulant, which is a raw material of the LED encapsulant.

One embodiment of the present invention will be described below, but the present invention is not limited to this. The present invention is not limited to each configuration described below, and various modifications can be made within the scope shown in the claims, and the technical means disclosed in different embodiments or examples can be applied. Embodiments and examples obtained by appropriately combining them are also included in the technical scope of the present invention. Further, all of the academic documents and patent documents described in the present specification are incorporated herein by reference. Unless otherwise specified in this specification, “A to B” representing a numerical range means “A or more and B or less”.

In the present specification, the “LED encapsulant” means an object that seals the electrode of the LED and protects the electrode from corrosive gas, heat change, impact, and the like. The “resin composition for LED encapsulant” means an uncured resin composition which is a raw material of the LED encapsulant. The resin composition for LED encapsulant becomes a cured product when properly heated. An LED encapsulant can be produced by appropriately heating and/or molding the resin composition for an LED encapsulant.

The resin composition for LED encapsulant of the present embodiment includes (A) a compound having a hydrosilyl group, (B) a compound having two or more alkenyl groups in one molecule, (C) a hydrosilylation catalyst, And at least one component of the component (B) is an organic compound having a bisphenol skeleton (d). Each component will be described below.

[1. (A) Compound Having Hydrosilyl Group]
The compound (A) having a hydrosilyl group in the present invention is not particularly limited as long as it is a compound containing a hydrosilyl group (SiH) in the molecule.

From the viewpoint of heat resistance, for example, the compound described in International Publication WO96/15194, which has at least one hydrosilyl group per molecule, can be used as the component (A) in the present invention. .. Among the compounds, those represented by the following chemical formulas are specific examples of preferable compounds.

On the other hand, from the viewpoint of gas barrier properties, it is desirable to use the modified polyhedral polysiloxane (A′) as the component (A).

[1'. (A') Polyhedral modified polysiloxane]
In one embodiment of the present invention, the modified polyhedral polysiloxane (A′) is a hydrosilylated product of (a) a polysiloxane compound having an alkenyl group and (b) a compound having a hydrosilyl group.

In another embodiment of the present invention, (A') modified polyhedral polysiloxane is (a) a polyhedral polysiloxane compound having an alkenyl group, (b) a compound having a hydrosilyl group, and (c) one molecule. It is a hydrosilylated product with an organosilicon compound having one alkenyl group therein.

Hereinafter, each of the above components will be described individually.

[1'-1. (A) Polyhedral polysiloxane compound having an alkenyl group]
The polyhedral polysiloxane compound having an alkenyl group (a) in one embodiment of the present invention is not particularly limited as long as it is a polysiloxane having an alkenyl group in the molecule and a polyhedral skeleton.

For example, the following formula [R ^X SiO _3/2 ] _m [R ^Y SiO _3/2 ] _n
(In the above formula, m+n is an integer of 6 to 24; m is an integer of 1 or more, n is 0 or an integer of 1 or more; R ^X is an alkenyl group or a group having an alkenyl group; R ^Y Is a group linked to any organic group or other polyhedral polysiloxane compound)
A polyhedral polysiloxane compound having an alkenyl group and composed of a siloxane unit represented by is preferably used.

More specifically, (Equation 1)
^{_{[AR 1 2 SiO-SiO 3/2}} ] a [R 2 3 SiO-SiO 3/2] b ··· ( Equation 1)
(In the above formula, a+b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ¹ is an alkyl group or an aryl group. R ² is a hydrogen atom, an alkyl group, an aryl group, or a group linked to another polyhedral polysiloxane compound)
An example of a more preferable compound is a polysiloxane compound having a polyhedral structure having an alkenyl group, which is composed of a siloxane unit represented by

A is an alkenyl group. Specific examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group. From the viewpoints of heat resistance and light resistance, A in the present invention is preferably a vinyl group.

R ¹ is an alkyl group or an aryl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a cyclopentyl group. Specific examples of the aryl group include a phenyl group and a tolyl group. From the viewpoint of heat resistance and light resistance, R ¹ in the present invention is preferably a methyl group.

R ² is a hydrogen atom, an alkyl group, an aryl group, or a group linked to another polyhedral polysiloxane compound. 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. Specific examples of the aryl group include a phenyl group and a tolyl group. From the viewpoint of heat resistance and light resistance, R ² in the present invention is preferably a methyl group.

There is no particular limitation except that a is an integer of 1 or more. However, from the viewpoint of the ease of handling the polyhedral polysiloxane compound and the physical properties of the cured product obtained, 2 or more is preferable, and 3 or more is more preferable. On the other hand, b is not particularly limited except that it is 0 or an integer of 1 or more.

The sum of a and b (a+b) is an integer of 6 to 24, and is preferably 6 to 12 in view of the stability of the polyhedral polysiloxane compound and the stability of the obtained cured product, and 6 10 is more preferable.

The method for synthesizing the (a) polyhedral polysiloxane compound having an alkenyl group is not particularly limited, and a known method can be used for synthesis. For example, a silane represented by the formula R′SiX ^a ₃ (wherein R′ represents R ^X and R ^Y described above; X ^a represents a hydrolyzable functional group such as a halogen atom and an alkoxy group). By hydrolyzing and condensing the compound, a polyhedral polysiloxane compound having an alkenyl group (a) is obtained. As another method, R′SiX ^a ₃ is hydrolyzed and condensed to synthesize ^a trisilanol compound having three silanol groups in the molecule, and then a trifunctional silane compound which is the same as or different from the trisilanol compound is used. There is also known a method of synthesizing a polyhedral polysiloxane compound having an alkenyl group by ring closure by reaction.

In addition, for example, a method of hydrolyzing and condensing a tetraalkoxysilane such as tetraethoxysilane in the presence of a base such as quaternary ammonium hydroxide can be used. That is, it is a method of synthesizing a silicate having a polyhedral structure by a hydrolytic condensation reaction of tetraalkoxysilane, and then reacting the silicate with a silylating agent such as an alkenyl group-containing silyl chloride. As a product of the reaction, a polyhedral polysiloxane compound in which a Si atom forming a polyhedral structure and an alkenyl group are bonded via a siloxane bond is obtained. In the present method, a polyhedral polysiloxane compound having an alkenyl group can be obtained from a substance containing silica, such as rice hulls, instead of tetraalkoxysilane.

The above-mentioned (a) polyhedral polysiloxane compound having an alkenyl group may be used alone or in combination of two or more.

[1'-2. (B) Compound Having Hydrosilyl Group]
The compound (b) having a hydrosilyl group used when synthesizing the modified polyhedral polysiloxane (A′) is preferably a siloxane compound having a hydrosilyl group from the viewpoints of transparency, heat resistance and light resistance. Furthermore, it is more preferable that the siloxane compound having a hydrosilyl group is selected from the group consisting of a cyclic siloxane having a hydrosilyl group and a linear siloxane having a hydrosilyl group at the molecular end. Taking the gas barrier property into consideration, the cyclic siloxane is more preferable.

Specific examples of the linear siloxane having a hydrosilyl group at the molecular end include a copolymer of a dimethylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, a diphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethyl group. Copolymers with siloxy units, copolymers of methylphenylsiloxane units with methylhydrogensiloxane units and terminal trimethylsiloxy units, polydimethylsiloxanes end-capped with dimethylhydrogensilyl groups, with dimethylhydrogensilyl groups Examples thereof include polydiphenylsiloxane having a terminal blocked, and polymethylphenylsiloxane having a terminal blocked with a dimethylhydrogensilyl group.

From the viewpoints of reactivity when reacting with the component (a), heat resistance and light resistance of the resulting cured product, the linear siloxane having a hydrosilyl group at the molecular end is a dimethylhydrogensilyl group. A polysiloxane having a molecular terminal blocked is preferable, and a polydimethylsiloxane having a molecular terminal blocked with a dimethylhydrogensilyl group is more preferable. More specifically, tetramethyldisiloxane and hexamethyltrisiloxane are examples of preferred component (b).

Specific examples of the cyclic siloxane having a hydrosilyl group include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 1-propyl-3,5,7-tri. Hydrogen-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, 1,3,3 5,7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane. The cyclic siloxane of the present invention is 1,3,5,7-tetrahydrogen-based on the viewpoints of industrial availability, reactivity, and heat resistance, light resistance and strength of a cured product obtained. 1,3,5,7-Tetramethylcyclotetrasiloxane is an example of a preferred component (b).

The above-mentioned compound (b) having a hydrosilyl group may be used alone or in combination of two or more.

[1'-3. (C) Organosilicon compound having one alkenyl group in one molecule]
In one aspect of the present invention, (c) the organosilicon compound having one alkenyl group in one molecule reacts with the hydrosilyl group of the compound (b) having a hydrosilyl group. When the component (c) is used, the elastic modulus of the obtained cured product is lowered and the thermal shock resistance is improved.

Specific examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group. From the viewpoint of heat resistance and light resistance, the alkenyl group is preferably a vinyl group.

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. However, from the viewpoint of gas barrier property and refractive index, a compound having at least one aryl group in one molecule is preferable. In view of heat resistance and light resistance, a compound in which the aryl group is directly bonded to a silicon atom is more preferable.

From the viewpoint of heat resistance and light resistance, the component (c) in the present invention is preferably silane or polysiloxane.

Specific examples of the silane having one alkenyl group in one molecule include trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, triphenylvinylsilane, triethylvinylsilane, diethylphenylvinylsilane, ethyldiphenylvinylsilane, allyltrimethylsilane, allyldimethylphenyl. Examples thereof include silane, allylmethyldiphenylsilane, allyltriphenylsilane, allyltriethylsilane, allyldiethylphenylsilane, and allylethyldiphenylsilane. From the viewpoint of heat resistance and light resistance, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, and triphenylvinylsilane are preferable examples of the component (c). Further, from the viewpoints of gas barrier property and refractive index, dimethylphenylvinylsilane, methyldiphenylvinylsilane, and triphenylvinylsilane are more preferable examples of the component (c).

Examples of polysiloxanes include linear polysiloxanes having one alkenyl group, polysiloxanes having one alkenyl group at the molecular end, and cyclic siloxanes having one alkenyl group.

Specific examples of the linear-structured polysiloxane having one alkenyl group include polydimethylsiloxane in which one end is blocked by dimethylvinylsilyl group and one end by trimethylsilyl group, and dimethylvinylsilyl group and trimethylsilyl group. Polymethylphenyl siloxane with one end blocked, polydiphenylsiloxane with one end each with dimethylvinylsilyl group and trimethylsilyl group, one each with dimethylvinylsilyl group and trimethylsilyl group , A copolymer of a dimethylsiloxane unit and a methylphenylsiloxane unit, a copolymer of a dimethylsiloxane unit and a diphenylsiloxane unit, each having one end blocked with a dimethylvinylsilyl group and one trimethylsilyl group, dimethyl Examples thereof include a copolymer of a methylphenylsiloxane unit and a diphenylsiloxane unit, each of which has one end blocked with a vinylsilyl group and one end with a trimethylsilyl group.

Specific examples of the polysiloxane having one alkenyl group at the molecular end include a polysiloxane group having one end each blocked with a dimethylvinylsilyl group and a trimethylsilyl group exemplified in the preceding paragraph, and a SiO ₂ unit. , A polysiloxane consisting of at least one siloxane unit and one dimethylvinylsiloxane unit selected from the group consisting of SiO _3/2 units, SiO units and SiO _1/2 units.

Specific examples of the cyclic siloxane having one alkenyl group include 1-vinyl-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane and 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.

The organosilicon compound having one alkenyl group in one molecule (c) may be used alone or in combination of two or more.
[Synthesis of 1′-4(A′) Polyhedral Modified Polysiloxane]
In one embodiment of the present invention, the modified polyhedral polysiloxane (A′) comprises a polyhedral polysiloxane compound (a) having an alkenyl group and a hydrosilyl group (b) in the presence of a hydrosilylation catalyst described below. It is synthesized by a hydrosilylation reaction with a compound having. At this time, the alkenyl group of the component (A′) does not have to react completely and may partially remain.

(B) The addition amount of the compound having a hydrosilyl group is (a) one alkenyl group of the polyhedral polysiloxane compound having an alkenyl group and (b) the hydrogen atom directly bonded to the Si atom contained in the component. It is preferable to add it so that the number is more than 1, more preferably 2.5 to 20. However, the appropriate addition amount depends on the compound. If the amount added is too small, the reaction product gels due to the crosslinking reaction, and the modified polyhedral polysiloxane (A′) having poor handling properties is obtained. On the contrary, if the addition amount is too large, the physical properties of a cured product obtained by using the modified polyhedral polysiloxane may be adversely affected.

During the reaction between the component (a) and the component (b), an excessive amount of the component (b) is present. Therefore, after completion of the reaction, unreacted by a suitable method such as evaporation of the solvent under reduced pressure and heating conditions. It is preferable to distill off the component (b).

The addition amount of the hydrosilylation catalyst used for the synthesis of the component (A′) is not particularly limited. Preferably, it is added within a range of 10 ⁻¹ to 10 ⁻¹⁰ mol with respect to ¹ mol of the alkenyl group of the component (a). More preferably, it is added within the range of 10 ⁻⁴ to 10 ⁻⁸ mol. If the amount of the hydrosilylation catalyst is too large, the resulting cured product may foam. Further, depending on the type of the hydrosilylation catalyst, it absorbs light having a short wavelength, which may cause coloring or reduce the light resistance of the cured product. On the other hand, if the amount of the hydrosilylation catalyst is too small, the reaction may not proceed and the component (A') may not be obtained.

The reaction temperature of the hydrosilylation reaction is preferably 30 to 400°C, more preferably 40 to 250°C, still 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, the reaction product may gel and the handling property of the component (A′) may deteriorate.

The component (A') obtained by the above method can ensure compatibility with various compounds. In particular, there is a feature that very good compatibility can be secured with respect to an organic compound having a bisphenol skeleton. Furthermore, since a hydrosilyl group is introduced into the molecule, it is possible to react with compounds having various alkenyl groups. For example, a cured product is obtained when the compound (B) described later is reacted with a compound containing two or more alkenyl groups. At the time of the reaction, at least three hydrosilyl groups in the component (A′) are preferably contained in the molecule. When the number of hydrosilyl groups is less than 3, the strength of the cured product may be insufficient.

The modified polyhedral polysiloxane (A′) in the present invention can be in a liquid state at a temperature of 20° C. The liquid component (A') is obtained, for example, by using a cyclic siloxane or a linear polysiloxane having a hydrosilyl group as the component (b), and reacting the component (b) with the component (a). The liquid component (A') is preferable because it is excellent in handleability.

The modified polyhedral polysiloxane (A′) in this embodiment is composed of siloxane units represented by the following (Formula 2), and is based on the viewpoints of heat resistance, light resistance, and strength of the obtained cured product. Is a preferable example.

[XR ³ ₂ SiO-SiO _3/2 ] _a [R ⁴ ₃ SiO-SiO _3/2 ] _b ... (Formula 2)
(In the above formula, a+b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is alkenyl A group, a hydrogen atom, an alkyl group, an aryl group, or a group linked to another polyhedral polysiloxane compound; X has the structure of the following general formula (1) or the structure of the general formula (2). When there are a plurality of Xs in the siloxane unit represented by (Formula 2), each X may have a different specific chemical structural formula, and is represented by (Formula 2). The structure of the general formula (1) and the structure of the general formula (2) may be mixed in the siloxane unit)

(In the above formula, l is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; R is a hydrogen atom, an alkyl group or an aryl group; Y is a hydrogen atom, A site that is bonded to a polyhedral polysiloxane compound through an alkenyl group, an alkyl group, an aryl group, or an alkylene chain, and when there are a plurality of Y in the siloxane unit represented by (Formula 2), Y May be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a moiety bonded to the polyhedral polysiloxane compound via an alkylene chain; When there are a plurality of Zs in the siloxane unit represented by formula 2), Zs may be the same or different; at least one of Y or Z is a hydrogen atom).

In another embodiment of the present invention, the modified polyhedral polysiloxane (A′) is (a) a polyhedral polysiloxane compound having an alkenyl group and (b) a hydrosilyl group in the presence of a hydrosilylation catalyst described below. It is synthesized by a hydrosilylation reaction of a compound having the formula (c) with an organosilicon compound (c) having one alkenyl group in one molecule.

The reaction process for obtaining the modified polyhedral polysiloxane (A′) of the present invention is not particularly limited and can be set variously. For example, the component (a) and the component (b) may be reacted in advance and then the component (c) may be reacted, or the component (c) and the component (b) may be reacted in advance and then (a ) Component may be reacted, or (a) component and (c) component may be allowed to coexist and reacted with (b) component. After the completion of each reaction, the volatile unreacted components may be distilled off by an appropriate method such as evaporation of the solvent under reduced pressure and heating conditions to obtain the desired product or intermediate. In order to suppress the production of a compound that does not contain the component (a) in which only the component (c) and the component (b) have reacted, the component (a) and the component (b) are reacted with each other and the unreacted (b) The method of reacting the component (c) after distilling off the component) is preferred.

It is not necessary that all the alkenyl groups of the component (A') have reacted at the stage where the above-mentioned reaction is completely completed, and some of them may remain.

The description of the addition amount of the component (b) has been given in the above-mentioned aspect. Therefore, repetitive description is omitted for this item.

The component (c) may be added so that the number of alkenyl groups contained in the component (c) is 0.01 to 0.36 with respect to one hydrosilyl group contained in the component (b). preferable. If the added amount is too small, the cold shock resistance of the resulting component (A') may be reduced, and if the added amount is large, the resulting cured product may be insufficiently cured.

The addition amount of the hydrosilylation catalyst used for the synthesis of the component (A'), the reaction temperature, and the properties of the component (A') have been described in the above-mentioned embodiment. Therefore, repetitive description is omitted for this item.

The modified (A′) polyhedral polysiloxane of the present embodiment is preferably composed of siloxane units represented by the following (formula 3) from the viewpoint of heat resistance.

[XR ³ ₂ SiO-SiO _3/2 ] _a [R ⁴ ₃ SiO-SiO _3/2 ] _b ... (Formula 3)
(A+b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom , An alkyl group, an aryl group, or a group linked to another polyhedral polysiloxane compound; X is a structure represented by the following general formula (1) or a general formula (2), When there are a plurality of Xs in the siloxane unit represented by (Formula 3), the specific chemical structural formula of each X may be different, and in the siloxane unit represented by (Formula 3) The structure of general formula (1) and the structure of general formula (2) may be mixed.

(L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; R is an alkyl group or an aryl group; Y is a hydrogen atom, an alkenyl group, an alkyl group, aryl A group that is bonded to a polyhedral polysiloxane compound through a group or an alkylene chain, and when there are a plurality of Y in the siloxane unit represented by (Formula 3), Y may be the same or different. Z is a site bonded to a polyhedral polysiloxane compound through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain, and is a siloxane unit represented by (formula 3). When there are a plurality of Zs, Z may be the same or different; when two or more Y and Z are contained in total in the siloxane unit represented by (Formula 3), Y or At least one of Z is a hydrogen atom, and at least one of Y and Z has a structure of the following general formula (3)):

(1 is an integer of 2 or more; R ⁵ is a group having an organosilicon compound).

R ⁵ is not particularly limited as long as it is a group containing an organosilicon compound. However, from the viewpoint of gas barrier properties and refractive index, it is preferable that at least one aryl group is contained in one molecule. Further, from the viewpoints of heat resistance and light resistance, it is more preferable that the aryl group is directly bonded to a silicon atom.

[2. (B) Compound Having Two or More Alkenyl Groups in One Molecule]
The compound (B) having two or more alkenyl groups in one molecule in the present invention reacts with the compound (A) having a hydrosilyl group in the presence of the (C) hydrosilylation catalyst to be cured.

The number of alkenyl groups contained in the component (B) may be 2 or more per molecule. It is preferably 2 to 10 per molecule. If the number of alkenyl groups in one molecule is large, the gas barrier property is further improved due to an increase in the crosslinked structure, but if it is too large, the heat resistance and light resistance may decrease.

Specific examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group. From the viewpoint of heat resistance, the alkenyl group is preferably a vinyl group or an allyl group.

As the component (B) in the present invention, a linear or branched siloxane compound, a cyclic siloxane compound, other organic compounds, etc. can be used.

Specific examples of the linear or branched siloxane compound include:
_{CH 2 = CHSiMe 2 O (SiMe} 2 O) n SiMe 2 CH = CH 2 (n = 0~10),
_{CH 2 = CHSiMe 2 O (SiMe} 2 O) m (SiPh 2 O) n SiMe 2 CH = CH 2 (m = 0~5, n = 1~4),
_{CH 2 = CHSiPh 2 O (SiMe} 2 O) m (SiPh 2 O) n SiPh 2 CH = CH 2 (m = 0~3, n = 1~2),
_{CH 2 = CHSiMe 2 O (SiMe} 2 O) m (SiPhMeO) n SiMe 2 CH = CH 2 (m = 0~5, n = 1~6),
_{Me 3 SiO (SiMe 2 O)} m (SiMe (CH = CH 2) O) n SiMe 3 (m = 0~5, n = 1~9),
_{MeSi [O (SiMe 2 O)} m SiMe 2 CH = CH 2] 3 (m = 0~2)
(In the above formula, Me represents a methyl group and Ph represents a phenyl group.)
Is mentioned.

Specific examples of the cyclic siloxane compound include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-pentamethylcyclotetrasiloxane, and ,3-divinyl-hexamethylcyclotetrasiloxane, 1,5-divinyl-hexamethylcyclotetrasiloxane, 1,3,5,7-tetravinyl-1-phenyl-3,5,7-trimethylcyclotetrasiloxane, 1 ,3,5,7-Tetravinyl-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7-tetravinyl-1,5-diphenyl-3,7-dimethylcyclotetrasiloxane 1,3,5,7-tetravinyl-1,3,5-triphenyl-7-methylcyclotetrasiloxane, 1-phenyl-3,5,7-trivinyl-1,3,5,7-tetramethyl Cyclotetrasiloxane, 1,3-diphenyl-5,7-divinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-diphenyl-3,7-divinyl-1,3,5,7- Tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclo Mention may be made of pentasiloxane and 1,3,5,7,9,11-hexavinyl-1,3,5,7,9,11-hexamethylcyclohexasiloxane.

Specific examples of the other organic compounds include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2-tetraallyloxyethane. , Diarylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes (purity 50-100%) , Preferably having a purity of 80 to 100%), divinylbiphenyl, 1,3-diisopropenylbenzene, and 1,4-diisopropenylbenzene.

[2-1. (D) Organic compound having bisphenol skeleton]
At least one of the components (B) in the present invention is (d) an organic compound having a bisphenol skeleton. As a more specific constitution of the organic compound having a bisphenol skeleton (d), an organic compound in which hydrogen of two phenolic hydroxyl groups on the bisphenol skeleton is substituted with an alkenyl group can be mentioned. By containing the component (B) satisfying the condition, the gas barrier property of the obtained cured product is enhanced, and the function as the LED sealing agent is further improved. Further, effects such as improvement in strength, toughness, and refractive index of the obtained cured product can be obtained.

In the present specification, the bisphenol skeleton means a known bisphenol structure having two phenolic hydroxyl groups. Specific examples include bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bisphenol B (2,2-bis(4-hydroxyphenyl)butane), bisphenol F (bis(4-hydroxyphenyl)methane. ), bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol AF (2,2-bis(4-hydroxyphenyl)hexafluoropropane), bisphenol BP (bis(4-hydroxy) (Phenyl)diphenylmethane), bisphenol C (2,2-bis(3-methyl-4-hydroxyphenyl)propane), bisphenol C (bis(4-hydroxyphenyl)-2,2-dichloroethylene), bisphenol E (1,1) -Bis(4-hydroxyphenyl)ethane), bisphenol G (2,2-bis(4-hydroxy-3-isopropylphenyl)propane), bisphenol M (1,3-bis(2-(4-hydroxyphenyl)-) 2-propyl)benzene), bisphenol S (bis(4-hydroxyphenyl)sulfone), bisphenol P(1,4-bis(2-(4-hydroxyphenyl)-2-propyl)benzene), bisphenol PH(5. 5'-(1-methylethylidene)-bis(1,1'-(bisphenyl)-2-ol)propane), bisphenol TMC(1,1-bis(4-hydroxyphenyl)-3,3,5- Trimethylcyclohexane) and bisphenol Z (1,1-bis(4-hydroxyphenyl)cyclohexane). However, the structure is not limited to the illustrated structure.

The bisphenol skeleton contained in the structure of the component (d) is not particularly limited. However, from the viewpoint of light resistance, it is preferable that the component (d) includes a structure having two benzene rings per molecule.

The positions occupied by the two phenolic hydroxyl groups in the component (d) are not particularly limited, except that they are bonded to the aromatic ring. However, from the viewpoint of availability, it is preferable that each phenolic hydroxyl group is bonded to a different aromatic ring.

The two or more alkenyl groups contained in the component (d) may be located anywhere in the structural formula. However, an organic compound in which hydrogen of two phenolic hydroxyl groups on the bisphenol skeleton is replaced with an alkenyl group is preferable because a cured product having sufficient hardness can be obtained during the hydrosilylation reaction.

The number of moles of the alkenyl group contained in the component (d) per unit weight is preferably in the range of 1.0 to 12 mmol/g from the viewpoint of the balance between the gas barrier property and the thermal shock resistance. , 2.0 to 10 mmol/g is more preferable, and 3.0 to 8 mmol/g is further preferable. When the number of moles of alkenyl groups per unit weight is less than 1.0 mmol/g, the gas barrier properties of the LED encapsulant may be insufficient. On the other hand, when the number of moles of alkenyl groups per unit weight exceeds 12 mmol/g, stress tends to accumulate in the obtained cured product, and the thermal shock resistance of the LED encapsulant may deteriorate.

On the other hand, from the viewpoint of handling property, the number average molecular weight of the component (d) is preferably less than 1000, more preferably less than 500.

When the above conditions are combined, specific examples of the organic compound preferable as the component (d) include 2,2-bis(4-allyloxyphenyl)propane and 2,2-bis(3-allyl-4-hydroxyphenyl). Examples include propane and 2,2-bis(3-methyl-4-allyloxyphenyl)propane.

[2-2. (D) Introduction of alkenyl group into organic compound having bisphenol skeleton]
An organic compound having two or more alkenyl groups in one molecule and having a bisphenol skeleton in the structure is synthesized by a known method. For example, there is a manufacturing method disclosed in International Publication WO2012/133108 A1.

The 2,2-bis(4-allyloxyphenyl)propane mentioned as a specific example of the organic compound preferable as the component (d) can be obtained by allylating 2,2-bis(4-hydroxyphenyl)propane. , Easily available through the market.

[3. (C) Hydrosilylation catalyst]
In the present invention, (A) a compound having a hydrosilyl group and (B) a compound having two or more alkenyl groups in one molecule are reacted and cured, and (A′) a polyhedral modified polysiloxane is synthesized. In doing so, a hydrosilylation catalyst is used.

A known hydrosilylation catalyst can be used as the hydrosilylation catalyst, and is not particularly limited.

Specific examples of the hydrosilylation catalyst include a platinum-olefin complex, chloroplatinic acid, a simple substance of platinum, a substance in which solid platinum is supported on a carrier (alumina, silica, carbon black, etc.), a platinum-vinylsiloxane complex (for example, [Pt _n (ViMe ₂ SiOSiMe ₂ Vi) _n and Pt(MeViSiO) ₄ ] _m ), platinum-phosphine complexes (eg Pt(PPh ₃ ) ₄ and Pt(PBu ₃ ) ₄ ), platinum-phosphite complexes (eg Pt[P]P). (OPh) ₃ ] ₄ and Pt[P(OBu) ₃ ] ₄ ) and Pt(acac) ₂ . Further, the platinum-hydrocarbon complexes described in Ashby et al., US Pat. Nos. 3,159,601 and 3,159,662, and the platinum alcoholate catalysts described in Lamoreaux, et al., US Pat. No. 3,220,972. Can also 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 ₂ . ₄ is mentioned.
(In the formulas in the preceding paragraph and this paragraph, Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group; acac represents acetylacetone; and n and m represent integers).

From the viewpoint of catalytic activity, the (C) hydrosilylation catalyst of the present invention is preferably chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex, Pt(acac) ₂ or the like.

The above-mentioned catalysts may be used alone or in combination of two or more.

[Production of LED sealant]
The above-mentioned compound (A) having a hydrosilyl group, (B) a compound having two or more alkenyl groups in one molecule (at least one component of which is (d) an organic compound having a bisphenol skeleton) and (C) a hydrosilylation catalyst. By heating and/or molding the resin composition for LED encapsulant containing it by an appropriate method, a cured product suitable as an LED encapsulant can be produced.

[1. Preparation of resin composition for LED encapsulant]
The breakdown of the resin composition for LED encapsulant is as follows: Component (A) 30 to 95 parts by weight, component (B) 1 to 40 parts by weight (of which component (d) component 1 to 35 parts by weight), component (C) 0. It is generally from 0 to 5 parts by weight. It is preferably 40 to 95 parts by weight of the component (A), 1 to 35 parts by weight of the component (B) (including 1 to 30 parts by weight of the component (d)), and 0.01 to 2.5 parts by weight of the component (C), More preferably, it is 50 to 95 parts by weight of component (A), 1 to 30 parts by weight of component (B) (1 to 25 parts by weight of component (d)), and 0.01 to 1 part by weight of component (C).

The order of mixing the respective components may be such that after adding the component (B) to the component (A), the component (C) may be added, or the component (C) may be added to the component (B) and then the component (A). The component may be added, or the component (A) may be added after the component (C) is added to the component (B). From the viewpoint of workability, it is convenient to adopt the procedure of adding the component (A) after adding the component (C) to the component (B).

If each of the above components, or each of the above components and optional components described below are mixed using a kneader such as a roll, a Banbury mixer, a kneader, or a planetary stirring and defoaming machine, a uniformly mixed LED seal is obtained. A resin composition for a stopper can be prepared.

[1-1. Curing retarder]
The resin composition for LED encapsulant is cured as a component for improving the storage stability and stability of the resin composition for LED encapsulant or for adjusting the reactivity of hydrosilylation reaction in the curing process. A retarder may be included. As the curing retarder in the present invention, a known substance that exhibits addition-type curability with a hydrosilylation catalyst and is used for a resin composition for an LED encapsulant can be used. Examples include compounds having an aliphatic unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds, and organic peroxides.

Specific examples of the compound having an aliphatic unsaturated bond include propargyl alcohols (3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne, 3,5-dimethyl- 1-hexyn-3-ol, 1-ethynyl-1-cyclohexanol, etc.), ene-yne compounds, maleic anhydride, maleic acid esters (dimethyl maleate, etc.).

Specific examples of the organophosphorus compound include triorganophosphines, diorganophosphines, organophosphons, and triorganophosphites.

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 Examples include'-bipyridine.

Specific examples of the tin compound include stannous halide dihydrate and stannous carboxylate.

Specific examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

Among the above-mentioned curing retardants, dimethyl maleate, 3,5-dimethyl-1-hexyn-3-ol and 1-ethynyl-1-cyclohexanol are examples of particularly preferable curing retarders.

Only one type of the above-mentioned curing retarder may be used, or two or more types may be used in combination.

The addition amount of the curing retarder is not particularly limited, but it is preferably used within the range of 10 ⁻¹ to 10 ³ mol, and more preferably within the range of 1 to 100 mol, based on ¹ mol of the hydrosilylation catalyst.

[1-2. Adhesiveness imparting agent]
In one aspect of the present invention, an adhesiveness-imparting agent is added to the above polyhedron for the purpose of improving the adhesiveness between a resin composition for LED encapsulant (A′) containing a modified polyhedral polysiloxane and a substrate. It can be added to the resin composition for LED encapsulant containing the modified polysiloxane. Any substance can be used as the above-mentioned adhesiveness-imparting agent without particular limitation, as long as it is a substance capable of improving the adhesiveness. An example of a suitable substance is a silane coupling agent.

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. The group reactive with the organic group is at least 1 selected from the group consisting of an epoxy group, a methacrylic group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group and a carbamate group, from the viewpoint of easy handling. Individual functional groups are preferred. Further, from the viewpoints of curability and adhesiveness, an epoxy group, a methacrylic group, and an acrylic group are more preferable. The hydrolyzable silicon group is preferably an alkoxysilyl group from the viewpoint of easy handling. Further, from the viewpoint of reactivity as well, a methoxysilyl group and an ethoxysilyl group are more preferable.

Specific examples of alkoxysilanes having an epoxy functional group, which are suitable as a silane coupling agent, include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropyltriethoxy. Silane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4- Examples thereof include epoxycyclohexyl)ethyltriethoxysilane and 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane.

On the other hand, specific examples of alkoxysilanes having a methacryl group or an acryl group, which are suitable as a silane coupling agent, include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrisilane. Examples thereof include methoxysilane, 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane and acryloxymethyltriethoxysilane.

The above-mentioned silane coupling agents may be used alone or in combination of two or more.

The addition amount of the silane coupling agent is 100 parts by weight of a mixture of (A') modified polyhedral polysiloxane, (B) a compound having two or more alkenyl groups in one molecule, and (C) a hydrosilylation catalyst. , Preferably 0.05 to 30 parts by weight, more preferably 0.1 to 10 parts by weight. If the added amount is too small, the effect of improving the adhesiveness does not appear, and conversely, if the added amount is too large, the physical properties of the obtained cured product may be adversely affected.

In this embodiment, a publicly known adhesion promoter can be used in order to enhance the effect of the adhesion promoter. Specific examples of the adhesion promoter include epoxy-containing compounds, epoxy resins, boronic acid ester compounds, organoaluminum compounds, and organotitanium compounds.

[1-3. Inorganic filler]
By adding an inorganic filler to the resin composition for LED encapsulant, the LED encapsulant of the present invention has strength, hardness, elastic modulus, coefficient of thermal expansion, thermal conductivity, heat dissipation, electrical characteristics, and light resistance. Physical properties such as reflectance, flame retardancy, fire resistance, and gas barrier property are improved.

The inorganic filler is not particularly limited as long as it is an inorganic substance or a compound containing an inorganic substance. Specific examples include silica-based inorganic fillers (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine amorphous silica, etc.), alumina, zircon, iron oxide, zinc oxide, oxidized Titanium, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, glass flakes, alumina fiber, carbon fiber, mica, graphite, carbon black, ferrite, graphite, diatomaceous earth, clay, talc, aluminum hydroxide, Examples thereof include calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloons, and silver powder.

The above-mentioned inorganic fillers may be used alone or in combination of two or more.

The surface of the inorganic filler may be appropriately surface-treated. Specific examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, and treatment with a silane coupling agent.

As the shape of the inorganic filler, various shapes such as crushed shape, flaky shape, spherical shape, and rod shape are used. The average particle size and particle size distribution of the inorganic filler are not particularly limited. However, from the viewpoint of gas barrier properties, the average particle size is preferably 0.005 to 50 μm, more preferably 0.01 to 20 μm. The BET specific surface area of the inorganic filler is also not particularly limited. However, from the viewpoint of gas barrier properties, 70 m ² /g or more is preferable, 100 m ² /g or more is more preferable, and 200 m ² /g or more is further preferable.

The addition amount of the inorganic filler is not particularly limited. With respect to 100 parts by weight of a mixture of (A) a compound having a hydrosilyl group, (B) a compound having two or more alkenyl groups in one molecule, and (C) a hydrosilylation catalyst, preferably 1 to 1000 parts by weight, more preferably Is 3 to 500 parts by weight, more preferably 5 to 300 parts by weight. If the amount of the inorganic filler added is too large, the fluidity may deteriorate. On the contrary, if the amount of the inorganic filler added is too small, the desired physical properties may not be obtained.

The order of mixing the inorganic fillers is not particularly limited. In order to obtain good storage stability, a method of mixing the inorganic filler and the component (B) and then the component (A) is desirable. On the other hand, in order to mix the pre-reaction substances well and to easily obtain a stable molded product, it is preferable to mix an inorganic filler in the mixture of the components (A) and (B).

The means for mixing the inorganic filler is not particularly limited. Specific examples thereof include a stirrer (two-roll or three-roll, planetary stirring and defoaming device, homogenizer, dissolver, planetary mixer, etc.) and melt kneader (Plastomill, etc.). The inorganic filler can be mixed at room temperature or under heating. Similarly, the mixing of the inorganic filler can be performed under normal pressure or under reduced pressure. However, if the temperature at the time of mixing is high, the resin composition for LED encapsulant may be cured before being molded.

[1-4. Other ingredients]
In the resin composition for the LED encapsulant, various additives such as a phosphor, a colorant and a heat resistance improver, a reaction control agent, a release agent or a dispersant for a filler may be optionally added to the resin composition for the LED encapsulant. Can be added at. Specific examples of the filler dispersant include diphenylsilanediol, various alkoxysilanes, carbon functional silanes, and silanol group-containing low molecular weight siloxanes.

In order to enhance the effect of the LED encapsulant of the present invention, the thermal shock resistance can be improved by adding, for example, fused spherical silica. In addition, heat dissipation can be improved by adding alumina.

However, [1-1. Curing retarder] to [1-4. The optional components described in [Other components] are preferably added to the minimum amount so as not to impair the effects of the present invention.

[2. Curing and molding of resin composition for LED encapsulant]
A cured product is obtained by heating the resin composition for LED encapsulant. A suitable temperature for curing is 30 to 400°C, preferably 50 to 250°C. If the temperature for curing is too high, the resulting cured product tends to have a poor appearance. Conversely, if the temperature for curing is too low, the curing will be insufficient. In this step, temperature conditions of two or more stages can be combined. As an example, there is a method of gradually increasing the temperature such as 70° C., 120° C. and 150° C. to proceed the reaction. According to this method, a cured product suitable as an LED sealant can be obtained.

The time required for curing is the temperature at the time of curing, the amount of the (C) hydrosilylation catalyst, the amount of the reactive groups contained in the (A) component and the (B) component, and the resin composition for the LED encapsulant. Can be appropriately selected depending on the combination of other compounds contained in. Generally, heating for 1 minute to 12 hours, preferably heating for 10 minutes to 8 hours gives a good cured product.

The resin composition for LED encapsulant can be molded by any molding method such as extrusion molding, compression molding, blow molding, calender molding, vacuum molding, foam molding, injection molding, liquid injection molding, and cast molding.

The LED encapsulant can be produced from the resin composition for LED encapsulant by the heating method and/or the molding method exemplified above.

Below, [1. Preparation of resin composition for LED encapsulant]], an example of a method for producing an LED encapsulant from the resin composition for LED encapsulant obtained in the following. However, the LED encapsulant using the resin composition for an LED encapsulant of the present invention as a raw material is not limited to the production method described below.

To 25 g of the prepared resin composition for LED encapsulant, 0.225 g of a phosphor (NYAG4454-S manufactured by Intematics) was added and stirred. Further, using a rotation/revolution mixer (Awatori Kentaro AR-250 manufactured by Thinky Co.), stirring 3 minutes, defoaming 3 minutes, and stirring 3 minutes were sequentially performed. Next, the obtained uncured composition was syringe-mounted on a reflector (TOP LED 1-IN-1 manufactured by Enomoto Co., Ltd.) mounted with a blue LED chip (12 Mil×13 mil angle B1213AAA0 S46B/C-19/20 manufactured by Generights Co., Ltd.) Was injected using. Finally, by curing in a convection oven in three steps of 80° C. for 30 minutes, 120° C. for 2 hours, and 170° C. for 1 hour, an LED sealed with an LED sealing agent was obtained.

Hereinafter, the resin composition for LED encapsulant and the LED encapsulant of the present invention will be described in more detail based on examples. However, the present invention is not limited to the examples below.

First, the tests conducted on the polyhedral polysiloxane-based compositions of Examples and Comparative Examples will be described. The polyhedral polysiloxane composition was obtained by stirring modified polyhedral polysiloxane, various compounds having two or more alkenyl groups in one molecule, and diallyl monomethyl isocyanurate, as described later. It is a thing. In the examples, the compound having two or more alkenyl groups in one molecule has a bisphenol skeleton. On the other hand, in Comparative Example, the compound having two or more alkenyl groups in one molecule does not have a bisphenol skeleton.

[Sulfuration resistance test]
The polyhedral polysiloxane composition is injected into an LED package (TOP LED 1-IN-1 manufactured by Enomoto Co., Ltd.), and the mixture is heated in a convection oven in the order of 80° C.×2 hours, 100° C.×1 hour, 150° C.×5 hours. Then, the polyhedral polysiloxane composition was thermally cured to prepare a sample. The sample was put into a flow type gas corrosion tester (KG130S manufactured by Fact Cay), and a hydrogen sulfide exposure test was performed for 96 hours under the conditions of 40° C., 80% RH, and 3 ppm of hydrogen sulfide. After the test, ◎ if the reflector of the package maintains the same gloss and color tone as before the test, ○, although the gloss of the package reflector is slightly reduced, ○ if not discolored, slightly discolored with the decrease in gloss When it was seen, it was evaluated as Δ, and when it became black and lost, it was evaluated as ×.

[Transparency test]
The polyhedral structure polysiloxane composition is filled in a mold, and the polyhedral structure polysiloxane composition is thermally cured in a convection oven in the order of 80° C.×2 hours, 100° C.×1 hour, 150° C.×5 hours, A sample having a thickness of 1 mm was manufactured. With respect to the sample, a light transmittance at a wavelength of 450 nm was measured and evaluated by an ultraviolet-visible spectrophotometer (JASCO V 560 manufactured by JASCO Corporation).

[Gelization time (snap-up time)]
A small amount of the polyhedral polysiloxane-based composition was placed on an aluminum plate heated on a hot plate set at 150° C., and while mixing with a toothpick tip, the time required to reach a cured state was visually measured.

Next, a method for synthesizing a modified polyhedral polysiloxane will be described in Production Example 1 and Production Example 2.

[Production Example 1]
1083 g of tetraethoxysilane was added to 1262 g of a 48 wt% choline aqueous solution (trimethyl-2hydroxyethylammonium hydroxide aqueous solution), and the mixture was vigorously stirred at room temperature for 2 hours. When the reaction system generated heat and became a uniform solution, the stirring was slowed down and the reaction was continued for 12 hours. Next, 1000 mL of methanol was added to the solid substance generated in the reaction system to form a uniform solution.

While vigorously stirring a solution containing 537 g of dimethylvinylchlorosilane, 645 g of trimethylsilyl chloride, and 1942 mL of hexane, a methanol solution was slowly added dropwise to the solution. After completion of the dropping, the reaction was carried out for 1 hour, and then the organic layer was extracted and concentrated to obtain a solid substance. Next, the produced solid matter is washed by vigorously stirring in methanol, and the washed solid matter is separated by filtration to obtain an alkenyl group-containing polyhedral polyhedron structure having 16 Si atoms and 3 vinyl groups. The siloxane compound, tris(vinyldimethylsiloxy)pentakis(trimethylsiloxy)octasilsesquioxane (Fw=1166.2), was obtained as a white solid in an amount of 592 g.

[Production Example 2]
30 g of the alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 1 was dissolved in 60 g of toluene, and the solution was further added with a xylene solution of a platinum vinyl siloxane complex (a platinum vinyl siloxane complex containing 3 wt% as platinum, Umicore). 4.2 μL of Pt-VTSC-3X manufactured by Precious Metals Japan Co., Ltd. was dissolved. 45.0 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (the alkenyl group-containing polyhedral polysiloxane-based compound used was used). The mixture was added dropwise to a mixed solution of 22.5 g of toluene and 102.5 hydrosilyl groups per 1 alkenyl group, and the mixture was heated at 105° C. for 2 hours. When the solution was subjected to ¹ H-NMR measurement, it was confirmed that the alkenyl group derived from the alkenyl group-containing polyhedral polysiloxane compound had disappeared. After completion of the reaction, toluene and unreacted components were distilled off, and then 45 g of toluene was added again to dissolve the product. In the solution, 16.5 g of vinyldiphenylmethylsilane prepared separately (per 1 hydrosilyl group of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane used) A solution of 0.96 alkenyl groups) dissolved in 16.5 g of toluene was added dropwise and heated at 105° C. for 2 hours. When the solution was subjected to ¹ H-NMR measurement, it was confirmed that the vinyl group derived from vinyldiphenylmethylsilane had disappeared. After cooling to room temperature, toluene was distilled off to obtain 60.3 g of a liquid modified polyhedral polysiloxane (SiH value: 1.56 mol/kg).

[Example 1]
To 75 g of the modified polyhedral polysiloxane obtained in Production Example 2, 10.5 g of diallyl monomethyl isocyanurate and 6.2 g of 2,2-bis(4-allyloxyphenyl)propane were added and stirred to give a polyhedral polysiloxane. A siloxane composition was prepared. The above-mentioned various evaluations were performed using the composition, and the results are shown in Table 1.

[Example 2]
To 75 g of the modified polyhedral polysiloxane obtained in Production Example 2, 10.5 g of diallyl monomethyl isocyanurate and 6.2 g of 2,2-bis(3-allyl-4-hydroxyphenyl)propane were added and stirred, A polyhedral polysiloxane-based composition was prepared. The above-mentioned various evaluations were performed using the composition, and the results are shown in Table 1.

[Example 3]
To 75 g of modified polyhedral polysiloxane obtained in Production Example 2, 10.5 g of diallyl monomethyl isocyanurate and 5.68 g of 2,2-bis(3-methyl-4-allyloxyphenyl)propane were added and stirred. A polyhedral polysiloxane composition was prepared. Using the said, the above-mentioned various evaluations were performed and the results are shown in Table 1.

[Example 4]
To 75 g of the modified polyhedral polysiloxane obtained in Production Example 2, 10.5 g of diallyl monomethyl isocyanurate and 5.4 g of 2,2-bis(4-allyloxyphenyl)butane were added and stirred to form a polyhedral polysiloxane. A siloxane composition was prepared. The above-mentioned various evaluations were performed using the composition, and the results are shown in Table 1.

[Example 5]
To 75 g of the modified polyhedral polysiloxane obtained in Production Example 2, 10.5 g of diallyl monomethyl isocyanurate and 6.37 g of 1,1-bis(4-allyloxyphenyl)-1-phenylethane were added and stirred. A polyhedral polysiloxane composition was prepared. The above-mentioned various evaluations were performed using the composition, and the results are shown in Table 1.

[Comparative Example 1]
75 g of the modified polyhedral polysiloxane obtained in Production Example 2 was added to 10.5 g of diallyl monomethyl isocyanurate, and 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane 7 0.75 g was added and stirred to prepare a polyhedral polysiloxane composition. The above-mentioned various evaluations were performed using the composition, and the results are shown in Table 1.

[Comparative example 2]
To 75 g of modified polyhedral polysiloxane obtained in Production Example 2, 10.5 g of diallyl monomethyl isocyanurate and 3.77 g of 1,3-divinyltetramethyldisiloxane were added and stirred to prepare a polyhedral polysiloxane composition. Was prepared. The above-mentioned various evaluations were performed using the composition, and the results are shown in Table 1.

〔result〕
A cured product prepared from a composition containing a compound having a bisphenol skeleton and having two or more alkenyl groups in one molecule is more than a cured product prepared from a composition not containing the compound. , Showed a high gas barrier property (hydrogen sulfide resistance).

The present invention can be used in the field of manufacturing LEDs.

Claims (11)

(A) a compound having a hydrosilyl group,
(B) a compound having two or more alkenyl groups in one molecule,
(C) a hydrosilylation catalyst,
Wherein at least one component of the component (B), Ri organic compound der having (d) is bisphenol skeleton,
(A) A polyhedral modified polysiloxane, wherein the compound having a hydrosilyl group (A) is a hydrosilylation product of (a) a polyhedral polysiloxane compound having an alkenyl group and (b) a compound having a hydrosilyl group. A resin composition for an LED encapsulant , which is (A) a compound having a hydrosilyl group,
(B) a compound having two or more alkenyl groups in one molecule,
(C) a hydrosilylation catalyst,
At least one component of the component (B) is (d) an organic compound having a bisphenol skeleton,
(A) The compound having a hydrosilyl group is (a) a polyhedral polysiloxane compound having an alkenyl group, (b) a compound having a hydrosilyl group, and (c) an organic silicon having one alkenyl group in one molecule. A resin composition for an LED encapsulant, which is (A') modified polyhedral polysiloxane, which is a hydrosilylation product with a compound. The LED encapsulation according to claim 1 or 2 , wherein the (a) polyhedral polysiloxane compound having an alkenyl group is composed of a siloxane unit represented by the following (Formula 1). Resin composition for inhibitors:
^{_{[AR 1 2 SiO-SiO 3/2}} ] a [R 2 3 SiO-SiO 3/2] b ··· ( Equation 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; A is an alkenyl group; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom, an alkyl group, an aryl group, or a group linked to another polyhedral polysiloxane compound). The compound (b) having a hydrosilyl group is at least one selected from the group consisting of a cyclic siloxane having a hydrosilyl group and a linear siloxane having a hydrosilyl group at the molecular end . The resin composition for an LED encapsulant according to any one of 3 above. The resin composition for LED encapsulant according to any one of claims 1 to 4 , wherein the compound (b) having a hydrosilyl group is a cyclic siloxane having a hydrosilyl group. (B) The compound having a hydrosilyl group is 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, any one of claims 1 to 5 characterized in that The resin composition for an LED encapsulant according to item 1. The resin composition for an LED encapsulant according to claim 1 , wherein the modified polyhedral polysiloxane (A′) is composed of a siloxane unit represented by the following (formula 2). Stuff:
[XR ³ ₂ SiO-SiO _3/2 ] _a [R ⁴ ₃ SiO-SiO _3/2 ] _b ... (Formula 2)
(A+b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom , An alkyl group, an aryl group, or a group linked to another polyhedral polysiloxane compound; X is a structure represented by the following general formula (1) or a general formula (2), When there are a plurality of Xs in the siloxane unit represented by (Formula 2), the specific chemical structural formulas of each X may be different, and in the siloxane unit represented by (Formula 2) The structure of general formula (1) and the structure of general formula (2) may be mixed):

(L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; R is a hydrogen atom, an alkyl group or an aryl group; Y is a hydrogen atom, an alkenyl group, an alkyl A group that is bonded to a polyhedral polysiloxane compound through a group, an aryl group, or an alkylene chain, and when there are a plurality of Y in the siloxane unit represented by (Formula 2), Y is the same. Z may be different or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a moiety bonded to the polyhedral polysiloxane compound via an alkylene chain, and in the formula (2) When there is more than one Z in the represented siloxane unit, Z may be the same or different; at least one of Y or Z is a hydrogen atom). The resin composition for LED encapsulant according to claim 2 , wherein the modified polyhedral polysiloxane (A′) is composed of siloxane units represented by the following (formula 3). Stuff:
[XR ³ ₂ SiO-SiO _3/2 ] _a [R ⁴ ₃ SiO-SiO _3/2 ] _b ... (Formula 3)
(A+b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom , An alkyl group, an aryl group, or a group linked to another polyhedral polysiloxane compound; X is a structure represented by the following general formula (1) or a general formula (2), When there are a plurality of Xs in the siloxane unit represented by (Formula 3), the specific chemical structural formula of each X may be different, and in the siloxane unit represented by (Formula 3) The structure of general formula (1) and the structure of general formula (2) may be mixed):

(L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; R is an alkyl group or an aryl group; Y is a hydrogen atom, an alkenyl group, an alkyl group, aryl A group that is bonded to a polyhedral polysiloxane compound through a group or an alkylene chain, and when there are a plurality of Y in the siloxane unit represented by (Formula 3), Y may be the same or different. Z is a site bonded to a polyhedral polysiloxane compound through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain, and is a siloxane unit represented by (formula 3). When there are a plurality of Zs, Z may be the same or different; when two or more Y and Z are contained in total in the siloxane unit represented by (Formula 3), Y or At least one of Z is a hydrogen atom, and at least one of Y and Z has a structure of the following general formula (3)):

(1 is an integer of 2 or more; R ⁵ is a group having an organosilicon compound). (D) The organic compound having a bisphenol skeleton is an organic compound having a number average molecular weight of less than 1000, The resin composition for LED encapsulant according to any one of claims 1 to 8 , characterized in that (D) The organic compound having a bisphenol skeleton is an organic compound in which hydrogen of two phenolic hydroxyl groups on the bisphenol skeleton is replaced by an alkenyl group, and the organic compound is any one of claims 1 to 9. The resin composition for an LED encapsulant according to the item. An LED sealant resin composition according to any one of claims 1 to 10, LED sealants.