JP2017095540A - Led device sealant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealing agent for an LED device which gives a cured product having further enhanced gas barrier performance. The encapsulant for an LED device of the present invention includes (A) a compound having two or more SiH groups in one molecule, and (B) a compound having two or more alkenyl groups in one molecule. C) Contains an isocyanate compound as an essential component. [Selection diagram] None

Description

  The present invention relates to a sealant for an LED device.

  The LED device is manufactured by arranging a semiconductor light emitting element, an electrode, wiring connecting the semiconductor element and the electrode, etc. in a cup, cavity or package recess, and sealing (covering) them with a resin.

  Polysiloxane-based curable compositions are used in various industries because of their good heat resistance, light resistance, chemical stability, electrical properties, transparency, non-corrosion properties, etc. It is also used as a sealant (Patent Documents 1 to 6).

JP 2014-181287 A International Publication No. 2008/010545 Pamphlet International Publication No. 2008/133138 Pamphlet Special table 2012-507582 JP 2013-124343 A JP2013-159670A

  In recent years, among the characteristics required for sealants for LED devices, there is an increasing demand for improving gas barrier properties. Silver and copper used for the electrodes constituting the LED device and the wiring connecting the electrodes and the LED elements are easily affected by sulfur-based outgas such as hydrogen sulfide and sulfur dioxide. Such sulfur-based outgas is known to be generated from the packaging materials of LED devices in addition to being contained in the atmosphere. Especially, since LED devices are relatively small, even a very small amount of sulfur-based outgas has an effect. There is a problem that the electrodes and the like corrode, and the brightness is lowered even with the product before use as well as with time. Moreover, in the high-intensity white LED whose use is expanding, the reduction in luminance due to such outgassing is a serious problem that lowers the commercial value.

  The present invention has been made by paying attention to the above-described circumstances, and its purpose is to provide a sealant for an LED device that provides a cured product having further improved gas barrier performance in addition to transparency and chemical stability. Is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have combined a specific SiH group-containing compound and a specific alkenyl group-containing compound with an isocyanate compound as constituent components of an LED device sealant. It was found that the gas barrier properties of the cured product can be further enhanced by using the present invention, and the present invention has been completed.

The sealant for LED device of the present invention is
(A) a compound having two or more SiH groups in one molecule;
(B) a compound having two or more alkenyl groups in one molecule;
(C) It is characterized by including an isocyanate compound as an essential component.

  The isocyanate compound (C) is preferably an isocyanate silane coupling agent, or a polyisocyanate compound having two or more isocyanate groups independently and / or in a large amount in one molecule. It is recommended that the amount of the isocyanate compound (C) be 0.001 to 50 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B).

  It is preferable that the sealing agent for an LED device further includes (D) a compound having one or more epoxy groups in one molecule.

  The compound (A) having two or more SiH groups in one molecule includes a polyhedral polysiloxane compound (a) having an alkenyl group, a compound (b) having a hydrosilyl group, and an alkenyl group in one molecule. It is preferably obtained by hydrosilylation reaction of an organosilicon compound (c) having 1 and / or a cyclic olefin compound (d) having 1 carbon-carbon double bond in one molecule.

  In addition, as the organosilicon compound (c) having one alkenyl group in one molecule, an organosilicon compound having one or more aryl groups is preferably used. The molecular weight of the cyclic olefin compound (d) having one carbon-carbon double bond in one molecule is desirably 1000 or less.

  The compound (b) having a hydrosilyl group is preferably a cyclic siloxane or a linear siloxane having a hydrosilyl group.

The polyhedral polysiloxane compound (a) containing the alkenyl group has the general formula
[AR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(In the general 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; Represents an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane)
It is preferably a polyhedral polysiloxane compound containing an alkenyl group composed of a siloxane unit represented by the formula:

  In addition to the above components (A) to (C), the LED device encapsulant may contain a curing retarder, or may contain a hydrosilylation catalyst, and further a phosphor. May be included.

  Since the sealing agent for LED devices of the present invention provides a cured product having excellent gas barrier properties, if an LED device is produced using this sealing agent for LED devices, electrodes and wirings provided in the LED device Corrosion due to the outgas (especially sulfur-based gas) can be prevented, and as a result, a decrease in luminance of the LED device can be suppressed.

  The sealant for an LED device of the present invention includes (A) a compound having two or more SiH groups in one molecule, (B) a compound having two or more alkenyl groups in one molecule, and (C) an isocyanate. System compounds are included as essential components. First, (A) a compound having two or more SiH groups in one molecule will be described.

<(A) Compound having two or more SiH groups in one molecule>
Examples of the compound (A) having two or more SiH groups in one molecule include, for example, a polyhedral polysiloxane compound (a) having an alkenyl group, a compound (b) having a hydrosilyl group, and one molecule. Compounds obtained by hydrosilylation of an organosilicon compound (c) having one alkenyl group and / or a cyclic olefin compound (d) having one carbon-carbon double bond in one molecule are included (hereinafter, A compound (A) having two or more SiH groups in one molecule may be referred to as a modified polyhedral polysiloxane (A)).

-Polyhedral polysiloxane compounds having alkenyl groups (a)
The polyhedral 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:
[R ⁶ SiO _3/2 ] _x [R ⁷ SiO _3/2 ] _y
(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 ⁶ is an alkenyl group or a group having an alkenyl group; R ⁷ is any organic group, or Groups linked to other polyhedral skeleton polysiloxanes)
An alkenyl group-containing polyhedral polysiloxane compound composed of a siloxane unit represented by the following formula can be preferably used.
[AR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom or an alkyl group , Aryl groups, or groups linked to other polyhedral skeleton polysiloxanes)
An alkenyl group-containing polyhedral polysiloxane compound composed of siloxane units represented by the formula:

  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 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. Examples of the aryl group include aryl groups such as a phenyl group and a tolyl group. Is done. R ¹ in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.

R ² 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 ² in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.

  a is not particularly limited as long as it is an integer of 1 or more, but is preferably 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 of 6 to 24. However, from the viewpoint of the stability of the compound and the stability of the resulting cured product, it is preferably 6 to 12, and more preferably 6 to 10 is 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 ⁸ SiX ^a ₃ (wherein R ⁸ represents R ⁶ or R ⁷ described above, and X ^a represents a hydrolyzable functional group such as a halogen atom or an alkoxy group) The hydrolysis condensation reaction of the silane compound represented by a formula is mentioned. Alternatively, after synthesizing a trisilanol compound having three silanol groups in the molecule by hydrolysis and condensation reaction of R ⁸ SiX ^a _3, the ring is closed by reacting the same or different trifunctional silane compounds, and polyhedral Methods for synthesizing structural polysiloxanes are also known.

  In addition, for example, there is a method of hydrolytic condensation of tetraalkoxysilane such as tetraethoxysilane in the presence of a base such as quaternary ammonium hydroxide. In the present synthesis method, a silicate having a polyhedral structure 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 becomes possible to obtain a polyhedral polysiloxane in which Si atoms and alkenyl groups forming a polyhedral structure are bonded via a siloxane bond. In the present invention, the same polyhedral polysiloxane can be obtained from a substance containing silica such as silica or rice husk instead of tetraalkoxylane.

.Compound (b) having a 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 of the resulting polyhedral polysiloxane modified product (A), From the viewpoint of heat resistance and light resistance, a siloxane compound having a hydrosilyl group is preferable, and a cyclic siloxane having a hydrosilyl group or a linear polysiloxane having a hydrosilyl group is more preferable. 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 molecular ends blocked with dimethylhydrogensilyl groups can be suitably used. Specific examples 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. Examples of the cyclic siloxane include, for example, 1,3,5,7-tetrahydrogen-1,3, from the viewpoint of industrial availability and reactivity, or heat resistance, light resistance, strength, and the like of the obtained cured product. 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.

-Organosilicon compound having one alkenyl group in one molecule (c)
The organosilicon compound (c) having one alkenyl group in one molecule reacts with the hydrosilyl group of the compound (b) having a hydrosilyl group. By using the component (c), the elastic modulus of the cured product obtained from the sealant for an LED device of the present invention can be reduced, and the thermal shock resistance can be improved.

  Examples of the alkenyl group that component (c) has include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, but a vinyl group is preferred 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) is preferably silane or polysiloxane from the viewpoint of heat resistance and light resistance. As the case where the component (c) is a silane having one alkenyl group in one molecule, specifically, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, triphenylvinylsilane, triethylvinylsilane, diethylphenylvinylsilane, Examples include 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.

  On the other hand, examples of the case where the component (c) is a polysiloxane include a polysiloxane having a linear structure having one alkenyl group, a polysiloxane having one alkenyl group at the molecular end, and a cyclic siloxane having one alkenyl group. Is done.

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

Specifically, in the case of a polysiloxane having one alkenyl group at the molecular end, specifically, a polysiloxane having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group as exemplified above, SiO ₂ unit, SiO ₂ Examples include at least one siloxane unit selected from the group consisting of _3/2 units, SiO units, and SiO _1/2 units, and polysiloxane composed of one dimethylvinylsiloxane unit.

  As the case where the component (c) is a cyclic siloxane having one alkenyl group, specifically, 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.

  These organosilicon compounds having one alkenyl group in one molecule, which is component (c), may be used alone or in combination of two or more.

-Cyclic olefin compound having one carbon-carbon double bond in one molecule (d)
The cyclic olefin compound (d) having one carbon-carbon double bond in one molecule undergoes hydrosilylation reaction with the hydrosilyl group of the compound (b) having a hydrosilyl group. By using the component (d), the elastic modulus of the resulting cured product can be reduced, and the thermal shock resistance can be improved. Further, by using the component (d), the gas barrier property and light extraction efficiency of the obtained cured product can be improved.

  The component (d) may be any cyclic olefin compound having one carbon-carbon double bond in one molecule, and this carbon-carbon double bond is any one of a vinylene group, a vinylidene group, and an alkenyl group. Also good. 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 (d) preferably has an average molecular weight of 1000 or less from the viewpoint of reactivity with the component (b). Examples of the cyclic olefin compound (d) include an aliphatic cyclic olefin compound and a substituted aliphatic cyclic olefin compound.

  Specific examples of the aliphatic cyclic olefin compound include cyclohexene, cycloheptene, cyclooctene, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, allylcyclohexane, allylcycloheptane, allylcyclooctane, and methylenecyclohexane. Can be mentioned.

  Specific examples of the substituted aliphatic cyclic olefin compound include norbornene, 1-methylnorbornene, 2-methylnorbornene, 7-methylnorbornene, 2-vinylnorbornane, 7-vinylnorbornane, 2-allylnorbornane, and 7-allylnorbornane. , 2-methylenenorbornane, 7-methylenenorbornane, camphene, vinylnorcamphene, 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 (d) components may be used independently and may use 2 or more types together.

  The compound (A) having two or more SiH groups in one molecule is composed of a polyhedral polysiloxane compound (a) having an alkenyl group and one alkenyl group in one molecule in the presence of a hydrosilylation catalyst described later. It is obtained by hydrosilylation reaction of the organosilicon compound (c) having one and / or the cyclic olefin compound (d) having one carbon-carbon double bond in one molecule with the compound (b) having a hydrosilyl group. .

  The method for obtaining the compound (A) is not particularly limited and can be variously set. However, after reacting the component (a) and the component (b) in advance, the component (c) and / or the component (d) are reacted. Alternatively, the component (c) and / or the component (d) and the component (b) may be reacted in advance, and then the component (a) may be reacted, or the component (a) and the component (c) and / or Alternatively, the component (d) may be allowed to coexist with the component (b). After completion of each reaction, for example, volatile unreacted components may be distilled off under reduced pressure and heating conditions, and used as a target product or an intermediate for the next step. In order to suppress the formation of the compound which does not contain the component (c) and / or the component (d) and the component (b) and does not contain the component (a), the component (a) and the component (b) are reacted. The method of reacting the component (c) and / or the component (d) after distilling off the unreacted component (b) is preferred. It is preferable from the viewpoint of heat resistance that only the component (c) and / or the component (d) and the component (b) react to suppress the formation of the compound not containing the component (a).

  The compound (A) thus obtained has a bond in which the SiH group of the component (b) is added to the alkenyl group of the component (a), the alkenyl group (carbon-carbon 2) of the component (c) and / or the component (d). (Double bond) and a bond to which the SiH group of component (b) is added. In the compound (A), a part of the alkenyl group of the component (a) used in the reaction may remain.

  Component (b) is preferably added so that the number of hydrosilyl groups is 2.5 to 20 with respect to one alkenyl group of component (a). When the addition amount is small, gelation proceeds due to a crosslinking reaction, so that the handleability of the modified polyhedral polysiloxane may be inferior, and when the addition amount is large, the physical properties of the cured product may be adversely affected.

  Component (c) is preferably added so that the number of alkenyl groups in component (c) is 0.01 to 0.36 with respect to one hydrosilyl group in component (b). 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.

  The amount of component (d) used is such that the number of carbon-carbon double bonds in component (d) is 0.01 to 0.5 for one hydrosilyl group in component (b). Is preferred. 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.

The addition amount of the hydrosilylation catalyst used in the synthesis of the compound (A) is not particularly limited, but is 10 with respect to 1 mol of the alkenyl group of the component (a), the component (c) and / or the component (d) used in the reaction. ^It is preferable to use in the range of ^-1 to 10 ^-10 mol. Preferably, it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. If there are many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it absorbs light with a short wavelength, which may cause coloring of the cured product or decrease the light resistance of the resulting cured product. There is also a risk that things will foam. On the other hand, when there are few hydrosilylation catalysts, there exists a possibility that reaction may not progress and it may become difficult to obtain a target object.

  The reaction temperature of the hydrosilylation reaction is preferably 30 ° C to 400 ° C, more preferably 40 ° C to 250 ° C, and further preferably 45 ° C to 140 ° C. If the temperature is too low, there is a tendency that the reaction does not proceed sufficiently. On the other hand, if the temperature is too high, gelation occurs and handling properties may be deteriorated.

  The compound (A) thus obtained can ensure compatibility with various compounds, particularly siloxane compounds, and further has a compound having various alkenyl groups since a hydrosilyl group is introduced into the molecule. It becomes possible to make it react. Specifically, a cured product can be obtained by reacting with a compound (B) having two or more alkenyl groups in one molecule described below.

  The compound (A) can also be made liquid at a temperature of 20 ° C. If the compound (A) is liquid, it is preferable because of excellent handling properties.

The compound (A) in the present invention has the general formula:
[XR ³ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
[In the general 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 an alkenyl group, a hydrogen atom, an alkyl group; A group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane, X has a structure of the following general formula (1) or general formula (2), and when there are a plurality of X The structure of general formula (1) or general formula (2) may be different, and the structure of general formula (1) or general formula (2) may be mixed.

{L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain Yes, they may be the same or different. However, at least one of Y or Z is a hydrogen atom, and at least one has the structure of the following general formula (3).
-[CH ₂ ] _l -R ⁵ (3)
(In general formula (3), l is an integer of 2 or more; R ⁵ is a group containing an organosilicon compound); R is an alkyl group or an aryl group}]
It is a polyhedral polysiloxane compound composed of siloxane units represented by the formula:

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

<(B) Compound having two or more alkenyl groups in one molecule>
The sealing agent for LED devices of this invention contains the compound (B) which has a 2 or more alkenyl group in 1 molecule. A cured product can be obtained by hydrosilylating the alkenyl group of compound (B) with the hydrosilyl group of compound (A).

  As the compound (B), for example, polysiloxane (B1) having two or more alkenyl groups in one molecule, an organic compound (B2), and the like are preferable. In the compound (B), the component (B1) or the component (B2) may be used alone, or the component (B1) and the component (B2) may be used in combination.

・ 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 is not particularly limited, but is preferably 2 or more, and more preferably 2 to 10. 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 (B1) having two or more alkenyl groups in one molecule preferably has an aryl group from the viewpoint of gas barrier properties. Moreover, it is preferable that the polysiloxane having two or more alkenyl groups in one molecule having an aryl group has an aryl group bonded directly on 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 end of the molecule, and the molecular structure of such an aryl group-containing polysiloxane is not limited. For example, the aryl group-containing polysiloxane has a straight chain, branched chain, or partially branched chain. 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-t-butylphenyl group, 4-t-butylphenyl group, 3-pentylphenyl group, 4-pentylphenyl group, 3-hexylphenyl group, 4-hexylphenyl Group, 3-cyclohexylphenyl group, 4-cyclohexylphenyl group, 2,3-dimethylphenyl Nyl 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- Examples include trimethylphenyl 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. It is done. 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.

  From the viewpoint of heat resistance and light resistance, the polysiloxane (B1) having two or more alkenyl groups in one molecule is a linear polysiloxane having two or more alkenyl groups, and two alkenyl groups at the molecular ends. Preferred examples include polysiloxanes having the above 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 dimethylvinylsilyl groups 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.

  The polysiloxane (B1) having two or more alkenyl groups in one molecule may be used alone or in combination of two or more.

・ Organic compound (B2)
The component (B2) in the present invention specifically serves as a crosslinking agent for the component (A), and by using the component (B2), the heat resistance, light resistance, and The gas barrier property can be improved.

  Although it will not specifically limit if it is an organic compound which contains two or more alkenyl groups in 1 molecule as an organic compound (B2), For example, the organic compound represented by following General formula (4) is mentioned.

(In General Formula (4), R ⁹ represents a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and each R ⁹ may be different or the same.)

  Since the component (B2) contains two or more alkenyl groups in one molecule, the strength, gas barrier property, heat resistance, light resistance and the like of the obtained cured product are excellent. From the viewpoint of gas barrier properties, the component (B2) preferably has a number average molecular weight of less than 900.

Examples of the organic group include an alkyl group, an alkenyl group, an epoxy group, an acrylic group (acryloyl group), and a group having two or more of these groups. In addition, although the hetero atom may be contained in the organic group which an organic compound (B2) has, a silicon atom is not contained. In the compound (B2), one R ⁹ may have two or more alkenyl groups, and two or more R ⁹ may have one or more alkenyl groups.

  As the component (B2), for example, from the viewpoint of adhesiveness between the sealant (cured product) and the base material, isocyanuric represented by the general formula (4) and containing two or more alkenyl groups in one molecule It is preferably an acid derivative, and from the viewpoint of the balance between heat resistance and light resistance, triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoglycidyl isocyanurate are more preferred, and particularly, thermal shock resistance From the viewpoint, diallyl monomethyl isocyanurate is more preferable.

  The component (B2) may have a functional group other than an alkenyl group in its skeleton, but from the viewpoint of compatibility with the compound (A), a straight chain such as a methyl group, an ethyl group, or a propyl group. It is preferable that it is a functional group with low polarity, such as a shaped aliphatic hydrocarbon group, and a methyl group is particularly preferable from the viewpoint of heat resistance and light resistance.

  An organic compound (B2) may be used independently and may be used in combination of 2 or more types.

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

<(C) Isocyanate compound>
The sealing agent for LED devices of this invention contains (C) isocyanate type compound. In the present invention, the isocyanate compound (C) is used for the purpose of further improving the gas barrier properties of the cured product.

  The isocyanate compound (C) may be any compound having an isocyanate group, and specifically, an aliphatic isocyanate compound; an alicyclic isocyanate compound; an aromatic isocyanate compound; an isocyanurate ring-modified product; A silane coupling agent etc. are mentioned. As the isocyanate compound (C), adducts and multimers of the above various isocyanate compounds can also be used. These isocyanate compounds (C) may be used alone or in combination of two or more. The isocyanate compound (C) is different from the above component (B2) in that it does not have an alkenyl group. Moreover, it is preferable that (C) component does not have an epoxy group.

  Examples of the aliphatic isocyanate compound include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and the like.

  Examples of the alicyclic isocyanate compound include isophorone diisocyanate, cyclohexylene-1,4-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and the like.

  Examples of the aromatic isocyanate compound include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, and diphenylmethane-4. , 4′-diisocyanate, 1,3-bis (isocyanatomethyl) benzene and the like.

  The isocyanurate ring-modified product is a polyisocyanate compound having two or more isocyanate groups independently and / or in a large amount in one molecule, and is represented, for example, by the following general formula (5).

In General Formula (5), R ¹¹ represents a hydrogen atom, —R ¹² —SiMe _s X ¹ _(3-s) , or an alkyl isocyanate group having 1 to 20 carbon atoms, and R ¹² has 2 to 6 carbon atoms. Represents an alkylene group, and at least one R ¹¹ is —R ¹² —SiMe _s X ¹ _(3-s) or an alkyl isocyanate group having 1 to 20 carbon atoms, and s represents an integer of 0 to 2. The hydrolyzable group X ¹ is preferably an alkoxy group having 1 to 20 carbon atoms. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, and a 2-methoxyethoxy group.

  As a compound represented by General formula (5), it is a trimer of an isocyanate compound, Comprising: The compound which has an isocyanurate ring, or the compound which has an isocyanurate ring and an isocyanate group is mentioned. Specifically, N, N ′, N ″ -tri (1-isocyananaatehexyl) isocyanuric acid obtained by adding hexamethylene diisocyanate or Vernock DN-950 manufactured by Dainippon Ink & Chemicals, Inc. , DN-980, DN-902S, DN-990 and other isocyanurate type polyisocyanates; isocyanurate type silane coupling agents such as tris- (trimethoxysilylpropyl) isocyanurate and tris- (triethoxysilylpropyl) isocyanurate Is mentioned.

The isocyanate-based silane coupling agent is not particularly limited as long as it is a compound having at least one isocyanate group and one hydrolyzable group bonded to a silicon atom in the molecule. Specific examples of the isocyanate-based silane coupling agent include compounds represented by the following general formula (6) having an isocyanate group and a reactive hydrolyzable group X ¹ in the molecule.
X ¹ _(3-s) Me _s Si—R ¹⁰ —N═C═O (6)

In General Formula (6), R ¹⁰ represents an ethylene group or a propylene group, and s represents an integer of 0 to 2. The hydrolyzable group X ¹ is preferably an alkoxy group having 1 to 20 carbon atoms. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, and a 2-methoxyethoxy group.

  Specific isocyanate-based silane coupling agents represented by the general formula (6) include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropyldimethoxymethylsilane, and 3-isocyanatepropyl. Examples include diethoxymethylsilane.

  An isocyanate type compound (C) may be used independently and may use 2 or more types together.

  When using an aliphatic isocyanate compound, an alicyclic isocyanate compound, an aromatic isocyanate compound, and / or an isocyanurate type polyisocyanate as the compound (C), it is preferable to use a polyisocyanate compound having two or more isocyanate groups. The number of isocyanate groups is more preferably 1 or more per molecule, preferably 3 or less, and more preferably 2 or less.

  Among the isocyanate compounds (C), an isocyanate silane coupling agent or a polyisocyanate compound having two or more isocyanate groups independently and / or in a large amount in one molecule is preferably used. Further, when the isocyanate compound (C) has an isocyanate group at the molecular end, it is preferable because the gas barrier property of the cured product tends to be further enhanced.

  The addition amount of the isocyanate compound (C) is 0.001 part by mass or more and 50 parts by mass with respect to 100 parts by mass of the mixture of the compound (A) and the compound (B) having two or more alkenyl groups in one molecule. The amount is preferably 0.05 parts by mass or more and 30 parts by mass or less, more preferably 0.1 parts by mass or more and 30 parts by mass or less. If the amount added is too small, the effect of improving the gas barrier properties may be difficult to obtain, whereas if the amount added is too large, the physical properties of the cured product may be adversely affected.

<(D) Compound having one or more epoxy groups in one molecule>
The encapsulant for LED device of the present invention may contain (D) a compound having one or more epoxy groups in one molecule. The gas barrier property of the cured product can be further improved by using the compound (D) in addition to the compounds (A) to (C).

  The compound (D) is not particularly limited as long as it has one or more epoxy groups in one molecule. For example, glycidyl polyol such as diglycidyl hexanediol, ethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, etc. Diglycidyl ether of ether or polyol; epoxidized phenol and aldehyde novolac resin such as phenol novolac type epoxy resin and orthocresol novolac type epoxy resin; bisphenol A type epoxy resin (bisphenol A diglycidyl ether, etc.), Diglycidyl ethers such as bisphenol F type epoxy resins (bisphenol F diglycidyl ether, etc.), bisphenol S type epoxy resins and alkyl-substituted bisphenols; Dicarboxylic acid diglycidyl esters derived from nurate, triglycidyl isocyanurate and 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid (eg 1,2-cyclohexanedicarboxylic acid) Diglycidyl, etc.); glycidylamine type epoxy resins obtained by reaction of polyamines such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin; linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid; and fats Cyclic epoxy resin; (D1) a compound having an alkenyl group and an epoxy group in the same molecule; (D2) a compound containing two or more SiH groups in one molecule; and (D3) a reactivity with the SiH group. One carbon-carbon double bond having Hydrosilylation reaction products of a compound containing two or more in the child and the like. Among these, from the viewpoint of compatibility with the above compounds (A) and (B), a compound having both an epoxy group and a SiH group in one molecule is preferable.

  Examples of the compound having both an epoxy group and an SiH group in one molecule include (D1) a compound having an alkenyl group and an epoxy group in the same molecule, and (D2) two or more SiH groups in one molecule. The hydrosilylation reaction product of the compound to contain and the compound which contains 2 or more of carbon-carbon double bonds (D3) reactive with SiH group in 1 molecule is mentioned.

  The component (D1) is not particularly limited as long as it is a compound having an alkenyl group and an epoxy group in the same molecule. For example, vinylcyclohexene oxide, allyl glycidyl ether, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanate Examples include nurate.

  The component (D2) is not particularly limited as long as it has two or more hydrosilyl groups in one molecule. From the viewpoint of transparency, heat resistance, and weather resistance of the finally obtained cured product, hydrosilyl It is preferably a siloxane compound having a group, and more preferably a cyclic siloxane having a hydrosilyl group or a linear polysiloxane having a hydrosilyl group. In particular, a cyclic siloxane is preferable from the viewpoint of compatibility with the compound (A).

  Specific examples of the component (D2) include the same components as the component (b). In addition, from the viewpoints of industrial availability and reactivity, or heat resistance, light resistance, strength, and the like of the resulting cured product, for example, 1,3,5,7-tetrahydrogen-1,3,5, 7-tetramethylcyclotetrasiloxane is preferably used.

  The component (D3) is not particularly limited as long as it is a compound containing two or more carbon-carbon double bonds having reactivity with the SiH group in one molecule. For example, the component (B) in one molecule The same compounds as those having two or more alkenyl groups can be used. Among the compounds (B), the component (B2) is preferable, and the compound represented by the general formula (4) having an isocyanurate ring structure is more preferable. . Among those obtained by reacting the components (D1) to (D3), for example, some of the SiH groups of 1,3,5,7-tetramethylcyclotetrasiloxane (D2) are allyl glycidyl ether (D1) and triallyl. What reacted with isocyanurate (D3) is preferable.

  Although the synthesis method of compound (D) is not particularly limited, (D3) component may be reacted after (D1) component and (D2) component are reacted, and (D2) component and (D3) component are reacted. Then, the component (D1) may be reacted, or the component (D2) may be reacted with the component (D2) in the coexistence of the component (D1) and the component (D3).

  The amount of component (D2) used is preferably 2 to 6 hydrosilyl groups in the component (D2), more preferably 3 to 5 per alkenyl group of the component (D1). Yes, more preferably 3-4.

  The amount of component (D3) used is preferably in the range of 2 to 6 hydrosilyl groups contained in compound (D2) per alkenyl group of component (D3), more preferably 3 to 3. The number is 5, more preferably 3 to 4.

Although there is no restriction | limiting in particular as the addition amount of the hydrosilylation catalyst used at the time of the synthesis | combination of a compound (D), 10 ^<-8 > ^-10 < ^{-1 >} mol with respect to 1 mol of alkenyl groups of (D1) component and (D3) component used for reaction. It is good to use in the range. Preferably, it is used in the range of 10 ⁻⁶ to 10 ⁻² mol. If there are many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it absorbs light with a short wavelength, which may cause coloring of the cured product or decrease the light resistance of the resulting cured product. There is also a risk that things will foam. On the other hand, when there are few hydrosilylation catalysts, there exists a possibility that reaction may not progress and it may become difficult to obtain a target object.

  The reaction temperature of the hydrosilylation reaction is preferably 30 ° C to 400 ° C, more preferably 40 ° C to 250 ° C, and further preferably 45 ° C to 140 ° C. If the temperature is too low, there is a tendency that the reaction does not proceed sufficiently. On the other hand, if the temperature is too high, gelation occurs and handling properties may be deteriorated.

  The compound thus obtained has a bond in which the SiH group of the (D2) component is added to the alkenyl group (carbon-carbon double bond group) of the (D1) component and the (D3) component. Further, the compound (D) obtained from the components (D1) to (D3) can also be used as the compound (A) by having two or more SiH groups in one molecule.

  It is preferable that the molecular weight of a compound (D) is 50-3000, More preferably, it is 800-2500, More preferably, it is 900-2000. A molecular weight exceeding this range is not preferable from the viewpoint of solubility.

  The addition amount of the compound (D) is 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the mixture of the compound (A) and the compound (B) having two or more alkenyl groups in one molecule. It is preferably 5 parts by mass or more and 95 parts by mass or less, and more preferably 10 parts by mass or more and 90 parts by mass or less. If the amount added is too small, there is a risk of hardening, while if the amount added is too large, there is a risk of coloring.

<Hydrosilylation catalyst>
In the present invention, a hydrosilylation catalyst is used in synthesizing the compound (A) and curing the sealant for an LED device containing the compound (A). As the hydrosilylation catalyst, a conventionally known hydrosilylation catalyst can be used, and there is no particular limitation.

Specific hydrosilylation catalysts include platinum-olefin complexes, chloroplatinic acid, platinum alone, a carrier (alumina, silica, carbon black, etc.) supported by solid platinum, 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 represent an integer) ), Pt (acac) _2, also platinum described in U.S. Patent 3,159,601 and in Pat 3159662 of Ashby et al - hydrocarbon complex, and Lamorea Platinum alcoholate catalysts described in U.S. Patent No. in 3,220,972 Pat of x et also included.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl ₄ , and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) _{2 and the} like are preferable.

<Curing retarder>
The curing retarder is a component for improving the storage stability of the sealant for an LED device of the present invention or adjusting the reactivity of the hydrosilylation reaction during the curing process. 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-hexyne- Examples include propargyl alcohols such as 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. These curing retarders may be used alone or in combination of two or more.

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.

<Phosphor>
The sealant for an LED device of the present invention can be used in combination with any phosphor as long as it is a conventionally known phosphor. The phosphor that can be combined with the sealant for LED device of the present invention is not particularly limited. For example, YAG phosphor, LuAG phosphor, TAG phosphor, BOS phosphor, orthosilicate alkaline earth. And the like phosphors, α-sialon phosphors, β-sialon phosphors, CASN phosphors, SCASN phosphors, nitrides and oxynitride phosphors. One type or two or more types of phosphors can be used in any ratio and combination.

  Although the present inventors have not grasped the detailed reason so far, among these phosphors, when using a YAG phosphor and a β-sialon phosphor together with a sealant for an LED device, This is preferable because deterioration over time of the phosphor can be suppressed.

  There is no restriction | limiting in particular in the usage-amount of fluorescent substance, Although arbitrary amounts can be used in order to obtain the luminescent color which an LED device requires, if it dares to illustrate, it is preferable in the sealing agent for LED devices. Is 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass 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 handling properties of the sealant will be reduced. Or the use efficiency of the phosphor may be lowered due to optical interference.

<Other additives>
The sealing agent for LED devices of this invention may contain the adhesion imparting agent which improves the adhesiveness of the hardened | cured material of the sealing agent for LED devices, and a base material as needed. Although there is no restriction | limiting in particular as an adhesive provision agent, The silane coupling agent which has at least 1 each of the functional group reactive with an organic group and a hydrolyzable silicon group in a molecule | numerator is mentioned as a preferable example. 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, a vinyl group, and a carbamate group from the viewpoint of handleability, and from the viewpoint of curability and adhesiveness. An epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Specific preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldisilane. Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- Alkoxysilanes having an epoxy functional group such as (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysila Alkoxysilanes having a methacrylic group or an acrylic group such as 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Is mentioned. These may be used alone or in combination of two or more.

  As addition amount of a silane coupling agent, it is preferable that it is 0.05-30 mass parts with respect to 100 mass parts of mixtures of a compound (A) and a compound (B), More preferably, it is 0.1-10. Part by mass. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the properties of the cured product may be adversely affected.

  In the present invention, a known adhesion promoter can be used to enhance the effect of the adhesion promoter. Adhesion promoters include, but are not limited to, epoxy-containing compounds, epoxy resins, boronic ester compounds, organoaluminum compounds, and organotitanium compounds.

  Moreover, the sealing agent for LED devices of this invention can add an inorganic filler as needed. By using an inorganic filler, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical characteristics, light reflectance, flame retardancy, fire resistance, gas barrier properties, etc. of the molded product obtained Various physical properties can be improved.

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

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

As the shape of the inorganic filler, various types such as a crushed shape, a piece shape, a spherical shape, and a rod shape can be used. The average particle size and particle size distribution of the inorganic filler are not particularly limited, but from the viewpoint of gas barrier properties, the average particle size is preferably 0.005 to 50 μm, more preferably 0.01 to 20 μm. More preferably. Similarly, the BET specific surface area, although not particularly limited, from the viewpoint of gas barrier properties, it is preferably 70m ² / g or more, more preferably 100 m ² / g or more, further 200 meters ² / It is especially preferable that it is g or more.

  Although the addition amount of an inorganic filler is not specifically limited, It is preferable to set it as 1-1000 mass parts with respect to 100 mass parts of mixtures of a compound (A) and a compound (B), More preferably, it is 3-500 mass parts, Furthermore, Preferably it is 5-300 mass parts. When the amount of the inorganic filler added is large, the fluidity may be deteriorated, and when the amount of the inorganic filler added is small, desired physical properties may not be obtained.

  The order of mixing the inorganic filler is not particularly limited, but a method of mixing the compound (A) with the mixture of the compound (B) and the inorganic filler is desirable in that the storage stability tends to be good. In addition, the compound (A) and the compound (B), which are reaction components, are mixed well and a stable molded product is easily obtained. Are preferably mixed.

<LED device sealant>
The sealant for an LED device of the present invention comprises a compound (A) having two or more SiH groups in one molecule, a compound (B) having two or more alkenyl groups in one molecule, and an isocyanate compound (C ) Can be obtained by adding a hydrosilylation catalyst, a curing retarder and a phosphor as necessary. The sealant for an LED device of the present invention can be handled as a liquid resin composition. By using a liquid resin composition, a light emitting element can be sealed in a mold or the like by being injected or applied to a mold, a package, a substrate, or the like and cured. Since the sealant for an LED device of the present invention provides a cured product having excellent gas barrier properties, permeation of the oxygen-based gas or sulfur-based gas in the cured product is suppressed, and an electrode, a lead frame, an LED element and an electrode, etc. As a result of suppressing the corrosion of the constituent material of the LED device which is sealed simultaneously with the LED element such as the LED element such as a reflector, the decrease in luminous intensity and total luminous flux is suppressed, and the LED device capable of maintaining high luminance can be maintained. Provision is possible.

  The conditions for curing the LED device sealant are not particularly limited, but the curing temperature is preferably 30 ° C to 400 ° C, more preferably 50 ° C to 250 ° C. If the curing temperature is too high, the resulting cured product may be defective in appearance, whereas if the curing temperature is too low, curing may be insufficient. Moreover, you may make it harden | cure combining the temperature conditions of two or more steps. Specifically, it is preferable to raise the curing temperature stepwise such as 70 ° C., 120 ° C., and 150 ° C. because a good cured product can be obtained.

  The curing time can be appropriately determined according to the curing temperature, the amount of hydrosilylation catalyst used and the amount of reactive groups, and other components contained in the LED device sealant. It is preferable to set the time, and more preferably, a cured product is easily obtained by performing the curing reaction for 10 minutes to 8 hours.

  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, “%” means “mass%” unless otherwise specified.

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

(Analysis of polyhedral polysiloxane units)
Analysis of polyhedral polysiloxane units was performed by ²⁹ Si-NMR using INOVAAS600 manufactured by VARIAN. When polyhedral polysiloxane units are contained, sharp peaks are observed.

(SiH value)
NMR measurement (300 MHz NMR, manufactured by Varian Technologies Japan Limited) was performed on a sample obtained by dissolving a mixture of the compound obtained in the following production example and dibromoethane in deuterated chloroform, and the obtained integral value was calculated by the following formula ( Substituting into 1), the SiH value was calculated.
SiH value (mol / kg) = [integral value of peak attributed to SiH group of compound] / [integral value of peak attributed to methyl group of dibromoethane] × 4 × [weight of dibromoethane in mixture] / [Molecular weight of dibromoethane] / [weight of compound in mixture] (1)

(Production Example 1)
To 1262 g of a 48% choline aqueous solution (trimethyl-2hydroxyethylammonium hydroxide aqueous solution), 1083 g of tetraethoxysilane was added and stirred vigorously at room temperature for 2 hours. When the reaction system generated heat and became a homogeneous solution, the stirring was loosened and the reaction was further continued for 12 hours. Next, 1000 mL of methanol was added to the reaction system in which the solid was generated to obtain a uniform solution. The methanol solution was slowly added dropwise thereto while vigorously stirring a solution of 716 g of dimethylvinylchlorosilane, 516 g of trimethylsilyl chloride and 1942 mL of hexane. After completion of the dropwise addition, the mixture was reacted for 1 hour, and then the organic layer was extracted and concentrated to obtain a solid. The resulting solid was washed by vigorous stirring in methanol and filtered to obtain tetrakis (vinyldimethyl), which is an alkenyl group-containing polyhedral polysiloxane compound having 16 Si atoms and 4 vinyl groups. 601 g of siloxy) tetrakis (trimethylsiloxy) octasilsesquioxane (Fw = 1178.2) was obtained as a white solid.

(Production Example 2)
100 g of tetrakis (vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane, which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 1, and 105.1 g of vinyldiphenylmethylsilane (1,3 used) , 5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane is dissolved in 420 g of toluene in an amount of 0.34 alkenyl groups per one hydrosilyl group. 18.6 μL of a xylene solution of a complex (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) was added. The solution thus obtained was mixed with 81.7 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (tetrakis (vinyldimethylsiloxy) tetrakis (trimethyl used). Siloxy) An amount of 4 hydrosilyl groups per 1 alkenyl group of octasilsesquioxane) was slowly added dropwise to a solution of 81.7 g of toluene and reacted at 105 ° C. for 2 hours. After completion of the reaction, 35.5 μL of ethynylcyclohexanol and 8.2 μL of dimethyl maleate were added, and toluene was distilled off to obtain 280.1 g (SiH value 1.80 mol / kg) of a modified liquid polyhedral polysiloxane. It was.

(Production Example 3)
Into a 2 L autoclave, 720 g of toluene and 240 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane were added, and the gas phase was replaced with nitrogen. Heated and stirred. A mixed solution of 171 g of allyl glycidyl ether, 171 g of toluene and 0.049 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 90 minutes. After completion of dropping, the jacket temperature was raised to 60 ° C. for 40 minutes, and ¹ H-NMR confirmed that the reaction rate of allyl group was 95% or more.

A mixed liquid of 17 g of triallyl isocyanurate and 17 g of toluene was added dropwise thereto, the jacket temperature was raised to 105 ° C., and 66 g of triallyl isocyanurate, 66 g of toluene and a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum). ) 0.033 g of the mixture was added dropwise over 30 minutes. Four hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling. The unreacted rate of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane was 0.8%.

By-product of unreacted 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and toluene and allyl glycidyl ether (internal transfer of vinyl group of allyl glycidyl ether (cis And the trans isomer)) were distilled off under reduced pressure until the total amount became 5,000 ppm or less to obtain a colorless and transparent liquid. ^{As a result of 1} H-NMR measurement, some of the SiH groups of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane are allyl glycidyl ether and triallyl isocyanurate. It turned out that it was what reacted.

(Formulation example 1)
To 6.91 g of the polyhedral polysiloxane modified product obtained in Production Example 2 and 2.37 g of the triallyl isocyanate modified product obtained in Production Example 3, 1,5-divinyl-3,3-diphenyl-1,1, 2.64 g of 5,5-tetramethyltrisiloxane was added and stirred, and then the mixture was subjected to vacuum stirring for 3 minutes using Thinky Awatori Netaro (registered trademark) ARV-310, thereby organically modified polyhedral structure A curable composition containing polysiloxane was prepared.

(Examples 1-4)
To the curable composition obtained in Formulation Example 1, 0.065 g of the isocyanate compound shown in Table 1 was added and stirred. Further, a phosphor manufactured by Intematix (product number: N-YAG4454EL) 14 g was added, and vacuum stirring was performed for 3 minutes using Awatori Nertaro (registered trademark) ARV-310 manufactured by Thinky. Separately, a 12 mil × 13 mil square blue LED chip (product number: B1213AAA0 S46B / C-19 / 20) manufactured by Genelights was mounted on a MAP type package using a gold wire and a die bond agent KER-3000 manufactured by Shin-Etsu Chemical Co., Ltd. The composition obtained here was poured and heat-cured in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 5 hours.

  Using the total luminous flux measurement (φ300 mm) system (product number: HM-0930) manufactured by Otsuka Electronics Co., Ltd., the obtained evaluation sample was made to emit light when energized under the conditions of a temperature of 25 ° C., a current of 30 mA, and a standby time of 30 seconds. The luminance of the luminescent color was measured, and the average value of the luminance of the luminescent color of 500 samples measured was calculated.

Thereafter, this sample was put in a flow type gas corrosion tester (Fact Kay KG130S), and a hydrogen sulfide exposure test was conducted for 96 hours under conditions of 40 ° C., 80% RH, and 3 ppm of hydrogen sulfide. After the test, again using the Otsuka Electronics total luminous flux measurement (φ300mm) system (Part No .: HM-0930), electricity was emitted under the conditions of a temperature of 25 ° C., a current of 30 mA, and a standby time of 30 seconds. Was measured, and the average value of the luminance of the luminescent color of 500 measured samples was calculated. The luminance maintenance rate before and after the test was compared by the following formula (2). The results are shown in Table 1.
Luminance maintenance rate (%) = (Brightness after test) / (Brightness before test) x 100 (2)

(Comparative Examples 1-4)
To the curable composition obtained in Formulation Example 1, 0.065 g of the compound shown in Table 2 was added and stirred. Further, 1.14 g of a phosphor (product number: N-YAG4454EL) manufactured by Intematix Co., Ltd. was added. In addition, vacuum stirring was performed for 3 minutes using Awatori Nertaro (registered trademark) ARV-310 manufactured by Thinky. Separately, a 12 mil × 13 mil square blue LED chip (product number: B1213AAA0 S46B / C-19 / 20) manufactured by Genelights was mounted on a MAP type package using a gold wire and a die bond agent KER-3000 manufactured by Shin-Etsu Chemical Co., Ltd. The composition obtained here was poured and heat-cured in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 5 hours.

  Using the total luminous flux measurement (φ300 mm) system (product number: HM-0930) manufactured by Otsuka Electronics Co., Ltd., the obtained evaluation sample was made to emit light when energized under the conditions of a temperature of 25 ° C., a current of 30 mA, and a standby time of 30 seconds. The luminance of the luminescent color was measured, and the average value of the luminance of the luminescent color of 500 samples measured was calculated.

  Thereafter, this sample was put in a flow type gas corrosion tester (Fact Kay KG130S), and a hydrogen sulfide exposure test was conducted for 96 hours under conditions of 40 ° C., 80% RH, and 3 ppm of hydrogen sulfide. After the test, again using the total luminous flux measurement (φ300mm) system (product number: HM-0930) manufactured by Otsuka Electronics Co., Ltd., electricity was emitted under the conditions of a temperature of 25 ° C., a current of 30 mA, and a standby time of 30 seconds. The luminance was measured, and the average value of the luminance of the luminescent color of 500 measured samples was calculated. From the above equation (2), the average value of the luminance of the luminescent color of 500 samples measured was calculated. The results are shown in Table 2.

  As shown in Table 1, when the sealants for LED devices of Examples 1 to 4 containing the isocyanate compound (C) were used, they had a high luminance maintenance rate even after the gas corrosion test. On the other hand, when the sealants for LED devices of Comparative Examples 1 to 4 that do not contain an isocyanate compound (C) are used, the luminance is about 80% before the test after the gas corrosion test. Declined.

  From the above results, the compound (A) having two or more SiH groups in one molecule, the compound (B) having two or more alkenyl groups in one molecule, and an isocyanate compound (C) are essential. It turns out that the sealing agent for LED devices made into a component gives the hardened | cured material which has the outstanding gas barrier property.

Claims (12)

(A) a compound having two or more SiH groups in one molecule;
(B) a compound having two or more alkenyl groups in one molecule;
(C) A sealant for an LED device containing an isocyanate compound as an essential component.   2. The LED device according to claim 1, wherein the isocyanate compound (C) is an isocyanate silane coupling agent, or a polyisocyanate compound having two or more isocyanate groups independently and / or in a large amount in one molecule. Sealing agent.   The compounding quantity of an isocyanate type compound (C) is 0.001 mass part-50 mass parts with respect to a total of 100 mass parts of (A) component and (B) component. For LED devices of Claim 1 or 2 Sealant.   Furthermore, (D) Sealant for LED devices of any one of Claims 1-3 containing the compound which has a 1 or more epoxy group in 1 molecule.   The compound (A) having two or more SiH groups in one molecule contains a polyhedral polysiloxane compound (a) having an alkenyl group, a compound (b) having a hydrosilyl group, and an alkenyl group in one molecule. The organic silicon compound (c) having one and / or the cyclic olefin compound (d) having one carbon-carbon double bond in one molecule is obtained by hydrosilylation reaction. The sealing agent for LED devices of any one of Claims.   The encapsulant for an LED device according to claim 5, wherein the organosilicon compound (c) having one alkenyl group in one molecule is an organosilicon compound having one or more aryl groups.   The encapsulant for an LED device according to claim 5 or 6, wherein the cyclic olefin compound (d) having one carbon-carbon double bond in one molecule has a molecular weight of 1000 or less.   The encapsulant for an LED device according to any one of claims 5 to 7, wherein the compound (b) having a hydrosilyl group is a cyclic siloxane or a linear siloxane having a hydrosilyl group. The polyhedral polysiloxane compound (a) containing an alkenyl group has the general formula
[AR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(In the general 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; Represents an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane)
The encapsulant for an LED device according to claim 5, which is a polyhedral polysiloxane compound containing an alkenyl group composed of a siloxane unit represented by the formula:   Furthermore, the sealing agent for LED devices of any one of Claims 1-9 containing a curing retarder.   Furthermore, the sealing agent for LED devices of any one of Claims 1-10 containing a hydrosilylation catalyst.   Furthermore, the sealing agent for LED devices of any one of Claims 1-11 containing a fluorescent substance.