JP2002327114A - Composition for optical material, optical material, method for producing the same, and liquid crystal display and light-emitting diode each using the optical material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for an optical material which has high heat resistance, low birefringence, low photoelastic coefficient, high optical transparency and toughness, to provide such an optical material, to provide a method for producing the optical material, and to provide a liquid crystal display and a light-emitting diode each using the optical material. SOLUTION: This composition for optical material essentially comprises (A) an organic compound having in one molecule at least two carbon-carbon double bonds reactive to SiH group, (B) a silicon compound having in one molecule at least two SiH groups, (C) a hydrosilylating catalyst and (D) a granular filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical material, and more particularly, to a composition for an optical material having high heat resistance, high optical transparency and toughness.
The present invention relates to an optical material, a manufacturing method thereof, and a liquid crystal display device and a light emitting diode using the same.

[0002]

2. Description of the Related Art Materials having a low birefringence, a small photoelastic coefficient and a high optical transparency are used as optical materials for liquid crystal display devices. In the case of a material for a liquid crystal display device or the like, a material used in a manufacturing process needs to have high heat resistance. Conventionally, glass or the like has been used as a material satisfying such requirements.

[0003] Optical materials for liquid crystal display devices and the like are often used in the form of thin films or thin tubes or rods. In accordance with recent market demands, optical materials in the form of thinner films or thinner tubes or rods are used. Use is becoming necessary. However, conventionally used glass has a brittle property in terms of strength, so that the range of use has been limited.

As a tough material, there is a polymer material. For example, in the case of a thermoplastic resin, when an aromatic skeleton is generally introduced to exhibit high heat resistance, the birefringence increases and the photoelastic coefficient increases. Therefore, it is difficult to achieve both high heat resistance and optical performance. In the case of thermosetting resins, conventionally known thermosetting resins are generally colored and are not suitable for use in optical materials. Further, they generally have polarity, which is disadvantageous for optical performance.

For example, in a sealing material application of a light emitting diode,
As a special thermosetting resin, a transparent epoxy resin using an acid anhydride-based curing agent has been widely used. However, even in such a transparent epoxy resin, the moisture resistance is low due to the high water absorption of the resin, or the light resistance is low due to low light transmittance particularly to low wavelength light, or the resin is colored by light deterioration. Had the disadvantage that On the other hand, a silicone resin is used as a coating material having high light resistance and durability, but since it is generally soft and has a surface tackiness, a foreign matter may adhere to a light emitting surface during mounting, or a mounting device may be used. There is a problem that the light emitting surface is damaged.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide high heat resistance, low birefringence, low photoelastic coefficient, high optical transparency, high toughness, A composition for optical materials, an optical material, a method of manufacturing the same, and a method of using the same, which do not cause deterioration such that foreign matter is not attached to the light emitting surface during mounting and the light emitting surface is damaged by a mounting tool during mounting. A liquid crystal display device and a light emitting diode are provided.

[0007]

Means for Solving the Problems In order to solve the above problems, the present inventors have made intensive studies and found that an organic compound containing at least two carbon-carbon double bonds having a reactivity with a SiH group in one molecule. A compound and at least two S
The present inventors have found that the above-mentioned problems can be solved by using an iH group-containing silicon compound, a hydrosilylation catalyst, and a particulate filler as an essential component in a composition for an optical material, and have accomplished the present invention.

That is, the present invention relates to (A) an organic compound containing at least two carbon-carbon double bonds reactive with a SiH group per molecule, and (B) at least two SiH groups per molecule. An optical material composition (claim 1) comprising, as essential components, a silicon compound having a group, (C) a hydrosilylation catalyst, and (D) a particulate filler, wherein the component (A) Is an organic compound containing at least one vinyl group reactive with a SiH group in one molecule, the composition for an optical material according to claim 1 (claim 2), wherein (A) ) Component is Si
The composition for an optical material according to claim 1, wherein the composition is an organic compound containing at least one allyl group reactive with an H group in one molecule (claim 3).
The composition for an optical material according to claim 1, wherein the component is 1,2-polybutadiene, vinylcyclohexene, cyclopentadiene, dicyclopentadiene, divinylbiphenyl, or bisphenol A diallyl ether (claim 4). The composition for an optical material according to claim 1, wherein the component (A) is triallyl isocyanurate or trivinylcyclohexane (claim 5). The composition for an optical material according to any one of claims 1 to 5, wherein the composition is a particulate filler having a light transmittance of 80% or more. The optical material according to any one of claims 1 to 6, wherein the component is a particulate filler having an average particle diameter equal to or smaller than a wavelength of target light. A composition (claim 7), (D)
The difference between the refractive index of the component and the refractive index of the cured product obtained by curing the curable composition comprising the component (A), the component (B), and the component (C) is ± 0.05 or less. The composition for an optical material according to any one of claims 1 to 7, wherein the composition is a particulate filler (claim 8),
The optical material is a liquid crystal film, the optical material composition according to any one of claims 1 to 8 (claim 9), and the optical material is a liquid crystal plastic cell.
The composition for an optical material according to any one of claims 1 to 8, wherein the optical material is a sealing material for a light emitting diode. A composition (Claim 11), wherein the composition for an optical material according to any one of Claims 1 to 11 is previously mixed, and a carbon-carbon double bond having reactivity with a SiH group in the composition. And an optical material (Claim 12) cured by reacting a part or all of SiH groups.
The composition for an optical material according to any one of claims 1 to 11, which is mixed in advance, and reacts a part or all of a carbon-carbon double bond having a reactivity with a SiH group in the composition with a SiH group. A method for producing the optical material according to claim 12 (claim 13), and a liquid crystal display device using the optical material according to claim 12 (claim 14). A light-emitting diode using the optical material described in claim 15.

Further, the light emitting diode of the present invention comprises (A)
An organic compound containing at least two carbon-carbon double bonds in one molecule reactive with a SiH group, (B) a silicon compound containing at least two SiH groups in one molecule, and (C) hydrosilylation. A light-emitting diode in which a light-emitting element is coated with a curable composition containing a catalyst and (D) a particulate filler as essential components (Claim 16), wherein the component (A) is reactive with a SiH group. 17. The light-emitting diode according to claim 16, which is an organic compound containing at least one vinyl group in one molecule having the formula (A), wherein the component (A) has a reactivity with the SiH group. The light-emitting diode according to claim 16, wherein the compound is an organic compound containing at least one allyl group in one molecule.
17. The light-emitting diode according to claim 16, wherein the light-emitting diode is 1,2-polybutadiene, vinylcyclohexene, cyclopentadiene, dicyclopentadiene, divinylbiphenyl, or bisphenol A diallyl ether. Is a triallyl isocyanurate or trivinylcyclohexane, the light emitting diode according to claim 16 (claim 20).

21. The light emitting diode according to claim 16, wherein the component (D) is a particulate filler having a desired light transmittance of 80% or more. (21) The component according to any one of (16) to (21), wherein the component (D) is a particulate filler having an average particle diameter equal to or smaller than the wavelength of target light. A light emitting diode (claim 22);
Component (D) has a refractive index difference of ± 0.05 from the refractive index of a cured product obtained by curing a curable composition comprising components (A), (B) and (C). 23. A particulate filler comprising:
The light-emitting diode according to any one of claims (claim 23)
It is. Since the light-emitting diode thus configured is formed of a sealing material having excellent light-transmitting properties, reliability can be improved without lowering light-transmitting properties from the light-emitting element, which is preferable. Further, a sealing material obtained from the curable composition, a first layer covering the light-emitting element,
The light-emitting diode according to any one of claims 16 to 23, wherein the light-emitting diode comprises a second layer that covers the first layer and has a higher light-transmitting property than the first layer. Can improve the reliability around the light emitting element, which is a place where a high temperature state occurs and a strong thermal stress is generated, and a light emitting diode excellent in reliability and optical characteristics can be obtained.

According to a twenty-fifth aspect of the present invention, in the light emitting diode, the encapsulant obtained from the curable composition is prepared by mixing the curable composition in advance and forming a carbon material having a reactivity with SiH groups in the composition. The light emitting diode according to any one of claims 16 to 24, wherein the light emitting diode is obtained by curing by reacting a carbon double bond with part or all of a SiH group.

Further, the method for manufacturing a light emitting diode of the present invention is characterized in that (A) an organic compound containing at least two carbon-carbon double bonds reactive with a SiH group per molecule;
(B) a silicon compound containing at least two SiH groups in one molecule, (C) a hydrosilylation catalyst, and (D)
A method for producing a light emitting diode in which a light emitting element is coated with a curable composition containing a particulate filler as an essential component, wherein the component (A), the component (B) and the component (C) are mixed in advance. Then, a first step of reacting a part or all of the SiH group with a carbon-carbon double bond reactive with the SiH group in the composition, and (D) a mixture obtained in the first step. A second step of mixing and dispersing the components,
And a third step of coating the light emitting element with the curable composition obtained in the second step.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

First, the component (A) in the present invention will be described. The component (A) is not particularly limited as long as it is an organic compound containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule. The organic compound does not include a siloxane unit (Si—O—Si) such as a polysiloxane-organic block copolymer or a polysiloxane-organic graft copolymer, and contains only C, H, N, O, S, and halogen as constituent elements. It is preferable that it contains. In the case of those containing a siloxane unit, there are problems of gas permeability and repellency.

The bonding position of the carbon-carbon double bond reactive with the SiH group is not particularly limited, and may be anywhere in the molecule.

The organic compound (A) can be classified into an organic polymer compound and an organic monomer compound.

Examples of the organic polymer compounds include polyether compounds, polyester compounds, polyarylate compounds, polycarbonate compounds, saturated hydrocarbon compounds, unsaturated hydrocarbon compounds, and the like.
Polyacrylate, polyamide, phenol-formaldehyde (phenol resin), and polyimide compounds can be used.

Examples of the organic monomer compound include, for example,
Examples include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene; aliphatic hydrocarbons such as linear and alicyclic; heterocyclic compounds and mixtures thereof.

The carbon-carbon double bond reactive with the SiH group of the component (A) is not particularly limited, but may be represented by the following general formula (I):

[0020]

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(Wherein R ¹ represents a hydrogen atom or a methyl group) is preferred from the viewpoint of reactivity. Also, from the availability of raw materials,

[0022]

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The group represented by is particularly preferred.

The carbon-carbon double bond reactive with the SiH group of the component (A) is represented by the following general formula (II):

[0025]

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An alicyclic group represented by the formula (wherein R ¹ represents a hydrogen atom or a methyl group) is preferred from the viewpoint that the cured product has high heat resistance. Also, from the availability of raw materials,

[0027]

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The alicyclic group represented by the following is particularly preferred.

The carbon-carbon double bond reactive with the SiH group may be directly bonded to the skeleton of the component (A), or may be covalently bonded via a divalent or higher valent substituent. The divalent or higher substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms.
Those containing only N, O, S, and halogen are preferable. Examples of these substituents include

[0030]

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[0031]

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[0032] Two or more of these divalent or more substituents are connected by a covalent bond to form one
It may constitute a substituent having a valence of at least.

Examples of the group covalently bonded to the skeleton as described above include vinyl, allyl, methallyl, acryl, methacryl, 2-hydroxy-3- (allyloxy) propyl, and 2-allylphenyl. Group, 3-allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group,
-(Allyloxy) phenyl group, 2- (allyloxy)
Ethyl group, 2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group,

[0034]

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And the like.

Specific examples of the component (A) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2-tetrayl Allyloxyethane, dialylidenepentaerythrit, triallyl cyanurate, triallyl isocyanurate, 1,2,4-
Trivinylcyclohexane, divinylbenzenes (purity 50 to 100%, preferably 80 to 100%
), Divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof, 1,2-polybutadiene (1,2-polybutadiene having a 1,2 ratio of 10 to 100%, preferably , 2
Ratio of 50 to 100%), allyl ether of novolak phenol, allylated polyphenylene oxide,

[0037]

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[0038]

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In addition, there may be mentioned a conventionally known epoxy resin in which a glycidyl group is replaced with an allyl group.

As the component (A), a low-molecular-weight compound, which is difficult to be divided into a skeleton portion and a carbon-carbon double bond as described above, can also be used. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene, and decadiene; and cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene, and norbornadiene. Aliphatic cycloolefin compounds, substituted aliphatic cyclic olefin compounds such as vinylcyclopentene, vinylcyclohexene and the like.

From the viewpoint that the heat resistance can be further improved, the component (A) contains a carbon-carbon double bond reactive with a SiH group in an amount of 0.000 g / g of the component (A).
What is necessary is just to contain 1 mol or more.
Those containing 0.005 mol or more per g are preferable, and those containing 0.008 mol or more are particularly preferable.

The number of carbon-carbon double bonds reactive with the SiH group of the component (A) should be at least two per molecule on average, but if the mechanical strength is desired to be further improved, two is required. Preferably, the number is more than three, and more preferably three or more. When the number of carbon-carbon double bonds having reactivity with the SiH group of the component (A) is 1 or less per molecule, when the reaction with the component (B) occurs, only a graft structure is formed and a crosslinked structure is formed. No.

As the component (A), those having fluidity at a temperature of 100 ° C. or less are preferable in order to obtain uniform mixing with other components and good workability, and may be linear or branched. Although the molecular weight is not particularly limited, 50
Any of ~ 100,000 can be suitably used. If the molecular weight is 100,000 or more, the raw material generally has a high viscosity and is inferior in workability. In addition, the carbon-carbon double bond and SiH
The effect of cross-linking due to the reaction with the group is hardly exhibited.

The component (A) preferably has a low content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group from the viewpoint of suppressing coloring, particularly yellowing. Those containing no compound having a derivative of a phenolic hydroxyl group are more preferred. The phenolic hydroxyl group in the present invention refers to a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by a benzene ring, a naphthalene ring, an anthracene ring, etc. A group substituted by an alkyl group such as a methyl group and an ethyl group, an alkenyl group such as a vinyl group and an allyl group, and an acyl group such as an acetoxy group.

From the viewpoint of good optical characteristics such as low birefringence and low photoelastic coefficient and good weather resistance, the weight ratio of the aromatic ring to the component (A) is preferably It is preferably 50% by weight or less, more preferably 40% by weight or less, even more preferably 30% by weight or less. Most preferred are those that do not contain an aromatic hydrocarbon ring.

From the coloring properties and optical properties of the obtained cured product, as the component (A), vinyl cyclohexene, dicyclopentadiene, triallyl isocyanurate, 2,2
-Diallyl ether of -bis (4-hydroxycyclohexyl) propane, 1,2,4-trivinylcyclohexane is preferred, triallyl isocyanurate, 2,2-
The diallyl ether of bis (4-hydroxycyclohexyl) propane, 1,2,4-trivinylcyclohexane, is particularly preferred.

Next, the compound having a SiH group as the component (B) will be described.

The compound having a SiH group that can be used in the present invention is not particularly limited.
/ 15194, compounds having at least two SiH groups in one molecule can be used.

Of these, from the viewpoint of availability, a chain and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule is preferable, and has good compatibility with the component (A). From the viewpoint of, the following general formula (III)

[0050]

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(Wherein, R ² represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10), and a ring having at least two SiH groups in one molecule. Polyorganosiloxanes are preferred. Note that the substituent R ² in the compound represented by the general formula (III) is preferably composed of C, H, and O, and more preferably a hydrocarbon group.

In addition, from the viewpoint of having good compatibility with the component (A), one selected from a chain and / or cyclic polyorganosiloxane and an organic compound having a carbon-carbon double bond. Reaction products with more than one compound (hereinafter referred to as component (E)) are also preferred. In this case, in order to further increase the compatibility of the reactant with the component (A), a product obtained by removing unreacted siloxanes and the like from the reactant by devolatilization or the like can be used.

The component (E) is an organic compound containing at least one carbon-carbon double bond reactive with a SiH group in one molecule, and the same description as the component (A) can be used. . The organic compound of the component (E) may be the same as or different from the organic compound of the component (A). It is also possible to use one or a mixture of two or more. When it is desired to increase the compatibility of the component (B) with the component (A), the component (E) is preferably the same as the component (A).

The chain and / or cyclic polyorganosiloxane to be reacted with the organic compound (E) is preferably 1,3 from the viewpoint of industrial availability and good reactivity in the reaction. , 5,7-Tetramethylcyclotetrasiloxane is preferred.

As the component (B), similarly to the component (A),
From the viewpoint of suppressing coloration, especially yellowing, those having a low content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group are preferable, and those not containing a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group. Is more preferred. The phenolic hydroxyl group in the present invention is a benzene ring, a naphthalene ring,
A hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by an anthracene ring or the like. And a group substituted by an alkenyl group such as a group or an acyl group such as an acetoxy group.

From the viewpoint of good optical characteristics such as low birefringence and low photoelastic coefficient and good weather resistance, the weight ratio of the aromatic ring in the component (B) is preferably It is preferably 50% by weight or less, more preferably 40% by weight or less, even more preferably 30% by weight or less. Most preferred are those that do not contain an aromatic hydrocarbon ring.

The component (B) more preferable from the viewpoint of good optical properties includes a reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane and vinylcyclohexene, and 1,3,5,7-tetra Reaction product of methylcyclotetrasiloxane and dicyclopentadiene,
Reaction product of 5,7-tetramethylcyclotetrasiloxane and triallyl isocyanurate, 1,3,5,7-tetramethylcyclotetrasiloxane and 2,2-bis (4-
(Hydroxycyclohexyl) propane diallyl ether reactant; 1,3,5,7-tetramethylcyclotetrasiloxane and 1,2,4-trivinylcyclohexane reactant; particularly preferred component (B) is A reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane and triallyl isocyanurate,
5,7-tetramethylcyclotetrasiloxane and 2,2
A reaction product of diallyl ether of -bis (4-hydroxycyclohexyl) propane, and a reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane and 1,2,4-trivinylcyclohexane.

The mixing ratio of component (A) and component (B) as described above is not particularly limited as long as the required strength is not lost, but the number of SiH groups in component (B) (Y) (A) )) The ratio of the number of carbon-carbon double bonds (X) in the component is
2.0 ≧ Y / X ≧ 0.9, preferably 1.8
≧ Y / X ≧ 1.0 is more preferable. When 2.0 <Y / X, sufficient curability may not be obtained, and sufficient strength may not be obtained. When Y / X <0.9, the carbon-carbon double bond becomes excessive and It can cause coloring.

Next, the hydrosilylation catalyst as the component (C) will be described.

As the hydrosilylation catalyst, hydrosilyl
The catalyst is not particularly limited as long as it has catalytic activity for the oxidation reaction.
For example, simple platinum, alumina, silica, carbon black
Solid platinum supported on a carrier such as chloroplatinic acid, salt
Complex of chloroplatinic acid with alcohol, aldehyde, ketone, etc.
, A platinum-olefin complex (for example, Pt (CH₂= C
H ₂)₂(PPh₃)₂, Pt (CH₂= CH₂)₂C
l₂), A platinum-vinylsiloxane complex (for example, Pt
(ViMe₂SiOSiMe₂Vi)_n, Pt [(Me
ViSiO)₄]_m), Platinum-phosphine complexes (eg,
If Pt (PPh₃)₄, Pt (PBu₃)₄),platinum
-Phosphite complex (for example, Pt [P (OPh)₃]
₄, Pt [P (OBu)₃]₄(Where Me is methyl
Group, Bu is butyl group, Vi is vinyl group, Ph is phenyl
Represents a group, and n and m represent integers. ), Dicarbonyldi
Chloroplatinum, Karstedt touch
Medium, also Ashby US Pat.
59601 and 3159662.
Platinum-hydrocarbon complex, as well as Lamorrow
oreaux) in U.S. Pat. No. 3,220,972.
The platinum alcoholate catalyst described in the above. Further
No. 35169 to Modic.
No. 46, a platinum chloride-olefin composite
Bodies are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , and RhAl ₂ O
₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlC
l ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiC
l _4, and the like.

Among these, chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex and the like are preferred from the viewpoint of catalytic activity. These catalysts may be used alone or in combination of two or more.

The amount of the catalyst to be added is not particularly limited. However, in order to have sufficient curability and keep the cost of the curable composition relatively low, 10 ⁻⁸ to 10 mol per mol of SiH group is used.
10 ^- preferably ¹ mole, more preferably in the range of 10
The range is from ^-6 to 10 ^-2 mol.

Further, a co-catalyst is used in combination with the above-mentioned catalyst.
Is possible, for example, triphenylphosphine
1,2-diester such as dimethyl maleate
Compound, 2-hydroxy-2-methyl-1-butyne
Acetylene alcohol-based compounds such as
Amine compounds such as yellow compounds and triethylamine
No. The amount of the cocatalyst added is not particularly limited.
10 moles per mole of medium ^-2-10²Molar range preferred
And more preferably 10^-1In the range of 10 to 10 moles
You.

Further, a curing retarder can be used for the purpose of improving the storage stability of the composition of the present invention or for adjusting the reactivity of the hydrosilylation reaction in the production process. Examples of the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, and an organic peroxide, and these may be used in combination. As a compound containing an aliphatic unsaturated bond, propargyl alcohols,
Examples include ene-yne compounds, maleic esters and the like. Examples of the organic phosphorus compound include triorganophosphines, diorganophosphines, organophosphones, and triorganophosphites. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, benzothiazole disulfide, and the like. Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of the tin compound include stannous halide dihydrate, stannous carboxylate, and the like.
As the organic peroxide, di-t-butyl peroxide,
Examples thereof include dicumyl peroxide, benzoyl peroxide, t-butyl perbenzoate and the like.

Among these curing retarders, benzothiazole, thiazole, dimethyl maleate, and 3-hydroxy-3-methyl-1-butyne are preferred from the viewpoint of good delay activity and good availability of raw materials.

[0067] The addition amount of the curing retarder, with respect to hydrosilylation catalyst 1mol ^used, and is preferably from 10 -1 to 10 ³ mols, more preferably from 1 to 50 mol.

Next, the particulate filler as the component (D) will be described.

Various types of particulate fillers can be used. For example, inorganic fillers may be mentioned. Specifically, alumina, aluminum hydroxide, fused silica, crystalline silica such as quartz, amorphous silica, hydrophobic silica, talc, barium sulfate, titanium oxide, aluminosilicate, crystal crushed Things and the like. Among these, silica-based particles such as fused silica, crystalline silica, amorphous silica, hydrophobic silica, aluminosilicate, and crushed quartz are preferred from the viewpoint of being more transparent.

Further, for example, hydrolyzable silane monomers or oligomers such as alkoxysilane, acyloxysilane, and halogenated silane, and alkoxides, acyloxides, and halides of metals such as titanium and aluminum are mixed with a medium such as a solvent or (A). ), A component obtained by dispersing in a composition comprising the component (B) and the component (C) and then reaction-cured, and a product obtained by reaction-curing and then pulverized.

Examples of the particulate filler include organic fillers, and examples thereof include those obtained by making various resins into particles. In this case, examples of various resins include polycarbonate resin, polyether sulfone resin, polyarylate resin, epoxy resin, cyanate resin, phenol resin, acrylic resin, polyimide resin, polyvinyl acetal resin, urethane resin, and polyester resin. Among these, epoxy resins are preferred from the viewpoint of high heat resistance and high transparency, such as bisphenol A diglycidyl ether, 2,2′-bis (4-glycidyloxycyclohexyl) propane,
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1 Epoxy resins such as 2,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyldiglycidylisocyanurate, and diallylmonoglycidylisocyanurate. A transparent epoxy resin obtained by curing with an aliphatic acid anhydride such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, or hydrogenated methylnadic anhydride is more preferable. In this case, the epoxy resin or the curing agent may be used alone or in combination.

The shape of the particulate filler is not particularly limited, and various shapes can be used. For example, in addition to a spherical shape, a plate shape, a rod shape, and a layer shape, a material having no specific shape such as a crushed material may be used. Among them, spherical ones are preferred from the viewpoint that the viscosity of the composition is low and the moldability is easily improved.

As the particulate filler, those having a smooth surface are preferred. When the surface is not smooth due to the attachment of fine particles or the like, the transparency tends to be low due to light scattering and the like.

As the particulate filler (D) of the present invention, those having a target light transmittance of 80% or more are preferred in that the transparency of the cured product is increased. In this case, the target light differs depending on the application. For example, when the application is a display device such as a liquid crystal display device, the target light is visible light, and when the application is a light emitting diode, light emitted from a light emitting element is used. It is. The light transmittance of the particulate filler is the light transmittance of the same composition equivalent to the particulate filler at a thickness of 1 mm, and when the particulate filler is a crushed material, the light transmittance of the material before crushing. Is determined by a conventionally known method. Further, as described above, hydrolyzable silane monomers or oligomers, titanium, alkoxides of metals such as aluminum, acyloxides, halides and the like are reacted in the composition or a partial reactant of the composition, and in the composition In the case where an inorganic filler has been formed, it can be obtained by measuring the light transmittance of a material obtained by curing these alone, not in the composition, by a conventionally known method.

The average particle diameter of the particulate filler (D) of the present invention is preferably not more than the wavelength of the target light in that the transmittance of the target light of the cured product is increased. In this case, the target light is as described above. The particle system may have a distribution, may have a single dispersion or may have a plurality of peak particle diameters, but from the viewpoint that the viscosity of the curable composition tends to be good and the moldability is good, the particle diameter is small. Is preferably 10% or less.

The refractive index of the particulate filler (D) of the present invention is determined by curing the curable composition obtained by curing the curable composition comprising the components (A), (B) and (C). Is preferably ± 0.05 or less from the viewpoint of increasing the transparency of the cured product. When the particulate filler is a pulverized product, the refractive index of the particulate filler can be determined by measuring the refractive index of the particulate filler before pulverization using an Abbe refractometer. Further, as described above, a hydrolyzable silane monomer or oligomer, titanium,
Alkoxides, acyloxides of metals such as aluminum,
In the case where a halide or the like is reacted in the composition or in a partial reactant of the composition to generate an inorganic filler in the composition, the refractive index of a material obtained by curing these materials alone in the composition is determined. It is determined by measuring with an Abbe refractometer.

The addition amount of the particulate filler (D) is not particularly limited, but is preferably from 5 to 70% by weight of the whole composition. If the addition amount is small, the effect of reducing the linear expansion coefficient is hardly obtained,
If the amount is too large, the viscosity becomes high and the moldability tends to be impaired. Further, from the viewpoint that optical transparency tends to be high, 5 to 20% by weight of the whole composition is preferable.

The particulate filler may be contained uniformly or may be contained with a gradient in the content.

As the composition of the present invention, various combinations can be used as described above. From the viewpoint of good heat resistance, the cured product obtained by curing the composition has a Tg of 50 ° C. or higher. Are preferable, those having a temperature of 100 ° C or higher are more preferable, and those having a temperature of 150 ° C or higher are particularly preferable.

Although the composition of the present invention can be formed into a film or the like as it is, the composition can be dissolved in an organic solvent to form a varnish. Solvents that can be used are not particularly limited, and if specifically exemplified,
Hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane,
Ether solvents such as diethyl ether, acetone, ketone solvents such as methyl ethyl ketone, chloroform,
Halogen solvents such as methylene chloride and 1,2-dichloroethane can be suitably used. The solvent can be used as a mixed solvent of two or more kinds. As the solvent,
Preferred are toluene, tetrahydrofuran and chloroform. The amount of the solvent used is based on 1 g of the component (A) used.
It is preferably used in the range of 0 to 10 mL, and 0.5 to 5 mL.
It is more preferably used in the range of mL, and particularly preferably used in the range of 1-3 mL. If the amount is small, it is difficult to obtain the effect of using a solvent such as a low viscosity,
Further, when the amount is large, the solvent remains in the material, which tends to cause problems such as thermal cracks. Further, the cost is disadvantageous and the industrial utility value is reduced.

The composition of the present invention may further include an antioxidant, a radical inhibitor, an ultraviolet absorber, an adhesion improver, a flame retardant, a surfactant, a storage stability improver, an ozone deterioration inhibitor, and a light stabilizer. , Thickener, plasticizer, coupling agent, antioxidant, heat stabilizer, conductivity imparting agent, antistatic agent, radiation blocking agent, nucleating agent, phosphorus-based peroxide decomposer, lubricant, pigment, metal-free An activator, a physical property modifier and the like can be added as long as the object and effects of the present invention are not impaired.

Incidentally, examples of the coupling agent include a silane coupling agent. The silane coupling agent is not particularly limited as long as it has 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 preferably at least one functional group selected from an epoxy group, a methacryl group, an acryl group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handleability. From the viewpoints of properties and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

Preferred silane coupling agents include
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4
Alkoxysilanes having an epoxy functional group such as -epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxy Silane, 3-acryloxypropyltrimethoxysilane, 3
-Alkoxysilanes having a methacryl group or an acrylic group such as acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane. .

Further, various additives for improving the characteristics of the light emitting diode may be added to the composition of the present invention. As an additive, for example, a fluorescent substance such as a yttrium aluminum garnet-based fluorescent substance activated with cerium, which absorbs light from a light emitting element and emits longer-wavelength fluorescence,
Coloring agents such as bluing agents that absorb specific wavelengths, silicon oxides such as titanium oxide, aluminum oxide, silica and quartz glass for diffusing light, talc, calcium carbonate, melamine resin, CTU guanamine resin, benzoguanamine resin, etc. And inorganic or organic diffusing materials such as the above, glass, metal oxides such as aluminosilicate, and heat conductive fillers such as metal nitrides such as aluminum nitride and boron nitride.

The additive for improving the characteristics of the light emitting diode may be uniformly contained, or may be contained with a gradient in the content. Such a filler-containing resin portion can be formed as a mold member behind the light-emitting surface by flowing a resin containing a filler after flowing the resin for the mold member on the front surface of the light-emitting surface into the mold. Also, after the molding member is formed, the lead terminals are covered by applying tapes from both front and back surfaces, and in this state, the entire lead frame is immersed in a lower half of the light emitting diode molding member in a tank containing a filler-containing resin. It may be pulled up and dried to form a filler-containing resin portion.

The optical material referred to in the present invention generally means a material used for the purpose of transmitting light such as visible light, infrared light, ultraviolet light, X-ray, and laser through the material.

More specifically, a liquid crystal display such as a substrate material, a light guide plate, a prism sheet, a deflecting plate, a retardation plate, a viewing angle correction film, an adhesive, and a polarizer protective film in the liquid crystal display field. Material around the device. In addition, color PDP (plasma display) encapsulants, anti-reflection films, optical correction films, housing materials, front glass protection films, front glass replacement materials, adhesives expected as next-generation flat panel displays; Light emitting element molding material, light emitting diode sealing material, front glass protection film, front glass substitute material, adhesive used in display devices;
Also, substrate materials for plasma-addressed liquid crystal (PALC) displays, light guide plates, prism sheets, polarizing plates, retardation plates, viewing angle correction films, adhesives, polarizer protective films; and front glass for organic EL (electroluminescence) displays. Protective film, alternative material for front glass, adhesive; various film substrates in field emission display (FED); protective film for front glass, alternative material for front glass, adhesive.

In the field of optical recording, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-
R / DVD-RAM, MO / MD, PD (phase change disk), disk substrate material for optical card, pickup lens, protective film, sealing material, adhesive, etc.

In the field of optical instruments, materials for steel camera lenses, finder prisms, target prisms,
The viewfinder cover and light receiving sensor. Also, it is a shooting lens and a finder of a video camera. Further, it is a projection lens of a projection television, a protective film, a sealing material, an adhesive or the like. Materials for optical sensing devices such as lenses, sealing materials, adhesives, and films.

In the field of optical components, there are fiber materials, lenses, waveguides, sealing materials for elements, adhesives, etc. around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. In the case of an optical passive component or an optical circuit component, it is a lens, a waveguide, a sealing material for a light emitting element, an adhesive or the like. Optoelectronic integrated circuits (OEI
C) Peripheral substrate material, fiber material, element sealing material,
An adhesive or the like.

In the field of optical fibers, they are optical fibers for industrial use such as illumination and light guides for decorative displays, displays and signs, and for communication infrastructure and for connecting digital equipment in homes.

The semiconductor integrated circuit peripheral material is a resist material for microlithography for LSI and super LSI materials.

In the field of automobiles and transportation equipment, lamp reflectors for automobiles, bearing retainers, gears, corrosion-resistant coatings, switches, headlamps, engine parts, electric parts, various interior and exterior parts, drive engines, brake oil tanks, Rustproof steel plates for automobiles, interior panels,
It is an interior material, protection and bundling wire, fuel hose, car lamp, and glass substitute. Further, it is a double glazing for railway vehicles. In addition, toughness imparting agent for aircraft structural materials,
Peripheral components for the engine, wireness for protection and binding, and corrosion-resistant coating.

In the architectural field, there are materials for interior and processing, electric covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a film for house coating.

The next generation optical / electronic functional organic materials include:
Organic EL element peripheral materials, organic photorefractive elements, light-to-light conversion devices such as optical amplifier elements, optical operation elements, substrate materials around organic solar cells, fiber materials, element sealing materials, adhesives, and the like.

The composition for an optical material of the present invention is mixed in advance and cured by reacting a part or all of the SiH group with a carbon-carbon double bond having reactivity with the SiH group in the composition. It can be an optical material.

Various methods can be used for mixing. The component (A), the component (B), and the component (C) are obtained by mixing the component (A) with the component (C).
A method of mixing the component (B) is preferred. When the method of mixing the component (C) with the mixture of the component (A) and the component (B), it is difficult to control the reaction. When the method of mixing the component (A) with the component (B) mixed with the component (C),
In the presence of the component (C), the component (B) has a reactivity with moisture, and may be deteriorated during storage. The component (D) can be previously mixed with the component (A), the component (B) or the component (C).
A method of mixing the component (D) with the mixture of the component, the component (B) and the component (C) may be used. Further, the component (A),
The components (B) and (C) are mixed, and a carbon-carbon double bond having a reactivity with the SiH group in the composition is reacted with part or all of the SiH group, and then the component (D) is mixed. In addition, the viscosity of the composition for suppressing the sedimentation of the component (D) when the component (D) is mixed can be adjusted.

In the case of reacting and curing the composition, the required amounts of each of the components (A), (B), (C) and (D) may be mixed at once and reacted. And reacting only a part of the functional groups in the composition by controlling the reaction conditions and using the difference in the reactivity of the substituents after mixing. (B stage) and then a process such as molding and further curing may be employed. According to these methods, viscosity adjustment at the time of molding becomes easy.

As a curing method, the reaction can be carried out simply by mixing, or the reaction can be carried out by heating. From the viewpoint that the reaction is fast and a material having high heat resistance is generally easily obtained, a method of performing the reaction by heating is preferable.

The reaction temperature can be variously set. For example, a temperature of 30 to 300 ° C. can be applied, and a temperature of 100 to 250 ° C.
Is more preferable, and 150 to 200C is further preferable.
When the reaction temperature is low, the reaction time for causing a sufficient reaction is prolonged, and when the reaction temperature is high, molding tends to be difficult.

The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as needed.

The reaction time can be variously set.

The pressure during the reaction can be variously set as required.
The reaction can be performed at normal pressure, high pressure, or reduced pressure.

The shape of the optical material obtained by curing can be various depending on the application, and is not particularly limited. For example, the optical material is formed into a shape such as a film, a sheet, a tube, a rod, a coating, and a bulk. be able to.

Various molding methods can be used, including a conventional thermosetting resin molding method. For example, a molding method such as a casting method, a pressing method, a casting method, a transfer molding method, a coating method, and a RIM method can be applied. As the molding die, a polishing glass, a hard stainless steel polishing plate, a polycarbonate plate, a polyethylene terephthalate plate, a polymethyl methacrylate plate, or the like can be used. In addition, a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyimide film, or the like can be used to improve releasability from a mold.

Various processes can be performed as necessary at the time of molding. For example, a process of defoaming the composition or a partially reacted composition by centrifugation, decompression, or the like to suppress voids generated during molding, a process of once releasing the pressure during pressing, and the like can be applied.

A liquid crystal display device can be manufactured using the optical material of the present invention.

In this case, the optical material of the present invention may be used as a liquid crystal film such as a plastic cell for a liquid crystal, a polarizing plate, a retardation plate, a protective film for a polarizer, etc., and a liquid crystal display device may be manufactured by an ordinary method.

A light emitting diode can be manufactured using the optical material of the present invention. In this case, the light emitting diode can be manufactured by coating the light emitting element with the curable composition as described above.

In this case, the light emitting element is not particularly limited, and a light emitting element used for a conventionally known light emitting diode can be used. As such a light emitting element, for example, M
Examples thereof include those formed by laminating a semiconductor material on a substrate provided with a buffer layer such as GaN or AlN as necessary by various methods such as an OCVD method, an HDVPE method, and a liquid phase growth method. Various materials can be used for the substrate in this case, for example, sapphire, spinel,
SiC, Si, ZnO, GaN single crystal and the like can be mentioned.
Of these, sapphire is preferably used from the viewpoint that GaN having good crystallinity can be easily formed and the industrial utility value is high.

The semiconductor material to be laminated is GaAs
s, GaP, GaAlAs, GaAsP, AlGaIn
P, GaN, InN, AlN, InGaN, InGaAs
1N, SiC and the like. Among these, from the viewpoint of obtaining high luminance, a nitride-based compound semiconductor (I
n _x Ga _y Al _z N) are preferred. Such a material may contain an activator or the like.

The structure of the light emitting element includes a MIS junction, p
Examples include an n-junction, a homojunction having a PIN junction, a heterojunction, and a double heterostructure. Also, a single or multiple quantum well structure can be used.

The light emitting element may or may not be provided with a passivation layer.

An electrode can be formed on the light emitting element by a conventionally known method.

The electrodes on the light emitting element can be electrically connected to lead terminals and the like by various methods. As the electric connection member, those having good ohmic mechanical connection with the electrode of the light emitting element and the like are preferable, and examples thereof include a bonding wire using gold, silver, copper, platinum, aluminum, or an alloy thereof. Alternatively, a conductive adhesive or the like in which a conductive filler such as silver or carbon is filled with a resin can be used. Of these, from the viewpoint of good workability, it is preferable to use an aluminum wire or a gold wire.

A light emitting device is obtained as described above.
In the light emitting diode of the present invention, any light emitting element having a vertical luminous intensity of 1 cd or more can be used as the luminous intensity of the light emitting element. Is remarkable, and the effect of the present invention is further remarkable when a light emitting element of 3 cd or more is used.

The light-emitting output of the light-emitting device can be any one without any particular limitation. However, when a light-emitting device of 1 mW or more at 20 mA is used, the effect of the present invention is remarkable. The effect of the present invention is more remarkable when a device is used, and the effect of the present invention is more remarkable when a light emitting device of 5 mW or more at 20 mA is used.

The light emitting element can emit light of various wavelengths from the ultraviolet region to the infrared region. The effect of the present invention is particularly remarkable when the light emitting device has a main light emission peak wavelength of 550 nm or less.

A single type of light emitting element may be used to emit monochromatic light, or a plurality of light emitting elements may be used to emit monochromatic or multicolor light.

As the lead terminals used in the light emitting diode of the present invention, those having good adhesion to an electric connection member such as a bonding wire and electric conductivity are preferable.
The electrical resistance of the lead terminal is preferably 300 μΩ-cm or less, more preferably 3 μΩ-cm or less.
Examples of these lead terminal materials include iron, copper, copper with iron, copper with tin, and those plated with silver, nickel, or the like. The glossiness of these lead terminals may be appropriately adjusted in order to obtain good light spread.

The light-emitting diode of the present invention can be manufactured by coating a light-emitting element with the curable composition as described above, but in this case, the coating is not limited to one that directly seals the light-emitting element. And indirect coating. Specifically, the light emitting device may be directly encapsulated with the curable composition of the present invention by various methods conventionally used, or a conventionally used epoxy resin, silicone resin, acrylic resin, urea resin, imide resin, etc. After the light-emitting element is sealed with the sealing resin or glass described above, the light-emitting element may be coated on or around the light-emitting element with the curable composition of the present invention. After the light emitting element is sealed with the curable composition of the present invention, it may be molded with a conventionally used epoxy resin, silicone resin, acrylic resin, urea resin, imide resin, or the like. By the above-described method, various effects such as a lens effect can be provided by a difference in refractive index and specific gravity.

Various methods can be applied as the sealing method. For example, a liquid curable composition may be poured into a cup, a cavity, a package concave portion, or the like having a light emitting element disposed at the bottom by a dispenser or other method and cured by heating or the like, or may be a solid or high-viscosity liquid. The curable composition may be flowed by heating or the like, and may be similarly poured into a package recess or the like and further cured by heating or the like. The package in this case can be made using various materials, and examples thereof include a polycarbonate resin, a polyphenylene sulfide resin, an epoxy resin, an acrylic resin, a silicone resin, and an ABS resin. Alternatively, a method in which a curable composition is previously injected into a mold frame, and a lead frame or the like to which a light emitting element is fixed is immersed therein and then cured, or a method in which a light emitting element is inserted into a mold frame can be applied. A sealing layer made of a curable composition may be molded and cured by injection using a dispenser, transfer molding, injection molding, or the like. further,
The curable composition simply in a liquid or fluid state may be dropped or coated on the light emitting element and cured.
Alternatively, the composition can be molded and cured by stencil printing, screen printing, or application via a mask on the light emitting element. Alternatively, a method in which a curable composition partially cured or cured in advance into a plate shape, a lens shape, or the like may be fixed on a light emitting element. Furthermore, it can be used as a die bonding agent for fixing a light emitting element to a lead terminal or a package,
It can also be used as a passivation film on a light emitting element. Further, it can be used as a package substrate.

The shape of the covering portion is not particularly limited, and can take various shapes. For example, a lens shape, a plate shape, a thin film shape, a shape described in JP-A-6-244458, and the like can be mentioned. These shapes may be formed by molding and curing the curable composition, or may be formed by post-processing after curing the curable composition.

The light emitting diode of the present invention can be of various types, for example, any type such as a lamp type, an SMD type and a chip type. Various types of SMD type and chip type package substrates are used, for example, epoxy resin, BT resin,
Ceramics and the like can be mentioned.

In addition, various conventionally known methods can be applied to the light emitting diode of the present invention. For example, a method of providing a layer for reflecting or condensing light on the back of the light emitting element, a method of forming a complementary colored portion on the bottom corresponding to yellowing of the sealing resin,
A method in which a thin film that absorbs light having a wavelength shorter than the main emission peak is provided on the light emitting element, a method in which the light emitting element is sealed with a soft or liquid sealing material, and then the surroundings are molded with a hard material, A method in which a light-emitting element is sealed with a material containing a phosphor that emits longer-wavelength fluorescent light by absorption and then molding is performed around the light-emitting element; a method in which a material containing the phosphor is molded in advance and then molded together with the light-emitting element; As described in −244458, a method of increasing the luminous efficiency by using a molding material in a special shape, a method of forming a two-step recessed package to reduce uneven brightness, a method of inserting and fixing a light emitting diode in a through hole, and light emission A method of forming a thin film on the element surface that absorbs light having a wavelength shorter than the main emission wavelength, and connecting the light emitting element by flip chip connection using solder bumps etc. Method in which light is taken out from the substrate direction by connecting the lead member or the like Te, and the like.

The light emitting diode of the present invention can be used for various known applications. Specifically, for example, a backlight, an illumination, a sensor light source, an instrument light source for a vehicle, a signal light, an indicator light, a display device, a light source of a planar light emitter, a display, a decoration, various lights, and the like can be given.

[0127]

EXAMPLES Examples and comparative examples of the present invention will be shown below, but the present invention is not limited by the following. (Synthesis Example 1) A stirrer and a condenser were set in a 1 L three-necked flask. In this flask, add bisphenol A1
14 g, potassium carbonate 145 g, allyl bromide 14
0 g and acetone (250 mL) were added, and the mixture was stirred at 60 ° C. for 12 hours. The supernatant was taken, washed with an aqueous sodium hydroxide solution using a separating funnel, and then washed with water. After the oil layer was dried over sodium sulfate, the solvent was distilled off using an evaporator, and 126 g of a pale yellow liquid was obtained. ¹ H-
NMR revealed that the bisphenol A diallyl ether had the OH group of bisphenol A allyl etherified. The yield was 82% and the purity was 95% or more.

(Synthesis Example 2) A stirrer, a condenser, and a dropping funnel were set in a 1 L four-necked flask. In this flask, 150 g of toluene, 15.6 μL of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum),
500 g of 1,3,5,7-tetramethylcyclotetrasiloxane was added, and the mixture was heated to 70 ° C. and stirred in an oil bath. 64 g of bisphenol A diallyl ether produced in Synthesis Example 1 was diluted with 40 g of toluene and added dropwise from a dropping funnel. After stirring at the same temperature for 60 minutes, the mixture was allowed to cool, and 4.74 mg of benzothiazole was added. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a slightly viscous liquid. ^{According to 1} H-NMR, this was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with bisphenol A diallyl ether (referred to as partial reactant A)
It turned out to be.

(Synthesis Example 3) A magnetic stirrer and a condenser were set in a 200 mL two-necked flask. 50 g of toluene, 11.3 μL of a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum), 5.0 g of triallyl isocyanurate, 37.04 g of 1,3,5,7-tetramethylcyclotetrasiloxane were added to the flask. Then, the mixture was heated and stirred in a 90 ° C. oil bath for 30 minutes. Further, the mixture was heated and refluxed for 2 hours in a 130 ° C. oil bath.
176 mg of 1-ethynyl-1-cyclohexanol was added. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. ¹ H-
NMR revealed that this was a product in which part of the SiH groups of 1,3,5,7-tetramethylcyclotetrasiloxane had reacted with triallyl isocyanurate (referred to as partial reactant B).

(Example 1) 16.1 g of bisphenol A diallyl ether produced in Synthesis Example 1, 15.4 g of the partially reacted product A produced in Synthesis Example 2, and a visible light transmittance of 90% were obtained.
% Or more of the quartz is crushed and classified to reduce the average particle diameter to 0.1%.
3.5 g of the particulate filler having a particle size of 3 μm was mixed in a cup, and defoamed under a reduced pressure of about 1 torr for 1 hour to obtain a curable composition. As shown in Synthesis Example 2, partial reactant A contains a platinum vinyl siloxane complex as component (C) of the present invention. Put this one cm wide along the edge, 0.36
A mirror-polished (# 1200 polished) stainless steel polishing plate with a silicone rubber sheet having a thickness of 1 mm is poured, and one more mirror-polished (# 1200)
100 ° C
/ 45 minutes, and subsequently heating at 150 ° C./2.5 hours to obtain a visually uniform and colorless and transparent sheet. The obtained cured product was hard and had no surface tack.

(Example 2) 16.1 g of bisphenol A diallyl ether prepared in Synthesis Example 1, 15.4 g of the partially reacted product A prepared in Synthesis Example 2, and crystalline silica having an average particle diameter of 5 μm (Crysta manufactured by Tatsumori Co., Ltd.) 3.5 g of Light 5X) were mixed in a cup, and the mixture was defoamed under reduced pressure of about 1 torr for 1 hour to obtain a curable composition. As shown in Synthesis Example 2, partial reactant A contains a platinum vinyl siloxane complex as component (C) of the present invention. This was poured into an ointment can covered with a polyimide film, and 50 ° C./15 hours.
80 ° C / 7 hours, 100 ° C / 17 hours, and 150 ° C
Heating was performed for 24 hours to obtain a colorless, almost transparent, film-like cured product that was slightly cloudy visually. The obtained cured product was hard and had no surface tack.

Example 3 16.1 g of bisphenol A diallyl ether produced in Synthesis Example 1, 15.4 g of the partially reacted product A produced in Synthesis Example 2, and crystalline silica having an average particle diameter of 5 μm (Crysta, manufactured by Tatsumori Co., Ltd.) Light 5X) 31.5g
Was mixed in a cup, and the mixture was defoamed under a reduced pressure of about 1 torr for 1 hour to obtain a curable composition. As shown in Synthesis Example 2, partial reactant A contains a platinum vinyl siloxane complex as component (C) of the present invention. This was poured into an ointment can covered with a polyimide film, and was then heated at 50 ° C / 15 hours, 80 ° C / 7 hours, 100 ° C / 17 hours,
Heating was performed at 0 ° C. for 24 hours to obtain a colorless cured film which was cloudy visually. The obtained cured product was hard and had no surface tack.

Example 4 16.1 g of bisphenol A diallyl ether produced in Synthesis Example 1, 15.4 g of the partially reacted product A produced in Synthesis Example 2, and an average particle diameter of 10 μm
Spherical silica (Silstar MF-10 manufactured by Nippon Chemical Co., Ltd.) 3
1.5 g was mixed in a cup and defoamed under reduced pressure of about 1 torr for 1 hour to obtain a curable composition. As shown in Synthesis Example 2, partial reactant A contains a platinum vinyl siloxane complex as component (C) of the present invention. This was poured into an ointment can covered with a polyimide film,
Heating was carried out for 15 hours, 80 ° C./7 hours, 100 ° C./17 hours, and further 150 ° C./24 hours to obtain a colorless film-like cured product which became cloudy visually. The obtained cured product was hard and had no surface tack.

Example 5 16.1 g of bisphenol A diallyl ether produced in Synthesis Example 1, 15.4 g of the partially reacted product A produced in Synthesis Example 2, and an average particle size of 0.07 g
μm fine silica powder (Aerosil 3 manufactured by Nippon Aerosil Co., Ltd.)
00) and 3.5 g were mixed in a cup, and the mixture was defoamed under a reduced pressure of about 1 torr for 1 hour to obtain a curable composition. As shown in Synthesis Example 2, partial reactant A contains a platinum vinyl siloxane complex as component (C) of the present invention. Pour this into an ointment can covered with a polyimide film,
Heating was performed at 0 ° C./15 hours, 80 ° C./7 hours, 100 ° C./17 hours, and further at 150 ° C./24 hours to obtain a colorless, almost transparent, filmy, slightly cloudy visually. The obtained cured product was hard and had no surface tack.

Example 6 16.1 g of bisphenol A diallyl ether produced in Synthesis Example 1, 15.4 g of partially reacted product A produced in Synthesis Example 2, and an average particle size of 0.07 g
μm fine silica powder (Aerosil R manufactured by Nippon Aerosil Co., Ltd.)
972) in a cup with 7.8 g, about 1 torr
The mixture was defoamed under reduced pressure for 1 hour to obtain a curable composition. Synthesis Example 2
As shown in the above, the partial reactant A contains the platinum vinyl siloxane complex as the component (C) of the present invention. Pour this into a polyimide film ointment can,
Heating was performed at 50 ° C./15 hours, 80 ° C./7 hours, 100 ° C./17 hours, and further at 150 ° C./24 hours to obtain a colorless, almost transparent, filmy, slightly cloudy visually. The obtained cured product was hard and had no surface tack.

Example 7 2.5 g of triallyl isocyanurate and 3.0 g of the partially reacted product B synthesized in Synthesis Example 3
And 0.6 g of fine powder silica (Aerosil 300 manufactured by Nippon Aerosil Co., Ltd.) having an average particle diameter of 0.007 μm were mixed in a cup, and the mixture was defoamed under reduced pressure of about 1 torr for 30 minutes. As shown in Synthesis Example 3, the partial reactant B contains the platinum vinyl siloxane complex as the component (C) of the present invention.
This was poured into a cell formed by inserting a 3 mm thick silicone rubber sheet as a spacer between two glass plates, and was poured at 80 ° C./60 minutes, 100 ° C./60 minutes, and 120 ° C.
Heating was performed at 60 ° C. for 60 minutes to obtain a visually uniform and colorless and transparent cured product. The obtained cured product was hard and had no surface tack.

Example 8 5.0 g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and 6.7 g of methylhexahydrophthalic anhydride were mixed and poured into an ointment can at 100 ° C. / Heat-cured for 14 hours. The resulting cured product has a total light transmittance of 80.
% Or more. The cured product was pulverized and classified to obtain a particulate filler having an average particle diameter of 0.3 μm.

2.5 g of triallyl isocyanurate,
3.0 g of the partial reactant B synthesized in Synthesis Example 3 and 1.4 g of the particulate filler described above were mixed in a cup, and the mixture was mixed for about 1 ton.
Degassing was performed under reduced pressure of rr for 30 minutes. As shown in Synthesis Example 3, partial reactant B contains a platinum vinyl siloxane complex as component (C) of the present invention. This was poured into a cell made by inserting a 3 mm thick silicone rubber sheet as a spacer between two glass plates, and then flowing at 80 ° C. /
Heating was performed for 60 minutes, 100 ° C./60 minutes, and 120 ° C./60 minutes to obtain a visually uniform, colorless and transparent cured product. The obtained cured product was hard and had no surface tack.

(Measurement Example 1) The cured products obtained in Examples 7 and 8 were subjected to a suga tester SX120 type xenon weather meter (black panel temperature 63 ° C., irradiation for 2 hours with rain 18
), And the state of the cured product was visually observed. The cured product did not show yellowing and maintained a colorless and transparent state.

Example 9 2.5 g of triallyl isocyanurate and 3.0 g of the partially reacted product B synthesized in Synthesis Example 3
And 0.6 g of a particulate filler having an average particle diameter of 0.3 μm after pulverizing quartz having a visible light transmittance of 90% or more and mixing them in a cup, and then under reduced pressure of about 1 torr for 30 minutes. It was defoamed to obtain a curable composition. As shown in Synthesis Example 3, the partial reactant B contains the platinum vinyl siloxane complex as the component (C) of the present invention. This one, 2
A glass rubber sheet with a thickness of 0.5 mm is flowed into a cell created by inserting a silicone rubber sheet as a spacer,
Heating was performed at 80 ° C./60 minutes, 100 ° C./60 minutes, and 120 ° C./60 minutes to obtain a visually uniform, colorless and transparent cured sheet. The obtained cured product was hard and had no surface tack.

The sheet-like cured product prepared as described above is cut into an appropriate shape, and fixed to a light transmitting window provided on a metal cap for a can type. On the other hand, MOC
A light emitting device having a double hetero structure in which an InGaN active layer doped with Si and Zn formed on a sapphire substrate by a VD (metal organic chemical vapor deposition) method is sandwiched between n-type and p-type AlGaN cladding layers is prepared. . Subsequently, after mounting this light emitting element on a metal stem for a can type, the p-electrode and the n-electrode are wire-bonded to the respective leads with an Au wire. This is hermetically sealed with the above-mentioned metal cap for can type. In this manner, a can-type light emitting diode can be manufactured.

(Example 10) An n-type GaN layer, which is an undoped nitride semiconductor, and a Si-doped n-type layer were formed on a cleaned sapphire substrate by MOCVD (metal organic chemical vapor deposition).
GaN layer serving as an n-type contact layer formed with a type electrode, an n-type GaN layer serving as an undoped nitride semiconductor, a GaN layer serving as a barrier layer forming a light emitting layer, an InGaN layer forming a well layer, and a barrier layer A GaN layer (quantum well structure), an AlGaN layer as a Mg-doped p-type cladding layer, and a GaN layer as a Mg-doped p-type contact layer are sequentially laminated on the light emitting layer. The surface of each pn contact layer is exposed on the same side of the nitride semiconductor on the sapphire substrate by etching. On each contact layer,
Al is deposited using a sputtering method to form positive and negative electrodes. After a scribe line is drawn on the completed semiconductor wafer, the semiconductor wafer is divided by an external force to form light emitting elements.

The light emitting element is die-bonded on the bottom surface of the cup of the mount lead made of iron-containing copper plated with silver on the surface by using an epoxy resin composition as a die-bonding resin. This is heated at 170 ° C. for 75 minutes to cure the epoxy resin composition and fix the light emitting element. Next, the positive and negative electrodes of the light emitting element are wire-bonded to the mount lead and the inner lead with an Au wire to establish electrical continuity.

The curable composition prepared in the same manner as in Example 9 is poured into a casting case which is a shell-shaped mold. A part of the mount lead and the inner lead in which the light emitting element is arranged in the cup is inserted into a casting case, and initial curing is performed at 100 ° C. for 1 hour. The light emitting diode is extracted from the casting case and cured at 120 ° C. for 1 hour in a nitrogen atmosphere. Thereby, a lamp type light emitting diode such as a shell type can be produced. (Example 11) A curable composition and a light emitting device are prepared by the method described in Example 10.

A substrate having lead electrodes is formed by forming a pair of copper foil patterns on a glass epoxy resin by etching. The light emitting element is die-bonded on a glass epoxy resin using an epoxy resin. Each electrode of the light emitting element and each lead electrode are wire-bonded with an Au wire, respectively, to establish electrical continuity. A glass epoxy resin having a through hole as a mask and a side wall is fixedly arranged on the substrate with the epoxy resin. In this state, the curable composition is dispensed on a glass epoxy resin substrate on which a light emitting element is disposed, and the curable composition is filled in a cavity using a through hole. In this state, it is cured at 100 ° C. for 1 hour and further at 150 ° C. for 1 hour. By dividing each light emitting diode chip, a chip type light emitting diode can be produced. (Example 12) A curable composition and a light emitting device are prepared by the method described in Example 10.

A chip type light emitting diode package is formed by insert molding using PPS resin. The inside of the package has an opening in which the light emitting element is arranged, and a silver-plated copper plate is arranged as an external electrode. A light emitting element is fixed inside the package by die bonding using an epoxy resin. An Au wire, which is a conductive wire, is wire-bonded to each electrode of the light-emitting element and each external electrode provided on the package to be electrically connected.
The curable composition is filled in the package opening as a mold member. In this state, at 100 ° C. for 1 hour,
Cure at 0 ° C. for 1 hour. Thus, a chip type light emitting diode can be manufactured. (Example 13) A curable composition and a light emitting device are prepared by the method described in Example 10.

The curable composition is heated to 90 ° C. for 30 minutes to be B-staged.

A substrate having lead electrodes is formed by forming a pair of copper foil patterns on a glass epoxy resin by etching. The light emitting element is die-bonded on a glass epoxy resin using an epoxy resin. Each electrode of the light emitting element and each lead electrode are wire-bonded with an Au wire, respectively, to establish electrical continuity. The light emitting element and a part of the lead electrode are sealed by transfer molding using the curable composition in the B-stage. An SMD type light emitting diode can be manufactured.

(Embodiment 14) A nitride semiconductor is sequentially etched from the p-type nitride semiconductor layer side by an RIE (reactive ion etching) apparatus to form a negative electrode in the same manner as in the ninth embodiment. The surface of the n-type contact layer is exposed. Next, Ni / Au is applied to almost the entire surface of the uppermost p-type contact layer by a lift-off method to a film thickness of 60 /.
Laminate at 200 ° to form a first positive electrode with good ohmic contact and excellent transparency. Further, Au is laminated on a part of the translucent first positive electrode to a thickness of 1 μm to form a second positive electrode to be a positive electrode side bonding portion.

On the other hand, W / Al / W / Au was sputtered on the surface of the n-type contact layer exposed by etching to a film thickness of 200.degree.
000Å / 2000Å / 3000Å
An unnecessary resist film is removed to form a negative electrode, thereby forming an LED element. As a result, a negative electrode having good ohmic contact without performing annealing is formed. Further, although the negative electrode serves as a bonding portion, the above-described configuration has high mechanical strength, and thus an LED element that can be driven stably can be obtained.

Next, the bonding of each electrode is performed by patterning.
Only the exposed portion is exposed to contact the entire surface of the device.
₂An insulating inorganic compound layer made of
D element. The insulating inorganic compound layer is at least short.
What is necessary is just to be formed so as to prevent the
If provided on the upper surface of the semiconductor layer between the pole and the negative electrode
Good. Providing the insulating inorganic compound layer in this manner,
When mounting miniaturized light emitting devices with high reliability,
Always important. The material of the insulating inorganic compound layer is small.
Both may be insulating, for example, SiO 2₂, TiO₂,
Al₂O₃, Si ₃N₄Single layer or multiple layers consisting of
Can be.

In this embodiment, the insulating inorganic compound layer is provided continuously up to the end face of the light emitting element. Thereby, the shaved end surface and the exposed surface of the substrate can be protected from high temperature and high humidity, and a light emitting element capable of maintaining high reliability even when used for a long time under severe environmental conditions can be obtained. Further, the insulating inorganic compound layer provided in direct contact with the sapphire substrate or gallium nitride preferably has a thermal expansion coefficient close to that of the member in contact therewith, whereby reliability can be further improved. Incidentally, the thermal expansion coefficient of each material is 7.5 to 8.5 for the sapphire substrate.
× 10 ⁻⁶ / k, gallium nitride is 3.2 to 5.6 × 10
⁻⁶ / k, silicon dioxide 0.3 to 0.5 × 10 ⁻⁶ /
k, silicon nitride is 2.5 to 3.0 × 10 ⁻⁶ / k.

In the light-emitting element used in this embodiment, most of the light emitted from the light-emitting layer is totally reflected at the interface between the upper and lower layers, and tends to emit light from the light-emitting end with a high light density. When such a light emitting element is directly covered with a resin, light and heat from the light emitting element concentrate on the light emitting element, so that an adjacent resin portion is significantly deteriorated locally. It is considered that this causes a change in color tone and a decrease in reliability of the light emitting diode. Therefore, in this example, a light-emitting element having an insulating inorganic compound layer on the surface thereof has a relatively high adhesiveness to the insulating inorganic compound layer and a composition of the present invention having excellent light resistance and heat resistance. By directly covering the light emitting region, light emitted from the end of the light emitting region is efficiently extracted to the outside, deterioration at the interface is suppressed, and a highly reliable light emitting device is provided.

The light emitting end means the light emitting layer and the end of the n-type contact layer. Therefore, it is preferable that the insulating inorganic compound layer provided at these ends is made of an inorganic substance having a smaller refractive index than GaN, which is often used as an n-type contact layer. Thereby, deterioration of the composition can be suppressed. Further, the insulating inorganic compound is, for example, SiO ₂ as a first layer directly in contact with a light emitting end of a light emitting element, and a _second layer having a higher refractive index than the first layer in contact with the first layer. T with TiO ₂ laminated as a layer of
and iO ₂ / SiO _2, and a two-layer structure such as TiO 2 / MgF _2, by providing the optical multilayer film having a three-layer structure formed by laminating the insulating film and the metal as SiO 2 / Al / SiO ₂ , Can also be reflective. In the case of a plurality of layers, the film thickness is preferably 5000 to 5 μm, more preferably 1 to 3 μm.

When a light emitting device having an inorganic compound layer on its surface is directly coated with the composition of the present invention, the inorganic compound layer preferably contains silicon in consideration of light refraction and thermal expansion. The inorganic compound layer containing silicon is not particularly limited as long as at least silicon is contained in the inorganic compound. Specifically, SiO ₂ , SiN, SiON,
And an inorganic compound layer made of SiH ₄ or the like. In addition, when an inorganic compound layer containing silicon is provided and this inorganic compound layer is directly coated with the composition of the present invention, reliability is improved as compared with the case where another inorganic compound layer is provided, and high temperature, high humidity, etc. Under such environmental conditions, high reliability and optical characteristics tend to be maintained. The reason for this is not clear, but it is considered that the silicon-containing inorganic compound layer forms an interface with good affinity and high adhesion with the composition of the present invention, and the intrusion of moisture and outside air is suppressed.

The wafer having the LED elements formed as described above is polished by a polishing process to a scribeable substrate thickness, and placed on an adhesive sheet so that the substrate surface is in contact with the adhesive sheet. Divided into The divided LED chips are fixed inside the same package as in the twelfth embodiment by the same method, and are electrically connected by wire bonding with an Au wire.

Next, triallyl isocyanurate 2.5
g and 100 g of a mixed solution obtained by mixing 3.0 g of the partial reactant B synthesized in Synthesis Example 3 were crushed with quartz having a visible light transmittance of 90% or more, followed by classification, followed by classification and average particle diameter. Of silica as a particulate filler having a particle size of 7 μm
The mixed solution contained in parts by weight is injected into the package while stirring. After injection, 60 ° C for 6 hours, 70 ° C
By curing for 1 hour, 80 ° C. for 1 hour, and 120 ° C. for 1 hour, the first layer that covers the LED chip and contains a large amount of silica and has a lower silica content than the first layer and a higher translucency A sealing material having a two-layer structure with the second layer is formed.

Here, the average particle size in the present specification is a value measured by a sub-sieve sizer method based on an air permeation method as a basic principle.

Since the light emitting diode thus formed is made of a sealing material having excellent heat resistance and toughness, cracks are generated in the resin and the light emitting element due to thermal stress during mounting and lighting. And wire breakage can be prevented.

Further, the light emitting element generates heat when it is turned on, and the vicinity of the light emitting element is particularly in a high temperature state, and a large thermal stress is generated. Therefore, in this embodiment, a sealing material having a two-layer structure of a first layer covering the light-emitting element and a second layer covering the first layer and having a higher light-transmitting property than the first layer By reducing the difference in thermal expansion coefficient between the members in the vicinity of the light emitting element, peeling and cracking at each interface can be prevented. The second layer is preferably constituted by the composition of the present invention having a lower content of the component (D) than the composition of the present invention constituting the first layer. Further, it is preferable that the first layer is provided continuously from the surface of the lead electrode exposed from the bottom surface of the package to the surface of the light emitting element. Thereby, heat generated from the light emitting element can be radiated to one surface of the lead electrode via the first layer. Further, the first layer serves as a buffer layer between the insulating inorganic compound layer provided around the light emitting element and the second layer, so that thermal stress can be reduced. In wire bonding, one end of the wire is generally formed into a ball shape by applying a discharge, and is pressed on a light emitting element. However, due to the discharge, the interface between the wire and the upper end portion of the ball becomes brittle. Often become. Therefore, in the present invention,
It is preferable to provide an interface between the first layer containing the filler that tends to concentrate thermal stress and the second layer not containing the filler in contact with the ball portion of the wire formed on the light emitting element, Thereby, wire breakage due to thermal stress can be suppressed.

As described above, since the light emitting diode of the present invention has excellent heat resistance, even if the light emitting diode is mounted on a conductive member having no Pb and having a high melting point, the chromaticity fluctuation and the reliability may be reduced. Since no deterioration occurs, an environment-friendly display device can be realized.

Further, the sealing material of the present invention is a cured product having flexibility in thermal stress. Conventionally, rubber-like elastic resins, gel resins, and the like are known as resins having flexibility in thermal stress, but these resins have low mechanical strength because they have a low crosslinking density or do not have a crosslinking structure, and Due to the tackiness, there are problems such as foreign matter easily adhering,
It was not suitable for forming a light emitting surface to be the outermost surface. On the other hand, the composition of the present invention does not have a risk of adhering foreign matter and being damaged by the mounting device. As described above, according to the present invention, by using the composition of the present invention, a member for covering a light emitting element and a wire portion and a member for a light emitting surface serving as a surface portion of a light emitting device can be integrally formed, and mass productivity and workability can be improved. Thus, a light emitting diode having excellent characteristics can be obtained. Further, since it has excellent light resistance to sunlight, the light emitting surface is not discolored even when mounted on an outdoor display substrate, and good reliability can be maintained.

In the present invention, various fluorescent substances such as an inorganic fluorescent substance and an organic fluorescent substance can be contained in each constituent member. As an example of such a fluorescent substance, there is a fluorescent substance containing a rare earth element which is an inorganic fluorescent substance. As the rare earth element-containing phosphor, specifically, Y, Lu, Sc, La,
A garnet-type phosphor having at least one element selected from the group of Gd and Sm and at least one element selected from the group of Al, Ga, and In may be used.
In particular, a yttrium / aluminum oxide-based phosphor activated with cerium is preferable. In addition to Ce, Tb, Cu, Ag, Au, Fe, Cr, Nd, Dy, N
It is also possible to contain i, Ti, Eu, Pr and the like. In addition, the composition of the present invention includes a substance which can absorb a part of the light of the light-emitting element and emit light of another wavelength and has a surface containing an inorganic element common to the composition of the present invention. When a coated inorganic fluorescent substance is added, these interfaces tend to have good adhesion due to chemical bonding or the like. In addition, the above-described fluorescent substance is fixed in a well dispersed state in the composition. Thus, a color conversion type light-emitting diode capable of uniformly emitting light with high luminance can be obtained by improving the light absorption rate and light extraction efficiency of the inorganic fluorescent substance.

(Embodiment 15) In the same manner as in Embodiment 12, a light emitting element is mounted in a package and is electrically connected by wires. Here, a resist film is formed on the surface excluding the opening of the package. The package on which the LED chips are placed is placed in a container containing pure water.

On the other hand, for the particulate phosphor, a solution in which rare earth elements of Y, Gd, and Ce are dissolved in an acid at a stoichiometric ratio is coprecipitated with oxalic acid. This is mixed with a coprecipitated oxide obtained by calcination and aluminum oxide to obtain a mixed raw material. This is mixed with aluminum fluoride as a flux, packed in a crucible, and fired in air at a temperature of 1400 ° C. for 3 hours to obtain a fired product. The calcined product is ball-milled in water, washed, separated, dried, and finally passed through a sieve (Y _0.8 Gd _0.2 ) ₃
An Al ₅ O ₁₂ : Ce phosphor is formed. A mixed solution obtained by dispersing the fluorescent substance thus obtained in a SiO ₂ sol is formed.

Next, after adjusting the pH to 5.0 with acetic acid,
Immediately pour the mixed solution into the container in which the package is placed. After standing (Y _0.8 Gd _0.2 ) ₃ Al
₅ O _{1 2:} Ce phosphor is settling in the package opening and the light emitting element. The package in which the waste liquid in the container is removed and the particulate phosphor is deposited on the LED chip is dried at 120 ° C.

Next, the light emitting diode is taken out of the container, and the particulate phosphor adhered to the non-light emitting portion of the light emitting diode is removed together with the resist mask. The light emitting diode thus obtained has an inorganic compound layer in which the thickness of both the LED chip and the package bottom is substantially equal to about 40 μm. Further, a composition prepared in the same manner as in Example 9 as a mold member in a package having an inorganic compound layer formed thereon for the purpose of protecting the LED chip and the particulate phosphor from external stress, sunlight, moisture, dust and the like. And cured at 150 ° C. for 5 hours.

The light-emitting diode thus obtained is composed of a sealing member having excellent durability and having a reduced difference in thermal expansion coefficient from other members. It has excellent reliability without color shift and color unevenness during use.

Example 16 A light emitting diode was formed in the same manner as in Example 4, except that the composition of the present invention was used as a die bond resin. With such a structure, all of the members around the light emitting element can be made of a composition having excellent heat resistance and light resistance, and a light emitting diode with higher reliability can be obtained. Further, light emitted from the bottom surface of the light emitting element is reflected and scattered in the die bonding material, and can be efficiently extracted in the light emitting surface direction.

[0170]

The material produced from the composition of the present invention has high optical transparency, high toughness, low light degradation, and is used for optical materials which are hard and have no surface tackiness. Suitable material.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) G02F 1/1335 500 G02F 1/1335 500 H01L 33/00 H01L 33/00 N (72) Inventor Manabu Tsumura Settsu-shi, Osaka 5-72 Torikai Nishi 5-101 Hironori Dormitory A 101 (72) Inventor Harumi Sakamoto 1-28-28 Torikai Wado, Settsu-shi, Osaka Sunny Court Room 401 (72) Inventor Masayuki Fujita 5-5-55 Torikai Nishi, Settsu-shi, Osaka −32−102 (72) Inventor Masafumi Kuramoto 491-100 Kaminakacho Oka, Anan City, Tokushima Prefecture Inside Nichia Chemical Industry Co., Ltd. F-term in Industrial Co., Ltd. (reference) 2H090 JB03 JB06 JD04 JD18 2H091 FA08X FA08Z FA11X FA11Z FB02 FB13 LA16 4J002 CP041 EA016 EA026 EA036 EC077 EU196 EZ007 FD018 FD157 FD206 GP00 HA01 5F041 DA46

Claims (26)

[Claims] (A) a carbon having a reactivity with a SiH group;
An organic compound containing at least two carbon double bonds in one molecule, (B) a silicon compound containing at least two SiH groups in one molecule, (C) a hydrosilylation catalyst, and (D) a particulate filler. , As an essential component. 2. The composition for an optical material according to claim 1, wherein the component (A) is an organic compound containing at least one vinyl group reactive with a SiH group in one molecule. 3. The composition for an optical material according to claim 1, wherein the component (A) is an organic compound containing at least one allyl group reactive with a SiH group in one molecule. 4. The optical material according to claim 1, wherein the component (A) is 1,2-polybutadiene, vinylcyclohexene, cyclopentadiene, dicyclopentadiene, divinylbiphenyl, or bisphenol A diallyl ether. Composition. 5. The composition for an optical material according to claim 1, wherein the component (A) is triallyl isocyanurate or trivinylcyclohexane. 6. The optical material according to claim 1, wherein the component (D) is a particulate filler having a target light transmittance of 80% or more. Composition. 7. The optical material according to claim 1, wherein the component (D) is a particulate filler having an average particle diameter equal to or smaller than a target light wavelength. Composition. 8. The component (D) has a refractive index of the component (A),
The difference between the refractive index of the cured product obtained by curing the curable composition comprising the component (B) and the component (C) is ± 0.05.
The composition for an optical material according to any one of claims 1 to 7, wherein the composition is a particulate filler as follows. 9. The composition for an optical material according to claim 1, wherein the optical material is a liquid crystal film. 10. The composition for an optical material according to claim 1, wherein the optical material is a plastic cell for a liquid crystal. 11. The composition for an optical material according to claim 1, wherein the optical material is a sealing material for a light emitting diode. 12. The composition for an optical material according to claim 1, which is previously mixed, and a carbon-carbon double bond having a reactivity with a SiH group in the composition and SiH.
An optical material cured by reacting a part or all of the groups. 13. A carbon-carbon double bond having a reactivity with a SiH group in a composition, wherein the composition for an optical material according to any one of claims 1 to 11 is mixed in advance and SiH
2. The method according to claim 1, wherein a part or all of the groups are reacted.
3. A method for producing the optical material according to item 2. 14. A liquid crystal display device using the optical material according to claim 12. 15. A light-emitting diode using the optical material according to claim 12. 16. An organic compound containing (A) at least two carbon-carbon double bonds reactive with a SiH group in one molecule, and (B) an organic compound containing at least two SiH groups in one molecule. A silicon compound, (C) a hydrosilylation catalyst,
And (D) a light-emitting diode coated with a light-emitting element using a curable composition containing a particulate filler as an essential component. 17. The light emitting diode according to claim 16, wherein the component (A) is an organic compound containing at least one vinyl group reactive with a SiH group in one molecule. 18. The light emitting diode according to claim 16, wherein the component (A) is an organic compound containing at least one allyl group reactive with a SiH group in one molecule. 19. The light emitting diode according to claim 16, wherein the component (A) is 1,2-polybutadiene, vinylcyclohexene, cyclopentadiene, dicyclopentadiene, divinylbiphenyl, or bisphenol A diallyl ether. 20. The light emitting diode according to claim 16, wherein the component (A) is triallyl isocyanurate or trivinylcyclohexane. 21. The light emitting diode according to claim 16, wherein the component (D) is a particulate filler having a target light transmittance of 80% or more. 22. The light-emitting diode according to claim 16, wherein the component (D) is a particulate filler having an average particle diameter equal to or smaller than a target light wavelength. . 23. The component (D) has a difference in refractive index from the refractive index of a cured product obtained by curing a curable composition comprising the components (A), (B) and (C). Is ± 0.
The light emitting diode according to any one of claims 16 to 22, wherein the light emitting diode is a particulate filler having a particle size of not more than 05. 24. A sealing material obtained from the curable composition comprises a first layer covering the light-emitting element, and a second layer covering the first layer and having a higher light-transmitting property than the first layer. The light emitting diode according to any one of claims 16 to 23, comprising a layer of: 25. A sealing material obtained from the curable composition is obtained by mixing the curable composition in advance, forming a carbon-carbon double bond reactive with SiH groups in the composition and SiH.
The light emitting diode according to any one of claims 16 to 24, obtained by curing by reacting a part or all of the groups. 26. (A) an organic compound containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule, and (B) an organic compound containing at least two SiH groups in one molecule. A silicon compound, (C) a hydrosilylation catalyst,
And (D) a method for producing a light-emitting diode in which a light-emitting element is coated with a curable composition containing a particulate filler as an essential component, wherein the component (A)
The component (B) and the component (C) are mixed, and SiH in the composition is mixed.
A first step of reacting a carbon-carbon double bond having reactivity with a group and part or all of the SiH group, and a second step of mixing and dispersing the component (D) in the mixture obtained in the first step. And a third step of coating the light-emitting element with the curable composition obtained in the second step.