JP2003147205A - Curable composition for optical material, optical material, method for producing optical material and light-emitting diode using the optical material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition for an optical material having heat resistance even when a functional group is introduced and high transparency for light on a shorter wavelength than visible light, the optical material and a light-emitting diode using the optical material. SOLUTION: The curable composition for the optical material consists essentially of (A) an organic compound containing at least 2 carbon-carbon double bonds having reactivity with SiH group in one molecule, (B) a silicon compound containing at least 2 SiH groups in one molecule and (C) a hydrosilylating catalyst. When the component (B) has an aliphatic ether structure, the amount of the compound is such that the content of ether groups based on the component (A) is <=13.2 mequivalents/g-component (A).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable composition for optical materials, an optical material, and a method for producing an optical material. More specifically, the present invention relates to a curable composition suitable for a light emitting diode encapsulant. And a light emitting diode using the curable composition thereof.

[0002]

2. Description of the Related Art Conventionally, it has been usual to use light having a wavelength longer than visible light when processing an optical material to manufacture an optical medium or extracting information from the optical medium. However, recently, light having a wavelength lower than that of visible light has been used in many cases. The reason is that the use of light having a wavelength lower than that of visible light makes it possible to process finer optical materials and record more information on the optical medium. In addition, by using light having a wavelength lower than that of visible light, a large amount of information can be extracted from a finely processed optical medium.
In order to respond to the technological trend of processing such optical materials and using light with a wavelength lower than visible light when extracting information, the optical materials that make up the optical medium are However, it is now required to have highly transparent characteristics. Since an aliphatic compound having no conjugated bond does not absorb low wavelength light, it has been studied when designing an optical material having a property of being highly transparent to light having a wavelength lower than visible light. However, there is a problem that an optical material using such an aliphatic compound has low heat resistance, and when a functional group is introduced to impart a function, the heat resistance is further lowered. When used as a coating material (also referred to as a sealing material or a molding material) for a light emitting element that constitutes a light emitting diode, similarly, low heat resistance poses a problem.

[0003]

An object of the present invention is to provide an optical material composition, an optical material, which has heat resistance even when a functional group is introduced and has high transparency to light having a wavelength lower than visible light.
And to provide a light emitting diode using an optical material.

[0004]

In order to solve such a problem, the inventors of the present invention have earnestly studied and as a result, (A) at least one carbon-carbon double bond reactive with a SiH group in one molecule. Organic compound containing two, (B) Silicon compound containing at least two SiH groups in one molecule, (C)
A curable composition for an optical material, which comprises a hydrosilylation catalyst as an essential component, and when the component (B) has an aliphatic ether structure, the amount of the compound is 1 relative to the component (A).
The inventors have found that the above problems can be solved by using a curable composition for optical materials characterized by having 3.2 meq ether groups / g- (A) component or less, and have reached 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 in one molecule, and (B) at least two SiH in one molecule. A curable composition for optical materials, comprising a silicon compound having a group and (C) a hydrosilylation catalyst as essential components, and when the component (B) has an aliphatic ether structure, the amount of the compound is (A). For the components, 13.
A curable composition for optical materials (claim 1), characterized in that it is 2 meq ether groups / g- (A) component or less, and the use of the optical material is a sealing material for a light emitting diode. A curable composition for optical materials (claim 2) according to claim 1, wherein the curable composition for optical materials according to claim 1 is mixed in advance, and carbon-carbon dioxide having reactivity with the SiH group in the composition. An optical material (claim 3) obtained by curing a heavy bond by reacting a part or all of the SiH group, and a light emitting diode (claim 4) using the optical material according to claim 3. And the curable composition for optical materials according to claim 1 is mixed in advance to obtain S in the composition.
a carbon-carbon double bond reactive with an iH group, and SiH
The method for producing an optical material according to claim 3, which is obtained by curing a part or all of the groups to react (claim 5).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

First, the component (A) in the present invention will be described.

The component (A) is an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule. The organic skeleton constituting the component (A) is not particularly limited as to the organic skeleton constituting the organic skeleton, and examples thereof include polyether-based, polyester-based, polyarylate-based, polycarbonate-based, saturated hydrocarbon-based, polyacrylic acid ester-based, Polyamide-based, phenol-formaldehyde-based (phenol resin-based), polyimide-based organic polymer skeletons, phenol-based, bisphenol-based, aromatic hydrocarbon-based such as benzene and naphthalene, aliphatic hydrocarbon-based, and the like, and two of these An organic monomer skeleton composed of the above is mentioned. The organic compound as the component (A) includes the organic skeleton portion and a group having a carbon-carbon double bond that is reactive with the SiH group that is covalently bonded to the organic skeleton portion. When represented in this way, the group having a carbon-carbon double bond reactive with the SiH group may be covalently bonded to any part of the organic skeleton.

The carbon-carbon double bond reactive with the SiH group of the component (A) is not particularly limited as long as it has reactivity with the SiH group.

The following general formula (I)

[0011]

[Chemical 1] An alkenyl group represented by the formula (R ¹ represents a hydrogen atom or a methyl group) is preferable from the viewpoint of reactivity.

From the ease of obtaining the raw materials,

[0013]

[Chemical 2] Is particularly preferable.

The alkenyl group of the component (A) is represented by the following general formula (II)

[0015]

[Chemical 3] An alkenyl group represented by the formula (R ¹ represents a hydrogen atom or a methyl group) is preferable from the viewpoint of high heat resistance of the cured product.

Further, from the viewpoint of easy availability of raw materials,

[0017]

[Chemical 4] Is particularly preferable.

The alkenyl group may be covalently bonded to the organic skeleton portion of the component (A) via a divalent or higher valent substituent.

The divalent or higher valent substituent has 0 to 10 carbon atoms.
There is no particular limitation as long as it is a substituent of Examples of such substituents include:

[0020]

[Chemical 5]

[0021]

[Chemical 6] Etc.

Further, two or more of these substituents may be connected by a covalent bond to form one divalent or higher valent substituent.

Examples of the group covalently bonded to the organic skeleton as described above include vinyl group, allyl group, methallyl group,
Acrylic group, methacrylic group, 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3-
Allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis (allyloxy) Methyl)
Butyl group, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group,

[0024]

[Chemical 7] Etc.

As the organic compound as the component (A), the above organic skeleton portion and S which is covalently bonded to the organic skeleton portion.
It is also possible to use a low molecular weight compound that is difficult to express by being divided into an iH group and a group having a reactive carbon-carbon double bond. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, cyclopentadiene,
Examples thereof include aliphatic cyclic polyene compound systems such as cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene, and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.

As the component (A), from the viewpoint that the heat resistance can be further improved, a carbon-carbon double bond reactive with a SiH group is added in an amount of 0.001 m per 1 g of the component (A).
It is sufficient if it contains ol or more, but preferably contains 0.005 mol or more per 1 g,
Those containing 0.008 mol or more are particularly preferable. Specific examples include butadiene, isoprene, vinylcyclohexene, cyclopentadiene, dicyclopentadiene, cyclohexadiene, decadiene, diallyl phthalate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, divinylbenzenes (purity 50-100%). Of preferably 8
0 to 100%), 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof,

[0027]

[Chemical 8] And so on. In the present invention, these may be used alone or in combination of two or more.

From the viewpoint that the component (A) has good optical properties such as a low birefringence and a low photoelastic coefficient, the weight ratio of the aromatic ring in the component (A) is high. Is preferably 50 wt% or less, 40
It is more preferably not more than wt%, further preferably not more than 30 wt%. Most preferred are those containing no aromatic ring.

The number of carbon-carbon double bonds reactive with the SiH group of the component (A) may be at least two per molecule on average, but from the viewpoint that the heat resistance can be further improved, It is preferably more than 2, more preferably 3 or more, and particularly preferably 4 or more. The component (A) is preferably one that has fluidity at a temperature of 100 ° C. or lower in order to obtain uniform mixing with other components and good workability, and may be linear or branched. The lower limit of the molecular weight is 50 and the upper limit is 100,000.
Any value of 0 can be used, but a preferred lower limit is 54,
A preferred upper limit is 70,000, and a more preferred lower limit is 6.
8 and the more preferable upper limit is 50,000. Those with a molecular weight lower than 50 are highly volatile and have a molecular weight of 10
If it exceeds 50,000, the raw material generally has a high viscosity and is inferior in workability, and the effect of crosslinking due to the reaction between the alkenyl group and the SiH group is hardly exhibited.

Next, the silicon compound containing at least two SiH groups in one molecule 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, and for example, International Publication WO96.
/ 15194, compounds having at least two SiH groups in one molecule, and the like can be used.

Of these, chain-like and / or cyclic polyorganosiloxanes having at least two SiH groups in one molecule are preferable from the viewpoint of availability, and have good compatibility with the component (A). From the viewpoint, further, the following general formula (III)

[0033]

[Chemical 9] (In the formula, R ² represents an organic group having 1 to 6 carbon atoms, and n is 3 to
Represents the number 10. A cyclic polyorganosiloxane having at least two SiH groups in one molecule represented by the formula (1) is preferable. In addition, 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.

Further, a reaction product of a chain and / or cyclic polyorganosiloxane and one or more compounds selected from organic compounds having a carbon-carbon double bond (hereinafter referred to as component (D)) Is also preferable. The component (D) is an organic compound having an organic skeleton containing at least one carbon-carbon double bond reactive with a SiH group in one molecule, and the same description as the component (A) is also available. Can be used.

Preferred specific examples of the component (D) include allyl ether of novolac phenol and diallyl ether of bisphenol A, diallyl ether of hydrogenated bisphenol A, 2,2'-diallyl bisphenol A, diallyl phthalate and bis (2) of phthalic acid. -Allyloxyethyl) ester, styrene, α-methylstyrene, allyl-terminated polypropylene oxide, polyethylene oxide and the like. The organic compounds as the component (D) can be used alone or in combination of two or more.

When the component (B) has an aliphatic ether structure, for example, at least two S in one molecule.
Examples thereof include those having a chain and / or cyclic polyorganosiloxane having an iH group as a skeleton and having an ether bond through the skeleton portion and one or more aliphatic carbon atoms. Specific examples thereof include reaction products using allyl ether, hydrogenated bisphenol A diallyl ether, and allyl-terminated polyethylene oxide as the component (D). In the present invention, the amount of the compound having an aliphatic ether structure is 14 meq ether group / g-based on the component (A) from the viewpoint of heat resistance in that the cured product does not cause thermal decomposition.
It is preferable that the component (A) is not more than 13.2 meq.
The ether group / g- (A) component is particularly preferable. The heat resistance here is 180 ° C assuming product manufacturing
It does not cause thermal decomposition even if it is exposed to heat. When the amount of the compound having an aliphatic ether structure is more than 14 meq ether group / g- (A) component with respect to the (A) component, thermal decomposition may occur.

Component (D) and at least 2 in one molecule.
The reaction of the chain and / or cyclic polyorganosiloxane having one SiH group can be carried out using the hydrosilylation catalyst which is the component (C) of the present invention. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-
A vinyl siloxane complex and the like are preferable. Further, these catalysts may be used alone or in combination of two or more kinds. The addition amount of the catalyst is not particularly limited, has sufficient curability, and to reduce the cost of the curable composition relatively low, relative to SiH groups to 1 mole, the lower limit 10 ^-1 mol, the upper limit 10 ^- The range is preferably ⁸ mol, more preferably the lower limit is 10 ^-2 mol and the upper limit is 10 ^-6 mol. The solvent that can be used in the reaction is not particularly limited, and specific examples thereof include hydrocarbon solvents such as benzene, toluene, hexane, and heptane, tetrahydrofuran, 1,4-
Ether solvents such as dioxane and diethyl ether,
A ketone solvent such as acetone or methyl ethyl ketone, or a halogen solvent such as chloroform, methylene chloride, or 1,2-dichloroethane can be preferably used. The solvent may be used as a mixed solvent of two or more kinds.
As the solvent, toluene, tetrahydrofuran and chloroform are preferable. The amount of solvent used is 0 mL for the lower limit and 10 mL for the upper limit with respect to 1 g of the reactive [(D) + (chain-like and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule)] component used. The lower limit is 0.5 mL, the upper limit is 5 mL
Is more preferable, and the lower limit is 1 mL and the upper limit is 3 mL. The molar ratio (D) of the chain-like and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule (D)
/ A chain having at least two SiH groups in one molecule,
And / or cyclic polyorganosiloxane), from the viewpoint of yield, the lower limit is preferably 5 and the upper limit is 100, the lower limit is preferably 7 and the upper limit is 50, and the lower limit is 8 and the upper limit is 20.
Is particularly preferable.

Next, the hydrosilylation catalyst which is the component (C)
Will be described. As a hydrosilylation catalyst, hydr
There is no particular limitation as long as it has catalytic activity for the rosilylation reaction.
However, for example, simple substance of platinum, alumina, silica, carbon
Solid platinum supported on a carrier such as black, chloride
Platinic acid, chloroplatinic acid and alcohols, aldehydes, ketones
Complex with platinum-olefin complex (for example, Pt
(CH₂= CH₂)₂(PPh₃)₂, Pt (CH₂= C
H₂)₂Cl₂), Platinum-vinyl siloxane complex (eg,
For example, Pt (ViMe₂SiOSiMe₂Vi)_n, Pt
[(MeViSiO)_Four]_m), Platinum-phosphine complex
(For example, Pt (PPh₃)_Four, Pt (PBu₃)_Four),White
Gold-phosphite complex (for example, Pt [P (OP
h)₃]_Four, Pt [P (OBu) ₃]_Four) (Where Me is the
Cyl, Bu, butyl, Vi, vinyl, Ph.
Represents a nyl group, and n and m represent integers. ), Dicarboni
Ludichloroplatinum, Karstedt
Catalysts and Ashby US Patent No. 3
159601 and 3159662
Platinum-hydrocarbon composite, as well as Lamoreau (La
moreaux) U.S. Pat. No. 3,220,972.
The platinum alcoholate catalysts described therein may be mentioned. It
In addition, Modic US Pat. No. 3516
Platinum chloride-olefin compound described in Japanese Patent No. 946
Coalescence is also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ ,
RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdC
l ₂ .2H ₂ O, NiCl ₂ , TiCl ₄ , and the like.

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

The amount of the catalyst added is not particularly limited, but in order to have sufficient curability and to keep the cost of the curable composition relatively low, the lower limit is 10 ^-1 per mol of SiH group.
The molar range is preferably in the upper limit of 10 ^-8 mol, and more preferably in the lower limit of 10 ^-2 mol and the upper limit is 10 ^-6 mol. In addition, the catalyst amount is not necessarily added when the remaining amount used during the synthesis of the component (B) shows sufficient curability, but in order to adjust the curability, the catalyst amount is newly added within the above range. It can also be added.

A cocatalyst may be used in combination with the above catalyst, and examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl maleate, and 2-hydroxy-2-. Examples thereof include acetylene alcohol compounds such as methyl-1-butyne, sulfur compounds such as sulfur alone, and amine compounds such as triethylamine. The amount of the co-catalyst added is not particularly limited, but a lower limit of 10 ^-2 mol and an upper limit of 10 ² mol are preferable with respect to 1 mol of the catalyst, and a lower limit of 10 is more preferable.
^-1 mol and the upper limit is 10 mol.

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 compounds containing an aliphatic unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds and organic peroxides, and these may be used in combination. Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, en-yne compounds, maleic acid esters and the like. Examples of the organic phosphorus compound include triorganophosphines, diorganophosphines, organophosphines, triorganophosphites and the like. 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-based compound include stannous halide dihydrate and stannous carboxylate. Examples of organic peroxides include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide,
T-butyl perbenzoate and the like are exemplified.

Of these curing retarders, benzothiazole, thiazole, dimethylmalate and 3-hydroxy-3-methyl-1-butyne are preferable from the viewpoint of good delay activity and good availability of raw materials.

The addition amount of the storage stability improver is preferably in the range of lower limit of 10 ^-1 mol and upper limit of 10 ³ mol, and more preferably lower limit of 1 to 1 mol of the hydrosilylation catalyst used.
Mol, and the upper limit is 50 mol.

For the purpose of modifying the properties of the composition of the present invention,
It is also possible to add various resins. Examples of the resin include polycarbonate resin, polyether sulfone resin, polyarylate resin, epoxy resin, cyanate resin, phenol resin, acrylic resin, polyimide resin,
Examples thereof include polyvinyl acetal resin, urethane resin, and polyester resin, but are not limited thereto.

The composition of the present invention can be directly molded into a film or the like, but it is also possible to dissolve the composition in an organic solvent to form a varnish. The solvent that can be used is not particularly limited, and if specifically illustrated,
Hydrocarbon solvent such as benzene, toluene, hexane, heptane, ether solvent such as tetrahydrofuran, 1,4-dioxane, diethyl ether, ketone solvent such as acetone and methyl ethyl ketone, chloroform, methylene chloride, 1,2-dichloroethane, etc. The halogen-based solvent can be preferably used. The solvent is 2
It can also be used as a mixed solvent of more than one kind. As the solvent, toluene, tetrahydrofuran and chloroform are preferable. The amount of the solvent used is preferably in the range of lower limit 0 mL and upper limit 10 mL, more preferably in the range of lower limit 0.5 mL and upper limit 5 mL, and lower limit 1 mL, with respect to the reactive (B) component 1 g used. Upper limit 3 mL
It is particularly preferable to use the above range. If the usage is low,
It is difficult to obtain the effect of using a solvent such as lowering the viscosity, and if the amount used is large, the solvent remains in the material and problems such as thermal cracks easily occur, and it is also disadvantageous in cost and industrial use Value decreases.

Other than the above, the composition of the present invention includes an antiaging agent, 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. , Thickeners, plasticizers, coupling agents, antioxidants, heat stabilizers, conductivity imparting agents, antistatic agents, radiation blocking agents, nucleating agents, phosphorus-based peroxide decomposers, lubricants, pigments, metal-free agents. An activator, a physical property modifier, etc. can be added within a range that does not impair the objects and effects of the present invention.

If necessary, an inorganic filler may be added to the composition of the present invention. Addition of an inorganic filler is effective in preventing the fluidity of the composition and increasing the strength of the material. As the inorganic filler, fine particles are preferable, which do not deteriorate the optical properties, and alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine amorphous silica and hydrophobic ultrafine silica, talc, barium sulfate, etc. You can

Examples of the method of adding the filler include hydrolyzable silane monomers or oligomers such as alkoxysilane, acyloxysilane and halogenated silane, and alkoxides, acyloxides and halides of metals such as titanium and aluminum. The method of adding to the composition of the invention and reacting in the composition or a partial reaction product of the composition to form an inorganic filler in the composition can also be mentioned.

Further, various thermosetting resins can be added for the purpose of modifying the characteristics of the composition of the present invention. Examples of the thermosetting resin include epoxy resin, cyanate resin, phenol resin, polyimide resin, urethane resin and the like, but are not limited thereto. Among these, the transparent epoxy resin is preferable from the viewpoint of high transparency and excellent practical properties such as adhesiveness.

Examples of the transparent epoxy resin include bisphenol A diglycidyl ether and 2,2'-bis (4
-Glycidyloxycyclohexyl) propane, 3,4
-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexenedioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane , Bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, and other epoxy resins are treated with hexahydrophthalic anhydride. Examples thereof include those cured with an aliphatic acid anhydride such as methyl hexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride and hydrogenated methyl nadic acid anhydride. These epoxy resins or curing agents may be used alone or in combination.

Further, various additives for improving the characteristics of the light emitting diode may be added to the composition of the present invention. Examples of the additive include phosphors such as yttrium-aluminum-garnet-based phosphors activated by cerium, which absorb light from the light-emitting element and emit fluorescence having a longer wavelength, and blue which absorbs a specific wavelength. Coloring agents such as infusion agents, titanium oxide for diffusing light, aluminum oxide, silica, various oxides such as talc, calcium carbonate, melamine resin, CTU guanamine resin, benzoguanamine resin, etc. Examples thereof include a heat conductive filler such as a diffusion material, glass, a metal oxide such as aluminosilicate, a metal nitride such as aluminum nitride and boron nitride.

The additive for improving the characteristics of the light emitting diode may be contained uniformly or may be contained with a graded content. Such a filler-containing resin portion can be formed as a molding member on the rear side of the light emitting surface by pouring the resin for the molding member on the front surface of the light emitting surface into the mold, and subsequently, flowing the resin containing the filler. In addition, after forming the molding member, the lead terminals are covered by applying tape from both the front and back sides, and in this state, the lower half of the molding member of the light emitting diode is immersed in the tank containing the filler-containing resin, and then pulled up and dried to fill the filler. You may form a containing resin part.

The optical material referred to in the present invention means a general material used for the purpose of passing light such as visible light, infrared rays, ultraviolet rays, X-rays and lasers through the material.

More specifically, a liquid crystal display such as a substrate material in the field of liquid crystal displays, a light guide plate, a prism sheet, a deflection plate, a retardation plate, a viewing angle correction film, an adhesive, a film for liquid crystal such as a polarizer protective film, and the like. It is a material around the device. In addition, encapsulant for color PDP (plasma display), anti-reflection film, optical correction film, housing material, front glass protective film, front glass substitute material, adhesive, and light emitting diode, which are expected as next-generation flat panel displays. Molding material for light emitting elements used for display devices, sealing material for light emitting diodes, protective film for front glass, front glass substitute material, adhesive,
In addition, the substrate material in a plasma addressed liquid crystal (PALC) display, a light guide plate, a prism sheet, a deflection plate, a retardation plate, a viewing angle correction film, an adhesive, a polarizer protective film, and a front glass in an organic EL (electroluminescence) display. It is a protective film, a front glass substitute material, an adhesive, various film substrates in a field emission display (FED), a protective film for a front glass, a front glass substitute material, and an adhesive.

In the optical recording field, 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, sealant, adhesive and the like.

In the field of optical equipment, materials for steel camera lenses, finder prisms, target prisms,
It is a finder cover and a light receiving sensor. It is also a shooting lens and viewfinder for video cameras. Further, it is a projection lens of a projection television, a protective film, a sealing agent, an adhesive agent and the like. Materials for lenses of optical sensing devices, sealants, adhesives, films, etc.

In the field of optical components, there are fiber materials, lenses, waveguides, element sealants and adhesives around optical switches in optical communication systems. Examples include optical fiber materials around optical connectors, ferrules, sealants, and adhesives. Optical passive components and optical circuit components include lenses, waveguides, light emitting element sealants, adhesives, and the like. Optoelectronic integrated circuit (OEI
C) Substrate material, fiber material, element sealant,
For example, an adhesive.

In the optical fiber field, it is an optical fiber for industrial displays such as lighting and light guides for decorative displays, sensors for industrial use, displays and signs, and also for communication infrastructure and connection of digital devices at home.

The peripheral material for semiconductor integrated circuits is a resist material for microlithography for LSI and VLSI materials.

In the field of automobiles and transportation equipment, lamp reflectors for automobiles, bearing retainers, gears, corrosion-resistant coatings, switch parts, headlamps, engine internal parts, electrical parts, various internal and external parts, drive engines, brake oil tanks, Anti-corrosion steel plate for automobiles, interior panel,
Interior materials, protection and binding wireness, fuel hoses, automobile lamps, glass substitutes. In addition, it is a double glazing for railway vehicles. Also, a toughening agent for aircraft structural materials,
Engine peripherals, protection / bundling wireness, corrosion-resistant coating.

In the field of construction, materials for interior and processing, electric covers, sheets, glass interlayer films, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house coating film.

As the next-generation optical / electronic functional organic material,
Materials include organic EL element peripheral materials, organic photorefractive elements, light amplification elements that are light-to-light conversion devices, optical operation elements, substrate materials around organic solar cells, fiber materials, element sealants, and adhesives.

The composition for optical materials of the present invention is mixed in advance and the carbon-carbon double bond reactive with the SiH group in the composition is reacted with a part or all of the SiH group to form a metal atom or / Also, an optical material can be obtained by curing a hydrolyzable group bonded to a semimetal atom by a hydrolytic condensation reaction.

Various methods can be used for mixing the components (A), (B) and (C).
A method of mixing the component (A) with the component (C) and the component (B) is preferable. When the method of mixing the component (C) with the mixture of the components (A) and (B) is difficult to control the reaction. When the method of mixing the component (A) with the mixture of the component (B) with the component (B) is used, the component (B) is reactive with moisture in the environment in the presence of the component (C). It may deteriorate during storage.

When the composition is reacted and cured, the necessary amounts of the components (A), (B) and (C) may be mixed at once, and the reaction may be carried out by mixing a part of them. After the reaction, a part of the functional groups in the composition is reacted (B stage) by using the method of mixing the remaining amount and further reacting, or controlling the reaction conditions after mixing and utilizing the difference in reactivity of the substituents. It is also possible to adopt a method in which the resin is cured, and then it is further cured by performing a treatment such as molding. According to these methods, the viscosity adjustment during molding becomes easy.

As a method of curing, the reaction can be performed by simply mixing, or the reaction can be performed by heating. The method of heating and reacting is preferable from the viewpoint that the reaction is fast and a material having high heat resistance is generally easily obtained.

The reaction temperature can be set variously, but a lower limit of 25 ° C. and an upper limit of 300 ° C. is preferable, and a lower limit of 50.
C, the upper limit of 250 ° C is more preferable, and the lower limit of 100 ° C and the upper limit of 200 ° C are more preferable. If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, the molding process 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 if necessary. It is preferable to carry out the reaction while raising the temperature in multiple stages or continuously rather than to carry out at a constant temperature, because a uniform cured product free from distortion can be easily obtained.

Although the reaction time can be set variously, it is preferable to carry out the reaction at a relatively low temperature for a long time, as compared with the reaction at a high temperature for a short time, since a cured product having no distortion can be easily obtained.

The pressure during the reaction can be set variously as necessary,
The reaction can be carried out under normal pressure, high pressure, or reduced pressure. It is preferable to carry out the reaction under reduced pressure from the viewpoint of easily removing the volatile components generated by hydrolysis condensation.

The shape of the optical material obtained by curing may be various according to the use and is not particularly limited. For example, a shape such as a film shape, a sheet shape, a tube shape, a rod shape, a coating film shape, and a bulk shape. can do.

Various molding methods can be used including the conventional molding method of thermosetting resin. For example, a molding method such as a casting method, a pressing method, a casting method, a transfer molding method, a coating method, or a RIM method can be applied. As the mold, polishing glass, hard stainless steel polishing plate, polycarbonate plate, polyethylene terephthalate plate, polymethylmethacrylate plate or the like can be applied. Further, in order to improve the releasability from the molding die, 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 applied.

If necessary, various treatments may be applied during molding. For example, a treatment of defoaming the composition or a partially reacted composition by centrifugation, reduced pressure, or the like, or a treatment of temporarily releasing the pressure at the time of pressing can be applied to suppress voids generated during molding.

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 in a conventionally known light emitting diode can be used. As such a light emitting element, for example, M
Examples include those prepared by laminating a semiconductor material on a substrate provided with a buffer layer such as GaN or AlN, if necessary, by various methods such as an OCVD method, an HDVPE method, and a liquid phase growth method. As the substrate in this case, various materials can be used, for example, sapphire, spinel,
Examples thereof include SiC, Si, ZnO, and GaN single crystal.
Of these, sapphire is preferably used from the viewpoint that GaN having good crystallinity can be easily formed and has high industrial utility value.

GaA is used as the semiconductor material to be laminated.
s, GaP, GaAlAs, GaAsP, AlGaIn
P, GaN, InN, AlN, InGaN, InGaA
1N, SiC, etc. are mentioned. Of these, from the viewpoint of obtaining high brightness, a nitride-based compound semiconductor (I
nx GayAlz N) is preferred. Such a material may contain an activator or the like.

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

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

Electrodes 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. The electrical connection member preferably has good ohmic mechanical connectivity with the electrodes of the light emitting element, and examples thereof include bonding wires using gold, silver, copper, platinum, aluminum or alloys thereof. . A conductive adhesive or the like in which a conductive filler such as silver or carbon is filled with a resin can also be used. Among these, it is preferable to use an aluminum wire or a gold wire from the viewpoint of good workability.

A light emitting device is obtained as described above,
In the light emitting diode of the present invention, any luminous intensity of the light emitting element can be used as long as the luminous intensity in the vertical direction is 1 cd or more. However, depending on the case where the luminous intensity in the vertical direction is 2 cd or more, the present invention can be used. The effect of the present invention is remarkable, and the effect of the present invention is more remarkable when a light emitting device of 3 cd or more is used.

The light emission output of the light emitting element is not particularly limited and any one can be used, but the effect of the present invention is remarkable when a light emitting element of 1 mW or more at 20 mA is used, and a light emission of 4 mW or more at 20 mA. The effect of the present invention is more remarkable when an element is used, and the effect of the present invention is more remarkable when a light emitting element of 5 mW or more at 20 mA is used.

Various emission wavelengths of the light emitting element can be used from the ultraviolet region to the infrared region, and the effect of the present invention is particularly remarkable when the main emission peak wavelength is 550 nm or less.

One type of light emitting element may be used for single color light emission, or a plurality of light emitting elements may be used for single color or multicolor light emission.

The lead terminal used in the light emitting diode of the present invention is preferably one having good adhesion to an electric connection member such as a bonding wire and good electric conductivity.
The electric 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, iron-containing copper, tin-containing copper, and those obtained by plating these with silver, nickel, or the like. The glossiness of these lead terminals may be adjusted appropriately in order to obtain good light spread.

The light emitting diode of the present invention can be manufactured by coating the light emitting element with the above-mentioned curable composition. In this case, the coating is not limited to the one which directly seals the light emitting element. Including the case of indirectly coating. Specifically, the light emitting device may be sealed with the curable composition of the present invention directly by various methods conventionally used, or conventionally used epoxy resin, silicone resin, acrylic resin, urea resin, imide resin, etc. After encapsulating the light emitting element with the encapsulating resin or glass, the top or the periphery thereof may be coated with the curable composition of the present invention. Further, the light emitting element may be sealed with the curable composition of the present invention and then molded with a conventionally used epoxy resin, silicone resin, acrylic resin, urea resin, imide resin or the like. It is possible to provide various effects such as a lens effect by the difference in refractive index and specific gravity by the above method.

Various methods can be applied as a sealing method. For example, a liquid curable composition may be injected into a cup, a cavity, a package recess or the like having a light emitting element arranged at the bottom by a dispenser or other method and cured by heating, or a solid or high viscosity liquid. The curable composition may be heated to make it flow, and similarly, it may be injected into the concave portion of the package and further heated to be cured. The package in this case can be manufactured using various materials, and examples thereof include polycarbonate resin, polyphenylene sulfide resin, epoxy resin, acrylic resin, silicone resin, ABS resin, polybutylene terephthalate resin, polyphthalamide resin, and the like. be able to. Alternatively, a method of injecting a curable composition into a mold form in advance, immersing a lead frame or the like having a light emitting element fixed therein and then curing the composition may be applied. The sealing layer of the curable composition may be molded and cured by injection with a dispenser, transfer molding, injection molding, or the like. Further, a curable composition which is simply in a liquid or fluid state may be dropped or coated on the light emitting element to be cured. Alternatively, the curable resin can be molded and cured by stencil printing, screen printing, or application through a mask on the light emitting element. Other,
Alternatively, a curable composition that has been partially cured or cured into a plate shape or a lens shape in advance may be fixed on the light emitting element. Further, it can be used as a die bonding agent for fixing the light emitting element to a lead terminal or a package, or can be used as a passivation film on the light emitting element. It can also be used as a package substrate.

The shape of the covered portion is not particularly limited and can be various shapes. Examples thereof include a lens shape, a plate shape, a thin film shape, and the shape described in JP-A-6-244458. 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, such as epoxy resin, BT resin,
Examples include ceramics.

In addition, various conventionally known methods can be applied to the light emitting diode of the present invention. For example, a method in which a layer for reflecting or condensing light is provided on the back surface of the light emitting element, a method in which a complementary color coloring portion is formed on the bottom in response to yellowing of the sealing resin,
A method in which a thin film that absorbs light of 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 encapsulating material and then the surroundings are molded with a hard material, and light from the light emitting element is A method in which a light emitting element is sealed with a material containing a phosphor that absorbs and emits fluorescence of a longer wavelength, and then the periphery is molded, a method in which a material containing the phosphor is molded in advance and then molded with the light emitting element. -244458, a molding material having a special shape to improve light emission efficiency, a method in which a package is formed into a two-step recess for reducing uneven brightness, a method in which a light emitting diode is inserted and fixed in a through hole, and light emission is performed. By a method of forming a thin film that absorbs light of a wavelength shorter than the main emission wavelength on the element surface, flip-chip connection of the light emitting element 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 in various conventionally known applications. Specifically, examples thereof include a backlight, an illumination, a sensor light source, a vehicle instrument light source, a signal light, an indicator light, a display device, a light source of a planar light emitter, a display, a decoration, and various lights.

[0094]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. (Synthesis Example 1) Synthesis of 1,3,5,7-tetramethylcyclotetrasiloxane modified product (1) with 2,2-bis (4-allyloxycyclohexyl) propane 1L equipped with a cooling tube, a stirrer, and a thermometer Put 288 g of 1,3,5,7-tetramethylcyclotetrasiloxane manufactured by Shin-Etsu Chemical Co., Ltd. into a four-necked flask and add 260 g of toluene to dissolve it, and then heat up to 50 ° C. to obtain platinum-divinyltetramethyldisiloxane. 0.06 g of a xylene solution of the complex (containing 3% by weight of platinum) was added. Separately, a solution prepared by dissolving 77 g of 2,2-bis (4-allyloxycyclohexyl) propane in 87 g of toluene was prepared, and this was added dropwise to the solution in the four-neck flask over 45 minutes, followed by stirring for 9 hours. It was made to react. After the reaction, 0.12 g of 1-ethynyl-1-cyclohexanol was added and dissolved, and then allowed to cool to room temperature. Then, the reaction solution was transferred to a 1 L eggplant flask, and the volatile matter was distilled off at 50 ° C. under reduced pressure to obtain 161 g of modified product (1). The hydrosilyl group content of the modified product (1) was determined by proton NMR analysis.
It was 99 mmol / g. No allyl residue was detected. The content of the hydrosilyl group and the residual amount of the allyl group were 1,2-dibromoethane as an internal standard, and the chemical shift (3.65 ppm) of the proton of this standard substance and the chemical shift of the proton of the hydrosilyl group (4.7 pp) were used.
m) Area or chemical shift of allyl protons (4.
5 ppm) area was determined by comparison. Further, the molecular weight of the modified product (1) was calculated from the hydrosilyl group content, and it was found to be 1363 (the number of ether groups: 4). (Synthesis Example 2) 1, using triallyl isocyanurate
Synthesis of 3,5,7-tetramethylcyclotetrasiloxane modified product (2) In a 1 L four-necked flask equipped with a cooling tube, a stirrer, and a thermometer, 1,3,5,7-tetramethylcyclo manufactured by Shin-Etsu Chemical Co., Ltd. 288 g of tetrasiloxane was added, 360 g of toluene was added and dissolved, and then the temperature was maintained at 110 ° C. Separately, dissolve 40 g of triallyl isocyanurate in 40 g of toluene,
A solution was prepared by adding 0.3 g of a xylene solution of a platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum), and this was added dropwise to the solution in the four-neck flask over 10 minutes, and then stirred. The reaction was carried out for 6 hours. After the reaction, 1
After 0.6 g of -ethynyl-1-cyclohexanol was added and dissolved, the mixture was allowed to cool to room temperature. After that, add 1 L of reaction liquid.
The mixture was transferred to an eggplant flask and the volatile matter was distilled off at 60 ° C. under reduced pressure to obtain 130 g of modified product (2). The hydrosilyl group content of the modified product (2) was 8.04 mmol / g as a result of the proton NMR analysis. Further, the residual amount of allyl group was 0.10 mmol / g. (Synthesis Example 3) Synthesis of 1,3,5,7-tetramethylcyclotetrasiloxane modified product (3) with 1,2,4-trivinylcyclohexane (1L) four ports equipped with a cooling pipe, a stirrer and a thermometer Put 288 g of 1,3,5,7-tetramethylcyclotetrasiloxane manufactured by Shin-Etsu Chemical Co., Ltd. in a flask, add 260 g of toluene to dissolve it, and then raise the temperature to 50 ° C. to obtain a solution of platinum-divinyltetramethyldisiloxane complex in xylene. 0.06 g (containing 3% by weight of platinum) was added. Separately, a solution of 26 g of 1,2,4-trivinylcyclohexane dissolved in 26 g of toluene was prepared.
After dropping over 5 minutes, the mixture was reacted for 4 hours with stirring. After the reaction, 0.12 g of 1-ethynyl-1-cyclohexanol was added and dissolved, and then allowed to cool to room temperature. Then, the reaction solution was transferred to a 1 L eggplant flask, and the pressure was reduced to 5
The volatile matter was distilled off at 0 ° C. to obtain 127 g of modified product (3). The hydrosilyl group content of the modified product (3) was 9.61 mmol / g as a result of the proton NMR analysis. A vinyl residue (chemical shift of proton NMR: 5 ppm) was not detected. (Synthesis Example 4) 1,3,5,7-using divinylbenzene
Synthesis of tetramethylcyclotetrasiloxane modified product (4) Put 1,3,5,7-tetramethylcyclotetrasiloxane 288 g manufactured by Shin-Etsu Chemical Co., Ltd. in a 1 L four-necked flask equipped with a cooling tube, a stirrer, and a thermometer, After adding and dissolving 360 g of toluene, the temperature was raised to 50 ° C., and 0.025 g of a xylene solution of a platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum) was added. Separately, prepare a solution of 31 g of divinylbenzene dissolved in 90 g of toluene,
This was added dropwise to the solution in the four-neck flask over 30 minutes, and then reacted for 2 hours while stirring. After the reaction, the mixture was allowed to cool to room temperature and 55 mg of benzothiazole was added to toluene.
A solution dissolved in 2 g was added and stirred. Then, the reaction solution was transferred to a 1 L eggplant flask, and the volatile matter was distilled off at 60 ° C. under reduced pressure to obtain 140 g of modified product (4). The hydrosilyl group content of modified product (4) is proton N
As a result of MR analysis, it was 9.59 mmol / g. No vinyl residue was detected. (Example 1) 0.897 g of triallyl isocyanurate
Was mixed with 0.0044 g of a xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum), and the mixture was stirred and defoamed to obtain a liquid A. In addition, Synthesis Example 1
1.803 g of modified product (1) prepared in 1 and 1-ethynyl-
0.0024 g of 1-cyclohexanol was mixed, stirred, and defoamed to obtain B liquid. Then, the liquid A and the liquid B were mixed, stirred, and defoamed. The amount of ether groups in the mixed solution was calculated as 5.9 meq with respect to 1 g of triallyl isocyanurate from the molecular weight of the modified product (1), the number of ether groups and the blending amount. 3.5 mg of this mixed solution is weighed into an aluminum cell, and a differential thermogravimetric simultaneous measurement device DT manufactured by Shimadzu Corporation is used.
In G-50, the weight change was measured in an air atmosphere at a temperature rising rate of 10 ° C./min. As a result, the temperature at which weight reduction (decomposition) started after curing was 260 ° C. The total light transmittance of the cured product was 93%. (Example 2) 1,61,2,4-trivinylcyclohexane (0.661 g) was weighed out to obtain a liquid A. In addition, Synthesis Example 1
The modified product (1) (2.039 g) prepared in (2) was weighed out to obtain a liquid B. Then, the liquid A and the liquid B were mixed, stirred, and defoamed.
The amount of ether groups in the mixed solution was calculated to be 9.05 meq with respect to 1 g of 1,2,4-trivinylcyclohexane from the molecular weight of modified product (1), the number of ether groups and the blending amount.
Weigh 3.5 mg of this mixed solution into an aluminum cell,
With a differential thermogravimetric simultaneous measurement apparatus DTG-50 manufactured by Shimadzu Corporation, the weight change was measured in an air atmosphere at a temperature rising rate of 10 ° C./min. As a result, the temperature at which weight reduction (decomposition) started after curing was 220 ° C. Met. The total light transmittance of the cured product was 93%. (Example 3) 0.757 g of divinylbenzene was weighed out to obtain a liquid A. In addition, 1.943 g of the modified product (1) prepared in Synthesis Example 1 was weighed out to prepare a solution B. afterwards,
Solution A and solution B were mixed, stirred and defoamed. The amount of ether groups in the mixed solution was 7.53 meq based on 1 g of divinylbenzene, based on the molecular weight of modified product (1), the number of ether groups and the blending amount.
Was calculated. 3.5 mg of this mixed solution was weighed into an aluminum cell, and in a differential thermogravimetric simultaneous measurement apparatus DTG-50 manufactured by Shimadzu Corporation, in an air atmosphere, a temperature rising rate of 10 ° C.
As a result of measuring the change in weight per minute, the temperature at which weight reduction (decomposition) started after the completion of curing was 240 ° C. The total light transmittance of the cured product was 93%. (Example 4) 1.086 g of triallyl isocyanurate
Was mixed with 0.0054 g of a xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum), and the mixture was stirred and defoamed to obtain a liquid A. In addition, Synthesis Example 2
1.614 g of modified product (2) prepared in 1 and 1-ethynyl-
0.0029 g of 1-cyclohexanol was mixed, stirred, and defoamed to obtain B liquid. Then, the liquid A and the liquid B were mixed, stirred, and defoamed. Since the modified product (2) containing no ether group is used here, the amount of ether group in the mixed solution is 0 me with respect to 1 g of triallyl isocyanurate.
q. 3.5 mg of this mixed solution is weighed into an aluminum cell, and a differential thermogravimetric simultaneous measurement device DT manufactured by Shimadzu Corporation is used.
In G-50, the weight change was measured in an air atmosphere at a temperature rising rate of 10 ° C./min. As a result, the temperature at which weight reduction (decomposition) started after the completion of curing was 310 ° C. The total light transmittance of the cured product was 92%. (Example 5) 1,23,4-trivinylcyclohexane (0.923 g) was weighed out to obtain a liquid A. In addition, Synthesis Example 3
1.777 g of the modified product (3) prepared in (3) was weighed out to prepare a solution B. Then, the liquid A and the liquid B were mixed, stirred, and defoamed.
Since the modified product (3) containing no ether group is used here, the amount of ether group in the mixed solution is 0 meq with respect to 1 g of 1,2,4-trivinylcyclohexane. 3.5 mg of this mixed solution was weighed into an aluminum cell, and the weight change was measured at a temperature rising rate of 10 ° C./minute in an air atmosphere using a differential thermogravimetric simultaneous measurement apparatus DTG-50 manufactured by Shimadzu Corporation. The temperature at which the weight reduction (decomposition) started was 330 ° C. The total light transmittance of the cured product was 93%. (Example 6) 1.038 g of divinylbenzene was weighed out to obtain a liquid A. In addition, 1.662 g of modified product (4) prepared in Synthesis Example 4 was weighed out and used as solution B. afterwards,
Solution A and solution B were mixed, stirred and defoamed. Since the modified product (4) containing no ether group is used here, the amount of ether group in the mixed solution is 0 m with respect to 1 g of divinylbenzene.
eq. 3.5 mg of this mixed solution was weighed into an aluminum cell and manufactured by Shimadzu's differential thermogravimetric simultaneous measurement apparatus D.
In TG-50, in an air atmosphere, the temperature rising rate is 10 ° C /
As a result of measuring the weight change in minutes, the temperature at which the weight reduction (decomposition) started after the completion of curing was 310 ° C. The total light transmittance of the cured product was 90%. (Comparative Example 1) 0.461 g of 1,2,4-trivinylcyclohexane was weighed out to obtain a liquid A. In addition, Synthesis Example 1
2.239 g of the modified product (1) prepared in (3) was weighed out to prepare a solution B. Then, the liquid A and the liquid B were mixed, stirred, and defoamed.
The amount of ether groups in the mixed solution was calculated to be 14.3 meq with respect to 1 g of 1,2,4-trivinylcyclohexane from the molecular weight of modified product (1), the number of ether groups and the blending amount.
Weigh 3.5 mg of this mixed solution into an aluminum cell,
Weight difference was measured at a temperature rising rate of 10 ° C./min in an air atmosphere with a differential thermogravimetric simultaneous measurement apparatus DTG-50 manufactured by Shimadzu Corporation. As a result, the temperature at which weight reduction (decomposition) started after curing was 170 ° C. Met. The total light transmittance of the cured product was 93%. (Example 7) From the results of Example 1, Example 2, Example 3, Example 4, Example 5, Example 6, and Comparative Example 1,
The relationship between the amount of the component (B) having an aliphatic ether structure and the decomposition initiation temperature of the cured product with respect to the component (A) is illustrated in FIG. From this result, in order to have the heat resistance of 180 ° C. or higher necessary for manufacturing the product, the amount of the component (B) was 13.2 meq ether group / g-
It has been found that the component (A) may be used below. (Example 8) A mixed solution of solution A and solution B prepared with the same composition as in example 1 was heated at 60 ° C for 6 hours, and then at 70 ° C for 1 hour.
Further, it was cured by heating at 80 ° C. for 1 hour and finally at 120 ° C. for 1 hour. This cured product is cut into an appropriate shape and fixed to a light transmitting window portion provided on a can type metal cap. On the other hand, 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 MOCVD (Metal Organic Chemical Vapor Deposition) method is sandwiched by n-type and p-type AlGaN cladding layers. To prepare. Then, after mounting this light emitting element on a can type metal stem, the p electrode and the n electrode are wire-bonded to the respective leads by Au wires. This is hermetically sealed with the can type metal cap described above. In this way, a can type light emitting diode can be manufactured. (Example 9) MOCVD on a cleaned sapphire substrate
An n-type GaN layer that is an undoped nitride semiconductor, a GaN layer that forms an n-type contact layer by forming an Si-doped n-type electrode, and an n-type GaN that is an undoped nitride semiconductor by the (metal organic chemical vapor deposition) method. Layer, then a GaN layer that will become a barrier layer that constitutes the light emitting layer, and InGaN that constitutes a well layer
Layer, a GaN layer (quantum well structure) serving as a barrier layer, and an AlGa layer as a p-type cladding layer doped with Mg on the light emitting layer.
Ga which is an N layer and a p-type contact layer doped with Mg
N layers are sequentially stacked. The surface of each pn contact layer is exposed on the same side of the nitride semiconductor on the sapphire substrate by etching. Al is vapor-deposited on each contact layer by a sputtering method to form positive and negative electrodes, respectively. After the scribe line is drawn on the completed semiconductor wafer, it is divided by an external force to form a light emitting element which is a light emitting element.

The above light emitting device is die-bonded onto the bottom surface of the cup of the mount lead made of iron-containing copper whose surface is plated with silver 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 and the mount lead and the inner lead are wire-bonded with an Au wire to establish electrical conduction.

The curable composition used in Example 1 is poured into a casting case which is a shell type mold. A part of the mount lead and the inner lead in which the above light emitting element is arranged in the cup is inserted into the 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 manufactured. (Example 10) After a light emitting device is manufactured, a pair of copper foil patterns is formed on a glass epoxy resin by etching to form a substrate having lead electrodes. The light emitting element is die-bonded onto 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 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 by the epoxy resin. In this state, the curable composition is dispensed on the glass epoxy resin substrate on which the light emitting element is disposed while being disposed in the vacuum device, and the curable composition used in Example 1 is filled in the cavity utilizing the through holes. To do. In this state, it is cured at 100 ° C. for 1 hour and further at 150 ° C. for 1 hour. A chip type light emitting diode can be manufactured by dividing each light emitting diode chip. (Example 11) After manufacturing a light emitting device, a chip type light emitting diode package is formed by insert molding using PPS resin. The package has an opening in which a light emitting element is arranged, and a silver-plated copper plate is arranged as an external electrode. The light emitting element is fixed inside the package by die-bonding with 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 used in Example 1 is filled in the package opening as a mold member. In this state, it is cured at 100 ° C. for 1 hour and further at 150 ° C. for 1 hour. In this way, a chip type light emitting diode can be manufactured.

[0097]

INDUSTRIAL APPLICABILITY The material produced from the composition of the present invention has high optical transparency and heat resistance, and is industrially very useful.

[Brief description of drawings]

FIG. 1 is a diagram showing the relationship between the amount of component (B) having an aliphatic ether structure relative to component (A) and the decomposition start temperature of a cured product.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J002 BG07W CC03W CF27W CG02W                       CH05W CL07W CM04W CP04X                       DD077 EW067 EX016 EX036                       EZ007 FD010 FD157 GP01                 5F041 AA31 DA46 DB01 DB06 DB09

Claims (5)

[Claims] 1. An organic compound containing (A) at least two carbon-carbon double bonds reactive with a SiH group in one molecule, and (B) containing at least two SiH groups in one molecule. A curable composition for optical materials, which comprises a silicon compound and (C) a hydrosilylation catalyst as essential components,
When the component (B) has an aliphatic ether structure, the amount of the compound is 13.2 meq ether group / g- (A) component or less relative to the component (A), which is a curing agent for optical materials. Sex composition. 2. The curable composition for an optical material according to claim 1, wherein the use of the optical material is a sealing material for a light emitting diode. 3. The curable composition for optical materials according to claim 1 is mixed in advance, and the carbon-carbon double bond reactive with the SiH group in the composition and a part or all of the SiH group are mixed. An optical material that is cured by reaction. 4. A light emitting diode using the optical material according to claim 3. 5. The curable composition for optical materials according to claim 1 is mixed in advance, and a carbon-carbon double bond reactive with the SiH group in the composition and a part or all of the SiH group are formed. The method for producing an optical material according to claim 3, wherein the optical material is cured by being reacted.