JP2003034743A - Optical material composition, optical material, method of manufacturing the same, liquid crystal display device and light-emitting diode using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical material composition, an optical material, a method of manufacturing the same and a liquid crystal display device and a light-emitting diode using the same which have high optical transparency, little photodeterioration and toughness. SOLUTION: This optical material composition contains as an essential component (A) triallyl isocyanurate, (B) a silicon compound containing at least two SiH groups in a molecule, (C) a hydrosilylation catalyst and (D) a thermoplastic resin wherein the (D) component is one or more polymers selected from among a butyl acrylate-based polymer, a butyl methacrylate-based polymer and a methyl methacrylate/butyl acrylate-based copolymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an optical material, and more specifically to a composition for an optical material having high optical transparency and toughness, an optical material, a method for producing the same, and the same. The present invention relates to a liquid crystal display device and a light emitting diode used.

[0002]

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

Optical materials such as those for liquid crystal display devices are often used in the form of thin films or thin tubes or rods, but in accordance with recent market demands, thinner films or thinner tubes or rods are used. The use of is becoming necessary. However, the conventionally used glass has a brittle property in terms of strength, so that the range of use is becoming limited.

Polymer materials are known as tough materials. For example, in the case of thermoplastic resin, generally, when an aromatic skeleton is introduced in order to develop high heat resistance, the birefringence becomes high and the photoelastic coefficient becomes high. 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 optical material applications. In addition, it is generally polar and is disadvantageous in expressing optical performance. Therefore, for example, in the use of a sealant for light emitting diodes, a transparent epoxy resin using an acid anhydride-based curing agent has been widely used as a special thermosetting resin. However, even in such a transparent epoxy resin, the moisture absorption durability of the resin is high, so that the moisture resistance and durability are low, or
In particular, it has a drawback that it has low light resistance due to its low light transmittance for light of low wavelength, or that it is colored due to photodegradation.

Further, thermosetting resins are generally fragile, and there is a problem that cracks and peeling occur when a thermal shock is applied to a cured product or a product prepared from the cured product.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a composition for optical materials having high optical transparency, little photodegradation, and toughness, an optical material, and a method for producing the same.
Another object of the present invention is to provide a liquid crystal display device and a light emitting diode using the same.

[0008]

In order to solve the above problems, the present inventors have earnestly studied, and as a result, triallyl isocyanurate, a silicon compound containing at least two SiH groups in one molecule, and a hydrosilyl group. The inventors have found that the above problems can be solved by using a chemical catalyst and a specific thermoplastic resin as essential components in a composition for optical materials, and have completed the present invention.

That is, according to the present invention, (A) triallyl isocyanurate and (B) at least two S in one molecule.
A composition for an optical material comprising a composition containing an iH group-containing silicon compound, (C) a hydrosilylation catalyst, and (D) a thermoplastic resin as essential components, wherein the (D) component is a butyl acrylate-based compound. A composition for an optical material (claim 1), which is one or a plurality of polymers selected from a polymer, a butyl methacrylate-based polymer, and a methyl methacrylate / butyl acrylate-based copolymer. Component is a reaction product of 1,3,5,7-tetramethyltetracyclosiloxane and triallyl isocyanurate, and the optical material composition (claim 2) according to claim 1, wherein the optical material is liquid crystal. A film for optical use, which is the composition for optical materials according to claim 1 or 2 (claim 3), wherein the optical material is a plastic cell for liquid crystals. The composition for optical material (claim 4)
6. The optical material composition according to claim 1 or 2, wherein the optical material is a sealing material for a light emitting diode (claim 5), and the optical material according to claim 1 or 2. The material composition is mixed in advance and Si in the composition is mixed.
An optical material (claim 6) obtained by curing by reacting a carbon-carbon double bond reactive with an H group and a part or all of a SiH group, and the method according to any one of claims 1 to 5. The 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 is reacted with a part or all of the SiH group. It is a manufacturing method (Claim 7) of the optical material of Claim 6, and is a liquid crystal display device (Claim 8) using the optical material of Claim 6, and uses the optical material of Claim 6. The light emitting diode (claim 9).

[0010]

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

The component (A) of the present invention is triallyl isocyanurate.

The triallyl isocyanurate as the component (A) can be produced by various methods. For example, JP-A-2000-109314 and JP-A-2000-119.
No. 016 report, JP-A-11-255753 report, JP-A-9
-208564, JP-A-8-259711, JP-A-4-321655, JP-A-4-49284, JP-A-62-48671, JP-A-62-455.
78, JP-A-58-85874, JP-A-57-
No. 200371, No. 54-130591, No. 53-92791, No. 50-95289, No. 48-26022, No. 47-225.
88, JP-A-47-14395, JP-A-43-
29395, JP-A-45-15981, JP-A-43-29146, USP3376301, U.S. Pat.
SP3322271 report, SUP1121260 report,
SUP1121259, SUP765265,
DEP2126296, and Bull. Che
m. Soc. Jpn. (1966), 39 (9), 19
The method described on page 22 and the like can be mentioned.

The triallyl isocyanurate as the component (A) may be purified if necessary. Purification methods include vacuum distillation, washing with acidic water, alkaline water and / or neutral water, adsorption treatment with adsorbents such as silica gel, activated carbon and aluminum silicate, treatment with various desiccants such as molecular sieves, and toluene. Examples of the dehydration treatment include azeotropic distillation.

If desired, the triallyl isocyanurate as the component (A) may contain additives. Examples of the additives include radical polymerization inhibitors such as hydroquinone and 2,6-t-butyl-4-methylphenol (BHT).

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, 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, from the viewpoint of availability, a chain-like 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, the following general formula (I)

[0018]

[Chemical 1] (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. The substituent R ² in the compound represented by the general formula (I) is preferably composed of C, H and O, more preferably a hydrocarbon group.

From the viewpoint of having a better compatibility with the component (A), it is selected from chain and / or cyclic polyorganosiloxanes and organic compounds having a carbon-carbon double bond. One or more compounds (hereinafter (E)
(Referred to as components) are preferred. In this case, in order to further improve the compatibility with the component (A) of the reaction product, it is possible to use a product obtained by removing unreacted siloxanes and the like from the reaction product by devolatilization.

The component (E) 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 is the same as the component (A). Can also be used. The organic compound as the component (E) may be the same as or different from the organic compound as the component (A). Further, it is possible to use a single kind or a mixture of two or more kinds. 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-like and / or cyclic polyorganosiloxane to be reacted with the organic compound of the component (E) is 1,3 from the viewpoint of industrial availability and good reactivity when reacted. , 5,7-Tetramethyltetracyclosiloxane is preferred.

As the component (B), the same as the component (A),
It is preferable that the content of the compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group is small, especially from the viewpoint of suppressing yellowing, and that does not include a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group. Is 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 the anthracene ring, and the phenolic hydroxyl group derivative is a hydrogen atom of the above-mentioned phenolic hydroxyl group. A group substituted with 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 properties such as low birefringence and low photoelastic coefficient and good weather resistance, the weight ratio of the components in the component (A) of the aromatic ring is It is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less. Most preferred are those containing no aromatic hydrocarbon rings.

More preferable component (B) from the viewpoint of good optical properties is a reaction product of 1,3,5,7-tetramethyltetracyclosiloxane and vinylcyclohexene, 1,3,5,7-tetra. Reaction product of methyltetracyclosiloxane and dicyclopentadiene, 1,3
Reaction product of 5,7-tetramethyltetracyclosiloxane and triallyl isocyanurate, 1,3,5,7-tetramethyltetracyclosiloxane and 2,2-bis (4-
Specific examples of the component (B) include a reaction product of a diallyl ether of hydroxycyclohexyl) propane and a reaction product of 1,3,5,7-tetramethyltetracyclosiloxane and 1,2,4-trivinylcyclohexane. Reaction product of 1,3,5,7-tetramethyltetracyclosiloxane and triallyl isocyanurate, 1,3,5
5,7-Tetramethyltetracyclosiloxane and 2,2
-A reaction product of diallyl ether of bis (4-hydroxycyclohexyl) propane, a reaction product of 1,3,5,7-tetramethyltetracyclosiloxane and 1,2,4-trivinylcyclohexane, and the like.

In total, the reaction product of 1,3,5,7-tetramethyltetracyclosiloxane and triallyl isocyanurate is most preferable.

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

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

The hydrosilylation catalyst is not particularly limited as long as it has catalytic activity for the hydrosilylation reaction. For example, a simple substance of platinum, a carrier such as alumina, silica, carbon black or the like on which solid platinum is supported, chloroplatinic acid chloride. , Complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc., platinum-olefin complexes (eg Pt (CH ₂ ═C
H ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ = CH ₂ ) ₂ Cl ₂ ),
Platinum-vinyl siloxane complex (for example, Pt (ViMe
₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSi
O) ₄ ] _m ), a platinum-phosphine complex (for example, Pt (P
_{Ph 3) 4, Pt (PBu} 3) 4), platinum - phosphite complex _{(e.g., Pt [P (OPh) 3} ] 4, Pt [P (OB
u) ₃ ] ₄ ) (wherein Me is a methyl group, Bu is a butyl group,
Vi represents a vinyl group, Ph represents a phenyl group, and n and m are
Indicates an integer. ), Dicarbonyldichloroplatinum, Karstedt catalyst, and Ashby US Pat. Nos. 3,159,601 and 3.
Platinum-hydrocarbon complexes described in 159662, as well as platinum alcoholate catalysts described in Lamoreaux, U.S. Pat. No. 3,209,972. In addition, Modic (Mo
The platinum chloride-olefin composites described in U.S. Pat. No. 3,516,946 to Dic) are 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, it is 10 ^-1 to 1 ^{-1 with} respect to 1 mol of SiH groups.
The range of 0 ^-8 mol is preferable, and more preferably 10 ^-2 to
It is in the range of 10 ⁻⁶ mol.

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 elemental sulfur, and amine compounds such as triethylamine. The amount of the cocatalyst added is not particularly limited, but is preferably in the range of 10 ^-2 to 10 ² mol, and more preferably in the range of 10 ^-1 to 10 mol, per 1 mol of the catalyst.

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.
Organic sulfur compounds include organomercaptans,
Examples thereof include 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, and t-butyl perbenzoate.

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 amount of the storage stability improver added is preferably in the range of 10 ^-1 to 10 ³ mol, more preferably 1 to 50 mol, based on 1 mol of the hydrosilylation catalyst used.

Next, the thermoplastic resin as the component (D) will be described.

Component (D) is one or more polymers selected from butyl acrylate polymers, butyl methacrylate polymers and methyl methacrylate / butyl acrylate copolymers. When triallyl isocyanurate is used as the component (A), it has good compatibility with the component (A) when these components (D) are used, and is obtained by curing the composition for optical materials of the present invention. The light resistance of the optical material used is increased.

The butyl acrylate polymer as the component (D) is 50 to 100% by weight, preferably 80 to 100% by weight of n-butyl acrylate, and 0 to 50% by weight of a vinyl monomer copolymerizable therewith. %, Preferably 0 to 20% by weight.

In this case, examples of vinyl monomers include methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, methacrylic acid -tert-. Butyl, methacrylic acid-n-pentyl,
Methacrylic acid-n-hexyl, cyclohexyl methacrylate, methacrylate-n-heptyl, methacrylate-n-octyl, methacrylate-2-ethylhexyl, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate,
Phenyl methacrylate, toluyl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylic acid Stearyl,
Glycidyl methacrylate, 2-aminoethyl methacrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of methacrylic acid, trifluoromethylmethyl methacrylate, methacrylic acid -2-trifluoromethylethyl, methacrylic acid-2-perfluoroethylethyl, methacrylic acid-2-perfluoroethyl-2-perfluorobutylethyl, methacrylic acid-2-perfluoroethyl, perfluoromethylmethacrylate, methacryl Acid diperfluoromethylmethyl, methacrylic acid-2-perfluoromethyl-2-perfluoroethylmethyl, methacrylic acid-2-perfluorohexylethyl, methacrylic acid-2-perfluorodecylethyl, methacrylic acid-2-perful Methacrylic acid; b hexadecyl ethyl, allyl methacrylate, methacrylic acid esters such as methacrylic acid-2-Arirokishiechiru
Acrylic acids such as acrylic acid; methyl acrylate, ethyl acrylate, acrylate-n-propyl, isopropyl acrylate, acrylate-n-butyl, acrylate butyl, acrylate-t-butyl, acrylate-n-pentyl , Acrylate-n-hexyl, acrylate cyclohexyl, acrylate-n-heptyl, acrylate-n-octyl, acrylate-2-ethylhexyl, nonyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, acrylic Toluyl acid, Benzyl acrylate, Isobornyl acrylate, 2-Methoxyethyl acrylate, 3-Methoxybutyl acrylate, Acrylic acid-
2-hydroxyethyl, 2-hydroxypropyl acrylate, stearyl acrylate, glycidyl acrylate,
2-Aminoethyl acrylate, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2 acrylate -Perfluorobutylethyl, 2-perfluoroethyl acrylate, Perfluoromethyl acrylate, Diperfluoromethylmethyl acrylate, 2-Perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-Peracrylic acrylate Acrylic esters such as fluorohexylethyl, 2-perfluorodecylethyl acrylate, 2-perfluorohexadecylethyl acrylate, allyl acrylate and 2-allyloxyethyl acrylate; styrene, α-methylstyrene, p -Methyl styrene, p-methoxy styrene Aromatic alkenyl compounds of acrylonitrile, methacrylonitrile vinyl cyanide compounds such as acrylonitrile; butadiene, conjugated diene compounds such as isoprene; vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene,
Halogen-containing unsaturated compounds such as vinylidene fluoride; Silicon-containing unsaturated compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; Maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, fumaric acid Unsaturated dicarboxylic acid compounds such as monoalkyl esters and dialkyl esters; vinyl acetate compounds such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, Butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide,
Examples thereof include maleimide compounds such as cyclohexylmaleimide. These may be used alone or in combination of two or more thereof.

Among these, in terms of availability, methyl methacrylate, ethyl methacrylate, allyl methacrylate, -n-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, methyl acrylate, acryl Ethyl acid, Allyl acrylate, Acrylic acid
-n-Butyl, 2-ethylhexyl acrylate and lauryl acrylate are preferred.

Specific examples of such a butyl acrylate polymer include homopolymers of n-butyl acrylate,
A copolymer of 85 to 100% by weight of acrylic acid-n-butyl and 0 to 15% by weight of allyl acrylate, a copolymer of 85 to 100% by weight of acrylic acid-n-butyl and 0 to 15% by weight of allyl methacrylate, A copolymer of 50 to 100% by weight of acrylic acid-n-butyl and 0 to 50% by weight of methacrylic acid-n-butyl may be mentioned.

The butyl methacrylate polymer as the component (D) is 50 to 100% by weight, preferably 80 to 100% by weight of n-butyl methacrylate, and 0 to 50% by weight of a vinyl monomer copolymerizable therewith. %, Preferably 0 to 20% by weight.

In this case, the vinyl-based monomer and its preferred examples are the same as the vinyl-based monomer in the case of the butyl acrylate polymer and its preferred examples.

Specific examples of such a butyl methacrylate polymer include homopolymers of n-butyl methacrylate and 85 to 100% by weight of n-butyl methacrylate and 0 to 15% by weight of allyl acrylate. Polymer, methacrylic acid
85 to 100% by weight of n-butyl and 0 of allyl methacrylate
~ 15 wt% copolymer, n-butyl methacrylate 50
~ 100% by weight and 0-50% by weight of n-butyl acrylate
And the like.

Component (D), a methyl methacrylate / butyl acrylate copolymer, is methyl methacrylate 10
50-60% by weight, preferably 20-55% by weight, and a mixture of 40-90% by weight of n-butyl acrylate, preferably 45-80% by weight, 50-100% by weight, preferably 80-10%.
0% by weight and 0 to 50% of vinyl monomers copolymerizable therewith
50% by weight, preferably 0 to 20% by weight of a copolymer.

In this case, the vinyl-based monomer and its preferred examples are the same as the vinyl-based monomer in the case of the butyl acrylate polymer and the preferred examples thereof.

Specific examples of such a methyl methacrylate / butyl acrylate type copolymer include 10 to 60% by weight of methyl methacrylate and 40-n-butyl acrylate.
~ 90 wt% copolymer, methyl methacrylate 10-6
A mixture of 0% by weight and 40-90% by weight of n-butyl acrylate 90-100% by weight and 0-10 allyl methacrylate
Wt% copolymer, a mixture of 10-60 wt% methyl methacrylate and 40-90 wt% methyl n-butyl acrylate 9
Copolymers of 0 to 100% by weight and allyl acrylate 0 to 10% by weight can be mentioned.

As the various polymers as the component (D), linear, cyclic, branched, star-shaped polymers of various shapes can be used. The copolymer may be any type of copolymer such as random copolymer, block copolymer, graft copolymer.

The terminal structure of various polymers as the component (D) is not particularly limited as long as the requirements of the present invention are satisfied, and a suitable functional group may be introduced if necessary. Examples of the functional group include a hydroxyl group, a carboxyl group, a trimethoxysilyl group,
An alkoxysilyl group such as a methyldimethoxysilyl group,
Examples thereof include radically polymerizable unsaturated groups such as acryloyl group and methacryloyl group, allyl group, amino group, epoxy group, isocyanate group and halogen group.

The glass transition temperature of the thermoplastic resin as the component (D) is not particularly limited and various ones can be used.
The glass point transfer temperature is preferably 100 ° C. or lower, more preferably 50 ° C. or lower, and further preferably 0 ° C. or lower in that the obtained cured product is likely to be tough. The glass transition temperature can be obtained as a temperature at which tan δ has a maximum in viscoelasticity measurement.

The thermoplastic resin as the component (D) may have a carbon-carbon double bond and / or a SiH group reactive with the SiH group in the molecule. From the viewpoint that the resulting cured product is likely to be tougher, it has at least one carbon-carbon double bond or / and SiH group reactive in the molecule with SiH group in one molecule. It is preferable.

The thermoplastic resin as the component (D) may have other crosslinkable groups. As the crosslinkable group in this case, a radically polymerizable unsaturated group such as an epoxy group, an amino group, an acryloyl group and a methacryloyl group, a carboxyl group, an isocyanate group, a hydroxyl group, a trimethoxysilyl group, an alkoxy such as a methyldimethoxysilyl group. Examples thereof include a silyl group. From the viewpoint that the heat resistance of the obtained cured product is likely to be high, it is preferable to have one or more crosslinkable groups in one molecule on average.

The molecular weight of the thermoplastic resin as the component (D) is not particularly limited, but the number average molecular weight is 2000 in that the compatibility with the components (A) and (B) tends to be good. It is preferably below, and more preferably below 5000. Conversely, the number average molecular weight is preferably 10,000 or more, and more preferably 100,000 or more, in that the obtained cured product is likely to be tough. Although the molecular weight distribution is not particularly limited, the molecular weight distribution is preferably 3 or less, more preferably 2 or less, and 1.6 or less from the viewpoint that the viscosity of the mixture is low and the moldability is likely to be good. The following is more preferable.

As the thermoplastic resin as the component (D), a single resin may be used, or a plurality of resins may be used in combination.

The blending amount of the thermoplastic resin as the component (D) is not particularly limited, but is preferably 3 to 50% by weight, and more preferably 3 to 20% by weight based on the whole composition. When the amount is small, the obtained cured product tends to be brittle, and when the amount is large, heat resistance (elastic modulus at high temperature) tends to be low.

The thermoplastic resin as the component (D) preferably has a desired light transmittance of 80% or more. In this case, the intended light differs depending on the application, but for example, when the application is a display device such as a liquid crystal display device, the intended light is visible light, and when the application is a light emitting diode, the light emitted from the light emitting element. Is. The light transmittance of the thermoplastic resin is the light transmittance at a thickness of 1 mm, and can be determined by measuring with a conventionally known method such as a spectral hardness meter.

The refractive index of the thermoplastic resin as the component (D) is different from the refractive index of the cured product obtained by curing the curable composition comprising the components (A), (B) and (C). Is ±
It is preferably 0.05 or less. The refractive index is obtained by measuring with an Abbe refractometer.

The thermoplastic resin as the component (D) may be dissolved in the component (A) and / or the component (B) and mixed in a uniform state, or may be pulverized and mixed in a particle state. You may make it a dispersion state by melt | dissolving in a solvent and mixing. From the viewpoint that the obtained cured product is likely to be more transparent, it is preferable to dissolve it in the component (A) and / or the component (B) and mix them in a uniform state. Also in this case, the thermosetting resin of the component (D) may be directly dissolved in the component (A) and / or the component (B), or may be uniformly mixed with a solvent, and then the solvent may be used. However, it may be in a uniformly dispersed state and / or a mixed state. The thermoplastic resin as the component (D) may be contained uniformly or may be contained with a graded content.

When the thermoplastic resin as the component (D) is dispersed and used, the average particle size is preferably not more than the wavelength of the intended light. In this case, the target light is as described above. The particle system may have a distribution, and may have a single dispersion or a plurality of peak particle sizes, but the particle size may be reduced from the viewpoint that the viscosity of the curable composition is low and the moldability tends to be good. It is preferable that the coefficient of variation is 10% or less.

As the thermoplastic resin as the component (D), a resin having a small content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group is preferable from the viewpoint that the resistance to photodegradation is likely to be high. Those which do not contain a compound having a derivative of a hydroxyl group and / or a phenolic hydroxyl group are preferable. 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 the anthracene ring, and the phenolic hydroxyl group derivative is a hydrogen atom of the above-mentioned phenolic hydroxyl group. A group substituted with 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.

As the thermoplastic resin as the component (D), one having a low carbon-carbon double bond content is preferable from the viewpoint that the resistance to light deterioration is likely to be high. Specifically, the content of the carbon-carbon double bond in the component (D) is 0.0
It is preferably 1 mol / g or less, 0.001 m
More preferably, it is 0.0001 or less.
Those with a mol / g or less are more preferable.

From the viewpoint of good optical characteristics such as low birefringence and low photoelastic coefficient and good weather resistance, the weight ratio of the components in the component (A) of the aromatic ring is high. It is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less. Most preferred are those containing no aromatic hydrocarbon rings.

As the composition of the present invention, various combinations can be used as described above, but from the viewpoint of good heat resistance, the cured product obtained by curing the composition has a Tg of 50 ° C. or higher. Is preferably 100 ° C.
The above is more preferable, and the one having a temperature of 150 ° C. or higher is particularly preferable.

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 to be used is preferably 0 to 10 mL, more preferably 0.5 to 5 mL, and further preferably 1 to 3 mL with respect to 1 g of the reactive component (A) used. Is particularly preferable. If the amount used is small, it is difficult to obtain the effect of using a solvent such as viscosity reduction, and if the amount used is large, the solvent is likely to remain in the material and cause problems such as thermal cracks, and also in terms of cost. It becomes disadvantageous and the industrial utility value decreases.

In the composition of the present invention, other than these, 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, 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 which do not deteriorate the optical properties are preferable, and alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine amorphous silica or hydrophobic ultrafine silica, talc, barium sulfate, etc. may be mentioned. You can

Examples of the method for 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-epoxycyclohexane carboxylate, vinylcyclohexenedioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3- Epoxy resins such as dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate and hexahydroanhydride Examples thereof include those cured with an aliphatic acid anhydride such as an acid, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hydrogenated methylnadic 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 a phosphor such as yttrium-aluminum-garnet-based phosphor activated with cerium, which absorbs light from the light-emitting element and emits fluorescence having a longer wavelength,
Coloring agents such as bluing agents that absorb specific wavelengths, titanium oxide, aluminum oxide, silica, silica oxide such as silica glass, talc, calcium carbonate, melamine resin, CTU guanamine resin, benzoguanamine resin, etc. Examples thereof include various inorganic or organic diffusion materials, 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 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 mold member, cover the lead terminals by attaching tape from both the front and back sides, and in this state, immerse the lower half of the mold member of the light emitting diode in the tank containing the resin containing the filler, and then pull it up. It may be dried to form the filler-containing resin portion.

The term "optical material" used in the present invention refers to 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, and a film for liquid crystal such as a polarizer protective film. 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 field of optical fibers, 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 for communication infrastructure and for connecting 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 / transportation machines, lamp reflectors for automobiles, bearing retainers, gears, anticorrosion coats, 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 a 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 It is possible to obtain an optical material that is cured by subjecting a hydrolyzable group bonded to / and / or a metalloid atom to 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) with each other 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. As the method of mixing the component (D), various methods can be used for the purposes of compatibility, storage stability, viscosity adjustment and the like. It may be mixed with the component (A) or the component (B),
The components (A) and (B) may be separately mixed at an appropriate ratio.

When the composition is reacted and cured, the necessary amounts of the respective components (A), (B) and (C) may be mixed at once and reacted, but a part of them may be mixed and reacted. After mixing, the remaining amount is mixed and further reacted, or after mixing, only a part of the functional groups in the composition is reacted by controlling the reaction conditions and utilizing the difference in reactivity of the substituents (B stage conversion) It is also possible to adopt a method in which after the treatment, a treatment such as molding is performed to further cure. According to these methods, the viscosity adjustment during 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. 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 variously set, but for example, a temperature of 30 to 300 ° C. can be applied, and 100 to 250 ° C.
Are more preferable, and 150-200 degreeC is still 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 stages or continuously if necessary. It is preferable to carry out the reaction while raising the temperature in multiple stages or continuously, as compared with the case where it is carried out at a constant temperature, because it is easy to obtain a uniform cured product without distortion.

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 uniform cured product without 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 that volatile components generated by hydrolysis condensation are easily removed.

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 can 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 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 is used as a liquid crystal film such as a plastic cell for liquid crystal, a polarizing plate, a retardation plate, and a polarizer protective film, and a liquid crystal display device may be manufactured by a usual 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 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.

As the semiconductor material to be laminated, GaA is used.
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 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 emission, or a plurality of light emitting elements may be used for single color or multicolor emission.

The lead terminal used in the light emitting diode of the present invention is preferably one having good adhesion to an electrical connecting member such as a bonding wire and good electrical 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 made 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 various shapes can be adopted. 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.

[0113]

EXAMPLES Examples and comparative examples of the present invention will be shown below, but the present invention is not limited thereto. (Synthesis example 1) A magnetic stir bar and a cooling tube were set in a 200 mL two-necked flask. Toluene 50 in this flask
g, a xylene solution of a platinum vinyl siloxane complex (containing 3 wt% as platinum) 11.3 μL, 5.0 g of triallyl isocyanurate, 37.04 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and 90 ° C. The mixture was heated and stirred in the oil bath for 30 minutes. Further, it was heated under reflux in an oil bath at 130 ° C. for 2 hours. 1-ethynyl-
176 mg of 1-cyclohexanol was added. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. ^{By 1} H-NMR, it was found that this product was obtained by reacting a part of SiH groups of 1,3,5,7-tetramethylcyclotetrasiloxane with triallyl isocyanurate (referred to as partial reaction product A). . (Synthesis Example 2) The inside of a polymerization vessel of a 5 l separable flask was replaced with nitrogen, 11.3 g of copper bromide was weighed out, and 180 mL of acetonitrile (dried with molecular sieves and then subjected to nitrogen bubbling) was added. After heating and stirring at 70 ° C. for 5 minutes, the mixture was cooled to room temperature again, and 5.7 g of diethyl 2,5-dibromoadipate as an initiator and 804.6 g of n-butyl acrylate were added. The mixture was heated and stirred at 80 ° C., and 1.6 ml of the ligand diethylenetriamine was added to initiate polymerization. About 0.2 ml of the polymerization solution for sampling was sampled from the polymerization solution at regular intervals from the start of the polymerization, and the conversion rate of -n-butyl acrylate was determined by gas chromatogram analysis of the sampling solution. The polymerization rate was controlled by adding triamine from time to time. When the conversion rate of n-butyl acrylate was 95%, methyl methacrylate 34
5.7 g, copper chloride 7.8 g, diethylenetriamine 1.
6 ml and 1107.9 ml of toluene (dried with molecular sieves and then bubbled with nitrogen) were added. Similarly, the conversion rate of methyl methacrylate was determined. When the conversion rate of methyl methacrylate was 85% and the conversion rate of -n-butyl acrylate was 98%, 1500 ml of toluene was added, and the reactor was cooled in a water bath to terminate the reaction. The polymerization solution was always green during the reaction.

The copper complex was removed by filtering the reaction solution through activated alumina. The obtained filtrate was added to a large amount of methanol to precipitate the polymer, and the obtained polymer was heated at 60 ° C.
By vacuum-drying for 24 hours, a block copolymer was obtained (referred to as polymer A). The analysis method and results of the obtained polymer are as follows.

(Molecular weight / molecular weight distribution) GPC using polystyrene gel column with chloroform as mobile phase
The measurement was performed to determine the polystyrene-equivalent molecular weight.

(Composition ratio of BA and MMA (wt%)) ¹ H-
The weight fractions of polybutyl acrylate and methyl polymethacrylate in the block copolymer were confirmed by NMR.

Number average molecular weight = 1500, weight average molecular weight / number average molecular weight = 1.50, BA / MMA = 70/3
0 (Synthesis Example 3) 115.72 g of acrylic acid-n-butyl, 60.00 g of methyl methacrylate, allyl methacrylate 2
0.16 g, n-dodecyl mercaptan 6.46 g, azobisisobutyronitrile 2.0 g, toluene 400 m
The solution of L was refluxed with 50 mL of toluene 1
It dripped into the L flask under a nitrogen atmosphere from a dropping funnel over about 2 hours. After the dropping was completed, the reaction was continued for 2 hours.
The reaction solution was evaporated and further dried under reduced pressure at 80 ° C. for 3 hours to obtain about 195 g of a pale yellow viscous liquid oligomer (referred to as polymer B). The number of moles of allyl group determined by iodine value titration is 0.0818 mol / 100.
g, the molecular weight by VPO was 2950, and it was found that an average of 2.4 allyl groups was introduced per molecule. Synthesis Example 4 162.90 g of n-butyl acrylate, 18.78 g of allyl methacrylate, 6.02 g of n-dodecyl mercaptan, 1.87 of azobisisobutyronitrile
A solution of g and 370 mL of toluene was dropped into a 1 L flask in which 50 mL of toluene was refluxed under a nitrogen atmosphere from a dropping funnel over about 2 hours. After the dropping was completed, the reaction was continued for 2 hours. By evaporating the reaction solution, about 178 g of a colorless viscous liquid oligomer was obtained (referred to as polymer C). (Synthesis example 5) 170.00 g of -n-butyl methacrylate,
A solution consisting of 1.00 g of n-dodecyl mercaptan, 2.00 g of azobisisobutyronitrile, and 400 mL of toluene was dropped into a 1 L flask in which 50 mL of toluene was refluxed under a nitrogen atmosphere from a dropping funnel over about 2 hours. . After the dropping was completed, the reaction was continued for 2 hours. The reaction solution was evaporated to give about 1 colorless polymer.
60 g was obtained (referred to as polymer D). (Example 1) 4.0 g of triallyl isocyanurate,
0.7 g of the polymer A synthesized in Synthesis Example 2 and 30 mg of a xylene solution of a platinum vinyl siloxane complex (containing 3 wt% as platinum) were mixed. To this, a mixture of 6.0 g of the partial reaction product A synthesized in Synthesis Example 1 and 30 mg of 1-ethynylcyclohexanol was added in advance and mixed to obtain a curable composition. This is 3m on 2 glass plates
Pour a m-thick silicone rubber sheet into a cell made by sandwiching it as a spacer, 60 ℃ / 6 hours, 70 ℃
/ 1 hour, 80 ° C / 1 hour, 120 ° C / 1 hour heating to obtain a colorless transparent sheet-like cured product. (Example 2) A colorless transparent sheet-like cured product was prepared in the same manner as in Example 1 except that 4.0 g of the polymer B synthesized in Synthesis Example 3 was used instead of 0.7 g of the polymer A synthesized in Synthesis Example 2. Obtained. (Example 3) A colorless and transparent sheet-like cured product was prepared in the same manner as in Example 1 except that 4.0 g of the polymer C synthesized in Synthesis Example 4 was used instead of 0.7 g of the polymer A synthesized in Synthesis Example 2. Obtained. Example 4 A colorless transparent sheet-like cured product was prepared in the same manner as in Example 1 except that 1.0 g of the polymer D synthesized in Synthesis Example 5 was used in place of 0.7 g of the polymer A synthesized in Synthesis Example 2. Obtained. Comparative Example 5.62 g of a trial sale acrylic plate (polymethylmethacrylate) was dissolved in 100 g of acetone. 22.48 g of triallyl isocyanurate was added thereto and evaporated to obtain a transparent uniform mixture of 15% by weight of polymethylmethacrylate and 85% by weight of triallyl isocyanurate. 0.85 g of this mixture and the partial reaction product A synthesized in Synthesis Example 1 (as shown in Synthesis Example 1, the partial reaction product A contains a platinum vinyl siloxane complex as the component (C) of the present invention). Although 1.08 g was mixed, polymethyl methacrylate was deposited and could not be mixed uniformly. (Embodiment 5) The sheet-shaped cured product prepared by the method of any of Embodiments 1 to 4 is cut into an appropriate shape and fixed to the light transmitting window portion provided on the can type metal cap. To do. On the other hand, MOCVD (metal organic chemical vapor deposition)
Si and Zn-doped InGaN active layer formed on a sapphire substrate by the n-type
A light emitting element having a double hetero structure sandwiched between clad layers is prepared. 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 produced. (Example 6) 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 copper containing iron 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 and the mount lead and the inner lead are wire-bonded with an Au wire to establish electrical conduction.

The curable composition prepared in the same manner as in Examples 1 to 4 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 device 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 produced. Example 7 A curable composition and a light emitting device are prepared by the method described in Examples 1 to 4.

By forming a pair of copper foil patterns on the glass epoxy resin by etching, a substrate having lead electrodes is formed. 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,
The curable composition is filled in the cavity using the through holes. 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 produced by dividing each light emitting diode chip. Example 8 A curable composition and a light emitting device are prepared by the method described in Examples 1 to 4.

A chip type light emitting diode package is formed using PPS resin by insert molding. 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.
A curable composition is filled in the package opening as a mold member. In this state, 100 ℃ for 1 hour, then 15
Cure at 0 ° C. for 1 hour. In this way, a chip type light emitting diode can be manufactured.

[0122]

Since the composition of the present invention has good compatibility, the material obtained by curing the composition has high optical transparency,
It is a material suitable for optical materials that has little toughness and has toughness.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 83/05 G02B 1/04 G02B 1/04 5/30 5/30 G02F 1/1333 500 G02F 1/1333 500 1 / 1335 1/1335 C08K 5/54 F-term (reference) 2H049 BA02 BB28 BB39 BC22 2H090 JB03 JC06 JD01 JD08 JD13 2H091 FB02 FB13 FC01 GA01 LA02 LA04 LA06 4F071 AA33 AA67 AB06 AC12 AC16 AE02 AE03 BA02 BB01 BC01 4J002 BG041 BG051 CP042 DA118 DE148 DJ018 EU196 EX007 EZ008 FD146 FD158 GP00

Claims (9)

[Claims] 1. (A) triallyl isocyanurate,
A composition for an optical material comprising (B) a silicon compound containing at least two SiH groups in one molecule, (C) a hydrosilylation catalyst, and (D) a thermoplastic resin as essential components. And (D) component is one or more polymers selected from butyl acrylate-based polymers, butyl methacrylate-based polymers, and methyl methacrylate / butyl acrylate-based copolymers. object. 2. The composition for optical materials according to claim 1, wherein the component (B) is a reaction product of 1,3,5,7-tetramethyltetracyclosiloxane and triallyl isocyanurate. 3. The composition for optical materials according to claim 1, wherein the optical material is a liquid crystal film. 4. The composition for optical materials according to claim 1, wherein the optical material is a plastic cell for liquid crystals. 5. The composition for optical materials according to claim 1, wherein the optical material is a sealing material for a light emitting diode. 6. An optical material composition according to any one of claims 1 to 5 is mixed in advance to obtain Si in the composition.
An optical material obtained by curing by reacting a carbon-carbon double bond reactive with an H group and a part or all of a SiH group. 7. The composition for optical material according to claim 1 is mixed in advance to obtain Si in the composition.
The method for producing an optical material according to claim 6, wherein a carbon-carbon double bond reactive with an H group is reacted with a part or all of the SiH group. 8. A liquid crystal display device using the optical material according to claim 6. 9. A light emitting diode using the optical material according to claim 6.