WO2006027956A1 - Resin composition for optical material - Google Patents

Abstract

A resin composition for an optical material, characterized in that nano phosphor particles having a number average primary particle diameter of 0.1 to 100 nm and having a surface modified with a vinyl polymer having an SH group at a terminal thereof are dispersed in a polymer; and a light-emitting device using said resin composition for an optical material. The resin composition for an optical material has nano phosphor particles having a size being smaller by far than that of a conventional bulk phosphor which are dispersed in a polymer without agglomeration, and thus can exhibit excellent luminous efficiency.

Description

 Specification

 Resin composition for optical materials

 Technical field

 TECHNICAL FIELD [0001] The present invention relates to a resin composition for an optical material that exhibits excellent luminous efficiency by dispersing nanophosphor particles much smaller than a conventional Balta phosphor in a polymer without agglomeration. .

 Background art

 [0002] Nanoparticles with a particle size of ~ ~ lOOnm are more mechanical, optical, and magnetic than particles with submicrometers or larger, which are produced by ordinary mechanical grinding. Attention has been focused on the fact that it has properties and that there is a marked difference in chemical reactivity. As a phenomenon that does not appear in the Balta state of the material as the particle size decreases, for example, the carrier kinetic energy increases due to the confinement effect! ], External dielectric effect, increased band gap, decreased electron affinity energy, increased ionization potential, improved carrier-recombination efficiency. These unique physical properties can be applied to various functional materials such as EL devices, photoconductive devices, and piezo devices.

 [0003] In order to take advantage of the properties of nanoparticles, it is usually desired that the nanoparticles are dispersed in the medium without aggregating or condensing. However, since nanoparticles have a remarkably large surface energy, they tend to agglomerate between particles and bond between the agglomerated particles, resulting in large particles, and once agglomeration occurs and the particle size increases, Dispersion becomes extremely difficult. Furthermore, in the case of inorganic nanoparticles, since the particle surface has a large polarity, it is difficult to disperse it in an organic medium such as a low polarity organic solvent or polymer. In particular, dispersion of nanoparticles in a polymer such as a polymer in order to prevent aggregation of the nanoparticles is usually that the polarity of the polymer and the nanoparticles are significantly different and the viscosity of the solution in solution and in the molten state is high. It is generally very difficult because it is not easy to give. Therefore, polymer / nanoparticle composite materials have reached the point of widespread industrial widespread use! /, NA! /.

[0004] On the other hand, using the feature that organic thiol compounds easily bind to metal surfaces, Various methods for organic modification of the nanoparticle surface using a compound having a thiol group on the surface have been studied. For example, as shown in Patent Document 1 and Non-Patent Document 1, nano-dispersible materials that can be uniformly dispersed in an organic solvent are disclosed. It is also possible to obtain particles. Although such a method can be used to obtain nanoparticles that can be stably dispersed in an organic solvent, the same technique can be used to disperse nanoparticles in a polymer such as a polymer. Due to differences in polarity and viscosity between the modifier and the polymer, it was not easy.

 [0005] In order to solve such a problem, for example, in Non-Patent Document 2, a polymer having a molecular weight and a terminal group controlled by key-on polymerization is first polymerized, and this terminal group is converted into propylene sulfide. After the substitution, a polymer having a mercapto group at the end is obtained, and the surface of the metal nanoparticles is modified with this polymer, thereby realizing the dispersion of the metal nanoparticles in the polymer. This method is very interesting in that a composition in which nanoparticles are dispersed can be obtained by simply mixing prepolymerized polymers and pre-synthesized nanoparticles. However, the types of polymers that can be polymerized by such a method are limited, and since it is necessary to undergo many steps of terminal substitution reaction to obtain a polymer for modifying nanoparticles, it is generally used. It is not a technology that can be applied on an industrial scale.

 On the other hand, in recent years, blue LED chips that emit blue light and ultraviolet LED chips that emit ultraviolet light have been used as light-emitting elements using gallium nitride compound semiconductors (eg, GaN, InGaN, AlGaN, InGaAlN, etc.). It has been developed. The light emitted from these LED chip cartridges is characterized by having a single-wavelength emission peak with a narrow half-value width. On the other hand, these LED chips are expected to be applied to display and lighting applications, but white light is often required for display and lighting applications. Therefore, by combining LED chips that emit blue light or ultraviolet light with various phosphor powders that emit light using a part of the emitted light as an excitation source, Research and development of light emitting devices that emit light with a color different from the emission color are being carried out in various places. This type of light emitting device has advantages such as small size, light weight, and power saving, and is currently widely used as a light source for display, an alternative light source for small light bulbs, a light source for liquid crystal panels, and the like.

[0007] For example, Patent Documents 2, 3, and 4 disclose a light-emitting device using a combination of an LED chip and a phosphor powder as described above. The light emitting devices disclosed in these publications are L Common in that phosphor powder that is excited by the light emitted from LED chip force and dispersed in light-transmitting resin (for example, epoxy resin) used as the sealing part and mold part of ED chip is dispersed. There are features. In such a light emitting device, part of the light emitted by the LED chip force is also transmitted through the translucent resin as it is, and transmitted by the other part of the emitted light from the LED chip force. Light whose wavelength is converted by excitation of the phosphor powder in the synthetic resin is also emitted to the outside. Therefore, for example, white light can be obtained as the combined light of the light emitted from the LED chip cover and the light emitted from the phosphor powder. In other words, when the LED chip is a blue LED chip, the phosphor emitting yellow light using the blue light from the LED chip as an excitation light is combined, or the phosphor emitting red light and green is emitted. If two types of phosphors are combined, white light can be obtained as synthetic light. If the LED chip is an ultraviolet LED chip, white light can be obtained as combined light by combining three types of phosphors that emit red, green, and blue light using the ultraviolet light from the LED chip as excitation light. be able to. By obtaining white light in this way, in recent years it has become possible to apply LED chips to lighting applications. Patent Document 1: Japanese Patent Laid-Open No. 11-60581

 Patent Document 2: JP-A-5-152609

 Patent Document 3: Japanese Patent Laid-Open No. 7-99345

 Patent Document 4: Japanese Patent Laid-Open No. 10-242513

 Non-Patent Document 1: S. Huang et al., J. Vac. Sci. Technol., B 19 卷, 2 045 (2001)

 Non-Patent Document 2: M. K. Corbierr et al., J. Am. Chem. Soc., 123 卷, 10411 (2001)

 Disclosure of the invention

 Problems to be solved by the invention

 [0008] By the way, the phosphor powder in the above-described light-emitting device is a phosphor having an average particle diameter of several μm (approximately 5 μm), which has been conventionally used in cathode ray tubes (CRT) and fluorescent lamps ( Hereinafter, it is generally used as a Balta phosphor).

However, Balta phosphors have a sufficiently large particle size compared to the wavelength of visible light or excitation light. Due to the large size, the excitation light is irradiated only on the surface of the phosphor powder, and there is a problem that the light emission efficiency is lowered with respect to the amount of the phosphor powder used. Further, since the phosphor powder itself blocks the visible light obtained from the phosphor powder, the obtained light cannot be taken out to the outside sufficiently, which also reduces the luminous efficiency. It was.

 [0010] Also, when LED chips are applied to lighting devices, the luminous flux per LED chip is relatively small, so it is necessary to collect a large number of LED chips to make a module. Become. However, Balta phosphors generally have a characteristic (temperature quenching) in which the luminous efficiency decreases at high temperatures, although the degree varies depending on the material. Therefore, in a lighting device combining a Balta phosphor and an LED chip, due to the large luminous flux, even if the LED chip integration density (arrangement density) is increased, the current quenching is sufficient. There is another problem that the luminous flux cannot be obtained.

 [0011] In view of the above situation, the object of the present invention is to develop a technique for dispersing nanophosphor particles in a polymer, thereby generating light emitted from a conventional light emitting device using a Balta phosphor. It is an object to provide a light emitting device that can increase the light efficiency and is less likely to cause a decrease in luminance due to a temperature rise.

 Means for solving the problem

[0012] As a result of diligent studies to solve the above-mentioned problems, the present inventor polymerizes a bulle-based polymer having an SH group at the terminal, and modifies the surface of the nanophosphor particle with the obtained polymer. As a result, the present inventors succeeded in obtaining a rosin composition in which nanophosphor particles are well dispersed in a polymer, leading to the present invention.

That is, in the present invention, nanophosphor particles having an average particle diameter of 0.1 nm to 100 nm are provided at the ends.

A resin composition for optical materials, wherein the composition is dispersed in a polymer by modification with a vinyl polymer having an SH group.

[0014] In a preferred embodiment, (1) the number average molecular weight of the vinyl polymer having an SH group at the terminal is 2000 or more and 100000 or less.

 (2) The molecular weight distribution represented by the ratio between the weight average molecular weight and the number average molecular weight of the vinyl polymer having an SH group at the terminal is 1.5 or less.

(3) A vinyl polymer having an SH group at the end is used for acrylic acid, methacrylic acid, gold acrylate Metal salt, metal methacrylate, acrylic acid ester, methacrylic acid ester, styrene, acrylo-tolyl, butyl acetate, butyl chloride, N-alkylacrylamide, N-alkylmethacrylamide, N, N dialkylacrylamide, N, N It is obtained by radical polymerization of one or more monomers selected from dialkylmethacrylamide, N-bulupyridine, 2-bulupyridine, 4-vinylpyridine, maleic anhydride, maleimide, and powerful compounds.

 (4) A vinyl polymer having an SH group at the terminal is a polymer that transmits visible light.

(5) A vinyl polymer having an SH group at the end is obtained by treating a polymer polymerized by reversible addition / desorption chain transfer polymerization with a treating agent,

 (6) The number average primary particle size of nanophosphor particles in an unaggregated state is Inn! ~ 30nm,

(7) The emission peak wavelength of nanophosphor particles is in the wavelength range of 380 nm to 800 nm, and it is powerful 20 Οηπ! It is a particle that can emit light when irradiated with light in the wavelength range of ~ 500 nm.

 (8) The nanophosphor particle is an undoped semiconductor nanophosphor particle consisting only of a host crystal,

 (9) The nanophosphor particle is a doped semiconductor nanophosphor particle in which a luminescent ion is added to a host crystal,

 (10) A nanophosphor particle modified with a vinyl-based resin having an SH group at its end is mixed with a thermosetting resin.

 (11) The thermosetting resin is a silicon-based thermosetting resin.

 (12) a silicon-based thermosetting resin having (A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule; (B) at least two in one molecule; A resin composition for an optical material, characterized in that it is a silicone-based thermosetting resin containing a silicon compound containing a single Si H group and (C) a hydrosilylation catalyst. .

 [0015] Further, the present invention relates to a light emitting device using the resin composition for optical material.

 The invention's effect

[0016] In the resin composition for optical materials obtained by the present invention, nanophosphor particles are used as the fluorescent material and dispersed in the polymer without aggregation. As a result, the quantum size effect appears, and as a luminescent material, Balta firefly with a particle size of several / zm as in the past is used. Compared to the case of using a light body, the luminous efficiency of the fluorescent material can be increased only by nano-size the particle size without changing the composition. Furthermore, since temperature quenching can be reduced, it is possible to increase the luminous efficiency of the entire device as compared with the conventional case, and to suppress a decrease in luminance due to a rise in temperature.

 Brief Description of Drawings

[0017] FIG. 1 is a TEM photograph of a resin film obtained in Example 1.

 FIG. 2 is a TEM photograph of a resin film obtained in Comparative Example 2.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0018] The composition of the vinyl polymer having an SH group at the terminal used in the present invention is not particularly limited. Here, the vinyl polymer means a polymer obtained by polymerizing a vinyl monomer capable of radical polymerization. Such a radically polymerizable vinyl monomer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, metal acrylate, metal methacrylate, acrylate monomer, and methacrylate. Monomers, styrene monomers, vinyl cyanide monomers, unsaturated amide monomers, conjugation monomers, halogen-containing butyl monomers, butyl ester monomers, Examples thereof include unsaturated dicarboxylic acid compounds and derivatives thereof, and maleimide compounds.

[0019] Examples of the metal acrylate include sodium acrylate, potassium acrylate, zinc acrylate, and the like.

 [0020] Examples of the metal methacrylate salt include sodium methacrylate, potassium methacrylate, zinc methacrylate, and the like.

[0021] Acrylic acid ester monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, n-xyl acrylate, acrylic 2-ethylhexyl acid, n-octyl acrylate, n-decyl acrylate, n-dodecyl acrylate, tridecyl acrylate, stearyl acrylate, cyclohexyl acrylate, phenol acrylate, benzyl acrylate, 2-Methylethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, 3-atallyloyloxy pill dimethoxymethylsilane, 3-atallyloylo Xylpropyltrimethoxysilane, Atari Examples include 2,2,2-trifluoroethyl oxalate, allyl acrylate, and the like.

[0022] Methacrylic acid ester monomers include methyl methacrylate, ethyl acetate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-xyl methacrylate, and methacrylic acid. 2-Ethylhexyl, n-octyl methacrylate, n-decyl methacrylate, n-dodecyl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid 2-methoxyethyl, 3-methoxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, 3-methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyloxy Trimethoxysilane, methacrylic acid 2, 2, 2-triflate Ruo Roe chill include Ariru methacrylate.

 [0023] Examples of the styrenic monomer include styrene, α-methylstyrene, ρ-methylstyrene, ρ-methoxystyrene, and indene.

[0024] Examples of the cyanide bur monomer include acrylonitrile and meta-tallow-tolyl.

 [0025] Examples of the unsaturated amide monomer include acrylamide and methacrylamide.

[0026] Examples of the conjugation-based monomer include butadiene, isoprene, black-opened plane, and the like.

[0027] Examples of the halogen-containing bur monomer include butyl chloride, vinylidene chloride, tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride.

[0028] Examples of the butyl ester monomer include butyl acetate, butyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate.

[0029] Examples of unsaturated dicarboxylic acid compounds and derivatives thereof include maleic anhydride, maleic acid, maleic acid monoester, maleic acid diester, fumaric acid, fumaric acid monoester, and fumaric acid diester.

[0030] Examples of the maleimide compound include maleimide, methylmaleimide, ethylmaleimide, phenol maleimide, cyclohexylmaleimide and the like.

[0031] These monomers may be used alone or in combination. Multiple In the case where a copolymer is formed by combining these, the form is not particularly limited, and examples thereof include a random copolymer, a block copolymer, a graft copolymer, and a gradient copolymer. What is necessary is just to select the monomer to be used according to the required characteristic of a resin composition.

 [0032] Among these monomers, when used as an optical material, in consideration of necessary properties such as visible light and ultraviolet light transmittance, weather resistance, heat resistance, and affinity for thermosetting resin. Preferred monomers include acrylic acid, methacrylic acid, metal acrylate, metal methacrylate, acrylate, methacrylate, styrene, acrylonitrile, butyl acetate, butyl chloride, N-alkylacrylamide, N —Selected from alkylmethacrylamide, N, N-dialkylacrylamide, N, N-dialkylmethacrylamide, N-Burpyridine, 2-Byrpyridine, 4-Burpyridine, Maleic anhydride, Maleimide, Powerful compound 1 Mention may be made of more than one species of monomer.

 [0033] Furthermore, considering the visible light and ultraviolet light transmittance particularly when used as an optical material, the vinyl polymer having an SH group at the end is preferably a polymer that transmits visible light. Good. Here, the polymer that transmits visible light specifically indicates a resin having a total light transmittance of 50% or more measured at a thickness of 2 mm based on ASTM D1003. The larger the value of the total light transmittance, the more suitable it is, and it is preferably 60% or more, more preferably 70% or more, still more preferably 80% or more, and most preferably 85% or more. For a resin that transmits visible light, it is preferable that the haze value measured at a thickness of 2 mm based on ASTM D1003 is also small. Specifically, the haze value is 10% or less, preferably 7% or less, more preferably 5% or less, and most preferably 3% or less. These polymers can be used as a mixture of two or more. However, when two or more kinds of polymers are mixed and used, it is preferable that visible light can be transmitted even after the two are mixed.

 [0034] Of these, particularly preferred! /, The monomers are methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and force. One or more monomers selected from compounds.

[0035] The structure of the vinyl polymer having an SH group at the terminal used in the present invention is not particularly limited, but the modification efficiency when modifying the nanophosphor particles and the handling when used as an optical material The number average molecular weight (Mn) of the polymer is 2000 considering the ease of It is preferably 100000 or less. More preferably, it is 2500 or more and 80000 or less, more preferably <is 2700 or more and 60000 or less, and most preferably <is 3000 or more and 50000 or less. If the Mn of the polymer is less than 2000, only the same effect as that obtained by modification with an SH group-containing low molecular weight compound can be obtained, and the dispersibility of the nanophosphor particles tends to be insufficient in the composition. . If the Mn of the polymer exceeds 100000, the number of SH groups in the polymer decreases, so that modification of the nanophosphor particles tends to be difficult.

 [0036] The molecular weight distribution represented by the ratio of the weight average molecular weight and the number average molecular weight of the vinyl polymer having an SH group at the terminal used in the present invention is the reactivity between the SH group and the nanophosphor particle surface. From the point that it is easy to control, it is preferably 1.5 or less. More preferably, it is 1.4 or less, more preferably 1.3 or less.

 [0037] The three-dimensional structure of the polymer having an SH group at the terminal used in the present invention is not particularly limited, and may be linear or branched in the molecule. The branching in the molecule may be regular or irregular, and there is no limit to the number of branching 'lengths'. It may be a cage polymer having a large number of branches. Further, it may have SH groups at all terminals of the polymer branch, or may have a structure having SH groups only at a part of the terminals or at only one of the terminals. However, in consideration of the reactivity between the polymer and the surface of the nanophosphor particle, it is preferable that the polymer is linear when the polymer has fewer branches. When the polymer is linear, it may have an SH group only at one end, or may have an SH group at both ends.

[0038] The polymerization method of the polymer having an SH group at the terminal used in the present invention is not particularly limited, but it is possible to introduce the SH group surely, the molecular weight and molecular weight distribution, the regularity of the monomer, etc. It is preferable to use a reversible addition-elimination chain transfer (RAFT) polymerization method for the reason that it is easy to impart the. In other words, this is a method of radical polymerization of a bull monomer using a compound having a dithioester structure as a chain transfer agent, and is a kind of controlled radical polymerization. The polymer obtained by this method has a dithioester structure or a trithiocarbonate structure at the molecular end or in the molecular chain. Preferably, the polymer used in the present invention as an embodiment is obtained by treating a polymer having a dithioester structure or trithiocarbonate structure obtained by RAFT polymerization with a treating agent, and then dithioester. It can be obtained by reacting a portion of the thiol structure or trithiocarbonate structure and converting it to an SH group.

 [0039] The chain transfer agent having a dithioester structure used in the RAFT polymerization is not particularly limited, and examples thereof include compounds described in JP 2000-515181 A and compounds represented by the following general formula (1). Can be used.

 [0040] [Chemical 1]

[0041] (wherein R is a monovalent organic group having 1 or more carbon atoms; Z is a sulfur atom (when p = 2), an oxygen atom (when p = 2), a nitrogen atom (p = 3) Or a p-valent organic group having 1 or more carbon atoms; p is an integer of 1 or more; and when p is 2 or more, Rs may be the same or different)

 In the above compound, the monovalent organic group R having 1 or more carbon atoms is not particularly limited, and in addition to a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a key atom, a phosphorus atom, And a high molecular weight polymer that may contain at least one of metal atoms. Examples of R include an alkyl group, an aralkyl group, and substituents thereof. From the viewpoint of availability and polymerization activity, the structures of the following general formulas (2) and (3) are preferred.

[0042] [Chemical 2] MM c ————

e Me Me Me

C CN I

C—— Me CH ₂ -C—— Me e II

 Me Me

e c M M—— e

 I

S -Me CH ₂ CH ₂ COOH CH— CN e

Me

 I

C CN ― CH ₂ COOH CH ₂ CN

Et

[0043] (In the formula, Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, and Ac represents a acetyl group). [0044] O

CH ₂ -CO ~ (cH ₂ CH ₂ 0 CH ₃

CN O

C― CH ₂ CH ₂ — CO ~ (cH ₂ CH ₂ 0 CH ₃

O CH,

CH ₂ CH ₂ — CO ~ (cHCH ₂ o "CH ₃

CN

CI—— CH ₂ CH ₂ COOH

 I

CH ₃

[0045] (wherein n is an integer of 1 or more, and r is an integer of 0 or more)

 In the above formula, from the viewpoint of availability, n and r are preferably 500 or less, more preferably 200 or less, and even more preferably 100 or less. R is particularly preferably a group having 2 to 30 carbon atoms in view of availability and polymerization activity.

[0046] The RAFT polymerization reaction conditions are not particularly limited, and conventionally known conditions such as Patent Document 5 can be applied. However, in terms of reactivity, it is preferable to react at a temperature of 70 ° C or higher, more preferably 80 ° C or higher. The type of polymerization is bulk polymerization, solution weight However, bulk polymerization or solution polymerization is preferred in that it can be easily carried out for conversion to SH groups after polymerization.

[0047] The treating agent used for converting the polymer obtained by RAFT polymerization into a polymer having an SH group is not particularly limited, but a compound containing hydrogen and nitrogen bonds is high in terms of high efficiency of conversion to an SH group. A compound selected from the group consisting of a base and a reducing agent is preferred.

 [0048] Among the treatment agents, the hydrogen-nitrogen bond-containing compound is not particularly limited. For example, ammonia, hydrazine, primary amine compound, secondary amine compound, amide compound, and amine hydrochloride Examples thereof include compounds, hydrogen-nitrogen bond-containing polymers, and hindered amine light stabilizers (HALS).

 [0049] Among the hydrogen-nitrogen bond-containing compounds, specific examples of primary amine compounds include 3-amino-1-propanol, arylamine, isopropylamine, monoethylamine, 2-ethylhexylamine, n-butylamine, and t-butylamine. , N-propylamine, 3-methoxypropylamine, 2-aminoethanol, ethylenediamine, diethylenetriamine, triethylenetetramine, 1,4-diaminobutane, 1,2 diaminopropane, 1,3 diaminopropane, diaminomaleonitrile, cyclohexane Hexylamine, hexamethylenediamine, n-hexylamine, monomethylamine, monomethylhydrazine, anisidine, aniline, p-aminobenzoyl ethyl, aminophenol, toluidine, phenolhydrazine, phenol-diamine, phenene Ruamin, Benjiruamin, Meshijin, Aminobirijin, leaving the melamine in Ageruko transgression.

 [0050] Among the hydrogen-nitrogen bond-containing compounds, specific examples of secondary amine compounds include diarylamine, diisopropylamine, jetylamine, diisobutylamine, di-2-ethylhexylamine, and bis (hydroxyethyl). Amine, N-ethylethylenediamine, Ethyleneimine, Dicyclohexylamine, Di-n-Butylamine, Di-t-Butylamine, Dimethylamine, N-Ethylamine, Diphenylamine, Dibenzylamine, N-Methylamine, Imidazole, 2,5 Dimethylbiperazine, piperazine, piperidine, pyrrolidine, morpholine and the like can be mentioned.

[0051] Among the hydrogen-nitrogen bond-containing compounds, specific examples of amide compounds include adip Acid dihydrazide, N isopropylacrylamide, carbohydrazide, guarthiourea, glycylglycine, oleic acid amide, stearic acid amide, adipic acid dihydrazide, formamide, methacrylamide, acetolide, acetoacetate lide, acetoacetate Examples include toluidoide, toluenesulfonamide, phthalimide, isocyanuric acid, succinimide, hydantoin, ferrazolidone, benzamide, acetoamide, acrylamide, propionic acid amide, 2, 2, 2-trifluoroacetamide and the like.

[0052] Among the hydrogen-nitrogen bond-containing compounds, specific examples of ammine hydrochloride-based compounds include: acetamidine hydrochloride, monomethylamine hydrochloride, dimethylamine hydrochloride, monoethylamine hydrochloride, jetylamine hydrochloride, monopropylamine hydrochloride Salt, dipropylamine hydrochloride, semicarbazide hydrochloride, guanidine hydrochloride, disteamine hydrochloride and the like.

 [0053] Among the hydrogen-nitrogen bond-containing compounds, specific examples of the hydrogen-nitrogen bond-containing polymer include trade names: Polyment (manufactured by Nippon Shokubai Co., Ltd.), polyethyleneimine, aminopolyacrylamide, nylon. 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, nylon MXD6, nylon 46, polyamideimide, polyallylamine, polyurethane, etc.

 [0054] Among the hydrogen-nitrogen bond-containing compounds, as a hindered amine light stabilizer (HALS), trade name: ADK STAB LA-77 (manufactured by Asahi Denki Kogyo Co., Ltd.), trade name: Chimassorb 944LD (Chino) (Trade name: Tinuvin 144 (manufactured by Chinoku 'specialty' chemicals)), product name: ADK STAB LA-57 (manufactured by Asahi Denki Kogyo Co., Ltd.), product name: ADK STAB LA—67 (Asahi Denki Kogyo Co., Ltd.), trade name: ADK STAB LA—68 (Asahi Denka Kogyo Co., Ltd.), trade name: ADK STAB LA—87 (Asahi Denki Kogyo Co., Ltd.) And Goods name: Goodrite UV-3034 (manufactured by Goodrich).

[0055] Among the treatment agents, the base is not particularly limited, and specific examples thereof include sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and zinc hydroxide. Examples thereof include metal hydroxides; metal alkoxides such as sodium methoxide, sodium ethoxide, sodium phenoxide, magnesium methoxide; sodium carbonate, potassium carbonate, and the like. [0056] Among the treating agents, the reducing agent is not particularly limited, and specifically, metal hydrogen such as sodium hydride, lithium hydride, calcium hydride, lithium aluminum hydride, sodium borohydride, and the like. C), LiBEt H, hydrogen, hydrogen-containing gas, etc.

 Three

 I can do it.

 [0057] These treatment agents may be used alone or in combination of two or more. Among the above-mentioned treatment agents, a hydrogen-nitrogen bond-containing compound having a boiling point of 20 ° C. to 200 ° C. and a reducing agent are preferable because the reaction efficiency and handling are easy. Of these, monomethylamine, monoethylamine, dimethylamine, jetylamine, monobutylamine, dibutylamine, and cyclohexylamine are more preferable in terms of availability and ease of recovery and removal. The amount of the treatment agent used is not particularly limited. When a base is used as the treating agent, 0.01 to 100 parts by weight is preferable with respect to 100 parts by weight of the polymer in terms of ease of handling and reactivity, and 0.05 to 50 parts by weight is more preferable. 0.1 to 30 parts by weight is particularly preferred.

 [0058] The present invention is characterized in that nanophosphor particles having an average particle size of 0.1 nm to 100 nm are modified with a bull polymer having an SH group at the terminal and dispersed in the polymer. The nanophosphor particles having a number average primary particle size of 0.1 nm to 100 nm used in the present invention include undoped semiconductor nanophosphor particles consisting of only a host crystal, and a doped type in which a luminescent ion is added to the host crystal. The semiconductor nanophosphor particles can also be used preferably.

[0059] In the case of undoped semiconductor nanophosphor particles that only have a host crystal power, light having a wavelength corresponding to the bandgap is irradiated by irradiating light having a wavelength larger than the band gap of the host crystal. This is preferable because light can be emitted. Among these, a nanoparticle containing a transition metal element corresponding to any of Groups 8 to 13 of the periodic table is capable of forming a coordination bond between the SH group of the polymer having an SH group at the end and the transition metal element. It is preferable because the surface modification reaction of nanophosphor particles progresses rapidly. These undoped semiconductor nanophosphor particles that can only be used as a base crystal and have a light emission band in and around the visible region include GaN, GaP, GaAs, InN, InP and other periodic group 13 elements. And compounds of group 15 of the periodic table, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, etc. Compound of In O , In S and the like. Among them, the controllability of the grain size of semiconductor crystals and the light emission ability are suitable.

twenty three

 Industrially important are compound semiconductors of Group 12 elements of the periodic table and Group 16 elements of the periodic table such as ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, etc., especially ZnO, Zn S ZnSe, CdS, CdSe, etc. are more preferably used for this purpose.

 [0060] In addition, in the case of doped semiconductor nanophosphor particles in which luminescent ions are added to the host crystal, light of a desired wavelength can be emitted by appropriately selecting the host crystal and the luminescent ions according to the excitation wavelength. I like it because it is possible. Examples of doped semiconductor nanophosphor particles include the following.

 [0061] The peak wavelength at which the emission intensity is maximum is 380 ηπ! Examples of doped semiconductor nanophosphor particles of up to 500 nm include, for example, BaMgAl 2 O: Eug BaMg Al 2 O: Eu, M (PO 2) Cl: Eu

 10 17 2 16 27 5 4 3

(However, M is at least one element selected from among Sr, Ca, Ba, and Mg), M (PO

 Ten

) C1: Eu (where M is at least one element selected from Sr, Ca, Ba, Mg)

4 6 2

 , Sr Al O: Eu, (Sr, Ba) Al Si O: Eu, 2SrO-XP O -YB O: Eu (however, X +

4 14 25 2 2 8 2 5 2 3

 Y = l), ZnS: Ag ゝ ZnS: Ag, Al, ZnS: Ag, Cl, (ZnCd) S: Ag, (ZnCd) S: Ag, A1, (ZnCd) S: Ag, CI, etc. .

[0062] The peak wavelength at which the emission intensity is maximum is 500 nn! As the doped semiconductor nanophosphor particles of ~ 600 nm, for example, Sr 2 Si 2 O 2 SrCl: Eu, Ba MgSi 2 O: Eu, SrGa S: Eu,

 2 3 8 2 3 2 8 2 4

Y SiO: Ce, Tb ゝ LaPO: Ce, Tb ゝ MgAl O: Ce, Tb ゝ GdMgB O: Ce, Tb ゝ Z

2 5 4 11 19 5 10 n SiO: Mn, Re M O: Ce (where Re is selected from Y, Lu, Se, La, Gd, Sm)

2 4 3 5 12

 At least one element selected, M is at least one selected element of Al, Ga, In), ZnS: Cu ゝ ZnS: Cu, Cl, ZnS: Cu, Al, ZnS: Cu, Ag ZnS: Cu, Au, Al, (ZnCd) S: Cu, (ZnCd) S: Cu, Cl, (ZnCd) S: Cu, Al, (ZnCd) S: Cu, Ag, (ZnC d) S: Cu , Au, Al and the like.

[0063] The peak wavelength at which the emission intensity is maximum is 600 nn! Examples of doped semiconductor nanophosphor particles of up to 800 nm include Y O: Eu, Y O S: Eu, Y O S: Eu, Bi, YVO: Eu, YV

 2 3 2 2 2 2 4

 O: Eu, Bi, Y (PV) 0: Eu, Y (PV) 0: Eu, Bi ゝ CaS: Eu ゝ SrS: Eu, (CaSr) S: E

4 4 4

 u, 3.5MgO-0.5MgF-GeO: Mn, Re M O: Ce, Pr (where Re is Y, Lu, Se

 2 2 3 5 12

, La, Gd, Sm At least one element selected for its medium strength, M from Al, Ga, In Selected at least one element).

[0064] The emission peak wavelength of these nanophosphor particles is 380ηπ! It is preferable to have a wavelength range of ˜800 nm. By having this peak wavelength, it can be used as a visible light emitting element. A more preferable emission peak wavelength is 390 nm to 780 nm. In addition, by using nanophosphor particles having a plurality of emission peak wavelengths in combination, the light emitting device as a whole can obtain synthesized light having the emission peak wavelength of each nanophosphor particle, so that a light emitting element that emits white light is produced. It is also possible. Each nanophosphor for obtaining white light As a wavelength range including the emission peak wavelength of each nanoparticle, 380ηπ! It is sufficient to select from the three wavelength regions of ~ 500nm, 500nm ~ 600nm, 600nm ~ 800nm.

 [0065] The nanophosphor particles are preferably particles that can emit light when irradiated with light in a wavelength range of 200 nm to 500 nm. Thereby, a white light emitting element can be obtained by a combination with a blue light emitting element or an ultraviolet light emitting element. A more preferable wavelength range of the excitation light is 250 nm to 450 nm, and an even more preferable wavelength range of the excitation light is 300ηπ! ˜400 nm, the most preferable wavelength range of excitation light is 350 nm to 400 nm.

 [0066] The nanophosphor particles used in the present invention are generally produced by synthesizing the precursor power of a semiconductor using a commonly used nanoparticle production method such as a gas phase method or a liquid phase method. The production method of nanophosphor particles is not limited to these methods, and any known method can be used. For example, a method in which a raw material aqueous solution is present in reverse micelles of a non-polar organic solvent to grow crystals (reverse micelle method), and a method in which thermally decomposable raw materials are grown in a high-temperature liquid organic solvent (hot soap method). It can be produced by spray drying method, spray pyrolysis method, CVD method, etc., and these methods are preferably used because the particle size of the nanoparticles obtained can be easily controlled.

[0067] The number average primary particle diameter of the nanophosphor particles used in the present invention in an unaggregated state is from 0. Inm to 100 nm. The upper limit of the particle diameter is preferably 50 nm or less, more preferably 30 nm or less, and even more preferably 15 nm or less. If the number-average primary particle size in the unaggregated state is larger than 10 Onm, it is difficult to expect improvement in luminous efficiency because it exhibits the same characteristics as a Balta state material. In addition, the excellent dispersibility from the viewpoint of nanophosphors The preferred lower limit of the number average primary particle size in the unaggregated state of the particles is 0.2 nm, more preferably lnm. In addition, the coefficient of variation (particle size distribution) of the number average primary particle diameter in the non-aggregated state of the nanophosphor particles is preferably 50% or less, and more preferably 30% or less. If the particle size distribution of the nano-phosphor particles is too wide, that is, if the coefficient of variation of the particle size exceeds 50%, the light emission efficiency may decrease or the light emission characteristics may vary widely from one light emitting device to another.

 [0068] The number average primary particle size in the unaggregated state in the present invention is a particle size of at least 100 particles using a photograph taken with a transmission electron microscope or a scanning electron microscope. It is a number average particle diameter measured by a ruler and calculated by number average. However, if the particle photograph taken with an electron microscope is not circular, the circle diameter can be used when the area occupied by the particle is calculated and then replaced with a circle having the same area.

 [0069] The shape of the nanophosphor particles that can be used in the present invention can be any shape without particular limitation. Specifically, three-dimensional shapes close to a sphere such as a sphere, rugby ball, soccer ball, and icosahedron, hexahedron, rod, needle, plate, scale, crushed, irregular shape, etc. Shape. Furthermore, it may be a porous particle having a large number of holes on the surface or inside which may have a cavity or a defect on the surface or inside of the particle. However, the nano-phosphor particles are easy to manufacture, easy to disperse in the resin, and easy to treat the particle surface. U, preferred to be cubic. Close to a sphere! The cubic shape means (particle surface area) / (sphere surface area of the same volume as the particle) specific force, preferably less than 3 times, more preferably less than 2 times, especially 1.5 It is preferable that it is less than 2 times. Further, the nanophosphor particles used in the present invention may be used alone or in combination of two or more kinds of particles having different types or shapes. Sarasako may be used in combination of two or more types with different particle size distribution.

 [0070] The nanophosphor particles used in the present invention are excellent because the dispersibility in the resin composition is remarkably improved by modifying the surface with a vinyl polymer having an SH group at the terminal. Thus, it is possible to easily obtain a resin composition for optical material having luminous efficiency.

[0071] Method for modifying surface of nanophosphor particle with vinyl polymer having SH group at terminal There is no particular limitation, and any method can be used. For example, when it is possible to dissolve a vinyl polymer having an SH group at the terminal in a solvent capable of dispersing nanophosphor particles, the nanophosphor particles are dispersed in a solvent and then the terminal By dissolving a vinyl polymer having SH groups in the same solvent and stirring, the SH group at the end of the bull polymer is bonded to the surface of the nanophosphor particles, and the nanophosphor particle surface is modified. Is possible.

 [0072] If the vinyl polymer having an SH group at the end of the solvent in which the nanophosphor particles can be dispersed does not dissolve or is difficult to dissolve, the nanoparticle can be prepared by various operations as described below. It is possible to modify the surface.

 [0073] For example, a modifying agent that has a relatively weak coordinating ligand such as an amino group, a phosphine oxide group, or a phosphine group in the molecule and is soluble in a solvent in which nanophosphor particles are dispersed. In addition, a ligand having a weak coordinating power is previously bonded to the surface of the nanophosphor particle. Therefore, the nanoparticles are isolated by an operation such as centrifugation, and dispersed again in a solvent in which a vinyl polymer having an SH group at a terminal can be dissolved, and the vinyl polymer having an SH group at the terminal is added to the solvent. If the ligand exchange reaction is caused by contact with the solution in a liquid phase containing nanophosphor particles, the coordination power is weak and the ligand can be replaced with an SH group. is there. In the first step of dispersing a weakly coordinating compound such as pyridine in a liquid phase containing a large excess (usually used as a solvent), a vinyl polymer having an SH group at the terminal is added in the first step. Ligand exchange by a two-step process, which can be as powerful as possible, may be preferred.

 [0074] Further, nanophosphor particles are dispersed in a dispersible solvent in advance, and a beryl polymer having an SH group at the end is dissolved in a separately dissolvable solvent, and both solutions are mixed. In some cases, the surface of the nanophosphor particle can be modified. At this time, the solvent in which the nanophosphor particles are dispersed is not compatible with the solvent in which the vinyl polymer is dissolved! In this case, nanophosphor particles are extracted to the solvent side in which the bull polymer is dissolved as the surface modification of the nanophosphor particles progresses, so it is easy to check whether the modification is complete. I like it. In this case, it is preferable to use a phase transfer catalyst such as tetraalkyl ammonium salt or tetraalkylphosphonium salt in some cases.

[0075] Further, when the nanophosphor particles are produced in the liquid phase, an SH group is added at the end to the reaction liquid phase. It is also effective to add a vinyl polymer having the same. According to this method, the modification of the surface of the nanophosphor particle can be completed simultaneously with the synthesis of the nanophosphor particle, and the effect of preventing the nanophosphor particles from aggregating with each other during the synthesis of the nanophosphor particle. Therefore, it is preferable as a modification method.

 [0076] When the nanophosphor particles are modified with a vinyl polymer having an SH group at the terminal, the modification reaction can be completed more efficiently by stirring uniformly. When stirring, the surface can be uniformly modified while preventing aggregation by irradiating ultrasonic waves. In addition, irradiation with microwaves can locally impart energy to the particles, which may significantly improve the efficiency of surface modification.

 [0077] The weight ratio between the vinyl polymer having an SH group at the terminal and the nanophosphor particle is determined by the purpose of use, the composition and molecular weight of the vinyl polymer, the specific gravity of the nanophosphor particle, It depends on the particle size and surface area, the surface state of the nanophosphor particles, and the like. That is, when the molecular weight of the vinyl polymer is relatively large, the number of SH groups in the vinyl polymer is small V. Therefore, in order to modify the entire particle surface, a relatively large amount of the bull polymer is used. In contrast, when the molecular weight of the vinyl polymer is relatively small, the number of SH groups in the bull polymer is large, so the amount of vinyl polymer added is small. It may be good. In addition, when the particle size of the nanophosphor particle is relatively small, the number of nanophosphor particles is increased and the surface area ratio is increased. Therefore, a relatively large amount of vinyl-based weight is necessary to modify the entire particle surface. While it is necessary to use a coalescence, the addition amount of the vinyl polymer may be small if the particle diameter of the nanophosphor particle is relatively large.

[0078] As a general guideline of the weight ratio between the vinyl polymer having an SH group at the terminal and the nanophosphor particle, the number of atoms present on the surface of the particle among the atoms constituting the nanophosphor particle And the number of SH groups in the bull polymer may be calculated and used so that they are close to each other. That is, if the ratio of the atoms present on the particle surface among the atoms constituting the nanophosphor particle is high, such as the particle size of the nanophosphor particle is small, the particle surface is uneven, or the particle is porous, etc. As is apparent, the dispersibility tends to be better when more vinyl polymers having SH groups at the ends are used. [0079] When the polymer-modified nanophosphor particles obtained as described above are used as a light-emitting device, a method of mixing and dispersing the polymer-modified nanophosphor particles in a thermosetting resin is preferred.ヽ. For mixing the thermosetting resin and the polymer-modified nanophosphor particles, any known mixing method with no particular limitation can be used.

 [0080] For example, polymer-modified nanophosphor particles are dispersed in a solvent that can dissolve the resin, and the monomer or oligomer of the thermosetting resin and the curing agent are simultaneously dissolved in the solvent to be uniform. Then, a resin composition in which nanophosphor particles are dispersed in a thermosetting resin can be easily obtained by a method such as evaporation and curing of the solvent, and other generally known methods. I can do things. When such a method is used, the solution of the nanophosphor particles can be stirred with various known devices for the purpose of improving the dispersibility of the nanophosphor particles or preventing the aggregation of the nanophosphor particles. This is preferable because a resin composition in which particles are well dispersed can be obtained. Stirring methods include a method of rotating a rotating device such as a stir bar and a stirring rod in a solvent, a method of stirring using a medium such as beads, a method of stirring by irradiating with ultrasonic waves, a high speed rotation, etc. Examples of the method include stirring by applying a high shear force, but are not limited thereto.

 [0081] The thermosetting resin used when the polymer-modified nanophosphor particles are used as a light-emitting device is not particularly limited, and one kind of various thermosetting resins known as necessary may be used. Alternatively, two or more types can be selected and used in any combination. Examples of thermosetting resins include, but are not limited to, epoxy resins, silicone resins, cyanate resins, phenol resins, polyimide resins, polyurethane resins, and modified resins thereof. It is not something. Among these, from the viewpoint of high transparency and excellent practical properties such as adhesiveness, a transparent epoxy resin, a silicone-based thermosetting resin containing a key molecule in the molecule, and a transparent polyimide resin are preferable.

 [0082] Examples of the transparent epoxy resin include bisphenol A diglycidyl ether, 2, 2,

Bis (4 glycidinole oxycyclohexenole) propane, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, butylcyclohexenedioxide, 2- (3,4 epoxy cyclohexyl) -5 , 5-spiro (3,4 epoxy cyclohexyl) 1,3 dioxane, bis (3,4 epoxy cyclohexylene) 1, 2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isolate and other epoxy resins are hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hydrogen methyl Examples thereof include those cured with an aliphatic acid anhydride such as nadic acid anhydride. These epoxy resins or curing agents may be used alone or in combination. Examples of the transparent polyimide resin include a fluorine-containing polyimide resin.

 [0083] Among the thermosetting resins described above, a silicon-based thermosetting resin is preferable because it is excellent in weather resistance, light transmittance, heat resistance, and the like. Examples of silicone-based thermosetting resins include silicone resins, modified silicone resins, epoxy group-containing silicone resins, and curable resins made of caged silsesquioxane having reactive functional groups. Is mentioned.

 [0084] Among the above silicon-based thermosetting resins, (A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, (B) in one molecule It is more preferable to use a silicone-based thermosetting resin comprising a silicon compound containing at least two SiH groups, and (C) a hydrosilylation catalyst.

 [0085] The component (A) in the silicone-based thermosetting resin is described below.

 [0086] The component (A) is not particularly limited as long as it is an organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule. Examples of the organic compound include polysiloxane-organic block copolymer and polysiloxane-organic graft copolymer.

Further, as a constituent element other than the compound containing a siloxane unit (Si 2 O 3 Si), a compound containing no element other than C, H, N, 0, S and halogen is more preferable. In the case of a compound containing a siloxane unit, there are problems such as reactivity. The bonding position of the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and may be present anywhere in the molecule. Component (A) may be used alone or in combination of two or more.

[0087] The compound of component (A) can be classified into an organic polymer compound and an organic monomer compound. The organic polymer-based compound is not particularly limited. For example, polyether-based, polyester-based, polyarylate-based, polycarbonate-based, saturated hydrocarbon-based, unsaturated carbon Examples thereof include hydrogen fluoride-based, polyacrylic acid ester-based, polyamide-based, phenol-formaldehyde-based (phenolic resin), and polyimide-based compounds.

 [0088] The organic monomer-based compound is not particularly limited, but examples thereof include a phenol-based, bis-phenol-based, aromatic hydrocarbon-based such as benzene, naphthalene, etc .; linear, cyclic, etc. aliphatic hydrocarbon-based; complex Ring system compounds; and mixtures thereof.

[0089] The carbon-carbon double bond reactive with the SiH group of component (A) is not particularly limited, but the following general formula (4)

(Wherein R ¹ is a hydrogen atom! / Represents a methyl group) is preferred from the viewpoint of reactivity. Among them, a group in which R ¹ is a hydrogen atom is particularly preferable because of easy availability of raw materials.

 [0090] Further, the carbon-carbon double bond having reactivity with the SiH group of component (A) includes the following general formula (5)

— R ² C = CR ² — (5)

(In the formula, R represents a hydrogen atom or a methyl group. Two R ² may be the same or different.) An alicyclic group having a partial structure represented in the ring. The point power that the heat resistance of the cured product is high is also suitable. Of these, the group in which both R ² are hydrogen atoms is particularly preferred because of the availability of raw materials.

 [0091] The carbon-carbon double bond having reactivity with the SiH group may be directly bonded to the skeleton of the component (A) or may be covalently bonded via a divalent or higher substituent. The divalent or higher valent substituent is not particularly limited, but is preferably a substituent that does not contain any element other than C, H, N, 0, S, and neurogen as a constituent element that is preferably a substituent having 0 to 10 carbon atoms. Groups are more preferred.

 [0092] Examples of the group covalently bonded to the skeleton of the component (A) include a vinyl group, an aryl group, a methallyl group, an acrylic group, a methacryl group, a 2-hydroxy-1- (aryloxy) propyl group, and a 2-arylphenol. Group, 3-arylphenyl group, 4-arylphenyl group, 2- (aryloxy) phenol group, 3 (aryloxy) phenol group, 4 (aryloxy) phenyl group, 2 (aryloxy) ethyl group Group, 2,2 bis (aryloxymethyl) butyl group, 3 allyloxy-2,2-bis (aryloxymethyl) propyl group, and the like.

[0093] The organic compound of component (A) includes a skeleton portion and a group having a carbon-carbon double bond. Low molecular weight compounds that are difficult to express separately can also be used. Specific examples of the low molecular weight compound include aliphatic chain polyene compound systems such as butadiene, isoprene, octacene and decadiene, cyclopentagen, cyclooctagen, dicyclopentagen, tricyclopentagen and norbornagen. Examples thereof include aliphatic cyclic polyphenylene compound systems, and substituted aliphatic cyclic olefinic compound systems such as vinyl cyclopentene and burcyclohexene.

 [0094] From the viewpoint of improving heat resistance as component (A), carbon double bonds that are reactive with SiH groups are contained in an amount of not less than 0.001 mol per lg of component (A). Those containing 0.05 mol or more are more preferred, and those containing 0.008 mol or more are more preferred.

 [0095] As specific examples of the component (A), in addition to the above, diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1, 1, 2, 2-tetraaryloxyethane, diarylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, 2, 2 bis (4 hydroxycyclohexyl) propane diaryl ether, 1 , 2, 4 Tributylcyclohexane, dibutylbenzenes (purity of 50 to 100%, preferably purity of 80 to 100%), dibibibiol, 1, 3 diisopropenebenzene, 1, 4-diisopropylbenzene, oligomers thereof, 1,2-polybutadiene (1,2 ratio 10-100%, preferably 1,2 ratio 50-100% ), Novolak phenol aryl ether, arylated polyphenylene oxide, epoxy resin, in which part or all of the glycidyl group of the epoxy resin is replaced with an aryl group,

[0096] [Chemical 4]

 OSOMM

[0097] [Chemical 5]

[0098] and the like.

 [0099] Among these, from the viewpoint of good optical properties such as birefringence and ultraviolet transparency, the strength of the component (A) is that the aromatic ring component weight ratio is 50% by weight or less. More preferred is 40% by weight or less, and more preferred is 30% by weight or less. Most preferred U is one that does not contain an aromatic hydrocarbon ring.

 [0100] The number of carbon-carbon double bonds reactive with the SiH group of component (A) may be at least two per molecule, but from the viewpoint of further improving heat resistance, two carbon-carbon double bonds may be used. It is more preferable to have 3 or more, and 4 or more is particularly preferable. However, if component (A) is a mixture of various compounds and the number of carbon-carbon double bonds of each compound cannot be identified, the average number of carbon-carbon double bonds per molecule for the entire mixture And that is the number of carbon-carbon double bonds in component (A). If the number of carbon-carbon double bonds that are reactive with the SiH group of component (A) is 1 or less per molecule, only a graft structure is formed even if it reacts with component (B). Don't be.

 [0101] The component (A) preferably has fluidity at a temperature of 100 ° C or lower in order to obtain uniform mixing with other components and good workability. The component (A) may be linear or branched. The molecular weight of component (A) is not particularly limited, but any of 50 to LOOO can be preferably used. The component (A) preferably has a molecular weight of less than 900, more preferably less than 700, and even more preferably less than 500.

 [0102] As the component (A), from the viewpoint of availability and reactivity, bisphenol A diallyl ether, 2,2'-diallylbisphenol A, novolak phenol aryl ether, diallyl phthalate, burcyclohexene, dibi- Norebenzene, di-bibiphenol, trilinoleisocyanurate, diaryl ether of 2, 2 bis (4 hydroxycyclohexyl) propane, 1, 2, 4 Trivinylcyclohexane is preferred heat resistance 'Triallyl isocyanurate from the point of light resistance Is particularly preferred!

 Next, the component (B) in the silicone-based thermosetting resin is described.

[0104] The component (B) is not particularly limited as long as it is a compound containing at least two SiH groups in one molecule. For example, a compound described in International Publication W096Z15194, Those having at least two SiH groups in one molecule can be used.

[0105] From the viewpoint of availability, linear and Z- or cyclic organopolysiloxanes having at least two SiH groups in one molecule are preferable. Among these, from the viewpoint of good compatibility with the component (A), the following general formula (6)

[0106] [Chemical 6]

[In the formula, R ³ represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10], and has at least two SiH groups in one molecule. Cyclic polyorganosiloxane is more preferred. In addition, the substituent R ³ in the compound represented by the general formula (6) includes an element other than C, H, and O, preferably a substituent, and more preferably a hydrocarbon group.

 [0108] Component (B) is selected from a chain-like and Z- or cyclic polyorganosiloxane having at least two SiH groups in one molecule, and an organic compound having a carbon-carbon double bond having reactivity with SiH groups. A reaction product with one or more kinds of compounds (hereinafter referred to as component (E)) is also preferred. In this case, in order to further enhance the compatibility of the reactant with the component (A), a product obtained by removing unreacted siloxanes from the reactant by devolatilization or the like can be used.

[0109] The component (E) contains at least one carbon-carbon double bond reactive with the SiH group in one molecule. An organic compound containing the same component as the component (A) can be used.

[0110] From the viewpoint that the compatibility of the component (B) with the component (A) can be increased, preferred specific examples of the component (E) include triallyl isocyanurate, novolak phenol aryl ether, bisphenol A Diaryl ether, 2,2'-diarylbisphenol A, diallyl phthalate, bis (2-aryloxetyl) ester of phthalic acid, styrene, α-methylstyrene, aryl-terminated polypropylene oxide, polyethylene oxide, etc. Is mentioned. The organic compound (有機) may be used alone or in combination of two or more.

 [0111] The component (ii) may be used alone or in combination of two or more.

[0112] The viewpoint power that optical characteristics are good is also more preferable. (Β) The component includes a reaction product of 1, 3, 5, 7-tetramethylcyclotetrasiloxane and butylcyclohexene, 1, 3, 5, 7— Reaction of tetramethylcyclotetrasiloxane and dicyclopentagen, reaction of 1, 3, 5, 7-tetramethylcyclotetrasiloxane and triallyl isocyanurate, 1, 3, 5, 7-tetramethylcyclo Reaction of tetrasiloxane and 2,2 bis (4-hydroxycyclohexyl) propane diallyl ether, reaction of 1, 3, 5, 7-tetramethylcyclotetrasiloxane and 1, 2, 4-tributylcyclohexane Is mentioned. Particularly preferred (Β) components include a reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane and triallyl isocyanurate, 1,3,5,7-tetramethylcyclotetrasiloxane and 2,2 bis. Examples include a reaction product of (4-hydroxycyclohexyl) propane diallyl ether, a reaction product of 1,3,5,7-tetramethylcyclotetrasiloxane and 1,2,4 trivinylcyclohexane.

[0113] The mixing ratio of component (Α) and component (Β) is not particularly limited as long as the required strength is not lost! The specific force of the total number of SiH groups in the component (Β) (Υ) to the total number of carbon-carbon double bonds (X) in the component (Α) is 2.0≥Y / X≥0.9. 1. 8≥Υ / Χ≥1.0 is more preferred. If Υ / Χ> 2.0, sufficient curability may not be obtained and sufficient strength may not be obtained. If Y / X <0.9, the carbon-carbon double bond will be excessive and colored. Can be a cause of

 [0114] Next, the component (C) in the silicone-based thermosetting resin will be described.

[0115] The hydrosilylation catalyst as component (C) has a catalytic activity for the hydrosilylation reaction. Although not particularly limited, for example, a simple substance of platinum, a support of solid platinum on a support such as alumina, silica, or carbon black, a complex of chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone, or the like. , Platinum-olefin complexes (eg, Pt (CH = CH) (PPh)

 2 2 2 3 2

, Pt (CH = CH) CI), platinum-vinylsiloxane complexes (eg Pt (ViMe SiOSiM

 2 2 2 2 2 e Vi), Pt [(MeViSiO)]), platinum-phosphine complexes (eg Pt (PPh), Pt (PBu

2 n 4 m 3 4

)), Platinum monophosphite complex (eg Pt [P (OPh)], Pt [P (OBu)]) (where Me

3 4 3 4 3 4

 Represents a methyl group, Bu represents a butyl group, Vi represents a bull group, Ph represents a phenol group, and n and m represent integers. ), Dicarbo-dichloroplatinum, Karstedt catalyst, Ashby US Pat. No. 3159601, US Pat. No. 3159662, platinum-hydrocarbon complex, Lamoreaux Examples thereof include platinum alcoholate catalysts described in US Pat. No. 3,220,972. In addition, the salt-platinum-olefin complex described in Modic US Pat. No. 3516946 is also useful in the present invention.

[0116] Examples of hydrosilylation catalysts other than platinum compounds include RhCl (PPh), RhCl, RhAl

 3 3 2

O, RuCl, IrCl, FeCl, A1C1, PdCl · 20, NiCl, TiCl and the like.

 3 3 3 3 3 2 2 2 4

 Of these, chloroplatinic acid, platinum 1-year-old refin complex, platinum-bulusiloxane complex and the like are preferred from the viewpoint of catalytic activity. The hydrosilylation catalyst may be used alone or in combination of two or more.

[0118] The addition amount of the hydrosilylation catalyst is not particularly limited, but in order to have sufficient curability and keep the cost of the composition for optical materials relatively low, the preferred lower limit of the addition amount is (B) 10 to ⁸ mol, more preferably 10 to ⁶ mol, per mol of SiH group in the component, and the upper limit of the preferred amount of added calorie is 10 to ¹ mol per mol of SiH group of component (B). preferably ^10-2 mole.

[0119] In the resin composition for optical materials of the present invention, the lower limit of the content of the nanophosphor particles in 100% by weight of the composition is preferably 0.0001% by weight, more preferably 0.8%. 001% by weight, more preferably 0.01% by weight, and most preferably 0.1% by weight. The upper limit of the blending amount is preferably 95% by weight, more preferably 70% by weight, further preferably 50% by weight, and most preferably 20% by weight. If the content of the nanophosphor particles is less than 0.0001% by weight, there is a tendency that sufficient light emission intensity cannot be obtained. When the content is more than 95% by weight, it tends to be difficult to disperse the nanophosphor particles in the composition.

 [0120] An inorganic filler may be added to the composition for optical materials of the present invention as necessary. The addition of an organic filler is effective in preventing fluidity of the composition and increasing the strength of the material. As an inorganic filler, alumina, hydroxyaluminum, fused silica, crystalline silica, ultrafine powder amorphous silica, hydrophobic ultrafine silica, talc, sulfuric acid, which do not degrade optical properties and are preferred to be fine particles, are preferred. Barium etc. can be mentioned. Among them, it is preferable to use nanoparticles having a particle size of 0.1 nm to 100 nm because of excellent light transmittance. A more preferred particle size range is 1 nm to 50 nm, most preferred! /, And a particle size range is 2 nm to 20 nm.

 [0121] Examples of the method for adding the filler include hydrolyzable silane monomers or oligomers such as alkoxysilanes, acyloxysilanes, and halogenosilanes, and metal alkoxides, acyloxides, halides such as titanium and aluminum. Can be added to the composition of the present invention and reacted in the composition or a partial reaction product of the composition to form an inorganic filler in the composition.

[0122] In order to improve the properties of the optical material, various additives may be added to the resin composition for optical material of the present invention. Examples of additives include colorants such as bluing agents that absorb a specific wavelength, acid titanium such as acid titanium, acid aluminum, silica, and quartz glass for diffusing light, and talc. Various inorganic or organic diffusion materials such as calcium carbonate, melamine resin, CTU guanamine resin, benzoguanamine resin, glass, metal oxides such as aluminosilicate, metal nitride such as aluminum nitride, boron nitride, etc. The thermal conductivity of the filler can be mentioned. Additives for improving optical material characteristics may be contained uniformly, or may be contained with a gradient in content. As a method for curing the composition for optical elements of the present invention, the reaction can be carried out by simply mixing, or the reaction can be carried out by heating. If the reaction is fast and generally easy to obtain a material with high heat resistance, V, the method of reacting by heating the viewpoint power is preferred.

[0123] The reaction temperature can be variously set. For example, a temperature of 30 to 300 ° C can be applied, and 80 to 250 ° C is more preferable, and 100 to 200 ° C is more preferable. If the reaction temperature is low, the reaction time for sufficient reaction will be long, and if the reaction temperature is high, molding will tend to be difficult. [0124] The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. It is preferable that the reaction is carried out while increasing the temperature in a multistage or continuous manner rather than at a constant temperature, so that a uniform cured product can be obtained without distortion.

 [0125] Although various reaction times can be set, it is easier to obtain a uniform cured product without distortion by reacting at a relatively low temperature for a longer time than at a high temperature for a short time. I like it.

 [0126] The pressure during the reaction can be variously set as required, and the reaction can be carried out under normal pressure, high pressure, or reduced pressure. In terms of easy removal of volatile matter generated by hydrolysis condensation, the reaction is preferably carried out under reduced pressure.

 [0127] The shape of the optical material obtained by curing can be variously selected depending on the application, and is not particularly limited. For example, it may be a film, sheet, tube, rod, film, or butter shape. It can be a shape.

 [0128] Various molding methods can be employed including a conventional thermosetting resin molding method. For example, a molding method such as a casting method, a pressing method, a casting method, a transfer molding method, a coating method, or a RIM method can be applied. As the mold, polishing glass, hard stainless steel polishing plate, polycarbonate plate, polyethylene terephthalate plate, polymethyl methacrylate plate and the like can be applied. In addition, polyethylene terephthalate film, polycarbonate film, polychlorinated bure film, polyethylene film, polytetrafluoroethylene film, polypropylene film, polyimide film, etc. may be applied to improve the releasability from the mold. it can.

 [0129] Various treatments may be performed as necessary during molding. For example, a treatment for defoaming the composition or a partially reacted composition by centrifugation, decompression, etc., or a treatment for releasing pressure during pressing can be applied to suppress voids generated during molding. .

[0130] Various light emitting devices such as light emitting diodes can be produced using the resin composition for optical elements of the present invention. The light emitting device in this case can be manufactured by a method of coating the light emitting element with the resin composition for an optical element of the present invention. It is not limited to the law. The light-emitting element is not particularly limited, and a light-emitting element that can be used for a light-emitting device can be used. For example, it can be produced by laminating a semiconductor material on a substrate provided with a buffer layer of GaN, A1N or the like, if necessary, by various methods such as MOCVD, HDVPE, and liquid phase growth.

 [0131] The substrate is not particularly limited, and examples thereof include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. Of these, sapphire is preferable because GaN having good crystallinity can be easily formed and the industrial power is high.

 [0132] The semiconductor material to be laminated is not particularly limited, and examples thereof include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, A1N, InGaN, InGaAIN, and SiC. Of these, nitride-based compound semiconductors (inxGayAlzN) are preferred because of their high level of brightness. The semiconductor material may contain an activator or the like!

 [0133] The structure of the light-emitting element is not particularly limited, and examples thereof include a MIS junction, a pn junction, a homojunction having a PIN junction, a heterojunction, and a double heterostructure. It can also be a single or multiple quantum well structure.

 [0134] The light-emitting element may or may not be provided with a passivation layer. An electrode can be formed on the light emitting element by a conventionally known method.

 [0135] The electrode on the light-emitting element can be electrically connected to the lead terminal or the like by various methods. The electrical connection member is not particularly limited, but preferably has good ohmic mechanical connectivity with the electrode of the light emitting element, for example, bonding using gold, silver, copper, platinum, aluminum, or an alloy thereof. A wire etc. are mentioned. It is also possible to use a conductive adhesive filled with a resin filler such as silver or carbon. Of these, aluminum wire or gold wire is preferred from the viewpoint of good workability.

 Example

[0136] The ability to explain the present invention with reference to the following examples is not limited thereto. Measurement of the number average primary particle size of nanophosphor particles in an unaggregated state: Ultrasonic dispersion of an appropriate amount of nanophosphor particles in a dispersible solvent and then fixation on a mesh with a collodion film attached And observed with a transmission electron microscope (TEM). Use an electron micrograph to measure the particle size of 100 or more nanophosphor particles using a ruler with a scale. The number average primary particle diameter was measured by measuring.

[0137] Measurement of dispersion state of nano-phosphor particles in rosin composition: Ultrafine for TEM observation using ultramicrotome (Leica Ultracut UCT) from rosin composition obtained by the method shown in Examples After preparing a thin section, the dispersion state of the nanoparticles was photographed at a plurality of locations at a magnification of 100,000 to 400,000 using a transmission electron microscope (TEM) (JEOL JEM—1200 EX). Using multiple TEM photographs obtained, the number of independent particles that can be confirmed in the field of view is counted in the range of 100 m ² or more, and the number of particles that exist independently of the total number of particles is counted. The percentage was calculated.

 [0138] Measurement of emission wavelength: PERKIN—ELMER fluorometer LS55 was used. Particles dispersed in the solvent were placed in a quartz cell (12.5 X 12.5 X 45 mm). Measured the emission wavelength when irradiated with excitation light while still in a film or sheet.

 [0139] Visible light transmission measurement: 50mm X 50mm with 80t injection molding machine manufactured by Nissei Sewa Kogyo Co., Ltd.

 A test piece having a size of X 2 mm was formed. Using this test piece, the total light transmittance was measured based on ASTM D1003 under the conditions of a temperature of 23 ° C ± 2 ° C and a humidity of 50% ± 5% with a turbidimeter 300A manufactured by Nippon Denshoku Industries Co., Ltd.

 [0140] Measurement of molecular weight and molecular weight distribution: Water permeation gel permeation chromatography (GPC) system, Kuroguchi form solvent, Showa Denko Co., Ltd. Shodex K-805 and K-806 columns, RI detector Was used to measure the molecular weight calculated with polystyrene standard samples.

 [0141] The following were used as the undoped semiconductor nanophosphor particles consisting only of the host crystal:

• Undoped nanophosphor particles l (CdSe nanoparticles 1): synthesized according to Non-Patent Document 8. The number average primary particle size of CdSe particles by TEM observation was 5 nm. The shape was a spherical particle. When the toluene solution was irradiated with excitation light having a wavelength of 365 nm by a fluorometer, light was emitted with a peak wavelength of 595 nm and a half-value width of 40 nm.

• Undoped nanophosphor particle 2 (CdSe nanoparticle 2): M. Kawa et al., J. Nano part. Res., 5 卷, 81 (2003). TEM observation The number average primary particle size of these CdSe particles was 4 nm. The shape was a true spherical particle. Fluorometer When a toluene solution was irradiated with excitation light having a wavelength of 365 nm, light was emitted with a peak wavelength of 555 nm and a half-value width of 47 nm.

 • Undoped nanophosphor particle 3 (CdSe nanoparticle 3): synthesized according to Non-Patent Document 8. The number average primary particle size of CdSe particles by TEM observation was about 3 nm, and the shape was a true spherical particle. When the toluene solution was irradiated with excitation light having a wavelength of 365 nm by a fluorometer, the light emitted at a peak wavelength of 519 nm and a half-value width of 48 nm.

 • Non-doped nanophosphor particles 4 (CdSe core ZZnS shell composite nanoparticles): Manufactured according to Production Example 1 below.

 (Production Example 1)

In a brown glass flask filled with dry argon gas, put 15 g of trioctylphosphine oxide, and melt it at 130-150 ° C for about 2 hours while repeating vacuuming and injecting dry argon gas. Stir and dry the trioctylphosphine oxide. After cooling this to 100 ° C., a solution prepared by dissolving 0.094 g of CdSe nanoparticle solid powder in 1.5 g of trioctylphosphine was added to obtain a CdSe nanoparticle solution. This was stirred at 100 ° C. under reduced pressure for 60 minutes, the temperature was set to 180 ° C., and the pressure was returned to atmospheric pressure with dry argon gas. Separately, in a glove box with a dry nitrogen atmosphere, a raw material solution prepared by dissolving 1.34 mL of 1N n-hexane solution of jetyl zinc and 0.239 g of bis (trimethylsilyl) sulfide in 9 mL of trioctylphosphine was shielded from light. Prepared in a glass bottle. This raw material solution was dropped into the CdSe solution with a syringe over 20 minutes, and the temperature was lowered to 90 ° C. and stirring was continued for 60 minutes. After standing at room temperature for about 24 hours, the mixture was again heated and stirred at 90 ° C for 3 hours. To this, 8 mL of n-butanol was added and cooled to room temperature to obtain a transparent red solution. A part of this red solution (8 mL) was dropped into 16 mL of anhydrous methanol at room temperature under a dry nitrogen stream, and a red insoluble matter was obtained by precipitation operation in which stirring was continued for 20 minutes. This red insoluble matter was separated by centrifugation and decantation, and redissolved in 14 mL of purified toluene. This re-dissolved toluene solution power The core-shell type CdSe nanoparticle solid powder having a ZnS shell was obtained by repeating the same series of purification operations such as precipitation, centrifugation, and decantation again twice. . The particle size by TEM observation is about 3ηπ! The number average primary particle size was 4.5 nm and the shape was a true spherical particle. This When the body powder was dispersed in toluene, it became a homogeneous solution, and when irradiated with excitation light having a wavelength of 468 nm, light was emitted with a peak wavelength of 555 nm and a half-value width of 96 nm.

[0143] The following were used as doped semiconductor nanophosphor particles in which luminescent ions were added to the host crystal.

 • Doped nanophosphor particles 5 (Y O: Eu nanoparticles): B. Xia et al., Adv. Mater

 twenty three

 , 13 (20), 1579 (2001), H. Chang et al., Jpn. J. Appl. Phy s., 43 (6A), 3535 (2004). Y O: Eu by TEM observation

 The number average primary particle size of the 2 3 particles was about 40 nm and the shape was almost spherical. When irradiating excitation light with a wavelength of 365 nm with a fluorimeter, it emits light with a peak wavelength of 611 nm and a half-value width of 20 ηm.

 • Doped nanophosphor particles 6 (LaPO: Ce, Tb nanoparticles): B. Xia et al., Adv.

 Four

 Mater., 13 (20), 1579 (2001), I. W. Lenggoro et al., Mater. Lett., 50, 92 (2001). LaPO: Ce, Tb by TEM observation

 The number average primary particle size of the 4 particles was about 23 nm and the shape was almost spherical. When irradiating 365nm wavelength excitation light with a fluorometer, the peak wavelength is 543nm and the half-value width is 21ηm.

 • Doped nanophosphor particles 7 (BaMgAl 2 O: Eu, Mn nanoparticles): B. Xia et al.,

 10 17

 Adv. Mater., 13 (20), 1579 (2001), Y. C. Kang et al., Appl.

Phys. A, 72 (1), 103 (2001). Number average primary particle diameter of BaM gAl 2 O: Eu, Mn particles by TEM observation is about 27nm, and the shape is almost spherical.

10 17

 Met. When excitation light with a wavelength of 365 nm was irradiated with a fluorimeter, it emitted light with a peak wavelength of 486 nm and a half-value width of 26 nm.

[0144] Bulle polymers having an SH group at the end were produced according to Production Examples 2-3.

[0145] (Production example 2)

 Production of poly (methyl methacrylate) containing terminal SH groups

In a reactor equipped with a reflux condenser, nitrogen gas inlet tube, thermometer, and magnetic stirrer, 1.21 g of 2- (2-phenolpropyl) dithiobenzoate as a chain transfer agent and 2, 2, as a polymerization initiator —Azobisisopetite-tolyl 0.27 g was weighed. Methacryl as monomer in a separate container 149.9 g of methyl acid and 149.2 g of toluene as a solvent were weighed, both containers were connected with a cannula, and deoxygenation and nitrogen substitution were performed by reducing the pressure in the system while introducing nitrogen gas. About 1Z10 of methyl methacrylate Z toluene solution was transferred to the reactor through cannula and heated to 70 ° C. with stirring. After 1 hour, the remaining methyl methacrylate / toluene solution was added slowly. After completion of the addition over 3 hours, the mixture was further stirred at 70 ° C for 7 hours. The reaction solution was poured into 2 L of methanol to precipitate a polymer, further washed with methanol and dried to obtain 78.2 g of polymethyl methacrylate having a thiothio group at one end. The obtained polymer was dissolved in 220 mL of toluene, 45.5 g of n-butylamine was added, stirred at room temperature for 30 hours, and then poured into 2 L of methanol to precipitate the polymer. Furthermore, it was washed with methanol and dried to obtain 74. lg of polymethyl methacrylate having an SH group at one end. The molecular weight was Mw = 25,000, Mn = 21100, Mw / Mn = l.19. The sulfur content measured by the oxygen flame combustion method was 0.25% by weight before the addition of the amine and 0.14% by weight after the amine treatment. The total light transmittance was 93% of a polymer that transmitted visible light.

[0146] (Production Example 3)

 Production of n-butyl polyacrylate containing terminal SH groups

 Poly-n-butyl acrylate having an SH group at one end was obtained in substantially the same manner as in Production Example 8 except that n-butyl acrylate was used instead of methyl methacrylate as the monomer. The molecular weights were Mw = 22000, Mn = 18000, Mw / Mn = 1.22. It was a polymer that transmitted visible light with a total light transmittance of 87%.

[0147] A partially cured product of a silicone-based thermosetting resin was produced according to Production Example 4.

[0148] (Production Example 4)

 Manufacture of partially cured silicone thermosetting resin

To a 5 L separable flask was added 1.8 L of toluene and 1.44 kg of 1,3,5,7-tetramethylcyclotetrasiloxane, and the mixture was heated to an internal temperature of 104 ° C. Thereto was added dropwise a mixture of 200 g of triallyl isocyanurate, 1.44 mL of a platinum butylsiloxane complex in xylene solution (containing 3 wt% as platinum) and 200 mL of toluene. The mixture was heated to reflux in an oil bath at 120 ° C for 7 hours. 1-Lu 1-cyclohexanol 1.7 g was added. Unreacted 1 , 3, 5, 7-Tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. According to 1H-NMR, this was obtained by reacting part of the SiH group of 1, 3, 5, 7-tetramethylcyclotetrasiloxane with triallyl isocyanurate (referred to as partial reactant A, SiH value: 9. Omm ol / g, aryl value: 0.13 mmol Zg).

 [Example 1]

 2g of undoped nanophosphor particle 1, 2g of undoped nanophosphor particle 2, 2g of undoped nanophosphor particle 3, 200g of terminal SH group-containing polymethyl methacrylate obtained in Production Example 2 All were dissolved in 5.5 L of toluene, and 80 W 38 kHz ultrasonic waves were irradiated through the temperature-controlled water in the water tank while stirring at 23 ° C. in the water tank. After stirring for 24 hours and ultrasonic irradiation, 20 L of anhydrous methanol was injected to produce insoluble matter. This insoluble matter was separated from the supernatant by centrifugation and vacuum-dried at room temperature for about 1 day to obtain a surface-modified CdSe nanoparticle solid powder. The obtained surface-modified nanoparticles were dispersed in 5.5 L of toluene, and after adding 400 g of terminal SH group-containing polymethyl methacrylate obtained in Production Example 2, the temperature was adjusted to 20 ° C. in a water bath. While stirring, an ultrasonic wave of 80W38kHz was irradiated through the temperature-controlled water in the water tank. A toluene solution of CdSe nanophosphor particles whose surface was modified with a polymer was obtained by allowing the mixture to stand for 24 hours after stirring and ultrasonic irradiation.

 [0150] This solution was uniformly applied to an evaporating dish, and the solvent was evaporated and dried for about one day to obtain a PMMA resin film in which non-dope nanophosphor particles were dispersed. The appearance of the obtained film was uniform and transparent, and the average thickness was 60 m. When the obtained resin film was irradiated with excitation light having a wavelength of 365 ηm, it emitted white light. Figure 1 shows the TEM observation results of the obtained resin film.

 [0151] (Example 2)

 Undoped nanophosphor particles Dispersed undoped nanophosphor particles in the same manner as in Example 1 except that the undoped nanophosphor particles 4 obtained in Production Example 1 were used instead of the three types. A PMMA resin film was obtained. The appearance of the obtained film was uniform and transparent, and the average thickness was 60 m. When the obtained resin film was irradiated with excitation light having a wavelength of 468 nm, light was emitted almost white.

[0152] (Example 3) 9.9 g of triallyl isocyanurate, 70 mg of a platinum butylsiloxane complex in xylene solution (containing 3 wt% as platinum), 13.9 g of the partial reaction product A obtained in Production Example 4, and 1% obtained in Example 1 A pulverized product of a fat film 1.2 g (containing 5 wt%) and 70 mg of 1-etul-1-cyclohexanol were stirred and degassed at 23 ° C. Pour this into a cell made by sandwiching a 3 mm thick silicone rubber sheet between two glass plates as a spacer, 60 ° CZ6 hours, 70 ° CZl hours, 80 ° CZl hours, 100 ° CZl hours air Heating was performed in the middle to obtain a colorless and transparent sheet-like cured product. When the obtained sheet was irradiated with excitation light having a wavelength of 365 nm, white light was emitted.

 [Example 4]

 Instead of the terminal SH group-containing polymethyl methacrylate obtained in Production Example 2, the terminal SH group-containing poly (n-butyl acrylate) obtained in Production Example 3 was used as the bull polymer having an SH group at the terminal. In the same manner as in Example 1 except for the above, an n-butyl acrylate resin film in which undoped nanophosphor particles were dispersed was obtained. The appearance of the obtained film was uniformly transparent, and the average thickness was 60 m. When the obtained resin film was irradiated with excitation light having a wavelength of 365 nm, it emitted white light.

 [Example 5]

 A colorless and transparent sheet-like cured product was obtained in the same manner as in Example 3, except that the pulverized product of the mortar film obtained in Example 4 was used instead of the mortar film obtained in Example 1. When the obtained sheet was irradiated with excitation light having a wavelength of 365 nm, it emitted white light.

 [0155] (Example 6)

 Undoped nanophosphor particles Instead of 3 types, doped nanophosphor particles 5 2. Og, doped nanophosphor particles 6 2. Og, doped nanophosphor particles 7 Og, total 6. A PMMA resin film in which doped nanophosphor particles were dispersed was obtained in the same manner as in Example 1 except that Og was used. The appearance of the obtained film was uniform and transparent, and the average thickness was 60 m. When the obtained resin film was irradiated with 365 nm wavelength excitation light, it emitted white light

[Example 7]

The powder of the resin film obtained in Example 6 instead of the resin film obtained in Example 1 A colorless and transparent sheet-like cured product was obtained in the same manner as in Example 3 except that 1.2 g of crushed material was used. When the obtained sheet was irradiated with excitation light having a wavelength of 365 nm, it emitted white light.

 [Example 8]

 The sheet-like cured product prepared in Example 7 is cut into an appropriate shape and fixed to a light transmitting window provided on a can-type metal cap. On the other hand, a double heterostructure light-emitting device formed on a sapphire substrate by MOCVD (metal organic vapor phase epitaxy) method, with an InGaN active layer doped with Si and Zn sandwiched between n-type and p-type AlGaN cladding layers Prepare. Next, this light-emitting element is placed on a can-type metal stem, and then p-electrode and n-electrode are wire-bonded to each lead with Au wire. This is hermetically sealed with the above-described metal cap for can type. In this way, a can-type light emitting diode could be produced.

 [0158] (Comparative Example 1)

 Instead of polymethylmethacrylate containing terminal SH groups used in Example 1, ordinary PMMA resin having no SH group at the terminal (Aldrich, Mw = 120,000, total light transmittance 93%) A PMMA resin film containing undoped nanophosphor particles was obtained in the same manner as Example 1 except that was used. The appearance of the film was colored and opaque and hardly transmitted visible light. The obtained resin film was irradiated with excitation light with a wavelength of 365 nm with a fluorometer, but it did not emit light.

 [0159] (Comparative Example 2)

2 g of undoped nanophosphor particle 1, 2 g of undoped nanophosphor particle 2, 2 g of undoped nanophosphor particle 3, 12 g of dodecanethiol 12 g in toluene 5.5 3 While stirring while adjusting the temperature to ° C, 80 W 38 kHz ultrasonic waves were irradiated through the temperature-controlled water in the water tank. After stirring for 24 hours and ultrasonic irradiation, 20 L of anhydrous methanol was injected to produce insoluble matter. This insoluble material was separated from the supernatant by centrifugation and vacuum-dried at room temperature for about 1 day to obtain a surface-modified CdSe nanoparticle solid powder. The obtained surface-modified nanoparticles are dispersed in 5.5 L of toluene, and further, ordinary PMMA resin having no SH group at the end (Aldrich, Mw = 120,000, total light transmittance 93%) By adding 588 g and stirring, a toluene solution of PMMA resin containing surface-modified CdSe nanophosphor particles was obtained. [0160] This solution was uniformly applied to an evaporating dish, and the solvent was evaporated and dried for about one day to obtain a PMMA resin film containing non-dope nanophosphor particles. The appearance of the obtained resin film was such that the particles were agglomerated so that the agglomerated portion of the particles could be visually confirmed, and had a non-uniform appearance, and the average thickness was 60 m. Even when the obtained resin film was irradiated with excitation light having a wavelength of 365 nm with a fluorometer, no clear emission peak was observed. Figure 2 shows the TEM observation results of the obtained resin film.

 [0161] (Comparative Example 3)

 Instead of the three types of doped nanophosphor particles used in Example 6, three types of commercially available blue butterfly phosphor, green butterfly phosphor, and red butterfly phosphor (all manufactured by Kasei Optonitas Co., Ltd.) A PMMA resin film in which Balta phosphor particles were dispersed was obtained in the same manner as in Example 6 except that 2. Og of each was added. When the obtained resin film was irradiated with excitation light having a wavelength of 365 nm with a fluorimeter, white light was emitted as in Example 6, but when the excitation light was continuously irradiated, the temperature gradually increased due to heat generation, After continuous irradiation for 1 hour, the resin began to dissolve due to heat generation.

 Industrial applicability

[0162] By using the composition of the present invention, it is possible to exhibit excellent luminous efficiency by dispersing nanophosphor particles much smaller than the conventional Balta phosphor without aggregation in the polymer. The rosin composition for optical materials can be obtained. A light emitting device using this composition can greatly improve the light emission efficiency as compared with the conventional one, so that it can be expected to be widely used as a future lighting material and is very useful industrially.

Claims

The scope of the claims

 [1] Number average primary particle size is 0. Inn! A resin composition for an optical material, characterized in that nano-phosphor particles of ~ lOOnm are modified with a vinyl polymer having an SH group at the end and dispersed in the polymer.

 [2] The resin composition for an optical material according to claim 1, wherein the number average molecular weight of the bull polymer having an SH group at the terminal is 2000 or more and 100000 or less.

[3] The optical material cage according to claim 1 or 2, wherein the vinyl polymer having a terminal SH group has a molecular weight distribution represented by a ratio of a weight average molecular weight to a number average molecular weight of 1.5 or less. Fat composition.

 [4] Bull-type polymer with terminal SH group Acrylic acid, methacrylic acid, metal acrylate, metal methacrylate, acrylate, methacrylate, styrene, Atari nitrile, butyl acetate, butyl chloride, N-alkylacrylamide, N-alkylmethacrylamide, N, N-dialkylacrylamide, N, N-dialkylmethacrylamide, N-bulupyridine, 2-bulupyridine, 4-bulupyridine, maleic anhydride, maleimide, power 4. The resin composition for optical materials according to any one of claims 1 to 3, which is obtained by radical polymerization of one or more monomers selected from compounds.

 [5] The resin composition for an optical material according to any one of [1] to [4], wherein the vinyl polymer having a terminal SH group is a polymer that transmits visible light.

 [6] The vinyl polymer having a terminal SH group is obtained by treating a polymer that is polymerized by reversible addition / elimination chain transfer polymerization with a treating agent. The resin composition for optical materials described in 1.

 [7] The number average primary particle size of nanophosphor particles in an unaggregated state is Inn! The resin composition for optical materials according to any one of claims 1 to 6, which is ˜30 nm.

 [8] The emission peak wavelength of nanophosphor particles is in the wavelength range of 380 nm to 800 nm, and it is powerful 200 ηπ! The resin composition for an optical material according to any one of claims 1 to 7, which is a particle capable of emitting light by irradiating light in a wavelength region of ~ 500 nm.

[9] The resin composition for an optical material according to any one of [1] to [8], wherein the nanophosphor particles are non-doped semiconductor nanophosphor particles having only a host crystal force.

[10] The resin composition for an optical material according to any one of [1] to [8], wherein the nanophosphor particles are doped semiconductor nanophosphor particles in which a luminescent ion is added to a host crystal.

 [11] The optical material according to any one of [1] to [10], wherein nanophosphor particles modified with a vinyl polymer having an SH group at a terminal are mixed with a thermosetting resin. A rosin composition.

 12. The resin composition for an optical material according to claim 11, wherein the thermosetting resin is a silicon-based thermosetting resin.

 [13] The silicon-based thermosetting resin is (A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (B) at least in one molecule. 13. A resin composition for an optical material according to claim 11 or 12, which is a silicone-based thermosetting resin comprising a silicon compound containing two SiH groups and (C) a hydrosilylation catalyst. object.

 [14] A light-emitting device using the resin composition for optical material according to any one of claims 1 to 13.