JP4733402B2 - Light control optical element - Google Patents

Description

  The present invention is a light control optical element that controls light transmission, refraction, light collection, diffusion, and the like while controlling light transmittance or absorbance of a specific wavelength or wavelength body.

  The vision, the sense of hearing, the sense of skin, the sense of smell, and the sense of taste that have been called “the five senses” for a long time are said to be that 80% of the information we obtain from the environment outside the human body is obtained through vision. It is an inseparable sense of life. (Non-Patent Document 1) As human organs that control this vision, in addition to the eyes, it is known that the pineal body of the brain and the hypothalamus are light receptors. As the French philosopher Descartes referred to as “the seat of the spirit”, it is closely related to the human spirit and physiology. (Non-patent document 2) This means that even if it is natural light, the midsummer sunlight that shines is dazzling and uncomfortable, and foods illuminated by white fluorescent light, which is artificial light, are also slightly reddish. By making it light, it feels delicious and enhances appetite, making it extremely familiar in human daily life.

  On the other hand, light can be received by humans through various optical elements that control light transmission, refraction, collection, diffusion, and the like. Optical elements include, for example, lenses used for eyeglasses, covers and lighting windows used for various lighting fixtures, optical filters used for television receivers, and windows or lenses used for industrial and medical goggles such as welding. Although not limited to these examples, it has an important function of controlling light transmission, refraction, light collection, diffusion, and the like in various optical instruments. Such optical elements usually have a high transmittance for visible light, but control the transmittance or absorbance of natural light and various artificial light, such as dimming lenses and dimming glass. Many optical elements used for the purpose are collectively referred to as light control optical elements.

  Among the lenses for eyeglasses exemplified above, the lens for sunglasses reduces the discomfort of dazzling by reducing the strong light amount, and is the most representative example of the light control optical element. Particularly, sunglasses with a high antiglare effect can be obtained by reducing the amount of light having a wavelength of 400 to 500 nm. Specific for visually impaired people who have the same spectacle lens but have a sensitivity curve that is different from the sensitivity curve of the normal human eye, which can make color identification difficult There is a correction lens that adjusts the light transmittance in accordance with the visual sensitivity of the visually impaired person by selectively increasing the absorbance with respect to light having a wavelength of. Of the illumination windows or covers exemplified above, with respect to illumination using a halogen lamp such as an automobile headlight, a window with a high antiglare effect can be obtained by suppressing the transmittance of light having a wavelength of about 560 to 600 nm. A cover is obtained.

  As described above, as a technique for controlling the transmittance or absorbance of light having a specific wavelength or wavelength band, a technique is known in which various light-absorbing materials such as dyes are doped into a material that forms an optical element. Among them, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium or / and the fourth period The transition metals vanadium, chromium, manganese, iron, cobalt, nickel, and copper exhibit a steep and large absorption spectrum in the specific wavelength band for each element, so light of a specific wavelength or wavelength band depends on the application and purpose. It is known that it is excellent as a dope material for controlling the transmittance or the absorbance. As an invention using the characteristics of such a rare earth metal and / or the fourth period transition metal, a contrast-enhancing glass obtained by doping neodymium oxide (Nd2O3) into glass and a lens using the same (Patent Document 1) 2), windows (see Patent Document 3), automotive headlights (see Patent Document 4), optical filters in which various rare earth elements such as holmium, praseodymium, dysprosium are doped into glass (see Patent Document 5), etc. Has been.

On the other hand, as materials for various optical elements that control light transmission, refraction, condensing, diffusion, etc., polymer materials that are excellent in molding processability, economy, and lightness are spreading, and light weight for glasses It is an indispensable material technology for modern society, such as lenses and lenses for optical disk devices. Accordingly, an optical element doped with a rare earth metal and / or a fourth periodic transition metal as seen in the previous paragraph is also required to use a polymer material.
However, since the rare earth metal and / or the fourth period transition metal has a property that it is difficult to dissolve and disperse in an organic medium, a polymer material that expresses light transmission / absorption characteristics peculiar to rare earth is used as a base material. This has hindered the practical application of optical elements.

  In order to solve such problems, conventionally, (a) a complex of an organic ligand such as pyridines, phenanthrolines, quinolines, β-diketones and the like and a rare earth metal or / and a fourth periodic transition metal is formed. (B) Disperse the rare earth metal or / and the fourth periodic transition metal in the organic inclusion compound and then disperse the rare earth metal or / and the fourth periodic transition metal in the organic medium. (C) An organic-inorganic composite synthesis method has been proposed, for example, in which a polymer is produced using a polysynthetic monomer of a rare earth metal and / or a fourth period transition metal.

The techniques (a) and (b) are not necessarily intended for application to the light control optical element intended by the present invention, but many proposals such as Non-Patent Documents 3 and 4 have been made. ing. However, when these methods are used, absorption in the ultraviolet region derived from organic ligands and organic inclusion compounds tends to increase, and energy transfer from organic ligands and organic inclusion compounds to the base polymer material In addition, there is a problem of inducing ultraviolet degradation of the base polymer material due to generation of radicals accompanying molecular chain breakage in organic ligands and organic inclusion compounds. In addition, many of such organic ligands and organic inclusion compounds are expensive in raw materials, which impairs the high economic efficiency that is characteristic of polymer optical elements.
In addition, as the method (c), a rare earth metal (meth) acrylate, hydroxyalkyl (meth) acrylate, phthalic acid, and a polymerizable monomer copolymerizable therewith are mixed and polymerized. A method of generating is known. However, when this method is used, the polymer material that can be used as the base material is limited to a very limited polymer such as an acrylic resin or a styrene resin. There remains a problem that it is not possible to satisfy the needs for polymer optical elements that have been developed using various polymer materials such as olefin resin, polyester resin, and epoxy resin as a base material.

Japanese Patent Application Laid-Open No. 08-301632 US Pat. No. 6,604,824 US Pat. No. 6,416,867 US Pat. No. 5,916,208 US Pat. No. 4,106,857 JP 2004-226913 A Takao Matsuda “Visual Perception” Baifukan (1995) Oishi Tadashi “Light and Human” Asakura Shoten (1999) L. H. Slooff et al., Journal of Applied Physics, 83, 497 (1998). Y. Hasegawa et al., Chemistry Letters, (1999), p. 35.

  As described above, methods for synthesizing organic-inorganic composites in which rare earth metals and / or fourth-period transition metals are doped into organic polymers by various methods have been proposed. Suppression of deterioration of the base polymer material, high concentration doping of rare earth metal and / or fourth period transition metal into various polymer materials, and further, molding processability and light weight characteristic of polymer optical elements No material is known that can be used as a dimming optical element while satisfying all five points of ensuring economic efficiency.

  The present invention has been made in view of the circumstances as described above, and its purpose is (1) high-concentration doping of rare earth metals and / or fourth period transition metals, and (2) matrix polymer materials. (3) A specific wavelength or wavelength band using rare earth metals and / or fourth-period transition metal-containing organic-inorganic composites that ensure high moldability, lightness, and economy. It is providing the light control optical element used in order to control the transmittance | permeability and light absorbency of light.

The inventors of the present application have made extensive studies in order to achieve the above object. As a result, the inventors have found that the above object can be achieved by applying the organic-inorganic composite or the like invented by the present inventors and filed in Japanese Patent Application No. 2004-197711, and have completed the present invention.
That is, in the light control optical element according to the present invention, an inorganic dispersed phase in which another metal species is coordinated to the rare earth metal or / and the fourth period transition metal via oxygen is combined with the organic polymer. An optical element using a rare earth metal and / or a fourth periodic transition metal-containing organic-inorganic composite. As a result, a high concentration doping of rare earth metal and / or fourth period transition metal becomes possible. Further, even if the absorption of the rare earth metal and / or the fourth periodic transition metal itself is in the ultraviolet region, the excited state energy of the rare earth metal that has absorbed the ultraviolet light is coordinated with another metal via oxygen. It is not transferred to the matrix polymer material via the ligand of the present invention, and radical generation due to the cleavage of the ligand itself does not occur. Furthermore, the raw materials necessary for the practice of the present invention are highly available and economical, and can be doped with rare earth metals and / or fourth period transition metals into various polymer materials. It does not impair the characteristics, such as economy, moldability, and lightness.

  In order to solve the above-described problem, the light control optical element according to claim 1 is a composite in which at least one rare earth metal and / or a fourth periodic transition metal is dispersed in an organic polymer. The rare earth metal and / or the fourth periodic transition metal is characterized in that another metal species is coordinated via oxygen.

  According to said structure, high concentration dope in an organic polymer is attained by coordinating another metal seed | species via oxygen with rare earth metal and / or 4th period transition metal. Further, other metal species are coordinated via oxygen, thereby suppressing energy transfer between the CH group or OH group in the organic polymer and the rare earth metal.

  Application of coordination compounds for the purpose of dispersing rare earth metals and / or fourth period transition metals in organic polymers is also described in the above prior art, and generally oxygen or nitrogen capable of metal coordination. The coordination of the organic compound takes place via However, coordination with an organic compound as a ligand can suppress energy transfer between the CH group or OH group in the organic polymer shown above and the rare earth metal or / and the fourth period transition metal. I can't.

In the present invention, the rare earth metal is coordinated through oxygen bonded to other metal species.
The inorganic dispersed phase of the present invention is schematically shown in FIG. As shown in the figure, the rare earth metal and / or the fourth period transition metal-containing organic-inorganic composite used in the light control optical element of the present invention is coordinated with other metal species (3) via oxygen. Formed of a complex including an inorganic dispersed phase composed of a rare earth metal or / and a fourth periodic transition metal (2) and an organic polymer (not shown). Here, what is important in the dispersed phase is to reduce as much as possible the presence of the same kind of rare earth metal and / or fourth-period transition metal at adjacent positions via oxygen. Therefore, the number and species of ligands composed of oxygen and other metal species are not fixed, and are not strictly limited to the molecular structure as shown in FIG .
When the organic polymer according to the present invention is used for an optical material or the like, it is desirably optically transparent (transmittance). Although the transmittance | permeability of an organic polymer will not be specifically limited if it is the range which has permeability | transmittance, it is preferable that it is 30-100% as a transmittance | permeability, and it is more preferable that it is 80-100%.
In addition, the rare earth metal and / or the fourth periodic transition metal-containing organic-inorganic composite used in the light control optical element of the present invention can reduce the presence of the same kind of rare earth metal at an adjacent position through oxygen as much as possible. If possible, it is also possible to take a meeting structure. Here, R in FIG. 2 is an alkylcarbonyl group such as an alkyl group or an acetyl group, hydrogen or the like.

The dimming optical element according to claim 2 has a diameter of the entire inorganic dispersed phase obtained by coordinating a rare earth metal and / or a fourth periodic transition metal and other metal species to this via oxygen. It is characterized by being.
According to the above configuration, the rare earth metal or the rare earth metal dispersed phase formed by coordinating the other metal with the rare earth metal or / and the fourth period transition metal via oxygen is within the above range. Since the same diameter is relatively smaller than the wavelength of light transmitted through the / and fourth-period transition metal-containing organic / inorganic composite, the rare earth or / and the fourth-period transition metal-containing organic / inorganic composite is highly transparent. Sex can be secured.

In the light control optical element according to claim 3, in order to solve the above-mentioned problem, the ratio of the rare earth metal and / or the fourth period transition metal is, in terms of solid content, the organic polymer, the rare earth metal, and the It is characterized by being 90% by weight or less of the total amount of the inorganic dispersed phase formed by coordination of other metal species with oxygen.
According to the above configuration, there is no light scattering loss due to secondary aggregation of rare earth metals in which other metal species are coordinated via oxygen, and high light transmission in an optical function application field deeply related to the present invention. Sex can be expressed.

In the light control optical element according to claim 4, in order to solve the above problems, the metal coordinated to the rare earth metal and / or the fourth period transition metal via oxygen is a group 3B, 4A, or 5A. It is characterized by being one or more elements selected from the group consisting of metals.
According to the above configuration, the coordination of other metal species to the rare earth metal via oxygen is facilitated, the dispersion in the organic polymer, and the emission process of the rare earth metal and / or the fourth period transition metal It can effectively suppress quenching.

The dimming optical element according to claim 5 is obtained by coordinating a rare earth metal or / and a fourth periodic transition metal and another metal species to the rare earth metal or / and the fourth periodic transition metal via oxygen. The inorganic dispersed phase is formed of a rare earth metal salt and another metal alkoxide.
With the above configuration, a dispersed phase in which other metal species are coordinated to the rare earth metal and / or the fourth period transition metal via oxygen is efficiently formed.

As described above, the rare earth or / and the fourth periodic transition metal-containing organic-inorganic composite used in the light control optical element of the present invention has other metal species in the rare earth metal or / and the fourth periodic transition metal via oxygen. And a dispersed phase containing a rare earth metal coordinated and / or a fourth periodic transition metal, and an organic polymer.
Therefore, it is highly doped with rare earth metals, and does not induce degradation of the matrix polymer material due to energy transfer of absorbed ultraviolet light or molecular chain breakage, and optical transparency and specific wavelength. Alternatively, there is an effect that it is possible to provide a light-modulating optical element that can ensure transmission and absorption control for light in the wavelength band.

  The dimming optical element of the present invention is a general term for optical elements having an important function of controlling light transmission, refraction, light collection, diffusion, and the like in various optical instruments. Such dimming optical elements usually have a high transmittance for visible light, but control the transmittance or absorbance of natural light and various artificial light, such as dimming lenses and dimming glass It can be used for the purpose.

  FIGS. 1A to 1D are explanatory views showing representative examples of the light control optical element of the present invention. In FIG. 1A, the light control optical element is used as a lens 1a for a spectacle lens. In FIG.1 (b), a light control optical element is the cover 1b (or illumination window) used for various lighting fixtures. FIG.1 (c) is a figure which shows the lens 1c (or window) used for goggles, such as industry, medical treatment, such as welding. FIG. 1D is a diagram in which the light control optical element is an optical filter 1d used in a television receiver.

  Of the lens 1a for spectacles shown in FIG. 1A, the lens for sunglasses reduces the unpleasant feeling of dazzling by reducing the strong light quantity, and is the most representative example of the light control optical element. is there. Particularly, sunglasses with a high antiglare effect can be obtained by reducing the amount of light having a wavelength of 400 to 500 nm. Specific for visually impaired people who have the same spectacle lens but have a sensitivity curve that is different from the sensitivity curve of the normal human eye, which can make color identification difficult There is a correction lens that adjusts the light transmittance in accordance with the visual sensitivity of the visually impaired person by selectively increasing the absorbance with respect to light having a wavelength of. In the illumination window or cover shown in FIG. 1B, the antiglare effect is achieved by suppressing the transmittance of light having a wavelength of about 560 to 600 nm for illumination using a halogen lamp such as an automobile headlight. High windows and covers.

  The rare earth metal and / or the fourth period transition metal-containing organic-inorganic composite used in the light modulating optical element of the present invention is capable of transmitting, refracting light while controlling the light transmittance or absorbance of a specific wavelength or wavelength body. Rare earth metal or / and a composite of a fourth periodic transition metal and an organic polymer that is suitably used for a light control optical element that controls light collection, diffusion, etc., and other metal species coordinate via oxygen. An inorganic dispersed phase (rare earth metal or / and a fourth periodic transition metal dispersed phase) and an organic polymer are included.

The constitution of the rare earth metal or / and fourth period transition metal-containing organic-inorganic composite used in the light control optical element of the present invention includes rare earth metal or / and fourth period transition metal, rare earth metal or / and fourth period transition. Any combination may be used as long as it is a complex including a metal capable of coordinating to oxygen via oxygen and an organic polymer.
A method for forming an inorganic dispersed phase in which other metal species are coordinated to oxygen through rare earth metal and / or the fourth period transition metal is not particularly limited. For example, rare earth metal salt and metal alkoxide Formed by the reaction of

  A composite of an inorganic dispersed phase coordinated to another metal via oxygen and an organic polymer is formed, for example, by a reaction between the metal alkoxide and a rare earth metal salt or / and a fourth period transition metal salt. It can be adjusted by mixing and dispersing the inorganic dispersed phase and the organic polymer.

[Rare earth metal]
Examples of rare earth metals include scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
[Fourth transition metal]
As the fourth period transition metal, vanadium, chromium, manganese, iron, cobalt, nickel, or copper is used.

Any one of the rare earth metal and the fourth period transition metal may be used, or two or more of them may be used in combination.
[Other metal species coordinated to rare earth metal and / or fourth period transition metal via oxygen]
Other metal species are elements that can be coordinated to the rare earth metal via oxygen, and are not particularly limited as long as the target properties are not adversely affected. Preferably, Group 3B, Group 4A, and Group 5A metals are used. It is done. More preferably, aluminum, gallium, titanium, zirconium, niobium, or tantalum is used.

[Preparation of inorganic dispersed phase]
The method for forming the inorganic dispersed phase is not particularly limited as long as the metal coordination via oxygen to the target rare earth can be formed. For example, a method of mixing a rare earth or / and a fourth period transition metal raw material and a coordinating metal raw material, followed by heat treatment and pulverization (starting raw materials include metal salts, hydroxides, oxides, etc.) , A method of dissolving a rare earth metal salt or / and a metal salt capable of coordinating with a fourth period transition metal salt in a solvent, and then precipitating by precipitation, a rare earth metal salt and / or a fourth period transition metal in an organic solvent There is a method of reacting a salt and a metal alkoxide capable of coordination.

  In order to obtain a nanometer-sized rare earth metal or / and a fourth periodic transition metal dispersed phase, a method of reacting a rare earth metal salt or / and a fourth periodic transition metal salt with a metal alkoxide capable of coordination in an organic solvent. Are preferably used. The solvent to be used is not particularly limited, and any solvent may be used as long as the final product having a coordination structure can be dispersed in the organic polymer. Examples of such solvents include primary alcohols such as methanol, ethanol, 1 propanol, 2 propanol, 1 butanol, 2 butanol, and t butanol; polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; ethylene glycol monomethyl ether Glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol-α-monomethyl ether, propylene glycol α-monoethyl ether; ketones such as acetone and methyl ethyl ketone; cyclic ethers such as tetrahydrofuran and dioxane; acetic acid Esters such as methyl, ethyl acetate and propyl acetate; Aromatic compounds such as acetonitrile, benzene, toluene and xylene; Pentane Hexane, heptane, hydrocarbon compounds such as cyclohexane; and the like are used.

  In order to form the coordination compound, it is possible to use a method of heating to the reflux temperature of the solvent, and this method is effective because it can accelerate the reaction rate in many cases. It is also possible to control the size of the inorganic dispersed phase by adding water to the resulting coordination product and hydrolyzing it.

  As starting materials for rare earth metals and / or fourth period transition metals, mineral salts such as nitrates, sulfates, carbonates, chlorides, organic acid salts such as formates, acetates, oxalates, alkoxides, etc. are used. It is done. Considering the reduction of anionic impurities, it is preferable to use organic acid salts such as formate, acetate and oxalate and alkoxides. More preferably, acetate is used.

  The rare earth metal and / or the fourth period transition metal acetate usually contains water of crystallization and can be used as it is depending on the type of metal to be coordinated. preferable.

The functional group R of the dispersed phase shown in FIG. 2 is not particularly limited and is selected depending on the type of organic polymer to be combined. In order to improve the compatibility with the organic polymer, it can be selected for the purpose of imparting polymerizability with the organic polymer or a monomer component capable of forming the organic polymer. For example, as R, hydrogen, an alkyl group, a reactive vinyl group, an allyl group, a diazo group, a nitro group, a cinnamoyl group, an acryloyl group, an imide group, an epoxy group, a cyano group, or an alkyl group containing these functional groups , Alkylsilyl groups, alkylcarbonyl groups, and the like.

  In addition, if it can be homogeneously combined with the organic polymer to be combined, the activity of carboxylate groups such as poly (meth) acrylic acid, polyethylene glycol, polyethylene oxide, celluloses, hydroxyl groups, amino groups, amide groups, etc. A polymer having a functional group containing hydrogen can also be used.

  As a method for introducing the functional group R into the inorganic dispersed phase, (1) a method of introducing it by the reaction after forming the inorganic dispersed phase, or (2) a rare earth metal or / and a fourth periodic transition metal through oxygen in advance. There is a method of introducing an R group into an alkoxide as a starting material capable of coordinating with a rare earth metal salt and / or a fourth period transition metal salt.

  The compound to be reacted with the inorganic dispersed phase is not particularly limited as long as it can form the above-mentioned target structure. However, the method (1) has an active hydrogen such as a carboxylate group, a hydroxyl group, an amino group, an amide group at the terminal. Compounds, (2) include alkyl groups, reactive vinyl groups, allyl groups, diazo groups, nitro groups, cinnamoyl groups, acryloyl groups, imide groups, epoxy groups, cyano groups, or these functional groups Alkoxysilane containing an alkyl group (R1R2R3SiOR4: R1 represents an alkyl group, a reactive vinyl group, an allyl group, a diazo group, a nitro group, a cinnamoyl group, an acryloyl group, an imide group, an epoxy group, a cyano group, or a functional group thereof. Contains alkyl group, R2 and R3 are alkyl group, reactive vinyl group, allyl group, diazo group, nitro , Cinnamoyl group, acryloyl group, imide group, epoxy group, cyano group or alkyl group containing these functional groups, alkoxyl group, R4 is alkyl group), alkoxygermane (R1R2R3GeOR4: R1 is alkyl group, has reactivity Vinyl group, allyl group, diazo group, nitro group, cinnamoyl group, acryloyl group, imide group, epoxy group, cyano group or alkyl group containing these functional groups, R2 and R3 are alkyl groups, reactive vinyl groups , Allyl groups, diazo groups, nitro groups, cinnamoyl groups, acryloyl groups, imide groups, epoxy groups, cyano groups, or alkyl groups containing these functional groups, alkoxyl groups, and R4 is an alkyl group). A compound capable of reacting with the dispersed phase is preferably used.

[Organic polymer]
The organic polymer is not particularly limited as long as it can disperse the rare earth metal coordinated with other metal species without agglomeration, but preferably the wavelength at which the expression of the optical function is utilized. A material having substantially transparency in the band is used. Here, the wavelength band in which the manifestation of the optical function is used is not limited to the purple to red visible band, but ultraviolet and X-rays having a shorter wavelength than purple having a wavelength of about 400 nm, and red having a wavelength of about 750 nm. It may be an infrared band having a longer wavelength.
Examples of such an organic polymer include polymethyl methacrylate, polycyclohexyl methacrylate, polybenzyl methacrylate, polyphenyl methacrylate, polycarbonate, polyethylene terephthalate, polystyrene, polytetrafluoroethylene, poly-4-methylpentene-1, and polyvinyl alcohol. , Polyethylene, polyacrylonitrile, styrene-acrylonitrile copolymer, polyvinyl chloride, polyvinyl carbazole, styrene-maleic anhydride copolymer, polyolefin, polyimide, epoxy resin, polysiloxane, polysilane, polyamide, cyclic olefin resin, hydroxypropyl cellulose However, it is not limited to these. These organic polymers may be used alone or in combination of two or more. In addition, those organic polymers dissolved in a solvent or melted by heating or the like can be processed into the desired rare earth metal and / or fourth period transition metal-containing organic-inorganic composite form. Polymerization in the process of processing into the form of the target rare earth metal and / or fourth period transition metal-containing organic / inorganic composite using precursor monomers, oligomers, and mixtures of monomers and oligomers with organic polymers as starting materials You can also

  Furthermore, these organic polymers may have a functional group that promotes a reaction such as addition, crosslinking, or polymerization by light or heat in the main chain or side chain. Examples of such a functional group include a hydroxyl group, a carbonyl group, a carboxyl group, a diazo group, a nitro group, a cinnamoyl group, an acryloyl group, an imide group, and an epoxy group.

  The organic polymer may contain additives such as stabilizers such as plasticizers and antioxidants, surfactants, dissolution accelerators, polymerization inhibitors, and colorants such as dyes and pigments. Furthermore, in order to improve molding processability such as coating properties, organic polymers are made of organic solvents such as solvents (water, alcohols, glycols, cellosolves, ketones, esters, ethers, amides, hydrocarbons). Solvent).

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
[Example 1]
<Preparation of inorganic dispersed phase>
Add neodymium acetate dehydrated under reduced pressure at 110 ° C. for 1 hour in propylene glycol α-monomethyl ether and add tri-sbutoxyaluminum (Nd / Al = 3 mol, total oxide equivalent concentration of Nd and Al of 5% by weight) for 1 hour. As a result of refluxing, a light purple transparent solution was obtained. The particle size of the obtained reaction product was measured by a dynamic scattering method, and it was confirmed that the peak top of the particle size distribution was a composite nanoparticle of 2.3 nm. Moreover, the coordination of Al via oxygen to Nd was confirmed from the change in 27Al-NMR spectrum before and after the reaction of tri-sbutoxyaluminum.

<Preparation of composite of inorganic dispersed phase and transparent organic polymer>
Hydroxypropyl cellulose (manufactured by Nippon Soda Co., Ltd.) was used as the transparent organic polymer. This organic polymer and the NdAl-containing composite nanoparticles prepared by the above method were mixed in ethyl cellosolve and stirred at room temperature for 2 hours to obtain a mixed solution. The mixing ratio was adjusted so that the Nd ratio in the composite composition was 8% by weight with respect to the total solid content.

  A polytetrafluoroethylene container is used as a mold, and the mixed liquid prepared as described above is poured into the mold. Further, ethyl cellosolve is evaporated and dried at 120 ° C. to dry the Nd-containing organic-inorganic composite. A cast body of the body was obtained.

<Spectral absorption characteristic measurement>
Spectral absorption characteristics of the Nd-containing organic-inorganic composite thus obtained were measured using a self-recording spectrophotometer. FIG. 3 is a spectral absorption spectrum of the NdAl-containing composite nanoparticle / hydroxypropylcellulose composite prepared by the above method. It can be seen that light absorption in the wavelength bands of about 500 to 540 nm and about 560 to 600 nm derived from Nd absorption can be ensured even in the NdAl-containing composite nanoparticle / hydroxypropylocellulose composite.

<Production of lighting window>
A coating layer of an Nd-containing organic-inorganic composite was formed on a commonly used halogen lamp cover in accordance with the above-described method for producing an Nd-containing organic-inorganic composite. When this cover was used, the glare peculiar to a halogen lamp was reduced, and it was confirmed that it was effective as a headlight of an automobile.
[Example 2]
<Preparation of inorganic dispersed phase>
Prose glycol α monomethyl ether was added with praseodymium acetate dehydrated under reduced pressure at 110 ° C. for 1 hour and tri-sbutoxyaluminum (Pr / Al = 3 mol, Pr and Al total oxide equivalent concentration 5% by weight) and refluxed for 1 hour. As a result, a light green transparent solution was obtained. The particle size of the obtained reaction product was measured by a dynamic scattering method, and it was confirmed that the peak top of the particle size distribution was a composite nanoparticle of 6.5 nm. In addition, the coordination of Al via oxygen to Pr was confirmed from the change in 27Al-NMR spectrum before and after the reaction of tri-sbutoxyaluminum.

<Preparation of composite of inorganic dispersed phase and transparent organic polymer>
As the transparent organic polymer, a photopolymerizable acrylic resin “Cyclomer” (manufactured by Daicel Chemical Industries) was used. This organic polymer, the PrAl-containing composite nanoparticles prepared by the above method, and the photoradical generator “Irgacure369” (trade name, manufactured by Ciba Geigy) are mixed in PGMEA and stirred for 2 hours at room temperature. A liquid was obtained. The mixing ratio was adjusted so that the ratio of Pr in the composite composition was 10% with respect to the total solid content.

  Using a polytetrafluoroethylene container as a molding die, the mixed liquid prepared as described above is poured into the mold, and further, PGMEA is evaporated and dried at 120 ° C. to dry the Pr-containing organic-inorganic composite. A cast molding was obtained.

<Spectral absorption characteristic measurement>
The spectral absorption characteristics of the Pr-containing organic-inorganic composite thus obtained were measured using a self-recording spectrophotometer. FIG. 4 is a spectral absorption spectrum of the PrAl-containing composite nanoparticle / photopolymerizable acrylic resin composite prepared by the above method. From this result, it can be seen that light absorption with respect to the wavelength band of about 440 to 490 nm derived from Pr absorption can be secured even in the PrAl-containing composite nanoparticle / photopolymerizable acrylic resin composite.

<Production of lens>
A lens was produced according to the method for producing the Pr-containing organic-inorganic composite. This lens was confirmed to be suitable as an anti-glare lens because it selectively absorbs blue light components.
[Example 3]
<Preparation of inorganic dispersed phase>
Results obtained by adding nickel acetate and pentaethoxyniobium (Ni / Nb = 2 mol, total oxide equivalent concentration of Ni and Nb of 5% by weight) in ethylene glycol monomethyl ether at 110 ° C. under reduced pressure for 1 hour and refluxing for 1 hour A green transparent solution was obtained. The particle size of the obtained reaction product was measured by a dynamic scattering method, and it was confirmed that the peak top of the particle size distribution was a composite nanoparticle of 2.9 nm.
<Preparation of composite of inorganic dispersed phase and transparent organic polymer>
As the transparent organic polymer, a photopolymerizable acrylic resin “Cyclomer” (manufactured by Daicel Chemical Industries) was used according to Example 2. This organic polymer and the Ni—Nb-containing composite nanoparticles prepared by the above method were mixed in ethyl cellosolve and stirred at room temperature for 2 hours to obtain a mixed solution. The mixing ratio was adjusted so that the proportion of Ni in the composite composition was 8% by weight with respect to the total solid content.

  A polytetrafluoroethylene container is used as a mold, and the mixed liquid prepared as described above is poured into the mold. Further, the ethyl cellosolve is evaporated and dried at 120 ° C. to dry the Ni-containing organic-inorganic composite. A transparent cast molded body was obtained.

<Spectral transmittance characteristics measurement>
The spectral transmittance characteristics of the Ni-containing organic-inorganic composite thus obtained were measured using a self-recording spectrophotometer. FIG. 5 is a spectral transmission spectrum of the Ni—Nb-containing composite nanoparticles / photopolymerizable acrylic resin composite prepared by the above method. From this result, it can be seen that light absorption with respect to wavelength bands of about 900 to 600 nm and about 450 nm or less derived from absorption of Ni can be ensured even in the Ni—Nb-containing composite nanoparticles / photopolymerizable acrylic resin composite.

From the above results, according to the present invention, it is possible to supply an organic-inorganic composite in which an organic polymer is doped with a rare earth metal / and a fourth period transition metal in a high concentration, and exhibits the inherent absorption characteristics of the doped element. Is possible.
<Production of lens>
A lens was produced according to the above method for producing the Ni-containing organic-inorganic composite. Since this lens selectively absorbs ultraviolet light components from blue light, it is suitable as an anti-glare lens and has been confirmed to be highly effective in preventing visual impairment caused by ultraviolet light.

INDUSTRIAL APPLICABILITY The present invention is used for a dimming optical element used for controlling the transmittance and absorbance of light of a specific wavelength or wavelength band, and can be used in various forms according to needs.
An example of such a light control lens is a light control lens. Specific examples of this application include sunglasses, anti-glare lenses, lenses for the visually impaired, industrial welding goggles (protective glasses), medical goggles, and the like.
Cases and window materials for various light sources are also used as the application of the present invention. Specific examples of applications include window materials such as automobile headlights and various spot light sources, and lens cover materials.
By applying the present invention to a decorative window or the like for illumination such as various discharge tube illuminations and reflex lamps that are widely used in general households, it can also be used to control the spectrum of illumination light to be extracted. For example, the color rendering can be controlled, for example, by reducing the blue component of the white fluorescent lamp to obtain a warm color tone.
It can also be applied to architectural window materials and industrial window materials having a filter effect using a transparent polymer material, or a display filter such as a television. For example, a window material having a heat ray dimming effect can be obtained by doping a rare earth metal such as neodymium that selectively absorbs light in the red band.

(A)-(d) is a figure which shows the typical light control optical element which concerns on this invention. Of the rare earth metal and / or the fourth periodic transition metal-containing organic-inorganic composite according to the present invention, the dispersed phase formed by coordination of other metal species with oxygen through the rare earth metal and / or the fourth periodic transition metal. It is a schematic diagram. It is a figure which shows the spectral absorption spectrum of the neodymium containing organic inorganic composite used in Example 1 among the rare earth metals and / or 4th period transition metal containing organic inorganic composite based on this invention. It is a figure which shows the spectral absorption spectrum of the praseodymium containing organic inorganic composite used in Example 2 among the rare earth metals and / or 4th period transition metal containing organic inorganic composite which concern on this invention. It is a figure which shows the spectral transmittance | permeability of the nickel containing organic inorganic composite used in Example 3 among the rare earth metals and / or 4th period transition metal containing organic inorganic composite concerning this invention.

Explanation of symbols

1a Lens (light control optical element)
1b Cover (light control optical element)
1c Lens (light control optical element)
1d Optical filter (dimming optical element)
2 Rare earth metal 3 Metal coordinated to rare earth metal via oxygen

Claims (5)

While controlling light transmitted through the transmittance or absorbance of light having a specific wavelength or wavelength thereof, refraction, light condensing, a modulating optical element to control the diffusion, to absorb light of a particular wavelength or wavelength thereof It is formed by a composite of at least one rare earth metal or / and a fourth periodic transition metal and an organic polymer, and at least one rare earth metal and / or the fourth periodic transition metal is oxygenated by another metal species. A light-modulating optical element, characterized in that an inorganic dispersed phase is formed through coordination. 2. The diameter of an inorganic dispersed phase formed by coordinating a rare earth metal and / or a fourth periodic transition metal and another metal species thereto via oxygen is 0.1 to 1000 nm in average. Dimming optical element. The ratio of the rare earth metal or / and the fourth period transition metal is obtained by coordinating the organic polymer with the rare earth metal or / and the fourth period transition metal and other metal species via oxygen in terms of solid content. 3. The light control optical element according to claim 1, wherein the light control optical element is 90% by weight or less of the total amount with the inorganic dispersed phase. A combination of one or two or more elements selected from the group consisting of Group 3B, Group 4A, Group 5A metals, wherein the other metal species coordinated to the rare earth metal and / or the fourth period transition metal via oxygen The light control optical element according to any one of claims 1 to 3. A rare earth metal or / and a fourth periodic transition metal and an inorganic dispersed phase obtained by coordinating another metal species via oxygen to the rare earth metal salt or / and the fourth periodic transition metal salt and another metal alkoxide The light control optical element according to any one of claims 1 to 4, wherein the light control optical element is formed.