JP4849208B2 - Light emitting element - Google Patents

Description

  The present invention relates to a light-emitting element, and more particularly to a light-emitting element including a light-emitting material containing an organic molecule that exhibits fluorescence or phosphorescence.

  Conventionally, organic light emitting materials can be classified into low molecular weight and high molecular weight materials. The former low molecular weight light emitting materials include aromatic fluorescent dyes such as anthracenes, benzenes and biphenyls, aluminum complexes, There are complexes such as iridium complexes and rare earths, and the latter polymeric light-emitting materials include polyphenylene vinylenes, polyfluorenes, polythiophenes, dye-containing non-conjugated polymers, etc. {for example, Kazuyuki Horie et al., “Light Science of Functional Molecules-Molecular Photonics ", published by Kodansha Co., Ltd., August 7, 2001, 7th edition, page 58 (Non-patent Document 1)}. However, such a conventional organic light-emitting material has a problem that a decrease in light emission luminance due to concentration quenching is observed due to intermolecular interaction, and sufficient light emission luminance and light emission efficiency cannot be obtained. In addition, the lifetime of organic light emitting materials is generally shorter than that of other light emitting materials, and it has been difficult to maintain stable light emission characteristics over a long period of time.

  In addition, various light-emitting elements including such a light-emitting material have been researched and disclosed. For example, Japanese Patent Laid-Open No. 2001-202827 (Patent Document 1) discloses a light emitting element having a low refractive index in contact with the surface of a light emitting layer. However, the light emitting device described in Patent Document 1 has a problem in that the light emitting layer has a multilayer structure, so that the number of lamination steps is increased and the manufacturing cost is increased.

  In JP 2002-40240 (Patent Document 2), the pores of the silica mesostructure having rod-shaped pores with uniaxial orientation on the orientation regulating film subjected to the orientation treatment on the substrate. A light emitting device (fluorescent device) formed by forming a fluorescent thin film holding a fluorescent dye has been disclosed. However, in such a light-emitting device described in Patent Document 2, although a silica thin film that emits polarized fluorescence is used, the silica mesostructure does not absorb ultraviolet light or the like, In this case, the lifetime and light resistance of the organic light emitting material are improved but insufficient.

  Furthermore, Japanese Patent Application Laid-Open No. 3-152897 (Patent Document 3) describes a light-emitting element in which light emitted from a light emitter is absorbed by a fluorescent material separated and arranged in a plane, and multicolor fluorescence is emitted from each phosphor. Has been. However, in the light emitting device described in Patent Document 3, there is a problem that the dispersibility of the phosphor with respect to the binder greatly affects the light emission characteristics. Further, in such a light emitting device, when a phosphor having a particle size of submicron to several μm is used, its cohesion has been a problem.

On the other hand, various organic-inorganic composite materials of organic materials such as benzene and inorganic materials such as silicon compounds have been developed and reported recently as materials having nanostructures {for example, JP 2001-114790 A (Patent Document) 4) See}. However, in various organic-inorganic composite materials having such nanostructures, there has been no report on light emission characteristics, and there has been no report suggesting that it becomes a light emitting material.
JP 2001-202827 A Japanese Patent Laid-Open No. 2002-40240 Japanese Patent Laid-Open No. 3-152897 JP 2001-114790 A Kazuyuki Horie et al., “Science of Optical Functional Molecules-Molecular Photonics”, published by Kodansha Co., Ltd., August 10, 2001, 7th edition, page 58

  The present invention has been made in view of the above-described problems of the prior art, and has improved light emission efficiency, excellent light absorption efficiency, and excellent heat resistance that enables uniform light emission in a plane. An object is to provide a light-emitting element.

  As a result of intensive studies to achieve the above object, the present inventors have obtained a light emitting material comprising a polymer obtained by polymerizing a specific organosilicon compound containing an organic molecule exhibiting fluorescence or phosphorescence such as benzene and biphenyl. Surprisingly, the luminous efficiency is improved by providing the light-emitting layer containing the light source and the light source, and the light emission has excellent light absorption and excellent heat resistance that enables uniform light emission in the surface. The inventors have found that an element can be obtained and have completed the present invention.

  That is, the light emitting device of the present invention has the following general formula (1):

[ Wherein X is benzene, biphenyl, terphenyl, quaterphenyl, benzophenone, fluorene, anthraquinone, naphthalene, acenaphthene, carbazole, triphenylene, phenanthrene, acridine, acridone, azulene, chrysene, pyrene, anthracene, perylene, biacetyl, benzyl , fluorescein, eosin, rhodamine B, and an organic molecule that exhibits at least one of fluorescence of those fluorinated compound, R ¹ is at least one selected from an alkoxy group or Ranaru group having 1 to 5 carbon atoms N represents 3 and m represents 2 . ]
The light emitting layer containing the light emitting material consisting of the polymer of the organosilicon compound represented by this, and the light source, The polymer of the said organosilicon compound is the following general formula (2):
[Wherein, X represents an organic molecule exhibiting fluorescence. ]
Than is characterized Rukoto that having a repeating unit represented by in.

In the light emitting device of the present invention, the polymer of the organosilicon compound preferably has a peak appearing in a region of d = 5 nm or less in X-ray diffraction (XRD) measurement .

  In the light emitting device of the present invention, the polymer of the organosilicon compound is preferably a porous body.

  In the light emitting device of the present invention, the polymer of the organosilicon compound is preferably a mesoporous material having a central pore diameter of 1 to 30 nm.

In the light emitting device of the present invention, the polymer of the organosilicon compound is a porphyrin, anthracene, aluminum complex, rare earth element or complex thereof, fluorescein, rhodamine, coumarin, pyrene, dansylic acid, cyanine dye, merocyanine dye, It is preferable to further include at least one other luminescent compound selected from a styryl dye and a benzstyryl dye .

  In the light emitting device of the present invention, the other light emitting compound is in any state selected from the group consisting of adsorption, bonding, filling and mixing with the polymer of the organosilicon compound. Is preferred.

  In the light emitting device of the present invention, the polymer of the organosilicon compound is preferably in the form of particles having an average particle size of 1 μm or less.

  In the light emitting device of the present invention, the polymer of the organosilicon compound is preferably a thin film having an average film thickness of 1 μm or less.

  In the light emitting device of the present invention, the polymer of the organosilicon compound is preferably a layered material in which nanosheets each having a thickness of 10 nm or less are laminated.

  Although the reason why the above object can be achieved by the light emitting device of the present invention is not necessarily clear, the present inventors speculate as follows. In other words, conventional organic molecules that exhibit fluorescence or phosphorescence (hereinafter referred to as “fluorescent molecules”) are quenched by the interaction between molecules and do not emit light efficiently in a high concentration state. There were limits. However, in the light-emitting material used in the light-emitting device of the present invention, the hydrophobic fluorescent molecule and the hydrophilic silicon-containing group are chemically bonded to each other, thereby causing an intermolecular interaction (hydrophobic-hydrophilic property). Even if the concentration of fluorescent molecules is usually in a high concentration state where concentration quenching occurs, a unique arrangement structure in which fluorescent molecules and silica are regularly arranged is formed based on the interaction or π-π interaction) Because of its unique arrangement structure, quenching is suppressed, and each fluorescent molecule emits light efficiently. Therefore, in the light emitting element of the present invention, the light emission efficiency can be improved even in a high concentration state that causes concentration quenching. Furthermore, in the light emitting device of the present invention, since the silica in the light emitting layer is transparent to ultraviolet light, the fluorescent molecule absorbs ultraviolet light in the light emitting layer, and high light absorption efficiency can be obtained. They guess. In the light emitting device of the present invention, since the contained light emitting material is a chemically bonded fluorescent molecule and inorganic silica, the heat resistance of the fluorescent molecule is improved and stable over a long period of time. It is presumed that the light emission characteristics are maintained.

  In the light-emitting device of the present invention, when a light-emitting material in which other light-emitting compounds are adsorbed, dispersed, and mixed is used, a unique arrangement structure in which fluorescent molecules and silica are regularly arranged Therefore, other light-emitting compounds can be regularly arranged by the interaction between molecules, and if there are pores, they can be adsorbed to each pore without causing concentration quenching. Further, since the silica in the light emitting layer is transparent to ultraviolet light, the fluorescent molecules absorb the ultraviolet light and transfer energy directly to other luminescent compounds, or Since the energy can be transferred indirectly through the emission of fluorescent molecules, the present inventors speculate that higher light absorption efficiency and light emission efficiency can be obtained, and that ultraviolet light resistance can be obtained. To do. Further, in the light emitting device of the present invention, the light emitting material composed of a thin film or fine particles of 1 μm or less is uniformly dispersed in the plane of the light emitting layer, so that light can be emitted more uniformly. Furthermore, in the light emitting device of the present invention, when mesopores are formed in the light emitting material, a light emitting layer having a low density and a low refractive index is formed, and the present inventors can expect higher light extraction efficiency. I guess.

  According to the present invention, it is possible to provide a light emitting device with improved light emission efficiency, excellent light absorption efficiency, and excellent heat resistance that enables uniform light emission in the surface.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

[Luminescent material]
The luminescent material according to the present invention has the following general formula (1):

It consists of the polymer of the organosilicon compound represented by these.

  In the general formula (1), X represents an organic molecule exhibiting fluorescence or phosphorescence (hereinafter referred to as “fluorescence molecule”), and examples of such a fluorescence molecule include a singlet excited state or a triplet excited state and a ground state. The energy difference of 40 to 140 kcal / mol is preferable. If this energy difference is less than the above lower limit, the wavelength of fluorescence or phosphorescence tends to be difficult because the wavelength is too long.On the other hand, if it exceeds the upper limit, the wavelength of fluorescence or phosphorescence tends to be too short and difficult to use. is there.

  As such fluorescent molecules according to the present invention, specifically, benzene, biphenyl, terphenyl, quaterphenyl, benzophenone, fluorene, anthraquinone, naphthalene, acenaphthene, carbazole, triphenylene, phenanthrene, acridine, acridone, azulene, Examples include chrysene, pyrene, anthracene, perylene, biacetyl, benzyl, fluorescein, eosin, rhodamine B, and fluorinated compounds thereof. Among them, benzene, biphenyl, naphthalene, anthracene, triphenylene, pyrene, terphenyl, fluorene, acridine, acridone, Quaterphenyl is preferred.

In the general formula (1), R ¹ represents a lower alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms (RO—)), a hydroxyl group (—OH), an allyl group (CH ₂ ═CH—CH ₂ —). ), An ester group (preferably an ester group having 1 to 5 carbon atoms (RCOO-)) and a halogen atom (a chlorine atom, a fluorine atom, a bromine atom, an iodine atom), From the viewpoint of easy control of the condensation reaction, a lower alkoxy group and / or a hydroxyl group are preferred. In addition, when several R < ¹ > exists in the same molecule, R < ¹ > may be same or different.

In the general formula (1), R ² represents at least one selected from the group consisting of a lower alkyl group {preferably an alkyl group having 1 to 5 carbon atoms (R-)} and a hydrogen atom. In addition, when ^two or more R < ² > exists in the same molecule, R < ² > may be the same or different.

Further, n and (3-n) in the general formula (1) are the numbers of R ¹ and R ² bonded to the silicon atom (Si), respectively, and such n is an integer of 1 to 3. As shown, it is particularly preferable that n = 3 from the viewpoint that the structure after condensation is stable. In the general formula (1), m is the number of silicon atoms (Si) bonded to the fluorescent molecule (X), and such m represents an integer of 1 to 4, but stable siloxane. It is particularly preferable that m = 2 from the viewpoint of easily forming a network.

  The light emitting material according to the present invention is obtained by polymerizing the organosilicon compound represented by the above general formula (1), and a kind of monomer is polymerized as the organosilicon compound represented by the above general formula (1). Alternatively, two or more types of monomers may be copolymerized. The luminescent material according to the present invention includes (i) an organic silicon compound represented by the general formula (1) and an organic silicon in which X in the general formula (1) is an organic molecule that does not exhibit fluorescence or phosphorescence. And (ii) a copolymer obtained by copolymerizing the organosilicon compound represented by the above general formula (1) with other monomers. Also good. Hereinafter, the organosilicon compound represented by the general formula (1) and the monomer used for copolymerization as necessary are collectively referred to as “monomer”.

  Examples of such organic molecules that do not exhibit fluorescence or phosphorescence include, but are not limited to, monovalent or higher-valent organic groups generated by removing one or more hydrogens from hydrocarbons such as alkanes, alkenes, alkynes, and cycloalkanes. It may be one having an amide group, amino group, imino group, mercapto group, sulfone group, carboxyl group, ether group, acyl group, vinyl group or the like. Examples of the monomer other than the organosilicon compound represented by the general formula (1) include silicon compounds such as alkoxysilane and alkylalkoxysilane, and further aluminum, titanium, magnesium, zirconium, tantalum, niobium, molybdenum. Metal compounds containing inorganic components such as cobalt, nickel, gallium, beryllium, yttrium, lanthanum, hafnium, tin, lead, vanadium, and boron may be used. In the case of copolymerization such as (i) or (ii), the proportion of the organosilicon compound represented by the general formula (1) in all monomers to be copolymerized is preferably 30% or more.

When the organosilicon compound represented by the general formula (1) is polymerized, a siloxane bond (Si) is obtained by hydrolysis and subsequent condensation reaction in the portion where R ¹ is bonded to Si in the general formula (1). -O-Si) is formed. At this time, a part of the group may be a silanol group (Si—OH), but even if the silanol group is formed, the light emission characteristics are not affected. For example, the reaction formula in the case of polymerizing an organosilicon compound in which R ¹ in the general formula (1) is an ethoxy group, n is 3, and m is 2 is the following general formula (3):

[Wherein X represents an organic molecule exhibiting fluorescence or phosphorescence, and p represents an integer corresponding to the number of repeating units. ]
become that way. The number of p is not particularly limited, but generally it is preferably in the range of about 10 to 1000.

  The polymer obtained by polymerizing the above monomers is an organic silica material in which a skeleton is formed with fluorescent molecules (X), silicon atoms (Si), and oxygen atoms (O) as main components. It has a highly cross-linked network structure based on a skeleton (—X—Si—O—) in which silicon atoms bonded to molecules are bonded through oxygen atoms.

  The method for polymerizing the monomer is not particularly limited, but it is preferable to use water or a mixed solvent of water and an organic solvent as a solvent, and subject the monomer to hydrolysis and condensation reaction in the presence of an acid or base catalyst. Examples of the organic solvent suitably used here include alcohol, acetone and the like, and the content of the organic solvent in the mixed solvent is preferably about 5 to 50% by weight. Examples of the acid catalyst used include mineral acids such as hydrochloric acid, nitric acid, and sulfuric acid, and the solution in the case of using the acid catalyst is acidic with a pH of 6 or less (more preferably 2 to 5). preferable. Furthermore, examples of the base catalyst used include sodium hydroxide, ammonium hydroxide, potassium hydroxide, and the like. When using the base catalyst, the basic solution has a pH of 8 or more (more preferably 9 to 11). It is preferable that

  The content of the monomer in such a polymerization step is preferably about 0.0055 to 0.33 mol / L in terms of silicon concentration. In addition, various conditions (temperature, time, etc.) in the polymerization step are not particularly limited and are appropriately selected according to the monomer used, the target polymer, and the like, but generally a temperature of about 0 to 100 ° C. It is preferable that the organosilicon compound is hydrolyzed and condensed for about 1 to 48 hours.

(Light-emitting material with a periodic structure resulting from the regular arrangement of fluorescent molecules)
The polymer obtained by polymerizing the monomers (the polymer of the organosilicon compound represented by the general formula (1)) usually has an amorphous structure, but is caused by the regular arrangement of the fluorescent molecules depending on the synthesis conditions. It is possible to have a periodic structure. Such periodicity depends on the molecular length of the monomer used, but a periodic structure of 5 nm or less is preferable. This periodic structure is retained even after the monomer is polymerized. The formation of this periodic structure can be confirmed by the appearance of a peak in a region of d = 5 nm or less by X-ray diffraction (XRD) measurement. Even when such a peak is not confirmed in the X-ray diffraction measurement, a periodic structure may be partially formed. Such a periodic structure is generally formed with a layered structure described later, but is not limited to this case.

  When the periodic structure resulting from the regular arrangement of the fluorescent molecules is formed in the luminescent material according to the present invention, the luminescence intensity tends to be greatly improved. Although the mechanism by which the emission intensity is greatly improved by the formation of the periodic structure in this way is not necessarily clear, the present inventors infer as follows. That is, normally, when a fluorescent molecule is in a high concentration (high density) state, concentration quenching occurs, and the light emission efficiency decreases. However, when the fluorescent molecules are regularly arranged as described above, a uniform band structure is formed and maintained, efficient light emission is possible even at a high concentration, and the occurrence of concentration quenching is more sufficiently suppressed. The present inventors speculate.

Suitable conditions for forming a periodic structure resulting from such a regular arrangement of fluorescent molecules include the following conditions.
(i) Since the periodic structure is formed by an interaction between monomers, it is preferable to use an organic group (X) that increases the interaction between monomers, that is, benzene, biphenyl, naphthalene, or anthracene.
(ii) The pH of the solution is preferably 1 to 3 (acidic) or 10 to 12 (basic), and more preferably 10 to 12 (basic).

  Such a periodic structure can be obtained in accordance with the method described in S. Inagaki et al., Nature, (2002) 416, 304-307.

(Light-emitting material that is porous)
By controlling the synthesis conditions when polymerizing the monomer, or by mixing a surfactant with the raw material, the resulting polymer (polymer of the organosilicon compound represented by the general formula (1)) It is possible to form pores. In the former case, the solvent serves as a template, and in the latter case, a surfactant micelle or liquid crystal structure serves as a template to form a porous body having pores.

  In particular, the use of a surfactant described later is preferable because a mesoporous material having mesopores with a central pore diameter of 1 to 30 nm in the pore diameter distribution curve can be obtained. The central pore diameter is a curve (pore diameter distribution curve) in which a value (dV / dD) obtained by differentiating the pore volume (V) with respect to the pore diameter (D) is plotted against the pore diameter (D). ) At the maximum peak, and can be determined by the method described below. That is, the porous body is cooled to a liquid nitrogen temperature (−196 ° C.), nitrogen gas is introduced, the adsorption amount is determined by a constant volume method or a gravimetric method, and then the pressure of the introduced nitrogen gas is gradually increased, The adsorption amount of nitrogen gas with respect to each equilibrium pressure is plotted to obtain an adsorption isotherm. Using this adsorption isotherm, a pore size distribution curve can be obtained by a calculation method such as Cranston-Inklay method, Pollimore-Heal method, BJH method or the like.

Such a mesoporous material preferably contains 60% or more of the total pore volume in a range of ± 40% of the center pore diameter in the pore diameter distribution curve. A mesoporous material satisfying this condition means that the pore diameter is very uniform. The specific surface area of the mesoporous material is not particularly limited, but is preferably 400 m ² / g or more. The specific surface area can be calculated as a BET specific surface area from the adsorption isotherm using the BET isotherm adsorption equation.

  Further, such a mesoporous material preferably has one or more peaks at a diffraction angle corresponding to a d value of 1.5 to 30.5 nm in its X-ray diffraction (XRD) pattern. The X-ray diffraction peak means that a periodic structure having a d value corresponding to the peak angle is present in the sample. Therefore, having one or more peaks at a diffraction angle corresponding to a d value of 1.5 to 30.5 nm indicates that the pores are regularly arranged at intervals of 1.5 to 30.5 nm. means.

  Moreover, the pore which such a mesoporous body has is formed not only on the surface of the porous body but also inside. The arrangement state (pore arrangement structure or structure) of the pores in such a porous body is not particularly limited, but is preferably a 2D-hexagonal structure, a 3D-hexagonal structure, or a cubic structure. Such a pore arrangement structure may have a disordered pore arrangement structure.

  Here, that the porous body has a hexagonal pore arrangement structure means that the arrangement of the pores is a hexagonal structure (S. Inagaki et al., J. Chem. Soc., Chem. Commun., p.680 (1993), S. Inagaki et al., Bull. Chem. Soc. Jpn., 69, p.1449 (1996), Q. Huo et al., Science, 268, p.1324 (1995) ). Further, the porous body having a cubic pore arrangement structure means that the arrangement of the pores is a cubic structure (JCVartuli et al., Chem. Mater., 6, p. 2317 (1994), Q. Huo et al., Nature, 368, p. 317 (1994)). Further, that the porous body has a disordered pore arrangement structure means that the arrangement of the pores is irregular (PTTanev et al., Science, 267, p.865 (1995), SABagshaw et al., Science, 269, p. 1242 (1995), R. Ryoo et al., J. Phys. Chem., 100, p. 17718 (1996)). The cubic structure is preferably Pm-3n, Ia-3d, Im-3m, or Fm-3m symmetry. The symmetry is determined based on a space group notation.

  As described above, when the light emitting material according to the present invention has pores, the porous body can be adsorbed (physical adsorption and / or chemical bond) and filled with other light emitting compounds described later. In that case, energy transfer from the aforementioned fluorescent molecule to another luminescent compound occurs, and light emission having a wavelength different from the original emission wavelength of the fluorescent molecule occurs. Thereby, multicolor light emission becomes possible according to the combination of the fluorescent molecule and the luminescent compound to be introduced. In addition, if the above-mentioned periodic structure is formed on the pore walls of such a porous body, energy transfer from the fluorescent molecules in the pore walls to other luminescent compounds will occur more efficiently, and strong emission of different wavelengths will occur. Can be achieved. In order to obtain the mesoporous material, it is desirable to add a surfactant to the monomer of the present invention and perform polycondensation. This is because when the monomer undergoes polycondensation, the added surfactant forms a mesopore using the template.

  The surfactant used for obtaining the mesoporous material is not particularly limited, and may be any of cationic, anionic, and nonionic, specifically, alkyl. Chloride, bromide, iodide or hydroxide such as trimethylammonium, alkyltriethylammonium, dialkyldimethylammonium, benzylammonium; fatty acid salt, alkylsulfonate, alkylphosphate, polyethylene oxide nonionic surfactant, Primary alkylamine and the like can be mentioned. These surfactants may be used alone or in combination of two or more.

Among the above surfactants, examples of the polyethylene oxide nonionic surfactant include a polyethylene oxide nonionic surfactant having a hydrocarbon group as a hydrophobic component and polyethylene oxide as a hydrophilic portion. . Such surfactants, for example, the general formula _{C n H 2n + 1 (OCH} 2 CH 2) expressed in m OH, n is 10 to 30, m can be preferably used those which are 1 to 30. As such a surfactant, an ester of a fatty acid such as oleic acid, lauric acid, stearic acid, palmitic acid and sorbitan, or a compound obtained by adding polyethylene oxide to these esters can also be used.

Further, as such a surfactant, a triblock copolymer type polyalkylene oxide may be used. Examples of such surfactants include those composed of polyethylene oxide (EO) and polypropylene oxide (PO) and represented by the general formula (EO) _x (PO) _y (EO) _x . x and y represent the number of repetitions of EO and PO, respectively, x is preferably 5 to 110, y is preferably 15 to 70, x is preferably 13 to 106, and y is more preferably 29 to 70. Examples of the triblock copolymer include (EO) ₁₉ (PO) ₂₉ (EO) ₁₉ , (EO) ₁₃ (PO) ₇₀ (EO) ₁₃ , (EO) ₅ (PO) ₇₀ (EO) ₅ , (EO). ₁₃ (PO) ₃₀ (EO) ₁₃ , (EO) ₂₀ (PO) ₃₀ (EO) ₂₀ , (EO) ₂₆ (PO) ₃₉ (EO) ₂₆ , (EO) ₁₇ (PO) ₅₆ (EO) ₁₇ , ( EO) ₁₇ (PO) ₅₈ (EO) ₁₇ , (EO) ₂₀ (PO) ₇₀ (EO) ₂₀ , (EO) ₈₀ (PO) ₃₀ (EO) ₈₀ , (EO) ₁₀₆ (PO) ₇₀ (EO) ₁₀₆ , (EO) ₁₀₀ (PO) ₃₉ (EO) ₁₀₀ , (EO) ₁₉ (PO) ₃₃ (EO) ₁₉ , (EO) ₂₆ (PO) ₃₆ (EO) ₂₆ . These triblock copolymers are available from BASF, Aldrich, etc., and triblock copolymers having desired x and y values can be obtained at a small scale production level.

Also, a star diblock copolymer in which two polyethylene oxide (EO) chains-polypropylene oxide (PO) chains are bonded to two nitrogen atoms of ethylenediamine can be used. Examples of such star diblock copolymers include those represented by the general formula ((EO) _x (PO) _y ) ₂ NCH ₂ CH ₂ N ((PO) _y (EO) _x ) ₂ . Here, x and y represent the number of repetitions of EO and PO, respectively, x is preferably 5 to 110, y is preferably 15 to 70, x is 13 to 106, and y is 29 to 70. preferable.

Among such surfactants, since a highly crystalline mesoporous material can be obtained, a salt (preferably a halide salt) of alkyltrimethylammonium [C _p H _{2p + 1} N (CH ₃ ) ₃ ] is used. It is preferable. In that case, the alkyl group in the alkyltrimethylammonium preferably has 8 to 22 carbon atoms. Examples include octadecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, decyltrimethylammonium bromide, octyltrimethylammonium bromide, and docosyltrimethylammonium chloride. It is done.

  When a mesoporous material is obtained as a polymer of the monomer, the monomer is polymerized in a solution containing the surfactant, and the concentration of the surfactant in the solution is 0.05 to 1 mol / L. It is preferable. If this concentration is less than the lower limit, the formation of pores tends to be incomplete. On the other hand, if the concentration exceeds the upper limit, the amount of unreacted surfactant remaining in the solution increases, resulting in uniform pores. Tend to decrease.

  Moreover, you may remove the surfactant contained in the mesoporous material obtained in this way. As a method for removing the surfactant in this way, for example, (i) the surfactant is immersed in an organic solvent (for example, ethanol) or a supercritical fluid having high solubility in the surfactant to immerse the surfactant. A method of removing, (ii) a method of removing the surfactant by baking the mesoporous material at 300 to 1000 ° C., and (iii) heating the mesoporous material by immersing the mesoporous material in an acidic solution. An ion exchange method in which ions are exchanged can be mentioned.

  Such a mesoporous material can be obtained according to the method described in JP-A-2001-114790.

  As described above, the merit of making the luminescent material according to the present invention porous is that (i) by introducing another luminescent compound into the pores, the excitation energy of the pore walls is efficiently converted into the luminescent compound. It is possible to emit multicolor light by moving, (ii) the durability of the luminescent compound introduced into the pores is improved, and (iii) the refractive index of the luminescent layer is reduced, thereby reducing the light emission. There is an advantage that the extraction efficiency can be improved. For example, when a lens and a light emitting layer are formed on the light source, the light emitted from the light source is reflected at the interface between the light source and the lens, the interface between the lens and the light emitting layer, or the interface between the light emitting layer and the air. There is a problem that the efficiency of taking out is reduced. In general, when the refractive index of the light emitting layer is closer to the refractive index of air, the light extraction efficiency is higher. By making the light emitting material porous, the refractive index can be made closer to the refractive index of air.

(Luminescent material further comprising other luminescent compounds)
The structure of the luminescent material according to the present invention further comprising another luminescent compound is not particularly limited. However, in the non-porous or porous luminescent material according to the present invention, the other luminescent compound is adsorbed, bonded, or packed. , It may be in any state of mixing. In the case of non-porous luminescent materials, adsorption means the state in which a luminescent compound is attached to the surface of particles or membranes of the luminescent material, and in the case of porous luminescent materials, to the inside or outside of the pores of the luminescent material. Say. Bonding refers to the case where this attachment involves a chemical bond. Filling is a state in which another luminescent compound exists in the pores of the porous luminescent material, and in this case, it does not have to be attached to the inner surface of the pores. A substance other than the other luminescent compound is filled in the pores, and the other luminescent compound may be contained in the substance. Substances other than the luminescent compound include surfactants. Mixing refers to a state in which a non-porous or porous light emitting material and other light emitting compounds are physically mixed. At this time, another material other than the light emitting material and the other light emitting compound may be further mixed.

  Although it does not specifically limit as a method further provided with another luminescent compound, There exists a method of mixing a nonporous or porous luminescent material and another luminescent compound. At this time, when other luminescent compounds are dissolved in a suitable solvent and then mixed, a more uniform mixing can be achieved and light can be emitted efficiently.

  In addition, there is a method in which another luminescent compound is introduced simultaneously with the synthesis of the luminescent material. That is, the other monomer is added to the monomer for polymerization. In this case, a surfactant may be further added for polymerization. When a surfactant is added, a porous structure is formed in the polymer due to the template effect of the surfactant, but the pores are filled with the surfactant and other luminescent compounds, There are no typical pores. The amount of the other light-emitting compound is not particularly limited, but if 1 to 10 mol% is added to the monomer, the skeleton energy can be sufficiently transferred to the light-emitting compound.

  In polymers with other luminescent compounds, the skeleton composed of the polymer of the monomer can efficiently absorb light and transfer its energy to other luminescent compounds efficiently. Light emission of different wavelengths based on the luminescent compound can be obtained. At this time, the skeleton composed of the polymer of the monomer serves as a light collecting antenna, and the collected light energy can be injected intensively into other light emitting compounds, thereby realizing high efficiency and strong light emission. Can do.

  The method for adsorbing, bonding, filling, or mixing (hereinafter, collectively referred to as “attachment” in some cases) other luminescent compounds to the polymer of the organosilicon compound according to the present invention is not particularly limited, and ordinary methods are used. it can. For example, a method of spraying, impregnating or immersing a solution of another light-emitting compound to be attached to the polymer and then drying can be used. At this time, you may wash | clean as needed. Moreover, you may depressurize or vacuum deaerate at the time of attachment or drying. By such attachment, other luminescent compounds are attached to the surface of the polymer, filled in the pores, or adsorbed. The principle of multicolor emission is not the same depending on the type and composition of such organosilicon compound and other luminescent compounds, the distance and bonding strength between the two compounds, the presence or absence of surfactants, etc. Color emission is possible. In the luminescent material according to the present invention, the other luminescent compounds attached to the polymer of the organosilicon compound can be used alone or in combination of two or more.

  When the luminescent material according to the present invention is the porous body, as described above, it is preferable to adsorb (physically adsorb and / or chemically bond) other luminescent compounds to the porous body.

  When the other luminescent compound adsorbed on the porous body is provided, the other luminescent compound is preferably adsorbed on the surface of the porous body, particularly the inner wall surface of the pore. Such adsorption may be physical adsorption caused by the interaction between the other luminescent compound and the functional group present on the surface of the porous body, but one end of the other luminescent compound is attached to the surface of the porous body. It may be immobilized by chemically bonding to an existing functional group. In the latter case, another luminescent compound has a functional group chemically bonded to a functional group present on the surface of the porous body (for example, trialkoxysilyl group, dialkoxysilyl group, monoalkoxysilyl group, It is preferable to have a trichlorosilyl group or the like.

  As a method of adsorbing other luminescent compounds to the porous body, the porous body is immersed in an organic solvent solution (for example, benzene, toluene) in which the other luminescent compound is dissolved, and the temperature is about 0 to 80 ° C. A method of stirring for about 24 hours is preferable, whereby other luminescent compounds are adsorbed (immobilized) to the porous body by physical adsorption and / or chemical bonding.

  Such other light-emitting compounds are not particularly limited, and are porphyrins, anthracenes, aluminum complexes, rare earth elements or complexes thereof, fluorescein, rhodamine (B, 6G, etc.), coumarin, pyrene, dansylic acid, cyanine dyes. Photofunctional molecules such as merocyanine dyes, styryl dyes, and benzstyryl dyes. Further, the amount of the other luminescent compound adsorbed on the porous body is not particularly limited, but is generally preferably about 0.5 to 50 parts by weight with respect to 100 parts by weight of the porous body.

  In addition, phosphorescent materials are preferable as other light-emitting compounds according to the present invention, and some of these phosphorescent materials have large differences in absorption and emission wavelengths compared to fluorescent materials. Therefore, by using such a phosphorescent material, it is possible to absorb short-wavelength ultraviolet light and efficiently emit long-wavelength red light. By combining such a phosphorescent material with an organosilicon compound having light emission in the ultraviolet light region, light emission in a wide wavelength region from blue to red can be achieved. The phosphorescent material to be used is not particularly limited, and preferred examples include those having the following structural formulas capable of emitting light with relatively high efficiency at room temperature.

(Light-emitting material in the form of a thin film)
The polymer obtained by polymerizing the monomer (the polymer of the organosilicon compound represented by the general formula (1)) is usually in the form of particles, but is in the form of a thin film, and the thin film is subjected to predetermined patterning. It is also possible to have a pattern shape.

  Thus, when obtaining a thin-film-like luminescent material, first, the monomer is stirred in an acidic solution (aqueous solution of hydrochloric acid, nitric acid or the like, or an alcohol solution) to cause a reaction (partial hydrolysis and partial condensation reaction). A sol solution containing a partial polymer is obtained. Since such a monomer hydrolysis reaction is likely to occur in a low pH region, partial polymerization can be promoted by lowering the pH of the system. At this time, the pH is preferably 2 or less, and more preferably 1.5 or less. Moreover, the reaction temperature in that case can be made into about 15-25 degreeC, and reaction time can be made into about 30 to 90 minutes.

  Next, a thin-film luminescent material can be produced by applying this sol solution to a substrate by various coating methods. In addition, as various coating methods, it can apply | coat using a bar coater, a roll coater, a gravure coater, etc. Moreover, dip coating, spin coating, spray coating, etc. are also possible. Furthermore, it is also possible to form a patterned light emitting material on a substrate by applying a sol solution by an ink jet method.

  Next, the obtained thin film is preferably heated to about 40 to 150 ° C. and dried, and then the condensation reaction of the partial polymer is advanced to form a three-dimensional crosslinked structure. The average film thickness of the obtained thin film is preferably 1 μm or less, and more preferably 0.1 to 0.5 μm. When the film thickness exceeds 1 μm, the luminous efficiency tends to decrease.

  In addition, if the above-mentioned periodic structure is formed in such a thin film, the emission intensity from the thin film can be further improved by forming the periodic structure of the fluorescent molecules in the thin film. Moreover, it becomes possible to form a regular pore structure in the thin film by adding the above-mentioned surfactant to the sol solution. Thus, when the thin film is a porous body, the other luminescent compound can be adsorbed to the porous body, and thereby light emission having a wavelength different from the original emission wavelength of the fluorescent molecule can be generated. Become.

  Such a thin-film luminescent material can be obtained in accordance with a method described in JP-A-2001-130911.

(Light-emitting material that is a layered substance)
As a form of a polymer obtained by polymerizing the monomer (a polymer of an organosilicon compound represented by the general formula (1)), a layered substance formed by laminating nanosheets each having a thickness of 10 nm or less is used. It is also possible. That is, when the monomer is polymerized (hydrolysis and condensation) in the presence of the surfactant, such a layered material can be obtained by controlling the synthesis conditions.

  As described above, when the light emitting material according to the present invention is formed into a layered substance, the nanosheet can be swollen by being immersed in a solvent, and a thin film (preferably a nanosheet having a thickness of 10 nm or less) is easily produced. Will be able to.

[Light emitting layer]
The light emitting layer according to the present invention includes the light emitting material. Such a light emitting layer is not particularly limited. For example, the light emitting layer can be obtained by monolayering or laminating a thin film light emitting material as described above, or a particulate light emitting material as described above can be dispersed in a matrix. A thin film-like material is mentioned. Examples of the matrix capable of dispersing such particulate light emitting materials include (meth) acrylic acid-based resins, epoxy, urethane crosslinkable, crosslinkable resins such as UV curing, polycarbonate, silicon resin, rubber, Polyvinyl resin, polyethylene resin, polypropyl resin, polyester resin, etc. are mentioned, and epoxy resin, polycarbonate, silicon resin, rubber, etc. are preferable from the viewpoint of translucency, heat resistance, durability, dispersibility, etc. .

  Moreover, when the said luminescent material is disperse | distributed to a matrix, it is preferable to contain about 10-400 mass parts of said luminescent materials with respect to 100 mass parts of matrices. If the content of the light emitting material is less than the lower limit, the light emitting element obtained tends to have insufficient light emission. On the other hand, if the content exceeds the upper limit, the luminous efficiency tends to decrease due to aggregation of the light emitting material powder. is there. In the present invention, since the light emitting layer emits light more uniformly by dispersing the light emitting material more uniformly in the matrix, when the light emitting material is dispersed in the matrix, the light emitting material is used in the matrix. After the addition, it is preferable to uniformly disperse the mixture by sufficiently stirring, mixing, etc. using a Henschel mixer, homomixer, homogenizer, ribbon blender, ball mixer or the like.

  Moreover, as thickness of a light emitting layer, although it changes with uses etc. of the light emitting element obtained, it is preferable that it is 0.05-2 micrometers, and it is more preferable that it is 0.1-1 micrometer. If the thickness of the light emitting layer is less than the lower limit, the light absorption rate tends to decrease. On the other hand, if the thickness exceeds the upper limit, the light emission efficiency tends to decrease.

  Furthermore, when a lens is disposed on the light source and a light emitting layer is formed on the lens, the refractive index of the light emitting layer is preferably 1.5 or less. As the refractive index value is 1.5 or less and closer to the refractive index 1 of air, when light is emitted from the light emitting layer into the air, loss due to reflection or the like is suppressed, and the light extraction rate tends to be improved. .

[light source]
The light source according to the present invention is not particularly limited, and a light source capable of emitting excitation light to the light emitting material can be used. For example, an AlGaN ultraviolet light emitting diode (peak wavelength: 352 nm), sapphire substrate + AlGaN Conductive layer (peak wavelength: 290 nm, 275 nm: Sandia National Laboratory), diamond LED (peak wavelength: 235 nm: National Institute for Materials Science), ultraviolet light emission using p-type semiconductor described in JP-A-2004-228489 Element, combination with UV-LED such as InAlGaN-based ultraviolet LED (peak wavelength: 300 to 350 nm) described in JP-A No. 2001-237455; trade name “NSHU590B” (peak wavelength: 365 nm) manufactured by Nichia Chemical; Product name “E1L5M-4P0A2” manufactured by Toyoda Gosei (peak wavelength: 38 nm), a commercial LED such as a trade name “LED3-UV-400-30” (peak wavelength: 400 nm) manufactured by BivarOpto; ultraviolet light; germicidal lamp (peak wavelength: 254 nm); black light (peak wavelength: 352 nm) A UV-B lamp (peak wavelength: 306 nm).

[Light emitting element]
The light emitting element of this invention is equipped with the light emitting layer containing the said luminescent material, and the said light source. With such a light emitting element, excellent light absorption efficiency is achieved, the light emission efficiency is improved, and uniform light emission in the surface is possible, as well as imparting excellent heat resistance to the light emitting element. It becomes possible.

  Hereinafter, preferred embodiments of the light emitting device of the present invention will be described with reference to the drawings. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and duplicate descriptions are omitted.

  As a preferred embodiment of the light emitting device of the present invention, the light emitting device shown in FIG. 1 can be exemplified. The light emitting element shown in FIG. 1 includes a light source 1, a lens 2, a light emitting layer 3, and a table 4. In the light emitting element shown in FIG. 1, a lens 2 is disposed on a light source 1, a light emitting layer 3 is disposed on the surface of the lens 2, and the light source 1 is fixed on a table 4. ing.

  In the light emitting device having the configuration in which the light emitting layer 3 is disposed on the surface of the lens 2 as shown in FIG. 1, the light extraction layer 3 has a lower refractive index than that of the lens, thereby extracting higher light. Efficiency tends to be demonstrated. In addition, a hard glass lens etc. can be used suitably as the lens 2 shown in FIG. 1, and the stand 4 is not specifically limited, For example, ceramics, resin, etc. can be used suitably.

  Next, as another preferred embodiment of the light emitting device of the present invention, a light emitting device shown in FIG. 2 will be described. The light emitting element shown in FIG. 2 includes a light source 1, a lens 2, a light emitting layer 3, and a table 4. In the light emitting element shown in FIG. 2, the light emitting layer 3 is disposed on the surface of the light source 1, and the lens 2 is disposed on the light emitting layer 3. In the light emitting element shown in FIG. 2, the light source 1 is fixed on the base 4.

  In addition, in the light emitting device having the configuration in which the light emitting layer 3 is arranged on the surface of the light source 1 as shown in FIG. Tend to be achieved. In addition, when the light emitting layer 3 made of the light emitting material containing another light emitting compound (colorant or the like) is used, the light emitting layer 3 can absorb ultraviolet light and convert it into visible light to emit light. Therefore, when the lens 2 is arranged, for example, a resin lens can be used as the lens 2, and it is possible to reduce the cost and weight.

  The preferred embodiment of the light emitting device of the present invention has been described above with reference to the drawings. However, the light emitting device of the present invention is not limited to the embodiment shown in FIG. 1 or FIG. The light emitting element can also be used. Moreover, in this invention, if it is provided with the light source concerning the above-mentioned this invention and the light emitting layer concerning the above-mentioned this invention, it can be set as the light emitting element of the form match | combined to these uses freely. Is possible.

  The method for producing the light emitting device of the present invention is not particularly limited, and for example, the above-described sol solution containing the light emitting material is appropriately applied to the surface of the light source by employing a known coating method. A method of manufacturing a light emitting device by directly forming a thin film (light emitting layer) of the light emitting material on the surface, or a dispersion in which a powder of the light emitting material is dispersed in a matrix resin (binder) on the surface of the light source A method of manufacturing a light-emitting device by applying a known coating method as appropriate and forming a thin film (light-emitting layer) of the light-emitting material directly on the surface thereof can be mentioned.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. Note that FP-6600 Spectrofluorometer manufactured by JASCO was used for measurement of fluorescence or phosphorescence spectrum and excitation spectrum. In addition, the intensity (Intensity) on the vertical axis of the fluorescence or phosphorescence spectrum is expressed as an energy amount.

<Synthesis and emission characteristics test of phenyl silica composite material>
Example 1
To a mixture of ion-exchanged water (500 g) and 6N NaOH aqueous solution (40 g, 200 mmol NaOH), octadecyltrimethylammonium chloride (ODTMA, [C ₁₈ H ₃₇ N (CH ₃ ) ₃ Cl], manufactured by Tokyo Chemical Industry) (16.665 g, 47.88 mmol) was dissolved at 50-60 ° C. To the solution, 1,4-bistriethoxysilylbenzene (BTEB, manufactured by Azmax) (20 g, 49.67 mmol) was added at room temperature with vigorous stirring. The mixed solution was dispersed in an aqueous solution over 20 minutes using an ultrasonic device to disperse the hydrophobic BTBB that had been separated, and stirring was continued for 20 hours at room temperature. The solution was left in an oil bath at 95 ° C. for 20 hours. The white precipitate formed was filtered and dried to obtain a mesoporous material precursor (8.22 g) containing a surfactant. 1 g of the precursor was dispersed in ethanol (250 ml) to which 9 g of 36% HCl aqueous solution was added, and the surfactant in the precursor was extracted with a solvent by heating and stirring at 70 ° C. for 8 hours. A mesoporous material (Ph-HMM-c) of a phenyl silica composite material was obtained.

(Example 2)
A mixed solution of 50 g of water and 4 g of NaOH was stirred, and 2 g of BTEB was quickly put therein. It was then sonicated for 20 minutes. At this point, the solution began to become cloudy. And after stirring for 24 hours at room temperature, it became a translucent liquid. Thereafter, it was left to reflux at 98 ° C. for 20 hours. The solution started to become cloudy after the temperature was applied, and then a precipitate gradually formed. The precipitate was filtered and dried at room temperature to obtain phenyl silica composite material (Ph-Si) as a white powder.

(Example 3)
A triblock copolymer poly (ethylene oxide) ₂₀ -poly (propylene oxide) ₇₀ -poly (ethylene oxide) ₂₀ ; (P123: Mav = 5800) was used from Aldrich. After 0.99 g of P123 was dissolved in 36 ml of ion exchange water, 200 ml of hydrochloric acid (36 wt%) was added. To this solution was added 1.01 g of BTEB at 0 ° C. (in an ice bath), and the mixture was stirred for 1 hour and then heated and stirred at 35 ° C. for 20 hours. This was transferred to a sealed container and further heated at 100 ° C. for 24 hours. After allowing to cool to room temperature, filtration, washing and drying were performed to obtain a mesoporous material precursor containing a surfactant. This precursor was dispersed in 60 times the amount of ethanol, stirred for 1 hour or more, filtered, dried, and then fired in air at 350 ° C. for 2 hours to obtain 0.3 g of a mesoporous body of phenyl silica composite material ( Ph-HMM-a) was obtained.

FIG. 3 shows the X-ray diffraction patterns of Ph-HMM-c obtained in Example 1 and Ph-Si obtained in Example 2. C ₁₈ TMA ⁺ Cl as templates ^- in Ph-HMM-c was synthesized by adding, with peak indicating the mesostructure (2D hexagonal) in 2 [Theta] = 1 to 3 °, 7.6 indicating the periodicity of benzene in the backbone , 3.8, and 2.5 nm peaks were confirmed. Ph-Si synthesized without adding a surfactant did not show a peak showing mesostructure, but a peak showing periodicity of benzene in the skeleton was confirmed. Further, in order to examine the respective pore structure was measured N ₂ adsorption isotherm. FIG. 4 shows the N ₂ adsorption isotherm of Ph-HMM-c. The adsorption isotherm was type IV and was confirmed to have a typical mesoporous structure, and the pore diameter and specific surface area were 3.0 nm and 835 m ² / g, respectively. However, it was confirmed that the specific surface area of Ph-Si was small and it did not have mesopores. From the above results, it is confirmed that Ph-HMM-c has both a pore structure and a periodic structure of benzene, and Ph-Si does not have a pore structure, but has a benzene periodic structure in the skeleton. did it.

On the other hand, FIG. 5 shows the X-ray diffraction pattern of Ph-HMM-a synthesized in Example 3 under acidic conditions. A peak showing a mesostructure (2D hexagonal) was observed at 2θ = 0.5 to 1 °. However, no peak indicating the periodicity of benzene in the skeleton was observed. In addition, the N ₂ adsorption isotherm shown in FIG. 4 is type IV, and it is confirmed to have a typical mesoporous structure, and the pore diameter and specific surface area are 6.3 nm and 773 m ² / g, respectively. Met. From the above results, it can be confirmed that Ph-HMM-a synthesized with P123 as a template under acidic conditions has a regular pore structure but no periodicity of benzene in the pore skeleton. It was.

  The synthesis conditions in Examples 1 to 3 and the structures of the obtained samples are shown in Table 1.

  In FIG. 6, the SEM photograph of Ph-Si obtained in Example 2 is shown. It was confirmed that the particle size of this substance was about 100 nm. In addition, it was confirmed by thermogravimetric analysis that the structure of Ph-Si maintained up to 500 ° C.

The visible absorption spectrum of each sample obtained in Examples 1 to 3 is shown in FIG. The absorption spectrum of Ph-HMM-a was broad, and the maximum absorption wavelength (λ _max ) was 285 nm. The absorption terminal was observed up to a long wavelength of 550 nm (2.3 eV). On the other hand, the absorption spectrum of Ph-HMM-c showed large absorption at 285 nm and 240 nm, which is the same as λ _max of Ph-HMM-a. The peak width was narrower than that of Ph-HMM-a, and the absorption end was 310 nm (4.0 eV). In addition, although it is thought that the peak of 240 nm exists also in Ph-HMM-a, since the peak is broad, it is considered that it overlaps with 280 nm. In addition, the same absorption spectrum as Ph-HMM-c was obtained in Ph-Si, so the difference in absorption spectrum strongly depends on the periodicity of benzene in the skeleton, not on the pore structure of each sample. It was confirmed that

  FIG. 8 shows the fluorescence spectrum of each sample obtained in Examples 1-3. Ph-HMM-a, which has a mesopore structure but has almost no benzene periodicity in the skeleton, did not show strong fluorescence. This can be explained by the following characteristics of Ph-HMM-a. First, in Ph-HMM-a, since the UV absorption terminal is long and broad, it is expected that various energy levels exist in the excited state. For this reason, it is considered that the fluorescence was weakened after passing through various levels when returning to the ground state after being excited at 260 nm. In addition, because of the low regularity of benzene in the skeleton, quenching due to the formation of excimers and the possibility of energy being released out of the system due to heat are also considered.

  On the other hand, in Ph-HMM-c, which has a mesoporous structure and benzene periodicity in the skeleton, and Ph-Si that has no mesopores but benzene periodicity, the excitation light was weak. Even so, the intensity of the emitted fluorescence was strong. In addition, a sharp absorption was observed at 280 nm according to the UV-vis absorption spectrum, but interestingly, an absorption wavelength of 310 nm or more was not observed. It shows that the level between the ground state and the excited state is degenerated, that is, each band is narrowed. For these reasons, it was confirmed that the energy transfer in the phenyl group was stably caused by the regular arrangement of the phenyl group in the skeleton. In addition, the quantum well effect can be cited as another reason for showing fluorescence in Ph-HMM-c and Ph-Si in spite of weak excitation light. In other words, both Ph-HMM-c and Ph-Si have a regular structure in which phenyl groups and silicate layers are alternately arranged, so that when excited at 260 nm, silicate layers with high absorption energy are excited. Instead, light acts only on the phenyl group layer. Since the excited phenyl group layer is sandwiched between silicate layers that do not contribute to light absorption, light is confined in the phenyl group layer, and as a result, benzene silica is considered to emit strong fluorescence.

<Synthesis of biphenyl silica composite and emission characteristics test>
(Examples 4 to 5)
ODTMA (3.2 mmol) was dissolved at 50-60 ° C. in a mixture of ion-exchanged water (3.3 mol) and 6N NaOH aqueous solution (30.4 mmol). To the solution, 4,4′-bistriethoxysilylbiphenyl (BTEBP, manufactured by Azmax) (2.5 mmol) was added at room temperature with vigorous stirring, and stirring was continued for 20 hours at room temperature. The solution was left in an oil bath at 95 ° C. for 22 hours. The white precipitate thus formed was filtered and dried to obtain a mesoporous material precursor (BiPh-HMM-cs) containing a surfactant. Disperse 0.75g of the precursor in ethanol (150ml) with 3.1g of 2M aqueous hydrochloric acid solution and stir at room temperature for 8 hours to extract the surfactant in the precursor with a solvent, biphenyl silica composite material The mesoporous material (BiPh-HMM-c) was obtained.

(Example 6)
A mixed solution of water (120 ml) and NaOH (6 g) was stirred, and 2 g of BTEBP was quickly put therein. It was then sonicated for 20 minutes. At this point, the solution was still clear and BTEBP and water separated into two layers. And it became a uniform transparent solution by stirring for 24 hours at room temperature. Thereafter, the mixture was allowed to stand at 98 ° C. for 72 hours under reflux. After 24 hours, it started to become cloudy and precipitation started. The solid content was filtered and then dried at room temperature to obtain a biphenyl silica composite material (BiPh-Si-Base) as a powder.

(Example 7)
To an acidic solution obtained by adding 2 ml of 12N HCl to 36 g (2 mol) of water, 0.6 g (1.25 mmol) of BTEBP was added, subjected to ultrasonic treatment for 20 minutes, and then stirred at room temperature for 24 hours. The resulting mixture was stirred at 35 ° C. for 24 hours, filtered and washed to obtain a white powder. The mixing ratio of the synthesis was BTEBP: H ₂ O: HCl = 1: 412: 4.8. This white powder was calcined in air at 300 ° C. for 2 hours to obtain the target biphenyl silica composite material (BiPh-Si-Acid).

(Examples 8 to 9)
BTEBP (1.2 g) was added to a mixed solution of P123 (0.99 g) and 2N aqueous hydrochloric acid (40 ml) with vigorous stirring. The mixing temperature was 30 ° C. The mixture was stirred at 30 ° C. for 20 hours and then allowed to stand at room temperature for 48 hours. Next, this mixed solution was put in a Teflon autoclave and heated at 100 ° C. for 24 hours. The solid content was filtered and dried at room temperature to obtain a precursor of mesoporous material (BiPh-HMM-as) containing a surfactant. 0.5 g of this precursor was added to a mixture of ethanol (200 ml) and 2N aqueous hydrochloric acid (0.5 g), and stirred at room temperature for 8 hours. This operation was repeated once more to obtain a biphenyl silica composite mesoporous material (BiPh-HMM-a) from which the surfactant was completely removed.

The X-ray diffraction pattern of BiPh-HMM-c obtained in Example 4 is shown in FIG. 9, and the X-ray diffraction pattern of BiPh-HMM-cs obtained in Example 5 is shown in FIG. In both cases, a peak at 1.19 nm indicating the periodicity of biphenyl in the skeleton was confirmed along with a peak indicating a mesostructure (2D hexagonal) at 2θ = 1 to 3 °. Further, FIG. 11 shows the result of measuring the N ₂ adsorption isotherm in order to investigate the pore structure of BiPh-HMM-c obtained in Example 4. The adsorption isotherm was type IV, and it was confirmed to have a typical mesoporous structure. The pore size and specific surface area of BiPi-HMM-c were 3.0 nm and 709 m ² / g, respectively.

  The X-ray diffraction pattern of BiPh-Si-Base obtained in Example 6 is shown in FIG. 12, and the X-ray diffraction pattern of BiPh-Si-Acid obtained in Example 7 is shown in FIG. In these, no peak indicating a mesostructure on the low angle side was observed, and only a peak at 1.19 nm indicating biphenyl periodicity was observed. From this, it was confirmed that the biphenyl silica composite material synthesized without a surfactant also has a structure in which biphenyl groups are regularly arranged. An SEM photograph of BiPh-Si-Base obtained in Example 6 is shown in FIG. From this SEM photograph, it was confirmed that the primary particle diameter of BiPh-Si-Base obtained in Example 6 was as small as 100 nm or less.

The X-ray diffraction pattern of BiPh-HMM-a obtained in Example 8 is shown in FIG. 15, and the X-ray diffraction pattern of BiPh-HMM-as obtained in Example 9 is shown in FIG. BiPh-HMM-a and BiPh-HMM-as synthesized under acidic conditions using a surfactant showed a clear peak with a mesostructure at 2θ = 0.5 to 1 °. The peak showing sex was small. The nitrogen adsorption isotherm of BiPh-HMM-a obtained in Example 8 is shown in FIG. The specific surface area was as high as 926 m ² / g. The pore diameter was 5.5 nm. From the above results, it was confirmed that the sample synthesized using P123 as a template under acidic conditions has a regular pore structure, but the periodicity of biphenyl in the pore skeleton is low.

  The synthesis conditions in Examples 4 to 9 and the structures of the obtained samples are shown in Table 2.

Visible absorption spectra of BiPh-HMM-a obtained in Example 8 and BiPh-HMM-c obtained in Example 4 are shown in FIGS. 18 and 19, respectively. The absorption spectrum of BiPh-HMM-a was broad, and the maximum absorption wavelength (λ _max ) was 300 nm. The absorption terminal was observed up to a long wavelength of 600 nm. On the other hand, the absorption spectrum of BiPh-HMM-c showed a large absorption at 303 nm, which is the same as λ _max of BiPh-HMM-a. The peak width was narrower than that of BiPh-HMM-a, and the absorption end was 325 nm. In BiPh-HMM-a, a peak at 240 nm is considered to exist, but since the peak is broad, it is considered that it overlaps with 280 nm.

FIG. 20 shows fluorescence spectra measured with 300 nm excitation light for the samples obtained in Examples 4-9. The mesoporous material BiPh-HMM-a with low regularity of biphenyl did not show strong fluorescence. However, the mesoporous material BiPh-HMM-c having a high biphenyl periodic structure showed strong fluorescence. BiPh-HMM-c was confirmed to glow blue when the sample was irradiated with excitation light (250 nm). Compared with biphenyl (C ₆ H ₅ -C ₆ H ₅ ), an increase in the fluorescence intensity of BiPh-HMM-c and a red shift of the maximum emission wavelength toward the visible light side were confirmed. When compared with benzene silica, the maximum emission wavelength due to the difference in π conjugation was red-shifted and the fluorescence intensity was increased. This is probably because the increase in fluorescence intensity is due to the higher biphenylene quantum yield (0.69) than that of benzene (0.29).

  On the other hand, it was found that Ph-HMM-a-s and BiPh-HMM-c-s containing surfactants in the mesopores showed stronger fluorescence than mesoporous materials from which the surfactant was removed. This is considered to be because the template (surfactant) was still introduced into the mesopores, so that oxygen could not contact the biphenyl group and quenching by oxygen was suppressed.

  In addition, BiPh-Si synthesized without template showed strong fluorescence intensity. However, the fluorescence intensity of BiPh-Si-Acid synthesized under acidic conditions was stronger than that of BiPh-Si-Base. This is probably because BiPh-Si-Acid synthesized under acidic conditions has higher biphenyl orientation than BiPh-Si-Base.

<Synthesis of thin-film luminescent material and luminescent property test (1)>
(Example 10)
To 2 g of ethanol (EtOH), 0.09 g of ion exchange water and 10 μl of 2N aqueous hydrochloric acid were added to obtain a uniform solution. To this solution, 0.6 g of BTEBP was added with stirring. After stirring at room temperature for 1 hour, a solution prepared by dissolving 0.43 g of the surfactant Brij76 (C ₁₈ H ₃₇ (EO) ₁₀ ) in 2 g of EtOH was added, and the mixture was further stirred for 1 hour to obtain a transparent sol. A solution was obtained. The composition of the sol solution was BTEBP: Brij76: H ₂ O: HCl: EtOH = 1: 0.48: 4: 0.016: 69.4. This sol solution was coated on a glass substrate by a dip coating method to obtain a uniform coating film (film thickness: 450 nm). The dipping conditions were a dipping speed of 2 cm / min and an immersion time of 2 minutes.

  The photograph which shows the light emission state of the thin film when the X-ray diffraction pattern of the thin film (BiPh-HMMc-s-film) obtained by Example 10 (BiPh-HMMc-s-film), a fluorescence spectrum, and the backlight of 254 nm is irradiated 21, 22, and 23, respectively. In the X-ray diffraction pattern, a strong peak was observed at d = 6.4 nm, and it was confirmed that a regular mesostructure was present (FIG. 21). However, a peak at d = 1.19 nm corresponding to the periodic structure of biphenyl was not observed. In the fluorescence spectrum, strong emission centered on 380 nm was confirmed (FIG. 22). Further, it was confirmed that when the thin film was irradiated with light of 254 nm, it glowed blue (FIG. 23).

(Examples 11 to 13)
10 μl of 2N hydrochloric acid aqueous solution was added to a mixed solvent of 2 g of ethanol (EtOH) and 0.09 g of ion-exchanged water. To this solution, 0.6 g of BTEBP was added with vigorous stirring and stirred at room temperature for 30 minutes. A solution obtained by dissolving 0.43 g of Brij76 (C ₁₈ H ₃₇ (EO) ₁₀ ) as a surfactant in 2 g of EtOH was added thereto, and the mixture was further stirred for 30 minutes to obtain a transparent sol solution. The composition of the sol solution was BTEBP: Brij76: H2O: HCl: EtOH = 1: 0.48: 4: 0.016: 69.44. This sol solution was diluted with 2.65 g of EtOH to prepare Solution A. On the other hand, 0.01 g of polyvinylcarbazole (PVK) was dissolved in 5 g of tetrahydrofuran to prepare a solution B.

  Predetermined amount of solution so that the content ratio (solid content) of PVK and BiPh-HMM in the thin film (PVK / BiPh-HMM film) of the obtained PVK-containing biphenyl silica composite material becomes the composition (weight basis) shown in Table 3 A and B are mixed to prepare a mixed solution, and the resulting mixed solution is spin-coated at a rotation speed of 3000 rpm and a rotation time of 30 s, so that a uniform coating film (film thickness: 100 to 300 nm) is formed on the glass substrate. Got. In Example 11, 2.65 g of EtOH was not diluted, and a coating film was prepared by a dip coating method.

  FIG. 24 is a photograph showing the light emission state of the thin film when the sample 1 obtained in Example 11, the sample 2 obtained in Example 12, and the sample 3 obtained in Example 13 were each irradiated with a backlight of 254 nm. Shown in Strong luminescence was confirmed in all samples. The fluorescence spectra of Samples 1 to 3 obtained in Examples 11 to 13 are shown in FIG.

<Comparison test of luminescent properties with conventional luminescent materials>
(Comparative Examples 1-3)
In order to compare the emission spectrum of the present invention with the typical emission materials of conventional light emitting materials, the following three types of light emitting materials were used as typical conventional light emitting materials. A powder of these luminescent materials and a coating film (film thickness: 200 nm) formed on a glass substrate were prepared. In addition, about the coating film, each luminescent material was formed into a film by the sputtering method.
Comparative Example 1: Bis [N- (1-naphthyl) -N-phenyl] benzidine (NPB)
Comparative Example 2: 4,4'-Bis (9-carbazolyl) -biphenyl (CBP)
Comparative Example 3: Poly (9-vinylcarbazole) (PVK).

  The fluorescence spectrum of the mesoporous material (surfactant-containing BiPh-HMM-cs) powder of the biphenyl silica composite material obtained in Example 5 and the luminescent material powders of Comparative Examples 1 to 3 were measured and obtained. The results are shown in FIG. The excitation wavelength was 300 nm for BiPh-HMM-c-s and 365 nm for CBP, NBP, and PVK.

  Moreover, the fluorescence spectrum of the thin film (BiPh-HMM-cs-film) of the biphenyl silica composite material obtained in Example 10 and the thin film of the light emitting material of Comparative Examples 1 to 3 was measured, and the obtained results are shown in FIG. Shown in The excitation wavelength was 300 nm for BiPh-HMM-c-s-film and 256 nm for CBP, NBP, and PVK.

  Comparing the results shown in FIG. 26 and FIG. 27, both the BiPh-HMM-cs and BiPh-HMM-cs-film, which are the luminescent materials of the present invention, emit light as strongly as or more than the conventional luminescent materials. It was confirmed that

<Comparison test with light emission characteristics of monomer solution>
(Comparative Example 4)
A solution in which dichloromethane and monomer reagent 1,4-bistriethoxysilylbenzene (BTEB) were mixed at each mixing ratio (unit: mM) shown in FIG. 28 was prepared, and the fluorescence spectrum of the sample solution was measured. The obtained result is shown in FIG.

(Comparative Example 5)
A solution in which dichloromethane and monomer reagent 1,4-bistriethoxysilylbiphenyl (BTEBP) were mixed at each mixing ratio (unit: mM) shown in FIG. 29 was prepared, and the fluorescence spectrum of the sample solution was measured. The obtained result is shown in FIG.

  Both BTEB and BTEBP had a concentration that showed a maximum in fluorescence intensity. The cause of quenching before and after the maximum concentration is due to concentration quenching when the sample concentration is high, and due to a decrease in emission of the number of molecules per se when the sample concentration is low.

(Comparative Example 6)
A solution in which dichloromethane and benzene that does not contain a Si source as a monomer reagent were mixed at each mixing ratio (unit: mM) shown in FIG. 30 was prepared, and the fluorescence spectrum of the sample solution was measured. The obtained result is shown in FIG.

(Comparative Example 7)
A solution in which dichloromethane and biphenylene not containing a Si source as a monomer reagent were mixed at each mixing ratio (unit: mM) shown in FIG. 31 was prepared, and the fluorescence spectrum of the sample solution was measured. The obtained result is shown in FIG.

  As is clear from the relationship between the maximum fluorescence intensity and the concentration shown in FIG. 32, the maximum emission intensity of benzene and biphenylene was lower than that of BTEB and BTEBP containing the Si source. This is considered to be an influence by a substituent.

FIG. 33 shows the results of plotting the maximum emission wavelength (λ _max ) of all the samples against the concentration. The maximum emission wavelengths of BTEB and BTEBP with silica source were greatly blue shifted at low concentrations. Nevertheless, the phenomenon was not observed with benzene and biphenylene. This difference is considered to be due to the formation of molecular aggregates at high concentrations because the substituents of BTEB and BTEBP have ethoxy groups.

  Next, the mesoporous material of biphenyl silica composite material (BiPh-HMM-cs) obtained in Example 5 and the mesoporous material of biphenyl silica composite material obtained in Example 9 (BiPh-HMM-as) The fluorescence spectrum of a solution of BTEBP as a powder and monomer was measured, and the results are shown in FIG. As a result, the fluorescence intensity of the mesoporous material of the biphenyl silica composite material obtained in Example 5 was about 10 times higher than the maximum fluorescence intensity of the monomer solution, and the mesoporous material of the biphenyl silica composite material obtained in Example 9 It was confirmed that the fluorescence intensity of was higher than the maximum fluorescence intensity of the monomer solution.

  FIG. 35 shows a comparison between the change in the fluorescence intensity of the BTEBP solution and the change in the fluorescence intensity of the mesoporous material of the biphenyl silica composite material obtained in Examples 5 and 9. The biphenyl group density in BiPh-HMM corresponds to a biphenyl concentration of 1000 mM. The biphenyl silica mesoporous material (BiPh-HMM-cs) obtained in Example 5, in which biphenyl is regularly arranged, has strong fluorescence even though concentration quenching occurs completely in the 1000 mM biphenyl monomer. It was confirmed that On the other hand, the mesoporous material (BiPh-HMM-as) of the biphenyl silica composite material obtained in Example 9 in which the ordered structure of biphenyl is not observed shows only the same fluorescence intensity as the BTEBP solution, and BiPh-HMM-cs It was confirmed that the unique fluorescence structure of biphenyl had an effect on the strong fluorescence.

<Synthesis and luminescent property test of layered phenylsilica composite material>
(Example 14)
ODTMA (16.665 g, 47.88 mmol) was dissolved at 50-60 ° C. in a mixture of ion-exchanged water (500 g) and 6N aqueous NaOH (40 g, 200 mmol NaOH). To the solution was added BTEB (20 g, 49.67 mmol) at room temperature with vigorous stirring. The mixed solution was dispersed in an aqueous solution over 20 minutes using an ultrasonic device to disperse the hydrophobic BTBB that had been separated, and stirring was continued for 20 hours at room temperature. The solid content was filtered and dried to obtain a layered phenylsilica composite material (9.5 g).

  FIG. 36 shows a powder X-ray diffraction pattern of the obtained layered phenylsilica composite material. Clear diffraction peaks of d = 37.2 mm and 18.6 mm were observed in the low angle region below 2θ = 10 °, confirming that this material had a layered structure. Furthermore, since a peak of d = 4.2Å was observed in the wide angle region, it was confirmed that a structure in which phenyl groups were regularly arranged was formed.

FIG. 37 shows a ²⁹ Si MAS NMR spectrum of the obtained layered phenylsilica composite material. Two signals are observed at d = −72.7 and −81.2 ppm, which are attributed to T2 [SiC (OH) (OSi) ₂ ] and T3 [SiC (OSi) ₃ ], respectively. From these results, it was confirmed that the obtained layered phenylsilica composite material had a layered structure in which the thickness of one sheet of phenylsilica was about 10 mm, as shown in FIG. Further, as apparent from the fluorescence spectrum (excitation light wavelength: 260 nm) shown in FIG. 39, it was confirmed that the obtained layered phenylsilica composite material showed strong fluorescence.

<Synthesis and luminescent property test of layered biphenyl silica composite>
(Example 15)
4.5 g of ODTMA was dissolved in 50 ml of water, and 800 μl of 6N NaOH aqueous solution was added. This solution was cooled to 4 ° C. by ice cooling, 2 g of BTEBP was added, sonication was performed for 20 minutes, and stirring was performed for 24 hours while cooling with ice. A white precipitate was formed, which was collected by filtration and dried to obtain a layered biphenyl silica composite material (8.9 g).

  FIG. 40 shows a powder X-ray diffraction pattern of the obtained layered biphenyl silica composite material. From the XRD pattern shown in FIG. 40, it was confirmed that this sample had a layered structure with an interlayer distance of 30.0 mm. This interlayer distance corresponded to a layered structure consisting of a monolayer of surfactant and a crosslinked organosilane.

  Next, toluene (10 μl) was dropped on the obtained layered biphenyl silica composite material (0.08 g), and the powder X-ray diffraction pattern was measured again. As is clear from the XRD pattern shown in FIG. 41, expansion between layers was observed. From this, in the obtained layered biphenyl silica composite material, it was confirmed that the nanosheets of biphenyl silica can be dispersed separately. Further, as apparent from the fluorescence spectrum (excitation light wavelength: 300 nm) shown in FIG. 42, it was confirmed that the obtained layered biphenyl silica composite material showed strong fluorescence.

<Introduction of anthracene and emission characteristics test>
(Examples 16 to 18)
9,10-bistriethoxysilylanthracene (BTEA) used was purchased from Azmax. Using the mesoporous material (Ph-HMM-c) of the phenyl silica composite material obtained in Example 1, BTEA was modified on the —OH group on the pore surface by the following method. Specifically, BTEA (0.1 to 0.8 g) was dissolved in a toluene solvent (65 ml), and then Ph-HMM-c (1 g) was dispersed therein and stirred at 50 ° C. for 5 hours. Then, after leaving to room temperature, the mixture was filtered, and the resulting solid was washed with acetone and diethyl ether and dried to obtain a slightly yellowish powder. Thus, Ant / Ph-HMM0.1 (Example 16) and Ant / Ph-HMM0.2 (Example) were obtained by changing the concentration of BTEA as shown in Table 4 with respect to 1 g of Ph-HMM-c. 17) A mesoporous material of a phenyl silica composite material in which three types of anthracene of Ant / Ph-HMM0.8 (Example 18) were immobilized was obtained.

FIG. 43 shows the X-ray diffraction patterns of the samples obtained in Examples 16 to 18 and the Ph-HMM-c obtained in Example 1. In each sample, peaks of d ₁₀ , d ₁₁ , and d ₂₀ showing a hexagonal structure at 2θ = 2 to 5 ° were observed, and it was confirmed that a regular mesostructure was constructed. In addition, three peaks indicating that the phenyl groups of the skeleton were periodically arranged at 2θ = 10 to 40 ° were also observed, and a crystalline skeleton structure was confirmed. From the above results, it was confirmed that BTEA could be introduced while maintaining the pore structure and the periodicity of the skeleton, although the peak intensity was reduced by introducing BTEA. Ant / Ph-HMM0.1 and Ant / Ph-HMM0.2, which have a smaller amount of BTEA, show similar X-ray diffraction patterns, and BTEA can be introduced while maintaining the pore structure and skeleton periodicity. It was.

44 shows the N ₂ adsorption isotherm of Ph-HMM-c obtained in Example 1, FIG. 45 shows the N ₂ adsorption isotherm of the sample obtained in Example 16, and FIG. 45 shows the sample obtained in Example 17. the N ₂ adsorption isotherm in FIG. 46, respectively the N ₂ adsorption isotherm of the sample obtained in example 18 in Figure 47. Based on these N ₂ adsorption isotherms, the specific surface area of each sample obtained in Examples 16 to 18 and Ph-HMM-c obtained in Example 1 was determined by the BET method, and the center pore diameter was determined by the BJH method. Thus, the pore volume was calculated by the t-plot method, and the obtained results are shown in Table 5.

  All the samples shown in FIGS. 44 to 47 show the type IV adsorption isotherm specific to the mesoporous material, and it was confirmed that the sample has uniform pores with a central pore diameter of 2.5 to 3 nm. . Further, as the amount of BTEA introduced increased, the specific surface area and pore volume decreased, and the center pore diameter decreased. This is considered to be due to the introduction of anthracene into the pores.

FIG. 48 shows the results of ¹³ C-CP-NMR of the sample of Example 18 in which BTEA was introduced into Ph-HMM. Compared with the NMR results of only Ph-HMM without BTEA, the peaks other than the peak (*) seen at around 60 ppm were the same, and almost no peaks of BTEA itself were confirmed.

In addition, FIG. 49 shows the ²⁹ Si-MAS-NMR result of the sample of Example 18 in which BTEA was introduced into Ph-HMM. ²⁹ Si-MAS-NMR confirmed a peak derived from BTEA anthracene around 60 to 70 ppm and a peak derived from benzene from Ph-HMM around 70 to 80 ppm. From this, it was confirmed that the T ³ site of anthracene and the T ² site of benzene overlapped at around 70 ppm. Moreover, since the peak of the Q site of 100-120 ppm was not seen, it was also confirmed that the aromatic ring and Si were not cut | disconnected and the structure was hold | maintained.

  Next, in order to investigate the optical characteristics of Ph-HMM in which BTEA was fixed, an absorption spectrum (reflection method) and a fluorescence spectrum were measured. FIG. 50 shows the absorption spectrum of Ph-HMM-c obtained in Example 1, FIG. 51 shows the absorption spectrum of the sample obtained in Example 16, and FIG. 52 shows the absorption spectrum of the sample obtained in Example 17. FIG. 53 shows the absorption spectrum of the sample obtained in Example 18. In Ph-HMM, benzene absorption (260-280 nm) was observed, whereas after BTEA fixation, anthracene absorption was observed at 350-400 nm in addition to benzene absorption. On the other hand, in the absorption spectrum (not shown) of the physical mixture of Ph-HMM and BTEA, the anthracene peak was sharp and shifted to the longer wavelength side, and the tendency was different from that obtained by immobilizing BTEA. This is considered to be a difference caused by chemical bonding of BTEA anthracene to Ph-HMM, and it was confirmed that it was not a simple physical mixture.

  Next, the amount of BTEA immobilized on Ph-HMM was quantified by an absorption spectrum. When the sample was measured as it was, the reflection of the spectrum was too strong and an accurate spectrum could not be obtained. Therefore, the spectrum was measured by diluting with blank barium sulfate. That is, first, reflection spectra of samples in which Ph-HMM and barium sulfate were mixed at various ratios were measured. When Ph-HMM was 0.03 g against 2 g of barium sulfate, two peaks peculiar to phenyl groups were observed at 270 to 290 nm, but at higher mixing ratios the absorption was close to saturation and the two peaks were unclear Became. Therefore, the absorption spectrum was measured by mixing 0.03 g of Ph-HMM with 2 g of barium sulfate.

Subsequently, in order to prepare a calibration curve for BTEA, a sample in which a predetermined amount (0.0011 to 0.0146 g) of BTEA was mixed with Ph-HMM / BaSO ₄ (0.03 g / 2 g) was prepared. And it plotted by Kubelka-Munk function using the maximum value ratio of the absorption peak of benzene and anthracene. The results are shown in FIG. The plot showed a good linear relationship through zero. Therefore, it was decided to quantify using this calibration curve. The Kubelka-Munk functional equation is K / S = (1-R _∞ ) ² / 2R _∞ {where R _∞ is the maximum value of the anthracene absorption peak (Max 390 nm), K is the absorption coefficient, and S is the scattering coefficient. Indicates. }.

  It was also confirmed from this calibration curve that the peak maximum value of BTEA in the reflection spectrum increased as the amount of BTEA increased. Therefore, the amount of BTEA with fixed BTEA was calculated from the peak maximum value of BTEA in the absorption spectra (FIGS. 51 to 53) of the samples actually fixed with BTEA, using the calibration curve shown in FIG. The results are shown in Table 6.

  Next, in order to investigate the energy transfer from benzene to anthracene, the fluorescence spectrum was measured. First, the wavelength suitable for observing the energy transfer from benzene to anthracene was confirmed as follows. That is, from the result of the absorption spectrum of the BTEA monomer shown in FIG. 55, it was confirmed that BTEA has no absorption at 260 nm and has anthracene-derived absorption at around 450 nm. FIG. 56 shows the fluorescence spectra of Ph-HMM and BTEA at an excitation wavelength of 260 nm. The fluorescence spectrum of Ph-HMM showed a large peak near 320 nm, but no peak was observed in the fluorescence spectrum of BTEA. It was confirmed. Therefore, it was confirmed that the excitation wavelength of 260 nm is suitable for observing the energy transfer from benzene to anthracene.

  Next, the result of having measured the fluorescence spectrum with each excitation wavelength of 260 nm with respect to each sample obtained in Examples 16-18 is shown in FIG. In the sample after BTEA introduction, peaks of phenyl group and anthracene were observed at 320 nm and 430 nm, respectively. This indicates that BTEA was fixed in the pores of Ph-HMM. As the amount of BTEA introduced increased, the anthracene peak increased and the phenyl group peak decreased. Since there was no change in the amount of Ph-HMM itself, it was confirmed from the above fact that energy was transferred from the phenyl group to anthracene.

  From the above results, the anthracene precursor (BTEA) can be introduced into the pores of the mesoporous material (Ph-HMM-c) of the phenyl silica composite material, which causes energy transfer from the phenyl group to the anthracene. It was confirmed that

<Introduction of porphyrin and emission characteristics test>
(Examples 19 to 20)
The mesoporous material (Ph-HMM-c) of the phenyl silica composite material obtained in Example 1 and the mesoporous material (BiPh-HMM-c) of the biphenyl silica composite material obtained in Example 4 were used. Then, an aluminum porphyrin complex (Al-TPPEt) (0.32 g) is dissolved in benzene (100 ml), and the mesoporous material (1 g) obtained in Example 1 and Example 4 is added to the aluminum porphyrin complex (Al-TPPEt). Stirring was performed at 24 ° C. for 24 hours to physically adsorb Al-TPPEt to each mesoporous material. The obtained powder was filtered while sufficiently washing with ethanol and benzene to obtain a red powder. These were Al-TPPEt / Ph-HMM (Example 19) and Al-TPPEt / BiPh-HMM (Example 20), respectively.

58 shows X-ray diffraction patterns of Ph-HMM-c, BiPh-HMM-c, Al-TPPEt / Ph-HMM, and Al-TPPEt / BiPh-HMM. _{^{(C 18 TMA + Cl -)}} ODTMA as a template in Ph-HMM-c and BiPh-HMM-c was synthesized by adding, together with a peak indicating a mesostructure (2D hexagonal) in 2 [Theta] = 1 to 3 °, skeletal The peaks of 0.76 and 1.19 nm indicating the periodicity of benzene were confirmed. Adsorption of Al-TPPEt / Ph-HMM and Al-TPPEt / BiPh-HMM with TPPEt introduced into mesopores was observed at the same positions as Ph-HMM-c and BiPh-HMM-c. It was confirmed that the structure of Ph-HMM-c and BiPh-HMM-c was not broken by the treatment.

Next, the UV-vis spectrum of Al-TPPEt / Ph-HMM is shown in FIG. 59, and the UV-vis spectrum of Al-TPPEt / BiPh-HMM is shown in FIG. Absorption attributed to the π-π ^* transition of benzene and biphenyl on the wall of mesoporous silica was observed around 260-320 nm. Between 400 and 700 nm, absorption spectra attributed to the Soret band and Q band of Al-TSPP were observed, and both of them were confirmed in the composite. The association state of Al-TPPEt in the mesopores can be estimated by shifting the Soret band of Al-TPPEt. The Soret bands of Al-TPPEt in Al-TPPEt / Ph-HMM and Al-TPPEt / BiPh-HMM were 406 and 413 nm, respectively, and were blue-shifted from the band that did not have an association state (422 nm) in chloroform. This result indicates that Al-TPPEt forms an H aggregate in Ph-HMM-c and BiPh-HMM-c. The reason for forming such an H-aggregate is thought to be that hydrophobic porphyrins are adsorbed side by side on the hydrophobic parts regularly arranged in the pores.

  When comparing Al-TPPEt / Ph-HMM with Al-TPPEt / BiPh-HMM, the blue shift of the Soret band of Al-TPPEt was larger in the former. From this result, it was confirmed that the pore wall surface of Ph-HMM-c is easier to take H aggregates. This is presumably because the width of the hydrophobic part of BiPh-HMM-c is wider than that of Ph-HMM-c, and Al-TPPEt is inclined and adsorbed, making it difficult to remove H aggregates.

  Next, the fluorescence spectrum of the Al-TPPEt / Ph-HMM complex is shown in FIG. When Ph-HMM-c was excited with 260 nm light, strong fluorescence was observed around 300 nm, but the complex with Al-TPPEt was quenched. FIG. 62 shows the fluorescence spectrum of the Al—TPPEt / BiPh—HMM complex. In this case as well, when BiPh-HMM-c was excited with 300 nm light, strong fluorescence was observed at around 380 nm, but the complex into which Al-TPPEt was introduced was quenched. Such a result indicates that energy was transferred from Ph-HMM-c and BiPh-HMM-c to Al-TPPEt. However, it is considered that the fluorescence derived from Al-TPPEt was not detected by this apparatus because it was hidden in the second harmonic of the excitation light or absorbed in the far infrared.

  Therefore, while irradiating with an ultraviolet lamp (254 nm), light emission of Al-TPPEt powder, Al-TPPEt / Ph-HMM powder, Ph-HMM-c powder, BiPh-HMM-c powder and Al-TPPEt / BiPh-HMM powder The state is observed, and photographs showing the light emission state of these powders are shown in FIGS. 63 to 67, respectively. From the results shown in FIGS. 63 to 67, it was confirmed that only the samples (Al-TPPEt / Ph-HMM and Al-TPPEt / BiPh-HMM) supporting Al-TPPEt emit light. This fact also indicates that energy transfer from Ph-HMM-c and BiPh-HMM-c to Al-TPPEt occurs.

  From the above results, the mechanism of energy transfer from Ph-HMM-c to Al-TPPEt is considered as follows. That is, since Al-TPPEt exists in the mesopores, the two molecules are close to each other, and the Perran model of energy transfer depending on this distance can be applied. The Perran model is often used when considering energy transfer in rigid solutions and solid phases. In this model, spectral overlap is not important, and energy transfer occurs efficiently when an acceptor is present in the quenching space of the donor. In this complex system, Al-TPPEt is adsorbed as an H aggregate on the wall of the donor Ph-HMM-c. Therefore, Al-TPPEt exists sufficiently in the quenching space of Ph-HMM-c, and it is considered that energy transfer from Ph-HMM-c to Al-TPPEt occurred efficiently.

Thus, it was confirmed that energy transfer was efficiently performed from the phenyl silica composite material and the biphenyl silica composite material to the aluminum porphyrin in the mesopores. Porphyrin that has obtained light energy can be expected to have various applications such as CO ₂ fixation and polymer synthesis. In addition, it is possible to freely control the color and energy of fluorescence by adsorbing various fluorescent materials to the mesoporous material of a phenyl silica composite material and a biphenyl silica composite material that emit fluorescence in the ultraviolet region.

<Heat resistance test>
(Example 21 and Comparative Examples 8-9)
A biphenyl silica composite thin film (BiPh-HMMc-s-film) (Example 21) obtained in the same manner as in Example 10 and a conventional film-like phosphor {Bis [N- (1- naphthyl) -N-phenyl] benzidine (NPB) (Comparative Example 8) and 4,4′-Bis (9-carbazolyl) -biphenyl (CBP)} (Comparative Example 9) in an electric furnace at 150 ° C. for 30 minutes After standing, the appearance of the thin film after heat treatment was observed with the naked eye.

  In the BiPh-HMMc-s-film obtained in Example 21 (Example 10), there was no change in the transparency of the thin film, whereas the conventional film-like phosphors for comparison (NPB and CBP) ) (Comparative Examples 8 to 9) were all cloudy. Such cloudiness is considered to be due to crystallization of the fluorescent material. From this result, it was confirmed that the light emitting material of the present invention is excellent in heat resistance.

<Synthesis of thin-film luminescent material and luminescent property test (2)>
(Example 22)
A solution obtained by adding 320 μl of ion-exchanged water, 10 μl of 2N hydrochloric acid aqueous solution and 0.86 g of nonionic surfactant Brij-76 (C ₁₈ H ₃₇ (EO) ₁₀ ) as a template to 4 g of ethanol (EtOH) has the following structure. 1.2 g of BTEBP was added and stirred at room temperature for 1 hour to obtain a sol solution. Using this sol solution, a coating film (film thickness: 100 to 500 nm) was obtained on a glass substrate by spin coating. The coating conditions were a rotation speed of 4000 rpm and a rotation time of 1 minute. Further, the obtained film was dried at 100 ° C. for 1 hour or longer.

  The X-ray diffraction pattern of the biphenyl silica composite thin film (BiPh-HMMc-s-film2) obtained in Example 22 is shown in FIG. 68. The fluorescence spectrum (solid line, excitation wavelength: 280 nm) and excitation spectrum (dashed line, measurement wavelength) : 360 nm) is shown in FIG. In the X-ray diffraction pattern, a strong peak was observed at d = 7.2 nm, confirming the presence of a regular mesostructure (FIG. 68). Further, when the fluorescence spectrum was measured at an excitation wavelength of 280 nm, it was confirmed that strong emission centered at 360 nm was exhibited (FIG. 69).

(Examples 23 to 24)
So as to have the composition shown in Table 7, the ion-exchanged water in ethanol, a nonionic surfactant as a 2N aqueous hydrochloric acid solution and template P123 and the respectively added _{[(EO) 20 - (EO} ) 20 - (PO) 70] To the solution, the amount of BTB (Example 23) or BTEBP (Example 24) shown in Table 7 was added as a Si source and stirred at room temperature for 1 hour to obtain a transparent uniform sol solution. This sol solution was coated on a glass substrate by a dip coating method to obtain a uniform coating film (film thickness: 450 nm). The dipping conditions were a dipping speed of 2 cm / min and an immersion time of 2 minutes. Further, the obtained film was baked at 250 ° C. in air for 2 hours.

  70 and FIG. 70 show X-ray diffraction patterns before and after firing of the thin film of phenyl silica composite material (Ph-HMM) obtained in Example 23 and the thin film of biphenyl silica composite material (BiPh-HMM) obtained in Example 24. 71 respectively. It was confirmed that the Ph-HMM thin film and BiPh-HMM thin film have regular mesostructures before and after firing.

  Next, fluorescence spectra before and after firing the Ph-HMM thin film and the BiPh-HMM thin film are shown in FIGS. 72 and 73, respectively. It was confirmed that the Ph-HMM thin film and the BiPh-HMM thin film each showed strong fluorescence before and after firing.

(Example 25)
0.3 g of BTEBP was added to a solution obtained by adding 90 μl of ion-exchanged water and 10 μl of 2N aqueous hydrochloric acid to 2 g of ethanol (EtOH), and stirred at room temperature for 1 hour 30 minutes to obtain a sol solution. Using this sol solution, a coat film (film thickness: 100 to 500 nm) was obtained by spin coating in the same manner as in Example 22, and then the obtained film was dried.

  FIG. 74 shows the fluorescence spectrum (solid line, excitation wavelength: 280 nm) and excitation spectrum (dashed line, measurement wavelength: 360 nm) of the biphenyl silica thin film (BiPh-acid-film) obtained in Example 25, and FIG. 75 shows the UV spectrum. Each is shown. When the fluorescence spectrum was measured with an excitation wavelength of 280 nm, it was confirmed that strong emission centered at 360 nm was exhibited (FIG. 74). Further, from the result of the UV spectrum, it was confirmed that it has a light absorption band centered on 250 to 270 nm (FIG. 75).

(Example 26)
A solution obtained by adding ₂₁ μl of ion-exchanged water, 5 μl of 2N aqueous hydrochloric acid and 0.07 g of Brij-76 (C ₁₈ H ₃₇ (EO) ₁₀ ) to 1 g of a mixed solvent of ethanol / THF (weight ratio 1: 1) has the following structure. A solution in which 0.1 g of BTETP was dissolved in 1 g of a mixed solvent of ethanol / THF (weight ratio 1: 1) was added and stirred at room temperature for 24 hours or more to obtain a sol solution. Using this sol solution, a coat film (film thickness: 100 to 300 nm) was obtained by spin coating as in Example 22, and then the obtained film was dried.

  FIG. 76 shows the X-ray diffraction pattern of the terphenyl silica composite thin film (TPh-HMMc-s-film) obtained in Example 26. The fluorescence spectrum (solid line, excitation wavelength: 280 nm) and excitation spectrum (dashed line, measurement) (Wavelength: 420 nm) is shown in FIG. In the X-ray diffraction pattern, although broad, a peak was observed at d = 7.2 nm, confirming the existence of a regular mesostructure (FIG. 76). Further, when the fluorescence spectrum was measured at an excitation wavelength of 280 nm, it was confirmed that strong emission centered on 360 nm and 410 nm was exhibited (FIG. 77).

(Example 27)
BTETP 0.1g was dissolved in ethanol / THF (weight ratio 1: 1) mixed solvent 1g in the solution which added ion exchange water 43μl and 2N hydrochloric acid aqueous solution 10μl to ethanol / THF (weight ratio 1: 1) mixed solvent 1g. The solution was added and stirred at room temperature for 24 hours or more to obtain a sol solution. Using this sol solution, a coat film (film thickness: 100 to 300 nm) was obtained by spin coating as in Example 22, and then the obtained film was dried.

  FIG. 78 shows the fluorescence spectrum (solid line, excitation wavelength: 280 nm) and excitation spectrum (dashed line, measurement wavelength: 400 nm) of the terphenyl silica thin film (TPh-acid-film) obtained in Example 27. When the fluorescence spectrum was measured at an excitation wavelength of 280 nm, it was confirmed that strong emission centered at 420 nm was exhibited (FIG. 78).

(Example 28)
A solution obtained by adding ₂₁ μl of ion-exchanged water, 5 μl of 2N aqueous hydrochloric acid and 0.07 g of Brij-76 (C ₁₈ H ₃₇ (EO) ₁₀ ) to 1 g of a mixed solvent of ethanol / THF (weight ratio 1: 1) has the following structure. A solution prepared by dissolving 0.1 g of 1,6-BTEPyr in 1 g of a mixed solvent of ethanol / THF (weight ratio 1: 1) was added and stirred at room temperature for 15 hours to obtain a sol solution. Using this sol solution, a coat film (film thickness: 100 to 300 nm) was obtained by spin coating as in Example 22, and then the obtained film was dried.

  The X-ray diffraction pattern of the thin film (Pyr-HMMc-s-film) of the pyrene silica composite material obtained in Example 28 is shown in FIG. 79, and the fluorescence spectrum (solid line, excitation wavelength: 350 nm) and excitation spectrum (dashed line, measurement wavelength: 450 nm) is shown in FIG. 80, and the UV spectrum is shown in FIG. In the X-ray diffraction pattern, a strong peak was observed at d = 6.5 nm, confirming the presence of a regular mesostructure (FIG. 79). Further, when the fluorescence spectrum was measured at an excitation wavelength of 350 nm, it was confirmed that strong emission centered at 450 nm was exhibited (FIG. 80). Further, from the result of the UV spectrum, it was confirmed that it has light absorption bands centered around 245 nm, 280 nm and 350 nm (FIG. 81).

(Example 29)
To a solution obtained by adding 10 μl of ion-exchanged water and 2 μl of 2N hydrochloric acid aqueous solution to 1 g of ethanol, a solution in which 1,6-BTEPyr 0.1 g was dissolved in 1 g of ethanol was added and stirred at room temperature for 1 hour to obtain a sol solution. . Using this sol solution, a coat film (film thickness: 100 to 300 nm) was obtained by spin coating as in Example 22, and then the obtained film was dried.

  FIG. 82 shows the fluorescence spectrum (solid line, excitation wavelength: 350 nm) and excitation spectrum (dashed line, measurement wavelength: 450 nm) of the pyrene silica thin film (Pyr-acid-film) obtained in Example 29, and FIG. 83 shows the UV spectrum. Show. When the fluorescence spectrum was measured at an excitation wavelength of 350 nm, it was confirmed that strong emission centered at 470 nm was exhibited (FIG. 82). Further, from the result of the UV spectrum, it was confirmed that it has an absorption band of light centering around 240 nm, 280 nm and 350 nm (FIG. 83).

(Example 30)
A solution obtained by adding ₄₃ μl of ion-exchanged water, 10 μl of 2N hydrochloric acid aqueous solution and 0.07 g of Brij-76 (C ₁₈ H ₃₇ (EO) ₁₀ ) to 1 g of a mixed solvent of ethanol / THF (weight ratio 1: 1) has the following structure. A solution prepared by dissolving 0.1 g of BTEAnt in 1 g of a mixed solvent of ethanol / THF (weight ratio 1: 1) was added and stirred at room temperature for 20 hours or more to obtain a sol solution. Using this sol solution, a coat film (film thickness: 100 to 300 nm) was obtained by spin coating as in Example 22, and then the obtained film was dried.

  FIG. 84 shows the X-ray diffraction pattern of the anthracene silica composite thin film (Ant-HMMc-s-film) obtained in Example 30, and the fluorescence spectrum (solid line, excitation wavelength: 390 nm) and excitation spectrum (dashed line, measurement wavelength). : 500 nm) is shown in FIG. 85, and the UV spectrum is shown in FIG. In the X-ray diffraction pattern, although broad, a peak was observed at d = 5.8 nm, confirming the presence of a regular mesostructure (FIG. 84). Further, when the fluorescence spectrum was measured at an excitation wavelength of 390 nm, it was confirmed that strong emission centered on 500 nm was exhibited (FIG. 85). Furthermore, from the result of UV spectrum, it was confirmed that it has light absorption bands centered around 250 nm and 380 nm (FIG. 86).

(Example 31)
A solution of 4,4′-dibromooctafluorobiphenyl (1.01 g) in THF (2.9 ml) was added to THF (2.9 ml) containing magnesium (0.22 g), iodine (0.10 g) and chlorotriethoxysilane (1.05 g). ml) The solution was added dropwise at 60 ° C. under an argon atmosphere. The reaction mixture was refluxed at 75 ° C. for 18 hours, and then the solvent was distilled off. Next, the product was extracted from the residue using hexane (30 ml) to obtain a yellow oily crude product. This was heated at 350 ° C. under reduced pressure (100 hPa) to obtain octafluorobiphenyl silica as a brown glassy solid.

  The obtained octafluorobiphenyl silica was fixed to a sample folder, and the fluorescence spectrum and the excitation spectrum were measured.When the fluorescence spectrum was measured with an excitation wavelength of 360 nm, it was confirmed that a fluorescence peak was observed at 440 nm ( FIG. 87). Furthermore, when the excitation spectrum was measured at a measurement wavelength of 430 nm, it was confirmed that a broad excitation peak ranging from 350 nm to 400 nm centered at 370 nm was shown (FIG. 87).

<Synthesis of powdered luminescent material and luminescent property test>
(Examples 32-36)
Two solutions prepared by mixing 6 g of ion-exchanged water and 333 μl of 12N hydrochloric acid aqueous solution (for Examples 35 and 36) were further added to the surfactant 1,12-bis (octadecyldimethylammonium) dodecanedibromide (C _{18 Three} solutions (for Examples _32-34 ) in which 0.08 g of _-12-18 ) was dissolved were prepared. Next, a solution prepared by dissolving 0.1 g of an organosilicon compound (organic crosslinked silica precursor) shown in Table 8 in 1 g of ethanol was added to these solutions while vigorously stirring, and sonication was performed for 15 minutes. Each obtained mixture was stirred at room temperature for 24 hours, then heated in a sealed container at 100 ° C. for 20 hours, cooled to room temperature, filtered, washed and dried to obtain a desired powdery sample.

  The fluorescence spectrum and excitation spectrum of each sample obtained in Examples 32-36 were measured. The obtained results are shown in FIG. 88 (Example 32), FIG. 89 (Example 33), FIG. 90 (Example 34), FIG. 91 (Example 35), and FIG. 92 (Example 36). Table 8 shows the excitation wavelength and the maximum emission wavelength.

  Both the sample obtained in Example 32 (TPh-HMM-acid) synthesized using BTETP and the sample obtained in Example 35 (TPh-acid) showed an excitation spectrum centered on 340 nm, and 420 nm was obtained. It was confirmed that the emission spectrum centered was shown. In addition, both the sample obtained in Example 33 (Pyr-HMM-acid) synthesized using 1,6-BTEPyr and the sample obtained in Example 36 (Pyr-Acid) centered around 390 to 410 nm. It was confirmed that an emission spectrum centering on 460 to 480 nm was exhibited. Furthermore, it was confirmed that the sample (Ant-HMM-Acid) obtained in Example 34 synthesized using BTEAnt showed an excitation spectrum centered at 420 nm and an emission spectrum centered at 520 nm.

<Introduction of other luminescent compounds and emission characteristics test>
(Example 37)
A basic aqueous solution (6N NaOH + H ₂₎ shown in the same table having octadecyltrimethylammonium chloride (ODTMA) as a template and fluorescein (Fl, manufactured by Tokyo Chemical Industry Co., Ltd.), which is a photofunctional molecule, having the composition shown in Table 9, respectively. O) and sonicated to dissolve. Next, the amount of BTEBP shown in Table 9 was added to these solutions, and stirred for 20 minutes using ultrasonic waves. Each mixture thus obtained was stirred for 1 day at room temperature, then heated at 100 ° C. overnight, and the resulting precipitate was removed by filtration and washed with distilled water to obtain the desired sample. It was.

  X-ray diffraction patterns of Sample 1 (BiPh-HMM powder), Sample 2 (F1 (0.5 mg) / BiPh-HMM powder), and Sample 5 (F1 (5 mg) / BiPh-HMM powder) obtained in Example 37 are shown. 93, 94, and 95, respectively. Similar to Sample 1 that does not support Fl, both Sample 2 and Sample 5 have a diffraction peak due to the mesostructure near 2θ = 2 °, and a biphenyl group in the pore skeleton near 2θ = 8, 15 °. Periodic structure diffraction peaks indicating that the are regularly arranged were confirmed. Thus, it was confirmed that BiPh-HMM powder having a crystal skeleton could be prepared in the system to which Fl was added.

  In addition, FIG. 96 shows fluorescence spectra (excitation wavelength: 300 nm) of Samples 1 to 5 obtained in Example 37. Only a peak having a maximum value at 370 nm was observed in the fluorescence spectrum of Sample 1 not supporting Fl. On the other hand, in samples 2 to 5 carrying Fl, both a peak at 370 nm and a peak of Fl having a maximum value at 530 nm were confirmed. The ethanol solution of Fl showed no fluorescence when excited at 300 nm, confirming that light was emitted at 530 nm by energy transfer from BiPh-HMM to Fl. As the amount of Fl increased, the fluorescence spectrum of BiPh-HMM at 370 nm decreased and the fluorescence spectrum of Fl at 530 nm increased. From this, it was confirmed that the energy transfer from BiPh-HMM to Fl occurred as Fl increased.

  Further, the surfactant was removed from the sample 5 obtained in Example 37 by ethanol extraction, and the change in its structure and fluorescence characteristics was examined. As a result, the ordered structure of the mesostructure and the biphenyl group did not change at all. In contrast, no fluorescence was shown. From this, it was confirmed that F1 was incorporated into the surfactant. FIG. 97 shows a structural schematic diagram of the sample (F1 / BiPh-HMM powder) obtained in Example 37.

(Example 38)
0.43 g of Brij76 (C ₁₈ H ₃₇ (EO) ₁₀ ) as a template and a predetermined amount {0 mg (sample 1), 11 mg (sample 2), 30 mg (sample 3)} of photofunctional molecules and fluorescein (F1) Was added to a solution containing 0.09 g of ion-exchanged water, 3 g of ethanol and 0.01 g of 2N hydrochloric acid aqueous solution, and stirred for 20 minutes to obtain a uniform solution. Next, 0.6 g of BTEBP was added to these solutions, and the mixture was further stirred for 2 hours. Each solution thus obtained was coated on a glass substrate by a dip coating method and dried at 60 ° C. for 2 hours to obtain a uniform coating film (film thickness: 450 nm). The molar ratio of Fl to BTEBP was 0 mol% for sample 1, 2 mol% for sample 2, and 5 mol% for sample 3.

  An X-ray diffraction pattern of Sample 2 (F1 (2 mol%) / BiPh-HMM thin film) obtained in Example 38 is shown in FIG. In this sample, a peak attributed to the mesostructure was observed in the vicinity of 2θ = 1 to 2 °, and it was confirmed that the sample had a regular mesostructure.

  In addition, FIG. 99 shows the fluorescence spectra (excitation wavelength: 300 nm) of Samples 1 to 3 obtained in Example 38. The BiPh-HMM thin film (Sample 1) showed only the maximum fluorescence wavelength of 370 nm, whereas when Fl was introduced, the fluorescence peak at 370 nm decreased, the peak near Fl of 530 nm increased, and the amount of Fl increased. It was confirmed that the tendency became remarkable.

  When each sample obtained in Example 38 was observed under ultraviolet light irradiation, it showed blue violet when the amount of Fl was 0 mol%, blue when it was 2 mol%, and green when it was 5 mol%.

  Next, when the sample 2 obtained in Example 38 (F1 (2 mol%) / BiPh-HMM thin film) was excited with 300 nm light having an absorption wavelength of a biphenyl group and 420 nm light having an absorption wavelength of Fl, Comparison of fluorescence spectra was performed. The obtained result is shown in FIG. When excited at 300 nm, strong emission of Fl (530 nm) was observed, but when excited at 420 nm, only weak fluorescence was observed. This indicates that Fl can be efficiently emitted by energy transfer from the biphenyl group, and the light collection effect by the mesoporous skeleton was confirmed.

(Examples 39 to 40)
Brij76 (C ₁₈ H ₃₇ (EO) ₁₀ ) 0.5 g serving as a template and a predetermined amount of rhodamine B (Example 39, manufactured by Aldrich) or pyrene (Example 40, manufactured by Tokyo Chemical Industry Co., Ltd.) as a photofunctional molecule Was added to a solution containing 360 μl of ion-exchanged water, 4 g of ethanol and 0.01 g of 2N hydrochloric acid aqueous solution, and stirred to obtain a uniform solution. Next, 0.6 g of BTEBP was added to these solutions, and further stirred for 1 hour to obtain a transparent uniform sol solution. Each sol solution thus obtained was coated on a glass substrate by a dip coating method and dried at 60 ° C. for 2 hours to obtain a uniform coating film (film thickness: 450 nm).

  In Example 39, the amount of rhodamine was changed to 0 mg (0 mol%), 2.6 mg (0.5 mol%), 5.2 mg (1 mol%), 10 mg (2 mol%), and 26 mg (5 mol%). In Example 40, the amount of pyrene was changed to 12 mg (5 mol%), 25 mg (10 mol%), and 50 mg (20 mol%). In parentheses is the molar ratio of rhodamine or pyrene to BTEBP.

  When X-ray structural analysis was performed on each sample obtained in Examples 39 and 40, a peak (d = 6.5 nm) indicating a mesostructure was observed in any of the BiPh-HMM thin films into which a dye (rhodamine or pyrene) was introduced. It was confirmed to show.

  Further, the fluorescence spectrum (excitation wavelength: 300 nm) of each sample (rhodamine / BiPh-HMM thin film) obtained in Example 39 is shown in FIG. 101, and each sample (pyrene / BiPh-HMM thin film) obtained in Example 40 is shown in FIG. The fluorescence spectrum (excitation wavelength: 300 nm) is shown in FIG. In both the rhodamine-introduced sample and the pyrene-introduced sample, a decrease in biphenyl group fluorescence and an increase in dye fluorescence were observed as the amount of dye introduced increased. It was confirmed that energy transfer was taking place.

  Furthermore, in each sample (pyrene / BiPh-HMM thin film) obtained in Example 40, the intensity of monomer emission was high even when pyrene was introduced until the amount of dye introduced to BTEBP reached 20 mol%. From this, it was confirmed that in the mesopores, the dye hardly associates even at a high concentration.

(Examples 41 to 42)
Brij76 (C ₁₈ H ₃₇ (EO) ₁₀ ) 0.5 g serving as a template and EuCl ₃ (Example 41, manufactured by Wako Pure Chemical Industries, Ltd.) 40 mg or TbCl ₃ (Example 42, Wako Pure Chemical Industries, Ltd.) as a photofunctional molecule 38 mg) was added to a solution containing 360 μl of ion exchange water, 4 g of ethanol and 0.01 g of 2N hydrochloric acid aqueous solution, and stirred to obtain a uniform solution. Next, 0.6 g of BTEBP was added to these solutions, and further stirred for 1 hour to obtain a transparent uniform sol solution. Each sol solution thus obtained was coated on a glass substrate by a dip coating method and dried at 60 ° C. for 2 hours to obtain a uniform coating film (film thickness: 450 nm).

When X-ray structural analysis was performed on each sample obtained in Examples 41 and 42, a peak (d = 6.3) indicating a mesostructure in any of the BiPh-HMM thin films into which rare earth ions (EuCl ₃ or TbCl ₃ ) were introduced. nm).

EuCl ₃ and TbCl ₃ have absorption (EuCl ₃ : 250, 270 nm, TbCl ₃ : 220 nm) in the ultraviolet region, as is apparent from FIG. 103 showing the absorption spectra of these ethanol solutions. Even when they were excited at their respective maximum absorption wavelengths, almost no fluorescence spectrum was observed.

The fluorescence spectrum (excitation wavelength: 280 nm) of the sample (EuCl ₃ / BiPh-HMM-film) obtained in Example 41 is shown in FIG. 104 together with the fluorescence spectra of the BiPh-HMM-film and EuCl ₃ ethanol solution. Further, the fluorescence spectrum (excitation wavelength: 300 nm) of the sample (TbCl ₃ / BiPh-HMM-film) obtained in Example 42 is shown in FIG. 105 together with the fluorescence spectra of the BiPh-HMM-film and the TbCl ₃ ethanol solution. In both the sample introduced with EuCl ₃ and the sample introduced with TbCl ₃ , a decrease in biphenyl group fluorescence and an increase in dye fluorescence were observed with an increase in the amount of dye introduced. It was confirmed that energy transfer to

In addition, when these samples were irradiated with ultraviolet rays (254 nm), it was confirmed that EuCl ₃ / BiPh-HMM-film was strongly emitting reddish purple and TbCl ₃ / BiPh-HMM-film was strongly emitting blue light.

(Example 43)
Ion exchange between 0.43 g of Brij76 (C ₁₈ H ₃₇ (EO) ₁₀ ) used as a template and a predetermined amount of 7-diethylamino-4-methylcoumarin (manufactured by Sigma-Aldrich, hereinafter referred to as “coumarin”) as a fluorescent dye It was added to a solution containing 0.18 g of water, 4 g of ethanol and 0.01 g of 2N hydrochloric acid aqueous solution, and stirred to obtain a uniform solution. Next, 0.6 g of BTEBP was added to these solutions, and further stirred at room temperature for 2 hours to obtain sol solutions.

  The amount of coumarin is 0 mg (0 mol%), 0.188 mg (0.06 mol%), 0.37 mg (0.12 mol%), 0.56 mg (0.18 mol%), 0.75 mg (0.24 mol%), 0.94 mg (0.3 mol) %), 1.88 mg (0.6 mol%), 3.7 mg (1.2 mol%), 5.6 mg (1.8 mol%), 7.5 mg (2.4 mol%), 9.4 mg (3.0 mol%), 18.8 mg (6.0 mol%) And changed. In parentheses is the molar ratio of coumarin to BTEBP.

  In addition, in order to prevent degradation due to photodimerization reaction of coumarin and the like, the above sol solution was prepared under light shielding. Each sol solution thus obtained was coated on a glass substrate by a dip coating method and dried at 60 ° C. for 2 hours to obtain a uniform coating film (film thickness: 450 nm).

  FIG. 106 shows the X-ray diffraction pattern of BiPh-HMM-film without coumarin introduced, and FIG. 107 shows the X-ray diffraction pattern of coumarin (3 mol%) / BiPh-HMM-film introduced with 3 mol% coumarin. . In both thin films, diffraction due to the mesostructure was observed at 2θ = 1 to 2 °. This confirmed that the mesostructure of the BiPh-HMM film was retained even when coumarin was introduced.

  FIG. 108 shows fluorescence spectra (excitation wavelength: 270 nm) of coumarin / BiPh-HMM-film into which various amounts of coumarin were introduced. In the fluorescence spectrum of BiPh-HMM-film into which coumarin was not introduced, light emission due to the biphenyl group was observed only at 370 nm. On the other hand, when coumarin was introduced, 430 nm emission due to coumarin was observed, and at the same time, a sharp decrease in 370 nm emission intensity caused by biphenyl occurred. When 1.8 mol% or more of coumarin was introduced to the biphenyl group in BiPh-HMM, the biphenyl group emitted almost zero light. This coumarin / BiPh-HMM-film was confirmed to emit sharp blue light under UV irradiation.

  FIG. 109 shows comparison of fluorescence and excitation spectra of BiPh-HMM-film, ethanol solution of coumarin, and coumarin (1.8 mol%) / BiPh-HMM-film. From this figure, it can be seen that the excitation wavelengths of BiPh-HMM-film and coumarin hardly overlap. That is, it can be seen that BiPh-HMM-film is preferentially excited with 270 nm light. From this, it was confirmed that energy transfer from BiPh-HMM to coumarin occurred.

  In addition, when coumarin (1.8mol%) / BiPh-HMM-film was excited at 270nm and 380nm, it was found that the fluorescence intensity of coumarin was 8 times (area ratio) stronger than 380nm excitation. FIG. 109). Furthermore, when the amount of coumarin introduced was 0.12 mol%, the ratio of the fluorescence intensities at both excitation wavelengths was 48 times. That is, it was confirmed that coumarin can emit light more efficiently by transferring energy from BiPh-HMM than by direct excitation of coumarin. The present inventors infer that this is because BiPh-HMM was able to efficiently collect light and efficiently inject the energy into coumarin.

(Example 44)
A predetermined amount of coumarin as a fluorescent dye was added to a solution containing 0.18 g of ion exchange water, 4 g of ethanol and 0.01 g of 2N hydrochloric acid aqueous solution, and stirred to obtain a uniform solution. Next, 0.6 g of BTEBP was added to these solutions, and further stirred at room temperature for 2 hours to obtain sol solutions.

  The amount of coumarin was 0 mg (0 mol%), 0.047 mg (0.015 mol%), 0.094 mg (0.03 mol%), 0.47 mg (0.15 mol%), 0.94 mg (0.3 mol%), 4.7 mg (1.5 mol%). %) And 9.4 mg (3.0 mol%). In parentheses is the molar ratio of coumarin to BTEBP.

  In addition, in order to prevent degradation due to photodimerization reaction of coumarin and the like, the above sol solution was prepared under light shielding. Each sol solution thus obtained was coated on a glass substrate by a dip coating method and dried at 60 ° C. for 2 hours to obtain a uniform coating film (film thickness: 450 nm).

  When the X-ray diffraction pattern of the composite film of coumarin and biphenyl silica obtained in Example 44 (coumarin / BiPh composite film) was confirmed, no clear diffraction peak was observed, and a regular mesostructure was formed. Not confirmed.

  FIG. 110 shows fluorescence spectra (excitation wavelength: 270 nm) of coumarin / BiPh composite films into which various amounts of coumarin were introduced. From the results, it was confirmed that the excitation energy from the biphenyl group to the coumarin was transferred even in a system not using a surfactant. It was also confirmed that this coumarin / BiPh composite film also emitted sharp blue light under ultraviolet irradiation.

(Example 45 and Comparative Examples 10-11)
A phosphorescent complex Ir (ppy) ₃ solution having a constant concentration (solvent mixing ratio, ethanol: THF = 1: 4) was prepared in the following manner. That is, first, Ir (ppy) ₃ (manufactured by Dojindo) 23 mg (3.5 × 10 ⁻⁵ mol) was added to a solution containing 30.7 g of THF and 7.8 g of ethanol, and stirred to obtain a uniform solution. Let this solution be X.

Next, assuming that the concentration of the solution X is a, four types (a, 0.75a, 0.5a, and 0.25a) of solutions (referred to as D, C, B, and A, respectively) are prepared. However, the weight of each solution is 8 g, and the solvent mixing ratio is ethanol: THF = 1: 4. In each of these A, B, C, and D solutions, 0.43 g of Brij76 (C ₁₈ H ₃₇ (EO) ₁₀ ) as a surfactant, 10 μl of 6N hydrochloric acid aqueous solution, and 180 μl of pure water were mixed and stirred for 10 minutes. (These are A ′, B ′, C ′, and D ′, respectively). Thereafter, 0.6 g of BTEBP was added to each of the solutions A ′, B ′, C ′, and D ′, and stirred for 1 day to prepare uniform sol solutions (A ″, B ″, C ″, and D ″, respectively) To do).

The molar ratios of Ir (ppy) ₃ to BTEBP in the sol solutions of A ″, B ″, C ″, and D ″ thus obtained are 0.14 mol%, 0.28 mol%, 0.42 mol%, and 0.58 mol, respectively. %.

  Each sol solution thus obtained is dip-coated with a quartz substrate (dip time is 1 minute, takes 2 minutes each for vertical movement) and dried at 60 ° C. for 2 hours to obtain a uniform coating film ( Film thickness: 450 nm) was obtained.

Next, since the phosphorescent peak wavelength of Ir (ppy) ₃ is 511 nm, the excitation spectrum for obtaining the emission was measured. Figure 111, Ir (ppy) ₃ excitation spectra of _{Ir (ppy) 3 / BiPh-} HMM film was introduced 0.14 mol% of, Ir the Ir (ppy) ₃ for comparison were introduced 0.1wt% (ppy) ₃ It shows with the excitation spectrum of a / PMMA thin film (Comparative Example 10) and a PMMA thin film into which Ir (ppy) ₃ is not introduced (Comparative Example 11). From the excitation spectrum of the PMMA thin film (film thickness 1.1 to 1.2 μm), it is optically inactive at around 220 nm. Also, from the excitation spectrum of the optically inactive PMMA doped Ir (ppy) ₃ thin film (thickness 1.1 to 1.2 μm), it can be seen that Ir (ppy) ₃ is not directly excited at around 220 nm. . On the other hand, since the BiPh-HMM thin film itself is excited at around 220 nm, the excitation wavelength of the Ir (ppy) ₃ / BiPh-HMM thin film was set to 220 nm.

FIG. 112 shows the phosphorescence spectrum of each Ir (ppy) ₃ / BiPh-HMM thin film obtained in Example 45. Ir (ppy) _3- derived green light emission (peak emission wavelength: 511 nm) was obtained even when the phosphorescent material Ir (ppy) ₃ was excited at a wavelength that was not excited (excitation wavelength: 220 nm, Photon Energy = 5.64 eV) Therefore, it was confirmed that energy transfer from BiPh-HMM to phosphorescent material occurred. In addition, as the Ir (ppy) ₃ concentration increases, the intensity of the biphenyl-derived ultraviolet emission peak (emission wavelength: 370 nm, Photon Energy = 3.3 eV) decreases, and the Ir (ppy) _3- derived green emission peak (emission) The result that the intensity | strength of wavelength: 511nm and Photon Energy = 2.4eV) increases was obtained. The emission intensity is compared by normalizing with the peak intensity of the excitation light.

(Examples 46 to 48)
Biphenyl silica composite mesoporous material obtained in Example 4 (BiPh-HMM-c) and biphenyl silica composite mesoporous material precursor containing the surfactant obtained in Example 5 (BiPh-HMM-cs) was used.

  First, 55 mg of rhodamine 6G (R6G, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 24 g of ethanol to prepare R6G solution A. Similarly, R6G 55 mg was dissolved in 11.4 g of ethanol to prepare R6G solution B.

  Next, 2.56 g of R6G solution A was poured into 1 g of BiPh-HMM-c, and after ultrasonic dispersion for 1 minute, ethanol was evaporated at room temperature to attach R6G to the surface of BiPh-HMM-c. A sample 1 (filled in the holes) (Example 46, the amount of R6G added was 0.59 wt% with respect to BiPh-HMM-c) was obtained.

  Similarly, R6G solution A2.56g or R6G solution B2.48g was poured into 1g each of BiPh-HMM-cs, and dispersed for 1 minute with ultrasound, then ethanol was evaporated at room temperature, BiPh-HMM- Sample 2 (Example 47, the amount of R6G applied was 0.59 wt% with respect to BiPh-HMM-cs) and sample 3 (Example 48) in which R6G was attached to c-s (attached or filled in pores). The amount of R6G added was 1.2 wt% with respect to BiPh-HMM-cs.

  Thus, the fluorescence spectra of Samples 1 to 3 (mixture of R6G and BiPh-HMM) obtained in Examples 46 to 48 were combined with the fluorescence spectrum of BiPh-HMM-c-s obtained in Example 5. As shown in FIG. When excited with light at 300 nm, fluorescence around 370 nm peculiar to BiPh-HMM-cs and fluorescence around 560 nm due to R6G attachment were observed. Although it is not always clear whether the fluorescence near 560 nm is due to energy transfer from BiPh-HMM-cs, excitation at 300 nm, or both, samples 1 to 1 compared to BiPh-HMM-cs In Fig. 3, the fluorescence intensity near 370 nm decreases, and the fluorescence intensity ratio between 370 nm and 560 nm varies depending on the presence or absence of surfactants and the amount of attachment, so it is confirmed that color mixing can be adjusted by these controls. It was done.

(Example 49)
The biphenyl silica composite mesoporous precursor (BiPh-HMM-cs) containing the surfactant obtained in Example 5 was used.

  57 mg of Dansyl Acid (DANS, 1-dimethylaminonaphthalene-5-sulfonic acid, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in a mixed solution of 18.5 g of acetone and 23.5 g of ion-exchanged water to prepare a DANS solution. Next, 9.65 g of DANS solution is poured into 1 g of BiPh-HMM-c-s, and after ultrasonic dispersion for 1 minute, the solvent is evaporated at room temperature, and DANS is attached (attached or adhered) to BiPh-HMM-c-s. A sample filled in the pores (the amount of DANS attached was 1.3 wt% with respect to BiPh-HMM-cs) was obtained.

  The fluorescence spectrum of the sample (mixture of DANS and BiPh-HMM) obtained in Example 49 in this way is shown in FIG. When excited with light at 300 nm, the fluorescence around 370 nm peculiar to BiPh-HMM-cs decreased, and strong blue fluorescence around 440 nm due to DANS attachment was confirmed.

(Examples 50 to 53)
1 ml of 2N hydrochloric acid aqueous solution and 0.178 g of Brij76 (C ₁₈ H ₃₇ (EO) ₁₀ ) as a surfactant were added to 36 g of ion-exchanged water and mixed to obtain a homogeneous solution. To this solution, 0.598 g of BTEBP was added with stirring, and sonication was performed for 20 minutes. The obtained solution was stirred at room temperature for 72 hours, and further stirred at 100 ° C. for 24 hours, and then allowed to cool to room temperature, filtered, washed and dried to obtain a surfactant-containing biphenyl silica composite material. A precursor of a mesoporous material (Example 50, BiPh-HMM-c2-s) was obtained. In the X-ray diffraction pattern of BiPh-HMM-c2-s obtained in Example 50, peaks were observed in the low-angle region (5 degrees or less) showing a regular mesostructure. The peak shown was not observed.

  Here, the BiPh-HMM-c2-s obtained in Example 50, the mesoporous material (BiPh-HMM-c) of the biphenyl silica composite material obtained in Example 4, and the obtained in Example 5 were used. A biphenyl silica composite mesoporous precursor (BiPh-HMM-cs) containing a surfactant was used.

  First, 104 mg of coumarin (7-Diethylamino-4-methylcoumarin, manufactured by Aldrich) was dissolved in 20 g or 35 g of ethanol to prepare coumarin solutions A and B. Next, 3.174 g of the coumarin solution A is poured into 1 g of BiPh-HMM-c, and after ultrasonic dispersion for 1 minute, ethanol is evaporated at room temperature, and coumarin is attached to the surface of BiPh-HMM-c. Sample 1 (Example 51, the amount of coumarin added was 1.82 mol% with respect to BiPh-HMM-c) was obtained.

  Similarly, pour Coumarin Solution B2.842g into BiPh-HMM-c-s1g and Coumarin Solution B3.086g into BiPh-HMM-c2-s1g, respectively, and disperse with ultrasound for 1 minute, then evaporate ethanol at room temperature. Sample 2 in which coumarin was attached (attached or filled in pores) to BiPh-HMM-c-s or BiPh-HMM-c2-s (Example 52, the amount of coumarin attached was BiPh-HMM-c-s) 1.87 mol%) and sample 3 (Example 53, the amount of coumarin added was 2.03 mol% with respect to BiPh-HMM-c2-s).

  Thus, the fluorescence spectra of Samples 1 to 3 (mixture of coumarin and BiPh-HMM) obtained in Examples 51 to 53 were used as the fluorescence spectrum of BiPh-HMM-c2-s obtained in Example 50. FIG. 115 (excitation wavelength: 270 nm) and FIG. 116 (excitation wavelength: 370 nm) are also shown.

<White light emission test by combination of introduced dyes>
(Example 54)
Brij76 (C ₁₈ H ₃₇ (EO) ₁₀ ) 0.5g, Rhodamine 6G2mg and Coumarin 152 (Aldrich) 10mg are added to a solution containing 4g of ethanol, 360μl of water and 0.01g of 2N hydrochloric acid, and stirred. A uniform solution was obtained. Next, 0.6 g of BTEBP was added to the solution and further stirred for 1 hour to obtain a transparent uniform sol solution. The sol solution thus obtained was coated on a glass substrate by a dip coating method and dried at 60 ° C. for 2 hours to obtain a uniform coating film (film thickness: 450 nm).

  When the X-ray structural analysis was performed on the sample obtained in Example 54, it was confirmed that the BiPh-HMM thin film into which rhodamine and coumarin were introduced also showed a peak (d = 6.3 nm) indicating a mesostructure.

  The fluorescence spectrum of the sample obtained in Example 54 is shown in FIG. In the BiPh-HMM thin film into which rhodamine and coumarin were introduced, both emission of coumarin 152 at 460 nm and emission of rhodamine at 550 nm were observed. It was confirmed that when this thin film was irradiated with ultraviolet light (254 nm), the thin film emitted white light (FIG. 118).

<Measurement of refractive index of porous biphenyl silica composite material>
(Example 55)
Add 0.3 g of BTEBP to a solution of 90 g of ion-exchanged water, 10 μl of 2N aqueous hydrochloric acid and 0.2 g of nonionic surfactant P123 ((EO) ₂₀ (PO) ₇₀ (EO) ₂₀ ) as a template) in 2 g of ethanol. The mixture was stirred at room temperature for 1 hour to obtain a sol solution. Using this sol solution, a coat film (film thickness: 300 to 600 nm) was obtained on a glass substrate by spin coating. The coating conditions were a rotation speed of 4000 rpm and a rotation time of 1 minute. Further, the obtained coating film was baked in air at 250 ° C. for 2 hours to obtain porous BiPh-HMM-a-film (film thickness: 500 nm).

  An X-ray diffraction pattern of the BiPh-HMM-a-film obtained in Example 55 is shown in FIG. This BiPh-HMM-a-film had a peak at d = 5.6 nm, and it was confirmed that a regular mesostructure was present.

  Table 10 shows the results of measuring the refractive index of the BiPh-HMM-a-film obtained in Example 55 by ellipsometry. The porous film obtained in Example 55 had a refractive index of 1.34, which was lower than that of glass having no pores (refractive index = 1.7). Therefore, it was confirmed that the light emitting material of the present invention, which is porous, can achieve high light extraction efficiency.

<Fluorescence quantum yield measurement of biphenyl silica composite material>
(Example 56)
For powders and thin films, there is generally no problem of light scattering and there is no appropriate comparative sample, so that the accurate fluorescence quantum yield cannot be determined. Therefore, a biphenyl silica composite fine particle (diameter: about 200 nm) dispersed in a solvent and causing no light scattering was synthesized, and 9,10-diphenylanthracene with a known quantum yield (quantum yield: 0.90) as a standard sample. Was used to determine the quantum yield of the biphenyl silica composite material.

  That is, first, fine particles of a biphenyl silica composite material were synthesized as follows. 0.31 g of 6N sodium hydroxide aqueous solution and 50 ml of ion-exchanged water were mixed, and 1 g of BTEBP was added thereto. This solution was stirred at room temperature for 5 minutes and then subjected to ultrasonic treatment for 20 minutes. As a result, the solution became a white emulsion. This emulsion was put in an autoclave made of Teflon on the inside and metal on the outside, and stirred at 120 ° C. for 15 hours in a rotary oven. The obtained solution became translucent, and this was filtered with a Teflon filter paper (100 μm diameter). When the water was exhausted, 500 ml of water was added on the filter paper and washed. This washing operation was repeated once more, followed by drying treatment for one day and night under vacuum to obtain fine particles of a biphenyl silica composite material.

  120 and 121 show scanning electron micrographs of the synthesized biphenyl silica fine particles. It was confirmed that fine particles having a diameter of about 200 nm were generated. Moreover, there was almost no aggregation of particles and it was confirmed that each was isolated.

  FIG. 122 shows an X-ray diffraction pattern of the obtained biphenyl silica fine particles. Several peaks were observed, confirming that this material had a molecular scale periodic structure. Each peak is assigned as 12.0Å (001), 5.9Å (002), 3.9Å (003), 2.9Å (004), 2.4Å (005) and has a layered structure with an interlayer distance of 12Å. You can see that

  FIG. 123 shows a fluorescence spectrum (excitation wavelength: 300 nm) of the obtained biphenyl silica fine particles in a powder state. From the result, it was confirmed that strong fluorescence centering on 370 nm was exhibited.

  Next, a method for measuring the fluorescence quantum yield will be described. In addition, Shimadzu MPS-2400 spectrophotometer was used for the absorption spectrum measurement, and JASCO FP6600 spectrofluorometer was used for the fluorescence spectrum measurement. Further, a square cell (10 mm) was used for measuring the absorption spectrum, and a triangular cell was used for measuring the fluorescence spectrum.

First, the biphenyl silica fine particles synthesized above were dispersed in 2-propanol (refractive index at a wavelength of 260 nm: about 0.4) having a close refractive index, and subjected to ultrasonic treatment to obtain a transparent solution. Two types of dispersions with different concentrations were prepared. The biphenyl silica unit concentration calculated from the unit formula of biphenyl silica (SiO _1.5 -C ₆ H ₄ -C ₆ H ₄ -SiO _1.5 : MW256) was 6.4 × 10 ⁻⁶ respectively. ^{mol / L, 4.8x10 -6 mol /} L, was a 3.2 × 10 ^-6.

  The haze value of the dispersion at each concentration was 6.4% (the haze value of the solvent alone was 0.5%), and it was confirmed that the influence of scattering by the particles was negligibly small. The absorption spectra of these two types of biphenyl silica fine particles / 2-propanol dispersion are shown in FIG. 124, and the fluorescence spectrum (excitation wavelength: 260 nm) is shown in FIG. In these concentration ranges, linearity with respect to the concentration of absorbance and integrated fluorescence intensity can be obtained, and it is considered that there is no concentration effect such as self-quenching.

On the other hand, a 9,10-diphenylanthracene solution as a standard sample was prepared using cyclohexane as a solvent according to the conditions described in the literature (J. Phys. Chem., 1983, Vol. 87, page 83). The absorption spectrum of the 9,10-diphenylanthracene / cyclohexane solution is shown in FIG. 126, and the fluorescence spectrum (excitation wavelength: 370 nm) is shown in FIG. In these concentration ranges (0.31 to 1.2 × 10 ⁻⁶ mol / L), linearity with respect to the concentration of absorbance and integrated fluorescence intensity was obtained.

Next, the integrated fluorescence intensity of the biphenyl silica fine particle dispersion and the standard sample was plotted against the absorbance (FIG. 128). The fluorescence quantum yield was calculated from the slope of the graph (grad _x and grad _st , subscript x and st indicate the sample to be obtained and the standard sample) according to the following equation.

Φ _x = φ _st (grad _x / grad _st ) x (h ² _x / h ² _st )
Here, Φ is the fluorescence quantum yield, and h is the refractive index of the solvent. For h of 2-propanol and cyclohexane, 1.3972 (wavelength: 260 nm) and 1.4405 (wavelength: 370 nm) were used, respectively. As a result of the calculation, the fluorescence quantum yield of the biphenyl silica fine particles was determined to be 0.28.

Fluorescence quantum of 4,4'-bis (triethoxysilyl) biphenyl [(EtO) ₃ Si-C ₆ H ₄ -C ₆ H ₄ -Si (OEt) ₃ ], a raw material for biphenyl silica fine particles, by the same method The yield was determined. The absorption spectrum of the BTEBP / 2-propanol solution is shown in FIG. 129, and the fluorescence spectrum (excitation wavelength: 255 nm) is shown in FIG. Further, the relationship between the integrated fluorescence intensity and the absorbance is plotted in FIG. From these slopes, the fluorescence quantum yield of BTEBP was determined to be 0.27.

(Examples 57 to 58)
After adding 90 μl of ion-exchanged water and 5 μl of 2N aqueous hydrochloric acid to 2 g of ethanol, 0.215 g of Brij76 (C ₁₈ H ₃₇ (EO) ₁₀ ) as a surfactant was added and mixed to obtain a homogeneous solution. To this solution, 0.3 g of BTEBP was added and stirred for 24 hours to obtain a sol solution. After diluting this sol solution 4 times with ethanol, a coating film was produced on a quartz substrate by spin coating and dried at room temperature to obtain a BiPh-HMM-film having a film thickness of about 100 nm (Example 57).

  Further, when Brij76 was dissolved in the solution before the addition of BTEBP, a coumarin-carrying BiPh was carried out in the same manner as in Example 57, except that a quantity of 3 mol% of coumarin (manufactured by Aldrich) was added to BTEBP. -HMM-film was obtained (Example 58).

The quantum yield of the obtained film was measured using an organic EL quantum yield measuring device (C9920-01) manufactured by Hamamatsu Photonics Co., Ltd. In this apparatus, AlQ ₃ (see Jpn.J.Appl.Phys., 43,11A, (2004) 7730) whose quantum yield is known to be 0.2 is measured and corrected in advance. . The obtained results are shown in Table 11.

  The BiPh-HMM-film obtained in Example 57 had a quantum yield of 0.56, which was higher than that of the powder sample. In addition, the coumarin / BiPh-HMM-film obtained in Example 58 has a quantum yield of almost 1, the energy absorbed by the biphenyl skeleton was transmitted to almost 100% coumarin, and was almost converted to light. confirmed.

<Synthesis of fluorene silica composite and emission characteristics test>
(Example 59)
After dissolving 0.08 g of triblock copolymer P123 in a solution obtained by adding 43 μl of ion-exchange water and 10 μl of 2N aqueous hydrochloric acid to 2 g of a mixed solvent of ethanol / THF (weight ratio 1: 1), 2,7-BTEFlu0 having the following structure was dissolved. .1 g was added and stirred at room temperature for 20 hours or more to obtain a sol solution. A coating film (film thickness: 100 to 300 nm) was obtained by spin coating using this sol solution. The coating conditions were a rotation speed of 4000 rpm and a rotation time of 1 minute. Further, the obtained film was dried at 100 ° C. for 1 hour or longer.

  131 shows an X-ray diffraction pattern of a fluorene silica composite thin film (Flu-HMM-s-film), FIG. 132 shows a fluorescence spectrum and an excitation spectrum, and FIG. 133 shows a UV spectrum. In the X-ray diffraction pattern, a peak was observed at d = 9.3 nm, and it was confirmed that a regular mesostructure was present (FIG. 131). Further, when the fluorescence spectrum was measured at an excitation wavelength of 270 nm, it was confirmed that strong emission centered on 380 nm was exhibited (FIG. 132). Further, from the result of the UV spectrum, it was confirmed that it has light absorption bands centered around 270 nm and 305 nm (FIG. 133).

(Example 60)
In a solution obtained by adding 667 μl of 12N aqueous hydrochloric acid solution to 12 g of ion-exchanged water, 0.154 g of 1,12-bis (octadecyldimethylammonium) dodecane dibromide (C _18-12-18 ) was dissolved, and 2,7-BTEFlu0. 2 g was added and stirred vigorously. After sonication for 2 minutes, the mixture was stirred at room temperature for 24 hours. The mixture was further stirred at 40 ° C. for 3 days, filtered and dried to obtain a fluorene silica composite material having a mesostructure.

  FIG. 134 shows an X-ray diffraction pattern of the obtained powder of fluorene silica composite material (Flu-HMM-powder), and FIG. 135 shows fluorescence and excitation spectra. In the X-ray diffraction pattern, a peak due to the mesostructure was observed at d = 4.5 nm, and it was confirmed that a regular mesostructure was present (FIG. 134). In addition, when the fluorescence spectrum was measured at an excitation wavelength of 320 nm, it was confirmed that strong emission centered on 385 nm was exhibited (FIG. 135).

<Manufacture of pyrene composite material and emission characteristics test>
(Example 61)
Brij-76 (C ₁₈ H ₃₇ (EO) ₁₀ ) 0.07 as a nonionic surfactant in a solution obtained by adding 21 μl of ion-exchanged water and 5 μl of 2N hydrochloric acid aqueous solution to 1 g of ethanol / THF (weight ratio 1: 1) mixed solvent To the solution in which g is dissolved, a solution in which 0.1 g of 1,8-BTEPyr having the following structure is dissolved in 1 g of a mixed solvent of ethanol / THF (weight ratio 1: 1) is added and stirred at room temperature for 15 hours to obtain a sol solution Got. Using this sol solution, a coat film (film thickness: 100 to 300 nm) was obtained by spin coating. The coating conditions were a rotation speed of 4000 rpm and a rotation time of 1 minute. The obtained film was dried at 100 ° C. for 1 hour or longer.

  FIG. 136 shows an X-ray diffraction pattern of the obtained pyrene silica thin film (Pyr-HMM-s-film), FIG. 137 shows fluorescence and excitation spectra, and FIG. 138 shows UV spectra. A strong peak was observed at d = 6.5 nm in the X-ray diffraction pattern, confirming the presence of a regular mesostructure (FIG. 136). When the fluorescence spectrum was measured at an excitation wavelength of 350 nm, it was confirmed that strong emission having a 450 nm peak was exhibited (FIG. 137). Further, from the results of the UV spectrum, it was found that there are light absorption bands centered around 245 nm, 280 nm, and 350 nm (FIG. 138).

(Example 62)
0.08 g of 1,12-bis (octadecyldimethylammonium) dodecane dibromide (C _18-12-18 ) was dissolved in a solution obtained by adding 333 μl of 12N hydrochloric acid solution to 6 g of ion-exchanged water, and 1,6-BTEPyr0. A solution prepared by dissolving 1 g in 1 g of ethanol (EtOH) was added and stirred vigorously. Sonication was performed for 15 minutes and then stirred at room temperature for 24 hours. And it heated at 100 degreeC for 20 hours further. Filtration and drying were performed to obtain a pyrene silica composite material having a mesostructure.

  FIG. 139 shows an X-ray diffraction pattern of the obtained pyrene silica composite powder (Pyr-Acid-powder), and FIG. 140 shows fluorescence and excitation spectra. In the X-ray diffraction pattern, a peak due to the mesostructure was observed at d = 4.4 nm, and it was confirmed that a regular mesostructure was present (FIG. 139). Further, when the fluorescence spectrum was measured at an excitation wavelength of 400 nm, it was confirmed that strong emission centered at 465 nm was exhibited (FIG. 140).

<Manufacture of anthracene composite material and emission characteristics test>
(Example 63)
0.08 g of 1,12-bis (octadecyldimethylammonium) dodecane dibromide (C _18-12-18 ) was dissolved in a solution obtained by adding 333 μl of 12N aqueous hydrochloric acid solution to 6 g of ion-exchanged water. A solution in which 0.1 g of 6-BTEAnt was dissolved in 1 g of ethanol was added and stirred vigorously. Sonication was performed for 15 minutes and then stirred at room temperature for 24 hours. And it heated at 100 degreeC for 20 hours further. Filtration and drying yielded an anthracene silica composite material having a mesostructure.

  The X-ray diffraction pattern of the obtained anthracene silica composite powder (Ant-Acid-powder) is shown in FIG. 141, and the fluorescence and excitation spectra are shown in FIG. 142, respectively. In the X-ray diffraction pattern, a peak due to the mesostructure was observed at d = 4.3 nm, and it was confirmed that a regular mesostructure was present (FIG. 141). Further, when the fluorescence spectrum was measured at an excitation wavelength of 420 nm, it was confirmed that strong emission centered at 515 nm was exhibited (FIG. 142).

<Manufacturing of acridine composite material and light emission characteristic test>
(Example 64)
0.08 g of triblock copolymer P123 was dissolved in 2 g of ethanol / THF (1: 1 by weight) mixed solvent with 43 μl of ion-exchanged water and 10 μl of 2N hydrochloric acid solution, and then 0.1 g of BTEAcr having the following structure was added. The mixture was stirred at room temperature for 20 hours or more to obtain a sol solution. Using this sol solution, a coat film (film thickness: 100 to 300 nm) was obtained by spin coating. The coating conditions were a rotation speed of 4000 rpm and a rotation time of 1 minute. The obtained film was dried at 100 ° C. for 1 hour or longer.

  FIG. 143 shows fluorescence and excitation spectra of an acridine silica composite thin film (Acr-HMM-s-film). When the fluorescence spectrum was measured at an excitation wavelength of 370 nm, it was confirmed that long-wavelength emission centered on 560 nm and 600 nm was exhibited (FIG. 143). On the other hand, in the X-ray diffraction pattern, a peak indicating a mesostructure could not be recognized. I think that the regularity of the mesostructure was not so high and it was hidden in the direct beam.

(Example 65)
0.16 g of octadecyltrimethylammonium chloride was dissolved in a solution obtained by adding 0.2 g of 6N NaOH aqueous solution to 12 g of ion-exchanged water, and 0.27 g of 2,7-BTEAcr was added thereto and stirred vigorously. Sonication was performed for 15 minutes and then stirred at room temperature for 24 hours. And it heated at 100 degreeC for 20 hours further. Filtration and drying yielded an acridine silica composite material having a mesostructure.

  FIG. 144 shows the X-ray diffraction pattern of the obtained powder of acridine silica composite material (Acr-HMM-powder), and FIG. 145 shows the fluorescence and excitation spectra. In the X-ray diffraction pattern, a peak due to the mesostructure was observed at d = 4.5 nm, and it was confirmed that a regular mesostructure was present (FIG. 144). Further, when the fluorescence spectrum was measured at an excitation wavelength of 400 nm, it was confirmed that strong emission centered at 515 nm was exhibited (FIG. 145).

<Synthesis and Luminescent Property Test of 4,4 '''-QuaterphenylComposite>
Example 66
0.08 g of 1,12-bis (octadecyldimethylammonium) dodecane dibromide (C _18-12-18 ) was dissolved in a solution obtained by adding 333 μl of 12N hydrochloric acid solution to 6 g of ion-exchanged water, and 4,4 ''' A solution prepared by dissolving 0.1 g of bistriethoxysilylquaterphenyl (4,4 ′ ″-BTEQua) in a mixed solvent of 1 g of ethanol and 0.5 g of THF was added and vigorously stirred. Sonication was performed for 15 minutes and then stirred at room temperature for 24 hours. And it heated at 100 degreeC for 20 hours further. Filtration and drying yielded a quaterphenyl silica composite material.

  FIG. 146 shows the X-ray diffraction pattern of the obtained powder of quaterphenyl silica composite material (Qua-HMM-powder), and FIG. 147 shows the fluorescence and excitation spectra. In the X-ray diffraction pattern, no peak indicating a mesostructure was observed, but a peak attributed to the periodic structure of quaterphenyl was observed at d = 1.99 nm (FIG. 146). Further, when the fluorescence spectrum was measured with an excitation wavelength of 400 nm, it was confirmed that strong emission centered at 465 nm was exhibited (FIG. 147).

<Synthesis of naphthalene composite material and emission characteristics test>
(Example 67)
After dissolving 0.087 g of octadecyltrimethylammonium chloride in a solution obtained by adding 90 μl of ion-exchanged water and 10 μl of 2N hydrochloric acid solution to 2 g of ethanol, add 0.28 g of bistriethoxysilylnaphthalene (BTENph) and stir at room temperature for 1 hour or more. A sol solution was obtained. Using this sol solution, a coat film (film thickness: 100 to 300 nm) was obtained by spin coating. The coating conditions were a rotation speed of 4000 rpm and a rotation time of 1 minute. The obtained film was dried at 100 ° C. for 1 hour or longer.

  FIG. 148 shows an X-ray diffraction pattern of a thin film (Nph-HMM-s-film) of a naphthalene silica composite material, and FIG. 149 shows fluorescence and excitation spectra. In the X-ray diffraction pattern, a peak was observed at d = 3.4 nm, confirming the presence of a regular mesostructure (FIG. 148). Further, when the fluorescence spectrum was measured at an excitation wavelength of 280 nm, it was confirmed that strong emission centered at 395 nm was shown (FIG. 149).

Example 68
0.16 g of octadecyltrimethylammonium chloride was dissolved in a solution obtained by adding 0.2 g of 6N NaOH aqueous solution to 12 g of ion-exchanged water, and 0.2 g of BTENph was added thereto and stirred vigorously. Sonication was performed for 10 minutes and then stirred at room temperature for 24 hours. And it heated at 100 degreeC for 24 hours. Filtration and drying yielded a naphthalene silica composite material having a mesostructure.

  The X-ray diffraction pattern of the obtained naphthalene silica composite powder (Nph-HMM-powder) is shown in FIG. 150, and the fluorescence and excitation spectra are shown in FIG. 151, respectively. In the X-ray diffraction pattern, a peak attributed to the mesostructure was observed near 2Θ = 1 °, confirming the presence of a regular mesostructure (FIG. 150). In addition, a peak attributed to the periodic structure of skeleton naphthalene was observed near 2Θ = 9 °. Furthermore, when the fluorescence spectrum was measured at an excitation wavelength of 340 nm, it was confirmed that strong emission centered at 360 nm was exhibited (FIG. 151).

<Synthesis and emission characteristics test of acridone composite material>
(Example 69)
After 0.08 g of triblock copolymer P123 was dissolved in 1 g of ethanol / THF (1: 1 by weight) mixed solvent with 43 μl of ion exchange water and 10 μl of 2N hydrochloric acid aqueous solution, 0.1 g of BTEAcd having the following structure was added to ethanol. / THF (weight ratio 1: 1) mixed solvent 1.5g was added and stirred at room temperature for 1 hour to obtain a sol solution. Using this sol solution, a coat film (film thickness: 100 to 300 nm) was obtained by spin coating. The coating conditions were a rotation speed of 4000 rpm and a rotation time of 1 minute. The obtained film was dried at 100 ° C. for 1 hour or longer.

  152 shows an X-ray diffraction pattern of an acridone silica composite thin film (Acd-HMM-s-film), FIG. 153 shows fluorescence and excitation spectra, and FIG. 154 shows a UV spectrum. In the X-ray diffraction pattern, a sharp peak was observed at d = 9.6 nm, confirming the presence of a regular mesostructure (FIG. 152). Further, when the fluorescence spectrum was measured at an excitation wavelength of 400 nm, it was confirmed that strong emission centered on 500 nm was exhibited (FIG. 153). Further, from the result of the UV spectrum, it was confirmed that it has light absorption bands centered around 255 nm and 400 nm (FIG. 154).

(Example 70)
To a solution obtained by adding 0.2 g of a 6N NaOH aqueous solution to 12 g of ion-exchanged water, 0.16 g of octadecyltrimethylammonium chloride was dissolved, and a solution obtained by dissolving 0.2 g of BTEAcd in 1 g of ethanol was added thereto and vigorously stirred. Sonication was performed for 15 minutes and then stirred at room temperature for 24 hours. And it heated at 100 degreeC for 24 hours. Filtration and drying yielded an acridine silica composite material having a mesostructure.

  FIG. 155 shows the X-ray diffraction pattern of the obtained powder of acridone silica composite material (Acd-HMM-powder), and FIG. 156 shows the fluorescence and excitation spectra. In the X-ray diffraction pattern, a peak due to the mesostructure was observed at d = 4.6 nm, and it was confirmed that a regular mesostructure was present (FIG. 155). Further, when the fluorescence spectrum was measured at an excitation wavelength of 400 nm, it was confirmed that strong emission centered at 494 nm was exhibited (FIG. 156).

<Test of film thickness and light absorption rate>
(Example 71)
A thin film (approx. 500 nm coat) of biphenyl silica composite material was produced on the glass substrate by the dip coating method using the same method as in Example 10 except that a quartz substrate was used instead of the glass substrate.

  Using the biphenyl silica composite thin film thus obtained, the transmittance of the thin film was measured using a Shimadzu MPS-2400 spectrophotometer. As a result of such measurement, the transmittance drastically decreased from a wavelength of 300 nm, and the transmittance of the thin film becomes 0 in a wavelength region of 285 nm or less. Therefore, it was confirmed that the thin film absorbs 100% at a wavelength of 285 nm or less. It was.

(Example 72)
After adding 180 μl of ion-exchanged water and 5 μl of 2N hydrochloric acid aqueous solution to 3 g of ethanol, 0.4 g of nonionic triblock copolymer P123 was added and mixed to obtain a homogeneous solution. Next, 0.6 g of BTEBP was added to this solution and stirred for 1 hour at room temperature, and then 2 g of ethanol was added and stirred for 20 minutes to obtain a sol solution. Using this sol solution, a coat film was obtained on a quartz substrate by spin coating (film thickness 300 μm). The coating conditions were a rotation speed of 4000 rpm and a rotation time of 1 minute. Furthermore, the obtained coat film was dried at room temperature.

(Example 73)
Before dissolving P123 in the solution before the addition of BTEB, a coumarin-supporting coat film was prepared in the same manner as in Example 72 except that a quantity of 1.8 mol% of coumarin (manufactured by Aldrich) was added to BTEBP. Obtained.

(Comparative Example 12)
To 1.9 g of TMOS (tetramethoxysilane), 0.5 g of ion exchange water and 12.5 μl of 2N hydrochloric acid aqueous solution were added, and the mixture was stirred at room temperature for 1 hour. A solution obtained by adding 0.9 g of nonionic triblock copolymer P123, 1.25 ml of ion-exchanged water, 1.25 ml of ethanol, and 12.5 μl of 2N hydrochloric acid aqueous solution to an amount of 1.8 mol% of coumarin (manufactured by Aldrich) with respect to TMOS. After stirring for 20 minutes, 5 g of ethanol was further added and stirred for 20 minutes to obtain a sol solution. Using this sol solution, the same method as in Example 72 was adopted to obtain a coat film on a quartz substrate by spin coating.

<Measurement of absorption rate and quantum yield>
Using the coating films obtained in Example 57, Example 58, Example 72, Example 73 and Comparative Example 12, respectively, the organic EL quantum yield measuring device C9920-01 manufactured by Hamamatsu Photonics was used in the same manner as in Examples 57-58. Was used to measure the absorptance and quantum yield for 266 nm ultraviolet light, and the luminous efficiency was calculated as absorptivity × quantum yield. Furthermore, for the coating films obtained in Example 72, Example 73, and Comparative Example 12, the absorptance and quantum yield for 350 nm ultraviolet light were measured using the above-mentioned apparatus, and the luminous efficiency was calculated. The results obtained are shown in Table 12.

  As is apparent from the results shown in Table 12, the quantum yield of the coating films obtained in Example 57 and Example 72 at 266 nm ultraviolet light was 0.51. In Example 57 and Example 72, the surfactant contained in the sol solution used is different in Brij76 and P123, respectively, but the quantum yield of the coating film formed using each sol solution is 0. .51 did not change. Similarly, the quantum yield at 266 nm ultraviolet light of the coating films obtained in Example 58 and Example 73 to which 1.8 mol% of coumarin was added was 0.99. On the other hand, the absorptance in ultraviolet light at 266 nm is about 0.66, 0.67 for the coating films obtained in Example 57 and Example 58, and about 0.87, 0.86 for the coating films obtained in Example 72 and Example 73. There was a difference in the absorption rate. It is considered that such a difference in absorption rate is caused not by the presence or absence of addition of coumarin but by the thickness of the coat film. Also, the composition of the sol solution mainly differs only in the amount of ethanol, and the sol solutions obtained in Example 57 and Example 58 are more diluted than the sol solutions obtained in Example 72 and Example 73. The coating film produced by employing the spin coating method has a low viscosity and becomes thin.

  Since the sol solution compositions obtained in Example 57 and Example 71 are the same except for the concentrations of ethanol and 2N aqueous hydrochloric acid, the coating film compositions after drying are the same. On the other hand, in Example 57, a spin coat method was used to produce a coat film having a thickness of about 100 nm, and in Example 71, a dip coat method was used to produce a coat film having a thickness of about 500 nm. When each ultraviolet ray was subjected to an ultraviolet light absorption test, the coat film obtained in Example 57 having a coat film thickness of about 100 nm absorbed about 67% of 266 nm ultraviolet light. The coat film obtained in Example 71 of about 500 nm absorbed 100% of light of 285 nm or less. From these results, it was confirmed that in the BTEBP system, if the coat film thickness is increased, the biphenyl skeleton absorbs 100% of ultraviolet light of 285 nm or less and emits light with a quantum yield of about 51%. . In addition, it was confirmed that when coumarin was present, the energy absorbed by the biphenyl skeleton was transmitted to almost 100% coumarin and almost converted to light.

  On the other hand, the coating film obtained in Example 73 had an absorption rate at 266 nm ultraviolet light of 0.86, a quantum yield of 0.99, and a luminous efficiency of 0.85, whereas a comparison was made by adding coumarin to mesoporous silica having no biphenyl skeleton. The absorptivity of the coat film obtained in Example 12 at 266 nm ultraviolet light was as low as 0.55, the quantum yield was 0.71, and the light emission efficiency was 0.39. Thus, the quantum yield in 350 nm ultraviolet light directly exciting coumarin is 1.00 compared to the coating film obtained in Example 73, whereas the coating film obtained in Comparative Example 12 is as low as 0.68. The coating film obtained in Comparative Example 12 is considered to have a concentration quenching of coumarin. Further, if the amount of coumarin is reduced in the coating film obtained in Comparative Example 12, the quantum yield in 350 nm ultraviolet light approaches 1, but the absorption rate for 266 nm ultraviolet light decreases from 0.55. The superiority of the coating film obtained in 73 is not changed.

<Light emitting element>
(Examples 74 to 75)
A sol solution similar to the sol solution obtained in Example 28 and Example 30 was produced, and each of the sol solutions was provided with “NSHU590B” (a shell-type light emitting diode, peak wavelength of UV LED manufactured by Nichia Corporation). 365 nm) was dipped and dried to form a coat film (film thickness 500 nm) on the surface of the glass lens of the LED to obtain a light emitting device of the present invention (Examples 74 and 75). A schematic diagram of the light-emitting element thus obtained is shown in FIG. The aforementioned ultraviolet LED manufactured by Nichia Corporation comprises a light source 1 and a lens 2 as shown in FIG. The light emitting device obtained in this example shown in FIG. 157 includes the light emitting layer 3 made of the above light emitting material on the surface of the lens 2 of the ultraviolet LED.

  When a constant current of 20 mA was passed through the ultraviolet LED using the light emitting device thus obtained, the same fluorescence as in Example 28 and Example 30 was visually recognized.

<Extraction efficiency due to low refraction>
(Example 76 and Comparative Example 13)
First, a method for calculating the extraction efficiency will be described. The light-emitting element of the present invention is characterized by comprising a light-emitting layer containing a light-emitting material made of a polymer of an organosilicon compound and a light source. Light emitted from the light source passes through the light emitting layer and is extracted into the air. A light wave incident on a medium having a different refractive index is lost by reflecting part of the incident light on the surface of the medium having a different refractive index (Fresnel loss). The transmittance and reflectance of light waves incident on media having different refractive indexes can be obtained from the Fresnel reflection / transmission coefficient obtained from the incident angle of the light waves and the refractive index of the medium.

FIG. 158 shows the states of incident light, reflected light, and transmitted light incident on media having different refractive indexes. Here, when the electric field vector parallel to the incident surface is p-polarized light and the electric field vector perpendicular to the incident surface is s-polarized light, the incident light is superposed of these two linearly polarized components (p-polarized light and s-polarized light). When considered, Fresnel reflection coefficients r _p and r _s for s-polarized light and p-polarized light are expressed by two equations shown in FIG.

  Here, when light is vertically incident, the above Fresnel equation is expressed by the following simple equation.

  Using such an equation, the reflectance of the light emitting element having the configuration shown in FIG. 159 (Example 76) and the light emitting element without the coating film shown in FIG. 160 (Comparative Example 13) were calculated, and the transmittance was obtained. The light source 1 uses a general GaN-based LED (refractive index of about 2.4) as a UV-LED, and the light emitting layer 3 has the same BiPh-HMM-a-film (refractive index n = 1.34) as in Example 55. Arranged. Further, when determining the transmittance, the refractive index n of air was set to 1, and the refractive index n of the lens was calculated in two ways: 1.5 and 1.7. Moreover, the transmittance | permeability in each interface from which the refractive index differs differs for the whole transmittance | permeability, and each transmittance | permeability was integrated | accumulated all. The measurement results of the devices obtained in Example 76 and Comparative Example 13 are shown in Tables 13 and 14, respectively.

  In the light-emitting layer, it has been found that the transmittance is improved by 0.015 to 0.03 and the light extraction efficiency is improved by reducing the refractive index from 1.5 to 1.7 of the lens to 1.34.

  From such a result, it considers in the case of making another luminescent compound (pigment) contain and light-emit multicolor. Conventionally, a dye is often dispersed in the lens 2 in the configuration shown in FIG. 160. For example, an inorganic phosphor is dispersed in the lens. However, in the light emitting element having such a configuration, irregular reflection is caused by the inorganic phosphor, and the extraction efficiency is further reduced.

  On the other hand, in the light-emitting element having the structure shown in FIG. 159, the light-emitting layer is a layer obtained by uniformly coating BiPh-HMM containing a dye, and light from a light source is vertically applied to such a light-emitting layer. Since the light can be incident and the excitation light can be absorbed with high efficiency, the light extraction efficiency can be improved. In the light-emitting element having the structure illustrated in FIG. 159, higher light extraction efficiency can be obtained by designing the light-emitting layer to have a film thickness that can absorb 100% of the excitation light.

  As described above, according to the present invention, it is possible to provide a light emitting device with improved light emission efficiency, excellent light absorption efficiency, and excellent heat resistance that enables uniform light emission in the surface. It becomes possible. Therefore, the light emitting device of the present invention is useful for a multicolor display device and the like.

It is the schematic which shows suitable one Embodiment of the light emitting element of this invention. It is the schematic which shows other suitable embodiment of the light emitting element of this invention. 3 is a graph showing X-ray diffraction patterns of Ph-HMM-c obtained in Example 1 and Ph-Si obtained in Example 2. FIG. Is a graph showing the N ₂ adsorption isotherm of the sample obtained in Example 1-3. 4 is a graph showing an X-ray diffraction pattern of Ph-HMM-a obtained in Example 3. 4 is a SEM photograph of Ph—Si obtained in Example 2. It is a graph which shows the visible absorption spectrum of each sample obtained in Examples 1-3. It is a graph which shows the fluorescence spectrum of each sample obtained in Examples 1-3. 6 is a graph showing an X-ray diffraction pattern of BiPh-HMM-c obtained in Example 4. 6 is a graph showing an X-ray diffraction pattern of BiPh-HMM-c-s obtained in Example 5. 6 is a graph showing an N ₂ adsorption isotherm of BiPh-HMM-c obtained in Example 4. 7 is a graph showing an X-ray diffraction pattern of BiPh-Si-Base obtained in Example 6. 6 is a graph showing an X-ray diffraction pattern of BiPh-Si-Acid obtained in Example 7. 6 is a SEM photograph of BiPh-Si-Base obtained in Example 6. 10 is a graph showing an X-ray diffraction pattern of BiPh-HMM-a obtained in Example 8. 10 is a graph showing an X-ray diffraction pattern of BiPh-HMM-as obtained in Example 9. 10 is a graph showing a nitrogen adsorption isotherm of BiPh-HMM-a obtained in Example 8. 10 is a graph showing a visible absorption spectrum of BiPh-HMM-a obtained in Example 8. 6 is a graph showing a visible absorption spectrum of BiPh-HMM-c obtained in Example 4. It is a graph which shows the fluorescence spectrum of each sample obtained in Examples 4-9. 10 is a graph showing an X-ray diffraction pattern of BiPh-HMMc-s-film obtained in Example 10. 10 is a graph showing the fluorescence spectrum of BiPh-HMMc-s-film obtained in Example 10. 6 is a photograph showing the light emission state of the BiPh-HMMc-s-film thin film obtained in Example 10. FIG. It is a photograph which shows the light emission state of the thin film of the samples 1-3 obtained in Examples 11-13. It is a graph which shows each fluorescence spectrum of the samples 1-3 obtained in Examples 11-13. It is a graph which shows the fluorescence spectrum of the powder of the luminescent material obtained in Example 5, and the powder of the luminescent material of Comparative Examples 1-3. It is a graph which shows the fluorescence spectrum of the thin film of the luminescent material obtained in Example 10, and the thin film of the luminescent material of Comparative Examples 1-3. It is a graph which shows the fluorescence spectrum of a BTEB solution. It is a graph which shows the fluorescence spectrum of a BTEBP solution. It is a graph which shows the fluorescence spectrum of a benzene solution. It is a graph which shows the fluorescence spectrum of a biphenylene solution. It is a graph which shows the relationship between the maximum fluorescence intensity and a density | concentration. It is a graph which shows the result of having plotted the maximum light emission wavelength ((lambda) _max ) with respect to the density | concentration. It is a graph which shows the fluorescence spectrum of the solution of the luminescent material obtained in Example 5 and 9, and BTEBP. It is a graph which shows the density | concentration change of the fluorescence intensity of the luminescent material and BTEBP solution which were obtained in Example 5 and 9. 14 is a graph showing a powder X-ray diffraction pattern of the layered phenylsilica composite material obtained in Example 14. 6 is a graph showing a ²⁹ Si MAS NMR spectrum of the layered phenylsilica composite material obtained in Example 14. FIG. 14 is a schematic diagram showing the structure of a layered phenylsilica composite material obtained in Example 14. FIG. 6 is a graph showing the fluorescence spectrum of the layered phenylsilica composite material obtained in Example 14. 16 is a graph showing a powder X-ray diffraction pattern of the layered biphenyl silica composite material obtained in Example 15. 16 is a graph showing a powder X-ray diffraction pattern in a state where toluene is dropped on the layered biphenyl silica composite material obtained in Example 15. 14 is a graph showing the fluorescence spectrum of the layered biphenyl silica composite material obtained in Example 15. The X-ray-diffraction pattern of each sample obtained in Examples 16-18 and Ph-HMM-c obtained in Example 1 is shown. ₂ is a graph showing an N ₂ adsorption isotherm of Ph-HMM-c obtained in Example 1. FIG. 14 is a graph showing an N ₂ adsorption isotherm of a sample obtained in Example 16. 14 is a graph showing an N ₂ adsorption isotherm of a sample obtained in Example 17. 10 is a graph showing an N ₂ adsorption isotherm of a sample obtained in Example 18. ¹⁴ is a graph showing the results of ¹³ C-CP-NMR of the sample obtained in Example 18. 2 is a graph showing the ²⁹ Si-MAS-NMR result of the sample obtained in Example 18. FIG. 2 is a graph showing an absorption spectrum of Ph-HMM-c obtained in Example 1. FIG. 14 is a graph showing an absorption spectrum of a sample obtained in Example 16. 10 is a graph showing an absorption spectrum of a sample obtained in Example 17. 14 is a graph showing an absorption spectrum of a sample obtained in Example 18. It is a graph which shows the calibration curve of BTEA. It is a graph which shows the absorption spectrum in the monomer of BTEA. It is a graph which shows the fluorescence spectrum of Ph-HMM and BTEA in excitation wavelength 260nm. It is a graph which shows the result of having measured the fluorescence spectrum with excitation wavelength 260nm with respect to each sample obtained in Examples 16-18. It is a graph which shows the X-ray-diffraction pattern of Ph-HMM-c, BiPh-HMM-c, Al-TPPEt / Ph-HMM, and Al-TPPEt / BiPh-HMM. It is a graph which shows the UV-vis spectrum of Al-TPPEt / Ph-HMM. It is a graph which shows the UV-vis spectrum of Al-TPPEt / BiPh-HMM. It is a graph which shows the fluorescence spectrum of Al-TPPEt / Ph-HMM. It is a graph which shows the fluorescence spectrum of Al-TPPEt / BiPh-HMM. It is a photograph which shows the light emission state of Al-TPPEt powder. It is a photograph which shows the light emission state of Al-TPPEt / Ph-HMM powder. It is a photograph which shows the light emission state of Ph-HMM-c powder. It is a photograph which shows the light emission state of BiPh-HMM-c powder. It is a photograph which shows the light emission state of Al-TPPEt / BiPh-HMM powder. 14 is a graph showing an X-ray diffraction pattern of BiPh-HMMc-s-film 2 obtained in Example 22. 22 is a graph showing fluorescence and excitation spectra of BiPh-HMMc-s-film 2 obtained in Example 22. 14 is a graph showing X-ray diffraction patterns before and after firing of a Ph-HMM film obtained in Example 23. FIG. 6 is a graph showing X-ray diffraction patterns before and after firing of a BiPh-HMM film obtained in Example 24. FIG. 14 is a graph showing fluorescence spectra before and after baking of a Ph-HMM film obtained in Example 23. FIG. 14 is a graph showing fluorescence spectra before and after baking of a BiPh-HMM film obtained in Example 24. FIG. It is a graph which shows the fluorescence and excitation spectrum of BiPh-Acid-film obtained in Example 25. 20 is a graph showing the UV spectrum of BiPh-Acid-film obtained in Example 25. 22 is a graph showing an X-ray diffraction pattern of TPh-HMMc-s-film obtained in Example 26. FIG. 14 is a graph showing fluorescence and excitation spectrum of TPh-HMMc-s-film obtained in Example 26. FIG. 6 is a graph showing fluorescence and excitation spectrum of TPh-Acid-film obtained in Example 27. FIG. 42 is a graph showing an X-ray diffraction pattern of Pyr-HMMc-s-film obtained in Example 28. 42 is a graph showing fluorescence and excitation spectra of Pyr-HMMc-s-film obtained in Example 28. 42 is a graph showing a UV spectrum of Pyr-HMMc-s-film obtained in Example 28. FIG. 6 is a graph showing fluorescence and excitation spectrum of Pyr-Acid-film obtained in Example 29. FIG. 4 is a graph showing the UV spectrum of Pyr-Acid-film obtained in Example 29. FIG. 6 is a graph showing an X-ray diffraction pattern of Ant-HMMc-s-film obtained in Example 30. FIG. 6 is a graph showing fluorescence and excitation spectrum of Ant-HMMc-s-film obtained in Example 30. FIG. 6 is a graph showing a UV spectrum of Ant-HMMc-s-film obtained in Example 30. FIG. 2 is a graph showing fluorescence and excitation spectrum of octafluorobiphenyl silica obtained in Example 31. FIG. 6 is a graph showing the fluorescence and excitation spectrum of TPh-HMM-Acid obtained in Example 32. FIG. 4 is a graph showing the fluorescence and excitation spectrum of Pyr-HMM-Acid obtained in Example 33. 4 is a graph showing the fluorescence and excitation spectrum of Ant-HMM-Acid obtained in Example 34. 42 is a graph showing the fluorescence and excitation spectrum of TPh-Acid obtained in Example 35. 4 is a graph showing the fluorescence and excitation spectrum of Pyr-Acid obtained in Example 36. 6 is a graph showing an X-ray diffraction pattern of Sample 1 (BiPh-HMM powder) obtained in Example 37. FIG. 42 is a graph showing an X-ray diffraction pattern of Sample 2 (F1 (0.5 mg) / BiPh-HMM powder) obtained in Example 37. 42 is a graph showing an X-ray diffraction pattern of Sample 5 (F1 (5 mg) / BiPh-HMM powder) obtained in Example 37. 6 is a graph showing fluorescence spectra of Samples 1 to 5 obtained in Example 37. 6 is a structural schematic diagram of a sample (F1 / BiPh-HMM powder) obtained in Example 37. FIG. 42 is a graph showing an X-ray diffraction pattern of Sample 2 (F1 (2 mol%) / BiPh-HMM thin film) obtained in Example 38. 10 is a graph showing fluorescence spectra of Samples 1 to 3 obtained in Example 38. 14 is a graph showing the excitation wavelength dependence of the fluorescence spectrum of Sample 2 obtained in Example 38. It is a graph which shows the fluorescence spectrum of each sample (rhodamine / BiPh-HMM thin film) obtained in Example 39. It is a graph which shows the fluorescence spectrum of each sample (pyrene / BiPh-HMM thin film) obtained in Example 40. EuCl is a graph showing the ₃ and absorption spectra of the ethanol solution of TbCl _3. 4 is a graph showing the fluorescence spectrum of EuCl ₃ / BiPh-HMM-film obtained in Example 41. 4 is a graph showing the fluorescence spectrum of TbCl ₃ / BiPh-HMM-film obtained in Example 42. It is a graph which shows the X-ray-diffraction pattern of BiPh-HMM-film. 4 is a graph showing an X-ray diffraction pattern of coumarin (3 mol%) / BiPh-HMM-film obtained in Example 43. It is a graph which shows the fluorescence spectrum of coumarin / BiPh-HMM-film which introduce | transduced various quantity coumarin. It is a graph which shows the fluorescence and excitation spectrum of BiPh-HMM-film, the ethanol solution of coumarin, and coumarin / BiPh-HMM-film. It is a graph which shows the fluorescence spectrum of the coumarin / BiPh composite film which introduce | transduced various quantity coumarin. It is a graph which shows the excitation spectrum of an Ir (ppy) ₃ / BiPh-HMM thin film, an Ir (ppy) ₃ / PMMA thin film, and a PMMA thin film. 42 is a graph showing phosphorescence spectra of each Ir (ppy) ₃ / BiPh-HMM thin film obtained in Example 45. It is a graph which shows the fluorescence spectrum of the mixture of R6G and BiPh-HMM obtained in Examples 46-48. 10 is a graph showing a fluorescence spectrum of a mixture of DANS and BiPh-HMM obtained in Example 49. It is a graph which shows the fluorescence spectrum of the mixture of the coumarin obtained in Examples 51-53 and BiPh-HMM, and BiPh-HMM-c2-s obtained in Example 50. It is a graph which shows the fluorescence spectrum of the mixture of the coumarin obtained in Examples 51-53 and BiPh-HMM, and BiPh-HMM-c2-s obtained in Example 50. It is a graph which shows the fluorescence spectrum of the BiPh-HMM thin film which introduce | transduced the rhodamine and coumarin obtained in Example 54. It is a photograph in which the BiPh-HMM thin film introduced with rhodamine and coumarin obtained in Example 54 emits white light. 42 is a graph showing an X-ray diffraction pattern of BiPh-HMM-a-film obtained in Example 55. 2 is a scanning electron micrograph of biphenyl silica fine particles synthesized in Example 56. FIG. 2 is a scanning electron micrograph of biphenyl silica fine particles synthesized in Example 56. FIG. 6 is a graph showing an X-ray diffraction pattern of biphenyl silica fine particles synthesized in Example 56. FIG. 42 is a graph showing a fluorescence spectrum of the biphenyl silica fine particles synthesized in Example 56 in a powder state. It is a graph which shows the absorption spectrum of a biphenyl silica fine particle / 2-propanol dispersion liquid. It is a graph which shows the fluorescence spectrum of a biphenyl silica fine particle / 2-propanol dispersion liquid. It is a graph which shows the absorption spectrum of a 9,10- diphenylanthracene / cyclohexane solution. It is a graph which shows the fluorescence spectrum of a 9,10- diphenylanthracene / cyclohexane solution. It is a graph which shows the relationship between integrated fluorescence intensity and a light absorbency. It is a graph which shows the absorption spectrum of a BTEBP / 2-propanol solution. It is a graph which shows the fluorescence spectrum of a BTEBP / 2-propanol solution. 42 is a graph showing an X-ray diffraction pattern of Flu-HMM-s-film obtained in Example 59. 42 is a graph showing fluorescence and excitation spectra of Flu-HMM-s-film obtained in Example 59. 42 is a graph showing the UV spectrum of the Flu-HMM-s-film obtained in Example 59. 6 is a graph showing an X-ray diffraction pattern of Flu-HMM-powder obtained in Example 60. FIG. 6 is a graph showing the fluorescence and excitation spectrum of Flu-HMM-powder obtained in Example 60. FIG. 2 is a graph showing an X-ray diffraction pattern of Pyr-HMM-s-film obtained in Example 61. FIG. 2 is a graph showing fluorescence and excitation spectrum of Pyr-HMM-s-film obtained in Example 61. FIG. 2 is a graph showing the UV spectrum of Pyr-HMM-s-film obtained in Example 61. FIG. 2 is a graph showing an X-ray diffraction pattern of Pyr-Acid-powder obtained in Example 62. FIG. 2 is a graph showing the fluorescence and excitation spectrum of Pyr-Acid-powder obtained in Example 62. FIG. 2 is a graph showing an X-ray diffraction pattern of Ant-Acid-powder obtained in Example 63. FIG. 2 is a graph showing fluorescence and excitation spectrum of Ant-Acid-powder obtained in Example 63. FIG. 6 is a graph showing fluorescence and excitation spectrum of Acr-HMM-s-film obtained in Example 64. FIG. 42 is a graph showing an X-ray diffraction pattern of Acr-HMM-powder obtained in Example 65. 42 is a graph showing fluorescence and excitation spectra of Acr-HMM-powder obtained in Example 65. 42 is a graph showing an X-ray diffraction pattern of Qua-HMM-powder obtained in Example 66. 42 is a graph showing the fluorescence and excitation spectrum of Qua-HMM-powder obtained in Example 66. 42 is a graph showing an X-ray diffraction pattern of Nph-HMM-s-film obtained in Example 67. 42 is a graph showing fluorescence and excitation spectra of Nph-HMM-s-film obtained in Example 67. 2 is a graph showing an X-ray diffraction pattern of Nph-HMM-powder obtained in Example 68. FIG. 2 is a graph showing the fluorescence and excitation spectrum of Nph-HMM-powder obtained in Example 68. FIG. 42 is a graph showing an X-ray diffraction pattern of Acd-HMM-s-film obtained in Example 69. 42 is a graph showing fluorescence and excitation spectra of Acd-HMM-s-film obtained in Example 69. 42 is a graph showing a UV spectrum of Acd-HMM-s-film obtained in Example 69. 6 is a graph showing an X-ray diffraction pattern of Acd-HMM-powder obtained in Example 70. FIG. 6 is a graph showing fluorescence and excitation spectrum of Acd-HMM-powder obtained in Example 70. FIG. It is the schematic of the light emitting element obtained in Examples 74-75. It is a graph which shows the state of the incident light, reflected light, and transmitted light which inject into the medium from which a refractive index differs. 7 is a schematic diagram of a configuration of a light emitting device obtained in Example 76. FIG. 14 is a schematic view of a configuration of a light emitting device obtained in Comparative Example 13. FIG.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Light source, 2 ... Lens, 3 ... Light emitting layer, 4 ... Table, 5 ... Air layer, L ... Light.

Claims (9)

The following general formula (1):
[ Wherein X is benzene, biphenyl, terphenyl, quaterphenyl, benzophenone, fluorene, anthraquinone, naphthalene, acenaphthene, carbazole, triphenylene, phenanthrene, acridine, acridone, azulene, chrysene, pyrene, anthracene, perylene, biacetyl, benzyl , fluorescein, eosin, rhodamine B, and an organic molecule that exhibits at least one of fluorescence of those fluorinated compound, R ¹ is at least one selected from an alkoxy group or Ranaru group having 1 to 5 carbon atoms N represents 3 and m represents 2 . ]
The light emitting layer containing the light emitting material consisting of the polymer of the organosilicon compound represented by this, and the light source, The polymer of the said organosilicon compound is the following general formula (2):
[Wherein, X represents an organic molecule exhibiting fluorescence. ]
The light emitting element characterized by having the repeating unit represented by these . 2. The light-emitting element according to claim 1, wherein the polymer of the organosilicon compound has a peak appearing in a region of d = 5 nm or less in X-ray diffraction (XRD) measurement . The light emitting device according to claim 1 or 2 , wherein the polymer of the organosilicon compound is a porous body. The light emitting device according to any one of claims 1 to 3 , wherein the polymer of the organosilicon compound is a mesoporous material having a central pore diameter of 1 to 30 nm. The polymer of the organosilicon compound is selected from porphyrins, anthracenes, aluminum complexes, rare earth elements or complexes thereof, fluorescein, rhodamine, coumarin, pyrene, dansylic acid, cyanine dyes, merocyanine dyes, styryl dyes, and benzstyryl dyes. light-emitting device according to any one of claims 1-4, characterized by further comprising at least one other luminescent compound. It said another luminescent compound, the adsorption of the polymer of the organic silicon compound, coupling, according to claim 5, characterized in that has become one of conditions selected from the group consisting of filled and mixtures Light emitting element. The light emitting device according to any one of claims 1 to 6 , wherein the polymer of the organosilicon compound is in the form of particles having an average particle size of 1 µm or less. The polymer of the organic silicon compound, light-emitting device according to any one of claims 1 to 6 in which the average film thickness is characterized in that the following thin-film 1 [mu] m. The light emitting device according to any one of claims 1 to 6 , wherein the polymer of the organosilicon compound is a layered material formed by laminating nanosheets each having a thickness of 10 nm or less. .