JP2001282153A - Ultraviolet fluorescence method and display device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a UV fluorescence method with which prescribed fluorescence may be obtained and a display device using same. SOLUTION: UV fluorescent glass containing SiO2 exceeding 60 wt.% of the total amount as a glass component and containing rare earth element- containing oxide containing at least one rare earth elements selected from among the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Gd, Dy, Er, Ho, Tm, Yb and Lu is irradiated with UV rays within a range of a wavelength 100 to 400 nm, by which the fluorescence is generated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ultraviolet fluorescent method and a display device using the same. More specifically, the present invention relates to an ultraviolet fluorescent method using a specific ultraviolet fluorescent glass and a display device using the same.

[0002]

2. Description of the Related Art Conventionally, an ultraviolet fluorescent glass which emits fluorescence by irradiating ultraviolet light (hereinafter sometimes simply referred to as fluorescent glass) is known, and is used for a fluorescent material for a lamp, a fluorescent material for a cathode ray tube and the like. ing. Such fluorescent glass is disclosed in, for example, Japanese Patent Publication No. 57-27047 and Japanese Patent Publication No. 57-27048,
It is composed of glass components such as ₂ and B ₂ O ₃ and rare earth elements such as Tb ₂ O ₃ and Eu ₂ O ₃ .

[0003] Also, Japanese Patent Application Laid-Open No. 8-133780,
Japanese Patent Application Laid-Open No. 9-202642 discloses a glass containing at least phosphorus (P), oxygen (O), and fluorine (F), and a fluorescent agent containing Eu or Tb as a fluorescent agent, or Eu, Tb,
A fluorophosphate fluorescent glass containing Sm and Mn is disclosed. Further, JP-A-10-167755 discloses a glass containing at least silicon (Si), boron (B), and oxygen (O).
An oxide containing _{2 to} 60 mol% of iO _{2 and} 2 to 60 mol% of B ₂ O ₃ and containing _{2 to} 15 mol% of Eu ₂ O _{3 and} 2 to 15 mol% of Tb ₂ O ₃ as a fluorescent agent A fluorescent glass is disclosed.

On the other hand, Japanese Patent Application Laid-Open No. 11-283415 discloses a display device comprising a black light and a fluorescent glass disposed in front of the black light. As the fluorescent glass, an ion is added to an amorphous inorganic compound. compounds were, for _{example, P 2 O 5 · SF 2} · BaF 2 · Eu 3+ or, P ₂ O ₅ · Al
A display device using F ₃ .MgF ₂ .Tb ³⁺ or the like is disclosed.

[0005]

However, JP-B-57-27047, JP-B-57-27048, JP-A-8-133780, and JP-A-9-202.
The fluorescent glasses disclosed in JP-A-642 and JP-A-10-167755 all use Tb ₂ O ₃ or Eu ₂ O ₃ as a fluorescent agent, and thus are obtained when fluorescent light is emitted. Problems such as low fluorescence intensity and variation in values were observed. Further, Japanese Unexamined Patent Application Publication No. 11-283415
The fluorescent glass used in the display device disclosed in Japanese Patent Application Laid-Open Publication No. H10-163, pp. 147-64, uses ions of Tb ₂ O ₃ or Eu ₂ O ₃ , and thus has problems such as low fluorescence intensity and variation in values. Was done.

[0006] Under such circumstances, the present inventors exhibit excellent ultraviolet fluorescence when irradiated with ultraviolet light of a predetermined wavelength simply by combining a specific glass component and a specific rare earth element-containing oxide. The inventors have found that the present invention has been completed. That is, an object of the present invention is to provide an ultraviolet fluorescent method capable of obtaining excellent fluorescence when irradiated with ultraviolet light, and a display device using such a fluorescent method.

[0007]

According to the present invention, according to the present invention, Sc, Y, La, and La are contained in a glass component containing, for example, more than 60% by weight of SiO ₂ with respect to the total amount.
Ce, Pr, Nd, Pm, Gd, Dy, Er, Ho, T
The ultraviolet fluorescent glass containing a rare earth element-containing oxide containing at least one rare earth element selected from the group consisting of m, Yb, and Lu is irradiated with ultraviolet light having a wavelength of 100 to 400 nm using an ultraviolet irradiation device. In addition, there is provided an ultraviolet fluorescent method characterized by generating fluorescence. By carrying out in this manner, the irradiated ultraviolet light can be effectively changed to fluorescence (including phosphorescence), and can be used as a light emitter. For example, by using the ultraviolet fluorescent glass of the present invention as a glass container for fragrance to be used in a car or a room, and by irradiating ultraviolet light in the vicinity of a black light or the like, the glass container for fragrance is used. Can emit fluorescent light. Therefore, the decorativeness and distinctiveness of the glass container for fragrance can be significantly improved.

In carrying out the ultraviolet fluorescent method of the present invention, it is preferable that the ultraviolet fluorescent glass is dispersed in a polymer material or an inorganic material. By implementing in this manner, ultraviolet fluorescent glass can be used as a composite material. For example, by dispersing ultraviolet fluorescent glass in a polymer material and then molding, a plastic plate capable of emitting fluorescence can be formed, or after dispersing ultraviolet fluorescent glass in an inorganic material, By molding, a glass plate in which the fluorescent light emitting portions are dispersed can be formed. Further, by uniformly dispersing the ultraviolet fluorescent glass in the polymer solution, a coating material containing the ultraviolet fluorescent glass can be formed.

In carrying out the ultraviolet fluorescent method of the present invention, it is preferable that the ultraviolet fluorescent glass is laminated on the adherend. By carrying out in this manner, the ultraviolet fluorescent glass is laminated on an arbitrary portion of the adherend, and then, by irradiating the ultraviolet light, excellent ultraviolet fluorescent property is obtained on the surface of the adherend and the inside of the adherend. Can be

In carrying out the ultraviolet fluorescent method of the present invention, it is preferable that the ultraviolet fluorescent glass displays characters, numerals, symbols, figures, patterns, or symbols. By carrying out in this manner, arbitrary information can be displayed using the ultraviolet fluorescent glass.

In carrying out the ultraviolet fluorescent method of the present invention, it is preferable to use a mask having an ultraviolet light transmitting portion and to irradiate ultraviolet light through the mask. With such an implementation, the mask can appropriately block or transmit the ultraviolet light. Therefore, since fluorescent light can be emitted by irradiating only an arbitrary portion with ultraviolet rays, the information display property of the ultraviolet fluorescent glass can be further improved.

In carrying out the ultraviolet fluorescent method of the present invention, it is preferable to irradiate ultraviolet rays through a liquid crystal cell. By carrying out in this manner, ultraviolet rays can be appropriately shielded or transmitted by the liquid crystal cell.
Therefore, it is possible to emit fluorescent light by irradiating an ultraviolet ray to an arbitrary portion of the ultraviolet fluorescent glass, and it is possible to further improve information displayability.

In practicing the ultraviolet fluorescent method of the present invention, it is preferable to irradiate ultraviolet rays with an ultraviolet irradiating device and irradiate visible light with a white lamp. In this manner, by using a white light in combination, the light transmitted through the ultraviolet fluorescent glass can be used as white light, so that the information display property of the ultraviolet fluorescent glass can be further improved.

Another embodiment of the present invention is a display device using any one of the above-described ultraviolet fluorescent methods. With this configuration, it is possible to efficiently provide a display device that can display predetermined information by using the fluorescence of the ultraviolet fluorescent glass.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments relating to an ultraviolet fluorescent method using a specific ultraviolet fluorescent glass and a display device using the same in the present invention will be specifically described.

[First Embodiment] In a first embodiment, a glass component (glass network component, glass mesh component,
And a glass network modifying component), an ultraviolet fluorescent component,
This is an ultraviolet fluorescent method in which an ultraviolet fluorescent glass containing a decoloring agent and a reducing agent is irradiated with ultraviolet light to generate fluorescence in the ultraviolet fluorescent glass. Hereinafter, constituent components and characteristics of the ultraviolet irradiation device and the ultraviolet fluorescent glass in the first embodiment will be specifically described.

1. Ultraviolet irradiation device (1) Specific examples Lights The ultraviolet irradiation device is not particularly limited as long as it can irradiate ultraviolet rays, and examples thereof include a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, and an excimer lamp. However, in order to more effectively use the obtained fluorescence, it is more preferable to use a black light as shown in FIG. 4 as the ultraviolet irradiation device. That is, the low-pressure mercury lamp 105 and the predetermined wavelength transmission filter 104
, A choke coil 106, a blinking switch 103,
It is preferable that the black light 100 includes the handle portion 102 and the AC power supply 107. With such a black light 100, while it is possible to irradiate ultraviolet rays of a predetermined wavelength, the luminescence of the black light 100 itself is not recognized so much, so that the fluorescence emitted from the ultraviolet fluorescent glass can be effectively used.

Light Guide Member It is also preferable to use a light guide member formed by bundling a number of optical fibers or a light guide plate as the ultraviolet irradiation device, and to irradiate ultraviolet rays through these light guide members. When such an ultraviolet irradiation device is used, an arbitrary minute portion of the ultraviolet fluorescent glass can be irradiated with ultraviolet light, so that the information display property can be further improved. Further, with these light guide members, the luminous properties of the light guide members themselves are not recognized so much, so that the fluorescent light emitted from the ultraviolet fluorescent glass can be effectively used.

Scanning Irradiation Apparatus In addition, it is preferable to irradiate the ultraviolet rays while scanning them as convergent light obtained by using a lens or a polygon mirror. With such an ultraviolet irradiation device,
Since it is possible to continuously and intermittently scan with ultraviolet light to irradiate an arbitrary minute portion of the ultraviolet fluorescent glass, information display performance can be further improved. In addition, if the light is convergent, the light emitting property of the light itself is not recognized so much, so that the fluorescence emitted from the ultraviolet fluorescent glass can be effectively used.

Irradiation device with pattern mask An irradiation device 50 provided with a mask 51 having an ultraviolet light transmitting portion 52 of a predetermined pattern as shown in FIG. Is preferred. When such an ultraviolet irradiation device 50 is used, an arbitrary portion of the ultraviolet fluorescent glass can be continuously and intermittently irradiated with ultraviolet light by a simple device, so that the information display property can be further improved. Also,
Since the light emission of the light source itself is not recognized by the mask, only the fluorescence emitted from the ultraviolet fluorescent glass can be effectively used. In addition, replacement of the pattern mask,
When the position can be moved, not only fixed information but also various information can be displayed.

(2) UV Irradiation Conditions Wavelength It is preferable that the wavelength of the ultraviolet rays to be irradiated is a value within a range of 100 to 400 nm. The reason for this is that such ultraviolet light can effectively emit fluorescence in the ultraviolet fluorescent glass. However, it is more preferable to use near ultraviolet rays.
A value within a range of 0 to 400 nm.
Wavelength in the range of 230 to 260 nm, or 330 to 370 n
It is preferred to use wavelengths in the range of m.

Irradiation dose It is preferable that the irradiation dose of ultraviolet rays is set to a value within a range of 1 to 3000 cd / m ² . The reason for this is that if the irradiation amount of the ultraviolet light is less than 1 cd / m ² , it may be difficult to cause the ultraviolet fluorescent glass to emit the fluorescent light effectively. , 0
If the value exceeds 00 cd / m ² , the irradiation time may be prolonged or the type of usable ultraviolet irradiation device may be limited. Therefore, it is more preferably set to a value within the range of dose of 5~2,000cd / m ² UV, still more preferably a value within the range of 10~1,000cd / m ^2.

2. Ultraviolet fluorescent glass (1) Glass network component The glass network component is a component that serves as the skeleton of the ultraviolet fluorescent glass. Specific examples of such a glass network component include SiO ₂ . Further, it is preferable that the addition amount of the glass network component is a value exceeding at least 60% by weight when the total amount is 100% by weight. The reason for this is that when the added amount of the glass network component is 60% by weight or less, the water resistance and mechanical properties are remarkably reduced, while the fluorescence coloring property is remarkably reduced. On the other hand, when the addition amount of the glass network component exceeds 80% by weight, the meltability decreases,
In some cases, bubbles may be easily entrained. Therefore, since the balance between the fluorescent coloring property and the melting property becomes better, the amount of the glass network component added to the total amount is 61%.
More preferably, the value is in the range of ~ 80% by weight,
More preferably, the value is in the range of 65 to 75% by weight.

(2) Glass network modifying component It is preferable to add an alkali metal oxide or an alkaline earth metal oxide as a glass network modifying component. Specifically, Na ₂ O, K ₂ O, Li ₂ O, CaO, MgO, Ba
O, B ₂ O ₃ , Al ₂ O _{3 and the} like can be used alone or in combination of two or more kinds of glass network modifying components.

Of these glass network modifying components, Na
₂ O, K ₂ O and Li ₂ O are alkali metal oxides and are added as fluxes to improve the solubility of the UV fluorescent glass raw material. Further, when the total amount of these alkali metal oxides is 100% by weight, it is preferable that the addition amount be a value within a range of 10 to 30% by weight, and a value within a range of 11 to 20% by weight. Is more preferable. The reason is that the addition amount of the alkali metal oxide is 1
If the amount is less than 0% by weight, the effect as a flux may not be exhibited. On the other hand, if the amount of the alkali metal oxide exceeds 30% by weight, water resistance and weather resistance may be reduced. This is because

Of the glass network modifying components described above, CaO, MgO and BaO are alkaline earth metal oxides and are added to obtain a stable ultraviolet fluorescent glass. When the total amount of these alkaline earth metal oxides is 100% by weight, 5 to 30%
The value is preferably in the range of wt%, more preferably in the range of 7 to 20 wt%. The reason for this is that if the amount of the alkaline earth metal oxide is less than 5% by weight, the effect as a glass stabilizer may not be exhibited, while the amount of the alkaline earth metal oxide may be less than 30% by weight. If the content is more than 10% by weight, the obtained ultraviolet fluorescent glass may be easily devitrified.

Of the above-mentioned glass network modifying components, B ₂ O ₃ and Al ₂ O ₃ are added to further improve the water resistance and weather resistance of the ultraviolet fluorescent glass. Also,
The total amount of these inorganic oxides such as B ₂ O ₃
When it is 0% by weight, the value is preferably in the range of 0.1 to 20% by weight, and more preferably in the range of 0.2 to 10% by weight. The reason for this is that if the addition amount of these inorganic oxides is less than 0.1% by weight, the effect of addition may not be exhibited, while the addition amount of these inorganic oxides exceeds 20% by weight. This is because the transparency of the obtained ultraviolet fluorescent glass may be reduced.

(3) Rare earth element-containing oxide type The rare earth element-containing oxide used in the ultraviolet fluorescent glass of the first embodiment is a part of a glass component.
Y, La, Ce, Pr, Nd, Pm, Gd, Dy, E
It is necessary to include an oxide containing at least one rare earth element selected from the group consisting of r, Ho, Tm, Yb, and Lu. The reason for this is that if these rare earth element-containing oxides are added in a relatively small amount, they can effectively absorb ultraviolet rays and exhibit an excellent ultraviolet fluorescent effect.

Further, among these rare earth element-containing oxides, CeO ₂ is more preferable. The reason for this is
If CeO ₂ is used, an excellent ultraviolet fluorescent effect can be obtained with a smaller amount of addition, but even when the glass is melted in a melting furnace, the glass is less likely to be colored.
This is because by adding CeO ₂ , an excellent ultraviolet shielding effect can be exhibited. Specifically, CeO
The ultraviolet absorbing property of No. ₂ will be described with reference to FIGS. In FIG. 7, the horizontal axis indicates the wavelength (nm) of the ultraviolet light, and the vertical axis indicates the transmittance (%) of the ultraviolet fluorescent glass having a thickness of 4 mm. The ultraviolet absorption spectrum in the chart shown in FIG. 7 corresponds to Examples 1 to 5 and Comparative Example 1 described below. FIG. 8 is a partial plot of the data of FIG. 7, in which the horizontal axis indicates the amount (% by weight) of CeO ₂ in the ultraviolet fluorescent glass, and the vertical axis indicates the ultraviolet fluorescent glass. The value of the ultraviolet absorption edge (the maximum wavelength of ultraviolet light that can be absorbed) (n
m). As is apparent from FIGS. 7 and 8, it is understood that the larger the amount of CeO ₂ added to the ultraviolet fluorescent glass, the larger the value of the ultraviolet absorption edge (the maximum wavelength of the absorbable ultraviolet light). Further, when the addition amount of CeO ₂ in the ultraviolet fluorescent glass is 0.1 to 0.2% by weight, the value of the ultraviolet absorption edge sharply increases.
That is, the ultraviolet region that can be absorbed is significantly widened. When the addition amount of CeO ₂ was set to a value of 0.3% by weight or more, the value of the ultraviolet absorption edge was further increased, while the saturation tendency was also observed. Therefore, CeO
It has been confirmed that an excellent ultraviolet absorbing effect can be obtained by adding ₂ in a relatively small amount, and it is understood that CeO ₂ is a more preferable material as the rare earth element-containing oxide used in the present invention.

Addition amount The addition amount of the rare earth element-containing oxide is determined in consideration of the ultraviolet fluorescent effect of the ultraviolet fluorescent glass to be obtained, the type of the decolorizing agent used in combination, and the like.
When the weight% is used, the value is preferably in the range of 0.01 to 30% by weight. The reason for this is that if the amount of the rare earth element-containing oxide is less than 0.01% by weight, ultraviolet fluorescence may not be exhibited, while the amount of the rare earth element-containing oxide may be 30% by weight. If exceeded,
This is because the obtained ultraviolet fluorescent glass may be colored, excessively foamed, or expensive. Therefore, since the balance between the ultraviolet fluorescent property and the coloring property becomes better, the addition amount of the rare earth element-containing oxide is set to a value within the range of 0.05 to 10% by weight based on the total amount. More preferably, the value is more preferably in the range of 0.1 to 1% by weight.

(4) Decoloring Agent Type The decoloring agent used in the first embodiment is added to suppress coloring of the glass indirectly caused by the ultraviolet fluorescent component. However, MnO ₂ , CoO and NiO are used. It is preferable to add at least one inorganic compound selected from the group consisting of Among them, particularly MnO ₂ or Mn
A combination of O ₂ and CoO is preferred. The reason is that M
This is because nO ₂ can provide an excellent decoloring effect with a small amount of addition, and is extremely inexpensive as compared with neodymium oxide, erbinium oxide and the like. In addition, MnO ₂
This is because a more excellent decoloring effect can be obtained by using a combination of and CoO. MnO ₂ is more preferable because it can further increase the fluorescence intensity of the fluorescent glass and functions not only as a decoloring agent but also as a fluorescence intensity increasing agent.

Addition amount The addition amount of the decoloring agent is determined in consideration of the transparency of the ultraviolet fluorescent glass to be obtained.
When it is 0% by weight, the value is preferably in the range of 0.000002 to 1.0% by weight. The reason is that when the amount of the decoloring agent is less than 0.000002% by weight,
This is because the decoloring effect may not be exhibited,
If the amount of the decoloring agent exceeds 1.0% by weight, the obtained ultraviolet fluorescent glass may be expensive or may be colored. Therefore, since the balance between the decoloring effect and the cost becomes better, the amount of the decoloring agent to be added is set to a value within the range of 0.001 to 0.1% by weight based on the total amount. Preferably, 0.01 to 0.0
More preferably, the value is in the range of 5% by weight.

When MnO ₂ and CoO are used in combination, the addition amount of MnO ₂ is a value within the range of 0.0001 to 0.05% by weight when the total amount is 100% by weight. In addition, the amount of CoO to be added is preferably set to a value within a range of 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ wt% based on the total amount, and 2 × 10 ⁻⁶ to 1 × 10 ^−. More preferably, the value is in the range of ⁵ % by weight. That is, MnO
₂ CoO is preferably added in a proportion of 1 / 50,000 to 1 part by weight based on 100 parts by weight.

(5) Reducing Agent Type The reducing agent used in the first embodiment is added for adjusting the oxidation-reduction index described later. That is, by adding a reducing agent, the oxidation-reduction index is adjusted to an appropriate range, and it is added to more efficiently obtain an ultraviolet fluorescent glass excellent in transparency with less entrapment of bubbles and the like. Here, preferable reducing agents include SnO, Al ₂ O ₃ and Zn.
Examples include at least one compound selected from the group consisting of O, SiO ₂ , C (carbon), S, metal tin, metal aluminum, metal zinc, and metal silicon.

The amount of the reducing agent to be added is preferably determined in consideration of the oxidation-reduction index.
, It is preferable to set the value in the range of 0.1 to 30% by weight. This is because the amount of the reducing agent added is 0.1%.
If the amount is less than 30% by weight, the effect of suppressing foaming may not be exhibited. On the other hand, the amount of the reducing agent added may be 30% by weight.
This is because, if it exceeds 300, it may be difficult to vitrify. Therefore, since the balance between the foaming suppression effect and vitrification becomes better, the amount of the reducing agent to be added is more preferably set to a value within the range of 0.5 to 20% by weight based on the total amount, More preferably, the value is in the range of 1 to 10% by weight.

(6) Redox Index In the ultraviolet fluorescent glass of the first embodiment, the redox index is preferably set to a value in the range of 20 to 40.
The reason for this is that if the oxidation-reduction index is less than 20, the types of usable ultraviolet fluorescent components and glass components may be excessively limited. On the other hand, if the oxidation-reduction index exceeds 40, This is because bubbles are likely to be generated in the manufacturing process, and the production efficiency may be reduced. Therefore, since the balance between the selectivity of the glass component and the prevention of bubble generation becomes better, it is more preferable to set the oxidation-reduction index of the ultraviolet fluorescent glass to a value within the range of 20 to 35, more preferably from 20 to 30. More preferably, the value is within the range.

The redox index (Re) of the ultraviolet fluorescent glass is calculated by calculating the Simpson-Meyer redox index (Re _{1 to} Re _n ) of _n components by weight% of each component relative to 2000 kg of silica sand. (W _{1 to} W _n )
It can be calculated by substituting into the following equation (1). Re = Re ₁ W ₁ + Re ₂ W ₂ + Re ₃ W ₃ ... + Re _n W _n (1)

(7) Colorant Type The colorant used in the first embodiment is added to adjust the color tone of the ultraviolet fluorescent glass. That is, by adding a coloring agent, it is added in order to obtain an ultraviolet fluorescent glass excellent in decorativeness more efficiently. Here, preferred coloring agents include Cr ₂ O ₃ , Fe ₂ O ₃ , FeO, M
nO ₂ , NiO, CoO, Se, AuCl ₃ , TiO ₂ ,
At least one compound selected from the group consisting of CuO, V ₂ O ₅ and AgNO _{3 is} exemplified.

The amount of the colorant is preferably determined in consideration of the color tone of the ultraviolet fluorescent glass.
When it is set to 00% by weight, it is preferable to set the value in the range of 0.1 to 30% by weight. The reason for this is that if the amount of the coloring agent is less than 0.1% by weight, the effect of adding the coloring agent may not be exhibited.
If the content exceeds the weight percentage, vitrification becomes difficult,
This is because ultraviolet fluorescence may decrease. Therefore, since the balance between the coloring property and the vitrification becomes better, the amount of the coloring agent to be added is 0.1 to the total amount.
The value is more preferably in the range of 5 to 20% by weight, and still more preferably in the range of 1 to 10% by weight.

(8) Other Additives In the ultraviolet fluorescent glass of the first embodiment, antibacterial agents, antifungal agents, electromagnetic wave shielding agents, fining agents,
It is also preferable to add a foaming agent, a reducing agent and the like. In particular, it is preferable to add a fining agent, since it is possible to obtain an ultraviolet fluorescent glass having less transparency and excellent transparency. Examples of such a fining agent include sulfates, for example, Na ₂ SO ₄ , K ₂ SO ₄ , BaSO ₄ , CaSO ₄ and the like, and fluorides, for example, fluorite and fluorinated silicon compounds. Further, it is preferable that the added amount of these fining agents is a value within the range of 0.5 to 5.0% by weight based on the total amount.

Further, the ultraviolet fluorescent glass in the first embodiment may contain Fe ₂ O _3, but even in such a case, the content of Fe ₂ O ₃ is reduced to the total amount in order to improve the transparency. On the other hand, the value is preferably 0.5% by weight or less, and more preferably 0.4% by weight or less. The reason for this is that if a large amount of Fe ₂ O ₃ is contained, it may react with the ultraviolet fluorescent component and become more colored.

(9) Basic Composition of Ultraviolet Fluorescent Glass The basic composition of the ultraviolet fluorescent glass in the first embodiment is as follows.
Then, for example, SiO _Two, Na_TwoO, K_TwoO, CaO, M
gO, B_TwoO_Three, Al_TwoO_Three, CeO_TwoAnd MnO _TwoPair of
Alignment, SiO_Two, Na_TwoO, K_TwoO, CaO, Mg
O, B_TwoO_Three, Al_TwoO_Three, CeO_Two, MnO_TwoAnd CoO
Combinations. Combine like this
Inexpensive, yet excellent UV fluorescence and transparency
Can be obtained.

Form and Processing The form of the ultraviolet fluorescent glass is not particularly limited, either. For example, it is preferably plate-like, spherical, polygonal, cylindrical, rod-like, or irregularly shaped according to the application. In addition, UV fluorescent glass, cosmetic bottles, decorative glass, liquid crystal display substrate, CRT, glass tableware, lighting equipment glass, beverage container bottles, storage bottles,
It is also preferable to process ultraviolet fluorescent glass products such as lenses, vase, ashtray, window glass, sash glass, glass plate, glass particles, glass tube, automotive glass, glass fiber, light source, and toy glass.

Composite Material It is preferable that the ultraviolet fluorescent glass is dispersed in a polymer material or an inorganic material to form a composite material.
When the composite material is configured in this manner, it can be applied as a paint containing ultraviolet fluorescent glass, and thus can be laminated on any base material or adherend. For example, in the case of a glass substrate or a PET substrate, an ultraviolet fluorescent glass layer tightly bonded to a substrate is formed by coating a coating material composed of a polymer material such as polyvinyl butyral and an ultraviolet fluorescent glass. be able to. In addition, when the composite material is configured in this manner, not only the usability is improved, but also it is possible to print on an arbitrary portion or pattern, so that the range of information display properties can be expanded. For example, an arbitrary fluorescent display portion can be easily formed by printing a composite material containing ultraviolet fluorescent glass on a glass substrate or a plastic substrate in characters, figures, symbols, patterns, and the like. When the ultraviolet fluorescent glass is added to the polymer material or the inorganic material, when the polymer material or the inorganic material is 100 parts by weight, the amount of the ultraviolet fluorescent glass is in the range of 0.1 to 100 parts by weight. Is preferable.

[Second Embodiment] In a second embodiment, an ultraviolet irradiation device (black light) 10 as shown in FIG.
0, a liquid crystal cell 120, an ultraviolet fluorescent glass 140,
This is a display device 200 using an ultraviolet fluorescent method, including a color filter 160. Hereinafter, referring to FIG.
The display device 200 according to the second embodiment will be specifically described.

1. Basic Structure (1) Ultraviolet Irradiation Apparatus The ultraviolet irradiation apparatus can be the same as that described in the first embodiment, and therefore, the description thereof is omitted here.

(2) Liquid Crystal Cell As shown in FIG. 2, the liquid crystal cell 120 comprises a lower polarizing plate 121, a lower substrate 122, and a lower electrode 123 from below.
A lower liquid crystal alignment film 124; a liquid crystal layer 126 including liquid crystal molecules 125; an upper liquid crystal alignment film 127;
8, an upper electrode 129, and an upper deflection plate 130. Then, by applying a predetermined voltage between the lower electrode 122 and the upper electrode 128 using a control means (not shown) of the liquid crystal cell 120, the orientation of the liquid crystal molecules 125 can be controlled. It is configured as follows. Therefore, this liquid crystal cell 120
It can exhibit a function as an optical shutter, and can transmit or block ultraviolet light emitted from an ultraviolet irradiation device arranged behind.

(3) Ultraviolet Fluorescent Glass The ultraviolet fluorescent glass can be the same as that described in the first embodiment, and the description is omitted here. However, when used for a display device, it is preferable that the ultraviolet fluorescent glass be in a plate shape. Specifically, the thickness is preferably set to a value in the range of 0.1 to 10 mm, more preferably to a value in the range of 0.5 to 5 mm, and more preferably in the range of 0.7 to 3 mm. More preferably, it is set to a value.

(4) Color Filter The configuration of the color filter 160 shown in FIG. 1 is not particularly limited as long as it is a color conversion medium capable of emitting fluorescence in the visible region. It is preferable to adopt a configuration as shown. That is, 16
First, a red fluorescent medium (R pixel) 162 obtained by photo-curing a composition for a red fluorescent medium containing a photo-curable resin and a red organic fluorescent dye that emits fluorescence in the visible region; A green fluorescent medium (G pixel) 163 obtained by photocuring a composition for a green fluorescent medium containing a green organic fluorescent dye that emits fluorescence in the visible region, a photocurable resin, and emits fluorescence in the visible region. Blue fluorescent medium (B pixel) 164 obtained by photo-curing a composition for a blue fluorescent medium containing a blue organic fluorescent dye.
And a color conversion medium containing: And
In order to prevent color mixing, between each of the RGB pixels,
Preferably, 65 is provided.

2. Display Operation (1) In the case of displaying information In the case of displaying information using the display device 200 shown in FIG. 1, the ultraviolet irradiation device 100 is turned on and the liquid crystal cell 120 is operated to change the orientation of the liquid crystal molecules to the ultraviolet light. Is in an alignment state that allows transmission. Therefore, the ultraviolet light emitted from the ultraviolet irradiation device 100 can pass through the liquid crystal cell 120, and the ultraviolet light thus transmitted can reach the plate-shaped ultraviolet fluorescent glass 140 and be incident thereon. Then, the ultraviolet light incident on the ultraviolet fluorescent glass 140 induces an ultraviolet fluorescent phenomenon and can generate fluorescence. Thus, the generated fluorescence is emitted with the surface of the ultraviolet fluorescent glass 140 opposite to the liquid crystal cell 120 as the emission side. Next, the emitted fluorescent light enters the color filter 160 arranged on the front surface of the ultraviolet fluorescent glass 140. Then, each color conversion unit 161 in the color filter 160,
According to 162 and 163, the wavelength is appropriately converted into a different color, and then extracted outside. Therefore, the predetermined information display is performed in full color.

(2) When Information Is Not Displayed On the other hand, when information is not displayed using the display device 200 shown in FIG. 1, it is possible to stop lighting of the ultraviolet irradiation device 100. It is also possible to operate the liquid crystal cell 120 while keeping the irradiation device 100 lit, so that the alignment of the liquid crystal molecules is set to an alignment state in which ultraviolet rays are not transmitted. That is, by operating the liquid crystal cell 120, the ultraviolet light emitted from the ultraviolet irradiation device 100 can be blocked in the liquid crystal cell 120. Therefore, the ultraviolet ray cannot be incident on the ultraviolet fluorescent glass 140, so that the fluorescent light cannot be generated and the information display can be stopped.

[0052]

The present invention will be further described below with reference to examples. However, needless to say, the scope of the present invention is not limited to the description of the examples.

Example 1 (1) Preparation of Ultraviolet Fluorescent Glass Ultraviolet fluorescent glass was prepared using a manufacturing apparatus as shown in FIG. That is, in the first step, the melting furnace
73% by weight of the added amount of SiO ₂ , Na ₂
O + K ₂ O addition amount: 14% by weight, CaO + MgO addition amount: 11% by weight, Al ₂ O ₃ addition amount: 1.679% by weight, CeO ₂ addition amount: 0.3% by weight, MnO ₂ addition 0.0015% by weight, and the amount of CoO ₂ added is 0.000%.
Raw materials of ultraviolet fluorescent glass such as silica sand, soda ash, lime, cullet, Na ₂ SO ₄ , CeO ₂ , MnO _2, and CoO are respectively placed in a melting furnace so that the concentration becomes 6% by weight, and the concentration of CeO ₂ is measured by a spectrophotometer. It was put in while monitoring indirectly. Further, as shown in Table 1, a predetermined amount of carbon (C) was added as a reducing agent for the glass raw material.

Next, the ultraviolet fluorescent glass raw material is charged in three stages, and in one stage, it is melted under the conditions of 1470 ° C. for 20 hours, and in the second stage, the temperature is 1470 ° C.
Dissolved under the condition of 7 hours.
Melting was carried out at 48 ° C. for 48 hours, and only the melt obtained in three steps was used as an ultraviolet fluorescent glass melt. At this time, the oxidation-reduction index was calculated to be 28. In addition, 1
When the redox index of the melt obtained in the step was calculated,
19, which was a dilute cullet for a raw material of ultraviolet fluorescent glass. Further, the oxidation-reduction index of the melt obtained in the two steps was calculated to be 25, which was a thick cullet for a raw material of ultraviolet fluorescent glass.

Next, the ultraviolet fluorescent glass melt obtained in the three steps is passed through a melting furnace and a working room connected to the melting furnace.
It was subjected to a second step, which was a forehearth. In the second step, the ultraviolet fluorescent glass melt is supplied into a forehath having a length of about 10 m, and then the temperature of the ultraviolet fluorescent glass melt is maintained at 1250 to 1300 ° C. using a burner. It was transferred to a glass forming machine at a transfer speed of 10 m / min. Then, the melt for ultraviolet fluorescent glass transferred from the second step was subjected to a third step, a step of forming ultraviolet fluorescent glass. And a thickness of 1 mm and 4
mm fluorescent glass in the form of a plate was molded by a glass molding machine.

(2) Evaluation of Ultraviolet Fluorescent Glass Ultraviolet Fluorescence Using a black light on an ultraviolet fluorescent glass plate having a thickness of 1 mm, while changing the irradiation position, a wavelength of 360 μm was used.
m near ultraviolet rays. And the ultraviolet fluorescent property of the obtained ultraviolet fluorescent glass container was evaluated visually by the following criteria. Table 1 shows the results of the evaluation. ◎: Blue color develops even when irradiated at a distance of 3 cm or more. 〇: Blue color is emitted even when irradiated at a distance of 1 cm or more. Δ: When irradiated with light of less than 1 cm, a blue color is formed. ×: No color is generated even when irradiation is performed at less than 1 cm.

Ultraviolet Absorption The light transmittance (wavelength 250 to 450 nm) of an ultraviolet fluorescent glass plate having a thickness of 4 mm was measured using a spectrophotometer. FIG. 2 shows the obtained ultraviolet absorption spectrum. Then, an ultraviolet absorption edge was calculated from the ultraviolet absorption spectrum, and evaluated based on the following criteria. Table 1 shows the results of the evaluation. A: The ultraviolet absorption edge is 330 nm or more. 〇: UV absorption edge is 310 nm or more. Δ: UV absorption edge is 300 nm or more. X: The ultraviolet absorption edge is less than 300 nm.

Transparency The transparency of a 1 mm thick ultraviolet fluorescent glass plate in visible light was visually evaluated according to the following criteria. Table 1 shows the results of the evaluation. A: Colorless and transparent. 〇: Slightly colored. Δ: Colored. ×: Notably colored.

Foamability 1 The foamability of a 1 mm thick ultraviolet fluorescent glass plate was visually evaluated according to the following criteria. Table 1 shows the results of the evaluation. ◎: 0 bubbles / 10 cm ² with a diameter of 0.1 mm or more. 〇: 5 bubbles or less of 0.1 mm or more in diameter / 10 cm ²
It is. △: 10 bubbles or less / 10 cm in diameter of 0.1 mm or more
² ×: More than 10 bubbles with a diameter of 0.1 mm or more / 10 cm ²
It is.

Foamability 2 In the first step, the raw material of the ultraviolet fluorescent glass is
470 ° C, 48 hours instead of 1470 ° C,
A 1 mm thick UV fluorescent glass plate was obtained under the same conditions, except that the UV fluorescent glass melt was melted under conditions that were likely to be non-uniform, under the same conditions as those for foaming 1 evaluated. Table 1 shows the results of the evaluation.

(3) Evaluation of Display Device The display device of the second embodiment was constructed (excluding the color filters), and the display performance of the display device was visually evaluated according to the following evaluation criteria. In addition, the liquid crystal cell of the display device was driven to display the alphabet “A”. ：: Vivid blue alphabet “A” display can be recognized. 〇: Blue alphabet “A” display can be sufficiently recognized. Δ: The blue alphabet “A” is partially unclear, but can be recognized. ×: It is impossible to recognize the display of the blue alphabet “A”.

[Examples 2 to 6] CeO in Example 1
₂ was added from 0.3% by weight based on the total amount to 0.1% by weight.
1% by weight (Example 2), 0.2% by weight (Example 3),
0.3% by weight (Example 4), 0.4% by weight (Example 5)
Example 1 was changed except that the concentration of the reducing agent (C) was doubled while changing the concentration to 0.5% by weight (Example 6).
In the same manner as in the above, an ultraviolet fluorescent glass container was prepared, and ultraviolet fluorescent properties and the like were evaluated. The results obtained are shown in Table 1 and FIG.

Comparative Example 1 A glass container was prepared in the same manner as in Example 1, except that CeO ₂ as an ultraviolet fluorescent component was not added. Was done. Table 1 shows the obtained results.

[0064]

[Table 1]

[0065]

According to the ultraviolet fluorescent method of the present invention and the display device using the same, it is possible to provide an ultraviolet fluorescent method capable of effectively obtaining a predetermined fluorescent light and a display device using the same. became.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a display device according to a second embodiment.

FIG. 2 is a diagram showing a liquid crystal cell.

FIG. 3 is a diagram illustrating a color filter.

FIG. 4 is a diagram showing a black light.

FIG. 5 is a view showing an irradiation device with a pattern mask.

FIG. 6 is a view showing an apparatus for manufacturing an ultraviolet fluorescent glass.

FIG. 7 is a view showing an ultraviolet absorption spectrum of the ultraviolet fluorescent glass.

FIG. 8 is a diagram showing the relationship between the amount of CeO ₂ added to the ultraviolet fluorescent glass and the ultraviolet absorption edge.

[Explanation of symbols]

 REFERENCE SIGNS LIST 100 UV irradiation device 120 Liquid crystal cell 140 UV fluorescent glass 160 Color filter 200 Display device

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C09K 11/00 C09K 11/00 D 11/78 CPB 11/78 CPB F term (reference) 4G062 AA01 AA10 BB01 CC01 CC02 CC04 DA07 DB03 DC01 DD01 DE01 DF01 EB01 EB02 EB03 EB04 EC01 EC02 EC03 EC04 ED01 ED02 ED03 ED04 EE01 EE02 EE03 EE04 EF01 EG01 FA01 FB01 FC01 FD01 FE01 HFFH FG01 FH01 FJ02 FK12 H01 H01 H01 H01 H01 GE01H01 HH17 HH20 JJ01 JJ03 JJ05 JJ07 JJ10 KK01 KK02 KK03 KK04 KK05 KK06 KK07 KK08 KK10 MM12 NN21 4H001 CC11 XA08 XA21 XA39 XA57 XA58 XA59 XA60 XA61 XA64 XA66 XA67 XA01 XA67 XA68 XA67 XA6 XA67 XA6 XA67 XA68 XA67 XA68 CJ11 CJ13 EA03

Claims (8)

[Claims] 1. Sc, Y, La, C in a glass component
e, Pr, Nd, Pm, Gd, Dy, Er, Ho, T
The ultraviolet fluorescent glass containing a rare earth element-containing oxide containing at least one rare earth element selected from the group consisting of m, Yb, and Lu is irradiated with ultraviolet light having a wavelength in the range of 100 to 400 nm using an ultraviolet irradiation device. And generating fluorescence. 2. The ultraviolet fluorescent method according to claim 1, wherein the ultraviolet fluorescent glass is dispersed in a polymer material or an inorganic material. 3. The ultraviolet fluorescent method according to claim 1, wherein the ultraviolet fluorescent glass is laminated on an adherend. 4. The method according to claim 1, wherein the ultraviolet fluorescent glass comprises letters, numerals,
The ultraviolet fluorescent method according to any one of claims 1 to 3, wherein a sign, a graphic, a pattern, or a sign is displayed. 5. The ultraviolet fluorescent method according to claim 1, wherein ultraviolet light is irradiated through a mask having the ultraviolet light transmitting portion through the mask. 6. The ultraviolet fluorescent method according to claim 1, wherein the ultraviolet light is irradiated through a liquid crystal cell. 7. The ultraviolet fluorescent method according to claim 1, wherein the ultraviolet light is radiated by the ultraviolet irradiating device, and visible light is radiated by using a white light. 8. A display device using the ultraviolet fluorescent method according to claim 1.