JP5337604B2 - Luminescent molded body and method for producing the phosphorescent molded body - Google Patents

Description

  The present invention relates to a phosphorescent molded body and a method for producing the phosphorescent molded body.

  In the dark at night, in the subway, underground malls, etc., when all the power, such as the power that is constantly supplied and the power supplied from the backup power supply, is cut off due to a disaster, the evacuation guide light, etc., emits light No longer. As a result, there is a risk of catastrophe.

  In view of such circumstances, it has been studied to use a phosphorescent molded article containing a phosphorescent pigment capable of accumulating light in the light and emitting light in the dark for wall materials and floor materials such as passages and corridors. Yes. As the phosphorescent molded product, the luminous pigment is white, and when a chromatic inorganic pigment is contained separately from the luminous pigment, the luminous intensity due to phosphorescence in the dark tends to decrease. There were many white molded bodies such as white tiles. However, when such a white molded body is used, the design is limited, and it has been difficult to make a highly designable passage or corridor.

  Thus, examples of the color phosphorescent molded product include glass products described in Patent Document 1. In Patent Document 1, an inorganic mixed powder composed of 20 to 70% by weight of a low melting glass powder, 30 to 60% by weight of a phosphorescent pigment and 0 to 20% by weight of an inorganic pigment is added to 0 to 30% by weight of the mixed powder. A composition comprising an organic vehicle mixed with a phosphorescent surface on which a ceramic color composition capable of forming a phosphorescent film that emits light in a dark place is baked on a glass material at a temperature of 500 to 700 ° C. A glass product is described.

  Moreover, as a molded object using luminous property, the afterglow display thing of patent document 2, etc. are mentioned, for example. Patent Document 2 has a surface including a light-emitting portion and a non-light-emitting portion having a phosphor, and the surfaces of adjacent light-emitting portions and non-light-emitting portions are the same in at least a region including a portion in contact with the boundary between them. In an environment where the light emission of the phosphor cannot be visually recognized due to the color, the light emission portion and the non-light emission portion due to the phosphor cannot be substantially distinguished, and the light emission of the phosphor can be visually recognized. A display object whose display contents change in an environment where it cannot be displayed is described.

JP-A-9-142882 JP-A-10-171388

  According to Patent Document 1, it is disclosed that a bright phosphorescent film that is vividly colored in a dark place and has a high afterglow is formed, and a fashionable and fantastic design can be added. However, only by forming the phosphorescent film on the surface of the glass product, the shape that can be visually recognized in the light and the shape that can be confirmed by the phosphorescence in the dark are the same. And although the base material here is a glass material, even if it used a tile base material etc. as a base material, a design was limited and it was difficult to make it a high design passage or corridor.

  In addition, the molded body only emits light in the dark such as when the power supply is cut off in a dark place, such as at the time of a disaster, and is particularly suitable for designs that are exposed in light and dark. There was no change. That is, it is difficult to display information indicating the exit, for example, in the dark.

  According to Patent Document 2, since it is possible to display a display that is not recognized at all in an environment where light emission of the phosphor cannot be recognized, without requiring an electric system or the like in an environment where light emission of the phosphor can be recognized, It is disclosed that an emergency display is provided while maintaining an aesthetic appearance, and that it is useful for manufacturing decorations, toys and the like using the unexpectedness of changing the display. However, the layer constituting the light emitting part and the non-light emitting part is composed of a layer containing a phosphor and a resin, and such a layer has low heat resistance and may burn. And when such a layer burned, there was a possibility that toxic gas was generated. Therefore, the display object described in Patent Document 2 is not appropriate for use in a disaster or the like. In addition, when measuring the luminance of the light emitting part, it is irradiated with light having a high luminance of about 5400 lux, and actually emits light sufficiently at the time of a disaster, specifically, for example, a standard conforming to JIS Z9107. It was not intended to meet.

  The present invention has been made in view of such circumstances, and has a heat-resisting molded body that has a high heat resistance and exhibits a design different from that at the time of light in the dark, and a method for producing the phosphorescent molded body. The purpose is to provide.

  A phosphorescent molded article according to an aspect of the present invention is a phosphorescent molded article comprising a substrate, a first coating formed on the substrate, and a second coating formed on the substrate. The first coating is composed of a first composition containing a luminous pigment capable of accumulating light in the light and emitting light in the dark, a lead-free glass powder, and a chromatic inorganic pigment, and the second coating. The coating comprises a second composition containing an achromatic inorganic oxide, the lead-free glass powder, and the inorganic pigment, and in the first composition, the phosphorescent pigment, the lead-free glass powder, and the By adjusting the content ratio of the inorganic pigment and the content ratio of the inorganic oxide, the lead-free glass powder, and the inorganic pigment in the second composition, respectively, the first coating and the The second film is a similar color .

  According to such a structure, the area | region covered with the said 1st film and the area | region covered with the said 2nd film are formed on the said base material. In addition, since the first film and the second film have the same color at the time of light, the area covered with the first film and the area covered with the second film are almost all at the time of light. It is a molded object such as a tile that cannot be distinguished, for example, a tile composed of one color. On the other hand, in the dark, the first film made of the first composition containing the luminous pigment emits light, so that a design different from that in the light appears.

  Moreover, what constitutes the phosphorescent molded body, such as the inorganic oxide, has a much higher heat resistance than a resin or the like, and no toxic gas is generated even when a fire or the like is in close proximity.

  From the above, it is possible to obtain a phosphorescent molded body having high heat resistance and exhibiting a design different from that at the time of light in the dark.

  In addition, the first composition is 50 to 90 parts by weight of the phosphorescent pigment, 10 to 50 parts by weight of the lead-free glass powder, and the inorganic to 100 parts by weight of the total of the phosphorescent pigment and the lead-free glass powder. It is preferable to contain 0.05-5 mass parts of pigments. According to such a structure, what obtained the 1st film of the obtained luminous storage object is a chromatic color in the bright time, and light-emits in the dark time is obtained. And the said 1st film can exhibit the afterglow brightness | luminance which satisfy | fills the standards based on JISZ9107 (April 2008 revision), for example, a "JB" standard.

  Moreover, it is preferable that the said 1st film exhibits the afterglow brightness which satisfy | fills the standard based on JISZ9107.

Further, when the colors of the first film and the second film are expressed by the L ^* a ^* b ^* system, the difference (ΔL ^*) between the L ^* value of the first film and the L ^* value of the second film ), wherein the first ^{a *} value of the coating difference between the second ^{a *} value of the coating (.DELTA.a ^*), and the difference between ^{b *} values of the second film and the ^{b *} value of the first coating ([Delta] b ^* ) Preferably satisfies (ΔL ^{* 2} + Δa ^{* 2} + Δb ^{* 2} ) ^1/2 ≦ 7. Specifically, the similar color is due to satisfying the above relationship.

  Moreover, it is preferable that the phosphorescent pigment is a strontium aluminate phosphorescent pigment and the inorganic oxide is at least one of aluminum oxide and strontium oxide. According to such a configuration, light is emitted well in the dark, and there is little color difference between the first coating and the second coating in the bright.

  Moreover, it is preferable that melting | fusing point of the said lead-free glass powder is 750-780 degreeC. According to such a configuration, since the first coating can be melted at a relatively low temperature, a phosphorescent pigment that is easily deactivated by heat can be used. That is, the deactivation of the phosphorescent pigment can be suppressed regardless of the type of the phosphorescent pigment. Therefore, a luminous storage product that can emit light in the dark is obtained.

  In addition, the inorganic pigment is at least one selected from the group consisting of pottery red, Shin-Kusu, Turkish blue and praseo yellow, and the content ratio of the pottery red, the new Kousu, the Turkish blue and the praseo yellow It is preferable that the color tone is adjusted to a predetermined color by adjusting. According to such a configuration, various chromatic colors can be obtained as colors at the time of light.

  Moreover, it further includes a transparent protective film formed on the first film and the second film so as to cover the first film and the second film, and the transparent protective film comprises lead-free glass powder. It is preferable to consist of the 3rd composition to contain. According to such a configuration, the surface can be protected. That is, durability, contamination resistance, chemical resistance, and gloss of the phosphorescent molded body can be improved.

Further, said first membrane and said second membrane, the difference in linear expansion coefficient between the base material is preferably a ^{5.5 × 10 -6 ~7 × 10 -6} / ℃ respectively. According to such a configuration, the occurrence of penetration at the interface between the first coating and the second coating and the lower layer of the first coating and the second coating, for example, the base material, is suppressed. can do.

  Further, it is preferably a tile shape or a block shape, and is embedded so that the first coating and the second coating are exposed. According to such a configuration, it is easy to use for wall materials, flooring materials, etc., and even when used in such applications, the effect of emitting light in the dark as described above and expressing a design different from that at the time of light. Can be fully demonstrated.

  In addition, a method for producing a luminous storage product according to another aspect of the present invention includes a luminous pigment capable of accumulating light in the light and emitting light in the dark in a predetermined first region on the substrate, and lead-free glass. A first application step of applying a liquid first composition containing a powder and a chromatic inorganic pigment; and an achromatic inorganic oxidation in a second region on the substrate other than the first region A second application step of applying a liquid second composition containing a product, the lead-free glass powder, and the inorganic pigment, and firing the first composition and the second composition. 1st baking process which forms 1 film and 2nd film, It is a manufacturing method of a luminous composition, Comprising: The said luminous pigment, the said lead-free glass powder, and the said inorganic pigment in a said 1st composition Content ratio, and the inorganic oxide and the lead-free glass powder in the second composition By adjusting the content ratio of the inorganic pigment, respectively, and the second coating and the first coating during Ming is characterized in that it is similar colors.

  According to such a structure, the area | region covered with the said 1st film and the area | region covered with the said 2nd film are formed on the said base material. Since the first coating and the second coating have the same color in the bright time, the region covered with the first coating and the region covered with the second coating are distinguished at the bright time. What is not possible, for example, a molded body such as a tile of one color. On the other hand, in the dark, the first film made of the first composition containing the luminous pigment emits light, so that a design different from that in the light appears. In addition, the phosphorescent molded body is formed from a material having a much higher heat resistance than the resin or the like, such as the inorganic oxide. Therefore, no toxic gas is generated even when a fire or the like is brought close to the obtained phosphorescent molded article.

  From the above, it is possible to easily manufacture a phosphorescent molded article that has high heat resistance and that exhibits a different design from that of light when dark.

  In addition, a third coating step of applying a liquid third composition containing lead-free glass powder to the first coating and the second coating, and firing the third composition, the first coating and It is preferable to include a second baking step of forming a transparent protective film on the first film and the second film so as to cover the second film. According to such a configuration, it is possible to manufacture a phosphorescent molded body on which a transparent protective film capable of protecting the surface is formed.

  Further, the first application step and the second application step may be a step of applying the first composition and the second composition, respectively, to a thickness of 200 to 300 μm on the substrate. preferable. According to such a configuration, it is possible to easily manufacture a phosphorescent molded article that sufficiently exhibits the effect that the first coating emits light in the dark and displays a design different from that in the light.

  Moreover, after said 1st baking process heated up the said 1st composition and the said 2nd composition to 780-810 degreeC over 5 to 6 hours, respectively, the raised temperature is 5 to 30 minutes. It is preferable that it is the process to hold | maintain. According to such a configuration, it is possible to more easily manufacture a phosphorescent molded body in which a design different from that at the time of light appears in the dark.

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the manufacturing method of the luminous storage molded object from which the heat resistance is high, and the design different from the time of light is exposed at the time of darkness, and a luminous storage molded object.

2 is a plan view showing the surface of a luminous storage body 11. FIG. It is the schematic sectional drawing which looked at the luminous formation body 11 shown in FIG. 1 from cut surface line II-II. It is explanatory drawing for demonstrating an example of the usage condition of the said luminous luminous body. It is explanatory drawing for demonstrating another example of the usage condition of the said luminous luminous body.

  Hereinafter, although embodiment of this invention is described, this invention is not limited to these.

  A phosphorescent molded article according to an aspect of the present invention is a phosphorescent molded article comprising a substrate, a first coating formed on the substrate, and a second coating formed on the substrate. The first coating is composed of a first composition containing a luminous pigment capable of accumulating light in the light and emitting light in the dark, a lead-free glass powder, and a chromatic inorganic pigment, and the second coating. The coating comprises a second composition containing an achromatic inorganic oxide, the lead-free glass powder, and the inorganic pigment, and in the first composition, the phosphorescent pigment, the lead-free glass powder, and the By adjusting the content ratio of the inorganic pigment and the content ratio of the inorganic oxide, the lead-free glass powder, and the inorganic pigment in the second composition, respectively, the first coating and the The second film is a similar color .

  Specifically, the phosphorescent molded body 11 has a structure as shown in FIGS. 1 and 2, for example. FIG. 1 is a plan view showing the surface of the luminous storage body 11. FIG. 2 is a schematic cross-sectional view of the phosphorescent molded body 11 shown in FIG. 1 as viewed from the cutting plane line II-II. As shown in FIG. 1, the phosphorescent molded body 11 includes a first region 12 covered with the first coating and a second region 13 covered with the second coating. The first region 12 and the second region 13 have similar colors, whereas the first region 12 emits light when dark. Therefore, it is difficult to distinguish the first region 12 and the second region 13 during light, whereas the first region 12 and the second region 13 are clearly different during dark. It is a phosphorescent molded body in which the design different from the time, that is, the shape of the first region 12 appears. Note that the phosphorescent molded body 11 has a surface on which the first coating 22 and the second coating 23 are covered with respect to the base 21, and the first coating 22 and the second coating 23. The side that is not covered is the back side.

  In addition, as shown in FIG. 2, the phosphorescent molded body 11 includes the base material 21, a first film 22 formed on the base material 21, and a second film formed on the base material 21. 23. Then, a transparent protective film 24 may be formed on the first film 22 and the second film 23 so as to cover the first film 22 and the second film 23, and formed. It does not have to be. By forming the transparent protective film 24, the surface can be protected, and even if the surfaces of the first coating 22 and the second coating 23 are rough, the phosphorescence of a smooth surface is obtained. The molded product 11 is obtained. That is, when the durability, contamination resistance, chemical resistance, gloss, etc. are particularly required, it is preferable that the transparent protective film 24 is formed.

  In addition, the phosphorescent molded body 11 may include a white layer 25 made of a white basic glaze between the base material 21 and the first coating 22 and the second coating 23. . By providing the white layer 25, a molded product of a desired color can be obtained regardless of the color of the base material 21, and moreover, a design different from the light time is more clearly expressed in the dark state. The first coating 22 can sufficiently exhibit the effect that the afterglow luminance is higher.

Here, the similar color refers to the L ^* value of the first coating and the L ^{* of} the second coating when the colors of the first coating and the second coating are expressed by the L ^* a ^* b ^* method ^. difference between the value (ΔL ^*), b of the said the first ^{a *} value of the coating difference between the second ^{a *} value of the coating (Δa ^*), and said second coating and ^{b *} values of the first coating The difference (Δb ^* ) from the ^* value satisfies (ΔL ^{* 2} + Δa ^{* 2} + Δb ^{* 2} ) ^1/2 ≦ 7. Note that a value represented by (ΔL ^{* 2} + Δa ^{* 2} + Δb ^{* 2} ) ^1/2 is called a color difference. If the value of the color difference is too large, the difference between the first region 12 covered with the first film and the second region 13 covered with the second film can be easily understood even during bright hours. Tend to be. That is, there is a tendency that it cannot be said that it is a similar color. In addition, each value of L ^* value, a ^* value, and b ^* value here can be measured using a color difference meter (spectral colorimeter SC-T made by Suga Test Instruments Co., Ltd.), for example. it can.

  As said 1st composition, if it contains the said luminous pigment, the said lead-free glass powder, and the said inorganic pigment, and can form the 1st film of the same color as the said 2nd film, There is no particular limitation. Specifically, for example, with respect to a total of 100 parts by mass of the phosphorescent pigment and the lead-free glass powder, the phosphorescent pigment 50 to 90 parts by mass, the lead-free glass powder 10 to 50 parts by mass, and the inorganic pigment Examples thereof include 0.05 to 5 parts by mass. Moreover, as content of the said luminous pigment, it is preferable that it is 50-90 mass parts as above-mentioned with respect to a total of 100 mass parts of the said luminous pigment and the said lead-free glass powder. More preferably, it is part by mass. Within the range, afterglow luminance satisfying a standard based on JIS Z 9107, for example, “JB” standard can be achieved, and light emission in a dark place can be sufficiently secured. And if it is 55-80 mass parts, even if there is much content of the said inorganic pigment, the said afterglow brightness | luminance can be achieved. This will be described in detail later.

The luminous pigment is not particularly limited as long as it is a pigment exhibiting luminous properties. Here, the phosphorescent property refers to a property capable of accumulating light during light and emitting light during dark. More specifically, the phosphorescent pigment absorbs energy by being stimulated mainly by light such as visible light and ultraviolet light at the time of bright light, and is excited to a high electronic state. When the stimulus is stopped, it refers to a pigment exhibiting a light emission phenomenon that, when falling to the ground state, converts the absorbed energy into visible light, and gradually releases and releases the visible light for a certain period. Specific examples of the phosphorescent pigment include, for example, strontium aluminate phosphorescent pigments mainly composed of strontium and aluminum, phosphorescent pigments principally composed of strontium, magnesium and silicon, and sulfide phosphorescent pigments. Is mentioned. Among these, a strontium aluminate phosphorescent pigment is preferable because of its high afterglow luminance. Examples of strontium aluminate phosphorescent pigments include Sr ₄ Al ₁₄ O ₂₅ and SrAl ₂ O _4. Examples of pigments containing strontium, magnesium and silicon as main components include Sr ₂ MgSi _2. O ₇ etc. are mentioned. The strontium aluminate phosphorescent pigments include yellowish green and blue-green pigments, and the phosphorescent pigments mainly composed of strontium, magnesium and silicon include blue pigments. More specifically, Sr ₄ Al ₁₄ O ₂₅ is a blue-green phosphorescent pigment, SrAl ₂ O ₄ is a yellow-green phosphorescent pigment, and Sr ₂ MgSi ₂ O ₇ is a blue-based phosphorescent pigment. .

  The lead-free glass powder is not particularly limited. Specifically, what is called a so-called lead-free frit etc. are mentioned, for example. Among these, a low melting point lead-free frit having a relatively low melting point is preferably used from the viewpoint of suppressing deactivation of the luminous property of the luminous pigment when the first coating is formed. More specifically, for example, those having a melting point of 750 to 780 ° C. can be mentioned, and examples thereof include a Kyo lead-free frit. More specifically, the Kyo-lead-free frit includes, for example, those described in JP-A-9-1000018.

  The inorganic pigment is not particularly limited as long as it has a chromatic color and can make the first coating a predetermined color. Specifically, a pigment that can be adjusted to a predetermined color by using at least one of a cyan pigment, a magenta pigment, and a yellow pigment and adjusting the content ratio thereof. Examples of the cyan pigment include Shin-Kusu and Turkish Blue, examples of the magenta pigment include ceramic red, and examples of the yellow pigment include praseo yellow.

  As said 2nd composition, if it contains the said inorganic oxide, the said lead-free glass powder, and the said inorganic pigment, and can form the 2nd film of the same color as the said 1st film, There is no particular limitation. Specifically, for example, the inorganic oxide, the lead-free glass powder, and the inorganic pigment are adjusted so that the respective contents have the same color as the first coating. . More specifically, for example, 40 to 70 parts by mass of the inorganic oxide, 60 to 30 parts by mass of the lead-free glass powder, and the inorganic system with respect to a total of 100 parts by mass of the inorganic oxide and the lead-free glass powder. What contains 1-10 mass parts of pigments is mentioned. That is, the thing containing the said inorganic oxide instead of the said luminous pigment is mentioned.

  The inorganic oxide is not particularly limited as long as it is contained in place of the phosphorescent pigment and can form a second coating having the same color as the first coating. The inorganic oxide may or may not have a phosphorescent property, but is different from the phosphorescent pigment in the phosphorescent emission color. Specifically, when the phosphorescent pigment is a strontium aluminate phosphorescent pigment, examples thereof include a white powder having high heat resistance that does not deteriorate at 800 ° C. or higher, such as aluminum oxide and strontium oxide. Among these, aluminum oxide and strontium oxide are preferable from the viewpoint of easy color matching with the first coating.

  The particle diameter of the inorganic oxide is about the same as the particle diameter of the phosphorescent pigment, and the surface of the phosphorescent molded article, for example, the smoothness of the first coating and the second coating It is preferable from the point of increase. More specifically, the particle diameter of the inorganic oxide and the luminous pigment is preferably 30 to 60 μm, and the difference in particle diameter is preferably 20 μm or less. The particle diameter here is, for example, the median diameter.

  The lead-free glass powder and the inorganic pigment are not particularly limited. Specific examples include the lead-free glass powder and the inorganic pigment in the first composition.

The substrate is not particularly limited. Specifically, for example, it is preferable that the difference in linear expansion coefficient between the first coating and the second coating is 5.5 × 10 ^{−6 to} 7 × 10 ⁻⁶ / ° C., respectively. More specifically, for example, a base material made of a porcelain material, a semi- porcelain material, and a foundation-covered substrate can be used. When such a base material is used, when the first coating and the second coating are formed, for example, it is possible to suppress the penetration of the first coating and the second coating during firing and slow cooling. it can.

The white layer is not particularly limited as long as it is made of a white basic glaze. This white layer is a layer formed by a so-called underlaying process. The white layer has a difference in linear expansion coefficient between the first coating and the second coating of 5.5 × 10 ^{−6 to} 7 × 10 ⁻⁶ / ° C., respectively, like the base material. Is preferred. By doing so, when forming the 1st coat and the 2nd coat, it can control that penetration occurs in the 1st coat and the 2nd coat at the time of baking and slow cooling, for example.

  The transparent protective film is not particularly limited. Specifically, what consists of the 3rd composition containing the said lead-free glass powder in a said 1st composition etc. are mentioned, for example.

  It is preferable that the phosphorescent molded body has a tile shape or a block shape, and is used in a usage mode in which the first coating and the second coating are exposed. By doing so, this phosphorescent molded article is easy to use as a wall material, a flooring material, etc., and even when used in such applications, it emits light in the dark as described above and represents a design different from that at light time. The effect of letting out can be fully demonstrated.

  Specific examples of the use mode as described above include those shown in FIG. 3 and FIG. 3 and 4 are explanatory views for explaining an example of a usage mode of the phosphorescent molded body. 3A and 4A show the bright time, and FIGS. 3B and 4B show the dark time. Even if it combines as shown to FIG.3 and FIG.4, the said luminous storage compact | molding | casting can be used so that the design displayed may differ in the light time and the dark time. Further, in the case shown in FIG. 4, information such as direction can be displayed in the dark while it is a simple design in the dark.

  Moreover, it does not specifically limit as a manufacturing method of the said luminous storage molded object. Specifically, for example, a first application step of applying the liquid first composition to a predetermined first region on the substrate, and a second region other than the first region on the substrate. A second application step of applying a liquid second composition containing an achromatic inorganic oxide, the lead-free glass powder, and the inorganic pigment; and the first composition and the second composition. What comprises the 1st baking process which forms a 1st film and a 2nd film by baking, etc. are mentioned. At that time, the content ratio of the phosphorescent pigment, the lead-free glass powder and the inorganic pigment in the first composition, and the inorganic oxide, the lead-free glass powder and the inorganic system in the second composition By adjusting the content ratio with the pigment, the first coating film and the second coating film have similar colors in the bright time.

  The first application process and the second application process are not particularly limited. Specifically, for example, a method of applying the first composition and the second composition with a brush so as to have a thickness of 200 to 300 μm on the substrate, a silk printing method, a brush coating method, etc. And the like. Moreover, it is preferable to dry immediately after the said 1st application process and the said 2nd application process to such an extent that the fluidity of the said 1st composition and the said 2nd composition is lose | eliminated.

  In addition, as the first baking step, specifically, for example, the first composition and the second composition are heated to 780 to 810 ° C. over 5 to 6 hours, respectively, and then the rising temperature is increased. The process etc. which hold | maintain the warmed temperature for 5 to 30 minutes are mentioned.

  And when forming the said transparent protective film, the 3rd application | coating process which apply | coats the liquid 3rd composition containing a lead-free glass powder to the said 1st film and the said 2nd film further, The said 3rd And a second baking step of forming a transparent protective film on the first film and the second film so as to cover the first film and the second film by baking the composition, etc. Is mentioned.

  The third application process is not particularly limited. Specifically, for example, a method of applying the third composition with a brush so as to have a thickness of 100 to 300 μm on the first coating and the second coating, a silk printing method, a brush coating method, and the like. And the like.

  Further, the second baking step is not particularly limited as long as a transparent protective film can be formed. Specifically, for example, a step of raising the temperature of the third composition to 780 to 810 ° C. over 5 to 6 hours and holding the elevated temperature for 5 to 30 minutes may be mentioned.

[Example 1]
(Preparation of the first composition)
70 parts by mass of a blue-green phosphorescent pigment (Sr ₄ Al ₁₄ O ₂₅ ), 30 parts by mass of Kyo-Lead Free Frit, and 0.55 parts by mass of Shin Kuresu (manufactured by Kyoto Iwasaki Co., Ltd.) were mixed. The mixture was added to squeegee oil (OS-4500 manufactured by Kyoyo Chemical Co., Ltd.) and kneaded. At that time, squeegee oil was used so that the solid content concentration would be 75 mass%. And what was obtained by this kneading was made into the 1st composition.

(Preparation of second composition)
50 parts by mass of alumina oxide, 50 parts by mass of Kyoto lead-free frit, 1.65 parts by mass of Shin Kuresu (manufactured by Kyoto Iwasaki Co., Ltd.), and 1 part by mass of Praseo Huang (manufactured by Kyoto Iwasaki Co., Ltd.) were mixed. The mixture was added to squeegee oil (OS-4500 manufactured by Kyoyo Chemical Co., Ltd.) and kneaded. At that time, squeegee oil was used so that the solid content concentration would be 75 mass%. And what was obtained by this kneading was made into the 2nd composition.

(Manufacture of phosphorescent molded products)
First, the first composition was silk-printed to a thickness of 250 μm on a white basic hanging porcelain tile in a state where a second region other than the predetermined first region was masked. Thereafter, the first composition was dried at 70 ° C. for 15 minutes.

  Next, the first region was masked on the porcelain tile to which the first composition was applied. Then, the second composition was silk-printed to a thickness of 250 μm on the porcelain tile with the predetermined first region masked. Thereafter, the second composition was dried at 70 ° C. for 15 minutes.

  And after heating up the porcelain tile with which the said 1st composition and the said 2nd composition were apply | coated to 800 degreeC over 5 hours, by holding the said temperature raised for 10 minutes, said 1st The composition and the second composition were fired. By doing so, the luminous storage body concerning Example 1 was obtained.

[Example 2]
(Preparation of the first composition)
70 parts by mass of a blue-green phosphorescent pigment (Sr ₄ Al ₁₄ O ₂₅ ), 30 parts by mass of Kyo Unleaded frit, and 1.7 parts by mass of Praseo Yellow (manufactured by Kyoto Iwasaki Co., Ltd.) were mixed. The mixture was added to squeegee oil (OS-4500 manufactured by Kyoyo Chemical Co., Ltd.) and kneaded. At that time, squeegee oil was used so that the solid content concentration would be 75 mass%. And what was obtained by this kneading was made into the 1st composition.

(Preparation of second composition)
50 parts by mass of alumina oxide, 50 parts by mass of Kyoto lead-free frit, 6.0 parts by mass of praseo yellow (manufactured by Kyoto Iwasaki Co., Ltd.), and 0.25 parts by mass of Turkish blue (manufactured by Kyoto Iwasaki Co., Ltd.) were mixed. The mixture was added to squeegee oil (OS-4500 manufactured by Kyoyo Chemical Co., Ltd.) and kneaded. At that time, squeegee oil was used so that the solid content concentration would be 75 mass%. And what was obtained by this kneading was made into the 2nd composition.

(Manufacture of phosphorescent molded products)
First, the first composition was silk-printed to a thickness of 230 μm on a white basic hanging porcelain tile in a state where a second region other than the predetermined first region was masked. Thereafter, the first composition was dried at 70 ° C. for 15 minutes.

  Next, the first region was masked on the porcelain tile to which the first composition was applied. Then, the second composition was silk-printed on the porcelain tile in a state where the predetermined first region was masked so as to have a thickness of 230 μm. Thereafter, the second composition was dried at 70 ° C. for 15 minutes.

  And after heating up the porcelain tile with which the said 1st composition and the said 2nd composition were apply | coated to 800 degreeC over 5 hours, by holding the said temperature raised for 10 minutes, said 1st The composition and the second composition were fired. By doing so, the luminous storage body concerning Example 2 was obtained.

[Evaluation]
(Color difference)
Each of the phosphorescent molded bodies thus obtained was obtained by using a color difference meter (spectral colorimeter SC-T manufactured by Suga Test Instruments Co., Ltd.), respectively, in a first region (first coating) and a second region ( The L ^* value, a ^* value, and b ^* value of the second coating) were measured, and (ΔL ^{* 2} + Δa ^{* 2} + Δb ^{* 2} ) ^1/2 was calculated. As a result, the luminous composition according to Example 1 was 1.6, and the luminous composition according to Example 2 was 4.9. That is, in all cases, (ΔL ^{* 2} + Δa ^{* 2} + Δb ^{* 2} ) ^1/2 ≦ 7 was satisfied.

(Afterglow brightness)
Moreover, the afterglow brightness | luminance was measured by the method based on JISZ9107 for each phosphorescent molded object obtained as mentioned above. Specifically, first. The object to be measured (luminescent storage product) was shielded from light for 48 hours or more. Then, using a D65 standard light source, light adjusted so that the illuminance on the surface of the object to be measured becomes 200 lux at an angle of 45 ° with respect to the surface of the object to be measured after light shielding is applied to the object to be measured for 20 minutes. After the irradiation, the irradiation was stopped, and the luminance after 10 minutes, 20 minutes, 30 minutes, and 60 minutes after the irradiation was measured using a luminance meter (BM-5A manufactured by Topcon Corporation).

As a result, the phosphorescent molded bodies according to Example 1 were 107 mcd / m ² , 57 mcd / m ² , 38 mcd / m ² , and 19 mcd / m ² , respectively. Moreover, the phosphorescent molded bodies according to Example 2 were 115 mcd / m ² , 60 mcd / m ² , 41 mcd / m ² , and 20 mcd / m ² , respectively.

The reference of compliant JIS Z 9107 (JB basis), ^{respectively,} a ^{105mcd / m 2, 50mcd / m} 2, 31mcd / m 2, 15mcd / m 2, luminous according to Example 1 and Example 2 Both molded bodies met this criterion.

  From the above, in the phosphorescent molded bodies according to Example 1 and Example 2, the first coating (first region) and the second coating (second region) are both in the same color at the bright time, and are distinguished from each other. Further, it has been found that the first region can satisfy the standard based on JIS Z 9107 in the dark.

DESCRIPTION OF SYMBOLS 11 Luminescent molded object 12 1st area | region 13 2nd area | region 21 Base material 22 1st film 23 2nd film 24 Transparency protective film 25 White layer

Claims (13)

A tile-shaped phosphorescent molded body comprising a base material, a first film formed on the base material, and a second film formed on the base material,
The first coating comprises a first composition containing a luminous pigment capable of accumulating light in the light and emitting light in the dark, a lead-free glass powder, and a chromatic inorganic pigment,
The second coating comprises a second composition containing an achromatic inorganic oxide, the lead-free glass powder, and the inorganic pigment,
The content ratio of the phosphorescent pigment, the lead-free glass powder, and the inorganic pigment in the first composition, and the inorganic oxide, the lead-free glass powder, and the inorganic pigment in the second composition. by adjusting the content ratio, respectively, Ri is similar colors der and the second coating and the first coating during bright,
The first composition is 50 to 90 parts by mass of the phosphorescent pigment, 10 to 50 parts by mass of the lead-free glass powder, and the inorganic pigment with respect to a total of 100 parts by mass of the phosphorescent pigment and the lead-free glass powder. 0.05 to 5 parts by mass,
The phosphorescent pigment is a strontium aluminate phosphorescent pigment,
The inorganic oxide is at least one of aluminum oxide and strontium oxide;
The lead-free glass powder has a melting point of 750 to 780 ° C. The second composition is 40 to 70 parts by mass of the inorganic oxide, 30 to 60 parts by mass of the lead-free glass powder, and the inorganic pigment with respect to a total of 100 parts by mass of the inorganic oxide and the lead-free glass powder. The phosphorescent molded product according to claim 1, containing 1 to 10 parts by mass .   The phosphorescent molded article according to claim 1 or 2, wherein the first film exhibits afterglow luminance that satisfies a standard conforming to JIS Z9107. A difference (ΔL ^* ) between the L ^* value of the first film and the L ^* value of the second film, when the colors of the first film and the second film are expressed by the L ^* a ^* b ^* method, the difference between ^{a *} values of ^{a *} value and the second coating of the first coating (Δa ^*), and the difference between ^{b *} values of the second film and the ^{b *} value of the first coating ([Delta] b ^*) The phosphorescent molded article according to any one of claims 1 to 3, which satisfies (ΔL ^{* 2} + Δa ^{* 2} + Δb ^{* 2} ) ^1/2 ≤7. The strontium phosphorescent pigment _aluminate, phosphorescent molded body according to any one of claims 1 to 4 at least one of Sr _{4 Al} 14 _{O 25} and SrAl ₂ O _4. The inorganic pigment is at least one selected from the group consisting of pottery red, Shin Wusu, Turkish blue, and praseo yellow;
The phosphorescent molded article according to any one of claims 1 to 5 , which is toned to a predetermined color by adjusting a content ratio of the pottery red, the new Kuresu, and the praseo yellow. A transparent protective film formed on the first film and the second film so as to cover the first film and the second film;
The phosphorescent molded article according to any one of claims 1 to 6 , wherein the transparent protective film is made of a third composition containing lead-free glass powder. Said first membrane and said second membrane, the difference in linear expansion coefficient between the base material is any one of claims 1 to 7 is ^{5.5 × 10 -6 ~7 × 10 -6} / ℃ respectively 1 The phosphorescent molded article according to Item. Phosphorescent molded article according to any one of claims 1 to 8, pre-Symbol first membrane and said second membrane is embedded so as to expose. A liquid first composition containing a luminous pigment capable of accumulating light in the light and emitting light in the dark, a lead-free glass powder, and a chromatic inorganic pigment in a predetermined first region on the substrate. A first application step of applying;
Second, applying a liquid second composition containing an achromatic inorganic oxide, the lead-free glass powder, and the inorganic pigment to a second region other than the first region on the substrate. Application process;
A method for producing a tile-shaped luminous storage product, comprising: a first firing step of firing the first composition and the second composition to form a first coating and a second coating;
The content ratio of the phosphorescent pigment, the lead-free glass powder, and the inorganic pigment in the first composition, and the inorganic oxide, the lead-free glass powder, and the inorganic pigment in the second composition. by adjusting the content ratio, respectively, Ri is similar colors der and the second coating and the first coating during bright,
The first composition is 50 to 90 parts by mass of the phosphorescent pigment, 10 to 50 parts by mass of the lead-free glass powder, and the inorganic pigment with respect to a total of 100 parts by mass of the phosphorescent pigment and the lead-free glass powder. 0.05 to 5 parts by mass,
The phosphorescent pigment is a strontium aluminate phosphorescent pigment,
The inorganic oxide is at least one of aluminum oxide and strontium oxide;
Melting | fusing point of the said lead-free glass powder is 750-780 degreeC , The manufacturing method of the phosphorescent molded object characterized by the above-mentioned . A third application step of applying a liquid third composition containing lead-free glass powder to the first coating and the second coating;
A second baking step of forming a transparent protective film on the first film and the second film so as to cover the first film and the second film by baking the third composition; The manufacturing method of the phosphorescent molded object of Claim 10 provided. Said first coating step and the second coating step, the each of the first composition and the second composition, a step of applying to a thickness of 200~300μm on the substrate according to claim 10 or The manufacturing method of the luminous molded object of Claim 11 . The first baking step raises the temperature of the first composition and the second composition to 780 to 810 ° C. over 5 to 6 hours, and then holds the raised temperature for 5 to 30 minutes. method for manufacturing a phosphorescent molded article according to any one of claims 10-12 is a process.

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