JP2017226812A - Color luminophore emitting light without electric power - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a structure capable of visibly recognizing color development in daytime with high chroma saturation and brightness by a fluorescence agent, having color development in the dark with high chroma saturated and brightness by exciting the fluorescence agent, and capable of daytime night color development of a hue of same series by color matching.SOLUTION: Transmission of interconnect light between particles with suppressing loss of light due to refractive light compared to a heterogeneous transparent layer is made easy and coloring effects are enhanced by setting a structure arranged by separating a lower layer part responding to light emission and an upper layer part responding to light emission and luminous in a same transparent resin. 1: fluorescence agent particles. 2: luminous agent particles. 7:laminate.SELECTED DRAWING: Figure 1

Description

The present invention relates to a color development structure that enables day and night color development without power by combining a phosphorescent agent and a fluorescent agent or a powder pigment.

The conventional color development structure includes an edge color that develops color at the periphery, a method of dyeing the white layer by reflection from the edge color, a mixture of a phosphorescent agent and a dye / pigment sold in the hobby industry, and a bottom part. There are those in which a colored plate is provided as a reflector and the color is observed by transmitting through the phosphorescent layer, and those using a red light-emitting sulfur-based phosphorescent agent.

JP 2002-105448 A JP-A-9-197989 Japanese Patent Application No. 2011-239585 Japanese Patent Application No. 2012-238344 Japanese Patent Application No. 2013-14790 Japanese Patent Application No. 11-502020 JP 2001-3046 JP

Phosphorescent item shop uetaya web site DNT Coating Technical Report No. 12P46-53 Published October 2012 Utilization of fluorescent paint with good visibility "Fluorescent paint for compartment lines" NIMS Molecular / Material Synthesis Platform Fluorescence Lifetime Measurement BASF Product Information Light-collecting fluorescent dye LumogenF Nitto Kasei Kogyo Co., Ltd. Transparent Epoxy Resin Adhesive Plastic Seal E-384 Nemoto Special Chemistry Comparison of characteristics of N Yoko G series and conventional phosphorescent pigments Ver. Comparison of April 2010 N Nightlight BG Series Characteristics with Conventional Luminescent Pigments Ver. April 2010 Paint Works website Fluorescent powder explanation Internet shop LOVERT Internet shop tama

Conventional phosphorescent agents based on alkaline earth metal aluminates have a long luminance emission time, but the green emission color or blue emission color is within tens of minutes, and the duration of saturation is also short.

In addition, all the color development structures in the known literature have a drawback that the saturation is low and the area of the fluorescent layer must be wide. In addition, when the saturation of the transparent fluorescent plate is increased, the transmittance decreases and the phosphorescent ability and afterglow ability decline.

It is difficult to color the ones sold for hobbies and nails, and there is a big difference that it can not color the daytime visible state and the night light emission color, the afterglow time is extremely short, the light emission within almost 30 minutes, or Color development cannot be continued without the help of black light. The fact that the light emission is thirty minutes means that the color development takes about 15 minutes.

Color development function and effect were low compared to general industrial identification and coloring applications such as

Further, in the conventional color developing structure, the contrast between the fluorescent storage layer and the display unit cannot be achieved, and the function as a display plate is low.

In addition, in the case of a structure in which the phosphorescent agent is sparse or the phosphorescent layer is thinned and the saturation is obtained by the transmitted color from the reflective layer, the effect of reducing the ability of the paints at the expense of both saturation and luminance There was a bug.

In addition, there is a phenomenon that the emission color is suppressed when the saturation of concentration quenching is increased in the fluorescent agent, and if the phosphorescent agent is used with a lot of phosphorescent powder to increase the luminance, the phosphorescence in the thickness direction is limited to the limit of saturation thickness. There was a phenomenon / limitation that even if the amount was increased, the luminance could not be increased.

In addition, the transmission loss is increased due to the generation of reflected waves due to the difference in the refractive index of different transparent materials in the laminated panel, and the distance / gap between the laminated panels and the air layer are used to transfer light between the fluorescent agent and the phosphorescent agent. Giving a big loss.

Sulfuric phosphorescent agents have problems in light emission time and weather resistance, and those with paints mixed in the phosphorescent agent for coloring are based on alkaline earth metal aluminates with a short color development time and visual brightness of 30 minutes or less. The phosphorescent material achieves long-lasting afterglow and high-luminance light emission while significantly reducing color.

In addition, those using the edge color effect require a large area for the fluorescent layer as the light condensing part and the phosphorescent layer as the light emitting layer, so that it is difficult to express the thin line on the neon sign, and the panel also increases the weight and has problems such as high cost. It was.

Moreover, the transparent color fluorescent screen is a mass-produced product, and it has not been possible to freely control the saturation, transmittance and thickness on the customer side.

The present invention is intended to solve the problems of such a conventional configuration, and the color development in the daytime is highly saturated by the fluorescent agent and can be vividly recognized (for example, the fluorescent agent according to Non-Patent Document 2). Effect, reflectance comparison according to FIG. 9),

Even in the dark, the phosphorescent material emits light to excite the fluorescent agent (for example, due to the effect of the fluorescent agent described in Non-Patent Document 2). A completely new structure was devised.
In order to achieve the above-mentioned object effectively, the present invention provides a phosphorescent agent in which a lower layer portion responsible for color development and an upper layer portion responsible for color development / storage are separately provided in a transparent resin. And a structure in which the interaction cycle between the fluorescent agent and the fluorescent agent is smoothly performed.

In addition, in this laminated double structure, a transparent body with low saturation also uses the physical and natural phenomenon that the saturation appears high when the thickness is increased, and although the phosphorescent agent is not a permeable substance, the phosphorescent agent particles In the case of a small one of about 5 to 50 microns, a phenomenon is used in which the hue of the lower layer is transmitted to some extent in a sparse state. This is conventionally known as a phenomenon caused by utilizing the phenomenon that the white reflective layer plays a large role in improving luminous agent luminance.

In other words, by providing the fluorescent layer, the fluorescent layer, and the phosphorescent layer separately in the same transparent resin, it prevents gaps in the connection surface, eliminates the need for surface matching, and eliminates the presence of an air layer, compared to a laminate of heterogeneous transparent layers. The aim is to suppress the loss of light due to reflected light.
In order to produce this structure, the lower fluorescent layer is first molded with an epoxy resin with excellent transparency and a long curing time, and the phosphorescent / fluorescent layer as the upper layer is additionally molded in a semi-cured state without sufficient drying time. A method was devised.

When an epoxy resin having a total light transmittance of 90.8% and a demoldable time of 24 hours or more (Non-Patent Document 5) is used, the semi-cured state is 5 hours to 20 hours. When layered, it is not mixed with the lower layer and has good adhesion, so it can be considered as a resin layer made of the same component, and reflection due to the difference in refractive index at the adhesive surface does not occur, and the transparent body In this case, it can be regarded as a good light guiding state with no internal transmission loss.

According to JISK7117, the base material is 1000, the curing agent is 200, the base material to curing agent mixing ratio is 5: 2, and the fluorescent agent is precipitated in a weight ratio of 0.003 to 0.01 percent. A light colored body can be obtained without any inconvenience.
Here, the phosphor emitting blue light has little coloring effect, is expensive, and is difficult to obtain from the market, so that the coloring effect can be obtained even if pigment powder is used.

A phosphorescent agent based on an alkaline earth metal aluminate (Non-patent Document 6) has a specific gravity of about 3.7 and a high luminance particle having a particle size of 300 microns has a poor flow and a thickness of 1 It is difficult to mold a uniform phosphorescent / fluorescent layer on the order of millimeters. In addition, the phosphorescent agent is not uniformly dispersed and is settled, and even a transparent phosphorescent / fluorescent layer having a thickness of about 2 mm is difficult to obtain a uniform light emitting surface during light emission. Although the intergranular gap is large, the transmitted light from the reflecting surface cannot be expected so much because the transparency of the particles themselves is inferior. In addition, since the luminance is high, the saturation of the green light emission color is high in the initial stage. If a large amount of fluorescent agent is not used, the green color is strong and the color saturation is difficult to obtain.
In the trial production according to the present invention, a bright red color was possible, but the viewing time was about 2 hours (see 8 test piece in FIG. 8).

In order to bring out a good toning effect, a green emission particle size of 5 to 50 microns is appropriate. The body color is N Glow G series and Easy Bright EZCB25 (currently discontinued) is light yellow to light green.

The EZCB25 blue luminescent phosphorescent agent was able to obtain effective blue luminescence when combined with powder paint blue (reference numeral 11 in FIG. 8).

A small amount of phosphorescent agent (peak particle size 5 to 50 microns) is sparse (volume ratio 15 to 30 percent) with a small amount of fluorescent agent, transparent epoxy resin, transparent urethane resin, transparent glass, transparent clear lacquer, transparent When cured in a light resin, it is possible to obtain a layer that transmits the base color to some extent and also transmits light from the outside. When the thickness is about 1 mm, a transparent body can be obtained which can obtain the effects of both the transmission of the base and the transmission of itself.

In addition, since the fluorescent agent and the phosphorescent agent are present in the vicinity, it is easy to exchange light with each other. Excitation of upper layer phosphorescent agent by external light, excitation of fluorescent agent and excitation light of lower layer fluorescent agent layer and light guide to the upper layer part can be performed very efficiently to obtain a structure with excellent color development did it.

The purpose of bonding and integrating epoxy resin in a semi-cured state is to reduce the attenuation factors such as no angle adjustment, anti-reflection, anti-reflection in the gap at the joint, etc. This is because, since the curing time is long, the bonding and integration work time can be performed with a margin.

As the fluorescent substance that can be used, a known fluorescent substance such as a phosphor, a fluorescent pigment, and a fluorescent dye can be used. Examples of organic phosphors include allylsulfoamide / melamine formaldehyde co-condensed dyes and perylene phosphors, and examples of inorganic phosphors include aluminates, phosphates, silicates, and the like. Can do. Of these, perylene phosphors and yttrium aluminate are particularly preferable because they can be used for a long time.
As a combination of the phosphor and the activator, yttrium aluminate and cerium are preferable.
In the present invention, NKP-8303 red, NKP-8304 orange, NKP-8306 orange yellow, NKP-8315 yellow, NKP-8912 green, NKP, which are yttrium aluminate phosphors or perylene phosphors of Nippon Fluorochemicals, Inc. -8307 Pink, NKP-8329 White, according to the product details, it is mainly used for automobile painting and has high weather resistance.

In addition, blue used was Pepares Manufacturing Co., Ltd. PPLS pigment powder blue. Although this pigment powder did not develop color by black light, it was possible to observe the color development for about 2 hours in the blue light emission time (reference numeral 11 in FIG. 8) when combined with the blue light-emitting phosphorescent agent.

Vivid red, orange, pink, yellow, green, and blue can be seen in the daytime, and red, orange, pink, yellow, green, and blue can be seen in the dark at night. It was possible to see the same color day and night, and it was possible to realize an epoch-making light emitting structure different from the conventional light-emitting agent-only light emission and light emission by the edge color effect. Even when powder pigment blue was used, a color luminescent material having a color development time of 2 hours (reference numeral 11 in FIG. 8) having a longer color development time than that of the luminous agent blue light emission could be obtained.

Moreover, taking advantage of the advantages of alkaline earth metal aluminate phosphorescent agents (for example, it does not hydrolyze and does not generate sulfur gas), the emission time is longer than that of red light-emitting sulfide-based phosphorescent agents. 8 code 8), stable to the environment could be manufactured.

Because of such high color saturation and high brightness, it is possible to realize a color structure even with a 1 mm or 2 mm wide engraving groove, and to produce a thin linear light emitter that cannot be realized with a neon tube. did it.

The structure of the most basic form of the present invention is shown in a side view. It shows that the transparent resin layer is divided into an upper layer portion and a lower layer portion by the boundary line code 3. Reference numeral 1 denotes fluorescent particles or pigment powder particles. When the lower layer is mixed in a sparse state and is in a pale hue state, if there is a certain thickness (1 mm to 2 mm), the saturation appears to increase. Reference numeral 2 denotes phosphorescent agent particles. The upper part of the transparent resin layer is kneaded in a loose state together with the fluorescent agent or pigment powder particles 1, and can slightly transmit the hue of the lower layer. Since the epoxy resin takes a long time to cure, it is preferable to select a particle size of 25 to 50 microns so that the phosphorescent agent particles do not settle rapidly. Side view in which a phosphor or pigment powder particles and a phosphorescent material are kneaded in a sparse state in a transparent resin and a reflector 4 is installed on the bottom of the laminate Sectional view in which a reflector 4 is installed around the laminate of FIG. Sectional drawing which installed the reflecting plate of the code | symbol 4 in the laminated body bottom face of FIG. Sectional view in which a reflector 4 is installed around the laminate of FIG. Sectional drawing in which a transparent fluorescent plate code 5 is installed on the top surface of the laminate of FIG. FIG. 6 is a cross-sectional view in which a concave groove is provided on the bottom surface side of the transparent fluorescent plate symbol 5 in FIG. Measured values obtained by measuring the luminance of the color light emitting plate prototyped in the present invention Fluorescent agent reflectance comparison chart in Non-Patent Document 2

Hereinafter, embodiments of the present invention will be described with reference to FIGS.

FIG. 8 shows the luminance measurement results after 2 minutes, 30 minutes and 60 minutes by the embodiment of the present invention and a public organization. Since the color development changes depending on the toning, thickness, reflector, etc., luminance was measured until 60 minutes later, and the color development was only confirmed by exciting or irradiating the fluorescent agent or pigment powder.
Although the signs 8 and 11 in FIG. 8 were also visible in the dark room even after 2 hours, a fluorescent agent is used for the blue color of the sign 8. In the case of the reference numeral 8, the visual recognition time can be further extended by adopting a laminated structure.
The test piece is an acrylic plate white, a square base having a size of 40 × 40 × 3 mm, a groove having a diameter of 33 mm and a depth of 1.2 mm is formed in the center, and an epoxy resin is first poured into the groove.
Thickness can be controlled by filling while weighing on a precision balance.
The first filled epoxy resin becomes hard from about 12 hours. In the case of Plaseal E-384, it is the HDD 30 after 24 hours, and the hardness before and after the HDD 30 is appropriate for lamination.
48 hours later, the HDD 70 may still adhere if it is placed on top of each other. However, dust may adhere to the adhesion surface, and the upper layer may be filled before and after 24 hours.
If the layers are laminated at a depth of 1.2 mm, the lower layer and upper layer will be slightly thicker.
The upper layer portion is raised and filled using surface tension, but flows during curing. In addition, the phosphorescent agent does not spread uniformly, and the emission hue is uneven.
In another embodiment, a machined machine with a depth of 2 mm and a width of 15 mm was produced.
Since the thickness of the lower layer can be secured by about 1 mm, the hue is clear, and the phosphorescent / fluorescent layer of the upper layer can secure the thickness and saturation, and the color development is beautiful.

The thing of the form of FIG. 1 can also be manufactured by shape | molding with a silicon type. Light plastic and faint light emission / coloring can be used by filling transparent plastic.
The finished product looks vivid with increased saturation when placed on a white background or on fluorescent paper or fluorescent color plastic.

When the reflector is made of fluorescent paper in the form of FIG. 4, the same effect as described above is exhibited, but it becomes difficult to set the mold on the measuring instrument, and when the phosphorescent layer becomes thicker than 1 mm, the phosphorescent excitation and fluorescence are performed. It takes 1-2 minutes longer than usual until light emission is visible.

In the case of FIG. 6 and FIG. 7, if a fluorescent plate is inserted into the upper surfaces 5 and 6 and a fluorescent paper cut letter or fluorescent cloth is inserted, the contrast with the lower part can be adjusted and a sign that can be clearly recognized can be formed.

In this way, by using the transparent resin shown in FIG. 1 as the same component, when light passes from the upper layer portion to the lower layer portion, the reflection phenomenon due to the difference in refractive index can be suppressed and transmission loss can be suppressed.

The above effect is also applied when light moves from the lower layer to the upper layer. The reflected light and excitation light from the bottom reflector can be sent to the upper layer without reflection loss.

In order to reduce the internal loss due to the mixing of the phosphorescent agent, the fluorescent agent and the pigment, the upper layer fluorescent agent 1 and the phosphorescent agent 2 are mixed in a sparse state, and the thickness is preferably suppressed to about 1 mm or less. This is to facilitate the passage of light from the outside and to easily transmit the lower hue.

In the upper layer, the concentration of the fluorescent agent is prevented from being extinguished, and the fluorescent agent is placed in close proximity so that it can easily receive the light emitted from the fluorescent agent, and the fluorescent agent emits the phosphorescent agent to facilitate the phosphorescent emission. It is.

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Global industrial development sites, which will continue in the future, will use large amounts of electricity to develop the economy, but negative effects will destroy the global environment and cause abnormal weather. The industry has also developed energy-saving products and products with low greenhouse gas emissions, but it has not been able to cope with population explosions and total midstreaming in developing countries 20 to 30 years later. There is also a forecast that growth will reach its peak. In the industrial world, it is necessary to adopt a power saving and power saving system expressed in negative watts.

The present invention does not require electrical work, and has evolved greatly from the monochromatic emission colors of green and blue light emission possessed by portable and conventional phosphorescent agents, so that fashionable red, pink, orange, yellow, green and blue The application has been expanded by enabling the coloring of
The orange color is highly visible in the warehouse and has excellent visibility in the tunnel.
In addition, the sign with the same color scheme as in the daytime is a safe sign with little change in the image of the sign even during a sudden power failure.

By color-coding pipelines such as plants, it is possible to easily perform maintenance and to operate quickly and with less risk by preventing erroneous operations.
It is said that there is a big change in the growth of plants due to light in the plant factory, and it is possible to increase the yield by producing the effect of adjusting the sunshine hours.

The colors that can be seen by honeybees are said to be from ultraviolet to white and pale pink, which can be used for helping homing after pollination in the house, or for directing the direction of sea turtles after spawning sea turtles. Helps the food chain and greatly helps the food industry.
Even in the purification of drinking water, blue is said to be a color disliked by microorganisms, increasing the efficiency of filters and improving the situation of drinking water in developing countries.

DESCRIPTION OF SYMBOLS 1 Fluorescent agent particle 2 Phosphorescent agent particle 3 Transparent resin joint surface 4 Reflector 5 Transparent fluorescent plastic 6 Transparent fluorescent color paint 7 Laminated body 8 Measurement test piece Red 9 Measurement test piece Orange 10 Measurement test piece Green 11 Measurement test piece Blue

Claims (7)

In the same type of transparent resin laminate, the upper layer is weighed and controlled in a proportion of the phosphorescent agent and color coloring fluorescent agent or pigment powder mixed layer, and the lower layer is weighed and controlled in the proportion of color coloring fluorescent agent or pigment powder. Multi-layered color development structure that can be set as a resin layer mixed with water and color can be developed day and night without electricity Light and color can be developed day and night without power, with a phosphorescent agent and color coloring fluorescent agent or pigment powder uniformly distributed in the transparent resin layer and a white or color coloring fluorescent reflector on the bottom. Color development structure. 3. The color coloring structure according to claim 2, wherein a white reflecting plate or a color coloring fluorescent reflecting plate is provided on the outer periphery of the four sides of the transparent resin layer so that color can be developed day and night without power. 2. The color coloring structure according to claim 1, wherein a white reflecting plate or a color coloring fluorescent reflecting plate is provided at the bottom of the lower layer. 5. The color coloring structure according to claim 4, wherein a white reflecting plate or a color coloring fluorescent reflecting plate is provided on the outer peripheral edge of the transparent resin layer. A color coloring structure in which a transparent plastic plate containing a color fluorescent dye is provided on the upper surface of the upper layer portion according to claim 1.2.3.4.5 A color coloring structure having a structure in which engraving grooves are provided inside a transparent plastic containing a color fluorescent dye provided on the upper surface of the upper layer portion and a transparent resin mixed with a measured and controlled phosphorescent agent and a fluorescent agent is injected.

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