JP2012056096A - Phosphorescent water discoloration body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphorescent water discoloration body capable of visually recognizing phase change by making water adhere to a porous layer in a bright place, of effectively developing the effects of each function of water discoloration properties and phosphorescent properties by providing the porous layer with a permanently light-emitting function in a dark place, and permanently usable in the bright place and the dark place.SOLUTION: The phosphorescent water discoloration body 1 is constituted by laminating the porous layer 3 in which a pigment with a low refractive index and a phosphorescent pigment are fixed, on a support body 2, to binder resin in a dispersed state and transparency thereof varies according to either a liquid absorbable state or a liquid non-absorbable state. The phosphorescent pigment is subjected to heating treatment after mixed with phosphate or brought into contact with the phosphate in a phosphate solution.

Description

  The present invention relates to a phosphorescent water color change body. More specifically, the present invention relates to a phosphorescent water discoloration body that absorbs water and changes to a different state from a dry state, returns to its original state when dried, and is visible in a dark place.

Conventionally, a discolorable laminate in which a porous layer in which a low refractive index pigment and a phosphorescent pigment are fixed in a dispersed state in a binder resin is provided on a support has been disclosed (for example, see Patent Document 1).
In the light place, the laminate can change the appearance by adhering water to the porous layer. In the dark place, the porous layer containing the phosphorescent pigment emits light. Therefore, the laminate can be used in both the light place and the dark place. It is.
However, when the laminate is repeatedly applied with water to the porous layer, the light emission of the porous layer is reduced in a dark place and is difficult to use permanently in a dark place.

JP 2006-43971 A

  The present invention can provide a change in appearance by attaching water to the porous layer in a bright place, and can visually recognize light emitted from the porous layer in a dark place, and can be used permanently in a bright place and a dark place. It is intended to provide a discoloration body.

In the present invention, a porous layer having a low refractive index pigment and a phosphorescent pigment fixed in a dispersed state on a binder resin and having different transparency in a liquid absorbing state and a non-liquid absorbing state is laminated on a support. The phosphorescent pigment requires a phosphorescent water colorant that is a phosphorescent pigment that has been mixed with phosphate or contacted in a phosphate solution and then heat-treated.
Furthermore, it is required that a colored layer containing a color pigment is provided between the support and the porous layer, and that the porous layer forms an image.

  The present invention can visually recognize a change in appearance by attaching water to a porous layer in a bright place, and has a function of permanently emitting light in a dark place. The effect of each function can be effectively expressed, and a phosphorescent water colorant that can be used permanently in light and dark places can be provided, and the exquisiteness, specificity, decorativeness, design effect, etc. of color change can be provided. It can be applied to various required fields.

It is a longitudinal cross-sectional explanatory drawing of one Example of this invention luminous water discoloration body. It is longitudinal cross-sectional explanatory drawing of the other Example of this invention luminous water discoloration body. It is longitudinal cross-sectional explanatory drawing of the other Example of this invention luminous water discoloration body.

The material and form of the support are not particularly limited, but the material is paper, synthetic paper, knitted fabric, woven fabric, non-woven fabric, etc., flocked or raised fabric, synthetic leather, leather, plastic, metal, glass, Examples include ceramics, wood, and stone.
When a fabric is used as the support, the porous layer is generally printed using water-based ink. At that time, the phosphorescent pigment that has been subjected to water resistance treatment in a pre-prepared water-based ink does not decrease the light emission intensity, and thus can form a porous layer having good phosphorescent properties.

On the support, a porous layer having a low refractive index pigment and a phosphorescent pigment fixed in a dispersed state in a binder resin and having different transparency in a liquid absorbing state and a non-liquid absorbing state is provided.
Examples of the low refractive index pigment include silicic acid and salts thereof, barite powder, barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, talc, alumina white, magnesium carbonate, and the like. It is in the range of 1.8 and exhibits good transparency when liquid is absorbed.
Examples of the silicic acid salts include aluminum silicate, aluminum potassium silicate, sodium aluminum silicate, aluminum calcium silicate, potassium silicate, calcium silicate, calcium sodium silicate, sodium silicate, magnesium silicate, and magnesium potassium silicate.
The particle size of the low refractive index pigment is not particularly limited, but 0.03 to 10.0 μm is preferably used.
Two or more of the low refractive index pigments can be used in combination.
In addition, silicic acid is mentioned as a low refractive index pigment used suitably.
The silicic acid may be silicic acid produced by a dry process (hereinafter referred to as dry process silicic acid), but is preferably silicic acid produced by a wet process (hereinafter referred to as wet process silicic acid).
This point will be described below.
Silicic acid is produced as amorphous amorphous silicic acid, and depending on its production method, the dry method using a gas phase reaction such as thermal decomposition of silicon halide such as silicon tetrachloride and the decomposition by acid such as sodium silicate. It is roughly classified into those by a wet method using a liquid phase reaction such as.
The structure of the dry process silicic acid and that of the wet process silicic acid are different, and the dry process silicic acid has a structure in which silicic acid is closely bound, whereas the wet process silicic acid has a structure part in which a long molecular arrangement is formed by condensation of silicic acid. have.
Therefore, the wet process silicic acid has a rough molecular structure compared to the dry process silicic acid, so when applying the wet process silicic acid, the wet process silicic acid is superior in the diffused reflection of light in the dry state compared to the system using the dry process silicic acid, It is presumed that the concealment will increase.
In addition, since the porous layer absorbs water, the wet process silicic acid has more hydroxyl groups present as silanol groups on the particle surface than the dry process silicic acid, and has a high degree of hydrophilicity. It is done.

The phosphorescent pigment is a phosphorescent pigment obtained by mixing a phosphorescent pigment obtained by doping an alkaline earth metal oxide with a rare earth oxide with a phosphate or bringing it into contact with a phosphate solution, and then heat-treating the phosphorescent pigment.
The luminous pigment is, for example, SrAl ₂ O ₄ , Sr ₄ Al ₁₄ O ₂₅ , or CaAl ₂ O ₄ disclosed in JP-A-7-11250, with europium, dysprosium, samarium or the like added as an activator. Sr (AlB) ₂ O ₄ ; EuDy, Sr (AlB) ₃ O ₆ ; EuDy, or Sr (AlB) ₄ O ₇ ; EuDy disclosed in JP-A-10-168448.
In the phosphorescent pigment, when water adheres, the alkaline earth oxide reacts with water to form a hydrate, and at the same time, ions exhibiting alkalinity are released, and the function of emitting light for a long time is likely to deteriorate.
Therefore, as a phosphorescent pigment having water resistance, a phosphorescent pigment that is mixed with phosphate or brought into contact in a phosphate solution and then heat-treated is used.
The phosphorescent pigment that has been mixed with the phosphate or brought into contact in the phosphate solution and then heat-treated is reacted with the alkaline earth metal and phosphorus on the pigment surface to make the surface insoluble or sparingly soluble in water. As the phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium dihydrogen phosphate dihydrate, sodium ammonium hydrogen phosphate tetrahydrate, sodium hexametaphosphate, etc. And potassium salts and the like can also be used.
The phosphorescent pigment and phosphate are mixed or brought into contact in a phosphate solution and heated at a temperature of 150 ° C. to 300 ° C., preferably 200 ° C. to 250 ° C., to obtain a phosphorescent pigment having water resistance.
Conventional phosphorescent pigments that do not have water resistance (untreated phosphorescent pigments) tend to decrease in light emission intensity when water adheres to them, and it is difficult to satisfy repeated use. Even when water is attached, the emission intensity is hardly lowered, and repeated use can be satisfied.

Examples of the binder resin include urethane resin, nylon resin, vinyl acetate resin, acrylic ester resin, acrylic ester copolymer resin, acrylic polyol resin, vinyl chloride-vinyl acetate copolymer resin, maleic resin, polyester resin, styrene. Resin, styrene copolymer resin, polyethylene resin, polycarbonate resin, epoxy resin, styrene-butadiene copolymer resin, acrylonitrile-butadiene copolymer resin, methyl methacrylate-butadiene copolymer resin, butadiene resin, chloroprene resin, melamine resin, and the above Examples thereof include binder resins such as resin emulsions, casein, starch, cellulose derivatives, polyvinyl alcohol, urea resins, and phenol resins.
The mixing ratio of the low refractive index pigment and the binder resin depends on the kind and properties of the low refractive index pigment, but preferably the binder resin solid content is 0.5 to 2 weights with respect to 1 part by weight of the low refractive index pigment. Part, more preferably 0.8 to 1.5 parts by weight. When the binder resin solid content is less than 0.5 parts by weight with respect to 1 part by weight of the low refractive index pigment, it is difficult to obtain a practical film strength of the porous layer to be formed. When exceeding, the water permeability to the inside of the porous layer is deteriorated.
Since the porous layer has a smaller mixing ratio of the binder resin to the colorant than a general coating film, it is difficult to obtain sufficient film strength. Therefore, among the binder resins, it is preferable to increase the scratch resistance using a nylon resin or a urethane resin.
Examples of the urethane resin include a polyester urethane resin, a polycarbonate urethane resin, and a polyether urethane resin, and two or more of them can be used in combination. In addition, a urethane emulsion resin in which the resin is emulsified and dispersed in water, or a colloid in which the resin is self-emulsified without the need for an emulsifier by an ionic group of the ionic urethane resin (urethane ionomer) itself and dissolved or dispersed in water. A dispersion type (ionomer type) urethane resin can also be used.
The urethane-based resin may be either an aqueous urethane-based resin or an oil-based urethane-based resin, but an aqueous urethane-based resin, particularly a urethane-based emulsion resin or a colloidally dispersed urethane-based resin is preferably used.
The urethane resin can be used alone, but other binder resins can be used in combination depending on the type of support and the performance required for the coating. When a binder resin other than the urethane resin is used in combination, in order to obtain a practical film strength, it is preferable to contain a urethane resin in a solid content ratio of 30% by weight or more in the binder resin of the porous layer.
In the binder resin, the crosslinkable resin can be further improved in film strength by adding an arbitrary crosslinking agent and crosslinking.
The binder resin has a large or small affinity with water. By combining these, the penetration time into the porous layer, the degree of penetration, and the slow speed of drying after the penetration can be adjusted. Furthermore, the said adjustment can be controlled by adding a dispersing agent suitably.
A colorant may be contained in the porous layer.
Since the porous layer is an image (porous image), the porous image can be visually recognized when used in a dark place, and therefore, the decorative property is excellent.

The porous layer is a known means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer printing, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller It can be formed by coating, dip coating or the like.
A colored layer may be provided between the support and the porous layer.

Examples are shown below. The part in an Example is a mass part.
Example 1 (see FIG. 1)
15 parts of wet-process fine particle silica [trade name: NIPSEAL E-220, manufactured by Nippon Silica Kogyo Co., Ltd.] on a red synthetic paper as the support 2, a phosphorescent pigment having an emission color of yellow-green (average particle diameter: 2 to 60 μm) , Emission maximum wavelength 520 nm) 10 parts, urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30%] 45 parts, water 40 parts, silicone-based antifoaming agent 0. 5 parts, 3 parts of thickener for water-based ink, 1 part of ethylene glycol, 3 parts of blocked isocyanate-based cross-linking agent were mixed uniformly and stirred using white screen printing ink. Printed, dried and cured at 130 ° C. for 5 minutes to form a porous layer 3, and a luminous water discoloration body 1 was obtained.
The phosphorescent pigment is heated in a dryer preliminarily heated to 200 ° C. after adding and mixing phosphate (diammonium hydrogen phosphate) with SrAl ₂ O ₄ : Eu, Dy. Subsequently, it is taken out from the dryer and allowed to cool, and impurities are removed with pure water and dried.

In the phosphorescent water discolored body, a white porous layer is visually recognized in a dry place (non-water absorbing state) in a bright place, and when water is attached using a brush impregnated with water, the porous layer is transparent due to liquid absorption. As a result, a red image is visually recognized by the support, and the original white porous layer is visually recognized again by drying. The aspect change could be repeated.
Moreover, since the porous layer emits yellow-green light, the phosphorescent water-colored substance can be used even in a dark color.
Furthermore, even when the phosphorescent water color changing body was immersed in water at 25 ° C. for 24 hours, the color changing function was maintained without impairing the light emission intensity.

Example 2 (see FIG. 2)
On a white synthetic paper as a support 2, 2 parts of a blue pigment, 100 parts of an acrylic ester resin emulsion (solid content: 50%), 0.5 part of a silicone-based antifoaming agent, 5 parts of a thickener, a leveling agent The colored layer 4 was formed by solid printing using 0 parts and a blue ink in which 2.0 parts of a crosslinking agent were uniformly dispersed, followed by drying and curing at 70 ° C. for 30 minutes.
On the colored layer, 15 parts of wet-process fine particle silica [trade name: NIPSEAL E-220, manufactured by Nippon Silica Kogyo Co., Ltd.], phosphorescent pigment whose emission color is yellow-green (average particle size: 2 to 40 μm, maximum emission) Wavelength 520 nm) 12 parts, urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30%] 45 parts, water 40 parts, silicone-based antifoaming agent 0.5 part, aqueous system Using a white screen printing ink obtained by uniformly mixing and stirring 3 parts of an ink thickener, 1 part of ethylene glycol, and 3 parts of a blocked isocyanate crosslinking agent, the entire surface is solid-printed on a 100 mesh screen plate. A porous layer 3 was formed by drying and curing at 5 [deg.] C. for 5 minutes to obtain a luminous water discoloration body 1.
The phosphorescent pigment is heated in a dryer preliminarily heated to 200 ° C. after adding and mixing phosphate (diammonium hydrogen phosphate) with SrAl ₂ O ₄ : Eu, Dy. Subsequently, it is taken out from the dryer and allowed to cool, and impurities are removed with pure water and dried.

In the phosphorescent water discolored body, a white porous layer is visually recognized in a dry place (non-water absorbing state) in a bright place, and when water is attached using a brush impregnated with water, the porous layer is transparent due to liquid absorption. And a blue image by the colored layer is visually recognized, and the original white porous layer is visually recognized again by drying. The aspect change could be repeated.
Moreover, since the porous layer emits light, the phosphorescent water color change material can be used even in a dark color.
Furthermore, even when the phosphorescent water color changing body was immersed in water at 25 ° C. for 24 hours, the color changing function was maintained without impairing the light emission intensity.

Example 3 (see FIG. 3)
10 parts of a pink fluorescent pigment, 100 parts of an acrylic ester resin emulsion (solid content: 45%) on a white Tetoron / cotton broad fabric (65/35, basis weight: 100 g / m ² ) as a support 2, silicone Solid printing with 0.5 parts of antifoaming agent, 5 parts of thickener, 1.0 part of leveling agent, 5.0 parts of epoxy crosslinking agent and uniformly dispersed in pink ink, at 130 ° C. for 5 minutes The colored layer 4 was formed by drying and curing.
On the colored layer, 15 parts of wet-process fine particle silica [trade name: NIPSEAL E-220, manufactured by Nippon Silica Kogyo Co., Ltd.], phosphorescent pigment whose emission color is yellow-green (average particle size: 2 to 40 μm, maximum emission) Wavelength 520 nm) 12 parts, urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30%] 45 parts, water 40 parts, silicone-based antifoaming agent 0.5 part, aqueous system Using a white screen printing ink obtained by uniformly mixing and stirring 3 parts of an ink thickener, 1 part of ethylene glycol, and 3 parts of a blocked isocyanate-based crosslinking agent, a star pattern is printed on a 100 mesh screen plate, A porous image 31 was formed by drying and curing at 130 ° C. for 5 minutes to obtain a phosphorescent water color change body 1.
The phosphorescent pigment is heated in a dryer preliminarily heated to 200 ° C. after adding and mixing phosphate (diammonium hydrogen phosphate) with SrAl ₂ O ₄ : Eu, Dy. Subsequently, it is taken out from the dryer and allowed to cool, and impurities are removed with pure water and dried.

When the phosphorescent water discoloration body is in a dry state (non-water absorbing state) in a bright place, a porous image made of a white star pattern is visually recognized on a pink fabric.
When water is attached to the porous image, the porous image becomes transparent due to liquid absorption and the image disappears, and a pink discolored body is visually recognized on the entire surface, but the porous image is visually recognized again after drying. The aspect change could be repeated.
In addition, since the phosphorescent water discolorant emits a porous image, a star-shaped porous image is emitted and visually recognized in a dark place.
Furthermore, even when the phosphorescent water color changing body was immersed in water at 25 ° C. for 24 hours, the color changing function was maintained without impairing the light emission intensity.

Example 4
Support + porous layer As a support, on a pink Tetron / Cotton broad fabric (65/35, basis weight: 100 g / m ² ), wet method fine particle silica [trade name: NIPSEAL E-220, Nippon Silica Kogyo ( Co., Ltd.] 15 parts, 12 parts of luminous pigment (average particle diameter: 2 to 40 μm, emission maximum wavelength 520 nm) with yellowish green emission color, 1 part of blue pigment, urethane emulsion [trade name: Hydran AP-10, large Nippon Ink Chemical Co., Ltd., solid content 30%] 45 parts, water 40 parts, silicone antifoam 0.5 parts, water based ink thickener 3 parts, ethylene glycol 1 part, block isocyanate crosslinking agent Using a white screen printing ink with 3 parts uniformly mixed and stirred, the entire surface is solid-printed on a 100 mesh screen plate, dried and cured at 130 ° C. for 5 minutes, and porous. Form, to obtain a phosphorescent water metachromatic member.
The phosphorescent pigment is heated in a dryer preliminarily heated to 200 ° C. after adding and mixing phosphate (diammonium hydrogen phosphate) with SrAl ₂ O ₄ : Eu, Dy. Subsequently, it is taken out from the dryer and allowed to cool, and impurities are removed with pure water and dried.

In the phosphorescent water discolored body, a light blue porous layer is visually recognized in a dry place (non-water-absorbing state) in a bright place, and when the water is attached using a brush impregnated with water, the porous layer is formed by absorbing liquid. The purple color, which is transparent and becomes a mixed color of the pink color of the colored layer and the blue color of the porous layer, is visually recognized, and the original pale blue porous layer is visually recognized again by drying. The aspect change could be repeated.
Moreover, since the porous layer emits light, the phosphorescent water color change material can be used even in a dark color.
Furthermore, even when the phosphorescent water color changing body was immersed in water at 25 ° C. for 24 hours, the color changing function was maintained without impairing the light emission intensity.

Example 5
On a white polyester satin fabric (weight per unit area: 120 g / m ² ) as a support, 10 parts of a pink fluorescent pigment, 100 parts of an acrylate resin emulsion (solid content: 45%), a silicone-based antifoaming agent 0.5 Part, thickener 5 parts, leveling agent 1.0 part, epoxy cross-linking agent 5.0 parts solidly printed with a pink ink, and dried and cured at 130 ° C. for 5 minutes to form a colored layer Formed.
On the colored layer, 15 parts of wet method fine particle silica [trade name: Nipseal E-220, manufactured by Nippon Silica Industry Co., Ltd.], urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc.] , Solid content 30%] 45 parts, water 40 parts, silicone-based antifoaming agent 0.5 part, water-based ink thickener 3 parts, ethylene glycol 1 part, block isocyanate-based crosslinking agent 3 parts uniformly mixed and stirred Using the white screen printing ink, a solid was printed on the entire surface with a 180 mesh screen plate and dried and cured at 130 ° C. for 5 minutes to form a porous layer (a porous layer containing no phosphorescent pigment).
On the porous layer, 15 parts of wet-process fine particle silica [trade name: NIPSEAL E-220, manufactured by Nippon Silica Kogyo Co., Ltd.], phosphorescent pigment having an emission color of yellow-green (average particle size: 2 to 40 μm, light emission) 12 parts of urethane emulsion (trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30%) 45 parts, water 40 parts, silicone antifoaming agent 0.5 part, A star pattern is printed on a 100-mesh screen plate using white screen printing ink that is obtained by uniformly mixing and stirring 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 3 parts of a block isocyanate-based crosslinking agent. Then, it was dried and cured at 130 ° C. for 5 minutes to form a porous image to obtain a luminous water discoloration.
The phosphorescent pigment is heated in a dryer preliminarily heated to 200 ° C. after adding and mixing phosphate (diammonium hydrogen phosphate) with SrAl ₂ O ₄ : Eu, Dy. Subsequently, it is taken out from the dryer and allowed to cool, and impurities are removed with pure water and dried.

In the phosphorescent water discolored body, a white porous layer is visually recognized in a dry place (non-water absorbing state) in a bright place, and when water is attached using a brush impregnated with water, the porous layer is transparent due to liquid absorption. And a pink image by the colored layer is visually recognized, and the original white porous layer is visually recognized again by drying. The aspect change could be repeated.
Moreover, since the porous layer emits light in the dark place, the phosphorescent water-colored body could be used even in a dark color.
In addition, since the phosphorescent water discolorant emits a porous image, a star-shaped porous image is emitted and visually recognized in a dark place.
Furthermore, even when the phosphorescent water color changing body was immersed in water at 25 ° C. for 24 hours, the color changing function was maintained without impairing the light emission intensity.

Comparative Example 1
On a red synthetic paper as a support, 15 parts of wet method fine particle silica [trade name: NIPSEAL E-220, manufactured by Nippon Silica Kogyo Co., Ltd.], a luminous pigment (SrAl ₂ O ₄ : Eu, Dy) whose emission color is yellow-green , Average particle size: 2 to 60 μm, emission maximum wavelength 520 nm) 10 parts, urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30%] 45 parts, water 40 parts 100 parts of white screen printing ink obtained by uniformly mixing and stirring 0.5 parts of a silicone-based antifoaming agent, 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 3 parts of a blocked isocyanate-based crosslinking agent. The entire surface was solid-printed with a mesh screen plate and dried and cured at 130 ° C. for 5 minutes to form a porous layer, whereby a phosphorescent water discoloration was obtained.

In the phosphorescent water discolored body, a white porous layer is visually recognized in a dry place (non-water absorbing state) in a bright place, and when water is attached using a brush impregnated with water, the porous layer is transparent due to liquid absorption. As a result, a red image is visually recognized by the support, and the original white porous layer is visually recognized again by drying. The aspect change could be repeated.
Although the phosphorescent water-colored substance emits light in a dark color, repeated application of water causes the luminous intensity of the phosphorescent pigment to decrease, making it difficult to emit light in a dark color, thus failing to satisfy practicality.

Comparative Example 2
On a white synthetic paper as a support, 2 parts of a blue pigment, 100 parts of an acrylic ester resin emulsion (solid content: 50%), 0.5 part of a silicone-based antifoaming agent, 5 parts of a thickener, 1.0 of a leveling agent A solid layer was printed using a blue ink in which 2.0 parts of a cross-linking agent was uniformly dispersed and dried and cured at 70 ° C. for 30 minutes to form a colored layer.
On the colored layer, 15 parts of wet-process fine particle silica [trade name: NIPSEAL E-220, manufactured by Nippon Silica Kogyo Co., Ltd.], luminous pigment with yellowish green emission color (SrAl ₂ O ₄ : Eu, Dy, average) Particle size: 2-40 μm, emission maximum wavelength 520 nm) 12 parts, urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30%] 45 parts, water 40 parts, silicone 100 mesh screen using white screen printing ink prepared by uniformly mixing and stirring 0.5 part of defoamer, 3 parts of thickener for water-based ink, 1 part of ethylene glycol and 3 parts of blocked isocyanate-based crosslinking agent The entire surface was solid-printed with a plate, dried and cured at 130 ° C. for 5 minutes to form a porous layer, and a phosphorescent water discoloration was obtained.

In the phosphorescent water discolored body, a white porous layer is visually recognized in a dry place (non-water absorbing state) in a bright place, and when water is attached using a brush impregnated with water, the porous layer is transparent due to liquid absorption. And a blue image by the colored layer is visually recognized, and the original white porous layer is visually recognized again by drying. The aspect change could be repeated.
Although the phosphorescent water-colored substance emits light in a dark color, repeated application of water causes the luminous intensity of the phosphorescent pigment to decrease, making it difficult to emit light in a dark color, thus failing to satisfy practicality.

DESCRIPTION OF SYMBOLS 1 Phosphorescent water color change body 2 Support body 3 Porous layer 31 Porous image 4 Colored layer

Claims (3)

  On the support, a low-refractive-index pigment and a luminous pigment are laminated in a binder resin in a dispersed state, and a porous layer having different transparency in a liquid-absorbing state and a non-liquid-absorbing state is laminated. Is a phosphorescent water colorant which is a phosphorescent pigment which is mixed with phosphate or brought into contact in a phosphate solution and then heat-treated.   The phosphorescent water color changer according to claim 1, wherein a colored layer containing a color pigment is provided between the support and the porous layer.   The phosphorescent water discoloration body according to claim 1 or 2, wherein the porous layer forms an image.

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