JP2012056095A - 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, effectively developing the effects of each function of water discoloration properties and phosphorescent properties by providing a phosphorescent layer with a permanently light-emitting function in a dark place, and permanently applying change properties between the bright place and the dark place.SOLUTION: The phosphorescent water discoloration body 1 is constituted by laminating the phosphorescent layer 2 including a phosphorescent pigment obtained by doping rare-earth oxide with respect to alkaline-earth metal oxide and the porous layer 3 in which a pigment with a low refractive index is fixed 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 discolorant that absorbs water and changes to a state different from a dry state, which can be visually recognized even in a dark place, and returns to its original state upon drying.

Conventionally, cosmetics and curtains provided with a phosphorescent image on a support have been disclosed, and although different aspects are visible in bright places and dark places, variability is poor in bright places (for example, Patent Documents 1 and 2). reference).
Therefore, a phosphorescent layer containing a phosphorescent pigment is provided on the support, and a low refractive index pigment is fixed to the binder resin in a dispersed state on the phosphorescent layer, so that the transparency is different between the liquid absorbing state and the non-liquid absorbing state. A discolorable laminate having a porous layer is disclosed (for example, see Patent Document 3).
The laminated body can give a change in appearance by adhering water to the porous layer in a bright place, and can visually recognize the light emitted by the light-accumulating layer containing a phosphorescent pigment in the dark place. It can be done.
However, in the laminate, when water is repeatedly applied to the porous layer, a decrease in light emission of the phosphorescent layer is observed in a dark place, and it is difficult to permanently impart a change in appearance in the dark place.

JP-A-61-132346 JP-A-10-127478 JP-A-11-227314

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

The present invention provides a phosphorescent layer containing a phosphorescent pigment obtained by doping a rare earth oxide into an alkaline earth metal oxide, a liquid absorbing state and a non-liquid absorbing state in which a low refractive index pigment is fixed to a binder resin in a dispersed state. A porous layer having different transparency is laminated, and the phosphorescent pigment is mixed with a phosphate or brought into contact in a phosphate solution, and then a phosphorescent water colorant that is a phosphorescent pigment that is heat-treated. Requirement.
Further, the phosphorescent layer contains a color pigment, the phosphorescent layer and a porous layer are laminated on a support, and a non-discoloration containing a color pigment between the support and the phosphorescent layer. It is necessary to provide a layer, and to include a color pigment in the porous layer.

  The present invention can visually recognize a change in appearance by attaching water to the porous layer in a bright place, and in the dark place, the phosphorescent layer has a function of emitting light permanently. The effect of each function can be effectively expressed, and a phosphorescent water discoloration that can be permanently changed in bright and dark places can be provided, and the exquisite taste, specificity, decoration, and design effects of color change It can be applied to various fields that require it.

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 present invention will be described in more detail. A water discoloration body in which a porous layer having different transparency in a liquid absorption state containing a low refractive index pigment and a non-liquid absorption state is laminated on the light storage layer containing the above-described light storage pigment. , It has an effect that cannot be achieved by a system in which each layer is provided.
When only the phosphorescent layer is provided, an image that was not visually recognized in the bright place is emitted and visually recognized in the dark place. Therefore, the change in the appearance is visually recognized by light and dark, but the visibility of the image in a bright place is poor.
When only the porous layer is provided, the porous layer becomes transparent by application of water, and the porous layer becomes opaque when dried. It is hard to do.
In the present invention, by stacking the phosphorescent layer and the porous layer, it is possible to obtain a water discoloration body that is rich in decoration and appearance change in both a bright place and a dark place.

The phosphorescent layer containing a phosphorescent pigment will be described below.
The phosphorescent layer contains a phosphorescent pigment in the layer, and the phosphorescent pigment is prepared by mixing a phosphorescent pigment obtained by doping an alkaline earth metal oxide with a rare earth oxide with a phosphate or in a phosphate solution. It is a phosphorescent pigment that has been contacted and then heat-treated.
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.
The luminous layer is a luminous layer in which the luminous pigment is dispersed and fixed in a binder resin on a support, in addition to a molded body formed by blending the luminous pigment in a thermoplastic resin or a thermosetting resin. Also good.
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.

The material of the support is not particularly limited, but the material is paper, synthetic paper, fabric, flocked or brushed fabric, non-woven fabric, synthetic leather, leather, plastic, metal, glass, ceramics, wood, stone. Etc.
When a fabric is used as the support, the phosphorescent layer and porous layer are generally printed using water-based ink. At this 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 therefore can form a phosphorescent layer having good luminous properties.
In addition, when providing a luminous layer on the said support body, a colored layer can also be provided between a support body and a luminous layer.

The binder may be a transparent film-forming resin, and various conventional binders can be applied.
Examples of the resin include ionomer resin, isobutylene-maleic anhydride resin copolymer resin, acrylonitrile-acrylic styrene copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile chlorinated polyethylene-styrene copolymer. Resin, ethylene-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride graft copolymer resin, vinylidene chloride resin, vinyl chloride resin, chlorinated vinyl chloride resin, vinyl chloride-vinylidene chloride Polymer resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polystyrene resin, high imp Polystyrene resin, polypropylene resin, polymethylstyrene resin, polyacrylate resin, polymethyl methacrylate resin, epoxy acrylate resin, alkylphenol resin, rosin modified phenol resin, rosin modified alkyd resin, phenol resin modified alkyd resin, epoxy resin modified alkyd Resin, styrene-modified alkyd resin, acrylic-modified alkyd resin, amino alkyd resin, vinyl chloride-vinyl acetate resin, styrene-butadiene resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyurethane resin, alkyd resin, natural rubber, poly Isobutylene, butyl rubber, polyvinyl alkyl ether, rosin, rosin ester, rosin derivative, polyterpene resin, oil-soluble phenol resin, petroleum hydrocarbon Fat, shellac, cyclized rubber, vinyl acetate emulsion resin, styrene-butadiene emulsion resin, acrylate emulsion resin, water-soluble alkyd resin, water-soluble melamine resin, water-soluble urea resin, water-soluble phenol resin, water-soluble An epoxy resin, a water-soluble polybutadiene resin, cellulose acetate, cellulose nitrate, ethyl cellulose, and the like can be given, and it can be applied by dissolving or dispersing in an appropriate solvent such as water or an organic solvent.
The above-mentioned luminous layer can contain a general pigment.

On the luminous layer, there is provided a porous layer in which a low refractive index pigment is fixed to a binder resin in a dispersed state and has different transparency in a liquid absorption state and a non-liquid absorption state.
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.

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.

  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.

Examples are shown below. The part in an Example is a mass part.
Example 1 (see FIG. 1)
10 parts of a luminous pigment having an emission color of yellowish green (average particle size: 2 to 60 μm, maximum emission wavelength of 520 nm), 2 parts of red pigment, 188 parts of acrylonitrile-butadiene-styrene copolymer resin, and an extruder at 230 ° C. The mixture was dissolved and mixed to obtain pellets.
By using the pellets and injection-molding into a flat plate shape at 240 ° C., a phosphorescent layer 2 was obtained in which red was visually recognized in a bright place and light yellowish green was emitted in a dark place.
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.
Wet process fine particle silica [trade name: Nipseal E-220, manufactured by Nippon Silica Industry Co., Ltd.] 15 parts on the phosphorescent layer, urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc.] Solid content 30%] 45 parts, 40 parts of water, 0.5 part of silicone-based antifoaming agent, 3 parts of thickener for water-based ink, 1 part of ethylene glycol and 3 parts of blocked isocyanate-based crosslinking agent were mixed and stirred uniformly. Using the resulting white screen printing ink, the entire surface was solid-printed on a 100-mesh screen plate and dried and cured at 130 ° C. for 5 minutes to form the porous layer 3, thereby obtaining a phosphorescent water colorant 1.

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 red image by the phosphorescent layer is visually recognized, and the original white porous layer is visually recognized again by drying. The aspect change could be repeated.
In addition, in the phosphorescent water color change body, when an image is formed on the porous layer in a dark place, an image emitted by the lower phosphorescent layer emitting yellow-green light is visible, and the porous layer is dried. The emitted image is not visible. The aspect change could be repeated.
Further, even when the phosphorescent water color changing material 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)
50 parts of luminous pigment (average particle diameter: 2 to 40 μm, emission maximum wavelength 520 nm) having a luminescent color of yellow-green on blue synthetic paper as support 4, 40 parts of acrylate resin, silicone-based antifoaming agent The phosphorescent layer 2 was formed by solid printing using a phosphorescent ink in which 5 parts, 20 parts of butyl acetate and 15 parts of an aromatic medium boiling point solvent were uniformly dispersed.
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.
Wet process fine particle silica [trade name: Nipseal E-220, manufactured by Nippon Silica Industry Co., Ltd.] 15 parts on the phosphorescent layer, urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc.] Solid content 30%] 45 parts, 40 parts of water, 0.5 part of silicone-based antifoaming agent, 3 parts of thickener for water-based ink, 1 part of ethylene glycol and 3 parts of blocked isocyanate-based crosslinking agent were mixed and stirred uniformly. Using the resulting white screen printing ink, the entire surface was solid-printed on a 100-mesh screen plate and dried and cured at 130 ° C. for 5 minutes to form the porous layer 3, thereby obtaining a phosphorescent water colorant 1.

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 blue 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.
In addition, in the phosphorescent water color change body, when an image is formed on the porous layer in a dark place, an image emitted by the lower phosphorescent layer emitting yellow-green light is visible, and the porous layer is dried. The emitted image is not visible. The aspect change could be repeated.
Further, even when the phosphorescent water color changing material 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)
On white Tetron / cotton broad fabric (65/35, basis weight: 100 g / m ² ) as support 4, 2 parts of green pigment, 100 parts of acrylate resin emulsion (solid content: 45%), silicone Solid printing with 0.5 parts of foaming agent, 5 parts of thickener, 1.0 part of leveling agent and 5.0 parts of epoxy cross-linking agent uniformly dispersed and dried and cured at 130 ° C for 5 minutes Thus, a colored layer 5 was formed.
On the colored layer, 50 parts of a luminous pigment having an emission color of yellowish green (average particle size: 2 to 40 μm, emission maximum wavelength 520 nm), 100 parts of an acrylate resin emulsion (solid content: 45%), silicone-based extinction pigment Solid print using phosphorescent ink in which 0.5 parts of foaming agent, 5 parts of thickener, 1.0 part of leveling agent and 5.0 parts of epoxy crosslinking agent are uniformly dispersed, and dried and cured at 130 ° C. for 5 minutes. Thus, the phosphorescent layer 2 was formed.
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.
Next, 15 parts of wet process fine particle silica [trade name: Nipseal E-220, manufactured by Nippon Silica Industry Co., Ltd.] on the phosphorescent layer, urethane emulsion [trade name: Hydran AP-10, Dainippon Ink & Chemicals, Inc.] Manufactured, 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 thus formed, the entire surface was solid-printed with a 100-mesh screen plate and dried and cured at 130 ° C. for 5 minutes to form a porous layer 3, thereby obtaining a luminous water-colored product 1. .

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 green image due to the colored layer is visually recognized, and the original white porous layer is visually recognized again by drying. The aspect change could be repeated.
In addition, in the phosphorescent water color change body, when an image is formed on the porous layer in a dark place, an image emitted by the lower phosphorescent layer emitting yellow-green light is visible, and the porous layer is dried. The emitted image is not visible. The aspect change could be repeated.
Further, even when the phosphorescent water color changing material was immersed in water at 25 ° C. for 24 hours, the color changing function was maintained without impairing the light emission intensity.

Example 4
2 parts of blue pigment, 100 parts of acrylic ester resin emulsion (solid content: 45%), silicone antifoam on white Tetron / cotton broad fabric (65/35, basis weight: 100 g / m ² ) as support Solid printing using blue ink in which 0.5 part of agent, 5 parts of thickener, 1.0 part of leveling agent and 5.0 parts of epoxy crosslinking agent are uniformly dispersed, and dried and cured at 130 ° C. for 5 minutes. A colored layer was formed.
On the colored layer, 50 parts of a luminous pigment having an emission color of yellowish green (average particle size: 2 to 40 μm, emission maximum wavelength 520 nm), 100 parts of an acrylate resin emulsion (solid content: 45%), silicone-based extinction pigment Solid print using phosphorescent ink in which 0.5 parts of foaming agent, 5 parts of thickener, 1.0 part of leveling agent and 5.0 parts of epoxy crosslinking agent are uniformly dispersed, and dried and cured at 130 ° C. for 5 minutes. A phosphorescent layer was formed.
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.
Next, 15 parts of wet method fine particle silica [trade name: Nipseal E-220, manufactured by Nippon Silica Kogyo Co., Ltd.] on the phosphorescent layer, pink fluorescent pigment [trade name: Sinroihi Color SX-117, Sinroihi Co., Ltd.] ] 3 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, for water-based ink Using a white screen printing ink obtained by uniformly mixing and stirring 3 parts of a thickener, 1 part of ethylene glycol, and 3 parts of a blocked isocyanate-based crosslinking agent, the entire surface was solid-printed on a 100 mesh screen plate at 130 ° C. A porous layer was formed by drying and curing for 5 minutes to obtain a phosphorescent water discoloration body.

In the phosphorescent water discolored body, a light pink porous layer is visually recognized in a dry state (non-water absorbing state) in a bright place, and when water is attached using a brush impregnated with water, the porous layer is absorbed by liquid absorption. Becomes transparent, and a purple color in which the blue color of the colored layer and the pink color of the porous layer are mixed is visually recognized, and the original light pink porous layer is visually recognized again by drying. The aspect change could be repeated.
In addition, in the phosphorescent water color change body, when an image is formed on the porous layer in a dark place, an image emitted by the lower phosphorescent layer emitting yellow-green light is visible, and the porous layer is dried. The emitted image is not visible. The aspect change could be repeated.
Further, even when the phosphorescent water color changing material 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 synthetic paper (thickness 200 μm) 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, A solid layer was printed using a blue ink in which 1.0 part of a leveling agent and 2.0 parts of a crosslinking agent were uniformly dispersed, and dried and cured at 70 ° C. for 30 minutes to form a colored layer.
On the colored layer, 50 parts of a luminous pigment having an emission color of yellowish green (average particle size: 2 to 40 μm, emission maximum wavelength 520 nm), 100 parts of an acrylate resin emulsion (solid content: 45%), silicone-based extinction pigment Solid printing was performed using water-based phosphorescent ink in which 0.5 part of foaming agent, 5 parts of thickener, 1.0 part of leveling agent, and 5.0 parts of epoxy-based cross-linking agent were uniformly dispersed, and then at 70 ° C. for 30 minutes. A phosphorescent layer was formed by drying and curing.
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.
Next, 15 parts of wet process fine particle silica [trade name: Nipseal E-220, manufactured by Nippon Silica Industry Co., Ltd.] on the phosphorescent layer, urethane emulsion [trade name: Hydran AP-10, Dainippon Ink & Chemicals, Inc.] Manufactured, 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 thus formed, the entire surface was solid-printed on a 150-mesh screen plate and dried and cured at 130 ° C. for 5 minutes to form a porous layer, thereby obtaining a luminous water-colored product.

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 blue 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.
In addition, in the phosphorescent water color change body, when an image is formed on the porous layer in a dark place, an image emitted by the lower phosphorescent layer emitting yellow-green light is visible, and the porous layer is dried. The emitted image is not visible. The aspect change could be repeated.
Further, even when the phosphorescent water-colored material was immersed in 25 ° C. water at room temperature for 24 hours, the color-changing function was maintained without impairing the light emission intensity.

Example 6
A phosphorescent water discoloration was obtained in the same manner as in Example 5.
Next, a foamed urethane foam having an open cell (diameter: 200 mm) having a liquid composition for a discolored body in which 50 parts of polyethylene glycol (trade name: PEG6000, manufactured by Sanyo Chemical Industries, Ltd.) is uniformly dissolved in 50 parts of water is used as an absorbent material. , 5 mm thick) and housed in a circular container to produce a stamp stand.
The phosphorescent water color changing body and the stamp stand were combined to obtain a phosphorescent water color changing set.
When the infant's palm is pressed against the liquid absorbing material of the stamp table for about 10 seconds to uniformly adhere the liquid composition, the hand is pressed onto the porous layer of the phosphorescent water colorant for about 5 seconds. The layer became transparent by absorbing the liquid composition, and a blue handprint was collected by the lower non-discoloring layer, and the collected handprint image was retained even when water of the liquid composition for the color changing body evaporated.
The collected handprint could be removed by washing the discolored body with water, and after drying, the liquid composition was again attached to the hand and pressed onto the porous layer to collect the handprint.
In the dark place, the image of the collected handprint was emitted when the lower phosphorescent layer emitted yellow-green light.
The phosphorescent water discolorant formed with the hand shape maintained the same color density and shape as the initial state even when left for 3 months in an environment of 20 ° C., and was excellent in storage stability.

Comparative Example 1
Luminescent pigment of yellowish green color (SrAl ₂ O ₄ : Eu, Dy, average particle diameter: 2 to 60 μm, maximum emission wavelength of 520 nm) 10 parts, red pigment 2 parts, acrylonitrile-butadiene-styrene copolymer resin 188 parts Were kneaded and dissolved and mixed at 230 ° C. with an extruder to obtain pellets.
By using the pellets and injection-molding into a flat plate shape at 240 ° C., a phosphorescent layer was obtained in which red was visible in a bright place and light yellowish green was emitted in a dark place.
Wet process fine particle silica [trade name: Nipseal E-220, manufactured by Nippon Silica Industry Co., Ltd.] 15 parts on the phosphorescent layer, urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc.] Solid content 30%] 45 parts, 40 parts of water, 0.5 part of silicone-based antifoaming agent, 3 parts of thickener for water-based ink, 1 part of ethylene glycol and 3 parts of blocked isocyanate-based crosslinking agent were mixed and stirred uniformly. Using the white screen printing ink, the entire surface was solid-printed on a 100-mesh screen plate and dried and cured at 130 ° C. for 5 minutes to form a porous layer, thereby obtaining a luminous water-colored product.

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 red image by the phosphorescent layer is visually recognized, and the original white porous layer is visually recognized again by drying. The aspect change could be repeated.
In the state in which the phosphorescent water discolored body is dark and an image is formed on the porous layer, the lower phosphorescent layer emits yellow-green light, and the emitted light is visually recognized. As a result, the light emission intensity of the liquid crystal was lowered and it became difficult to emit light in a dark color, so that practicality could not be satisfied.

Comparative Example 2
50 parts of luminous pigment (SrAl ₂ O ₄ : Eu, Dy, average particle diameter: 2 to 40 μm, emission maximum wavelength 520 nm) having a luminescent color of yellow-green on blue synthetic paper as a support, 40 parts of acrylate resin A phosphorescent layer was formed by solid printing using a phosphorescent ink in which 0.5 part of a silicone-based antifoaming agent, 20 parts of butyl acetate and 15 parts of an aromatic medium boiling point solvent were uniformly dispersed.
Wet process fine particle silica [trade name: Nipseal E-220, manufactured by Nippon Silica Industry Co., Ltd.] 15 parts on the phosphorescent layer, urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc.] Solid content 30%] 45 parts, 40 parts of water, 0.5 part of silicone-based antifoaming agent, 3 parts of thickener for water-based ink, 1 part of ethylene glycol and 3 parts of blocked isocyanate-based crosslinking agent were mixed and stirred uniformly. Using the white screen printing ink, the entire surface was solid-printed on a 100-mesh screen plate and dried and cured at 130 ° C. for 5 minutes to form a porous layer, thereby obtaining a luminous water-colored product.

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 blue 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.
In the state in which the phosphorescent water discolored body is dark and an image is formed on the porous layer, the lower phosphorescent layer emits yellow-green light, and the emitted light is visually recognized. As a result, the light emission intensity of the liquid crystal was lowered and it became difficult to emit light in a dark color, so that practicality could not be satisfied.

DESCRIPTION OF SYMBOLS 1 Phosphorescent water discoloration body 2 Phosphorescent layer 3 Porous layer 4 Support body 5 Colored layer

Claims (5)

  A phosphorescent layer containing a phosphorescent pigment doped with a rare earth oxide in an alkaline earth metal oxide, a low refractive index pigment fixed in a dispersed state on a binder resin, and the transparency is different between a liquid absorbing state and a non-liquid absorbing state. A phosphorescent water colorant which is a phosphorescent pigment obtained by laminating a porous layer to be prepared, wherein the phosphorescent pigment is mixed with a phosphate or brought into contact with a phosphate solution and then heat-treated.   The phosphorescent water discoloration body according to claim 1, wherein a color pigment is contained in the phosphorescent layer.   The phosphorescent water discolorant according to claim 1, wherein the phosphorescent layer and the porous layer are laminated on a support.   The phosphorescent water discoloration body according to claim 3, wherein a colored layer containing a color pigment is provided between the support and the phosphorescent layer.   The phosphorescent water color changer according to any one of claims 1 to 4, comprising a coloring pigment in the porous layer.

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