JP6412792B2 - Glittering discolorant and glittering discolorant set using the same - Google Patents

Description

  The present invention relates to a glittering color changing body and a glittering color changing body set using the same. More specifically, the present invention relates to a glitter discolorant capable of producing a hologram image having excellent glitter and high contrast due to adhesion of a liquid such as water, and a glitter discolorant set using the same.

Conventionally, a water discoloration laminate in which a porous layer containing a low refractive index pigment is provided on a support having hologram properties, and the porous layer is made transparent by absorbing liquid to visually recognize the glitter of the hologram. A body is disclosed (see, for example, Patent Document 1).
Depending on the structure of the porous layer, it is difficult to develop a hologram image with high brightness, and the brightness value in the liquid-absorbing state and the non-liquid-absorbing state (dry state) of the porous layer was specified in order to solve this problem. A discolorable laminate having excellent luminance of a hologram image visually recognized in a liquid-absorbing state is disclosed (for example, see Patent Document 2).
However, even if the color-change laminate is excellent in the brightness of a hologram image that is visible when the porous layer is in a liquid-absorbing state, the effect is not sufficient, and the porous layer is in a non-liquid-absorbing state. It is difficult to visually recognize a clear hologram image because the contrast of the liquid absorption state is poor.
JP 2004-243656 A JP 2007-118198 A

  In the present invention, when the porous layer containing the low refractive index pigment is in a non-liquid-absorbing state, the color of the porous layer can be visually recognized, and the porous layer is wetted and transparent by application of water (liquid-absorbing state). Provides a bright chromatic image with high contrast and a contrast between the non-liquid-absorbing portion and the liquid-absorbing portion of the porous layer, and a set of brilliant colorants using the same. It is something to try.

The present invention is 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 on the surface of a holographic support having a reflective layer provided on a concavo-convex portion of a transparent substrate. A porous layer having different transparency is provided, the coating amount of the low refractive index pigment in the porous layer is 0.3 to 5.0 g / m ² , and the support having the hologram property is: comprising a colorant in a transparent substrate, or Ri support der having a colored layer containing a coloring agent is provided on the transparent substrate colored hologram of said porous layer is a non-liquid-absorbing The maximum concentration value (D1) measured with a Macbeth spectrophotometer in the state is 0.4 to 1.5, and the maximum concentration value (D2) in the liquid absorption state of the porous layer is 1.0 to 2.5. , and the bright discoloration difference between D1 and D2 (D2-D1) is characterized by 0.5 to 1.5 der Rukoto The body is a requirement.
Furthermore, prior Symbol support back surface be provided with a fabric, the is the thickness of the support is 25μm or less, the resin sheet to the rear surface of the support, waterproof paper, synthetic paper, a group selected from 25 g / m @ 2 or more paper The requirement is to provide materials.
Furthermore, a glittering discoloration body set comprising the glittering discoloration body and the water adhering tool is required.

  In the present invention, the color due to the porous layer is visually recognized in the non-liquid-absorbing state, and the hologram image in which the porous layer is visually recognized in the liquid-absorbing state by application of water or the like is excellent in luminance, and the non-liquid-absorbing porous layer A bright discoloration that has a high contrast with the liquid, satisfies the change between the non-absorbing state and the absorbing state, and has applicability to various fields such as the toy field, decoration field, and design field, and the like. It is possible to provide a glittering discoloration body set.

It is a longitudinal cross-sectional view of one Example of the luster discoloration body of this invention. It is a longitudinal cross-sectional view of the other Example of the glittering discoloration body of this invention.

The support having hologram properties can be exemplified by a relief type (embossed type) hologram in which a transparent reflection layer formed from a metal compound or the like is provided on a transparent hologram formation layer provided with a concavo-convex pattern on a substrate such as a transparent plastic. .
The holographic support is a transparent holographic support having transparency containing a colorant in a transparent base material, or a transparent layer provided with a colored layer on a transparent base material. It is a support having a colored hologram property.
Therefore, since the hologram having glitter is visually recognized through the colorant, it is visually recognized as a hologram having colored glitter.

The porous layer formed on the holographic support is a layer in which a low refractive index pigment is fixed in a dispersed state together with a binder resin.
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 shows good transparency when liquid such as water 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, since wet-process silicic acid has a coarser molecular structure than dry-process silicic acid, when wet-process silicic acid is applied to the porous layer, the diffused reflection of light in the dry state compared to systems using dry-process silicic acid It is presumed that the concealability in the normal state is increased.
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.
In addition, in order to adjust the concealability in the normal state of the porous layer and the transparency in the liquid absorption state, other low refractive index pigments can be used in combination with the wet method silicic acid.

The low refractive index pigment in the porous layer depends on properties such as particle diameter, specific surface area, oil absorption, etc., in order to satisfy both the concealability in the normal state and the transparency in the liquid absorption state, The coating amount is 0.3 to 5.0 g / m ² , preferably 0.5 to 4.0 g / m ² , and more preferably 0.5 to 3.0 g / m ² .
If it is less than 0.3 g / m ² , it is difficult to obtain sufficient concealability in a normal state, and if it exceeds 5.0 g / m ² , it becomes difficult to obtain sufficient transparency at the time of liquid absorption.
The low refractive index pigment is dispersed in a vehicle containing a binder resin as a binder, applied to a support, and then the volatile matter is dried to form a porous layer.
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 Each resin emulsion, casein, starch, cellulose derivative, polyvinyl alcohol, urea resin, phenol resin and the like can be mentioned.
The mixing ratio of the low refractive index pigment and these binder resins depends on the type and properties of the low refractive index pigment, but preferably the binder resin solid content is 0.5 to 1 part by mass with respect to 1 part by mass of the low refractive index pigment. 2.0 parts by mass, and more preferably 0.8 to 1.5 parts by mass. When the binder resin solid content is less than 0.5 parts by mass with respect to 1 part by mass of the low refractive index pigment, it is difficult to obtain a practical film strength of the porous layer, and 2.0 parts by mass If it exceeds, the contrast between the non-liquid absorbing state and the liquid absorbing state becomes poor.
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 in the present invention, an aqueous urethane-based resin, particularly a urethane-based emulsion resin or a colloidally dispersed urethane-based resin is preferable. Used for.
Although the said urethane type resin can also be used independently, another binder resin can also be used together as needed. 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 30% or more of the urethane resin in a solid mass ratio 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.
The coating amount of the porous layer is 1.0 to 30 g / m ² , preferably 2.0 to 10 g / m ² .
If it is less than 1 g / m ² , it is difficult to obtain sufficient concealability in a normal state, and if it exceeds 30 g / m ² , it becomes difficult to obtain sufficient transparency at the time of liquid absorption.
In the porous layer, various additives such as an antifoaming agent, a viscosity adjusting agent, a dispersing agent, a moisturizing agent, a wetting agent, a surfactant, a pH adjusting agent, a preservative, and a plasticizer are added as necessary. You can also

  The porous layer is a known means, for example, screen printing, offset printing, gravure printing, coater, tampo printing, transfer printing means, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller It can be formed by coating, dip coating or the like.

The porous layer has a maximum concentration value (D1) measured with a Macbeth spectrophotometer in a non-liquid-absorbing state of 0.4 to 1.5, and was measured with a Macbeth photometer in a liquid-absorbing state of the porous layer. The maximum concentration value (D2) is 1.0 to 2.5, and the difference (D2-D1) between the maximum concentration value (D2) in the liquid absorption state and the maximum concentration value (D1) in the non-liquid absorption state Is preferably 0.5 to 1.5.
This will be described in detail. When the reflection density of the porous layer in the non-liquid-absorbing state measured by a Macbeth spectrophotometer is less than 0.4, the concealability of the porous layer is too high. Due to the tendency, the brightness of the hologram in the liquid absorption state tends to be impaired, and if it exceeds 1.5, the concealment property of the porous layer tends to be too low, so the contrast between the non-liquid absorption state and the liquid absorption state is It becomes difficult to be expressed.
In addition, when the maximum density value (D2) measured by the Macbeth spectrophotometer for the reflection density in the liquid absorption state of the porous layer is less than 1.0, the color density is low, so the non-liquid absorption state and the liquid absorption state The upper limit of 2.5 is the highest concentration that can be measured with a Macbeth spectrophotometer.
Furthermore, the difference (D2−) between the maximum concentration value (D2) measured with the Macbeth spectrophotometer in the liquid absorption state of the porous layer and the maximum concentration value (D1) measured with the Macbeth photometer in the non-liquid absorption state. When the value of D1) is less than 1.0, the contrast between the non-liquid-absorbing state and the liquid-absorbing state is poor, and when it exceeds 1.5, the porous layer is sufficiently concealed in the non-liquid-absorbing state. The brightness of the hologram is poor.
Therefore, the maximum concentration value (D1) in the non-liquid-absorbing state is 0.4 to 1.5, the maximum concentration value (D2) in the liquid-absorbing state is 1.0 to 2.5, and D1 and D2 Satisfying that the difference (D2−D1) is 0.5 to 1.5 is concealing the glitter of the hologram in the non-liquid-absorbing state, and the image having an excellent hologram glitter in the liquid-absorbing state. Is an important requirement for imparting great variability between the non-liquid-absorbing state and the liquid-absorbing state, and an image having a sufficient density difference between the non-liquid-absorbing state and the liquid-absorbing state. It is.
The maximum density value measured with a Macbeth spectrophotometer is in accordance with DIN 16536, using a spectrophotometer manufactured by Gratag Macbeth (product name: Spectroeye D19C), with a black wavelength, a cyan wavelength, and a magenta color. The reflection density at each of the wavelength of yellow and the wavelength of yellow was measured, and the largest value was taken as the maximum density.

In addition, in a porous image, a general colored pigment may be added to color the porous image in a dry state, or a colored image may be provided on the porous layer to show a complicated change in appearance. it can.
The color material contained in the colored image is not limited to a color material containing a colorant such as a general-purpose dye or pigment, but reversible thermochromic property formed by a color material containing a reversible thermochromic material. It may be.

The back surface of the support can also be provided by sticking a fabric or sewing the periphery.
Examples of the fabric include a knitted fabric, a woven fabric, and a non-woven fabric, and preferably a woven fabric is used. Examples of the constituent fibers of the fabric include natural fibers such as cotton, hemp, and wool, polyamide-based, polyester-based, polyacrylonitrile-based synthetic fibers, acetate-based semi-synthetic fibers, and regenerated fibers such as rayon. The fabric having a basis weight of 10 to 500 g / m ² is preferably used.
If the weight per unit area is less than 10 g / m ² , the strength is poor, and if it exceeds 500 g / m ² , the thickness of the fabric becomes unnecessarily thick and the flexibility and workability are poor.
Further, when the support is made of a relatively thin material having a thickness of 25 μm or less, it is preferable to reinforce the support by providing a base material on the back surface of the support in order to form a clear image. Sheet, water-resistant paper, synthetic paper, and paper of 25 g / m ² or more.
Examples of the resin sheet include polyethylene, polypropylene, polyvinyl alcohol, polyethylene terephthalate, acrylonitrile-butadiene-styrene, acrylonitrile-styrene, polyamide, polyvinylidene chloride, polyacetal, polyvinyl chloride, polycarbonate, polyacryl, polystyrene, polycarbonate and polybutylene terephthalate. Or a resin such as a mixture of polycarbonate and acrylonitrile-butadiene-styrene, or a mixture of the above resins.
The resin sheet may be a sheet formed of a foamable resin.
As the water-resistant paper, a water-resistant base paper produced by adding an appropriate amount of a water-resistant agent such as a modified rosin emulsion to pulp, or a printing in which a water-resistant resin such as synthetic rubber or acrylic resin is coated on the surface of the water-resistant base paper. Water resistant paper is applied.
Examples of the synthetic paper include paper manufactured using a synthetic resin such as polyolefin resin or polystyrene resin as a main raw material.
The material of the paper is not particularly limited as long as it is 25 g / m ² or more.
In addition, it is preferable that the said base material is equipped with water resistance, and a resin sheet, water resistant paper, and synthetic paper are used suitably.

As means for adhering water to the glittering discolored body, a water adhering tool can also be applied in addition to direct immersion in water, wet hands and fingers with water, and contact.
Examples of the water adhering tool include a water gun, a sprayer, a writing or applicator having a brush tip or a fiber pen at the tip, a fiber body or a brush that contains water in the container and derives the water in the container A writing or applicator, a stamp, etc. provided with
As the water adhering tool, a writing tool or applicator using a plastic porous body or a fiber processed body having continuous pores as a pen tip member can easily form a writing image and can improve practicality.
The plastic porous body or fiber processed body having continuous pores in the above may be anything that absorbs and discharges water in an appropriate amount, and collects continuous pore bodies and fibers of general-purpose polyolefin-based, polyurethane-based and other various plastics. A brush-like material, a fiber-resin-processed or heat-bonded material, a felt, and a non-woven fabric can be used, and the shape and dimensions can be arbitrarily set according to the purpose.
In addition, a glitter color change body set can be configured by combining the water adhering tool and the glitter color change body.
In addition to water, the liquid to be attached to the glittering discolored body has a refractive index of 1.3 to 1.8 in the media described in JP-A-2005-15777 and JP-A-2014-193980. It is also possible to use a liquid composition for a color changing material in which the solid material is dissolved and / or dispersed.

Examples are shown below, but the present invention is not limited to the examples. In addition, the part in an Example shows a mass part.
Example 1 (see FIG. 1)
A blue pigment 2 having an average particle size of 0.03 μm as a colorant is formed on the surface of a holographic support 21 (reflection hologram sheet) having an aluminum vapor deposition layer formed on an embossed surface of a transparent polyethylene terephthalate sheet having a thickness of 12 μm. 180 mesh screen plate using blue screen printing ink prepared by mixing 0.0 part, 50 parts urethane resin emulsion, 0.5 part silicone antifoam, 3 parts aqueous thickener, and 44.5 parts water The support 2 having a colored hologram property was obtained by providing a blue colored layer 22 having a transparency by solid printing on the entire surface.
Next, a polyester taffeta fabric (weight per unit area: 70 g / m ² ) was stuck as a fabric 4 to the back surface of the support having colored hologram properties with an adhesive.
Furthermore, 10 parts of wet process silicic acid [trade name: Nipseal E-200A, manufactured by Nippon Silica Industry Co., Ltd.] on the colored layer, urethane emulsion [trade name: Hydran AP-20, manufactured by Dainippon Ink & Chemicals, Inc.] , Solid content 30%] 50 parts, water 30.5 parts, silicone-based antifoaming agent (solid content 100%) 0.5 parts, water-based ink thickener (solid content 40%) 3 parts, propylene glycol 1 part, Using a white screen printing ink obtained by mixing 5 parts of a carbodiimide-based crosslinking agent (solid content 40%), solid printing is performed on the entire surface with a 180-mesh screen plate to form a porous layer 3 and change the brightness. Body 1 was obtained.
The coating amount (dry weight) of the porous layer of the glitter discolorant was 12.5 g / m ² , and the coating amount of the wet method silicic acid as a low refractive index pigment was 4.4 g / m ^2. It was.
As a result of measuring the density of the porous layer in a non-liquid-absorbing state with a Macbeth spectrophotometer, the density of black wavelength (D _B ) = 0.47, the density of cyan wavelength (D _C ) = 0.64, magenta The wavelength density (D _M ) = 0.19, the yellow color wavelength density (D _Y ) = 0.19, and the maximum density (D1) in the non-liquid-absorbing state was 0.64. Moreover, as a result of measuring the density | concentration in the liquid absorption state of the said porous layer with a Macbeth spectrophotometer, the density | concentration of black wavelength (D _B ) = 0.63, the density of cyan wavelength (D _C ) = 1.26, magenta The color wavelength density (D _M ) = 0.27, the yellow color wavelength density (D _Y ) = 0.33, and the maximum density (D2) in the liquid absorption state was 1.26. The difference (D2-D1) between the maximum concentration value (D2) measured with the Macbeth spectrophotometer in the liquid absorption state and the maximum concentration value (D1) measured with the Macbeth photometer in the non-liquid absorption state was 0. 62.
When the glitter discolorant was in a dry state, a light blue porous layer was visually recognized on the entire surface, and the glitter of the hologram was not visually recognized.
When water is allowed to adhere from above the porous layer, the porous layer becomes transparent by absorbing liquid, and a hologram image having excellent blue glitter due to the underlying colored hologram support is visually recognized, and water adheres (absorbing liquid) ) And the non-adhered (non-liquid-absorbing) portion were excellent in contrast, so that a clear image could be visually recognized.
The hologram image having excellent blue glitter is maintained in the liquid-absorbing state, but the entire surface returned to a light blue state again by evaporation and drying of water.
The aspect change could be repeated.

Example 2
Preparation of glittering discoloration body set It has the glittering discoloration body obtained in Example 1, a bullet-shaped fiber pen body (made of nylon resin, diameter 7 mm) as a water attachment tool, and water is put into the shaft tube. A glittering discoloration body set was obtained by combining with a pen that could be accommodated.
When the glitter discolorant set is written on the porous layer of the glitter discolorant using a water adhering tool, a handwriting composed of a hologram image having a clear blue glitter having a width of 5 to 6 mm is formed.
Although the above-mentioned aspect was shown in the state where water was attached, the handwriting composed of the hologram image excellent in blue glitter was gradually faded as it dried, and returned to the original light blue again in the completely dried state.
The aspect change could be repeated.

Example 3
4. Blue pigment having an average particle size of 0.03 μm as a colorant on the surface of a hologram-supporting support (reflective hologram sheet) in which an aluminum vapor deposition layer is formed on the embossed surface of a transparent polyethylene terephthalate sheet having a thickness of 12 μm. 0 parts, urethane resin emulsion 50 parts, silicone antifoam 0.5 parts, leveling agent 1.0 parts, aqueous thickener 2.0 parts, water 10.0 parts, methanol 31.5 parts Using the mixed blue gravure printing ink, solid printing was performed on the entire surface with a 120 mesh gravure plate to provide a blue colored layer having transparency to obtain a support having colored hologram properties.
Furthermore, 15 parts wet-type silicic acid [trade name: Nipseal E-74P, manufactured by Nippon Silica Industry Co., Ltd.] on the colored layer, urethane emulsion [trade name: Permarin UA150, manufactured by Sanyo Chemical Industries, Ltd., solid content 30 %] 50 parts, water 9.5 parts, methanol 20.0 parts, silicone-based antifoaming agent (solid content 100%) 0.5 parts, water-based ink thickener (solid content 40%) 2.0 parts, carbodiimide Using a white screen printing ink obtained by mixing 3 parts of a system cross-linking agent (solid content 40%), a solid layer was printed twice on the entire surface with a 200 mesh gravure plate to form a porous layer.
Next, an adhesive made of a urethane resin is applied to the back surface of the support having the colored hologram property by a gravure printing machine, and 30d tricot (weight per unit area: 40 g / m ² ) made of nylon is adhered as a fabric to give the glitter. A discolored body was obtained.
The coating amount (dry weight) of the porous layer of the glitter discolorant was 4.0 g / m ² , and the coating amount of the wet method silicic acid as a low refractive index pigment was 1.9 g / m ^2. It was.
As a result of measuring the density of the porous layer in a non-liquid-absorbing state with a Macbeth spectrophotometer, the density of black wavelength (D _B ) = 0.54, the density of cyan wavelength (D _C ) = 0.73, magenta color The wavelength density (D _M ) = 0.37, the yellow color wavelength density (D _Y ) = 0.28, and the maximum density (D1) in the non-liquid-absorbing state was 0.73. Further, as a result of measuring the concentration of the porous layer in the liquid absorption state with a Macbeth spectrophotometer, the concentration of black wavelength (D _B ) = 1.18, the concentration of cyan wavelength (D _C ) = 1.94, magenta The color wavelength density (D _M ) = 0.82, the yellow color wavelength density (D _Y ) = 0.68, and the maximum density (D2) in the liquid absorption state was 1.94. The difference (D2−D1) between the maximum concentration value (D2) measured with the Macbeth spectrophotometer in the liquid absorption state and the maximum concentration value (D1) measured with the Macbeth photometer in the non-liquid absorption state is 1. .21.
When the glitter discolorant was in a dry state, a light blue porous layer was visually recognized on the entire surface, and the glitter of the hologram was not visually recognized.
When water is allowed to adhere from above the porous layer, the porous layer becomes transparent by absorbing liquid, and a hologram image having excellent blue glitter due to the underlying colored hologram support is visually recognized, and water adheres (absorbing liquid) ) And the non-adhered (non-liquid-absorbing) portion were excellent in contrast, so that a clear image could be visually recognized.
The hologram image having excellent blue glitter is maintained in the liquid-absorbing state, but the entire surface returned to a light blue state again by evaporation and drying of water.
The aspect change could be repeated.

Example 4
Production of a set of glittering discoloration body It has the glittering discoloration body obtained in Example 2, a bullet-type fiber pen body (made of nylon resin, diameter 7 mm) as a water attachment tool, and water is put into the shaft tube. A glittering discoloration body set was obtained by combining with a pen that could be accommodated.
When the glitter discolorant set is written on the porous layer of the glitter discolorant using a water adhering tool, a handwriting composed of a hologram image having a clear blue glitter having a width of 5 to 6 mm is formed.
Although the above-mentioned aspect was shown in the state where water was attached, the handwriting composed of the hologram image excellent in blue glitter was gradually faded as it dried, and returned to the original light blue again in the completely dried state.
The aspect change could be repeated.

Example 5
4. Blue pigment having an average particle size of 0.03 μm as a colorant on the surface of a hologram-supporting support (reflective hologram sheet) in which an aluminum vapor deposition layer is formed on the embossed surface of a transparent polyethylene terephthalate sheet having a thickness of 12 μm. 0 parts, urethane resin emulsion 50 parts, silicone antifoam 0.5 parts, leveling agent 1.0 parts, aqueous thickener 2.0 parts, water 10.0 parts, methanol 31.5 parts Using a blue gravure printing ink formed by mixing, a blue colored layer having transparency was formed by solid printing on the entire surface with a 120 mesh gravure plate to obtain a support having colored hologram properties.
Furthermore, 15 parts wet-type silicic acid [trade name: Nipseal E-74P, manufactured by Nippon Silica Industry Co., Ltd.] on the colored layer, urethane emulsion [trade name: Permarin UA150, manufactured by Sanyo Chemical Industries, Ltd., solid content 30 %] 50 parts, water 9.5 parts, methanol 20.0 parts, silicone-based antifoaming agent (solid content 100%) 0.5 parts, water-based ink thickener (solid content 40%) 2.0 parts, carbodiimide Using a white screen printing ink obtained by mixing 3 parts of a system cross-linking agent (solid content 40%), a solid layer was printed twice on a whole surface with a 150 mesh gravure plate to form a porous layer.
Next, an adhesive made of urethane resin is applied to the back surface of the support having the colored hologram property by a gravure printing machine, and a 40d tricot made of polyester (weight per unit area 60 g / m ² ) is adhered as a fabric to give the glitter. A discolored body was obtained.
The coating amount (dry weight) of the porous layer of the glitter discolorant was 5.5 g / m ² , and the coating amount of the wet method silicic acid which is a low refractive index pigment was 2.5 g / m ^2. It was.
As a result of measuring the concentration of the porous layer in the non-absorbing state with a Macbeth spectrophotometer, the concentration of black wavelength (D _B ) = 0.41, the concentration of cyan wavelength (D _C ) = 0.52, magenta The wavelength density (D _M ) = 0.29, the yellow color wavelength density (D _Y ) = 0.22, and the maximum density (D1) in the non-absorbing state was 0.52. Further, as a result of measuring the concentration of the porous layer in the liquid absorption state with a Macbeth spectrophotometer, the concentration of black wavelength (D _B ) = 1.23, the concentration of cyan wavelength (D _C ) = 1.99, magenta The color wavelength density (D _M ) = 0.86, the yellow color wavelength density (D _Y ) = 0.70, and the maximum density (D2) in the liquid absorption state was 1.99. The difference (D2−D1) between the maximum concentration value (D2) measured with the Macbeth spectrophotometer in the liquid absorption state and the maximum concentration value (D1) measured with the Macbeth photometer in the non-liquid absorption state is 1. 47.
When the glitter discolorant was in a dry state, a light blue porous layer was visually recognized on the entire surface, and the glitter of the hologram was not visually recognized.
When water is allowed to adhere from above the porous layer, the porous layer becomes transparent by absorbing liquid, and a hologram image having excellent blue glitter due to the underlying colored hologram support is visually recognized, and water adheres (absorbing liquid) ) And the non-adhered (non-liquid-absorbing) portion were excellent in contrast, so that a clear image could be visually recognized.
The hologram image having excellent blue glitter is maintained in the liquid-absorbing state, but the entire surface returned to a light blue state again by evaporation and drying of water.
The aspect change could be repeated.

Example 6
Production of a set of glittering discoloration bodies The glittering discoloration body obtained in Example 5 and a bullet-shaped fiber pen body (made of nylon resin, diameter 7 mm) as a water adhering tool, and water in the shaft tube. A glittering discoloration body set was obtained by combining with a pen that could be accommodated.
When the glitter discolorant set is written on the porous layer of the glitter discolorant using a water adhering tool, a handwriting composed of a hologram image having a clear blue glitter having a width of 5 to 6 mm is formed.
Although the above-mentioned aspect was shown in the state where water was attached, the handwriting composed of the hologram image excellent in blue glitter was gradually faded as it dried, and returned to the original light blue again in the completely dried state.

Example 7
A support having a hologram property in which an aluminum vapor deposition layer is formed on the embossed surface of a 25 μm thick transparent polyethylene terephthalate sheet as a support (reflective hologram sheet; a label type in which an adhesive layer is provided on the vapor deposition layer side and a release paper is bonded )) As a colorant, 3.0 parts of a red pigment having an average particle diameter of 0.05 μm, 50 parts of a urethane resin emulsion, 0.5 part of a silicone-based antifoaming agent, 3 parts of an aqueous thickener, water 44. Using a red screen printing ink prepared by mixing 0 parts, a solid support is provided on the entire surface with a 180 mesh screen plate to provide a transparent red colored layer to obtain a colored hologram support. It was.
Furthermore, 10 parts of wet process silicic acid [trade name: Nipseal E-200A, manufactured by Nippon Silica Industry Co., Ltd.] on the colored layer, urethane emulsion [trade name: Hydran AP-20, manufactured by Dainippon Ink & Chemicals, Inc.] , Solid content 30%] 50 parts, water 30.5 parts, silicone-based antifoaming agent (solid content 100%) 0.5 parts, water-based ink thickener (solid content 40%) 3 parts, propylene glycol 1 part, Using a white screen printing ink obtained by mixing 5 parts of a carbodiimide-based crosslinking agent (solid content: 40%), the entire surface was solid-printed with a 150 mesh screen plate to form a porous layer.
The coating amount (dry weight) of the porous layer of the glitter discolorant was 14.0 g / m ² , and the coating amount of the wet method silicic acid as a low refractive index pigment was 4.9 g / m ^2. It was.
As a result of measuring the concentration of the porous layer in the non-absorbing state with a Macbeth spectrophotometer, the concentration of black wavelength (D _B ) = 0.31, the concentration of cyan wavelength (D _C ) = 0.13, magenta The wavelength density (D _M ) = 0.46, the yellow wavelength density (D _Y ) = 0.17, and the maximum density (D1) in the non-liquid-absorbing state was 0.46. Further, as a result of measuring the concentration of the porous layer in the liquid absorption state with a Macbeth spectrophotometer, the concentration of black wavelength (D _B ) = 0.91, the concentration of cyan wavelength (D _C ) = 0, 49, magenta The color wavelength density (D _M ) = 1.89, the yellow color wavelength density (D _Y ) = 0.78, and the maximum density (D2) in the liquid absorption state was 1.89. The difference (D2−D1) between the maximum concentration value (D2) measured with the Macbeth spectrophotometer in the liquid absorption state and the maximum concentration value (D1) measured with the Macbeth photometer in the non-liquid absorption state is 1. 43.
When the glitter discolorant was in a dry state, a light red porous layer was observed on the entire surface, and the glitter of the hologram was not visually recognized.
When water is attached from above the porous layer, the porous layer becomes transparent by liquid absorption, and a hologram image excellent in red glitter due to the support having a colored hologram property in the lower layer is visually recognized, and water adheres (liquid absorption) ) And the non-adhered (non-liquid-absorbing) portion were excellent in contrast, so that a clear image could be visually recognized.
The hologram image excellent in red glitter is maintained in the liquid absorption state, but the entire surface returned to a light red state again by evaporation and drying of water.
The aspect change could be repeated.

Example 8
Production of a set of glittering discoloration bodies The glittering discoloration body obtained in Example 7 and a bullet-shaped fiber pen body (made of nylon resin, diameter 7 mm) as a water adhering tool, and water in the shaft tube. A glittering discoloration body set was obtained by combining with a pen that could be accommodated.
When the glitter color changing body set is written on the porous layer of the glitter color changing object using a water adhering tool, a handwriting composed of a hologram image having a clear red glitter having a width of 5 to 6 mm is formed.
Although the above-mentioned aspect was shown in a state where water was attached, the handwriting consisting of a hologram image excellent in red glitter was gradually faded as it dried, and returned to the original light red again in a completely dry state.

Example 9 (see FIG. 2)
A blue pigment 2 having an average particle size of 0.03 μm as a colorant is formed on the surface of a holographic support 21 (reflection hologram sheet) having an aluminum vapor deposition layer formed on an embossed surface of a transparent polyethylene terephthalate sheet having a thickness of 12 μm. 180 mesh screen plate using blue screen printing ink prepared by mixing 0.0 part, 50 parts urethane resin emulsion, 0.5 part silicone antifoam, 3 parts aqueous thickener, and 44.5 parts water The support 2 having a colored hologram property was obtained by providing a blue colored layer 22 having a transparency by solid printing on the entire surface.
Next, 10 parts of wet method silicic acid [trade name: Nipseal E-200A, manufactured by Nippon Silica Industry Co., Ltd.] on the colored layer, urethane emulsion [trade name: Hydran AP-20, manufactured by Dainippon Ink & Chemicals, Inc.] , Solid content 30%] 50 parts, water 30.5 parts, silicone-based antifoaming agent (solid content 100%) 0.5 parts, water-based ink thickener (solid content 40%) 3 parts, propylene glycol 1 part, Using a white screen printing ink obtained by mixing 5 parts of a carbodiimide-based crosslinking agent (solid content: 40%), a solid layer is printed on the entire surface with a 180 mesh screen plate to form the porous layer 3. A polypropylene resin sheet having a thickness of 3 mm was pasted on the back surface as a base material 5 with an adhesive to obtain a glittering discolored body 1.
The coating amount (dry weight) of the porous layer of the glitter discolorant was 12.5 g / m ² , and the coating amount of the wet method silicic acid as a low refractive index pigment was 4.4 g / m ^2. It was.
As a result of measuring the density of the porous layer in a non-liquid-absorbing state with a Macbeth spectrophotometer, the density of black wavelength (D _B ) = 0.47, the density of cyan wavelength (D _C ) = 0.64, magenta The wavelength density (D _M ) = 0.19, the yellow color wavelength density (D _Y ) = 0.19, and the maximum density (D1) in the non-liquid-absorbing state was 0.64. Moreover, as a result of measuring the density | concentration in the liquid absorption state of the said porous layer with a Macbeth spectrophotometer, the density | concentration of black wavelength (D _B ) = 0.63, the density of cyan wavelength (D _C ) = 1.26, magenta The color wavelength density (D _M ) = 0.27, the yellow color wavelength density (D _Y ) = 0.33, and the maximum density (D2) in the liquid absorption state was 1.26. The difference (D2-D1) between the maximum concentration value (D2) measured with the Macbeth spectrophotometer in the liquid absorption state and the maximum concentration value (D1) measured with the Macbeth photometer in the non-liquid absorption state was 0. 62.
When the glitter discolorant was in a dry state, a light blue porous layer was visually recognized on the entire surface, and the glitter of the hologram was not visually recognized.
When water was attached from above the porous layer using a brush containing water in the brush ear, the porous layer was made transparent by absorbing liquid and excellent in blue glitter due to the support having a colored hologram property of the lower layer Since the hologram image was visually recognized and the contrast between the place where water adhered (liquid absorption) and the area where water did not adhere (non-liquid absorption) was excellent, a clear image could be visually recognized.
The hologram image having excellent blue glitter is maintained in the liquid-absorbing state, but the entire surface returned to a light blue state again by evaporation and drying of water.
The aspect change could be repeated.

Example 10
Preparation of Glittering Color Changer Set A glittering color changer set obtained in Example 9 was combined with a brush as a water attachment tool to obtain a glittering color changer set.
When the glitter discolorant set is written on the porous layer of the glitter discolorant using a water adhering tool, a handwriting composed of a clear hologram image having excellent blue glitter is formed.
Although the above-described aspect was exhibited in a state where water was adhered, the handwriting composed of a hologram image excellent in red glitter was gradually faded as it dried, and returned to the original light blue again in a completely dry state.

Example 11
A support having a hologram property in which an aluminum vapor deposition layer is formed on the embossed surface of a 25 μm thick transparent polyethylene terephthalate sheet as a support (reflective hologram sheet; a label type in which an adhesive layer is provided on the vapor deposition layer side and a release paper is bonded )) As a colorant, 3.0 parts of a red pigment having an average particle diameter of 0.05 μm, 50 parts of a urethane resin emulsion, 0.5 part of a silicone-based antifoaming agent, 3 parts of an aqueous thickener, water 44. Using a red screen printing ink prepared by mixing 0 parts, a solid support is provided on the entire surface with a 180 mesh screen plate to provide a transparent red colored layer to obtain a colored hologram support. It was.
Next, a white water-resistant paper having a thickness of 0.5 mm was attached to the back surface of the support having colored hologram properties with an adhesive.
Furthermore, 10 parts of wet process silicic acid [trade name: Nipseal E-200A, manufactured by Nippon Silica Industry Co., Ltd.] on the colored layer, urethane emulsion [trade name: Hydran AP-20, manufactured by Dainippon Ink & Chemicals, Inc.] , Solid content 30%] 50 parts, water 30.5 parts, silicone-based antifoaming agent (solid content 100%) 0.5 parts, water-based ink thickener (solid content 40%) 3 parts, propylene glycol 1 part, Using a white screen printing ink obtained by mixing 5 parts of a carbodiimide-based crosslinking agent (solid content: 40%), the entire surface was solid-printed with a 150 mesh screen plate to form a porous layer.
The coating amount (dry weight) of the porous layer of the glitter discolorant was 14.0 g / m ² , and the coating amount of the wet method silicic acid as a low refractive index pigment was 4.9 g / m ^2. It was.
As a result of measuring the concentration of the porous layer in the non-absorbing state with a Macbeth spectrophotometer, the concentration of black wavelength (D _B ) = 0.31, the concentration of cyan wavelength (D _C ) = 0.13, magenta The wavelength density (D _M ) = 0.46, the yellow wavelength density (D _Y ) = 0.17, and the maximum density (D1) in the non-liquid-absorbing state was 0.46. Further, as a result of measuring the concentration of the porous layer in the liquid absorption state with a Macbeth spectrophotometer, the concentration of black wavelength (D _B ) = 0.91, the concentration of cyan wavelength (D _C ) = 0, 49, magenta The color wavelength density (D _M ) = 1.89, the yellow color wavelength density (D _Y ) = 0.78, and the maximum density (D2) in the liquid absorption state was 1.89. The difference (D2−D1) between the maximum concentration value (D2) measured with the Macbeth spectrophotometer in the liquid absorption state and the maximum concentration value (D1) measured with the Macbeth photometer in the non-liquid absorption state is 1. 43.
When the glitter discolorant was in a dry state, a light red porous layer was observed on the entire surface, and the glitter of the hologram was not visually recognized.
When water attached to the palm is attached from above the porous layer, the porous layer becomes transparent by absorbing liquid, and a hologram image (handprint) excellent in red glitter due to a support having colored hologram properties in the lower layer is visually recognized. Since the contrast between the place where water adhered (liquid absorption) and the area where water did not adhere (non-liquid absorption) was excellent, a clear image could be visually recognized.
The hologram image excellent in red glitter is maintained in the liquid absorption state, but the entire surface returned to a light red state again by evaporation and drying of water.
The aspect change could be repeated.

Example 12
For the color change body comprising 40 parts of polyethylene glycol (manufactured by Sanyo Chemical Co., Ltd., trade name: PEG # 6000P), 20 parts of ethylene glycol, and 20 parts of water from the porous layer of the glitter color change obtained in Example 11. When the liquid composition is attached to the palm and adhered, the porous layer is made transparent by absorbing liquid, and a hologram image (handprint) excellent in red glitter due to the support having a colored hologram property in the lower layer is visually recognized, and the liquid composition A clear image could be visually recognized because of the excellent contrast between the spot where the liquid adheres (absorbs liquid) and the part where it does not adhere (non-liquid absorption).
The glitter discoloration body on which the bill was formed was allowed to stand for 3 months in an environment at 20 ° C., but maintained the same glitter and shape as in the initial stage and was excellent in storage stability.
Further, since the solid matter contained in the liquid composition for a color changing body is soluble in water, the liquid composition adhering to the hand of the infant can be easily washed off with water when collecting the bill, and the bill Even in the case of failure in sampling, it is possible to completely remove the handprint by washing the glittering discolored body with water, and satisfy the repeated practical use that can form a bill on the glittering discolored body using the liquid composition again. It was something to be made.

Example 13
4. Blue pigment having an average particle size of 0.03 μm as a colorant on the surface of a hologram-supporting support (reflective hologram sheet) in which an aluminum vapor deposition layer is formed on the embossed surface of a transparent polyethylene terephthalate sheet having a thickness of 12 μm. 0 parts, urethane resin emulsion 50 parts, silicone antifoam 0.5 parts, leveling agent 1.0 parts, aqueous thickener 2.0 parts, water 10.0 parts, methanol 31.5 parts Using a blue gravure printing ink obtained by mixing, a blue colored layer having transparency was formed by solid printing on the entire surface with a 120 mesh gravure plate to obtain a support having colored hologram properties.
Next, 15 parts wet type silicic acid [trade name: Nipseal E-74P, manufactured by Nippon Silica Industry Co., Ltd.], urethane emulsion [trade name: Permarin UA150, manufactured by Sanyo Chemical Industries, Ltd., solid content 30 on the colored layer. %] 50 parts, water 9.5 parts, methanol 20.0 parts, silicone-based antifoaming agent (solid content 100%) 0.5 parts, water-based ink thickener (solid content 40%) 2.0 parts, carbodiimide Using a white screen printing ink obtained by mixing 3 parts of a system cross-linking agent (solid content 40%), a solid layer was printed twice on a whole surface with a 150 mesh gravure plate to form a porous layer.
Furthermore, a white synthetic paper having a thickness of 200 μm was stuck as a base material to the back surface of the support having colored hologram properties with an isocyanate-based adhesive to obtain a glittering discolored body.
The coating amount (dry weight) of the porous layer of the glitter discolorant was 5.5 g / m ² , and the coating amount of the wet method silicic acid which is a low refractive index pigment was 2.5 g / m ^2. It was.
As a result of measuring the concentration of the porous layer in the non-absorbing state with a Macbeth spectrophotometer, the concentration of black wavelength (D _B ) = 0.41, the concentration of cyan wavelength (D _C ) = 0.52, magenta The wavelength density (D _M ) = 0.29, the yellow color wavelength density (D _Y ) = 0.22, and the maximum density (D1) in the non-absorbing state was 0.52. Further, as a result of measuring the concentration of the porous layer in the liquid absorption state with a Macbeth spectrophotometer, the concentration of black wavelength (D _B ) = 1.23, the concentration of cyan wavelength (D _C ) = 1.99, magenta The color wavelength density (D _M ) = 0.86, the yellow color wavelength density (D _Y ) = 0.70, and the maximum density (D2) in the liquid absorption state was 1.99. The difference (D2−D1) between the maximum concentration value (D2) measured with the Macbeth spectrophotometer in the liquid absorption state and the maximum concentration value (D1) measured with the Macbeth photometer in the non-liquid absorption state is 1. 47.
When the glitter discolorant was in a dry state, a light blue porous layer was visually recognized on the entire surface, and the glitter of the hologram was not visually recognized.
When water is allowed to adhere from above the porous layer, the porous layer becomes transparent by absorbing liquid, and a hologram image having excellent blue glitter due to the underlying colored hologram support is visually recognized, and water adheres (absorbing liquid) ) And the non-adhered (non-liquid-absorbing) portion were excellent in contrast, so that a clear image could be visually recognized.
The hologram image having excellent blue glitter is maintained in the liquid-absorbing state, but the entire surface returned to a light blue state again by evaporation and drying of water.
The aspect change could be repeated.

Example 14
For the color change body comprising 40 parts of polyethylene glycol (manufactured by Sanyo Chemical Co., Ltd., trade name: PEG # 6000P), 20 parts of ethylene glycol, and 20 parts of water from the porous layer of the bright color change obtained in Example 13. When the liquid composition is attached to the palm and attached, the porous layer is made transparent by absorbing the liquid, and a hologram image (handprint) excellent in blue glitter due to the support having a colored hologram property in the lower layer is visually recognized. A clear image could be visually recognized because of the excellent contrast between the spot where the liquid adheres (absorbs liquid) and the part where it does not adhere (non-liquid absorption).
The glitter discoloration body on which the bill was formed was allowed to stand for 3 months in an environment at 20 ° C., but maintained the same glitter and shape as in the initial stage and was excellent in storage stability.
Further, since the solid matter contained in the liquid composition for a color changing body is soluble in water, the liquid composition adhering to the hand of the infant can be easily washed off with water when collecting the bill, and the bill Even in the case of failure in sampling, it is possible to completely remove the handprint by washing the glittering discolored body with water, and satisfy the repeated practical use that can form a bill on the glittering discolored body using the liquid composition again. It was something to be made.

Comparative Example 1
Wet silica (trade name: NIPSEAL E-200A, Nippon Silica Kogyo Co., Ltd.) on the surface of a holographic support (reflection hologram sheet) in which an aluminum vapor deposition layer is formed on the embossed surface of a 12 μm thick transparent polyethylene terephthalate sheet. 15 parts, urethane emulsion [trade name: Hydran AP-20, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30%] 50 parts, water 25.5 parts, silicone antifoam (solid) White screen printing ink prepared by mixing 0.5 part of 100%), 3 parts of water-based ink thickener (solid content 40%), 1 part of propylene glycol, and 5 parts of carbodiimide-based crosslinking agent (solid content 40%). Was used to form a porous layer by solid printing on the entire surface with a 180 mesh screen plate.
Subsequently, a polyester taffeta fabric (weight per unit area: 70 g / m ² ) was adhered as a fabric to the back surface of the support having hologram properties with an adhesive to obtain a discolored body.
The coating amount (dry weight) of the porous layer of the discolored body was 12.5 g / m ² , and the coating amount of the wet method silicic acid as a low refractive index pigment was 4.4 g / m ² .
As a result of measuring the concentration of the porous layer in a non-absorbing state with a Macbeth spectrophotometer, the concentration of black wavelength (D _B ) = 0.05, the concentration of cyan wavelength (D _C ) = 0.07, magenta color The concentration of wavelength (D _M ) = 0.05, the concentration of yellow wavelength (D _Y ) = 0.01, and the maximum concentration (D1) in the non-liquid-absorbing state was 0.07. Moreover, as a result of measuring the density | concentration in the liquid absorption state of the said porous layer with a Macbeth spectrophotometer, the density | concentration (D _B ) = 0.13 of black wavelength, the density (D _C ) of cyan wavelength = 0.15, magenta The color wavelength density (D _M ) = 0.14, the yellow color wavelength density (D _Y ) = 0.11, and the maximum density (D2) in the liquid absorption state was 0.15. The difference (D2-D1) between the maximum concentration value (D2) measured with the Macbeth spectrophotometer in the liquid absorption state and the maximum concentration value (D1) measured with the Macbeth photometer in the non-liquid absorption state was 0. 08.
In the discolored body, a white porous layer was visually recognized in the dry state, and the glitter of the hologram was not visually recognized.
When water is attached from above the porous layer, the porous layer becomes transparent by liquid absorption and a hologram image by a support having a lower holographic property is visible, but it adheres to the place where water adheres (liquid absorption). Since the contrast with the non-absorbed (non-liquid-absorbing) portion was poor, a clear image could not be visually recognized.
The image maintained its state in the liquid absorption state, but the entire surface returned to the white state again as the water evaporated and dried.
The aspect change could be repeated.

Comparative Example 2
Production of color changing body set The color changing body obtained in Comparative Example 1 and a bullet-type fiber pen body (made of nylon resin, 7 mm in diameter) as a water adhering tool and configured to accommodate water in the shaft tube The discolored body set was obtained by combining with the pen.
In the discolored body set, although a handwriting having a width of 5 to 6 mm is visually recognized when writing on the porous layer of the discolored body using a water adhering tool, it does not adhere to the place where water adheres (absorbs) (non-absorbing). Since the contrast with the (liquid) part was poor, clear handwriting could not be visually recognized.
The above-mentioned aspect was shown in a state where water was adhered, but the handwriting gradually faded as it dried, and returned to the original white color again in a completely dry state.

DESCRIPTION OF SYMBOLS 1 Glossy color change body 2 Support body which has colored hologram property 21 Support body which has hologram property 22 Colored layer 3 Porous layer 4 Fabric 5 Base material

Claims (5)

Transparency differs between liquid-absorbing state and non-liquid-absorbing state, in which a low refractive index pigment is fixed in a dispersed state in a binder resin on the surface of a holographic support provided with a reflective layer on the uneven portion of a transparent substrate. A porous layer is provided, and the coating amount of the low refractive index pigment in the porous layer is 0.3 to 5.0 g / m ² , and the holographic support is a transparent substrate. comprising a colorant in, or Ri support der having a colored hologram of having a colored layer containing a coloring agent on a transparent substrate, Macbeth spectral wherein the porous layer is in a non-liquid absorbing state The maximum concentration value (D1) measured with a photometer is 0.4 to 1.5, the maximum concentration value (D2) when the porous layer is in a liquid absorption state is 1.0 to 2.5, and D1 If the difference between D2 (D2-D1) is bright metachromatic member, wherein 0.5-1.5 der Rukoto. The glitter discoloration body according to claim 1, wherein a cloth is provided on the back surface of the support. The support has a thickness of 25 μm or less, and a resin sheet, water-resistant paper, synthetic paper, 25 g / m on the back surface of the support. ² The glitter discolorant according to claim 1, wherein a substrate selected from the above paper is provided. A glitter discolorant set comprising the glitter discolorant according to any one of claims 1 to 3 and a water adhering tool. The glittering discoloration body set according to claim 4, wherein the water adhering tool is selected from any one of a writing tool or an applicator form in which a plastic porous body or a fiber processed body having continuous pores is applied as a nib member, or a stamp tool. .

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