JP2016221854A - Brilliant discoloration body and brilliant discoloration body set using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a brilliant discoloration body capable of visibly recognizing a color produced by a porous layer when the porous layer is in a liquid non-absorption state and capable of visibly recognizing an image having high brightness when the porous layer is in a liquid absorption state by application of water or the like and to provide a brilliant discoloration body set using the brilliant discoloration body.SOLUTION: The brilliant discoloration body 1 comprises a porous layer 3 which is formed on the surface of a support 2 having brilliance by fixing a low refractive index pigment to a binder resin in a dispersed state and which has difference in transparency between a liquid absorption state and a liquid non-absorption state. The coating amount of the low refractive index pigment in the porous layer is 0.5 to 5.0 g/mand the porous layer in a liquid non-absorption state has a specular glossiness of 10 or less as measured at a measurement angle of 20° by a specular glossmeter and the porous layer in a liquid absorption state has specular glossiness of 80 or more as measured at a measurement angle of 20°. The brilliant discoloration body set comprises the brilliant discoloration body and a water application tool.SELECTED DRAWING: Figure 1

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 displaying an image excellent in glitter due to adhesion of a liquid such as water, and a glitter discolorant set using the same.

Conventionally, a water-discoloring property in which a porous layer containing a low-refractive index pigment is provided on a support having glitter and the liquid is made transparent by absorbing liquid into the porous layer so that an image having glitter can be visually recognized. A laminate is disclosed (see, for example, Patent Document 1).
Depending on the structure of the porous layer, it is difficult to produce a high-brightness image. To solve this problem, the porous layer has a light absorption value in which the lightness value is specified in a liquid-absorbing state and a non-liquid-absorbing state (dry state). A discolorable laminate in which a hologram image with high brightness is visually recognized in a liquid state is disclosed (for example, see Patent Document 2).
However, the discolorable laminate is not sufficiently effective even when the brightness of the hologram image that is visible when the porous layer is in a liquid-absorbing state is high, 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). Is intended to provide a glittering color changing body capable of clearly viewing an image having a high luminance and a glittering color changing object set using the same.

In the present invention, a porous layer having a low refractive index pigment fixed to a binder resin in a dispersed state and having a different transparency in a liquid absorbing state and a non-liquid absorbing state is provided on the surface of the support having glitter. The coating amount of the low refractive index pigment in the porous layer is 0.5 to 5.0 g / m ² , and the specular gloss at a measurement angle of 20 ° with a specular gloss meter when the porous layer is in a non-liquid-absorbing state. A requirement is a glitter discolorant having a degree of 10 or less and a specular gloss at a measurement angle of 20 ° in a liquid absorption state of 80 or more.
Further, when the porous layer is in a non-liquid-absorbing state, the specular gloss at a measurement angle of 20 ° with a specular gloss meter is 5 or less, and in the liquid absorption state, the specular gloss at a measurement angle of 20 ° with a specular gloss meter is It is 90 or more, the support having the glitter has optical properties selected from metallic luster, pearl luster, iris, hologram, light interference, and retroreflective, on the back of the support It is necessary to provide a substrate selected from fabric, resin sheet, water-resistant paper, synthetic paper, paper of 25 g / m ² or more, and the like.
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 a non-liquid-absorbing state, and a bright image is visually recognized in the liquid-absorbing state of the porous layer by application of water or the like. Can be provided, and a glittering discolorant having applicability to various fields such as the toy field, decoration field, and design field, and a glittering colorant set using the same.

It is a longitudinal cross-sectional view of one Example of the luster change color body of this invention.

As the support having glitter, a support having optical properties such as metallic luster, pearl luster, iris, hologram, light interference, and retroreflectivity is used.
Specifically, as a metallic glossy support, one or both sides of a film laminated with a metal thin film layer such as aluminum, chromium, silver, copper, etc., fine aluminum, copper, brass, gold, transparent resin solution, Examples thereof include metal powders such as silver and nickel, and metal foils such as gold foil and silver foil, which are appropriately coated on a base material together with a binder by plastic deposition powder obtained by metal deposition on a polyester resin, phenol resin or vinyl chloride resin by a conventional method. .
As the pearlescent support, pearlescent pigments (for example, natural mica, synthetic mica, glass pieces, and gold, silver, metallic red, metallic blue, metallic green, metallic coated with a metal oxide such as titanium oxide on the surface of alumina) Violet and other metallic colors) are suitably applied on a substrate together with a binder.
The iris support is a transparent metal compound having a refractive index of 0.05 or more different from that of the base material (for example, titanium oxide, silicon oxide, zinc oxide, cadmium sulfide, magnesium fluoride, fluorine fluoride). A thin film layer of cerium phosphide, etc., and laminated with an uneven transparent resin layer having a refractive index difference of 0.05 or more in that order, and a multilayer of transparent plastic thin films with different refractive indexes Can be illustrated.
As the holographic support, a light reflecting layer is provided on at least one surface of a fine uneven pattern, and is formed from a metal compound or the like on a transparent hologram forming layer provided with an uneven pattern on a substrate such as a transparent plastic. A relief type (embossed type) hologram provided with a transparent reflective layer is exemplified.
Examples of the light-interfering support may include a metallic mirror-finished substrate surface coated with a transparent film having a thickness that is thin enough to cause light interference with a colored or colorless paint.
Examples of the retroreflective support include those in which a single layer of high refractive index glass beads is provided on a light reflecting layer.

The porous layer formed on the glittering 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 salt include aluminum silicate, aluminum potassium silicate, sodium aluminum silicate, aluminum calcium silicate, potassium silicate, calcium silicate, sodium calcium silicate, sodium silicate, magnesium silicate, and potassium magnesium 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 0.5 to 5.0 g / m ² , preferably 0.7 to 4.0 g / m ² , and more preferably 1.0 to 3.0 g / m ² .
If it is less than 0.5 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 during 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 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.

When the porous layer has a specular gloss of 10 at a measurement angle of 20 ° with a specular gloss meter in a non-absorbing state, preferably 5 or less, more preferably 3 or less, the glitter due to the support is visually recognized. The color due to the porous layer is visually recognized, and the specular gloss at the measurement angle of 20 ° in the liquid absorption state is 80 or more, preferably 90 or more, more preferably 100 or more, so that the glitter by the support is obtained. Is clearly visible.
When the specular glossiness at a measurement angle of 20 ° with a specular gloss meter in a non-liquid-absorbing state exceeds 10, the glittering property of the support is easily recognized, so that a change between the non-liquid-absorbing state and the liquid-absorbing state is given. It becomes difficult to do.
If the specular gloss at a measurement angle of 20 ° in the liquid absorption state is less than 80, the glitter due to the support becomes insufficient, and it becomes difficult to impart changeability between the non-liquid absorption state and the liquid absorption state.
The specular gloss is a numerical value of the specular gloss of the surface, and is defined as a visual perception attribute defined by the intensity of the surface reflected light in JIS Z8741, and is a glass plate having a refractive index of 1.567. The glossiness of the surface (4.9% at an incident angle of 20 °, 10% at 60 °) is defined as 100 (%).

In addition, in the porous layer, a general colorant may be added to color the porous layer in a dry state, or a colored image may be provided on the porous layer to show a complicated aspect change. it can.
The colorant contained in the porous layer or the colored image is not limited to colors such as general-purpose dyes and pigments, and may be a reversible thermochromic material formed of a color material including a reversible thermochromic material. Good.

It can also be provided on the back surface of the support by sticking a fabric as a base material 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 of 25 μm or less, a resin sheet, water-resistant paper, synthetic paper, or paper of 25 g / m ² or more is selected on the back surface of the support to form a clear image. It is preferable to provide a substrate.
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.
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.
As the liquid to be adhered to the glittering discoloration body, in addition to water, a solid having a refractive index of 1.3 to 1.8 in a medium 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 a product 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)
As a support 2 having glitter, a wet-process silicic acid [trade name: NIPSEAL E-74P, Nippon Silica] Kogyo Co., Ltd.] 12 parts, urethane emulsion [trade name: Permarin UA150, manufactured by Sanyo Chemical Industries, solid content 30%] 50 parts, water 32.5 parts, silicone-based antifoaming agent (solid content 100% ) Using a white screen printing ink prepared by mixing 0.5 parts, 2.0 parts of a water-based ink thickener (solid content 40%) and 3 parts of a carbodiimide crosslinking agent (solid content 40%), 180 mesh A porous layer 3 is formed by solid printing with a screen plate of, and further, a polyester taffeta fabric (weight per unit area: 70 g / m ² ) is used as a fabric 4 on the back surface of the support. The glossy discoloration body 1 was obtained by sticking using.
The coating amount (dry weight) of the porous layer of the glitter discolorant was 10.0 g / m ² , and the coating amount of the wet method silicic acid as a low refractive index pigment was 3.7 g / m ^2. It was.
The specular gloss in the non-absorbing state of the porous layer was measured with a specular gloss meter (manufactured by Horiba, Ltd., IG-331) at a measurement angle of 20 °. As a result of measuring the specular gloss at a measurement angle of 20 ° with a specular gloss meter, it was 110.
When the glitter discolorant was in a dry state, a white porous layer was visually recognized on the entire surface, and the glitter due to the support was not visually recognized.
When water is attached from above the porous layer, the porous layer becomes transparent by liquid absorption, and a silver metallic gloss image with excellent glitter by the lower layer support is visually recognized, and water is attached (liquid absorption) and Since the contrast with the non-adhered (non-liquid-absorbing) portion was excellent, a clear image could be visually recognized.
The silver metallic gloss image maintained its state in the liquid absorption state, but the entire surface returned to the white state again by evaporating and drying the 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 glossy discolorant set was written on the porous layer of the glitter discolorant using a water adhering tool, a silver handwriting excellent in glitter of 5 to 6 mm width was visually recognized, and water adhered (liquid absorption). Since the contrast between the portion and the non-adhered (non-liquid absorbing) portion was excellent, clear handwriting could be visually recognized.
Although the above-mentioned aspect was shown in the state where water adhered, the handwriting gradually disappeared as it dried, and returned to the original color again in the completely dry state.

Example 3
As a support having glitter, a wet-processed silicic acid [trade name: NIPSEAL E-74P, Nippon Silica Kogyo Co., Ltd.] 9 parts, urethane emulsion [trade name: Permarin UA150, manufactured by Sanyo Chemical Industries, solid content 30%] 50 parts, water 35.5 parts, silicone-based antifoaming agent (solid content 100%) Using a white screen printing ink prepared by mixing 0.5 part, 2.0 parts of a water-based ink thickener (solid content 40%) and 3 parts of a carbodiimide-based crosslinking agent (solid content 40%), 300 mesh A solid layer is formed by screen printing to form a porous layer, and a polyester taffeta fabric (weight per unit area: 70 g / m ² ) is pasted on the back surface of the support as an fabric using an adhesive. A glossy discoloration was obtained.
The coating amount (dry weight) of the porous layer of the glitter discolorant was 5.3 g / m ² , and the coating amount of the wet method silicic acid as a low refractive index pigment was 1.8 g / m ^2. It was.
The specular gloss when the porous layer is in a non-liquid-absorbing state was measured at a measurement angle of 20 ° with a specular gloss meter (manufactured by Horiba, Ltd., IG-331). As a result of measuring the specular gloss at a measurement angle of 20 ° with a specular gloss meter, it was 199.
When the glitter discolorant was in a dry state, a white porous layer was visually recognized on the entire surface, and the glitter due to the support was not visually recognized.
When water is attached from above the porous layer, the porous layer becomes transparent by liquid absorption, and a silver metallic gloss image with excellent glitter by the lower layer support is visually recognized, and water is attached (liquid absorption) and Since the contrast with the non-adhered (non-liquid-absorbing) portion was excellent, a clear image could be visually recognized.
The silver metallic gloss image maintained its state in the liquid absorption state, but the entire surface returned to the white state again by evaporating and drying the water.
The aspect change could be repeated.

Example 4
Production of a set of glittering discoloration bodies The glittering discoloration body obtained in Example 3 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 glossy discolorant set was written on the porous layer of the glitter discolorant using a water adhering tool, a silver handwriting excellent in glitter of 5 to 6 mm width was visually recognized, and water adhered (liquid absorption). Since the contrast between the portion and the non-adhered (non-liquid absorbing) portion was excellent, clear handwriting could be visually recognized.
Although the above-mentioned aspect was shown in the state where water adhered, the handwriting gradually disappeared as it dried, and returned to the original color again in the completely dry state.

Example 5
2. A yellow pigment having a reddishness having an average particle diameter of 0.05 μm as a colorant as a colorant on an aluminum vapor deposition layer formed on a transparent polyethylene terephthalate sheet having a thickness of 12 μm as a support having glitter. 200 mesh gravure plate using 0 parts, 50 parts urethane resin emulsion, 0.5 parts silicone antifoam, 3 parts aqueous thickener, and 44.0 parts water. The wet metallic silicic acid [trade name: NIPSEAL E-74P, Nippon Silica Kogyo Co., Ltd.] Co., Ltd.] 15 parts, urethane emulsion [trade name: Permarin UA150, manufactured by Sanyo Chemical Industries, Ltd., solid content 30%] 50 parts, water 10.5 parts, methanol 20.0 parts, siri White mixed with 0.5 part of corn defoamer (solid content 100%), 1.0 part of water-based ink thickener (solid content 40%) and 3 parts of carbodiimide cross-linking agent (solid content 40%) Using a gravure printing ink, the entire surface was printed twice with a 200 mesh gravure plate to form a porous layer.
Next, an adhesive made of urethane resin was applied to the back surface of the support with a gravure printing machine, and a nylon 30d tricot (weight per unit area: 40 g / m ² ) was adhered as a fabric to obtain a glittering discoloration. .
The coating amount (dry weight) of the porous layer of the glitter discolorant was 6.6 g / m ² , and the coating amount of the wet method silicic acid which is a low refractive index pigment was 3.0 g / m ^2. It was.
The specular gloss when the porous layer is in a non-liquid-absorbing state was measured with a specular gloss meter (IG-331, manufactured by Horiba, Ltd.) at a measurement angle of 20 °. As a result of measuring the specular gloss at a measurement angle of 20 ° with a specular gloss meter, it was 197.
When the glitter discolorant was in a dry state, a pale yellow porous layer was visually recognized on the entire surface, and the glitter due to the support was not visually recognized.
When water is adhered from above the porous layer, the porous layer becomes transparent by liquid absorption, and a golden metallic gloss image with excellent luster due to the lower support is visually recognized, and water is adhered (liquid absorption) and Since the contrast with the non-adhered (non-liquid-absorbing) portion was excellent, a clear image could be visually recognized.
The golden metallic gloss image maintained its state in the liquid absorption state, but the entire surface returned to a pale yellow state again by evaporating and drying the 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 glossy discolorant set was written on the porous layer of the glitter discolorant using a water adhering tool, 5 to 6 mm wide gold handwriting with excellent glitter was visually recognized, and water adhered (absorbed). Since the contrast between the portion and the non-adhered (non-liquid absorbing) portion was excellent, clear handwriting could be visually recognized.
Although the above-mentioned aspect was shown in the state where water adhered, the handwriting gradually disappeared as it dried, and returned to the original color again in the completely dry state.

Example 7
As a support having glitter, 10 parts of wet-process silicic acid [trade name: NIPSEAL E-200A, manufactured by Nippon Silica Kogyo Co., Ltd.] is applied to the surface of an iris support having light interference obtained by laminating transparent films. Emulsion [trade name: Hydran AP-20, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30%] 50 parts, water 15.5 parts, methanol 20.0 parts, silicone-based antifoaming agent (solid content 100% ) 200 mesh using white gravure printing ink prepared by mixing 0.5 part, 1.0 part water based ink thickener (solid content 40%) 1.0 part, 3 parts carbodiimide crosslinking agent (solid content 40%) A porous layer was formed by printing twice on the entire surface with a gravure plate.
Further, a blue polyester taffeta fabric (weight per unit area: 70 g / m ² ) was adhered as a fabric to the back surface of the support using an adhesive to obtain a glittering discoloration.
The coating amount (dry weight) of the porous layer of the glitter discolorant was 5.4 g / m ² , and the coating amount of the wet method silicic acid which is a low refractive index pigment was 2.0 g / m ^2. It was.
The specular gloss when the porous layer is in a non-liquid-absorbing state was measured with a specular gloss meter (IG-331, manufactured by Horiba, Ltd.) at a measurement angle of 20 °. As a result of measuring the specular gloss at a measurement angle of 20 ° with a specular gloss meter, it was 110.
When the glitter discolorant was dried, a light blue porous layer was visually recognized on the entire surface, and the glitter due to the support was not visually recognized.
When water is allowed to adhere from above the porous layer, the porous layer becomes transparent by liquid absorption, and a blue-green image having excellent iris properties due to the underlying support is visually recognized, and water adheres (liquid absorption). A clear image could be visually recognized because the contrast between the spot and the non-adhered (non-liquid-absorbing) spot was excellent.
The blue-green image having the iris has maintained its state in the liquid absorption state, but the entire surface has returned to a light blue state again by evaporating and drying the 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 glossy discolorant set is written on the porous layer of the glitter discolorant using a water adhering tool, a blue-green handwriting having an iris with excellent brightness of 5 to 6 mm width is visually recognized, and water adheres. Since the contrast between the (absorbed) portion and the non-adhered (non-absorbed) portion was excellent, clear handwriting could be visually recognized.
Although the above-mentioned aspect was shown in the state where water adhered, the handwriting gradually disappeared as it dried, and returned to the original color again in the completely dry state.

Example 9
A blue pigment having an average particle diameter of 0.03 μm as a colorant on a hologram (reflection hologram sheet) in which an aluminum vapor-deposited layer is formed on an embossed surface of a 12 μm thick transparent polyethylene terephthalate sheet as a support having glitter 10.0 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 26.5 Using a blue gravure printing ink with a mixture of parts, a wet-processed silicic acid [trade name] is applied to the surface of a holographic support provided with a blue colored layer having transparency by solid printing with a 200 mesh gravure plate. : Nip seal E-200A, manufactured by Nippon Silica Kogyo Co., Ltd.] 15 parts, urethane emulsion [trade name: Hydran AP-20, Dainippon Ink & Chemicals, Inc. Manufactured, solid content 30%] 50 parts, water 13.5 parts, methanol 20.0 parts, silicone-based antifoaming agent (solid content 100%) 0.5 part, water-based ink thickener (solid content 40%) 1 Using a white gravure printing ink prepared by mixing 0.0 part and 3 parts of a carbodiimide-based crosslinking agent (solid content 40%), a porous layer is formed by printing once on the entire surface with a 200 mesh gravure plate. did.
Further, a white polyester taffeta fabric (weight per unit area: 70 g / m ² ) was adhered as a fabric to the back surface of the support using an adhesive to obtain a glittering discoloration.
The coating amount (dry weight) of the porous layer of the glitter discolorant was 3.2 g / m ² , and the coating amount of the wet method silicic acid which is a low refractive index pigment was 1.5 g / m ^2. It was.
The specular gloss when the porous layer is in a non-liquid-absorbing state was measured at a measurement angle of 20 ° with a specular gloss meter (manufactured by Horiba, Ltd., IG-331). As a result of measuring the specular gloss at a measurement angle of 20 ° with a specular gloss meter, it was 165.
When the glitter discolorant was dried, a light blue porous layer was visually recognized on the entire surface, and the glitter due to the support was not visually recognized.
When water is attached from above the porous layer, the porous layer becomes transparent by absorbing liquid, and a blue hologram image with excellent glitter by the underlying support is visually recognized, and where the water adheres (absorbs). Since the contrast with the non-absorbed (non-liquid-absorbing) portion was excellent, a clear image could be visually recognized.
The blue hologram image maintains its state in the liquid absorption state, but the entire surface returned to a light blue state again by evaporating and drying the water.
The aspect change could be repeated.

Example 10
Preparation of glittering discoloration body set The discoloration discoloration body obtained in Example 9 and a bullet-shaped fiber pen body (made of nylon resin, diameter 7 mm) as a water attachment 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 glossy discolorant set is written on the porous layer of the glitter discolorant using a water adhering tool, a blue holographic handwriting with excellent glitter of 5 to 6 mm width is visually recognized and water adheres (liquid absorption) ) And the non-adhered (non-liquid-absorbing) portion of the contrast, the clear handwriting could be visually recognized.
Although the above-mentioned aspect was shown in the state where water adhered, the handwriting gradually disappeared as it dried, and returned to the original color again in the completely dry state.

Example 11
2. A yellow pigment having a reddishness having an average particle diameter of 0.05 μm as a colorant as a colorant on an aluminum vapor deposition layer formed on a transparent polyethylene terephthalate sheet having a thickness of 12 μm as a support having glitter. 200 mesh gravure plate using 0 parts, 50 parts urethane resin emulsion, 0.5 parts silicone antifoam, 3 parts aqueous thickener, and 44.0 parts water. The wet metallic silicic acid [trade name: NIPSEAL E-74P, Nippon Silica Kogyo Co., Ltd.] Co., Ltd.] 15 parts, urethane emulsion [trade name: Permarin UA150, manufactured by Sanyo Chemical Industries, Ltd., solid content 30%] 50 parts, water 10.5 parts, methanol 20.0 parts, siri White mixed with 0.5 part of corn defoamer (solid content 100%), 1.0 part of water-based ink thickener (solid content 40%) and 3 parts of carbodiimide cross-linking agent (solid content 40%) Using a gravure printing ink, the entire surface was printed twice with a 200 mesh gravure plate to form a porous layer.
Furthermore, the adhesive which consists of an acrylic resin was apply | coated to the back surface of the said metallic gloss support body with the gravure printing machine, the white synthetic paper with a weight of 80 g / m < ² > was stuck, and the glossy discoloration body was obtained.
The coating amount (dry weight) of the porous layer of the glitter discolorant was 6.6 g / m ² , and the coating amount of the wet method silicic acid which is a low refractive index pigment was 3.0 g / m ^2. It was.
The specular gloss when the porous layer is in a non-liquid-absorbing state was measured with a specular gloss meter (IG-331, manufactured by Horiba, Ltd.) at a measurement angle of 20 °. As a result of measuring the specular gloss at a measurement angle of 20 ° with a specular gloss meter, it was 197.
When the glitter discolorant was in a dry state, a pale yellow porous layer was visually recognized on the entire surface, and the glitter due to the support was not visually recognized.
When water is adhered from above the porous layer, the porous layer becomes transparent by liquid absorption, and a golden metallic gloss image with excellent glitter due to the underlying support is visually recognized, and water is adhered (liquid absorption). Therefore, a clear image could be visually recognized.
The golden metallic gloss image maintained its state in the liquid absorption state, but the entire surface returned to a pale yellow state again by evaporating and drying the water.
The aspect change could be repeated.

Example 12
Production of a set of glittering discoloration body It has the glittering discoloration body obtained in Example 11 and a bullet-shaped fiber pen body (made of nylon resin, diameter 7 mm) as a water attachment tool. A glittering discoloration body set was obtained by combining with a pen that could be accommodated.
When the glossy discolorant set was written on the porous layer of the glitter discolorant using a water adhering tool, 5 to 6 mm wide gold handwriting with excellent glitter was visually recognized, and water adhered (absorbed). Since the contrast between the portion and the non-adhered (non-liquid absorbing) portion was excellent, clear handwriting could be visually recognized.
Although the above-mentioned aspect was shown in the state where water adhered, the handwriting gradually disappeared as it dried, and returned to the original color again in the completely dry state.

Example 13
As a support having glitter, a wet-process silicic acid [trade name: NIPSEAL E-74P, Nippon Silica Kogyo ( 9 parts, urethane emulsion [trade name: Permarin UA150, manufactured by Sanyo Chemical Industries, solid content 30%] 50 parts, water 35.5 parts, silicone-based antifoaming agent (solid content 100%) 0 A 300-mesh screen using white screen printing ink prepared by mixing 5 parts, 2.0 parts of a water-based ink thickener (solid content 40%) and 3 parts of a carbodiimide-based crosslinking agent (solid content 40%) and solid printing to form a porous layer in the plate, further, an adhesive made of an acrylic resin on the back surface of the support was coated by gravure printing machine, white basis weight 80 g / m ² The synthetic paper was adhered to obtain a bright metachromatic member.
The coating amount (dry weight) of the porous layer of the glitter discolorant was 5.3 g / m ² , and the coating amount of the wet method silicic acid as a low refractive index pigment was 1.8 g / m ^2. It was.
The specular gloss when the porous layer is in a non-liquid-absorbing state was measured at a measurement angle of 20 ° with a specular gloss meter (manufactured by Horiba, Ltd., IG-331). As a result of measuring the specular gloss at a measurement angle of 20 ° with a specular gloss meter, it was 199.
When the glitter discolorant was in a dry state, a white porous layer was visually recognized on the entire surface, and the glitter due to the support was not visually recognized.
When water is attached from above the porous layer, the porous layer becomes transparent by liquid absorption, and a silver metallic gloss image with excellent glitter by the lower layer support is visually recognized, and water is attached (liquid absorption) and Since the contrast with the non-adhered (non-liquid-absorbing) portion was excellent, a clear image could be visually recognized.
The silver metallic gloss image maintained its state in the liquid absorption state, but the entire surface returned to the white state again by evaporating and drying the water.
The aspect change could be repeated.

Example 14
Production of glittering discoloration body set It has the glittering discoloration body obtained in Example 13 and a bullet-shaped fiber pen body (made of nylon resin, diameter 7 mm) as a water adhering tool. A glittering discoloration body set was obtained by combining with a pen that could be accommodated.
When the glossy discolorant set was written on the porous layer of the glitter discolorant using a water adhering tool, a silver handwriting excellent in glitter of 5 to 6 mm width was visually recognized, and water adhered (liquid absorption). Since the contrast between the portion and the non-adhered (non-liquid absorbing) portion was excellent, clear handwriting could be visually recognized.
Although the above-mentioned aspect was shown in the state where water adhered, the handwriting gradually disappeared as it dried, and returned to the original color again in the completely dry state.

Application example 1
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 becomes transparent by absorbing liquid, and a golden metallic gloss image (handprint) with excellent glitter by the underlying support is visually recognized, and the liquid composition adheres (absorbs). A clear image could be visually recognized because of excellent contrast between the portion that was liquid) and the portion that was not attached (non-liquid absorbing).
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.

Application example 2
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 sole of the foot and attached, the porous layer becomes transparent by absorbing the liquid, and a silver metallic gloss image (foot shape) with excellent glitter by the underlying support is visually recognized, and the liquid composition is attached. Since the contrast between the (absorbed) portion and the non-adhered (non-absorbed) portion was excellent, a clear image could be visually recognized.
The glitter discoloration body on which the foot shape was formed was allowed to stand for 3 months in an environment of 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 infant's foot can be easily washed off with water when collecting the foot shape, Even in the case of failure to collect the radiant discolored body, the foot shape can be completely removed by washing with water, and it is possible to form the foot shape on the brilliant discolored material again using the liquid composition. It was something to be made.

Comparative Example 1
As a support having glitter, a wet-process silicic acid [trade name: NIPSEAL E-74P, Nippon Silica Kogyo Co., Ltd.] is applied to the surface of a silver metallic glossy support in which an aluminum deposition layer is formed on a transparent polyethylene terephthalate sheet having a thickness of 12 μm. Co., Ltd.] 15 parts, urethane emulsion [trade name: Permarin UA150, manufactured by Sanyo Chemical Industries, Ltd., solid content 30%] 50 parts, water 29.5 parts, silicone-based antifoaming agent (solid content 100%) Using a white screen printing ink prepared by mixing 0.5 parts, 2.0 parts of a water-based ink thickener (solid content 40%) and 3 parts of a carbodiimide-based crosslinking agent (solid content 40%), 100 mesh A solid printing is performed on a screen plate to form a porous layer, and a polyester taffeta fabric (weight per unit area: 70 g / m ² ) is used as a fabric on the back surface of the support using an adhesive. A discoloration was obtained by sticking.
The coating amount of the porous layer of the metachromatic member (dry weight) is 12.4 g / ^{m 2,} the coating amount of the wet process silica is the low refractive index pigment was 5.2 g / ^{m 2.}
The specular gloss in the non-absorbing state of the porous layer was measured with a specular gloss meter (manufactured by Horiba, Ltd., IG-331) at a measurement angle of 20 °. As a result of measuring the specular gloss at a measurement angle of 20 ° with a specular gloss meter, the specular gloss was 75.
As for the said discoloration body, the porous layer whose whole surface is white was visually recognized in the dry state, and the brightness by the support body was not visually recognized.
When water was attached from above the porous layer, the porous layer became transparent by liquid absorption, and although a silver metallic gloss image was visually recognized by the underlying support, the glitter was poor and water adhered (liquid absorption). Since the contrast between the spot and the non-adhered (non-liquid-absorbing) spot was poor, a clear image could not be visually recognized.
The silver metallic gloss image maintained its state in the liquid absorption state, but the entire surface returned to the white state again by evaporating and drying the water.
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.
Although the above-mentioned aspect was shown in the state where water adhered, the handwriting gradually faded as it dried, and returned to its original color again in the completely dry state.

Comparative Example 3
A blue pigment having an average particle diameter of 0.03 μm as a colorant on a hologram (reflection hologram sheet) in which an aluminum vapor-deposited layer is formed on an embossed surface of a 12 μm thick transparent polyethylene terephthalate sheet as a support having glitter 10.0 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 26.5 Using a blue gravure printing ink mixed with a part, a wet-processed silicic acid [trade name] is applied to the surface of a holographic support provided with a blue colored layer having transparency by solid printing with a 120 mesh gravure plate. : Nip seal E-200A, manufactured by Nippon Silica Industry Co., Ltd.] 7.5 parts, urethane emulsion [trade name: Hydran AP-20, Dainippon Ink & Chemicals, Inc. ), Solid content 30%] 50 parts, water 18.0 parts, methanol 20.0 parts, silicone-based antifoaming agent (solid content 100%) 0.5 parts, water-based ink thickener (solid content 40%) Using a white gravure printing ink prepared by mixing 1.0 part and 3 parts of a carbodiimide-based cross-linking agent (solid content 40%), the porous layer is printed once on the entire surface with a 300 mesh gravure plate. Formed.
Further, a white polyester taffeta fabric (weight per unit area: 70 g / m ² ) was adhered as a fabric to the back surface of the support using an adhesive to obtain a discolored body.
The coating amount (dry weight) of the porous layer of the discolored body was 1.3 g / m ² , and the coating amount of the wet method silicic acid which is a low refractive index pigment was 0.4 g / m ² .
The specular gloss in the non-absorbing state of the porous layer was measured at a measurement angle of 20 ° with a specular gloss meter (manufactured by Horiba, Ltd., IG-331). As a result of measuring the specular gloss at a measurement angle of 20 ° with a specular gloss meter, it was 199.
As for the said discoloration body, the light blue porous layer was visually recognized on the whole surface in the dry state, and the brightness by the support body was also visually recognized.
When water is attached from above the porous layer, the porous layer becomes transparent by absorbing liquid, and a blue hologram image having excellent glitter by the underlying support is visually recognized, but where water adheres (absorbs) The contrast with the non-adhered (non-absorbed) portion was poor and the changeability was poor.

DESCRIPTION OF SYMBOLS 1 Glossy discoloration body 2 Glossy support 3 Porous layer 4 Fabric

Claims (6)

A porous layer having a low refractive index pigment fixed to a binder resin in a dispersed state is provided on the surface of a support having glitter, and the transparency is different between a liquid absorbing state and a non-liquid absorbing state. The coating amount of the low refractive index pigment in the layer is 0.5 to 5.0 g / m ² and the specular gloss at a measurement angle of 20 ° with a specular gloss meter when the porous layer is in a non-liquid-absorbing state is 10 or less. And a specular gloss at a measurement angle of 20 ° in a liquid-absorbing state is 80 or more.   When the porous layer is in a non-absorbing state, the specular gloss at a measurement angle of 20 ° with a specular gloss meter is 5 or less, and the specular gloss at a measurement angle of 20 ° with a specular gloss meter in a liquid absorption state is 90 or more. The glitter discolorant according to claim 1.   The glitter discoloration body according to claim 1 or 2, wherein the support having glitter has optical characteristics selected from metallic luster, pearl luster, iris, hologram, light interference, and retroreflectivity. The glitter discoloration body according to any one of claims 1 to 3, wherein a substrate selected from a fabric, a resin sheet, water-resistant paper, synthetic paper, and paper of 25 g / m ² or more is provided on the back surface of the support.
The glitter discoloration body according to claim 1 or 2, wherein   A glitter discolorant set comprising the glitter discolorant according to any one of claims 1 to 5 and a water adhering tool.   The glittering discoloration body set according to claim 5, wherein the water adhering tool is selected from a writing tool or applicator form in which a plastic porous body or a fiber processed body having continuous pores is applied as a pen tip member, or a stamp tool. .

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