JP4499539B2 - Discolored body set - Google Patents

Description

  The present invention relates to a color changing body set. More specifically, the present invention relates to a color change body set that satisfies the persistence of an image formed on the color change object.

Conventionally, as an attempt to form an image on a discolored body, a doll comprising a doll or animal figure toy and a discolored body provided with a porous layer in which a low refractive index pigment is fixed in a dispersed state together with a binder resin on a support. Or the animal figure toy set is disclosed (for example, refer patent document 1).
The doll or animal figure toy set presses an arbitrary part of the liquid-absorbed doll or animal figure toy against the surface of the water discoloration body, allows water to permeate the porous layer of the place, and makes it transparent or translucent. The image is made visible, and when the liquid that has permeated the porous layer evaporates, the original state is restored and the image is no longer visible.
The medium to be absorbed by the toy is preferably water, and a small amount of a water-soluble organic solvent such as propylene glycol can be blended in order to adjust the drying speed and extend the visible time of the image. It is disclosed.
However, the image formed on the discolored body having the above structure is not visible due to evaporation of water, and the visible time of the image is slightly extended even when a water-soluble organic solvent such as propylene glycol is added. there were.
Therefore, it is unsuitable for applications in which an image is permanently formed and stored, for example, for collecting and storing an infant's handprint, footprint, etc., and a color change suitable for image storage and a liquid composition used therefor Things were longing for.
JP-A-11-216272

  The present invention, as a result of intensive studies on a color-changing body capable of forming an image and a liquid composition applied thereto, forms a liquid composition in which specific solid particles are dispersed in a medium of the liquid composition, and the color-changing body. By using a transparent plastic sheet material that protects the printed image, it is excellent in the permanent formation of the image formed on the discolored body, and collects and stores handprints, footprints, etc., and stores written images and stamp images An object of the present invention is to provide a color change body set capable of satisfying the permanent storage stability of an image suitable for an application.

In the present invention, a porous layer in which a low refractive index pigment having a refractive index of 1.4 to 1.8 is fixed together with a binder resin in a dispersed state is provided on a support, and the porous layer is transparent in a liquid-absorbing state. Alternatively, a color-changing body that changes color by being translucent, a liquid composition for a color-changing body in which a solid substance having a refractive index of 1.3 to 1.8 is dissolved and / or dispersed in a medium, and the color-changing body for a color-changing body A color-change body set comprising a transparent sheet material that protects an image formed by the liquid composition is a requirement.
Further, the medium of the liquid composition for a color changing body contains at least water, the solid material is dissolved in the medium, and the transparent sheet material encloses the color changing body in a bag-like body or a sandwich. The transparent sheet material is acrylonitrile-butadiene-styrene resin, acrylonitrile resin, cellulose acetate resin, polycarbonate resin, diallyl terephthalate resin, polyethylene resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polypropylene resin, polystyrene Selected from resin, polyurethane resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyester resin film, the liquid material for the discolored body is impregnated into the fiber material, and the fiber material is water-impermeable. Encapsulated in a bag-like body, It basis weight of the wood is 10 to 1000 g / ^{m 2,} a is a requirement such that said fibrous material is a nonwoven fabric.

  The present invention is excellent in density retention and shape retention of an image formed on a discolored body, and collects and stores handprints, footprints, etc., and permanent storage of images suitable for use in storing written images and stamp images It is possible to provide a color changing body set that satisfies the characteristics.

  In the present invention, the liquid composition is attached to a discolored body, the medium is infiltrated into the porous layer at the relevant location, and the image is visualized by making it transparent or translucent, and the medium infiltrated into the porous layer evaporates. However, since the solid substance contained in the liquid composition remains, the image is permanently visible.

As the medium used for the liquid composition, water is most preferably used in view of safety and cost, but a mixture of various organic solvents and water may be used. Further, depending on the use, various organic solvents can be applied, and as the organic solvent, normal hexane, normal heptane, normal octane, normal nonane, normal decane, cyclohexane, methylcyclohexane, decalin, petroleum ether, petroleum benzine, Carbonization of ligroin, mineral spirits, liquid paraffin, benzene, toluene, xylene, 0-xylene, m-xylene, p-xylene, p-cymene, solvent naphtha, tetrahydronaphthalene, α-pinene, turpentine oil, mineral oil, vegetable oil, etc. Hydrogens.
Monohydric alcohols such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, secondary butyl alcohol, tertiary butyl alcohol, isoamyl alcohol, fusel oil, benzyl alcohol, cyclohexanol, methylcyclohexanol Kind.
Ethylene glycol, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, Ethylene glycol monoisoamyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol monoethyl ether, triethylene glycol, triethylene glycol monoethyl ether, propylene glycol, butylene glycol, glycerin, polyglycerin, acetic acid monoglyceride, acetic acid diglyceride, triacetate Riserido, polyhydric alcohols and derivatives thereof such as butyric acid monoglycerides.
Ethyl ether, isopropyl ether, butyl ether, diisoamyl ether, phenyl methyl ether, phenyl ethyl ether, o-cresyl methyl ether, m-cresyl methyl ether, p-cresyl methyl ether, benzyl ethyl ether, diethylene oxide, cineol, Ethers and acetals such as furfural, furfuryl alcohol, furfuryl butyrate, tetrahydrofurfuryl alcohol, formal, and acetal;
Ketones such as acetone, acetone oil, methyl ethyl ketone, methyl isopropyl ketone, methyl butyl ketone, diacetone alcohol, acetophenone, cyclohexanone, methylcyclohexanone and camphor.
Methyl formate, ethyl formate, propyl formate, normal butyl formate, isobutyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, normal butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, acetic acid Benzyl, cyclohexyl acetate, butyl propionate, isoamyl propionate, ethyl butyrate, butyl butyrate, isoamyl butyrate, isoamyl isovalerate, butyl stearate, amyl stearate, methyl benzoate, ethyl benzoate, propyl benzoate, isoamyl benzoate Benzyl benzoate, ethyl cinnamate, ethyl adipate, butyl adipate, 2-ethylhexyl adipate, diisononyl adipate, di-n-hexyl adipate, di-n-octyl adipate, di-n-adipate Sil, dibutyl fumarate, diisobutyl fumarate, dibutyl maleate, bis (2 ethylhexyl) maleate, bis (2-ethylhexyl) azelate, dibutyl sebacate, bis (2 ethylhexyl) sebacate, bis (2-ethylhexyl) dodecanoate (2- Ethylhexyl), acetyl tributyl citrate, trimellitic acid tris (2 ethylhexyl), triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, 2,2,4-trimethyl-1,3-pentanediol monoiso Butyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, ethyl lactate, butyl lactate, amyl lactate, ethyl oxyisobutyrate, dibutyl tartrate, tributyl citrate, methyl salicylate, diethyl oxalate, dibutyl oxy Rate, diethyl malonate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diamyl phthalate, di-hexyl phthalate, di-n-octyl phthalate, esters such as diisononyl phthalate.
Fatty acids such as formic acid, acetic acid, acetic anhydride, cresol, and phenols. Nitrogen compounds such as aniline, o-toluidine, cyclohexylamine, pyridine, quinoline, acetonitrile, benzonitrile, nitrobenzene, nitroanisole can be exemplified, but liquid paraffin, vegetable oil, aliphatic esters such as adipic acid ester, propylene glycol, Glycerol and other glycols are preferably used because they are superior in safety compared to other organic solvents.

The solid substance dissolved and / or dispersed in the medium is a substance that exhibits a solid state at 20 ° C., and remains in the porous layer even when the medium dries, so that the image can be viewed permanently. Of 1.3 to 1.8, preferably 1.4 to 1.7.
This is because the refractive index of the low refractive index pigment contained in the porous layer of the discolored body is in the range of 1.4 to 1.7, so that the solid matter that has penetrated into the layer has a refractive index equivalent to that of the low refractive index pigment. This is because the layer can provide good transparency to the layer and can permanently show the effect of visually recognizing the color tone of the lower layer.
Therefore, by using the solid material, an image formed on the discolored body can be stored with the same shape and color tone as the initial state even after lapse of time.

  The solid material is not particularly limited as long as it is an organic or inorganic material that exhibits a solid state at 20 ° C. and has a refractive index in the range of 1.3 to 1.8. Polyacrylamide resin, isobutylene resin, isobutylene-maleic anhydride copolymer resin, acrylonitrile-acrylate-styrene copolymer resin, acrylonitrile-ethylene-styrene copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, Acrylonitrile-vinylidene chloride copolymer resin, acrylonitrile-chlorinated polyethylene-styrene copolymer resin, butadiene-styrene-methyl methacrylate copolymer resin, vinyl chloride resin, ethylene-propylene copolymer resin, ethylene acrylic acid Stell copolymer resin, ethylene-methacrylic acid copolymer resin, ethylene-vinyl chloride copolymer resin, vinyl chloride-propylene copolymer resin, vinyl chloride-vinylidene copolymer resin, ethylene-vinyl acetate copolymer resin, chlorinated ethylene-acetic acid Vinyl copolymer resin, ethylene-vinyl acetate-vinyl chloride copolymer resin, ethylene-vinyl alcohol copolymer resin, polyvinyl chloride resin, chlorinated polyethylene resin, chlorinated polypropylene resin, carboxy vinyl resin, ketone resin, norbornene resin, polyamide Resin, copolymerized polyamide resin, polyamideimide resin, methoxymethylated polyamide resin, polycarbonate resin, polybutadiene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polystyrene resin, high impact polystyrene Resin, styrene-maleic acid copolymer resin, acrylic-styrene copolymer resin, polyacetal resin, polyvinyl formal resin, polyvinyl butyral resin, polyarylate resin, polyetherimide resin, polyether resin, polyethylene resin, polypropylene resin, polymethyl Styrene resin, acrylic ester resin, vinyl acetate-acrylic ester copolymer resin, styrene-acrylic ester copolymer resin, polyvinyl acetate resin, polymethyl methacrylate resin, epoxy acrylate resin, alkylphenol resin, rosin-modified phenol resin, rosin Modified alkyd resin, funol resin modified alkyd resin, styrene modified alkyd resin, epoxy modified alkyd resin, acrylic modified alkyd resin, amino alkyd resin, butyral resin, Polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, epoxy resin, alkyd resin, styrene-butadiene copolymer resin, unsaturated polyester resin, saturated polyester resin, vinyl chloride-acrylic copolymer resin, polyvinyl acetate resin, polyvinylidene chloride Copolymer resin, polyolefin copolymer resin, rosin ester resin, polyisobutylene resin, isoprene rubber, butyl rubber, cyclized rubber, chlorinated rubber, polyvinyl alkyl ether resin, fluorine resin, silicone resin, phenol resin, petroleum hydrocarbon Resin, toluene resin, xylene resin, methacrylate copolymer resin, melamine resin, urea resin, phenoxy resin, benzoguanamine resin, polyethylene oxide, polyethylene glycol, polyvinyl pyrrolidone, vinyl pyrrolidone Vinyl acetate copolymer resin, vinyl pyrrolidone-vinyl imidazole copolymer resin, vinyl pyrrolidone-vinyl imidazole methyl sulfate copolymer resin, vinyl pyrrolidone-sodium methacrylate copolymer resin, vinyl pyrrolidone-vinyl caprolactam copolymer resin, polyvinyl pyrrolidone, Polyvinyl caprolactam, polyvinyl pyrrolidone-vinyl imidazole, polyvinyl alcohol, modified polyvinyl alcohol, polyacrylate, polymethacrylate, polyvinyl pyridine, polyacrylamide, polyethyleneimine, polyvinyl methyl ether, styrene-maleic anhydride copolymer resin, methyl vinyl ether -Maleic anhydride copolymer resin, synthetic resin such as polyphosphate, or oligomer.

  Cellulose acetate, cellophane, cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose, methylcellulose, ethylcellulose, carboxymethylcellulose, carboxymethylethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and other cellulose derivatives, starch, dialdehyde starch, carboxymethylated Starch, hydroxyethylated starch, starch derivatives such as phosphate starch, dextrin, gelatin, glue, rosin, shellac, casein, sodium caseinate, carnauba wax, alginic acid, sodium alginate, propylene glycol alginate, collagen, elastin, gum arabic , Ester gum, guar gum, glycyrrhizin, copal rubber, cod Natural or semi-synthetic products such as tont gum, danmar gum, locust bean gum, pentaploid, gallic, tannic acid, hyaluronic acid, show brain, synthetic show brain, lactose, glucose, pectin, polyphenol, beeswax, tree wax, gallic acid, pyrogallol resin.

  Solid fats such as coconut oil, palm oil, beef tallow, hydrogenated oil, higher fatty acid, higher alcohol, fatty acid ester, oxyacid ester, polyhydric alcohol fatty acid ester, alkyl glyceryl ether fatty acid ester.

  Fatty acid soap, N-acyl amino acid salt, polyoxyethylene carboxylate, polyoxyethylene alkyl ether carboxylate, acylated peptide, alkylsulfonate, alkylbenzenesulfonate, alkylnaphthalenesulfonate, naphthalenesulfonate Formalin condensate, melamine sulfonate-formalin condensate, dialkyl sulfosuccinate ester salt, alkyl sulfosulfosuccinate, polyoxyethylene alkyl sulfosuccinate, alkyl sulfoacetate, α-olefin sulfonate, N-acyl-N -Methyl taurine salt, dimethyl-5-sulfoisophthalate sodium salt, sulfated oil, alkyl sulfate, secondary higher alcohol sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene fat Alkanolamide sulfate, polyoxyethylene alkyl phenyl ether sulfate, monoglyculate, fatty acid alkyl amide sulfate sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, alkyl phosphate, aliphatic Amine salt, aliphatic quaternary ammonium salt, benzalkonium chloride salt, benzethonium chloride, pyridinium salt, imidazolinium salt, alkyldimethylbetaine, aminocarboxylate, imidazolinium betaine, lecithin, lecithin derivative, alkylamine oxide, Polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene Nranolin derivative, alkylphenol formalin condensate ethylene oxide derivative, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxy Ethylene sorbitol fatty acid ester, polyoxyethylene glycol fatty acid ester, ethylene glycol fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine Fluoroalkylcarboxylates, -Disodium perfluorooctanesulfonyl glutamate, sodium 3- [fluoroalkyloxy] -1-alkylsulfonate, sodium 3- [ω-fluoroalkanoyl-N-ethylamino] -1-propanesulfonate, N- [3- (Perfluorooctanesulfonamido) propyl] -N, N-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylcarboxylic acid, perfluorooctanesulfonic acid diethanolamide, perfluoroalkylsulfonate, N-propyl-N- (2-hydroxyethyl) perfluorooctanesulfonamide, perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, monoperful Interfaces such as oroalkylethyl phosphate, polyoxyethylene allyl glycidyl nonyl phenyl ether sulfate, polyoxyethylene allyl glycidyl nonyl phenyl ether, polyoxyethylene nonyl propenyl phenyl ether, polyoxyethylene nonyl propenyl phenyl ether sulfate ammonium salt Activators.

  Polysaccharides such as starch sugar, dextran, xanthan gum, curdlan, pullulan, cycloamylose, chitin, chitosan, hyaluronic acid, sodium chondroitin sulfate;

  G-glycosides such as D-sorbitol, mannitol, maltitol, inositol, phytic acid, and arbutin.

  Vitamin A, vitamin B1, vitamin B2, vitamin B6, vitamin B12, vitamin C, calcium ascorbate, vitamin D, vitamin E, vitamin F, vitamin G, vitamin H, vitamin K, vitamin L, vitamin M, vitamin P, vitamin Vitamins such as R, vitamin S, vitamin T, vitamin U, vitamin V, vitamin W, vitamin X, vitamin Y, pantothenic acid, nicotinic acid, lipoic acid and lipoamide.

  L-aspartic acid, L-aspartate, D-aspartic acid, DL-alanine, L-alanine, D-alanine, β-alanine, L-arginine, L-isocyanine, glycine, L-glutamine, L-glutamic acid, L-cystine, derivatives of L-cysteine, L-threonine, L-serine, L-tyrosine, L-tryptophan, L-valine, L-histidine, L-phenylalanine, L-proline, DL-methionine, L-methionine, Amino acids such as L-lysine, L-leucine, glycylglycine, glutathione, oxidized glutathione, γ-aminobutyric acid, ε aminocaproic acid, L-ornithine hydrochloride, L-citrulline and the like.

  Hormones such as cortisone, testosterone, thyroxine, adrenaline, and insulin.

  Adenine, adenosine, 5'-adenylic acid, 3 ', 5'-cyclic adenylic acid, adenosine triphosphate sodium salt, 6-allyl adenine, 6-benzyl adenine, 6-allyl adenosine, 6-benzyl adenosine, deoxyadenosine Monophosphate, guanine, guanosine, guanylate sodium salt, deoxyguanosine monophosphate, uracil, uridine, 5'-uridylic acid disodium salt, deoxyuridine, 5'-iododeoxyuridine, uridine-5'-diphosphate glucose Orotic acid, cytosine, cytidine, 5'-cytidylic acid, cytidine-5'-triphosphate, deoxycytidine monophosphate, cytidine-5'-diphosphate choline sodium salt, arabinosylcytosine, pipeoxanthin, inosine Sodium 5'-inosinate 6-mercaptopurine, 6-methylmercaptopurine, nicotinamide mononucleotide, nicotinamide adenine dinucleotide, nicotinamide adenine dinucleotide reduced sodium salt, nicotinamide adenine dinucleotide phosphate, nicotinamide adenine dinucleotide phosphate reduced sodium salt, Nucleic acids and lipids such as cholesterol and γ-oryzanol.

  In addition, urea, N, N'-ethylenebis (stearoamide), oleic acid amide, stearic acid amide, N, N'-methylenebis (stearoamide), methylol stearamide, potassium stearate, sodium stearate, CTU, CTU guanamine , Sebacic acid, dodecanedioic acid, dodecanedioic acid dihydrazide, pentaerythritol, malonic acid, itaconic anhydride, maleic anhydride, acetanilide, acetoacetanilide, p-aminoacetanilide, isophthalic acid, dimethyl terephthalate, 4,4'-dimethoxy Benzophenone, diphenylacetic acid, diphenylsulfone, dimethyl terephthalate, hydrogenated bisphenol A, bisphenol A, bis (4-hydroxyphenyl) sulfone, P-hydroxybenzoic acid, gallic acid steer Le, laurone, the stearone like.

  Examples of inorganic substances include calcium chloride, sodium chloride, sodium silicate, salicy powder, disodium carbonate, soda lime, aluminum silicate, aluminum sulfate, ammonium alum, ammonium sulfate, calcium carbonate, colloidal silica, and the like.

  The solid matter contained in the medium is 3.0% by weight or more, preferably 3.0 to 90.0% by weight. If the amount is less than 3.0% by weight, the image-forming property is unsatisfactory. If the amount exceeds 90.0% by weight, depending on the solid material applied, the viscosity increases and the initial image-forming property tends to be impaired.

In order to efficiently impregnate the porous layer with the solid material, those having a particle size of 10 μm or less, preferably 0.01 μm to 10 μm, are used.
It is difficult to finely disperse a solid material to less than 0.01 μm, and when it exceeds 10 μm, solid particles are difficult to enter into the voids of the porous layer, and it is difficult to form a clear image by adhering to the surface of the porous layer. It becomes.

If water-soluble material is used as the solid material, the liquid composition can be applied to the discolored body, and the image formed by the solid material due to evaporation of the medium can be removed by washing with water. This is practical because it can be used repeatedly without discarding the discolored body when it fails to form an image. In that case, the support constituting the discolored body is preferably a water-resistant material.
Furthermore, when a bill or foot is collected, the solid matter attached to the hand or foot can be easily washed away with water, and the safety to the human body is increased, which is optimal.

The discolored body is provided with a porous layer in which a low refractive index pigment is fixed in a dispersed state together with a binder resin on a support, and the porous layer absorbs a liquid composition and is transparent or translucent. The color tone of the lower layer can be visually recognized.
The material of the support for the discolored body is not particularly limited as long as it has water resistance, and examples thereof include synthetic paper, fabric, film, plastic, rubber, synthetic leather, leather, glass, ceramics, wood, and stone. .
Further, even a material having poor water resistance, such as high-quality paper, art paper, and coated paper, can be used as a support by a method such as laminating with a film or applying or impregnating a resin.
The support is preferably in the form of a plane, but may be in the form of irregularities.

  In addition, when an attachment tool such as an applicator or a stamp tool used when the liquid composition is attached to the porous layer is relatively hard, the liquid composition receives elastically the pressure applied by the contact of the attachment tool. In order to form a clear image by the permeation of the substrate, the support can be formed of a material having flexibility or elasticity, for example, a cloth, rubber, or a foam having closed cells. Further, even if the support is formed of a material having poor elasticity such as synthetic paper, a clear image can be formed by providing a layer having flexibility or elasticity under the support.

The porous layer formed on the 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 when the liquid composition is absorbed, good transparency is exhibited.
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, a particulate silica is mentioned as a low refractive index pigment used suitably.
Particulate silicic acid is produced as amorphous amorphous silicic acid, and is produced by a dry process using a gas phase reaction such as thermal decomposition of silicon halide such as silicon tetrachloride (hereinafter referred to as dry process particulate silicic acid). And by a wet method using a liquid phase reaction such as decomposition with an acid such as sodium silicate (hereinafter referred to as wet method fine particle silicic acid), and any of them can be used. When wet method fine particle silicic acid is used, since the concealment property in the normal state is larger than that of dry method fine particle silicic acid, it is possible to increase the mixing ratio of the binder resin to the fine particle silicic acid. Since the film strength of the film can be improved, it is more preferably used.
As described above, as the fine particulate silicic acid used for satisfying the normal concealability of the porous layer, wet method fine particulate silicic acid is preferable. This is because the dry method fine particle silicic acid and the wet method fine particle silicic acid have different structures, and the dry method fine particle silicic acid forms a three-dimensional structure in which the silicic acid is intimately bonded, whereas the wet method fine particle silicic acid forms a three-dimensional structure. Has a so-called two-dimensional structure part in which silicic acid is condensed to form a long molecular arrangement. Accordingly, since the molecular structure is coarser than that of the above-mentioned dry method fine particle silicic acid, when wet method fine particle silicic acid is applied to the porous layer, the light in the dry state compared to the system using the dry method fine particle silicic acid Therefore, it is presumed that the concealability in the normal state is increased.
Further, the low refractive index pigment contained in the porous layer preferably has an appropriate hydrophilicity since the medium to penetrate is mainly water from the viewpoint of safety and cost. Accordingly, wet process fine particle silicic acid is preferably used because it has a higher hydrophilicity than the dry process fine particle silicic acid because it has more hydroxyl groups present as silanol groups on the particle surface.

When the wet method fine particle silicic acid is used as a low refractive index pigment, it depends on the properties of the wet method fine particle silicic acid, the particle diameter, the specific surface area, the oil absorption amount, etc. to satisfy transparency together is preferably applied amount is ^{1g / m 2 ~30g / m 2} , more preferably ^{5g / m 2 ~20g / 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 is difficult to obtain sufficient transparency upon water absorption.

The low refractive index pigment is dispersed in a vehicle containing a binder resin as a binder, and after coating on a support, 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, epoxy resin and the like can be mentioned.

Since the porous layer has a small mixing ratio of the binder resin to the colorant as compared with a conventionally known general coating film, it is difficult to obtain sufficient film strength. Therefore, in applications where scratch resistance is required, it is preferable to use a urethane-based resin or a nylon resin as the above-mentioned binder resin, or to contain at least the resin.
Examples of the urethane resin include a polyester urethane resin, a polycarbonate urethane resin, and a polyether urethane resin, and two or more of them can be used in combination. In addition, a urethane emulsion resin in which the resin is emulsified and dispersed in water, or a colloid in which the resin is self-emulsified without the need for an emulsifier by an ionic group of the ionic urethane resin (urethane ionomer) itself and dissolved or dispersed in water. A dispersion type (ionomer type) urethane resin can also be used.
The urethane-based resin may be either an aqueous urethane-based resin or an oil-based urethane-based resin, but an aqueous urethane-based resin, particularly a urethane-based emulsion resin or a colloidally dispersed urethane-based resin is preferably used.
The urethane resin can be used alone, but other binder resins can be used in combination depending on the type of support and the performance required for the coating. When a binder resin other than the urethane resin is used in combination, in order to obtain a practical film strength, it is preferable to contain 30% or more of the urethane resin in a solid content weight 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 a medium. 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 above-mentioned penetration performance can be controlled by adding a dispersant as appropriate.

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

  Further, in the porous layer, conventionally known titanium dioxide-coated mica, iron oxide-titanium dioxide-coated mica, iron oxide-coated mica, guanine, sericite, basic lead carbonate, acidic lead arsenate, bismuth oxychloride, etc. It is also possible to add various metallic luster pigments or add general dyes and pigments to make the color change diverse.

If necessary, the discolored body formed as described above may be provided with a non-discoloring layer with a general dye or pigment, a non-discoloring ink containing a fluorescent dye or pigment, or coated with titanium dioxide-coated mica or iron oxide-titanium dioxide. A metallic luster layer can also be provided by applying an ink containing a metallic luster pigment such as mica, iron oxide-coated mica, guanine, sericite, basic lead carbonate, lead acid arsenate, or bismuth oxychloride.
The non-color-changing layer is disposed under the porous layer, so that a color-changing body excellent in color change between a dry state and a water-absorbing state can be obtained.

In the structure of the above-described discolored body, a protective layer and a light stabilizer layer can be appropriately provided. Specifically, the light stabilizer layer is selected from ultraviolet absorbers, antioxidants, anti-aging agents, singlet oxygen quenchers, superoxide anion quenchers, ozone decolorizers, visible light absorbers, and infrared absorbers. This is a layer in which the light stabilizer is fixed in a dispersed state.
In addition, an anti-aging agent, an antistatic agent, a polarity imparting agent, a thixotropic imparting agent, an antifoaming agent and the like can be added to each layer as necessary to improve the function.

As a method for adhering the liquid composition to the discolored body, a method in which a finger is wetted with the liquid composition and brought into contact with the discolored body, a liquid composition is applied to an applicator or sponge having a brush tip or a fiber pen body at the tip. A method of impregnating and contacting the discolored body, a method of bringing a container containing the liquid composition into contact with or in contact with the discolored body, and attaching the liquid composition by deriving from the container, foaming having open cells or closed cells on the marking surface Examples of the method include impregnating a liquid composition on a stamp to which a body is fixed and attaching the liquid composition to the discolored body, and attaching the liquid composition to a stamp having a rough surface of plastic or rubber and contacting the discolored body. When collecting handprints and footprints, the liquid composition was adhered by bringing the hands and feet into contact with a fiber material or foamed material (sponge) having open cells impregnated with the liquid composition as an impregnation material. rear The metachromatic member is brought into contact with the hands and feet are suitable methods of collecting bills and footprints to be conveniently form a clear and homogeneous bills and footprints.
A fiber material is particularly preferable as the impregnating material, and a fiber material having a basis weight of 10 to 1000 g / m ² can uniformly adhere the liquid composition to the hands and feet, and thus has a clear hand shape and foot shape. Can be formed into a discolored body.
If the amount is less than 10 g / m ² , the liquid composition cannot be sufficiently impregnated, so that a clear hand shape or foot shape cannot be formed. On the other hand, if it exceeds 1000 g / m ² , the liquid composition is impregnated with a necessary amount or more. become.
Furthermore, since a nonwoven fabric is used as the fiber material, it is excellent in processability and can be manufactured at a lower cost.
The fiber material is preferably enclosed in a water-impermeable bag so that the medium in the liquid composition does not evaporate when not in use, and the water-impermeable material has a water vapor permeability of 10 A film material of 0.0 g / m ² · 24 hr or less is applied.
The material is not particularly limited as long as the water vapor transmission rate is 10.0 g / m ² · 24 hr or less. For example, a laminated film composed of 20 μm stretched polypropylene and 30 μm unstretched polypropylene, 15 μm stretched nylon and none Laminated film made of stretched polypropylene 60 μm, laminated film made of polyethylene terephthalate 12 μm, aluminum 9 μm, stretched nylon 15 μm, unstretched polypropylene 60 μm, cellophane # 300, polyethylene 13 μm, aluminum 9 μm, polyethylene 20 μm, polyethylene terephthalate 12 μm, Laminated film consisting of polyethylene 13μm, aluminum 6μm and polyethylene 30μm, stretched polypropylene 20μm, ethylene vinyl alcohol 15μm and poly Laminated film consisting of 40 μm of polyethylene, laminated film consisting of 12 μm polyethylene terephthalate, 9 μm aluminum, 12 μm polyethylene terephthalate and 40 μm linear low density polyethylene, laminated film consisting of 12 μm polyethylene terephthalate, 12 μm aluminum vapor deposited polyethylene terephthalate and 50 μm linear low density polyethylene Film, polyethylene terephthalate 12 μm, aluminum 9 μm, laminated film composed of linear low density polyethylene 40 μm, polyethylene terephthalate 12 μm, aluminum 9 μm, ethylene / methacrylic acid copolymer 40 μm, polyethylene terephthalate 12 μm, aluminum 9 μm and Admer 20 μm And a laminated film consisting of 20 μm of linear low density polyethylene Laminated film comprising oriented polypropylene 20μm and aluminum deposited cast polypropylene 25 [mu] m, the laminated film or the like is used consisting of polyethylene terephthalate 12μm aluminum 9μm and polyacrylonitrile 30 [mu] m.

The transparent sheet material is used to prevent the liquid such as water from adhering to the image formed by the color changing liquid composition on the color changing body, and any material having transparency may be used. However, in order to prevent moisture in the atmosphere from passing through the sheet material due to condensation or the like and absorbing into the porous layer, it is preferably a water-impermeable or hardly-permeable sheet material. Examples of the material of the transparent sheet material include a glass plate and a plastic sheet material, but a plastic sheet material that is easy to handle and process is preferably used, and acrylonitrile-butadiene-styrene resin, acrylonitrile resin, cellulose acetate resin, Polycarbonate resin, diallyl terephthalate resin, polyethylene resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polypropylene resin, polystyrene resin, polyurethane resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyester resin and the like are used.
The transparency may be colorless and transparent, colored transparent, translucent, and colored translucent.
The shape of the transparent plastic sheet material is a bag-like body or a narrow body covering the entire surface of the discolored body, the bag-shaped body is configured to enclose the discolored body, and the narrow body is a porous material of the discolored body. Examples include a configuration that covers only the quality layer, a configuration in which the sheet material is provided with a crease at a substantially central portion, and a configuration in which separate sheet materials that cover the upper surface and the lower surface of the discolored body are attached or pressed.

Examples are shown below.
In addition, the part in an Example shows a weight part and the refractive index of a solid substance is a value in 20 degreeC in the D line | wire (589 nm) of sodium in a solid state.
Example 1
Preparation of discolored body On a white synthetic paper (size 200 mm × 180 mm, thickness 130 μm) as a support, 5 parts of a blue pigment, 50 parts of an acrylate emulsion (solid content 50%), 0.2 part of a silicone-based antifoaming agent Using a 180 mesh screen plate, blue screen printing ink was uniformly mixed and stirred with 3 parts thickener, 2 parts wetting agent, 1 part leveling agent, 10 parts water, and 2.5 parts epoxy crosslinking agent. The whole surface was printed to form a non-discoloring layer.
Next, on the non-discoloring layer, 15 parts of a particulate silicic acid produced by a wet method as a low refractive index pigment [trade name: Nipsil E-200A, manufactured by Nippon Silica Kogyo Co., Ltd.], an aqueous urethane resin as a binder resin [ Product name: Hydran AP-10, polyester urethane resin, solid content 30%, manufactured by Dainippon Ink & Chemicals, Inc.] 50 parts, water 30 parts, silicone antifoam 0.5 parts, water-based ink thickener 3 parts, 1 part of ethylene glycol, 2 parts of epoxy cross-linking agent are uniformly mixed and stirred using white screen printing ink, dried and cured at 70 ° C. for 15 minutes to form a porous layer Then, a discolored body that changed from white to blue by liquid absorption was obtained.

Preparation of liquid composition for discoloration body 45 parts of polyvinyl pyrrolidone [trade name: Rubiscol K-17, manufactured by BASF, refractive index 1.50] as a solid substance is stirred into 55 parts of water and uniformly dissolved. A liquid composition for a color changing body was obtained.
5.0 g of the liquid composition for a color changing body is uniformly impregnated into a nonwoven fabric made of cellulose (150 mm × 200 mm, weight per unit area: 40 g / m ² ) as a fiber material, folded, and polyethylene terephthalate 12 μm, polyethylene 13 μm, aluminum 6 μm, and polyethylene. It was enclosed in a bag-like product made of a laminated film of 30 μm.
Even if the bag-like material enclosing the discolorable liquid composition is left in an environment of 40 ° C. and humidity 50% RH for one month, there is no change in weight, and moisture evaporates outside the bag-like material. There wasn't.

Production of Transparent Sheet Material A transparent sheet material was obtained by forming a bag-like body (160 mm × 210 mm) from a transparent polypropylene resin (thickness 40 μm).

A discolored body set was obtained by combining the discolored body, a bag-like material enclosing the discolorable liquid composition, and a transparent sheet material.
After removing the fiber material impregnated with the liquid composition for the color changing body by cutting the front end portion of the bag-like material and bringing it into contact with the entire palm of the infant to uniformly adhere the liquid composition, the porous layer of the color changing body When a hand was pressed on for 5 seconds, the porous layer absorbed the liquid composition and became transparent, and a blue handprint due to the lower non-discoloring layer was collected.
The discolored body on which the bill is formed is left to dry in an environment of 20 ° C. and a humidity of 50% RH for 30 minutes, and then encapsulated in a transparent sheet material (bag-like body), and 20 ° C. and a humidity of 50%. Even if it is left for 3 months in an RH environment, it maintains the same color density and shape as the initial stage, and even if water or the like is accidentally attached, the bill does not change at all and has excellent storage stability. It was.
In addition, since the solid substance contained in the liquid composition for a color changing body is soluble in water, when collecting a bill, the liquid composition adhering to the hand can be easily washed off with water and collecting the bill. In the case of failure, it was possible to completely remove the bill by washing the discolored body with water and to satisfy the repeated practical use in which the bill can be formed again using the liquid composition.
Furthermore, since the liquid composition is colorless and transparent, it does not become dirty even if it accidentally adheres to clothes, etc., and can be easily removed by washing with water, etc., for convenience and safety of collecting infants' bills. Was also excellent.

Example 2
Preparation of discolored body On white synthetic paper (size: 280 mm × 280 mm, thickness: 200 μm) as a support, 5 parts of a pink pigment, 50 parts of an acrylic ester emulsion (solid content 50%), a silicone-based antifoaming agent 0.2 180 screen mesh of pink screen printing ink with uniform mixing and stirring of 1 part, 3 parts thickener, 2 parts wetting agent, 1 part leveling agent, 10 parts water, 2.5 parts epoxy crosslinker Was used for solid printing on the entire surface to form a non-discoloring layer.
Next, on the non-discoloring layer, 15 parts of a particulate silicic acid produced by a wet method as a low refractive index pigment [trade name: Nipsil E-200A, manufactured by Nippon Silica Kogyo Co., Ltd.], an aqueous urethane resin as a binder resin [ Product name: Hydran AP-10, polyester urethane resin, solid content 30%, manufactured by Dainippon Ink & Chemicals, Inc.] 50 parts, water 30 parts, silicone antifoam 0.5 parts, water-based ink thickener 3 parts, 1 part of ethylene glycol and 2 parts of epoxy cross-linking agent are uniformly mixed and stirred with white screen printing ink to form a porous layer and change from white to pink by liquid absorption A discolored body was produced.

Preparation of liquid composition for discoloration body Cyclodextrin [trade name: Isoelite P, manufactured by Nikken Chemical Co., Ltd., refractive index 1.47] as a solid substance is added to 50 parts of water with stirring and dissolved uniformly. Thus, a liquid composition for a color changing body was obtained.
6.0 g of the liquid composition for a color changing body is uniformly impregnated into a polyester non-woven fabric (100 mm × 200 mm, basis weight: 70 g / m ² ) as a fiber material, folded, and polyethylene terephthalate 12 μm, aluminum 9 μm, polyethylene terephthalate 12 μm, It was enclosed in a bag-like product made of a laminated film made of 40 μm linear low density polyethylene.
Even if the bag-like material enclosing the discolorable liquid composition is left in an environment of 40 ° C. and humidity 50% RH for one month, there is no change in weight, and moisture evaporates outside the bag-like material. There wasn't.

Production of Transparent Sheet Material A transparent sheet material was obtained by forming a sandwich (120 mm × 220 mm) with a translucent polyethylene resin (thickness: 100 μm). The transparent sheet material is obtained by half-folding a 240 mm × 220 mm polyethylene resin to a size of 120 mm × 220 mm and heat-sealing only one side of the bottom.

A discolored body set was obtained by combining the discolored body, a bag-like material enclosing the discolorable liquid composition, and a transparent sheet material.
After removing the fiber material impregnated with the liquid composition for the color changing body by cutting the front end portion of the bag-like material and bringing it into contact with the entire sole of the infant's foot to uniformly adhere the liquid composition, the porous material of the color changing body is removed. When the foot was pressed on the porous layer for 5 seconds, the porous layer absorbed the liquid composition and became transparent, and a pink foot shape was collected from the lower non-discoloring layer.
The discolored body in which the foot shape is formed is left to dry in an environment of 20 ° C. and a humidity of 50% RH for 30 minutes, and is then sandwiched between transparent sheet materials (clamping bodies), and has a temperature of 20 ° C. and a humidity of 50% RH. Even if left in an environment for 3 months, it maintains the same color density and shape as the initial stage, and even when left in an environment of 20 ° C. and humidity of 95% RH, the footprint does not change and is stable in storage. It was excellent.
In addition, since the solid substance contained in the liquid composition for a color changing body is soluble in water, when collecting the footform, the liquid composition adhering to the foot can be easily washed off with water and the footform is collected. In the case of failure, it was possible to completely remove the footprint by washing the discolored body with water and to satisfy the repeated practical use in which the footprint can be formed again using the liquid composition.
Furthermore, since the liquid composition is colorless and transparent, it does not become soiled even if it accidentally adheres to clothes, etc., and can be easily removed by washing with water, etc. Was also excellent.

Example 3
Preparation of discolored body Fine-particle silicic acid produced by a wet method as a low refractive index pigment on a blue-colored polyester sheet (size: 200 mm × 250 mm, thickness: 50 μm) as a support [trade name: NIPSEAL E-74P , Manufactured by Nippon Silica Industry Co., Ltd.] 15 parts, pink fluorescent pigment 2 parts, aqueous urethane resin as binder resin [trade name: Hydran AP-10, polyester urethane resin, solid content 30%, Dainippon Ink & Chemicals, Inc. ( Co., Ltd.] Pink screen in which 50 parts, 30 parts of water, 0.5 part of a silicone-based antifoaming agent, 3 parts of a water-based ink thickener, 1 part of ethylene glycol and 2 parts of an epoxy-based crosslinking agent are uniformly mixed and stirred. Using printing ink, solid printing is performed on the entire surface to form a pink porous layer, and a color change body that changes from pink to purple by liquid absorption is produced. .

Preparation of liquid composition for discoloration body 50 parts of polyethylene glycol (trade name: PEG # 6000P, manufactured by Sanyo Chemical Co., Ltd., refractive index 1.48) as a solid substance is stirred into 50 parts of water and uniformly dissolved. Thus, a liquid composition for a color changing body was obtained.
A cellulose nonwoven fabric (150 mm × 200 mm, basis weight: 40 g / m ² ) was uniformly impregnated as a fiber material with 5.0 g of the liquid composition for a color changing body.

Production of Transparent Sheet Material A transparent sheet material was obtained by forming a sandwich (230 mm × 280 mm) with a transparent polymethyl methacrylate resin (thickness 300 μm).
The transparent sheet material is composed of two sheet materials, and holes are provided in the four corners of each sheet material.

A discolored body set was obtained by combining the discolored body, a bag-like material enclosing the discolorable liquid composition, and a transparent sheet material.
After the fibrous material is brought into contact with the infant's palm to adhere the uniform liquid composition, the porous layer absorbs the liquid composition and becomes transparent when the foot is pressed on the porous layer of the discolored body for 5 seconds. A purple handprint was collected.
The discolored body on which the bill was formed was left to dry in an environment of 20 ° C. and humidity 50% RH for 30 minutes, and then sandwiched between transparent sheet materials, and the four corners were fixed with bolts, 20 ° C. and humidity 90%. Even if it is left for 3 months in an RH environment, it maintains the same color density and shape as the initial stage, and even if water or the like is accidentally attached, the bill does not change at all and has excellent storage stability. It was.
In addition, since the solid substance contained in the liquid composition for a color changing body is soluble in water, when collecting a bill, the liquid composition adhering to the hand can be easily washed off with water and collecting the bill. In the case of failure, it was possible to completely remove the bill by washing the discolored body with water and to satisfy the repeated practical use in which the bill can be formed again using the liquid composition.
Furthermore, since the liquid composition is colorless and transparent, it does not become dirty even if it accidentally adheres to clothes, etc., and can be easily removed by washing with water, etc., for convenience and safety of collecting infants' bills. It was excellent.

Example 4
Preparation of discolored body 5 parts of black pigment, 50 parts of acrylic ester emulsion (solid content 50%), 0.2 part of silicone-based antifoaming agent on white coated paper (size 300 mm × 250 mm, thickness 100 μm) as a support 3 parts of thickener, 2 parts of wetting agent, 1 part of leveling agent, 10 parts of water, 2.5 parts of epoxy cross-linking agent were uniformly mixed and stirred on the entire surface using black screen printing ink. A discolored layer was formed.
Next, on the non-discoloring layer, 15 parts of a particulate silicic acid produced by a wet method as a low refractive index pigment [trade name: NIPSEAL E-74P, manufactured by Nippon Silica Kogyo Co., Ltd.], an aqueous urethane resin as a binder resin [ Product name: Hydran AP-10, polyester urethane resin, solid content 30%, manufactured by Dainippon Ink & Chemicals, Inc.] 50 parts, water 30 parts, silicone antifoam 0.5 parts, water-based ink thickener 3 parts, 1 part of ethylene glycol and 2 parts of an epoxy-based crosslinking agent are uniformly mixed and stirred using a white screen printing ink to form a porous layer, which changes from white to black by liquid absorption. A discolored body was obtained.

Preparation of liquid composition for discoloration body 45 parts of polyvinyl pyrrolidone [trade name: Rubiscol K-17, manufactured by BASF, refractive index 1.50] as a solid substance is stirred into 55 parts of water and uniformly dissolved. A liquid composition for a color changing body was obtained.

Production of Transparent Sheet Material A transparent sheet material was obtained by forming a sandwich (350 mm × 300 mm) from a transparent polyethylene terephthalate resin (thickness: 16 μm).
One of the transparent sheet materials is provided with an adhesive layer on the surface.

The color-changing body set was obtained by combining the color-changing body, the color-changing liquid composition, and the transparent sheet material.
The handwriting obtained by writing with the brush which impregnated the color-change body with the liquid composition for the color-change body maintained the same color shape as the initial stage even when water was evaporated.
Subsequently, the discoloration body was mounted in the center part on the adhesion layer of a transparent sheet material, and the other transparent sheet material was mounted on the discoloration body, and the sheet materials were stuck together.
The discolored body on which the handwriting is formed does not change even if water is mistakenly attached, and even if it is left for 3 months at 40 ° C. and a humidity of 90% RH, there is no change and storage stability is improved. It was excellent.
In addition, since the liquid composition for a color changing body is easily soluble in water, the liquid composition remaining on the writing brush after writing could be easily washed off with water.
Further, since the liquid composition is colorless and transparent, it does not become dirty even if it accidentally adheres to clothes, etc., and can be easily removed by washing with water, etc., and is excellent in convenience.

Claims (8)

A porous layer in which a low refractive index pigment having a refractive index of 1.4 to 1.8 is fixed together with a binder resin in a dispersed state is provided on a support, and the porous layer becomes transparent or translucent in a liquid absorption state. A discolored body that changes color, a liquid composition for a discolored body obtained by dissolving and / or dispersing a solid material having a refractive index of 1.3 to 1.8 in a medium, and a liquid composition for the discolored body. A discolored body set comprising a transparent sheet material for protecting the formed image.   The color-changing body set according to claim 1, wherein the medium of the liquid composition for the color-changing body contains at least water.   The discoloration body set according to claim 2, wherein the solid material is dissolved in a medium.   The color-change body set according to any one of claims 1 to 3, wherein the transparent sheet material is a bag-like body or a sandwich body that encloses the color-change body.   The transparent sheet material is acrylonitrile-butadiene-styrene resin, acrylonitrile resin, cellulose acetate resin, polycarbonate resin, diallyl terephthalate resin, polyethylene resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polypropylene resin, polystyrene resin, polyurethane resin, poly The color-change body set in any one of Claims 1 thru | or 4 chosen from the film of a vinyl chloride resin, a polyvinylidene chloride resin, and a polyester resin.   The color-change body set according to claim 2, wherein the liquid composition for the color-change body is impregnated in a fiber material, and the fiber material is enclosed in a water-impermeable bag-like body. Metachromatic member set according to claim 6, wherein the basis weight of the fibrous material is 10 to 1000 g / ^{m 2.}   The discoloration body set according to claim 7, wherein the fiber material is a nonwoven fabric.