JP6170701B2 - Discolored body set - Google Patents

Description

The present invention relates to a color change body set using a liquid composition for a color change object. Specifically, the present invention relates to a color changing body set using a liquid composition for a color changing body that forms a desired image on the color changing body.

Conventionally, as a liquid composition capable of forming an image on a discolored body, a particular solid particle is dispersed in a medium and used, thereby providing excellent permanent formation of the formed image and collecting handprints, footprints, etc. In other words, a liquid composition for a color-changing body is disclosed that can satisfy the permanent storage stability of an image suitable for use in storing a writing image or a stamp image (see, for example, Patent Document 1).
Even if the liquid composition for a color changing body can form a permanent image on the color changing body, the color change is monotonous and surprisingly poor.

JP 2005-15777 A

As a result of intensive investigations on the liquid composition applied to the color-changing body capable of forming an image, the present invention can be achieved by using a colorant and specific solid particles in the medium in combination to form the color of the image formed. It is an object of the present invention to provide a color change body set using a liquid composition for color change which is rich in change.

The present invention comprises a support, a low refractive index pigment porous layer was fixed in a dispersed state with a binder resin is provided, consisting of metachromatic member wherein the porous layer is discolored to transparent or semitransparent in liquid absorption state A color- changing body set comprising a toy and a liquid composition for a color- changing body , wherein a colorant and a solid material having a refractive index of 1.3 to 1.8 are dissolved and / or dispersed in a medium. Is a requirement.
Furthermore, the colorant is selected from a colored dye, a colored pigment, a metallic pigment, a thermochromic pigment, a photochromic pigment, and a phosphorescent pigment, and the particle size of a solid material dispersed in the medium is 10 μm or less. In addition, it is necessary to use a solid material that is soluble in water after the medium has evaporated.

The present invention is rich in color change of the image formed on the metachromatic member can provide a metachromatic member set using the to impart surprising to satisfy applicability to toys liquid composition for metachromatic members.

  The liquid composition for a color changing material is attached to a porous layer provided in the color changing material and permeates the porous layer at the relevant location to be transparent or translucent, and the liquid composition penetrated into the porous layer Even if the medium of the product evaporates, the solid matter contained in the liquid composition remains, so that the discolored state, that is, the color of the lower layer of the porous layer is permanently visible.

As a medium used in the liquid composition for a color changing body, water is preferably used from the viewpoints of safety and cost. However, the medium is not limited thereto, and may be an organic solvent or a mixture of an organic solvent and water.
Examples of the organic solvent include normal hexane, normal heptane, normal octane, normal nonane, normal decane, cyclohexane, methylcyclohexane, decalin, petroleum ether, petroleum benzine, ligroin, mineral spirit, liquid paraffin, benzene, toluene, xylene, 0- Hydrocarbons such as xylene, m-xylene, p-xylene, p-cymene, solvent naphtha, tetrahydronaphthalene, α-pinene, turpentine oil, mineral oil, vegetable oil.
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 adipate, di-n-octyl adipate adipate Di-n-decyl adipate adipate, dibutyl fumarate, diisobutyl fumarate, dibutyl maleate, bis (2-ethylhexyl) maleate, bis (2-ethylhexyl) azelate, dibutyl sebacate, bis (2ethylhexyl) sebacate, Dodecane diacid bis (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 monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, ethyl lactate, butyl lactate, amyl lactate, ethyl oxyisobutyrate, dibutyl tartrate, tributyl citrate, methyl salicylate Jie Ruokisareto, dibutyl oxalate, 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, nitrobenzol, nitroanisole and the like can be exemplified.
Among the above compounds, aliphatic esters such as liquid paraffin, vegetable oil, and adipic acid ester, and glycols such as propylene glycol and glycerin are preferably used because they are superior in safety compared to other organic solvents.

The solid matter dissolved and / or dispersed in the medium is a substance that shows a solid state at 20 ° C., and remains in the porous layer even when the medium is dried, so that the discolored state is visually recognized. 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 1.8, 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 impart good transparency to the layer and can permanently show the effect of visually recognizing the hue of the lower layer.
Therefore, by using the solid matter, the discolored discolored body is preserved with the same hue even after aging.

  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. Ionomer resin, aminopolyacrylamide 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 terpolymer, vinyl chloride resin, ethylene-propylene copolymer resin, ethylene Crylate ester copolymer, 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- Vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride copolymer resin, ethylene-vinyl alcohol copolymer resin, polyvinyl chloride resin, chlorinated polyethylene resin, chlorinated polypropylene resin, carboxyvinyl polymer, ketone resin, norbornene resin, Polyamide resin, copolymerized polyamide resin, polyamideimide resin, methoxymethylated polyamide, polycarbonate resin, polybutadiene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polystyrene resin, high impact polymer Styrene 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, poly Vinylidene chloride copolymer resin, polyolefin copolymer resin, rosin ester resin, polyisobutylene resin, isoprene rubber, butyl rubber, cyclized rubber, chlorinated rubber, polyvinyl alkyl ether resin, fluororesin, silicone resin, phenol resin, petroleum Hydrocarbon resin, toluene resin, xylene resin, methacrylate ester copolymer resin, melamine resin, urea resin, phenoxy resin, benzoguanamine resin, polyethylene oxide, polyethylene glycol, polyvinyl pyrrolidone, vinyl pyro Don-vinyl acetate copolymer resin, vinyl pyrrolidone-vinyl imidazole copolymer resin, vinyl pyrrolidone-vinyl imidazole methylsulfate copolymer resin, vinyl pyrrolidone-sodium methacrylate copolymer resin, vinyl pyrrolidone-vinyl caprolactam copolymer resin, polyvinyl Polypyrrolidone, polyvinylcaprolactam, polyvinylpyrrolidone-vinylimidazole, polyvinyl alcohol, modified polyvinyl alcohol, polyacrylate, polymethacrylate, polyvinylpyridine, polyacrylamide, polyethyleneimine, polyvinyl methyl ether, styrene-maleic anhydride copolymer resin , Synthetic resins such as methyl vinyl ether-maleic anhydride copolymer resin and polyphosphate, or oligomers.

  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, glue, alginic acid, sodium alginate, propylene glycol alginate, collagen, elastin, Arabic gum, ester gum, guar gum, glycyrrhizin, copalgo , Tarakantogamu, Danmarugomu, gallnut, gallic, tannic acid, hyaluronic acid, camphor, synthetic camphor, lactose, glucose, pectin, polyphenols, beeswax, Japan wax, gallic acid, natural products such as pyrogallol, or semi-synthetic 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, alkyl dimethyl bentine, aminocarboxylate, imidazolium bentine, lecithin, lecithin derivative, alkylamine oxide, poly Oxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene Lenlanolin 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 , Fluoroalkyl carboxylates Disodium N-perfluorooctanesulfonyl glutamate, sodium 3- [fluoroalkyloxy] -1-alkylsulfonate, sodium 3- [ω-fluoroalkanoyl-N-ethylamino] -1-propanesulfonate, N- [3 -(Perfluorooctanesulfonamido) propyl] -N, N dimethyl-N-carboxymethyleneammonium bentyne, N- [3- (perfluorooctanesulfonamido) propyl] -N, N-dimethyl-N-carboxymethyleneammonium bentine Perfluoroalkylcarboxylic acid, perfluorooctanesulfonic acid diethanolamide, perfluoroalkylsulfonate, N-propyl-N- (2-hydroxyethyl) perfluorooctanesulfonamide, perfluoroa Rualkyl-N-ethylsulfonylglycine salt, bis (N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, monoperfluoroalkylethyl phosphate ester, polyoxyethylene allyl glycidyl nonyl phenyl ether sulfate salt, polyoxy Surfactants such as ethylene allyl glycidyl nonyl phenyl ether, polyoxyethylene nonyl propenyl phenyl ether, polyoxyethylene nonyl propenyl phenyl ether sulfate ammonium salt.

  Polysaccharides such as starch sugar, dextran, curdlan, pullulan, cycloamylose, chitin, chitosan, hyaluronic acid, chondroitin sodium 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-isorocyanine, glycine, L-glutamine, L-glutamic acid, L-cystine, derivatives of L-cysteine, L-threoin, 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 adenosine, 6-benzyl adenine, 6-allyl adenosine, 6-benzyl adenosine, dexadenosine 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 the inorganic substance 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 mass or more, preferably 3.0 to 90.0% by mass. If the amount is less than 3.0% by mass, the formation of a clear image is poor, and if it exceeds 90.0% by mass, the viscosity increases depending on the applied solid matter, and the practicality tends to be impaired.

Further, in a system in which a solid material is dispersed in a liquid composition, in order to efficiently impregnate the porous material with the solid material, the particle size of the solid material is 10 μm or less, preferably 0.01 μm to 10 μm, Preferably, the thing of 0.01 micrometer-5 micrometers is used.
It is difficult to finely disperse the solid matter to 0.01 μm or less, and when it is 10 μm or more, the solid matter particles are difficult to enter into the voids of the porous layer, and it is difficult to clearly discolor by adhering to the surface of the porous layer.

When water soluble in the solid material is used, the liquid composition can be applied to the discolored body, and the portion where the solid material remains after evaporation of the medium can be easily removed by washing with water. Can be changed back to
Moreover, even if a solid object adheres to the hand, it can be easily washed away with water.

A colorant is contained in the liquid composition, and a unique aspect change can be imparted.
This will be explained in detail. In a system using a colored dye or a colored pigment as a colorant, when the liquid composition is attached to the porous layer to make the porous layer transparent or translucent, The color of the lower layer of the layer and the color of the liquid composition are visually recognized as a mixed color.
In a system using a metallic pigment as a colorant, the color of the lower layer of the porous layer is visually recognized when the liquid composition is attached to the porous layer to make the porous layer at that portion transparent or translucent. At the same time, the glitter due to the metallic pigment can be combined to give a high-class feeling.
In a system using a thermochromic pigment or a pigment having a photochromic property as the colorant, the color of the lower layer of the porous layer and the color of the liquid composition are mixed as in the system using a colored dye or a colored pigment. In addition, different aspects can be visually recognized by temperature change and light irradiation.
In a system using a phosphorescent pigment as a colorant, the color of the lower layer of the porous layer is visually recognized when the liquid composition is attached to the porous layer to make the porous layer at that location transparent or translucent. At the same time, it is possible to impart visibility in the dark due to the phosphorescent pigment.

As the colored dye, an acid dye, a basic dye, a direct dye, or the like can be used.
Examples of the acid dye include New Coxin (CI. 16255), Tartrazine (CI. 19140), Acid Blue Black 10B (CI. 20470), Guinea Green (CI. 42085), Brilliant Blue FCF. (CI.42090), Acid Violet 6B (C.I.42640), Soluble Blue (C.I.42755), Naphthalene Green (C.I.44025), Eosin (C.I.45380), Phloxin (C.I. 45410), erythrosine (C.I. 45430), nigrosine (C.I. 50420), acid flavin (C.I. 56205) and the like are used.
Examples of basic dyes include chrysoidine (C.I. 11270), methyl violet FN (C.I. 42535), crystal violet (C.I. 42555), malachite green (C.I. 42000), Victoria blue FB ( CI 44045), rhodamine B (C.I. 45170), acridine orange NS (C.I. 46005), methylene blue B (C.I. 52015) and the like are used.
As direct dyes, Congo Red (C.I. 22120), Direct Sky Blue 5B (C.I. 24400), Violet BB (C.I. 27905), Direct Deep Black EX (C.I. 30235), Kaya Las Black G Conch (C.I. 35225), Direct Fast Black G (C.I. 35255), Phthalocyanine Blue (C.I. 74180) and the like are used.

Examples of the colored pigment include inorganic pigments such as carbon black and ultramarine blue, and organic pigments such as copper phthalocyanine blue and benzidine yellow, as well as water that has been finely and stably dispersed in an aqueous medium in advance using a surfactant or resin. Dispersed pigment products and the like are used. I. Pigment Blue 15: 3B [Product name: Sandy Super Blue GLL, pigment content 24%, manufactured by Sanyo Dye Co., Ltd.], C.I. I. Pigment Red 146 [Product name: Sandy Super Pink FBL, pigment content 21.5%, manufactured by Sanyo Dye Co., Ltd.], C.I. I. Pigment Yellow 81 [Product name: TC Yellow FG, pigment content about 30%, manufactured by Dainichi Seika Kogyo Co., Ltd.], C.I. I. Pigment Red 220/166 [Product name: TC Red FG, pigment content of about 35%, manufactured by Dainichi Seika Kogyo Co., Ltd.].
As the fluorescent pigment, a fluorescent pigment in the form of fine particles of a synthetic resin in which various fluorescent dyes are formed into a solid solution in a resin matrix can be used.

As the metallic luster pigment, metal powder such as aluminum and brass, natural mica, synthetic mica, glass pieces, alumina, and transparent metallic luster in which the surface of a film piece is coated with a metal oxide such as titanium oxide. Pigment, transparent metallic luster pigment with color flop, metallic glossy film with transparent or colored transparent film on one or both sides of the metal vapor-deposited film, glittering fine pieces finely cut, and multiple transparent resin layers Illustrative examples include glittering fine pieces obtained by finely cutting an iris film.
Of these, natural mica, synthetic mica, glass pieces, alumina, transparent metallic luster pigments with the surface of film pieces coated with metal oxides such as titanium oxide, and transparent metallic luster pigments with color flop properties. The glittering fine pieces obtained by finely cutting an iris film in which a plurality of transparent resin layers are laminated are excellent in transparency, and thus are preferably used.
The metal powder such as aluminum and brass having the light shielding property should be non-leafy metal powder so as not to cover the entire surface of the porous layer, or the addition amount in the liquid composition should be reduced. become.
The transparent metallic luster pigment with natural mica as a core material is effective when the surface of natural mica particles is coated with titanium oxide, or the upper layer of titanium oxide is coated with iron oxide or non-thermochromic dye. The surface of the natural mica is coated with 41 to 44% by mass of titanium oxide, and the metallic metallic luster pigment having a particle size of 5 to 50 μm. The surface of the natural mica is coated with 30 to 38% by mass of titanium oxide, Gold metallic luster pigment having a particle size of 5 to 60 μm coated with 0.5 to 10% by mass of non-thermochromic colored pigment, particle size of 5 to 100 μm coated with 16 to 39% by mass of titanium oxide on the surface of natural mica Silver metallic luster pigment, metallic metallic luster pigment with natural mica surface coated with 45-58 mass% titanium oxide, natural mica surface coated with 45-58 mass% titanium oxide, 0.5 on top -10 mass% non Metallic color metallic luster pigment obtained by coating a discoloring colored dye pigments.
Specific examples of pigments obtained by coating the surface of the natural mica with a metal oxide such as titanium oxide include trade names “Iriodin” manufactured by Merck & Co., Inc., product number: 100 (particle size distribution: 10 to 60 μm: silver pearl), 120 (particle size distribution) 5-25 μm: raster satin), 201 (particle size distribution 5-25 μm: rutile fine gold), 205 (particle size distribution 10-60 μm: rutile platinum gold), 221 (particle size distribution 5-25 μm: rutile fine blue), 225 (particle size Distribution: 10-60 μm: rutile blue pearl), 231 (particle size distribution: 5-25 μm: rutile fine red), 235 (particle size distribution: 10-60 μm: rutile green pearl), trade name “Lumina Colors” manufactured by BASF Corporation (Particle size distribution 10 to 48 μm: gold), Lumina red (particle size distribution 10 to 48 μm) Metallic red), lumina red blue (particle size distribution 10 to 48 μm: metallic blue), lumina aqua blue (particle size distribution 10 to 48 μm: metallic blue), lumina green (particle size distribution 10 to 48 μm: metallic green), lumina turquoise (particle size distribution 10 ˜48 μm: metallic green).

Transparent metallic luster pigments with synthetic mica as the core material and coated with a metal oxide such as titanium oxide are metal ions that become coloring factors such as impurities and iron compared to systems using natural mica as the core material. In addition to being excellent in glitter, it has a glittering appearance and excellent transparency.
The metallic luster pigment exhibits a metallic luster of gold, silver or metallic color depending on the coverage of the metal oxide covering the surface of the synthetic mica.
As the synthetic mica, KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ may be mentioned.
Although the shape of the mica is not specified, a flat shape or a scale shape can be exemplified.
Examples of the metal oxide that covers the surface of the synthetic mica include metal oxides such as titanium, zirconium, chromium, vanadium, and iron. Preferred examples include metal oxides mainly composed of titanium oxide.
The metallic luster pigment has an average thickness of 0.1 to 5 μm and an average particle diameter of 2 to 200 μm, preferably 2 to 100 μm.
Specific examples of pigments in which the surface of the synthetic mica is coated with a metal oxide are trade names “ultimica” manufactured by Nippon Koken Kogyo Co., Ltd., product number: SB-100 (5 to 30 μm: silver), SD-100 ( 10-100 μm: silver), SE-100 (15-100 μm: silver), SF-100 (44-150 μm: silver), SH-100 (150-600 μm: silver), YB-100 (5-30 μm: gold) YD-100 (10-60 μm: gold), YE-100 (15-100 μm: gold), YF-100 (44-150 μm: gold), RB-100 (5-300 μm: metallic red), RD-100 ( 10-60 μm: metallic red), RE-100 (15-100 μm: metallic red), RF-100 (44-150 μm: metallic red), RBB- 00 (5-30 μm: metallic purple), RBD-100 (10-60 μm: metallic purple), RBE-100 (15-100 μm: metallic purple), RBF-100 (44-150 μm: metallic purple), VB-100 ( 5-30 μm: metallic violet), VD-100 (10-60 μm: metallic violet), VE-100 (15-100 μm: metallic violet), VF-100 (44-150 μm: metallic violet), BB-100 (5- 30 μm: metallic blue), BD-100 (10-60 μm: metallic blue), BE-100 (15-100 μm: metallic blue), BF-100 (44-150 μm: metallic blue), GB-100 (5-30 μm: metallic Lean), GD-100 (10~60μm: metallic green), GE-100 (15~100μm: metallic green), GF-100 (44~150μm: metallic green) and the like can be exemplified.

A transparent metallic luster pigment having a flat glass piece as a core material and the surface thereof coated with a metal oxide such as titanium oxide exhibits a metallic luster of gold, silver or metallic color depending on the coverage of the metal oxide.
Specifically, as a pigment in which the surface of the flat glass piece is coated with a metal oxide, a trade name “META SHINE” MC5090RS (90 μm: silver) manufactured by Nippon Sheet Glass Co., Ltd., in which a scaly glass piece is coated with titanium oxide. MC5090RY (90 μm: gold), MC5090RR (90 μm: red), MC5090RV (90 μm: purple), MC5090RB (90 μm: blue), MC5090RG (90 μm: green), MC1080RS (80 μm: silver), MC1080RY (80 μm: gold), MC1080RR (80 μm: red), MC1080RB (80 μm: blue), MC1080RG (80 μm: green), MC1040RS (40 μm: silver), MC1040RY (40 μm: gold), MC1040RR (40 μm: red), MC1040RB (40 μm) Blue), MC1040RG (40 μm: Green), MC1020RS (20 μm: Silver), MC1020RY (20 μm: Gold), MC1020RR (20 μm: Red), MC1020RB (20 μm: Blue), MC1020RG (20 μm: Green), MC1080RSS1 (80 μm: Silver) ), MC1080RYS1 (80 μm: gold), and the like.

The transparent metallic luster pigment with flaky aluminum oxide as the core material and the surface coated with a metal oxide such as titanium oxide has less impurity content than the system of natural mica, making it brilliant. Are better.
Examples of the metal oxide covering the surface of the aluminum oxide include metal oxides such as titanium, zirconium, chromium, vanadium, iron, etc., preferably a metal oxide mainly composed of titanium oxide is applied, Depending on the coverage of the metal oxide, it exhibits a metallic color such as gold, silver or metallic.
The metallic luster pigment has an average thickness of 0.1 to 5 μm and an average particle diameter of 2 to 200 μm, preferably 2 to 100 μm.
Specific examples of pigments obtained by coating the surface of the flaky aluminum oxide with a metal oxide include trade names “Silary” manufactured by Merck Co., Ltd .: T50-10 (10-30 μm: silver), T60-10 WNT (10-30 μm). : Silver), T60-20WNT (10-30 μm: Gold), T60-24WNT (10-30 μm: Metallic Green), T60-23WNT (10-30 μm: Metallic Blue), and the like.

Examples of the transparent metallic luster pigment having color flop include a cholesteric liquid crystal type metallic luster pigment and a transparent metallic luster pigment formed by coating silicon oxide with one or more metal oxides.
The cholesteric liquid crystal type bright pigment will be described.
The liquid crystal polymer used as the cholesteric liquid crystal type bright pigment has a property that only a part of the incident light is reflected in a wide spectral region due to the interference effect of light, and the light is transmitted through all other regions. The region of the reflection spectrum is determined by the pitch width of the helical polymer and the refractive index of the material, and the reflection spectral region is divided into light components polarized in the left and right helices, with the direction of rotation of the helix. Accordingly, one can be reflected and the other can be transmitted. As a result, the cholesteric liquid crystal type glittering material has the property of transmitting and reflecting over the entire spectral region, that is, the color flop property in which the hue changes depending on the excellent metallic luster and the viewpoint.
Further, the cholesteric liquid crystal type glitter pigment has transparency as well as glitter.
Examples of the cholesteric liquid crystal glitter pigment include materials based on a siloxane skeleton having a mesogen in the side chain.
Specific examples of the cholesteric liquid crystal type bright pigment include trade name “Helicone HC” manufactured by Wacker Chemie, product number: Sapphire (SLM90020) [blue → dark], Scarabeus (SLM90120) [green → blue], Jade (SLM90220). ) [Gold color → green blue], Maple (SLM90320) [red copper color → green], and the like.
The cholesteric liquid crystal type bright pigment preferably has an average thickness of 3 to 15 μm, preferably 5 to 10 μm, and an average particle size of 1 to 100 μm, preferably 10 to 60 μm.

The metallic luster pigment formed by coating the silicon oxide with one or more kinds of metal oxides has light transmittance and expresses various colors depending on the viewing angle and the light hitting angle by the interference effect of light. Can have color flop and metallic luster.
Further, when silicon oxide is coated in multiple layers with two or more kinds of metal oxides, color flop properties and metal gloss can be more effectively imparted by using metal oxides having different light reflectivities.
Examples of the metal oxide include tin oxide, titanium oxide, and iron oxide.
Examples of the metallic luster pigment include trade names manufactured by Merck & Co., Inc .: Colorstream T10-01 Viola Fantasy, Colorstream T10-00 Autum Mystery, and the like.
The metallic luster pigment can be used with any particle size as long as it has color flop properties, but preferably has an average particle size of 1 to 100 μm, preferably 5 to 50 μm.

Examples of the thermochromic pigment include reversible color reactions of inorganic materials such as Ag ₂ HgI ₄ and Cu ₂ HgI ₄ , liquid crystals, electron-donating color-forming organic compounds, and electron-accepting compounds. A reversible thermochromic microcapsule pigment in which a reversible thermochromic composition composed of three components with an organic compound medium to be encapsulated is encapsulated is used.
A reversible thermochromic composition comprising the electron donating color-forming organic compound, an electron-accepting compound, and an organic compound medium that reversibly causes a color reaction between the two will be described.
Examples of the reversible thermochromic composition include those described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-29398, etc., at a predetermined temperature (discoloration point). Discolored before and after, decolored state in the temperature range above the high temperature side discoloration point, color development state in the temperature range below the low temperature side discoloration point, only one specific state exists in the normal temperature range among the two states, The other state is maintained while the heat or cold necessary to develop the state is applied, but when the heat or cold is no longer applied, the heating and decoloring type returns to the state exhibited at room temperature. No. 4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, etc. have a large hysteresis characteristic (ΔH _B = 8-50 ° C. ), That is, when the shape of the curve plotting the change in the color density due to the temperature change is lowering the temperature from the lower temperature side than the color changing temperature range, as opposed to increasing the temperature from the lower temperature side. A reversible thermochromic composition of a color erasing type that has a color memory property that changes color by following different routes, JP-A-11-129623, JP-A-11-5973, JP-A-2001-105732 The reversible thermochromic composition of the heat coloring type described in 1) can be applied.

  As the photochromic pigment, a spirooxazine compound, a spiropyran compound, or a diarylethene compound can be dispersed in various resins to form a granular material, or encapsulated in a capsule wall film and used as a microcapsule pigment.

The phosphorescent pigment is a general-purpose pigment as long as it absorbs and accumulates light from the sun, electric light, etc., and emits light by gradually emitting light in the dark (this is called afterglow). A phosphorescent pigment such as CaS / Bi system, CaSrS / Bi system, ZnS / Cu system, ZnCdS / Cu system, SrAl ₂ O ₄ / rare earth metal system, etc. can be applied.

Furthermore, by including a surfactant in the liquid composition, the liquid composition can be applied to the discolored body with a uniform thickness, and uniform discoloration becomes possible.
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and zwitterionic surfactants. Examples of the nonionic surfactants include fatty acids, higher alcohols, Examples of the alkylphenol-based surfactant include the fatty acid-based, linear alkylbenzene-based, anionic higher alcohol-based, alpha-olefin-based, and normal paraffin-based surfactants. Examples of cationic surfactants include quaternary ammonium salt surfactants, and examples of amphoteric surfactants include amino acid, verine, and amino oxide surfactants.
Of the surfactants, those for cosmetics and food additives are preferably used because of their excellent safety.

As a method of attaching the liquid composition to the discolored body, a method of attaching a finger to the discolored body by wetting the finger with the liquid composition, an applicator having a brush tip or a fiber pen body at the tip or a sponge is impregnated with the liquid composition A method of attaching the liquid composition to the discolored body, a method of bringing the 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, a foam having open cells or closed cells on the marking surface There are a method of impregnating a liquid composition on a stamp with a liquid adhered and adhering it to the discolored body, and a method of adhering the liquid composition to a stamp having a rough surface of plastic or rubber and bringing it into contact with the discolored body.
In addition, as a method of bringing the container containing the liquid composition into contact with or in contact with the discolored body and deriving and attaching the liquid composition from the container, the liquid composition is stored in the container and the liquid in the container is placed. A method of applying a liquid composition by providing a fibrous body and a brush for deriving the composition, a method of storing a liquid composition in a container and providing a spray device to spray the liquid composition, and a syringe Examples include a method of pressing the liquid composition in the container and ejecting the liquid composition.
Further, a fiber material or a foam material having open cells (sponge) impregnated with a liquid composition, a fiber material in which a container is impregnated with a liquid composition, or a foam material having open cells (sponge) is contained. There is a method of bringing a discolored body into contact with a model imitating a stamp stand.
In addition, when a liquid composition is attached to the discolored body, a clear image can be formed by using a stencil, so that playability can be improved.

The discolored body is provided with a porous layer that is transparent or translucent in a liquid absorption state in which a low refractive index pigment is fixed in a dispersed state together with a binder resin on a support.
The material of the support is not particularly limited, and plastic, elastomer, rubber, metal, wood, fabric, stone, leather, synthetic leather, and the like are used.
The support may have a planar shape or a three-dimensional shape.
As the discoloration body, stuffed animals, dolls, doll for a costume, umbrellas and dolls for accessories such as bags, animal, plant, miniature car or the like of the vehicle, building, star, toys in the form of food, such as imitating, accessories toys Is mentioned.
Examples of the accessory toy include false nails, rings, bracelets, crowns, tiaras, hair ornaments, brooches, necklaces, pendants, earrings, earrings, buttons, tie pins, cuffs, anklets, straps, and the like.

On the support, a porous layer having a low refractive index pigment fixed to a binder resin in a dispersed state and having different transparency in a liquid-absorbing state and a non-liquid-absorbing state is provided.
Examples of the low refractive index pigment include silicic acid and / or silicate, barite powder, barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, talc, alumina white, magnesium carbonate, and the like. It is in the range of 4 to 1.8, and exhibits good transparency when liquid is absorbed.
Examples of the silicate include aluminum silicate, aluminum potassium silicate, aluminum sodium silicate, aluminum calcium silicate, potassium silicate, calcium silicate, sodium calcium silicate, sodium silicate, magnesium silicate, and magnesium potassium silicate.
The particle size of the low refractive index pigment is not particularly limited, but 0.03 to 10.0 μm is preferably used.
Two or more of the low refractive index pigments can be used in combination.
In addition, silicic acid is mentioned as a low refractive index pigment used suitably.
The silicic acid may be silicic acid produced by a dry process (hereinafter referred to as dry process silicic acid), but is preferably silicic acid produced by a wet process (hereinafter referred to as wet process silicic acid).
This point will be described below.
Silicic acid is produced as amorphous amorphous silicic acid, and depending on its production method, the dry method using a gas phase reaction such as thermal decomposition of silicon halide such as silicon tetrachloride and the decomposition by acid such as sodium silicate. It is roughly classified into those by a wet method using a liquid phase reaction such as.
The structure of the dry process silicic acid and that of the wet process silicic acid are different, and the dry process silicic acid has a structure in which silicic acid is closely bound, whereas the wet process silicic acid has a structure part in which a long molecular arrangement is formed by condensation of silicic acid. have.
Therefore, the wet process silicic acid has a rough molecular structure compared to the dry process silicic acid, so when applying the wet process silicic acid, the wet process silicic acid is superior in the diffused reflection of light in the dry state compared to the system using the dry process silicic acid, It is presumed that the concealment will increase.
In addition, since the porous layer absorbs water, the wet process silicic acid has more hydroxyl groups present as silanol groups on the particle surface than the dry process silicic acid, and has a high degree of hydrophilicity. It is done.

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

Is the porous layer known means, for example, screen printing, offset printing, gravure? It can be formed by printing means such as printing, coater, tampo printing, transfer, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating and the like.
In addition, a colorant may be contained in the porous layer, or a non-discoloring layer containing a colorant may be provided between the support and the porous layer.

The porous layer may be provided with a water repellent resin layer.
The water-repellent resin layer is formed by appropriately forming an image of a water-repellent treatment liquid containing a water-repellent resin containing a water-repellent resin selected from silicon-based, paraffin-based, polyethylene-based, alkylethyleneurea-based, and fluorine-based water-repellent resins on a porous layer. It is a layer that exists in the porous layer and coexists, which is obtained by adhering so as to form and osmotically drying.
Since the water-repellent resin layer is inherent in a part of the porous layer and disposed in a coexisting state, the water-absorbing state is not formed in the porous layer at the coexisting location of the water-repellent resin layer, The opaque state is maintained.
Accordingly, the water-repellent resin layer and the porous layer that are difficult to discriminate in the dry state can be discriminated by absorbing liquid into the porous layer at the non-arranged portion of the water-repellent resin layer.
Here, the water-repellent resin layer disposed in the coexisting state in the porous layer is a porous layer in addition to the state in which the water-repellent resin layer coexists from the upper layer of the porous layer to the lower layer of the porous layer located on the surface of the support. The water repellent resin layer coexists from the upper layer of the porous layer to the intermediate layer of the porous layer, the water repellent resin layer coexists in the intermediate layer of the porous layer, from the intermediate layer of the porous layer to the lower layer of the porous layer A state where the water-repellent resin layer coexists is mentioned.

Further, the porous layer contains a transparent metallic luster pigment in which a transparent core material is coated with a metal oxide or a transparent metallic luster pigment having color flop properties, and in the dry state, the color due to the low refractive index pigment It is possible to obtain a discolored body that is visually recognized and in which the metallic gloss color due to the transparent metallic gloss pigment is visually recognized in the liquid absorption state.
Examples of the transparent metallic luster pigment include pigments in which natural mica, synthetic mica, glass pieces, alumina, and film pieces are used as a core substance, and the surface thereof is coated with a metal oxide such as titanium, zirconium, chromium, vanadium, and iron. It is done.
Examples of the transparent metallic luster pigment having color flop include a cholesteric liquid crystal type transparent metallic luster pigment and a transparent metallic luster pigment in which silicon oxide is coated with one or more metal oxides.
In addition, in order to visually recognize a clear metallic luster color in the liquid absorption state, an optical interference film composed of one or more kinds of metal vapor-deposited film, oxide and sulfide, and 100 composed of two or more polymers. An iris film, a hologram film, a processed film having the film disposed on the surface thereof, a processed body having a metal vapor-deposited foil disposed on the surface, a pearl pigment or an aluminum fine powder. It is preferable to use a support having a metallic luster such as a processed body in which a metallic luster pigment such as bronze powder is coated or kneaded on the surface, a processed body in which glass beads having retroreflective properties are uniformly coated on the surface, or the like. .

Furthermore, a plurality of glittering fine pieces can be fixed on the porous layer to add a high-class feeling to the monotonous appearance of the porous layer in the dry state.
The brilliant micro-piece is a micro-piece showing optical properties such as light brightness reflectivity, light coherence, iris, hologram, metal gloss, pearl luster, etc. A hologram film, an iris film, a pearly luster film, a transparent hologram film or the like subjected to the above process can be used as fine pieces by appropriate means such as high-frequency fusing, cutting, Thomson punching, die cutting, or etching.
Further, a reversible thermochromic material or a photochromic material is contained in the porous layer, a reversible thermochromic material or a photochromic material is contained in the support, or the support and the porous layer are interposed. By providing a layer containing a reversible thermochromic material or photochromic material, various color changes can be imparted by temperature change or light irradiation.

Examples are shown below, but the present invention is not limited to these examples.
In addition, the part in an Example is a mass part.
Preparation of a liquid composition for a color changer The following table shows the solids used in the liquid composition for a color changer, the refractive index of the solids [value at 20 ° C. at sodium D-line (589 nm)], the medium, and the solids State in medium, colorant.
The particle size is a value measured using a laser diffraction / scattering particle size distribution measuring device (manufactured by HORIBA, Partica LA950V2).

Preparation of thermochromic pigments in the table and pigments having photochromic properties are described below.
Thermochromic pigment (i) 1.5 parts of 3- (4-diethylamino-2-hexyloxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide as component (b) 1,1-bis (4'-hydroxyphenyl) -2-ethylhexane as component, 5.0 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, (c) Behen as component A reversible thermochromic composition comprising 50.0 parts of acid-3,5,5-trimethylhexyl is heated and dissolved, and microencapsulated using an aromatic polyisocyanate prepolymer as a wall film material at 28 ° C. or lower. A thermochromic pigment (reversible thermochromic microcapsule pigment) having an average particle diameter of 6 μm that turns blue and colorless at 32 ° C. or higher was obtained.
Pigment having photochromic properties 1,3,3-trimethyl-spiro [benzo [e] indoline-2,3 '-[3H] naphtho [2,1-b] [1,4] oxazine] 1 part, styrene-α -Methylstyrene copolymer [Rika Hercules Co., Ltd., trade name: Picorotic A-5, weight average molecular weight 317] A microcapsule using an aromatic polyvalent isocyanate prepolymer as a wall film material of a photochromic composition comprising 10 parts Thus, a pigment having a photochromic property that changes color from colorless to blue was obtained.

Example 1
Preparation of discolored body Wet powder fine silica (trade name: NIPSEAL E-1011, manufactured by Tosoh Silica Industry Co., Ltd.) on the surface of a blue polyvinyl chloride sheet having a thickness of 0.2 mm provided with an adhesive layer on the back as a support. ] 15 parts, urethane emulsion [trade name: Neorez R-966, manufactured by Avicia Co., Ltd., solid content 33% by weight] 45 parts, water 32.5 parts, silicone-based antifoaming agent 0.5 part, increased for water-based ink Printed with a screen printing ink consisting of 3 parts of a sticking agent, 1 part of ethylene glycol, and 3 parts of an isocyanate-based crosslinking agent, provided with a porous layer, and cut into a nail shape to form a discolored body (color-changing nail). Obtained.

Preparation of color-change body set The color-change body set was obtained by combining the color-change body and the liquid composition 1 in the table.
The liquid composition is contained in a transparent plastic container, and a brush is provided inside the lid of the container.

The discolored body is normally white, and when the pink liquid composition in the container is attached to the brush and applied to the porous layer of the discolored body, the porous layer becomes transparent, A purple color in which the pink color of the liquid composition was mixed was visually recognized.
The purple discolored body was allowed to stand for 3 months in an environment of 20 ° C., but maintained the same color as the initial stage and was excellent in storage stability.
Further, the discolored body could be returned to its original state by washing with water, and the discolored body could be discolored again using the liquid composition.

Example 2
Preparation of discolored body Wet powder fine powder silica [trade name: NIPSEAL E-1011, manufactured by Tosoh Silica Industries, Ltd.] on the surface of a 0.2 mm thick red polyvinyl chloride sheet provided with an adhesive layer on the back as a support ] 15 parts, urethane emulsion [trade name: Neorez R-966, manufactured by Avicia Co., Ltd., solid content 33% by weight] 45 parts, water 32.5 parts, silicone-based antifoaming agent 0.5 part, increased for water-based ink Printed with a screen printing ink consisting of 3 parts of a sticking agent, 1 part of ethylene glycol, and 3 parts of an isocyanate-based crosslinking agent, provided with a porous layer, and cut into a nail shape to form a discolored body (color-changing nail). Obtained.

Preparation of color-change body set The color-change body set was obtained by combining the color-change body and the liquid composition 2 in the table.
The liquid composition is contained in a transparent plastic container, and a brush is provided inside the lid of the container.

The discolored body is normally white, and when the blue liquid composition in the container is attached to the brush and applied to the porous layer of the discolored body, the porous layer becomes transparent and the red and liquid below are liquid. A purple color in which the blue color of the composition was mixed was visually recognized.
The purple discolored body was allowed to stand for 3 months in an environment of 20 ° C., but maintained the same color as the initial stage and was excellent in storage stability.
Further, the discolored body could be returned to its original state by washing with water, and the discolored body could be discolored again using the liquid composition.

Example 3
Preparation of discolored body Wet powder fine powder silica [trade name: NIPSEAL E-1011, manufactured by Tosoh Silica Industry Co., Ltd.] on the surface of a black polyvinyl chloride sheet having a thickness of 0.2 mm provided with an adhesive layer on the back as a support ] 15 parts, urethane emulsion [trade name: Neorez R-966, manufactured by Avicia Co., Ltd., solid content 33% by weight] 45 parts, water 32.5 parts, silicone-based antifoaming agent 0.5 part, increased for water-based ink Printed with a screen printing ink consisting of 3 parts of a sticking agent, 1 part of ethylene glycol, and 3 parts of an isocyanate-based crosslinking agent, provided with a porous layer, and cut into a nail shape to form a discolored body (color-changing nail). Obtained.

Preparation of color-change body set The color-change body set was obtained by combining the color-change body and the liquid composition 3 in the table.
The liquid composition is contained in a transparent plastic container, and a brush is provided inside the lid of the container.

The discolored body is normally white, and when the liquid composition in the container is attached to the brush and applied to the porous layer of the discolored body, the porous layer becomes transparent, the lower layer black, and the upper layer The silver color was visually recognized by the transparent metallic luster pigment of the liquid composition located in the area.
The silver discolored material was allowed to stand for 3 months in an environment of 20 ° C., but the same color as the initial color was maintained and the storage stability was excellent.
Further, the discolored body could be returned to its original state by washing with water, and the discolored body could be discolored again using the liquid composition.

Example 4
Preparation of discolored body 15 parts of wet-process fine powder silica [trade name: NIPSEAL E-1011, manufactured by Tosoh Silica Industry Co., Ltd.] on a 0.2 mm thick black polyvinyl chloride sheet surface provided with an adhesive layer on the back surface , Urethane emulsion [trade name: Neorez R-966, manufactured by Avicia Co., Ltd., solid content 33% by weight] 45 parts, water 32.5 parts, silicone-based antifoaming agent 0.5 part, thickener 3 for water-based ink A discolorable label was obtained by printing with a screen printing ink comprising 1 part, 1 part of ethylene glycol, and 3 parts of an isocyanate-based crosslinking agent to provide a porous layer.
The color-change adhesive label was stuck on a white miniature car (support) to obtain a color-change body (color-change miniature car).

Preparation of color-change body set The color-change body set was obtained by combining the color-change body and the liquid composition 4 in the table.
The liquid composition is contained in a transparent plastic container, and a brush is provided inside the lid of the container.

The discolored body is normally white, and when the liquid composition in the container is attached to the brush and applied to the porous layer of the discolored body, the porous layer becomes transparent, the lower layer black, and the upper layer The gold color was visually recognized by the transparent metallic luster pigment of the liquid composition located in the area.
The gold-colored discolored material was allowed to stand for 3 months in an environment of 20 ° C., but maintained the same color as in the initial stage and was excellent in storage stability.
Further, the discolored body could be returned to its original state by washing with water, and the discolored body could be discolored again using the liquid composition.

Example 5
Preparation of discolored body Wet powder fine powder silica [trade name: NIPSEAL E-1011, manufactured by Tosoh Silica Industries, Ltd.] on the surface of a 0.2 mm thick red polyvinyl chloride sheet provided with an adhesive layer on the back as a support ] 15 parts, urethane emulsion [trade name: Neorez R-966, manufactured by Avicia Co., Ltd., solid content 33% by weight] 45 parts, water 32.5 parts, silicone-based antifoaming agent 0.5 part, increased for water-based ink Printed with a screen printing ink consisting of 3 parts of a sticking agent, 1 part of ethylene glycol, and 3 parts of an isocyanate-based crosslinking agent, provided with a porous layer, and cut into a nail shape to form a discolored body (color-changing nail). Obtained.

Preparation of color-change body set The color-change body set was obtained by combining the color-change body and the liquid composition 17 in the table.
The liquid composition is contained in a transparent plastic container, and a brush is provided inside the lid of the container.

The discolored body is normally white, and when the liquid composition in the container is attached to the brush and applied to the porous layer of the discolored body, the porous layer becomes transparent, the lower layer red, and the upper layer The brightness due to the iris color of the liquid composition located in the region was visually confirmed.
The discolored body having glitter on the red background was left for 3 months in an environment of 20 ° C., but the same color as the initial color was maintained and the storage stability was excellent.
Further, the discolored body could be returned to its original state by washing with water, and the discolored body could be discolored again using the liquid composition.

Example 6
Production of discolored body On the white polyolefin sheet surface with a thickness of 0.3 mm provided with an adhesive layer on the back side, a non-discolored layer (non-discolored image) is provided by printing an engine pattern by offset printing using printing ink, Next, on the non-discolored layer, 15 parts of wet-process fine powder silica [trade name: Nipseal E-1011, manufactured by Tosoh Silica Industry Co., Ltd.], urethane emulsion [trade name: Neorez R-966, manufactured by Avicia Co., Ltd.] , Solid content 33% by weight] Screen printing comprising 45 parts, water 32.5 parts, silicone-based antifoaming agent 0.5 parts, aqueous ink thickener 3 parts, ethylene glycol 1 part, isocyanate-based crosslinking agent 3 parts The ink is used to print a porous layer, and the printing ink is printed on the porous layer to form a non-color-changeable contour image. Obtained.
The discoloration label was attached to a white miniature car (support) to obtain a discoloration body (discoloration miniature car).

Preparation of color-change body set The color-change body set was obtained by combining the color-change body and the liquid composition 18 in the table.
The liquid composition is contained in a transparent plastic container, and a brush is provided inside the lid of the container.

The discolored body normally shows a state in which the outline (line drawing) of the engine is drawn on a white background. When the liquid composition in the container is attached to the brush and applied to the porous layer of the discolored body, the discolored body becomes porous. The layer became transparent, and the engine pattern by the non-discoloring layer was visually recognized, and at the same time, the glittering effect by the transparent metallic luster powder was given.
The discolored body was allowed to stand for 3 months in an environment of 20 ° C., but maintained the same color as the initial stage and had excellent storage stability.
Further, the discolored body could be returned to its original state by washing with water, and the discolored body could be discolored again using the liquid composition.

Example 7
Preparation of discolored body 15 parts of wet-process fine powder silica [trade name: NIPSEAL E-1011, manufactured by Tosoh Silica Industry Co., Ltd.] on a 0.2 mm thick red polyvinyl chloride sheet surface provided with an adhesive layer on the back surface , Urethane emulsion [trade name: Neorez R-966, manufactured by Avicia Co., Ltd., solid content 33% by weight] 45 parts, water 32.5 parts, silicone-based antifoaming agent 0.5 part, thickener 3 for water-based ink A discolorable label was obtained by printing using a screen printing ink comprising 1 part, 1 part of ethylene glycol, and 3 parts of an isocyanate crosslinking agent to provide a porous layer.
Next, the discoloration label (the discoloration miniature car) was obtained by sticking the discoloration label to a miniature car (support).

Preparation of color-change body set The color-change body set was obtained by combining the color-change body and the liquid composition 19 in the table.
The liquid composition is contained in a transparent plastic container, and a brush is provided inside the lid of the container.

The discolored body is normally white, and when the blue liquid composition in the container is attached to the brush and applied to the porous layer of the discolored body, the porous layer becomes transparent and the red and liquid below are liquid. A purple color in which the blue color of the composition was mixed was visually recognized.
The purple discolored body was allowed to stand for 3 months in an environment of 20 ° C., but maintained the same color as the initial stage and was excellent in storage stability.
When the discolored body was heated by hand, the thermochromic pigment changed from blue to colorless depending on the body temperature, so that the discolored body changed to red and turned to purple again when the touch was stopped.
Further, the discolored body could be returned to its original state by washing with water, and the discolored body could be discolored again using the liquid composition.

Example 8
Preparation of discolored body Wet powder fine powder silica [trade name: NIPSEAL E-1011, manufactured by Tosoh Silica Industries, Ltd.] on the surface of a 0.2 mm thick red polyvinyl chloride sheet provided with an adhesive layer on the back as a support ] 15 parts, urethane emulsion [trade name: Neorez R-966, manufactured by Avicia Co., Ltd., solid content 33% by weight] 45 parts, water 32.5 parts, silicone-based antifoaming agent 0.5 part, increased for water-based ink Printed with a screen printing ink consisting of 3 parts of a sticking agent, 1 part of ethylene glycol, and 3 parts of an isocyanate-based crosslinking agent, provided with a porous layer, and cut into a nail shape to form a discolored body (color-changing nail). Obtained.

Preparation of color-change body set The color-change body set was obtained by combining the color-change body and the liquid composition 19 in the table.
The liquid composition is contained in a transparent plastic container, and a brush is provided inside the lid of the container.

The discolored body is normally white, and when the colorless liquid composition in the container is attached to the brush and applied to the porous layer of the discolored body, the porous layer becomes transparent and depends on the underlying support. Red color was visible.
The purple discolored body was allowed to stand for 3 months in an environment of 20 ° C., but maintained the same color as the initial stage and was excellent in storage stability.
When the discolored body was attached to a finger and exposed to sunlight, the discolored body's photochromic pigment changed from colorless to blue, so that the discolored body changed to purple and turned red again when left in the dark.
Further, the discolored body could be returned to its original state by washing with water, and the discolored body could be discolored again using the liquid composition.

Example 9
Preparation of discolored body 15 parts of wet-process fine powder silica [trade name: NIPSEAL E-1011, manufactured by Tosoh Silica Industry Co., Ltd.] on a 0.2 mm thick red polyvinyl chloride sheet surface provided with an adhesive layer on the back surface , Urethane emulsion [trade name: Neorez R-966, manufactured by Avicia Co., Ltd., solid content 33% by weight] 45 parts, water 32.5 parts, silicone-based antifoaming agent 0.5 part, thickener 3 for water-based ink A discolorable label was obtained by printing using a screen printing ink comprising 1 part, 1 part of ethylene glycol, and 3 parts of an isocyanate crosslinking agent to provide a porous layer.
The discoloration label was attached to a miniature car (support) to obtain a discoloration body (discoloration miniature car).

Preparation of color-change body set The color-change body set was obtained by combining the color-change body and the liquid composition 21 in the table.
The liquid composition is contained in a transparent plastic container, and a brush is provided inside the lid of the container.

The discolored body is normally white, and when the colorless liquid composition in the container is attached to the brush and applied to the porous layer of the discolored body, the porous layer becomes transparent and the underlying red color is visible. It was done.
The red discolored body was allowed to stand for 3 months in an environment of 20 ° C., but maintained the same color as the initial stage and was excellent in storage stability.
When the discolored body was visually recognized in a dark place, the phosphorescent pigment emitted light, and thus the discolored body was visually recognized as green.
Further, the discolored body could be returned to its original state by washing with water, and the discolored body could be discolored again using the liquid composition.

Claims (4)

A toy comprising a discolored body in which a porous layer in which a low refractive index pigment is fixed in a dispersed state together with a binder resin is provided on a support, and the porous layer is transparent or translucent in a liquid-absorbing state and changes color, and a medium A color changer set comprising a colorant and a liquid composition for color change, wherein a solid material having a refractive index of 1.3 to 1.8 is dissolved and / or dispersed therein . The color changer set according to claim 1, wherein the colorant is selected from a colored dye, a colored pigment, a metallic pigment, a thermochromic pigment, a pigment having a photochromic property, and a phosphorescent pigment . The color-change body set according to claim 1 or 2, wherein the particle size of the solid material dispersed in the medium is 10 µm or less . The discoloration body set according to any one of claims 1 to 3, wherein a solid material that is soluble in water after the medium evaporates is used .