JP2009074012A - Allochroic coating liquid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an allochroic coating liquid with high commodity value enriched with decoration property and unexpected nature capable of forming a coating film in which color tone by low refractive index pigment is visually recognized in a dry state and a metal luster color of a plurality of colors with different color tone is visually recognized at an angle that it is visually recognized by a transparent metal luster pigment having color flop property in a liquid absorption state. <P>SOLUTION: The allochroic coating liquid capable of being used for a coating and a printing ink comprises at least the low refractive index pigment, the transparent metal luster pigment having the color flop property, a resin, and a liquid medium. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a color-changing coating liquid. More specifically, the present invention relates to a color-changing coating solution capable of forming a coating film that changes color to a state different from a normal state by application of water.

Conventionally, as a coating liquid for forming a coating film that changes its color to a state different from the normal state by application of water, a moisture-sensitive color-changing printing agent containing fine powder silicic acid and an iris pearl pigment has been disclosed (for example, Patent Document 1). reference).
The coating film formed using the above printing agent has a diffused reflection of light by silicic acid when concealed and conceals the lower layer so that the white color is visually recognized. The glossy color becomes visible.
However, the pearl pigment contained in the textile printing agent has only a single metallic luster color visually recognized and has a poor color change.
JP-A-1-260075

  The present invention further pursues a coating solution that can form a coating film that changes color by the application of this kind of water, and the color tone due to a low refractive index pigment such as silicic acid is visible in the dry state, and the color flop property in the liquid absorption state. It is an object of the present invention to provide a color-changing coating liquid that is rich in unexpected color change in which a plurality of metallic glossy colors having different color tones are visually recognized at a viewing angle.

The present invention requires a color-changing coating liquid comprising at least a low refractive index pigment, a transparent metallic luster pigment having a color flop property, a resin, and a liquid medium.
Further, the transparent metallic luster pigment having color flop is selected from a cholesteric liquid crystal type metallic luster pigment, a metallic luster pigment obtained by coating silicon oxide with one or more metal oxides, It is required that the weight ratio of the refractive index pigment and the transparent metallic luster pigment is 1: 0.2 to 1: 3, and that the color-changing coating liquid is selected from paints and printing inks.

  In the present invention, the color tone due to the low refractive index pigment is visually recognized in the dry state, and in the liquid absorption state, a plurality of metallic glossy colors having different color tones are visually recognized at the viewing angle due to the transparent metal gloss pigment having color flop properties. It is possible to provide a highly color-changing coating liquid that is rich in decorativeness and unexpectedness that can form a coated film.

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 color tone changes depending on the excellent metallic luster and the viewpoint.
Further, the cholesteric liquid crystal type glitter pigment has transparency as well as glitter.
Specific examples of the cholesteric liquid crystal glitter pigment include materials based on a siloxane skeleton having a mesogen in the side chain.
As the cholesteric liquid crystal type bright pigment, specifically, 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 glitter pigment 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.
When the average thickness and particle size are out of the above ranges, the glitter and color flop properties may be impaired, and the orientation and stability of the pigment in the coating film may be adversely affected, limiting practical use.

Among the transparent metallic luster pigments having the color flop properties, metallic luster pigments formed by coating silicon oxide with one or more metal oxides are light transmissive and visually affected by light interference effects. It has a color flop that can express various colors depending on the angle at which it is illuminated and the angle of light, and has excellent 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.
When the average particle size is out of the range of 1 to 100 μm, the glitter and color flop properties may be impaired, and the orientation and stability of the metallic luster pigment in the liquid composition may be adversely affected, which limits the practical use. Sometimes.

Examples of the low refractive index pigment include silicic acid and salts thereof, barite powder, barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, talc, alumina white, magnesium carbonate, and the like. It is in the range of 1.8 and exhibits good transparency when liquid is absorbed.
Examples of the silicic acid salts include aluminum silicate, aluminum potassium silicate, sodium aluminum silicate, aluminum calcium silicate, potassium silicate, calcium silicate, calcium sodium silicate, sodium silicate, magnesium silicate, and magnesium potassium silicate.
The particle size of the low refractive index pigment is not particularly limited, but 0.03 to 10.0 μm is preferably used.
Two or more of the low refractive index pigments can be used in combination.
In addition, silicic acid is mentioned as a low refractive index pigment used suitably.
The silicic acid may be silicic acid produced by a dry process (hereinafter referred to as dry process silicic acid), but is preferably silicic acid produced by a wet process (hereinafter referred to as wet process silicic acid).
This point will be described below.
Silicic acid is produced as amorphous amorphous silicic acid, and depending on its production method, the dry method using a gas phase reaction such as thermal decomposition of silicon halide such as silicon tetrachloride and the decomposition by acid such as sodium silicate. It is roughly classified into those by a wet method using a liquid phase reaction such as.
The structure of the dry process silicic acid and that of the wet process silicic acid are different, and the dry process silicic acid has a structure in which silicic acid is closely bound, whereas the wet process silicic acid has a structure part in which a long molecular arrangement is formed by condensation of silicic acid. have.
Therefore, the wet process silicic acid has a rough molecular structure compared to the dry process silicic acid, so when applying the wet process silicic acid, the wet process silicic acid is superior in the diffused reflection of light in the dry state compared to the system using the dry process silicic acid, It is presumed that the concealability in the normal state will increase.
In addition, since the coating film 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 and is preferably used. .
The wet type silicic acid and other low refractive index pigments can be used in combination.
The mixing ratio of the low refractive index pigment and the metallic luster pigment is 0.2 to 3 parts by weight, more preferably 0.3 to 2 parts by weight with respect to 1 part by weight of the low refractive index pigment. . When the metallic luster pigment is less than 0.2 parts by weight with respect to 1 part by weight of the low refractive index pigment, it becomes difficult to show the metallic luster in the liquid absorption state, and the metallic luster pigment with respect to 1 part by weight of the low refractive index pigment. When the amount exceeds 3 parts by weight, the color tone of the metallic luster pigment becomes easily visible in the dry state, the color tone due to the desired low refractive index pigment becomes difficult to see, and the taste of the color change between the dry state and the liquid absorption state is impaired.

Examples of the 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 each of the above Examples thereof include resin emulsions, caseins, starches, cellulose derivatives, polyvinyl alcohol, urea resins, binder resins such as phenol resins.
The mixing ratio of the low refractive index pigment and these binder resins depends on the kind and properties of the low refractive index pigment, but preferably the binder resin solid content is 0.5 to 1 part by weight with respect to 1 part by weight of the low refractive index pigment. 2 parts by weight, more preferably 0.8 to 1.5 parts by weight. When the binder resin solid content is less than 0.5 parts by weight with respect to 1 part by weight of the low refractive index pigment, it is difficult to obtain a practical film strength of the formed coating film, and it exceeds 2 parts by weight. In this case, the water permeability into the coating film is deteriorated.
Since the coating film has a smaller mixing ratio of the binder resin to the colorant than a general coating film, it is difficult to obtain sufficient film strength. Therefore, among the binder resins, it is preferable to increase the scratch resistance using a nylon resin or a urethane resin.
Examples of the urethane resin include a polyester urethane resin, a polycarbonate urethane resin, and a polyether urethane resin, and two or more of them can be used in combination. In addition, a urethane emulsion resin in which the resin is emulsified and dispersed in water, or a colloid in which the resin is self-emulsified without the need for an emulsifier by an ionic group of the ionic urethane resin (urethane ionomer) itself and dissolved or dispersed in water. A dispersion type (ionomer type) urethane resin can also be used.
The urethane-based resin may be either an aqueous urethane-based resin or an oil-based urethane-based resin, but an aqueous urethane-based resin, particularly a urethane-based emulsion resin or a colloidally dispersed urethane-based resin is preferably used.
The urethane resin can be used alone, but other binder resins can be used in combination depending on the type of support and the performance required for the coating. When a binder resin other than the urethane resin is used in combination, in order to obtain a practical film strength, it is preferable to contain a urethane resin in a solid content ratio of 30% by weight or more in the binder resin of the coating film.
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 coating film, the degree of penetration, and the speed of drying after the penetration can be adjusted. Furthermore, the said adjustment can be controlled by adding a dispersing agent suitably.

As the liquid medium, water is preferably used in view of safety and cost, but a mixture of water and various organic solvents or an organic solvent may be used.
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.

The color-changing coating liquid is used as a paint or printing ink depending on the type of medium and resin.
It can also be used as ink for writing instruments, paints, cosmetics and the like.

A coating film is formed on a support such as paper, synthetic paper, thread, fabric, flocked or brushed fabric, non-woven fabric, synthetic leather, leather, plastic, glass, ceramics, wood, stone, metal using the discoloring coating solution. It can be formed to obtain painted or printed matter.
The coating film is a porous layer formed by the other compound by volatilization of the medium in the coating solution, and the transparent metallic luster pigment and the low refractive index pigment are fixed to the resin in a dispersed state. Become.
The support preferably has a dark color such as black. This is because the transparent metallic luster pigment has a dichroic effect of reflected color and transmitted color and absorbs water. Sometimes, when the lower layer is a light color such as white, the incident light is totally reflected and it is difficult to visually recognize the metallic luster color. On the other hand, when the lower layer is a dark color such as black, the transmitted color is absorbed by black and the reflected color This is because the metallic gloss color can be clearly recognized.
In addition, when a support body is light colors, such as white, a dark printing layer can be provided between a support body and a coating film.
Furthermore, when the support is transparent, a dark color printing layer can be provided between the support and the coating film or on the back side of the support.

Examples and application examples are shown below, but the present invention is not limited thereto. In addition, the part in an Example is a weight part.
Example 1
Preparation of color-changing coating solution 5 parts of bright pigment coated with flaky silicon oxide with tin oxide and further coated with titanium oxide (Merck, Colorstream T10-01 (Viola Fantasy) particle size 5 to 50 μm), wet Method Silicic acid [trade name: Nipseal E-200, manufactured by Nippon Silica Kogyo Co., Ltd.] 15 parts, urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink & Chemicals, Inc., solid content 50%] 30 parts , 40 parts of water, 0.5 part of a silicone-based antifoaming agent, 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 3 parts of an isocyanate-based crosslinking agent were uniformly mixed and stirred to obtain a discoloring coating solution. .

Preparation of discolored body The coating solution was applied to a black support (paper) and then dried to provide a porous layer (coating film) to obtain a discolored body.
The discolored body is visually recognized as a white state by the porous layer in the dry state.
When water is attached to the porous layer, the porous layer becomes transparent and the black of the support and the transparent metallic luster pigment in the porous layer make the metallic luster of gold, silver, green and purple depending on the viewing angle Each color becomes a visible color change. Moreover, this aspect change could be repeated.

Example 2
Preparation of Discoloring Coating Liquid After coating flaky silicon oxide with tin oxide and further coating with titanium oxide, 10 parts of luster pigment (manufactured by Merck, Colorstream T10-02 (Arctic Fire)), wet process silicic acid [trade name : Nip seal E-200, manufactured by Nippon Silica Industry Co., Ltd.] 5 parts, urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink & Chemicals, Inc., solid content 50%] 15 parts, water 30 parts, A discoloring coating solution was obtained by uniformly mixing and stirring 0.5 part of a silicone-based antifoaming agent, 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 3 parts of an isocyanate-based crosslinking agent.

Preparation of discolored body The coating solution was applied to a black support (paper) and then dried to provide a porous layer (coating film) to obtain a discolored body.
The discolored body is visually recognized as a white state by the porous layer in the dry state.
When water is adhered to the porous layer, the porous layer becomes transparent, and the metallic luster of gold, silver, green and red depends on the viewing angle by the black color of the support and the transparent metallic luster pigment in the porous layer. Each color becomes a visible color change. Moreover, this aspect change could be repeated.

Example 3
Preparation of discoloring coating solution: A lustrous pigment coated with flaky silicon oxide with tin oxide, and further coated with titanium oxide [manufactured by Merck, Colorstream T10-03 (Tropic Sunrise)], a wet process silicic acid [trade name] : Nip seal E-200, manufactured by Nippon Silica Industry Co., Ltd.] 15 parts, urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink & Chemicals, Inc., solid content 50%] 30 parts, water 40 parts, A discoloring coating solution was obtained by uniformly mixing and stirring 0.5 part of a silicone-based antifoaming agent, 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 3 parts of an isocyanate-based crosslinking agent.

Preparation of discolored body The coating solution was applied to a black support (paper) and then dried to provide a porous layer (coating film) to obtain a discolored body.
The discolored body is visually recognized as a white state by the porous layer in the dry state.
When water is attached to the porous layer, the porous layer becomes transparent, and the metal of silver, green, red, and orange depends on the viewing angle by the black color of the support and the transparent metallic luster pigment in the porous layer. Each gloss color is a visible color change. Moreover, this aspect change could be repeated.

Example 4
Preparation of discoloring coating liquid Transparent metallic luster pigment coated with flaky silicon oxide with iron oxide (Merck, Colorstream F10-00 (Autumn Mystery) particle size 5 to 50 μm), 10 parts by wet method silicic acid [trade name: Nip seal E-1011, manufactured by Nippon Silica Industry Co., Ltd.] 15 parts, urethane emulsion [trade name: Permarin UA-150, manufactured by Sanyo Chemical Industries, Ltd., solid content 30%] 50 parts, water 30 parts, isopropyl alcohol 10 Part, 0.5 part of a silicone-based antifoaming agent, 3.0 parts of a leveling agent, and 2 parts of an isocyanate-based crosslinking agent were uniformly mixed and stirred to obtain a color changing coating solution.

Preparation of discolored body The coating solution was applied to a black support (resin molded product) and then dried to provide a porous layer (coating film) to obtain a discolored body.
The discolored body is visually recognized as a white state by the porous layer in the dry state.
When water is attached to the porous layer, the porous layer becomes transparent and the support black, and the transparent metallic luster pigment in the porous layer gives a metallic luster color of gold and red purple depending on the viewing angle, respectively. It becomes a visible discoloration. Moreover, this aspect change could be repeated.

Example 5
Cholesteric liquid crystal type luster pigment [manufactured by Wacker Chemie, Helicone HC (Maple, SLM90320), average thickness 5 μm, average particle size 30 μm] 30 parts, wet process silicic acid [trade name: NIPSEAL E-200, Nippon Silica Kogyo Co., Ltd. )] 10 parts, urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30%] 50 parts, water 30 parts, silicone antifoam 0.5 parts, aqueous 3 parts of the ink thickener, 1 part of ethylene glycol, and 2 parts of the isocyanate-based crosslinking agent were uniformly mixed and stirred to obtain a color changing coating solution.

Preparation of discolored body The coating solution was applied to a black support (paper) and then dried to provide a porous layer (coating film) to obtain a discolored body.
The discolored body is visually recognized as a white state by the porous layer in the dry state.
When water is attached to the porous layer, the porous layer becomes transparent and the support black, and the transparent metallic luster pigment in the porous layer has a bright copper metal luster color with high brightness depending on the viewing angle. Each yellow-green metallic luster is a visible color change. Moreover, this aspect change could be repeated.

Example 6
Cholesteric liquid crystal type luster pigment [manufactured by Wacker Chemie, Helicone HC (Scarabeus, SLM90120), average thickness 5 μm, average particle size 30 μm] 10 parts, wet process silicic acid [trade name: Nipsil E-200, Nippon Silica Kogyo Co., Ltd. )] 15 parts, urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30%] 50 parts, water 30 parts, silicone-based antifoaming agent 0.5 part, aqueous system 3 parts of the ink thickener, 1 part of ethylene glycol, and 2 parts of the isocyanate-based crosslinking agent were uniformly mixed and stirred to obtain a color changing coating solution.

Preparation of discolored body The coating solution was applied to a black support (paper) and then dried to provide a porous layer (coating film) to obtain a discolored body.
The discolored body is visually recognized as a white state by the porous layer in the dry state.
When water is attached to the porous layer, the porous layer becomes transparent and the support black color and the transparent metallic luster pigment in the porous layer make the green metallic luster color and blue color brighter depending on the viewing angle. Each of the metallic luster colors becomes a discolored body that is visually recognized. Moreover, this aspect change could be repeated.

Example 7
Cholesteric liquid crystal type luster pigment [manufactured by Wacker Chemie, helicone HC (Jade, SLM90220), average thickness 5 μm, average particle size 30 μm] 10 parts, wet process silicic acid [trade name: NIPSEAL E-200, Nippon Silica Kogyo Co., Ltd. )] 10 parts, urethane emulsion [trade name: Hydran AP-10, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30%] 50 parts, water 30 parts, silicone antifoam 0.5 parts, aqueous 3 parts of the ink thickener, 1 part of ethylene glycol, and 2 parts of the isocyanate-based crosslinking agent were uniformly mixed and stirred to obtain a color changing coating solution.

Preparation of discolored body The coating solution was applied to a black support (paper) and then dried to provide a porous layer (coating film) to obtain a discolored body.
The discolored body is visually recognized as a white state by the porous layer in the dry state.
When water is attached to the porous layer, the porous layer becomes transparent and the support black color, and the transparent metallic luster pigment in the porous layer makes the golden metallic luster color and green color brighter depending on the viewing angle. Each of the metallic luster colors becomes a discolored body that is visually recognized. Moreover, this aspect change could be repeated.

Example 8
Cholesteric liquid crystal type luster pigment (manufactured by Wacker Chemie, Helicone HC (Sapphire, SLM90020), average thickness 5 μm, average particle size 30 μm)
2 parts, wet process silicic acid [trade name: NIPSEAL E-1011, manufactured by Nippon Silica Industry Co., Ltd.] 10 parts, urethane emulsion [trade name: Permarin UA-150, manufactured by Sanyo Chemical Industries, Ltd., solid content 30%] 50 parts, 30 parts of water, 10 parts of isopropyl alcohol, 0.5 parts of a silicone-based antifoaming agent, 3.0 parts of a leveling agent, and 2 parts of an isocyanate-based crosslinking agent were uniformly mixed and stirred to obtain a discoloring coating solution. .

Preparation of discolored body The coating solution was applied to a black support (resin molded product) and then dried to provide a porous layer (coating film) to obtain a discolored body.
The discolored body is visually recognized as a white state by the porous layer in the dry state.
When water is attached to the porous layer, the porous layer becomes transparent and the black color of the support and the transparent metallic luster pigment in the porous layer cause a blue metallic luster color and a dark purple metallic luster depending on the viewing angle. Each color becomes a visible color change. Moreover, this aspect change could be repeated.

Application example 1
Using the coating solution obtained in Example 1 as a support, printing on a 100-mesh screen plate on the entire surface of a polyester satin fabric having a black basis weight of 90 g / m ² , drying and curing at 130 ° C. for 5 minutes. Thus, a porous layer (coating film) was formed to obtain a water-discoloring fabric sheet.
The water discolorable fabric sheet is visually recognized as being white on the entire surface due to the porous layer in the dry state.
When writing on the water discolorable fabric sheet with a pen containing water, the porous layer of the portion becomes transparent, and the gold color, silver color and green color due to the transparent metallic luster pigment in the black color of the support and the porous layer. And purple metal glossy handwriting are visually recognized by the viewing angle. The appearance is kept in an undried state, and when dried, the original white color is restored and the handwriting is not visually recognized. This aspect change could be repeated.

Application example 2
The spray paint obtained in Example 4 was filled in a spray gun (caliber 0.6 mm), and the entire body of a miniature car that was injection-molded with black ABS resin was coated and then dried to obtain a porous layer (coating film) ) To obtain a water discoloration miniature car.
As for the miniature car, a miniature car whose entire surface is white due to the porous layer is visually recognized in a dry state.
When water is attached to the miniature car, the porous layer of the portion becomes transparent, and the black color of the support and the gold and red-purple metallic luster colors due to the transparent metallic luster pigment in the porous layer are visible. Visualized by angle. The aspect is kept in an undried state and returns to its original white color when dried. This aspect change could be repeated.

Application example 3
Using a coating solution obtained in Example 5 on a black synthetic paper with a basis weight of 100 g / m ² as a support, a heart pattern was printed with a 100-mesh screen plate and dried and cured at 70 ° C. for 10 minutes. Thus, a porous layer (coating film) was formed to obtain a water discolorable seal.
In the water discolorable fabric seal, a white heart pattern due to the porous layer is visually recognized on black synthetic paper in a dry state.
When water is sprayed on the heart pattern part with a spray containing water, the porous layer of the part to which the water has adhered becomes transparent, and by the transparent metallic luster pigment in the black color of the support and the porous layer, A bright copper-brown metal luster color and a yellow-green metal luster color are visually recognized by the respective viewing angles. The aspect is kept in an undried state and returns to its original white color when dried. This aspect could be repeated. Moreover, since it is a sealing material, it can be affixed to a three-dimensional object to enjoy the change in appearance.

Application example 4
Black nylon taffeta fabric was used as an umbrella upholstery. On the upper layer of the upholstery material, a polka dot pattern is printed with a 100-mesh screen plate using the coating solution obtained in Example 2, and dried and cured at 130 ° C. for 5 minutes to form a porous layer (coating film). Thus, a water-coloring umbrella upholstery material was obtained.
The water discolorable upholstery was prepared by attaching the water discolorable tension material to an umbrella bone.
The water discolorable umbrella is visually recognized as a white polka dot pattern made of a black base and a porous layer in a dry state.
When water is attached to the umbrella, the porous layer of the portion becomes transparent, and the metallic luster color of gold, silver, green and red due to the black color of the support and the transparent metallic luster pigment in the porous layer is obtained. Visualization is based on the viewing angle. The aspect is kept in an undried state, and when dried, the original white polka dot pattern is restored. This aspect change could be repeated.

Application example 5
The coating liquid obtained in Example 3 was printed on the entire surface of the black fabric using a 100-mesh screen plate, and then dried to form a porous layer (coating film) to obtain a discolorable fabric. Further, the fabric was sewn to prepare a swimsuit.
The swimsuit is visually recognized as a white swimsuit with a porous layer in the dry state.
When water is attached to the swimsuit, the porous layer of the part becomes transparent, and the metallic glossy color of silver, green, red, and orange due to the black support and the transparent metallic luster pigment in the porous layer Depending on the viewing angle. The aspect is kept in an undried state and returns to its original white color when dried. This aspect change could be repeated.

Claims (4)

  A color-changing coating liquid comprising at least a low refractive index pigment, a transparent metallic luster pigment having color flop properties, a resin, and a liquid medium.   The color-changing property according to claim 1, wherein the transparent metallic luster pigment having color flop is selected from a cholesteric liquid crystal type metallic luster pigment and a metallic luster pigment obtained by coating silicon oxide with one or more metal oxides. Coating liquid.   The discolorable coating solution according to claim 1 or 2, wherein the weight ratio of the low refractive index pigment to the transparent metallic luster pigment is 1: 0.2 to 1: 3.   The discolorable coating liquid according to any one of claims 1 to 3, which is selected from paints and printing inks.