JPH03224783A - Water color-deveropable sheet - Google Patents

Abstract

PURPOSE:To obtain a forgery preventing sheet capable of judging genuineness instantaneously by merely applying water by providing a water color-developable layer based on a colorless-light-colored basic dye, the coupler capable of forming a color upon the contact with said dye, a desensitizer and an adhesive to at least a part of a support. CONSTITUTION:A water color-developable layer based on a colorless -light- colored basic dye, the coupler capable of forming a color upon the contact with said dye, a desensitizer and an adhesive is provided to at least a part of a support. As the basic dye, a triallylmethane dye, a diphenylmethane dye, a spiro dye, a lactam dye and a fluorane dye are designated. As the coupler, a phenolic compound, aromatic carboxylic acid and a polyvalent metal salt of aromatic carboxylic acid are designated. The mixing ratio of the basic dye and the coupler is controlled so that the coupler is 50-500 pts.wt. per 100 pts.wt. of the dye. As the desensitizer, polyethyleneimine, polyolefin glycol, an anionic surfactant and a nonionic surfactant are used and the use amount thereof is 50-2000 pts.wt. per 100 pts.wt. of the coupler.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a water-chromic sheet whose parts develop color just by getting wet with water, and more specifically, to a water-colorable sheet that is useful for practicing calligraphy, etc. Anti-counterfeiting sheets useful for preventing counterfeiting of sheets, securities, banknotes, credit cards, gift certificates, admission tickets, product labels, etc., molding sheets useful for making flat molds, foot molds, fish prints, etc. The present invention relates to a water-colorable sheet that can be used for.

[Prior Art] Conventionally known water-colorable sheets are made by coating a colored base material with carbon black, etc., and then providing a white pigment layer with a low refractive index to hide the colored layer. There is a reversible water brush sheet in which the concealing part is wetted with a liquid such as water so that the colored layer underneath can be seen through. However, since this sheet has a colorant layer such as carbon black on the support and a white pigment layer to hide this colorant layer, it naturally requires at least two coatings. , and to completely hide the colorant layer, add 1 layer of white pigment.
It has to be applied at a rate of about 5 to 25 g/rrf, which poses a problem in terms of cost.

There is also an irreversible color-forming sheet in which a sheet containing a pH indicator is colored with a pH-adjusted aqueous solution, but it is not possible to color the sheet with just water.

In recent years, with the development of copying machines, especially color copying machines,
It has become relatively easy to forge printed materials.

To prevent counterfeiting, methods such as the Sammel letterpress printing method, the watermark method, and the tactile method of creating irregularities on the surface have been used to prevent counterfeiting. There are problems in that the device used to determine the authenticity is large-scale, and it takes time to perform the determination.

In addition, a method has been proposed that uses leuco dye and Lewis acid, one of which is hidden and printed, and the other is used in the form of a felt-tip pen, etc., to instantly determine authenticity, but it is necessary to always have chemicals on hand. It is necessary to do so.

On the other hand, flat type and foot type are used medically as a convenient way to understand the growth process of hands and feet. In particular, foot lasts are frequently used as a screening method for flat feet and as a simple method for custom-made shoe shape retention. Generally, when making a mold of a flat or foot shape, it is generally well known to apply ink or ink to the hand or foot to be molded, and to make a copy by contacting it with paper or the like. However, after making the mold, these methods
There is a problem in that it is difficult to remove vermilion or the like that has adhered to the hands or feet.

(Problems to be Solved by the Invention) The present invention provides a water-colorable sheet that colors the area simply by wetting it with water.Also, it is possible to simply apply water without using any special chemicals. The present invention provides an anti-counterfeiting sheet that can instantly determine the authenticity of the product by simply using the sheet.Furthermore, the present invention can prevent hands, feet, or other objects to be molded from being stained with vermillion ink, ink, etc. To provide a molding sheet with which handprints, footprints, and other objects can be easily molded.

[Means for Solving the Problems] The present invention mainly includes a colorless to light-colored basic dye, a coloring agent capable of forming a color upon contact with the dye, a G5 agent, and an adhesive on at least a portion of the support. This is a water coloring sheet characterized by having a water coloring layer as a component.

[Effect]

The water-color-forming sheet of the present invention is a water-color-forming sheet that utilizes a chemical reaction in which a visible image is obtained by adhesion of water. Colorless or light-colored basic dyes used include:
Various types are known, and examples include the following.

3.3-bis(p-dimethylaminophenyl)6-dimethylaminophthalide, 3.3-bis(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2 dimethyl indole-3-yl)
Phthalide, 3-(p-dimethylaminophenyl)-3
-(2-methylindol-3-yl)phthalide, 3,
3bis(1,2-dimethylindol-3-yl)5-
Dimethylaminophthalide, 3,3-bis(1,2-dimethylindol-3-yl)-6-dimethylaminophthalide, 3,3-bis(9-ethylcarbazol-3-yl)-6-dimethylamino Phthalide, 3,3-bis(2
-phenylindol-3-yl)-6-dimethylaminophthalide, 3-P-dimethylaminophenyl-3-(
Triallylmethane dyes such as 1-methylpyrrol-3-yl)-6-dimethylaminophthalide, 4゜4'-bis-
Dimethylaminobenzhydrylbenzyl ether, N-
Halophenyl-leukoolamine, N-2,4,5-1
Diphenylmethane dyes such as dichlorophenyl leuco auramine, thiazine dyes such as pensoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue, 3-methyl-spiro-dinaphthopyran, 3-ethyl-
Spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran,
Spiro dyes such as 3-methyl-naphtho(6'-methoxyhenzo)spiropyran, 3-propyl-spiro-dibenzopyran, rhodamine-B-anilinolactam, rhodamine(p-nitroanilino)lactam, rhodamine (0-
Lactam dyes such as chloroanilino)lactam, 3-dimethylamino-7-methoxyfluoran, 3-diethylamino-6-methoxyfluoran, 3-diethylamino-7
-Methoxyfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamine-6-methyl-7-chlorofluorane, 3-diethylamino-6,7-dimethylfluorane, 3-(N-ethyl-p-toluidino) )7-
Methylfluoran, 3-diethylamino-7-(N-acetyl-N-methylamino)fluorane, 3-diethylamino-7-(N-methylamino)fluorane, 3-diethylamino-7-dihendylaminofluorane, 3- Diethylamino 7-(N-methyl-N-benzylamino)
Fluoran, 3-diethylamino-7-(N-chloroethyl-N-methylaminocofluorane, 3-diethylamino-7-diethylaminofluorane, 3-(N-ethyl-p-toluidino)-6-methyl-7-phenyl Aminofluorane, 3-(N-ethyl-p-toluidino)-6
-Methyl-7-(p-1-luidino)fluoran, 3-
Diethylamino-6-methyl-7-phenylaminofluorane, 3-dibutylamino-6-methyl-7-phenylaminofluorane, 3-diethylamino-7-(2-
Carbomethoxyphenylamino)fluorane, 3-(N
-cyclohexyl-N-methylamino)6-methyl-7
-phenylaminofluorane, 3-pyrrolidinol 6-methyl-fufuninylaminofluorane, 3-piperidino-6-methyl-7phenylaminofluorane, 3-diethylamino-6-methyl-7-(2,4-dimethyl amino) fluoran, 3-diethylamino-7-(o-chlorophenylamino)fluoran, 3-dibutylamino-
7-(o-chlorophenylamino)fluoran, 3-pyrrolidino-6-methyl-7-(p-butylphenylamino)fluoran, 3-(N-methyl-N-n-amylamino)-6-methyl-7-phenylaminofluoran Oran, 3-
(N-ethyl-N-n-amylamino)-6-methyl-
7 Phenylaminofluorane, 3-(N-ethyl N-isoamylamino)-6-methyl-7-phenylaminofluorane, 3-(N-methyl-N-n-hexylamino)-6-methyl-7 -phenylaminofluorane, 3-
(N-ethyl-Nn-hexylamino)-6-methyl-
7-phenylaminofluorane, 3-(N-ethyl-N
Examples include fluoran dyes such as -βethylhexylamino)-6-methyl-7-phenylaminofluoran. Of course, the dyes are not limited to these dyes, and two or more types of dyes can be used in combination.

In the present invention, the coloring agent used in combination with the above-mentioned basic dye is exemplified by the following substances which are known in the fields of pressure-sensitive copying paper and pyrotechnics.

4-tert-butylphenol, α-naphthol, β
-naphthol, 4-acetylphenol, 4tert
-octylphenol, 4.4'-5ec-butylidenephenol, 4-phenylphenol, 4.4'-dihydroxy-diphenylmethane, 4°4'-isopropylidene diphenol, hydroquinone, 4,4'-cyclohexylidene diphenol, 4.4'-dihydroxydiphenyl sulfide, 4,4'-thiobis(6-te
rt-butyl 3-methylphenol), 4.4'-dihydroxydiphenylsulfone, hydroquinone monobenzyl ether, 4-hydroxybenzophenone, 2.4
-dihydroxybenzophenone, 2,4゜4'-trihydroxybenzophenone, 2.2'4.4'-tetrahydroxybenzophenone, dimethyl 4-hydroxyphthalate, methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, 4 -propyl hydroxybenzoate, 4
-5ec-butyl hydroxybenzoate, pentyl 4-hydroxybenzoate, phenyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, tolyl 4-hydroxybenzoate, chlorophenyl 4-hydroxybenzoate, phenyl 4-hydroxybenzoate Furovir, phenethyl 4-hydroxybenzoate, 4-hydroxybenzoic acid P
-Chlorobenzyl, p-methoxybenzyl 4-hydroxybenzoate, novolax type phenolic resin, phenolic compound consisting of phenol; benzoic acid, p-te
rt-butylbenzoic acid, trichlorobenzoic acid, terephthalic acid, 35ec-butyl-4-hydroxybenzoic acid,
3-Cyclohexyl-4-hydroxybenzoic acid, 3.5
-dimethyl-4-hydroxybenzoic acid, salicylic acid, 3
-Isopropylsalicylic acid, 3-tert-butylsalicylic acid, 3-hensylsalicylic acid, 3-(α-methylhensyl)salicylic acid, 3-chloro-5-(α-methylbenzyl)salicylic acid, 3.5-di-tert-butylsalicylic acid , 3-phenyl-5-(α,α-dimethylbenzyl)salicylic acid, 3,5-di(α-methynolabenzyl)salicylic acid, etc.5 These aromatic carboxylic acids and e.g. zinc, magnesium, aluminum , organic acidic substances such as salts with polyvalent metals such as calcium, titanium, manganese, tin, and nickel. Of course, it is also possible to use two or more of these coloring agents in combination, if necessary.

The basic dye and coloring agent are appropriately selected and used so as to obtain the desired color. In addition, the mixing ratio of the basic dye and the coloring agent is 50 to 6 parts by weight of the coloring agent to 100 parts by weight of the dye.
00 parts by weight, preferably about 100 to 400 parts by weight.

As the desensitizer, any known desensitizer can be used as long as it is easily soluble in water, and specific examples include glycerin; dodecylamine; 2,4.4-1-rifthyl-2oxazoline;
N-di(polyoxyethylene)ethylamine; polyoxypropylene/diethylamine adduct; polyethyleneimine; polyolefin glycols such as polyethylene glycol, polypropylene glycol, and copolymers of ethylene glycol and propylene glycol; dodecyl-trimethylammonium chloride, stearylamine acetate Cationic surfactants such as polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether sulfate triethanolamine, polyoxyethylene alkyl phenol ether sulfate sodium sulfate; polyoxyethylene lauryl ether, Examples include nonionic surfactants such as oxyethylene oleyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monolaurate, and polyethylene glycol monostearate.

Among these, polyethyleneimine, polyolefin glycol having an average molecular weight of about 300 to 2,000, anionic surfactants, and nonionic surfactants are particularly excellent in decoloring properties and water coloring properties, and are therefore preferably used. Of course, two or more of these desensitizers can also be used in combination.

The amount of desensitizer to be used cannot be definitively stated depending on the type of support, basic dye, and coloring agent used;
It may be in a range of about 50 to 2000 parts by weight.

In the water color-forming sheet of the present invention, a layer provided on a support and containing three essential components: a basic dye, a color former, and a desensitizer,
This is a particularly important configuration.

The mechanism by which the nuclear layer develops color due to the adhesion of water is thought to be due to the following phenomenon occurring. In other words, when water is applied, the desensitizer mixed in is easily soluble in water, so it dissolves in water, and the concentration in the layer is diluted, causing color development between the basic dye and the coloring agent. The ability to inhibit reactions decreases. As a result, a color reaction occurs between the dye and the coloring agent and a visible image appears. In this way, the water color-forming sheet of the present invention utilizes the balance of the composition of the three components.

Supports include paper, paperboard, cardboard, synthetic paper, nonwoven fabric, woven fabric, resin film, metallized paper, metal foil, metal plate,
Wooden boards, glass, etc. can be used. Among these, when a porous base material is used, the desensitizer dissolved in water penetrates into the porous base material, the ratio of the desensitizer in the three components becomes small, and water evaporates. After drying, the colored part remains. That is, when such a sheet is used, irreversible water coloring can be achieved. On the other hand, when a non-porous base material is used, the desensitizer dissolved in water does not penetrate into the base material, so the ratio of the three components remains unchanged even after the water evaporates and dries, and the coloring area remains uncolored. do. That is, when such a sheet is used, reversible water coloring can be performed and it can be used repeatedly.

Whether paper is porous or not can be determined by the flow length "°" measured by the following method. In other words, 20°C ± 2°
Polyoxyethylene sorbitan monolaurate (trade name Nileodor TW-L 1
20. 10μ of a liquid containing 1% by weight of Kao ■) from a height of 1cm! The length of the liquid flowing down until it dries is measured, and this value is defined as the flowing length. This flow length is 50
When using paper with a size of 40 mm or less, preferably 40 mm or less, it becomes an irreversible water-colorable sheet. On the other hand, paper having a flowing length of 55 mm or more, preferably 60 mm or more, becomes a reversible water-colorable sheet.

For example, when forming a water coloring layer by coating, examples of adhesives include starches such as grain starch, pregelatinized starch, oxidized starch, etherified starch, and esterified starch, gelatin, albumin, and casein. Proteins, celluloses such as carboxymethylcellulose and hydroxyethylcellulose, water-soluble natural polymer compounds such as agar, sodium alginate, multi-IR compounds such as gum arabic, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyacrylamide, and copolymerized maleic acid. Water-soluble synthetic polymer compounds such as polymers; water-dispersible polymer compounds such as styrene-butadiene copolymer latex, acrylic acid ester polymer latex, vinyl acetate polymer latex, vinyl chloride polymer; ethyl cellulose , hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, semi-synthetic resins such as nitrocellulose, phenolic resins, xylene resins, urea resins, melamine resins, ketone resins, coumaron/indene resins, petroleum resins,
Terpene resin, cyclized rubber, chlorinated rubber, alkyd resin, polyamide resin, acrylic resin, polyvinyl chloride, vinyl chloride/vinyl acetate copolymer, polyvinyl acetate, polyvinyl butyral (butyral resin), polyvinylpyrrolidone, chlorinated polypropylene resin , epoxy resin, polyurethane, and other synthetic resins.

On the other hand, when forming a water coloring layer by a printing method, for example, when preparing a flexo type or gravure type ink composition, the above-mentioned materials can be used as an adhesive. Among them, polyvinyl acetate, vinyl chloride/vinyl acetate copolymer, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, methyl vinyl ether-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer Preferred are polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, ethyl cellulose, nitrocellulose, hydroxypropyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, and the like.

Furthermore, waxes are mainly used as adhesives for hot melt inks. These waxes include animal waxes such as beeswax, spermaceti wax, and lanolin, vegetable waxes such as candelilla wax, carnauba wax, tree wax, rice wax, and sugarcane wax, and montan wax, osikerite, and lignite wax. Mineral waxes, paraffin waxes, petroleum waxes such as microcrystalline waxes, monokun wax derivatives,
Modified waxes such as paraffin wax derivatives and microcrystalline wax derivatives, hydrogenated waxes such as castor wax and opal wax, low molecular weight polyethylene and its derivatives, synthetic waxes such as acra wax and distearyl ketone, caproic acid amide, caprylic acid amide, pelargonic acid amide, capric acid amide, lauric acid amide, tridecylic acid amide, myristic acid amide, stearic acid amide, behenic acid amide, ethylene bisstearic acid amide, caproleic acid amide, oleic acid amide, linoleic acid amide, ricinoleic acid amide, Fatty acid amide waxes such as linoleic acid amide, fatty acid waxes such as stearic acid and behenic acid, alcohol waxes such as stearyl alcohol, and phosphoric ester waxes such as distearyl phosphate ester are used alone or in combination. Ru.

Furthermore, examples of adhesives for electron beam or ultraviolet curable inks include compounds having one or more, preferably a plurality of vinyl or vinylidene groups, such as acryloyl groups,
A reaction product of a polyol, polyamine or amino alcohol, etc. having a methacryloyl group, an allyl group, an unsaturated polyester, a vinyloxy group, an acrylamide group, etc., and an unsaturated carboxylic acid, a reaction product of an acrylate or methacrylate having a hydroxyl group, and a polyisocyanate. Can be mentioned. Typical compounds include, for example, polyethylene glycol diacrylate, propylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, hexanediol diacrylate, 1゜2-butane. Examples include diol diacrylate, a reaction product of epoxy resin and acrylic acid, a reaction product of methacrylic acid, pentaerythritol, and acrylic acid, a condensation product of maleic acid, diethylene glycol, and acrylic acid, methyl methacrylate, butyl methacrylate, and styrene.

When curing by ultraviolet rays, it is preferable to add a photoinitiator to the above adhesive, such as aromatic ketone,
Photopolymerization initiators such as quinone compounds, ether compounds, and nitro compounds are used.

Specifically, initiation of photopolymerization of benzoquinone, phenanthrenequinone, naphthoquinone, diisopropylphenanthrenequinone, benzoin butyl ether, benzoin, furoinbutyl ether, Mohiller ketone, Michler thioketone, fluorenone, trinitrofluorenone, β-benzoylaminonaphthalene, etc. Examples include agents.

These adhesives are used in an amount of 5 to 75% by weight, preferably 10 to 65% by weight of the total solid content of the Himi-iro layer.

Furthermore, in coating liquids or ink compositions, aggravating agents are added to improve color development sensitivity, ultraviolet absorbers and antioxidants are added to impart aging resistance, and additives are added to improve water repellency, improve whiteness and writeability. Inorganic pigments such as kaolin, clay, talc, calcium carbonate, calcined ash, titanium oxide, diatomaceous earth, and silica-activated clay can also be added in order to impart this. It is also possible to contain a colored dye or colored pigment that is different from the coloring hue of the dye used. Further, a dispersant, a preservative, an antifoaming agent, a fluorescent dye, etc. may be added as necessary.

The Himi color layer of the present invention is formed by applying or printing a coating liquid or ink composition containing the basic dye, coloring agent, desensitizer, and adhesive onto a support and drying. To prepare a coating liquid containing these, the dye and coloring agent are dispersed together or separately using water as a dispersion medium and a stirring or pulverizing machine such as a ball mill, attritor, or sand grinder to form a coating liquid. It is prepared by emulsifying a dye and/or a coloring agent to form a coating liquid, or by dissolving both in an organic solvent to form a coating liquid.

The method for forming the Himi-colored layer is not particularly limited, and can be formed according to conventionally well-known and commonly used techniques. For example, a suitable coating device such as a bar coater, air knife coater, blade coater, curtain coater, etc. can be used. In the case of printing methods, various printing machines such as letterpress, planographic, intaglio, flexo, gravure, screen, and hot melt printing can be used. Of course, it may also be applied with a brush, spray, etc.

There are no particular limitations on the amount of coating liquid or ink applied, and the dry weight is 0.3 to 15 g/rT? It is preferable to prepare the amount within the range of 1 to 12 g/%. Incidentally, if it is less than 0.3g/rrf, sufficient functionality as a Himi color sheet cannot be obtained, and if it is applied more than 15g/rrf, no further improvement in functionality or effectiveness will be observed. , the cost will be high.

The coating solution after application may be air-dried, but it is generally
It is dried at a temperature of about 120°C.

Of course, when forming the Himi color layer using an electron beam or ultraviolet ray curable ink composition, it is necessary to cure the coating layer by irradiating the electron beam or ultraviolet rays.

Further, after drying, a calender treatment may be performed if necessary.

The Himi color sheet thus obtained can be used, for example, for practicing calligraphy.

That is, the color develops simply by adding water to the brush and writing. Since only water is used, there is no need to get your hands dirty. When a reversible Himichromatic sheet is used, the coloring part disappears when it dries, so it can be used any number of times, contributing to resource conservation.

In the case of irreversible Himi colored sheets, there is no need to rub the ink.

Since the Himi colored sheet of the present invention is particularly useful as a counterfeit prevention sheet, this will be explained below.

A sheet in which a Himi color layer consisting of a basic dye, a coloring agent, a desensitizer, and an adhesive is provided on at least a portion of the support is colorless or light-colored and cannot be photographed or copied with a copier. Counterfeiting can be prevented. If you want to confirm the authenticity, you can easily check the authenticity by applying water to the area, which will develop color.

The Himi color layer does not necessarily need to be made invisible by hidden printing, and may contain, for example, a colored pigment having a different hue from that of the basic dye.

In this case, a colored pigment is expressed, and when water is attached to it to confirm authenticity, the hue of the basic dye appears, resulting in a color mixture. When the paper is copied with a color copying machine, the hue portion of the colored pigment is copied, but even if water is applied to the paper to confirm authenticity, no color mixing occurs, and forgery can be prevented.

The colored dye used may be any compound that has a hue different from that of the basic dye and has color mixing properties. Specific examples include methanyl yellow orange, methyl red, acid red, Victoria violet, and brilliant. Acidic dyes such as blue; azoic dyes such as Naphthol AS, Fast Red TR, Fast Blue BB Salt, and α-naphthylamine; basic dyes such as Rhodamine 6G, Crystal Violet, Methylene Blue, Malachite Green, and Acridine Yellow; Hermanent Orange, Day - Pigment dyes such as Bread and Phthalocyanine Blue; Examples include inorganic compounds such as Cobalt Green, Celsian Blue, Cobalt Violet, Barium Chromate, and Cadmium Red.

The colored pigment may be mixed into the Himi-colored material, and the colored pigment layer may be provided below or above the Himi-colored layer.

Furthermore, each layer may be provided over the entire surface of the base material,
Characters, symbols, or patterns or a combination thereof may be printed.

The anti-counterfeiting sheet thus obtained can be produced at low cost, and its authenticity can be easily confirmed without using chemicals, so it can be used for securities, banknotes, credit cards, gift certificates, etc. It is extremely useful for admission tickets, product labels, etc.

The Himi color sheet of the present invention is also useful as a molding sheet. In the Himi color layer of the Himi color sheet of the present invention,
By bringing a mold-making object coated with water into contact with the object, the contact area develops color and a record is obtained. in this way,
It is possible to do this without staining the object to be molded with vermilion or ink. In particular, if a porous material is used as the support, the coloring is irreversible, making it a practical molding sheet.

〔Example〕

The present invention will be described in more detail with reference to Examples below, but it is of course not limited thereto.

Further, unless otherwise specified, parts and percentages in the examples indicate parts by weight and percentages by weight, respectively. In addition, the flow length of the support is 20°C
Polyoxyethylene sorbitan monolaurate (product name Nileodor TW-
L 120. 1 c+ of a liquid containing 1% by weight of
10μ from the height of i! This is the length that the liquid flows down until it dries.

Example I Preparation of Solution A 3-(N-Ethyl-N-isoamyl)amino 6-methyl-7-phenylaminofluorane 10 parts Methylcellulose 5% aqueous solution 5 parts Water
40 parts of this composition was ground with a sand grinder until the average particle size was 3 μm.

Preparation of Solution B 4. 20 parts of 4'-isopropylidenediphenol 5% aqueous solution of methylcellulose 5 parts of water
55 parts of this composition was ground with a sand grinder until the average particle size was 3 μm.

55 parts of liquid A, 80 parts of liquid B, 55 parts of polyethylene glycol #600 (average molecular weight 600) as a desensitizer, 15 parts of silicon oxide pigment (oil absorption: 180d/100g), 2
50 parts of 0% oxidized starch aqueous solution and 10 parts of water were mixed and stirred to prepare a coating liquid. The obtained coating liquid was applied onto 127.9 g/rrf double-sided coated paper (flow length: 80 mm) using a wire bar so that the coating amount after drying was 6 g/rrr.
It was dried at 120°C for 1 minute to obtain a white water-colorable sheet.

When I wrote on this sheet with a brush moistened with water, it turned out to be a clear black color. When left as is and the water evaporated to dryness, it returned to its original white color and could be used repeatedly.

Example 2 A white water-colorable sheet was obtained in the same manner as in Example 1 except that polyethylene glycol #1000 (average molecular weight 1000) was used instead of polyethylene glycol #600. When I wrote on this sheet with a brush moistened with water, it turned out to be a clear black color. When the water evaporated, it returned to its original white color and could be used repeatedly.

Example 3 Instead of 55 parts of polyethylene glycol #600,
Polyethylene glycol #300 (average molecular weight 300)
A white water-colorable sheet was obtained in the same manner as in Example 1, except that 35 parts of polyethylene glycol #2000 (average molecular weight 2000) were used. When I wrote on this sheet with a brush moistened with water, it turned out to be a clear black color. When the water evaporated, it returned to its original white color and could be used repeatedly.

Example 4 3-(N-ethyl-N-isoamyl)amino-6 in solution A
-3 instead of methyl-7-phenylaminofluorane
A white water-colorable sheet was obtained in the same manner as in Example 1 except that -diethylamino-7-chlorofluoran was used. When I wrote on this sheet with a brush moistened with water, it turned a bright orange color.

When the water evaporated, it returned to its original white color and could be used repeatedly.

Example 5 3-(N-ethyl-N-isoamyl)amino-6 of solution A
-3 instead of methyl-7-phenylaminofluorane
．． A white water-colorable sheet was obtained in the same manner as in Example 1 except that 3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide was used. When I wrote on this sheet with a water-soaked brush, it developed a clear blue color. When the water evaporated, it returned to its original white color and could be used repeatedly.

Example 6 3.5-di(α-methylbenzyl) instead of 20 parts of 4,4′-isopropylidene diphenol in B solution of Example 1
Solutions A and B were prepared in the same manner as in Example 1 except that 20 parts of zinc salicylate was used.

55 parts of liquid A, 80 parts of liquid B, Emulgen 93 as a desensitizer
5 (manufactured by Kao ■; polyoxyethylene nonylphenyl ether), 55 parts of silicon oxide pigment (oil absorption: 180 d/
100 g), 150 parts of 48% styrene-butadiene copolymer latex, and 100 parts of water were mixed and stirred to prepare a coating liquid.

The obtained coating liquid was coated with 127.9 g/r+ (double-sided coated paper (
The coating amount after drying is 6g/r+(flow length: 80m+).
It was coated with a wire spar so that it would be as follows, and dried at 110°C for 1 minute to obtain a white water-colorable sheet. When I wrote on this sheet with a brush moistened with water, it turned out to be a clear black color. When the water evaporated, it returned to its original white color and could be used repeatedly.

Example 7 Emulgen 147 (Kao ■
A white water-color-forming sheet was obtained in the same manner as in Example 6 except that polyoxyethylene lauryl ether) was used. When I wrote on this sheet with a brush moistened with water, it turned out to be a clear black color. When the water evaporated, it returned to its original white color and could be used repeatedly.

Example 8 Rheodol TW-L12 instead of Emulgen 935
A white Himi-colored sheet was obtained in the same manner as in Example 6 except that 0 (manufactured by Kao Corporation; polyoxyethylene sorbitan monolaurate) was used. When I wrote on this sheet with a brush soaked in water, it turned black. When the water evaporated, it returned to its original white color and could be used repeatedly.

Example 9 Except for using Trunks N-300 (manufactured by NOF ■; anionic surfactant) instead of Emulgen 935,
A white Himichromic sheet was obtained in the same manner as in Example 6. When I wrote on this sheet with a brush soaked in water, it turned black.

When the water evaporated, it returned to its original white color and could be used repeatedly.

Example 10 A white Himi-colored sheet was obtained in the same manner as in Example 6, except that Evomin P-1000 (Nippon Shokubai Chemical Co., Ltd.; polyethyleneimine) was used instead of Emulgen 935. When I wrote on this sheet with a brush soaked in water, it turned black. When the water evaporated, it returned to its original white color and could be used repeatedly.

Example 11 3-(N-ethyl-N-isoamyl)amino- of Afi
A white Himichromatic sheet was obtained in the same manner as in Example 6, except that 3-diethylamino-7-chlorofluoran was used instead of 6-methyl-7-phenylaminofluoran. When written on this sheet with a brush moistened with water, it developed a vivid orange color.

When the water evaporated, it returned to its original white color and could be used repeatedly.

Example 12 3-(N-ethyl-N-isoamyl)amino-6 of solution A
-3 instead of methyl-7-phenylaminofluorane
, 3-bis(P-dimethylaminophenyl)-6-dimethylaminophthalide was used in the same manner as in Example 6 to obtain a white Himichromatic sheet. When written on this sheet with a brush moistened with water, it developed a clear blue color. When the water evaporated, it returned to its original white color and could be used repeatedly.

Example 13 Preparation of Solution A 5 parts of 3-(N-ethyl-N-isoamyl)amino 6-methyl-7-phenylaminofluorane were dissolved in 100 parts of alkylnaphthalene. This solution was added to 100 parts of a 3% aqueous solution of polyvinyl alcohol, and stirred for 3 minutes at 8500 rpm using a homomixer to prepare an emulsion.

Preparation of Solution B 3. Zinc 5-di(α-methylbenzyl)salicylate 10
A composition consisting of 1 part, 5 parts of a 5% methylcellulose aqueous solution, and 55 parts of water was ground with a sand grinder until the average particle size was 3 μm.

Next, 205 parts of liquid A, 70 parts of liquid B, 25 parts of polyethylene glycol #1000 (average molecular weight 1000), 100 parts of silicon oxide pigment (oil absorption 180 d/100 g), and 48% styrene-butadiene copolymer emulsion were added. and 300 parts of water were mixed and stirred to obtain a coating liquid.

On the other hand, a coating liquid consisting of 100 parts of 48% styrene-butadiene copolymer emulsion, 20 parts of calcium carbonate, and 100 parts of water was coated on high-quality paper with a weight of 104.7 g/rf using a wire bar and dried. A coating layer with a solid content of 5 g/rTf was provided (flow length: 160 mm). After suppressing the permeability of the coating liquid in this manner, the coating liquid was coated on the surface with a wire bar and dried at room temperature to obtain a white Himi-colored sheet. The coating amount after drying was 7 g/rrr. When writing on this sheet with a brush soaked in water, the areas to which water had been applied developed a clear black color. When left as is and the water evaporated to dryness, it returned to its original white color and could be used repeatedly.

Example 14 A white Himi-colored sheet was obtained in the same manner as in Example 13, except that Emulgen 935 (polyoxyethylene nonylphenol ether, manufactured by Kao ■) was used instead of polyethylene glycol #1000. When writing on this sheet with a brush soaked in water, the areas to which water had been applied developed a clear black color. When left as is and the water evaporated to dryness, it returned to its original white color and could be used repeatedly.

Example 15 3-(N-ethyl-N-isoamyl)amino-6 of solution A
-3 instead of methyl-7-phenylaminofluorane
．． A white water-colorable sheet was obtained in the same manner as in Example 13 except that 3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide was used. When writing on this sheet with a brush soaked in water, the areas to which water had been applied developed a clear blue color. When left as is and the water evaporated to dryness, it returned to its original white color and could be used repeatedly.

Example 16 Preparation of Solution C 92 parts of 3-(N-ethyl-N-isoamyl)amino-6-1thyl-'11-funinylaminofluoro, 10 parts of zinc 3.5-di(α-methylbenzyl)salicylate was dissolved in 100 parts of alkylnaphthalene. This solution was added to 100 parts of a 3% aqueous solution of polyvinyl alcohol, and stirred with a homomixer at a rotation speed of 850 rpm for 3 minutes to prepare an emulsion.

A white water-coloring sheet was obtained in the same manner as in Example 13, except that 215 parts of Solution C was used instead of 205 parts of Solution A and 70 parts of Solution B. When writing on this sheet with a brush soaked in water, the areas to which water had been applied developed a clear black color. If you leave it as is and allow the water to evaporate and dry, it will return to its original white color.
It could be used repeatedly.

Example 17 A solution was prepared as described below.

Preparation of Solution A 3,3-bis(P-
35% aqueous dispersion of dimethylaminophenyl)-6-dimethylaminophthalide 30 parts 30% aqueous dispersion of zinc 3,5-di(α-methylbenzyl)salicylate atomized by sand mill 70
48% styrene-butadiene copolymer Latinx

100 parts Preparation of liquid B Polyethylene glycol; #1000 (average molecular weight 10
00) 100 parts water
While stirring 100 parts of Solution A, Solution B was gradually added and mixed at a ratio of A:B=100:50 to prepare a coating solution.

This coating liquid was coated with a basis weight of 64 g/nfC size degree: 30 seconds.

Coating with a blade on base paper with flow length = 10■), 100°
After drying for 1 minute, a white water-colorable sheet was obtained. The coating amount was 3.5 g/po in terms of dry weight.

When writing on this water-chromic sheet with a brush soaked in water, the areas to which water had adhered developed a clear blue color.

Even if it was left as is, the colored part remained.

Example 18 Basis weight 64 g/% (Size degree: 30 seconds, flow length: 10
m) Except for using base paper with a basis weight of 64 g/rrf (size degree near 0 seconds, flow length: 20++ m) instead of base paper,
A white water-colorable sheet was obtained in the same manner as in Example 17.

When this sheet was sprayed with water, the areas with water droplets remained irreversibly.

Example 19 The mixing ratio of liquid A and liquid B was set to A:B = 100 near 5, and
Basis weight 64g/rdc size degree: 1 second or less.

Flow length: 10) A white water-colorable sheet was obtained in the same manner as in Example 17, except that the base paper was used.

When a hand moistened with water was pressed onto this sheet, a blue-colored flat mold was obtained, and the colored portion remained irreversibly.

Example 20 3.3bis(p-dimethylaminophenyl)-6 of solution A
Example 17 except that 3-diethylamino-7-chlorofluoran was used instead of -dimethylaminophthalide
A white water-colorable sheet was obtained in the same manner as above. When this sheet was written with a brush moistened with water, it developed a clear orange color, and the colored area remained irreversibly.

Example 21 Oligoester acrylate (manufactured by Toagosei Chemical Industry Co., Ltd.;
3.3-bis(p-dimethylaminophenyl)-6- to 80 parts of Aroex M-8030), 80 parts of monofunctional acrylate (manufactured by Synthetic Kagaku Kogyo Co., Ltd.; Aroex MIOI)
Add 10 parts of dimethylaminophthalide, 25 parts of zinc 3,5-di(α-methylbenzyl)salicylate, and 65 parts of polyethylene glycol #1000 (average molecular weight 1000), heat and melt at 60°C for 1 hour, and cure with ionizing radiation. A mold coating solution was obtained.

This coating liquid was printed on double-sided coated paper (flow length: 80an) using a white board printing device to print a floral pattern, and then an electrocurtain type electron beam irradiation device (manufactured by ESI, CB-
150 type) at an irradiation dose of 2 Mrad to obtain a white sheet.

When this sheet was copied using a copying machine, only a blank copy with no floral pattern was obtained. On the other hand, when gauze moistened with water was applied to the sheet, the floral pattern turned blue. When the water was left to evaporate, the color disappeared, indicating reversibility.

Example 22 A sheet with a light blue floral pattern was prepared in the same manner as in Example 21, except that 64 g/I high-quality paper (flow length: 10 mm) was used instead of the double-sided coated paper (flow length = 8011I11) as the base material. I got it.

When water is applied to a part of the sheet using gauze moistened with water, the floral pattern in the area where the water has adhered becomes even darker (color develops,
It shows irreversibility even if left as it is and the water evaporates to dryness.
The colored areas remained dark and the colored areas and non-colored areas could be clearly distinguished.

On the other hand, when the sheet was copied using a commercially available color copying machine, the pale blue floral pattern could be copied, but of course no change occurred even when water was attached.

Example 23 Preparation of liquid A Polyvinyl butyral (manufactured by Block Chemical Industry ■; BC3)
100 parts 3.3-bis(p-
(dimethylaminophenyl)6-dimethylaminophthalide 10 parts 3.5-di(α-methylbenzyl)zinc salicylate 20 parts Polyethylene glycol #1000 (molecular weight 100)
40 parts ethyl alcohol
400 parts methyl ethylene ketone
200 parts were mixed and stirred to obtain a coating liquid. This coating liquid is applied to synthetic paper (product name: "YUPO" made from egg oil synthetic paper ■, basis weight: 1.
10 g/m) with a wire bar so that the dry coating amount was 3.0 g/rd, and dried at 80° C. for 30 seconds to obtain a white sheet. Black characters were printed on the coated surface of the sheet using a flexo printing machine.

When water was applied to the white part of this printing sheet with a brush, it developed a blue color. When the water was left to evaporate, the color disappeared, indicating reversibility. On the other hand, when the printed sheet was copied using a copying machine, the black characters could be copied. Naturally, no change occurred even when water was applied.

Example 24 Colored dye Rhodamine 6G (manufactured by Kishida Chemical Co., Ltd.) 0.
A red sheet was obtained in the same manner as in Example 23 except that 8 parts were added. Black characters were printed on the coated surface of the sheet using a flexo printing machine. When water was applied to the ground color portion of this printing sheet with a brush, a mixed color (purple) developed. When the water was left to evaporate, the color disappeared, indicating reversibility. on the other hand,
When this printed sheet was copied using a commercially available color copying machine, a copy with the same hue as that of the printed sheet was obtained, but no change occurred even when water was attached.

Example 25 30 parts of a 35% aqueous dispersion of 3-diethylamino-7-chlorofluorane micronized by a sand mill, 38% water dispersion of 3°5-di(α-methylbenzyl)zinc salicylate micronized by a sand mill Mix 55 parts of dispersion, 55 parts of Emulgen 935 (manufactured by Kao ■, polyoxyethylene nonymphenol ether), 40 parts of calcium carbonate (oil absorption 95 m/100 g), 150 parts of 48% styrene-butadiene copolymer latex, and 100 parts of water. The mixture was stirred to obtain a Himi color coating liquid.

On the other hand, styrene-butadiene copolymer Latte Nox: 48% liquid 100
parts, calcium carbonate (oil absorption: 95d7100g) 20
A coating liquid consisting of 100 parts of water and 100 parts of water was previously applied with a blade and dried to provide an undercoat layer with a solid amount of 3 g/rrr. The running length of the coating layer was 128 mm.

The above-mentioned Himi color dye was applied to the surface of this undercoat layer using a wire paper so that the coating amount after drying was 5 g/n (100 g/n).
A white sheet was obtained by drying at °C for 30 seconds. Color designs including letters were transferred onto this sheet using a commercially available thermal transfer device. When water was applied to the sheet with a brush, the white part developed a red color, and the colored letters and designs changed to a mixed color, and when left as is and the water evaporated, the color disappeared, showing reversibility. On the other hand, when the transfer sheet was copied using a commercially available color copying machine, copies with the same hue as the sheet were obtained, but no change in hue due to water adhesion occurred.

〔effect〕

As described above, the Himi color sheet of the present invention has the following features: (1) The color tone can be easily changed by selecting a basic dye, and (2) Reversible or irreversible color can be obtained by selecting a support. ■ It can be manufactured with a coating machine or a printing machine, so it can be mass produced. ■ It can be obtained by coating in a small amount of 2 to 12 g/rrr. ■ If a non-porous material is used as the support, it will develop color with water. As it can be used repeatedly, it contributes to resource saving. ■For calligraphy, there is no need to rub the ink.
In addition, there is no need to worry about stains. ■For counterfeit prevention,
You can instantly check the authenticity just by applying water without using special chemicals or equipment.
You can make clear impressions of foot prints, fish prints, rubbings, and other objects without staining them with vermilion or ink. ■Since the color develops with water, it can be used in survival games using water leak detectors and water guns (
It is extremely practical, such as survival games).

Claims (4)

[Claims] (1) At least a portion of the support is provided with a water coloring layer containing as main components a colorless to light-colored basic dye, a coloring agent capable of forming a color upon contact with the dye, a desensitizer, and an adhesive. A water-coloring sheet that is characterized by: (2) The water coloring sheet according to claim (1), wherein the desensitizer is at least one selected from polyolefin glycol, surfactant, and polyethyleneimine. (3) A counterfeit prevention sheet having the structure according to claim (1). (4) A molding sheet having the structure according to claim (1).