JPH0412887A - Aqueous color-developable recording transfer material and formation of water developable recording image - Google Patents

Abstract

PURPOSE:To develop a recording image by merely applying water by providing a transfer layer containing an aqueous color-developable material consisting of a colorless or light-colored basic dye, a developer, a desensitizing agent and adhesive and transferred from a base material to a recording sheet by pressure or heating on the base material. CONSTITUTION:A transfer layer containing an aqueous color-developable material consisting of a colorless or light-colored basic dye, a developer capable of developing a color upon the contact with the dye, a desensitizing agent and an adhesive is provided on a base material and superposed on a recording sheet under pressure or heating to transfer the aqueous color-developable material to the recording sheet. As the basic dye used in the aqueous color- developable material, a fluorane type dye is designated and, as the developer used in combination with the basic dye, an org. acidic substance such as a polyvalent metal salt is designated. As the desensitizing agent, polyethyleneimine, polyolefin glycol with an average MW of about 300-200, an anionic surfactant and a noionic surfactant are pref. used because color erasing properties and aqueous color-developability are especially excellent.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a sheet that is invisible in a normal state;
The present invention relates to a material and method for forming a recorded image made of a material that develops color when water adheres to it.

[Prior art] Conventionally, a recording method that is normally invisible but becomes visible when necessary is to draw pictures or letters on paper with squeezed orange juice, etc., and when it dries, it becomes difficult to see after writing. When it is exposed to fire, the pictures and letters turn black and brown again, causing so-called aburidashi. However, this overflowing material shows discoloration even before it overflows.

On the other hand, methods have been proposed in which the latent image of an ultraviolet absorber is visualized in the dark under a fluorescent lamp, and the latent image of an electron-accepting color developer is visualized by spraying an organic solvent in which an electron-donating dye is dissolved. However, these methods have problems such as the need to select a special location for visualization and the use of organic solvents.

[Problem to be solved by the invention]

The present invention makes it possible to inexpensively and easily create a Himichromatic recorded image, in which a recorded image appears simply by applying water, without selecting a special location or using special equipment or chemicals. Materials and methods.

[Means to solve problems]

The present invention contains, on a base material, a Himichromatic material consisting of a colorless to light-colored basic dye, a coloring agent that can change color when it comes into contact with the dye, a desensitizer, and an adhesive, and Alternatively, it is a Himi chromatic recording transfer material provided with a transfer layer that is transferred from a base material to a recording sheet by heating.

The present invention provides a transfer layer containing a colorless or light-colored basic dye, a coloring agent capable of forming a color upon contact with the dye, a desensitizer, and a Himichromatic material consisting of an adhesive on a base material. transfer material;
This method of forming a Himi chromatic recorded image is characterized in that a Himi chromatic material is transferred to the recording sheet by overlapping the recording sheets and applying pressure or heat.

[Function] The present invention provides a transfer material having a transfer layer on a base material containing a Himichromatic material consisting of a basic dye, a coloring agent capable of forming a color upon contact with the dye, a desensitizer, and an adhesive. , is characterized in that a Himichromatic recorded image is formed on the recording sheet by overlapping the transfer material and the recording sheet and applying pressure or heating.

Examples of basic dyes used in the Himi color material include the following.

3.3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3,3-bis(P-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(L2 dimethylindole -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-dimethylaminophthalide, 3.3-bis(2-phenylindol-3-yl)-6-dimethylaminophthalide, 3-p-dimethylaminophenyl-3-(1methylvirol-3-yl)-6 - Triallylmethane dyes such as dimethylaminophthalide, 4゜4'-bis-dimethylaminohenzhydrylhenzyl ether, N-halophenyl-leucoauramine, N-2,4,5-)lichlorophenylleucoauramine, etc. diphenylmethane dyes, thiazine dyes such as hendiyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue, etc., 3-
Methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spirodinaphthopyran, 3-methyl-naphtho(6'-methoxybenzo)spiropyran, 3
- Spiro dyes such as propyl-spiro-dibenzopyran, rhodamine-B-anilinolactam, rhodamine (P
Lactam dyes such as nitroanilino)lactam, rhodamine(0-chloroanilino)lactam, 3dimethylamino-7-methoxyfluorane, 3diethylamino-6-
Methoxyfluorane, 3-diethylamino-7-methoxyfluorane, 3-diethylamine-7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6,7-dimethylfluorane, 3 -(N-ethyl-p-toluidino)7-methylfluorane, 3-diethylamino-7-(N-acetyl-
N-methylamino)fluoran, 3-diethylamino-
7-(N-methylamino)fluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino 7-(N-methyl-N-benzylamino)fluorane, 3-diethylamino-7-(N-chloroethyl-
N-methylamino)fluoran, 3-diethylamino-
7-diethylaminofluorane, 3-(N-ethyl-p
-Toluidino)-6-methyl-7-phenylaminofluorane, 3-(N-ethyl-p-toluidino)-6-methyl-7-(p-toluidino)fluoran, 3-diethylamino-6-methyl-7-phenyl aminofluorane,
3-dibutylaminol 6-methyl-fufuninylaminofluorane, 3-diethylamino-7-(2-carbomethoxyphenylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)-6-methyl- 7-phenylaminofluorane, 3-pyrrolidino-6-methyl-
7-phenylaminofluorane, 3-piperidino-6-
Methyl-7phenylaminofluorane, 3-diethylamino-6-methyl-7-(2,4-dimethylamino)fluorane, 3-diethylamino-7-(o-chlorophenylamino)fluorane, 3-dibutylamino-7- (
o-chlorophenylamino)fluoran, 3-pyrrolidino-6-methyl-7-(p-butylphenylamino)fluoran, 3-(N-methyl-Nn-amylamino)
-6-methyltwophenylaminofluorane, 3-(N
-ethyl-N-n-amylamino)-6-methyl-7phenylaminofluorane, 3-(N-ethyl N-isoamylamino)-6-methyl-7-phenylaminofluorane, 3-(N-methyl -Nn-hexylamino)-6
-Methyl-7-phenylaminofluorane, 3-(N-
Fluoran dyes such as ethyl-Nn-hexylamino)-6-methyl-7-phenylaminofluorane, 3-(N-ethyl-N-βethylhexylamino)-6-methyl-7-phenylaminofluorane, etc. can be mentioned. Of course, the dyes are not limited to these dyes, and two or more types of dyes can be used in combination.

Regarding coloring agents used in combination with the above basic dyes,
For example, the following materials which are known in the fields of pressure-sensitive copying paper and heat-sensitive recording paper are exemplified.

4 tert-butylphenol, α-naphthol,
β-naphthol, 4-acetylphenol, 4-ter
t-octylphenol, 4.4'-5ec-butylidenephenol, 4-phenylphenol, 4.4'
-dihydroxy-diphenylmethane, 44'-isopropylidene diphenol, hydroquinone, 4,4'-cyclohexylidene diphenol, 4,4'-dihydroxydiphenyl sulfide, 4,4'-thiobis(6-
tert-butyl 3-methylphenol), 4.4'
-dihydroxydiphenyl sulfone, hydroquinone monohensyl ether, 4-hydroxyhensiphenone, 2
．． 4-dihydroxybenzophenone, 244'-trihydroxyhensiphenone, 2,2'4.4'-tetrahydroxyhensiphenone, 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,
Phenylpropyl 4-hydroxybenzoate, phenethyl 4-hydroxybenzoate, p-
Phenolic compounds such as chlorohensyl, p-methoxyhensyl 4-hydroxybenzoate, tuborax type phenolic resin, phenol polymer; benzoic acid, p-ter
t-Methylbenzoic acid, trichlorobenzoic acid, terephthalic acid, 3-sec-butyl-4-hydroxybenzoic acid, 3
-Cyclohexyl-4-hydroxybenzoic acid, 35-dimethyl-4-hydroxybenzoic acid, salicylic acid, 3-isopropylsalicylic acid, 3-tert-butylsalicylic acid, 3-hendylsalicylic acid, 3-(α-methylhensyl)salicylic acid , 3-ri-5-(α-methylbenzyl)salicylic acid, 3,5-di-tert-butylsalicylic acid, 3-phenyl-5-(α α-dimethylhensyl)salicylic acid, 3,5-di(α - Aromatic carboxylic acids such as (methylhensyl) salicylic acid; Organic acidic substances such as salts of these aromatic carboxylic acids and polyvalent metals such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, and nickel. It will be done. 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 specifically, glycerin; dodecylamine i2.4.1-)tumethyl-2-oxazoline, N,
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 1-.

Among these, polyethyleneimine, polyolefin glycol having an average molecular weight of about 300 to 2000, anionic surfactants, and nonionic surfactants are preferably used because they are particularly excellent in color erasing properties and Himi color properties. 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 addition, as an adhesive, for example, when provided by a coating method,
Specifically, starches such as grain starch, pregelatinized starch, oxidized starch, etherified starch, and esterified starch, proteins such as gelatin, albumin, and casein, celluloses such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, and sodium alginate. , water-soluble natural polymer compounds such as polysaccharides such as gum arabic, polyvinyl alcohol,
Water-soluble synthetic polymer compounds such as polyvinylpyrrolidone, polyacrylic acid, polyacrylamide, maleic acid copolymers, etc.; styrene-butadiene copolymer latex,
Water-dispersible polymer compounds such as acrylic acid ester polymer latex, vinyl acetate polymer latex, vinyl chloride polymer, wax emulsion; ethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, cellulose acetate propionate, cellulose acetate Semi-synthetic resins such as butyrate, nitrocellulose, phenolic resins, xylene resins, urea resins, melamine resins, ketone resins, coumaron/indene resins, petroleum resins, terpene resins, cyclized rubbers, chlorinated rubbers, alkyd resins, polyamide resins, acrylics Examples include synthetic resins such as resin, polyvinyl chloride, vinyl chloride/vinyl acetate copolymer, polyvinyl acetate, polyvinyl butyral (butyral resin), polyvinylpyrrolidone, chlorinated polypropylene resin, epoxy resin, and polyurethane.

On the other hand, when forming by a printing method, for example, when preparing a flexo type or gravure type ink composition, the above-mentioned materials can be used as the 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, lanolin, vegetable waxes such as candelilla wax, carnauba wax, tree wax, rice wax, and sugarcane wax, montan wax, osikerite, lignite wax, etc. Mineral waxes, paraffin waxes, petroleum waxes such as microcrystalline waxes, montan 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 hehenic acid, and alcohol waxes such as stearyl alcohol.

Phosphate ester waxes such as wax and distearyl phosphate are used alone or in combination.

These adhesives have a content of 5 to 50% based on the total solid content of the Himi color material.
It is used in an amount of about 75% by weight, preferably about 10 to 65% by weight.

Furthermore, the coating composition contains a sensitizer to improve color development sensitivity, an ultraviolet absorber and an antioxidant to impart aging resistance, and kaolin, clay, etc. to impart whiteness.
Inorganic pigments such as talc, calcium carbonate, calcined clay, titanium oxide, diatomaceous earth, and silica-activated clay can also be added. Furthermore, a dispersant, preservative, antifoaming agent, fluorescent dye, etc. may be added as necessary.

These materials are prepared by dispersing the dye and/or coloring agent together or separately using water as a dispersion medium and using a stirring or crushing machine such as a ball mill, attritor, or sand grinder. A coating liquid is prepared by making an emulsion or further dissolving both in a solvent to form a coating liquid.

The method of forming the transfer layer is not particularly limited, and can be formed using conventionally well-known and commonly used techniques. For example, suitable coating equipment such as bar coater, air knife coater, blade coater, curtain coke, letterpress, lithography, intaglio, flexo, gravure, screen, etc.
Various printing machines such as hot melt printing can be used. Various printing machines can be used.

The base material of the transfer material is not particularly limited, and various materials can be used, such as paper, coated paper, synthetic paper, synthetic resin film, metal foil, nonwoven fabric, or a composite material combining these. It will be done. The shape of the base material can be appropriately selected depending on the recording method, such as a sheet shape or a ribbon shape.

In the present invention, the transfer layer of the transfer material obtained in this way and the recording sheet are stacked facing each other, and a writing instrument such as a ballpoint pen, etc.
By applying pressure using a typewriter, impact printer, etc., or heating using a thermal printer, etc., the transfer material in the area is transferred onto the recording sheet to form a water-colorable recorded image.

The obtained water-colorable recorded image develops color simply by applying water, for example, by applying a water-containing brush or water spray, and can be identified as a colored printed image.

Although the mechanism by which a water-chromogenic recorded image develops color due to adhesion of water has not been completely elucidated, it is presumed to be as follows. In other words, the desensitizing agent present in a water-color-forming recorded image is easily soluble in water, and when water adheres, its concentration is diluted and the color-forming reaction between the basic dye and the coloring agent is inhibited. The ability to prevent this decreases. As a result, a color reaction occurs between the dye and the coloring agent, and a visible image appears. If a large amount of water is applied, such as by using a water-containing brush or water spray, the dissolved desensitizer may penetrate into the base material of the recording sheet or diffuse to the periphery of the recorded image. It is thought that the proportion of the desensitizer in the visual image becomes small and the visible part irreversibly remains even after the water evaporates and dries.

On the other hand, if a small amount of water is applied, such as by blowing or exposing it to steam, the dissolved desensitizer may penetrate into the base material.
Alternatively, the diffusion to the vicinity of the Himi chromatic recorded image is suppressed, and the adhering water evaporates and decreases within the visible coefficient of seconds to several seconds, and the desensitizer in the visible image is concentrated again, and the dye and coloring agent are reduced. The function of inhibiting the color reaction becomes stronger, causing the visible image to disappear.

In other words, it is thought that the concentration of the desensitizer changes due to the adhesion and evaporation of water, and a reversible reaction occurs between the desensitizer and the dye, resulting in coloring and decoloring phenomena.

〔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 % in the examples indicate parts by weight and % by weight, respectively.

Example 1 3,3-bis(p-
35% aqueous dispersion of dimethylaminophenyl)-6-dimethylaminophthalide 30 parts 38% aqueous dispersion of zinc 3,5-di(α-methylbenzyl)salicylate reprocessed to fine powder by sand mill
55 parts 48% styrene-butadiene copolymer latex 100 parts Polyethylene glycol #1000 (average molecular weight 10
00) 50 parts calcium carbonate (absorption amount 95d/100g) 10 parts water
Mix 100 parts and stir. The resulting coating liquid was coated on synthetic paper (
Made of egg oil synthetic paper ■, product name [YUPO J FD (, #60
) was coated with a wire spar so that the coating amount after drying was 6 g/n, and dried at 90° C. for 30 seconds to obtain a white water-colorable recording transfer sheet.

Lay the coated side of the obtained transfer sheet on top of the high-quality paper,
Printing was performed on the non-coated surface of the transfer sheet using a typewriter.

After printing, it was not possible to identify the print on the recording section on the high-quality paper. Subsequently, when water was applied to the recording area using water-containing gauze, a clear blue printed image was discernible. Even if it was left as is, the colored part remained.

Example 2 30 parts of a 35% aqueous dispersion of 3-jethylamino-macrofluorane micronized by a sand mill 38% aqueous dispersion of zinc 3,5-di(α-methylhensyl)salicylate micronized by a sand mill
55 parts 48% styrene-butadiene copolymer latex 60 parts Polyethylene glycol #1000. Average molecular weight 100
0) 50 parts calcium carbonate (
Oil absorption 195m/100g) 50 parts water 1
00 parts were mixed and stirred to obtain a coating liquid.

On the other hand, a coating liquid consisting of 48% styrene-butadiene copolymer latex loo parts, 50 parts of calcium carbonate (oil absorption 95 d/100 g), and 150 parts of water was applied in advance to base paper with a basis weight of 40 g/rrf using a wire bar. , and dried to form a coating layer with a solid content of 4 g/po.

After suppressing the permeability of the coating liquid in this manner, the above-mentioned coating liquid was applied to the surface in the same manner as in Example 1 to obtain a white water-chromic recording transfer sheet.

The coated side of the resulting transfer sheet was stacked on synthetic paper (manufactured by Tamago Yuka Synthetic Paper ■, trade name: Yupo JFPG #150), and printing was performed on the non-coated side of the transfer sheet using a ballpoint pen.

After printing, the synthetic paper recording section could not identify the print. Subsequently, when breathing on the recording section, a clear red printed image was identified, and the color disappeared after 2 to 3 seconds. Then, when the printed area was exposed to steam from a kettle for 1 second, a clear red printed image was again identified, and the color disappeared after 14 to 15 seconds. Furthermore, when water was applied to a newly printed recording area with a brush containing water, the printed area developed a red color, and even after the water was left as it was and the water evaporated to dryness, the print remained as an afterimage.

Example 3 100 parts of a 50% aqueous solution of paraffin wax emulsion dibon (Middle East Oil ■, product name "Cellosol J686") was added to the coating solution of Example 2, and the support was changed to synthetic paper and PET film (Toshi ■, product name) was added. A translucent water-chromic recording transfer sheet was obtained in the same manner as in the previous example, except that Luminar 4μ was used.

Lay the coated side of the obtained transfer sheet on top of the high-quality paper,
Printing was performed using a thermal printer from the non-coated side of the transfer sheet. After printing, the printed image could not be identified on the recording section on the high-quality paper. Next, when I applied water to the transfer area with a brush containing water, a clear blue printed area was identified.
The colored area remained even after the water evaporated and dried.

Example 4 Example 1 except that 35 parts of Emulgen 935 (manufactured by Kao ■; polyoxyethylene nonylphenyl ether) was used instead of 50 parts of polyethylene glycol #1000.
A white water-chromic recording transfer sheet was obtained in the same manner as above.

The coated side of the resulting transfer sheet was placed on a government-made postcard, and printing was performed on the non-coated side of the transfer sheet using a ballpoint pen.

After printing, it was not possible to identify the printing on the recording section on the official postcard. Subsequently, when water was applied to the recording area using a water-soaked brush, a clear blue printed image was discernible. Even if it was left as is, the colored part remained.

Example 5 A white water-colorable recording transfer sheet was prepared in the same manner as in Example 1, except that Epomin P-1000 (manufactured by Nippon Shokubai Chemical Co., Ltd.; 30% aqueous solution of polyethyleneimine) was used instead of polyethylene glycol #1000. I got it. The coated side of the resulting transfer sheet was placed on top of high-quality paper, and printing was performed using a pencil from the non-coated side of the transfer sheet.

After printing, it was not possible to identify the print on the recording section on the high-quality paper. Subsequently, when water was sprayed onto the recording area, a clear blue printed image was discernible. Even if it was left as is, the colored part remained.

[Effect] The present invention can transfer the Himi coloring material to another base material by applying pressure or heating to provide a water colorable recorded image.
In addition to writing, it is possible to record with popular inexpensive office automation equipment such as typewriters, impact printers, and thermal printers.

In addition, the obtained water-chromic recorded image is normally invisible and information can be obtained simply by adding water, so it can be widely applied to the creation of secret documents, secret postcards, etc.

Claims (3)

[Claims] (1) Contains a colorless or light-colored basic dye, a coloring agent capable of coloring upon contact with the dye, a desensitizer, and an adhesive on the base material, and contains a water-colorable material consisting of a colorless to light-colored basic dye, a desensitizer, and an adhesive; A water-chromic recording transfer material that has a transfer layer that transfers from the base material to the recording sheet when heated. (2) The water color-forming recording transfer material according to claim (1), wherein the desensitizer is at least one selected from polyolefin glycol, surfactant, and polyethyleneimine. (3) Transfer in which a transfer layer is provided on a base material, which includes a water-chromic material consisting of a colorless or light-colored basic dye, a coloring agent that can develop color upon contact with the dye, a desensitizer, and an adhesive. A method for forming a water-chromic recorded image, which comprises transferring the water-chromic material to the recording sheet by overlapping the material and the recording sheet and applying pressure or heat.