JP3355292B2 - Copy protection recording method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION In the present invention, recorded information such as letters, numbers, symbols, and patterns can be directly recognized by the naked eye, but the recorded information is copied or copied by a full-color copying machine (including an image scanner). In this case, the present invention relates to a copy prevention recording method in which it can be clearly recognized by a naked eye or a device that it is a copy / duplicate. More specifically, when recording information such as letters, numbers, symbols, patterns, etc., when a base material such as a substrate to be printed is colored using a fluorescent dye, the color tone of the copied material is Since it is significantly different from the original, the naked eye can be easily determined. Also, the determination can be made by measuring the fluorescence with a device or measuring the color difference.

[0002]

2. Description of the Related Art Conventionally, as a method for preventing counterfeiting of securities such as stock certificates, public and corporate bonds, air tickets, checks, etc.
A method of printing such words and patterns in advance as hidden characters to prevent counterfeiting on these printed materials, dark red brown,
By recording information on paper such as dark Bordeaux or deep sepia, when this recorded matter is copied, the whole becomes black, etc., and the copied matter cannot be discriminated. Also, an inconspicuous fluorescent dye symbol or one point A method of recording pattern information and distinguishing it from a copy has been proposed.

[0003]

In these prior arts, hidden characters and patterns of securities and the like have been effective means to some extent, but are difficult to apply to simple printed materials other than securities and the like. In addition, as described above, printing paper such as dark reddish brown is difficult to read as a printed matter due to its dark color tone, and generally has a poor impression even if effective for the purpose of preventing abuse. At that point, the method using a fluorescent dye is often used because it is clear and has a large prevention effect. However, most of the fluorescent dyes generally have poor light resistance, and thus lose fluorescence when exposed to strong light for a long period of time. Further, since the fluorescent dye has poor coloring power and hiding power, it can only be used in combination with other pigments or used in a simple one-point pattern or the like.

The inventors of the present invention have intensively studied to develop a fluorescent dye particularly effective in preventing full-color copying in which the above-mentioned problems have been solved. As a result, the fluorescent dye emits strong fluorescence even though it is a crystalline fine particle like a pigment. A series of azo compounds has been found. Since these azo compounds have coloring power and sufficiently high hiding power, they can record information such as letters, numbers, symbols, and patterns even when used alone, and are sufficiently legible. Furthermore, the light resistance is very strong. Compared with a fluorescent pigment, which is conventionally called a fluorescent pigment, which is obtained by dissolving a fluorescent dye in a resin and finely pulverizing, or a carrier in which a fluorescent dye is deposited, etc.
It showed twice or more the durability and could withstand outdoor use.

[0005]

That is, the present invention relates to a method for recording colored information on an arbitrary substrate, by recording at least a part of a recording surface during, before, or after recording the information. Coloring with an azo fluorescent dye obtained by coupling a diazo component represented by the general formula (1) or (2) with a coupling component represented by the following general formula (3) or (4). This is a copy prevention recording method characterized by the following.

[0006]

[0007]

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to embodiments of the present invention. The feature of the present invention is that the fluorescent dye to be used is one of so-called azo dyes, and is a sharp colorant itself. Therefore, it can be handled in exactly the same way as a recording method using a general pigment ink or the like. In addition, since it also has very strong fluorescent light, it absorbs a part of visible light and generates new light emission in a long wavelength part. As a result, when full-color copying is performed, a copy that has been re-synthesized by performing filter spectroscopy cannot reproduce the original, thereby exhibiting a copy preventing effect.

As the substrate of the material to be printed used in the present invention, for example, any conventionally known printable articles such as paper, chemical fiber mixed paper, synthetic paper, plastic film and plastic sheet can be used. it can. Among them, various papers are preferably used according to uses such as high-quality paper, art paper, lightweight coated paper, web offset printing paper, matte coated paper, and paper changing. The shape of the base material to be used may be a cut card size or the like in addition to the various standard sizes, and is not particularly limited.

In the present invention, any method for recording colored image information on the above-mentioned substrate can be a conventionally known method, and is not particularly limited. For example, any conventionally known methods such as printing, recording, and entry of image information such as letters, numbers, symbols, and patterns can be used. Means such as a printing machine or a recording device used for recording image information is used for image formation. And is not particularly limited. For example, the printing method includes letterpress printing, planographic printing, intaglio printing, gravure printing, stencil screen printing, and the like.In a recording device, a thermal transfer method using a heating method, an ink jet printing method using a pressure-sensitive action, and the like, Impact printing method using the action of impact or contact,
Any conventionally known recording method such as a dot printer can be used.

The fluorescent dye used in the above-mentioned recording method is a kind of azo dye. The diazo component is diazotized in water or an appropriate organic solvent, and a coupling reaction is performed with the coupling component under appropriate conditions. The obtained dye is further obtained by heating and stirring using a suitable solvent to adjust the crystal form. The hue is from the red yellow orange <br/>及beauty red.

As the diazo component of such a dye, a compound represented by the above general formula (1) or (2) is used. The substituents X and Y in these formulas may be the same or different and are a methyl group, a methoxy group and an ethoxy group. Further, the substituent Z is a -NHCO-A group or a -NH-A
And A is an aromatic ring such as a benzene ring, a naphthalene ring and a biphenyl which may have a substituent such as a halogen, an alkoxy group and a lower alkyl group.

The compound represented by the general formula (1) is, for example, 4-benzoylamino-2-methyl-5
-Methoxyaniline, 4-benzoylamino-2,5-
Dimethoxyaniline, 4-benzoylamino-2,5-
Diethoxyaniline, 4'-phenylbenzoylamino-2,5-dimethoxyaniline, 4 '(3', 4'-isoindolinonecarbamoyl) -2,5-dimethoxyaniline, 4'-chlorobenzoyl-2,5- Dimethoxyaniline, 3 ', 5'-dichlorobenzoyl-2,5-
Dimethoxyaniline, 4'-chlorobenzoyl-2,5
-Diethoxyaniline and the like.

The compound represented by the general formula (2) includes, for example, 4-aminodiphenylamine, 4 '
-Methoxyaminodiphenylamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl and the like.

As the coupling component, a compound represented by the above general formula (3) or (4) is used.
The substituent L in the formula (3) is an ester group having 0 to 4 halogen atoms or alkyl groups selected from fluorine, chlorine and bromine and having about 1 to 10 carbon atoms. m is 0 or 1. The substituent L in the general formula (4) is the same as that in the general formula (3).

The compound represented by the general formula (3) includes, for example, acetoaceto-4-chloroanilide, acetoaceto-2-chloroanilide, acetoaceto-2,
Halogen derivatives such as 4-dichloroanilide and acetoaceto-2,4,6-trichloroanilide;
4-butoxycarbonylanilide, acetoaceto-2-
Carboxylic acid ester derivatives such as butoxycarbonylanilide and acetoaceto-4-ethoxycarbonylanilide, 5-aminoisoindolinone acetoacetanilide, 2-chloro-5-phenylcarbamoyl-acetoacetanilide, 2-chloro-5- (2'-chlorophenyl ) Mixed derivatives such as carbamoyl-acetoacetanilide and the like.

The compound represented by the general formula (4) includes, for example, 2-acetoacetamidobenzothiazole.

The azo fluorescent dye used in the present invention is obtained by coupling the diazo component and the coupling component according to a conventional method. The combination of the coupling, orange Iro及beauty red color of the fluorescent dye can be obtained from the reddish yellow.

In the present invention, in order to prevent copying of the printed matter, while recording information on the above-mentioned arbitrary substrate using a known colored printing ink, or before or after recording the information, the recording surface of the recording surface can be prevented. It is necessary to print or apply a coating agent containing the above-mentioned azo fluorescent dye on at least a part of the coating agent to color the coating agent.

The content of the fluorescent dye in the coating agent is
Types and application conditions of printing machine, printing equipment, coater, etc. when printing or applying, various conditions such as composition of printing ink and coating agent and composition of base such as paper to be printed and applied, absorbency, glossiness etc. , The optimum conditions are different, and the optimum amount is determined in each case. Coating agents containing fluorescent dyes, like conventional coating agents, are aqueous solutions, aqueous emulsions, aqueous dispersions or mixtures thereof in aqueous systems, and oily solutions, oily emulsions, and oily dispersions in oily systems. It may be used in any form such as a liquid system or a mixed system thereof, and the form of use is not particularly limited.

Printing inks for recording information in color include letterpress inks, planographic inks, gravure inks of intaglio inks, stencil screen inks, heat transfer inks, etc., depending on the printing method. And oil ink, solvent ink, water-based ink and the like.

As the coating agent and the resin component of the printing ink, conventionally known ones are used and are not particularly limited. Examples of resin components such as aqueous coating agents and aqueous printing inks include, for example, casein, starch, polyvinyl alcohol, hydroxyethylcellulose, sodium carboxymethylcellulose, a water-soluble salt of a styrene-maleic acid copolymer, and a (meth) acrylic ester. Water-soluble salts of (co) polymers, water-soluble salts of styrene- (meth) acrylic ester polymers, water-soluble alkyds, styrene-butadiene-based copolymer latex, styrene-
(Meth) acrylic ester copolymer latex, ethylene-vinyl acetate copolymer latex, styrene-
(Meth) acrylic ester-based copolymer latex, polystyrene-based dispersion, and the like.

As the resin component of the oily coating agent and the oily printing ink, for example, cellulose butyrate acetate, nitrocellulose, vinyl acetate (co) polymer, styrene (co) polymer, vinyl chloride-vinyl acetate ( (Co) polymer, (meth) acrylic ester (co) polymer, polybutyral, alkyd resin, phenol-modified alkyd resin, aminoalkyd resin, polyester polymer, polyurethane polymer, acrylic polyol urethane, soluble polyamide, phenol Resin, rosin-modified phenol resin, rosin-modified maleic resin, and the like.

As the resin for the thermal transfer ink, for example, polystyrene, styrene- (meth) acrylate copolymer,
Examples thereof include (meth) acrylate (co) polymers, styrene-butadiene copolymers, polyurethanes, waxes, epoxy resins , and polyester resins, with ester waxes and paraffin waxes being particularly preferred.

The method of applying the coating agent containing a fluorescent dye is selected from conventionally known methods according to the coating agent. Examples thereof include a blade coater, a rod coater, a knife coater, a squeegee coater, an air doctor coater, and a transfer coater. Coaters, gravure coaters, kiss coaters, spray coaters and the like can be mentioned. After the application of the coating agent, the coating agent may be dried or calendered.

[0026]

Next, the present invention will be described more specifically with reference to examples. In the following description, parts and percentages are by weight unless otherwise specified.

(Synthesis Example of Azo Dye) Using the diazo component and the coupling component shown in Tables 1 and 2, an azo fluorescent dye was synthesized by coupling according to a conventional method. AA in each table is an acetoacetamide group (CH
₃ COCH ₂ CONH-).

[0028]

[0029]

Example 1 An offset lithographic printing ink was prepared according to the following formulation. Fluorescent dye (Compound 5) 18.0 parts Preparation varnish for offset lithographic ink 77.8 parts 5% Cobalt dryer 0.2 part 8% Manganese dryer 1.0 part Ink solvent 3.0 parts Total 100.0 parts

The preparation varnish for offset lithographic ink used had the following composition. Rosin modified phenolic resin 35.0 parts Dry oil 25.0 parts Dry oil modified isophthalic acid alkyd 10.0 parts Ink solvent 29.5 parts Aluminum chelate 1.5 parts Total 100.0 parts

The printing ink for lithographic printing was used to print characters and pictures on high quality paper using an offset printing machine. When this was copied using a full-color copying machine, the characters and patterns of the copy became red and had a hue different from that of the orange copy source (original).

Example 2 According to the following formulation, each component was dispersed using an attritor to obtain an oil-based flexographic ink. Fluorescent dye (compound 9) 4.5 parts Oil-soluble polyamide resin 17.8 parts Nitrocellulose 7.2 parts Isopropyl alcohol 42.0 parts Ethyl acetate 28.5 parts Total 100.0 parts

An oil-based flexographic ink having the above composition was coated on the entire surface of a coated paper with a coater. A full car copy of this in the same manner as in Example 1 had exactly the same results.

Example 3 According to the following formulation, each component was kneaded with a hot roll to prepare a thermal transfer recording ink. This ink was applied to a polyester film and cut into a width of 6 mm to obtain a yellowish red fluorescent heat transfer ink ribbon. Paper for a thermal transfer printer was set in a word processor, and characters, symbols, etc. were printed. The full-color copy of this was purple red and was distinctly different from the original.

Fluorescent dye (compound 16) 18.0 parts Styrene-methacrylate copolymer resin 7.0 parts Ester wax 36.0 parts Paraffin wax 36.0 parts Silica 3.0 parts Total 100.0 parts

[0037]

In the past, it was generally necessary to process the base material itself, such as paper, or to make the base color darker, darker, and darker in order to completely prevent the copy protection of printed matter and the like. Because of that, it becomes expensive or recorded characters,
Image information such as numbers, symbols, and patterns became difficult to read. On the other hand, the present invention can overcome the above-mentioned drawbacks by coating or printing a pigment-like fluorescent dye on a base or image information, and can make duplication by copying impossible. The information record prepared by the method of the present invention was copied by a commercially available full-color copying machine. As the pigment of the toner used in these, yellow is usually C.I. I. Pigment Yellow 17, Magenta is C.I. I. Pigment Red 122 and Cyan are C.I. I. Pigment Blue 15-3 and black are C.I. I. Pigment Black 7 or the like is used, and any of the pigments is non-fluorescent. Therefore, the fluorescence of the copy was naturally not detected by a detector such as a black light. In addition, the orange and red colors were significantly red-shifted, completely different from the original.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B41M 3/14 B42D 15/10 C09B 29/085 C09B 29/09 C09D 11/02

Claims (1)

(57) [Claims] When recording colored information on an arbitrary substrate, during or before or after recording the information,
At least a part of the recording surface is formed by coupling a diazo component represented by the following general formula (1) or (2) with a coupling component represented by the following general formula (3) or (4). A copy prevention recording method characterized by coloring with an azo fluorescent dye.