JP2000026745A - Azo-based fluorescent pigment and coloring agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject fluorescent pigment having a coloring capacity and a sufficiently high concealing property, capable of recording characters, numbers, marks, patterns, or the like, even by using it singly and excellent in light fastness by coupling a specific diazo component with a specific coupling component. SOLUTION: This azo-based fluorescent pigment is obtained by coupling a diazo component of formula I or II X, Y are each methyl, methoxy or ethoxy; Z is NHCOA [A is a (substituted) aromatic ring] or NHA} with a coupling component of formula III or IV [L is a halogen or an ester; (n) is 0-4; M is CONHA or NH(CO)2; (m) is 0, 1].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel azo-based fluorescent dye and a general azo fluorescent dye containing the dye as a coloring agent for recording general image information and for directly recognizing recorded information such as letters, numbers, symbols and patterns with the naked eye. It is possible, but if the recorded information is copied or duplicated by a full-color copying machine (including an image scanner, etc.), the image information is clearly identifiable as a copy or duplicate, even if it is a device. The present invention relates to a colorant composition for preventing copying of a record. 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 provides a diazo component represented by the following general formula (1) or (2) and a coupling represented by the following general formula (3) or (4). A coloring composition for image information recording, comprising: an azo fluorescent dye characterized by being coupled with a component; and the azo fluorescent dye described above as a colorant.

[0006] Diazo component (X and Y in the formula may be the same or different and each represents a methyl group, a methoxy group or an ethoxy group, and Z represents an -NHCO-A- group or an -NH-A group (A represents an aromatic group which may have a substituent. Represents an aromatic ring).

[0007] Coupling component

[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 azo fluorescent dye of the present invention is a kind of azo dye, and a dye obtained by diazotizing a diazo component in water or an appropriate organic solvent and performing a coupling reaction with a coupling component under appropriate conditions is used. Further, it is obtained by adjusting the crystal form by heating and stirring using an appropriate solvent. The hue ranges from reddish yellow to orange and slightly reddish 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. Examples of the compound represented by the general formula (4) include 2-acetoacetamidobenzothiazole.

The azo fluorescent dye of the present invention can be obtained by coupling the diazo component and the coupling component according to a conventional method. The combination of the couplings results in reddish yellow to orange and slightly reddish red fluorescent dyes.

The azo fluorescent dye of the present invention is a kind of so-called azo dye, and is a clear 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 recombined by performing filter spectroscopy cannot reproduce the original, thereby exhibiting a copy prevention effect. The colorant composition of the present invention containing the azo fluorescent dye as a colorant is used for general image information recording and for preventing copying of image information recording.

As a base material for a printing material or the like used for recording image information, any of conventionally known printable articles such as paper, paper mixed with chemical fibers, synthetic paper, plastic film and plastic sheet can be used. can do. 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.

Any of the methods for recording colored image information on the above-mentioned base material can use 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, printing methods include letterpress printing,
Examples include lithographic printing, intaglio printing, gravure printing, and stencil screen printing. In the case of recording equipment, a thermal transfer method using a heating method, an ink jet printing method using a pressure-sensitive effect, and other impacts using the effect of impact or contact Any of conventionally known recording methods such as a printing method and a dot printer can be used.

In order to prevent the printed matter from being copied using the colorant composition of the present invention, while recording information on any of the above-mentioned substrates using a known colored printing ink or before or after recording the information, After recording, it is necessary to color at least a part of the recording surface by printing or applying a coating agent containing the azo fluorescent dye of the present invention.

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 resins for thermal transfer inks, for example, polystyrene, styrene- (meth) acrylate copolymer,
Examples thereof include (meth) acrylate (co) polymers, styrene-butadiene copolymers, polyurethanes, waxes, and epoxy resin polyester resins. Particularly, ester waxes and paraffin waxes are preferable.

The method of applying the coating agent containing a fluorescent dye is selected from conventionally known methods according to the coating agent, and 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.

[0025]

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.

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

Table 1

Table 2

Example 2 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

Using the above lithographic printing ink, characters and pictures were printed 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 3 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 Isopropyl alcohol 42.0 parts Ethyl acetate 28.5 parts Total 100.0 parts

The oil-based flexographic ink of the above composition was coated on the entire 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 4 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

[0036]

According to the present invention, there is provided an azo fluorescent dye useful as a colorant for recording general image information and for preventing copying of image information recording. Conventionally, in general, in order to completely prevent the copy protection of a printed matter or the like, it has been necessary to process the base material itself such as paper or to make the base color dark and dark. That makes it expensive,
Image information such as recorded letters, numbers, symbols, and patterns became difficult to read. On the other hand, by applying or printing the pigment-like fluorescent dye of the present invention on a base or image information, the above-mentioned drawbacks can be overcome, and duplication by copying can be made 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, no fluorescence was observed on the copy in a detector such as a black light. In addition, the orange and red colors were significantly red-shifted, completely different from the original.

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Claims (2)

[Claims] 1. A method comprising 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): Azo fluorescent dye. Diazo component Coupling component 2. A colorant composition comprising the azo fluorescent dye according to claim 1 as a colorant.