JPH0416069B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to printed matter that utilizes the reflective and absorbing properties of visible light and infrared rays of pigments, and a method for producing the same.More specifically, the present invention relates to printing inks and the like containing pigments that reflect infrared rays. Printed matter printed or coated with a combination of printing ink, etc. containing a pigment that absorbs infrared rays, and its manufacturing method, and can be used as a means of detecting forgery or alteration of securities, etc., or as a means of concealing confidential information. The purpose is to provide educational materials, picture books, etc. that utilize differences in infrared sensitivity. (Problems to be solved by the prior art and the invention) Conventionally, as a method to prevent forgery of securities such as stock certificates, public and corporate bonds, airline tickets, checks, etc., counterfeiting by electronic photocopying has been In order to prevent counterfeiting, printed words or patterns are printed as hidden characters in advance on the printed matter, or as a means to make it easier to detect counterfeit products, magnetic ink can be partially applied or characters, symbols, or patterns can be printed on the printed matter as hidden characters to prevent counterfeiting. A method has been proposed in which the information is printed in the form of a magnetic reader and detected by a magnetic reader. Hidden characters and patterns on securities, etc. have been an effective method in their own way, but they are difficult to use on simple printed matter, and the designs and patterns are limited because of this, so they are not widely used. Hardly used. Additionally, counterfeit detection systems using magnetic ink have the property that the magnetic strength changes or disappears when the magnetic material used is exposed to heat or placed in an environment with a strong magnetic field. It is also quite difficult to uniformly disperse magnetic materials in ink, and it is also quite difficult to store them stably and print them uniformly. The inventors of the present invention have conducted various research into printed materials that are not affected by the environment and can be easily printed, and their manufacturing methods, for the purpose of detecting counterfeiting and alteration of securities, etc. mentioned above. The present invention was completed based on the discovery that a printed matter that is printed or coated by combining the properties of infrared absorption and infrared ray absorption provides an effective means for solving the problem. (Means for Solving the Problems) That is, the present invention is characterized by printing or coating a combination of an ink containing a pigment that reflects infrared rays and an ink containing a pigment that absorbs infrared rays. , in a printed matter that is given information such as characters and images under visible light as well as other information when irradiated with infrared rays, the pigment having the property of reflecting infrared rays has an azomethine group represented by the following general formula. The above-mentioned printed matter is characterized in that it is an azo organic pigment or dye having a residue in the molecule, and a method for producing the same. However, Ar in the above formula is a residue of an aromatic or heterocyclic compound, X is a hydrogen atom or a halogen atom, and m is an integer of 1 to 2 or more depending on the substitution position of Ar. To explain the present invention in more detail, black so-called black ink, which is generally used for printing, including the above-mentioned securities, uses carbon black pigment as a pigment. When the black printed matter is irradiated with infrared rays, carbon black pigment has the property of absorbing infrared rays and not reflecting them, so the black printed matter also absorbs infrared rays and does not reflect them. Therefore, infrared rays are emitted by a light emitting diode,
When the above-mentioned black print made of carbon black pigment is inspected using an infrared reader that detects the reflection of infrared rays from the target object with an infrared light receiving sensor and converts the presence or absence of reflection and the degree of reflected light into electrical signals. It emits a signal that there is no reflection. However, a black azo pigment, which also has a residue containing an azomethine group in its molecule, shows black color under visible light, that is, to the naked eye, but shows almost no absorption of infrared rays. , it was found that it exhibits very high reflection. Therefore, when a printed matter using the black azo pigment having an azomethine group is inspected using the above-mentioned infrared reader, it shows a signal indicating that it strongly reflects infrared rays. The present inventors have investigated the properties of inks using carbon black pigments etc. that have infrared absorbing properties as pigments and inks using azo dyes having infrared ray reflective properties and azomethine group-containing residues in their molecules as pigments. By effectively utilizing
They may look exactly the same under visible light and cannot be distinguished, but they can be distinguished by an infrared reader, or they may be distinguished by various aspects of hue, brightness, and saturation under visible light, but cannot be distinguished under infrared light. It is also possible to reverse the color recognition under visible light and the sensitive signal under infrared light due to the difference in hue, brightness, and saturation, and it is possible to reverse the color recognition under visible light and the sensing signal under infrared rays. It can be used as a means of discovering information, or as a means of concealing confidential information from third parties, or as information on the difference in sensitivity between visible light and infrared light to create teaching materials, picture books, etc. , used for toys, play equipment, etc. The dye used in the present invention will be explained. Azo organic pigments or dyes that have a residue containing an azomethine group in the molecule and are used as pigments that reflect infrared rays are residues that contain an azomethine chromophore represented by the following general formula ().
It is an azo dye which has on the diazo component side of the azo dye, on the coupling component side, or on both of them. Ar, X, and m in the above formula have the same meanings as above. The diazo component having an azomethine group is diazotized according to a conventional method and subjected to a coupling reaction with a conventionally known coupling component or a coupling component having the azomethine group to obtain an azo dye having an azomethine group. Further, a conventionally known diazo component is diazotized and subjected to a coupling reaction with the coupling component having an azomethine group, thereby producing an azo dye having an azomethine group. In the above residue () having an azomethine group, Ar is a residue of an aromatic or heterocyclic compound, such as a benzene ring, a naphthalene ring,
These include anthracene ring and pyridine ring. In the above, the diazo component having the azomethine group is, for example, 3-(4'-aminophenylimino)-1-oxo-
4,5,6,7-tetrachloroisoindoline, 3-(3'-aminophenylimino)-1-oxo-
4,5,6,7-tetrachloroisoindoline, 3-(2'-aminophenylimino)-1-oxo-
4,5,6,7-tetrachloroisoindoline, 3-(4″-amino-diphenyl-4′-imino)-1
-oxo-4,5,6,7-tetrachloroisoindoline, etc., and a halogen atom, methyl group, methoxy group in the phenylene group or diphenylene group,
These include amino compounds substituted with one or more substituents such as ethoxy group and nitro group. A conventional method for diazotizing aromatic amines can be directly used to diazotize this diazo component. For example, a sodium nitrite solution is used to diazotize a cold aqueous solution of a mineral acid salt of the diazo component. It can be carried out by the method disclosed in Japanese Patent Publication No. 45-18383, Japanese Patent Publication No. 46-37189, Japanese Patent Publication No. 56-2102, and Japanese Patent Application Laid-Open No. 49-120923. Conventionally known coupling components used for coupling with the above diazo component having an azomethine group include, for example, CI Azoic Coupling Components 1, 2, 10, 22, 17, 27, 18, 31, 8. ,21,29,
20, 34, 41, 6, 11, 24, 19, 12, 23, 14, 30,
46, 4, 7, 40, 3, 32, 36, 25, 13, 15, 16,
5, 35, 13, 19, acetoacetate anilide, acetoacetate-2-methylanilide, acetoacetate-4-methylanilide, acetoacetate-2,4-dimethylanilide, acetoacetate-2-methoxyanilide, Acetoacetic acid-2-chloroanilide, Acetoacetic acid-2-methoxy-5-methyl-4-chloroanilide, Acetoacetic acid-2,5-dimethoxy-4-chloroanilide, Acetoacetic acid-4-chloro-2- Acetoacetic acrylamides such as nitroanilide; 3-methyl-1-phenyl-5-pyrazolone, 1-phenyl-5-pyrazolone-3-carboxylic acid ethyl ester, hydroxynaphthoic acid, phenol, and the like. The aforementioned coupling components having an azomethine group are, for example, 2-hydroxy-3-naphthoic acid, 2-hydroxy-anthracene-3-carboxylic acid, 3-hydroxybenzofuran-2-carboxylic acid, 2-hydroxycarbazole-3 -carboxylic acid, 2-hydroxy-α-benzocarbazole-3-
It is obtained by a condensation reaction between carboxylic acids that can be coupled, such as carboxylic acid, 1-phenyl-5-pyrazolone-3-carboxylic acid, and acetoacetic acid, and an amino compound having an azomethine group as described above as the diazo component having an azomethine group. These are things that can be done. Conventionally known diazo components used for coupling with the above coupling component having an azomethine group include, for example, CI Azoik Diazo Component 44, 2,
3, 6, 7, 37, 9, 16, 49, 17, 18, 19, 26,
33, 46, 11, 32, 34, 12, 8, 10, 5, 13, 1,
29, 31, 42, 14, 24, 43, 41, 40, 20, 15, 38,
51, 21, 23, 4, 27, 39, 48, 22, 47, 35, 45,
36, aniline, toluidine, anisidine, naphthylamine, etc. Diazotization of the above components, coupling reaction,
Purification and, in the case of pigments, conversion into pigments are carried out according to conventional methods. This is carried out in a suitable medium, aqueous or organic. Particularly preferred azo dyes having an azomethine group are, for example, JP-A-58-174446, Japanese Patent Application No. 59-4775, Japanese Patent No. 1063816, Japanese Patent No. 1052019, and Japanese Patent No. 1141514. These are the azo dyes used in the specification, Japanese Patent No. 1141515, and Japanese Patent Application No. 168540/1982 and Japanese Patent Application No. 277929/1982. In particular, azo pigments with an azomethine group using 2-hydroxy-α-henzocarbazole-3-carboxylic acid allylamide and its derivatives as a coupling component exhibit a dark green to black tone under visible light, especially in black. It showed a clear black color with a high degree of blackness. However, it showed almost no absorption of infrared rays and a high reflectance. The above-mentioned azo dye having an azomethine group has excellent heat resistance, light resistance, water resistance, and chemical resistance, and also has high coloring power. In addition, pigment-type dyes also exhibited extremely excellent solvent resistance. In the present invention, as the pigment having the property of absorbing infrared rays, conventionally known pigments and dyes having such a property are used, and particularly preferred ones are, for example, carbon black pigment, aniline black pigment, iron oxide black pigment, and oxidized black pigment. These include titanium-based black pigments and spinel-type structural black pigments. In addition, if additional pigments are required, they can be appropriately selected from conventionally known pigments or dyes. For example, organic pigments and dyes include phthalocyanine, azo, anthraquinone, Perinone/perylene type, indigo, thioindigo type, dioxazine type, quinacridone type, isoindolinone type, etc. Inorganic pigments include:
These include titanium oxide type, iron oxide type, fired pigment type, metal powder pigment, extender pigment, etc. In the present invention, reflection refers to the practical properties of the printed material, and includes cases where the dye itself is reflective and the dye itself has light transmittance, and the printing material such as paper is reflected. In the case where the material or the base is coated or printed, it also includes cases where the coated film or printed film has reflective properties, resulting in reflective properties. As the printing material used in the present invention, conventionally known printable or coatable articles such as paper, paper mixed with chemical fibers, synthetic paper, plastic film, and plastic sheet are used. Among them, various types of paper are suitably used depending on the purpose, such as high-quality paper, art paper, coated paper, lightweight coated paper, offset rotary printing paper, matte coated paper, and coated paper. As mentioned above, the printing ink containing the above-mentioned pigment is an appropriate known printing ink system, such as letterpress ink, lithographic ink, gravure ink for concave plates, screen ink for stencil printing, etc. Also, depending on the media type, oil ink may be used. , solvent ink, water-based ink, etc. Furthermore, as the coating ink containing the above-mentioned pigment, conventionally known coating ink systems suitable for the above-mentioned printing materials are used, and the aqueous system includes an aqueous solution system, an aqueous emulsion system, and an aqueous dispersion system. , or a mixture thereof, and the oil-based system may be an oil-based solution system, an oil-based emulsion system, an oil-based dispersion system, or a mixture thereof. The resin components used in these printing inks and coating inks are conventionally known, and the resins for water-based printing inks and coating inks include casein, hydroxyethyl cellulose, and water-soluble styrene-maleic acid ester copolymers. water-soluble salts of (meth)acrylic ester-based (co)polymers, water-soluble salts of styrene-(meth)acrylic ester latexes, water-soluble alkyd-based resins, styrene-butadiene-based copolymer latexes, ) Acrylic ester copolymer latex, styrene-(meth)acrylic ester copolymer latex, ethylene-vinyl acetate copolymer latex, polyethylene dispersion, ethylene copolymer dispersion, etc. . Resin components of oil-based printing inks and coating inks include cellulose acetate butyrate resins, nitrocellulose resins, vinyl acetate (co)polymers, styrene (co)polymers, and vinyl chloride-vinyl acetate copolymers. , ethylene-vinyl acetate copolymer, polyvinyl butyral resin, alkyd resin, phenol-modified alkyd resin, styrenated alkyd resin, amino alkyd resin, polyester polymer, polyurethane polymer, acrylic polyol urethane polymer Examples include soluble polyamide polymers, phenolic resins, rosin-modified phenolic resins, and rosin-modified maleic acid resins. Further, printing methods include letterpress printing, planographic printing, intaglio printing, gravure printing, screen printing, and the like. The method for applying the coating ink is selected from conventionally known methods depending on the coating ink, such as a blade coater, a rod coater, a knife coater, a squeeze coater, an air doctor coater, a gravure coater, and a spray coating. Reflection or absorption of infrared rays and their degree are confirmed using an infrared reader or an infrared photograph. In an infrared reader, first,
Infrared rays are irradiated at 700 to 900n.
Semiconductor lasers that emit near-infrared rays of 790 nm and infrared light-emitting diodes that emit infrared rays of around 790 nm are used. These infrared rays are irradiated either directly or after being modulated to increase the sensitivity of light reception. The infrared rays reflected by the printed matter are received by an infrared receiving sensor. If the absorption of the printed surface is large and there is no or very weak reflection of infrared rays, the light receiving sensor will give an electrical signal indicating that there is no reflection. Regarding the degree of light received, it converts it into an electrical signal and gives information such as that it is a very strong reflection, or that the reflection is considerably weakened due to partial absorption. These electrical signals are connected to various recognition methods and recognized as clear information. For example, turning on a warning light,
These include the generation of alarm sounds, the generation of synthesized voices, the performance of melodies, displays with cathode ray tubes, recording with recorders or printers, signs or movement by motor operation, and combinations thereof. The capabilities of these infrared readers allow us to use our normal perception of color to incorporate information into print that is invisible to the naked eye. The infrared reader varies depending on the initial settings and sensitivity adjustment, so it cannot be determined definitively, but if there is no or very low reflection (A), if the reflection is intermediate (B) Suppose that the signals are output separately for cases (C) and (C) when the reflection is very strong. When the entire surface is coated with printing ink using carbon black pigment that absorbs infrared rays, (A) is a dark gray to black with a brightness of 6 or less in the Munsell display system, (B) is a light gray with a brightness of 7 to 8, (C) is a dull white to white color with a rating of 9 or higher, and the screen density is 50 lines in offset printing, and the screen density is approximately 50% of (A).
or more preferably 70% or more dark gray to black, (B) is
40%-10% light gray, (C) 0% white. On the other hand, in the case of an azo pigment having an azomethine group that reflects infrared rays, when a black pigment that absorbs visible light is applied as ink to the entire surface, at all lightness levels from 1.0 to 9.5,
It reflects infrared rays and is (C) above, and even when offset printing is performed, it is 0% of the flattened density.
It shows infrared reflection at all concentrations of ~100%, and is (C) above. When printing letters, patterns, symbols, etc. on printed materials using the differences in the functions of the dyes mentioned above, separate areas are determined, and infrared absorbing dyes are applied to one side.
On the other hand, by printing with an infrared reflective dye, it is impossible to tell them apart with the naked eye, but they can be distinguished and recognized only with an infrared reader. Furthermore, by printing continuous characters, patterns, symbols, etc. with a mixture of infrared absorbing dyes and infrared reflecting dyes, things that are indistinguishable to the naked eye can be distinguished and recognized by an infrared reader. In addition, an infrared reflective pigment is printed as a base, and on top of that, letters of the same color infrared absorbing pigment are printed.
By printing patterns, symbols, etc., they can be concealed and cannot be recognized with the naked eye, but can be recognized with an infrared reader. In addition, when printing chromatic colors, it is necessary to make the three attributes of Munsell display (hue, brightness, and saturation) almost the same, and of course to make the colors appear almost the same under visible light, and to change the pigments used. By effectively utilizing infrared absorption and infrared reflection, the signal of the infrared reader can be changed to (A), (B) or (C) as described above. Conversely, under visible light, one or all of the hue, brightness, and saturation can be changed to create a different color.
The signal of the infrared reader can be the same as (A), (B) or (C) above, or it can give a signal opposite to what is expected from the color under visible light. Further, in these cases, three-color printing can be performed using separate inks, or it can also be achieved by applying or printing with inks that have been adjusted in color in advance. (Function/Effects) In contrast to the general perception of color, the present invention combines a pigment that absorbs infrared rays and a pigment that reflects infrared rays in various ways as described in detail above to produce printed matter. By detecting infrared information as a signal with an infrared reader or the like, the difference in color recognition under visible light is used as unexpected or unrecognized information. These include forgery, alteration, etc. of securities such as stock certificates, public and corporate bonds, airline tickets, checks, important documents such as bankbooks, credit cards, bank cards, lottery tickets, pari-mutuel betting tickets, and confidential documents. It is used as a prevention method and as a means of detecting counterfeit products, altered products, etc. using an infrared reader. In addition, the difference in sensitivity between visible light and infrared light can be used as a surprise or as a means of concealing information, and it can be used as teaching materials and picture books for elementary school students and young children, as well as as toys and play equipment. used. Next, the present invention will be specifically explained with reference to Examples. Note that parts and percentages in the text are based on weight. Example 1 3-(4'-aminophenylimino)-1-oxo-4,5,6,7-tetrachloroisoindoline was diazotized to form 2-hydroxy-α-benzocarbazole-3-carb (2'-Methyl-4'-methoxy)anilide was carried out to obtain an azo pigment having an azomethine group. The azo raw material exhibited a black color and had a decomposition point of 360°C (black pigment R-1). A black ink for offset lithography (black ink R-1) was prepared using the following recipe. Black pigment R-1 obtained above 30.0 parts Mixed varnish for offset lithographic ink 61.7 parts Dryer 0.8 parts Ink solvent 7.5 parts Total 100.0 parts In the above, the mixed varnish for offset lithographic ink includes rosin-modified phenolic resin, drying oil-modified isophthalic acid The main ingredients are alkyd and drying oil, with the addition of ink solvent and aluminum chelate. Separately, a black ink for offset lithographic printing (black ink A-1) was prepared using the following formulation. Furnace type carbon black pigment (referred to as black pigment A-1) 23.0 parts Mixed varnish for offset lithographic ink 71.2 parts Dryer 0.8 parts Ink solvent 5.0 parts Total 100.0 parts Black ink R-1 and black ink A obtained above -1 was used to print on the entire surface of art paper using an offset printing machine with a screen line count of 150 lines and a screen density of 100% to obtain black printed paper. In order to examine the visible light and infrared ray properties of each of the above-mentioned printed materials, the reflectance of ultraviolet, visible, and near-infrared wavelengths was measured using a 330-type self-recording spectrophotometer manufactured by Hitachi, Ltd. The reflectance at each wavelength was as shown in the table below.

[Table] In the above table, wavelengths are in nanometers, R-1 is a printed matter printed with black ink R-1, and A-1 is a printed matter printed with black ink A-1. Further, the reflectance of the printed matter was measured by applying an alumina white plate from the back side. Printed matter using black ink R-1 shows almost no reflection in ultraviolet and visible light and is absorbed, so it naturally appears black, but it shows very high reflection in near-infrared light. In contrast, the printed matter printed using black ink A-1 showed no reflection in any of the ultraviolet, visible, and near-infrared wavelengths, indicating that it was completely absorbed. From the above, both the printed matter of black ink R-1 and the printed matter of black ink A-1 appear black when viewed with the naked eye, but black ink A-1 has a black color when viewed with the naked eye. Compared to the printed matter which absorbs and shows no reflection, black ink R-1
The printed matter shows almost the same reflection as the white printed matter, and the difference in properties between the two brings about a very large function. Example 2 A black letterpress ink (black ink R-2) was prepared using the black pigment R-1 used in Example 1. Further, a black letterpress ink (black ink A-2) was prepared using the furnace type carbon black pigment used in black ink A-1. Securities such as stock certificates and bonds were printed using the above-mentioned black ink R-2 and black ink A-2 in combination to print letters, symbols, and designs.
These letters, symbols, and designs appeared black to the naked eye, making it impossible to distinguish between them. However, when irradiated with infrared rays using an infrared reader, the areas printed with black ink R-2 showed a signal indicating strong reflection of infrared rays. In contrast, the areas printed with black ink A-2 showed a signal indicating that there was no or very little reflection of infrared rays. With this method, it is possible to distinguish between genuine and counterfeit securities such as stock certificates and securities using an infrared reader.
Since the signal can be changed depending on the presence or absence of reflection from infrared irradiation or the intensity of the reflection, counterfeit products can be easily detected. The above-mentioned infrared reader generates infrared rays using an infrared light emitting diode (for example, TLM105 manufactured by Tokyo Shibaura Electric Co., Ltd.), modulates this to enhance the reception of the infrared rays, and uses an infrared light receiving sensor (for example, The light is received by the Tokyo Shibaura Electric Co., Ltd. TPS105), and the presence or absence of reflection and the degree of reflection can be recognized by lighting a warning light and making a sound from a small speaker. Example 3 The black ink R-1 obtained in Example 1 was printed using an offset printing machine with a screen number of 150 lines and a plain dot density.
The entire surface was printed on art paper at 100% to obtain black printing paper. Then, black ink A-1 obtained in Example 1 was printed thereon in the same manner. The reflectance of this overprinted printed matter was measured using a self-recording spectrophotometer in the same manner as in Example 1.

[Table] From the above results, when black ink R-1 was used for underprinting and black ink A-1 was printed on top of that, there was almost no reflection in the ultraviolet, visible, and near-infrared wavelengths. It was found that it was absorbed. From this, of course, the prints showed a black color and the infrared reader showed a signal indicating no or very low reflection. Example 4 Using black ink A-1 obtained in Example 1 to identify parts of securities, bankbooks, credit cards, bank cards, lottery tickets, pari-mutuel betting tickets, etc. that should be kept secret or forgeries. By first printing a specific area, and then covering the entire area with black ink R-1 obtained in Example 1, or printing another area for recognition, both inks are visible to the naked eye. The printed area becomes a printed matter that cannot be distinguished or identified. Conversely, by first printing black ink R-1 instead of black ink A-1, and then printing on top of it or another part with black ink A-1, it is possible to Areas printed with both inks result in printed matter that cannot be distinguished or recognized. However, if you use an infrared reader like the one described in Example 2, you can recognize these based on the difference in their infrared properties, so you can write information that you want to keep secret from third parties, or you can find counterfeits. , is an effective means for discovering fecal matter. Example 5 Process yellow ink was prepared using CI Pigment Yellow 12, process red ink was prepared using CI Red 57-1, and process blue ink was prepared using CI Pigment Blue 15. The black inks include a process black ink (black ink A-3) using the carbon black pigment used in Example 1, and a process black ink (black ink R-3) using the black pigment R-1 synthesized in Example 1. 3), and prepare six colors of process black ink (black ink AR-3) obtained by taking 20 parts of the above black ink A-3 and 80 parts of black ink R-3 and kneading them with a three-roll roll. did. In order to print a slightly dull reddish-purple color and a dull yellow-green color by offset printing, a plate was made as described below. For black ink, black ink A-
3, black ink R-3, black ink AR-3
Prepared separately. The number of screen lines is 150 lines, and the values in the table below are the % values of the screen density.

[Table] Printing was carried out using the above-mentioned plate using the above-mentioned 6 colors of offset ink. In printed matter, the colors red-purple-A, red-purple-B, red-purple-C, yellow-green-A, yellow-green-B, and yellow-green-C shown in the table above have almost the same color pattern and are difficult to distinguish with the naked eye. I couldn't do it. However, when these were examined using the infrared reader described in Example 2, the red-purple-A and yellow-green-A areas showed signals indicating that there was no or very little reflection of infrared rays, and the red-purple-A and yellow-green areas showed a signal indicating that there was no or very little reflection of infrared rays. Locations B and yellow-green-B showed signals indicating medium reflection of infrared rays, and locations labeled red-purple-C and yellow-green-C showed signals indicating very strong reflection. From these printed materials, information that is different from what is recognized with the naked eye can be recognized as a signal by using an infrared reader. These materials are used in teaching materials, picture books, toys, play equipment, etc. aimed at elementary school students and young children. In addition, securities as described in Example 2 above,
It is also effective in preventing forgery and alteration of important documents, secret documents, etc., and in detecting counterfeit and altered products. Example 6 Diazotization of 3-(4′-aminophenylimino)-1-oxo-4,5,6,7-tetrachloroisoindoline to 2-hydroxy-α-benzocarbazole-3-carbo-(4 '-methoxy)-anilide and a black ink obtained using a black pigment obtained by a coupling reaction in place of black inks R-1 to R-3 and black ink AR-3 of Examples 1 to 5. Various characters, symbols, and patterns were printed in the same manner as in Examples 1 to 5, and a signal indicating infrared reflection was measured by a self-recording spectrophotometer in the same manner as in Examples 1 to 5. Inks A-1 to A-3 and process three primary color inks combined to produce printed matter that exhibits excellent infrared ray performance. Example 7 Diazotization of 3-(4'-amino-3',6'-dimethoxyphenylimino)-1-oxo-4,5,6,7-tetrachloroisoindoline to 2-hydroxy-3-naphthoate A purple pigment was obtained by coupling reaction with acid anilide. Separately, 3-(4'-aminophenylimino)-1-
Diazotization of oxo-4,5,6,7-tetrachloroisoindoline and acetoacetate
A yellow pigment was obtained by a coupling reaction with (2'-chloro)anilide. A black ink was prepared by blending the purple pigment and yellow pigment obtained above. Black ink R of Examples 1 to 5
-1 to R-3 and black ink AR-3 in the same manner as in Examples 1 to 5 to create various characters,
Symbols and patterns are printed and measured with a self-recording spectrophotometer in the same manner as in Examples 1 to 5 to show a signal indicating the reflection of infrared rays. Printed matter showing excellent functionality was obtained.

Claims (1)

[Claims] 1. By printing or coating a combination of ink containing a pigment that reflects infrared rays and ink containing a pigment that absorbs infrared rays, characters, images, etc. under visible light can be printed or coated. In addition to information on infrared irradiation, the printed matter is given with other information regarding infrared irradiation, and the dye that has the property of reflecting infrared rays is an azo type having a residue having an azomethine group in the molecule represented by the general formula below. The above-mentioned printed material is characterized by being an organic pigment or dye. (However, Ar in the above formula is a residue of an aromatic or heterocyclic compound, X is a hydrogen atom or a halogen atom, and m is an integer of 1 to 2 or more depending on the substitution position of Ar. ) 2 The pigment having the property of absorbing infrared rays is one or more types selected from the group consisting of carbon black pigments, aniline black pigments, iron oxide black pigments, titanium oxide black pigments, and spinel structure black pigments. The printed material according to claim 1, which is a black pigment. 3. In order to obtain printed materials that can provide information such as characters and images under visible light as well as other information in response to infrared irradiation, inks containing pigments that reflect infrared rays and inks that absorb infrared rays are used. In a method for producing printed matter in which inks containing pigments having the property of reflecting infrared rays are printed or coated in combination, the pigment having the property of reflecting infrared rays is an azo type having a residue having an azomethine group represented by the following general formula in the molecule. The method for producing the above-mentioned printed matter, characterized in that it is an organic pigment or dye. (However, Ar in the above formula is a residue of an aromatic or heterocyclic compound, X is a hydrogen atom or a halogen atom, and m is an integer of 1 to 2 or more depending on the substitution position of Ar. ) 4 The pigment having the property of absorbing infrared rays is one or more selected from the group consisting of carbon black pigments, aniline black pigments, iron oxide black pigments, titanium oxide black pigments, and spinel structure black pigments. The method for producing a printed matter according to claim 3, which is a black pigment.