JPH0786179B2 - Bar code printed matter and detection method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a bar code printed matter which selectively absorbs light of a specific wavelength, and the bar code printed matter is irradiated with light of a wavelength of 600 to 700 nm. The present invention relates to a detection method for reading information by measuring the reflection intensity or the transmission absorption intensity of. More specifically, the present invention relates to a color barcode, a multiple barcode, a tamper-proof / counterfeit-proof barcode printed matter, and a detection method.

(Prior art) Conventionally, prepaid cards, credit cards, bank cards, identification cards, licenses, tickets, admission tickets, membership cards, securities cards, tickets, certificates are generally printed on the surface of paper or plastic substrates.・ Processing means such as engraving, embossing, laser, electric discharge, laminating or vapor deposition,
Magnetic material, conductive material, photosensitive material, heat sensitive material, foam material,
Various attempts to fulfill the purpose of tampering / counterfeiting prevention, verification means for identification, or improvement of environment resistance of built-in information, etc., by using functional materials such as light-emitting materials and detection means according to the functions alone or in combination. Has been done.

Among these functional materials, a method of reading information by using a substance that selectively absorbs light having a specific wavelength is already known, and various methods using a near-infrared absorber have been proposed. For example, a method of forming letters / images using dyes that have a difference in the reflectance of near-infrared rays, and identifying through a filter that transmits light of 650 nm or more (Japanese Patent Publication No. 46-25288), there is a difference in the reflectance of near-infrared rays. A method in which two or more kinds of inks are arranged in parallel or laminated, or a method of coating with an ink that transmits near-infrared rays and further printing (JP-A-58-134782), a method of identifying using a phthalocyanine-based near-infrared absorber ( JP Sho 59
-138284), a method of printing a near-infrared absorbing substance on securities by thermal transfer (Japanese Patent Laid-Open No. 61-146589), and a method of combining a magnetic recording layer, an infrared reflecting layer and an infrared absorbing layer (Japanese Patent Laid-Open No. 61-29).
7192), a method using a dye reflecting near infrared rays and a dye absorbing near infrared rays (JP-A-63-91283, JP-A-63-9248).
6), a method of overcoating a near-infrared absorbing ink with a dark-colored ink (Japanese Patent Publication No. 63-144075), and a method of forming a negative / positive image using two kinds of inks having different near-infrared absorbing characteristics (JP-A-63 -307996), and a method of using a phthalocyanine-based near-infrared absorber as a thermal transfer material (JP-A-64-3078).
8) etc. are proposed.

In recent years, management systems such as bar code distribution management, product management, material management, inventory management, and POS system have been developed, and have been applied in various fields as an effective means for eliminating the complexity of key input / bookkeeping. There is. Bar code marking is offset printing, gravure printing, flexo printing,
Source marking that creates a large amount of the same type of barcode by letterpress printing, screen printing, etc., and individual printers such as thermal transfer type, thermal color development type, wire dot type barcode printer, ink jet printer, laser printer, etc. There are in-store markings, in-house markings, on-demand markings, etc. that create a limited amount of barcodes. The printed barcodes or printed matter can be printed with 632.8nm He-N.
Easily enter code information by measuring the reflection intensity using a light source such as e-laser, 660 nm light emitting diode, 670 nm visible light semiconductor laser, 690 nm light emitting diode, 780 nm semiconductor laser, 940 nm infrared light emitting diode Then
Data is being processed by the computer.

The inks used in these barcodes generally use carbon black, which has a wide range of absorption from the visible region to the near infrared region, as a dye. Utilizes dark chromatic inks such as brown, dark blue, and dark green in combination with carbon black, or inks using blue and green pigments detected using a visible light source of 600 to 700nm, and coloring of leuco dyes The aforesaid heat-sensitive coloring paper or ink-jet ink using a nigrosine-based dye has been award-winning.

In any application, it is important to have sufficient absorption characteristics in the wavelength range of the light source or detector to be detected. Especially, the selection of the absorber for a specific wavelength is the hue, saturation, lightness, etc. of the ink, and the detection. This is the point that determines the sensitivity or weather resistance of recorded matter.

However, the ink using the so-called near-infrared absorbing agent that absorbs near-infrared rays has a maximum absorption wavelength outside the visible range, and thus a relatively colorless and transparent substance can be selected. For example, phthalocyanine type, naphthalocyanine type, metal complex salt type, anthraquinone type, cyanine dye type, polymethine type and the like are known.

When these near-infrared absorbing agents are used, there is no absorption in the visible range, so the so-called tint such as lightness, hue, saturation, etc. of the dye itself does not change even when used in combination with other chromatic color dyes. . However, when the code is read by detecting the presence or absence of absorption of light in the so-called visible light region with a wavelength of 600 to 700 nm, the absorbent itself has a color, so the recorded matter in a color other than blue or green is not recorded. It was impossible.

On the other hand, in recent years, bar code readers have been shortening the detection wavelength due to the development of semiconductor lasers, gas lasers, or CCD sensors, and increasing the sensitivity of detection elements.
The number of cases using the visible light wavelength region is increasing.

In view of the above problems, the present invention has the following characteristics required for an absorbent used in the visible light wavelength range of 600 to 700 nm: 1) It has sufficient absorption in the wavelength range of 600 to 700 nm.

2) Less absorption in the wavelength range of 400 to 600 nm.

3) It has light resistance equal to or higher than that of conventional printing inks.

As a result of pursuing the above three conditions, halogenated copper phthalocyanine is added in an amount of 0.1 g / m ² or less, and by using it alone or in combination with other dyes, a wider range of colors can be used as ink for barcode readers. The inventors have discovered what is possible and have completed the present invention.

[Structure of Invention]

(Means for Solving the Problems) That is, in the present invention, the content of halogenated copper phthalocyanine is
It is a bar code printed matter which is 0.1 g / m ² or less and is characterized by reading information by measuring a reflection intensity or a transmission intensity using a light source or a detector having a main wavelength of 600 to 700 nm. The larger the amount of the copper phthalocyanine halide added, the larger the absorption and the higher the reading sensitivity. However, as easily predicted, the higher the density, the higher the visual sensitivity. Especially when used in combination with other dyes, the decrease in lightness, hue, and saturation is severe, and so-called color turbidity increases. Cause Therefore, preferably 0.1 g / m ² or less as an additive amount results in a drawback that the color turbidity made larger at 0.1 g / m ² or more. More preferably, 0.0
Was ^{8g / m 2 ~0.005g / m 2} , in the case of 0.005 g / m ² or less but becomes less color turbidity, have the disadvantage that the detection sensitivity in the opposite decreases.

Furthermore, the halogenated copper phthalocyanine is a brominated copper phthalocyanine, which is a bar code printed matter. In general, a phthalocyanine-based green pigment has a benzene ring halogenated on the basis of a phthalocyanine skeleton, and the degree of halogenation or the type of halogen is changed to shift the main wavelength to a longer wavelength side and adjust the tint. Chlorine or bromine is usually used as halogen, and bromine shifts to a longer wavelength than chlorine, giving a so-called bluish to yellowish green color. Especially when used in combination with other dyes to realize barcodes of warm colors such as red, orange, and yellow, yellowish green is less turbid than blueish green as a hue.

Further, the bar code printed material is characterized by using a halogenated copper phthalocyanine in combination with another dye. Other dyes are red, orange, except blue and green, which have been used conventionally.
One or more dyes and pigments such as yellow, purple, white, pastel, fluorescent, metallic, and pearl. Realization of these wide range of colors is possible in the present invention. Therefore, it is clear that the range of application to cards, tickets and certificates will be greatly expanded compared to the conventional dark ink.

Furthermore, the detection method is characterized in that the bar code printed matter is read by measuring the reflection intensity or the transmission intensity using a light source or a detector having a main wavelength of 600 to 700 nm.

Furthermore, at the same place as or near the bar code printed matter,
Print or print in a shape according to the information using ink containing other dyes with different absorption wavelengths, superimpose multiple pieces of information, and use multiple light sources or detectors with a dominant wavelength of 600 to 1500 nm to reflect Alternatively, it is a detection method characterized by reading a plurality of information by measuring the transmission absorption intensity. In this case, the wavelength of the light source or detector used is preferably a single wavelength, and a laser light source is useful. Further, the light absorber used also has a maximum absorption peak at the wavelength to be detected, and the smaller the full width at half maximum of the absorption spectrum is, the smaller the mutual interference of the absorption spectrum is and the higher the detection accuracy is. For that purpose, the halogenated phthalocyanine to be used is also increased in dispersion as much as possible, the absorption spectrum becomes sharper and the half-value width becomes smaller as it becomes closer to the dissolved state, and further, there is a merit that the addition amount is small, and so on. Need to be careful.

The bar code printed matter of the present invention is, for example, a gravure ink,
It is manufactured using printing ink such as flexo ink, offset ink, screen ink, letterpress ink, etc., or ink for various printers such as thermal transfer printer, ink jet printer, impact printer and laser printer.

As an example, a case where the present invention is applied to a transfer ribbon for a thermal transfer printer will be described.

The transfer ribbon is provided with a heat-meltable ink layer on one side of a base film as a base material, and a heating means such as a thermal head is provided from the other side of the base film in a state where the ink layer and the transfer target sheet are superposed. It is used to melt and transfer the heat-fusible ink layer to obtain a print or image according to the information given to the heating means on the transferred sheet.

As a material used for such a transfer ribbon, a conventionally known material can be used.

For example, the base film used as a substrate includes a polyester film (polyethylene terephthalate, polyethylene naphthalate, etc.), a polyamide film (nylon, etc.), a polyolefin film (polypropylene, etc.), a cellulosic film (triacetate, etc.), a polycarbonate film, etc. . The polyester film is most preferable because it has excellent heat resistance, mechanical strength, tensile strength, and tensile stability. The thinner this substrate is, the better the thermal conductivity is, but the most preferable is 3 μ to 50 μ in view of strength and easy coating of the ink layer. Further, a back coat layer made of a heat resistant resin may be provided on the surface of the base material opposite to the heat fusible ink layer.

Wax and thermoplastic resin are used as the main vehicle for the hot-melt ink layer, and the melting point of the wax is
Those having a temperature range of 50 to 100 ° C., preferably 50 to 90 ° C. are used. For example, natural waxes such as candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil, and other plant waxes, beeswax, lanolin, whale. Animal waxes such as waxes, mineral waxes such as montan wax, ozokerite and cesylene, petroleum waxes such as paraffin wax, microcrystalline wax, petrolatum, synthetic hydrocarbons such as Fischer-Tropsch wax and polyethylene wax. , Modified wax such as montan wax derivative, paraffin wax derivative, microcrystalline wax derivative, hydrogenated wax such as hydrogenated castor oil, hydrogenated castor oil derivative, lanolinic acid, palmitic acid, myristic acid, stearic acid, 12-hydride There are resin acids such as Kishisutearin acid The thermoplastic resin, the softening point
200 ° C or less, preferably 180 ° C or less, for example, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyethylene, polypropylene, polyacetal, ethylene-vinyl acetate copolymer, ethylene- Ethyl acrylate copolymer, polystyrene, polyacrylic acid ester, polyamide, ethyl cellulose, epoxy resin, xylene resin, ketone resin, petroleum resin, rosin or its derivative, coumarone indene resin, terpene resin, polyurethane resin, styrene-butadiene rubber , Polyvinyl butyral, nitrile rubber, acrylic rubber, ethylene-propylene rubber, and other synthetic rubber. Further, a softening agent such as oil, an ultraviolet absorber for increasing weather resistance, a radical polymerization inhibitor, a peroxide decomposing agent, an extender pigment or the like can be used as an additive. A halogenated copper phthalocyanine is dispersed or dissolved in a vehicle using the above material to obtain a heat-meltable near-infrared absorbing ink. In order to provide it on the ink base material, there is a hot melt coating method or, more preferably, a method of solvent coating a coating liquid in which the above materials are dispersed in a solvent. The coated film is printed on a bar code or a desired pattern using a thermal transfer printer to obtain a recorded matter. In the case of multiple bar codes, record again.

When using two or more kinds of inks such as a multi-coat according to the present invention, for example, a printer such as a thermal transfer printer may be used for the first recording, then the recording may be performed by printing, or the recording method may be reversed. The recording method of can also be used.

Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, parts are parts by weight.

The following ink compositions A to E were dispersed in an attritor at room temperature for a predetermined time to obtain gravure inks A to D and E and G. Further, the ink composition F was sufficiently kneaded with a three roll heated to 90 to 120 ° C. to obtain a hot melt ink. The kneading time of the ink is as follows.

Specific structures of the used ink compositions A to G are shown below.

Ink composition A Carnauba wax 18 parts Ethylene-vinyl acetate copolymer ("Evaflex 420" manufactured by Mitsui Polychemicals) 2 parts IPA 15 parts Toluene 65 parts Ink composition B Fluorescent pigment pink (manufactured by Nippon Shokubai Chemical Co., Ltd.) Epocolor FP-112 ") 10 parts Alicyclic saturated hydrocarbon resin (" Arcon P-100 "manufactured by Arakawa Chemical Industry Co., Ltd.) 5 parts Carnauba wax 5 parts IPA 15 parts Toluene 65 parts Ink composition C Vermilion pigment (Toyo Ink) Manufacturing Co., Ltd. “Rake Red CN Conc” 5 parts Alicyclic saturated hydrocarbon resin (Arakawa Chemical Co., Ltd. “Alcon P-100”) 7.5 parts Carnauba wax 7.5 parts IPA 15 parts Toluene 65 parts Ink composition D Brominated copper phthalocyanine (Toyo Ink Mfg. Co., Ltd. "Rionol Green 6YK") 1.5 parts Alicyclic saturated hydrocarbon resin (Arakawa Chemical Co., Ltd. "Arcon P-100") 9.5 parts Lunava wax 10 parts IPA 15 parts Toluene 64 parts Ink composition E Chlorinated copper phthalocyanine (Toyo Ink Mfg. Co., Ltd. "Rionol Green B-201") 1.5 parts Alicyclic saturated hydrocarbon resin (Arakawa Chemical Industry Co., Ltd.) "Alcon P-100") 9.5 parts Carnauba wax 10 parts IPA 15 parts Toluene 64 parts Ink composition F Carbon black (Mitsubishi carbon "MA-600") 0.7 parts Ethylene vinyl acetate copolymer (Mitsui Polychemical Co., Ltd.)
"Eva Flex 420") 5.0 parts Carnauba wax 35.3 parts Paraffin wax 59.0 parts Ink composition G Near-infrared absorber with the following structure 1.5 parts Alicyclic saturated hydrocarbon resin (Arakawa Chemical Industries, Ltd. "Alcon P- 90) 9.5 parts Rice wax 10 parts IPA 15 parts Toluene 64 parts The above seven inks were used to form the following thermal transfer ribbon shape. Regarding the ink application method, the obtained ink was applied on a 6 μm polyethylene terephthalate film by the gravure coating method for the inks A to E and G and by the hot melt coating method for the ink F at a predetermined application amount.

The types of transfer ribbons created are as follows.

Ribbon 1 Ink A was applied at 1 g / m ² and Ink B was applied at 3 g / m ² to obtain a pink thermal transfer ribbon.

Ribbon 2 Ink A was applied at 1 g / m ² and ink C was applied at 3 g / m ² to obtain a vermilion heat-sensitive transfer ribbon.

Ribbon 3 1g / m ² for ink A, 2g / m ² for ink B, 0.4g / m ² for ink D
It was applied to obtain a fluorescent pink color thermal transfer bon.

Ribbon 4 1g / m ² for ink A, 2g / m ² for ink C, 0.4g / m ² for ink D
It was applied to obtain a vermilion heat-sensitive transfer bon.

Ribbon 5 Ink A and 1 g / m ^2, the ink B 2g / m ^2, the ink E 0.6 g / m ²
It was applied to obtain a fluorescent pink color thermal transfer bon.

Ribbon 6 Ink A and ^{1g / m 2, 2g / m} 2 of the ink C, and ink E 0.6 g / m ²
It was applied to obtain a vermilion heat-sensitive transfer bon.

Ribbon 7 ink A 1g / m ^2, the ink G 0.3g / m ^2, the ink A 2 g / m ²
After coating, a nearly transparent thermal transfer ribbon was obtained.

Ribbon 8 Ink A and ^{1g / m 2, 2g / m} 2 of the ink B, and ink F 0.6 g / m ²
It was applied to obtain a greyish-reddish red thermal transfer bon.

Examples 1 to 4 Bar code printer "B-30-S" manufactured by Tokyo Electric Co., Ltd.
"1""is used to print the barcode pattern" Code 39 "on the ribbons 3, 4, 5 and 6 and it is used as a color barcode record.
1,2,3,4 records were obtained. The obtained bar code was slightly cloudy, but had a color tone that reproduced almost the color tone of the primary color. Next, "TCD-4000 &T" manufactured by Barcode Reader Co., Ltd.
When the recorded matter was read with the "BR-4000" (using a CCD as a sensor), it was possible to read according to the code.

Comparative Examples 1 to 3 When the ribbons 1 and 2 were evaluated in the same manner, they could not be read by the bar code reader at all. In addition, ribbon 8
In the same manner, the barcode 3 can be read by the barcode reader, but the ribbon 3 and the ribbon 5 can be read.
Compared with, the color was obviously inferior.

Example 5 Furthermore, with a bar code printer, different codes of the ribbon 5 and the ribbon 7 were recorded at the same location as "code 39", and the example 5 was obtained. This printed matter is read on the ribbon 5 with a bar code verifier SYMBOL TECHNOLOGIES, INC. “LASERCHEK LC2811” that uses a He-Ne laser of 632.8 hm as a light source. −6000 & TBR−600
When the recorded matter was read with "0" (using a 780 nm laser as a light source), it was possible to read according to each code.

Comparative Example 4 Furthermore, a ribbon printer 8 and a ribbon 7 were similarly recorded at the same location with a bar code printer to obtain Comparative Example 4. When this printed matter was also read using two types of barcode readers, it was possible to read 632.8 nm.
Reading at 80 nm was completely impossible.

(Operation and Effect of the Invention) As described above, the bar code printed matter containing the halogenated copper phthalocyanine of the present invention can produce a light color bar code, which has been impossible in the past, and the color can be easily identified, so that the defective rate / area can be reduced. It is convenient for sorting by size, size, manufacturer, etc., and there are no restrictions on design colors. Furthermore, 780nm semiconductor laser or 940nm infrared LED, which has been used as a near-infrared detector, has almost no absorption in the visible range.
It is possible to coexist with a system that uses a near-infrared absorber such as, and it is possible to detect even if two or more types of codes are recorded in the same place. The color barcode superimposed on the transparent barcode makes the printing of the transparent barcode difficult to see, and at the same time plays a role of a pseudo barcode for copying and enhances the falsification prevention function. Because there are various effects such as
It is a material that can essentially solve various drawbacks that were impossible in the past.

Further, although the transfer ribbon is exemplified in the present invention, it goes without saying that a general printing ink also has the same effect.

 ─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP-A-64-30788 (JP, A) JP-A-59-138284 (JP, A) JP-A-63-92486 (JP, A) JP-A-63- 293081 (JP, A)

Claims (5)

[Claims] 1. The content of halogenated copper phthalocyanine is 0.
A bar code printed matter, which is 1 g / m ² or less, and which reads information by measuring a reflection intensity or a transmission intensity using a light source or a detector having a main wavelength of 600 to 700 nm. 2. The bar code printed matter according to claim 1, wherein the halogenated copper phthalocyanine is brominated copper phthalocyanine. 3. The bar code printed matter according to claim 1 or 2, wherein the halogenated copper phthalocyanine is used in combination with another dye. 4. A method for reading information by measuring the reflection intensity or the transmission intensity of the bar code printed matter according to any one of claims 1 to 3 using a light source or a detector having a main wavelength of 600 to 700 nm. Method. 5. A plurality of pieces of information are printed at the same position as or near the bar code printed matter according to any one of claims 1 to 3 by using an ink containing another dye having a different absorption wavelength in a shape according to the information. A detection method characterized by reading a plurality of information by superimposing and measuring a reflection intensity or a transmission intensity using a plurality of light sources or detectors having a main wavelength of 600 to 1500 nm.