JPH03111462A - Barcode printed matter and detection method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to an ink that selectively absorbs light of a specific wavelength, and uses the ink to print or print in a shape according to information. The present invention relates to a detection method for reading information by measuring the reflected intensity or transmitted absorption intensity of light of a certain wavelength. More specifically, the present invention relates to color barcodes, multiplex barcodes, inks for preventing constitutional revision and counterfeiting, and detection methods.

(Prior art) Conventionally, cards, tickets, and documents such as prepaid cards, credit cards, bank cards, identification cards, driver's licenses, tickets, admission tickets, membership cards, and securities are generally printed on the surface of paper or plastic substrates.・Engraving, embossing, laser, discharge, lamination, or σ1 uses processing methods such as vapor deposition, functional materials such as magnetic materials, conductive materials, photosensitive materials, heat-sensitive materials, foam materials, and luminescent materials, and detection means according to their functions. Various attempts have been made to achieve the objectives of preventing intentional counterfeiting or forgery, as a verification means for identification, or to improve the environmental resistance of built-in information, either singly or in combination.

Among these functional materials, methods of reading information using substances that selectively absorb light of specific wavelengths are already known, and in particular, various methods using near-infrared absorbers have been proposed. For example, a method in which letters and images are formed using dyes with different reflectances of near-infrared rays and then passed through a filter that transmits light of 650 nm or more for identification (Tokyo Publication No. 46-25
288), two or more types of ink having different near-infrared reflectances are arranged side by side or laminated. Alternatively, a method of further printing after coating with an ink that transmits near infrared rays (Japanese Patent Application Laid-Open No. 58-134
782).

An identification method using a phthalocyanine-based near-infrared absorbing agent (Japanese Patent Laid-Open No. 59-138284), a method of printing a near-infrared absorbing substance on securities by thermal transfer (Japanese Patent Laid-Open No. 61-1465)
89), a method of combining a magnetic recording layer, an infrared reflective layer, and an infrared absorbing layer (JP-A-61-297192), a method of using a dye that reflects near-infrared rays and a dye that absorbs near-infrared rays (JP-A-63-91283, Japanese Patent Publication No. 63-92486
), a method of overcoating a near-infrared absorbing ink with a dark ink (Japanese Patent Publication No. 63-144075), a method of forming negative and positive images using two types of ink with different near-infrared absorption characteristics (Japanese Patent Publication No. 63-1989) 307996), a method of using a phthalocyanine-based near-infrared absorbent in a heat-sensitive transfer material (Japanese Patent Laid-Open No. 64-30788), etc. have been proposed.

In recent years, barcodes have also been used for logistics management and product management.

Management systems such as material management, inventory management, and POS systems have been developed and are being applied in various fields as an effective means to eliminate the complexity of key human labor and bookkeeping. Barcode markings include source marking, which creates large quantities of the same type of barcode by offcent printing, gravure printing, flexo printing, letterpress printing, screen printing, etc., and thermal transfer type, thermal coloring type, and wire tod type barcodes. There are in-house markings, in-house markings, and on-demand markings that create a limited number of individual barcodes using printers such as printers, inkjet printers, and laser printers.

Recorded barcode printing or printed material at 632°8n
m He-Ne laser, 660 nm light emitting diode,
By measuring the reflection intensity using a light source such as a 670 nm visible light semiconductor laser, a 690 nm light emitting diode, a 780 nm semiconductor laser, or a 940 nm infrared light emitting diode, the code information can be easily input and the data can be processed by a computer. It is being said.

What ink is used in these barcodes?

Carbon black, which has a wide absorption range from the visible region to the near-infrared region, is generally used as a pigment, and for design reasons or to increase the value of the product, carbon black is used in combination to create brown, dark blue, and dark green colors. dark chromatic inks, inks using blue or green pigments that are detected using a visible light source of 600 to 700 nm, angry color paper using leuco dye coloring, or nigrosine dyes. Inks such as shared inks have been used for prizes.

For any application, it is important to have sufficient absorption characteristics in the wavelength range of the light source or detector to be detected. In particular, the selection of an absorbent for a specific wavelength will affect the hue, saturation, brightness, 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 absorber that absorbs the above-mentioned near-infrared rays has a maximum wavelength of absorption outside the visible range, so a relatively colorless and transparent substance can be selected. For example, phthalocyanine-based, naphthalocyanine-based, metal complex salt-based, anthraquinone-based, cyanine dye-based, polymethine-based, etc. are known.

When these near-infrared absorbers are used, there is no absorption in the visible range, so even if they are used in conjunction with other chromatic dyes, the so-called color tone such as brightness, hue, and saturation of the dye itself will not change. . However, when reading codes 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 recorded matter in colors other than blue or green cannot be detected. It was impossible.

On the other hand, in recent years, the detection wavelength of barcode readers has become shorter and the detection element has become more sensitive due to the development of semiconductor lasers, gas lasers, or CCD sensors.
The number of cases in which the visible light wavelength region of 0.00 nm is used is increasing.

In view of the above problems, the present invention has the following characteristics as required for an absorbent used in the wavelength range of visible light from 600 to 700 nm: 1) 60 nm
Must have sufficient absorption in the wavelength range of 0 to 700 nm.

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

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

As a result of pursuing the following three conditions, by adding halogenated copper phthalocyanine in an amount of 0.1 g/m or less and using it alone or in combination with other pigments, an even wider range of colors can be produced as ink for barcode readers. It was discovered that the present invention can be used, and the present invention was completed.

[Structure of the invention]

(Means for Solving the Problems) That is, the present invention provides a method in which the content of halogenated copper phthalocyanine contained in the ink of barcode printed matter is 0°1 g/m
``This is a barcode ink characterized by the following: The greater the amount of copper halide phthalocyanine added, the greater the absorption and the higher the reading sensitivity.However, as can be easily predicted, the higher the concentration, the higher the concentration. Visual sensitivity increases, especially when used in combination with other dyes, brightness of 1 hue,
Severe loss of color saturation.

This results in the disadvantage that so-called color turbidity increases. Therefore, the amount added is preferably 0.1 g/m" or less; if it is more than 0.1 g/m", the color becomes cloudy. More preferably, O,OSg/m"~0.0
0.05 g/m", and if it is less than 0.005 g/m", the color becomes less cloudy.

On the contrary, it has the disadvantage that the detection sensitivity becomes low.

Furthermore, the barcode ink is characterized in that the halogenated copper phthalocyanine is brominated copper phthalocyanine. In general, phthalocyanine-based green pigments are based on a phthalocyanine skeleton, and the benzene ring is halogenated, and by changing the degree of halogenation or the type of halogen, the dominant wavelength is shifted to the longer wavelength side and the color tone is adjusted. Usually, chlorine or bromine is used as the halogen, and bromine shifts to a longer wavelength than chlorine, giving a so-called bluish to yellowish green color. In particular, when used in combination with other dyes to realize barcodes with warm colors such as red, orange, and yellow, yellowish green is less cloudy than bluish green as the two hues.

Furthermore, it is a barcode ink characterized by using halogenated copper phthalocyanine and other pigments in combination.

With the exception of blue and green, which have traditionally been used as other pigments.

Red, orange, yellow, purple, white, pastel, fluorescent, metallic.

Refers to one or more types of dyes and pigments such as pearls. The realization of these wide ranges of colors is possible with the present invention.

Therefore, it is clear that the scope of application to cards, tickets, and documents will be greatly expanded compared to conventional dark-colored inks.

Furthermore, the detection method is characterized in that information is read from the barcode printed material by measuring reflection intensity or transmission intensity using a light source or detector having a dominant wavelength in the range of 600 to 700 nm.

Furthermore, ink containing the above-mentioned halogenated copper phthalocyanine and/or other pigments are used in combination, and multiple inks with different absorption wavelengths from visible to near infrared rays are used to print shapes corresponding to multiple pieces of information at the same location or in the vicinity. Or a patterning method characterized by printing, superimposing information, and reading a plurality of pieces of information by measuring the reflected intensity or transmitted absorption intensity using a plurality of light sources or detectors having a dominant wavelength in the range of 600 to 1500 nm. This is a detection method. In this case, the wavelength of the light source or detector used is preferably a single wavelength, and a laser light source is useful. Furthermore, the more the light absorbent used has a maximum absorption peak at the wavelength to be detected and the half-width of the absorption spectrum is smaller, the less mutual interference of the absorption spectra occurs and the detection accuracy increases. For this purpose, the halogenated phthalocyanine used has the advantage of increasing its dispersion as much as possible, and the closer it is to the dissolved state, the sharper the absorption spectrum and the smaller the half-width, and the smaller the amount added. need to be very careful.

The barcode ink referred to in the present invention can be applied to any printing ink or ink for various printers, such as gravure ink, flexo ink, offset ink,
Printing inks such as screen inks and letterpress inks,
Or thermal transfer printer, ink shared printer, impact printer.

Refers to ink for various printers such as laser printers.

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

In the transfer ribbon, a heat-melting ink layer is provided on one side of a base film, and a heating means such as a thermal head is applied from the other side of the base film while the ink layer and the transfer sheet are overlapped. make use of.

A heat-melting ink layer is melted and transferred to obtain a print or an image on a transfer sheet according to information given to a heating means.

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

For example, for a base film used as a base material.

Examples include polyester films (polyethylene terephthalate, polyethylene naphthalate, etc.), polyamide films (nylon, etc.), polyolefin films (polypropylene, etc.), cellulose films (triacetate, etc.), and polycarbonate films. Polyester film has heat resistance and mechanical strength of 9.

It is most preferred because of its excellent tensile strength and tensile stability. The thinner the base material is, the better the thermal conductivity is, but from the viewpoint of strength and ease of application of the ink layer, it is most preferably 3 to 50 microns.

Further, a back coat layer made of a heat-resistant resin may be provided on the opposite side of the heat-melting ink layer of the base material.

For the heat-melting ink layer, a wax or a thermoplastic resin is used as the main vehicle, and the wax has a melting point in the range of 50 to 100°C2, preferably 50 to 90°C1.For example, as a natural wax. Candelilla wax, carnauba wax.

Plant-based waxes such as rice wax, wood wax, and jojoba oil; animal-based waxes such as beeswax, lanolin, and spermaceti;
Monokun wax. Mineral waxes such as osichelite and secilene, petroleum waxes such as paraffin wax, microcrystalline wax, and petrolatum; synthetic waxes include synthetic hydrocarbons such as Fischer-Tropish wax and polyethylene wax; montan wax derivatives, paraffin wax derivatives, and microcrystalline waxes; Modified waxes such as crystalline wax derivatives, hydrogenated waxes such as hydrogenated castor oil, hydrogenated castor oil derivatives, and lanolinic acid.

There are fatty acids such as palmitic acid, myristic acid, stearic acid, and 12-hydroxystearic acid, and as a thermoplastic resin, the softening point is 200°C or less.

Preferably, the temperature is 180°C or lower.9 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 1 petroleum resin, rosin or its derivatives, coumaron indene resin, terpene resin, polyurethane resin, styrene-butadiene rubber, polyvinyl butyral, nitrile rubber, acrylic rubber, There are synthetic rubbers such as ethylene propylene rubber. Additionally, additives include softeners such as oil, ultraviolet absorbers, radical polymerization inhibitors, and peroxide decomposers to increase weather resistance.

Extender pigments and the like can be used. A heat-melting near-infrared absorbing ink is obtained by dispersing or dissolving copper halide phthalocyanine in a vehicle using the above material.

In order to provide the ink on the base material, there is a hot melt coating method or, more preferably, a solvent coating method using a coating liquid in which the above-mentioned material is dispersed in a solvent.

A bar code or desired pattern is printed on the coated film using a thermal transfer blinker to obtain a recorded matter. In the case of multiple barcodes, they are recorded overlappingly.

When using two or more types of ink such as multiple coating according to the present invention, 2. For example, first recording with a printer such as a thermal transfer printer, then recording by printing, etc. 9. Further, multiple methods such as reversing the recording method. You can also use the recording method.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the examples, 2 parts are parts by weight.

The following ink compositions A-E were dispersed in an attritor at room temperature for a predetermined period of time to obtain gravure inks A-D, F, and G.

Further, ink composition E was sufficiently kneaded using three rolls heated to 90 to 120°C to obtain a hot melt ink.

The ink kneading time is as follows.

The specific compositions of the ink compositions A to G used are shown below.

Ink composition A Carnauba wax 18 parts Ethylene-vinyl acetate copolymer (Mitsui Polychemical Co., Ltd. "Evaflex 420J") 2 parts IPA
15 parts toluene
65 parts Ink composition Fluorescent pigment pink (manufactured by Nippon Shokubai Chemical Co., Ltd.
FP-112J) 10-part alicyclic saturated hydrocarbon resin (Alcon P-10 manufactured by Arayo Kagaku Kogyo Co., Ltd.)
04) 5 parts carnauba wax 5 parts IPA
15 parts toluene
65 parts Ink composition C Vermilion pigment (“Lake Red CN” manufactured by Toyo Ink Manufacturing Co., Ltd.)
5-part alicyclic saturated hydrocarbon resin (Alcon P-10 manufactured by Arayo Kagaku Kogyo Co., Ltd.)
0J) 7.5 parts carnauba wax
7.5 parts IPA
15 parts toluene 65 parts Ink composition Brominated copper phthalocyanine ("Lionol Green 6YKJ" manufactured by Toyo Ink Manufacturing Co., Ltd.) 1.5 parts Alicyclic saturated hydrocarbon resin ("Alcon P-" manufactured by Arayo Kagaku Kogyo Co., Ltd.)
1004) 9.5 parts carnauba wax
100 parts IPA
15 parts toluene 64
Part Ink Composition E Chlorinated copper phthalocyanine (Lionol Gree 7 B-201J manufactured by Toyo Ink Manufacturing Co., Ltd.) 1.5 parts Alicyclic saturated hydrocarbon resin (manufactured by Arayo Kagaku Kogyo Co., Ltd. [Alcon P-1004) ) 9.5 parts carnauba wax 100 parts IPA
15 parts toluene
64 parts Ink composition F Carbon black (Mitsubishi Carbon rMA-600J)
0.7 parts ethylene vinyl acetate copolymer (Evaflex 420J manufactured by Mitsui Polychemical Co., Ltd.)
) 5.0 parts carnauba wax
35.3 parts paraffin wax 5
9.0 parts Ink composition G Near-infrared absorber having the following structure 1.5 parts Alicyclic saturated hydrocarbon resin ("Alcon" manufactured by Arayo Chemical Industry Co., Ltd.)
P-90) 9.5 parts rice wax
1o part IPA
15 parts toluene
64 parts or more of seven types of ink were used to form the shape of the thermal transfer ribbon shown below. Regarding the method of applying the ink, the obtained ink was applied to a 6 μm polyethylene terephthalate film to a predetermined coating amount using a gravure coating method for inks A-E and G, and a hot melt coating method for ink F.

The types of transfer ribbons created are as follows.

Ribbon 1 Ink A 1 g/+m", Ink B 3 germ"
A pink heat-sensitive transfer ribbon was obtained.

Ribbon 2 Ink A 1 g/'I"+ Ink C 3 g/n+"
A vermilion heat-sensitive transfer ribbon was obtained.

Ribbon 3 Ink A: Ig/a+”, Ink B: 28/l”, Ink D: 0, 4 g/1atW! ! A fluorescent pink heat-sensitive transfer bong was obtained.

Ribbon 4 Ink A 1 g/m"+ Ink C 2 g/+@",
Ink D was applied at a rate of 0.4 g/a+'' to obtain a vermilion thermal transfer bond.

Ribbon 5 1 g/m'' of ink A + 2 g of ink B
/vb ” * Ink E 0, 6 g/l *”
A fluorescent pink heat-sensitive transfer bong was obtained.

Ribbon 6 Ink A at 1 g/m", Ear-1-C at 2 g/m"
, Ia-t-E was applied at a rate of 0.6 g/m'' to obtain a vermilion heat-sensitive transfer bond.

Ribbon ink A 1 g 7 m", ink G 0, 3 g/1
1" and Ink A was applied at 2 g/m" to obtain a transparent heat-sensitive transfer bond.

Ribbon 8 Ink A 1g7m", Ink B 2g/a+",
Ink F was applied at 0.6 g/m"e! to obtain a grayish-vermilion heat-sensitive transfer bond.

Examples 1 to 4 Barcode printer "B50-3" manufactured by Tokyo Electric Co., Ltd.
A barcode pattern "Code 39" was printed on ribbons 3, 4, and 5.6 using IJ to obtain the recorded matter of Example 1.2.3.4 as a color barcode recorded matter. The obtained barcode was slightly cloudy, but had a color tone that almost reproduced the color tone of the primary color. Next, when the recorded matter was read with a barcode reader rTCD-4000 & TBR-4000J manufactured by Token Co., Ltd. (which uses a CCD as a sensor), reading according to the code was possible.

Comparative examples 1 to 3 Ribbon 1.2 was similarly evaluated.

The barcode reader could not read it at all.

Furthermore, ribbon 8 was also evaluated in the same manner.

Although it can be read with a barcode reader.

Compared to Ribbon 3 and Ribbon 5, the color tone was clearly inferior.

Example 5 Furthermore, ribbon 5. and ribbon 7
Codes with different contents were recorded at the same location as "Code 39", and Example 5 was obtained.

This printed material is used as a light source for ribbon 5 at 632.8
Barcode verifier SYMBOL TBC) INOLOGIEs, INc using He-Ne laser
, manufactured by rLAsERcHEK LC2811J, and for 780ns+, use a barcode reader (
rTHLs-6000 & TBR-6000 manufactured by Token Co., Ltd.
(Using a 7BOn- laser as a light source)
When I read the recorded materials, I was able to read each code according to its code.

Comparative Example 4 Furthermore, ribbon 8. and ribbon 7
Comparative Example 4 was obtained by similarly recording at the same location. When this printed matter was similarly read using two types of barcode readers, it was possible to read 632.8 nm, but it was not possible to read 7BOnm at all.

(Operations and Effects of the Invention) The recorded matter using the ink containing the halogenated copper phthalocyanine of the present invention as described above is capable of creating a bright color barcode, which was previously impossible, and can easily identify colors, so that it is defective. It is convenient for sorting by rate, area, size, manufacturer, etc., and there are no restrictions on color in design. Furthermore, -f- or 940 nm semiconductors, which have almost no absorption in the visible range and have been conventionally used for detection in the near-infrared range,
It can coexist with systems using near-infrared absorbers such as n-infrared LEDs, and detection is possible even when two or more types of codes are recorded at the same location.

For example, a colored barcode superimposed on a near-infrared absorbent transparent barcode on cards, tickets, and documents can simultaneously make the transparent barcode print difficult to see.

It also acts as a pseudo barcode for copying.

It can also enhance its ability to prevent constitutional amendments. Since it has various effects such as, it can essentially solve various drawbacks that were previously impossible.

Further, in the present invention, the transfer ribbon is exemplified, but it goes without saying that the same effect can be obtained with general printing ink.

Claims (1)

[Claims] 1. An ink for barcodes, characterized in that the content of halogenated copper phthalocyanine contained in the ink for barcode printed matter is 0.1 g/m^2 or less. 2. The barcode ink according to claim 1, wherein the halogenated copper phthalocyanine is brominated copper phthalocyanine. 3. The barcode ink according to claim 1 or 2, characterized in that it is formed by using a halogenated copper phthalocyanine and another dye in combination. 4. A detection method characterized in that information is read from the barcode printed matter by measuring reflection intensity or transmission intensity using a light source or detector having a dominant wavelength in the range of 600 to 700 nm. 5. Using an ink containing the above-mentioned halogenated copper phthalocyanine and an ink containing other pigments, use multiple inks with different absorption wavelengths from visible to near infrared rays to print at the same location or in the vicinity, each in a shape corresponding to multiple pieces of information. A detection method characterized by reading a plurality of pieces of information by printing or printing information on the paper, superimposing the information, and measuring the reflection intensity or transmission absorption intensity using a plurality of light sources or detectors having a dominant wavelength in the range of 600 to 1500 nm. .