JP2507819B2 - Information recording and detection method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to an information recorded material and an ink formed with an ink layer that selectively absorbs light having a specific wavelength. Printing or printing in a shape according to the information using 600
The present invention relates to a detection method for reading information by measuring reflection intensity or transmission absorption intensity of light having a wavelength of up to 700 nm.
More specifically, the present invention relates to information recording, color bar code, multiple bar code, tampering prevention / counterfeit prevention ink, and detection method.

(Prior art) Conventionally, prepaid cards, credit cards, bank cards, identification cards, licenses, tickets, entrance tickets, membership cards, securities cards, tickets, certificates are generally printed on the surface of paper or plastic. Sculpture / embossing /
Tampering / counterfeiting with laser or electrical discharge / laminating or vapor deposition processing means and functional materials such as magnetic material, conductive material, photosensitive material, heat sensitive material, foam material, light emitting material, etc. and detection means according to the function. Various attempts have been made in order to fulfill the purpose such as a collation means for prevention and identification, or improvement of the environmental resistance of the built-in information.

Among these functional materials, a method for 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 with different near-infrared reflectance, and identifying through a filter that transmits light of 650 nm or more (Japanese Patent Publication No. 46-25288),
Two or more types of ink having different near infrared reflectances are arranged or laminated in parallel. Alternatively, a method of coating after coating with an ink that transmits near infrared rays (JP-A-58-134782), a method of identifying by using a phthalocyanine-based near-infrared absorber (JP-A-59-138284), a near infrared absorbing substance Is printed on securities by thermal transfer (JP-A 61-146589), and a method of combining a magnetic recording layer, an infrared reflection layer and an infrared absorption layer (JP-A 61-146589).
-297192), a method using a dye that reflects near infrared rays and a dye that absorbs near infrared rays (JP-A-63-91283), JP-A-63-63
-92486), a method of overcoating a near-infrared absorbing ink with a dark color ink (Japanese Patent Publication No. 63-144075), and a method of forming a negative / positive image by using two kinds of inks having different near-infrared absorbing characteristics (Japanese Patent Application Laid-Open No. Sho-62-1987). 63-307996), a method in which a phthalocyanine-based near-infrared absorber is based on a heat-sensitive transfer material (Japanese Patent Laid-Open No. 64-64996)
-30788) etc. have been proposed.

In recent years, management systems such as bar code distribution management, product management, quality material management, inventory management, and POS system have been developed and applied in various fields as an effective means to eliminate the complexity of key input / bookkeeping. There is. Bar code marking is offset printing, gravure printing, flexo printing,
Source marking that creates a large number of barcodes of the same type by letterpress printing, screen printing, etc. and individual printers by thermal transfer type, thermal color development type, wire dot type barcode printer, ink jet printer, laser printer, etc. There are in-store marking, in-house marking, or on-demand marking that creates a limited amount of barcodes.Recorded barcode printing or printed matter, and further recorded matter of characters is 632.8 nm He-Ne laser, 660 nm Easy to input code information or character information by measuring reflection intensity using light source such as light emitting diode, 670nm visible light semiconductor laser, 690nm light emitting diode, 780nm semiconductor laser, 940nm infrared light emitting diode. Is processed by computer I have.

The ink used for these barcodes or characters generally uses carbon black, which has a wide absorption in the visible to near-infrared region, as a pigment, because of design problems or to enhance the value of the product. To
We used brown, dark blue, and dark green chromatic color inks that used carbon black, or inks that used blue-based and green-based pigments that were detected using a visible light source of 600 to 700 nm, and the coloring of leuco dyes. Thermally sensitive color papers, ink jet inks using nigrosine dyes, and the like have been studied.

In 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 the absorber for a specific wavelength is the hue, saturation, brightness, etc. This is the point that determines the sensitivity or weather resistance of the recorded matter.

A so-called near-infrared absorber that absorbs near-infrared rays has a maximum absorption wavelength outside the visible region, and is relatively colorless and transparent.
As such a near-infrared absorber, for example, phthalocyanine-based / naphthalocyanine-based / metal complex salt-based / anthraquinone-based, cyanine dye-based / polymethine-based dyes, etc. are known.

On the other hand, in recent years, bar code readers have been
With the development of gas lasers or CCD sensors, the detection wavelength has become shorter, and the sensitivity of the detection element has increased.
The number of cases using the visible light wavelength region is increasing.

When using the above-mentioned near-infrared absorber, since there is no absorption in the visible region, even when used in combination with other chromatic color dyes,
It is possible to obtain ink for information recorded matter having a wide range of colors without changing the so-called tint such as lightness, hue and saturation of other dyes themselves, but using visible light of 600 to 700 nm as the detection wavelength. It cannot cope with the social tendency to do.

On the other hand, when a so-called visible light absorbing agent that absorbs visible light of 600 to 700 nm is used, it is possible to meet the requirements from the social and device sides, but the absorbing agent itself is a black type, a blue type,
Since it has a greenish color, information recording inks and information recording materials are limited to black, brown, blue, green, etc., red,
It has been impossible to obtain those having color tones such as orange, yellow, purple, white, pastel, fluorescent, metallic and pearl.

In view of the above problems, the present invention has as a required property of 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, carbon black, which has absorption at 600 to 700 nm, and a dye (A) excluding halogenated copper phthalocyanine and another dye (B) are used in combination, and the dye is recorded in an information recording material. By containing 0.005 to 0.1 g / m ^{2 of} (A), it was possible to obtain an information record having a wide range of colors, and the information record could be used for a visible light compatible bar code reader or OCR. The present invention has been completed and the present invention has been completed.

[Structure of Invention]

(Means for Solving the Problems) That is, the present invention is an ink layer containing carbon black and halogenated copper phthalocyanine, and the content of the dye (A) having an absorption at 600 to 700 nm is 0.005 to 0.1 g / m ^2. And an ink layer for information recording formed by the information recording ink having the dye (A), and another dye (B). An information recorded matter comprising an ink layer formed of ink, wherein the content of the dye (A) in the information recorded matter is 0.005 to 0.1 g / m ^2. is there.

These information recording materials can be used for a visible light compatible bar code reader or OCR.

The greater the amount of the dye (A) having an absorption at 600 to 700 nm, excluding carbon black and halogenated copper phthalocyanine, in the information recording material, the greater the absorption and the higher the reading sensitivity. However, as easily predicted, the higher the amount, the higher the density and the higher the visual sensitivity. In the present invention, an information recorded matter having a wide range of colors can be obtained by using the dye (A) in combination with another dye (B). Therefore, the visual sensitivity of the dye (A) is improved. As a result, there is a drawback in that the lightness, hue, and saturation are severely reduced, and so-called color turbidity increases.

Therefore, when a bar code or character information of warm color such as red, orange, yellow, etc. is realized in combination with other dyes, the dye (A) is added in an amount of 0.005 to 0.1 g / m ² in the information recorded matter. It is necessary to be contained, and more preferably 0.005
~ 0.08 g / m ² .

If the content of the dye (A) exceeds 0.1 g / m ² , the color turbidity becomes large as described above. On the other hand, if the content of the dye (A) is less than 0.005 g / m ² , the turbidity of the color is reduced, but the detection sensitivity is decreased.

Except for carbon black and halogenated copper phthalocyanine used in the present invention, the dye (A) having absorption at 600 to 700 nm includes inorganic pigments such as manganese purple, cobalt purple (dark mouth), cobalt purple (thin mouth), and fast pigments. Azo pigments such as violet B, basic dye lakes such as methyl violet lake, rhodamine lake B, and purple dyes represented by vat dyes such as dioxazine violet, induslen brilliant biot, induslen red biot, Inorganic pigments such as ultramarine, dark blue, cobalt blue, cerulean blue, acid dye lakes such as alkali blue lake, peacock blue lake, basic dye lakes such as Victoria blue lake,
Phthalocyanine pigments such as phthalocyanine blue, fast sky blue and metal-free phthalocyanine blue, blue pigments represented by vat dye pigments such as indigo and indanthrene blue BC, chrome green, zinc green, chromium oxide, viridian, emerald green.・ Inorganic pigments such as cobalt green, nitroso pigments such as pigment green B and naphthol green B, azo pigments such as green gold, acid dye lakes such as acid green lake, and basic dye lakes such as malachide green lake. 1 or 2 or more selected from the group of green dyes represented by.

The dye (A) absorbs light at 600 to 700 nm to the extent that it can be detected, and should be called a dye for visible detection.

Other dyes (B) used in the present invention include red, orange, yellow, violet, except for blue and green which have been conventionally used.
One or more dyes and pigments such as white, pastel, fluorescent, metallic, and pearl, which should be called a visual pigment, and by combining this with a pigment (A),
It is now possible to obtain an information recording material having a wide range of colors.

There are mainly the following methods for obtaining an information recorded material having a wide range of colors, which is a combination of the dye (A) and the dye (B).

That is, a method of obtaining an information recording ink containing a dye (A) and a dye (B), and using the information recording ink to obtain an information recorded matter having a wide range of colors.

An information recorded matter comprising an ink layer for information recording formed by an information recording ink containing a dye (A) and a visual ink layer formed by an ink containing a dye (B) is obtained. There are two methods.

As described above, according to the present invention, it is possible to obtain an information recorded matter having a wide range of colors by using the dye (A) together with the dye (B). Now, it is possible to apply to cards, tickets, and certificates that are difficult to handle.

In the present invention, the information recording material is irradiated with light having a main wavelength of 600 to 700 nm, and a detector having a detection region of 600 to 700 nm is used to measure reflection intensity or transmission intensity after irradiation. This is a detection method for reading the information in the information recorded matter.

Furthermore, the present invention, the information recording material having a plurality of different information, a plurality of light having different wavelengths from a plurality of light sources having a main wavelength of 600 ~ 1500nm, irradiating a plurality of light having a detection area at 600 ~ 1500nm. It is a detection method for reading information in an information recorded matter by measuring the reflection intensity or the transmission intensity of a plurality of irradiated lights having different wavelengths, respectively.

The information recorded matter having a plurality of different information used in the present invention includes the dye (A) and the other dye (B).
And a shape corresponding to a plurality of pieces of information, using a visible light-compatible information recording ink containing and a second information recording ink containing a dye (C) having absorption in the visible to near-infrared region. For information recording formed by printing or printing multiple information on the same place or in the vicinity of the material to be printed, or information recording formed by the information recording ink containing the dye (A). A second ink layer formed of an ink layer, an ink layer formed of an ink containing another dye (B), and an information recording ink containing a dye (C) having absorption in the visible to near infrared region. An ink layer for recording information. It is an information recorded matter in which a plurality of pieces of information are superposed, and each of the information recorded matters contains the dye (A) in an amount of 0.005 to 0.1 g / m ² .

The wavelength of the light source or detector is preferably a single wavelength,
A laser light source is effective. In addition, the light absorber used
As the wavelength to be detected has the maximum absorption peak and the half width of the absorption spectrum is smaller, the mutual interference of the absorption spectrum is smaller and the detection accuracy is higher. For that purpose, the dye (A) having an absorption at 600 to 700 nm to be used is also increased in dispersion as much as possible, the absorption spectrum becomes sharper as it is closer to the dissolved state, the half width becomes smaller, and the addition amount is small. Since there are merits such as, it is necessary to pay sufficient attention to the dispersed state.

The recording ink meant in the present invention can be applied to any of printing ink and various printer inks, for example, printing ink such as gravure ink, flexo ink, offset ink, screen ink, letterpress ink, or thermal transfer. Ink for printers, ink jet printers, impact printers, laser printers and other printers.

When using two or more kinds of ink such as a multiple code according to the present invention, a plurality of recording methods are used, such as first recording with a printer such as a thermal transfer printer and then recording with printing. You can also

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples.

 In the examples, parts are parts by weight.

Example 1 Inks A and B were obtained by sufficiently dispersing a coating liquid having the following composition with an attritor at room temperature.

[Ink A]

Carnauba wax 18 parts Ethylene-vinyl acetate copolymer 2 parts (Mitsui Polychemical Co., Ltd. Evaflex 420) IPA 15 parts Toluene 65 parts [Ink B] CIPigment Violet 1 1.5 parts (Toyo Ink Mfg. Co., Ltd. Ultrarose 3B) Alicyclic saturated hydrocarbon resin 9.5 parts (Arakawa Chemical Industry Co., Ltd. Alcon P-100) Carnauba wax 10 parts IPA 15 parts Toluene 64 parts Furthermore, three materials heated to 90 to 120 ° C Thoroughly kneading with a roll, a hot melt ink C was obtained.

[Ink C]

Fluorescent pigment pink 20 parts (Nippon Shokubai Chemical Co., Ltd. Epocolor FP-10) Ethylene-vinyl acetate copolymer 5 parts (Mitsui Polychemical Co., Ltd. Evaflex 577-
2) Carnauba wax 16 parts Paraffin wax 59 parts (Nippon Seiwa Co., Ltd. HNR-9) The obtained ink A was dried on a 6 μm polyethylene terephthalate film using a gravure printing machine to give a dry coating film of 1 g / m 2.
² coats, ink C is coated on it with a hot melt coater at 3 g / m ² and ink B is further coated with a gravure printer at 1 g / m ² to give a pink thermal transfer material. Got

When a bar code pattern was printed using the obtained thermal transfer material, a slightly cloudy but pink bar code recorded matter was obtained, and a bar code verifier with a reading wavelength of 632.8 nm (LASERCHECK manufactured by SYMBOL TECHNOLOGIES, Inc. was used. LC281
Information corresponding to the code was read in 1).

Comparative Example 1 Ink A obtained in Example 1 was applied to a 6 μm polyethylene terephthalate film as a dry coating film at 1 g / m ² using a gravure printing machine, and then ink C was applied to the hot melt coating machine. It was applied at 3 g / m ² to obtain a pink thermal transfer material.

When a bar code pattern was printed using the obtained thermal transfer material, a bright pink bar code recorded matter was obtained, but the information could not be read by the bar code verifier with a reading wavelength of 632.8 nm. .

Example 2 A coating liquid having the following formulation was heated to 200 ° C. to dissolve the resin and produce a varnish.

[Rosin-modified phenolic resin varnish]

Rosin-modified phenolic resin 50 parts (Tamanol 356 manufactured by Arakawa Chemical Co., Ltd.) Linseed oil 15 parts Solvent 35 parts (Nippon Petrochemical Co., Ltd. No. 3 solvent) Next, materials with the following composition are kneaded using a three-roll mill. Ink D was obtained by fleshing.

[Ink D]

CIPigment Green8 4.3 parts (Sumitomo Chemical Co., Ltd. Sumitone Green B) CIPigment Red38 13 parts (Toyo Ink Mfg. Co., Ltd. Lionol Red B) Rosin-modified phenolic resin varnish 68 parts Solvent 14.7 parts (Japan Petrochemical Co., Ltd. ) No. 3 solvent) Using the obtained ink D, a bar code was printed on the art paper by offset printing so that the dry coating film would be 1 g / m ^2, and it was a slightly dull red bar code recorded matter. Was obtained, and the information corresponding to the code was read by the bar code verifier with the reading wavelength of 632.8 nm.

Comparative Example 2 Ink E was obtained by kneading materials having the following composition using a three-roll mill.

[Ink D]

CIPigment Red38 15 parts (Toyo Ink Mfg. Co., Ltd., Rionol Red B) Rosin-modified phenolic resin varnish 70 parts Solvent 15 parts (Nippon Petrochemical Co., Ltd. No. 3 solvent) When a bar code was printed by offset printing on the dry coating film at 1 g / m ² , a red bar code recorded product was obtained, but the information can be read with a bar code verifier with a reading wavelength of 632.8 nm. I couldn't.

Example 3 An ink FG was obtained by sufficiently dispersing a coating solution having the following composition with an attritor at room temperature.

[Ink F]

Fluorescent pigment Pink 10 parts (Nippon Shokubai Chemical Co., Ltd. Epocolor FP-10) Alicyclic saturated hydrocarbon resin 5 parts (Arakawa Chemical Co., Ltd. Alcon P-100) Carnauba wax 5 parts IPA 15 parts Toluene 65 Part [Ink G] CIPigment Blue 1 1.5 parts (Toyo Ink Mfg. Co., Ltd. Ultra Blue B) Alicyclic saturated hydrocarbon resin 9.5 parts (Arakawa Chemical Co., Ltd. Alcon P-100) Carnauba wax 10 parts IPA 15 Parts Toluene 64 parts Ink A obtained in Example 1 was applied to a 6 μm polyethylene terephthalate film as a dry coating film at 1 g / m ² using a gravure printing machine, and then ink F was applied at 3 g / m ² thereon. Then, 1 g / m ^{2 of} ink G was applied to obtain a pink heat-sensitive transfer material.

When a bar code pattern was printed using the obtained thermal transfer material, a slightly turbid pink bar code recorded matter was obtained, and the information corresponding to the code could be read by a bar code verifier with a reading wavelength of 632.8 nm. It was

Comparative Example 3 Ink H was obtained by sufficiently dispersing a coating liquid having the following composition with an attritor at room temperature.

[Ink H]

Carbon black 0.7 parts (Mitsubishi Carbon Co., Ltd. MA-600) Alicyclic saturated hydrocarbon resin 10.3 parts (Arakawa Chemical Co., Ltd. Alcon P-100) Carnauba wax 10 parts IPA 15 parts Toluene 64 parts Example 1 1 g / m ^{2 of} the ink A obtained in Example 1 was applied to a 6 μm polyethylene terephthalate film as a dry coating film using a gravure printing machine, and then 3 g / m ^{2 of} the ink F obtained in Example 3 was applied thereon. Then, 1 g / m ^{2 of} ink H was applied to obtain a grayish pink thermal transfer material.

In the bar code recorded matter printed using the obtained thermal transfer material, the information according to the code could be read by the bar code verifier with the reading wavelength of 632.8 nm, but it was clearly colored as compared with the recorded matter of Example 3. The taste was dirty and inferior.

Example 4 Ink I was obtained by sufficiently dispersing a coating liquid having the following composition with an attritor at room temperature.

[Ink I]

Alicyclic saturated hydrocarbon resin 10 parts (Arakawa Chemical Co., Ltd. Alcon P-100) Carnauba wax 10 parts Near infrared absorber 0.2 parts (ICI Japan Co., Ltd. PRO-JET IR SC101756) IPA 14.8 parts Toluene 65 Part 1 Ink A obtained in Example 1 was applied to a 6 μm polyethylene terephthalate film with a dry coating film at 1 g / m ² using a gravure printing machine, and then ink I was applied at 1 g / m ² and further Ink A was applied at ² g / m ² to obtain a substantially transparent heat-sensitive transfer material.

Using the heat-sensitive transfer material and the heat-sensitive transfer material of Example 3, codes having different contents were printed at the same location to obtain a double bar code recorded matter. This recorded material is read at a wavelength of 780n
When read with a m barcode reader (TBR-6000 manufactured by Token Co., Ltd.), information corresponding to the code printed with the thermal transfer material of the example was read, and read with a barcode verifier with a reading wavelength of 632.8 nm. However, information corresponding to the code printed with the heat-sensitive transfer material of Example 3 was read.

Comparative Example 4 Using the heat-sensitive transfer material of Comparative Example 3 and the heat-sensitive transfer material of Example 4, codes having different contents were printed at the same location,
A double bar code record was obtained. This recorded material was read by a bar code verifier with a reading wavelength of 632.8 nm, and information corresponding to the code printed with the heat-sensitive transfer material of Comparative Example 3 was read.
The information corresponding to the code printed with the thermal transfer material of No. could not be read.

(Operation and Effect of the Invention) As described above, the recorded matter using the ink containing the specific dye of the present invention in the specific ratio enables the color bar code of the light color, which has been impossible in the past, to easily identify the color. Defect rate because you can
It is convenient for sorting areas, sizes, manufacturers, etc.,
Also, the color restrictions on the design should disappear. Furthermore, 780nm semiconductor laser or 940nm infrared LE, which has been used for near infrared detection, has almost no absorption in the visible range.
It can coexist with a system using a near-infrared absorber such as D, and can detect even if two or more types of codes are recorded in the same place. For example, near-infrared absorption in cards, tickets, certificates, etc. The color barcode that is superimposed on the transparent barcode of the agent makes the printing of the transparent barcode difficult to see, and at the same time plays the role of a pseudo barcode for copying and can also improve the tampering prevention function. Since it has various effects, etc., it can essentially solve various drawbacks that were not possible in the past.

Claims (6)

(57) [Claims] 1. An ink layer having a content of the dye (A) having an absorption at 600 to 700 nm of 0.005 to 0.1 g / m ² except carbon black and halogenated copper phthalocyanine. Information record to be done. 2. An information recording comprising an ink layer for information recording formed by an ink for recording information having the dye (A) and an ink layer formed by an ink containing other dye (B). An information recorded matter, wherein the content of the dye (A) in the information recorded matter is 0.005 to 0.1 g / m ² . 3. The dye (A) is an inorganic pigment such as manganese purple / cobalt purple (dark mouth) / cobalt purple (thin mouth), an azo pigment such as fast violet B or a base such as methyl violet lake or rhodamine lake B. Dye-based lakes, purple dyes represented by vat dye-based pigments such as dioxazine violet, indanthrene brilliant violet, and indanthrene red violet, inorganic pigments such as ultramarine blue, dark blue, cobalt blue, cerulean blue, and alkaline blue lake. Acid dye-based lakes such as peacock blue lake, basic dye-based lakes such as Victoria blue lake, phthalocyanine-based pigments such as phthalocyanine blue / fast sky blue / metal-free phthalocyanine blue,
Blue pigments represented by vat dye pigments such as Indigo and Induslen Blue BC, inorganic pigments such as chrome green, zinc green, chromium oxide, viridian, emerald green and cobalt green, Pigment Green B, Naphthol Green B, etc. 1 selected from the group of green pigments represented by nitroso pigments, azo pigments such as green gold, acid dye lakes such as acid green lake, and basic dye lakes such as malachite green lake
3. The information recording material according to claim 1, wherein the information recording material is one kind or two or more kinds. 4. The information recording material according to claim 1, which is irradiated with light having a main wavelength of 600 to 700 nm to obtain 600 to 7
A detection method characterized by reading information in an information recorded matter by measuring a reflection intensity or a transmission intensity of irradiated light using a detector having a detection area at 00 nm. 5. An information recording ink containing a dye (A) having an absorption at 600 to 700 nm, excluding carbon black and a halogenated copper phthalocyanine, and a dye (C) having an absorption in the visible to near infrared region. An information recording material in which the second information recording ink contained therein is printed or printed at the same position or in the vicinity of the printing medium in a shape corresponding to a plurality of information, respectively, and a plurality of information are mainly superimposed. Therefore, the content of the dye (A) in the recorded information is 0.005 to
An information recording material of 0.1 g / m ² is irradiated with a plurality of light beams having different wavelengths from a plurality of light sources having a dominant wavelength of 600 to 1500 nm, and 60
Characteristic of reading multiple information in an information recording material by measuring the reflection intensity or transmission intensity of multiple radiated lights of different wavelengths using multiple detectors with detection ranges from 0 to 1500 nm And the detection method. 6. An ink layer for information recording formed by an information recording ink containing a dye (A) having an absorption at 600 to 700 nm, excluding carbon black and halogenated copper phthalocyanine, and other dyes ( From an ink layer formed by an ink containing B) and a second ink layer for information recording formed by an information recording ink containing a dye (C) having absorption in the visible to near infrared region The information recorded matter in which a plurality of pieces of information are superposed, wherein the content of the dye (A) in the information recorded matter is
Information recorded matter of 0.005 to 0.1 g / m ² is irradiated with a plurality of lights of different wavelengths from a plurality of light sources having a dominant wavelength of 600 to 1500 nm, and a plurality of detectors having a detection range of 600 to 1500 nm are used. Then, a plurality of pieces of information in the information recorded matter are read by measuring the respective reflection intensities or transmission intensities of the plurality of irradiated lights having different wavelengths.