JP2002363454A - Ink detection method and ink therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for detecting an ink for ink jet recording and effective for preventing the erroneous loading of an ink with an inexpensive detector without lowering the chroma of the image or lowering the preservability and ejection stability of the ink. SOLUTION: The ink detection method comprises the use of an ink jet recording ink containing an infrared-absorbing coloring material to give the peak of the spectral absorbance in infrared range to be smaller than 20% of the peak of the spectral absorbance of the existing image-forming coloring material in the visible light range and the determination of the ink jet recording ink with an infrared detector of an ink jet printer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a method for detecting ink loaded in an ink jet printer and an ink used therefor.

[0002]

2. Description of the Related Art If the ink loaded in an ink jet printer is wrong, different types of inks are mixed in the head, so that the head may be clogged and become unusable. Therefore, it is desired that the printer determine whether the ink is proper or not, and if the loading is wrong, display a warning or stop printing.

[0003] It is conceivable to make an ink contain an infrared-absorbing color material and to discriminate it with an infrared sensor. However, in general, an infrared-absorbing color material has absorption in a region other than the infrared region. There is a problem that the saturation of a visible image to be displayed is reduced.

In the case where an ink contains an ultraviolet absorber and the determination is made by an ultraviolet sensor, since many image forming color materials also have large absorption in the ultraviolet region, it is necessary to add a large amount of the ultraviolet absorber for the determination. As a result, the solid content of the ink increases, and the storage stability and the ejection performance decrease.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to reduce the storage stability and ejection stability of ink without lowering the saturation of an image. Another object of the present invention is to provide a method for detecting an ink jet recording ink that can prevent erroneous loading using a low-cost detector.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an image forming color material in which the maximum value of the spectral absorbance is less than 20% of the maximum value of the spectral absorbance in the visible light region of the contained image forming color material. The maximum value of the spectral absorbance in the infrared region is less than 10% of the maximum value of the spectral absorbance in the visible light region. That the image forming color material is a yellow pigment, a magenta pigment or a cyan pigment, that the image forming color material is a dye, and that the spectral absorption of the infrared absorbing color material
The ratio of the maximum absorbance at a wavelength of less than 700 nm to the maximum absorbance at 0 nm or more is 0.1 or less. In spectral absorption, the ratio of the maximum absorbance at a wavelength of less than 700 nm to the maximum absorbance at a wavelength of 700 nm or more is 0.1. An ink detection method for determining an ink jet recording ink containing an infrared-absorbing color material by an infrared detector included in an inkjet printer, an ink detection method for determining the ink using an infrared detector included in the inkjet printer, Achieved by

In other words, the present inventor, when incorporating an infrared-absorbing color material into an ink, sets the spectral absorbance in the infrared region to a predetermined range based on the spectral absorbance in the visible light region of the image forming color material. By setting, it has been found that a decrease in the saturation of the visible image to be formed can be suppressed, and the present invention has been achieved.

Japanese Patent Application Laid-Open No. 2000-248214 discloses an ink jet recording ink containing a composition other than visible light having a unique absorbance peak in a region other than the visible region. This is for reading an image with light, and contains a considerable amount of an infrared-absorbing coloring material for the reading, which is different from the concept of the present invention.

Hereinafter, the present invention will be described in detail. According to the present invention, the maximum value of the spectral absorbance in the infrared region of the ink for inkjet recording is less than 20%, preferably 0.0%, of the maximum value of the spectral absorbance in the visible light region of the image forming color material contained therein.
An infrared-absorbing coloring material is contained so as to have a value of 1% or more and less than 10%.

The spectral absorbance is determined by adding ion-exchanged water to the ink so that the maximum value of the spectral absorbance in the visible light region is 1.0 to 2.0.
It can be diluted to zero and measured with a spectrophotometer (for example, U-3200 manufactured by Hitachi, Ltd.).

The ink for ink jet recording is generally prepared by dissolving a coloring material in a solvent or dispersing in a dispersion medium.

As image forming color materials, yellow pigment, magenta pigment and cyan pigment have low absorption in the infrared region,
Particularly, since the yellow pigment and the magenta pigment have a small absorption, they can be detected with a small addition amount, which is preferable.

The infrared detector of the printer is installed in a flow path between the ink cartridge (container) and the head.

As image forming color materials, pigments, direct dyes,
Acid dyes, reactive dyes, basic dyes, food colorings and the like can be used, and may be water-soluble or water-insoluble. Specific examples are shown below, but the present invention is not limited to these.

As the water-soluble dye, <direct dye> C.I. I. Direct Yellow: 1, 4,
8, 11, 12, 24, 26, 27, 28, 33, 3,
9, 44, 50, 58, 85, 86, 100, 110,
142, 144 C.I. I. Direct Red: 1, 2, 4, 9, 11, 1
3, 17, 20, 23, 24, 28, 31, 33, 3
7, 39, 44, 47, 48, 51, 62, 63, 7
5, 79, 80, 81, 83, 89, 90, 94, 9
5, 99, 220, 224, 227, 243 C.I. I. Direct Blue: 1, 2, 6, 8, 15, 2
2, 25, 71, 76, 78, 80, 86, 87, 9
0, 98, 106, 108, 120, 123, 163,
165, 192, 193, 194, 195, 196, 1
99, 200, 201, 202, 203, 207, 23
6, 237 C.I. I. Direct black: 2, 3, 7, 17, 1
9, 22, 32, 38, 51, 56, 62, 71, 7
4, 75, 77, 105, 108, 112, 117, 1
54.

<Acid dye> C.I. I. Acid Yellow:
2, 3, 7, 17, 19, 23, 25, 29, 38, 4
2, 49, 59, 61, 72, 79, 99 C.I. I. Acid Orange: 56, 64 C.I. I. Acid Red: 1, 8, 14, 18, 26,
32, 37, 42, 52, 57, 72, 74, 80, 8
7, 115, 119, 131, 133, 134, 14
3, 154, 186, 249, 254, 256 C.I. I. Acid Violet: 11, 34, 75 C.I. I. Acid Blue: 1, 7, 9, 29, 87, 1
26, 138, 171, 175, 183, 234, 23
6, 249 C.I. I. Acid Green: 9, 12, 19, 27, 4
1 C. I. Acid Black: 1, 2, 7, 24, 26,
48, 52, 58, 60, 94, 107, 109, 11
0, 119, 131, 155 BASCID Black X34.

<Reactive dye> C.I. I. Reactive Yellow: 1, 2, 3, 13, 14, 15, 17, 37, 4
2, 76, 85, 95, 168, 175 C.I. I. Reactive Red: 2, 6, 11, 21, 2
2, 23, 24, 33, 45, 111, 112, 11
4, 180, 218, 226, 228, 235 C.I. I. Reactive Blue: 7, 14, 15, 18,
19, 21, 25, 38, 49, 72, 77, 176,
203, 220, 230, 235 C.I. I. Reactive Orange: 5, 12, 13, 3
5, 95 C.I. I. Reactive Brown: 7, 11, 33, 3
7, 46 C.I. I. Reactive Green: 8, 19 C.I. I. Reactive violet: 2, 4, 6, 8,
21, 22, 25 C.I. I. Reactive Black: 5, 8, 31, 39.

<Basic dye> C.I. I. Basic Yellow: 11, 14, 21, 32 C.I. I. Basic Red: 1, 2, 9, 12, 13 C.I. I. Basic violet: 3, 7, 14 C.I. I. Basic blue: 3, 9, 24, 25.

Other examples of the dye used in the ink of the present invention include a chelate dye and an azo dye used in a so-called silver dye bleaching light-sensitive material (for example, Cibachrome manufactured by Ciba Geigy). Regarding the chelate dye, for example, the description in British Patent 1,077,484 can be referred to. Regarding the azo dye of the silver dye bleaching photographic material, for example, British Patent 1,039,45
No. 8, No. 1,004,957, No. 1,077,628
And U.S. Pat. No. 2,612,448 can be referred to.

Examples of the water-insoluble dye include, for example, Japanese Patent Application 200
C. 0-186170. I. Disperse
Yellow, C.I. I. Disperse Orange
e, C.I. I. Disperse Red, C.I. I. Di
sperse Violet, C.I. I. Dispers
e Green, C.I. I. Disperse Blu
e. Chelating dyes described in Japanese Patent Application No. 2000-315812.

As the pigment that can be used in the present invention, conventionally known organic and inorganic pigments can be used. For example, azo lake, insoluble azo pigment, condensed azo pigment, chelate azo pigment, and phthalocyanine pigment, perylene and perylene pigment,
Polycyclic pigments such as anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, quinophthaloni pigments, and dye lakes such as basic dye lakes and acid dye lakes, and nitro pigments.
Organic pigments such as nitroso pigments, aniline black and daylight fluorescent pigments, and inorganic pigments such as carbon black can be exemplified.

The water-soluble organic solvent that can be used in the present invention includes alcohols (methanol, ethanol,
Propanol, isopropanol, butanol, isobutanol, etc.), polyhydric alcohols (ethylene glycol, propylene glycol, 1,2-butanediol,
1,4-butanediol, 1,2-pentanediol,
Glycerin, thiodiglycol, etc., polyhydric alcohol ethers (ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethylene) Glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, etc.), amines (ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, etc.),
Heterocycles (eg, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone) and sulfoxides (eg, dimethyl sulfoxide).

The ink jet recording ink of the present invention comprises:
A surfactant may be included to adjust the surface tension. Surfactants preferably used in the ink of the present invention include anionic surfactants such as dialkyl sulfosuccinic acids, alkyl naphthalene sulfonic acids, and fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, and acetylene. Examples include nonionic surfactants such as glycols and polyoxyethylene / polyoxypropylene block copolymers. In particular, anionic surfactants can be preferably used.

Examples of the infrared absorbing colorant used in the present invention include IR-820B manufactured by Mitsui Chemicals, Inc.
Particularly preferred examples of the infrared-absorbing coloring material having a maximum spectral absorption in the visible light region of less than 10% of the maximum spectral absorption in the infrared region include the following compounds.

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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(Synthesis of IR-1)

[0031]

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2.39 g of intermediate 1 and croconic acid
75 g of 1-propanol was refluxed under heating for 1 hour, and the reaction product was extracted with ethyl acetate, washed with water, and the solvent was removed therefrom. Recrystallization from methanol gave dark green crystals (yield 7).
2%). The structure was confirmed by MS and NMR.

(Synthesis of IR-11)

[0034]

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3.68 g of intermediate 2 and squaric acid
60 g was refluxed with heating for 8 hours while removing water generated in the ester tube together with 30 ml of butanol and 30 ml of toluene. After completion of the reaction, the solvent was removed and purification was performed by column chromatography to obtain dark green crystals (yield 8%). The structure was confirmed by MS and NMR.

(Synthesis of IR-17) 2,6-di-tert-butyl-4-methylthiopyrylium perchlorate 1.51
g and squaric acid 0.26 g in 1-butanol 50 m
1, 30 ml of toluene and 0.65 g of quinoline.
The mixture was heated at reflux for 5 hours, and the reaction product was extracted with ethyl acetate and then recrystallized from acetonitrile to obtain dark green crystals (yield: 68%). The structure was confirmed by MS and NMR.

[0037]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. still,
In the following, "parts" represents parts by mass unless otherwise specified.

Example 1 Comparative inks were prepared according to the following formulation, and infrared absorbing dyes were added as shown in Table 1 to prepare Example Inks 1 to 4 of the present invention.

[Comparative ink 1] (Dark yellow ink) Ethylene glycol 18 parts Propylene glycol 27 parts Direct Yellow 86 (10% aqueous solution) 7.88 parts Acid Yellow 79 (10% aqueous solution) 40.95 parts Priventol ( 0.2 parts Proxel GXL (Zeneca) 0.04 parts Finish to 100 parts with ion-exchanged water.

(Dark magenta ink) Ethylene glycol 7.5 parts Propylene glycol 40 parts Acid Red 249 (10% aqueous solution) 38.25 parts Ethylenediaminetetraacetic acid / 4Na 0.3 parts Priventol (described above) 0.2 parts Proxel GXL (described above) 0.04 parts Finish to 100 parts with ion-exchanged water.

(Dark cyan ink) Ethylene glycol 7.5 parts Propylene glycol 40 parts Direct Blue 199 (10% aqueous solution) 36.9 parts Preventol (described above) 0.2 parts Proxel GXL (described above) 0.04 Part Finish to 100 parts with ion exchanged water.

[Preparation of Ink] The absorbance of the infrared-absorptive coloring material with respect to the maximum absorbance of the image forming coloring material in the ink was 1%.
The inks soluble in the solvent of the ink were added as they were, and the insoluble ones were added as dispersions, and the dispersion was added to 100 parts with ion-exchanged water to prepare Examples Inks 1 to 4.
A comparative ink 2 was prepared in the same manner as in Example ink 1 except that the ratio of the absorbance was 3/10.

[Method of Dispersing Infrared Absorbing Coloring Material] Infrared absorbing coloring material 10.5 parts Acrylic-styrene resin 6.0 parts (Johncryl, manufactured by Johnson Company) Glycerin 10.0 parts Ion-exchanged water 13 And 0.5 parts of zirconia beads in a volume ratio of 5 parts.
The mixture was dispersed by using a 0% -enriched sand grinder to obtain an infrared absorbing colorant dispersion.

[0044]

[Table 1]

[Preparation of Comparative Ink 3] A comparative ink 3 having a magenta ink having the following formulation was prepared.

(Magenta Pigment Dispersion) I. Pigment Red 122 105 parts Acrylic-styrene resin 60 parts Glycerin 100 parts Ion-exchanged water 130 parts were mixed, and 0.5 mm zirconia beads were mixed at a volume ratio of 5 parts.
The mixture was dispersed using a sand grinder with 0% enrichment to prepare a magenta pigment dispersion, and the sediment was removed by a centrifuge.

(Preparation of Ink) Magenta Pigment Dispersion 14 parts Nipol SX1105 5.6 parts (manufactured by Nippon Zeon Co., Ltd .: solid content: 45%) Ethylene glycol 15 parts Diethylene glycol 12 parts Perex OT-P (manufactured by Kao Corporation) 0.4 parts Proxel GXL (supra) 0.2 parts Sodium hydroxide pH adjustment amount Dioctyl sodium sulfosuccinate (only the following inks) 0.01 parts Potassium nitrate 0.18 parts 100 parts with ion-exchanged water After the mixture was sufficiently stirred and passed through a millipore filter having a diameter of 1 μm twice, Comparative Ink 3 was obtained.

The average particle size of the pigment in the obtained ink is 85.
nm. [Preparation of Example Inks 5 to 8 and Comparative Ink 4] Example inks 5 to 8 and Comparative Ink 4 of the present invention were prepared in the same manner except that an infrared absorbing coloring material was added as shown in Table 2. Prepared.

[0049]

[Table 2]

As schematically shown in FIG. 1, an ink printer 1 in which 500 ml of yellow ink, magenta ink and cyan ink are sealed is set in an ink jet printer, and a line for feeding liquid from each back to the ink jet head 2 is provided. A measuring cell 3 was provided in the middle, and an infrared light source LED 4 (wavelength 810 nm) and a photodiode 5 as an infrared sensor were arranged with the cell interposed therebetween.

Using this printer, 100% coated color patches were printed on inkjet paper QP.Pro manufactured by Konica Corporation.

[Evaluation] (Image color reproduction) A color patch was measured with a colorimeter, and L ^* a ^*
The distance R from the L ^* axis when plotted on the b ^* coordinate was determined. The ratio of R when no infrared-absorbing color material was added to R when the infrared-absorbing color material was added was used as an index of color reproducibility. Not less than 0.95 and less than 0.85 were evaluated.

(Detectability) The detection mechanism measures the current of the photodiode to determine the difference, and the reproducibility of the difference in the current value improves the detectability. で き る The presence or absence of the infrared absorbing coloring material can be reliably detected. % The presence or absence of an infrared-absorbing color material may not be determined with a probability of less than 10%. The evaluation is made because the presence or absence of an infrared-absorbing color material cannot be detected with a probability of 10% or more.

Table 3 shows the above results.

[0055]

[Table 3]

The evaluation result is the lowest evaluation among the yellow, magenta and cyan inks.

[0057]

According to the present invention, erroneous loading of ink into an ink jet printer can be effectively prevented.

[Brief description of the drawings]

FIG. 1 is a diagram schematically illustrating an example of an ink detection method.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 ink back 2 inkjet head 3 measurement cell 4 LED 5 photodiode

Claims (7)

[Claims] 1. An infrared-absorbing color such that the maximum value of the spectral absorption in the infrared region is less than 20% of the maximum value of the spectral absorption in the visible light region of the contained image forming colorant. An ink-jet recording ink comprising a material. 2. The maximum value of the spectral absorbance in the infrared region is:
The ink for ink-jet recording according to claim 1, wherein the spectral absorbance in the visible light region is less than 10% of the maximum value. 3. The ink jet recording ink according to claim 1, wherein the image forming color material is a yellow pigment, a magenta pigment or a cyan pigment. 4. The ink jet recording ink according to claim 1, wherein the colorant for forming an image is a dye. 5. In the spectral absorption of an infrared-absorbing coloring material, a wavelength of 700 n with respect to a maximum absorbance at a wavelength of 700 nm or more.
5. The ink for inkjet recording according to claim 1, wherein the ratio of the maximum absorbance at less than m is 0.1 or less. 6. An ink-jet printer comprising an ink-jet recording ink containing an infrared-absorbing coloring material having a ratio of the maximum absorbance at a wavelength of less than 700 nm to the maximum absorbance at a wavelength of 700 nm or more in the spectral absorption is 0.1 or less. An ink detection method characterized in that the detection is performed by an infrared detector. 7. An ink detection method, wherein the ink according to claim 1 is determined by an infrared detector included in an ink jet printer.