JP2013082922A - Printing apparatus using natural coloring matter-containing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a container for ink containing natural coloring matter of high concentration, which is produced by adding a surfactant etc., to the natural coloring matter and a solvent therefor, or to provide a printing apparatus in which a toner containing the natural coloring matter of high concentration is stored.SOLUTION: The ink containing natural coloring matter of high concentration, which is produced by adding any one or more of a surfactant, an emulsifier, a dispersant, a particle size controlling agent or a humectant to the natural coloring matter and the solvent therefor, is stored in the ink container, wherein the surfactant is a polyoxyethylene sorbitan fatty acid ester, and the natural coloring matter is any one or more of carotenoid-based coloring matter, flavonoid-based coloring matter, anthocyanin-based coloring matter, melanin-based coloring matter and indole-based coloring matter.

Description

  The present invention relates to a printing apparatus that stores an ink container or the like containing a natural pigment at a high concentration.

  From the viewpoint of privacy and security, it is desirable to dispose of documents, specifications, utility bills, etc. that contain personal information and confidential matters without leaking the information to the outside after the documents are no longer needed. . Conventionally, these documents have been discarded after being shredded using a shredder or the like. In recent years, inks that can erase the printed portion after printing have been developed.

  For example, Patent Documents 1 and 2 disclose inks that can erase characters and the like by heating a printed portion after printing. Patent Documents 3 and 4 disclose inks that can erase characters and the like by applying friction to a printed part after printing.

  On the other hand, natural pigments are known to have an action of fading gradually when exposed to light or oxygen. For example, Patent Document 5 discloses that a natural pigment containing Rafu hemp extract as an active ingredient fades.

JP-A-10-88046 JP 2001-302954 A JP 2000-351922 JP2003-335095A JP 2005-087147 A

  In the prior art, it is necessary to perform a specific operation such as heating to erase characters or the like, or applying friction. Such work is particularly useless when it is known that the printed part will be erased later. On the other hand, although conventional inks containing natural pigments have a fading action, the concentration of the natural pigments contained is low, and in the first place, there is a problem that printing cannot be performed clearly. Furthermore, in the prior art, there was no viewpoint of controlling the fading time of natural pigment.

  Therefore, the present application proposes an ink container containing a high concentration of a natural dye or a toner containing a toner containing a high concentration of a natural dye produced by adding a surfactant to the natural dye and its solvent. To do.

  The printing apparatus manufactured by the manufacturing method of the present application can print clearly while having a fading action because the stored ink and toner contain a natural pigment at a high concentration. Further, the printing method of the present application can adjust the fading speed of the natural pigment, and can be decolored after a desired period of time has passed. Further, by using the printing apparatus of the present application, it is possible to appropriately adjust the fading speed of the natural pigment.

The figure which shows an example of the method of manufacturing the ink storage container of Embodiment 1. The figure which shows an example of the method of manufacturing the natural pigment | dye toner of Embodiment 2. FIG. 10 is a diagram illustrating an example of a specific hardware configuration of a printing apparatus according to a third embodiment. FIG. 10 is a diagram illustrating an example of internal processing of the printing apparatus according to the third embodiment. FIG. 10 is a diagram illustrating another example of internal processing of the printing apparatus according to the third embodiment. The figure which shows the fading change of the high concentration astaxanthin containing ink which added the antioxidant or not added Photograph of inkjet paper shot with ink of Formulation 1 twice The figure which shows the fading speed of the beta-carotene containing ink in the dark place when the overprinting of the oxidation accelerator-containing transparent ink is performed and when it is not performed The figure which shows the fading speed of the beta-carotene containing ink under the fluorescent lamp when not performing it when overprinting the oxidation accelerator containing transparent ink The figure which shows the fading speed of the beta-carotene containing ink in the dark place when the overprinting of the oxidation accelerator-containing transparent ink is performed and when it is not performed The figure which shows the fading speed of the beta-carotene containing ink under the fluorescent lamp when not performing it when overprinting the oxidation accelerator containing transparent ink Photo taken of paper with Method 2 ink hit twice Photo taken of paper with black ink landed by inkjet printer

Hereinafter, embodiments of the present invention will be described.
<< Embodiment 1 >>
<Overview>

The method for producing an ink container of the present application is characterized in that an ink obtained by adding a surfactant to a natural pigment and its solvent is stored in the ink container. The printing apparatus provided with the ink container manufactured by the manufacturing method of the present embodiment can print clearly while having a fading action because the ink contains a natural pigment at a high concentration. It is.
<Ink components>

The ink storage container manufactured by the manufacturing method of the present embodiment is an ink storage container that stores ink containing a natural pigment at a high concentration. As described above, the feature of the production method of the present embodiment is that a surfactant or the like is added to the natural pigment and its solvent. Hereinafter, the details of the method for manufacturing the ink container of the present embodiment will be described.
(Ink components)

  Examples of main raw materials used in the ink production method of the present embodiment include “natural pigments”, “natural pigment solvents”, and “surfactants”. The ink component can be adjusted in density and printability by adding an appropriate amount of pure water or the like.

  Examples of the “natural pigment” include carotenoid pigments, flavonoid pigments, anthocyanin pigments, melanin pigments, and indole pigments. In addition, porphyrin dyes, quinone dyes, azaphyrone dyes, diketone dyes, betacyanin dyes, and the like are also conceivable.

  Examples of carotenoid pigments include astaxanthin, cryptoxanthin, fucoxanthin, lutein, lycopene, β-carotene, capsanthin, gardenia yellow, carrot carotene, palm oil carotene, anato pigment, dunari ela carotene, tomato pigment, paprika pigment, etc. .

  Examples of flavonoid pigments include safflower red pigments, safflower yellow pigments, rosewood pigments, carob pigments, suou pigments, tamarind pigments, cacao pigments, onion pigments, oyster pigments, licorice pigments and cucumber pigments.

  Examples of the anthocyanin pigment include grape juice pigment, grape skin pigment, red cabbage pigment, red radish pigment, perilla pigment, purple potato pigment, purple corn pigment, hibiscus pigment, elderberry pigment, and boysenberry pigment.

  In addition, examples of the porphyrin pigment include spirulina pigment, chlorophyllin, and chlorophyll. In addition, examples of the quinone dye include a silicon dye, a cochineal dye, an akane dye, and a rack dye. In addition, examples of the azaphyllon dye include red potato dye, examples of the diketone dye include turmeric dye, and examples of the betacyanin dye include red beet dye. Examples of indole dyes include violacein.

  Examples of the “solvent” include alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds. These may be used alone or in combination of two or more.

  Examples of the alcohol solvents include isopropyl alcohol, ethyl alcohol, methyl alcohol, 2 propanol, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3 butanediol, 1,4 butanediol, 3 methyl 1, butanediol, 1,5 pentanediol, 1,6 hexanediol, 1,2,4 butaneloliol, 1,2,3 butanetriol, 2 methyl Examples include 2,4 pentadiol, tetraethylene glycol, polyethylene glycol, 1,2,6 hexanetriol, and hetriol.

  In addition, the moisture retention effect of the ink is enhanced by including glycerin or ethylene glycol. For example, by including these substances, it is possible to prevent the ink from being dried and clogged in the head nozzle of the ink jet printer. Further, by changing the addition amount of these substances, the viscosity of the ink can be adjusted so that the ink is properly landed on the target as the ink for an ink jet printer.

  Examples of polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether. , Triethylene glycol isobutyl ether, tetraethylene glycol monoethyl ether, propylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene Recall mono-butyl ether, and the like.

  Examples of polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether. Examples of the nitrogen-containing heterocyclic compound include N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone and the like.

  Examples of amides include formamide, N-methylformamide, N, N-dimethylformamide, and the like. Examples of the amines include monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine, and the like. As other solvents, it is also possible to use a solvent such as acetone.

  Examples of the “surfactant” include polyoxyethylene sorbitan monolaurate (twin 20), polyoxyethylene sorbitan monopalmitate (twin 40), polyoxyethylene sorbitan monostearate (twin 60), polyoxyethylene sorbitan mono Examples include oleate (twin 80) and polyoxyethylene sorbitan trioleate (twin 85). It has been found that by using the polyoxyethylene sorbitan fatty acid ester as a raw material for ink, it is possible to make the ink contain a natural pigment more remarkably than other emulsifiers and surfactants. In particular, as shown in Example 1, the use of polyoxyethylene sorbitan monolaurate (twin 20) and polyoxyethylene sorbitan monopalmitate (twin 40) can significantly increase the content of natural pigments. It becomes possible.

  Examples of other “surfactants and the like” include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and the like. Examples of the anionic surfactant include carboxylate, sulfonate, sulfate ester salt, and the like. Examples of the cationic surfactant include amine salt type surfactants, quaternary ammonium salt type surfactants, methyl rosaniline chloride, quaternium, cocodimonium hydroxypropyl hydrolyzed collagen, cetylpyridinium chloride, polyquaternium, Etc. Examples of the amphoteric surfactant include carboxylate type surfactants, amino acid type surfactants, betaine type surfactants, and the like. Examples of the nonionic surfactant include ester surfactants, ether surfactants, ester / ether surfactants, alkanolamide surfactants, fatty acid alkanolamides, alkyl polyglucosides, stearamides, and the like. Is mentioned.

Other “surfactant and the like” further include emulsifiers. Examples of the emulsifier include (C30-38) copolymer, PCA isostearic acid PEG-30 hydrogenated castor oil, PCA glyceryl oleate, glyceryl PEG oleate, PPG glyceryl oleate, isostearamide, isostearyl glyceryl, erucic acid Glyceryl, oxyethylene behenyl alcohol, octyldodeces, cationized octyldecesses, bovine fatty acid glyceryl, cantalis tincture, glyceryl undecyl dimethicone, PEG-50 hydrogenated castor oil succinate, PEG-6 dimethicone acetate, glyceryl acetate, glyceryl monostearate, PEG glyceryl dioleate, glyceryl diacetate stearate, PEG glyceryl distearate, fatty acid glycol, hydroxylated lecithin, hydrogenated cocoglyceryl, hydrogenated lecithin PEG stearamide stearate, glycol stearate, glyceryl stearate, camellia oil fatty acid PEG, sodium tocopheryl phosphate, PEG triisostearate, PEG tristearate, glyceryl lactate fatty acid, glyceryl hydroxystearate, sodium stearylamide phthalate, Examples include sucrose hexaerucate, polysorbate, coconut fatty acid sorbitan, lauryl phosphate, lanolin fatty acid PEG, glyceryl ricinoleate, myristyl phosphate, and the like.
<Method for producing ink container containing ink containing high concentration of natural pigment>
(Conventional ink production method)

  In general, an ink jet ink mainly comprises a dye or pigment, an alcohol and water. In a general ink production method, a dye or pigment is dissolved in alcohols and further mixed with water. The present inventor tried to make an ink by dissolving it in a water-soluble organic solvent such as water-soluble alcohols or acetone because the natural dye is hydrophobic. However, natural pigments only dissolved in small amounts and the concentration remained low. For this reason, even when ejected from the ink head, almost no color was visible.

  On the other hand, since natural dyes are easily dissolved in chloroform, a liquid in which natural dyes are dissolved in chloroform and water are mixed to try to make ink. In this case, printing was possible when printing was performed after the cartridge containing the ink was vigorously stirred, but mottling occurred and solid printing could not be performed correctly. Further, when this ink was left for 3 to 4 minutes, it separated into a chloroform layer and an aqueous layer in which natural pigments were dissolved. Further, since chloroform is highly toxic and the solubility of the resin is high, the adhesive in the ink head may be dissolved and the head itself may be damaged. As described above, various problems occur when an ink is manufactured by a normal manufacturing method.

  Therefore, the present inventor has a hydrophilic group and a hydrophobic group in the same molecule, surrounds a hydrophobic molecule such as carotenoid, and forms micelles with the hydrophilic group facing the surface in contact with water. We focused on improving the dispersibility of hydrophobic molecules in water. By increasing the dispersibility of the dye molecules, the chromaticity, which is the strength of the color, increases, and the state becomes close to a solution.

  Specifically, the pigment is once dissolved in chloroform, and isopropyl alcohol as a water-soluble organic solvent and polyoxyethylene sorbitan monolaurate as a surfactant are added. Normally, a water-insoluble dye is easily dissolved in isopropyl alcohol by mixing a dye that does not dissolve in isopropyl alcohol with chloroform dissolved in high concentration and liquid-liquid extraction between chloroform and isopropyl alcohol. The reason why the surfactant is added is to extract at a higher concentration by the action of the surfactant. Then, chloroform is removed from the solution in which the water-insoluble dye is dissolved. Thereby, it is possible to prevent the adhesive in the ink head from being dissolved by chloroform and damaging the head itself.

As a result of studying the type and concentration of the surfactant, the present inventor succeeded in incorporating the natural pigment at a high concentration by appropriately selecting the surfactant and performing the procedure described below. Hereinafter, a method for manufacturing an ink container that stores ink capable of containing a natural pigment at a high concentration will be described in detail.
(Method for manufacturing ink container)

  FIG. 1 is a diagram showing an example of a method for producing an ink containing a high concentration of the natural pigment of this embodiment. First, in step S0101, a natural pigment (for example, astaxanthin) is mixed with a nonpolar solvent or a hydrophobic solvent (natural pigment mixing step). Next, in step S0102, a natural pigment solvent (for example, isopropyl alcohol) is mixed with the solution obtained in the natural pigment mixing step (solvent mixing step). Next, in step S0103, a surfactant or the like (for example, polyoxyethylene sorbitan monolaurate) is mixed with the solution obtained in the solvent mixing step (surfactant etc. mixing step). Here, it is preferable to perform stirring for mixing for about half a day to about 3 days. Next, in step S0104, the solvent mixed in the natural pigment mixing step is removed from the solution obtained in the surfactant etc. mixing step (solvent removal step). Here, the solvent is removed using, for example, a rotary evaporator. Next, in step S0105, pure water is mixed with the solution obtained in the solvent removal step (pure water mixing step). Here, in addition to water, glycerin or the like for enhancing the moisture retention of the ink may be added. Moreover, it is preferable to perform stirring for mixing for about 1 to 5 hours. By passing through the above processes, an ink containing a high concentration of natural pigments can be produced, so that the ink can contain a high concentration of natural pigments. In step S0106, the obtained ink is stored in the ink container (storage step).

In the above, as a blending amount of the ink, a solution (0.1 mg / ml to 0.5 mg / ml) composed of a natural pigment (for example, astaxanthin) and a nonpolar solvent or a hydrophobic solvent is 10 to 15 of the total amount (ml). %, Solvent (for example, isopropyl alcohol) 15 to 25%, surfactant and the like (for example, polyoxyethylene sorbitan monolaurate) 1 to 10%, pure water (including glycerin and the like) 60 to 70% It is suitable for the ink to contain a natural pigment at a high concentration.
<< Embodiment 2 >>
<Overview>

The method for producing a natural dye toner of the present application is characterized in that the natural dye is finely powdered. Since the toner produced by the production method of the present embodiment contains a natural pigment at a high concentration, it can be printed clearly while having a fading action.
<Toner component>

Hereinafter, the details of the method for producing the natural dye toner of this embodiment will be described.
(Natural dye toner component)

The main raw materials used in the method for producing the natural dye toner of the present embodiment include “natural dye”, “toner binder”, “wax”, “charge control agent”, and “fluidizing agent”.
The concentration of the toner component is adjusted by adding an appropriate amount of a toner binder or the like.

  Specific examples of “natural pigments” include carotenoid pigments, flavonoid pigments, pteridine pigments, melanin pigments, indole pigments, quinone pigments, porphyrin pigments, and the like. Alternatively, it is also possible to use a mixture of a plurality of these.

  Specific examples of the “toner binder” include a styrene / acrylic copolymer, a polyester resin, and an epoxy resin. Alternatively, it is also possible to use a mixture of a plurality of these.

  Specific examples of the “wax” include carnauba wax, paraffin wax, PE wax, PP wax, solid acid ester wax, and the like. Alternatively, it is also possible to use a mixture of a plurality of these.

  Specific examples of the “charge control agent” include negatively charged CCA such as chromium complex, iron complex, boric acid complex, and zinc complex, nigrosine, triphenylmethane, and quaternary ammonium. An electrostatic type CCA such as a system is mentioned. Alternatively, it is also possible to use a mixture of a plurality of these.

Specific examples of the “fluidizing agent” include fumed silica.
(Production method of natural pigment toner)

FIG. 2 is a diagram illustrating an example of a method for producing the natural pigment toner of the present embodiment. First, in step S0201, natural pigment is pulverized (a pulverization step). In step S0202, a toner containing a finely powdered natural pigment is manufactured (toner manufacturing step). As an example of a specific toner production procedure, it is performed by kneading a finely powdered natural pigment and other materials using an extruder or the like, and pulverizing the mixture obtained by kneading. Condition. The produced toner particles are desirably particles having a diameter of about 5 μm containing a toner binder, a wax, a charge control agent, a surface treatment agent, and the like in addition to the natural pigment.
<< Embodiment 3 >>
<Overview>

  The printing method of the present embodiment is characterized in that the fading speed of the natural pigment is adjusted by adding an oxidation accelerator to the ink containing a high concentration of the natural pigment at the time of printing. According to the printing method, after a desired period has elapsed, the printed description can be made almost colorless and transparent, and the display period of the printed description can be appropriately adjusted.

  As means for adding an oxidation accelerator to ink containing a high concentration of natural pigment during printing, a first ink container for storing ink containing a high concentration of natural pigment and a transparent ink containing an oxidation promoter are stored. It is conceivable that a second ink storage container to be provided is provided in each ink jet printer, and the amount of ejection from each ink storage container is controlled to land on the target correctly.

  The amount of the oxidation accelerator added to the ink containing the natural pigment at a high concentration can be adjusted, for example, by controlling the printer head. Various types of printer heads such as a piezo type and a thermal type are conceivable, but it is preferable to use a piezo type. The printer head is preferably provided with a natural dye and an oxidation accelerator.

  Examples of the “oxidation promoter” to be added include organic peroxides such as benzoyl peroxide (BPO) and azo compounds such as azobisisobutyronitrile (AIBN). When these oxidation promoters are added to natural pigments, the structure of the natural pigments is changed by the active oxygen / free radical reaction, and the natural pigments can be faded in a shorter period of time. Moreover, the oxidation accelerator does not need to be one type, and it is conceivable to use a combination of two or more. For example, by combining benzoyl peroxide (BPO) as the photoinitiator and azobisisobutyronitrile (AIBN) as the thermal initiator, the amount of fading acceleration can be adjusted according to the amount of ultraviolet light and the temperature environment. Is possible.

  The amount of addition of the oxidation accelerator is appropriately adjusted depending on the target fading rate of fading speed and the conditions of the surrounding environment where the printed matter by ink is placed. For example, if you want to increase the fading speed acceleration amount, add a large amount of oxidation accelerator, and it is assumed that the printed matter is placed in an environment with high UV intensity (for example, if the printed matter is placed outdoors). It is conceivable to reduce the addition amount of the oxidation accelerator as compared with an environment where the ultraviolet intensity is weak. These specific addition amounts can be determined based on the results of Example 2 described below.

  It is also conceivable to separately prepare a transparent ink containing an oxidation accelerator and add a predetermined amount of the transparent ink during printing. The transparent ink containing an oxidation accelerator is prepared by, for example, dissolving 0.01 to 5 mg of benzoyl peroxide in 1-2 ml of acetonitrile, 0.5 to 1 ml of ethylene glycol, 0.05 to 0.3 ml of glycerin, and 1 to 2 ml of isopropyl alcohol. It is made by adding 15-30 ml of pure water.

  In addition, an antioxidant may be added to the ink in advance in order to prevent the ink containing a high concentration of natural pigment from fading before printing. As the “antioxidant”, it is conceivable to use an antioxidant such as polyphenol. More specifically, ascorbic acids such as L-ascorbic acid, ascorbic acid esters such as L-ascorbic acid stearate, erythorbic acids such as erythorbic acid and sodium erythorbate, butylhydroxyanisole (BHA), dibutylhydroxytoluene It is conceivable to use (BHT), sulfites such as sodium sulfite, tocopherols such as α-tocopherol, gallic acid, organic acid, sulfur dioxide, chlorogenic acid, catechin, potassium metasulfite and the like. Note that it is not necessary to use one kind of antioxidant, and a plurality of antioxidants may be used in combination. Further, it is conceivable to adjust the amount of addition of an antioxidant or to use a plurality of antioxidants depending on the degree to suppress the fading action of natural pigments. Specifically, it is considered that titanium oxide, zinc oxide, cerium oxide, benzophenone series, benzotriazole series, octyl series, cinnamic acids, paraaminobenzoic acid series, salicylic acid derivatives, and mixtures thereof are used as ultraviolet absorbers. .

Furthermore, it is preferable to use an ink container of an appropriate material and shape or to prepare a storage environment so that the oxidation reaction does not start during storage of the ink. For example, when using a photoinitiator, it is possible to use a material that does not transmit ultraviolet light or the like, and when using a thermal initiator, it may be stored in an environment at a predetermined temperature or lower.
(Specific configuration and processing of inkjet printer)

  It is conceivable that the ink jet printer that realizes the printing method of the present embodiment has a hardware configuration as shown in FIG. 3, for example. In the example of this figure, the printing device includes “CPU” 0301, “RAM” 0302, “ROM” 0303, “first ink cartridge” 0304A, “second ink cartridge” 0304B, and “first cartridge”. From “head” 0305A, “second cartridge head” 0305B, “head drive unit” 0306, “communication equipment” 0307, “communication interface” 0308, “input equipment” 0309, and “input interface” 0310 Composed. These components are connected to each other via a data communication path of “system bus” 0311, and perform transmission / reception and processing of information. The “first ink cartridge” stores ink containing a natural pigment at a high concentration together with an antioxidant. The “second ink cartridge” stores a transparent ink containing an oxidation accelerator.

  As an example of the internal process of the ink jet printer, the process shown in FIG. 4 can be considered as an example. First, in step S0401, a desired display period for print display is received. The desired display period may be received via an input device or a communication device, or may be determined by an internal program.

  Next, in step S0402, a value indicating the average color fading rate of the oxidation accelerator held in the ROM and a value indicating the average color fading rate of the natural dye are stored at predetermined addresses in the RAM. It is conceivable that the average amount of fading speed of the oxidation accelerator and the average fading speed of the natural pigment are stored in a table format in association with the type and the mixing ratio.

  Next, in step S0403, the CPU performs a process of calculating a blending ratio for achieving the desired display period based on the average amount of fading speed of the oxidation accelerator and the average fading speed of the natural pigment.

  Next, in step S0404, the CPU performs a process of controlling the head drive unit so that an appropriate amount is ejected from each ink cartridge to a predetermined location via the ink cartridge head based on the calculated blending ratio.

In addition to the above treatment, it is also possible to detect the amount of ultraviolet rays with a sensor and perform treatment for adjusting the blending ratio of the oxidation accelerator and the natural pigment according to the amount of ultraviolet rays. In addition, it is possible to perform a process of forming a film for removing oxygen and ultraviolet rays on the printing surface. Further, titanium oxide, zinc oxide, cerium oxide, benzophenone series, benzotriazole series, octyl series, cinnamic acids, paraaminobenzoic acid series, salicylic acid derivatives, and mixtures thereof can be added as ultraviolet absorbers.
<Examples of other printing methods>

  The above printing method is a method in which an oxidation accelerator is added at the time of printing to an ink containing a high concentration of natural pigment, but the fade rate of the natural pigment is adjusted by further adding an antioxidant at the time of printing. It is also possible.

  As means for further adding an antioxidant during printing, in addition to the first ink cartridge and the second ink cartridge described above, a third ink cartridge for storing a transparent ink containing an antioxidant is further added to the inkjet printer. It is conceivable to properly land on the target by controlling the ejection amount from each ink cartridge. The amount of the oxidation accelerator and antioxidant added to the natural pigment can be adjusted by controlling the printer head, for example. The ink cartridge head is preferably provided with a natural pigment, an oxidation accelerator, and an antioxidant. When there are a plurality of types of natural pigment-containing inks, it is possible to provide a plurality of ink cartridges and ink cartridge heads corresponding to each type.

  As an internal process of the ink jet printer further including the third ink cartridge, a series of processes shown in FIG. 5 can be considered as an example. First, in step S0501, a desired display period for print display is received. The desired display period may be received via an input device or a communication device, or may be determined by an internal program.

  Next, in step S0502, a value indicating the average amount of fading speed of the oxidation accelerator held in the ROM, a value indicating the average amount of suppression of the fading speed of the antioxidant, and the average color fading speed of the natural dye. Is stored at a predetermined address in the RAM. The average amount of fading speed of the oxidation accelerator, the average amount of suppression of the fading speed of the antioxidant, and the average color fading speed of natural pigments are related to the type and addition amount (including the blending ratio) in a table format. It is possible to keep it.

  In step S0503, the CPU achieves the desired display period based on the average amount of fading speed of the oxidation accelerator, the average amount of fading speed of the antioxidant, and the average color fading speed of the natural pigment. The process which calculates the mixture ratio for doing is performed.

  Next, in step S0504, the CPU performs a process of controlling the head driving unit so as to eject appropriate amounts of an oxidation accelerator, an antioxidant, and a natural dye from each ink cartridge via the ink cartridge head based on the calculated blending ratio. .

In addition to the above treatment, it is also possible to detect the amount of ultraviolet rays with a sensor and perform a treatment for adjusting the blending ratio of the oxidation accelerator, the antioxidant and the natural pigment according to the amount of ultraviolet rays. In addition, it is possible to perform a process of forming a film for removing oxygen and ultraviolet rays on the printing surface.
(Printing method other than printing equipment)

  Here, as a printing method, in addition to a printing method using a printing device, a printing method using a manual sprayer (spray) or the like is also possible. In this case, it is possible to appropriately adjust the addition amount of the oxidation accelerator or antioxidant by adjusting the number of injections of the oxidation accelerator or antioxidant, the injection port diameter of the injector, and the like.

(Method for producing ink cartridge containing ink containing high concentration of astaxanthin)
A method for manufacturing the ink cartridge of this embodiment will be described. First, astaxanthin and nonpolar solvent or hydrophobic solvent are mixed (natural pigment mixing step). Next, isopropyl alcohol is mixed with the solution obtained in the natural dye mixing step (surfactant mixing step). Next, polyoxyethylene sorbitan monolaurate or polyoxyethylene sorbitan monopalmitate is mixed with the solution obtained in the solvent mixing step (fatty acid ester mixing substep). Here, stirring for mixing is performed for about half a day to about a day. Next, chloroform is removed from the solution obtained in the fatty acid ester mixing step using a rotary evaporator (solvent removal step). Next, pure water and glycerin are mixed with the solution obtained in the solvent removal step (pure water mixing step). Here, stirring for mixing is performed for about 1 to 3 hours. Then, the obtained ink is stored in the ink cartridge (storage step).
(Formulation 1 ink)

Table 1 shows an example of the blending amount of the ink of this embodiment (blending 1). The compounding amount of the ink for dividend 1 is 12% of the total amount (ml) of astaxanthin solution (0.1 mg / ml) composed of astaxanthin and chloroform, 20% of isopropyl alcohol, 5% of polyoxyethylene sorbitan monopalmitate, Glycerin was about 10% and pure water was about 53%.
(Formulation 1 landing test)

The ink of Formulation 1 was actually poured into an ink cartridge of an ink jet printer (EPSON PM780C), and a landing test was performed. When ink of Formulation 1 was hit once against inkjet paper, the color difference ΔE from the filter paper was measured with a chromaticity meter (X-Rite 520), and ΔE = 6.9. In addition, ΔE = 10.2 when hit twice (overstrike).
(Formulation 2 ink)

In addition, although the polyoxyethylene sorbitan monopalmitate was used in the ink of the composition 1, the same result can be obtained even with the polyoxyethylene sorbitan monolaurate. The blending amount of the ink of Formulation 2 is 12% of the total amount (ml) of astaxanthin solution (0.1 mg / ml) composed of astaxanthin and chloroform, 20% of isopropyl alcohol, 2% of polyoxyethylene sorbitan monolaurate, Glycerin was about 10% and pure water was about 53%.
(Formulation 2 landing test)

The landing test of the ink of Formulation 2 was performed in the same manner as the landing test of the ink of Formulation 1. When ink of Formulation 2 was hit once on inkjet paper, the color difference ΔE from the filter paper was measured with a chromaticity meter (X-Rite 520), and ΔE = 7.9. In addition, ΔE = 11.9 was obtained when the double strike (multiple strike) was performed.
(Summary)

  From the above, it was found that the astaxanthin-containing ink of this example can contain a higher concentration of astaxanthin than the conventional ink. In addition, it was found that an astaxanthin dye can be landed correctly on the target using an ink jet printer.

<Adjustment of fading speed with transparent ink containing oxidation accelerator>
Using high-concentration astaxanthin ink and an oxidation accelerator-containing transparent ink, it was confirmed whether the astaxanthin fading speed could be controlled.

  As the high-concentration astaxanthin ink, the ink of Formulation 1 of Example 1 was used. In addition, the oxidation accelerator-containing ink is formulated so that isopropyl alcohol, ethylene glycol, glycerin, and pure water are in a volume ratio of about 6: 1: 1: 12, and then benzoyl peroxide is added, and benzoyl peroxide is added. The concentration was adjusted so as to be about 10 mg / ml.

FIG. 6 shows a case where only high-concentration astaxanthin ink is landed by an ink jet printer (EPSON PM780C), a case where 25% of high-concentration astaxanthin ink is ejected, and a case where high-concentration astaxanthin ink is used. FIG. 5 is a diagram showing a color fading change when 50% of the ink is discharged and when 100% of the high-concentration astaxanthin ink is discharged with the oxidation accelerator transparent ink. As can be seen from this figure, it is possible to control the fading speed by controlling the spray amount% of the oxidation accelerator transparent ink.
(Summary)

  From the results of this example, it can be seen that the fading rate is greatly different when only the ink containing a high concentration of astaxanthin is landed and when the ink is landed together with the oxidation accelerator-containing transparent ink. It can also be seen that the fading speed can be controlled by controlling the discharge amount of the oxidation accelerator-containing transparent ink.

<Toner decoloring printing method using natural pigment and toner conversion>

In order to pulverize the carotenoid pigment, the pigment is sufficiently dissolved in a highly soluble solvent such as chloroform. The solvent is preferably an alcohol solvent such as ethanol if it is an indole dye. After dissolution, the dye solution is pulverized to a diameter of 1 μm or less with a Büch nanospray dryer B-90. In addition, it is also possible to use a spray dryer of another company in pulverization.
<Example of blending toner for printer>

The blending amount of the toner using the natural dye of this example is 85% for the toner binder, 10% for the finely powdered dye, 2% for the wax, 2% for the charge control agent, and about 1% for the fluidizing agent. It was made to become. In addition, you may mix each material in what order in the case of a mixing | blending.
<Control of fading speed>

  In order to control the fading speed of the printed matter printed using the toner of the present embodiment, it is conceivable to store the transparent decoloring accelerator-containing toner and the transparent decoloring inhibitor-containing toner in another cartridge. It is also possible to provide a plurality of these cartridges and control the fading speed by a combination of the plurality of cartridges.

(Manufacturing method of ink storage container storing ink containing high concentration of β-carotene)

A method for producing an ink container containing ink containing a high concentration of β-carotene of this example will be described. First, β-carotene and chloroform are mixed (natural pigment mixing step). Next, isopropyl alcohol is mixed with the solution obtained in the natural pigment mixing step (solvent mixing step). Next, polyoxyethylene sorbitan monourate is mixed with the solution obtained in the solvent mixing step (surfactant mixing step). Here, stirring for mixing is performed. Next, chloroform is removed from the solution obtained in the step of mixing the surfactant, etc. using a rotary evaporator (solvent removal step). Next, pure water and glycerin are mixed with the solution obtained in the solvent removal step (pure water mixing step). Here, stirring for mixing is performed for about 1 to 3 hours. Then, the obtained ink is stored in the ink container (storage step).
(Formulation 1 ink)

The blending amount of the ink of Formulation 1 is 12% of the total amount (ml) of β-carotene solution (1.0 mg / ml) composed of β-carotene and chloroform, 30% of isopropyl alcohol, polyoxyethylene sorbitan monourate 10%, glycerin 5%, and pure water 43%.
(Formulation 1 landing test)

The ink of Formulation 1 was actually poured into an ink cartridge of an ink jet printer (EPSON PX-V630), and a landing test was performed. When ink of Formulation 1 was hit once on inkjet paper, the color difference ΔE from the filter paper was measured with a chromaticity meter (X-Rite 520), and ΔE = 4.2. In addition, ΔE = 7.7 when hitting twice. FIG. 7 is a photograph of an inkjet paper that has been tapped twice.
(Inks of Formulations 2 and 3)

The blending amount of the ink of Formulation 2 is 12% of the total amount (ml) of β-carotene solution (1.0 mg / ml) composed of β-carotene and chloroform, 30% of isopropyl alcohol, polyoxyethylene sorbitan monourate 15%, glycerin 2%, and pure water 51%. Further, the blending amount of the ink of Formulation 3 is 12% of the total amount (ml) of β-carotene solution (1.0 mg / ml) composed of β-carotene and chloroform, 30% of isopropyl alcohol, and polyoxyethylene sorbitan mono Urate was 5%, glycerin was 10%, and pure water was about 53%.
(Print test of Formulations 2 and 3)

  When a printing test was actually performed with a thermal head printer (CANON MP500) using inks of Formulations 2 and 3, the discharge rate was low and the density was the same as that of ordinary ink at 5 degrees. When the ink of Formulation 2 was hit 5 times, the color difference ΔE with the filter paper was measured with a chromaticity meter (X-Rite 520), and ΔE = 9.5. Further, when the ink of Formulation 3 was hit five times, ΔE = 3.3.

(Adjustment of fading speed with transparent accelerator-containing transparent ink using a printer)

  The cartridge was actually filled with a β-carotene-containing ink and an oxidation accelerator-containing transparent ink, and it was confirmed that the fading speed could be controlled even with an ink jet printer. As the β-carotene-containing ink, the ink of Formulation 1 of Example 4 was used. The blending amount of the oxidation accelerator-containing transparent ink is 10.5% of the total amount (ml) of benzoyl peroxide (20 mg / ml), 30% of isopropyl alcohol, 5% of glycerin, 5% of ethylene glycol, Pure water was about 43%.

  FIG. 8 shows the fading speed of the β-carotene-containing ink in the dark when the oxidation accelerator-containing transparent ink is overprinted (A) and not (B). FIG. 9 shows the fading speed of the β-carotene-containing ink under fluorescent lamps when the oxidation accelerator-containing transparent ink is overprinted (A) and when it is not performed (B). From these results, it was confirmed that the fading of the β-carotene-containing ink was promoted by the overstrike of the oxidation accelerator-containing transparent ink regardless of the brightness.

  Further, the same experiment was conducted by replacing benzoyl peroxide with hydrogen peroxide. The blending agent for the transparent ink containing the oxidation accelerator was 10% of the total amount of hydrogen peroxide, 30% of isopropyl alcohol, 5% of glycerin, 5% of ethylene glycol, and about 50% of pure water.

  FIG. 10 shows the discoloration rate of the β-carotene-containing ink in the dark when the oxidation accelerator-containing transparent ink is overprinted (A) and when it is not performed (B). Further, FIG. 11 shows the fading speed of the β-carotene-containing ink under the fluorescent lamp when the oxidation accelerator-containing transparent ink is overprinted (A) and when it is not performed (B). From these results, it was confirmed that even when hydrogen peroxide was used instead of benzoyl peroxide, fading of the β-carotene-containing ink was promoted by overstrike of the oxidation accelerator-containing transparent ink.

(Manufacturing method of ink container containing violacein-containing blue ink)

A method for manufacturing an ink container containing the violacein-containing blue ink of this example will be described.
(Bacteria culture)

Violacein-producing bacteria such as Chromobacter violaceum are cultured to extract violacein, a natural blue pigment. First, pre-culture is performed for 1 day under conditions of normal bouillon: 1.8 g, agar: 1.5 g, and pure water: 100 ml. Next, King B medium (pH 7.2 ±) under conditions of polypeptone: 2.0 g, K ₂ HPO ₄ : 0.15 g, MgSO ₄ .7H ₂ O: 0.15 g, glycerin: 1 ml, pure water: 100 ml 0.2) is inoculated with the above-mentioned bacteria and shake-cultured at 25-37 ° C. for 2 days.
(Extraction of violacein)

The cultured bacteria are separated using a centrifuge under the conditions of a rotation speed of 20, a centrifugal force of 8000 × g, and a temperature of 4 ° C. After separation, the supernatant is removed, and 10 ml of ethanol is added to the precipitate, followed by ethanol extraction for 1 day.
(Production of ink by method 1)

Using the culture solution from which violacein has been extracted, ink is produced according to the following procedure (Method 1). Add 1.06 g polyoxyethylene sorbitan monourate to 7.4 ml culture. Stir for 12 to 24 hours. After stirring, add 10 g of glycerin and 10.5 ml of pure water. Stir again for 1 to 3 hours, and filter the resulting solution with a 0.2 μm syringe filter.
(Method 1 ink ejection test)

When the ink manufactured by the method 1 was filled in a cartridge and an ejection test was performed using an ink jet printer (EPSON PX-V630), the nozzle chip was severed and the printing was limited to 50%.
(Manufacture of ink by method 2)

Using the culture solution from which violacein has been extracted, ink is produced according to the following procedure (Method 2).
Add 2 ml ethylene glycol to 18 ml culture. Stir for 1 to 2 hours, and filter with a 0.2 μm syringe filter after stirring.
(Method 2 ink ejection test)

When the ink manufactured by Method 2 was filled into a cartridge and an ejection test was performed using an ink jet printer (EPSON PX-V630), the color difference ΔE when the ink was hit once was measured with a chromaticity meter (X-Rite 520). When measured, ΔE = 4.6. In addition, the color difference ΔE was 5.6 when hitting twice. FIG. 12 is a photograph of a sheet that has been tapped twice.
(Production of ink by method 3)

Using the culture solution from which violacein has been extracted, ink is produced according to the following procedure (Method 3). The culture solution is filtered through a 0.2 μm syringe filter.
(Method 3 ink ejection test)

When the ink manufactured by the method 3 was filled in the cartridge and the ejection test was performed using the ink jet printer (EPSON PX-V630), the ejection was not completed.
(Summary)

  It was confirmed that the ink produced by Method 2 using the culture solution extracted with violacein was normally ejected and landed by an ink jet printer.

(Manufacturing method of ink container containing black ink)

A method for producing black ink by mixing magenta ink, yellow ink, and cyan ink will be described. Specifically, a lycopene dye as a magenta ink, a β-carotene dye as a yellow ink, and a cyan compound in a solvent containing ethanol, ethylene glycol, and chloroform in a volume ratio of about 9: 1: 2.5. A violacein dye is dissolved as an ink so that the volume ratio is about 1: 1: 8.
(Measurement of printing and chromaticity by inkjet printer)

  FIG. 13 is a photograph of a paper on which the produced black ink is landed by an ink jet printer. As shown in FIG. 13, it was confirmed that substantially uniform landing was possible although some nozzle chipping was observed. When the chromaticity of the landing portion was measured with a colorimeter, it was L * 91.0, a * 1.7, b * -5.7, and a color difference ΔE = 3.0 from the paper.

  Ink jet printers generally control ink ejection and flight by adjusting voltage, frequency, and temperature applied to the head. It was confirmed that by using the ink jet printer used in each of the above examples, ink ejection and flight were correctly performed only by adjusting the viscosity based on the blending ratio of the ink. When using UV ink or ink having a higher concentration, it is possible to more accurately adjust ink ejection and flight by adjusting the voltage, frequency, and temperature applied to the head.

0301 ... CPU, 0302 ... RAM, 0303 ... ROM, 0304A ... first ink cartridge, 0304B ... second ink cartridge, 0305A ... first cartridge head, 0305B ... second cartridge head, 0306 ... head drive unit, 0307 ... communication equipment , 0308 ... Communication interface, 0309 ... Input device, 0310 ... Input interface, 0311 ... System bus

Claims (31)

An ink container that stores ink containing a high concentration of natural pigments by adding one or more of surfactants, emulsifiers, dispersants, particle size modifiers, and humectants to natural pigments and their solvents. The ink container according to claim 1, wherein the surfactant is a polyoxyethylene sorbitan fatty acid ester. 3. The ink container according to claim 1, wherein the natural pigment is at least one of a carotenoid pigment, a flavonoid pigment, an anthocyanin pigment, a melanin pigment, and an indole pigment. The ink container according to claim 3, wherein the carotenoid pigment is astaxanthin or β-carotene. The ink container according to claim 3, wherein the indole dye is violacein. Natural pigment mixing step that mixes natural pigment with nonpolar solvent or hydrophobic solvent, solvent mixing step that mixes natural pigment solvent with solution obtained in pigment mixing step, and solution obtained in solvent mixing step To the natural pigment mixing step from the solution obtained in the surfactant mixing step and the surfactant mixing step in which one or more of a surfactant, an emulsifier, a dispersant, a particle size adjusting agent, and a moisturizer are mixed. A solvent removal step that removes the mixed solvent, a pure water mixing step that mixes pure water with the solution obtained in the solvent removal step, and a natural solution that includes pure water mixed in the pure water mixing step. And a storing step of storing ink containing a high concentration of the coloring matter in the ink storage container. The method for manufacturing an ink container according to claim 6, wherein the mixing step of the surfactant or the like includes a fatty acid ester mixing substep in which polyoxyethylene sorbitan fatty acid ester is mixed. The method for producing an ink container according to claim 6 or 7, wherein the natural pigment is at least one of a carotenoid pigment, a flavonoid pigment, an anthocyanin pigment, a melanin pigment, and an indole pigment. The method for producing an ink container according to claim 8, wherein the carotenoid pigment is astaxanthin or β-carotene. The method for producing an ink container according to claim 8, wherein the indole dye is violacein. The method for producing an ink container according to any one of claims 6 to 10, wherein the solvent of the natural pigment contains a polar solvent or a hydrophilic solvent. A printing apparatus equipped with the ink container according to claim 1. A printing method for adjusting a fading speed of a natural pigment by adding an oxidation accelerator or an oxidation inhibitor to the ink ejected from the ink container according to any one of claims 1 to 5 at the time of printing. The ink storage container according to any one of claims 6 to 11, wherein the storing step includes a recycle storage sub-step of opening a part of the ink storage container in which the stored ink is empty and storing the ink again. Manufacturing method. A method for producing a natural dye toner, comprising: a fine powdering step for finely powdering a natural dye; and a toner manufacturing step for producing a toner containing the finely powdered natural dye. The natural pigment is at least one of a carotenoid pigment, a flavonoid pigment, an anthocyanin pigment, a melanin pigment, an indole pigment, a pteridine pigment, a quinone pigment, and a porphyrin pigment. Method for producing natural dye toner. The method according to claim 16, wherein the carotenoid pigment is astaxanthin or β-carotene. The method for producing a natural dye toner according to claim 16, wherein the indole dye is violacein. The method for producing a natural dye toner according to any one of claims 15 to 18, wherein the fine powdering step includes a first dissolution sub-step of dissolving a natural dye in chloroform. The method for producing a natural dye toner according to any one of claims 15 to 19, wherein the fine powdering step includes a second dissolution sub-step of dissolving the natural dye in an alcohol solvent. The method for producing a natural dye toner according to any one of claims 15 to 18, wherein the toner production step includes a wax blending sub-step of blending a wax with a fine powder natural pigment. The method for producing a natural pigment toner according to claim 21, wherein the wax is at least one of carnauba wax, paraffin wax, PE wax, PP wax, and solid acid ester wax. The method for producing a natural dye toner according to any one of claims 15 to 18, wherein the toner production step includes a charge control agent blending sub-step of blending a charge control agent with a finely powdered natural dye. 24. The charge control agent according to claim 23, wherein the charge control agent is any one or more of chromium complex, iron complex, boric acid complex, zinc complex, nigrosine, triphenylmethane, and quaternary ammonium. Method for producing natural dye toner. The method for producing a natural dye toner according to any one of claims 15 to 18, wherein the toner production step includes a fluidizing agent blending sub-step of blending a fluidizing agent with a finely powdered natural pigment. The method for producing a natural dye toner according to any one of claims 15 to 25, further comprising an oxidation inhibitor blending step of blending an oxidation accelerator. 27. The method for producing a natural dye toner according to claim 15, further comprising an oxidation accelerator blending step of blending an oxidation inhibitor. A toner storage container storing a natural pigment toner produced by the method according to any one of claims 15 to 27. A printing apparatus comprising the toner container according to claim 28. 30. The printing apparatus according to claim 29, further comprising an oxidation accelerator storage container storing an oxidation accelerator. 30. The printing apparatus according to claim 29, further comprising an oxidation inhibitor storage container storing an oxidation inhibitor.