WO2001062861A1 - Encre et cartouche pour impression jet d'encre - Google Patents

Encre et cartouche pour impression jet d'encre Download PDF

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Publication number
WO2001062861A1
WO2001062861A1 PCT/JP2000/001056 JP0001056W WO0162861A1 WO 2001062861 A1 WO2001062861 A1 WO 2001062861A1 JP 0001056 W JP0001056 W JP 0001056W WO 0162861 A1 WO0162861 A1 WO 0162861A1
Authority
WO
WIPO (PCT)
Prior art keywords
ink
jet recording
ink jet
water
repellent film
Prior art date
Application number
PCT/JP2000/001056
Other languages
English (en)
Japanese (ja)
Inventor
Shino Tokuyo
Mitsuo Ozaki
Shigeharu Suzuki
Original Assignee
Fujitsu Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujitsu Limited filed Critical Fujitsu Limited
Priority to PCT/JP2000/001056 priority Critical patent/WO2001062861A1/fr
Publication of WO2001062861A1 publication Critical patent/WO2001062861A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1606—Coating the nozzle area or the ink chamber

Definitions

  • the present invention relates to an ink for ink jet recording, and more particularly to an ink for ink jet recording, which has an excellent erosion suppressing effect on an acid generated from a coloring material in the ink and which can be stably supplied from a nozzle hole of the ink head for a long time.
  • an ink for ink jet recording which has an excellent erosion suppressing effect on an acid generated from a coloring material in the ink and which can be stably supplied from a nozzle hole of the ink head for a long time.
  • a water-soluble coloring material (hereinafter referred to as a dye) has been generally used as an ink for ink jet recording. These dyes are dissolved in water, and if necessary, various additives are added thereto before use as ink for ink jet recording.
  • additives to the ink include polyhydric alcohols, their dalicol ethers, and surfactants. These additives prevent ink clogging, ink bleeding on the recording medium after printing, or lead in color images (color mixing or bleeding in areas where different color areas contact each other). The image quality is reduced to achieve higher image quality.
  • inkjet inks in which polyester fine resin particles colored with dyes or pigments are finely dispersed in an aqueous medium in order to improve image quality and improve water resistance and light resistance, which are drawbacks of water-soluble dye inks.
  • Japanese Patent Application Laid-Open No. 7-97540 Japanese Patent Application Laid-Open No. 7-97540
  • the method for producing the aqueous dispersion of the polyester fine resin particles is described in detail, for example, in Japanese Patent Application Laid-Open No. HEI 4-296632.
  • Japanese Patent Application Laid-Open No. 7-196665 discloses a method of manufacturing an ink jet recording ink related thereto. It has been disclosed.
  • a fine nozzle hole for discharging ink is formed in a head of an ink jet recording apparatus using the above-described ink.
  • This nozzle hole is, for example, a stainless steel (SUS) nozzle plate provided with an opening having a diameter of about several tens / m.
  • SUS stainless steel
  • a water-repellent film is provided on the nozzle plate to protect the nozzle portion in contact with the ink and to stabilize the shape of the ejected ink droplet.
  • the water-repellent film is formed, for example, by coating a fluoropolymer or by eutectoid nickel monofluoride. In general, from the viewpoint of long-term stability, the latter, eutectoid nickel nickel fluoropolymer, is often used.
  • the color ink which is generally controlled so that its permeability is improved, tends to spread on the nozzle surface of the ink head, and the ink tends to wet and adhere to the nozzle surface for a long period of time.
  • the ink may erode the water-repellent film at the adhering portion. When such erosion occurs around the nozzle hole, the coloring material in the ink adheres and solidifies, changing the shape and surface condition of the hole. For this reason, conditions for ejecting ink droplets change, and there has been a problem that long-term ejection stability cannot be maintained.
  • the ink in which the dyed fine resin particles are dispersed undergoes long-term storage or storage at high temperatures, causing the resin that is the base material of the coloring material to be hydrated, oxidizing the ink, and water-repellent around the nozzle. There is a problem that the film is eroded.
  • an erosion inhibitor hereinafter referred to as an antioxidant
  • an antioxidant an erosion inhibitor
  • Some of these inhibitors include benzotriazole.
  • Japanese Patent Application Laid-Open No. Hei 7-222880 There is a disclosure regarding ink jet recording inks containing benzotriazole. However, this ink contains a special component, and benzotriazole is used to suppress the inconvenience caused by adding this component.Only the amount added to the ink composition containing the special component is determined. Stipulates. This has no effect on any colorant and cannot guarantee long-term effects.
  • the present inventors conducted various experiments on erosion of the metal-based water-repellent film provided in the ink nozzle portion in order to solve the above-mentioned problem. As a result, the present inventors have found suitable use conditions for the anti-oxidant contained in the ink for ink jet recording, and have reached the present invention. Disclosure of the invention
  • a water-repellent film can be prevented from being eroded by an acid by an appropriate amount of a water-proofing agent, and an excess water-proofing agent is added. Absent. Therefore, it can be provided as an ink for ink jet recording which has excellent printing quality and guarantees ejection stability.
  • the concentration of the coloring material in the ink is A% by weight and the number of the groups is B
  • the concentration of the protective agent is from (AXB) Z600 to (AXB). ) / 10% by weight.
  • AXB a preferable ink jet recording ink is obtained.
  • Yo more preferable range is Z 2 0 Weight 0/0 (AXB) from (AXB) Z 1 6 0. Further, the present inventors have studied the type of ink in which the dyed fine resin particles are dispersed, and have found preferable conditions.
  • At least water which contains a coloring material having a property of generating an acid with the passage of time and an antioxidant, and is used by being ejected from a nozzle hole in which a metal-based water-repellent film is formed and used for ink jet recording
  • the ink
  • an ink for ink jet recording wherein the coloring material contains in advance an antibacterial agent corresponding to the concentration of an acid generated during a maximum device life period.
  • the antioxidant is added in consideration of an acid that may be generated in the future. Therefore, even if the ink contains a coloring material having a property of increasing the amount of acid over time, it is possible to prevent the water-repellent film from being eroded by acid in the future. Therefore, it can be provided as an ink for inkjet recording which has excellent printing quality and guarantees ejection stability.
  • the maximum device lifetime corresponds to the expiration date of the ink cartridge or the like that stores ink.
  • the coloring material having a property of generating an acid by changing over time can be constituted as colored fine resin particles, and a polyester resin can be used as the resin.
  • a polyester resin can be used as the resin.
  • unsaturated polyester resins, alkyd resins, atalinole resins, and the like can also be used as the resins that can be similarly used.
  • Benzotriazole can be used as a protective agent for the two types of ink jet recording inks.
  • derivatives such as triazole and benzotriazole carboxylic acid, and organic inhibitors such as erythritol and ethylaniline can also be used as the protective agent.
  • Still another object of the present invention is to provide an ink cartridge having the above-described ink for ink jet recording.
  • the ink cartridge using the ink jet recording ink having the excellent erosion control effect as described above, Attached to the head of the printer device, it enables excellent image formation over a long period of time.
  • Still another object of the present invention includes providing an ink jet recording head including the above-described ink cartridge and having a metal water-repellent film formed on a nozzle portion. Such a head can prevent erosion of the nozzle portion for a long period of time, and can be provided as a component of an ink jet recording apparatus having excellent printing quality and stable ejection.
  • the water-repellent film of the inkjet recording head is preferably pre-treated with a gas-proofing agent solution. By performing this pretreatment, the amount of the protective agent contained in the ink side can be suppressed to a low level.
  • a benzotriazole solution can be used as the pretreatment antioxidant.
  • the water repellent film of the ink jet recording head may be made of eutectoid nickel monofluoride polymer.
  • Still another object of the present invention includes providing an inkjet recording apparatus having an inkjet recording head. Since the ink jet recording head maintains the ink jet recording head in a good state for a long period of time, it can be used as a printer having excellent image forming properties.
  • FIG. 1 is a perspective view showing a schematic configuration of an ink cartridge using the ink for ink jet recording of the embodiment and an ink jet recording head equipped with the ink cartridge.
  • Fig. 2 is a diagram showing the ink jet recording head from the nozzle plate (plate) side.
  • FIG. 3 is a diagram showing an overall outline of an ink jet recording apparatus equipped with the ink jet recording head shown in FIG. BEST MODE FOR CARRYING OUT THE INVENTION
  • the ink jet recording ink of the present invention will be specifically described below.
  • the first ink shown in the first embodiment contains a water-soluble dye.
  • water-soluble dyes often have an acidic functional group at the terminal group of the molecular structure.
  • the counter cation eg, sodium Is dissociated. Therefore, it is considered that the acidic functional group adheres to the water-repellent film and erodes.
  • the present inventors have examined this point, and have confirmed that the number of acid functional groups in the above dye molecules and the dye concentration in the ink can determine an appropriate amount of the antioxidant to be added to the ink. .
  • the second ink shown in the second embodiment uses colored fine resin particles as a coloring material.
  • This ink for ink jet recording has a tendency to generate acid with the passage of time, but the nozzle portion is eroded by a simple method of adding an antioxidant in advance in anticipation of the amount of acid generated in the future.
  • a general dye can be used.
  • a direct dye, an acidic dye, a reactive dye, or the like can be used.
  • the amount of these additives is determined by the type of dye, solvent component, and required characteristics, but is preferably added in the range of 0.2 to 7% by weight based on the total weight of the ink.
  • alcohols eg, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol / ray, hexylene glycol, polyethylene glycol, etc.
  • a highly hygroscopic additive such as a nitrogen-containing organic solvent (eg, N-methyl-2-pyrrolidone, triethanolamine, etc.) or urea.
  • the amount of these additives is preferably 4 to 30% by weight.
  • glycol ethers of polyhydric alcohols for example, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.
  • Etc. glycol ethers of polyhydric alcohols
  • the amount of these additives is preferably 3 to 20% by weight.
  • a surfactant nonionic, anionic, cationic
  • a known viscosity adjuster, an organic solvent such as an alkyl alcohol having 1 to 4 carbon atoms, an H adjuster, a force-proofing agent and the like may be added.
  • ink jet recording inks having the following compositions were used. (1 yellow, 2 magenta, 3 cyan, 4 black) were prepared. Benzotriazole was used as an anti-oxidant in the ink jet recording ink. For each of the four inks, the concentration of benzotriazole was 1) 0.01% by weight, 2) 0.05% by weight, 3) 0.1% by weight, 4) 0.5% by weight, 5). Seven types were prepared, 1% by weight, 6) 2% by weight, and 7) 5% by weight. The erosion state of the metallic hydrophobic water-repellent film formed at the nozzle was confirmed by changing the concentration of benzotriazole in each ink.
  • the erosion test with the ink was performed by immersing the nozzle plate in the ink. In order to shorten the test period, it was stored at 60 ° C for 3 months. After pulling up the nozzle plate from the dipping ink, the ink was dropped on the water-repellent film remaining on the nozzle plate, and the contact angle was measured.
  • the above storage conditions assume that normal storage is performed and about three years. This is because the expiration date of ink is usually set to about three years.
  • the contact angle was measured using a static contact angle meter (Kyowa Interface Science Co., Ltd.) and the value after 30 seconds was used as data.
  • the contact angle of the ink before storage was also measured, and the judgment was made based on the angle difference obtained by subtracting the contact angle after storage obtained after storage from the contact angle before storage.
  • the smaller the angle difference the higher the effect of suppressing erosion. Judgment was made according to the following evaluation criteria.
  • the above C.I. Acid Yellow 23 has a molecular structure 1 as shown below. Fees. Dissociated cation (Na) is in the ink solution, based on S0 3 and COO showing acidity appears at the end. In this molecular structure, the number of acidic groups is three.
  • Nonionic surfactant 1 is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • the CI director 46 is a dye having the following molecular structural formula 2. Dissociated cation (Na) is in the ink solution, it appears to S0 3 groups terminated exhibiting acidity. In this molecular structure, the number of acidic groups is four.
  • the CI Acid Blue 19 is a dye having the following molecular structural formula 3.
  • the cation (Na) is dissociated in the ink water, and the acidic S ⁇ 3 group appears on the 3 ⁇ 4. In this molecular structure, the number of acidic groups is two.
  • Direct Black 154 is a dye having the following molecular structural formula 4. Dissociated cation (Na) is in the ink solution, it appears to S0 3 groups terminated exhibiting acidity. In this molecular structure, the number of acidic groups is two.
  • the above-mentioned ink is supplied from the nozzle holes formed in the nozzle plate of the ink head It is discharged from.
  • a SUS plate having a thickness of about 80 ⁇ was used as a nozzle plate, and a nozzle hole was provided in the SUS plate.
  • This nozzle plate was subjected to eutectoid plating of nickel-polytetrafluoroethylene. Table 1 below summarizes the evaluation. Table 1: Evaluation results of each ink
  • the present inventors examined this result and confirmed that the number of acidic functional groups in the dye molecule (the dye concentration in the dye can be used to determine an appropriate amount of the protective agent to be added to the ink.
  • the product of the dye concentration (% by weight) ⁇ and the number of acidic functional groups (the number of groups exhibiting acidity) B is shown in Table 2 below: Table 2: AXB of each ink
  • dyed fine resin particles are used as a coloring material. It is preferable to use polyester resin particles that can be easily dyed as the fine resin particles. Oil-soluble dyes, disperse dyes and the like can be used as coloring materials for dyeing polyester resin particles.
  • the dye concentration in the polyester resin is preferably 2% by weight or more.
  • the amount of the resin particles added to the ink is preferably 20% by weight or less in order to maintain the stability of the ink itself.
  • the ink jet recording ink two types (yellow and magenta) having the following compositions were prepared as the ink jet recording ink.
  • Benzotriazole was used as a fire retardant in this ink jet recording ink.
  • the concentration of benzotriazole was 1) 0.01% by weight, 2) 0.05% by weight, 3) 0.1% by weight, 4) 0.5% by weight for each of the two types of ink. %, 5) 1% by weight, 6) 2% by weight, 7) 5% by weight.
  • the erosion state of the metallic hydrophobic water-repellent film formed at the nozzle was confirmed by changing the concentration of benzotriazole for each ink.
  • the erosion test using an ink was the same as that in the first example, and the above-mentioned nozzle plate was immersed in ink. In order to shorten the test period, they were stored for 3 months in an atmosphere of 60 ° C, and the contact angle of the water-repellent film at the nozzle was measured.
  • the polyester grease when immersed in water, it is hydrolyzed with time to generate an acid. Since this acid erodes the water-repellent film, a protective agent capable of resisting the total amount of generated acid is added.
  • Nonionic surfactant 1 5 wt% of glycerin 1 2 weight 0 /.
  • Polyester particles colored with C.I.D isp e r se re d 92
  • the present inventors have found that in the case of the polyester resin-dispersed aqueous ink of this example, the acid increases with the passage of time, and that benzotriazole, which is necessary in advance for the acid generated sequentially, is considered It was confirmed that erosion of the water-repellent film can be effectively prevented by adding an excess in the ink.
  • the test conditions of this embodiment are based on the expiration date of the ink, that is, the maximum device life period usually set to about three years. It is assumed. Therefore, if the amount of benzotriazole that prevents erosion of the water-repellent film in the erosion test of the present embodiment is added to the ink in advance, the ink for ink jet recording can suppress erosion.
  • the addition of an excess of the protective agent causes generation of a protective film around the nozzle.
  • the protective agent is consumed over time and functions. Further, even if the amount of the protective agent to be initially added is not affected, film formation does not pose a problem.
  • yellow ink can be stored in a yellow ink cartridge 18 and traded. Then, as shown in FIG. 1B, the ink jet recording head 10 is mounted.
  • the ink jet recording head 1 in Fig. (B) is for color, and the cartridges of the yellow ink cartridge 18, the magenta ink cartridge 19, the cyan ink cartridge 20, and the black ink cartridge 21 are installed. Is shown.
  • the ink cartridges 18, 19, 20 and 21 are mounted on an ink jet recording type printer to enable excellent image formation over a long period of time.
  • An ink-jet head using such an ink cartridge can prevent erosion of the nozzle portion for a long period of time, and can be provided as a component for a printer device having excellent printing quality and stable ejection.
  • FIG. 2 shows a nozzle plate 20 which is disposed below the ink jet recording head 10 of FIG. 1 (B) and is not shown in the drawing, and a plurality of nozzle holes 21 formed in the nozzle plate 20.
  • the nozzle plate 20 is, for example, a SUS plate, and on its surface, a water-repellent film is formed by eutectoid nickel monofluoride polymer.
  • the ink jet recording apparatus 30 equipped with the above-mentioned ink jet recording head 10 maintains the ink jet recording head in a good state for a long period of time. It can be an excellent printer device.
  • a pretreatment is performed on the water-repellent film formed on the nozzle side.
  • An example will be described in which the amount of the protective agent added is suppressed by this.
  • the water-repellent film formed on the nozzle plate was subjected to a pretreatment with an antioxidant solution.
  • an antioxidant solution A benzotriazole was also used as the antioxidant here, and the pretreatment was performed as follows.
  • a benzotriazole solution is prepared.
  • the solvent to be used may be water, but it is preferable that the benzotriazole solution is easily wetted by the water-repellent film (the contact angle of the benzotriazole solution to the water-repellent film: preferably 90 ° or less). Therefore, any of ethanol, glycols and glycol ethers, or a mixture thereof is used. Dissolve 0.1 to 2% by weight of benzotriazole in this solvent.
  • the nozzle plate provided with the water-repellent film is immersed in this solution and left for several minutes to several hours. Pull out the nozzle plate from the solution and let it dry. At this time, rapid drying with warm air is preferred.
  • the concentration of benzotriazole in the ink is lower than that in the above embodiment, the erosion prevention of the water-repellent film can be maintained.
  • the water-repellent film is eroded by the acid because it contains an appropriate amount of a protective agent. Can be prevented, and no extra protective agent is added. Therefore, it can be provided as an ink for inkjet recording which has excellent printing quality and guarantees ejection stability.
  • an antioxidant is added in consideration of an acid which may be generated in the future. Therefore, even if the ink contains a coloring material having a property of increasing the amount of acid with time, it is possible to prevent the water-repellent film from being eroded by acid in the future. Therefore, it can be provided as an ink for ink jet recording which has excellent print quality and guarantees ejection stability.
  • the ink cartridge using the ink jet recording ink having the excellent erosion suppressing effect as described above is mounted on a printer device and enables excellent image formation for a long period of time.
  • an ink head that uses the ink jet recording ink that exhibits the excellent anticorrosion effect described above can prevent corrosion of the nozzles for a long period of time, and is provided as an ink jet recording head that has excellent print quality and ejection stability. it can.
  • the ink jet recording apparatus having the above-mentioned ink jet recording head can maintain a good state of the ink jet recording head for a long period of time, so that it can be used as a printer apparatus having excellent image forming properties.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention concerne une encre pour impression jet d'encre comprenant de l'eau, un colorant et un antirouille. Cette encre et prévue pour être projetée par une buse dont la surface est pourvue d'un film hydrophobe contenant un métal. La teneur en antirouille est fonction du nombre de groupes du colorant susceptibles de libérer un contre cation susceptible d'acidité. Cette encre peut s'utiliser pour empêcher l'érosion d'un film hydrophobe formé sur la tête d'impression jet d'encre.
PCT/JP2000/001056 2000-02-24 2000-02-24 Encre et cartouche pour impression jet d'encre WO2001062861A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2000/001056 WO2001062861A1 (fr) 2000-02-24 2000-02-24 Encre et cartouche pour impression jet d'encre

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2000/001056 WO2001062861A1 (fr) 2000-02-24 2000-02-24 Encre et cartouche pour impression jet d'encre

Publications (1)

Publication Number Publication Date
WO2001062861A1 true WO2001062861A1 (fr) 2001-08-30

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PCT/JP2000/001056 WO2001062861A1 (fr) 2000-02-24 2000-02-24 Encre et cartouche pour impression jet d'encre

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0797540A (ja) * 1993-09-29 1995-04-11 Toyobo Co Ltd インクジェットプリンタ用インク
JPH07228808A (ja) * 1994-02-22 1995-08-29 Seiko Epson Corp インクジェット記録用インクおよびインクジェット記録方法
EP0859037A1 (fr) * 1997-02-17 1998-08-19 Seiko Epson Corporation Encre et appareil d'enregistrement par jet
JPH1191090A (ja) * 1997-09-24 1999-04-06 Ricoh Co Ltd インクジェット記録方法及びインクジェット記録用インク

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0797540A (ja) * 1993-09-29 1995-04-11 Toyobo Co Ltd インクジェットプリンタ用インク
JPH07228808A (ja) * 1994-02-22 1995-08-29 Seiko Epson Corp インクジェット記録用インクおよびインクジェット記録方法
EP0859037A1 (fr) * 1997-02-17 1998-08-19 Seiko Epson Corporation Encre et appareil d'enregistrement par jet
JPH1191090A (ja) * 1997-09-24 1999-04-06 Ricoh Co Ltd インクジェット記録方法及びインクジェット記録用インク

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