WO2005030885A1 - インク組成物、インクジェット記録方法及び記録物 - Google Patents
インク組成物、インクジェット記録方法及び記録物 Download PDFInfo
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- WO2005030885A1 WO2005030885A1 PCT/JP2004/014189 JP2004014189W WO2005030885A1 WO 2005030885 A1 WO2005030885 A1 WO 2005030885A1 JP 2004014189 W JP2004014189 W JP 2004014189W WO 2005030885 A1 WO2005030885 A1 WO 2005030885A1
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- ink composition
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- dye
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Classifications
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- 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
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
Definitions
- the present invention relates to an ink composition capable of improving the storage stability (gas resistance) of an image to be produced, and more particularly, to a metal phthalocyanine capable of effectively preventing discoloration and fading of an image.
- the present invention relates to an ink composition containing a cyan dye.
- an ink composition using a metal phthalocyanine-based cyan dye has been widely used as an ink composition for forming an image of an excellent cyan color or the like. Also recently, an ink composition using a metal phthalocyanine-based cyan dye has been widely used as an ink composition for forming an image of an excellent cyan color or the like. Also recently, an ink composition using a metal phthalocyanine-based cyan dye has been widely used as an ink composition for forming an image of an excellent cyan color or the like. Also recently, an ink composition using a metal phthalocyanine-based cyan dye has been widely used as an ink composition for forming an image of an excellent cyan color or the like. Also recently, an ink composition using a metal phthalocyanine-based cyan dye has been widely used as an ink composition for forming an image of an excellent cyan color or the like. Also recently, an ink composition using a metal phthalocyanine-based cyan dye has been widely used as an ink composition for
- An image is formed by using an ink composition for forming such an image together with one or more ink compositions for forming another color to form an image, and the resulting multicolor image (color one). It is common to post images) indoors.
- the metal phthalocyanine cyan dye has resistance to an oxidizing gas such as ozone, nitrogen oxide, and sulfur oxide present in the air.
- an oxidizing gas such as ozone, nitrogen oxide, and sulfur oxide present in the air.
- the image formed from the cyan dye causes discoloration at an early stage. There was a problem.
- WO99Z50363 discloses a cyan ink composition comprising a copper phthalocyanine cyan dye, an imidazole derivative, an antioxidant, a sugar, and a naphthalene 1-sulfonic acid having a hydroxyl group or an amino group at the 4-position. It is disclosed as a means for improving the performance (Patent Document 1).
- Patent Document 1 WO99Z50363
- an object of the present invention is to provide an ink composition that can improve the room preservability (gas resistance) of an image formed using an ink composition using a metal phthalocyanine cyan dye. .
- the inventors of the present invention have conducted intensive studies and have found that an ink composition containing a metal phthalocyanine-based cyan dye and a specific component can achieve the above object.
- the present invention has been made based on the above-described findings, and "1" includes at least water, a metal phthalocyanine-based cyan dye, and a sulfo represented by the following general formulas (1) and Z or (2). It is intended to provide an ink composition comprising an aromatic compound having a group and Z or a salt thereof.
- M 1 represents a counter ion constituting a salt
- X represents an integer of 1 to 3
- R 1 and R 2 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or
- M 2 represents a counter ion constituting a salt
- Y represents an integer of 1 to 4
- R 3 and R 4 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or
- the present invention provides the ink composition according to "1", which is "2" a metal phthalocyanine-based cyan dye which is a copper phthalocyanine-based dye represented by the following formula (3). :
- R 1 represents H, an alkali metal or mono-NH 4
- R 2 represents an alkali metal or mono-NH 4
- R 3 represents H, an optionally substituted alkyl group or substituted Represents a good group.
- Ink composition. “5"
- the metal phthalocyanine cyan dye is a dye having an absorption spectrum in a visible region (400 to 800 nm) having a maximum absorption peak at a wavelength of 590 to 615 nm.
- the metal phthalocyanine-based cyan dye has a visible range (400-8 The ink composition according to any one of “1” to “5", which is a dye having an absorption spectrum at OO nm) at a wavelength of 590 to 605 nm. : “7” The ink composition according to any one of “1” to “6”, wherein the aromatic compound having a sulfo group and Z or a salt thereof have two or more sulfo groups.
- An ink cartridge comprising at least the ink composition according to any one of “20”, “1” and “19”.
- An ink-jet recording method comprising using the ink composition according to any one of the preceding claims. : Write in either "22", “1” or "19” A recorded matter, wherein the recorded matter is recorded using the ink composition described above. : Are provided respectively.
- FIG. 1 is a view showing a spectral characteristic (absorption wavelength) of a dye (C.I. Direct Blue 199) (* 1) contained in a desirable ink composition of the first embodiment according to the present invention.
- a dye C.I. Direct Blue 199
- FIG. 2 is a view showing a spectral characteristic (absorption wavelength) of a dye (C.I. Direct Blue 86) (* 4) contained in a desirable ink composition of the second embodiment according to the present invention.
- a dye C.I. Direct Blue 86
- the ink composition of the present invention has at least water, a metal phthalocyanine-based cyan dye, and a sulfo group represented by the general formula (1) and Z or (2). It is characterized by comprising an aromatic compound and Z or a salt thereof.
- the ink composition of the present invention also has a strong constituent power, it is possible to effectively prevent early fading of a cyan image, and furthermore, to store an image produced thereby in a room. (Gas resistance) can be improved.
- the ink composition of the present invention comprises, in water or an aqueous medium comprising water and a water-soluble organic solvent, at least a metal phthalocyanine-based cyan dye and the above-mentioned general formula (1) and Z or (2). It contains the aromatic compound having a sulfo group represented and Z or a salt thereof, and may contain a humectant, a viscosity adjuster, a pH adjuster, and other additives as necessary.
- the cyan dye used in the ink composition of the present invention is not particularly limited as long as it is a metal phthalocyanine cyan dye.
- Examples of the copper phthalocyanine-based dye include a dye represented by the above formula (3).
- These dyes can be used alone or in combination. Can be used in combination with other dyes.
- the metal phthalocyanine cyan dye a dye having an absorption peak in the visible region (400 to 800 nm) having an absorption peak at 590 to 650 nm, particularly 590 to 615 nm, particularly 590 to 605 nm is used. Is preferred in terms of improving the ability to withstand ozone.
- the content of the metal phthalocyanine cyan dye is preferably 0.1 to 10% by weight, more preferably 0.1 to 10% by weight, based on the total weight of the ink composition, which is appropriately determined depending on the type of the dye, the type of the solvent component, and the like. Is in the range of 0.5-5% by weight. By setting the content to 0.1% by weight or more, color development or image density on a recording medium can be secured. And other characteristics can be easily secured.
- the metal phthalocyanine-based cyan dye has gas resistance, particularly
- the aromatic compound having a sulfo group represented by the general formula (1) and Z or (2) and Z or a salt thereof are used. Contains at least one.
- the present invention provides a method of using the aromatic compound having a sulfo group represented by the general formulas (1) and Z or (2) and Z or a salt thereof in combination with a metal phthalocyanine cyan dye. Green discoloration due to NOx gas Discoloration and discoloration of images due to ozone gas that does not cause black discoloration are suppressed, and the fading resistance of images is dramatically improved.
- a cyan ink composition containing water, the metal phthalocyanine-based cyan dye, and at least one aromatic compound having a sulfo group or a salt thereof is used.
- an ink composition having a color different from cyan such as a black ink composition, it is possible to effectively prevent discoloration seen in solid printing.
- These various ink compositions can be used in combination with other conventionally known dyes.
- an aromatic compound having at least one sulfo group in a molecular structure or an aromatic compound having the same Any salt may be used as long as it has two or more sulfo groups, in particular, 1,3-benzenedisulfonic acid, naphthalene 1,5-disulfonic acid, naphthalene 1,6 disulfonic acid, naphthalene 2,6 —At least one selected from the group consisting of disulfonic acid, naphthalene 2,7 disulfonic acid, naphthalene 1,3,6 trisulfonic acid, and a salt thereof is preferable from the viewpoint of improving the ozone resistance of the obtained image. .
- the salt of the aromatic compound having a sulfo group may be added in the form of a salt, and may be contained in the ink composition. It may be separately added and contained in the ink composition.
- Such salts are not particularly limited to the constituent counterions, and include, for example, a metal salt, an ammonium salt, and the like. Particularly, alkali metal salts are preferred. Specifically, sodium salts, lithium salts, And potassium salts.
- the content of the aromatic compound having a sulfo group and Z or a salt thereof is appropriately determined according to the type of the aromatic compound having a sulfo group and Z or a salt thereof, the type of a dye, the type of a solvent component, and the like.
- the force to be applied is preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, based on the total weight of the ink composition.
- the content ratio of the metal phthalocyanine cyan dye to the aromatic compound having a sulfo group and Z or a salt thereof effectively improves gas resistance and From the viewpoint of ensuring the reliability of the ink, the ratio is preferably in the range of 1: 0.1 to 1:10, and particularly preferably in the range of 1: 0.2 to 1: 5.
- the pH (20 ° C) of the ink composition In order to stably dissolve the predetermined dye and the amount of the aromatic compound having a sulfo group and Z or a salt thereof, the pH (20 ° C) of the ink composition must be 8.0 or more. I like it. In consideration of the material resistance to various members that come into contact with the ink composition, the pH of the ink composition is preferably 10.5 or less. In order to better balance these matters, it is preferable to adjust the pH of the ink thread to 8.0-10.5, especially 8.5-10.0.
- the ink composition of the present invention can further contain a water-soluble organic solvent having a vapor pressure lower than that of pure water, and a humectant selected from Z and saccharides.
- a humectant By including a humectant, evaporation of water can be suppressed in an ink jet recording system. Ink can be moisturized. In addition, with a water-soluble organic solvent, the viscosity can be easily changed without improving the ejection stability or changing the ink characteristics.
- the water-soluble organic solvent refers to a medium capable of dissolving a solute, and a water-soluble solvent having an organic vapor pressure lower than water is also selected.
- Polyethylene alcohols such as triethylene glycol and dipropylene glycol, ketones such as acetonyl acetone, esters such as ⁇ -butyrolataton and triethyl phosphate, furfuryl alcohol, tetrahydrofurfuryl alcohol, thiodiglycol and the like. Is desirable.
- saccharide maltitol, sorbitol, dalconolatatone, maltose and the like are preferable.
- the humectant is added in an amount of preferably 5 to 50% by weight, more preferably 5 to 30% by weight, and still more preferably 5 to 20% by weight based on the total amount of the ink composition. If it is 5% by weight or more, moisture retention can be obtained, and if it is 50% by weight or less, it is easy to adjust the viscosity to be used for ink jet recording.
- the ink composition of the present invention preferably contains a nitrogen-containing organic solvent as a solvent.
- the nitrogen-containing organic solvent include 1,3 dimethyl-2 imidazolidinone, 2-piperidone, ⁇ -methyl-2-pyrrolidone, ⁇ -force prolatatam and the like.
- 2-pyrrolidone is preferably used. Can be done. They tend to be used alone or in combination of two or more.
- the content is preferably 0.5-10% by weight, more preferably 115% by weight.
- the solubility of the coloring material of the present invention can be improved by adding the content, and when the content is 10% by weight or less, the ink composition comes into contact with the colorant. It does not deteriorate the material resistance with various members.
- the ink composition of the present invention is used as an additive which is effective in obtaining quick fixing (penetration) of the ink and maintaining the roundness of one dot. It preferably contains an activator.
- nonionic surfactants that can be used in the present invention include acetylenic glycol surfactants.
- acetylene glycol-based surfactants specifically, Surfynol 465, Surfynol 104 (above, manufactured by Air Products and Chemicals Inc.), Orfin E1010, Orufin PD001, Orufin STG (above, Nisshin Chemical Co., Ltd. ), Product name) and the like.
- the addition amount is preferably 0.1 to 5% by weight, more preferably 0.5 to 2% by weight.
- the amount is 0.1% by weight or more, sufficient permeability can be obtained, and when the amount is 5% by weight or less, the occurrence of image bleeding can be easily prevented.
- the ink composition of the present invention preferably further contains a penetration enhancer from the viewpoint that permeability can be improved.
- a penetration enhancer By adding a glycol ether as the penetration enhancer, the permeability is further increased, and bleeding at the border between adjacent color inks when color printing is performed is reduced, so that a very clear image can be obtained. Can be.
- glycol ethers examples include ethylene glycol monobutyl ether, styrene glycolone monobutynoether, triethylene glycolone monoethylenetin ether, propylene glycolone monomethinoleatenole, and dipropylene glycolone monoenoline. And propylene glycolone monobutynole ether, dipropylene glycolone monobutynole ether, triethylene glycol monobutyl ether and the like.
- the addition amount is 3 to 30% by weight, preferably 5 to 15% by weight. If the amount is less than 3% by weight, the effect of preventing bleeding may not be obtained. On the other hand, if the content exceeds 30% by weight, not only bleeding of the image occurs but also oil separation occurs, and a dissolving aid for these glycol ethers is required. In this case, ejection becomes difficult.
- the ink composition of the present invention may contain, if necessary, a pH adjuster such as triethanolamine-alkali metal hydroxide, a hydrotrope such as urea and its derivatives, a sodium alginate and the like.
- a pH adjuster such as triethanolamine-alkali metal hydroxide, a hydrotrope such as urea and its derivatives, a sodium alginate and the like.
- the respective components are sufficiently mixed and dissolved, and the mixture is pressure-filtered with a membrane filter having a pore diameter of 0.8 m, and then deaerated using a vacuum pump. There is a method of processing and preparing.
- the present invention can also provide an ink cartridge including at least the ink composition described above.
- ADVANTAGE OF THE INVENTION According to the ink cartridge of this invention, the preservation
- an ink jet recording method in which the ink composition is ejected as droplets of fine pore force and the droplets are adhered to a recording medium to perform recording can be particularly preferably used. Needless to say, it can also be used for applications such as pen plotters.
- any conventionally known method can be used.
- a method of ejecting liquid droplets using the vibration of a piezoelectric element an ink jet head for forming ink droplets by mechanical deformation of an electrostrictive element
- excellent image recording can be performed in the method using thermal energy).
- the recorded matter of the present invention is recorded using the above-described ink composition, and has excellent room preservability (gas resistance) of an image, and may cause early discoloration. Absent.
- Ratio of colorant and aromatic sulfonic acid 1 "l: 2 ⁇ l ⁇ 1 1 ⁇ 1 ⁇ ⁇ ⁇ " one— “ ⁇ 3“ ⁇ 2 ”” ⁇ —— ———
- Each component of the ink composition shown in Table 1 is based on the total amount of the ink composition.
- Evaluation B ROD is 80% or more and less than 90%
- a ⁇ is less than 3
- Evaluation B ⁇ is 3 or more and less than 10
- Evaluation c ⁇ is 10 or more and less than 20
- Evaluation D ⁇ is 20 or more
- the ink composition was filled in an ink jet printer EM-930C (manufactured by Seiko Epson Corporation) and printing was performed continuously for 10 minutes. After confirming that ink was ejected from the nozzles, printing was stopped. Without capping the head, the printer was left in an environment of 40 ° C. and 25% RH for each of the ink compositions of Example 18 and Comparative Example 16 for 2 weeks. After the standing, the nozzle was cleaned, and then printing was performed. The clogging characteristics of the ink were evaluated by the number of cleaning operations required until the same printing as in the initial stage, in which defective printing such as flaws and omissions, was eliminated.
- Evaluation B 6—When the same print as the initial print can be obtained by 10 cleaning operations
- Evaluation C When the same printing as the initial is obtained by 11 to 15 cleaning operations
- Evaluation D The same printing as the initial is not possible even after 16 or more cleaning operations
- Each component of the ink composition shown in Table 3 represents% by weight of each component with respect to the total amount of the ink composition, and the remaining amount is water.
- Ozone exposure was performed in the same manner as in the desirable first embodiment except that the ozone concentration was 2 ppm.
- the OD of each printed matter was measured using a densitometer (Spectrolino: manufactured by Gretag) to determine the residual optical density (ROD), which was evaluated according to the following criteria.
- a ROD is 90% or more
- Evaluation B ROD is 80% or more and less than 90%
- Evaluation C ROD is 70% or more and less than 80%
- a ⁇ ⁇ ⁇ is less than 3
- Evaluation B ⁇ ⁇ is 3 or more and less than 10
- Evaluation C ⁇ ⁇ is 10 or more and less than 20
- Evaluation D ⁇ ⁇ is 20 or more
- a test for clogging resistance was performed on each of the ink compositions of Examples 9 to 13 and Comparative Examples 7 to 9 in the same manner as in the desirable first embodiment, and the recoverability was evaluated according to the following criteria. .
- Evaluation B When the same print as the initial print is obtained after 6 to 10 cleaning operations
- Evaluation C When the same printing as the initial one is obtained by 11 to 15 cleaning operations
- Evaluation D The same printing as the initial one is not possible even after 16 or more cleaning operations
- the present invention relates to an ink composition using a metal phthalocyanine cyan dye, which can improve the storage stability (gas resistance) of a formed image, and can effectively prevent early discoloration and fading of an image.
- the present invention has industrial applicability as an ink thread that can be easily prevented, and as an ink jet recording method and a recorded matter using the same.
- the ink composition of the present invention can improve the room preservability (gas resistance) of an obtained image, and has an excellent effect of effectively preventing early discoloration and fading of an image. I do.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Ink Jet (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20040788256 EP1577355B1 (en) | 2003-09-30 | 2004-09-28 | Ink composition, method of ink-jet recording, and print |
DE200460019045 DE602004019045D1 (de) | 2003-09-30 | 2004-09-28 | Tintenzusammensetzung,tintenstrahldruckverfahren sowie druck |
US10/533,731 US7303616B2 (en) | 2003-09-30 | 2004-09-28 | Ink composition, ink jet recording method and recorded article |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003341633A JP4581364B2 (ja) | 2003-09-30 | 2003-09-30 | インク組成物、インクジェット記録方法及び記録物 |
JP2003-341633 | 2003-09-30 |
Publications (1)
Publication Number | Publication Date |
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WO2005030885A1 true WO2005030885A1 (ja) | 2005-04-07 |
Family
ID=34386228
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2004/014189 WO2005030885A1 (ja) | 2003-09-30 | 2004-09-28 | インク組成物、インクジェット記録方法及び記録物 |
Country Status (7)
Country | Link |
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US (1) | US7303616B2 (ja) |
EP (1) | EP1577355B1 (ja) |
JP (1) | JP4581364B2 (ja) |
CN (1) | CN100340620C (ja) |
AT (1) | ATE420928T1 (ja) |
DE (1) | DE602004019045D1 (ja) |
WO (1) | WO2005030885A1 (ja) |
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US7784367B2 (en) * | 2004-12-01 | 2010-08-31 | Canon Kabushiki Kaisha | Method of gas resistance test for image and ink set |
US7976623B2 (en) | 2005-04-19 | 2011-07-12 | Hewlett-Packard Development Company, L.P. | Ink-jet inks containing sulfonated aromatic compounds for reducing ozone fade |
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JP4533612B2 (ja) * | 2003-09-30 | 2010-09-01 | セイコーエプソン株式会社 | インク組成物、それを用いたインクジェット記録方法および記録物 |
JP4581364B2 (ja) * | 2003-09-30 | 2010-11-17 | セイコーエプソン株式会社 | インク組成物、インクジェット記録方法及び記録物 |
US7276111B2 (en) * | 2004-02-09 | 2007-10-02 | Seiko Epson Corporation | Ink composition, inkjet recording method and recorded matter |
JP4595341B2 (ja) * | 2004-02-19 | 2010-12-08 | セイコーエプソン株式会社 | インク組成物、インクジェット記録方法及び記録物 |
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US7923083B2 (en) * | 2004-03-11 | 2011-04-12 | Fujifilm Corporation | Recording medium, ink composition and recording method using the same |
US7279034B2 (en) * | 2005-03-11 | 2007-10-09 | Seiko Epson Corporation | Ink composition, ink cartridge, inkjet recording method, and recorded matter |
JP4766228B2 (ja) * | 2005-03-11 | 2011-09-07 | セイコーエプソン株式会社 | インク組成物、インクカートリッジ、インクジェット記録方法及び記録物 |
JP4911283B2 (ja) * | 2006-02-16 | 2012-04-04 | ブラザー工業株式会社 | インクジェット記録用シアンインク |
JP4457412B2 (ja) | 2006-12-14 | 2010-04-28 | セイコーエプソン株式会社 | インクセット、インクカートリッジ、インクジェット記録方法及び記録物 |
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US8974049B2 (en) * | 2011-10-25 | 2015-03-10 | Hewlett-Packard Development Company, L.P. | Fixer composition |
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US10647864B2 (en) * | 2015-10-08 | 2020-05-12 | Dic Corporation | Aqueous pigment dispersion, aqueous green ink for inkjet recording, and aqueous red ink for inkjet recording |
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2003
- 2003-09-30 JP JP2003341633A patent/JP4581364B2/ja not_active Expired - Fee Related
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2004
- 2004-09-28 CN CNB2004800014564A patent/CN100340620C/zh not_active Expired - Fee Related
- 2004-09-28 US US10/533,731 patent/US7303616B2/en not_active Expired - Fee Related
- 2004-09-28 WO PCT/JP2004/014189 patent/WO2005030885A1/ja active Application Filing
- 2004-09-28 EP EP20040788256 patent/EP1577355B1/en not_active Not-in-force
- 2004-09-28 AT AT04788256T patent/ATE420928T1/de not_active IP Right Cessation
- 2004-09-28 DE DE200460019045 patent/DE602004019045D1/de active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0354268A (ja) * | 1989-07-21 | 1991-03-08 | Mitsubishi Kasei Corp | 記録液 |
JP2002362004A (ja) * | 2001-03-21 | 2002-12-18 | Eastman Kodak Co | インクジェット印刷方法 |
JP2002332434A (ja) * | 2001-05-10 | 2002-11-22 | Canon Inc | インクセット、被記録媒体に着色部を形成する方法及びインクジェット記録装置 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7784367B2 (en) * | 2004-12-01 | 2010-08-31 | Canon Kabushiki Kaisha | Method of gas resistance test for image and ink set |
US7976623B2 (en) | 2005-04-19 | 2011-07-12 | Hewlett-Packard Development Company, L.P. | Ink-jet inks containing sulfonated aromatic compounds for reducing ozone fade |
Also Published As
Publication number | Publication date |
---|---|
US20060135646A1 (en) | 2006-06-22 |
CN100340620C (zh) | 2007-10-03 |
EP1577355B1 (en) | 2009-01-14 |
US7303616B2 (en) | 2007-12-04 |
DE602004019045D1 (de) | 2009-03-05 |
EP1577355A4 (en) | 2007-08-29 |
ATE420928T1 (de) | 2009-01-15 |
CN1717458A (zh) | 2006-01-04 |
EP1577355A1 (en) | 2005-09-21 |
JP4581364B2 (ja) | 2010-11-17 |
JP2005105166A (ja) | 2005-04-21 |
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