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WO2007132761A1 - Encre à pigments aqueux pour imprimante jet d'encre - Google Patents

Encre à pigments aqueux pour imprimante jet d'encre Download PDF

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Publication number
WO2007132761A1
WO2007132761A1 PCT/JP2007/059728 JP2007059728W WO2007132761A1 WO 2007132761 A1 WO2007132761 A1 WO 2007132761A1 JP 2007059728 W JP2007059728 W JP 2007059728W WO 2007132761 A1 WO2007132761 A1 WO 2007132761A1
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WO
WIPO (PCT)
Prior art keywords
ink
pigment
water
aqueous pigment
pigment ink
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2007/059728
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English (en)
Japanese (ja)
Inventor
Nagayuki Takao
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Individual
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Filing date
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Publication of WO2007132761A1 publication Critical patent/WO2007132761A1/fr
Anticipated expiration legal-status Critical
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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
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • 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
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black

Definitions

  • the present invention relates to a water-based pigment ink for an inkjet printer, which is at least a self-dispersing pigment and a hydraulic power.
  • Ink jets can print high-definition images with a simple recording method, making it possible to obtain high-quality images very inexpensively. For this reason, it is used for outputting small images such as photographs, graphics, and office documents, or for large outputs such as AO posters and signboards.
  • small images such as photographs, graphics, and office documents, or for large outputs such as AO posters and signboards.
  • water-based pigment inks have rapidly spread in recent years due to weather resistance and color development.
  • This water-based pigment ink has been improved in terms of color developability and bleeding from the idea of additives and the surface treatment of pigments.
  • self-dispersing pigments and microencapsulated pigments are often used as the pigment.
  • an aqueous pigment ink using self-dispersing carbon and trimethylolpropane has been proposed for the purpose of improving the prevention of nozzle clogging, intermittent ejection stability, and ejection durability (see Patent Document 1). .
  • this ink exhibits excellent ejection properties, there are problems in terms of blurring of the image when used with color ink and a decrease in print density depending on the type of recording medium.
  • Patent Document 3 JP-A-10-195360
  • Patent Document 2 JP 2000-198955
  • Patent Document 3 JP 2005-238415
  • the present invention has less storage blur even when an inexpensive recording medium (printing paper) having excellent storage stability is used, and further depends on the type of the recording medium. Therefore, it is an object to provide an aqueous pigment ink capable of forming a high-density image.
  • the present inventors have found that a self-dispersing pigment, water, an aqueous pigment containing a polyhydric alcohol and a trimellitic acid salt that are solid at 20 ° C.
  • the present invention has been completed by finding that the ink has excellent storage stability and the image blurs even when inexpensive printing paper is used, and that a high-density image is formed regardless of the type of recording medium.
  • the present invention provides an aqueous pigment ink for ink jetting containing at least a self-dispersing pigment and water, comprising a polyhydric alcohol and a trimellitic acid salt that are solid at 20 ° C. It relates to ink. Further, the present invention relates to an aqueous pigment ink containing trimethylolpropane and / or sorbitol as a polyhydric alcohol.
  • the present invention is a water-based pigment ink for ink jet printers containing at least a self-dispersing pigment and water. This makes it possible to provide an aqueous pigment ink for an ink jet printer that suppresses image bleeding, which has been a problem with water-based pigment inks, and image density reduction due to the type of recording medium.
  • self-dispersing pigment, water, polyhydric alcohol solid at 20 ° C and trimellit It is essential to contain an acid salt.
  • storage stability is excellent, blurring of images can be prevented, and reduction in image density can be suppressed even when printing on the type of recording paper, particularly inexpensive paper. This is due to the high affinity between the self-dispersing pigment and the recording paper.
  • the solid polyhydric alcohol increases the drying property and exhibits uniform permeability, and the trimellitic acid salt bleeds. By preventing this, a high-density image can be maintained even with an inexpensive recording medium. Furthermore, it is possible to prevent the bleeding with the dye from being accelerated and dry.
  • the self-dispersing pigment used in the present invention is preferably one in which at least one hydrophilic group is bonded to the pigment surface directly or via another atomic group. This atomic group maintains affinity with the recording medium and gives a high density image. Further, as the self-dispersing pigment, those having an ionic property, which are preferably charged in an anionic manner, and those charged in a cationic manner are suitable.
  • hydrophilic group bonded to the surface of the anionically charged pigment examples include C OOM, 1 SO M, 1 PO HM, 1 PO M, 1 SO NH, 1 SO NHCOR (provided that the formula
  • M represents a hydrogen atom, an alkali metal, an ammonia or an organic ammonium
  • R represents an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted group.
  • Etc. are preferred.
  • the substituent for the phenyl group and the naphthyl group is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. Of these, COOM and SOM bonded to the pigment surface are used.
  • the affinity with the recording medium is preferred.
  • M in the hydrophilic group is an alkali metal such as lithium, sodium, potassium, etc., ammonium, mono to trimethyl ammonium, mono to triethyl ammonium, mono to Organic ammonia such as trimethanol ammonia is preferred.
  • Examples of a method for obtaining an anionically charged pigment include a method in which -COONa is introduced into the pigment surface, for example, a method in which the pigment is oxidized with sodium hypochlorite. is not.
  • hydrophilic group bonded to the surface of the cationically charged pigment for example, a quaternary ammonium group is preferable, and a fourth group such as —NH + and —NR + is more preferable.
  • a quaternary ammonium group is preferable, and a fourth group such as —NH + and —NR + is more preferable.
  • the pigment is treated with 3-amino-N-ethylpyridyl-um bromide.
  • the power of the method The present invention is not limited to this.
  • the hydrophilic group may be bonded to the surface of the pigment via another atomic group.
  • the other atomic group is preferably an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent or a substituent, and a naphthyl group.
  • Examples of the hydrophilic group bonded to the pigment surface through other atomic groups include C H COOM, 1 PhSO M, 1
  • a method for introducing a hydrophilic group into the pigment surface via another atomic group a method in which p-aminobenzenesulfonic acid is diazotized and reacted with the pigment is preferable, but the present invention is not limited thereto.
  • the pigment when introducing a hydrophilic group by diazo, it is preferable that the pigment does not have a primary amine in order to suppress side reactions.
  • Self-dispersing pigments include azo, azomethine, polyazo, phthalocyanine, quinacridone, anthraquinone, indigo, thioindigo, quinophthalone, benzimidazolone, isoindoline, Isoindolinone and carbon black pigments are used.
  • the self-dispersing pigment used in the water-based pigment ink of the present invention is charged cationically or eonly by the hydrophilic group on the pigment surface, and has water dispersibility due to repulsion of ions. Moreover, hydrophilicity is also improved by the hydrophilic group. Therefore, an aqueous pigment ink that is stably dispersed in an aqueous medium without increasing the particle diameter or viscosity of the pigment even when left for a long period of time can be obtained.
  • the content of the self-dispersing pigment is preferably 2 to 7% by weight, preferably 1 to L0% by weight in all inks.
  • the content is less than 1% by weight, the concentration exceeds 10% by weight.
  • the viscosity of the ink increases and the discharge stability deteriorates.
  • polyhydric alcohol that is solid at 20 ° C. or less used in the present invention trimethylolpropane, sorbitol and the like are preferable, and these have high solubility in water and can increase the density of printed matter. In addition, these combinations are used to improve dryness, bleeding, and print density. preferable. In addition, sorbitol is excellent in re-solubility and excellent printing characteristics.
  • the content of the polyhydric alcohol solid at 20 ° C is preferably 1 to 25% by weight, and most preferably 2 to 20% by weight in the total ink. If the content is less than 1% by weight, the drying property is poor and bleeding tends to occur. If the content exceeds 25% by weight, the viscosity of the ink increases and the ejection stability deteriorates.
  • the trimellitic acid salt used in the present invention only needs to be neutralized with various bases and dissolved in water.
  • bases used include monovalent alkali metal ions such as lithium hydroxide, sodium hydroxide and potassium hydroxide, ammonia, triethylamine, triethanolamine, diethanolamine, ethanolamine, dimethylaminoethanol and the like.
  • Organic amines are listed.
  • ammonia salt whose base is ammonia is most preferred because it improves water resistance and printing density.
  • the trimellitic acid salt content is preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight in the total ink. If the content is less than 0.01% by weight, bleeding occurs, and if it exceeds 5% by weight, the self-dispersing pigment may be aggregated, resulting in poor storage stability.
  • the amount of the base used is preferably an amount in the range of 100 to 120%, more preferably an amount in the range of 80 to 150% of neutralization rate in order to neutralize trimellitic acid.
  • the above self-dispersing pigment, polyhydric alcohol and trimellitic acid salt solid at 20 ° C are essential.
  • Self-dispersing pigments have many hydrophilic groups on the pigment surface, which increases the affinity for paper fibers.
  • a substance having a melting point of 25 degrees or less can accelerate the drying property, thus allowing the pigment to remain on the surface of the paper.
  • trimellitic acid prevents bleeding. Therefore, these three parties have made it possible to increase the print density regardless of the type of paper.
  • the ink of the present invention includes a water-soluble organic solvent, a pH adjuster, a surfactant, an anti-clogging agent for the print head, an antifoaming agent, an antibacterial agent, an antifungal agent, and water resistance to printing. This can be achieved by adding various additives that have been used in ink jet printer inks such as property-imparting agents and charge control agents.
  • the ink of the present invention contains at least one water-soluble organic solvent to suppress the drying property of the ink and achieve redispersibility in which the pigment is redispersed in the solvent after drying.
  • the amount of the water-soluble organic solvent to be added is preferably 1 to 20% by weight, more preferably 1 to 15% by weight with respect to 100% by weight of the ink. If the amount of water-soluble organic solvent added is less than 1% by weight, the print head will become clogged. On the other hand, if the blending amount of the water-soluble organic solvent exceeds 20% by weight, the penetrability of the ink into the paper increases, resulting in a decrease in printing density or a high viscosity. Further, in the present invention, from the viewpoint of improving the print density, it is more preferable if the addition amount should be suppressed as much as possible.
  • Water-soluble organic solvents include polyhydric alcohols such as ethylene glycol, 1,2 butanediol, 1,4 butanediol, 1,3 butanediol, 2,4 pentanediol, 1,5 pentanediol, 2-methyl- 2,4 pentanediol, 1,2 cyclohexanediol, 1,4-cyclohexanediol, 1,2,4 butanetriol, 1,2,6 monohexanetriol, 1,2,5 pentanetriol, 3 —Methyl-1,5 pentanediol, 3 hexene 2,5 diol, polyethylene glycol, polypropylene glycol, diethylene glycol, glycerin.
  • polyhydric alcohols such as ethylene glycol, 1,2 butanediol, 1,4 butanediol, 1,3 butanediol, 2,4 pentanediol, 1,5 pentaned
  • Other water-soluble organic solvents include triethylene glycol, tripropylene glycol, dimethyl sulfoxide, diacetone alcohol, glycerin monoallyl ether, propylene glycol, polyethylene glycol, thiodiglycol, N-methyl-2- Pyrrolidone, 2 Pyrrolidone, ⁇ -Butyrolatatone, 1,3 Dimethyl-2 imidazolidinone, Sulfolane, Neopentyl glycol, Ethylene glycol monomethyl ether, Ethylene glycol-mono-mono-ethylenoate, Ethylene glycol-mono-monopropylenoate, Ethylene Glycolemonomonolinole ether, Diethyleneglycololemonomethinoleether, Diethyleneglycolenomonochinenoreethenore, Triethyleneglycolenomonomonomethino Reethenore, Triethyleneglycolenomonoeth
  • the pH adjuster at least one selected from water-soluble inorganic salts or hydroxides is used, and the pH of the ink-jet printer ink thus prepared is in the range of 7 to 10. Adjusting to this is effective for clogging the nozzles of ink.
  • water-soluble inorganic salts include sodium carbonate and calcium carbonate.
  • water-soluble inorganic hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide. Is mentioned.
  • a resin to the water-based pigment ink for ink jet printers of the present invention in order to improve the water resistance, gloss and abrasion resistance of the printed matter.
  • rosin examples include water-soluble or dispersed varieties having an average particle size of 10 to 300 nm.
  • chemical structure of rosin include acrylic, bulle, polyester, and amide copolymers.
  • the addition amount thereof is preferably in the range of 1 to 15% by weight and more preferably in the range of 2 to 10% by weight in 100% by weight of the ink.
  • antifoaming agent examples include cationic surfactants such as alkylbenzene sulfonic acid type, alkyl sulfate ester type, fatty acid salt type and quaternary ammonium salt type, alkyl betaine, amine oxide, etc.
  • Antifungal agents and fungicides include benzoates, alkylamine salts, and quaternary ammonium salts.
  • a surfactant to the ink of the present invention to adjust the surface tension and improve the printing stability.
  • the addition amount is preferably in the range of 0.05 to 5% by weight for printing stability.
  • the surfactant is not particularly limited as long as the water-soluble ionic surfactant or nonionic surfactant is preferably dissolved or dispersed in water.
  • Surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants are preferred. Of these, particularly preferred surfactants are anionic surfactants and nonionic surfactants.
  • surfactant surfactant examples include fatty acid salts such as sodium stearate soap, potassium oleate soap, and semi-cured beef tallow fatty acid soda soap, sodium lauryl sulfate, triethanolamine lauryl sulfate, and higher alcohol sodium sulfate.
  • fatty acid salts such as sodium stearate soap, potassium oleate soap, and semi-cured beef tallow fatty acid soda soap, sodium lauryl sulfate, triethanolamine lauryl sulfate, and higher alcohol sodium sulfate.
  • Examples of the cationic surfactant include coconutamine acetate, alkylamine salts such as stearylamine acetate, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and alkylbenzildimethylammonium chloride.
  • Examples include quaternary ammonium salts, alkylbetaines such as laurylbetaine and stearylbetaine, and amine oxides such as lauryldimethylamine oxide.
  • nonionic surfactant examples include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene glycol ether, polyoxyethylene higher alcohol ether, and other polyoxyethylenes.
  • Polyalkylene ethers such as lenalkyl ethers, polyoxyethylene octyl phenyl ethers and polyoxyethylene nonyl phenyl ethers, polyoxyethylene derivatives, oxyethylene 'oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Polyoxyethylene such as sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate or polyoxyethylene sorbitan trioleate Polyoxyethylene sorbitol fatty acid ester such as sorbitan fatty acid ester, polyoxyethylene sorbitol tetraoleate , Glycerin fatty acid esters, in consideration of the ejection stability even in a non-ionic surfactant is preferably tool in such as acetylene glycol surface active agents, acetylene grayed recall system is
  • acetylene glycol surfactant the Surfynol series manufactured by Nissin Chemical Industry Co., Ltd. and the acetylenol series manufactured by Kawaken Fine Chemical Co., Ltd. are preferable.
  • POE polyoxyethylene
  • the ink of the present invention can be used in all printers without any particular limitation as long as it is a commercially available piezo type, thermal type, or continuous ink jet type.
  • Aqueous pigment ink B was prepared in the same manner as in Example 1, except that “ion exchange water” was used instead of “trimellitic acid” and “10% aqueous ammonia” in Example 1.
  • Aqueous pigment ink C was prepared in the same manner as in Example 1 except that “glycerin (manufactured by Nippon Emulsifier)” was used instead of “sorbitol” in Example 1.
  • Example 1 Except that “ammonium acetate” was used instead of “trimellitic acid” in Example 1, and “ion-exchanged water” was used instead of “10% aqueous ammonia”, the same as Example 1 was used. Aqueous pigment ink D was adjusted.
  • Aqueous pigment ink E was prepared in the same manner as in Example 1, except that “trimethylolpropane” was used instead of “sorbitol” in Example 1.
  • an aqueous pigment ink F was prepared in the same manner as in Example 2, except that the aqueous pigment dispersion a was used in place of the self-dispersing carbon in Example 2.
  • An aqueous pigment ink G was prepared in the same manner as in Example 1 except that 2.5 parts of “10% dimethylaminoethanol water” was used instead of “10% aqueous ammonia” in Example 1.
  • Example 2 Instead of “Aqua-BlackOOl (self-dispersing pigment manufactured by Tokai Carbon Co., Ltd.)” in Example 1, “Aqua-Blackl62 (self-dispersing pigment manufactured by Tokai Carbon Co., Ltd.)” is replaced with “glycerin”. Except for the use of ⁇ trimethylolpropane '' Ink H was adjusted.
  • Table 1 shows the ink compositions of the aqueous pigment inks A to H in Examples 1 to 4 and Comparative Examples 1 to 4 described above. Moreover, the viscosity and the dispersion average particle diameter were measured by the following methods. Table 2 shows the results of these measurements.
  • Viscosity was measured under the condition of 25 ° C using a vibration viscometer Piscomate VM-10A-L (CBC).
  • the dispersion average particle size of the pigment particles was measured with a particle size distribution measuring device LB-550B (particle size distribution measuring device manufactured by Horiba Ltd.).
  • TMP Trimethylololepropane
  • the ink was sealed and stored in a high-temperature tank at 70 ° C for 21 days, and the rate of change in the average particle diameter of the ink was measured.
  • Canon Inkjet Printer MP—500 is filled with ink, Epson Inkjet exclusive paper (Paper A), very inexpensive Nakabayashi Corporation PPC paper (Paper B) and Golden copy paper (Paper C) are solid. The image was printed. The optical density of the solid image after printing was measured with a Macbeth densitometer. [0064] ⁇ Bludge>
  • Canon ink-jet printer MP-500 was filled with ink, and color images were printed using Nakabayashi PPC paper.
  • Example 14 As apparent from the results in Table 3 above, the aqueous pigment ink A E G H of Example 14 exhibited excellent storage stability, optical density, bleeding and drying properties. Even when inexpensive paper was used, it showed excellent optical density. The ink of Example 4 was the most balanced ink with excellent bleeding and dryness.
  • the ink B C F of Comparative Example 1 2 4 was inferior in optical density when inexpensive paper B C was used. Furthermore, although the ink D of Comparative Example 3 had a high optical density, it was inferior in storage stability and was not at a level that could be made into a product.

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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)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet (AREA)

Abstract

L'invention concerne une encre à pigments aqueux présentant une excellente stabilité au stockage, permettant de former une image de concentration élevée avec moins de déteintage, même lors de l'utilisation d'un support d'impression (papier d'impression) de faible coût. L'invention concerne notamment une encre à pigment aqueux, caractérisée en ce qu'elle contient un pigment autodispersible, de l'eau, un alcool polyhydrique qui se trouve à l'état solide à 20 °C et un sel de triméllitate. L'invention concerne également une encre à pigment aqueux pour imprimante jet d'encre de même constitution, caractérisée en ce que l'alcool polyhydrique qui se trouve à l'état solide à 20 °C est composé d'un sorbitol et/ou d'un triméthylolpropane.
PCT/JP2007/059728 2006-05-12 2007-05-11 Encre à pigments aqueux pour imprimante jet d'encre Ceased WO2007132761A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006160267A JP4939117B2 (ja) 2006-05-12 2006-05-12 インクジェットプリンタ用水性顔料インク
JP2006-160267 2006-05-12

Publications (1)

Publication Number Publication Date
WO2007132761A1 true WO2007132761A1 (fr) 2007-11-22

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PCT/JP2007/059728 Ceased WO2007132761A1 (fr) 2006-05-12 2007-05-11 Encre à pigments aqueux pour imprimante jet d'encre

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8408691B2 (en) 2009-01-22 2013-04-02 Canon Kabushiki Kaisha Ink jet recording ink, ink jet image forming method and ink jet recording apparatus

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5590806B2 (ja) * 2009-01-22 2014-09-17 キヤノン株式会社 インクジェット記録用インク及びインクジェット記録方法
EP2354197B1 (fr) 2010-01-29 2014-03-05 Brother Kogyo Kabushiki Kaisha Encre à base d'eau pour enregistrement à jet d'encre
JP5776883B2 (ja) * 2011-04-14 2015-09-09 セイコーエプソン株式会社 インクジェット記録用水性顔料インク

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1077432A (ja) * 1996-09-03 1998-03-24 Sakata Corp インクジェット記録用インク組成物
JPH10195360A (ja) * 1996-11-13 1998-07-28 Canon Inc 水性顔料インク、これを用いたインクジェット記録方法及びインクジェット記録装置
JP2004238415A (ja) * 2003-02-03 2004-08-26 Hitachi Maxell Ltd インクジェットプリンタ用インク

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1077432A (ja) * 1996-09-03 1998-03-24 Sakata Corp インクジェット記録用インク組成物
JPH10195360A (ja) * 1996-11-13 1998-07-28 Canon Inc 水性顔料インク、これを用いたインクジェット記録方法及びインクジェット記録装置
JP2004238415A (ja) * 2003-02-03 2004-08-26 Hitachi Maxell Ltd インクジェットプリンタ用インク

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8408691B2 (en) 2009-01-22 2013-04-02 Canon Kabushiki Kaisha Ink jet recording ink, ink jet image forming method and ink jet recording apparatus

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JP4939117B2 (ja) 2012-05-23
JP2007302857A (ja) 2007-11-22

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