Liquid Composition Flüssige Zusammensetzung Composition Liquide
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(19) & (11) EP 1 602 505 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: B41M 5/00 (2006.01) C09D 11/00 (2006.01) 16.11.2011 Bulletin 2011/46 B41J 2/01 (2006.01) (21) Application number: 04711703.1 (86) International application number: PCT/JP2004/001698 (22) Date of filing: 17.02.2004 (87) International publication number: WO 2004/071782 (26.08.2004 Gazette 2004/35) (54) LIQUID COMPOSITION FLÜSSIGE ZUSAMMENSETZUNG COMPOSITION LIQUIDE (84) Designated Contracting States: • TAKEMOTO, Kiyohiko, AT BE BG CH CY CZ DE DK EE ES FI FR GB GR c/o Seiko Epson Corporation HU IE IT LI LU MC NL PT RO SE SI SK TR Suwa-shi, Nagano 3928502 (JP) (30) Priority: 17.02.2003 JP 2003038880 • HASHIMOTO, Mitsumasa, 17.02.2003 JP 2003038895 c/o Nitto Boseki Co. Ltd. 17.02.2003 JP 2003038898 Kooriyama-shi, 01.04.2003 JP 2003098628 Fukushima 9638061 (JP) 31.07.2003 JP 2003204550 • TAKEUCHI, Minoru, c/o Nitto Boseki Co., Ltd. (43) Date of publication of application: Tokyo 1030006 (JP) 07.12.2005 Bulletin 2005/49 (74) Representative: Grünecker, Kinkeldey, (60) Divisional application: Stockmair & Schwanhäusser 11000446.2 / 2 305 484 Leopoldstrasse 4 80802 München (DE) (73) Proprietor: Seiko Epson Corporation Shinjuku-ku (56) References cited: Tokyo 163-0811 (JP) EP-A- 0 697 445 EP-A- 0 892 024 EP-A- 1 106 658 JP-A- 8 020 161 (72) Inventors: JP-A- 8 020 720 JP-A- 8 174 997 • KATAOKA, Shuichi, JP-A- 8 282 086 JP-A- 10 095 107 c/o Seiko Epson Corporation JP-A- 2000 034 432 JP-A- 2000 263 921 Suwa-shi, JP-A- 2001 315 425 JP-A- 2002 302 627 Nagano 3928502 (JP) Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 1 602 505 B1 Printed by Jouve, 75001 PARIS (FR) EP 1 602 505 B1 Description [TECHNICAL FIELD] 5 [0001] The present invention relates to a colorant-free liquid composition for use with a colorant-containing ink com- position. [BACKGROUND ART] 10 [0002] Ink jet recording is a printing method wherein droplets of an ink composition are ejected and deposited on recording media, such as paper, to perform printing. The feature of the ink jet recording method is that images having a combination of high resolution with high sharpness can be printed at a high speed by means of a relatively inexpensive apparatus. Various ink compositions for use in recording by this ink jet recording method have hitherto been proposed. In recent years, there is an increasing demand for higher-grade recorded images. Among others, various proposals 15 have been made for further improving the color development and gloss of recorded images. [0003] In order to realize high- quality images, a method has been proposed in which an ink composition and a second composition are deposited onto a recording medium to perform printing. For example, Japanese Patent Laid-Open Nos. 207424/1997 and 286940/1997 disclose an ink jet recording method in which an ink composition having a specific composition and a polyallylamine-containing reaction solution are deposited in combination onto a recording medium. 20 Further, Japanese Patent Laid- Open No. 81611/1996 discloses an ink jet recording method in which a cationic material- containing liquid composition and an ink composition are printed in combination. [0004] EP-A-1106658 and EP-A-0697445 disclose colorant-free liquid compositions comprising a polyallylamine and a water soluble organic solvent. 25 [SUMMARY OF THE INVENTION] [0005] The present inventors have now found a liquid composition having a specific formulation which, when deposited in combination with an ink composition on a recording medium, exhibits excellent properties. Among others, the present inventors have found a liquid composition which can realize a high level of storage stability of recorded matter and can 30 realize good cleaning operation without residence of the liquid composition or the ink composition or a mixed liquid composed of the liquid composition and the ink composition (hereinafter often referred to as "waste liquid") in a cleaning cap while maintaining good color development and gloss. [0006] Accordingly, an object of the present invention is to provide a liquid composition having good properties, especially a liquid composition which can realize a high level of storage stability of recorded matter and can realize good 35 cleaning operation without residence of the liquid composition or the ink composition or a waste liquid in a cleaning cap while maintaining good color development and gloss. [0007] The present invention provides a liquid composition adapted for use with an ink composition for deposition on a recording medium, said liquid composition comprising a modified polyallylamine, a water- soluble organic solvent, and water, and being free from any colorant, wherein said modified polyallylamine comprises recurring units (a) and (c) or 40 recurring units (a), (b) and (c): 45 50 55 wherein R1 and R2 each independently represent an alkyl group having 1 to 4 carbon atoms, X represents any of groups (i) to (v): 2 EP 1 602 505 B1 (i) -CONH2, (ii) -COOR3 wherein R3 represents an alkyl group having 1 to 12 carbon atoms, or an aryl group, 5 (iii) -COR4 wherein R4 represents an alkyl group having 1 to 12 carbon atoms, (iv) -CH2CH(R5)-A wherein R5 represents a hydrogen atom or a methyl group, and A is selected from the group consisting of -CONR 6R7 wherein R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms and the alkyl group is optionally substituted by a group selected from the group consisting of 10 a hydroxyl group, a keto group, a monoalkylamino group having 1 to 4 carbon atoms, a di(alkyl with 1 to 4 carbon atoms)amino group, or a tri(alkyl with 1 to 4 carbon atoms) ammonium group, or NR 6R7 combine together to represent a cyclic amino group of a piperidino or morpholino group; -CN; and -COOR8 wherein R8 represents an alkyl group having 1 to 8 carbon atoms and the alkyl group is optionally substituted by a group selected from the group consisting of a hydroxyl group, a keto group, a monoalkylamino group having 1 to 4 carbon atoms, a di (alkyl with 1 to 4 carbon 15 atoms)amino group, and a tri(alkyl with 1 to 4 carbon atoms)ammonium group, or (v) -CH2CH(OH)-B wherein B represents an alkyl group having 1 to 8 carbon atoms and the alkyl group is optionally substituted by a group selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and an alkenyloxy group, 20 Y has the same meaning as X, or is a hydrogen atom, and X and Y each may be the same or different for each recurring unit. [0008] The invention further provides an ink cartridge comprising said liquid composition contained therein. [0009] Moreover, the invention provides an ink set comprising: 25 the above liquid composition; and an ink composition comprising at least a colorant, a water-soluble organic solvent, and water. 30 [0010] The invention further provides an ink jet recording method comprising the step of depositing said liquid com- position and said ink composition onto a recording medium to perform recording. [0011] The invention further provides an ink jet recording method comprising the steps of: depositing said liquid composition and an ink composition onto a recording medium to perform recording; and 35 then heat-treating the recorded face at a temperature at or above the glass transition temperature of said polymer fine particles. [0012] Preferred embodiments of the present invention are set forth in the sub-claims. 40 [0013] The liquid composition according to the present invention is adapted for use with an ink composition for dep- osition on a recording medium and comprises a specific modified polyallylamine, a water soluble organic solvent, and water and is free from any colorant. The use of the modified polyallylamine-containing liquid composition can realize a high level of storage stability of recorded matter and can realize good cleaning operation without residence of the liquid composition or the ink composition or a waste liquid in a cleaning cap while maintaining good color development and gloss. 45 [BRIEF DESCRIPTION OF THE DRAWINGS] [0014] 50 Fig. 1 is a schematic diagram of an ink jet recording apparatus which can realize the recording method according to the present invention; Fig. 2 is a schematic diagram of a recording head in an ink jet recording apparatus; Fig. 3 is a simulated diagram of a print pattern formed by an ink jet recording apparatus; Fig. 4 is a schematic diagram showing the construction of nozzles in a recording head; 55 Fig. 5 is a schematic diagram of an ink jet recording apparatus which can realize the recording method according to the present invention; and Fig. 6 is a schematic diagram of an ink jet recording apparatus, provided with means for heating a recording medium, which can realize the recording method according to the present invention. 3 EP 1 602 505 B1 [DETAILED DESCRIPTION OF THE INVENTION] Definition 5 [0015] The term "alkyl group" as used herein as a group or a part of a group may be a straight chain or branched chain alkyl group.