JP5773248B2 - Inkjet recording treatment liquid, inkjet recording aqueous ink set, inkjet recording method, and inkjet recording apparatus - Google Patents

Description

  The present invention relates to an inkjet recording treatment liquid, an aqueous ink set for inkjet recording, an inkjet recording method, and an inkjet recording apparatus.

  For the purpose of improving the optical density (OD value) of the recorded matter, a treatment liquid containing polyallylamine, polyvalent metal ions or the like may be used before or after ink jet recording with aqueous ink (for example, patents). References 1-3). Polyallylamine, polyvalent metal ions, and the like contained in the treatment liquid can agglomerate the colorant in the aqueous ink, and as a result, the optical density (OD value) of the recorded matter is improved.

Japanese Patent Laid-Open No. 11-314449 JP 2002-79740 A JP 2002-86707 A

  However, the treatment liquid containing polyallylamine, polyvalent metal ions and the like only improves the optical density (OD value) of the recorded matter. On the other hand, the processing solution is also required to have the performance of marker resistance and storage stability. However, none of the conventional processing solutions are excellent in all the performances of optical density (OD value), marker resistance and storage stability of the recorded matter.

  Accordingly, an object of the present invention is to provide a processing liquid for ink jet recording which is excellent in all the performances of optical density (OD value), marker resistance and storage stability of a recorded matter.

一般式（１）において、
Ｒ^１は、塩基性官能基であり、
Ｒ^２は、中性官能基または酸性官能基であり、
ｍおよびｎは、それぞれ、ｎ／（ｍ＋ｎ）≧２／３を満たし、かつ、２０≦ｍ＋ｎ≦４０を満たす整数であり、
Ｒ^１およびＲ^２がそれぞれ複数存在する場合、それらは同一でも異なっていてもよい。 In order to achieve the above object, the treatment liquid of the present invention is a treatment liquid used for inkjet recording,
It contains a compound represented by the general formula (1) and water.

In general formula (1),
R ¹ is a basic functional group,
R ² is a neutral functional group or an acidic functional group,
m and n are integers satisfying n / (m + n) ≧ 2/3 and satisfying 20 ≦ m + n ≦ 40, respectively.
When a plurality of R ¹ and R ² are present, they may be the same or different.

  The treatment liquid for ink jet recording of the present invention is excellent in all the performances of optical density (OD value), marker resistance and storage stability of a recorded matter.

FIG. 1 is a schematic perspective view showing the configuration of an example of the ink jet recording apparatus of the present invention. 2A and 2B are diagrams showing a recording example by the ink jet recording method of the present invention.

  In the present invention, “marker resistance” means, for example, that when a character portion recorded with water-based ink is traced with a highlighter pen (marker), there is no ink flow from the character, no bleeding of the character, and the pen tip is dirty. Say not.

  As described above, the processing liquid of the present invention is a processing liquid used for ink jet recording, and includes a compound represented by the general formula (1) and water. The treatment liquid of the present invention may contain other components other than the compound represented by the general formula (1) and water.

  By blending the compound represented by the general formula (1) into the treatment liquid, it is possible to obtain a treatment liquid excellent in all the performances of optical density (OD value), marker resistance and storage stability of the recorded matter. it can. The compounding amount of the compound represented by the general formula (1) with respect to the total amount of the treatment liquid is not particularly limited, but is, for example, 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 1% by weight or more. Although the upper limit of the compounding quantity of the compound represented by General formula (1) is not specifically limited, For example, it is 10 weight% or less, Preferably, it is 7 weight% or less.

  In the general formula (1), m and n are integers satisfying n / (m + n) ≧ 2/3 and satisfying 20 ≦ m + n ≦ 40, respectively. In the general formula (1), a block copolymer is shown for convenience, but the compound represented by the general formula (1) is not limited to the block copolymer, and may be a random copolymer. .

In the general formula (1), R ¹ is a basic functional group. Examples of the basic functional group include a — (CH ₂ ) _p —X group (p is an integer of 1 to 4, and X is an amino group, a guanidino group, or an imidazole group). . This is summarized as shown in Table 1. However, Table 1 merely illustrates the basic functional group, and the present invention is not limited to this. Among these, R ¹ is particularly preferably a — (CH ₂ ) ₂ —X group (X is a guanidino group).

In the general formula (1), R ² is a neutral functional group or an acidic functional group. Examples of the neutral functional group include a hydrogen atom, an alkyl group having 1 to 7 carbon atoms which may have a branched chain having 1 to 3 carbon atoms (for example, methyl group, isopropyl group, isobutyl group, sec-butyl). group), benzyl group, - _{(CH 2)} q -X group (q is an integer from 1 to 4, X is, -CONH ₂ group, an indole group or a thiol group) and the like. Examples of the acidic functional groups, e.g., - _{(CH 2)} r -X group (r is an integer from 1 to 4, X is carboxyl group) and the like.

Examples of the compound represented by the general formula (1) include compounds represented by substance names 1 to 264 shown in Tables 2 to 5. However, these are, for example, when there are a plurality of R ¹ and R ² , respectively, and are merely examples of the case where they are the same. In the compound represented by the general formula (1), for example, R ¹ and R ² are When there are a plurality of each, they may be different. The compound represented by the general formula (1) may be a mixture of compounds represented by substance names 1 to 264.

  The compound represented by the general formula (1) may include a derivative of the compound represented by the general formula (1). In the case where an isomer such as a tautomer or a stereoisomer (eg, a geometric isomer, a conformer and a stereoisomer) exists in the compound represented by the general formula (1) and its derivative, These isomers can also be used in the present invention. In addition, the compounds represented by the general formula (1) and salts of derivatives thereof can also be used in the present invention. The salt may be an acid addition salt or a base addition salt. Furthermore, the acid forming the acid addition salt may be an inorganic acid or an organic acid, and the base forming the base addition salt may be an inorganic base or an organic base. The inorganic acid is not particularly limited. For example, hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, hypofluorite, hypochlorous acid, hypobromite, Hypoiodous acid, fluorinated acid, chlorous acid, bromic acid, iodic acid, fluoric acid, chloric acid, bromic acid, iodic acid, perfluoric acid, perchloric acid, perbromic acid, periodic acid, etc. can give. The organic acid is not particularly limited. For example, glutamic acid, p-toluenesulfonic acid, methanesulfonic acid, oxalic acid, p-bromobenzenesulfonic acid, carbonic acid, succinic acid, citric acid, benzoic acid, acetic acid, hydroxycarboxylic acid Propionic acid, malonic acid, adipic acid, fumaric acid, maleic acid and the like. Examples of the inorganic base include, but are not limited to, ammonium hydroxide, alkali metal hydroxide, alkaline earth metal hydroxide, carbonate, bicarbonate, sulfate, and the like. More specifically, Examples thereof include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydroxide, calcium carbonate, potassium sulfate, calcium sulfate and the like. The organic base is not particularly limited, and examples thereof include alcohol amine, trialkylamine, tetraalkylammonium, and tris (hydroxymethyl) aminomethane. Examples of the alcohol amine include ethanolamine. Examples of the trialkylamine include trimethylamine, triethylamine, tripropylamine, tributylamine, and trioctylamine. Examples of the tetraalkylammonium include tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetraoctylammonium and the like.

  As a compound represented by General formula (1), you may use the commercial item containing the compound represented by General formula (1). Examples of the commercially available products include protamine hydrochloride manufactured by Maruha Nichiro Holdings Co., Ltd., protamine sulfate (salmon derived, powder) manufactured by Wako Pure Chemical Industries, Ltd., and the like.

  The water is preferably ion exchange water or pure water. The blending amount of the water with respect to the total amount of the treatment liquid may be, for example, the remainder of the other components.

  The treatment liquid may further contain a water-soluble organic solvent. A conventionally well-known thing can be used as said water-soluble organic solvent. Examples of the water-soluble organic solvent include polyhydric alcohol, polyhydric alcohol derivative, alcohol, amide, ketone, keto alcohol, ether, nitrogen-containing solvent, sulfur-containing solvent, propylene carbonate, ethylene carbonate, 1,3-dimethyl- Examples include 2-imidazolidinone. Examples of the polyhydric alcohol include glycerin, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, trimethylolpropane, 1, Examples include 5-pentanediol and 1,2,6-hexanetriol. Examples of the polyhydric alcohol derivative include ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol-n-propyl ether, Diethylene glycol-n-butyl ether, diethylene glycol-n-hexyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol-n-propyl ether, triethylene glycol-n-butyl ether, propylene glycol methyl ether, propylene glycol ethyl Ether, propylene glycol-n-propyl Ether, propylene glycol-n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol-n-propyl ether, dipropylene glycol-n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, Examples include tripropylene glycol-n-propyl ether and tripropylene glycol-n-butyl ether. Examples of the alcohol include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, and benzyl alcohol. Examples of the amide include dimethylformamide and dimethylacetamide. Examples of the ketone include acetone. Examples of the keto alcohol include diacetone alcohol. Examples of the ether include tetrahydrofuran and dioxane. Examples of the nitrogen-containing solvent include pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, triethanolamine and the like. Examples of the sulfur-containing solvent include thiodiethanol, thiodiglycol, thiodiglycerol, sulfolane, dimethyl sulfoxide and the like. The blending amount of the water-soluble organic solvent with respect to the total amount of the treatment liquid is not particularly limited. The said water-soluble organic solvent may be used individually by 1 type, and may use 2 or more types together.

  The treatment liquid may or may not contain a colorant. When the processing liquid contains a colorant, the amount is preferably such that it does not affect the recorded image.

  The treatment liquid may further contain a conventionally known additive as necessary. Examples of the additive include a surfactant, a pH adjuster, a viscosity adjuster, a surface tension adjuster, an antioxidant, and an antifungal agent. Examples of the viscosity modifier include polyvinyl alcohol, cellulose, water-soluble resin and the like.

  The treatment liquid can be prepared, for example, by uniformly mixing the compound represented by the general formula (1) and water and, if necessary, other additive components by a conventionally known method.

  The water-based ink for ink-jet recording (hereinafter, simply referred to as “water-based ink” or “ink”) used together with the treatment liquid of the present invention is not particularly limited, and will be described in the following water-based ink set for ink-jet recording, for example. Water-based ink can be used.

  Next, the water-based ink set for ink-jet recording of the present invention (hereinafter sometimes simply referred to as “water-based ink set” or “ink set”) will be described. The water-based ink set of the present invention is a water-based ink set for ink-jet recording comprising a water-based ink for ink-jet recording and a treatment liquid, wherein the water-based ink is a water-based ink containing a colorant, water and a water-soluble organic solvent, The treatment liquid is the treatment liquid of the present invention. The water-based ink set of the present invention combining the water-based ink and the treatment liquid of the present invention is excellent in the optical density (OD value) and marker resistance of the recorded matter.

  The colorant may be a pigment or a dye. In addition, a pigment and a dye may be mixed and used as the colorant.

  Examples of the pigment include carbon black, inorganic pigments, and organic pigments. Examples of the carbon black include furnace black, lamp black, acetylene black, and channel black. Examples of the inorganic pigment include titanium oxide, iron oxide inorganic pigment, and carbon black inorganic pigment. Examples of the organic pigment include azo pigments such as azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments; phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, Examples thereof include polycyclic pigments such as quinophthalone pigments; dye lake pigments such as basic dye type lake pigments and acid dye type lake pigments; nitro pigments; nitroso pigments; aniline black daylight fluorescent pigments; Also, other pigments can be used as long as they can be dispersed in the aqueous phase. Specific examples of these pigments include C.I. I. Pigment Black 1, 6, and 7; C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 15, 16, 17, 55, 78, 150, 151, 154, 180, 185 and 194; I. Pigment oranges 31 and 43; C.I. I. Pigment Red 2, 3, 5, 6, 7, 12, 15, 16, 48, 48: 1, 53: 1, 57, 57: 1, 112, 122, 123, 139, 144, 146, 149, 166, 168, 175, 176, 177, 178, 184, 185, 190, 202, 221, 222, 224 and 238; I. Pigment violet 196; C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 16, 22 and 60; C.I. I. Pigment green 7 and 36, and the like.

  The pigment may be a self-dispersing pigment. In the self-dispersing pigment, for example, at least one of a hydrophilic functional group such as a carbonyl group, a hydroxyl group, a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, and a salt thereof is directly or other than the pigment particle. By being introduced through a chemical bond, it can be dispersed in water without using a dispersant. The self-dispersing pigment is treated with a pigment by a method described in, for example, JP-A-8-3498, JP-T 2000-513396, JP-T 2008-524400, JP-T 2009-515007, and the like. Can be used. As the raw material for the self-dispersing pigment, both inorganic pigments and organic pigments can be used. Examples of pigments suitable for performing the treatment include carbon black such as “MA8” and “MA100” manufactured by Mitsubishi Chemical Corporation and “Color Black FW200” manufactured by Degussa. As the self-dispersing pigment, for example, a commercially available product may be used. Examples of the commercially available products include “CAB-O-JET (registered trademark) 200”, “CAB-O-JET (registered trademark) 250C”, “CAB-O-JET (registered trademark)” manufactured by Cabot Specialty Chemicals. Trademark) 260M "," CAB-O-JET (registered trademark) 270Y "," CAB-O-JET (registered trademark) 300 "," CAB-O-JET (registered trademark) 400 "," CAB-O-JET " (Registered trademark) 450C "," CAB-O-JET (registered trademark) 465M "and" CAB-O-JET (registered trademark) 470Y ";" BONJET (registered trademark) BLACK CW- "manufactured by Orient Chemical Co., Ltd. 2 "and" BONJET (registered trademark) BLACK CW-3 ";" LIOJET (registered trademark) WD BLACK 0 "manufactured by Toyo Ink Manufacturing Co., Ltd. 2C "; and the like.

  The solid content blending amount of the pigment (pigment solid content) with respect to the total amount of the water-based ink is not particularly limited, and can be appropriately determined depending on, for example, a desired optical density or color. The pigment solid content is, for example, 0.1% by weight to 20% by weight, preferably 1% by weight to 10% by weight, and more preferably 2% by weight to 8% by weight.

  The dye is not particularly limited, and examples thereof include direct dyes, acid dyes, basic dyes, and reactive dyes. Specific examples of the dye include C.I. I. Direct black, C.I. I. Direct Blue, C.I. I. Direct Red, C.I. I. Direct yellow, C.I. I. Direct orange, C.I. I. Direct violet, C.I. I. Direct Brown, C.I. I. Direct Green, C.I. I. Acid Black, C.I. I. Acid Blue, C.I. I. Acid Red, C.I. I. Acid Yellow, C.I. I. Acid Orange, C.I. I. Acid Violet, C.I. I. Basic Black, C.I. I. Basic blue, C.I. I. Basic Red, C.I. I. Basic violet and C.I. I. For example, food black. C. above. I. Examples of direct black include C.I. I. Direct black 17, 19, 32, 51, 71, 108, 146, 154, 168 and the like can be mentioned. C. above. I. Examples of direct blue include C.I. I. Direct blue 6, 22, 25, 71, 86, 90, 106, and 199. C. above. I. Examples of direct red include C.I. I. Direct red 1, 4, 17, 28, 83, and 227. C. above. I. Examples of direct yellow include C.I. I. Direct yellow 12, 24, 26, 86, 98, 132, 142, 173 and the like. C. above. I. Examples of direct orange include C.I. I. Direct orange 34, 39, 44, 46 and 60 are listed. C. above. I. Examples of direct violet include C.I. I. And direct violet 47 and 48. C. above. I. Examples of direct brown include C.I. I. Direct brown 109 etc. are mention | raise | lifted. C. above. I. Examples of direct green include C.I. I. Direct green 59 etc. are raised. C. above. I. Examples of acid black include C.I. I. Acid Black 2, 7, 24, 26, 31, 52, 63, 112, 118 and the like. C. above. I. Examples of acid blue include C.I. I. Acid Blue 9, 22, 40, 59, 93, 102, 104, 117, 120, 167, 229, and 234. C. above. I. As acid red, for example, C.I. I. Acid Red 1, 6, 32, 37, 51, 52, 80, 85, 87, 92, 94, 115, 180, 256, 289, 315 and 317. C. above. I. Examples of acid yellow include C.I. I. Acid Yellow 11, 17, 23, 25, 29, 42, 61, 71 and the like. C. above. I. Examples of acid orange include C.I. I. Acid orange 7 and 19 etc. are mentioned. C. above. I. Examples of acid violet include C.I. I. Acid Violet 49 and the like. C. above. I. Examples of basic black include C.I. I. Basic black 2 etc. are raised. C. above. I. Examples of basic blue include C.I. I. Basic Blue 1, 3, 5, 7, 9, 24, 25, 26, 28, 29, and the like are listed. C. above. I. Examples of basic red include C.I. I. Basic Red 1, 2, 9, 12, 13, 14, and 37 are listed. C. above. I. Examples of basic violet include C.I. I. And basic violet 7, 14, and 27. C. above. I. Examples of food black include C.I. I. Food black 1 and 2 etc. are mentioned.

  The blending amount of the dye with respect to the total amount of the water-based ink is not particularly limited, and is, for example, 0.1% by weight to 20% by weight, and preferably 0.3% by weight to 10% by weight.

  The colorant may be used alone or in combination of two or more.

  The water used in the water-based ink is preferably ion exchange water or pure water. The blending amount (water ratio) of the water with respect to the total amount of the water-based ink is, for example, 10% by weight to 90% by weight, and preferably 40% by weight to 80% by weight. The said water ratio is good also as the remainder of another component, for example.

  Examples of the water-soluble organic solvent used in the water-based ink include a wetting agent that prevents drying of the water-based ink at the nozzle tip of the ink jet head and a penetrating agent that adjusts the drying speed on the recording medium.

  The wetting agent is not particularly limited, and examples thereof include lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol; dimethylformamide, dimethylacetamide Amides such as acetone; Ketones such as acetone; Keto alcohols such as diacetone alcohol; Ethers such as tetrahydrofuran and dioxane; Polyhydric alcohols such as polyalkylene glycol, alkylene glycol and glycerin; 2-pyrrolidone; N-methyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone and the like. Examples of the polyalkylene glycol include polyethylene glycol and polypropylene glycol. Examples of the alkylene glycol include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, thiodiglycol, and hexylene glycol. These wetting agents may be used alone or in combination of two or more. Among these, polyhydric alcohols such as alkylene glycol and glycerin are preferable.

  The blending amount of the wetting agent with respect to the total amount of the water-based ink is, for example, 0% by weight to 95% by weight, preferably 5% by weight to 80% by weight, and more preferably 5% by weight to 50% by weight. is there.

  Examples of the penetrant include glycol ether. Examples of the glycol ether include ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol-n-propyl ether, diethylene glycol-n-butyl ether, diethylene glycol-n-. Hexyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol-n-propyl ether, triethylene glycol-n-butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol-n-propyl ether, Propylene glycol-n-butyl ether , Dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol-n-propyl ether, dipropylene glycol-n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, tripropylene glycol-n-propyl ether And tripropylene glycol-n-butyl ether. The said penetrant may be used individually by 1 type, and may use 2 or more types together.

  The blending amount of the penetrant with respect to the total amount of the water-based ink is, for example, 0% by weight to 20% by weight, preferably 0.1% by weight to 15% by weight, and more preferably 0.5% by weight to 10% by weight.

  The water-based ink may further contain a conventionally known additive as required. Examples of the additive include a surfactant, a pH adjuster, a viscosity adjuster, a surface tension adjuster, and an antifungal agent. Examples of the viscosity modifier include polyvinyl alcohol, cellulose, water-soluble resin and the like.

  The water-based ink is obtained by, for example, uniformly mixing a colorant, water, a water-soluble organic solvent, and, if necessary, other additive components by a conventionally known method, and removing insoluble matters with a filter or the like. Can be prepared.

  Next, in the present invention, the water-based ink set for ink-jet recording can also be provided as an ink cartridge. For example, the ink cartridge of the present invention has an ink storage portion and a processing liquid storage portion, the water storage ink of the present invention is stored in the ink storage portion, and the processing liquid of the present invention is stored in the processing liquid storage portion. The ink cartridge of the present invention may have a storage portion for aqueous ink other than the aqueous ink of the present invention.

  The ink cartridge of the present invention may be an ink cartridge assembly in which a water-based ink cartridge and a processing liquid cartridge that are separately formed are assembled, and the inside thereof may be formed to form an ink storage section and a processing liquid storage section. May be an integrated ink cartridge partitioned. As the main body of the ink cartridge of the present invention, for example, a conventionally known one can be used.

  Next, the ink jet recording method and the ink jet recording apparatus of the present invention will be described.

  The ink jet recording method of the present invention is an ink jet recording method for recording using an aqueous ink set for ink jet recording including an aqueous ink for ink jet recording and a treatment liquid, the step of applying the treatment liquid to a recording medium, and the recording And a recording step of discharging and recording the water-based ink on a medium by an inkjet method, and using the water-based ink set for ink-jet recording of the present invention as the water-based ink set.

  The ink jet recording apparatus of the present invention is an ink jet recording apparatus including an ink set storage unit, a treatment liquid applying unit, and an ink discharge unit, and the water base ink set for ink jet recording of the present invention is included in the ink set storage unit. The treatment liquid contained and constituting the aqueous ink set is applied to the recording medium by the treatment liquid application means, and the aqueous ink constituting the aqueous ink set is ejected to the recording medium by the ink ejection means. It is characterized by that.

  The ink jet recording method of the present invention can be performed using, for example, the ink jet recording apparatus of the present invention. The recording includes printing, printing, printing, and the like.

  FIG. 1 shows the configuration of an example of the ink jet recording apparatus of the present invention. As shown in the figure, the ink jet recording apparatus 1 includes an ink cartridge assembly 2, an ink discharge means (ink jet head) 3, a head unit 4, a carriage 5, a drive unit 6, a platen roller 7, and a purge device 8. And as a major component.

  The ink cartridge assembly 2 includes a treatment liquid cartridge 2a and four water-based ink cartridges 2b. The processing liquid cartridge 2a contains the processing liquid of the present invention. The four water-based ink cartridges 2b contain one color each of four colors of water-based inks of yellow, magenta, cyan, and black.

  The ink jet head 3 installed in the head unit 4 performs recording on a recording medium (for example, recording paper) P. An ink cartridge assembly 2 and a head unit 4 are mounted on the carriage 5. The drive unit 6 reciprocates the carriage 5 in the linear direction. As the drive unit 6, for example, a conventionally known one can be used (for example, see Japanese Patent Laid-Open No. 2008-246821). The platen roller 7 extends in the reciprocating direction of the carriage 5 and is disposed to face the inkjet head 3.

  The ink jet head 3 installed in the head unit 4 performs recording on the recording paper P. An ink cartridge assembly 2 and a head unit 4 are mounted on the carriage 5. The drive unit 6 reciprocates the carriage 5 in the linear direction. As the drive unit 6, for example, a conventionally known one can be used (for example, see Japanese Patent Laid-Open No. 2008-246821). The platen roller 7 extends in the reciprocating direction of the carriage 5 and is disposed to face the ink jet head 3.

  The purge device 8 sucks out defective ink containing bubbles and the like accumulated in the ink jet head 3. As the purge device 8, for example, a conventionally known device can be used (see, for example, JP-A-2008-246821).

  A wiper member 20 is disposed adjacent to the purge device 8 at a position on the platen roller 7 side of the purge device 8. The wiper member 20 is formed in a spatula shape, and wipes the nozzle formation surface of the inkjet head 3 as the carriage 5 moves. In FIG. 1, a cap 18 covers a plurality of nozzles of the inkjet head 3 that is returned to the reset position when recording is completed in order to prevent the treatment liquid and water-based ink from drying.

  In the ink jet recording apparatus 1 of this example, the ink cartridge assembly 2 is mounted on one carriage 5 together with the head unit 4. However, the present invention is not limited to this. In the ink jet recording apparatus, each cartridge of the ink cartridge assembly 2 may be mounted on a carriage different from the head unit 4. Further, each cartridge of the ink cartridge assembly 2 may not be mounted on the carriage 5 but may be arranged and fixed in the ink jet recording apparatus. In these embodiments, for example, each cartridge of the ink cartridge assembly 2 and the head unit 4 mounted on the carriage 5 are connected by a tube or the like, and each cartridge of the ink cartridge assembly 2 is connected to the head unit 4 from the cartridge. A treatment liquid and the water-based ink are supplied.

  Ink jet recording using this ink jet recording apparatus 1 is performed as follows, for example. First, the treatment liquid of the present invention is applied (discharged) to the recording paper P from the inkjet head 3. The treatment liquid may be applied to the entire recording surface or a part of the recording surface of the recording paper P. In the case of applying to a part, at least a recording portion of the recording surface of the recording paper P by the water-based ink becomes the applying portion. When giving to a part, it is better that the size of the giving part is larger than the recording part. For example, as shown in FIG. 2A, when a character (X) is recorded on the recording paper P, the treatment liquid is applied so as to form the applying portion 30 with a line width larger than the line width of the character. It is preferable to give. In addition, as shown in FIG. 2B, when recording a design on the recording paper P, it is preferable to apply the treatment liquid so as to form an application portion 40 larger than the design.

  Next, the water-based ink is ejected from the inkjet head 3 to the treatment liquid application portion of the recording paper P. The time from the discharge of the treatment liquid to the discharge of the water-based ink is not particularly limited. For example, the water-based ink may be discharged within the same scan as the processing liquid. By contacting the treatment liquid and the water-based ink on the recording paper P, the optical density (OD value) and marker resistance of the recorded image are improved. Further, the treatment liquid of the present invention is excellent in storage stability and hardly discolors (yellows), and therefore does not affect the recorded image.

  As in this example, the treatment liquid is preferably used as a pretreatment liquid that is applied to the recording paper P prior to the ejection of the water-based ink. Thereby, for example, the aggregation efficiency of the colorant in the water-based ink can be increased. However, the present invention is not limited to this. In the present invention, the treatment liquid may be applied after the water-based ink is first ejected onto the recording paper P, or the treatment liquid is applied onto the recording paper P and the water-based ink is ejected simultaneously. Also good.

  In the ink jet recording apparatus 1 of this example, the ink discharge means also serves as the treatment liquid application means. However, the present invention is not limited to this. In the present invention, the treatment liquid may be applied by, for example, stamp coating, brush coating, roller coating, or the like.

  The recording sheet P recorded in this way is discharged from the inkjet recording apparatus 1. In FIG. 1, the paper feed mechanism and paper discharge mechanism for the recording paper P are not shown.

  The apparatus shown in FIG. 1 employs a serial type ink jet head, but the present invention is not limited to this. The ink jet recording apparatus may be an apparatus employing a line type ink jet head.

  Next, examples of the present invention will be described together with comparative examples. The present invention is not limited or restricted by the following examples and comparative examples.

(Preparation of treatment solution)
The components of the treatment liquid composition (Table 6) were uniformly mixed to obtain treatment liquids 1 to 10.

(Preparation of water-based ink)
In the aqueous ink composition (Table 7), components other than the pigment aqueous dispersion were uniformly mixed to obtain an ink solvent. Next, the ink solvent was added to the aqueous dispersion of the pigment and mixed uniformly. Thereafter, the obtained mixture was filtered with a cellulose acetate type membrane filter (pore size: 3.00 μm) manufactured by Toyo Roshi Kaisha, Ltd., thereby water-based black inks K1 to K3 for inkjet recording, water-based yellow inks Y1 and Y2, water-based Magenta inks M1 and M2 and water-based cyan inks C1 and C2 were obtained.

[Examples 1 to 23 and Comparative Examples 10 to 17]
As shown in Table 8, the treatment liquids 1 to 10 are used in combination with the aqueous black inks K1 to K3 for inkjet recording, the aqueous yellow inks Y1 and Y2, the aqueous magenta inks M1 and M2, and the aqueous cyan inks C1 and C2. (A) Evaluation of optical density (OD value) of recorded matter, (b) Evaluation of marker resistance, (c) Evaluation of storage stability of processing liquid, (d) Evaluation of jetting stability of processing liquid, and (e) Synthesis Evaluation was performed by the following method. Samples used for (a) optical density (OD value) evaluation of recorded matter and (b) marker resistance evaluation were prepared as follows.

[Production of evaluation samples]
The treatment liquids of Examples 1 to 23 and Comparative Examples 10 to 17 were spread uniformly on plain paper using a bar coater (bar coater rod No. 0 manufactured by Yasuda Seiki Seisakusho Co., Ltd.). The coating amount of the treatment liquid was 0.9 mg / cm ³ . Next, using a digital multifunction device DCP-595CN equipped with an ink jet printer manufactured by Brother Industries, Ltd., using the water-based ink for ink jet recording of Examples 1 to 23 and Comparative Examples 10 to 17, a resolution of 600 dpi × Single color patches were recorded at 600 dpi. The plain paper includes Ricoh's My Paper (Plain Paper 1), Steinbeis Temming Papier's Classic White (Plain Paper 2), and Fujitsu Cower Co., Ltd. Office Paper (Plain Paper 3). ) Was used.

(A) Evaluation of optical density (OD value) of recorded matter One day after production, the optical density (OD value) at five locations in the evaluation sample was measured using a spectrocolorimeter SpectroEye (light source: D ₅₀ , manufactured by Gretag Macbeth). (Viewing angle: 2 °, density: ANSI T, white standard: Abs), and evaluated according to the following evaluation criteria.

Evaluation of Optical Density (OD Value) of Recorded Material Evaluation Criteria AAA: The average value of optical density (OD value) in plain papers 1 to 3 is the same as in Examples 1 to 23 and Comparative Examples 10 to 17 without using the treatment liquid. AA increased by 0.15 or more in comparison with Comparative Examples 1 to 9 below using water-based inks: The average value of the optical density (OD value) in plain papers 1 to 3 does not use the treatment liquid, and Examples 1 to 23 And compared with the following comparative examples 1-9 using the same water-based ink as comparative examples 10-17, it rose 0.08 or more and less than 0.15 A: The average value of the optical density (OD value) in the plain papers 1-3 B was raised by 0.04 or more and less than 0.08 compared to Comparative Examples 1 to 9 using the same water-based ink as in Examples 1 to 23 and Comparative Examples 10 to 17 without using the treatment liquid. The average value of optical density (OD value) in No. 3 was carried out without using treatment liquid. Increased by 0.02 or more and less than 0.04 in comparison with Comparative Examples 1 to 9 using the same water-based ink as in Examples 1 to 23 and Comparative Examples 10 to 17 C: Optical density (OD value) in plain papers 1 to 3 The average value increased by less than 0.02 compared to Comparative Examples 1 to 9 below using the same water-based ink as Examples 1 to 23 and Comparative Examples 10 to 17 without using the treatment liquid

(B) Marker resistance evaluation One day after preparation, the character part in the evaluation sample was traced twice with a highlighter pen with a load of 1N, and the bleeding of the character and the dirt on the pen tip were visually observed and evaluated according to the following evaluation criteria. did.

Marker resistance evaluation Evaluation standard A: Almost no ink flow from characters was observed C: Ink flow from characters was observed

(C) Storage stability evaluation of treatment liquid The treatment liquids of Examples 1 to 23 and Comparative Examples 10 to 17 were stored at 60 ° C. for 2 weeks, cooled to room temperature (25 ° C.), and evaluated according to the following evaluation criteria. Evaluated according to.

Evaluation of Storage Stability of Treatment Liquid Evaluation Criteria A: The treatment liquid hardly discolored (yellowing) compared to before storage C: Discoloration (yellowing) of the treatment liquid compared to before storage

(D) Evaluation of jetting stability of processing liquid For the processing liquids of Examples 1 to 23 and Comparative Examples 10 to 17, using the above-described digital multifunction printer DCP-595CN equipped with an ink jet printer, office paper W manufactured by Fujitsu Kowako Co., Ltd. On (recording paper), 100 million dots (approximately 30,000 sheets) were continuously discharged. The results of the continuous discharge were evaluated according to the following evaluation criteria. The non-ejection is a state in which the nozzles of the inkjet head are clogged and the treatment liquid is not ejected. The discharge bend is a state in which a part of the nozzles of the inkjet head is clogged and the processing liquid is not discharged perpendicularly to the recording paper but is discharged obliquely.

Evaluation of jetting stability of treatment liquid Evaluation standard AA: No discharge and no discharge bend during continuous discharge A: No discharge or discharge bend during continuous discharge, but no non-discharge or discharge bend However, both recovered by purging within 5 times C: During continuous discharge, there were many non-discharges and discharge bends, and both the non-discharge and discharge bends were not recovered in a short time

(E) Comprehensive evaluation Comprehensive evaluation was performed according to the following evaluation criteria from the results of (a) to (d).

Overall evaluation Evaluation criteria G: B or C was not found in the results of (a) to (d) NG: B or C was found in any of the results of (a) to (d)

[Comparative Examples 1 to 9]
As shown in Table 8, the water-based black inks K1 to K3 for inkjet recording, the water-based yellow inks Y1 and Y2, the water-based magenta inks M1 and M2, and the water-based cyan inks C1 and C2 are used alone without being combined with the treatment liquid. (A) Evaluation of optical density (OD value) of recorded matter, (b) Evaluation of marker resistance, and (e) Comprehensive evaluation were performed by the above methods.

  Table 8 shows the evaluation results of Examples and Comparative Examples.

  As shown in Table 8, in Examples 1 to 23 using the treatment liquids 1 to 6 containing protamine hydrochloride or protamine sulfate which is a compound represented by the general formula (1), the optical density (OD value) of the recorded matter All results of evaluation, marker resistance evaluation, and storage stability evaluation of the treatment liquid were good. In particular, in Examples 1 to 3 and 5 to 23 using the treatment liquid in which the blending amount of protamine hydrochloride or protamine sulfate is 0.1% by weight or more, the optical density (OD value) of the higher recorded matter is improved. In Examples 1, 2, 5 to 8, 10 to 12, and 15 to 17 using processing solutions in which the blending amount of protamine hydrochloride or protamine sulfate is 1% by weight or more, higher recorded material An improvement in optical density (OD value) was observed. In Examples 1 to 23, the evaluation results of the jetting stability of the treatment liquid were also good. Further, in Examples 1 to 3, 5 and 7 to 23 using the treatment liquid in which the blending amount of protamine hydrochloride or protamine sulfate is 0.1% by weight to 7% by weight, the optical density of the higher recorded matter ( (OD value) was improved, and the jetting stability of the higher treatment liquid was improved, and the treatment liquid in which the blending amount of protamine hydrochloride or protamine sulfate was 1% by weight to 7% by weight was used. In Examples 1, 2, 5 to 8, 10 to 12, and 15 to 17, an even higher recorded matter optical density (OD value) was improved, and higher processing liquid injection stability was improved. It was. On the other hand, in Comparative Examples 1 to 9 in which no treatment liquid was used, the result of optical density (OD value) evaluation of the recorded material was bad. Also, in Comparative Examples 10 and 11 using the treatment liquid 6 containing albumin instead of the compound represented by the general formula (1), the result of the optical density (OD value) evaluation of the recorded matter was poor. In Comparative Examples 12 and 13 using the treatment liquid 7 containing a polyallylamine unneutralized product instead of the compound represented by the general formula (1), the storage stability evaluation of the treatment liquid and the injection stability of the treatment liquid are performed. The result of evaluation was bad. Further, in Comparative Examples 14 to 17 using the treatment liquid 8 or 9 containing calcium nitrate tetrahydrate or tetraethylammonium chloride instead of the compound represented by the general formula (1), the results of the marker resistance evaluation were bad. It was.

  As described above, the treatment liquid of the present invention is excellent in all the performances of the optical density (OD value), marker resistance and storage stability of the recorded matter and excellent in water resistance. The use of the treatment liquid of the present invention is not particularly limited, and can be widely applied to various ink jet recordings.

DESCRIPTION OF SYMBOLS 1 Inkjet recording device 2 Ink cartridge aggregate 3 Inkjet head 4 Head unit 5 Carriage 6 Drive unit 7 Platen roller 8 Purge device

Claims (12)

A treatment liquid used for inkjet recording,
A treatment liquid comprising a compound represented by the general formula (1) and water.

In general formula (1),
R ¹ is a — (CH ₂ ) _p —X group (p is an integer of 1 to 4, and X is a guanidino group) ;
R ² is a neutral functional group ,
m and n are integers satisfying n / (m + n) ≧ 2/3 and satisfying 20 ≦ m + n ≦ 40, respectively, and m ≠ 0.
When a plurality of R ¹ and R ² are present, they may be the same or different. The treatment liquid according to claim 1, wherein the compound represented by the general formula (1) includes a derivative, a tautomer or a stereoisomer of the compound represented by the general formula (1), or a salt thereof. . The treatment liquid according to claim 1 or 2, wherein the compounding amount of the compound represented by the general formula (1) is 0.1% by weight or more. The treatment liquid according to claim 3, wherein the compounding amount of the compound represented by the general formula (1) is 1% by weight or more. The treatment liquid according to claim 4, wherein the compounding amount of the compound represented by the general formula (1) is 1 to 7% by weight. The treatment liquid according to any one of claims 1 to 5, wherein the compound represented by the general formula (1) is at least one of protamine hydrochloride and protamine sulfate. A water-based ink set for ink-jet recording comprising a water-based ink for ink-jet recording and a treatment liquid,
The water-based ink is a water-based ink containing a colorant, water and a water-soluble organic solvent,
The water-based ink set for inkjet recording, wherein the processing liquid is the processing liquid according to any one of claims 1 to 6 . The colorant is a black pigment;
The weight ratio of the compounding amount (X) of the compound represented by the general formula (1) in the total amount of the treatment liquid and the compounding amount (Y) of the black pigment in the total amount of the water-based ink is X: Y = 0.025: The water-based ink set according to claim 7, which is 1 to 2.5: 1. The weight ratio of the compounding amount (X) of the compound represented by the general formula (1) in the total amount of the treatment liquid and the compounding amount (Y) of the black pigment in the total amount of the water-based ink is X: Y = 0.25: 9. The water-based ink set according to claim 8, wherein the ratio is 1 to 2.5: 1. The weight ratio of the compounding amount (X) of the compound represented by the general formula (1) in the total amount of the treatment liquid and the compounding amount (Y) of the black pigment in the total amount of the water-based ink is X: Y = 0.25: The water-based ink set according to claim 9, wherein the ratio is 1-1.75: 1. An inkjet recording method for recording using an aqueous inkjet recording ink set comprising an aqueous inkjet recording ink and a treatment liquid,
Applying the treatment liquid to a recording medium;
A recording step of discharging and recording the water-based ink on the recording medium by an inkjet method,
An ink jet recording method using the water based ink set for ink jet recording according to any one of claims 7 to 10 as the water based ink set. An ink jet recording apparatus including an ink set storage unit, a treatment liquid application unit, and an ink discharge unit,
In the ink set storage portion, the water-based ink set for inkjet recording according to any one of claims 7 to 10 is stored,
The treatment liquid constituting the water-based ink set is applied to a recording medium by the treatment liquid application unit,
An ink jet recording apparatus, wherein the water-based ink constituting the water-based ink set is discharged onto the recording medium by the ink discharge means.

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