JP3227259B2 - Aqueous ink and recording method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based ink composition suitable for ink-jet recording, and more particularly to a water-based ink composition exhibiting excellent properties as a color ink for so-called plain paper, and a recording method using the same.

[0002]

2. Description of the Related Art In recent years, ink jet printers have become popular because of their advantages such as low noise and low running cost, and color printers capable of printing on plain paper have also been put on the market. However, the color reproducibility of the image, waterfastness, lightfastness,
It is difficult to satisfy all of the dryness of an image, image bleeding, and the reliability of ejection. In particular, in the case of a color printer, even if the image quality is not deteriorated in the single-color printing portion of yellow, magenta, and cyan, the image quality is likely to be deteriorated in a portion where two colors of red, green, and blue are overlapped. In particular, when drying is performed without using a fixing device, since the drying property is improved by increasing the permeability as disclosed in Japanese Patent Application Laid-Open No. 55-29546, the paper bleeds significantly depending on the paper type. Japanese Patent Publication No. 60-23793 discloses that dialkylsulfosuccinic acid as a surfactant improves drying properties and causes less deterioration in image quality. On the alkali side, there is a problem that the activator is decomposed and the activating effect is lost during storage. In addition, Tokubo Sho 5
JP-A-8-6752 discloses a fast-drying ink with less bleeding by improving the permeability of an ethylene oxide adduct having an acetylene bond by using a surfactant. However, depending on the dye, there is a problem that the drying speed is not improved due to hydrophobic interaction with a direct dye such as DBK168.

Japanese Patent Application Laid-Open No. 56-57862 discloses an ink to which a strongly basic substance is added.
It is effective for rosin-sized acidic paper, but not for paper using alkyl ketene dimer or alkenyl sulfosuccinic acid as a sizing agent. In addition, even with acidic paper, there is no effect in the two-color overlapping portion.

JP-A-1-203483 discloses a recording liquid characterized by containing a polyhydric alcohol derivative and pectin. This recording liquid is prepared by adding pectin as a thickener to reduce bleeding. However, since pectin is nonionic having a hydroxyl group as a hydrophilic group, there is a problem in that the pectin lacks ejection stability after printing is stopped.

[0005]

SUMMARY OF THE INVENTION A first object of the present invention is to provide an aqueous ink recording composition which satisfies various characteristics as an ink-jet ink, has excellent drying properties, and has improved image quality deterioration. . Another object of the present invention is to provide a recording method for favorably forming an image using the ink composition.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that by using a specific sulfonic acid salt as an ink component, the surface tension is reduced to 50 mJ / m ² or less, and the ink and the paper surface are removed. It has been found that the wettability can be improved and that the image deterioration is extremely small as compared with conventionally known surfactants. That is, the present invention provides (1) an aqueous ink containing a colorant and a compound represented by the following structural formula.

[0007]

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(M is an alkali metal ion, quaternary ammonium, quaternary phosphonium, alkanolamine, R
₁ , R ₂ is an alkyl group having 4 or more carbon atoms which may be branched;
Is an integer of 1 or more) and (2) an ink jet recording method in which thermal energy is applied to the ink to eject the ink as droplets from the fine holes to perform the recording, and the recording method using the water-based ink according to the above 1 is summarized. It is assumed that.

In the compound represented by the above (I) used in the present invention, lithium ion,
In addition, when quaternary ammonium and quaternary phosphonium represented by the following general formulas are used, the ink exhibits excellent dissolution stability, and is more reliable in storage stability at low temperatures, ejection stability, and the like. be able to.

[0010]

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(Y: nitrogen or phosphorus R _{3 to} R ₆ : hydrogen, alkyl group having 1 to 4 carbon atoms, hydroxyalkyl group, halogenated alkyl group) The pH of the ink of the present invention is preferably 6 or more. preferable. Within this range, the storage stability of the ink is excellent,
Stable ejection is possible even after long-term printing is stopped or during continuous ejection. Copy papers, notes, etc. used in the office are p
In many cases, H is 5 to 6, but ink is ejected from these minute ejection openings of 30 to 60 μm onto these recording papers and the weight is 30 n.
To provide a recording method of forming a high-quality, high-resolution recording image by flying as a droplet of g to 160 ng at a speed of 6 to 20 m / s and recording in a so-called ordinary manner with a Steckigt sizing degree of 3 seconds or more. Can be. The compound (I) that can be used in the present invention is specifically shown below in the form of a free acid.

[0012]

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[0013]

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These compounds are referred to as Левис. м.
(Kolloidn 2h, 47, 303, 1985)
They can be easily synthesized by the same known methods as described above. However, it is necessary to sufficiently purify the inorganic salt by a method using an ion exchange resin or the like. Preferably, the amount of the inorganic salt in the activator is 1% or less.

Compound (I) which can be used in the present invention
Can be added to the ink properties required by the printer system in the range of 0.05 to 10% by weight to give desired permeability. Here, if it is less than 0.05%, bleeding occurs at the boundary of the two-color overlapping portion in any case,
If it is added in excess of 10% by weight, the compound (I) itself tends to precipitate at a low temperature, or precipitation of a dye may occur, resulting in poor reliability.

The pH of the aqueous ink of the present invention is adjusted by adding the above compound (I) in the form of a free acid and then adding sodium hydroxide, lithium hydroxide or a counter ion represented by the following formula. It is preferable to add a substance.

[0017]

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(Y: nitrogen or phosphorus R _{3 to} R ₆ : alkyl group, hydroxyalkyl group, halogenated alkyl group having 1 to 4 carbon atoms) For example, in the case of a lithium salt, it can be carried out by adding lithium hydroxide. For quaternary ammonium, phosphonium, alkanolamine cations of formula (II),
Specifically, it is performed by adding a hydroxide shown below.

[0019]

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(II-9) Triethanolamine cation (C ₂ H ₅ OH) ₃ NH.sup. + In the present invention, all the counter ions of the compound (I) are sodium, lithium and / or It need not be a compound of formula (II) and can be mixed with other alkali ions. It is preferable that sodium, lithium and / or the compound of the general formula (II) is added so that the amount of ions is at least 30%, more preferably at least 50%, based on the number of moles of the compound (I).

The ink of the present invention uses water as a liquid medium. However, in order to obtain desired physical properties of the ink, to prevent drying of the ink, and to improve the dissolution stability of the compound of the present invention. The following water-soluble organic solvents can be used for the purpose of, for example, preventing the following water-soluble drying for the purpose of improving the dissolution stability of the compound of the present invention.

Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6 hexanediol, glycerol,
Polyhydric alcohols such as 2,6-hexanetriol, 1,2,4-butanetriol, 1,2,3-butanetriol, petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Polyhydric alcohol alkyl ethers such as monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether; Methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-capro Nitrogen-containing heterocyclic compounds such as octamamide and γ-butyrolactone; amides such as formamide, N-methylformamide, formamide, N, N-dimethylformamide; monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine, etc. Amines, dimethyl sulfoxide, sulfolane, sulfur-containing compounds such as thiodiethanol, propylene carbonate, ethylene carbonate and the like. These solvents are used alone or in combination with water.

Of these, particularly preferred are diethylene glycol, thiodiethanol, polyethylene glycol 200 to 600, triethylene glycol, glycerol, 1,2,6-hexanetriol, 1,2,4
-Butanetriol, petriol, 1,5-pentanediol, N-methyl-2-pyrrolidone, and the use of these compounds has an excellent effect on the high solubility of the compound and the prevention of poor jetting properties due to moisture evaporation. Is obtained.

The penetrant other than the compound (I) of the present invention for adjusting the surface tension includes diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, Examples thereof include alkyl and aryl ethers of polyhydric alcohols such as diethylene glycol monobutyl ether, propylene glycol monobutyl ether, and tetraethylene glycol chlorophenyl ether, fluorine-based surfactants, ethanol, and lower alcohols such as 2-propanol. Is diethylene glycol monobutyl ether.

The surface tension referred to in the specification of the present invention is an index indicating the permeability to paper, and particularly indicates the dynamic surface tension in a short time of 1 second or less after the surface is formed, and the static tension measured by the saturation time. Different from surface tension. The measuring method is described in JP-A-63-3
Any method can be used as long as it can measure a dynamic surface tension of 1 second or less by a conventionally known method described in Japanese Patent No. 1237 or the like, but in the present invention, it was measured using a Wilhelmy type hanging plate type surface tensiometer. The value of surface tension is 50 mJ / m
^{When it is 2} or less, more preferably 40 mJ / m ² or less, excellent drying properties can be obtained.

As the water-soluble dye used as a coloring material, a dye classified into an acid dye, a direct dye, a basic dye, a reactive dye and an edible dye in a color index and having excellent water resistance and light resistance is used. Can be Specific examples of these dyes include acid dyes and food dyes such as C.I. I. Acid. Yellow 17,23,42,4
4,79,142 C.I. I. Acid. Red 1,8,13,14,1
8, 26, 27, 35, 37, 42, 52, 82, 8
7, 89, 9297, 106, 111, 114, 115, 134, 18
6,249,254,289 C.I. I. Acid. Blue 9,29,45,92,2
49 C.I. I. Acid. Black 1,2,7,24,2
6,94 C.I. I. hood. Yellow 3,4 C.I. I. hood. Red 7, 9, 14 C.I. I. hood. Black 1,2 As a direct dye, C.I. I. direct. Yellow 1,12,24,2
6, 33, 44, 50 120, 132, 142, 144, 86 C.I. I. direct. Red 1,4,9,13,1
7, 20, 28, 31, 39, 80, 81, 83, 8
9,225,227 C.I. I. direct. Orange 26,29,62,1
02 C.I. I. direct. Blue 1,2,6,15,2
2,25,71,76,79,86,87,90,9
8,163,165,199,202 C.I. I. direct. Black 19,22,32,3
8, 51, 56, 7174, 75, 77, 154, 168, 171 As basic dyes, C.I. I. basic. Yellow 1,2,11,13,
14, 15, 19, 21, 23, 24, 25, 28, 2
9, 32, 36, 40, 41, 45, 49, 51, 5
3,63,465,67,70,73,77,87,9
1, C.I. I. basic. Red 2,12,13,14,
15, 18, 22, 23, 24, 27, 29, 35, 3
6,38,39,46,49,51,52,54,5
9, 68, 69, 70, 73, 78, 82, 102, 1
04, 109, 112 C.I. I. basic. Blue 1,3,5,7,9,2
1,22,26,35,41,45,47,54,6
2,65,66,67,69,75,77,78,8
9, 92, 93, 105, 117, 120, 122, 1
24, 129, 137, 141, 147, 155 C.I. I. basic. Black 2,8 As a reactive dye, C.I. I. Reactive. Black 3,4,7,11,
12, 17 C.I. I. Reactive. Yellow 1,5,11,1
3,14,20,21,22,25,40,47,5
1, 55, 65, 67 C.I. I. Reactive. Red 1,14,17,2
5,26,32,37,44,46,55,60,6
6, 74, 79, 96, 97 C.I. I. Reactive. Blue 1,2,7,14,1
5, 23, 32, 35, 38, 41, 63, 80, 95, etc. can be used. Particularly, acid dyes and direct dyes can be preferably used.

As the pigment, organic pigments such as azo, phthalocyanine, anthraquinone, quinacridone,
Dioxazine-based, indigo-based, thioindigo-based, perylene-based, isoindolenone-based, aniline black, azomethine-based, rhodamine B lake pigment, carbon black, and the like. Examples include aluminum hydroxide, barium yellow, navy blue, cadmium red, chrome yellow, and metal powder.

As the pigment dispersant, as a hydrophilic polymer,
In natural systems, plant polymers such as gum arabic, gum tragan gum, guar gum, karaya gum, locust bean gum, arabinogalactone, pectin, quince seed starch, seaweed polymers such as alginic acid, carrageenan, agar, gelatin, casein, albumin , Animal macromolecules such as collagen, microbial macromolecules such as xanthene gum and dextran, and semi-synthetic microfibrous macromolecules such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and carboxymethylcellulose, sodium starch glycolate ,
Starch polymers such as sodium starch phosphate, seaweed polymers such as sodium alginate and propylene glycol alginate, and pure synthetic systems include vinyl polymers such as polyvinyl alcohol, polyvinylpyrrolidone and polyvinyl methyl ether, and non-crosslinked poly Acrylamide, polyacrylic acid and alkali metal salts thereof, acrylic resins such as water-soluble styrene acrylic resin, water-soluble styrene maleic acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic resin, polyvinyl pyrrolidone, polyvinyl alcohol, alkali metal salt of β-naphthalenesulfonic acid formalin condensate,
Examples include a polymer compound having a salt of a cationic functional group such as a quaternary ammonium or an amino group in a side chain, and a natural polymer compound such as shellac.

In the ink of the present invention, conventionally known additives can be added in addition to the coloring agent and the solvent.
For example, as a preservative and fungicide, sodium dehydroacetate,
Sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate, sodium pentachlorophenol, and the like can be used in the present invention.

As the pH adjuster, any substance can be used as long as it can adjust the pH to 7 or more without adversely affecting the prepared ink. Examples thereof include amines such as diethanolamine and triethanolamine, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide, and quaternary phosphonium. Examples include hydroxides, carbonates of alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate.

Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate and sodium uramil diacetate.

As the rust inhibitor, for example, acid sulfite,
Examples include sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite. Other water-soluble UV absorbers depending on the purpose,
A water-soluble infrared absorber and a surfactant can also be added.

[0033]

EXAMPLES Examples of the present invention and comparative examples are shown below. Example 1 A composition having the following formulation was stirred and dissolved at 60 ° C., allowed to cool at room temperature, and then adjusted with a 10% aqueous solution of lithium hydroxide so as to have a pH of 8. Then, the mixture was passed through a 0.22 μm Teflon filter. The mixture was filtered to produce Yellow Ink 1.

C. I. Acid Yellow 23 1.2% by weight Glycerol 5% by weight Diethylene glycol 5% by weight Compound (I-1) 0.8% by weight Sodium dehydroacetate 0.2% by weight Deionized water Remaining Example 2 Except for using the following composition Magenta ink 1 was prepared in the same manner as in Example 1 except that the pH was adjusted to 9 with sodium hydroxide.

C. I. Acid Red 254 1.7% by weight 1,2,6-hexanetriol 8% by weight 1,5-pentanediol 8% by weight Compound (I-2) 1.2% by weight Specific example (II-1) 25% aqueous solution 0 0.8% by weight 2-pyridinethiol-1-oxide sodium 0.2% by weight Remaining ion-exchanged water Example 3 The same procedure as in Example 1 was carried out except that the following composition was used.
Was changed to 9 with lithium hydroxide to prepare Cyan Ink 1.

C. I. Acid blue 249 1.9% by weight N-methyl-2-pyrrolidone 5% by weight Glycerol 2% by weight Propylene glycol monobutyl ether 2% by weight Compound (I-3) 0.5% by weight Specific example (II-3) 25% aqueous solution 0.2% by weight Sodium dehydroacetate 0.2% by weight Deionized water Remaining amount Example 4 The same procedure as in Example 1 was carried out except that the following composition was used.
Was changed to 9 with lithium hydroxide to prepare Black Ink 1.

C. I. Food black 2 3.2% by weight Ethylene glycol 5% by weight Glycerol 2% by weight 1,5-pentadiol 10% by weight Compound (I-4) 0.8% by weight Specific example (II-4) 25% aqueous solution 2% by weight Sodium benzoate 0.2% by weight Deionized water Remaining Example 5 The same procedure as in Example 1 was carried out except that the following composition was used.
Was adjusted to 9 with sodium hydroxide to prepare a yellow ink 2.

Direct Yellow 120 1% by weight Triethylene glycol 5% by weight Petriol 10% by weight Compound (I-5) 2% by weight Specific example (II-2) 25% aqueous solution 1.5% by weight Ion exchange water Remaining Example 6 The procedure of Example 1 was repeated, except that the following composition was used.
Was adjusted to 8 with lithium hydroxide to prepare a magenta ink 2.

Direct Red 9 1.5% by weight Propylene glycol 8% by weight Glycerol 7% by weight Compound (I-9) 2% by weight Specific example (II-7) 25% aqueous solution 1% by weight Remaining ion-exchanged water Example 7 Except using the following composition, it carried out similarly to Example 1, and carried out pH adjustment.
Was adjusted to 9 with lithium hydroxide to prepare a cyan ink 2.

Direct Blue 199 1.8 wt% N-hydroxyethyl-2-pyrrolidone 8 wt% 1,5-pentadiol 8 wt% Compound (I-1) 0.8 wt% Sodium benzoate 0.1 wt% Example 8 Except for using the following composition, the same procedure as in Example 1 was carried out except that the following composition was used.
Was adjusted to 8 with sodium hydroxide to obtain Black Ink 2.

Direct Black 168 2.8% by weight Thiodiethanol 5% by weight Glycerol 10% by weight Compound (I-7) 1.5% by weight Benzoic acid 0.1% by weight Ion-exchanged water Remaining Comparative Example 1 In Example 1 A yellow ink 3 was prepared in the same manner except that the compound (I-1) was omitted. Comparative Example 2 A magenta ink 3 was prepared in the same manner as in Example 2 except that the compound (I-2) was changed to sodium (2-ethylhexyl) sulfosuccinate.

Comparative Example 3 A cyan ink 3 was prepared in the same manner as in Example 3, except that the compound (I-3) was changed to dodecylbenzenesulfonic acid. Comparative Example 4 A black ink 4 was prepared in the same manner as in Example 4, except that the 25% aqueous solution was removed and the ink pH was set to 4.5.

Comparative Example 5 A yellow ink 4 was prepared in the same manner as in Example 5 except that the compound (I-5) was replaced by a nonionic surfactant BT7 (manufactured by Nikko Chemicals). Comparative Example 6 A magenta ink 4 was prepared in the same manner as in Example 6, except that the 25% aqueous solution of the specific example (II-7) was removed and the pH was adjusted to 8 with potassium hydroxide.

Comparative Example 7 Cyan ink 4 was prepared in the same manner as in Example 7 except that dodecyl sulfate was used instead of compound (I-1). Comparative Example 8 A black ink 5 was prepared in the same manner as in Example 8, except that (I-7) was changed to Surfynol 465 (manufactured by Air Products), a nonionic surfactant having an acetylene bond. Next, the following tests were performed on Examples 1 to 8 and Comparative Examples 1 to 8.

1) Clearness of image 300 dp of the thermal ink jet system shown in FIG.
i. Ink jet printer with nozzle and FIG.
The laminated PZT shown in FIG.
Printing is performed by an ink jet printer having a nozzle of dpi, and bleeding at the boundary of a two-color overlapping portion, image bleeding, color tone,
The concentration was visually judged comprehensively. The printing paper was printed on three types of commercially available recycled paper, high quality paper and bond paper.

2) Drying property of image The filter paper was pressed against the printed image under certain conditions, and the time until the ink was not transferred to the filter paper was measured. If any of the papers dried within 10 seconds, it was judged as "good". 3) Storage stability Each ink was placed in a polyethylene container and stored at -20 ° C, 5 ° C,
It was stored at 20 ° C. and 70 ° C. for 3 months under the respective conditions, and the surface tension, viscosity, and the presence or absence of precipitation of the precipitate after storage were examined. No change in physical properties and the like was observed regardless of the conditions of storage.

4) Reliability at the time of printing suspension During the operation of the printer having the head shown in FIG. 2, it is examined how much time (seconds) can be restored even if printing is suspended without capping or cleaning. Table 1 shows the results of evaluating the reliability depending on whether the ejection direction shifts or the weight of the ejected droplet changes.

[0048]

[Table 1]

[0049]

According to the present invention, the use of the compound represented by the structural formula (I) improves the wettability on the paper surface, satisfies various characteristics as an ink jet, is excellent in drying properties, and improves the deterioration of image quality. The aqueous ink composition can be provided.

Further, according to the recording method of the present invention, there is provided a recording method which shows good wettability to both so-called plain paper and coated paper for ink-jet, and can form a color image having a high penetration rate and little bleeding. be able to. As described above, according to the present invention, a high-quality color image can be stably recorded on plain paper, and this has the effect of promoting the spread of ink jet color printers.

[Brief description of the drawings]

FIG. 1 is a schematic view of an ink jet printer used for evaluating the ink of the present invention.

FIG. 2 is a schematic view of another ink jet printer.

Continuation of front page (56) References JP-A-56-95961 (JP, A) JP-A-4-39366 (JP, A) JP-A-1-275179 (JP, A) JP-A-6-313138 (JP) , A) (58) Fields studied (Int. Cl. ⁷ , DB name) C09D 11/00-11/20 B41J 2/01-2/21 B41M 5/00 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] A water-based ink comprising a colorant and a compound represented by the following structural formula. Embedded image (M is an alkali metal ion, quaternary ammonium,
Primary phosphonium, alkanolamine, R ₁ and R ₂ are a branched alkyl group having 4 or more carbon atoms, and m is an integer of 1 or more) 2. The compound of claim 1 wherein the counter ion is sodium, lithium and / or a quaternary ammonium, quaternary phosphonium or alkanolamine cation represented by the following general formula (II): The aqueous ink according to claim 1, wherein Embedded image (Y is nitrogen or phosphorus; R _{3 to} R ₆ are hydrogen;
Alkyl group, hydroxyalkyl group, halogenated alkyl group) 3. The compound (I) according to claim 1 in the form of a free acid, and sodium hydroxide, lithium hydroxide and a hydroxide of the counter ion (II) according to claim 2 are further added. 2. The aqueous ink according to claim 1, wherein the pH is adjusted to 6 or more. 4. An ink jet recording method in which recording is performed by applying thermal energy to ink to eject ink as droplets from micro holes, wherein the aqueous ink according to claim 1 is used. 5. A method for forming a color image on a recording material having a Steckigt sizing degree of 3 seconds or more using the water-based ink according to claim 1 and ejecting the water-based ink from a fine ejection port as a droplet. Characterized recording method.