JPH11236525A - Water-base refill ink composition for ink jet recording and recording method using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a refill ink which can prevent the corrosion and plugging of a nozzle in an ink jet printer. SOLUTION: This ink compsn., which is used for refilling an ink cartridge of an ink jet printer which carries out recording by causing a recording liquid to fly through an orifice formed on a metal plate, mainly comprises a colorant and a water-soluble org. solvent and has a chlorine content of 0.2 wt.% or lower.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous ink composition (refill ink) to be refilled into an ink cartridge of an ink jet printer and a recording method using the refill ink, and in particular, to a nozzle even when the refill ink is used. Corrosion and clogging can be prevented,
The present invention relates to a refill ink for inkjet recording having the same ejection stability, storage stability, and high quality printing quality as in the initial stage, and a recording method thereof.

[0002]

2. Description of the Related Art Conventionally, an ink cartridge used in an ink jet printer is used in a system in which if the ink is used until the ink is no longer discharged, the ink cartridge itself is discarded and replaced with a new ink cartridge. No consideration was given to reusing cartridges. But,
When designing a cartridge that provides stable ink that does not change its ink components or physical properties even during long-term storage or environmental fluctuations, the characteristics and life of the cartridge member and the absorber member that holds the ink can withstand repeated use. It turns out to be something. Also, recently, there has been an interest in reusing ink cartridges due to dust problems, environmental problems, costs, etc., but if ink can be refilled, cartridges can be reused without problems, Refill ink (refill ink) and a refill device that can refill the cartridge when the ink runs out have been provided.

[0003]

However, the problem with the use of the above-described refill ink is that when the refill ink is used, the color is similar to that of the initial color due to the difference in the maker or the like, but the color is initially filled. The material and the ink composition are different from the ink used. Further, in the case of refill ink, the purification of the dye may not be sufficient from the viewpoint of cost and the like.Therefore, in the refill ink, an inorganic salt added as a salting-out agent in addition to an inorganic salt by-produced in the process of dye synthesis. That is, a large amount of salt, Si, Ca, and Fe is contained.

However, the above inorganic salts, Si, Ca,
If the content of Fe is large, the formation of insoluble inorganic salts, the clogging of the nozzle due to the deposition of dye, and the corrosion of the nozzle formed on the metal plate are caused, and the same ejection stability and storage stability as the initial stage. Can not be obtained.

JP-A-7-60984 and JP-A-7-60984
Japanese Unexamined Patent Application Publication No. 7-90206 describes a method and an apparatus for refilling ink into an ink cartridge, and Japanese Unexamined Patent Application Publication No. 7-90206 discloses a refill ink having a specified surface tension. In Japanese Patent Application Laid-Open No. H11-163, it is described that the inorganic salt in the ink for initial filling is regulated. However, none of these conventional techniques can obtain a refill ink capable of preventing clogging and corrosion of the nozzle.

The present invention has been made in view of such circumstances, and particularly, ink jet recording that prevents corrosion and clogging of nozzles and has the same ejection stability, storage stability, and high-quality printing quality as the initial stage. An object of the present invention is to provide a refill ink for use and an ink jet recording method using the refill ink.

[0007]

According to the present invention, first, there is provided an aqueous cartridge which is refilled and used in an ink cartridge of an ink jet printer which performs recording by flying a recording liquid from an orifice formed on a metal plate. an ink composition, the composition composed mainly of a colorant and a water-soluble organic solvent, and, Cl is contained in the composition ^- concentration is equal to or less than 0.2 wt% inkjet An aqueous ink composition for recording refill is provided.

Secondly, in the refilling ink for ink jet recording described in the above item 1, wherein the pH of the aqueous ink composition is in the range of 9 or more and 11 or less. A composition is provided.

Third, an aqueous ink composition used by refilling an ink cartridge of an ink jet printer for performing recording by flying a recording liquid from an orifice formed on a metal plate, wherein the composition is colored And a water-soluble organic solvent as a main component, and the concentration of SO ₄ ²⁻ contained in the composition is 1.0% by weight or less. Provided.

Fourthly, in the refillable aqueous ink composition for ink-jet recording described in the third aspect, the amount of Si, Ca and Fe contained in the aqueous ink composition is preferably 100 ppm or less. A refillable aqueous ink composition for ink-jet recording is provided.

Fifthly, an aqueous ink composition to be refilled and used in an ink cartridge of an ink jet printer for performing recording by flying a recording liquid from an orifice formed on a metal plate, wherein the composition is colored and a water-soluble organic solvent as a main component, Cl is further contained in the composition ^- concentration of less 0.2wt%, SO ₄ ^2- concentration is 1.0
wt% or less and the amount of Si, Ca, Fe
pm or less is provided.

Sixth, the nozzle surface having an ink discharge port is made of Ni-PTF using any one of the aqueous ink compositions for refilling for ink jet recording described in the above first to fifth aspects.
An ink jet recording method is provided, in which ink is ejected and recorded by a recording head made of E-eutectoid plating.

Hereinafter, the present invention will be described in detail. As described above, the present invention includes a water-based ink composition that is refilled and used in an ink cartridge of an inkjet printer that performs recording by flying a recording liquid from an orifice formed on a metal plate. It has been found that by using an ink jet recording refill ink having a Cl ^- concentration of 0.2 wt% or less, corrosion of nozzles of an ink jet printer is suppressed, and the same ejection stability as in the initial stage can be obtained. . The Cl ^- concentration is 0.1. By controlling the content to 1 wt% or less, a more effective corrosion inhibiting effect can be obtained, and by setting the content to 0.05 wt% or less, a further effect can be obtained.

In the present invention, the pH of the refill ink is preferably 9 or more and 11 or less. Adjusting the pH to 9 or more has the effect of further preventing metal corrosion on the nozzle surface. Further, long-term storage stability of the ink can be ensured. On the other hand, if the pH value exceeds 11, a problem arises in the liquid contact property of a polymer member such as a plastic in a portion where the ink contacts. As the pH adjuster, any substance can be used as long as it can adjust the pH to a predetermined value without affecting the ink. For example, amines such as diethanolamine and triethanolamine; hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide;
For example, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, carbonates of alkali metals such as lithium carbonate, sodium carbonate and potassium carbonate can be used.

Further, the present invention is characterized in that the concentration of SO ₄ ²⁻ contained in the refill ink is 1.0% by weight or less. That is, SO ₄ ^2- affects the solubility of the dye in the ink, and when the content is large, aggregation and precipitation of the dye are caused. These cause nozzle clogging which should be most avoided in ink jet recording. By setting the concentration of SO ₄ ^2- in the refill ink to 1.0 wt% or less,
Ink storage stability and ejection reliability can be ensured. The SO ₄ ²⁻ concentration is 0. By setting the content to 1 wt% or less, higher storage stability and higher ejection reliability can be obtained.

Further, the present invention is characterized in that the amounts of Si, Ca and Fe contained in the refill ink are each 100 ppm or less. These amounts are 100p each
If it exceeds pm, it may cause nozzle clogging. When the ink comes into contact with the air, carbon dioxide gas in the air dissolves into the ink, and insoluble inorganic salts such as calcium carbonate are generated, causing nozzle clogging. Si,
Ca and Fe content is 100 ppm or less, more preferably 5 ppm or less.
By setting the content to 0 ppm or less, the same ejection reliability as in the initial stage can be obtained even when the refill ink is used.

Further, the present invention is characterized in that recording is performed using an ink jet recording head in which a nozzle surface having an ink discharge port is made of Ni-PTFE (polytetrafluoroethylene) eutectoid plating. That is, Ni-P
By using an ink jet recording head that has been subjected to TFE eutectoid plating, even when a refill ink is used, the same ink repellency to the ink as in the initial stage is obtained, and metal corrosion is suppressed, so that the ink has Stable discharge can be performed for a long time without flying bending or clogging. As a result, it is possible to obtain a high-quality image with fast drying property. Here, as the effect of suppressing metal corrosion, not only clogging but also prevention of uniform ink repellency from being obtained due to corrosion can be prevented.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The basic constitution of the refill ink of the present invention comprises water, a colorant dispersed or dissolved in water, and a water-soluble organic solvent. As the colorant, 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. These are added in such a range that the effect is not inhibited. Specific examples of these dyes include the following.

As acid dyes and food dyes, 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, 92, 97, 106, 111, 114, 11
5,134,186,249,254,289 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
6,33,44,50,86,120,132,14
2,144 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, 71, 74, 75, 77, 154, 1
68,171

As the basic dye, 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
3,63,64,65,67,70,73,77,8
7, 91 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 reactive dyes, 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. Further, a dye newly developed for ink jet can of course be used. For example, the Projet Fast marketed by Zeneca
B1ack 2, Project Fast Fast
nta 2, Pojet Fast Yellow
2, R's et FaIX Cyan 2 (registered trade name)
Is mentioned.

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 of inorganic pigments include iron oxide, titanium oxide, calcium carbonate, and barium sulfate. Examples include aluminum hydroxide, barium yellow, navy blue, cadmium red, chrome yellow, and metal powder.

Examples of the water-soluble organic solvent include, but are not limited to, the following. Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Polyhydric alcohol alkyl ethers such as diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monophenyl ether,
Polyhydric alcohol aryl ethers such as ethylene glycol monobenzyl ether, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-
Pentanediol, 1,6-hexanediol, glycerol, 1,2,6-hexanetriol, 1,2,4
-Butanetriol, 1,2,3-butanetriol,
Polyhydric alcohols such as petriol, N-methyl-2-
Pyrrolidone, N-hydroxyethyl-2-pyrrolidone,
2-pyrrolidone, 1,3-dimethylimidazolidinone,
Nitrogen-containing double-ring compounds such as ε-caprolactam; formamide, N-methylformamide, formamide, N, N
Amides such as dimethylformamide; monoethanolamine, diethanolamine, triethanolamine,
Examples include amines such as monoethylamine, diethylamine, and triethylamine; sulfur-containing compounds such as dimethylsulfoxide, sulfolane, and thiodiethanol; propylene carbonate; ethylene carbonate; and γ-butyrolactone.

Further, in order to adjust physical properties of the ink, it is preferable to include a surfactant. As a surfactant,
Examples include, but are not limited to, anionic and nonionic surfactants. Other, if necessary,
Preservatives, fungicides, antioxidants and UV absorbers can also be added.

[0026]

EXAMPLES Examples of the present invention and comparative examples are shown below. Examples 1 to 3 The aqueous ink compositions having the following formulations were sufficiently stirred and dissolved at room temperature, and the pH of the aqueous ink was adjusted to 10.5 with lithium hydroxide. Cl in the ink ^-, SO ₄ ^2-, S
After adjusting the amounts of i, Ca, and Fe to predetermined values as shown in Table 1 below, dust and the like were removed by filtration with a Teflon filter. Further, degassing was performed for about 30 minutes to prepare Inks 1 to 3. Dye 4.0 wt% Diethylene glycol 15 wt% glycerol 10 wt% surfactant (manufactured by ECTD3NEX Nikko Chemicals Co., Ltd.) of 1.5 wt% Ion-exchanged water Balance The ink composition, Cl ^-, SO ₄ ^2- accurately by ion chromatography Quantified. The contents of Si, Ca, and Fe were accurately quantified by a plasma emission spectrometer.
Table 1 shows the results of the quantification.

Next, a metal corrosion test and a discharge stability test were carried out using the above-mentioned inks 1 to 3 in the same manner as those performed on the initial filling ink shown below. Table 1 shows the results. Evaluation 1: Metal Corrosion Test Ni-PT was placed on a Ni plate in 20 ml of Ink 1.
Nozzle plate with FE eutectoid plating (size: 2 cm x 1
cm) was left immersed at 60 ° C. for 14 days, and the amount of Ni in the ink before and after the immersion was quantified. The quantification method is I
CP (Inductively coupled pl)
asma) Quantification by internal standard quantification method by emission spectroscopy. Yttrium was used as an internal standard. As an ICP emission spectrometer, Shimadz
uPS ICPS-1000IV was used. As an evaluation criterion, the amount of increase in Ni in the ink before and after standing was 1 p.
pm or less: ◎, 1 ppm or more and 2 ppm or less: 、 ２, 2 pp
m or more: x was used.

Evaluation 2: Discharge stability (clogging characteristic) test A Ni plate (FIG. 1) was used as an ink jet recording head.
Ink cartridge for inkjet printer using laminated PZT for pressurizing the liquid chamber flow path using a head having a nozzle surface (reference numeral 5 in FIG. 1) coated with Ni-PTFE eutectoid plating on the middle reference numeral 3). The ink was then refilled with Inks 1 to 3 and left for 3 months at room temperature with the cap capped, printing was performed, and the change from the initial state was observed. As evaluation criteria, ○: normal print record was obtained, Δ: flight bending of the recording droplet was observed, ×: recording droplet could not be ejected from the nozzle.

Comparative Examples 1 to 4 Cl ⁻ , SO ₄ ²⁻ , Si, Ca, F in the ink of Example 1
After adjusting the amount of e to each predetermined value as shown in Table 1, by filtering through a Teflon filter,
Dust was removed. Further, degassing was performed for about 30 minutes to prepare Inks 4 to 7. The prepared ink was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0030]

[Table 1]

Table 1 shows that the Cl ^- concentration in the ink composition was 0.2 wt% or less, more preferably 0.1 wt% or less,
If the content is 5 wt% or less, the metal corrosiveness is steadily reduced. On the other hand, if the SO ₄ ²⁻ concentration is 1.0 wt% or less, further 0.1 wt% or less, the clogging property is further improved. It can be seen that the improvement of the clogging characteristics also requires that the amounts of Ca, Si, and Fe be 100 ppm or less.

[0032]

As described above, according to the refill ink in which the Cl ^- concentration in the aqueous ink composition containing a colorant and a water-soluble organic solvent as the main components is 0.2 wt% or less, the refill ink is formed on the metal plate. Thus, even when the ink cartridge is refilled and used, the same ejection stability and storage stability as the initially filled ink can be obtained. Further, S in the aqueous ink composition
By setting the O ₄ ²⁻ concentration to 1.0 wt% or less, the solubility of the dye is secured, nozzle clogging due to dye deposition is prevented, and the amounts of Ca, Si, and Fe are reduced to 100 pp.
By setting it to m or less, clogging of the nozzle due to generation of an insoluble inorganic salt or the like can be prevented, and the same ejection stability and storage stability as in the initial stage can be obtained. Furthermore, the nozzle surface having such a refill ink discharge port is Ni-PT
By recording with a recording head made of FE eutectoid plating, corrosion of nozzles is prevented and ink repellency is obtained, so that ejection stability, storage stability and high-quality images can be obtained.

[Brief description of the drawings]

FIG. 1 is an enlarged sectional view showing an example of a recording head for inkjet recording according to the present invention.

[Explanation of symbols]

REFERENCE SIGNS LIST 1 ink flow path forming member 2 ink flow path 3 Ni plate 4 ink discharge port 5 nozzle surface having ink discharge port or Ni-PTF
E eutectoid plating layer 6 Ink ejection element 7 Drive line

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masato Igarashi 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Akiko Konishi 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Ricoh Co., Ltd. (72) Inventor Masayuki Kotani 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Company Ricoh Co., Ltd. (72) Inventor Hirotaka Mochizuki 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Company Ricoh ( 72) Inventor Takanori Tsukigi Ricoh Co., Ltd. 1-3-6 Nakamagome, Ota-ku, Tokyo

Claims (6)

[Claims] 1. An aqueous ink composition which is refilled and used in an ink cartridge of an ink jet printer which performs recording by flying recording liquid from an orifice formed on a metal plate, wherein the composition comprises a colorant and a colorant. A refillable aqueous ink composition for ink jet recording, comprising a water-soluble organic solvent as a main component, and having a Cl ^- concentration of 0.2 wt% or less in the composition. 2. The refill ink for ink-jet recording according to claim 1, wherein the pH of the aqueous ink composition is 9
An aqueous ink composition for refilling for inkjet recording, wherein the aqueous ink composition is in the range of 11 to 11. 3. An aqueous ink composition to be refilled and used in an ink cartridge of an ink jet printer for performing recording by flying a recording liquid from an orifice formed on a metal plate, wherein the composition comprises a colorant. SO ₄ containing a water-soluble organic solvent as a main component and contained in the composition
^{2- A} refillable aqueous ink composition for inkjet recording, having a concentration of 1.0 wt% or less. 4. The refillable aqueous ink composition for ink-jet recording according to claim 3, wherein the amounts of Si, Ca, and Fe contained in the aqueous ink composition are each 100 pp.
m or less, and a refillable aqueous ink composition for inkjet recording. 5. An aqueous ink composition to be refilled and used in an ink cartridge of an ink jet printer for performing recording by flying a recording liquid from an orifice formed on a metal plate, wherein the composition comprises a colorant and a colorant. A water-soluble organic solvent as a main component, and further containing Cl contained in the composition.
^- concentration of less 0.2wt%, SO ₄ ^2- concentration is 1.0 wt%
Wherein the amounts of Si, Ca, and Fe are 100 ppm or less, respectively. 6. A recording head using the aqueous ink composition for refilling for ink-jet recording according to any one of claims 1 to 5, wherein a nozzle surface having an ink discharge port is made of Ni-PTFE eutectoid plating. An ink jet recording method characterized by discharging and recording.