JP3205147B2 - Metal non-corrosive recording liquid, ink jet recording method, ink, recording unit, ink cartridge, ink jet recording apparatus and printing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates mainly to liquids in contact with a metal in order to improve the reliability of various devices and instruments having a structure in which a metal surface is used in contact with a liquid. The present invention relates to development of a metal non-corrosive recording liquid capable of effectively preventing metal corrosion. More specifically, in a non-impact recording method, particularly in a copying machine that performs recording by discharging recording droplets, a facsimile, a word processor, a device such as a printer and a plotter, when using the device,
Recording liquid capable of effectively preventing the corrosion of metal parts of the heating resistor and the conductor or the like provided in these devices caused by direct contact with metal, metals noncorrosive recording liquid, Lee
Ink jet recording method, ink, recording unit, ink
The present invention relates to a cartridge, an ink jet recording apparatus, and a printing method .

[0002]

2. Description of the Related Art Conventionally, various recording methods have been reported for a recording apparatus.
JP-A-8-36465 discloses an ink-on-demand printing system using a recording liquid containing capillary having an orifice from which the recording liquid is ejected. In the ink-on-demand printing system, a recording liquid heating element is arranged very close to the orifice. For this reason, the recording liquid containing capillary or the heating resistor provided in the vicinity is rapidly heated, and transmits a large amount of thermal energy to the recording liquid in the vicinity of the orifice, evaporating a minute portion to generate a bubble in the capillary. generate. This bubble generates a pressure wave that ejects one recording droplet from the orifice to the surface of the recording material. If the position of the recording liquid heating element relative to the orifice is suitably set and the energy transfer from the heating element to the recording liquid is carefully controlled, bubbles will disappear on or near the recording liquid heating element before the vapor escapes from the orifice.

It is known that the life of such a thermal ink-jet printer depends on the life of a conductor and a heating resistor in particular. Such remarkable failures occurring in the conductor and the heating resistor are caused by cavitation damage due to disappearance of bubbles and chemical damage due to the recording liquid. Therefore,
In order to extend the life of the thermal ink jet printer, it is desirable to prevent fatigue due to chemical change of the heating resistor and minimize damage due to cavitation.

On the other hand, for example, Japanese Patent Application Laid-Open No.
No. 372 discloses one solution for reducing fatigue of a heating resistor. That is, in general, the heating resistor is covered with a passivation layer in order to provide protection against chemical fatigue and mechanical fatigue during operation. A thin layer of silicon or aluminum oxide is disclosed. Japanese Patent Application Laid-Open No. 59-95157 discloses that in addition to silicon dioxide, silicon-
It is disclosed that an oxynitride, aluminum oxide, titanium dioxide or the like is used to first form a layer on an orifice plate, and that the heating resistor and the conductor are covered with these passivation layers. Also, Japanese Unexamined Patent Publication No.
No. 8,221,341 discloses coating a similar passivation layer made of silicon dioxide or silicon carbide on a heating resistor (tantalum / aluminum alloy) and a conductor (aluminum) already formed. Is disclosed. Japanese Patent Application Laid-Open No. 59-100214 discloses a structure of a passivation layer composed of two different layers of silicon carbide and silicon nitride or silicon oxide. The surface protection of the heating resistor and the like using the above inert substance is as follows.
Regarding the fatigue properties, all were satisfactory.

[0005]

However, if cracks or pinholes are present in the passivation layer or the surface protection layer provided on the heating resistor made of the above-mentioned inert substance, the surface protection layer becomes a desired one. There is a problem that the characteristics cannot be exhibited. In particular, when the surface protective layer is in contact with a liquid (for example, a recording liquid), the recording liquid and the heat generating resistor come into contact with each other through these cracks or pinholes, and the recording liquid forms the heat generating resistor. As a result, the existing metal is corroded and disconnected, and as a result, heat is not transferred to the recording liquid, and it becomes impossible to discharge recording droplets of a uniform size and a uniform speed from the ink jet head. . on the other hand,
In the actual manufacturing process of the heating resistor, it is difficult to eliminate cracks and pinholes on the surface protective layer, and it is desired to solve the above-mentioned problem at an early stage.

US Pat. No. 5,062,892 discloses a thermal ink jet recording liquid containing oxo anions such as phosphate, sulfate and oxalate. In the process of repeating ejection of thermal ink jet, the surface protection layer provided on the conductor or the heating resistor is dissolved or chemical damage such as kogation occurs, making it impossible to eject the recording liquid. There were also points.

Accordingly, it is an object of the present invention, such conventional to solve the problems of the art, even if the metal is in contact with the liquid metal noncorrosive generation is suppressed as much as possible of metal corrosion by liquid SL
To provide a recording solution . Further, another object of the present invention is to minimize the occurrence of corrosion caused by a recording liquid used in an ink jet recording apparatus or the like caused by a recording liquid used in the apparatus or the like. A novel metal non-corrosive recording liquid , an ink jet recording method , and an ink capable of significantly extending the life of an ink jet head, significantly increasing the reliability of the device, and further reducing the failure rate of the device. , Recording unit, ink car
An object of the present invention is to provide a cartridge, an inkjet recording apparatus, and a printing method .

[0008]

The above objects are achieved by the present invention described below. That is, the present invention provides at least
-COOM (M is an alkali metal or ammonium
Represents And a dye having at least one of the above, and dissolving or dispersing the dye.
A metallic non-corrosive recording liquid containing a liquid medium, 該記
The recording solution contains sulfate in an amount of 0.1 wt% to 1.
0.1 wt% to 0 wt%及beauty water oxides with respect to the recording liquid
1.0 wt% seen including, and the pH is adjusted to 7 to 10.5
It is to Rukin attribute noncorrosive recording liquid and said being.

Further , the present invention relates to a method for producing heat energy from a heating element.
Is applied to the recording liquid to eject recording droplets from the orifice.
Ink-jet recording method of recording
At least in a molecule of -COOM (M is an alkali metal
Or ammonium. ) And a dye having at least one
Metal non-corrosive records including liquid medium in which the filler is dissolved or dispersed
Liquid, wherein the recording liquid is a sulfate with respect to the recording liquid.
0.1 wt% to 1.0 wt% and hydroxide in the recording liquid
0.1 wt% to 1.0 wt%, and the pH is 7
Using metal non-corrosive recording liquid adjusted to ~ 10.5
An ink jet recording method characterized in that:
In addition, the present invention relates to a method wherein at least -COOM (M is
Represents the alkali metal or ammonium. ) Has at least one
With an ink containing a dye and a liquid medium for dissolving or dispersing the dye
The ink has a sulfate content of 0.1% with respect to the ink.
wt% to 1.0 wt% and hydroxide to the ink
Comprises 0.1wt% ~1.0wt%, pH Furthermore is 7-1
An ink characterized by being in the range of 0.5.

The present invention also relates to an ink containing ink.
Ink container and ink contained in the ink container
Recording unit having a recording head for discharging ink
Wherein the ink has at least -COO in the molecule.
M (M represents an alkali metal or ammonium) is 1
Dyes and a liquid medium for dissolving or dispersing the dyes.
And 0.1% by weight of sulfate to the ink.
0% by weight and 0.1% by weight of hydroxide based on the ink
~ 1.0wt%, pH range is 7 ~ 10.5
A recording unit characterized by being ink inside
is there. The present invention also relates to an ink container containing ink.
And a recording head for ejecting the ink.
The ink cartridge is configured to be detachable.
Thus, the ink has at least -COOM (M is in the molecule)
Represents an alkali metal or ammonium. )
Dye and a liquid medium for dissolving or dispersing the dye.
0.1 wt% to 1.0 wt% based on the ink
% And hydroxide to the ink from 0.1 wt% to 1. wt%.
0wt%, pH is in the range of 7-10.5
An ink cartridge characterized in that:

[0011] The present invention also relates to an ink container for storing ink.
And an ink jet head having a recording head for discharging the ink.
A jet recording apparatus, wherein the ink comprises at least
In the molecule, -COOM (M is an alkali metal or ammonium)
Represents a system. ) And a dye having at least one
Containing a liquid medium, and further adding a sulfate to the ink.
0.1 wt% to 1.0 wt% and hydroxide in the ink
0.1 wt% to 1.0 wt%, and the pH is 7
Characterized by being within the range of ~ 10.5
It is a unit recording device. Also, the present invention provides an ink
Printing on a recording material by the jet method,
When the ink has at least -COOM (M is an alkali)
Represents metal or ammonium. ) With one or more dyes
Look containing a liquid medium for dissolving or dispersing the dye, further sulfate
0.1% to 1.0% by weight of the ink and water
0.1 wt% to 1.0 wt% of the oxide with respect to the ink
Containing, and having a pH in the range of 7 to 10.5
There is provided a printing method.

[0012]

The present inventors have conducted intensive studies on the above-mentioned problems of the prior art, and found that if a liquid used in contact with a metal contains sulfate and / or hydroxide, The inventors have found that since these compounds have a film-forming ability, a metal non-corrosive liquid composition can be obtained, which led to the present invention. Further, the and contain a a manner specified amount of sulfuric acid Shio及beauty water oxides same by creating a metal-corrosive recording liquid, effectively prevents the corrosion of metal in contact with the recording liquid, ink-jet recording The present invention has been found that the life of the apparatus can be prolonged and the reliability of recording can be improved. That is, a so-called recording agent such as a dye or a pigment and a liquid medium for dispersing the same, and further, if necessary, additives such as a surface tension adjusting agent and a viscosity adjusting agent are added and prepared to prepare a recording liquid, and the recording is further performed. If the metal non-corrosive recording liquid of the present invention is prepared by adding a sulfate and a hydroxide to the liquid, when recording is performed using this compared to the case where recording is performed using a conventional recording liquid, The service life of the recording head is dramatically improved, and the reliability can be further improved. In addition, not only the recording liquid, but also a technical field having a similar problem, that is, a metal (including a semiconductor) comes into contact with a liquid for any purpose, and the corrosion of the metal caused by the contact with the liquid. The metal non-corrosive liquid composition of the present invention can be fully utilized in other fields in which generation is expected.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. The metal non-corrosive recording liquid of the present invention is contained in a liquid used in contact with a metal.
Characterized in that it contains a specific amount of sulfuric acid Shio及beauty water oxides. The sulfates and hydroxides used in the present invention are film-forming substances as described above, are dissolved or dispersed in a liquid medium, and have a function of forming a film on the wall surface of the liquid flow path,
Further, when added to the recording liquid, it is a substance that does not adversely affect the constituent components of other recording liquids, the recording head, the recording characteristics, and the like. That is, the sulfates and hydroxides that are the film-forming substances are used by being dissolved or dispersed in, for example, water or various water-soluble organic solvents, or a liquid medium that is a mixture thereof. Examples of the film forming material used in the present invention, in concrete terms, for example, as a sulfate, lithium sulfate, sodium sulfate, include such as potassium sulfate and ammonium sulfate, as the hydroxides, hydroxide Lithium, sodium hydroxide, potassium hydroxide, ammonium hydroxide and the like.

The content of the above-mentioned film-forming substance contained in the metal non-corrosive recording liquid of the present invention depends on the type of the liquid medium and the film-forming substance, the conditions to be used, and the amount of other additives. relationship, and it is appropriately determined in relation etc. between the desired liquid physical properties, 0.1 to the content of sulfuric acid salt
1.0 wt% and the content of hydroxide is 0.1 to 1.0
wt%, and most preferably, the content of sulfate is from 0.3 to 0.1%.
6 wt% and the content of hydroxide is 0.3-0.6 wt%
% Is desirable.

When the ratio between the sulfate concentration and the hydroxide concentration in the recording liquid is changed, the characteristics of the recording liquid change.
It is preferable to determine the use ratio of the sulfate and the hydroxide within the above range. For example, when tantalum (Ta) is used as a protective film on the conductor or the heating resistor in contact with the recording liquid,
When the sulfate ion concentration is as high as 1.0 wt% or more, the ability to dissolve tantalum, which is a protective film, becomes strong.
When the hydroxide concentration is as high as 1.0 wt% or more, the pH of the liquid exceeds 10.5, and phenomena such as corrosion of the constituent materials of the ink jet head occur, which is not preferable. Further, if the sulfate is not added or less than 0.1 wt%, the water resistance of the printed matter on the recording paper tends to deteriorate,
On the other hand, if the hydroxide is not added or is less than 0.1 wt%, the association of the dye is promoted, the viscosity of the recording liquid is increased, the volume of the droplet discharged from the printer head is reduced, and the print density is reduced. This is not preferable because the density and the density unevenness occur.

The metal non-corrosive recording liquid of the present invention comprises, in addition to the above, a liquid medium comprising water and a water-soluble organic solvent, and a recording agent such as a dye or pigment. The content of the water-soluble organic solvent in the recording liquid is 25 wt% or less, preferably 15 wt% or less of the total weight of the recording liquid, and the water content is 70 to 95 wt%, preferably 75 to 95 wt% of the total weight of the recording liquid.
wt% range. 25w content of water-soluble organic solvent
If the content exceeds t% or the water content is less than 70 wt%, the print quality on plain paper tends to be adversely affected, which is not preferable.

As the recording agent component contained in the metal non-corrosive recording liquid of the present invention, any one can be used. In particular, a —COOM group (M is an alkali metal or ammonium) Are preferably used in the present invention. Specifically, a dye represented by the following general formula [1] is effectively used in the present invention.

[0018]

Embedded image

Further, in the metal non-corrosive recording liquid of the present invention, Japanese Patent Application Nos. 5-116075 and 5-11-11.
No. 6076, Japanese Patent Application No. 5-116185, Japanese Patent Application No. 5-116186 and Japanese Patent Application No. 5-117176.
Dyes disclosed in Japanese Patent Application Laid-Open Publication No. H10-163, etc. can also be usefully used.

The metal non-corrosive recording liquid of the present invention is basically composed of the above-mentioned components, but can be applied to a wide range by adding various additives. An excellent recording liquid that can be effectively applied to the recording methods disclosed in the various publications described above can also be obtained. For example, various additives such as a pH adjuster, an anti-drying agent for a crystalline organic compound such as urea, a surface tension adjuster, a fungicide or a bactericide may be used to improve the physical properties.
In particular, the pH of the recording liquid is adjusted to 7 to 10.5 by a pH adjuster.
It is preferable to adjust to.

Next, a method of performing recording with the recording head shown in FIG. 2A using the non-corrosive recording liquid of the present invention will be described in detail. FIG. 2B is a cross-sectional view of FIG. The non-corrosive recording liquid of the present invention is shown in FIG.
When the electro-thermal converter 102 is introduced into the thermal action section 107 from the direction indicated by the arrow A in FIG. 2B and is driven under a predetermined condition, heat energy is instantaneously generated in the heat generating section 108, and the thermal action is performed. The liquid (recording liquid) in the heating section 107 is instantaneously heated via the surface 109. The heated recording liquid undergoes a sudden change in state and evaporates, and bubbles are formed in the heat acting portion 107 in an instant. When the power supply to the electro-thermal converter 102 is turned off, the bubbles generated in this way rapidly contract their volumes and repeat the process of disappearing.

In this repetitive process, since the metal non-corrosive recording liquid of the present invention contains a sulfate and / or hydroxide and is provided with a film forming means, the recording liquid is applied to the heat acting surface 109. If in contact or within close proximity, a film formation change occurs, causing the heat-acting surface 109 to be covered by the film. The film formed on the heat acting surface 109 in this way absorbs the shock wave generated by the high-speed contraction of the bubbles formed in the heat acting part 107 described above. Further, the heating resistance layer 111
When the upper layer 112 and the upper layer 112 are provided, the upper layer can also be protected by the above-mentioned coating.

Such a film formed on the heat acting surface 109 may be partially or completely damaged and peeled off during several shock waves. At the moment, a new film is instantaneously formed again. Therefore, in the recording process, it is equivalent to the film being constantly formed on the heat acting surface 109, and the electro-thermal converter 10 is formed.
The service life of No. 2 is much longer than in the past, the frequency of droplet formation per unit time can be increased, and printing can be performed continuously for a long time. In addition, since the above-mentioned film is dissolved or dispersed again in the liquid when released from the heat acting surface 109, the liquid flow path in the liquid discharge unit 106 is not clogged.

As described above, when the metal non-corrosive recording liquid of the present invention is used, the service life of the conventional recording head is drastically extended. In particular, German Offenlegungsschrift (DOLS) 284306
For example, in the case of a full-line type recording head having a high density multi-orifice as disclosed in Japanese Patent Publication No. 4 (1993) -1999, for example, if the recording head is an A4 size short direction full line type, about 1700 electric lines -Since the heat converter is provided, the probability of breakage of each electric-heat converter is significantly increased, which is not only a major factor for reducing the commercial value, but also causes a significant reduction in reliability. However, even in such a recording head, when the metal non-corrosive recording liquid of the present invention is used, not only the service life of each electro-thermal converter is significantly extended, but also the probability of breakage is remarkably reduced, resulting in a highly reliable device. obtain. Further, the present invention can be applied not only to the recording head recorded above, but also to any field in which a metal (including a semiconductor) comes into contact with a liquid and the liquid may cause corrosion of the metal. It is intended to significantly improve the reliability of products such as measuring devices and recording devices in the field.

FIG. 3 shows an example of an ink jet recording apparatus incorporating the above head. In FIG. 3, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to be a fixed end, and forms a cantilever. The blade 61 is arranged at a position adjacent to a recording area of the recording head, and in this example,
It is held in a form protruding into the movement path of the recording head.
Reference numeral 62 denotes a cap, which is disposed at a home position adjacent to the blade 61, and has a configuration in which the cap moves in a direction perpendicular to the direction in which the print head moves and comes into contact with the ejection port surface to perform capping. Further, an absorber 63 is provided adjacent to the blade 61 and, like the blade 61, is held in a form protruding into the movement path of the recording head.

The blade 61, the cap 62, and the absorber 63 constitute an ejection recovery section 64.
In addition, moisture and dust on the ink ejection port surface are removed by the absorber 63. USP-5062892 mentioned earlier
In the case where an ink containing phosphate or the like described in the specification is used alone or in combination, phosphate ions elute Sn ions contained in the absorber 63, and therefore, heat There has been a problem that chemical deposits such as kogation are formed on the working surface 109 and the service life of the electro-thermal converter is significantly reduced.

Reference numeral 65 denotes a recording head which has ejection energy generating means and performs recording by discharging ink on a recording material opposed to the ejection port surface provided with the ejection ports, and 66 designates a recording head on which the recording head 65 is mounted. 65 is a carriage for performing the movement of 65. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 driven by a motor 68 (not shown). As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move the recording area and the adjacent area.

Reference numeral 51 denotes a paper feed unit for inserting a recording material;
52 is a paper feed roller driven by a motor (not shown). With such a configuration, the recording material is fed to a position facing the ejection port surface of the recording head, and is discharged to a discharge section provided with a discharge roller 53 as recording proceeds. In the above configuration, when the recording head 65 returns to the home position at the end of recording or the like, the cap 62 of the head recovery unit 64 is retracted from the movement path of the recording head 65, but the blade 6
1 protrudes into the movement path. As a result, the ejection port surface of the recording head 65 is wiped. The cap 62
When the cap abuts on the ejection surface of the recording head 65 to perform capping, the cap 62 moves so as to protrude into the moving path of the recording head.

When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same position as the position at the time of wiping described above. As a result, the ejection port surface of the recording head 65 is also wiped during this movement. The above-described movement of the print head to the home position is performed not only at the end of printing and at the time of ejection recovery, but also at predetermined intervals while the print head moves through the printing area for printing to the home position adjacent to the printing area. Then, the wiping is performed along with this movement.

FIG. 4 is a view showing an example of an ink cartridge containing ink supplied to the head via an ink supply member, for example, a tube. Here, reference numeral 40 denotes an ink storage unit that stores the supply ink, for example, an ink bag, and a rubber stopper 42 is provided at the end thereof. By inserting a needle (not shown) into this stopper 42,
The ink in the ink bag 40 can be supplied to the head. Reference numeral 44 denotes an absorber for receiving the waste ink. It is preferable for the present invention that the ink container has a surface in contact with the ink made of polyolefin, particularly polyethylene.

The ink jet recording apparatus used in the present invention is not limited to the one in which the head and the ink cartridge are separate as described above, but is also suitable for the one in which they are integrated as shown in FIG. Used. In FIG. 5, reference numeral 70 denotes a recording unit, in which an ink storage unit storing ink, for example, an ink absorber is stored, and a head unit having a plurality of orifices in which the ink in the ink absorber is stored. It is configured to be ejected from 71 as ink droplets. It is preferable for the present invention to use polyurethane, cellulose or polyvinyl acetal as a material of the ink absorber. Reference numeral 72 denotes an atmosphere communication port for communicating the inside of the recording unit with the atmosphere. The recording unit 70 is used in place of the recording head shown in FIG. 2, and is detachable from the carriage 66.

[0032]

The present invention will be described more specifically below with reference to examples. The present invention is, of course, not limited to the embodiments. <Example 1> The following compositions were mixed to prepare a metal non-corrosive recording liquid of this example. -3 parts of Pro-jet fast black 2 liquid (manufactured by ICI)-10 parts of ethylene glycol-1 part of ammonium sulfate-1 part of sodium hydroxide-85 parts of water Also, when the pH of this recording liquid was measured, it was 10.5. Was. Next, the withstand voltage of the protective film formed on the aluminum surface was measured using the above-described recording liquid in a test form as shown in FIG. First, the positive electrode was connected to an aluminum substrate and the negative electrode was connected to a platinum plate using a variable current-voltmeter. Since the ink jet head shown in FIG. 2 is designed to be a positive electrode when energized, the aluminum side was used as the positive electrode in the test method shown in FIG. When the applied voltage was varied (increased) using a current-voltmeter, no current flow was observed even when a voltage of about 100 volts was applied.

Comparative Example 1 For comparison, a recording liquid was prepared by removing ammonium sulfate and sodium hydroxide from the recording liquid having the composition of Example 1.
However, the pH was adjusted to the same pH as that of the recording liquid using an aqueous ammonium solution. When the same experiment as described above was performed using this recording liquid, it was observed that a current was flowing at a low voltage (10 volts or less). Outbreaks were seen.

Example 2 The following composition was mixed to prepare a metal non-corrosive recording liquid of this example. -3 parts of Pro-jet fast black 2 liquid (manufactured by ICI)-10 parts of diethylene glycol-0.1 part of sodium hydroxide-0.1 part of ammonium sulfate-86.8 parts of water When the pH of this recording liquid was measured, 8.5. Next, the withstand voltage of the protective film formed on the aluminum surface was measured in exactly the same manner as in Example 1 except that the above-mentioned metal non-corrosive recording liquid was used. When the applied voltage was varied (increased) using a current-voltmeter, no current flow was observed even when a voltage of about 100 V was applied.

Comparative Example 2 A recording liquid having a composition excluding ammonium sulfate and sodium hydroxide was prepared from the recording liquid used in Example 2. However, the pH was adjusted to the same pH as the recording liquid of Example 2 using an aqueous ammonium solution. When a test similar to that of Example 1 was performed using this recording liquid, it was observed that a current was flowing at a low voltage (10 volts or less), and aluminum was eluted into the liquid when visually observed, and gas was generated. It was observed.

Example 3 An ink jet printer (BJ-10v (drive frequency: 3 kHz) using thermal energy as a recording liquid discharge source was used.
z, drive voltage: 23 V): BC- manufactured by Canon Inc.)
The non-corrosive recording liquid obtained in Example 1 was injected into the 01 ink cartridge, and recording was performed on SK paper (electrophotographic paper: manufactured by Canon Inc.). At this time, a head having almost no defects such as pinholes in the protective layer of the heating resistor was used as the head of the BC-01 ink cartridge. As a result, the printer head was able to continue printing normally even in a print durability test of 4 × 10E7 pulses or more. In addition, the ejection amount of the recording liquid from the nozzles, the print density of the recorded matter obtained, and the water resistance were also evaluated. Table 2 shows the results.

Comparative Example 3 The following composition was mixed, and the pH was adjusted to 8.5 in the same manner as in Example 2.
Thus, a recording liquid having the following composition was prepared. (Composition) 3 parts of Pro-jet fast black 2 liquid (manufactured by ICI) 10 parts of ethylene glycol 12 parts of sodium sulfate 0.6 parts of sodium hydroxide 88.5 parts of water In the same manner as described above, the ink was injected into a BC-01 recording liquid cartridge and subjected to a print durability test.
In printing with 10E7 pulses or more, the tantalum of the protective film was dissolved, the heater portion was electrically disconnected, and printing was impossible.

<Comparative Example 4> A liquid composition shown below was mixed, and p
The pH was adjusted to pH 8.5 with a pH adjuster to prepare a metal non-corrosive recording solution of the present invention. (Composition) 3 parts of Pro-jet fast black 2 liquid (manufactured by ICI) 10 parts of diethylene glycol 0.05 parts of sodium hydroxide 0.3 parts of ammonium sulfate 86.65 parts of water The obtained recording liquid was used in Example 3. In the same manner as described above, the ink was injected into a BC-01 recording liquid cartridge, and recording was performed on SK paper. The recording liquid ejection amount from the nozzles, the print density of the obtained recorded matter, and water resistance were evaluated. The results are shown in Table 1, but was inferior to the printing density of the printed matter.

<Comparative Example 5> The following liquid composition was mixed, and p
The pH was adjusted to pH 8.5 with a pH adjuster to prepare a metal non-corrosive recording solution of the present invention. (Composition)-3 parts of Pro-jet fast black 2 liquid (manufactured by ICI)-10 parts of diethylene glycol-0.4 parts of sodium hydroxide-0.05 parts of ammonium sulfate-86.65 parts of water The obtained recording liquid was used in Example 3. In the same manner as described above, the ink was injected into a BC-01 recording liquid cartridge, and recording was performed on SK paper. The recording liquid ejection amount from the nozzles, the print density of the obtained recorded matter, and water resistance were evaluated. The results are shown in Table 1. The printed matter was inferior in water resistance.

[0040]

[Table 1]

The details of each evaluation method in the table are shown below. * 1: Recording liquid ejection amount An inkjet printer using thermal energy (B
J-10v (drive frequency: 3 kHz, drive voltage: 23
V): BC-01 ink cartridge manufactured by Canon Inc.) was filled with each recording liquid, and Canon: NP-DRY
After printing several sheets on copy paper, the amount of recording liquid ejected from one nozzle was estimated from the weight change of the recording liquid cartridge (BC-01).

* 2: Print density evaluation Printing was performed on Canon: NP-DRY copy paper using the same ink jet recording apparatus as described above, and the print density of the printed matter was measured with a Macbeth densitometer (TR918).

* 3: Water resistance evaluation Printing was performed on Canon: NP-DRY copy paper using the same ink jet recording apparatus as described above, and after one hour, the printed matter was immersed in a water tank for three seconds, and the flow of the printed matter was observed. The following evaluations were made by different companies.・ ・ ・: Printed matter hardly flows into water. Δ: The printed matter slightly flows, but characters can be read. X: Most of the printed matter flows, making it impossible to read characters.

[0044]

As described above, according to the present invention, it is possible to reduce as much as possible the corrosion of metal caused by the contacted liquid, which occurs in an apparatus used in a state where the liquid contacts the metal. In particular, there is provided a metal non-corrosive recording liquid capable of effectively preventing disconnection or melting of a metal due to corrosion, which is generated when a metal acts as an electrode material or the like. Further, according to the present invention, there is provided a non-corrosive recording liquid for a metal. As a result, the life of the head of an ink jet recording apparatus utilizing thermal energy as a recording liquid discharge source can be remarkably extended, and furthermore, a failure of the apparatus can be achieved. Ink jet recording method , ink, recording unit, ink cartridge,
And an ink jet recording apparatus and a printing method .

[Brief description of the drawings]

FIG. 1 is a schematic view of a withstand voltage measuring device used in the present embodiment.

FIG. 2 is a schematic view of a head section of the ink jet recording apparatus.

FIG. 3 is a perspective view illustrating an example of an inkjet recording apparatus.

FIG. 4 is a longitudinal sectional view of the ink cartridge.

FIG. 5 is a perspective view of a recording unit.

[Explanation of symbols]

 40: ink storage unit 42: stopper 44: absorber 45: ink cartridge 51: paper feed unit 52: paper feed roller 53: paper discharge roller 61: blade 62: cap 63: absorber 64: discharge recovery unit 65: recording head 66: Carriage 67: Guide shaft 68: Motor 69: Belt 70: Recording unit 71: Head 72: Atmospheric communication port

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takashi Katsuragi 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Osamu Nishiwaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside (72) Inventor Keiichi Murai 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Norifumi Hattori 3-30-2, Shimomaruko, Ota-ku, Tokyo Canon Inc. (58) Field surveyed (Int. Cl. ⁷ , DB name) C23F 11/18 B41M 5/00 C09D 11/00 WPI (DIALOG)

Claims (24)

(57) [Claims] 1. A metal non-preservative comprising a dye having at least one —COOM (M represents an alkali metal or ammonium) in a molecule and a liquid medium in which the dye is dissolved or dispersed.
A food of the recording liquid, the recording liquid, the recording liquid of sulfuric acid salt
The a 0.1 wt% 1.0 wt% and hydroxides against
A non-corrosive recording liquid containing 0.1 wt% to 1.0 wt% of a recording liquid and having a pH adjusted to 7 to 10.5. Wherein said liquid medium is 70 to 95 wt% water and 25
The metal non-corrosive recording liquid according to claim 1 , comprising a water-soluble organic solvent of not more than wt%. 3. The method according to claim 1, wherein the non-corrosive recording liquid is an ink-jet recording liquid.
3. The ink according to claim 1, which is an ink used for recording.
Metallic non-corrosive recording liquid. 4. The dye has a structure represented by the following general formula:
The non-corrosive recording liquid according to claim 1, which has: 5. The ink-jet recording method of the thermal energy is caused to act on the recording liquid system which performs recording by discharging recording liquid droplets from the orifice from a heating element, according to claim 1
An ink jet recording method using the metal non-corrosive recording liquid according to any one of the items 4 to 4 . (6) at least -COOM (M is an a
Represents the alkali metal or ammonium. ) Has at least one
With an ink containing a dye and a liquid medium for dissolving or dispersing the dye
The ink has a sulfate content of 0.1% with respect to the ink.
wt% to 1.0 wt% and hydroxide to the ink
0.1 wt% to 1.0 wt%, pH is 7-1
An ink characterized by being in the range of 0.5. 7. The ink according to claim 1, wherein the ink is an ink for ink-jet recording.
The ink according to claim 6, which is an ink. 8. The ink according to claim 1 , wherein the ink is an electro-thermal converter.
Orifice by the action of thermal energy supplied from the
Used for ink jet recording of the type ejected from the
The ink according to claim 6, which is an ink to be used. 9. The dye has a structure represented by the following general formula:
An ink according to any one of claims 6 to 8, which has: 10. An ink container and an ink container containing ink.
And the ink container Eject the ink contained in the
Recording unit equipped with a recording head for
hand, When the ink has at least -COOM (M is
Represents potassium metal or ammonium. Dyeing with one or more
And a liquid medium for dissolving or dispersing the dye, and sulfuric acid.
0.1 wt% to 1.0 wt% of the salt with respect to the ink and
0.1 wt% to 1.0 wt of hydroxide to the ink
%, And the pH is in the range of 7 to 10.5.
Recording unit, characterized in that the recording unit is 11. The recording head according to claim 1,
Contractors with an electro-thermal converter to add energy
The recording unit according to claim 10. 12. The electro-thermal converter includes a metal part.
The recording unit according to claim 11. 13. The dye has a structure represented by the following general formula:
The recording according to any one of claims 10 to 12, which has:
Unit: embedded image 14. An ink storage unit that stores ink.
To the recording head for discharging the ink.
An ink cartridge configured to be detachable, The ink has at least -COOM (M is Al
Potassium metal or ammonium Represents a system. Dyeing with one or more
And a liquid medium for dissolving or dispersing the dye.
0.1% to 1.0% by weight of the acid salt with respect to the ink.
0.1 wt% to 1.0 w
t% and pH is in the range of 7 to 10.5
An ink cartridge characterized by the above-mentioned. 15. The dye has a structure represented by the following general formula:
The ink cartridge according to claim 14, which has: 16. An ink container containing ink and said ink container.
Ink jet with a recording head for discharging ink
A recording device, When the ink has at least -COOM (M is
Represents potassium metal or ammonium. Dyeing with one or more
And a liquid medium for dissolving or dispersing the dye.
0.1% to 1.0% by weight of the acid salt with respect to the ink.
0.1 wt% to 1.0 w
t% and pH is in the range of 7 to 10.5
An ink jet recording apparatus characterized by the above-mentioned. 17. The method according to claim 17, wherein the recording head is heated with respect to the ink.
Contractors with electro-thermal converters to add energy
An inkjet recording apparatus according to claim 16. 18. The electro-thermal converter includes a metal part.
The inkjet recording apparatus according to claim 17. 19. The dye has a structure represented by the following general formula:
The inn according to any one of claims 16 to 18, which has
Jet recording device: 20. The method according to claim 19, wherein the ink is applied by an ink-jet method.
In a method of printing on a recording material, the ink is at least
In the molecule, -COOM (M is an alkali metal or ammonium)
Represents a system. And a dye having at least one of
Containing a liquid medium, and further adding a sulfate to the ink.
0.1 wt% to 1.0 wt% and hydroxide in the ink
0.1 wt% to 1.0 wt%, and the pH is 7
Characterized in that the ink is within the range of ~ 10.5.
Printing method. 21. The ink jet method according to claim 1, wherein
Heat ink to turn the ink off.
Claim: It has a step of discharging from the orifice.
20. The printing method according to 20. 22. Application of thermal energy to ink
, A recording head having an electro-thermal converter in an ink flow path
22. The method according to claim 21, wherein the conversion is performed by the electro-thermal converter.
Printing method. 23. The electro-thermal converter includes a metal member.
The printing method according to claim 22. 24. The dye has a structure represented by the following general formula:
The printing according to any one of claims 20 to 23, comprising:
Method: