WO2001062861A1 - Ink for inkjet recording and ink cartridge having the ink therein - Google Patents

Abstract

An ink for inkjet recording which comprises water, a colorant and a rust inhibitor and is to be discharged through an opening of a nozzle having a water-repellent film containing a metal formed on the surface thereof, wherein the concentration of said rust inhibitor is determined on the basis of the number of groups contained in said colorant which may liberate an counter cation to show acidity. The ink can be used for inhibiting the erosion of a water-repellent film formed on a head for ink-jet recording.

Description

 Description: INK JET RECORDING INK AND INK CARTRIDGE HAVING THE INK

 The present invention relates to an ink for ink jet recording, and more particularly to an ink for ink jet recording, which has an excellent erosion suppressing effect on an acid generated from a coloring material in the ink and which can be stably supplied from a nozzle hole of the ink head for a long time. About the ink.

 Recently, as an output device of an information device such as a computer, a printer of an ink jet recording system, which has a low running cost, is highly accurate, and is easy to colorize, has attracted attention. There are many issues that need to be improved for the ink used in this printer. Background art

 Conventionally, a water-soluble coloring material (hereinafter referred to as a dye) has been generally used as an ink for ink jet recording. These dyes are dissolved in water, and if necessary, various additives are added thereto before use as ink for ink jet recording.

 Examples of additives to the ink include polyhydric alcohols, their dalicol ethers, and surfactants. These additives prevent ink clogging, ink bleeding on the recording medium after printing, or lead in color images (color mixing or bleeding in areas where different color areas contact each other). The image quality is reduced to achieve higher image quality.

Along with the improvement of the ink by the additive agent as described above, the color material side is also improved. For example, inkjet inks in which polyester fine resin particles colored with dyes or pigments are finely dispersed in an aqueous medium in order to improve image quality and improve water resistance and light resistance, which are drawbacks of water-soluble dye inks. (Japanese Patent Application Laid-Open No. 7-97540) is disclosed. The method for producing the aqueous dispersion of the polyester fine resin particles is described in detail, for example, in Japanese Patent Application Laid-Open No. HEI 4-296632. Further, Japanese Patent Application Laid-Open No. 7-196665 discloses a method of manufacturing an ink jet recording ink related thereto. It has been disclosed.

 By the way, a fine nozzle hole for discharging ink is formed in a head of an ink jet recording apparatus using the above-described ink. This nozzle hole is, for example, a stainless steel (SUS) nozzle plate provided with an opening having a diameter of about several tens / m. Then, a water-repellent film is provided on the nozzle plate to protect the nozzle portion in contact with the ink and to stabilize the shape of the ejected ink droplet. The water-repellent film is formed, for example, by coating a fluoropolymer or by eutectoid nickel monofluoride. In general, from the viewpoint of long-term stability, the latter, eutectoid nickel nickel fluoropolymer, is often used.

 However, the color ink, which is generally controlled so that its permeability is improved, tends to spread on the nozzle surface of the ink head, and the ink tends to wet and adhere to the nozzle surface for a long period of time. The ink may erode the water-repellent film at the adhering portion. When such erosion occurs around the nozzle hole, the coloring material in the ink adheres and solidifies, changing the shape and surface condition of the hole. For this reason, conditions for ejecting ink droplets change, and there has been a problem that long-term ejection stability cannot be maintained. In addition, the ink in which the dyed fine resin particles are dispersed, as described above, undergoes long-term storage or storage at high temperatures, causing the resin that is the base material of the coloring material to be hydrated, oxidizing the ink, and water-repellent around the nozzle. There is a problem that the film is eroded.

 It is considered that the problem of erosion due to ink as described above is caused by the fact that the metal contained in the water-repellent film is eroded (oxidized) by the acid generated by the ink. As a countermeasure, a method has been proposed in which the pH of the ink is adjusted to neutrality. However, even when the pH of the ink solution is adjusted, the dye molecule itself may have an acidic functional group as a terminal group. When such dye molecules adhere to the water-repellent film, it is difficult to effectively prevent erosion of the water-repellent film. In addition, it is difficult to adjust the pH of the fine resin-dispersed ink, and there is another problem that the stability of the ink is reduced when a pH adjuster is added too much.

In addition, there has been proposed a method of adding an erosion inhibitor (hereinafter referred to as an antioxidant) to the ink in order to protect the metal-based water-repellent film from being oxidized. Some of these inhibitors include benzotriazole. Also, Japanese Patent Application Laid-Open No. Hei 7-222880 There is a disclosure regarding ink jet recording inks containing benzotriazole. However, this ink contains a special component, and benzotriazole is used to suppress the inconvenience caused by adding this component.Only the amount added to the ink composition containing the special component is determined. Stipulates. This has no effect on any colorant and cannot guarantee long-term effects. In any of these cases, if the amount of the benzotriazole-containing antibacterial agent is too small, the water-repellent film cannot be sufficiently protected if the amount is too small, while the amount is too large. In this case, a problem arises in that the antibacterial agent itself forms a film on the water-repellent film and reduces the water-repellent action of the water-repellent film.

 A main object of the present invention is to provide an ink jet recording ink capable of suppressing erosion of a water-repellent film formed on a nozzle plate of an ink jet recording head. Another object of the present invention is to provide a related device using the above-described ink jet recording ink.

 The present inventors conducted various experiments on erosion of the metal-based water-repellent film provided in the ink nozzle portion in order to solve the above-mentioned problem. As a result, the present inventors have found suitable use conditions for the anti-oxidant contained in the ink for ink jet recording, and have reached the present invention. Disclosure of the invention

 The main purpose of the above is

 An ink jet recording ink containing at least water, a coloring material, and a waterproofing agent, which is used by being discharged from a nozzle hole in which a metal-based water-repellent film is formed,

 An ink for inkjet recording, wherein the concentration of the protective agent is determined in accordance with the number of groups of the coloring material, which dissociates the counter cation to exhibit acidity, is achieved.

ADVANTAGE OF THE INVENTION According to this invention, even if an acid is generate | occur | produced from a coloring material, a water-repellent film can be prevented from being eroded by an acid by an appropriate amount of a water-proofing agent, and an excess water-proofing agent is added. Absent. Therefore, it can be provided as an ink for ink jet recording which has excellent printing quality and guarantees ejection stability. According to the present inventors, when the concentration of the coloring material in the ink is A% by weight and the number of the groups is B, the concentration of the protective agent is from (AXB) Z600 to (AXB). ) / 10% by weight. If the values of AXB are determined so as to fall within this range, a preferable ink jet recording ink is obtained. Yo more preferable range is Z 2 0 Weight _^0/0 (AXB) from (AXB) Z 1 6 0. Further, the present inventors have studied the type of ink in which the dyed fine resin particles are dispersed, and have found preferable conditions.

 That is, at least water, which contains a coloring material having a property of generating an acid with the passage of time and an antioxidant, and is used by being ejected from a nozzle hole in which a metal-based water-repellent film is formed and used for ink jet recording The ink,

 An ink for ink jet recording, wherein the coloring material contains in advance an antibacterial agent corresponding to the concentration of an acid generated during a maximum device life period.

 According to the present invention, the antioxidant is added in consideration of an acid that may be generated in the future. Therefore, even if the ink contains a coloring material having a property of increasing the amount of acid over time, it is possible to prevent the water-repellent film from being eroded by acid in the future. Therefore, it can be provided as an ink for inkjet recording which has excellent printing quality and guarantees ejection stability. Note that the maximum device lifetime corresponds to the expiration date of the ink cartridge or the like that stores ink.

 Here, the coloring material having a property of generating an acid by changing over time can be constituted as colored fine resin particles, and a polyester resin can be used as the resin. Here, unsaturated polyester resins, alkyd resins, atalinole resins, and the like can also be used as the resins that can be similarly used.

 Benzotriazole can be used as a protective agent for the two types of ink jet recording inks. In addition, derivatives such as triazole and benzotriazole carboxylic acid, and organic inhibitors such as erythritol and ethylaniline can also be used as the protective agent.

Still another object of the present invention is to provide an ink cartridge having the above-described ink for ink jet recording. The ink cartridge using the ink jet recording ink having the excellent erosion control effect as described above, Attached to the head of the printer device, it enables excellent image formation over a long period of time. Still another object of the present invention includes providing an ink jet recording head including the above-described ink cartridge and having a metal water-repellent film formed on a nozzle portion. Such a head can prevent erosion of the nozzle portion for a long period of time, and can be provided as a component of an ink jet recording apparatus having excellent printing quality and stable ejection.

 The water-repellent film of the inkjet recording head is preferably pre-treated with a gas-proofing agent solution. By performing this pretreatment, the amount of the protective agent contained in the ink side can be suppressed to a low level. A benzotriazole solution can be used as the pretreatment antioxidant. Further, the water repellent film of the ink jet recording head may be made of eutectoid nickel monofluoride polymer. Still another object of the present invention includes providing an inkjet recording apparatus having an inkjet recording head. Since the ink jet recording head maintains the ink jet recording head in a good state for a long period of time, it can be used as a printer having excellent image forming properties. BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a perspective view showing a schematic configuration of an ink cartridge using the ink for ink jet recording of the embodiment and an ink jet recording head equipped with the ink cartridge.

 Fig. 2 is a diagram showing the ink jet recording head from the nozzle plate (plate) side.

 FIG. 3 is a diagram showing an overall outline of an ink jet recording apparatus equipped with the ink jet recording head shown in FIG. BEST MODE FOR CARRYING OUT THE INVENTION

The ink jet recording ink of the present invention will be specifically described below. The first ink shown in the first embodiment contains a water-soluble dye. In general, water-soluble dyes often have an acidic functional group at the terminal group of the molecular structure. When the dye is dissolved in water, the counter cation (eg, sodium Is dissociated. Therefore, it is considered that the acidic functional group adheres to the water-repellent film and erodes. The present inventors have examined this point, and have confirmed that the number of acid functional groups in the above dye molecules and the dye concentration in the ink can determine an appropriate amount of the antioxidant to be added to the ink. .

 The second ink shown in the second embodiment uses colored fine resin particles as a coloring material. This ink for ink jet recording has a tendency to generate acid with the passage of time, but the nozzle portion is eroded by a simple method of adding an antioxidant in advance in anticipation of the amount of acid generated in the future. To prevent (First embodiment)

 In the ink jet recording ink of the first embodiment, a general dye can be used. As the dye, a direct dye, an acidic dye, a reactive dye, or the like can be used. The amount of these additives is determined by the type of dye, solvent component, and required characteristics, but is preferably added in the range of 0.2 to 7% by weight based on the total weight of the ink.

 In order to prevent ink clogging, alcohols (eg, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol / ray, hexylene glycol, polyethylene glycol, etc.) Or a highly hygroscopic additive such as a nitrogen-containing organic solvent (eg, N-methyl-2-pyrrolidone, triethanolamine, etc.) or urea. The amount of these additives is preferably 4 to 30% by weight.

 In order to prevent clogging and increase the permeability of recording media, glycol ethers of polyhydric alcohols (for example, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.) Etc.) may be added. The amount of these additives is preferably 3 to 20% by weight. If permeability is required, a surfactant (nonionic, anionic, cationic) may be added. Further, a known viscosity adjuster, an organic solvent such as an alkyl alcohol having 1 to 4 carbon atoms, an H adjuster, a force-proofing agent and the like may be added.

In this example, four types of ink jet recording inks having the following compositions were used. (① yellow, ② magenta, ③ cyan, ④ black) were prepared. Benzotriazole was used as an anti-oxidant in the ink jet recording ink. For each of the four inks, the concentration of benzotriazole was 1) 0.01% by weight, 2) 0.05% by weight, 3) 0.1% by weight, 4) 0.5% by weight, 5). Seven types were prepared, 1% by weight, 6) 2% by weight, and 7) 5% by weight. The erosion state of the metallic hydrophobic water-repellent film formed at the nozzle was confirmed by changing the concentration of benzotriazole in each ink.

 The erosion test with the ink was performed by immersing the nozzle plate in the ink. In order to shorten the test period, it was stored at 60 ° C for 3 months. After pulling up the nozzle plate from the dipping ink, the ink was dropped on the water-repellent film remaining on the nozzle plate, and the contact angle was measured. The above storage conditions assume that normal storage is performed and about three years. This is because the expiration date of ink is usually set to about three years. The contact angle was measured using a static contact angle meter (Kyowa Interface Science Co., Ltd.) and the value after 30 seconds was used as data. The contact angle of the ink before storage was also measured, and the judgment was made based on the angle difference obtained by subtracting the contact angle after storage obtained after storage from the contact angle before storage. The smaller the angle difference, the higher the effect of suppressing erosion. Judgment was made according to the following evaluation criteria.

 ， The difference in contact angle before and after storage is within 5 degrees · · · ◎ (Excellent)

 • Difference in contact angle before and after storage is within 10 degrees · · · 〇 (good)

 'The contact angle difference before and after storage exceeds 10 degrees · · · Χ (bad)

(1) Yellow dye-based ink composition ratio

 C.I. Acid Yellow 2 32 2% by weight (Number of acidic groups 3) Diethylene glycol 8% by weight

 6% by weight of ethanol

 Triethanolamine 1% by weight

 Nonionic surfactant

 Residual pure water

The above C.I. Acid Yellow 23 has a molecular structure 1 as shown below. Fees. Dissociated cation (Na) is in the ink solution, based on S0 ₃ and COO showing acidity appears at the end. In this molecular structure, the number of acidic groups is three.

 (Molecular structural formula 1)

N

 ②Magenta dye ink composition ratio

 C.I. Direct red 46 4% by weight (Number of groups exhibiting acidity 4) Diethylene glycol 18% by weight

 Etano

 Triethanolamine 1 weight °

 Nonionic surfactant 1.

 Residual pure water

The CI director 46 is a dye having the following molecular structural formula 2. Dissociated cation (Na) is in the ink solution, it appears to S0 ₃ groups terminated exhibiting acidity. In this molecular structure, the number of acidic groups is four.

 (Molecular structural formula 2)

③Cyan dye ink composition ratio

 C. I. Acid Blue 93% by weight (Number of groups exhibiting acidity 2) Diethylene glycolone 19% by weight

 6% by weight of ethanol

0.5% by weight of triethanolamine Nonionic surfactant 1.1% by weight

 Residual pure water

The CI Acid Blue 19 is a dye having the following molecular structural formula 3. The cation (Na) is dissociated in the ink water, and the acidic S〇 ₃ group appears on the ¾. In this molecular structure, the number of acidic groups is two.

 組成 Black dye ink composition ratio

 C. I · Direct Black 154 5% by weight (Number of groups exhibiting acidity 2) Diethylene glycolone 19% by weight

 6% by weight of ethanol

 0.5% by weight of triethanolamine

 Nonionic surfactant

 Residual pure water

C.I. Direct Black 154 is a dye having the following molecular structural formula 4. Dissociated cation (Na) is in the ink solution, it appears to S0 ₃ groups terminated exhibiting acidity. In this molecular structure, the number of acidic groups is two.

 (Molecular structural formula 4)

The above-mentioned ink is supplied from the nozzle holes formed in the nozzle plate of the ink head It is discharged from. In this embodiment, a SUS plate having a thickness of about 80 μπι was used as a nozzle plate, and a nozzle hole was provided in the SUS plate. This nozzle plate was subjected to eutectoid plating of nickel-polytetrafluoroethylene. Table 1 below summarizes the evaluation. Table 1: Evaluation results of each ink

本発明者等はこの結果を検討して、 上記染料分子中の酸性官能基の数（ 中の染料濃度からィンクに添加すべき防鲭剤を適量に定めることができることを 確認した。 各インクにおける染料濃度 （重量％) Αと酸性官能基の数 （酸性を呈 する基の個数） Bの積を下記表 2に示した。 表 2 ：各インクの A X B

The present inventors examined this result and confirmed that the number of acidic functional groups in the dye molecule (the dye concentration in the dye can be used to determine an appropriate amount of the protective agent to be added to the ink. The product of the dye concentration (% by weight) Α and the number of acidic functional groups (the number of groups exhibiting acidity) B is shown in Table 2 below: Table 2: AXB of each ink

A: Dye concentration, B: Number of groups exhibiting acidity In the ink judged as particularly excellent or good in the above judgment, (A: Dye concentration) X (B: Number of groups exhibiting acidity) and benzotriazole at that time Table 3 below summarizes the relationship with concentration for each ink. Table 3-1: Yellow dye

上記表 3から [(AXB)Zへ"ンソ"トリァソ" -ル濃度]の値が 10から 600の範囲で良以 上の判定となることが確認できる。 よって、 （AXB)Z600から（AXB)Zl 0の 範囲となるようにインク中のベンゾトリァゾール濃度を定めると酸による浸蝕を 抑制し、 優れたインクジエツト記録用インクとなる。

From Table 3 above, it can be confirmed that a value of [(AXB) Z “concentration”) is within the range of 10 to 600. Therefore, it can be confirmed that the judgment is good or not. When the benzotriazole concentration in the ink is determined so as to be in the range of Z10, erosion by acid is suppressed, and an excellent ink jet recording ink is obtained.

Similarly, in the judgment of excellent or better, the value of [(AXB) Z, 'concentration of triso'-rule concentration] is in the range of 20 to 160. Therefore, if the benzotriazole concentration in the ink is determined within the range of (AXB) 160 to (AXB) / 20, it is possible to obtain an ink jet recording ink in which erosion is more reliably suppressed. (Second embodiment)

 In the ink of the second embodiment, dyed fine resin particles are used as a coloring material. It is preferable to use polyester resin particles that can be easily dyed as the fine resin particles. Oil-soluble dyes, disperse dyes and the like can be used as coloring materials for dyeing polyester resin particles. The dye concentration in the polyester resin is preferably 2% by weight or more. The amount of the resin particles added to the ink is preferably 20% by weight or less in order to maintain the stability of the ink itself.

 In this example, two types (yellow and magenta) having the following compositions were prepared as the ink jet recording ink. Benzotriazole was used as a fire retardant in this ink jet recording ink. As in the first embodiment, the concentration of benzotriazole was 1) 0.01% by weight, 2) 0.05% by weight, 3) 0.1% by weight, 4) 0.5% by weight for each of the two types of ink. %, 5) 1% by weight, 6) 2% by weight, 7) 5% by weight. The erosion state of the metallic hydrophobic water-repellent film formed at the nozzle was confirmed by changing the concentration of benzotriazole for each ink.

 The erosion test using an ink was the same as that in the first example, and the above-mentioned nozzle plate was immersed in ink. In order to shorten the test period, they were stored for 3 months in an atmosphere of 60 ° C, and the contact angle of the water-repellent film at the nozzle was measured.

 However, in the case of this example, when the polyester grease is immersed in water, it is hydrolyzed with time to generate an acid. Since this acid erodes the water-repellent film, a protective agent capable of resisting the total amount of generated acid is added.

⑤Yellow-colored polyester resin-dispersed aqueous ink composition ratio

 C. I. S o l v e n t Y e l ow 162 Polyester particles colored with

1 5 wt% of glycerin 1 2 weight ⁰ /. Nonionic surfactant

Residual pure water ⑥Magenta-colored polyester resin dispersed water-based ink Composition ratio

 Polyester particles colored with C.I.D isp e r se re d 92

The nozzle holes for ejecting Inku of the structure at 15 wt% glycerine 12 wt _^0/0 Roh two on-based surfactant 2% by weight residual pure water present embodiment, in eutectoid plated of nickel one fluoropolymer Those subjected to a water-repellent treatment were used. Table 4 below summarizes the evaluation. Table 4: Evaluation results of each ink

上記イェロー染料粒子及びマゼンタ染料粒子を含有するインクについて、 pH を測定するとインクの調製直後では、 略中性 （pH=7) にあり、 時間の経過と 共に 1ヶ月後では pH=5. 5あり、 3ヶ月後では pH=4となった。 時間の経 過と共にインク溶液が酸性側となる。 表 4には、 1ヶ月後と 3ヶ月後で耐浸蝕に 効果的なベンゾトリアゾールの添加量が示される。

When the pH of the ink containing the yellow dye particles and the magenta dye particles was measured, the pH was almost neutral (pH = 7) immediately after the ink preparation, and the pH was 5.5 after one month with the passage of time. After 3 months, pH = 4. Over time, the ink solution becomes acidic. Table 4 shows the amount of benzotriazole that is effective for erosion resistance after one month and three months.

From these results, the present inventors have found that in the case of the polyester resin-dispersed aqueous ink of this example, the acid increases with the passage of time, and that benzotriazole, which is necessary in advance for the acid generated sequentially, is considered It was confirmed that erosion of the water-repellent film can be effectively prevented by adding an excess in the ink. In particular, as described above, the test conditions of this embodiment are based on the expiration date of the ink, that is, the maximum device life period usually set to about three years. It is assumed. Therefore, if the amount of benzotriazole that prevents erosion of the water-repellent film in the erosion test of the present embodiment is added to the ink in advance, the ink for ink jet recording can suppress erosion. In addition, as pointed out as a conventional problem, the addition of an excess of the protective agent causes generation of a protective film around the nozzle. However, in the case of this embodiment, the protective agent is consumed over time and functions. Further, even if the amount of the protective agent to be initially added is not affected, film formation does not pose a problem.

 In the ink jet recording ink shown in the first and second embodiments, for example, as shown in FIG. 1A, yellow ink can be stored in a yellow ink cartridge 18 and traded. Then, as shown in FIG. 1B, the ink jet recording head 10 is mounted. The ink jet recording head 1 in Fig. (B) is for color, and the cartridges of the yellow ink cartridge 18, the magenta ink cartridge 19, the cyan ink cartridge 20, and the black ink cartridge 21 are installed. Is shown. The ink cartridges 18, 19, 20 and 21 are mounted on an ink jet recording type printer to enable excellent image formation over a long period of time. An ink-jet head using such an ink cartridge can prevent erosion of the nozzle portion for a long period of time, and can be provided as a component for a printer device having excellent printing quality and stable ejection.

 FIG. 2 shows a nozzle plate 20 which is disposed below the ink jet recording head 10 of FIG. 1 (B) and is not shown in the drawing, and a plurality of nozzle holes 21 formed in the nozzle plate 20. Have been. The nozzle plate 20 is, for example, a SUS plate, and on its surface, a water-repellent film is formed by eutectoid nickel monofluoride polymer. By using the ink jet recording head 10 having such a nozzle plate 20 and the above-described ink in combination, the ink jet recording head can be maintained in a good state for a long period of time.

 Further, as shown in FIG. 3, the ink jet recording apparatus 30 equipped with the above-mentioned ink jet recording head 10 maintains the ink jet recording head in a good state for a long period of time. It can be an excellent printer device.

(Third embodiment)

Hereinafter, as a third embodiment, a pretreatment is performed on the water-repellent film formed on the nozzle side. An example will be described in which the amount of the protective agent added is suppressed by this.

 In order to further enhance the above-described erosion control effect, the water-repellent film formed on the nozzle plate was subjected to a pretreatment with an antioxidant solution. A benzotriazole was also used as the antioxidant here, and the pretreatment was performed as follows.

 First, a benzotriazole solution is prepared. At this time, the solvent to be used may be water, but it is preferable that the benzotriazole solution is easily wetted by the water-repellent film (the contact angle of the benzotriazole solution to the water-repellent film: preferably 90 ° or less). Therefore, any of ethanol, glycols and glycol ethers, or a mixture thereof is used. Dissolve 0.1 to 2% by weight of benzotriazole in this solvent. The nozzle plate provided with the water-repellent film is immersed in this solution and left for several minutes to several hours. Pull out the nozzle plate from the solution and let it dry. At this time, rapid drying with warm air is preferred. By this treatment, even if the concentration of benzotriazole in the ink is lower than that in the above embodiment, the erosion prevention of the water-repellent film can be maintained.

 Although the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the specific embodiments, and various modifications may be made within the scope of the present invention described in the appended claims. · Changes are possible.

 According to the first ink jet recording ink of the present invention, even if an acid is generated from the coloring material immediately after the preparation of the ink, the water-repellent film is eroded by the acid because it contains an appropriate amount of a protective agent. Can be prevented, and no extra protective agent is added. Therefore, it can be provided as an ink for inkjet recording which has excellent printing quality and guarantees ejection stability.

 According to the second ink jet recording ink of the present invention, an antioxidant is added in consideration of an acid which may be generated in the future. Therefore, even if the ink contains a coloring material having a property of increasing the amount of acid with time, it is possible to prevent the water-repellent film from being eroded by acid in the future. Therefore, it can be provided as an ink for ink jet recording which has excellent print quality and guarantees ejection stability.

The ink cartridge using the ink jet recording ink having the excellent erosion suppressing effect as described above is mounted on a printer device and enables excellent image formation for a long period of time. In addition, an ink head that uses the ink jet recording ink that exhibits the excellent anticorrosion effect described above can prevent corrosion of the nozzles for a long period of time, and is provided as an ink jet recording head that has excellent print quality and ejection stability. it can.

 Further, the ink jet recording apparatus having the above-mentioned ink jet recording head can maintain a good state of the ink jet recording head for a long period of time, so that it can be used as a printer apparatus having excellent image forming properties.

Claims

The scope of the claims 1. An ink jet ink containing at least water, a colorant, and a fire retardant, which is used by discharging from a nozzle hole in which a metal-based water-repellent film is formed. An ink for ink jet recording, wherein the concentration of the protective agent is determined according to the number of groups of the coloring material. 2. The concentration of the anti鲭剤, the concentration of the coloring material in the ink is weight%, when the number of said groups of B, (AXB) from Z 6 0 0 (AXB) Z l O weight ⁰ The ink for ink jet recording according to claim 1, wherein the ratio is / ₀ . 3. Includes at least water, a coloring material having the property of generating acid upon aging, and a protective agent, and is used for ink jet recording which is used by discharging from a nozzle hole in which a metal-based water-repellent film is formed. Ink,  An ink for ink jet recording, wherein the coloring material contains in advance an antibacterial agent corresponding to the concentration of an acid generated during the maximum device life. 4. The ink for ink jet recording according to claim 3, wherein the coloring material is colored fine resin particles. 5. The ink for ink jet recording according to claim 4, wherein the resin is a polyester resin. 6. The ink for ink jet recording according to any one of claims 1 to 5, wherein the protective agent is benzotriazole. 7. An ink cartridge having the ink for ink jet recording according to claim 1. 8. An ink jet recording head comprising the ink cartridge according to claim 7, wherein a metal-based water-repellent film is formed on a nozzle portion. 9. The ink jet self-recording head according to claim 8, wherein the water-repellent film is pre-treated with an antioxidant solution. 10. The ink jet recording head according to claim 9, wherein the pretreatment agent solution is a benzotriazole solution. 11. The ink jet recording head according to claim 8, wherein the water-repellent film is a eutectoid nickel-fluoropolymer. 12. An ink jet recording apparatus comprising the ink jet recording head according to claim 11.