JP2005320529A - Ink for inkjet recording, inkjet recording method, ink cartridge and inkjet recording apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink for inkjet recording which can prevent a bronze phenomenon from being generated, can obtain an image excellent in weather resistance including gas resistance, etc., and do not cause corrosion/deterioration of a member subject to direct contact with ink on a recording head, nozzle, etc. <P>SOLUTION: The ink for inkjet recording comprises at least a copper phthalocyanine dye represented by general formula (1) in the drawing and further comprises a compound represented by general formula (2) in the same drawing. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an ink for ink jet recording, an ink jet recording method, an ink cartridge, and an ink jet recording apparatus.

  Conventionally, when a dye is used as the recording agent (coloring material in the recording liquid), as the recorded image dries, the dye crystals precipitate on the paper, and the recorded image reflects light and shines in yellow or brown to give a metallic luster. The so-called bronze phenomenon occurs. When the bronze phenomenon occurs, light is reflected, so that not only the density of the recorded image is lowered, but also the color tone is greatly deviated from that required for ink.

  In order to prevent this bronze phenomenon, it is known to add alkanolamines such as N-hydroxyethylmorpholine, monoethanolamine, diethanolamine, and triethanolamine to the ink. However, when these are added to the ink, the pH of the ink becomes as high as 9 or more even if the addition amount is small. Such an ink having a high pH has a problem of ejection stability due to corrosion of a nozzle touched by the ink, and may cause a problem in safety when it is accidentally touched by a person during handling. In addition, when the ink accidentally enters the eye or from the degree of freedom in selecting the member that contacts the ink, the pH is desired to be neutral (around pH 7). Further, when these alkanolamines are added to the ink, there is a problem that even if the bronzing phenomenon can be reduced, the water resistance is lowered.

  In addition, when para-toluenesulfonic acid amide ethylene oxide was added to the ink, the bronzing effect was effective, but the contact angle between the ink and the recording medium was reduced, resulting in feathering and OD (optical density). The print quality deteriorated significantly. Although addition of a basic amino acid to the ink has been studied, the addition amount needs to be at least 1% by mass to 2% by mass, and the pH is not so high that the solvent is not used. Depending on the composition, the pH is 8 or more, so it cannot be said that the ink has a neutral pH, and there is a concern such as corrosion of the nozzle touched by the ink (for example, see Patent Document 1).

  In recent years, dyes having particularly excellent weather resistance have been used. However, particularly in the case of copper phthalocyanine dyes, the weather resistance and the occurrence of bronzing have a trade-off relationship.

  The ink used in an ink jet recording apparatus such as an ink jet printer is prepared by selecting an optimum material from among many materials. For example, even if attention is focused only on dyes, there are direct dyes, acid dyes, etc., each having different characteristics. For example, when printing with ink using a direct dye, the formed image is characterized by relatively excellent weather resistance, and when printing with an ink using an acid dye, high brightness and saturation are obtained. This is characterized in that a printed material can be obtained.

  Ink for inkjet recording (1) No clogging at the nozzle tip, (2) Stable recording even during continuous recording or when recording is resumed after standing for a long time (intermittent ejection stability or recovery of fixation) (3) characteristics such as no change in physical properties even after long-term storage of the ink are required.

  Conventionally, urea, urea derivatives, thiourea, thiourea derivatives, and the like are added to ink as a moisturizing agent in order to prevent clogging of the nozzle tip due to water evaporation. In order to improve the intermittent ejection stability, urea or urea derivatives are added to the ink as a dye solubilizing agent in order to improve the solubility of the dye in water or various solvents. (For example, refer to Patent Document 2).

  However, some dyes produce aggregates or decompose due to ammonium ions generated by the decomposition of urea. For this reason, if the ink to which urea is added is stored for a long period of time, a precipitate is generated due to aggregation of the dye, and there is a problem that clogging occurs in the ink discharge port or the ink supply pipe of the ink jet recording apparatus. Furthermore, regardless of the type of color material, the urea-added ink may corrode the metal part due to ammonia generated by the decomposition of urea, or the odor of ammonia may make the user uncomfortable.

  By the way, in the conventional ink jet system, ink having a viscosity as low as 1 to 3 mPa · s is ejected from a nozzle or opening having a small diameter of about 30 to 50 μm. In other words, since the ink has a sufficiently low viscosity, ink replenishment (refilling) from the ink storage unit can be performed at high speed against a decrease in the amount of ink in the nozzle or opening due to ink ejection. As a result, since the meniscus (interface between ink and air) at the nozzle tip or opening is quickly recovered, ejection stability can be obtained even when high-speed printing with a repeated printing frequency exceeding 10 kHz is performed.

  However, when printing on a recording medium such as plain paper using low-viscosity ink, the ink permeates quickly into the recording medium, and bleeding (feathering) occurs along the fibers of the paper. Reduces image quality with a rough feeling. Further, when adjacent dots are connected by blurring, the resolution is reduced only by that portion, and there is a problem that the image quality is extremely lowered. In order to solve these problems, the penetration speed of the ink into the recording medium is suppressed by controlling the surface tension of the ink. However, when a color image is formed using ink with reduced penetration speed, mixed color bleeding (bleeding) occurs when inks of different colors are placed adjacent to each other on the recording medium and contact with each other. There was a problem of greatly lowering.

  With respect to the problems that occur when using the above-described low-viscosity ink, by using a high-viscosity ink, the penetration rate of the ink into the recording medium can be slowed to prevent bleeding. Further, since the mixing speed between different colors is also suppressed, color mixing can be prevented, which is a very effective means for solving the above-mentioned problems.

  With the spread of recording apparatuses using the ink jet method, the application is rapidly expanding, and along with this, the types of recording media are also diversified. Furthermore, it is expected to be applied not only to paper but also to non-liquid-absorbing media such as metal, plastic and glass, and the realization of an ink jet recording apparatus that can use high viscosity ink is awaited.

  However, in the conventional ink jet system, when the viscosity of the ink is increased, the flow path resistance is increased, and the ink supply speed into the nozzle or the opening is remarkably reduced. Further, in this case, the energy required for ink ejection is remarkably increased as the flow path resistance is increased. For example, when a high-viscosity ink is used in an ink jet apparatus that normally uses a commercially available water-based ink (viscosity 1 to 3 mPa · s), the ink viscosity may exceed 10 mPa · s into the ink nozzle or opening. The supply will not be in time, and the meniscus recovery will not be in time.

  If ink is discharged in such a state, ink is discharged from an unstable meniscus position, so that variations in the amount and direction of ink discharge increase and image quality deteriorates. Further, when the viscosity of the ink exceeds 20 mPa · s, the supply of the ink into the nozzle or the opening is not in time, and the discharge omission occurs. Further, when the viscosity of the ink exceeds 100 mPa · s, even if the ink is supplied to the nozzle or the opening in time, the energy for discharging the ink is insufficient in the conventional pressure generating means, and the ink is not discharged. It will be stable or will not discharge at all.

  On the other hand, in order to reduce the flow resistance, there has been proposed a printer for increasing the nozzle diameter from about 50 μm to about 70 μm and printing at a high speed using ink having a high viscosity of 10 to 100 mPa · s. (For example, see Patent Document 3). In this method, unless the nozzle diameter is increased by an amount corresponding to the increase in the viscosity of the ink, the ink supply speed is reduced, and the printing frequency is repeatedly decreased. However, when the nozzle diameter is increased, the diameter of the ejected ink droplet is relatively increased, leading to a problem that resolution and image quality are deteriorated.

JP 7-228810 A JP-A-2-173168 JP 9-169111 A

  As described above, an ink for ink jet recording that can suppress the occurrence of bronzing and satisfies various performances required for ink for ink jet recording has not been obtained.

  Accordingly, the first object of the present invention is to prevent the occurrence of bronzing, to provide an image having excellent weather resistance such as gas resistance, and to corrode members such as recording heads and nozzles that come into contact with ink. It is to provide an ink for inkjet recording that does not deteriorate.

  Compared with the conventional inkjet technology, the nozzle diameter is less than 20μm and the droplet volume is less than 4.5 picoliters for the purpose of reducing graininess in the trend toward higher image quality in recent inkjet recording technology. 2. Description of the Related Art Recording heads that have nozzles with such a fine diameter that they cannot be used have been used. With such an extremely fine nozzle, the influence of clogging becomes more conspicuous, and at the same time, the intermittent ejection stability is significantly deteriorated. As a result of studies by the present inventors, even in a low humidity environment, the tendency becomes remarkable as the temperature decreases, and in an environment of 15 ° C. or lower, the intermittent discharge stability is remarkably deteriorated, so that the print quality may be impaired.

  Therefore, the second object of the present invention is to satisfy the first object and further, when used in the ink jet recording method, the ink from the recording head does not cause clogging in the nozzle or the opening of the ink jet recording apparatus. There are no problems such as droplets not being ejected, and the same good intermittent ejection stability and fixing recovery as ink jet inks with the addition of ureas can be obtained. Another object of the present invention is to provide an ink for ink jet recording having an appropriate viscosity that does not cause flocculation and is excellent in long-term storage stability and ejection stability, and capable of producing a printed matter with high resolution and high image quality.

  Furthermore, another object of the present invention is to provide an ink jet recording method, an ink cartridge, and an ink jet recording apparatus using the ink for ink jet recording.

  As a result of intensive studies by the present inventors in view of the above-mentioned object, it is possible to increase the solubility of a copper phthalocyanine dye by adding an amine-based additive or the like to the ink or by improving the pH of the bronze. In addition to the means for obtaining the prevention effect, by adding a specific compound to the ink, it is possible to improve the effect of suppressing the occurrence of the bronze phenomenon without substantially changing the physical properties of the ink such as pH. Found an unimaginable technology.

  Specifically, when a copper phthalocyanine dye was used, it was found that the occurrence of bronzing can be prevented by using a compound represented by the following general formula (2) together, and the present invention has been completed. .

  In general, it is known that even in the case of dyes having the same color index (CI) number, the position and size of the peak of an absorption spectrum change depending on the type, position, and number of substituents. For example, in a copper phthalocyanine dye having absorption spectrum peaks in both the wavelength range of 600 nm to 640 nm and the range of 650 nm to 680 nm, the ratio of these two peak values varies depending on the dye. This difference is caused by the difference in the type, position, and number of substituents of the copper phthalocyanine dye.

  As a general trend, the copper phthalocyanine dye is strong between the number and ratio of substituents that absorb light in the wavelength range of 650 nm to 680 nm, and the weather resistance of the printed matter such as gas resistance and the appearance of bronze phenomenon. There is a correlation. That is, the smaller the substituent that absorbs light in the wavelength range of 650 nm to 680 nm, the better the weather resistance such as gas resistance, but on the other hand, the bronze phenomenon tends to occur. In other words, ink having a small absorption spectrum peak value in the wavelength range of 650 nm to 680 nm is excellent in weather resistance such as gas resistance, but tends to develop a bronze phenomenon.

  Therefore, in the present invention, as a means for solving the above-described problems, the following ink for ink jet recording (hereinafter sometimes simply referred to as ink) is provided.

  An ink for ink jet recording according to the present invention is an ink for ink jet recording containing at least a copper phthalocyanine dye represented by the following general formula (1), and further contains a compound represented by the following general formula (2). It is characterized by doing.

（一般式（１）中、Ｍはアルカリ金属又はアンモニウムであり、Ｒ₇はＯＨ、ＣＯＯＭ、Ｒ₈ＣＯＯＭ（Ｒ₈は炭素原子数４〜９のアルキル基、Ｍはアルカリ金属又はアンモニウム）であり、ｘ、ｙ、ｚはそれぞれ独立に０〜４の整数である。）

(In the general formula (1), M is an alkali metal or ammonium, R ₇ is OH, COOM, R ₈ COOM (R ₈ is an alkyl group having 4 to 9 carbon atoms, M is an alkali metal or ammonium) , X, y, and z are each independently an integer of 0 to 4.)

（一般式（２）中、Ｒ₁及びＲ₂はそれぞれ独立に、置換若しくは未置換の、アルキル基、アリール基、アリールアルキル基、又は水素原子の何れかであり、Ｒ₃及びＲ₅はそれぞれ独立に、カルボキシル基又はその塩、スルホン酸基又はその塩、リン酸基又はその塩、及びこれらの基で置換されたアルキル基であり、Ｒ₄及びＲ₆はそれぞれ独立に、Ｒ₃及びＲ₅に対して定義した以外の基であり、ｐ及びｒはそれぞれ独立に１〜５の整数であり、ｑ及びｓはそれぞれ独立に０〜４の整数であり、且つ、ｐ＋ｑ≦５、ｒ＋ｓ≦５である。）

(In General Formula (2), R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, aryl group, arylalkyl group, or hydrogen atom, and R ₃ and R ₅ are each Independently, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and an alkyl group substituted with these groups, and R ₄ and R ₆ are each independently R ₃ and R A group other than those defined for ₅ , p and r are each independently an integer of 1 to 5, q and s are each independently an integer of 0 to 4, and p + q ≦ 5, r + s ≦ 5)

The absorption spectrum of the copper phthalocyanine dye represented by the general formula (1) contained in the inkjet recording ink according to the present invention satisfies the following conditions [1] and [2]. It is preferable. In this case, the absorption spectrum is measured in accordance with, for example, JIS K 0115 “General rules for spectrophotometric analysis”.
[1] Absorption spectrum peaks exist both in the wavelength range of 600 nm to 640 nm and in the wavelength range of 650 nm to 680 nm.
[2] The ratio of the peak values of the absorption spectrum satisfies the relationship of the following formula.
B / A <0.75
(In the above formula, A is the peak value of the absorption spectrum in the wavelength range of 600 nm to 640 nm, and B is the peak value of the absorption spectrum in the wavelength range of 650 nm to 680 nm.)

  Moreover, as a preferable form of the ink for ink jet recording of the present invention, the content of the compound represented by the general formula (2) is 0.1% by mass or more and 3.0% by mass in the total ink mass. The content of the compound represented by the general formula (1) is in the range of 0.5% by mass or more and 5.0% by mass or less as a ratio of the total mass of the ink; The mass ratio of the content of the compound represented by the general formula (1) and the content of the compound represented by the general formula (2) is 15/1 or more and 50/1 or less; the pH of the ink is The range is from 4 to 7.5; the ethylene oxide adduct of acetylene glycol represented by the following general formula (3) is 0.1% by mass or more and 1.5% by mass in the total mass of the ink for inkjet recording. Containing in the ratio which occupies the following ranges And m and n of the compound represented by the following general formula (3) is, 6 <m + n <14, satisfy the relationship, and the like.

（一般式（３）中、ｍ及びｎはそれぞれに独立に整数である。）

(In general formula (3), m and n are each independently an integer.)

  Furthermore, as a result of intensive studies by the inventors in view of the above object, an ink composition using a specific solvent in a specific ratio with respect to the color material represented by the general formula (2) is obtained. And found to satisfy the basic performance as an ink for ink jet recording (no clogging at the nozzle tip, excellent intermittent ejection stability, and a viscosity ink capable of obtaining a high resolution image), The present invention for the second problem has been completed.

  The present invention for the second problem provides the following ink jet recording ink as means for solving the above problem.

  That is, the inkjet recording ink according to another aspect of the present invention is the inkjet recording ink having any one of the above-described configurations, and further includes glycerin as the first solvent and the following general formula (4) as the second solvent. The diol represented by the formula (3) includes at least three solvents selected from the group consisting of a urea derivative represented by the following general formula (5), ethylene glycol and 2-pyrrolidone, and The total content of the three solvents is in the range of 18% to 27% by mass with respect to the total mass of the ink, and the content of the first solvent and the content of the second solvent. The total is a range of 12% by mass or more and 20% by mass or less as a proportion of the total mass of the ink, and the mass ratio of the content of the first solvent and the content of the second solvent is 1.0 or more and 2 .0 or less And wherein the Rukoto.

（一般式（４）中、ｎは１〜６の整数である。）

(In general formula (4), n is an integer of 1-6.)

（一般式（５）中、ｎは０〜５の整数、ｍ及びｌはそれぞれ独立に１〜６の整数である。）

(In General Formula (5), n is an integer of 0 to 5, and m and l are each independently an integer of 1 to 6.)

  Further, as a more preferable form of the ink for ink jet recording of the present invention having the above-described configuration, the second solvent is 1,5-pentanediol; the urea derivative represented by the general formula (5) is It is ethylene urea; the third solvent is ethylene urea; the content of the compound represented by the general formula (2) is 0.2% by mass or more based on the total mass of the ink for inkjet recording. It is 3.0 mass% or less; and pH of the said ink for inkjet recording is the range of 5-7.5.

  In addition, as a result of intensive studies in view of the above objects, the inventors of the present invention are inks for ink jet recording including at least two kinds of color materials, a first color material and a second color material. It has been found that the above-mentioned problems can be solved by using an ink for ink-jet recording, wherein the second color material has an ability to suppress the occurrence of bronzing due to the first color material. .

  The bronze phenomenon in the present invention is a “phenomenon in which dye crystals are deposited on paper as the recorded image dries, and the recorded image reflects light and glows yellow or brown to give a metallic luster”. Moreover, the phthalocyanine dye represented by the general formula (1) is likely to cause a bronzing phenomenon, and the compound represented by the general formula (2) has an ability to prevent the bronzing phenomenon.

In addition, the ink jet recording method of the present invention is characterized in that an ink for ink jet recording having any one of the above structures is applied to a recording medium by an ink jet head to form an image.
The ink cartridge of the present invention is characterized by containing ink for ink jet recording having any one of the above-described configurations.
The ink jet recording apparatus of the present invention is characterized in that the ink for ink jet recording is mounted.

  According to the present invention capable of solving the first problem described above, the occurrence of bronzing can be suppressed, an image excellent in weather resistance such as gas resistance, and the like can be formed. It is possible to provide an ink for ink jet recording that does not corrode or deteriorate a member in contact with the ink.

  In addition, according to the present invention that can solve the second problem described above, the first problem is solved, and further, when used in an ink jet recording method, It does not cause clogging in the nozzles or openings, does not cause problems such as ink droplets no longer being ejected from the recording head, and has good intermittent ejection stability similar to that of conventional inkjet inks to which ureas are added. Fixation recovery is obtained, and there is no change in color or aggregation due to the decomposition of the dye, excellent long-term storage stability and ejection stability, and high-resolution, high-quality printed matter can be created. An ink for ink jet recording having an appropriate viscosity can be provided.

  Furthermore, according to the present invention, it is possible to provide an ink jet recording method, an ink cartridge, and an ink jet recording apparatus that can obtain the above-described effects by using the above ink jet recording ink.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the best mode for carrying out the invention.
[Ink for inkjet recording]
The ink according to the present invention must contain a copper phthalocyanine dye represented by the following general formula (1) and a compound represented by the following general formula (2). Further, an effect obtained by adding these third colorant to a commonly used dye or pigment other than those described above, or a newly synthesized dye or pigment, and the object of the present invention described above You may use together in the range which does not impair an effect. The total content of the color material in the ink is preferably 0.1% by mass to 15.0% by mass with respect to the total mass of the ink for inkjet recording.

（一般式（１）中、Ｍはアルカリ金属（例えば、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ及びＦｒ等）又はアンモニウムであり、Ｒ₇は、ＯＨ、ＣＯＯＭ、Ｒ₈ＣＯＯＭ（Ｒ₈は炭素原子数４〜９のアルキル基、Ｍはアルカリ金属又はアンモニウム）であり、ｘ、ｙ、ｚはそれぞれ独立に０〜４の整数である。）

(In General Formula (1), M is an alkali metal (for example, Li, Na, K, Rb, Cs, Fr, etc.) or ammonium, and R ₇ is OH, COOM, R ₈ COOM (R ₈ is a carbon atom) 4 to 9 alkyl groups, M is an alkali metal or ammonium), and x, y, and z are each independently an integer of 0 to 4).

（一般式（２）中、Ｒ₁及びＲ₂はそれぞれ独立に、置換若しくは未置換の、アルキル基、アリール基、アリールアルキル基、又は水素原子の何れかであり、Ｒ₃及びＲ₅はそれぞれ独立に、カルボキシル基又はその塩、スルホン酸基又はその塩、リン酸基又はその塩、及びこれらの基で置換されたアルキル基であり、Ｒ₄及びＲ₆はそれぞれ独立に、Ｒ₃及びＲ₅に対して定義した以外の基であり、ｐ及びｒはそれぞれ独立に１〜５の整数であり、ｑ及びｓはそれぞれ独立に０〜４の整数であり、且つ、ｐ＋ｑ≦５、ｒ＋ｓ≦５である。）

(In General Formula (2), R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, aryl group, arylalkyl group, or hydrogen atom, and R ₃ and R ₅ are each Independently, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and an alkyl group substituted with these groups, and R ₄ and R ₆ are each independently R ₃ and R A group other than those defined for ₅ , p and r are each independently an integer of 1 to 5, q and s are each independently an integer of 0 to 4, and p + q ≦ 5, r + s ≦ 5)

The copper phthalocyanine dye represented by the general formula (1) used in the ink according to the present invention has an absorption spectrum that satisfies the following conditions [1] and [2] for the reason described later. Is preferred.
[1] The peak of the absorption spectrum exists in both the wavelength range of 600 nm to 640 nm and the wavelength range of 650 nm to 680 nm.
[2] The ratio of the peak values of the absorption spectrum satisfies the relationship of the following formula.
B / A <0.75
(In the above formula, A is the peak value of the absorption spectrum in the wavelength range of 600 nm to 640 nm, and B is the peak value of the absorption spectrum in the wavelength range of 650 nm to 680 nm.)

  In the present invention, in order to make the ink have a desired hue, it is preferable that the peak value of the absorption spectrum exists in the wavelength range of 600 nm to 640 nm. However, when the absorption spectrum peak of the copper phthalocyanine dye exists only in the wavelength range of 600 nm to 640 nm, the bronzing phenomenon is very likely to occur, and the effect of preventing the bronzing phenomenon may be insufficient. Moreover, even if the peak of the absorption spectrum exists in both the wavelength range of 600 nm to 640 nm and the wavelength range of 650 nm to 680 nm, those that do not satisfy B / A <0.75 tend to be inferior in robustness. Because.

  From the viewpoint of effectively suppressing the bronze phenomenon, the content of the compound represented by the general formula (2) in the ink according to the present invention is 0.1% in the total mass of the ink for ink jet recording. It is preferable that it is the range in the mass%-3.0 mass%. If the content of the compound represented by the general formula (2) is less than 0.1% by mass, the effect of suppressing the bronze phenomenon may not be sufficiently obtained, while the compound represented by the general formula (2) This is because, even if the content of P exceeds 3.0% by mass, it is difficult to obtain a further suppressing effect on the occurrence of the bronze phenomenon.

  Further, the content of the compound represented by the general formula (1) is a ratio in the total mass of the ink for inkjet recording, and is preferably in the range of 0.5% by mass or more and 5.0% by mass or less. That is, when the content of the compound represented by the general formula (1) in the ink is less than 0.5% by mass, the color developability and the like may not be sufficiently exhibited. This is because if the content of the compound exceeds 5.0% by mass, the bronze suppression effect may be insufficient.

  Further, in the present invention, the content of the compound represented by the general formula (1) (referred to as color material A) in the ink and the compound represented by the general formula (2) (referred to as color material B). It is preferable that the ink has a mass ratio in the ink of Color material A / Color material B = 15/1 to 50/1. That is, when the content of the compound (B) represented by the general formula (2) is too small, a bronzing phenomenon may be easily manifested particularly when printing on a paper surface at a high concentration. On the other hand, when there is too much content of the compound (B) represented by the said General formula (2), the color of an ink may become near green. Such an ink has no problem when used as a green ink, but when used as a cyan ink, it may cause inconvenience in color. It is not preferable.

  However, in order to obtain a good effect even when the ink according to the present invention is used in an ink jet recording apparatus having a nozzle having a fine nozzle diameter of less than 20 μm and a droplet volume of less than 4.5 picoliter. Is configured such that the content of the compound represented by the general formula (2) is in a range of 0.2% by mass or more and 3.0% by mass or less as a proportion of the total mass of the ink for inkjet recording. It is preferable to do. That is, with such a configuration, the nozzle or opening of the ink jet recording apparatus having the above configuration does not clog, and there is no problem that ink droplets are not ejected from the recording head. In addition, good intermittent ejection stability similar to that of an inkjet ink to which conventional ureas are added can be obtained, and an ink having an appropriate viscosity capable of producing a printed matter with high resolution and high image quality can be obtained.

(Color material)
The color material essential in the present invention is a copper phthalocyanine dye represented by the following general formula (1) and a compound represented by the following general formula (2). Hereinafter, these color materials will be described.

（一般式（１）中、Ｍはアルカリ金属（例えば、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ及びＦｒ等）又はアンモニウムであり、Ｒ₇は、ＯＨ、ＣＯＯＭ、Ｒ₈ＣＯＯＭ（Ｒ₈は炭素原子数４〜９のアルキル基、Ｍはアルカリ金属又はアンモニウム）であり、ｘ、ｙ、ｚはそれぞれ独立に０〜４の整数である。） <Copper phthalocyanine dye represented by the following general formula (1)>

(In General Formula (1), M is an alkali metal (for example, Li, Na, K, Rb, Cs, Fr, etc.) or ammonium, and R ₇ is OH, COOM, R ₈ COOM (R ₈ is a carbon atom) 4 to 9 alkyl groups, M is an alkali metal or ammonium), and x, y, and z are each independently an integer of 0 to 4).

  Furthermore, in the above general formula (1), it is preferable to use a copper phthalocyanine dye that satisfies 1 ≦ x + y ≦ 4. The copper phthalocyanine dye is generally obtained as a mixture of the above general formula (1) having different substituent positions and numbers.

  When using the color material represented by the general formula (1), one type of color material selected from the group of color materials represented by the general formula (1) alone or two selected types The above color materials can also be mixed and used. Specific examples of the color material represented by the general formula (1) include C.I. I. Direct blue: 86, 87, 199 etc. are mentioned.

<Compound represented by the following general formula (2)>
In the present invention, a compound represented by the following general formula (2) is contained in the ink together with the copper phthalocyanine dye represented by the general formula (1). By coexisting the compound represented by the general formula (2), the bronze phenomenon of the general formula (1) can be reduced with a small addition amount without deteriorating the ink pH and other basic ink performance. Can be prevented.

（一般式（２）中、Ｒ₁及びＲ₂はそれぞれ独立に、置換若しくは未置換の、アルキル基、アリール基、アリールアルキル基、又は水素原子の何れかであり、Ｒ₃及びＲ₅はそれぞれ独立に、カルボキシル基又はその塩、スルホン酸基又はその塩、リン酸基又はその塩、及びこれらの基で置換されたアルキル基であり、Ｒ₄及びＲ₆はそれぞれ独立に、Ｒ₃及びＲ₅に対して定義した以外の基であり、ｐ及びｒはそれぞれ独立に１〜５の整数であり、ｑ及びｓはそれぞれ独立に０〜４の整数であり、且つ、ｐ＋ｑ≦５、ｒ＋ｓ≦５である。）

(In General Formula (2), R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, aryl group, arylalkyl group, or hydrogen atom, and R ₃ and R ₅ are each Independently, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and an alkyl group substituted with these groups, and R ₄ and R ₆ are each independently R ₃ and R A group other than those defined for ₅ , p and r are each independently an integer of 1 to 5, q and s are each independently an integer of 0 to 4, and p + q ≦ 5, r + s ≦ 5)

  Although it is not clear why the bronze phenomenon that occurs when the copper phthalocyanine dye represented by the general formula (1) is used can be prevented by using the compound represented by the general formula (2) together. Is estimated as follows. The compound represented by the general formula (1) causes regular stacking (association) on the paper surface (the surface of the recording medium). It is considered that the occurrence of bronze phenomenon could be prevented by successfully entering the compound represented by the general formula (2) into the stacking (association) structure formed by the general formula (1). The reason why the amount of the compound represented by the general formula (2) is effective even in a small amount is considered to be due to the structure of the compound represented by the general formula (2).

Specific examples of the compound represented by the general formula (2) are given below. In the present invention, any of these can be used, but among these, the following exemplified compound 1 can be most preferably used.

(Aqueous medium)
The ink according to the present invention is prepared by dissolving or dispersing the above-described coloring material in an aqueous medium mainly composed of water. As this aqueous medium, a mixed medium containing water and a water-soluble organic solvent can be used. Examples of the water-soluble organic solvent include alcohols, polyhydric alcohols, polyglycols, glycol ethers, nitrogen-containing polar solvents, sulfur-containing polar solvents, ureas, and saccharides, as long as they are generally used as ink-jet ink solvents. Can be used without problems. These solvents are appropriately used for the purpose of maintaining the moisture retention of the ink, improving the solubility and dispersibility of the coloring material, and penetrating the ink into the recording paper. These solvents can be used alone or in combination. The water is preferably deionized water (ion exchange water).

  The content of the water-soluble organic solvent is preferably in the range of 1% by mass to 50% by mass, more preferably in the range of 3% by mass to 40% by mass, based on the total mass of the ink for inkjet recording. The water content in the ink ranges from 30% by mass to 95% by mass in terms of the total mass of the ink for ink jet recording in order to maintain good dye solubility and ink ejection stability. preferable.

  Further, in the ink according to the present invention, a surfactant can be contained in the ink in order to reduce the surface tension of the ink and obtain better ink jet aptitude. As the surfactant used in this case, an ethylene oxide adduct of acetylene glycol represented by the following general formula (3) is suitable, and the surfactant is contained in the ink in an amount of 0.1% by mass to 1.5%. It is especially preferable to make it contain in the range of the mass%.

（一般式（３）中、ｍ及びｎはそれぞれに独立に、整数である。）

(In general formula (3), m and n are each independently an integer.)

  The ink according to the present invention preferably further has the following configuration in addition to the configuration described above. That is, glycerin as the first solvent, diol represented by the following general formula (4) as the second solvent, and urea derivative, ethylene glycol represented by the following general formula (5) as the third solvent, and It is preferable to make the ink using an aqueous medium containing at least three kinds of solvents selected from any one selected from 2-pyrrolidone.

（一般式（４）中、ｎは１〜６の整数である。）

(In general formula (4), n is an integer of 1-6.)

（一般式（５）中、ｎは０〜５の整数、ｍ及びｌはそれぞれ独立に１〜６の整数である。）

(In General Formula (5), n is an integer of 0 to 5, and m and l are each independently an integer of 1 to 6.)

  Further, the total content of at least three solvents of the first, second, and third solvents described above is in the range of 18% by mass to 27% by mass with respect to the total mass of the ink for inkjet recording. Preferably there is. That is, if the total content of these three solvents in the ink is less than 18% by mass, it is not preferable because the fixability of the ink nozzles may be deteriorated. On the other hand, if the total content of these three kinds of solvents exceeds 27% by mass, the viscosity of the ink is increased, and the ink supply rate into the nozzle or opening may be significantly reduced, which is not preferable.

  Furthermore, in the present invention, the ratio of the total content of the first solvent and the content of the second solvent in the ink is also important. That is, the ratio of the total content of the first solvent and the content of the second solvent in the total mass of the ink for inkjet recording is preferably 12% by mass or more and 20% by mass or less. That is, if the total content of the first solvent and the second solvent is less than 12% by mass, the fixing recovery property and the intermittent ejection stability may be deteriorated. In some cases, the viscosity increases, and the ink supply rate into the nozzle or opening is significantly reduced.

  Furthermore, in addition to the above, the mass ratio of the content of the first solvent and the content of the second solvent in the ink is preferably 1.0 or more and 2.0 or less. That is, if it is less than 1.0, the intermittent discharge stability may be deteriorated, while if it exceeds 2.0, the fixing recovery property may be deteriorated.

  It is possible to obtain an image in which the occurrence of bronzing is suppressed when used for image formation for the first time by using the color material described so far, and further, ink that satisfies all the conditions such as the solvent composition. At the same time, the ink has sufficiently achieved all the performances of fixing recovery, intermittent ejection stability, and high-speed printing ejection stability.

(Other components and ink properties)
A surfactant may be added to the ink according to the present invention. Specific examples of surfactants include anionic surfactants such as fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, alkylallylsulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters , Nonionic surfactants such as polyoxyethylene sorbitan alkyl esters, acetylene alcohol, acetylene glycol and the like, and one or more of these can be appropriately selected and used. At this time, the addition amount of the surfactant is determined so that the surface tension of the ink at 25 ° C. is 10 mN / m (dyn / cm) or more, more preferably 20 mN / m or more and 60 mN / m or less. Is preferred. By adding the surfactant to the ink, it is possible to effectively suppress the occurrence of printing misalignment (deviation of the landing point of the ink droplet) due to the wetness of the nozzle tip.

  In addition to the above-mentioned components, the ink according to the present invention may further include, for example, a pH adjuster, a rust inhibitor, a preservative, a fungicide, an antioxidant, a reduction inhibitor, an evaporation accelerator, a chelate Various additives such as an agent and a water-soluble polymer can be added. These additives can be contained within a range where the effects of adding these can be obtained and the object effects of the present invention are not impaired.

  Further, the ink according to the present invention is preferably adjusted so as to have a desired viscosity and pH in order to obtain good ejection characteristics when used in an ink jet recording apparatus. . In particular, the pH of the ink is preferably adjusted as described below. In order to sufficiently obtain the effect of suppressing the occurrence of the bronzing phenomenon when the image is formed as described above, the pH of the ink is preferably set to 4 or more. Further, in order to obtain long-term storage stability of the ink, it is preferable to set it to 7.5 or less. Furthermore, in order to obtain an ink that can provide intermittent ejection stability and prevent clogging at the nozzle tip, and in addition, can provide a high-resolution, high-quality printed matter, it is preferably 5 or more. In order to obtain the long-term storage stability of the ink, it is more preferable to adjust to 7.5 or less.

[recoding media]
As a recording medium used for forming an image using the ink according to the present invention, a special medium having a coating layer or an ink receiving layer on the surface, such as plain paper, glossy paper, coated paper, or glossy film, etc. And generally used recording media. Among these, a special medium having a hydrophilic porous particle layer, a porous polymer layer, etc. on a substrate is an example of a recording medium that can provide an image with higher vividness, contrast, and transparency. it can.

  An example of a special medium as a recording medium used in the present invention will be described in more detail. Color materials such as dyes and pigments are adsorbed on fine particles forming a hydrophilic porous structure in the ink receiving layer, and at least the adsorbed materials are adsorbed. This is a recording medium on which an image is formed by a color material, and is particularly suitable when an ink jet method is used. Such a recording medium is preferably a so-called absorption type in which ink is absorbed by a gap formed in an ink receiving layer on a support.

  The absorption type ink receiving layer is constituted as a hydrophilic porous layer mainly composed of fine particles and containing a binder and other additives as required. Examples of fine particles include inorganic pigments such as silica, clay, talc, calcium carbonate, kaolin, alumina or alumina hydrate, diatomaceous earth, titanium oxide, hydrotalcite, zinc oxide, urea formalin resin, ethylene resin, Examples thereof include organic pigments such as styrene resins, and one or more of these are used.

  Examples of suitable binders include water-soluble polymers and latex. For example, polyvinyl alcohol or a modified product thereof, starch or a modified product thereof, gelatin or a modified product thereof, gum arabic, carboxymethylcellulose, hydroxyethylcellulose, hydroxyprooylmethylcellulose and other cellulose derivatives, SBR latex, NBR latex, methylmethacrylate-butadiene Polymer latex, functional group modified polymer latex, vinyl copolymer latex such as ethylene vinyl acetate copolymer, polyvinyl pyrrolidone, maleic anhydride or copolymer thereof, acrylate copolymer, etc. are used and necessary Depending on the situation, two or more kinds can be used in combination. In addition, additives can also be used. For example, a dispersant, a thickener, a pH adjuster, a lubricant, a fluidity modifier, a surfactant, an antifoaming agent, a mold release agent, a fluorescence enhancer, if necessary. Whitening agents, ultraviolet absorbers, antioxidants and the like are used.

[Recording method and recording apparatus]
A recording method and a recording apparatus suitable for performing image recording on a recording medium using an ink according to the present invention by an ink jet recording method, for example, apply thermal energy corresponding to a recording signal to ink in a chamber of a recording head, and Examples thereof include a method and an apparatus for generating droplets by thermal energy.

  1 and 2 show an example of a schematic configuration of a printer using an ink jet recording method. In FIG. 1, the printer main body M1000 in this embodiment includes an exterior member including a lower case M1001, an upper case M1002, an access cover M1003, and a discharge tray M1004, and a chassis M3019 (see FIG. 1) housed in the exterior member. 2).

  The chassis M3019 is composed of a plurality of plate-shaped metal members having a predetermined rigidity, forms a skeleton of the recording apparatus, and holds each recording operation mechanism described later. The lower case M1001 forms a substantially lower half of the exterior of the apparatus main body M1000, and the upper case M1002 forms a substantially upper half of the exterior of the apparatus main body M1000. A hollow body structure having a storage space for storing the mechanism is formed. An opening is formed in each of the upper surface portion and the front surface portion of the apparatus main body M1000.

  Further, one end of the discharge tray M1004 is rotatably held by the lower case M1001, and the opening formed on the front surface of the lower case M1001 can be opened and closed by the rotation. For this reason, when executing the recording operation, the discharge tray M1004 is rotated to the front side to open the opening so that the recording sheets can be discharged and the discharged recording sheets P are sequentially stacked. It has come to be able to do. In addition, the discharge tray M1004 contains two auxiliary trays M1004a and M1004b. By pulling out each tray as needed, the paper support area can be expanded or reduced in three stages. It has become.

  One end of the access cover M1003 is rotatably held by the upper case M1002, and can open and close an opening formed on the upper surface. By opening the access cover M1003, the access cover M1003 is housed inside the main body. It is possible to replace the print head cartridge H1000 or the ink tank H1900. Although not specifically shown here, when the access cover M1003 is opened and closed, the protrusion formed on the back surface rotates the cover opening and closing lever, and the rotation position of the lever is detected by a micro switch or the like. Thus, the open / closed state of the access cover can be detected.

  On the upper surface of the rear portion of the upper case M1002, a power key E0018 and a resume key E0019 are provided so that they can be pressed, and an LED E0020 is provided. When the power key E0018 is pressed, the LED E0020 is lit and recording is possible. This is to inform the operator. Further, the LED E0020 has various display functions such as blinking method and color change, and informing the operator of printer troubles. When the trouble is solved, the recording is resumed by pressing the resume key E0019.

(Recording mechanism)
The recording operation mechanism includes an automatic feeding unit M3022 that automatically feeds the recording sheet P into the apparatus main body, and guides the recording sheet P that is sent one by one from the automatic feeding unit to a predetermined recording position. , A transport unit M3029 that guides the recording sheet P from the recording position to the discharge unit M3030, a recording unit that performs desired recording on the recording sheet P transported to the recording position, and a recovery unit that performs recovery processing on the recording unit and the like ( M5000).

(Recording part)
The recording unit includes a carriage M4001 that is movably supported by a carriage shaft M4021, and a recording head cartridge H1000 that is detachably mounted on the carriage M4001.

(Recording head cartridge)
A recording head cartridge used in the recording unit will be described with reference to FIGS.

  As can be seen from the perspective views of FIGS. 3A and 3B, the recording head H1001 is one constituent element of the recording head cartridge H1000. The recording head cartridge H1000 includes the recording head H1001 and the recording head H1001. And an ink tank H1900 (H1901, H1902, H1903, H1904) provided in a detachable manner. The recording head cartridge H1000 is fixedly supported by positioning means and electrical contacts of a carriage M4001 mounted on the ink jet recording apparatus main body, and is detachable from the carriage M4001. The ink tank H1901 is for black ink, the ink tank H1902 is for cyan ink, the ink tank H1903 is for magenta ink, and the ink tank H1904 is for yellow ink. In this way, each of the ink tanks H1901, H1902, H1903, and H1904 is detachable from the recording head H1001, and each ink tank can be replaced, thereby reducing the running cost of printing in the ink jet recording apparatus. The

  Next, the recording head H1001 will be described in detail for each component constituting the recording head. 4 to 10 are explanatory diagrams for explaining each of the suitable head cartridge, the recording head, and the ink tank and the relationship thereof in which the present invention is implemented or applied. Hereinafter, each component will be described with reference to these drawings.

(1) Recording Head The recording head H1001 is a bubble jet (registered trademark) side that performs recording using an electrothermal transducer that generates thermal energy for causing film boiling in ink according to an electrical signal. This is a recording head that is of a shooter type.
As shown in the exploded perspective view of FIG. 4, the recording head H1001 includes a recording element unit H1002, an ink supply unit H1003, and a tank holder H2000.

  Further, as shown in the exploded perspective view of FIG. 5, the recording element unit H1002 includes a first recording element substrate H1100, a second recording element substrate H1101, a first plate H1200, an electrical wiring tape H1300, and an electrical contact substrate H2200. The ink supply unit H1003 includes an ink supply member H1500, a flow path forming member H1600, a joint rubber H2300, a filter H1700, and a seal rubber H1800.

(1-1) Recording Element Unit FIG. 6 is a partially exploded perspective view for explaining the configuration of the first recording element substrate H1100. In the first recording element substrate H1100, for example, an anisotropic etching is performed in which an ink supply port H1102 including a long groove-like through-hole as an ink channel is formed on a Si substrate H1110 having a thickness of 0.5 to 1 mm using a crystal orientation of Si. The electrothermal transducers H1103 are arranged in a staggered pattern on both sides of the ink supply port H1102, and power is supplied to the electrothermal transducers H1103 and the electrothermal transducers H1103. The electric wiring such as Al to be supplied is formed by a film forming technique.

  Furthermore, electrode portions H1104 for supplying electric power to the electric wiring are arranged on both outer sides of the electrothermal transducer H1103, and bumps H1105 such as Au are formed on the electrode portion H1104. On the Si substrate H1110, an ink channel wall H1106 and an ejection port H1107 for forming an ink channel corresponding to the electrothermal conversion element H1103 are formed of a resin material by a photolithography technique, and an ejection port group H1108. Is forming. Accordingly, since the ejection port is provided to face the electrothermal conversion element H1103, the ink supplied from the ink flow path H1102 is ejected by bubbles generated by the electrothermal conversion element H1103.

  FIG. 7 is a partially exploded perspective view for explaining the configuration of the second recording element substrate H1101. The second recording element substrate H1101 is a recording element substrate for ejecting ink of three colors, and has three ink supply ports H1102 formed in parallel, and electric is provided on both sides of each ink supply port. A heat conversion element and an ink discharge port are formed. Of course, like the first recording element substrate H1100, an ink supply port, an electrothermal conversion element, an electric wiring, an electrode portion, and the like are formed on the Si substrate, and an ink flow path and an ink discharge are made of a resin material on the Si substrate by a photolithography technique. An exit is formed.

Similarly to the first recording element substrate, a bump H1105 such as Au is formed on the electrode portion H1104 for supplying electric power to the electric wiring.
Next, the first plate H1200 is made of, for example, an alumina (Al ₂ O ₃ ) material having a thickness of 0.5 to 10 mm. The material of the first plate is not limited to alumina, and has a linear expansion coefficient equivalent to that of the material of the recording element substrate H1100, and is equivalent to the thermal conductivity of the material of the recording element substrate H1100. Alternatively, it may be made of a material having an equivalent or higher thermal conductivity. Examples of the material of the first plate H1200 include silicon (Si), aluminum nitride (AlN), zirconia, silicon nitride (Si ₃ N ₄ ), silicon carbide (SiC), molybdenum (Mo), and tungsten (W). Either may be sufficient. The first plate H1200 has ink supply ports H1201 for supplying black ink to the first recording element substrate H1100 and inks for supplying cyan, magenta, and yellow ink to the second recording element substrate H1101. A supply port H1201 is formed, the ink supply port 1102 of the printing element substrate corresponds to the ink supply port H1201 of the first plate H1200, and the first printing element substrate H1100 and the second printing element substrate H1101. Are bonded and fixed to the first plate H1200 with high positional accuracy. The first adhesive H1202 (not shown) used for bonding is desirably a low viscosity, low curing temperature, cured in a short time, has a relatively high hardness after curing, and has ink resistance. . The first adhesive H1202 is, for example, a thermosetting adhesive mainly composed of an epoxy resin, and the thickness of the adhesive layer is desirably 50 μm or less.

  The electrical wiring tape H1300 applies an electrical signal for ejecting ink to the first recording element substrate H1100 and the second recording element substrate H1101, and includes a plurality of recording element substrates. It has an opening, an electrode terminal H1302 (not shown) corresponding to the electrode portion H1104 of each recording element substrate, and an external signal input terminal H1301 for receiving an electrical signal from the main body device located at the end of the wiring tape. The electrode terminal portion H1303 (not shown) for electrical connection with the electrical contact substrate H2200 is connected, and the electrode terminal H1302 and the electrode terminal 1303 are connected by a continuous copper foil wiring pattern.

  The electrical wiring tape H1300, the first recording element substrate 1100, and the second recording element substrate H1101 are electrically connected to each other, and the connection method is, for example, the electrode portion 1104 of the recording element substrate and the electrical wiring tape H1300. The electrode terminal H1302 is electrically bonded by a thermal ultrasonic pressure bonding method.

The second plate H1400 is, for example, a single plate-like member having a thickness of 0.5 to 1 mm, and is formed of a ceramic material such as alumina (Al ₂ O ₃ ) or a metal material such as Al or SUS. ing. The first recording element substrate H1100 and the second recording element substrate H1101 that are bonded and fixed to the first plate H1200 have openings that are larger than the outer dimensions thereof. Further, the first recording element substrate H1100 and the second recording element substrate H1101 and the electric wiring tape H1300 are bonded to the first plate H1200 with a second adhesive H1203 (not shown) so as to be electrically connected in a plane. The back surface of the electrical wiring tape H1300 is bonded and fixed by a third adhesive H1306 (not shown).

  The first recording element substrate H1100 and the second recording element substrate H1101 are electrically connected to the electrical wiring tape H1300 by a first sealant H1307 (not shown) and a second sealant H1308 (not shown). Sealed to protect the electrical connection from ink corrosion and external impact. The first sealing agent mainly seals the back surface side of the connection portion between the electrode terminal H1302 of the electric wiring tape and the electrode portion H1104 of the recording element substrate and the outer peripheral portion of the recording element substrate, and the second sealing agent. Seals the front side of the connecting part.

Further, an electrical contact substrate H2200 having an external signal input terminal H1301 for receiving an electrical signal from the main unit is connected to the end portion of the electrical wiring tape by thermocompression bonding using an anisotropic conductive film or the like.
The electric wiring tape H1300 is bent at one side surface of the first plate H1200, and is bonded to the side surface of the first plate H1200 with a third adhesive H1306 (not shown). As the third adhesive H1306, for example, a thermosetting adhesive having a thickness of 10 to 100 μm mainly composed of an epoxy resin is used.

(1-2) Ink Supply Unit The ink supply member H1500 is formed by resin molding, for example. As the resin material, it is desirable to use a resin material mixed with 5 to 40% of glass filler in order to improve the shape rigidity.

  As shown in FIGS. 5 and 8, the ink supply member H1500 is one component of the ink supply unit H1003 for guiding ink from the ink tank H1900 to the recording element unit H1002, and the flow path forming member H1600 is ultrasonically welded. As a result, an ink flow path H1501 is formed. Further, a filter H1700 for preventing entry of dust from the outside is joined to a joint H1517 (not shown) that engages with the ink tank H1900 by welding, and further, evaporation of ink from the joint H1517 portion is prevented. In order to achieve this, a seal rubber H1800 is attached.

  The ink supply member H1500 also has a part of the function of holding the removable ink tank H1900, and has a first hole H1503 for engaging the second claw H1910 of the ink tank H1900.

  Also, a mounting guide H1601 for guiding the recording head cartridge H1000 to the mounting position on the carriage M4001 of the ink jet recording apparatus main body, and an engaging portion H1508 (not shown) for mounting and fixing the recording head cartridge to the carriage M4001 by a head set lever. And an abutting portion H1509 in the X direction (carriage scanning direction) for positioning the carriage M4001 at a predetermined mounting position, an abutting portion H1510 in the Y direction (recording medium transport direction), and an abutting portion in the Z direction (ink ejection direction) A contact portion H1511 is provided. In addition, a terminal fixing portion H1512 for positioning and fixing the electrical contact substrate H2200 of the recording element unit H1002 is provided, and a plurality of ribs are provided around the terminal fixing portion H1512 to increase the rigidity of the surface having the terminal fixing portion H1512. ing.

(1-3) Coupling of recording head unit and ink supply unit As shown in FIG. 4 described above, the recording head H1001 is completed by coupling the recording element unit H1002 to the ink supply unit H1003 and further to the tank holder H2000. To do. The coupling is performed as follows.

  The ink supply port of the recording element unit H1002 (ink supply port H1201 of the first plate H1200) and the ink supply port of the ink supply unit H1003 (ink supply port H1601 of the flow path forming member H1600) are communicated so that ink does not leak. Therefore, each member is fixed with the screw H2400 so as to be pressure-bonded via the joint rubber H2300. At the same time, the recording element unit H1002 is accurately positioned and fixed with respect to the reference positions in the X, Y, and Z directions of the ink supply unit.

  The electrical contact substrate H1301 of the recording element unit H1002 is positioned and fixed to one side surface of the ink supply member H1500 by terminal positioning pins H1515 (2 places) and terminal positioning holes H1309 (2 places). The fixing method is, for example, fixing by crimping the terminal coupling pin H1515 provided on the ink supply member H1500, but may be fixed using other fixing means. The completed drawing is shown in FIG.

  Further, the recording head H1001 is completed by fitting the coupling hole and coupling portion of the ink supply member H1500 with the tank holder into the tank holder H2000 and coupling them. A completed drawing is shown in FIG.

(2) Recording Head Cartridge FIGS. 3A and 3B described above are diagrams for explaining mounting of the recording head H1001 and the ink tanks H1901, H1902, H1903, and H1904 constituting the recording head cartridge H1000. Corresponding color inks are stored in H1901, H1902, H1903, and H1904. Further, as shown in FIG. 8, each ink tank is formed with an ink supply port H1907 for supplying ink in the ink tank to the recording head H1001. For example, when the ink tank H1901 is attached to the recording head H1001, the ink supply port H1907 of the ink tank H1901 is brought into pressure contact with the filter H1700 provided in the joint portion H1520 of the recording head H1001, and the black ink in the ink tank H1901 is supplied with ink. The ink is supplied from the port H1907 to the first recording element substrate through the first plate H1200 through the ink flow path H1501 of the recording head H1001.

  Then, ink is supplied to the bubbling chamber H1109 having the electrothermal conversion element H1103 and the discharge port H1107, and is discharged toward a recording sheet as a recording medium by the thermal energy given to the electrothermal conversion element H1103.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited by the following Example, unless the summary is exceeded. In the following description, “%” is based on mass unless otherwise specified.

<Preparation of inks of Examples 1 to 3 and Comparative Examples 1 to 5>
The components shown in Table 1 below were mixed and dissolved with sufficient stirring. Then, pressure filtration was performed with a micro filter (manufactured by Fuji Film) having a pore size of 0.2 μm, and the pH was adjusted as necessary to prepare inks of Examples 1 to 3 and Comparative Examples 1 to 5.

（構造式１−１及び構造式１−２中、ＭはＮａであり、ｘ及びｙはそれぞれ独立に１〜４の整数である。） [Compounds of Structural Formula 1-1 and Structural Formula 1-2]

(In Structural Formula 1-1 and Structural Formula 1-2, M is Na, and x and y are each independently an integer of 1 to 4.)

  Both of the compounds represented by Structural Formula 1-1 and Structural Formula 1-2 are C.I. I. Direct Blue 199. C. I. Direct Blue 199 is a mixture of compounds having different substituent positions and numbers. Therefore, the C.I. I. The absorption spectra of the aqueous solutions of the compounds represented by Structural Formula 1-1 and Structural Formula 1-2, which are compounds included in Direct Blue 199, are different. Here, a 1% aqueous solution of the compound represented by Structural Formula 1-1 and Structural Formula 1-2 was diluted 1000 times with pure water, and an absorption spectrum was measured according to JIS K 0115 under the following conditions.

Equipment used: Spectrophotometer (U-3000, manufactured by Hitachi, Ltd.)
Cell: Quartz cell (optical path length 10mm)
Measurement temperature: 25 ° C

  From the respective absorption spectra of the compounds of Structural Formula 1-1 and Structural Formula 1-2 measured above, the ratio of the peak value in the wavelength range of 600 nm to 640 nm and the peak value in the wavelength range of 650 nm to 680 nm in these compounds. (B / A) was determined. The results obtained are shown below.

Compound of structural formula 1-1: B / A = 0.67
Compound of Structural Formula 1-2: B / A = 0.50
(In the above formula, A is the peak value of the absorption spectrum in the wavelength range of 600 nm to 640 nm, and B is the peak value of the absorption spectrum in the wavelength range of 650 nm to 680 nm.)

[Compound of Structural Formula 2]

（構造式３中、ｍ＋ｎ＝１０である。尚、本発明では、構造式３の化合物として川研ファインケミカル製のアセチレノールＥＨ（商品名）を用いた。） [Compound of Structural Formula 3]

(In Structural Formula 3, m + n = 10. In the present invention, acetylenol EH (trade name) manufactured by Kawaken Fine Chemical was used as the compound of Structural Formula 3.)

（構造式４中、Ｒ₁及びＲ₂はアルキル基又は水素原子、ｎ＝１０、ｌ＝７である。） [Compound of Structural Formula 4]

(In Structural Formula 4, R ₁ and R ₂ are alkyl groups or hydrogen atoms, n = 10, l = 7.)

<Evaluation of Inks of Examples 1 to 3 and Comparative Examples 1 to 5>
The ink obtained above was packed in an ink cartridge for Canon PIXUS 950i, and an image was formed using Canon PIXUS 950i. Each ink and the formed image were evaluated by the following methods and criteria. The evaluation results are summarized in Table 2.

(Storage pH stability)
The initial pH was measured after each ink preparation. Furthermore, each ink was put into a Teflon (registered trademark) container with a lid, sealed, stored in a thermostatic bath at 60 ° C. for 3 months, taken out, and the pH after storage after measuring the temperature to room temperature was measured. And the pH change amount was calculated | required from the measured initial value and the pH value after a preservation | save. The evaluation criteria for storage pH stability are as follows.
A: pH change amount is within 1.6 B: pH change amount exceeds 1.6

(Development of bronze phenomenon)
The bronze phenomenon is generally observed more markedly as the ink driving density (duty) is higher. Therefore, Canon HG-201 (glossy film) is used as the recording medium, and ink is applied to the recording medium so that the ink shot density (duty) is in the range of 0 to 100%, and the printed matter is printed. Created. In the obtained printed matter, the highest duty at which the bronze phenomenon started to appear was used as an index of the bronze phenomenon. In other words, it can be said that the higher the duty at which the bronze phenomenon occurs, the less likely the bronze phenomenon occurs.

<Preparation of inks of Examples 4 to 14 and Comparative Example 6>
The components shown in Table 3 below were mixed and dissolved with sufficient stirring. Then, pressure filtration was performed with a micro filter (manufactured by Fuji Film) having a pore size of 0.2 μm, and the pH was adjusted as necessary to prepare inks of Examples 4 to 14 and Comparative Example 6.

（構造式１−３、構造式１−４及び構造式１−５中、ＭはＮａであり、ｘ及びｙはそれぞれ独立に１〜４の整数である。） [Compound of Structural Formula 1-3 to Structural Formula 1-5]

(In Structural Formula 1-3, Structural Formula 1-4, and Structural Formula 1-5, M is Na, and x and y are each independently an integer of 1 to 4.)

  Similar to the structural formula 1-1 and the structural formula 1-2 described above, the compounds represented by the structural formula 1-3, the structural formula 1-4, and the structural formula 1-5 are all C.I. I. Direct Blue 199. A 1% by mass aqueous solution of the compound represented by Structural Formula 1-3, Structural Formula 1-4, and Structural Formula 1-5 is diluted 1,000 times with pure water, and the absorption spectrum is JIS K 0115 under the following conditions. Measured according to And the ratio (B / A) of the peak value in the wavelength range of 600 nm to 640 nm and the peak value in the wavelength range of 650 nm to 680 nm was determined. The results were as follows.

Compound of structural formula 1-3: having a peak only in the wavelength range of 600 nm to 640 nm Compound of structural formula 1-4: B / A = 0.74
Compound of structural formula 1-5: B / A = 0.75
(In the above formula, A is the peak value of the absorption spectrum in the wavelength range of 600 nm to 640 nm, and B is the peak value of the absorption spectrum in the wavelength range of 650 nm to 680 nm.)

<Evaluation of Inks of Examples 4 to 14 and Comparative Example 6>
Each ink obtained above was packed in an ink cartridge for PIXUS 950i manufactured by Canon, and an image was formed using the PIXUS 950i manufactured by Canon. Each formed image was evaluated by the following methods and criteria. The evaluation results are summarized in Table 4.

(Bronze phenomenon expression)
Canon HG-201 (glossy film) is used as the recording medium, and ink is applied to the recording medium so that the ink shot density (duty) is in the range of 0% to 100%. did. In the obtained printed matter, the highest duty at which the bronze phenomenon starts to appear was used as an index of the manifestation of the bronze phenomenon. The evaluation criteria for bronze phenomenon expression are as follows.

AA: Bronze is not generated even at 100% duty A: Bronze generation duty is 95% or more B: Bronze generation duty is 80% or more and less than 95% C: Bronze generation duty is less than 80%

(Gas resistance)
Using PR-101 (glossy paper) manufactured by Canon as a recording medium, a printed matter was produced with an ink shot density (duty) of 100%. The color difference ΔE was calculated from the obtained printed matter by the following method to evaluate gas resistance. The evaluation method and evaluation criteria for gas resistance are as follows.

Evaluation device; Ozone fade meter Exposure conditions; Exposure in a bath temperature of 40 ° C, relative humidity 55%, 3 ppm in an ozone atmosphere for 2 hours Evaluation method: CIE L ^* a ^* b ^* of test sample before and after exposure Was measured. And color difference (DELTA) E was computed from the following formula.
ΔE = (ΔL ^{* 2} + Δa ^{* 2} + Δb ^{* 2} ) ^1/2
AA: ΔE is less than 20 A: ΔE is 20 or more and less than 25 B: ΔE is 25 or more and less than 30 C: ΔE is 30 or more

  In Examples 4, 7, 8, 9, and 10, the ink density (duty) was increased to 200% and the bronzing phenomenon was confirmed. As a result, the compound represented by the structural formula 2 was used for inkjet recording. The bronzing phenomenon tended not to occur as the content relative to the total mass of the ink increased. However, when the results of Examples 9 and 10 were compared, when the content of the compound represented by Structural Formula 2 exceeded 3% by mass, there was almost no difference in the bronzing phenomenon.

<Preparation of inks of Examples 15 to 26>
The components shown in Table 5 below were mixed, dissolved sufficiently by stirring, and then filtered under pressure with a microfilter (manufactured by Fuji Film) having a pore size of 0.2 μm, and the pH was adjusted as necessary. 15-26 inks were prepared.

（構造式１−６中、ｘ及びｙはそれぞれ独立に１〜４の整数である。） [Compound of Structural Formula 1-6]

(In Structural Formulas 1-6, x and y are each independently an integer of 1 to 4.)

<Evaluation of Examples 15 to 26>
Each of the obtained inks was packed in an ink cartridge for PIXUS 950i manufactured by Canon, and an image was formed using a modified machine of PIXUS 950i manufactured by Canon. The ink jet recording characteristics of each ink were evaluated by the following methods and standards. The evaluation results are collectively shown in Table 6. The PIXUS950i used for the evaluation was modified to have a fine nozzle with a nozzle diameter of less than 20 μm and a droplet volume of less than 4.5 picoliters.

(Intermittent discharge stability)
Vertical ruled lines were printed at certain discharge pause time intervals under conditions where the temperature of the ink at the nozzle portion of the inkjet did not increase under an environment of a temperature of 15 ° C. and a relative humidity of 10%. And the vertical ruled line formed immediately after a stop was observed using the micrometer of 50 times objective magnification, and the following reference | standard evaluated. The evaluation criteria for intermittent discharge stability are as follows.
A: The vertical ruled lines can be printed normally without any disturbances. B: The vertical ruled lines have some disturbances, but there is no ejection failure.

(Adhesive recovery)
First, using a PIXUS 950i head cartridge in which an ink cartridge filled with each ink was mounted on a recording head, it was confirmed that printing was possible for all nozzles. Thereafter, the head cartridge was removed from the main body of the recording apparatus with the ink cartridge mounted, and left in a constant temperature bath at a temperature of 35 ° C. and a relative humidity of 10% for 2 weeks. Thereafter, the head cartridge was mounted again on the recording apparatus main body, and a suction recovery operation for enabling printing was performed. Then, the number of suction recovery operations until all the nozzles of the recording head were able to print was counted, and the number was used for evaluation. The evaluation criteria for fixing recovery are as follows.

A: All nozzles of the recording head can be printed within 2 times of suction. B: All nozzles of the recording head can be printed after 3 to 6 times of suction. C: Even if the number of suctions is 7 or more, the recording head can be printed. Not all nozzles can print

(High-speed printing discharge stability)
Each ink was used on an A4 size recording medium, and solid printing was performed with an ink ejection density (duty) of 100%. At that time, the ink supply speed (refill speed) to the nozzle was judged from the printing state, and the high-speed printing ejection stability was evaluated. Evaluation criteria for high-speed printing ejection stability are as follows.
A: Printing is possible without problems. B: Distortion, blurring, non-discharge, etc. due to insufficient refill speed. C: Refill speed slows down and all nozzles are not ejected.

<Preparation of inks of Examples 27 to 44>
The components shown in Table 7 below were mixed and dissolved by sufficiently stirring. Thereafter, pressure filtration was performed with a microfilter (manufactured by Fuji Film) having a pore size of 0.2 μm, and the pH was adjusted as necessary to prepare inks of Examples 27 to 44.

<Evaluation of Examples 27 to 44>
The obtained ink was packed in an ink cartridge for PIXUS 950i manufactured by Canon, and an image was formed using a modified machine of PIXUS 950i manufactured by Canon. The ink jet recording characteristics of each ink and the image formed with each ink were evaluated by the following methods and standards. The evaluation results are summarized in Table 8. PIXUS950i used was remodeled to have a fine nozzle having a nozzle diameter of less than 20 μm and a droplet volume of less than 4.5 picoliters.

(Bronze phenomenon expression)
Canon HG-201 (glossy film) was used as the recording medium, and ink was applied to the recording medium so that the ink shot density (duty) ranged from 0 to 100% in 5% increments to produce a printed matter. . In the obtained printed matter, the highest duty at which the bronze phenomenon starts to appear was used as an index of the manifestation of the bronze phenomenon. The evaluation criteria for bronze phenomenon expression are as follows.
AA: Bronze is not generated even at 100% duty A: Bronze generation duty is 95% or more B: Bronze generation duty is 80% or more and less than 95% C: Bronze generation duty is less than 80%

(Intermittent discharge stability)
Vertical ruled lines were printed at certain discharge pause time intervals under conditions where the temperature of the ink at the nozzle portion of the inkjet did not increase under an environment of a temperature of 15 ° C. and a relative humidity of 10%. And the vertical ruled line formed immediately after a stop was observed using the micrometer of 50 times objective magnification, and the following reference | standard evaluated. The evaluation criteria for intermittent discharge stability are as follows.
A: The vertical ruled lines can be printed normally without any disturbances. B: The vertical ruled lines have some disturbances, but there is no ejection failure.

(Adhesive recovery)
First, using a PIXUS 950i head cartridge in which an ink cartridge filled with ink was mounted on a recording head, it was confirmed that all nozzles could be printed. Thereafter, the head cartridge was removed from the main body of the recording apparatus with the ink cartridge mounted, and left in a constant temperature bath at a temperature of 35 ° C. and a relative humidity of 10% for 2 weeks. Thereafter, the head cartridge was mounted again on the recording apparatus main body, and a suction recovery operation for enabling printing was performed. Then, the number of suction recovery operations until all the nozzles of the recording head were able to print was counted, and the number was used for evaluation. The evaluation criteria for fixing recovery are as follows.

AA: All nozzles of the recording head can be printed with one suction. A: All nozzles of the recording head can be printed with two suctions. B: All of the recording head with three to six suctions. Nozzles can be printed. C: All nozzles of the recording head cannot be printed even if the number of suctions is 7 times or more.

(High-speed printing discharge stability)
Each ink was used on an A4 size recording medium, and solid printing with an ink ejection density (duty) of 100% was performed. At that time, the ink supply speed (refill speed) to the nozzle was judged from the printing state, and the high-speed printing ejection stability was evaluated. The criteria for high-speed printing ejection stability are as follows.
A: Printable without problems. A: A level of twist that causes no problem in actual use due to insufficient refill speed. B: A twist, blur, or non-discharge due to insufficient refill speed. You can see the state of disappearing

As an application example of the present invention, there is an ink for ink jet recording which is excellent in gas resistance and can obtain an image in which the so-called bronzing phenomenon is effectively prevented.
As an application example of the present invention, in addition to the above, a printed matter excellent in lightness and saturation can be provided, and a fine nozzle having a nozzle diameter of less than 20 μm and a flying droplet of less than 4.5 picoliters can be provided. An ink for ink jet recording suitable for the recording apparatus possessed can be mentioned. According to the ink of the present invention, in this case as well, the same intermittent discharge stability, prevention of clogging at the nozzle tip, high-speed printing, high resolution, and high image quality, which are equivalent to conventional urea-containing inks, are achieved. Prints can be provided.

It is a perspective view which shows the external appearance structure of an inkjet printer. It is a perspective view which shows the state which removed the exterior member of the apparatus shown in FIG. 3A is a perspective view of the recording head cartridge, and FIG. 3B is an exploded perspective view thereof. FIG. 4 is an exploded perspective view illustrating a configuration of the recording head illustrated in FIG. 3. FIG. 4 is an exploded perspective view in which the recording head shown in FIG. 3 is further finely disassembled. FIG. 4 is a partially cutaway explanatory perspective view illustrating a configuration of a recording element substrate of the recording head cartridge in FIG. 3. FIG. 4 is a partially cut-out explanatory perspective view illustrating a configuration of another recording element substrate of the recording head cartridge in FIG. 3. FIG. 4 is a cross-sectional view of a main part of the recording head cartridge in FIG. 3. FIG. 4 is a perspective view showing an assembly of a recording element unit and an ink supply unit of the recording head cartridge of FIG. 3. FIG. 4 is a perspective view showing a bottom surface side of the recording head cartridge in FIG. 3.

Explanation of symbols

M1000: apparatus main body M1001: lower case M1002: upper case M1003: access cover M1004: discharge tray M2015: paper gap adjusting lever M3001: LF roller M3006: paper discharge roller M3019: chassis M3022: automatic feeding unit M3029: transport unit M3030: Discharge unit M4001: Carriage M4002: Carriage cover M4007: Head set lever M4021: Carriage shaft M5000: Recovery unit E0001: Carriage motor E0002: LF motor E0018: Power key E0019: Resume key E0020: LED
H1000: Printhead cartridge H1001: Printhead (inkjet printhead)
H1002: Recording element unit H1003: Ink supply unit H1100: First recording element substrate H1101: Second recording element substrate H1102: Ink supply port (supply port)
H1103: Electrothermal conversion element (recording element)
H1104: Electrode portion H1105: Bump H1106: Ink flow channel wall H1107: Ejection port H1108: Ejection port group H1109: Foaming chamber H1110: Si substrate H1200: First plate (first support member)
H1201: Ink supply port H1300: Electrical wiring tape H1301: External signal input terminal H1302: Electrode terminal H1308: Second sealant H1309: Terminal positioning hole H1310: Terminal fixing part H1400: Second plate H1500: Ink supply member H1501 : Ink flow path H1503: first hole H1509: X-direction abutting portion H1510: Y-direction abutting portion H1511: Z-direction abutting portion H1512: terminal fixing portion H1515: terminal positioning pin H1520: joint portion H1600: Flow path forming member H1601: Installation guide (ink supply port)
H1602: Ink communication port H1700: Filter H1800: Seal rubber H1900: Ink tank H1901: Black ink tank H1902: Cyan ink tank H1903: Magenta ink tank H1904: Yellow ink tank H1907: Ink supply port H1910: Second claw H2000: Tank holder H2200: Electrical contact substrate H2300: Joint rubber H2400: Screw

Claims (17)

An ink for ink-jet recording containing at least a copper phthalocyanine dye represented by the following general formula (1), and further comprising a compound represented by the following general formula (2) .

(In the general formula (1), M is an alkali metal or ammonium, R ₇ is OH, COOM, R ₈ COOM (R ₈ is an alkyl group having 4 to 9 carbon atoms, M is an alkali metal or ammonium) , X, y, and z are each independently an integer of 0 to 4.)

(In General Formula (2), R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, aryl group, arylalkyl group, or hydrogen atom, and R ₃ and R ₅ are each Independently, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and an alkyl group substituted with these groups, and R ₄ and R ₆ are each independently R ₃ and R A group other than those defined for ₅ , p and r are each independently an integer of 1 to 5, q and s are each independently an integer of 0 to 4, and p + q ≦ 5, r + s ≦ 5) The ink for inkjet recording according to claim 1, wherein the absorption spectrum of the copper phthalocyanine dye represented by the general formula (1) satisfies the following conditions [1] and [2].
[1] The peak of the absorption spectrum exists in both the wavelength range of 600 nm to 640 nm and the wavelength range of 650 nm to 680 nm.
[2] The ratio of the peak values of the absorption spectrum satisfies the relationship of the following formula.
B / A <0.75
(In the above formula, A is the peak value of the absorption spectrum in the wavelength range of 600 nm to 640 nm, and B is the peak value of the absorption spectrum in the wavelength range of 650 nm to 680 nm.)   3. The inkjet recording according to claim 1, wherein the content of the compound represented by the general formula (2) is in a range of 0.1% by mass or more and 3.0% by mass or less as a proportion of the total mass of the ink. For ink.   The content of the compound represented by the general formula (1) is in a range of 0.5% by mass or more and 5.0% by mass or less as a proportion of the total mass of the ink. 2. Ink for ink jet recording described in 1.   The mass ratio of the content of the compound represented by the general formula (1) and the content of the compound represented by the general formula (2) is 15/1 or more and 50/1 or less. The ink for inkjet recording of any one.   The ink for inkjet recording according to any one of claims 1 to 5, wherein the pH of the ink is in a range of 4 to 7.5. Furthermore, an ethylene oxide adduct of acetylene glycol represented by the following general formula (3) is contained at a ratio occupying a range of 0.1% by mass to 1.5% by mass in the total mass of the ink. The ink for inkjet recording of any one of 1-6.

(In general formula (3), m and n are each independently an integer.)   The ink for inkjet recording according to claim 7, wherein m and n of the compound represented by the general formula (3) satisfy a relationship of 6 <m + n <14. Furthermore, glycerin as the first solvent, diol represented by the following general formula (4) as the second solvent, urea derivative represented by the following general formula (5) as the third solvent, ethylene glycol, and 2- Including at least three solvents of any one selected from pyrrolidone,
In addition, the total content of the three kinds of solvents is in a range of 18% by mass or more and 27% by mass or less as a proportion of the total mass of the ink.
And the sum total of content of said 1st solvent and content of 2nd solvent is 12 mass% or more and 20 mass% or less,
The ink ratio for ink-jet recording according to any one of claims 1 to 8, wherein a mass ratio of the content of the first solvent and the content of the second solvent is 1.0 or more and 2.0 or less.

(In general formula (4), n is an integer of 1-6.)

(In general formula (5), n is an integer of 0 to 5, and m and l are each independently an integer of 1 to 6.)   The ink for inkjet recording according to claim 9, wherein the second solvent is 1,5-pentanediol.   The ink for inkjet recording according to claim 9 or 10, wherein the urea derivative represented by the general formula (5) is ethylene urea.   The content of the compound represented by the general formula (2) is in a range of 0.2% by mass or more and 3.0% by mass or less as a proportion of the total mass of the ink. 2. Ink for ink jet recording described in 1.   The ink for inkjet recording according to any one of claims 9 to 12, wherein the pH of the ink for inkjet recording is in the range of 5 to 7.5.   An ink for ink jet recording comprising at least two kinds of color materials of a first color material and a second color material, wherein the second color material has a bronzing phenomenon caused by the first color material. An ink for ink-jet recording, which has an ability to suppress generation.   An ink jet recording method comprising forming an image by applying the ink for ink jet recording according to claim 1 to a recording medium by an ink jet head.   An ink cartridge comprising the ink for inkjet recording according to any one of claims 1 to 14. An ink jet recording apparatus comprising the ink for ink jet recording according to any one of claims 1 to 14.

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