JP4262105B2 - Ink, ink set, ink jet recording method, recording unit, ink cartridge, and ink jet recording apparatus - Google Patents

Description

  The present invention relates to an ink, an ink jet recording method, an ink cartridge, a recording unit, an ink set, and an ink that can be suitably used for ink jet recording in which recording is performed on a recording material by discharging ink from an orifice according to a recording signal. The present invention relates to an ink jet recording apparatus.

  In the ink jet recording method, ink droplets are ejected and ink is attached to a recording material such as paper to perform recording. In particular, according to the inkjet recording method disclosed in Patent Documents 1 to 3, the electrothermal converter is used as the discharge energy supply means, and droplets are generated by generating bubbles by applying thermal energy to the ink. Color images can be printed easily. In recent years, further reductions in price and improvement in printing speed have been promoted for inkjet recording apparatuses, and higher image quality has been promoted for inkjet recorded images. Further, color ink jet recording is being applied to various uses.

By the way, for color recording using the ink jet recording method, for example, water-based ink in which dyes having respective color tones are dissolved in a water-soluble medium is used. It is desirable that these inks satisfy the ink jet recording characteristics listed in (1) to (10) below at a high level, for example.
(1) To provide an image having a sufficient density (2) To have good drying properties on a recording material (3) To have no bleeding in a recorded image (4) To record a recorded image even when contacted with water, alcohol or the like No flow out (5) The recorded image has excellent light resistance (6) No clogging at the tip of the nozzle (7) The printed image is distorted at the start of recording after continuous printing or after standing for a long time (8) The ink is stable during storage (9) During use, no problem occurs even when it comes into contact with the member constituting the recording means (10) Excellent heat resistance, In addition, the thermal energy generating element should not be adversely affected.

  By the way, among the inks of various tones used for color recording, as dyes used for magenta water-based inks, azo dyes and xanthene dyes that can obtain magenta inks having excellent tones are mainly used. The presence of such magenta ink having an excellent color tone makes it possible to realize an inkjet image having a high image quality comparable to a recent silver salt photograph. However, in recent years, not only image quality but also durability of formed images has been demanded for ink jet recorded images.

Japanese Patent Publication No. 61-59911 Japanese Patent Publication No. 61-59912 Japanese Examined Patent Publication No. 61-59914

On the other hand, according to the study by the present inventors, azo-type and xanthene-type magenta dyes used in conventional magenta inks are inferior in light resistance compared to dyes used in other color inks. a color ink jet image formed with the magenta ink, as assessed by long-term light resistance test exceeding the assumed so far, the 褪 color magenta, it was confirmed that the color balance of the color image is lost . The present inventors have recognized that it is necessary to improve the light resistance of a magenta ink image from the viewpoint of further improving the durability of a color image obtained by an inkjet recording method. It came.

  In addition, when used in combination with magenta ink using azo or xanthene dyes with good color development as a colorant and cyan ink using copper phthalocyanine dye with excellent light resistance and color tone as a colorant In addition, in the mixed color portion of the cyan ink and magenta ink, the discoloration of the magenta dye becomes more prominent than when it is a single color, the color balance of the entire image is lost, and the image quality may be significantly lowered. A new magenta ink has been proposed in response to the technical problem of acceleration of light deterioration in a mixed color image of magenta ink and cyan ink. For example, in Japanese Patent Application Laid-Open No. 2-127482, in two or more types of magenta inks having different densities, a dye having excellent sharpness is used for dark ink, and a dye that does not promote light fading in a mixed color part is used for light ink. Thus, it has been proposed to suppress light fading in a highlight portion of an image. In Japanese Patent Application Laid-Open No. 11-315230, in a magenta ink containing an azo dye, a dye having a xanthene structure is used as a light resistance imparting agent / light resistance imparting agent / coloring material = 0.03 to 0.5. There has been a proposal to suppress the fading in the mixed color portion of the image by adding in the range.

  However, according to the study by the present inventors, the technique described in Japanese Patent Laid-Open No. 2-127482 is an extremely effective technique that can suppress a change in color balance over time with respect to a color image. Considering consumer demands for high reproducibility of photographic color images, the color tone changes due to the interaction between color materials that occur in the color mixture of dark magenta ink and cyan ink can be further improved. I came to the conclusion that it was necessary. Further, with the technique described in JP-A-11-315230, although the fading promotion effect on the color image is suppressed, it is still necessary to further improve the light resistance with respect to the magenta ink itself. I got the recognition that it is.

  Therefore, the object of the present invention is to satisfy the performance required as an ink for ink jet recording, and when recorded on various recording materials, all have good color developability, can realize high image density, and can be obtained. An object of the present invention is to provide an ink, particularly a magenta color ink, which can give excellent light resistance to a printed image. Another object of the present invention is to provide a recording method capable of obtaining an image that has an excellent color tone and that does not easily fade when the image is formed. Another object of the present invention is to provide a recording unit, an ink cartridge, an ink set, and a recording apparatus using the ink having the above-described excellent effects.

  Another object of the present invention is to further improve the light fastness of the magenta dye in the color mixture portion of cyan ink and magenta ink, and even when an image including the color mixture portion is formed, the color development is excellent and beautiful. In addition to obtaining a color image, there is little discoloration even after storage for a long time, and magenta discoloration, which was particularly noticeable in mixed-color images of magenta ink and cyan ink having copper phthalocyanine dye, is effectively suppressed. Another object of the present invention is to provide an ink set containing a novel magenta ink capable of forming a color image excellent in light resistance capable of maintaining excellent image quality even under severe conditions. Another object of the present invention is to provide an ink jet recording method, a recording unit, an ink cartridge, and an ink jet recording apparatus for obtaining a color image having excellent light resistance.

（上記一般式（Ｉ）中、Ｒ₁は、置換若しくは未置換のアルコキシル基、或いは置換若しくは未置換のアリール基を表し、Ｒ₂及びＲ₄は、各々独立に、水素原子或いは置換若しくは未置換のアルキル基を表し、Ｒ₃は、水素原子、置換若しくは未置換のアルキル基、置換若しくは未置換のアルコキシル基、置換若しくは未置換のアリールオキシ基或いはハロゲン原子を表す。Ｘ₁は、カルボキシル基若しくはその塩、或いはスルホン酸基若しくはその塩を表す。ｎは、１又は２を表す）

（上記一般式（II）中、Ａｒ₁は、置換若しくは未置換のフェニル基、或いは置換若しくは未置換のナフチル基を表わし、Ａｒ₂は、アセチル基、ベンゾイル基、１，３，５−トリアジニル基、ＳＯ₂−Ｃ₆Ｈ₅基或いはＳＯ₂−Ｃ₆Ｈ₄−ＣＨ₃基のいずれかを表す。Ｍはスルホン酸基の対イオンであり、水素原子、アルカリ金属、アンモニウム或いは有機アンモニウムのいずれかを表す）。 The above object is achieved by the present invention described below. That is, the present invention relates to C.I. I. And Acid Red 5 2, containing a colorant represented by the ink which is characterized by containing a coloring material and an aqueous medium, represented by the following general formula (I) (provided that the following general formula (II) Except when)

(In the above general formula (I), R ₁ represents a substituted or unsubstituted alkoxyl group or a substituted or unsubstituted aryl group, and R ₂ and R ₄ each independently represents a hydrogen atom or a substituted or unsubstituted group. R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, or a halogen atom, and X ₁ represents a carboxyl group or A salt thereof, or a sulfonic acid group or a salt thereof, n represents 1 or 2)

(In the above general formula (II), Ar ₁ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, and Ar ₂ represents an acetyl group, a benzoyl group, or a 1,3,5-triazinyl group. Represents an SO ₂ —C ₆ H ₅ group or an SO ₂ —C ₆ H ₄ —CH ₃ group, where M is a counter ion of the sulfonic acid group, and represents any of a hydrogen atom, an alkali metal, ammonium or organic ammonium. Represents).

  Next, the ink set of the present invention using the above-described inks of the respective forms in combination with other inks will be described. As an embodiment of the ink set according to the present invention, at least one color ink selected from yellow ink, cyan ink and black ink is combined with the magenta color ink according to various aspects of the present invention described above. The characteristic is mentioned.

  An ink set according to another embodiment of the present invention includes a combination of cyan ink and magenta ink according to various aspects described above. In particular, in the case of an ink set combined with a cyan ink containing a color material having a copper phthalocyanine structure, the fading acceleration phenomenon observed in the mixed color portion of magenta ink and cyan ink has been relieved very effectively. The effect that is done. These ink sets are also suitable for inkjet recording applications.

  Next, the ink jet recording method of the present invention using the ink or ink set of each of the above forms will be described. An ink jet recording method according to an embodiment of the present invention includes a step of discharging the magenta ink for ink jet recording according to various aspects of the present invention from an orifice according to a recording signal. In addition, an ink jet recording method according to another embodiment of the present invention includes a process of ejecting magenta ink for ink jet recording according to various aspects of the present invention from an orifice according to a recording signal, and a copper phthalocyanine structure. And a step of discharging cyan ink containing a dye having a color from an orifice in accordance with a recording signal. In particular, in this aspect, when the mixed color portion is formed by overlapping the magenta ink and the cyan ink on the recording material, conventionally, the fading acceleration observed in the mixed color portion of the magenta ink and the cyan ink is accelerated. The effect that it can suppress effectively is acquired.

  One embodiment of the recording unit according to the present invention includes an ink storage portion that stores ink for magenta inkjet recording according to various aspects of the present invention described above, and a head portion that discharges the ink. And is provided. Further, another embodiment of the recording unit according to the present invention includes an ink storage portion storing each ink constituting an ink set for ink jet recording according to the various aspects according to the present invention described above, and ejecting the ink. And a head portion for performing the operation.

  One embodiment of the ink cartridge according to the present invention is characterized in that an ink storage portion that stores the ink according to various aspects of the present invention described above is provided. Further, another embodiment of the ink cartridge according to the present invention is characterized in that an ink storage portion that stores each ink constituting the ink set according to the various aspects of the present invention described above is provided. To do.

  Next, an ink jet recording apparatus according to an embodiment of the present invention includes a recording head for ejecting magenta ink jet ink according to various aspects of the present invention described above, and an ink storage portion in which the ink is stored. And an ink supply unit for supplying ink from the ink cartridge to the recording head. An inkjet recording apparatus according to another embodiment of the present invention includes at least one inkjet recording ink of yellow ink, cyan ink, and black ink, and the magenta inkjet recording according to various aspects of the present invention described above. And a recording head for ejecting each of these inks. An ink jet recording apparatus according to another embodiment of the present invention includes a cyan ink jet recording ink, a magenta ink jet recording ink according to various aspects of the present invention, and an ink for ejecting each of these inks. And a recording head.

As described above, according to one embodiment of the present invention, an ink having a clear magenta color tone and image density and capable of providing an image exhibiting excellent light resistance when printed on various recording papers. , An ink set, an ink jet recording method, a recording unit, an ink cartridge, and an ink jet recording apparatus are provided.
Further, according to another embodiment of the present invention, the light fastness of an image having a color mixture portion of a magenta ink, which has been a problem in the past, and a cyan ink containing a dye having a copper phthalocyanine structure is improved. An ink set, an ink jet recording method, a recording unit, an ink cartridge, and an ink jet recording apparatus are provided.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.
In view of the above-mentioned object, the present inventors combined at least one of an azo-based magenta dye and a xanthene-based magenta dye with a magenta dye having an anthrapyridone skeleton in a process of studying various magenta dyes. Ink was prepared and images of this ink and images of this ink were evaluated. As a result, the ink having such a configuration satisfies the above-described inkjet recording characteristics (1) to (10) at a high level and has an excellent tint that can be used for photographic image formation. and, moreover, the image formed by such an ink was Heading that is excellent in light resistance.

  That is, according to the study by the present inventors, the light resistance of the image obtained by the ink having the above-described structure is significantly higher than that predicted from the light resistance of the image formed using the ink of the azo dye alone. It turned out to be a thing. The reason why such a result is obtained is not clear, but it is considered that the interaction between dye molecules caused by using a plurality of color materials in combination contributes.

  As a conventionally known magenta water-based ink and a recording method using the same, for example, JP-A-2-16171 discloses a magenta water-based dye ink using a dye having an anthrapyridone skeleton. , It is described that the dye is excellent in light resistance. Japanese Patent Application Laid-Open No. 57-197191 discloses an ink-jet color print system using a magenta aqueous dye ink containing a dye having an anthrapyridone skeleton. However, these inventions do not disclose any technique for mixing an anthrapyridone-based magenta dye with other magenta dyes, and even suggest the effect of improving the light fastness of an image caused by the mixed ink. Not even done.

  Further, Japanese Patent Application Laid-Open No. 10-306221 (US Pat. No. 6,152,969) and Japanese Patent Application Laid-Open No. 2000-109464 (EP 1067155) also disclose an ink containing an anthrapyridone compound having a structure similar to the present invention. However, the above-described features of the present invention are not disclosed at all, and there is no description suggesting the effect. Furthermore, WO A1 9946341 (corresponding to JP 2000-169776 A and EP 1063268 A1) published on March 4, 1999 discloses an ink containing an anthrapyridone compound. However, nothing is disclosed about the features of the present invention.

上記一般式（Ｉ）中、Ｒ₁は、置換若しくは未置換のアルコキシル基、或いは置換若しくは未置換のアリール基を表し、Ｒ₂及びＲ₄は、各々独立に、水素原子或いは置換若しくは未置換のアルキル基を表し、Ｒ₃は、水素原子、置換若しくは未置換のアルキル基、置換若しくは未置換のアルコキシル基、置換若しくは未置換のアリールオキシ基或いはハロゲン原子を表す。Ｘ₁は、カルボキシル基若しくはその塩、或いはスルホン酸基若しくはその塩を表す。ｎは、１又は２を表す。 First, an ink combining an azo magenta dye and a magenta dye having an anthrapyridone skeleton will be described below as a reference embodiment.
[Reference implementation form]
(Color material)
The ink according to the reference embodiment includes a color material and an aqueous medium. As the color material, a first color material represented by the following general formula (I) and a first color material represented by the following general formula (II) are used. 2 of the color material that has been used in combination.

In the general formula (I), R ₁ represents a substituted or unsubstituted alkoxyl group or a substituted or unsubstituted aryl group, and R ₂ and R ₄ each independently represents a hydrogen atom or a substituted or unsubstituted group. Represents an alkyl group, and R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, or a halogen atom. X ₁ represents a carboxyl group or a salt thereof, or a sulfonic acid group or a salt thereof. n represents 1 or 2.

For R ₁ to R ₄ in the general formula (I), more specifically, as the R _1, for example, a linear or branched alkoxyl group having 1 to 4 carbon atoms, a substituted or unsubstituted And the like. Examples of the substituent of the phenyl group include a methyl group, a hydroxyl group, a nitro group, a sulfonic acid group, or a salt thereof, a carboxyl group or a salt thereof, or a halogen atom (fluorine, chlorine, bromine, etc.). Examples of R ₂ include a hydrogen atom and a linear or branched lower alkyl group having 1 to 4 carbon atoms. Examples of R ₃ include a hydrogen atom and a linear chain having 1 to 4 carbon atoms. Examples of the linear or branched alkyl group, the linear or branched alkoxyl group having 1 to 4 carbon atoms, and the aryloxy group include a phenoxy group. The aryl group constituting the aryloxy group may be substituted with, for example, a linear or branched alkyl group having 1 to 10 carbon atoms, a sulfone group, a salt thereof, a carboxyl group, or a salt thereof. . Furthermore, examples of R ₄ include a hydrogen atom, a linear or branched lower alkyl group having 1 to 4 carbon atoms, and the like. Further, X ₁ in the above formula will be described in detail. Examples of X ₁ include —COOM and —SO ₃ M. Provided that M is a hydrogen atom, an alkali metal (eg, Li, Na, etc.), ammonium (NH ₄ ), organic ammonium (N (R ₅ ) ₄ ), etc., and R ₅ is a methyl group or an ethyl group. The thing which is is mentioned.

上記一般式（II）中、Ａｒ₁は、置換若しくは未置換のフェニル基、或いは置換若しくは未置換のナフチル基を表わし、Ａｒ₂は、アセチル基、ベンゾイル基、１，３，５−トリアジニル基、ＳＯ₂−Ｃ₆Ｈ₅基或いはＳＯ₂−Ｃ₆Ｈ₄−ＣＨ₃基のいずれかを表す。Ｍは、スルホン酸基の対イオンであり、上記一般式Ｍと同様に、水素原子、アルカリ金属（例えば、Ｌｉ、Ｎａ等）、アンモニウム（ＮＨ₄）或いは有機アンモニウム（Ｎ（Ｒ₆）₄）のいずれかを表す。ここで、Ｒ₆としては、例えばメチル基やエチル基が挙げられる。

In the general formula (II), Ar ₁ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, Ar ₂ represents an acetyl group, a benzoyl group, a 1,3,5-triazinyl group, It represents either an SO ₂ —C ₆ H ₅ group or an SO ₂ —C ₆ H ₄ —CH ₃ group. M is a counter ion of a sulfonic acid group, and similarly to the general formula M, a hydrogen atom, an alkali metal (for example, Li, Na, etc.), ammonium (NH ₄ ), or organic ammonium (N (R ₆ ) ₄ ) Represents one of the following. Here, examples of R ₆ include a methyl group and an ethyl group.

Furthermore, the phenyl group or naphthyl group of Ar ₁ includes, for example, a carboxyl group or a salt thereof, a sulfonic acid or a salt thereof, a linear or branched alkyl group having 1 to 4 carbon atoms, a halogen atom (fluorine, chlorine , Bromine, etc.), an alkoxyl group having 1 to 4 carbon atoms, an aryloxy group such as a phenoxy group, and the like, and may be substituted with one or more groups or atoms. When Ar ₂ is a benzoyl group or a 1,3,5-triazinyl group, at least one hydrogen atom in the benzene ring or 1,3,5-triazine ring is a carboxyl group or a salt thereof, a halogen atom It may be substituted with an atom (fluorine atom, chlorine atom, bromine atom or the like), or a primary to tertiary amino group, an alkoxyl group, a hydroxyl group, or the like.

  The magenta image obtained by the ink containing the first and second colorants represented by the above general formulas (I) and (II) exhibits a very excellent color tone and is also an azo dye. The light fastness superior to the light fastness expected from an ink containing only as a coloring material is exhibited.

Below, the illustration compounds 1-7 are shown as a specific example of the 1st coloring material shown by general formula (I). Even with an ink according to the present invention described later, but to use this first coloring material, the first coloring material, rather than being limited thereto, the same time two kinds of coloring materials such as listed below You may use above.

Examples of the color material of the compound of the general formula (II) used in the ink according to the reference embodiment include C.I. I. Examples include Reactive Red 180, Exemplified Compounds 8 to 13 having the following structures, and compounds having structures described in JP-A-8-73791, JP-A-11-209673, and the like.

The mass ratio of the first color material represented by the general formula (I) and the second color material represented by the general formula (II) contained in the ink according to the above-described reference embodiment is the first of these. In consideration of the effect that a clear color tone, a sufficient image density, and an excellent light resistance can be obtained by combining and using the second color material and the second color material, the general formula (I) It is preferable that the first colorant represented: the second colorant represented by the general formula (II) is in the range of 95: 5 to 20:80. The content of all color materials in the ink is preferably in the range of 0.1 to 15.0% by mass, particularly 0.5 to 5.0% by mass with respect to the total amount of ink.

(Aqueous medium)
The water-soluble organic solvent contained in the aqueous medium used in the ink according to the reference embodiment and the ink according to the present invention to be described later is not particularly limited as long as it shows water solubility, and alcohol, polyhydric alcohol, polyglycol Glycol ether, nitrogen-containing polar solvent, sulfur-containing polar solvent, and the like. These water-soluble organic solvents have a water-soluble organic solvent content of 1 to 40 of the whole ink in consideration of maintaining the moisture retention of the ink, improving the solubility of the coloring material, and effectively penetrating the ink into the recording paper. It is preferable to set it as the range of mass%, More preferably, it is set as the range of 3-30 mass%. In addition, the content of water in the ink is good because the colorant dye has good solubility in the ink, has a viscosity for stable ink ejection, and does not cause clogging at the nozzle tip. Is preferably in the range of 30 to 95% by mass.

(PH)
In the ink according to the reference embodiment and the ink of the present invention described later , when any of the color materials uses a color material containing at least one carboxyl group or salt thereof in the molecule, the solubility of the color material in water is reduced. In addition, from the viewpoints of preventing clogging at the tip of the nozzle and long-term storage stability of the ink, the pH of the ink is in a neutral to alkaline range, specifically within the range of pH 7.0 to 11.0. It is preferable to keep. In addition, when any of the color materials uses a color material that does not contain a carboxyl group or its salt in the molecule, the pH dependency of the solubility of the color material is weak, so that the pH of the ink is pH 4.0 to 11. It may be within the range of 0.

(Additive)
In addition, in order to maintain the moisturizing property of the ink, in the present invention, a moisturizing solid content such as urea, a urea derivative, trimethylolpropane, or the like may be used as the ink component, if necessary, in addition to the above components . In general, the content of moisturizing solids such as urea, urea derivatives, and trimethylolpropane in the ink is preferably in the range of 0.1 to 20.0% by mass, more preferably, based on the total amount of the ink. It is the range of 3.0-10.0 mass%. In addition to the above components, the ink of the present invention includes a surfactant, a pH adjuster, a rust inhibitor, an antiseptic, an antifungal agent, an antioxidant, an anti-reduction agent, an evaporation accelerator, a chelate as necessary. Various additives such as an agent and a water-soluble polymer may be contained.

Embodiment of the present invention
In click according to the present onset Ming, in the ink of Reference embodiment, as the second coloring material azo represented by general as listed above formula (II), represented by the following structural formula C. I. Acid Red 52 and C.I. I. Ru in Kudea made in place of the dye of xanthene having excellent magenta color including at least one of Acid Red 289. Instead of the azo-based second colorant represented by the general formula (II), a magenta dye containing at least one of the dyes listed above is used as the anthrapyridone represented by the general formula (I). According to the onset Ming ink in combination with a dye which is first coloring material having a skeleton, the resulting image is predicted from an image obtained by the ink containing only the xanthene dyes listed above as coloring materials An image having light fastness significantly exceeding the light fastness is obtained.

The weight ratio of the first color material represented by the general formula (I) in Lee in ink of the present invention, the colorant xanthene listed above is first represented by these general formulas (I) Considering the effects of vivid color tone, high image density, and excellent light resistance obtained by combining 1 colorant and xanthene colorant, the first color represented by the general formula (I) It is preferable that the material: xanthene-based coloring material be in the range of 95: 5 to 20:80.

Ink or according to the reference actual embodiments with described above, the ink of the present invention is especially suitable for use in an ink jet recording method which performs recording by ejecting droplets by the action of heat energy, other ink jet recording methods and general Needless to say, it can also be used as a writing instrument.

(Recording device, ink cartridge, recording unit, ink set)
Meanwhile, Suitable recording apparatus for performing recording by using the ink of the upper Symbol present invention, to an ink within a recording head having an ink storage portion in which these inks are accommodated, thermal energy corresponding to recording signals And an apparatus for generating ink droplets by the energy.

  1 to 3 show a configuration example of a recording head that is a main part of the recording head. The head 13 is a heat generating head 15 having a glass, ceramic, or plastic plate having a groove 14 through which ink passes and a heat generating resistor used for thermal recording (the head is shown in the figure, but is not limited thereto). It is obtained by adhering The heat generating head 15 has good heat dissipation such as a protective film 16 formed of silicon oxide or the like, aluminum electrodes 17-1 and 17-2, a heat generating resistor layer 18 formed of nichrome or the like, a livestock heat layer 19, and alumina. It consists of a substrate 20. The ink 21 is filled up to the discharge orifice (fine hole) 22, and a meniscus 23 is formed by the pressure P. When a pulsed electric signal is applied to the electrodes 17-1 and 17-2 of the head 13, the region (heater) indicated by n of the heating element substrate 15 is rapidly heated, and the ink in contact with the surface is heated. Bubbles are generated in the nozzle 21, and the meniscus 23 is discharged by the pressure. The ink 21 is discharged through the nozzle 14 of the head, becomes an ink droplet from the discharge orifice 22, and flies toward the recording material. FIG. 3 shows an external view of an example of a multi-head in which a large number of heads shown in FIG. 1 are arranged. This multi-head is made by adhering a glass plate 27 having multi-nozzles 26 and a heating head 28 similar to that described in FIG.

  FIG. 4 shows an example of an ink jet recording apparatus incorporating this head. In FIG. 4, 61 is a blade as a wiping member, one end of which is held by a blade holding member to become a fixed end and form a cantilever. The blade 61 is disposed at a position adjacent to the recording area by the recording head, and in the case of the example shown in FIG. 4, it is held in a form protruding in the moving path of the recording head. Reference numeral 62 denotes a cap, which is disposed at a home position adjacent to the blade 61 and moves in a direction perpendicular to the moving direction of the recording head so as to come into contact with the ejection surface and perform capping. Further, reference numeral 63 in FIG. 4 denotes an ink absorber provided adjacent to the blade 61 and, like the blade 61, is held in a form protruding in the moving path of the recording head.

The blade 61, the cap 62, and the absorber 63 constitute a discharge recovery portion 64, and the blade 61 and the absorber 63 remove moisture, dust, dust, and the like from the ink discharge port surface.
Reference numeral 65 denotes a recording head that has discharge energy generating means and performs recording by discharging ink onto a recording material facing the discharge port surface on which the discharge ports are arranged. Reference numeral 66 denotes a recording head 65 having the recording head 65 mounted thereon. It is a carriage for performing the movement. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 driven by a motor 68 (not shown). Accordingly, the carriage 66 can move along the guide shaft 67, and the recording area by the recording head 65 and its adjacent area can be moved.

  Reference numeral 51 denotes a paper feed unit for inserting a recording material, and 52 denotes a paper feed roller driven by a motor (not shown). With these configurations, a recording material is fed to a position facing the ejection port surface of the recording head, and is discharged to a paper discharge unit provided with a paper discharge roller 53 as recording progresses.

  In the above configuration, when the recording head 65 returns to the home position due to the end of recording or the like, the cap 62 of the head recovery unit 64 is retracted from the moving path of the recording head 65, but the blade 61 protrudes into the moving path. As a result, the ejection port surface of the recording head 65 is wiped. When the cap 62 is in contact with the ejection surface of the recording head 65 to perform capping, the cap 62 moves so as to protrude into the moving path of the recording head.

  When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same position as that at the time of wiping described above. As a result, even in this movement, the ejection port surface of the recording head 65 is wiped. The above-mentioned movement of the recording head to the home position is performed not only at the end of recording or at the time of recovery of ejection, but also to the home position adjacent to the recording area at a predetermined interval while the recording head moves the recording area for recording. In accordance with this movement, the wiping is performed.

  FIG. 5 is a cross-sectional view showing an example of an ink cartridge 45 that contains ink supplied to the head via an ink supply member, for example, a tube. Here, reference numeral 40 denotes an ink container, for example, an ink bag, in which supply ink is stored, and a rubber plug 42 is provided at the tip thereof. By inserting a needle (not shown) into the stopper 42, the ink in the ink bag 40 can be supplied to the head. An ink absorber 44 receives waste ink.

  The ink jet recording apparatus used in the present invention is not limited to the one in which the head and the ink cartridge as described above are separated, and an apparatus in which they are integrated as shown in FIG. 6 is also preferably used. In FIG. 6, reference numeral 70 denotes a recording unit, in which an ink storage portion that stores ink, for example, an ink absorber is stored, and the ink in the ink absorber has a plurality of orifices. 71 is ejected as ink droplets. Reference numeral 72 denotes an atmosphere communication port for communicating the inside of the recording unit with the atmosphere. The recording unit 70 is used in place of the recording head 65 shown in FIG. 4 and is detachable from the carriage 66.

Next, other specific examples of the recording apparatus and the recording head that can be suitably used in the present invention will be described. 7, the liquid discharge head of the bubble at a suitable discharge in the present invention as a liquid ejection head ejecting method for communicating with the atmosphere, and an example of a main part of an ink jet printer over as a liquid discharge apparatus using this liquid discharge head It is a schematic perspective view which shows. Inkjet printers over that shown in FIG. 7, in a casing 1008, a paper 1028 as a recording medium provided along the longitudinal direction, the conveying device for intermittently transported in the direction indicated by the arrow P shown in FIG. 7 1030, a recording unit 1010 that is reciprocated along the guide shaft 1014 substantially parallel to a direction S substantially perpendicular to the conveyance direction P of the paper 1028 by the conveying device 1030, and a drive for reciprocating the recording unit 1010 A moving drive unit 1006 as means is included.

  The conveying device 1030 includes a pair of roller units 1022a and 1022b that are arranged to face each other substantially in parallel, a pair of roller units 1024a and 1024b, and a drive unit 1020 for driving each of these roller units. Yes. With this configuration, when the driving unit 1020 of the transport device 1030 is activated, the paper 1028 is sandwiched between the roller units 1022a and 1022b and the roller units 1024a and 1024b, and the direction of the arrow P shown in FIG. Are conveyed intermittently.

  Further, the movement drive unit 1006 is disposed substantially parallel to the belt 1016 wound around the pulleys 1026a and 1026b disposed on the rotation shafts opposed to each other with a predetermined interval, and the roller units 1022a and 1022b, and the recording unit. The motor 1018 is configured to drive a belt 1016 coupled to a carriage member 1010a 1010 in the forward direction and the reverse direction.

  When the motor 1018 is activated and the belt 1016 rotates in the direction of arrow R in FIG. 7, the carriage member 1010a of the recording unit 1010 is moved by a predetermined amount of movement in the direction of arrow S in FIG. When the motor 1018 is activated and the belt 1016 rotates in the direction opposite to the arrow R direction in FIG. 7, the carriage member 1010a of the recording unit 1010 is predetermined in the direction opposite to the arrow S direction in FIG. Will be moved by the amount of movement. Further, a recovery unit 1026 for performing an ejection recovery process of the recording unit 1010 is opposed to the ink ejection port array of the recording unit 1010 at one end portion of the movement driving unit 1006 at a position serving as a home position of the carriage member 1010a. Is provided.

  In the recording unit 1010, inkjet cartridges (hereinafter simply referred to as cartridges) 1012Y, 1012M, 1012C, and 1012B are provided for each color, for example, for each of yellow, magenta, cyan, and black, a carriage member 1010a. Are detachably provided.

  FIG. 8 shows an example of an ink jet cartridge that can be mounted on the above-described ink jet recording apparatus. The cartridge 1012 in this example is of a serial type, and the main part is composed of an ink jet recording head 100 and a liquid tank 1001 for containing a liquid such as ink. The ink jet recording head 100 is formed with a large number of ejection ports 832 for ejecting liquid, and liquid such as ink is supplied from a liquid tank 1001 through a liquid supply passage (not shown) to a common liquid chamber ( (See FIG. 9). A cartridge 1012 shown in FIG. 8 integrally forms an ink jet recording head 100 and a liquid tank 1001 so that liquid can be supplied into the liquid tank 1001 as necessary. A structure in which a liquid tank 1001 is connected to 100 in a replaceable manner may be adopted.

Hereinafter, a specific example of the liquid discharge head can be installed in an inkjet printer over the structure as described above will be described in more detail.
FIG. 9 is a schematic perspective view schematically showing the main part of the liquid discharge head showing the basic form of the present invention, and FIGS. 10 to 13 show the discharge port shape of the liquid discharge head shown in FIG. FIG. Note that electrical wiring and the like for driving the electrothermal transducer are omitted.

  In the liquid discharge head of this example, for example, a substrate 934 made of glass, ceramics, plastic, metal or the like as shown in FIG. 9 is used. The material of such a substrate is not essential and functions as a part of the flow path component, and serves as a support for the material layer that forms the ink discharge energy generating element and the liquid flow path and discharge port described later. There is no particular limitation as long as it can function. Hereinafter, a case where a Si substrate (wafer) is used will be described. In addition to the forming method using laser light, the discharge port can be formed by an exposure apparatus such as MPA (Mirror Projection Aliner) using, for example, an orifice plate (discharge port plate) 935 described later as a photosensitive resin.

  In FIG. 9, reference numeral 934 denotes a substrate including an electrothermal conversion element (hereinafter also referred to as a heater) 931 and an ink supply port 933 including a long groove-like through-hole as a common liquid chamber portion. On both sides in the longitudinal direction of the 933, heaters 931, which are thermal energy generating means, are arranged in a staggered manner, one row at a time, for example, with an interval between electrothermal conversion elements (heaters) of 300 dpi. On the substrate 934, an ink flow path wall 936 for forming an ink flow path is provided. The ink flow path wall 936 is further provided with a discharge port plate 935 having a discharge port 832.

  Here, in FIG. 9, the ink flow path wall 936 and the ejection port plate 935 are shown as separate members. However, the ink flow path wall 936 is placed on the substrate 934 by a technique such as spin coating. By forming the same, the ink flow path wall 936 and the discharge port plate 935 can be simultaneously formed as the same member. In this example, the discharge port surface (upper surface) 935a side is further subjected to water repellent treatment.

In this example, a serial type head that performs recording while scanning in the direction of arrow S in FIG. 7 described above is used, and recording is performed at, for example, 1200 dpi. The drive frequency is 10 kHz, and one discharge port performs discharge at the shortest time interval of 100 μs. As an example of the actual dimensions of the head, for example, as shown in FIG. 10, the partition wall 936a that fluidly isolates adjacent nozzles has a width W = 14 μm. In the figure, 1337 is a foaming chamber. As shown in FIG. 13, the foaming chamber 1337 formed by the ink flow path wall 936 has N ₁ (foaming chamber width dimension) = 33 μm and N ₂ (foaming chamber length dimension) = 35 μm. The size of the heater 931 is 30 μm × 30 μm, the heater resistance value is 53Ω, and the drive voltage is 10.3V. The ink flow path wall 936 and the partition wall 936a can be 12 μm in height, and the discharge port plate 935 can be 11 μm in thickness.

  9 is a cross-sectional view of the discharge port portion 940 provided in the discharge port plate 935 including the discharge port 832 shown in FIG. 9, which is cut in a direction crossing the ink discharge direction (thickness direction of the orifice plate 935). As shown in FIG. 11, the shape is substantially a star shape, and is alternately arranged between six raised portions 832a having obtuse angles and these raised portions 832a, and has acute angles. It is comprised roughly from the six protuberance part 832b which has. That is, the bottom portion 832b as a region that is locally separated from the center O of the discharge port is the top portion, and the raised portion 832a as a region that is locally close to the center O of the discharge port adjacent to this region is the base portion. Six grooves 1141 are formed in the thickness direction (liquid discharge direction) of the orifice plate shown in FIG. 9 (see FIG. 11).

In this example, the discharge port portion 940 has a shape in which, for example, a cross section cut in a direction intersecting the thickness direction is a combination of two regular triangles each having a side of 27 μm and rotated by 60 degrees. T ₁ shown in FIG. 11 is 8 μm. The angles of the raised parts 832a are all 120 degrees, and the angles of the protuberance parts 832b are all 60 degrees. Therefore, a polygon formed by connecting the center O of the discharge port and the center of the groove adjacent to each other (the center (center of gravity) of the figure formed by connecting the top of the groove and the two bases adjacent to the top). The center of gravity G of the two coincides with each other. The opening area of the discharge port 832 in this example is 400 μm ² , and the opening area of the groove (the area of the figure formed by connecting the top of the groove and two bases adjacent to the top) is about 33 μm ² per one. It has become. FIG. 12 is a schematic diagram showing an ink adhesion state at the discharge port portion shown in FIG. 11, and C indicates an ink adhesion portion (wetting ink).

Above SL liquid discharge head, when the bubble for ejecting the liquid in a volume decrease stage after growing to a maximum volume, a plurality of grooves dispersed with respect to the center of the discharge port, the direction of the main liquid droplet during ejection Can be stabilized. As a result, it is possible to provide a liquid ejection head that has no deviation in the ejection direction and has high landing accuracy. In addition, high-speed and high-definition printing can be realized by being able to stably discharge even foaming variation at a high driving frequency.

  In particular, in the volume reduction stage of the bubble, by discharging the liquid by first communicating the bubble with the atmosphere, it is possible to prevent mist generated when the droplet is discharged by communicating the bubble to the atmosphere. It is also possible to suppress a state in which droplets adhere to the discharge port surface, which causes sudden discharge failure. In addition, as another embodiment of a recording head of a discharge method that can be suitably used in the present invention and communicates air bubbles with the atmosphere during discharge, for example, as described in Japanese Patent Registration No. 2783647, a so-called edge shooter type is available. Can be mentioned.

(Ink set)
The ink set of the present invention is a combination of yellow ink, cyan ink, and at least one color of the black ink, the ink of the present invention having the Magenta color previously described. A dye or pigment can be used as a color material contained in each color ink of yellow, cyan and black, which can be used at that time. As the dye, for example, any of the water-soluble xanthene, triphenylmethane, anthraquinone, monoazo, disazo, trisazo, and tetraazo dyes described in the Color Index can be preferably used.

As the pigment, in the case of black pigment ink, carbon black is suitable. 2300, no. 900, MCF88, No. 40, no. 52, MA7, MA8, no. 2200B (manufactured by Mitsubishi Kasei), RAVEN1255 (manufactured by Columbia), REGAL400R, REGAL660R, MOGUL L ( manufactured by Cabot), Color Black FW1, Color Black FW18, Color Black S170, Color Black S150, Printex 35, Printex U ( As described above, commercially available products such as Degussa) can be used.

  Examples of pigments used in yellow ink include C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 2, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 16, C.I. I. Pigment Yellow 83.

  Examples of pigments used for cyan ink include C.I. I. Pigment Blue 1, C.I. I. Pigment Blue 2, C.I. I. Pigment Blue 3, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 22, C.I. I. Vat Blue 4, C.I. I. Vat Blue 6 etc. are mentioned.

  The ink set of the present invention as described above is used in an ink jet recording apparatus having a recording unit provided with a storage unit for independently storing the ink constituting the ink set, an ink cartridge, and the like. In the above description, the ink jet recording apparatus has been described by taking as an example a recording apparatus that ejects ink droplets by applying thermal energy to ink, but in addition, a piezoelectric ink jet recording apparatus that uses piezoelectric elements. But you can use it as well.

Meanwhile, according to the study of the present inventors, in particular, a magenta ink according to the present onset bright, light resistance of the color mixture portion formed using a cyan ink containing a coloring material having a copper phthalocyanine structure is very It turned out to be excellent. The degree of the light fastness is the light fastness in the color mixture portion of the magenta ink containing the colorant represented by the general formula (I) alone and the cyan ink containing the colorant having a copper phthalocyanine structure, and the general formula (I) And the light resistance predicted based on the light resistance in the mixed color portion of each magenta ink containing each of the color materials used alone and the cyan ink containing the color material having a copper phthalocyanine structure.

The reason why such a result is obtained is not clear, but the use of a mixture of a plurality of coloring materials causes interactions between dye molecules, which contributes to a marked improvement in the light resistance of the image. It is thought that. Further, it has been found that this effect is particularly remarkable when glossy paper is used as the recording material. Further, in addition to the color material represented by the general formula (I), C.I. I. When Acid Red 289 is included, in addition to the effect that the light fastness in the mixed color portion of the magenta ink and cyan ink of the image described above is remarkably improved, an effect of high image density and high color development can be obtained. all right. As described above, as an ink set comprising in combination a cyan ink comprising a luma Zentainku written present invention, a coloring material having a copper phthalocyanine structure, it is possible to improve the light resistance of color mixing of these inks This is a particularly preferable aspect.

As the cyan ink constituting such an ink set, an ink containing a color material having a copper phthalocyanine structure is used. A cyan color material having a copper phthalocyanine structure is excellent in light resistance and color tone. As described above, when a cyan ink having such a color material and a conventional magenta ink are used, a color mixture portion of these inks is used. In this image, it was known that the magenta dark blue becomes more remarkable than the case of a single color. The present invention, such problems are those suppressed by constituting the magenta ink according to the present onset bright previously described. Here, specific examples of the color material having a copper phthalocyanine structure include C.I. I. Acid Blue 249, C.I. I. Direct Blue 86, C.I. I. Direct Blue 199, C.I. I. Direct Blue 307 etc. are mentioned.

  In addition, yellow ink, black ink, and the like may be further combined with the above ink set as necessary to form an ink set. Conventionally used dyes and pigments can be used as color materials to be included in yellow ink and black ink used in this case. As the dye, for example, any of the water-soluble xanthene, triphenylmethane, anthraquinone, monoazo, disazo, trisazo, and tetraazo dyes described in the color index can be used.

  As the pigment, in the case of black pigment ink, carbon black is suitable. 2300, no. 900, MCF88, No. 40, no. 52, MA7, MA8, no. 2200B (Mitsubishi Kasei), RAVEN 1255 (Colombia), REGAL400R, REGAL660R, MOGUL L (Cabot), Color Black FW1, Color Black FW18, Color Black S170, Color Black S150, U As described above, commercially available products such as Degussa) can be used.

  Examples of pigments used in yellow ink include C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 2, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 16, C.I. I. Pigment Yellow 83 and the like.

Next, the present invention will be described in more detail with reference to Examples , Reference Examples and Comparative Examples. Unless otherwise specified, the ink components in Examples, Reference Examples, and Comparative Examples mean “parts by mass”.

<Example 1 and Reference Examples 1 and 2 >
The following components were mixed, sufficiently stirred and dissolved, followed by pressure filtration with a 0.20 μm filter to prepare inks of Example 1 and Reference Examples 1 and 2 , respectively.

(Ink composition of Reference Example 1 )
-1st coloring material of the exemplified compound 1 2.2 parts-second coloring material of the exemplified compound 12 1.6 parts-2-pyrrolidone 8.0 parts-glycerin 10.0 parts-acetylenol EH ( (Made by Kawaken Fine Chemicals)
1.0 part, 77.2 parts of ion-exchanged water

(Ink composition of Reference Example 2 )
-2.2 parts of the exemplified compound 3 as the first coloring material-1.8 parts of the exemplified compound 9 as the second coloring material-7.0 parts of 1,5-pentanediol-8.0 parts of urea- Acetylenol EH (manufactured by Kawaken Fine Chemical Co., Ltd.)
0.3 parts, ethanol 1.5 parts, ion-exchanged water 79.2 parts

(Ink composition of Example 1 )
-3.0 parts of the exemplified compound 2 as the first color material-CI Acid Red 289 as the third color material
1.0 part, 10.0 parts of glycerin, 8.0 parts of urea, acetylenol EH (manufactured by Kawaken Fine Chemical Co., Ltd.)
0.3 parts, ethanol 4.0 parts, ion-exchanged water 73.7 parts

<Comparative Examples 1-3>
The following components were mixed, sufficiently stirred and dissolved, followed by pressure filtration with a 0.20 μm filter to obtain inks of Comparative Examples 1 to 3, respectively.
(Ink composition of Comparative Example 1)
-4.0 parts of the exemplified compound 1 as the first coloring material-10.0 parts of thiodiglycol-8.0 parts of urea-Acetylenol EH (manufactured by Kawaken Fine Chemical Co., Ltd.)
1.0 part, 77.0 parts of ion-exchanged water

(Ink composition of Comparative Example 2)
2.9 parts of the exemplified compound 8 as the second coloring material. 10.0 parts of ethylene glycol. 7.0 parts of 1,2,6-hexanetriol. 8.0 parts of urea. Acetyleneol EH (Kawaken Fine Chemical Co., Ltd.) Made)
1.0 part, 71.1 parts of ion exchange water

(Ink composition of Comparative Example 3)
・ The third colorant, CI Acid Red 52
2.5 parts, 10.0 parts of glycerin, 8.0 parts of urea, acetylenol EH (manufactured by Kawaken Fine Chemical Co., Ltd.)
0.3 parts, ethanol 4.0 parts, ion-exchanged water 75.2 parts

<Evaluation of ink>
Using the inks of the Examples , Reference Examples and Comparative Examples obtained above, printing was performed using an on-demand type ink jet printer using a heating element as an energy source for ink ejection as an ink jet recording apparatus, and the resulting image (1) Color developability, (2) Image density, and (3) Light resistance were evaluated according to the following methods and criteria. Table 1 summarizes the color materials of the inks of Examples , Reference Examples, and Comparative Examples, and the evaluation results obtained using these inks.

(1) Color development After filling the above-mentioned printer with predetermined ink and printing a solid part on two types of recording materials, PPC paper (made by Canon) and glossy paper (PR-101; made by Canon), 24 The mixture was naturally dried for a period of time, and the color developability of the subsequent images was visually evaluated.
A: having a bright magenta color tone B: having a slightly dull magenta color tone C: having a dull magenta color tone

(2) Image density [2-A]
After filling the above-mentioned printer with predetermined ink and printing a solid portion similar to that used in the evaluation (1) on PPC paper (manufactured by Canon), it was naturally dried for 24 hours, and then the optical density of the image thereafter Was measured with a reflection densitometer Macbeth RD-918 (trade name: manufactured by Macbeth Co., Ltd.), and the obtained measurement values were used to evaluate the following criteria.
A: Image density is 1.2 or more B: Image density is 1.1 or more and less than 1.2 C: Image density is less than 1.1

[2-B]
After filling the above-mentioned printer with a predetermined ink and printing a solid part on glossy paper (PR-101; manufactured by Canon), it is naturally dried for 24 hours, and the optical density of the subsequent image is measured by a reflection densitometer Macbeth RD-918. (Product name: manufactured by Macbeth Co., Ltd.), and the obtained measurement values were used for evaluation according to the following criteria.
A: Image density is 1.9 or more B: Image density is 1.8 or more and less than 1.9 C: Image density is less than 1.8

(3) Light resistance The above-mentioned printer is filled with a predetermined ink, and the same solid as that used in the evaluation (1) is applied to each of PPC paper (Canon) and glossy paper (PR-101; Canon). Printed. After that, the printed matter is naturally dried for 24 hours, and then used in a xenon fade meter Ci3000 (manufactured by Atlas Co., Ltd.) equipped with an ultraviolet cut filter under conditions of 35 ° C., 60% relative humidity, and 60 klux irradiation intensity for 100 hours. Exposure exposure. The density of the solid portion of the printed matter before and after this irradiation test was measured with a reflection densitometer Macbeth RD-918 (trade name: manufactured by Macbeth Co., Ltd.), and the residual density rate was obtained from these measured values. Sex was evaluated.
A: Concentration residual ratio is 80% or more B: Concentration residual ratio is 60% or more and less than 80% C: Concentration residual ratio is less than 60%

As shown in Table 1 above, the ink of Comparative Example 1 containing only the colorant of general formula (I) showed good color developability on glossy paper, but color developability on PPC paper and PPC paper In the case of the ink of Comparative Example 2 containing only the coloring material of the general formula (II) or the ink of Comparative Example 3 containing only the xanthene dye, the PPC paper is not obtained. In addition, it was found that an image having sufficient light resistance could not be obtained on glossy paper. In contrast, coloring material ink containing both a coloring material of the coloring material of the general formula (I) (II) (Reference Examples 1 and 2 is applicable), represented by 及 beauty, general formula (I) And xanthene-based dyes (Example 1 is applicable), color development, image density, light resistance than expected from the inks of comparative examples using the color materials used in these inks alone As shown in Table 1, good results were obtained for all evaluation items.

<Example 2, Reference Examples 3 to 5 and Comparative Examples 4 to 6>
First, the following components were mixed, sufficiently stirred and dissolved, and then subjected to pressure filtration with a 0.20 μm filter to prepare magenta inks 1 to 8 and cyan inks 1 and 2, respectively.

(Composition of magenta ink 1)
-3.0 parts of Exemplified Compound 1 as the first colorant-1.0 part of Exemplified Compound 12 as the second colorant-10.0 parts of glycerin-5.0 parts of urea-8.0 parts of diethylene glycol・ Acetylenol EH (manufactured by Kawaken Fine Chemical Co., Ltd.)
1.0 part, 72.0 parts of ion exchange water

(Composition of magenta ink 2)
-2.5 parts of Exemplified Compound 1 as the first color material-CI Reactive Red 180 as the second color material
1.0 part ・ Glycerin 5.0 part ・ Urea 5.0 part ・ Diethylene glycol 10.0 part ・ Acetylenol EH (manufactured by Kawaken Fine Chemical Co., Ltd.)
0.3 parts, ethanol 5.0 parts, ion-exchanged water 71.2 parts

(Composition of magenta ink 3)
-The said exemplary compound 2 which is a 1st coloring material 3.5 parts-The said exemplary compound 8 which is a 2nd coloring material 0.5 part-Glycerol 5.0 parts-Urea 5.0 parts-Diethylene glycol 10.0 parts・ Acetylenol EH (manufactured by Kawaken Fine Chemical Co., Ltd.)
0.3 parts, ethanol 5.0 parts, ion-exchanged water 70.7 parts

(Composition of magenta ink 5)
-4.0 parts of the exemplified compound 3 as the first color material-CI Acid Red 289 as the third color material
0.1 parts ・ Glycerin 5.0 parts ・ Urea 5.0 parts ・ Diethylene glycol 10.0 parts ・ Acetyleneol EH (manufactured by Kawaken Fine Chemical Co., Ltd.)
0.3 parts, ethanol 5.0 parts, ion-exchanged water 70.6 parts

(Composition of magenta ink 6)
・ The above-mentioned Exemplified Compound 8 as a second colorant 8 3.0 parts ・ Glycerin 5.0 parts ・ Urea 5.0 parts ・ Diethylene glycol 10.0 parts ・ Acetylenol EH (manufactured by Kawaken Fine Chemical Co., Ltd.)
0.3 parts, ethanol 5.0 parts, ion-exchanged water 71.7 parts

(Composition of magenta ink 7)
-CIReactive Red 180, the second colorant
3.5 parts, glycerin 5.0 parts, urea 5.0 parts, diethylene glycol 10.0 parts, acetylenol EH (manufactured by Kawaken Fine Chemical Co., Ltd.)
0.3 parts, ethanol 5.0 parts, ion-exchanged water 71.2 parts

(Composition of magenta ink 8)
・ CIAcid Red 289, the third colorant
1.5 parts CIReactive Red 180, the second colorant
2.0 parts, glycerin 5.0 parts, urea 5.0 parts, diethylene glycol 10.0 parts, acetylenol EH (manufactured by Kawaken Fine Chemical Co., Ltd.)
0.3 parts, ethanol 5.0 parts, ion-exchanged water 71.2 parts

(Composition of cyan ink 1)
・ CIDirect Blue 199 (copper phthalocyanine series)
3.0 parts, glycerin 5.0 parts, urea 5.0 parts, diethylene glycol 10.0 parts, acetylenol EH (manufactured by Kawaken Fine Chemical Co., Ltd.)
0.3 parts, ethanol 5.0 parts, ion-exchanged water 71.7 parts

(Composition of cyan ink 2)
・ CIDirect Blue 307 (copper phthalocyanine)
3.5 parts, glycerin 5.0 parts, urea 5.0 parts, diethylene glycol 10.0 parts, acetylenol EH (manufactured by Kawaken Fine Chemical Co., Ltd.)
1.0 part, 75.5 parts of ion-exchanged water

Next, using the magenta inks 1 to 8 and cyan inks 1 and 2 obtained above, the ink sets of Example 2, Reference Examples 3 to 5 and Comparative Examples 4 to 6 were combined in the combinations shown in Table 2 below. Got.

<Evaluation>
Using the ink sets of Examples, Reference Examples, and Comparative Examples obtained above, printing was performed with an on-demand type ink jet printer using a heating element as an energy source for ink ejection as an ink jet recording apparatus to obtain a printed matter. The obtained printed matter was evaluated for light resistance according to the following method and criteria. The obtained results are shown in Table 3.

(Light resistance)
The above-described printer was filled with a predetermined ink set, and solid patches of a magenta single color portion and a magenta and cyan mixed color portion (blue) were printed on PPC paper (Canon) and glossy paper (PR-101; Canon). After that, the printed matter was naturally dried for 24 hours, and exposed to irradiation with a xenon fade meter Ci3000 (manufactured by Atlas Co., Ltd.) equipped with an ultraviolet cut filter at a tank temperature of 35 ° C., a relative humidity of 60%, and an irradiation intensity of 60 klux. . From the L ^* a ^* b ^* calculated by measuring the solid part of the printed matter before and after the test with Spectrodensitometer X-rite 938 (trade name: manufactured by X-rite), the color difference ΔE before and after the test is obtained, the following criteria were evaluated for light resistance.
A: ΔE ≦ 5 (no visual difference before and after the test)
B: 5 <ΔE ≦ 15 (There is a slight difference between before and after the test visually)
C: 15 <ΔE (there is a large difference before and after the test visually)

As described above, examples of utilization of the present invention include inks and ink sets that have clear magenta color tone and image density and can provide images that exhibit excellent light resistance when printed on various recording papers. An inkjet recording method, a recording unit, an ink cartridge, and an inkjet recording apparatus.
Another example of the present invention is to improve the light resistance of an image having a color mixing portion of a magenta ink, which has been a problem in the past, and a cyan ink containing a dye having a copper phthalocyanine structure. Ink sets, inkjet recording methods, recording units, ink cartridges, and inkjet recording apparatuses that can be used.

It is a longitudinal cross-sectional view of the head part of an inkjet recording device. It is a cross-sectional view of the head part of an inkjet recording device. It is an external appearance perspective view of the head part of an inkjet recording device. It is a perspective view which shows an example of an inkjet recording device. It is a longitudinal cross-sectional view of an ink cartridge. It is a perspective view of a recording unit. It is a schematic perspective view showing an essential part of an example of mounting an ink jet printer over the liquid discharge head. It is a schematic perspective view showing an example of an ink jet cartridge provided with a liquid discharge head. It is a schematic perspective view which shows typically the principal part of an example of a liquid discharge head. FIG. 6 is a conceptual diagram in which a part of an example of a liquid discharge head is extracted. It is an enlarged view of the part of the discharge port shown in FIG. It is a schematic diagram which shows the ink adhesion state of the part of the ejection opening shown in FIG. It is a schematic diagram of the principal part in FIG .

Explanation of symbols

13: head 14: ink groove 15: heating head 16: protective film 17-1, 17-2: aluminum electrode 18: heating resistor layer 19: heat storage layer 20: substrate 21: ink 22: ejection orifice (micropore)
23: Meniscus 24: Ink droplet 25: Recording medium 26: Multi-nozzle 27: Glass plate 28: Heat generating head 40: Ink bag 42: Plug 44: Ink absorber 45: Ink cartridge 51: Paper feed unit 52: Paper feed roller 53: Paper discharge roller 61: Blade 62: Cap 63: Ink absorber 64: Discharge recovery unit 65: Recording head 66: Carriage 67: Guide shaft 68: Motor 69: Belt 70: Recording unit 71: Head unit 72: Atmospheric communication Port 100: Inkjet recording head 832: Ejection port 832a: Raising portion 832b: Bending portion 931: Electrothermal conversion element (heater, ink ejection energy generating element)
933: Ink supply port (opening)
934: Substrate 935: Orifice plate (discharge port plate)
935a: discharge port surface 936: ink flow path wall 936a: partition wall 940: discharge port portion 1001: liquid tank 1006: movement drive unit 1008: casing 1010: recording unit 1010a: carriage member 1012: cartridge 1012Y, M, C, B: inkjet cartridges 1014: guide shaft 1016: belt 1018: motor 1020: driver 1022a, 1022b: roller units 1024a, 1024b: roller unit 1026: recovery unit 1026a, 1026b: pulley 1028: paper 1030: transport equipment 1141: groove 1337: Foaming chamber 1338: Liquid flow path G: Center of gravity O: Center of discharge port P: Paper transport direction R: Belt rotation direction S: Direction substantially perpendicular to the paper transport direction T ₁ : Discharge port bottom dimension W: Partition Width dimensions

Claims (22)

C. I. And Acid Red 5 2, containing a colorant represented by the ink which is characterized by containing a coloring material and an aqueous medium, represented by the following general formula (I) (provided that the following general formula (II) Except when)

(In the above general formula (I), R ₁ represents a substituted or unsubstituted alkoxyl group or a substituted or unsubstituted aryl group, and R ₂ and R ₄ each independently represents a hydrogen atom or a substituted or unsubstituted group. R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, or a halogen atom, and X ₁ represents a carboxyl group or A salt thereof, or a sulfonic acid group or a salt thereof, n represents 1 or 2)

(In the above general formula (II), Ar ₁ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, and Ar ₂ represents an acetyl group, a benzoyl group, or a 1,3,5-triazinyl group. Represents an SO ₂ —C ₆ H ₅ group or an SO ₂ —C ₆ H ₄ —CH ₃ group, where M is a counter ion of the sulfonic acid group, and represents any of a hydrogen atom, an alkali metal, ammonium or organic ammonium. Represents). The colorant represented by the general formula (I) contains at least one carboxyl group or a salt thereof in the molecule, and the pH of the ink is in the range of 7.0 to 11.0. The ink according to 1. 2. The colorant represented by the general formula (I) does not contain a carboxyl group or a salt thereof in the molecule, and the pH of the ink is in the range of 4.0 to 11.0. The ink described.   The ink according to any one of claims 1 to 3, wherein the amount of all color materials in the ink is in the range of 0.1 to 15.0 mass% with respect to the total amount of ink.   The ink according to any one of claims 1 to 4, wherein the content of water in the ink is in the range of 30 to 95 mass% with respect to the total amount of the ink. The ink according to any one of claims 1 to 5 , which is an ink used for inkjet recording. An ink set comprising a combination of at least one color ink selected from a yellow ink, a cyan ink, and a black ink and the ink according to any one of claims 1 to 6 having a magenta color. Ink set and the cyan ink, characterized in that the ink according to any one of claims 1 to 6 having a magenta color are combined. The ink set according to claim 7 or 8 , wherein the cyan ink includes a color material having a copper phthalocyanine structure. The ink set according to any one of claims 7 to 9 , which is an ink set used for inkjet recording. An ink jet recording method comprising a step of discharging the ink according to claim 6 from an orifice according to a recording signal. 7. A process of ejecting the ink according to claim 6 having a magenta color from the orifice according to a recording signal, and a process of ejecting a cyan ink containing a dye having a copper phthalocyanine structure from the orifice according to the recording signal. An inkjet recording method characterized by the above. And said cyan ink and said magenta ink on a recording medium, ink jet recording method according to claim 1 2 comprising the step of overlapping. A recording unit, comprising: an ink storage unit storing the ink according to claim 6 ; and a head unit for discharging the ink. An ink storage unit that stores each ink constituting the ink set according to any one of claims 7 to 9 , and a head unit for discharging the ink are provided. To record unit. Ink cartridge, wherein the ink storage portion with ink is accommodated according to any one of claims 1 to 6 is provided. An ink cartridge, comprising: an ink storage unit that stores each ink constituting the ink set according to any one of claims 7 to 10 . An ink jet recording apparatus comprising: a recording unit having an ink containing portion containing the ink according to claim 6 and a head portion for discharging the ink. A recording head for ejecting ink according to claim 6 , an ink cartridge provided with an ink containing portion for containing the ink, and an ink for supplying ink from the ink cartridge to the recording head An ink jet recording apparatus comprising a supply unit. An ink for inkjet recording of at least one color selected from yellow ink, cyan ink, and black ink, the ink according to claim 6 having a magenta color, and a recording head for ejecting each of these inks. An ink jet recording apparatus. An ink jet recording apparatus comprising: the ink according to claim 6 having cyan ink and magenta color; and a recording head for ejecting each of these inks. The cyan ink-jet recording apparatus according to claim 2 0 or 2 1 containing a dye having a copper phthalocyanine structure as the coloring material.

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