JP2002069349A - Ink set, ink jet recording method, recording unit, ink cartridge and ink jet recording apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide high-quality color image, in which breed between inks having different colors is suppressed, especially exhibiting excellent light resistance in image of mixed part of cyan and magenta ink. SOLUTION: This ink set has magenta ink containing a coloring material represented by general formula (I) and a compound represented by general formula (II) [m and n are each an integer of >=0 and 4<=m+n<=20] and cyan ink containing a coloring material having copper phthalocyanine structure and the compound represented by general formula (II). A recording method, a recording apparatus, etc., are also disclosed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink set, and more particularly to an ink set, an ink jet recording method, and a recording unit which can be suitably used for ink jet recording in which ink is ejected from an orifice in accordance with a recording signal to perform recording on a recording material. And an ink cartridge and an ink jet recording apparatus.

[0002]

2. Description of the Related Art In color recording using an ink jet recording method, magenta, a dye in a water-soluble medium,
Cyan, yellow, and black water-based inks are generally used, but in order to improve the durability of the obtained image, images formed by these inks must have excellent durability. Is required. However, when a general dye such as an azo-based or xanthene-based dye having good coloring properties is used as a coloring material of the magenta ink, when a long-term light fastness test is performed that is longer than expected, other dyes may be used. Light resistance tends to be inferior to dyes used as coloring materials in color inks. Further, when a copper phthalocyanine dye having excellent light resistance and color tone is used as a coloring material of the cyan ink, a magenta dye is used in a mixed color portion of the cyan ink and the magenta ink using an azo coloring material. May become more remarkable than in the case of a single color, and the color balance of the entire image may be lost, and the image quality may be significantly reduced.

On the other hand, there has been proposed a magenta ink in which light degradation is not accelerated in an image of a mixed color portion with a cyan ink containing a copper phthalocyanine dye as a coloring material. Japanese Patent Application Laid-Open No. 2000-109466 (WO99
48981), JP-A-2000-169776 (WO
No. 9946341) and JP-A-2000-256587 disclose the use of a magenta ink containing a dye having a skeleton similar to the dye used in the magenta ink according to the present invention, and a cyan ink containing a copper phthalocyanine dye. It is described that the light fastness of the image in the mixing portion is improved.

On the other hand, as another problem in forming a color image using the ink jet recording method, when inks of different colors are applied to a recording material adjacent to each other, these inks are bordered by each other. They may mix with each other, resulting in a phenomenon (bleeding) in which the quality of the color image is reduced.

[0005]

Accordingly, an object of the present invention is to suppress the occurrence of bleeding between inks of different colors,
Moreover, it is an object of the present invention to provide a novel ink set capable of forming a high-quality color image with further improved light fastness of an image in a mixed color portion of cyan ink and magenta ink.
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 having excellent light resistance and obtaining a high quality color image.

[0006]

The above objects are achieved by the present invention described below. That is, an ink set according to one embodiment of the present invention includes a magenta ink containing a coloring material represented by the following general formula (I) and a compound represented by the following general formula (II), and a color having a copper phthalocyanine structure. And a cyan ink containing a compound represented by the following general formula (II). (In the general formula (I), R ₁ represents a substituted or unsubstituted aryl group; R ₂ and R ₄ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group;
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). (In the general formula (II), m and n are integers of 0 or more and 4 ≦ m + n ≦ 20 or less).

The ink jet recording method according to an embodiment of the present invention includes a step of ejecting magenta ink and cyan ink from orifices in accordance with recording signals, and superposing the magenta ink and cyan ink on a recording material. Wherein the magenta ink contains a colorant represented by the general formula (I) and a compound represented by the general formula (II), and the cyan ink has a copper phthalocyanine structure. And a compound represented by the above general formula (II).

An ink jet recording apparatus according to an embodiment of the present invention comprises a magenta ink containing a coloring material represented by the general formula (I) and a compound represented by the general formula (II), and a copper phthalocyanine structure And a recording head for ejecting each of the magenta ink and the cyan ink, each of which contains a coloring material having the formula (1) and a cyan ink containing the compound represented by the general formula (II). It is characterized by being.

Further, the recording unit and the ink cartridge according to one embodiment of the present invention include the above-described ink set, that is, the color material represented by the general formula (I) and the general formula (M) as the magenta ink. An ink set comprising a combination of a magenta ink containing the compound represented by the formula (II), a coloring material having a copper phthalocyanine structure, and a cyan ink containing the compound represented by the formula (II). I do.

[0010]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The magenta ink and cyan ink constituting the ink set of the present invention will be described below with reference to preferred embodiments. The present inventors have conducted intensive studies to solve the above-mentioned problems of the related art, and as a result, to improve the light resistance of an image of a mixed color portion using magenta ink and cyan ink, and to solve the problem of preventing bleeding. Further studies were conducted by combining various coloring materials, solvents and additives. In the course of the study, Japanese Patent Application Laid-Open No. 2000-169776 (WO994634) has been proposed.
The combination of the magenta ink containing the dye described in 1) and the cyan ink containing the copper phthalocyanine dye contained an ethylene oxide adduct of acetylene glycol as a permeability improver for preventing bleeding. As a result, it has been found that by adding an ethylene oxide adduct of acetylene glycol, in addition to the effect of suppressing the occurrence of bleeding, the light fastness of an image of a mixed color portion by the magenta ink and the cyan ink is further improved. That is, the present invention is achieved by finding an unexpected effect that the light resistance of an image in a mixed color portion of a magenta ink and a cyan ink is further improved by including an ethylene oxide adduct of acetylene glycol in the ink. It was done. With such a configuration, it has become possible not only to improve the image quality of the image, but also to obtain an image that can withstand long-term storage.

Although the reason why the light resistance of the mixed color image is improved by including the ethylene oxide adduct of acetylene glycol in the ink is not clear, it is considered that the reason may be as follows. The color mixture part (FIG. 24) of the magenta ink and the cyan ink which does not contain the ethylene oxide adduct of acetylene glycol is
Since both inks have low permeability, there is not much difference in the penetration of the recording material (2303) in the thickness direction, and as a result, the magenta color material and the cyan color material are uniformly present in a certain thickness range. I do. On the other hand, when the ink containing an ethylene oxide adduct of acetylene glycol is used, a color mixture portion (FIG. 2)
In 3), since the permeability is improved, the penetration of the magenta ink and the cyan ink in the thickness direction (deep portion) in the recording material is increased. However, the color material of magenta ink (2302) and the color material of cyan ink (23
Compared with (01), it is considered that the cyan color material is harder to penetrate deep into the recording material than the magenta color material because of its higher planarity (easy association) in structure. Therefore, the cyan color material (2301) exists relatively near the surface of the recording material, and the magenta color material (2302) penetrates to a relatively deep place in the recording material. 23
It is considered that the light irradiation to the light emitting device 02) is hindered by the cyan coloring material (2301), and the fading of the magenta coloring material (2302) by light is suppressed.

In the magenta ink used in the present invention, a coloring material represented by the following general formula (I) is used as a coloring material, and ethylene oxide is added to the acetylene glycol of the above general formula (II) as a penetrating agent. It is characterized by using a nonionic surfactant added. First, the coloring material represented by the following general formula (I) will be described.

[0013]

In the general formula (I), R ₁ represents a substituted or unsubstituted aryl group; R ₂ and R ₄ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group; 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 above general formula (I),
More specifically, examples of R ₁ include a substituted or unsubstituted phenyl group. Here, 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, and a halogen atom (such as fluorine, chlorine, and bromine). As R ₂ , for example,
Examples of the hydrogen atom include a linear or branched lower alkyl group having 1 to 4 carbon atoms, and R ₃ includes, for example, a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms. Group, a linear or branched alkoxyl group having 1 to 4 carbon atoms, and further as an aryloxy group, for example,
Phenoxy groups and the like. 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 sulfonic acid group or a salt thereof, a carboxyl group or a salt thereof, or the like. Furthermore, examples of R ₄ include a hydrogen atom and a linear or branched lower alkyl group having 1 to 4 carbon atoms. When X ₁ is described in detail, as X ₁ , for example, -COOM or -SO ₃ M [where M is
Hydrogen atom, alkali metal (eg, Li, Na, etc.), ammonium (NH ₄ ), organic ammonium (N
(R ₅ ) ₄ )]. Here, examples of R ₅ include a methyl group and an ethyl group.

In order to further improve the fixability on the recording material after printing, R ₁ is a substituted or unsubstituted aryl group, and R ₃ is a substituted aryloxy group. Is preferred. Examples of the substituent of the aryl group for R ₁ include a linear or branched alkyl group or alkoxyl group having 1 to 4 carbon atoms, and a halogen atom. The substituted aryloxy group for R ₃ has 1 to 10 carbon atoms.
And a linear or branched alkyl group, a carboxyl group or a salt thereof, or a sulfonic acid group or a salt thereof in which one or two or more are substituted with an aryl group.

[0017] Illustrative compounds 1 to 7 are shown below as specific examples of the coloring material represented by the general formula (I), but the present invention is not limited to these coloring materials. Further, two or more of these color materials may be used at the same time. Hereinafter, Exemplified Compound 1
M in to 7 represents H, Li, Na, one of NH ₄ and N (R _{5) 4.}

[0018]

[0019]

[0020]

The content of the coloring material in the magenta ink as described above is generally 0.1 to 1 with respect to the total amount of the ink.
It is preferably in the range of 5.0% by mass, more preferably in the range of 0.5 to 5.0% by mass.

Next, the following general formula (I) contained as a penetrant in the magenta ink and the cyan ink according to the present invention.
The nonionic surfactant obtained by adding ethylene oxide to acetylene glycol represented by I) will be described.

[0023]

In the general formula (II), m and n are integers of 0 or more, and the value of m + n is 4 or more and 20 or less in consideration of sufficient solubility and effectiveness in ink. Use things. The content of the penetrant in the ink is preferably in the range of 0.1 to 20% by mass, more preferably 0.5 to 5% by mass, based on the total amount of the ink.

The cyan ink constituting the ink set of the present invention together with the above-mentioned magenta ink includes a coloring material having a copper phthalocyanine structure as a coloring material and a penetrating agent of the above general formula (II) as a penetrating agent. Is used. A cyan coloring material having a copper phthalocyanine structure is excellent in weather resistance and color tone. Specific examples of the coloring material having a copper phthalocyanine structure that can be used in the present invention include, for example, C.I. I. AcidBlue 249, C.I. I. Di
Rect Blue 86, C.I. I. Direct B
lue 199, C.I. I. Direct Blue 3
07 and the like.

The ink set of the present invention is characterized in that the above-described magenta ink and cyan ink are combined, and in addition, if necessary, the ink set is formed by combining yellow ink, black ink, and the like. May be. Here, dyes and pigments can be used as the coloring material contained in the yellow ink and the black ink. Examples of the dye include water-soluble xanthene-based and triphenylmethane-based dyes described in the Color Index. And anthraquinone, monoazo, disazo, trisazo and tetraazo dyes.

In the case of a black pigment ink, carbon black is preferable as the pigment.
2300, no. 900, MCF88, No. 40, N
o. 52, MA7, MA8, No. 2200B (or more,
Mitsubishi Kasei), RAVEN 1255 (Colombia),
REGAL400R, REGAL660R, MOGUL
L (above, made by Cabot), Color Black
FW1, ColorBlack FW18, Colo
r Black S170, Color Black
S150, Printex 35, Printex U
Commercially available products such as the above (made by Degussa) can be used.

Examples of the pigment used for the yellow ink include C.I. I. Pigment Yellow
1, C.I. I. Pigment Yellow 2,
C. I. Pigment Yellow 3, C.I. I.
Pigment Yellow 13, C.I. I. Pigm
ent Yellow 16, C.I. I. Pigment
Yellow 83 and the like.

(Aqueous Medium) The magenta ink and the cyan ink constituting the ink set of the present invention are usually obtained by dissolving and dispersing the above-mentioned coloring material in an aqueous medium. The aqueous medium used at this time is composed of water and / or a water-soluble organic solvent. The water-soluble organic solvent is not particularly limited as long as it shows water solubility. Glycol,
Glycol ether, a nitrogen-containing polar solvent, a sulfur-containing polar solvent and the like can be used. These water-soluble organic solvents are
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, the content thereof is preferably in the range of 1 to 40% by mass of the entire ink. More preferably, it is in the range of 3 to 30% by mass.
Further, the solubility of the colorant dye in the ink is good, and has a viscosity for stable ink ejection, and
To prevent clogging at the nozzle tip, the water content in the ink is preferably in the range of 30 to 95% by mass.

(PH) In the magenta ink used in the present invention, when any of the coloring materials contains at least one carboxyl group or a salt thereof in the molecule,
The pH of the ink is in a neutral to alkaline range, specifically pH 7.0, from the viewpoints of preventing a decrease in solubility of the coloring material in water, preventing clogging at the tip of the nozzle, and maintaining the ink for a long period of time. It is preferable to keep within the range of 0 to 11.0. In addition, in the case of using a coloring material that does not contain a carboxyl group or a salt thereof in the molecule, the pH of the ink is pH 4.0 to 11. The value may be within a range of 0.

(Additives) In order to maintain the moisturizing property of the ink, in the present invention, a moisturizing solid such as urea, a urea derivative, trimethylolpropane or the like may be used as an ink component, if necessary. Good. In general, the content of the moisturizing solid in the ink, such as urea, a urea derivative, and trimethylolpropane, is preferably in the range of 0.1 to 20.0% by mass relative to the total amount of the ink, and more preferably. 3.
It is used in the range of 0 to 10.0% by mass. Further, the ink used in the present invention, in addition to the above components, if necessary, for example, a pH adjuster, a rust inhibitor, a preservative, a fungicide,
Antioxidants, reduction inhibitors, evaporation promoters, chelating agents,
And various additives such as a water-soluble polymer.

(Recording Material) The recording material used in the present invention is not particularly limited, but it is preferable to use a recording material having a coat layer such as glossy paper, coated paper, and glossy film. In order to improve absorption, color development, and resolution, for example, a porous particle layer on a substrate,
A recording material having a porous polymer layer or the like is preferable. An example of the recording material used in the present invention will be described in more detail. A coloring material such as a dye or a pigment is adsorbed to fine particles forming a porous structure in an ink receiving layer, and an image is formed from at least the adsorbed fine particles. This is a recording material to be used, and is particularly suitable when an inkjet recording method is used.

It is preferable that the recording material is of a so-called absorption type in which ink is absorbed by voids formed in the ink receiving layer on the support. The absorption type ink receiving layer is constituted as a porous layer mainly composed of fine particles and optionally containing a binder and other additives.

Examples of the fine particles include inorganic pigments such as aluminum oxide such as silica, clay, talc, calcium carbonate, kaolin, alumina and alumina hydrate, diatomaceous earth, titanium oxide, hydrotalcite and zinc oxide, and urea formalin resin. And organic pigments such as ethylene resin and styrene resin, and one or more of these are used.

Examples of the binder suitably used include a water-soluble polymer 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, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, hydroxyprooilmethylcellulose, SBR latex, NBR latex, methyl methacrylate-butadiene Polymer latex, functional group-modified polymer latex, vinyl-based copolymer latex such as ethylene-vinyl acetate copolymer, polyvinylpyrrolidone, maleic anhydride or its copolymer, acrylate ester copolymer, etc. are used. Can be used in combination of two or more.

In addition, additives can be used. For example, a dispersant, a thickener, a pH adjuster, a lubricant, a fluidity modifier, a surfactant, an antifoaming agent, a release agent may be used, if necessary. Fluorescent whitening agents, ultraviolet absorbers, antioxidants and the like are used.

In particular, as the above-mentioned fine particles, those having an ink receiving layer mainly formed of fine particles having an average particle diameter of 1 μm or less are preferable, and particularly preferable examples of the fine particles are silica or aluminum oxide fine particles. No. Preferred as silica fine particles are silica fine particles represented by colloidal silica. Colloidal silica itself is also available from the market,
Particularly preferred are, for example, Japanese Patent No. 280313.
No. 4 and Japanese Patent No. 2881847. Preferred examples of the aluminum oxide fine particles include alumina hydrate fine particles. As one of such alumina-based pigments, an alumina hydrate represented by the following general formula (III) can be preferably mentioned.

[0038]

In the above formula (III), n is 1, 2 or 3
M represents 0 to 10, preferably 0 to 5
Represents the value of However, m and n do not become 0 at the same time.
mH _TwoO is often mH_TwoInvolved in the formation of the O crystal lattice
M also represents a non-desorbable aqueous phase.
It can take on non-numeric or non-integer values. Also of this kind
When the material is heated, m can reach a value of zero.
Alumina hydrate is generally described in U.S. Pat.
No. 271 and U.S. Pat. No. 4,202,870.
Aluminum alkoxy as described in the specification
Hydrolysis of sides and hydrolysis of sodium aluminate
Una and described in Japanese Patent Publication No. 57-44605.
Sodium sulfate in an aqueous solution of sodium aluminate
For neutralization by adding an aqueous solution of aluminum chloride, aluminum chloride, etc.
Uses those manufactured by known methods, such as
can do.

FIG. 22 schematically shows a cross-sectional structure of one example of a so-called coated paper provided with an ink receiving layer on a support made of paper or the like. In FIG. 22, reference numeral 1000 denotes a support, and 1003 denotes a coat layer serving as an ink receiving layer held by the support 1000. Coat layer 1003
Are formed as a porous layer containing fine particles 1005, and the fine particles are fixed by a binder 1007. Then, in a process in which the ink droplets applied to such coated paper permeate into the coat layer 1003,
The color material 1009 contained in the ink is adsorbed on the surface of the fine particles 1005, and the color material adsorbed by the fine particles is fixed at the position, whereby an image is formed.

The ink set of the present invention is particularly preferably used in an ink jet recording system in which droplets are ejected by the action of thermal energy to perform recording. However, the ink set can be used as another ink jet recording method or a general writing instrument. Needless to say.

(Recording Apparatus, Ink Cartridge, and Recording Unit) As a recording apparatus suitable for performing recording using the magenta ink and the cyan ink according to the present invention, an ink in a room of a recording head corresponding to a recording signal is used. A device that gives thermal energy and generates droplets by the energy is used.

FIGS. 1, 2 and 3 show examples of the configuration of the recording head which is the main part. The head 13 includes a glass, ceramics, or plastic plate having a groove 14 through which ink passes, and a heating head 15 having a heating resistor used for thermal recording (a head is shown in the figure, but is not limited thereto. Is not obtained). The heating head 15 is formed of a protective film 1 made of silicon oxide or the like.
6, aluminum electrodes 17-1 and 17-2, a heating resistor layer 18 formed of nichrome or the like, a heat storage layer 19, and a substrate 20 having good heat dissipation such as alumina.

The ink 21 has a discharge orifice (micro hole).
22 and the meniscus 23
Is formed. FIG. 4 shows an example of an ink jet recording apparatus incorporating the above-described head. In FIG. 4, reference numeral 61 denotes a blade as a wiping member,
One end is held by a blade holding member to become a fixed end, and forms a cantilever. Blade 61
Is arranged at a position adjacent to the recording area of the recording head, and in the case of the example shown in FIG. 4, it is held in a form protruding into the movement path of the recording head. Reference numeral 62 denotes a cap, which is disposed at a home position adjacent to the blade 61 and has a configuration in which the cap moves in a direction perpendicular to the moving direction of the recording head to abut on the ejection surface to perform capping. Furthermore,
Reference numeral 63 denotes an ink absorber provided adjacent to the blade 61, and is held in a form protruding into the movement path of the recording head, similarly to the blade 61.

The blade 61, the cap 62, and the absorber 63 constitute an ejection recovery section 64. With the ejection recovery section 64, the blade 61 and the absorber 63 remove moisture, dust, dust, and the like on the ink ejection port surface. Done. Reference numeral 65 denotes a recording head which has ejection energy generating means and performs recording by discharging ink on a recording material facing the ejection port surface where ejection ports are arranged, and 66 designates a recording head 65 on which the recording head 65 is mounted. Is a carriage for performing the movement. The carriage 66 is slidably engaged with a 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 head 65 can move the recording area and the area adjacent thereto.

Reference numeral 51 denotes a paper feed unit for inserting a recording material, and reference numeral 52 denotes a paper feed roller driven by a motor (not shown). With these configurations, the recording material is fed to a position facing the discharge port surface of the recording head, and is discharged to a discharge section provided with a discharge roller 53 as recording proceeds. In the above configuration, when the recording head 65 returns to the home position at the end of recording or the like, the cap 62 of the head recovery unit 64 is retracted from the 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 capping is performed with the cap 62 in contact with the ejection surface of the recording head 65, the cap 62 moves so as to protrude into the movement 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 positions as the positions at the time of the wiping described above. As a result, even in this movement, the ejection port surface of the recording head 65 is wiped. The above-described movement of the print head to the home position is performed not only at the time of printing end and at the time of ejection recovery, but also at a predetermined interval to the home position adjacent to the print area while the print head moves through the print area for printing. Then, along with this movement, the wiping is performed.

FIG. 5 is a cross-sectional view showing an example of an ink cartridge 45 provided with an ink supply member, for example, an ink container containing ink supplied through a tube, in the head. Here, reference numeral 40 denotes an ink storage portion storing the supply ink, for example, an ink bag, and a rubber stopper 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 the 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 are separated as described above, and the one in which they are integrated as shown in FIG. 6 is also suitable. Used. In FIG. 6, reference numeral 70 denotes a recording unit, in which an ink storage unit storing ink, for example, an ink absorber is stored, and a head unit having a plurality of orifices in which the ink in the ink absorber is stored. It is configured to be ejected from 71 as ink droplets. 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.

Further, as the ink jet recording apparatus used in the present invention, a recording unit or an ink cartridge in which the magenta ink and the cyan ink constituting the ink set of the present invention as described above are stored in an ink storing section. Those having the same are also used.

Next, another specific example of a recording apparatus and a recording head which can be suitably used in the present invention will be described. FIG.
A liquid discharge head as a liquid discharge head of a discharge method that communicates bubbles with the atmosphere during discharge suitable for the present invention, and
FIG. 2 is a schematic perspective view illustrating a main part of an example of an ink jet printer as a liquid discharge device using the liquid discharge head. The ink jet printer shown in FIG. 7 is a transport device 1030 for intermittently transporting a sheet 1028 as a recording material provided along a longitudinal direction in a casing 1008 in a direction indicated by an arrow P shown in FIG. A recording unit 1010 reciprocated along a guide shaft 1014 substantially in parallel with a direction S substantially perpendicular to the conveyance direction P of the sheet 1028 by the conveyance device 1030, and a driving unit for reciprocating the recording unit 1010 Movement drive unit 10 as
06 is included.

The transport device 1030 includes a pair of roller units 1022a and 1022b, which are disposed substantially parallel to each other, a pair of roller units 1024a and 1024b, and a driving unit 1020 for driving each of these roller units. It has. With this configuration, when the drive unit 1020 of the transport device 1030 is activated, the paper 1028 is
2a and 1022b and the roller units 1024a and 1024b, and are conveyed intermittently in the direction of arrow P shown in FIG.

The movement driving unit 1006 is provided with a pulley 1026 disposed on a rotating shaft opposed to the predetermined distance.
a and a belt 1016 wound around 1026b;
The carriage member 101 of the recording unit 1010 is disposed substantially parallel to the roller units 1022a and 1022b.
And a motor 1018 for driving a belt 1016 connected to Oa in forward and reverse directions.

When the motor 1018 is activated and the belt 1016 rotates in the direction of arrow R in FIG.
The carriage member 1010a of the recording unit 1010 is moved by a predetermined amount 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 direction of the arrow R in FIG. 7, the carriage member 1010a of the recording unit 1010 moves in the predetermined direction in the direction opposite to the direction of the arrow S in FIG. Will be moved by the amount of movement. Further, a recovery unit 1 for performing a discharge recovery process of the recording unit 1010 is provided at one end of the movement driving unit 1006 at a position which is a home position of the carriage member 1010a.
Reference numeral 026 is provided to face the ink ejection port arrangement of the recording unit 1010.

The recording unit 1010 includes an ink jet cartridge (hereinafter, sometimes simply referred to as a cartridge) 1012Y, 1012M, 1012C, and 1012.
B is detachably provided to the carriage member 1010a for each color, for example, for each of yellow, magenta, cyan, and black.

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
And a liquid tank 100 for storing a liquid such as ink.
1 constitutes the main part. The ink jet recording head 100 has a large number of ejection ports 83 for ejecting liquid.
2 is formed, and a liquid such as ink is stored in a liquid tank 1
001 to a common liquid chamber (see FIG. 9) of the liquid ejection head 100 via a liquid supply passage (not shown). In the cartridge 1012 shown in FIG. 8, the ink jet recording head 100 and the liquid tank 1001 are integrally formed so that liquid can be supplied to the liquid tank 1001 as necessary. A structure in which a liquid tank 1001 is exchangeably connected to 100 may be adopted.

Hereinafter, a specific example of the liquid discharge head that can be mounted on the ink jet printer having the above-described configuration will be described in more detail. FIG. 9 is a schematic perspective view schematically showing a main part of a liquid discharge head showing a basic mode of the present invention. FIGS. 10 to 13 show the discharge port shapes 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 ejection head of this embodiment, 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,
There is no particular limitation as long as it can function as a part of the flow path constituent member and can function as a support for a material layer forming an ink discharge energy generating element and a liquid flow path and a discharge port described later. . In this example, a case where a Si substrate (wafer) is used will be described. In addition to the forming method using a laser beam, for example, an orifice plate (discharge port plate) 935 described later is made of a photosensitive resin, and the
It can also be formed by an exposure apparatus such as an error projection aligner.

In FIG. 9, reference numeral 934 denotes an ink supply port 9 comprising an electrothermal conversion element (hereinafter, sometimes referred to as a heater) 931 and a long groove-shaped through-hole serving as a common liquid chamber.
33, and a heater 931 serving as thermal energy generating means is provided on both sides of the ink supply port 933 in the longitudinal direction.
Are arranged in a zigzag pattern, for example, at an interval of 300 dpi between the electrothermal conversion elements (heaters). On this substrate 934, an ink flow path wall 936 for forming an ink flow path is provided. This ink flow path wall 936
Further includes a discharge port plate 93 having a discharge port 832.
5 are provided.

Here, in FIG.
36 and the discharge port plate 935 are shown as separate members, but the ink flow path wall 936 is formed on the substrate 934 by, for example, a method such as spin coating, so that the ink flow path wall 936 and the discharge port plate 935 are ejected. It is also possible to form the outlet plate 935 and the same member at the same time. In this example, the ejection port surface (upper surface) 935a is further subjected to a water-repellent treatment.

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

In the cross section of the discharge port portion 940 provided on the discharge port plate 935 including the discharge port 832 shown in FIG. 9, the section is cut in a direction intersecting the ink discharge direction (the thickness direction of the orifice plate 935). The shape of the cross section I saw is
As shown in FIG. 11, six raised portions 832 a having a general star shape and having obtuse angles, and these raised portions 832 a
And six ridges 832b having an acute angle alternately arranged between them. That is, the bottom 832b as a region locally distant from the center O of the discharge port is its top, and the rising portion 832a as a region locally close to the center O of the discharge port adjacent to this region is its base.
Six grooves 1141 are formed in the thickness direction (liquid ejection direction) of the orifice plate shown in FIG. 9 (FIG. 11).
reference).

In this example, the discharge port 940 has, for example, a cross section cut in a direction intersecting its thickness direction, and has a shape in which two equilateral triangles each having a side of 27 μm are combined in a state rotated by 60 degrees. cage, T ₁ shown in FIG. 11 8
μm. The angles of the raised portions 832a are all 120 degrees, and the angles of the bent portions 832b are all 60 degrees. Accordingly, 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 a figure formed by connecting the top of the groove and two bases adjacent to the top). With the center of gravity G. Discharge port 8 of this example
32 has an opening area of 400 μm ² , and the opening area of the groove (the area of a figure formed by connecting the top of the groove and two bases adjacent to the top) is about 33 μm ² per one. FIG. 12 is a schematic diagram showing the state of ink adhesion at the ejection port shown in FIG.

Next, the operation of discharging liquid by the ink jet recording head having the above-described structure will be described with reference to FIGS.
This will be described with reference to FIG. 14 to 21 are cross-sectional views for explaining the liquid discharging operation of the liquid discharging head shown in FIGS. 9 to 13, and are XX cross-sectional views of the foaming chamber 1337 shown in FIG. In this cross section, the end of the discharge port 940 in the thickness direction of the orifice plate shown in FIG.
41 is the top 1141a. FIG. 14 shows a state in which a film-like bubble is generated on the heater, and FIGS.
Represents the state of the subsequent bubbles over time.
That is, FIG. 15 shows about 1 μs after FIG.
4 about 2 μs later, FIG. 17 shows about 3 μs later in FIG.
8 is about 4 μs after FIG. 14, and FIG.
20. FIG. 20 is about 6 μs after FIG.
Respectively about 7 μs later. In the following description, "fall" or "drop", "drop"
Does not mean a so-called drop in the direction of gravity, but means a movement in the direction of the electrothermal transducer regardless of the mounting direction of the head.

First, as shown in FIG. 14, when the air bubbles 101 are generated in the liquid flow path 1338 on the heater 931 due to the energization of the heater 931 based on the recording signal or the like, about 2
During μs, as shown in FIG. 15 and FIG.
Grows rapidly with volume expansion. The height of the bubble 101 at the maximum volume is higher than the discharge port surface 935a, but at this time, the pressure of the bubble has been reduced from a fraction of the atmospheric pressure to a fraction of the atmospheric pressure.

Next, about 2 μs after the generation of the bubble 101,
At this point, as described above, the bubble 101 is
At about the same time, the meniscus 102
Also begins to form. As shown in FIG.
102 also retracts in the direction toward the heater 931 side, that is,
Go on. Here, in this example, as described above,
The discharge port has a plurality of grooves 1141 dispersed therein.
When the meniscus 102 retreats, the groove 114
In part 1, the meniscus 102 is in the retreating direction F _MAnd anti
Opposite direction F_CCapillary force acts on. As a result, if something
There is some variation in the state of the bubble 101 due to the cause
Meniscus 102 retreats even if
Liquid and ink (hereinafter sometimes referred to as liquid or ink)
A) I_aIs approximately symmetrical with respect to the center of the discharge port.
It is corrected so that

In this embodiment, the meniscus 102
Is faster than the contraction speed of the bubble 101,
As shown in FIG. 18, at about 4 μs after the bubble is generated, the bubble 101 communicates with the atmosphere near the lower surface of the discharge port 832. At this time, the liquid (ink) near the central axis of the ejection port 832 falls toward the heater 931. This negative pressure fluid that is drawn back to the heater 931 side by the (ink) I _a of the bubble 101 before communicating with the atmosphere, also holds the speed of the heater 931 side direction by inertia after the bubble 101 has communicated with the atmosphere Because it is. The liquid (ink) which has dropped toward the heater 931 reaches the surface of the heater 931 at about 5 μs after the generation of the bubble 101 as shown in FIG. 19, and as shown in FIG. It spreads to cover the surface of.

The liquid spread so as to cover the surface of the heater 931 has a horizontal vector along the surface of the heater 931. However, the liquid crossing the surface of the heater 931, for example, the vector in the vertical direction disappears. And the heater 93
1 and will pull the liquid above it, that is, the liquid that maintains the velocity vector in the ejection direction, downward. Thereafter, the liquid I _b between the liquid and the upper liquid spread on the surface of the heater 931 (main droplet) is Yuki tapered, as shown in FIG. 21, at a later time about 7μs from the generation of the bubble 101 liquid I _b is cut in the middle of the surface of the heater 931, a main liquid droplet I _a keeping a velocity vector in the ejecting direction, is separated into a liquid I _c that has spread on the surface of the heater 931. As described above, the position of the separation is determined by the liquid flow path 1338.
The inside, more preferably, the electrothermal conversion element (heater) 931 side than the discharge port 832 is desirable.

The main droplet _Ia is discharged from the central portion of the discharge port 832 without deviation in the discharge direction and without being distorted, and lands at a predetermined position on the recording surface of the recording material.
Further, the liquid I _c spread on the surface of the heater 931 flies as a satellite droplet following the main droplet in the related art, but stays on the surface of the heater 931.
No ejection. As described above, since the ejection of the satellite droplets can be suppressed, it is possible to prevent the splash which is likely to be generated by the ejection of the satellite droplets, and to prevent the recording surface of the recording material from being stained by the mist floating in a mist state. It can be reliably prevented. In addition, in FIGS.
_Id is the amount of ink (ink in the groove) attached to the groove,
_Ie represents the ink remaining in the liquid flow path.

As described above, in the liquid ejection head of the present embodiment, when the liquid is ejected in the volume reduction stage after the bubble has grown to the maximum volume, a plurality of grooves dispersed with respect to the center of the ejection port. Thereby, the direction of the main droplet at the time of ejection can be stabilized. As a result, it is possible to provide a liquid ejection head with high landing accuracy, which has no deviation in the ejection direction.
In addition, high-speed and high-definition printing can be realized because the ejection can be stably performed even with respect to foaming variation at a high driving frequency.

In particular, at the stage of reducing the volume of bubbles, by discharging the liquid by first communicating the bubbles with the atmosphere, it is possible to prevent mist generated when the bubbles are communicated with the atmosphere and the droplets are discharged. In other words, it is possible to suppress a state in which droplets adhere to the discharge port surface, which is a cause of sudden discharge failure. Further, as another embodiment of a recording head of a discharge method that allows bubbles to communicate with the atmosphere at the time of discharge, which can be suitably used in the present invention, for example, a so-called edge shooter type is described in Japanese Patent No. 2783647. No.

In the above description, an ink jet recording apparatus which ejects ink droplets by applying thermal energy to ink has been described as an example of the recording apparatus used in the present invention.
In addition, a piezo-type inkjet recording apparatus using a piezoelectric element can be similarly used.

[0073]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. Unless otherwise specified, ink components in Examples and Comparative Examples mean “parts by mass”. The ink compositions of Examples and Comparative Examples are shown below. The ink used was one obtained by mixing the components, thoroughly stirring and dissolving, and then performing pressure filtration with a 0.20 μm filter. Acetyleneol EH (manufactured by Kawaken Fine Chemical Co., Ltd.) is a compound represented by m + n = 10 in the general formula (II).

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

<Examples 1 to 4 and Comparative Examples 1 to 3> Examples 1 to 4 and Comparative Examples 1 to 4 were obtained by combining a magenta ink and a cyan ink having the main compositions shown in Table 1 below.
Ink set No. 3.

[0085]

<Evaluation> Using the ink sets of Examples 1 to 4 and Comparative Examples 1 to 3 composed of the above combinations, an on-demand type ink jet printer using a heating element as an energy source of ink discharge was used as an ink jet recording apparatus. The printed matter obtained was evaluated according to the following criteria.

(Lightfastness) A predetermined ink was filled in a printer, and a solid patch of a mixed color portion (blue) of magenta and cyan was printed on glossy paper (PR-101; manufactured by Canon). Then, the obtained printed matter is naturally dried for 24 hours,
Using a Xenon fade meter Ci3000 (manufactured by Atlas) equipped with an ultraviolet cut filter, the temperature in the bath was 3
100 at 5 ° C, 55% relative humidity and 60klux irradiation intensity
Exposure was irradiated for hours. The solid part of the printed matter before and after the test is Sp
Electrodensitometer X-write
The color difference ΔE before and after the test was determined from L ^* a ^* b ^* calculated by measuring with 938 (trade name: manufactured by X-rite), and the light resistance was evaluated according to the following criteria. Table 2 shows the evaluation results.

A: E ≦ 5 (no difference visually before and after the test) B:
5 <E ≦ 15 (There is a slight difference visually before and after the test) C: 15 <E (There is a great difference visually before and after the test)

[0089]

As a result, as shown in Table 2, Example 1
In the color-mixed areas using the ink sets of Nos. 1 to 4, the difference between the color fading after light irradiation was not visually observed, but the ink set using the magenta color material and the cyan color material according to the present invention. Are also compounds of the general formula (I
In the case of the ink set of Comparative Example 3 which did not contain the compound represented by I), the permeability of the magenta and cyan inks was low, and slight fading was observed in the mixed color portion. Even in the case of a highly permeable ink set containing the compound represented by the general formula (II), when the magenta coloring material according to the present invention is not used, as in Comparative Examples 1 and 2, Greater fading was observed in the parts.

[0091]

As described above, according to the present invention,
In particular, an ink set, an ink jet recording method, a recording unit, an ink cartridge, and an ink jet recording apparatus that can obtain a color image showing excellent light fastness in a mixed color image of magenta ink and cyan ink when printed on various recording papers. Provided.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of a head section of an ink jet recording apparatus.

FIG. 2 is a cross-sectional view of a head section of the inkjet recording apparatus.

FIG. 3 is an external perspective view of a head unit of the inkjet recording apparatus.

FIG. 4 is a perspective view illustrating an example of an ink jet recording apparatus.

FIG. 5 is a vertical sectional view of the ink cartridge.

FIG. 6 is a perspective view of a recording unit.

FIG. 7 is a schematic perspective view illustrating a main part of an example of an ink jet printer on which a liquid discharge head can be mounted.

FIG. 8 is a schematic perspective view showing an example of an ink jet cartridge provided with a liquid ejection head.

FIG. 9 is a schematic perspective view schematically showing a main part of an example of a liquid ejection head.

FIG. 10 is a conceptual diagram in which a part of an example of a liquid ejection head is extracted.

FIG. 11 is an enlarged view of a portion of a discharge port shown in FIG.

FIG. 12 is a schematic diagram showing the state of ink attachment at the ejection port shown in FIG. 11;

FIG. 13 is a schematic diagram of a main part in FIG. 10;

14 is a schematic cross-sectional view corresponding to the cross-sectional view taken along the line XX in FIG. 13 and illustrating the liquid discharge operation of the liquid discharge head with time along with FIGS. 15 to 21;

FIG. 15 is a schematic cross-sectional view corresponding to the cross-sectional shape taken along the line XX in FIG. 13 and illustrating the liquid discharge operation of the liquid discharge head with time along with FIGS. 14 and 16 to 21;

FIG. 16 is a schematic cross-sectional view corresponding to the cross-sectional shape taken along the line XX in FIG. 13 and illustrating the liquid discharging operation of the liquid discharging head with time along with FIGS. 14, 15, and 17 to 21; is there.

FIG. 17 is a schematic cross-sectional view corresponding to the cross-sectional shape taken along the line XX in FIG. 13 and illustrating the liquid discharge operation of the liquid discharge head with time along with FIGS. 14 to 16 and FIGS. is there.

FIG. 18 is a schematic cross-sectional view corresponding to the cross-sectional shape taken along the line XX in FIG. 13 and illustrating the liquid discharge operation of the liquid discharge head along with FIGS. 14 to 17 and FIGS. is there.

FIG. 19 is a schematic cross-sectional view corresponding to the cross-sectional shape taken along the line XX in FIG. 13 and illustrating the liquid discharging operation of the liquid discharging head with time along with FIGS. 14 to 18, FIGS. is there.

20 is a schematic cross-sectional view corresponding to the cross-sectional view taken along the line XX in FIG. 13 and illustrating the liquid discharge operation of the liquid discharge head with time along with FIGS. 14 to 19 and 21. FIG.

21 is a schematic cross-sectional view corresponding to the cross-sectional shape taken along the line XX in FIG. 13 and illustrating the liquid discharge operation of the liquid discharge head with time along with FIGS. 14 to 20;

FIG. 22 is a schematic diagram schematically showing a cross-sectional structure of one example of a recording material used in the present invention.

FIG. 23 is a sectional view of a mixed color portion of magenta ink and cyan ink using the ink set according to the present invention.

FIG. 24 is a cross-sectional view of a mixed color portion of magenta ink and cyan ink having low permeability.

[Explanation of symbols]

13: Head 14: 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: Discharge orifice (fine hole) 23: Meniscus 25: Recording material 28: Heating head 40: Ink bag 42: Plug 44: Ink absorber 45: Ink cartridge 51: Paper supply unit 52: Paper feed roller 53: Paper discharge roller 61: Wiping member 62: Cap 63: Ink absorber 64: Head recovery unit 65: Recording head 66: Carriage 67: Guide shaft 68: Motor 69: Drive belt 70: Recording unit 71: Head unit 72: Atmospheric communication port 100: Ink jet recording head 101: Bubbles 102: Meniscus 832: discharge port 832a: raised portion 832b: recessed portion 931: electrothermal conversion 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 1000 : Support 1001: Liquid tank 1003: Coating layer 1005: Fine particle 1006: Movement drive unit 1007: Binder 1008: Casing 1010: Recording unit 1010 a: Carriage member 1012: Cartridge 1012 Y, M, C, B: Ink jet cartridge 1014: Guide shaft 1016: Belt 1018: Motor 1020: Drive unit 1022a, 1022b: Roller unit 1024a, 1024b: Roller unit 1026: Recovery unit 1026a, 1026b: Pulley 1028: Paper 1030 Conveying apparatus 1141: Groove 1141a: top 1337: bubbling chamber 1338: the liquid flow path 2001: cyan color material 2002: Magenta coloring material 2003: a recording agent C: Wet Ink F _M: meniscus backward F _C: opposite meniscus retraction direction Direction G: Center of gravity I: Ink Ia: Main droplet (liquid, ink) Ib, Ic: Liquid (ink) Id: Ink attached to groove (ink in groove) Ie: Ink remaining in liquid flow path N ₁ : Width dimension of foaming chamber N ₂ : Length dimension of foaming chamber O: Center of discharge port P: Paper transport direction R: Belt rotation direction S: Direction substantially perpendicular to paper transport direction w: Partition wall Width dimension

Continued on front page F term (reference) 2C056 EA13 FA03 FA10 FC02 HA05 2H086 BA01 BA02 BA53 BA56 BA62 4J039 BC07 BC16 BC33 BC50 BC61 BC72 BC73 BC75 BC79 BE02 EA15 EA16 EA35 EA42 GA24

Claims (14)

[Claims] 1. A magenta ink containing a coloring material represented by the following general formula (I) and a compound represented by the following general formula (II), and a coloring material having a copper phthalocyanine structure and a coloring material represented by the following general formula (II) An ink set, which is combined with a cyan ink containing the compound represented by the formula: (In the general formula (I), R ₁ represents a substituted or unsubstituted aryl group; R ₂ and R ₄ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group;
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) (In the general formula (II), m and n are integers of 0 or more and 4 ≦ m + n ≦ 20 or less). 2. The ink set according to claim 1, wherein the amount of the coloring material contained in the magenta ink is in a range of 0.1 to 15.0% by mass of the whole ink. 3. The ink according to claim 1, wherein the amount of the compound represented by the general formula (II) contained in the magenta ink and the cyan ink is 0.1 to 20% by mass of the whole ink. set. 4. The ink according to claim 1, wherein the amount of the compound represented by the general formula (II) contained in the magenta ink and the cyan ink is 0.5 to 5% by mass of the whole ink. The ink set according to the item. 5. The ink set according to claim 1, wherein the magenta ink and the cyan ink are inks used for inkjet recording. 6. An ink jet recording method comprising a step of ejecting a magenta ink and a cyan ink from an orifice in accordance with recording signals, respectively, and superimposing the magenta ink and the cyan ink on a recording material. The cyan ink contains the coloring material represented by the general formula (I) and the compound represented by the following general formula (II), and the cyan ink is represented by the coloring material having a copper phthalocyanine structure and the following general formula (II) Ink-jet recording method comprising: (In the general formula (I), R ₁ represents a substituted or unsubstituted aryl group; R ₂ and R ₄ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group;
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) (In the general formula (II), m and n are integers of 0 or more and 4 ≦ m + n ≦ 20 or less). 7. The ink jet recording method according to claim 6, wherein the amount of the compound represented by the general formula (II) contained in the magenta ink and the cyan ink is 0.1 to 20% by mass of the whole ink. . 8. The ink jet printer according to claim 6, wherein the amount of the compound represented by the general formula (II) contained in the magenta ink and the cyan ink is 0.5 to 5% by mass of the whole ink. Recording method. 9. The ink jet recording method according to claim 6, wherein said step includes a step of ejecting the ink by applying thermal energy to the ink. 10. An ink set according to claim 5, further comprising: an ink storage unit for storing each ink constituting the ink set; and a head unit for discharging each ink. And a recording unit. 11. The recording unit according to claim 10, wherein the head unit includes a recording head that ejects the ink by applying thermal energy to the ink. 12. An ink cartridge, comprising: an ink storage section for storing each ink constituting the ink set according to claim 1. Description: 13. A magenta ink containing a coloring material represented by the following general formula (I) and a compound represented by the following general formula (II), and a coloring material having a copper phthalocyanine structure and a coloring material represented by the following general formula (II): An ink jet recording apparatus comprising: an ink container that contains a cyan ink containing a compound represented by the formula (1); and a recording head that ejects each of the magenta ink and the cyan ink. (In the general formula (I), R ₁ represents a substituted or unsubstituted aryl group; R ₂ and R ₄ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group;
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) (In the general formula (II), m and n are integers of 0 or more and 4 ≦ m + n ≦ 20 or less). 14. The ink jet recording apparatus according to claim 13, wherein the recording head is a head that ejects the ink by applying thermal energy to the ink.