JP3526279B2 - Ink, ink set, ink jet recording method, recording unit, ink cartridge, and ink jet recording apparatus - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ink, and further,
The present invention relates to an ink, an inkjet recording method, an ink cartridge, a recording unit, an ink set, and an inkjet recording apparatus that can be suitably used for inkjet recording in which ink is ejected from an orifice according to a recording signal to record on a recording material.

[0002]

2. Description of the Related Art An ink jet recording method is one in which a small droplet of ink is ejected to adhere the ink to a recording material such as paper for recording. In particular, Japanese Patent Publication No. 61-59911, Japanese Patent Publication No. 61-59912, and Japanese Patent Publication No. 61-5.
According to the ink jet recording method of the type disclosed in Japanese Patent Publication No. 9914, which uses an electrothermal converter as the ejection energy supply means and generates thermal energy by giving bubbles to the ink to generate droplets, it is possible to easily perform color printing. Images can be printed. Further, in recent years, further cost reduction and improvement in printing speed have been promoted for inkjet recording apparatuses, and further 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, an aqueous ink in which a dye having each color tone is dissolved in a water-soluble medium is used.
It is desirable that these inks satisfy, for example, the inkjet recording characteristics listed in (1) to (10) below at a high level. (1) To give an image of sufficient density (2) Good drying property on the recording material (3) No bleeding on the recorded image (4) Image quality of the recorded image even when contacted with water, alcohol, etc. No run-out (5) Recorded image has excellent light resistance (6) No clogging at the nozzle tip (7) Blurred image at continuous printing or at the start of recording after leaving for a long time (8) The ink is stable during storage (9) When used, no problem occurs even if it comes into contact with a member constituting the recording means (10) Excellent heat resistance, In addition, the heat energy generating element should not be adversely affected.

By the way, among the inks of various tones used for color recording, as the dyes used for the magenta water-based ink, azo or xanthene dyes which can obtain magenta inks of excellent tones are mainly used. The existence of such magenta ink having an excellent color tone makes it possible to realize an ink jet image having a high image quality comparable to that of silver halide photography in recent years. However, in recent years, not only the image quality but also the durability of the formed image is required for the ink jet recording image.

[0005]

On the other hand, according to the studies made by the present inventors, the azo-based or xanthene-based magenta dyes used in conventional magenta inks are dyes used in other color inks. Light resistance is inferior compared to
When a color inkjet image formed using this magenta ink was evaluated in a light resistance test for a longer period than previously assumed, it was confirmed that the color balance of the color image would be lost due to the fading of the magenta color. . 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. I arrived.

Further, as a coloring material, a magenta ink using a dye such as an azo-based or xanthene-based, which has good color developability,
When used together with a cyan ink that uses a copper phthalocyanine dye that is excellent in light resistance and color tone as a color material, the fading of the magenta dye becomes more prominent in the mixed color portion of this cyan ink and magenta ink than in the case of a single color. However, the color balance of the entire image may be lost and the image quality may be significantly deteriorated. A new magenta ink has been proposed for the technical problem of accelerating photodegradation in a mixed color image of magenta ink and cyan ink. For example, in Japanese Unexamined Patent Publication No. 2-127482, in two or more types of magenta inks having different densities, a dye having excellent sharpness is used as a dark ink, and a dye that does not promote photobleaching in a mixed color portion is used as a light ink. Therefore, it has been proposed to suppress light fading in the highlight portion of the image. Further, in JP-A-11-315230, in a magenta ink containing an azo dye, a dye having a xanthene structure is used as a light resistance-imparting agent.
By adding the coloring material in the range of 0.03 to 0.5,
Proposals have been made to suppress fading in the color mixing part of an image.

However, according to the studies by the present inventors, the technique described in Japanese Patent Laid-Open No. 2-127482 is a very effective technique capable of suppressing a change in color balance with time of a color image. Though
Considering consumer demand for high reproducibility of photographic color images in recent years, further improvement is made against changes in color tone due to interaction between color materials that occur in the mixed portion of dark magenta ink and cyan ink. Came to the conclusion that is necessary. Further, the above-mentioned JP-A-11-31
Regarding the technique described in Japanese Patent No. 5230, although it is true that the fading-promoting effect on a color image is suppressed, it has been recognized that the magenta ink itself still requires further improvement in light resistance. It was

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

Another object of the present invention is to further improve the light resistance of the magenta dye in the mixed color portion of the cyan ink and the magenta ink, and to provide excellent color development even when an image including the mixed color portion is formed. , A beautiful color image is obtained, and even after storage for a long time, there is little fading,
The fading of the magenta color, which was noticeable in the mixed color image of the magenta ink and the cyan ink having a copper phthalocyanine dye, is effectively suppressed, and a color image with excellent light fastness that can maintain excellent image quality even under severe conditions is obtained. An object of the present invention is to provide an ink set containing a novel magenta ink that can be formed. 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 the above-mentioned color image having excellent light resistance.

[0010]

The above objects can be achieved by the present invention described below. That is, the ink according to one embodiment of the present invention contains a first coloring material represented by the following general formula (I), a second coloring material represented by the following general formula (II), and an aqueous medium. Characterized by:

[0011] (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 are each independently a hydrogen atom or a substituted or unsubstituted aryl 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 Or a salt thereof, or a sulfonic acid group or a salt thereof, and n represents 1 or 2.)

[0012] (In the above general formula (II), Ar₁Is replaced or not replaced
Phenyl group or substituted or unsubstituted naphthyl group
Represents Ar₂Is an acetyl group, a benzoyl group, 1,
3,5-triazinyl group, SO₂-C₆H_FiveGroup or SO₂
-C₆H_Four-CH ₃Represents one of the groups. M is sulfonic acid
It is a counterion of the group, such as hydrogen atom, alkali metal,
Represents either aluminum or organic ammonium).

An ink according to another embodiment of the present invention is
In addition to the first coloring material represented by the general formula (I) and the second coloring material represented by the general formula (II), C.I. I. Acid Red 52 and C.I. I. Aci
At least one of d Red 289 is used and contained in an aqueous medium. By adopting such an embodiment, it is possible to obtain an effect that a magenta ink that is excellent in color tone and can give an image excellent in durability can be obtained.

In addition, an ink according to another embodiment of the present invention comprises a first coloring material represented by the general formula (I) and a second coloring material represented by the general formula (II). As a third color material, C.I. I. Acid Red 289 is used and contained in an aqueous medium. The ink of such a form is preferable because it has an excellent color tone and can give an image having excellent durability.

[0015]

Next, the ink set of the present invention which uses the above-mentioned inks 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 a yellow ink, a cyan ink and a black ink is combined with a magenta ink according to various aspects of the present invention. The thing characterized by.

An ink set according to another embodiment of the present invention includes a combination of cyan ink and magenta ink according to the above-mentioned various aspects. In particular, in the case of an ink set combined with a cyan ink containing a coloring material having a copper phthalocyanine structure, the fading acceleration phenomenon conventionally observed in the mixed color portion of the magenta ink and the cyan ink,
It is possible to obtain the effect of being extremely effectively alleviated. Also,
These ink sets are also suitable for inkjet recording applications.

Next, the ink jet recording method of the present invention using the above-described inks or ink sets will be described. An inkjet recording method according to an embodiment of the present invention is characterized by including a step of ejecting the magenta inkjet recording ink according to various aspects of the present invention from an orifice according to a recording signal. An inkjet recording method according to another embodiment of the present invention is a process of ejecting the magenta inkjet recording ink 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 ejecting a cyan ink containing a dye having a colorant from an orifice according to a recording signal. In particular, in this aspect, when the magenta ink and the cyan ink are overlapped on the recording material to form the mixed color portion, the fading acceleration conventionally observed in the mixed color portion of the magenta ink and the cyan ink is accelerated. The effect that it can be effectively suppressed is obtained.

An embodiment of the recording unit according to the present invention is for ejecting the ink containing portion containing the ink for magenta ink jet recording according to the various aspects of the present invention described above. Is provided. Further, another embodiment of the recording unit according to the present invention is an ink containing portion that contains each ink constituting the ink set for inkjet recording according to the above-described various aspects of the present invention, and ejects the ink. And a head section for doing so are provided.

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

Next, an ink jet recording apparatus according to an embodiment of the present invention is a recording head for ejecting the magenta ink jet ink according to the various aspects of the present invention, and an ink containing the ink. It is characterized by comprising an ink cartridge having a containing portion and an ink supply portion for supplying ink from the ink cartridge to the recording head. An inkjet recording apparatus according to another embodiment of the present invention is an inkjet recording ink of at least one color of yellow ink, cyan ink and black ink, and magenta inkjet recording according to various aspects of the present invention. 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 ink for ejecting each of these inks. And a recording head.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION 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, in the process of repeatedly studying various magenta dyes, combine at least one of an azo magenta dye and a xanthene magenta dye, and a magenta dye having an anthrapyridone skeleton. The above ink was prepared, and the ink and the image by the ink were evaluated. As a result, the ink having such a configuration satisfies the inkjet recording characteristics (1) to (10) described above at a high level and has an excellent tint that can be used for photographic image formation. Moreover, the inventors have found that an image formed with such an ink is also extremely excellent in light resistance, and have completed the present invention.

That is, according to the study by the present inventors, the light resistance of the image obtained by the ink having the above-mentioned structure is predicted from the light resistance of the image formed by using the ink containing the azo dye alone. It turned out to be significantly higher. Although the reason why such a result is obtained is not clear, it is considered that the interaction between the dye molecules caused by the combined use of a plurality of coloring materials is contributing.

As a conventionally known magenta-colored water-based ink and a recording method using the same, for example, a magenta-colored water-based dye ink using a dye having an anthrapyridone skeleton is disclosed in Japanese Patent Laid-Open No. 2-16171. Is disclosed, and it is described that the dye has excellent light resistance. Further, JP-A-57-197191 discloses an inkjet color printing method using a magenta aqueous dye ink containing a dye having an anthrapyridone skeleton. However, these inventions do not disclose any technique for mixing anthrapyridone-based magenta dyes with other magenta dyes, let alone suggest the effect of improving the light fastness of an image brought about by an ink of a mixed system. I haven't even been seen.

Further, JP-A-10-306221 (USP6152969) and JP-A-2000-109.
Japanese Patent No. 464 (EP 1067155) also discloses an ink containing an anthrapyridone compound having a structure similar to that of the present invention. However, the above-mentioned characteristic features of the present invention are not disclosed at all, and there is no description suggesting the effect thereof. Furthermore, the WO published on March 4, 1999
A1 9946341 (Japanese Patent Laid-Open No. 2000-169776)
The publication and EP1063268A1) also disclose an ink containing an anthrapyridone compound.
However, it does not disclose any feature of the present invention.

[First Embodiment] (Coloring Material) The ink according to one embodiment of the present invention has a coloring material and an aqueous medium, and the coloring material is represented by the following general formula (I). 1 colorant and the second represented by the following general formula (II)
The colorant is 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 are each independently a hydrogen atom or a substituted or unsubstituted aryl 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.

Regarding R _{1 to} R ₄ in the above general formula (I),
More specifically, R ₁ has, for example, 1 to 4 carbon atoms.
And straight-chain or branched-chain alkoxyl groups, and substituted or unsubstituted phenyl groups. 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, a halogen atom (fluorine, chlorine, bromine, etc.), and the like. As R ₂ ,
Examples thereof include a hydrogen atom, a linear or branched lower alkyl group having 1 to 4 carbon atoms, and R ₃ is, for example, a hydrogen atom or a linear or branched chain alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group, the straight-chain or branched-chain alkoxyl group having 1 to 4 carbon atoms, and the aryloxy group include, for example, a phenoxy group. The aryl group constituting the aryloxy group has, for example, 1 to 1 carbon atoms.
It may be substituted with a linear or branched alkyl group of 0, a sulfone group, a salt thereof, a carboxyl group or a salt thereof, and the like. Further, 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, when X ₁ in the above formula is described in detail, X ₁ is, for example, —CO
OM and -SO ₃ M, and the like. However, 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. What is.

[0028] 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, 1,
3,5-triazinyl group, SO ₂ -C ₆ H ₅ group, or SO ₂
-C ₆ H ₄ represents any of -CH ₃ groups. M is a counter ion of a sulfonic acid group, and like the general formula M, a hydrogen atom, an alkali metal (eg, Li, Na, etc.), ammonium (NH ₄ ) or organic ammonium (N (R ₆ ) ₄ ) Represents either Here, examples of R ₆ include a methyl group and an ethyl group.

Further, the phenyl group or naphthyl group of Ar ₁ is, 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, or the like, and may be substituted with one or more groups or atoms. In addition, the above Ar
_{When 2} is a benzoyl group or a 1,3,5-triazinyl group, at least one hydrogen atom in the benzene ring or the 1,3,5-triazine ring is a carboxyl group or a salt thereof, a halogen atom (a fluorine atom). , A chlorine atom, a bromine atom, etc.), or a primary to tertiary amino group, an alkoxyl group, a hydroxyl group or the like.

A magenta image obtained by the ink containing the first and second coloring materials represented by the above general formulas (I) and (II) shows a very excellent color tone and It exhibits light fastness superior to that expected from an ink containing only an azo dye as a coloring material.

Illustrative compounds 1 to 7 are shown below as specific examples of the first coloring material represented by the general formula (I), but the first coloring material used in the present invention is not limited to these. is not. Further, two or more kinds of coloring materials listed below may be used at the same time.

[0032]

[0033]

[0034]

[0035]

Examples of the coloring material of the compound of the general formula (II) used in the present invention include C.I. I. Reactive R
ed 180, Exemplified Compounds 8 to 13 having the structures shown below, and further compounds having the structures described in JP-A-8-73791 and JP-A-11-209673.

[0037]

[0038]

[0039]

The mass ratio of the first coloring material represented by the general formula (I) and the second coloring material represented by the general formula (II) contained in the ink according to the present embodiment is as follows. 1 colorant and 2nd
Taking into consideration the effect that a clear color tone, a sufficient image density, and further excellent light resistance can be obtained by combining and using the color materials of No. 1 of the general formula (I), Colorant: The second colorant represented by the general formula (II) is 9
It is preferable to set it in the range of 5: 5 to 20:80. The content of all coloring materials in the ink is 0.1 to 15.0% by mass, particularly 0.5 to 5% by mass based on the total amount of the ink.
The range of 0 mass% is preferable.

(Aqueous medium) The water-soluble organic solvent contained in the aqueous medium used in the present invention is not particularly limited as long as it exhibits water solubility, and alcohols, polyhydric alcohols, polyglycols, glycol ethers, nitrogen-containing solvents are included. A polar solvent, a sulfur-containing polar solvent, etc. are mentioned. These water-soluble organic solvents have a water-soluble organic solvent content of from 1 to 40 based on the total amount of the ink, in view of maintaining the moisture retention of the ink, improving the solubility of the coloring material, and effectively permeating the ink into the recording paper. It is preferably in the range of mass% and more preferably in the range of 3 to 30 mass%. In addition, the solubility of the dye, which is a coloring material, in the ink is good, the viscosity for stable ink ejection is good, and the content of water in the ink is included in order not to cause clogging at the nozzle tip. Is preferably in the range of 30 to 95 mass%.

(PH) In the ink of the present invention, when one of the coloring materials contains a coloring material containing at least one carboxyl group or a salt thereof in the molecule, the solubility of the coloring material in water is prevented from decreasing. From the viewpoint of preventing clogging at the tip of the nozzle and long-term storage stability of the ink, the pH of the ink is in the neutral to alkaline range, specifically, pH 7.0.
It is preferable to keep it within the range of 11.0. Further, in the case of using a coloring material that does not contain a carboxyl group or its salt in the molecule, any of the coloring materials has a weak pH dependence of the solubility of the coloring material.
It may be set within the range of 1.0.

(Additive) In order to maintain the moisturizing property of the ink, in the present invention, a moisturizing solid content such as urea, urea derivative, trimethylolpropane may be used as an ink component, if necessary. . 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 mass% with respect to the total amount of the ink, and more preferably 3.
It is in the range of 0 to 10.0 mass%. In addition to the above components, the ink of the present invention may further contain a surfactant, p
Various additives such as an H-adjusting agent, a rust preventive, an antiseptic, a fungicide, an antioxidant, an anti-reducing agent, an evaporation accelerator, a chelating agent and a water-soluble polymer may be contained.

[0044]

[0045]

[0046]

[Third Embodiment] Furthermore, an ink according to a third embodiment of the present invention has the same structure as the ink according to the first embodiment described above, and further, as a third coloring material. C., listed above. I. Acid Red 52 and C.I. I. Ink containing at least one xanthene-based dye selected from Acid Red 289 and having an excellent magenta color tone can be used. By adding these dyes, an image having a more excellent color tone can be obtained. Further, the light fastness of an image obtained by an ink obtained by combining such a xanthene-based dye with a dye which is the first and second coloring materials represented by the general formula (I) and the general formula (II). Is significantly higher than the light fastness predicted from an image obtained by an ink containing at least one of a xanthene dye and an azo dye as a coloring material. Such an effect is obtained from the effect obtained by the ink using each color material alone.
It cannot be guessed at all. Particularly, as the third coloring material, C.I. I. The color tone of the image formed by the ink containing Acid Red 289 is excellent. The ink according to the third embodiment of the present invention capable of forming an image having such an even more excellent color tone and high light fastness is, for example, a silver salt photograph in which particularly delicate color tone reproduction is required. As a magenta ink for inkjet printers for printing high-quality images comparable to
It can be used very suitably.

In the ink according to the third embodiment of the present invention described above, the amount (A) of the first coloring material represented by the general formula (I) and the first colorant represented by the general formula (II). The ratio between the amount (B) of the second coloring material and the amount (C) of the xanthene-based third coloring material mentioned above is extremely sharp and high obtained by combining these coloring materials. Considering the effect of image density and sufficient light fastness, the amount of the first coloring material represented by the general formula (I), the amount of the second coloring material represented by the general formula (II), and The ratio of the total amount of the xanthene-based coloring materials that are the third coloring materials listed above is A: (B + C) =
It is preferably in the range of 95: 5 to 20:80 (mass ratio).

The ink according to each of the first and third embodiments of the present invention described above is particularly suitable for use in an ink jet recording system in which droplets are ejected by the action of thermal energy for recording, but other inks are used. It goes without saying that it can also be used as an inkjet recording method or a general writing tool.

(Recording Device, Ink Cartridge, Recording Unit, Ink Set) By the way, as a recording device suitable for recording using the ink of the present invention having the first and third aspects,
An example is a device in which thermal energy corresponding to a recording signal is applied to ink in a chamber of a recording head having an ink accommodating portion that accommodates these inks, and ink droplets are generated by the energy.

1 to 3 show examples of the structure of the recording head, which is the main part of the recording head. The head 13 has a groove 1 through which ink passes.
4. A glass, ceramics, or plastic plate having No. 4 and a heating head 15 having a heating resistor used for heat-sensitive recording (a head is shown in the drawing, but not limited thereto) are bonded to each other. Obtained. The heating head 15 has a good heat dissipation property such as a protective film 16 formed of silicon oxide or the like, aluminum electrodes 17-1 and 17-2, a heating resistor layer 18 formed of nichrome or the like, a heat storage layer 19, alumina or the like. It consists of a substrate 20. Ink 21
The discharge orifice (fine hole) 22 is filled, and the pressure P forms a meniscus 23. When a pulsed electric signal is applied to the electrodes 17-1 and 17-2 of the head 13, the area (heater) indicated by n on the heating element substrate 15 is rapidly heated, and the ink in contact with this surface is heated. Bubbles are generated in 21 and the meniscus 23 is ejected by the pressure, and the ink 21 is ejected through the nozzle 14 of the head, becomes an ink droplet from the ejection 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 the heads shown in FIG. 1 are arranged. This multi-head is a glass plate 2 having a multi-nozzle 26.
7 and a heating head 28 similar to that described in FIG.
It is made by bonding.

FIG. 4 shows an example of an ink jet recording apparatus incorporating this head. In FIG. 4, reference numeral 61 denotes a blade as a wiping member, one end of which is
It is held by the blade holding member and becomes a fixed end, which is in the form of a cantilever. The blade 61 is disposed at a position adjacent to the recording area of the recording head,
In the case of the example shown in (1), the recording head is held in a protruding form in the movement path of the recording head. Reference numeral 62 denotes a cap, which is arranged at a home position adjacent to the blade 61, and has a configuration in which it moves in a direction perpendicular to the moving direction of the recording head and comes into contact with the ejection surface to perform capping. Furthermore, 63 in FIG.
Is an ink absorber provided adjacent to the blade 61, and like the blade 61, is held in a protruding form in the moving path of the recording head.

The blade 61, the cap 62, and the absorber 63 constitute a discharge recovery section 64.
Also, the absorber 63 removes water, dust, and dust from the surface of the ink ejection port. Reference numeral 65 denotes a recording head having ejection energy generating means, which ejects ink onto a recording material facing the ejection port surface where the ejection ports are arranged to perform recording, and 66 denotes
A carriage for mounting the recording head 65 and moving the recording head 65. The carriage 66 has a guide shaft 6
7, and a part of the carriage 66 is connected to a belt 69 driven by a motor 68 (not shown). As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move in the recording area and the area adjacent thereto.

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

In the above structure, when the recording head 65 returns to the home position after the recording is completed, the head recovery unit 64
The cap 62 is retracted from the moving path of the recording head 65, but the blade 61 is projected in the moving path.
As a result, the ejection port surface of the recording head 65 is wiped. When the cap 62 comes into contact with the ejection surface of the recording head 65 to perform capping, the cap 62 moves so as to project 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 in the same positions as the above wiping positions. As a result, even during 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 and at the time of ejection recovery, but also at the home position adjacent to the recording area at a predetermined interval while the recording head moves in the recording area for recording. Then, with this movement, the wiping is performed.

FIG. 5 is a sectional view showing an example of an ink cartridge 45 in which ink is supplied to the head via an ink supply member, for example, a tube. Here, 40 is an ink containing portion containing the ink for supply, for example,
It is an ink bag, and a rubber stopper 42 is provided at the tip thereof. By inserting a needle (not shown) into this 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 an apparatus in which they are integrated as shown in FIG. 6 is also preferable. Used. In FIG. 6, reference numeral 70 denotes a recording unit, in which an ink containing portion containing ink, for example, an ink absorber is contained, and the ink in the ink absorber has a head portion having a plurality of orifices. The ink is ejected from 71 as an ink droplet. Reference numeral 72 is 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 which can be preferably used in the present invention will be described. Figure 7
Is a liquid discharge head as a liquid discharge head of a discharge type that communicates bubbles with the atmosphere at the time of discharge suitable for the present invention, and
FIG. 3 is a schematic perspective view showing a main part of an example of an inkjet printer as a liquid ejection device using this liquid ejection head. The inkjet printer shown in FIG. 7 is a conveyance device 1030 for intermittently conveying a sheet 1028 as a recording material provided along the longitudinal direction in a casing 1008 in a direction indicated by an arrow P in FIG. And a recording unit 1010 that is reciprocated along a guide shaft 1014 substantially parallel to a direction S that is substantially orthogonal to the conveyance direction P of the sheet 1028 by the conveyance device 1030, and a driving unit that reciprocates the recording unit 1010. Drive unit 10 as
06 and are included.

The carrying device 1030 is provided with a pair of roller units 1022a and 1022b, which are arranged substantially parallel to each other, a pair of roller units 1024a and 1024b, and a drive unit 1020 for driving each of these roller units. Is equipped with. With this configuration, when the driving unit 1020 of the transport device 1030 is activated, the paper 1028 is transferred to the respective roller units 102.
It is nipped by 2a and 1022b and roller units 1024a and 1024b, and conveyed by intermittent feed in the direction of arrow P shown in FIG.

Further, the movement driving unit 1006 is provided with a pulley 102 arranged on a rotating shaft which is arranged to face each other with a predetermined interval.
Belt 1016 wrapped around 6a and 1026b
And the carriage member 1 of the recording unit 1010, which is disposed substantially parallel to the roller units 1022a and 1022b.
The belt 1016 connected to 010a includes a motor 1018 for driving the belt 1016 in the 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 in the direction of arrow S in FIG. Further, when the motor 1018 is activated and the belt 1016 rotates in the direction opposite to the arrow R direction in FIG.
The carriage member 1010a is moved by a predetermined movement amount in the direction opposite to the arrow S direction in FIG.
Further, at one end of the movement driving unit 1006, a recovery unit 1026 for performing the ejection recovery process of the recording unit 1010 is located at the home position of the carriage member 1010a so as to face the ink ejection port array of the recording unit 1010. Is provided.

In the recording section 1010, ink jet cartridges (hereinafter sometimes simply referred to as cartridges) 1012Y, 1012M, 1012C and 1012 are used.
B is detachably attached 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 which can be mounted on the above ink jet recording apparatus. The cartridge 1012 in this example is a serial type, and the ink jet recording head 100
And a liquid tank 100 for containing a liquid such as ink.
The main part is composed of 1. The inkjet recording head 100 has a large number of ejection openings 83 for ejecting liquid.
2 is formed, and the liquid such as ink is stored in the liquid tank 1
001 is led to a common liquid chamber (see FIG. 9) of the liquid ejection head 100 through 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 the liquid can be replenished into the liquid tank 1001 as needed. A liquid tank 1001 may be exchangeably connected to 100.

A specific example of the liquid ejection head which can be mounted on the ink jet printer having the above-mentioned structure will be described in more detail below. FIG. 9 is a schematic perspective view schematically showing a main part of a liquid ejection head showing a basic form of the present invention, and FIGS. 10 to 13 show ejection port shapes of the liquid ejection head shown in FIG. It is a front view shown. It should be noted that electrical wiring and the like for driving the electrothermal conversion element are omitted.

In the liquid discharge head of this 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 functions as a part of the flow path constituent member and can function as a support for the ink discharge energy generating element and the liquid flow path described later and the material layer forming the discharge port. . The case where a Si substrate (wafer) is used will be described below. In addition to the method of forming the discharge port by laser light, for example, an orifice plate (discharge port plate) 935, which will be described later, is used as a photosensitive resin and MPA (Mirr
or Projection Aliner) or the like.

In FIG. 9, reference numeral 934 denotes an ink supply port 9 composed of an electrothermal conversion element (hereinafter also referred to as a heater) 931 and a long groove-shaped through-hole as a common liquid chamber portion.
33 is a substrate provided with 33, and a heater 931 that is a thermal energy generating unit is provided on both sides of the ink supply port 933 in the longitudinal direction.
Are arranged in a staggered manner one row each, for example, with an electrothermal conversion element (heater) spacing of 300 dpi. An ink flow path wall 936 for forming an ink flow path is provided on the substrate 934. This ink flow path wall 936
The discharge port plate 93 further includes a discharge port 832.
5 are provided.

Here, in FIG. 9, the ink flow path wall 9
Although the 36 and the ejection port plate 935 are shown as separate members, the ink channel wall 936 and the ejection channel plate 935 are formed on the substrate 934 by, for example, a method such as spin coating. It is also possible to form the outlet plate 935 as the same member at the same time. In the present example, the water repellent treatment is further applied to the ejection port surface (upper surface) 935a side.

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

Of the cross section of the ejection port portion 940 provided in the ejection port plate 935 including the ejection port 832 shown in FIG. 9, cutting is performed in a direction intersecting with the ink ejection direction (thickness direction of the orifice plate 935). The shape of the cross section I saw is
As shown in FIG. 11, the six star-shaped portions 832a having a substantially star shape and having obtuse angles are provided, and these base portions 832a are provided.
It is roughly composed of six recesses 832b which are alternately arranged between and and have acute angles. That is, the recess 832b as a region locally separated from the center O of the discharge port is its top part, and the raised part 832a as a region locally close to the center O of the discharge port adjacent to this region is its base part.
Six grooves 1141 are formed in the thickness direction (liquid ejection direction) of the orifice plate shown in FIG. 9 (FIG. 11).
reference).

In the present example, the discharge port portion 940 has, for example, a cross-section cut in a direction intersecting the thickness direction thereof, in which two equilateral triangles each having a side of 27 μm are combined by being rotated by 60 degrees. And T ₁ shown in FIG. 11 is 8
μm. The angles of the raised portions 832a are all 120 degrees, and the angles of all the bent portions 832b are 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 a figure formed by connecting the top of the groove and two bases adjacent to this top) The center of gravity G of is matched. Discharge port 8 of this example
The opening area of 32 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 this top) is about 33 μm ² . FIG. 12 is a schematic diagram showing an ink adhering state of the ejection port portion shown in FIG. 11, and C shows an ink adhering portion (wet ink).

Next, the liquid ejecting operation by the ink jet recording head having the above-described structure will be described with reference to FIGS.
Will be explained. 14 to 21 are cross-sectional views for explaining the liquid discharge operation of the liquid discharge heads shown in FIGS. 9 to 13, and are XX cross-sectional views of the bubbling chamber 1337 shown in FIG. 13. In this cross section, the end portion in the thickness direction of the orifice plate of the discharge port portion 940 shown in FIG.
It is the top part 1141a of 41. FIG. 14 shows a state in which film-like bubbles are generated on the heater, and FIGS.
Shows the state of the bubbles thereafter with time.
That is, FIG. 15 shows about 1 μs of FIG. 14, and FIG.
4 about 2 μs, FIG. 17 shows about 3 μs of FIG.
8 is about 4 μs in FIG. 14, and FIG. 19 is about 5 μs in FIG.
s, FIG. 20 shows about 6 μs of FIG. 14, and FIG.
The state after about 7 .mu.s is shown. In the following explanation, "fall" or "drop", "drop"
The term does not mean so-called drop in the direction of gravity, but means movement in the direction of the electrothermal conversion element regardless of the mounting direction of the head.

First, as shown in FIG. 14, when air bubbles 101 are generated in the liquid flow path 1338 above the heater 931 as the heater 931 is energized based on a recording signal or the like, about 2
During μs, as shown in FIG. 15 and FIG.
Grows by rapidly expanding its volume. The height of the bubble 101 at the maximum volume exceeds the discharge port surface 935a, but at this time, the pressure of the bubble is reduced from a fraction of atmospheric pressure to a fraction of ten.

Next, about 2 μs after the generation of the bubble 101
At this point, as mentioned above, the bubble 101 is
It begins to decrease, but almost at the same time, the meniscus 102
Also begins to form. As shown in FIG. 17, this meniscus
102 also retreats toward the heater 931 side, that is, falls.
Go. Here, in this example, as described above,
It has a plurality of grooves 1141 dispersed in the discharge port.
As a result, when the meniscus 102 retracts, the groove 114
In part 1, the backward direction F of the meniscus 102 is _MOpposite to
Opposite direction F_CCapillary force acts on. As a result, if something
There is some variation in the state of bubbles 101 due to
Even if it is, the meniscus when the meniscus 102 retreats
Liquids and main liquid droplets (hereinafter sometimes referred to as liquid or ink
Yes) I_aThe shape of the
Is corrected so that

In this example, the meniscus 102 is
Since the falling speed of is faster than the contraction speed of the bubble 101,
As shown in FIG. 18, the bubble 101 communicates with the atmosphere in the vicinity of the lower surface of the ejection port 832 at a time point approximately 4 μs after the generation of the bubble. At this time, the liquid (ink) near the central axis of the ejection port 832 drops toward the heater 931. This is because the liquid (ink) I _a drawn back to the heater 931 side by the negative pressure of the bubble 101 before communicating with the atmosphere maintains the velocity in the heater 931 surface direction due to inertia even after the bubble 101 communicates with the atmosphere. Because it is. The liquid (ink) that has dropped toward the heater 931 side reaches the surface of the heater 931 about 5 μs after the generation of the bubble 101, as shown in FIG. 19, and the heater 931 as shown in FIG. Spreads to cover the surface of.

The liquid thus spread so as to cover the surface of the heater 931 has a vector in the horizontal direction along the surface of the heater 931, but a vector in the direction perpendicular to the surface of the heater 931 disappears, for example. And heater 93
1 tends to stay on the surface of No. 1, and the liquid above it, that is, the liquid that maintains the velocity vector in the ejection direction, is pulled downward. After that, the liquid I _b between the liquid spread on the surface of the heater 931 and the upper liquid (main liquid droplet) becomes thin, and as shown in FIG. 21, about 7 μs after the generation of the bubble 101. The liquid I _b is cut at the center of the surface of the heater 931 and is separated into a main droplet I _a that maintains the velocity vector in the ejection direction and a liquid I _c that spreads on the surface of the heater 931. In this way, the separation position is the liquid flow path 1338.
Inside, more preferably on the electrothermal conversion element (heater) 931 side with respect to the discharge port 832.

The main liquid droplet I _a has no deviation in the ejection direction, is ejected from the central portion of the ejection port 832 without being deflected, and is landed at a predetermined position on the recording surface of the recording material. Further, although the liquid I _c spread on the surface of the heater 931 would fly as satellite droplets following the main droplets in the conventional case, it remains on the surface of the heater 931.
Not discharged. In this way, since it is possible to suppress the discharge of satellite droplets, it is possible to prevent the splash that is likely to occur due to the discharge of satellite droplets, and to prevent the recording surface of the recording material from becoming dirty due to mist floating in a mist. It can be surely prevented. In addition, in FIGS.
I _d represents the ink attached to the groove (ink in the groove), and I _e represents the ink remaining in the liquid flow path.

As described above, in the liquid ejecting head of this example, when ejecting the liquid in the volume reduction stage after the bubbles have grown to the maximum volume, a plurality of grooves dispersed with respect to the center of the ejection port are formed. This makes it possible to stabilize the direction of the main liquid droplet during ejection. As a result, it is possible to provide a liquid ejection head with high accuracy in landing, which is free from deflection in the ejection direction. Further, high-speed and high-definition printing can be realized because the ejection can be stably performed even when the foaming variation occurs at a high driving frequency.

In particular, when the volume of the bubble is reduced, the liquid is discharged by communicating the bubble with the atmosphere for the first time, so that the mist generated when the bubble is communicated with the atmosphere and the droplet is discharged can be prevented. It is also possible to suppress a state in which droplets adhere to the ejection port surface, which causes so-called sudden ejection failure. Further, as another embodiment of a recording head of a discharge system in which air bubbles communicate with the atmosphere at the time of discharge that can be suitably used in the present invention, for example, as described in Japanese Patent Registration No. 27834747, a so-called edge shooter type is used. Can be mentioned.

(Ink Set) Further, the ink set of the present invention is a combination of at least one color of yellow ink, cyan ink and black ink and the ink of the present invention having the magenta color of the form described above. Is. A dye or a pigment can be used as a coloring material contained in the yellow, cyan, and black inks that can be used at that time. As the dye, for example,
Any of the water-soluble xanthene-based, triphenylmethane-based, anthraquinone-based, monoazo-based, disazo-based, trisazo-based, tetraazo-based dyes and the like described in the Color Index can be preferably used.

In the case of a black pigment ink, carbon black is suitable as the pigment.
o. 2300, No. 900, MCF88, No. Four
0, No. 52, MA7, MA8, No. 2200B
(Made by Mitsubishi Kasei), RAVEN1255 (Made in Colombia), REGAL400R, REGAL660R, M
OGUL L (made by Cabot), Color Blac
k FW1, ColorBlack FW18, Col
or Black S170, Color Black
S150, Printex 35, Printex
Commercially available products such as U (manufactured by Degussa) can be used.

Examples of pigments used in the yellow ink include C.I. I. Pigment Yellow
1, C.I. I. Pigment Yellow 2, C.I.
I. Pigment Yellow 3, C.I. I. Pi
gment Yellow 13, C.I. I. Pigme
nt Yellow 16, C.I. I. PigmentY
ellow 83 is mentioned.

As the pigment used for the cyan ink, for example, C.I. I. Pigment Blue
1, C.I. I. Pigment Blue 2, C.I. I.
Pigment Blue 3, C.I. I. Pigmen
t Blue 15: 3, C.I. I. Pigment B
lue 16, C.I. I. Pigment Blue 2
2, C.I. I. Vat Blue 4, C.I. I. Vat
Blue 6 and the like can be mentioned.

The ink set of the present invention as described above is an ink jet recording apparatus having a recording unit provided with a storage section for independently storing the inks constituting the ink set, an ink cartridge and the like. Used. In the above description, as the inkjet recording apparatus, a recording apparatus that applies thermal energy to ink to eject ink droplets has been described as an example.
A piezoelectric ink jet recording apparatus using a piezoelectric element can also be used.

According to a study by the present inventors, in particular, the magenta ink according to any one of the first and third embodiments of the present invention described above and the cyan ink containing a coloring material having a copper phthalocyanine structure. It was found that the light resistance of the mixed color portion formed by using and was extremely excellent. The degree of light fastness is determined by the light fastness in the mixed color portion of the magenta ink containing the coloring material represented by the general formula (I) alone and the cyan ink containing the coloring material having the copper phthalocyanine structure and the general formula (I). The light fastness exceeded the light fastness predicted based on the light fastness based on the light fastness in the mixed portion of each magenta ink containing the colorant used alone and the cyan ink containing the colorant having the copper phthalocyanine structure.

Although the reason why such a result is obtained is not clear, the use of a mixture of a plurality of coloring materials causes an interaction between dye molecules, which significantly improves the light fastness of an image. It is thought that it contributes to.
Further, it has been found that such an effect becomes remarkable especially when glossy paper is used as the recording material. Furthermore, the general formula (I)
In addition to the coloring material represented by I. Acid Red 2
It was also found that when 89 is contained, in addition to the effect that the light fastness in the mixed portion of the magenta ink and the cyan ink of the image is remarkably improved, the effects of high image density and high color development are obtained. . As described above , the ink set obtained by combining the magenta ink according to any one of the first and third embodiments of the present invention and the cyan ink containing the coloring material having the copper phthalocyanine structure is a mixed color of these inks. This is a particularly preferable aspect in that the light resistance of the part can be improved.

As the cyan ink constituting such an ink set, one containing a coloring material having a copper phthalocyanine structure is used. The cyan colorant having a copper phthalocyanine structure is excellent in light resistance and color tone,
As described above, it has been known that when a cyan ink having such a coloring material and a conventional magenta ink are used, the fading of magenta color is more remarkable in a mixed color image of these inks than in the case of a single color. . The present invention suppresses such problems by the configuration of the magenta ink according to any of the first and third aspects of the present invention described above. Here, specific examples of the coloring material having a copper phthalocyanine structure include C.I. I. Acid Blu
e 249, C.I. I. Direct Blue 86,
C. I. Direct Blue 199, C.I. I. D
direct Blue 307 etc. are mentioned.

[0088] Then, the ink set as described above, if necessary, may be formed by an ink set in combination further yellow ink, a black ink or the like. Conventionally used dyes and pigments can be used as the coloring material contained in the yellow ink and the black ink used at this time. As the dye, for example,
Any of the water-soluble xanthene-based dyes, triphenylmethane-based dyes, anthraquinone-based dyes, monoazo-based dyes, disazo-based dyes, trisazo-based dyes, and tetraazo-based dyes described in the Color Index can be used.

In the case of a black pigment ink, carbon black is suitable as the pigment.
o. 2300, No. 900, MCF88, No. Four
0, No. 52, MA7, MA8, No. 2200B
(Made by Mitsubishi Kasei), RAVEN1255 (Made in Colombia), REGAL400R, REGAL660R, M
OGUL L (above, made by Cabot), Color B
rack FW1, Color Black FW1
8, Color Black S170, Color B
rack S150, Printex 35, Prin
Commercially available products such as tex U (above, manufactured by Degussa) can be used.

As the pigment used in the yellow ink, for example, C.I. I. Pigment Yellow
w 1, C.I. I. Pigment Yellow 2,
C. I. Pigment Yellow 3, C.I. I.
Pigment Yellow 13, C.I. I. Pig
ment Yellow 16, C.I. I. Pigmen
t Yellow 83 and the like.

[0091]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. Unless otherwise specified, examples,
The ink component of the comparative example means “part by mass”.

<Examples 1 to 3 and 5> The following components were mixed, thoroughly stirred and dissolved, and then 0.20
The inks of Examples 1 to 3 and 5 were prepared by performing pressure filtration with a μm filter.

[0093]

[0094]

[0095]

[0096]

<Comparative Examples 1 to 3> The following components were mixed,
After sufficiently stirring and dissolving, pressure filtration was performed with a 0.20 μm filter to obtain inks of Comparative Examples 1 to 3, respectively.

[0098]

[0099]

<Evaluation of Ink> Using the inks of Examples 1 to 3 and 5 and Comparative Examples 1 to 3 obtained as described above, an on-demand ink jet recording apparatus using a heating element as an energy source for ink ejection is used as an ink jet recording apparatus. Printing was performed using a printer, and the obtained images were (1) color developability, (2) image density, (3)
Each item of light resistance was evaluated according to the following methods and criteria. Table 1 shows Examples 1 to 3 and 5 and Comparative Examples 1 to 3.
The coloring materials of the respective inks and the evaluation results obtained using these inks are collectively shown.

(1) Color developability The above-mentioned printer is filled with a predetermined ink, and PPC is added.
After printing solid areas on two types of recording materials, paper (made by Canon) and glossy paper (PR-101; made by Canon), 24
After air-drying for a period of time, color development was visually evaluated for the subsequent images. A: Vivid magenta color tone B: Slightly dull magenta color tone C: Dull magenta color tone

(2) Image Density [2-A] After the above printer was filled with a predetermined ink and a solid portion similar to that used in the evaluation (1) was printed on PPC paper (manufactured by Canon Inc.). Macbeth RD reflection densitometer
Measurement was performed with -918 (trade name: manufactured by Macbeth Co.), and the obtained measured values were used for evaluation according to 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] Glossy paper (PR-101; made by Canon) filled with a predetermined ink in the printer described above.
After printing the solid part on the surface, it is naturally dried for 24 hours, and the optical density of the image after that is measured by a reflection densitometer Macbeth RD-918
(Trade name: manufactured by Macbeth Co.), and the obtained measured 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 PPC is used.
The same solid portion as that used in Evaluation (1) was printed on each of the paper (made by Canon) and the glossy paper (PR-101; made by Canon). After that, the printed matter is naturally dried for 24 hours, and with a xenon fade meter Ci3000 (manufactured by Atlas Co., Ltd.) equipped with an ultraviolet cut filter, 100 hours under the conditions of a tank temperature of 35 ° C., a relative humidity of 60%, and an irradiation intensity of 60 klux. Exposure was irradiated. The density of the solid portion of the printed matter before and after this irradiation test was measured by the reflection densitometer Macbeth R.
D-918 (trade name: manufactured by Macbeth Co.) was measured, and the residual concentration ratio was determined from these measured values, and the light resistance was evaluated according to the following criteria. A: Concentration residual rate is 80% or more B: Concentration residual rate is 60% or more and less than 80% C: Concentration residual rate is less than 60%

[0105]

As shown in Table 1 above, the ink of Comparative Example 1 containing only the color material of the general formula (I) showed good color developability on glossy paper, but not on PPC paper. In 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-based dye, the image density on PPC paper and glossy paper was not sufficiently obtained. It was found that images having sufficient light resistance could not be obtained on PPC paper and glossy paper. On the other hand, the coloring material of the general formula (I) and the general formula (II)
Ink containing both of the coloring materials of (1) and (5), an ink containing xanthene dye in addition to these ((1) and 5), and the general formula (I ) ink having a dye colorant and xanthene represented by (relevant is example 1及 beauty 5) is expected from the ink of Comparative example using a color material used for these ink each independently The color development, the image density, and the light resistance were improved, and as shown in Table 1, good results were obtained for all evaluation items.

<Examples 6 to 9 and Comparative Examples 4 to 6> First, the following components were mixed and sufficiently stirred to dissolve them.
Magenta inks 1 to 4 and 6 to 8 and cyan inks 1 and 2 were prepared by performing pressure filtration with a 0.20 μm filter.

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

Next, the magenta inks 1 to 1 obtained above are
4, 6 to 8 and cyan inks 1 and 2 are used, and Table 2 below is used.
The combinations shown in Examples 6 to 9 and Comparative Examples 4 to 6
I got the ink set.

[0119]

<Evaluation> Using the ink sets of Examples 6 to 9 and Comparative Examples 4 to 6 obtained above, printing was performed with an on-demand type ink jet printer using a heating element as an ink discharge energy source as an ink jet recording apparatus. A printed matter was obtained. The obtained printed matter was evaluated for light resistance according to the following method and standard. The results obtained are shown in Table 3.

(Light resistance) The above printer was filled with a predetermined ink set, and a PPC paper (made by Canon) and a glossy paper (PR-101; made by Canon) were mixed with a magenta single color part and a mixed color part of magenta and cyan ( After printing the solid patch of (blue), the printed matter is naturally dried for 24 hours, and the temperature inside the tank is 35 ° C. with a xenon fade meter Ci3000 (manufactured by Atlas) equipped with an ultraviolet cut filter.
Irradiation was performed for 100 hours at a relative humidity of 60% and an irradiation intensity of 60 klux. Spe the solid part of the printed matter before and after the test
ctrodenitometer X-rite 9
The color difference ΔE before and after the test was determined from L ^* a ^* b ^* calculated by measuring with 38 (trade name: manufactured by X-rite), and light resistance was evaluated according to the following criteria. A: ΔE ≦ 5 (no visual difference before and after the test) B: 5 <ΔE ≦ 15 (slightly different before and after the test) C: 15 <ΔE (visually before and after the test)

[0122]

[0123]

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

[Brief description of drawings]

FIG. 1 is a vertical sectional view of a head portion of an inkjet recording apparatus.

FIG. 2 is a cross-sectional view of a head portion of an inkjet recording device.

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

FIG. 4 is a perspective view showing an example of an inkjet recording apparatus.

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

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

FIG. 7 is a schematic perspective view showing a main part of an example of an inkjet printer that can mount a liquid ejection head.

FIG. 8 is a schematic perspective view showing an example of an inkjet cartridge including 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.

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

FIG. 12 is a schematic diagram showing an ink adhering state at a portion of the ejection port shown in FIG.

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

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

16 is a schematic cross-sectional view corresponding to the cross-sectional shape taken along the line XX in FIG. 13 and for explaining the liquid discharge operation of the liquid discharge 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 for explaining the liquid discharge operation of the liquid discharge head with time along with FIGS. 14 to 16 and 18 to 21. 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 for explaining the liquid discharge operation of the liquid discharge head with time along with FIGS. 14 to 17 and 19 to 21. 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 for explaining with time the liquid discharge operation of the liquid discharge head together with FIGS. 14 to 18, 20 and 21. is there.

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

[Explanation of symbols]

13: Head 14: Ink groove 15: Heat generating head 16: Protective films 17-1 and 17-2: Aluminum electrode 18: Heat generating resistor layer 19: Heat storage layer 20: Substrate 21: Ink 22: Discharge orifice (fine hole) 23 : Meniscus 24: Ink droplet 25: Recording medium 26: Multi-nozzle 27: Glass plate 28: Heating head 40: Ink bag 42: Plug 44: Ink absorber 45: Ink cartridge 51: Paper feed section 52: Paper feed roller 53 : Paper discharge roller 61: Blade 62: Cap 63: Ink absorber 64: Ejection recovery section 65: Recording head 66: Carriage 67: Guide shaft 68: Motor 69: Belt 70: Recording unit 71: Head section 72: Atmosphere communication port 100: inkjet recording head 101: air bubble 102: meniscus 832: ejection port 832a: raised portion 832b: recessed portion 931 : Electrothermal conversion element (heater, ink ejection energy generating element) 933: ink supply port (opening) 934: substrate 935: orifice plate (ejection port plate) 935a: ejection port surface 936: ink flow channel wall 936a: partition wall 940 : Ejection port 1001: liquid tank 1006: movement drive unit 1008: casing 1010: recording unit 1010a: carriage member 1012: cartridges 1012Y, M, C, B: inkjet cartridge 1014: guide shaft 1016: belt 1018: motor 1020: drive Parts 1022a and 1022b: Roller units 1024a and 1024b: Roller unit 1026: Recovery unit 1026a and 1026b: Pulley 1028: Paper 1030: Conveying device 1141: Groove 1141a: Top portion 1337: Foaming chamber 1338: Flow path C: Wet Ink F _M: meniscus backward F _C: direction opposite to the meniscus retraction direction G: center of gravity I: Ink I _a: main droplet (liquid ink) I _b, I _c: liquid (ink) I _d : ink adhering to the groove (ink in the groove) I _e: ink N ₁ remaining in the liquid flow path: the width of the bubbling chamber dimensions N _2: the length O of the bubbling chamber: the center of the discharge port P: Paper transport direction R: Belt rotation direction S: Direction substantially orthogonal to the paper transport direction T ₁ : Discharge port dimension W: Partition wall width dimension

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C09B 29/30 CLA B41J 3/04 101Y (72) Inventor Yuko Yakushigawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. In-company (72) Inventor Takao Yamamoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) Reference JP-A-2-16171 (JP, A) JP-A-2002-69349 (JP, A) ) Japanese Patent Laid-Open No. 2001-354881 (JP, A) International Publication 99/046341 (WO, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09D 11/00-11/20 CA (STN) REGISTRY (STN)

Claims (27)

(57) [Claims] 1. A first color material represented by the following general formula (I), a second color material represented by the following general formula (II), and an aqueous medium. ink: (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 are each independently a hydrogen atom or a substituted or unsubstituted aryl 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 Or a salt thereof, or a sulfonic acid group or a salt thereof, and n represents 1 or 2.) (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, 1,
3,5-triazinyl group, SO ₂ -C ₆ H ₅ group, or SO ₂
-C ₆ H ₄ represents any of -CH ₃ groups. M is a counter ion of a sulfonic acid group and represents a hydrogen atom, an alkali metal, ammonium or organic ammonium). 2. Further, as a third coloring material, C.I. I. Aci
d Red 52 and C.I. I. Acid Red 28
The ink according to claim 1, comprising at least one of 9. 3. The third coloring material is C.I. I. Acid Red
The ink according to claim 2, which is 289. 4. One of the coloring materials has at least one in the molecule.
One of the carboxyl group or by comprise a salt thereof, and ink according to any one of claims 1 to 3, the pH of the ink is in the range of 7.0 to 11.0. 5. A but none of the coloring material does not contain a carboxyl group or a salt thereof in the molecule, and, according to claim 1 to 3 in which the pH of the ink is in the range of 4.0 to 11.0
The ink according to any one of 1. The amount of the total color material wherein the ink is in the range of 0.1 to 15.0 wt% based on the total amount of the ink according to claim 1 to 5
The ink according to any one of 1. 7. The ink according to any one of claims 1 to 6 the content of water in the ink is in the range of 30 to 95 wt% relative to the total amount of the ink. 8. The ink according to any one of claims 1 to 7, which is ink used in ink jet recording. 9. yellow ink, wherein at least one color ink selected from cyan ink, and black ink, that is the ink according to any one of claims 1 to 8 having a magenta color are combined And ink set. 10. The ink set of cyan ink, characterized in that the ink according to any one of claims 1 to 8 having a magenta color are combined. Wherein said cyan ink, ink set according to claim 9 or 1 0, including a coloring material having a copper phthalocyanine structure. 12. The ink set according to any one of claims 9 to 11, which is an ink set used for inkjet recording. 13. An ink jet recording method comprising a step of ejecting the ink according to claim 8 from an orifice in response to a recording signal. 14. A process of ejecting the ink according to claim 8 having a magenta color from an orifice according to a recording signal, and a cyan ink containing a dye having a copper phthalocyanine structure is ejected from the orifice according to a recording signal. An ink jet recording method comprising the step of: 15. The ink-jet recording method according to claim 1 4 having the heavy sleeping process and the cyan ink and the magenta ink on a recording material. 16. A method according to claim 1 3 in which the ink is reacted with thermal energy including the step of ejecting ink from the orifice
15. The inkjet recording method according to any one of 1 to 15 . 17. A recording unit, comprising: an ink containing portion containing the ink according to claim 8 ; and a head portion for ejecting the ink. 18. A claim 1 second ink container portion containing the respective inks constituting the ink set according to, characterized in that the head portion for ejecting the ink is provided Recording unit. 19. The head portion, the recording unit according by the action of thermal energy to claim 1 7 or 1 8 which comprises a head for discharging ink to the ink. 20. An ink cartridge, wherein the ink storage portion with ink is accommodated according to any one of claims 1 to 8 is provided. 21. An ink cartridge, comprising an ink containing portion for containing each ink constituting the ink set according to any one of claims 9 to 12 . 22. An ink jet recording apparatus comprising a recording unit having an ink containing portion containing the ink according to claim 8 and a head portion for ejecting the ink. 23. A recording head for ejecting the ink according to claim 8 , an ink cartridge provided with an ink containing portion containing the ink, and an ink from the ink cartridge to the recording head. An ink jet recording apparatus comprising: an ink supply unit for supplying the ink. 24. At least one ink for inkjet recording selected from a yellow ink, a cyan ink and a black ink, the ink according to claim 8 having a magenta color, and a recording for ejecting each of these inks. An inkjet recording apparatus comprising a head. 25. An ink jet recording apparatus comprising the ink according to claim 8 having cyan ink and magenta color, and a recording head for ejecting each of these inks. 26. The method of claim 25, wherein the cyan ink, according to claim 2 4, which contains a dye having a copper phthalocyanine structure as the coloring material
Alternatively, the inkjet recording device described in 25 . 27. The recording head is a head for causing thermal energy to act on ink to eject the ink.
2. The inkjet recording device according to any one of 2 to 26 .