JPH0976623A - Ink jet recording member, ink cartridge and ink jet recording apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording method preventing the hue of the black image formed on plain paper by combining inks of yellow, magenta and cyan from becoming a reddish hue and making the hue of the black image on the plain paper same to that of the black image on special paper. SOLUTION: When an ink image is formed on the same material to be recorded using a plurality of color inks containing a combination of three color inks of at least yellow, cyan and magenta, the chromaticities of respective color ink images are at least set to -10<=a*<=0 and 60<=b*<=80 in an yellow ink image, a*>=50 and -15<=b*<=0 in a magenta ink image and -20<=a*<0 and -40<=bu *<=-20 in a cyan ink image.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording method for recording an image by ejecting ink toward a recording material, and more specifically, it uses a specific ink jet head having ejection ports for ejecting a plurality of inks. In addition, the present invention relates to an inkjet recording method, an inkjet cartridge, and an inkjet recording apparatus that use an ink whose chromaticity of an ink image of each color satisfies a specific condition when recorded on a recording material.

[0002]

2. Description of the Related Art Conventionally, ink jet inks having various compositions have been studied. Particularly in recent years, there has been an increasing demand for inks capable of satisfying high color development and high-quality color image quality for so-called plain papers such as copy papers, report papers, notebooks, and notepapers generally used in offices. . However, in the inkjet printers on the general market,
When black ink formed using yellow ink, magenta ink, and cyan ink is recorded on plain paper, it becomes a reddish black color, and the sharpness of the black ink image is lost. is there. Further, by mixing a commercially available coated paper for inkjet recording, that is, a special paper having a recording surface coated with a sizing agent, a water resistant agent, etc., a yellow ink, a magenta ink and a cyan ink are mixed. There is also a problem that the tint of the formed black image and the tint of the black image on the plain paper formed in the same manner are different.

[0003]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to solve the above problems of the prior art and to produce a black image on plain paper formed by combining a yellow ink, a magenta ink and a cyan ink. Inkjet recording in which the tint is good without giving a reddish tint, and the tint of this black image on plain paper does not differ from the tint of a black image similarly obtained on special paper such as coated paper. A method, an inkjet cartridge, and an inkjet recording device are provided.

[0004]

The above object is achieved by the present invention described below. That is, the present invention provides an inkjet recording method for recording on a recording material by ejecting ink droplets of a plurality of colors from an orifice according to a recording signal,
An inkjet head having a plurality of ejection ports for ejecting a plurality of inks, which has a liquid chamber for temporarily holding the ink, is used, and at least three inks of yellow, cyan, and magenta are used by the inkjet head. When an ink image is formed by recording on the same recording material using a plurality of color inks including combinations, the chromaticity of each color ink image is at least −10 ≦ a in the yellow ink image. ^* ≦ 0, 60 ≦ b ^* ≦ 80, a ^* ≧ 50, −15 ≦ b ^* <0 for a magenta ink image, and −20 ≦ a ^* <0, −40 for a cyan ink image.
The inkjet recording method, the inkjet cartridge, and the inkjet recording apparatus are characterized in that ≦ b ^* ≦ −20. The chromaticity referred to here is a color space recommended by the International Commission on Illumination (abbreviated as CIE) in 1976, which has a perceptually nearly uniform rate, and is called CIELA.
It is called B, and is JIS Z 8722.
And JIS Z 8727, its explanation and calculation method are shown.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to preferred embodiments of the present invention. The inkjet recording method of the present invention is configured by using a specific inkjet head and using specific ones as a plurality of inks supplied to the inkjet head. First, the ink used in the present invention will be described. As the ink used in the present invention, at least three kinds of inks, that is, a yellow ink, a magenta ink and a cyan ink are used. When an image is recorded on the same recording material using these inks, It is characterized in that the chromaticity of each of these color images has the following specific relationship. Chromaticity here means 1 by the International Commission on Illumination (abbreviated as CIE).
It is a color space that has a perceptually nearly uniform rate recommended in 976, and is called CIELAB.
IS Z8722 and JIS Z 8727 show the explanation and calculation method. In the present invention,
When CIELAB is measured by the method of obtaining chromaticity from tristimulus values defined in JIS, the chromaticity of each ink image of at least yellow ink, magenta ink, and cyan ink on the same recording material But,
Inks having the following relationship (A) are used in combination. Relationship of chromaticity (A) Magenta ink image: a ^* ≧ 50, −15 ≦ b ^* <0, cyan ink image: −20 ≦ a ^* <0, −40 ≦ b ^* ≦
-20, yellow ink image: -10 ≦ a ^* ≦ 0, 60 ≦ b ^* ≦
80,

In the present invention, each ink used has a CIE of an image recorded on a recording material using these inks.
When the measured values of a ^* and b ^* of LAB satisfy the above relationship (A), yellow, magenta, and cyan inks have good color development, and these three colors of yellow, magenta, and cyan are good. The black image obtained by mixing the above inks by overprinting does not get reddish, and a high-quality image can be obtained. In particular, when the CIELAB b ^* measurement value of the black image thus formed satisfies the following relationship (B), a red-free black image is obtained, and a better high-quality image is obtained. can get. Relationship of chromaticity (B) Black image: b ^* <0

The following inks can be used in the present invention when the chromaticity of the recorded image of at least three colors of ink when recorded on a recording material such as plain paper can satisfy the relationship as described in (A) above. The following are listed. In the present invention,
Any ink can be used as long as it is an ink containing at least a coloring material and a liquid medium that is used in a general inkjet recording method, but preferably yellow,
Multiple inks are used, including a combination of three magenta and cyan inks. Further, as a color material constituting each of these color inks, for example, a combination of cyan ink containing at least a copper phthalocyanine dye, and yellow ink and magenta ink containing at least a dimer dye, respectively. It is preferable to use ink. More preferably, the coloring material at this time contains a dye having a carboxyl group as a water-soluble group.

Specific examples of the copper phthalocyanine dye used in the present invention include C.I. I. Direct Blue 199, C.I. I. Direct Blue 86, or those obtained by adding a carboxyl group as a water-soluble group to these, or the like can be given. The content of such a copper phthalocyanine dye is preferably about 0.5 to 8.0% by weight in the ink. In the present invention, the ink can be produced by a usual method, but at the time of production, the ink containing the copper phthalocyanine dye as described above is recorded on the recording material such as plain paper. In this case, the measured chromaticity of the obtained ink image is −20 ≦ a ^* <
0, −40 ≦ b ^* ≦ −20, the kind and content of the coloring material are adjusted. Since the copper phthalocyanine dye has high stability and strong color tone, it is possible to appropriately achieve the above-mentioned chromaticity even with a small amount, and an ink having a clear color tone can be obtained.

In the present invention, at least a dimer dye, more preferably a dye having a carboxyl group as at least a water-soluble group, is used as a coloring material for yellow ink and magenta ink. Furthermore, in the present invention, a yellow ink containing at least a coloring material represented by the following general formula (I) and at least the following general formula (I)
It is preferably used in combination with the magenta ink containing the color material represented by I). That is, with such a configuration, when the cyan ink containing the above-mentioned copper phthalocyanine coloring material is used in addition to these, when three colors of ink are overlaid and a black ink is synthesized, a reddish tint is produced. And a better black image can be obtained.
Further, the water resistance of each color can be improved.

General formula (I) {In the formula (I), Ar and Ar ₁ are each independently an aryl group or a substituted aryl group, and at least one of Ar and Ar ₁ is a substituent selected from a sulfone group, a carboxyl group and a thiocarboxyl group. Has at least one group,
n is 0 or 1, and J and J ₁ are independently the following formulas (1) to (3). [In the formulas (1) to (3), each R ₅ is independently selected from a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, a halogen atom, a CN group, a ureido group and an NHCOR ₆ group, and R ₆ Is a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group or a substituted aralkyl group, T is independently an alkyl group, W is independently a hydrogen atom, a CN group, CONR ₁₀ R ₁₁
Group, a pyridinium group and a COOH group, m is a C _{2 to} C ₈ alkylene chain, B is a hydrogen atom, an alkyl group or a COOH group, and R ₁₀ and R ₁₁ are each independently a hydrogen atom. , An alkyl group or a substituted alkyl group. ], R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group or a substituted alkyl group, L is a divalent linking group, and X is independent. Carbonyl group or the following formulas (4) to (6) [In the above formulas (4) to (6), Z is OR ₇ , SR ₇ or NR.
₈ R ₉ ; Y is a hydrogen atom, chlorine atom, CN group or Z, E is a chlorine atom or CN group, R ₇ , R ₈ and R
₉ is independently a hydrogen atom, an alkenyl group, a substituted alkenyl group, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group or a substituted aralkyl group, or R ₈ and R ₉ are these groups. May form a 5- or 6-membered ring together with the nitrogen atom to which is bonded. ] The compound of (a) is a SO ₃ H group (in the present specification, this term means a salt with a free sulfonic acid or any base in the text and structural formulas). In the case of not having at least two COOH groups and COSH groups, the compound of (a) is S
When it has O ₃ H groups, it has at least as many groups selected from COOH groups and COSH groups as SO ₃ H groups. ｝

General formula (II) Ar ₁ -N = N-J-X- (NR ₁ -L-NR ₂ -X) _n -J
During -N = N-Ar ₂ {formula (II), J is the following formula, Ar ₁ and Ar ₂ are each an aryl group or a substituted aryl group, and at least one of Ar ₁ and Ar ₂ is a COOH group and C
R having at least one substituent selected from the OSH group,
₁ and R ₂ are independently a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group or a substituted alkenyl group, and L is 2
Is a valent linking group, n is 0 or 1, X is independently a carbonyl group or the following formulas (1) to (3) [In the formulas (1) to (3), Z is independently NR ₃ R ₄ and SR ₅
Or OR ₅ and Y is independently a hydrogen atom, a chlorine atom,
Z, SR ₆ or OR ₆ , E is independently a chlorine atom or a CN group, and R ₃ , R ₄ , R ₅ , and R ₆ are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, or an alkenyl. A group, a substituted alkenyl group, an aryl group, a substituted aryl group, an aralkyl group or a substituted aralkyl group, or R ₃ and R ₄ together with the nitrogen atom to which they are bonded form a 5- or 6-membered ring. There is a case. ] The compound (b) has at least as many groups selected from COOH groups and COSH groups as the number of SO ₃ H groups. ｝

Among the compounds represented by the general formula (I) as described above, preferred compounds are Ar and Ar ₁ as a substituent.
Is an aryl group or a substituted aryl group having at least one carboxyl group, J and J ₁ are groups represented by the formula (1) or (2), and X is the formula (4) or (5). Is a compound represented by. Specific examples of more preferable compounds represented by the general formula (I) are shown below.

[0013]

[0014]

Among the compounds represented by the general formula (II), preferred compounds are an aryl group or a substituted aryl group in which Ar and Ar ₁ have at least one carboxyl group as a substituent, and X is a carbonyl group or the above. Formula (1)
Alternatively, it is a compound having a group represented by (2). Specific examples of more preferable compounds represented by the general formula (II) are shown below.

[0016]

[0017]

[0018]

The content of the coloring material as described above is preferably about 0.5 to 7.5% by weight in the ink. Further, the yellow ink and the magenta ink can be produced by the usual method similarly to the cyan ink. However, at the time of the production, the ink containing the coloring material as described above is used to record on a plain paper or the like. The measured chromaticity of the image formed on the material is −10 ≦ a ^* ≦ 0 for the yellow ink image,
In the image of magenta ink so that 60 ≦ b ^* ≦ 80, it is necessary to adjust the ink composition so that a ^* ≧ 50 and −15 ≦ b ^* <0.

Further, in the present invention, it is preferable to use the compound represented by the following general formula (A) together in the ink since the color mixture bleeding between different colors is good. General formula (A) (In the formula, a and b each represent an integer of 1 to 2, and n and m each represent an integer of 3 to 20)

The compound represented by the general formula (A) used in the present invention may be any compound as long as it has the above-mentioned structure, but a compound having a value of n + m in the range of 10 to 15 Is more preferable. Further, the above general formula (A)
As the content of the compound represented by in the ink,
It is preferable to add about 0.5 to 5% by weight to the ink. When the amount is less than 0.5% by weight, the color mixture bleeding between different colors is poor, and when the amount is more than 5% by weight, the color mixture bleeding between different colors is good, but the color development is deteriorated, which is not preferable.

Next, other constituent components of the ink used in the present invention will be described. The liquid medium used in the ink of the present invention is preferably a mixture of water and a water-soluble organic solvent. As the water-soluble organic solvent, it is preferable that the water-soluble organic solvent itself has a low vapor pressure, slows down the evaporation temperature of water in the ink, and has the solubility of a dye or the like, and thus has an effect as a fixing property improving agent. .

Preferred water-soluble organic solvents include polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, and Alkylene glycols having an alkylene group of 2 to 6 carbon atoms such as xylene glycol and diethylene glycol; glycerin; lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether and diethylene glycol monomethyl (or ethyl) ether Methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-bryl alcohol, ter -Alcohols such as butyl alcohol, isobutyl alcohol, benzyl alcohol and cyclohexanol; amides such as dimethylformamide and dimethylacetamide; ketones or ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; N- Examples thereof include nitrogen-containing heterocyclic ketones such as methyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone.

Among these, preferable solvents are ethylene glycol, triethylene glycol, hexylene glycol, diethylene glycol, thiodiglycol, glycerin, ethyl alcohol, isopropyl alcohol, cyclohexanol, etc. It is preferably 1 to 30% by weight.

Further, in the present invention, in order to enable smooth recording, the surface tension of the ink of each color composed of the coloring material and the liquid medium as described above should be 40 dyne / cm or less. In addition to these requirements, it is more preferable that the surface tension of the black ink is 35 dyne / cm or less when at least the yellow ink, the magenta ink, and the cyan ink are mixed at the same ratio and synthesized. It is preferable to use a combination of various inks. When an image is formed using such a combination of inks, a sharp black image without line thickening is obtained, and a higher quality image can be obtained. Furthermore, the surface tension of each ink,
Further, it is more preferable that the surface tension of the black ink is 25 dyne / cm or more when at least the yellow ink, the magenta ink and the cyan ink are mixed in the same ratio. The reason for this is that the value of the surface tension of the ink is 25 dyne.
This is because if it is less than / cm, the color developability and bleeding of each color deteriorate, and a good image cannot be obtained.

Therefore, the ink used in the present invention contains a nonionic surfactant, an ionic and amphoteric surfactant in order to adjust the surface tension to the above value and to improve the fixing property. Etc. can be contained. The surfactant that can be used in the present invention is not particularly limited,
Desirable ones are nonionic surfactants such as ethylene oxide adducts of alkyl phenyl ethers, polyethylene oxide-polypropylene oxide copolymers, ethylene oxide adducts of acetylene glycol, etc. 1 ~
It is in the range of about 10% by weight. The components of the ink used in the present invention are as described above, but in addition, if necessary, an antifungal agent, urea and its derivatives, thiourea and its derivatives and the like are within the range not hindering the achievement of the object of the present invention. Can be added at.

Next, an ink cartridge preferably used in the ink jet recording method of the present invention, which contains a plurality of colors of ink having the above-mentioned structure, will be described. The ink jet cartridge of the present invention comprises an ink jet head portion having a plurality of ejection ports and an ink tank portion, the interior of the ink tank portion is divided into a plurality of regions, and inks of different colors are respectively filled in the respective regions. It is stored. The respective regions of the ink tank section and the ejection ports of the inkjet head section are connected by a plurality of ink supply tubes, respectively, and the ink is supplied to the inkjet head section through these ink supply tubes. Has been done. Further, in the inkjet cartridge of the present invention, a plurality of regions for accommodating the plurality of inks in the ink tank are arranged in a line, and the ink supply pipes are provided vertically to the plurality of regions. At this time, a plurality of ink supply pipes may be arranged in parallel at the ends of a plurality of regions near the ejection openings of the inkjet head.

In addition, a plurality of areas in the ink tank are respectively
The atmosphere communication port that connects the internal space and the external space, the ink absorber that absorbs and holds the ink stored in each region, and the ink absorber that holds the inner wall surface of each region so that they do not adhere Then, a rib for providing a space connecting from the atmosphere communication port to a position of the ink tank farthest from the position where the ink supply pipe is arranged may be provided, and at this time, a compression direction of the ink absorber is provided. On the other hand, the ink supply pipe may be arranged vertically.

Further, in any of the above-mentioned ink jet cartridges, the ink jet head has an energy generating element for generating energy for ejecting the ink jet ink, and the energy generating element is driven based on an electric signal. Recording is preferably performed by ejecting ink from an ejection port provided in the inkjet head. Further, an electrothermal converter for generating thermal energy for ejecting ink may be provided as the energy generating element.

In the ink jet cartridge of the present invention configured as described above, the areas for containing the ink are arranged in a line, and the ink supply tubes are arranged vertically in the respective areas so that the ink supply tubes The length can be made uniform.
Further, at this time, the flow of the liquid chamber can be minimized by disposing the ink supply pipes at the end portions of the respective regions near the ejection port.

Next, the above ink jet cartridge will be described in more detail with reference to the drawings. FIG. 1 is a perspective view in an exploded state for explaining the configuration of the inkjet cartridge of the present invention, and FIG. 2 shows the configuration of a cap member inserted into the atmosphere communication port 110 of the color ink tank 10 shown in FIG. It is a perspective view. As shown in FIG. 1, the inkjet cartridge of the present invention includes a color ink tank 10 that contains ink, an inkjet head 20 that discharges the ink, and an ink supply body that connects the ink tank and the head. .

The color ink tank 10 includes a housing 100 for containing ink and a lid member 1 for sealing the housing 100.
04 and. In the example shown in FIG. 1, the inside of the housing 100 has two partitions arranged in parallel in order to separately store three color inks of yellow (Y), cyan (C) and magenta (M). It is divided into three regions by a member (not shown). The ink absorbers 101, 10 for absorbing and holding ink are provided in the respective areas.
2 and 103 are stored. Three ink supply ports 105, 106 and 107 are provided on the ink jet head mounting surface 111 of the housing 100 corresponding to the respective areas. Further, in order to prevent the negative pressure inside the housing 100 from rising when ink is supplied from each region,
Atmosphere communication port that communicates the air in each area with the outside air,
108, 109 and 110 are provided, and a cap member 112 for preventing evaporation of ink as shown in FIG. 2 is inserted into each of the atmosphere communication ports 108, 109 and 110, respectively. As shown in FIG. 2, the cap member 11
2 is provided with pores, and the pores ensure communication between the air in each region and the outside air.

The ink jet head 20 has ink supply tubes 21, 22 and 23 for drawing out each ink from the color ink tank 10 and a flow for temporarily holding each ink and supplying the ink to the ink ejecting portion. The passage 24, a nozzle portion (not shown) in which an energy generating element for generating energy for ejecting ink is formed, and an ejection port (formed at the bottom portion, not shown) for ejecting ink. The ink supply pipes 21, 22 and 23 are inserted into the ink supply ports 105, 106 and 107, respectively, when the inkjet head 20 is attached to the color ink tank 10, and the tip of the ink supply pipe is the ink absorber 101,
It is pressed against 102 and 103. As a result, the ink absorbers 101, 102 and 103 are compressed and the capillary force is increased, so that the ink is stably guided from the ink tank 10 to the inkjet head 20.

Further, each ink supply port 105, 106 and 1
At 07, the inserted ink supply tubes 21, 22 and 23 are inserted.
Packings 31, 32, and 33 for closing the gap between the ink supply port 1 and the packing are attached.
Ink leakage from 05, 106 and 107 is prevented.

Here, as shown in FIG. 1, the areas for containing ink are arranged in a line in the horizontal direction, and the ink supply pipe 2 is provided.
1, 22, and 23 are vertically inserted into the ink supply ports 105, 106, and 107 with respect to the respective regions. With such a configuration, the lengths of the ink supply tubes 21, 22 and 23 for supplying the ink to the inkjet head 20 can be made uniform. Also, by disposing the installation positions of the ink supply pipes 21, 22 and 23 in parallel below the color ink tank 10 close to the ejection port, the lengths of the ink supply pipes 21, 22 and 23 and the flow path 24 can be minimized. Can be Therefore, each ink supply pipe 21, 2
There is no difference in flow resistance due to the difference in length between 2 and 23,
Since it is possible to prevent the flow resistance of the flow path 24 from increasing, it becomes possible to stably supply the ink to the inkjet head 20, and to obtain stable ejection characteristics.

By the way, as shown in FIG. 1, ribs 1001 are provided on the upper surface of each region inside the housing 100, and partial ribs 1041 are provided on the lid member 104. For example, as shown in the figure, the ribs 1001 are provided in parallel with the longitudinal direction of each region, and the partial ribs 1041 are provided on the extension line of the ribs 1001 on the inner surface of the lid member 104. By providing these ribs 1001 and partial ribs 1041, it is possible to prevent the ink absorbers 101, 102, and 103 from coming into close contact with the inner surfaces of the respective regions.
A space is formed that communicates from a portion where the atmosphere communication ports 108, 109 and 110 are provided to a portion of the ink tank farthest from the ink supply ports 105, 106 and 107.

As described above, the internal space of the housing 100 and the external space are communicated with each other through the atmosphere communication ports 108, 109 and 110, the rib 1001 and the partial rib 1041. Since the ink does not stay, there is no risk of the ink leaking from the ink supply ports 105, 106 and 107 and the air communication ports 108, 109 and 110, and the ink consumption efficiency improves.
Further, even if the ambient temperature of the color ink tank 10 rises during recording of an image, the ink in the housing 100 is not pushed out to the outside. Further, since it is possible to reliably prevent the negative pressure in the housing 100 from rising, the ink supply port 105,
It is possible to more reliably guide the ink farthest from 106 and 107 to the respective ink supply ports 105, 106 and 107.

In the above description, the cap member 112 provided with the pores is connected to the atmosphere communication ports 108, 109 and 110.
The case where the cap member 112 is inserted is shown as an example.
Is not always necessary, and as shown in FIG. 3, the pores 42, 43 and 4 are directly provided in the casing 41 of the color ink tank 40.
4 may be provided.

[0039]

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the text, "part" and "%" are based on weight unless otherwise specified. After thoroughly stirring the ink compositions each having the following composition, pressure filtration was performed with a fluoropore filter (manufactured by Sumitomo Electric Industries, Ltd.) having a pore size of 0.22 μm to prepare three color inks used in the present invention. .
At the time of preparation, the ink was prepared so that the chromaticity and surface tension of each color ink when the recording material of the ink was plain paper were the values described in the parentheses.

Example 1 Yellow ink (chromaticity: −10 ≦ a ^* ≦ 0, 60 ≦ b ^* ≦ 80, surface tension: 31 d yne / cm) C.I. I. Direct Yellow 86 0.3% -Coloring material of Exemplified Compound 1 2.5% -Thiodiglycol 10.0% -Urea 5.0% -Compound of General Formula (A) (n + m = 10, a and b = 1) ) 1.0% -Pure water 81.2% Magenta ink (chromaticity: a ^* ≥50, -15≤b ^* <0, surface tension: 32 dyne / cm) -Color material of Exemplified Compound 6 2.5%- Thiodiglycol 10.0% -Urea 5.0% -Compound of general formula (A) (n + m = 10, a and b = 1) 1.0% -Pure water 81.5%

Cyan ink (chromaticity: −20 ≦ a ^* <0, −40 ≦ b ^* ≦ −20, surface tension: 30 dyne / cm) C.I. I. Direct Blue 199 3.5% -Thiodiglycol 10.0% -Urea 5.0% -Compound of general formula (A) (n + m = 10, a and b = 1) 1.0% -Pure water 80.5 % When the chromaticity of the black image obtained by repeatedly striking the three color inks of the yellow ink, the magenta ink and the cyan ink obtained above was measured, it was b ^* <0. or,
When the surface tension was measured by mixing the three color inks used in this example at the same ratio, the surface tension was 30 dyne /
cm.

[0042] Example 2 Yellow Ink ^{(chromaticity: -10 ≦ a * ≦ 0,60 ≦} b * ≦ 80, surface tension: 32d yne / cm) · C. I. Direct Yellow 142 1.0% -Coloring material of Exemplified Compound 1 2.5% -Glycerin 10.0% -Ethylene glycol 5.0% -Urea 5.0% -Compound of general formula (A) (n + m = 15, a and b = 1) 1.0% -Pure water 76.5% Magenta ink (chromaticity: a ^* ≥50, -15≤b ^* <0, surface tension: 29 dyne / cm))-Color of Exemplified Compound 6 Material 3.0% -Glycerin 10.0% -Ethylene glycol 5.0% -Urea 5.0% -Compound of general formula (A) (n + m = 15, a and b = 1) 1.0% -Pure water 76.0%

Cyan ink (chromaticity: -20≤a ^* <0, -40≤b ^* ≤-20, surface tension: 31 dyne / cm) C.I. I. Direct Blue 199 3.5% C.I. I. Acid Blue 9 0.5% -Glycerin 10.0% -Ethylene glycol 10.0% -Compound of general formula (A) (n + m = 15, a and b = 2) 1.0% -Pure water 75.0% When the chromaticity of the black image obtained by repeatedly striking the three color inks of the yellow ink, the magenta ink and the cyan ink obtained above was measured, it was b ^* <0. or,
When the surface tension was measured by mixing the three color inks used in this example at the same ratio, the surface tension was 29 dyne /
cm.

[0044]Comparative Example 1 Among the inks of Example 1, the color material of yellow ink
C. I. Instead of Direct Yellow 86 only, this inn
Image on plain paper similar to that measured in the example
And the chromaticity is 0 ≦ a^*≦ 15, 60 ≦ b^*≤8
Except that the yellow ink was set to 0
Same as Example 1. That is, magenta ink and cyan ink
For the link, use the same ones as in Example 1, and assemble them.
The inks used in Comparative Example 1 were combined. In this comparative example
Used yellow ink, magenta ink and cyan ink
Of a black image obtained by stacking three inks of different colors
When chromaticity was measured, b^*> 0.

Comparative Example 2 Among the inks of Example 1, the color material of magenta ink was C.I. I. Using this ink instead of Acid Red 289, an image is formed on the same plain paper as that measured in the example, and the chromaticity is 50 ≦ a ^* ≦ 70, 0 ≦ b ^* ≦ 15. Example 1 except that the magenta ink
Same as. That is, the same yellow ink and cyan ink as those used in Example 1 were used, and the inks used in Comparative Example 1 were combined. When the chromaticity of the black image obtained by repeatedly striking the three color inks of the yellow ink, the magenta ink and the cyan ink used in this comparative example was measured, it was b ^* > 0.

[Evaluation] BJC-4000 (commercial product) was used as an ink jet recording apparatus by using a combination of three color inks of yellow ink, magenta ink and cyan ink used in Examples 1 and 2 and Comparative Examples 1 and 2 described above. Inkjet recording was performed with a printer that operates the ink cartridge shown in FIG. 1 and manufactured by Canon Inc.) to form a recorded image. At this time, as the recording material, proper-bond paper is used as plain paper, LC-101 paper (trade name, manufactured by Canon Inc.) is used as special paper for inkjet, and each color ink is used alone to obtain a single color image. Was formed, and three colors of ink, yellow ink, magenta ink, and cyan ink, were overlaid, and these three colors of ink were mixed to form a black image. The obtained images were evaluated according to the following criteria, and the results are shown in Table 1.

(Evaluation Items and Evaluation Criteria) Tint of Black Image of Three Colors 1 The tint of the black image formed on the recording material was visually observed and compared, and evaluated according to the following criteria. ○: The black image is not reddish and the image is sharp. ×: The black image is reddish, and the image has no sharpness or impact. The tint of the black image consisting of 3 colors 2 Normal The difference in tint between the black image formed on the paper and the black image formed on the special paper was visually observed and compared, and evaluated according to the following criteria. ◯: The black images formed on the plain paper and the special paper have the same tint, and both black images are bluish or greenish. ×: Black between the plain paper and the special paper. The tint of the image was different, and one was reddish and the other was bluish or greenish.

Water resistance A plain ink is used as a recording material, and a printer using the ink jet cartridge of FIG. 1 is used as a printer. With a black ink obtained by overlapping printing of three colors of yellow, magenta and cyan. Print a character image,
After 1 hour of printing, the printed matter was held perpendicular to the ground, tap water was sprayed onto the printed surface with a commercially available mist, and the water resistance was evaluated according to the following criteria. ◯: Ink did not bleed around the characters, and tap water droplets contaminated with the ink coloring material did not flow from the characters. Δ: The ink was slightly blotted around the characters, but it was readable. A small amount of tap water droplets contaminated with the coloring material of the ink flowed, but was not noticeable on the recording material. X: Ink bleeds around the characters, making it difficult to read.
In addition, tap water droplets contaminated with the color material of the ink flowed to stain the recording material.

Table 1: Evaluation results

[0050]

As described above, according to the present invention, the color tone of the black image on the plain paper formed by combining at least the yellow ink, the magenta ink and the cyan ink is not reddish, A sharp high-quality image can be obtained, and the color tone of the black image on the plain paper does not differ from that of the black image on the special paper such as coated paper, and the image has excellent water resistance. An inkjet recording method, an inkjet cartridge, and an inkjet recording apparatus that can obtain the above are provided.

[Brief description of drawings]

FIG. 1 is a perspective view showing the configuration of an inkjet cartridge of the present invention.

FIG. 2 is a perspective view showing a configuration of a cap member that is inserted into an atmosphere communication port of the ink tank shown in FIG.

FIG. 3 is a perspective view showing a state where the atmosphere communication port of the inkjet cartridge shown in FIG. 1 is replaced with a pore.

4A and 4B are diagrams showing a configuration of a conventional inkjet cartridge, in which FIG. 4A is a front view, FIG. 4B is a side view, and FIG.
Is a bottom view.

5A and 5B are views showing a color ink tank mounted on the inkjet cartridge shown in FIG. 4, in which FIG. 5A is a partially cutaway side view, FIG. 5B is a partially broken front view, and FIG. ) Is a bottom view.

[Explanation of symbols]

 10, 40: Color ink tank 20: Inkjet cartridge 21, 22, 23: Ink supply pipe 24: Flow path 31, 32, 33: Packing 41, 100: Housing 42, 43, 44: Pore 101, 102, 103 : Ink absorber 104: Lid member 105, 106, 107: Ink supply port 108, 109, 110: Atmosphere communication port 111: Inkjet head mounting surface 112: Cap member 1001: Rib 1041: Partial rib

Claims (13)

[Claims] 1. An ink jet recording method for recording on a recording material by ejecting ink droplets of a plurality of colors from an orifice in response to a recording signal, a plurality of inks provided with a liquid chamber for temporarily holding the inks. The same recording material is formed by using an inkjet head in which a plurality of ejection ports for ejecting are formed, and the inkjet head uses a plurality of color inks including at least a combination of three color inks of yellow, cyan, and magenta. When an ink image is formed by recording on top, the chromaticity of each color ink image is at least −10 ≦ a ^* ≦ 0 for a yellow ink image,
60 ≦ b ^* ≦ 80, and a ^* ≧ for a magenta ink image
50, −15 ≦ b ^* <0, and −20 ≦ a ^* <0, −40 ≦ b ^* ≦ −20 for a cyan ink image. 2. A chromaticity of a black image formed by stacking a plurality of color inks containing a combination of at least three color inks of yellow, cyan and magenta on a recording material has b ^* <0. The inkjet recording method according to claim 1, wherein 3. The surface tension of each of the plurality of colors of ink is 4
0 dyne / cm or less, and the surface tension of the ink is 30 dyne / cm when at least the yellow ink, the magenta ink, and the cyan ink are mixed at the same ratio.
The inkjet recording method according to claim 1, wherein: 4. The ink jet recording method according to claim 1, wherein the compound of the following general formula (A) is used together as an ink component in each of the inks of a plurality of colors. General formula (A) (In the formula, a and b each represent an integer of 1 to 2, and n and m each represent an integer of 3 to 20) 5. The yellow coloring material contained in the yellow ink and the magenta coloring material contained in the magenta ink are dimer dyes, and the cyan coloring material contained in the cyan ink is a copper phthalocyanine dye. Item 2. The inkjet recording method according to Item 1. 6. The inkjet recording method according to claim 1, wherein the yellow coloring material and the magenta coloring material contain at least a coloring material having a carboxyl group as a water-soluble group. 7. As a coloring material having at least a carboxyl group as a water-soluble group, the coloring material of yellow ink contains at least the coloring material represented by the following general formula (I), and the coloring material of magenta ink The inkjet recording method according to claim 1, wherein the ink contains at least a coloring material represented by the following general formula (II). General formula (I) {In the formula (I), Ar and Ar ₁ are each independently an aryl group or a substituted aryl group, and at least one of Ar and Ar ₁ is at least a substituent selected from a sulfone group, a carboxyl group and a thiocarboxyl group. Have one and n is 0
Or 1, and J and J ₁ are independently the following formulas (1) to (3) [In the formulas (1) to (3), each R ₅ is independently selected from a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, a halogen atom, a CN group, a ureido group and an NHCOR ₆ group, and R ₆ Are hydrogen atoms, alkyl groups, substituted alkyl groups, aryl groups, substituted aryl groups, aralkyl groups or substituted aralkyl groups, T is independently an alkyl group, W is independently a hydrogen atom, a CN group. , CONR _1O R
Selected from ₁₁ groups, pyridinium group and COOH group, m
Is an alkylene chain of C ₂ -C _8, B is a hydrogen atom, an alkyl group or a COOH group, R _10, R ₁₁ are the respective independently, a hydrogen atom, an alkyl group or a substituted alkyl group. ], R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group or a substituted alkyl group, L is a divalent linking group, and X is Independently of a carbonyl group or the following formulas (4) to (6) [In the above formulas (4) to (6), Z is OR ₇ , SR ₇ or NR.
₈ R ₉ and Y is hydrogen atom, chlorine atom, CN group or Z
And E is a chlorine atom or a CN group, and R ₇ , R ₈ and R are
₉ is independently a hydrogen atom, an alkenyl group, a substituted alkenyl group, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group or a substituted aralkyl group, or R ₈ and R ₉ are these groups. May form a 5- or 6-membered ring together with the nitrogen atom to which is bonded. ] The compound of general formula (I) is SO
_At least two COOH if not having a ₃ H group (as used herein, the term means a salt with a free sulfonic acid or any base in the text and structural formulas).
Group and a group selected from COSH group, and when the compound of (I) has SO ₃ H group, COOH group and COSH group
It has at least as many groups selected from the groups as SO ₃ H groups. } General formula _{(II) Ar 1 -N = N} -J-X- (NR 1 -L-NR 2 -X) n -J-
N = N-Ar ₂ {In the formula (II), J is the following formula, Ar ₁ and Ar ₂ are each an aryl group or a substituted aryl group, and at least one of Ar ₁ and Ar ₂ is a COOH group and C
R having at least one substituent selected from the OSH group,
₁ and R ₂ are independently a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group or a substituted alkenyl group, and L is 2
Is a valent linking group, n is 0 or 1, X is independently a carbonyl group or the following formulas (1) to (3) [In the above formulas (1) to (3), Z is independently NR ₃ R ₄ ,
SR ₅ or OR ₅ , Y is independently hydrogen atom, chlorine atom, Z, SR ₆ or OR ₆ , E is independently chlorine atom or CN group, and R ₃ , R ₄ , R ₅ , R ₆ are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, an aralkyl group or a substituted aralkyl group, or R ₃ and R ₄ together with the nitrogen atom to which they are bound 5
A member ring or a 6-membered ring may be formed. ] The compound of (b) is a linking group represented by
It has at least as many groups selected from H groups as SO ₃ H groups. ｝ 8. An ink jet head having a plurality of ejection ports for ejecting ink, which has a liquid chamber for temporarily holding a plurality of inks, and a plurality of inks supplied to the ink jet heads, respectively. And an ink tank whose inside is divided into a plurality of regions, and a plurality of regions provided in the ink tank for guiding the ink from the ink tank to the inkjet head, respectively. In an ink jet cartridge having a plurality of ink supply pipes, the plurality of regions are provided in a line, and the plurality of ink supply pipes are arranged vertically to the plurality of regions, respectively, and further, an ink tank. A plurality of color inks containing a combination of at least three color inks of yellow, cyan and magenta, which are separately stored in When these were used to measure the chromaticity of ink images formed on the same recording material, at least for yellow ink images, −10 ≦ a ^* ≦ 0, 60 ≦
b ^* ≦ 80, and for a magenta ink image, a ^* ≧ 5
0, −15 ≦ b ^* <0, and in the cyan ink image −
20 ≦ a ^* <0, −40 ≦ b ^* ≦ −20, an inkjet cartridge. 9. The plurality of ink supply pipes are arranged in parallel at the ends of the plurality of regions provided in the ink tank, which face the ejection openings provided in the inkjet head, respectively. The inkjet cartridge described in. 10. An atmosphere communication port for communicating the space inside the ink tank with the space outside the ink tank, and the ink stored in each area is absorbed in each of the plurality of areas provided in the ink tank. And an ink absorber for holding the ink absorber so that the ink absorber does not come into close contact with the inner surface of each region, and from the portion where the atmosphere communication port is provided to the arrangement portion of the ink supply pipe. 9. The ink jet cartridge according to claim 8, further comprising a rib for providing a space that continues to the most distant site in the area. 11. The ink jet cartridge according to claim 9, wherein the ink supply pipe is arranged perpendicular to the compression direction of the ink absorber. 12. An inkjet recording apparatus having the inkjet cartridge according to claim 8, wherein an energy generating element for generating energy for ejecting ink is provided in the inkjet head portion, and the energy generating element is based on an electric signal. An ink jet recording apparatus characterized in that ink is ejected from an ejection port of an ink jet head when driven to perform recording. 13. The ink jet recording apparatus according to claim 12, wherein the energy generating element includes an electrothermal converter for generating thermal energy for ejecting ink.