JPH0699656A - Color image forming method - Google Patents

Abstract

PURPOSE:To obtain a high-quality color image using a colorant superior in shelf stability in a solvent by incorporating a dye shown by a specific general formula as a colorant in each of magenta ink, yellow ink, and cyan ink. CONSTITUTION:As a colorant, magenta ink incorporates one or more kinds of dyes shown by a formula I (Q1-Q4 individually respresent benzene ring or naphthalene ring; X represents -O- bond or the like; and (n) is 0 or 1). As a colorant, yellow ink incorporates one or more kinds of dyes shown by a formula II (Q is -NHCONH- bond or the like; X1, X2 are hydrogen atom or the like; R is methyl group or the like; and (n) is 0 or 1). As a colorant, cyan ink incorporates one or more kinds of dyes shown by a formula III (M is an alkali metal or the like; (m) is 1-4; and (n) is 0-3). As a colorant, black ink incorporates one or more kinds of dyes selected out of acid, neutral, and basic carbon blacks. This is used for forming a color image.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a color image, and more particularly to a method for forming a color image using a combination of yellow, magenta, cyan and black aqueous inks. The present invention relates to a color image forming method by an ink jet method in which ink is ejected from an orifice of a recording head by the action of thermal energy to form a color image on a recording material such as paper and a resin film. Further, the present invention relates to a method for forming a color image by an inkjet method in which the obtained image has improved fastness such as water resistance, light resistance and ozone resistance.

[0002]

2. Description of the Related Art An ink jet recording system has advantages that noise is not generated during recording and a high resolution recording image can be obtained at a high speed by using a highly integrated head. In such an inkjet recording system, a color image is formed by using, as the ink, inks having a plurality of different hues in which various water-soluble dyes and pigments are dissolved or dispersed in water or a mixed liquid of water and an organic solvent. It is possible to By the way, the following performance is required for the ink formed by the inkjet method. (1) An image excellent in water resistance, light resistance, abrasion resistance and the like can be obtained. (2) It is possible to obtain an image excellent in ozone resistance without causing discoloration due to ozone, temperature and humidity even in a place where light is not irradiated. (3) The resolution or color reproducibility in color imaging is excellent not only on coated paper but also on plain paper. (4) A color image having a high optical density and a clear color tone can be obtained. (5) It has high dissolution stability or storage stability with respect to liquid medium components, and is unlikely to cause clogging of the discharge orifice. Particularly in the case of forming a color image, if the ink fastness is poor even with one type of ink of each hue of yellow, magenta, cyan and black, the quality of the entire image will be impaired.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a color image which has all of the above-mentioned requirements (1) to (5) in a well-balanced manner and forms a sufficiently satisfactory color image. It is to provide a method for forming an image.

[0004]

The above objects can be achieved by the present invention described below. That is, the first invention of the present invention is a method of forming a color image by an inkjet method using each of yellow, magenta, cyan and black aqueous inks, wherein the following general formula (I) is used as a coloring material in the magenta ink. Contains one or more dyes represented,
Further, the yellow ink contains at least one kind of dye represented by the following general formula (II) as a coloring material, and the cyan ink contains at least one kind of dye represented by the following general formula (III) as a coloring material. In addition, at least one pigment selected from acidic carbon black, neutral carbon black and basic carbon black is contained as a coloring material of the black ink.

[Chemical 10] [However, Q _{1 to} Q ₄ in the above formula are each a sulfonic acid group,
A benzene ring or a naphthalene ring which may be substituted with a carboxyl group, an amino group, an anilino group or an acetylamino group, a hydroxyl group, a chloro group, an alkyl group or an alkoxyl group, and X is -NHCONH-, -NH-, -O. -Or

[Chemical 11] (R ₁ and R ₂ are a hydrogen atom or a hydroxyethyl group), n is 0 or 1, and the sulfonic acid group and the carboxyl group are any of an alkali metal atom, ammonia and an organic amine. It is salted with that base. ]

[Chemical 12] (However, Q in the above formula is -NHCONH- or

[Chemical 13] Represents a bond, X ₁ and X ₂ are a hydrogen atom, —SO ₃ M, —
COOM or a phenyl group substituted with a hydroxyl group and a naphthyl group, R represents a methyl group or a methoxy group, and n
Represents 0 or 1, and M represents an alkali metal, ammonium or an organic amine. )

[Chemical 14] (However, in the above formula, M represents an alkali metal, ammonium or an organic amine, m is 1 to 4, n is 0 to 3
Is. )

A second invention of the present invention is a method of forming a color image by an ink jet system using each of yellow, magenta, cyan and black aqueous inks. I)
Contains at least one type of dye represented by the following general formula (II) as a coloring material in the yellow ink, and contains at least one general formula (II) as a coloring material in the cyan ink. Characterized by containing at least one type of dye represented by III) and at least one type of pigment selected from acidic carbon black, neutral carbon black and basic carbon black as a coloring material for black ink And a method for forming a color image.

[Chemical 15] [Wherein R represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower acylamino group, a nitro group or a halogen atom, and X represents an acetyl group, a benzoyl group, a paratoluenesulfonyl group, 4-chloro- Represents any of a 6-hydroxy-1,3,5-triazin-2-yl group, M represents an alkali metal, ammonium or an organic amine, l represents 0 to 2, m or n represents 0 or 1. . ]

[Chemical 16] (However, Q in the above formula is -NHCONH- or

[Chemical 17] Represents a bond, X ₁ and X ₂ are a hydrogen atom, —SO ₃ M, —
COOM or a phenyl group substituted with a hydroxyl group and a naphthyl group, R represents a methyl group or a methoxy group, and n
Represents 0 or 1, and M represents an alkali metal, ammonium or an organic amine. )

[Chemical 18] (However, in the above formula, M represents an alkali metal, ammonium or an organic amine, m is 1 to 4, n is 0 to 3
Is. )

[0006]

The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object. As a result, it was found that only the water-soluble dye was used as the coloring material of the ink for ink jet recording as in the conventional case (1). It was judged that the characteristics (1) to (5) could not be satisfied by the inks of each color, and a study on pigments was conducted. As a result, they have found that a color image satisfying all the characteristics (1) to (5) can be formed by using an ink in which a specific dye and pigment are combined, and the present invention has been completed. That is, the present invention uses an inkjet ink containing a specific dye or pigment, and applies thermal energy according to a recording signal to the ink to eject the ink as droplets from the fine holes for recording. A color image is formed by the ink jet recording method of performing. The ink used in the present invention contains a specific dye or pigment, and is composed of a water-soluble resin and an aqueous medium containing a polyhydric alcohol and an aliphatic monohydric alcohol. It is natural that various performances are required for dyes and pigments which are coloring materials in the water-based ink used in the inkjet system, but particularly when forming a color image,
In addition, it is important that each of the dyes and pigments of black, yellow, magenta, and cyan have a balanced performance of mutual water resistance, light resistance, ozone resistance, and a good color rendering relationship. is there. 3 with such characteristics
Although it has been extremely difficult to find a combination of primary color dyes and pigments, detailed studies by the present inventors have shown that the most excellent ink jets can be obtained by a group of specific dyes and pigments as described below. A method of forming a color image by the method has been realized.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to preferred embodiments. (First Invention) The present invention relates to a method of forming a color image by an inkjet method using yellow, magenta, cyan and black aqueous inks. First, as a coloring material of the magenta ink, the following general formula (I ) A dye containing one or more kinds of dyes is used.

[Chemical 19] [However, Q _{1 to} Q ₄ in the above formula are each benzene which may be substituted with a sulfonic acid group, a carboxyl group, an amino group, an anilino group or an acetylamino group, a hydroxyl group, a chloro group, an alkyl group or an alkoxyl group. Represents a ring or a naphthalene ring, X represents -NHCONH-, -NH-, -O-,
Or

[Chemical 20] (Provided that R ₁ and R ₂ in the formula are hydrogen atoms or hydroxyethyl groups), and n is 0 or 1.
The sulfonic acid group and the carboxyl group are salted with any one of alkali metal atom, ammonia and organic amine. ]

A second feature of the present invention is to use, as the coloring material for the yellow ink, one containing at least one dye represented by the following general formula (II).

[Chemical 21] (However, Q in the above formula is -NHCONH- or

[Chemical formula 22] Represents a bond, X ₁ and X ₂ are a hydrogen atom, —SO ₃ M, —
COOM or a phenyl group substituted with a hydroxyl group and a naphthyl group, R represents a methyl group or a methoxy group, and n
Represents 0 or 1, and M represents an alkali metal, ammonium or an organic amine. )

The third feature of the present invention is that the cyan ink contains at least one dye represented by the following general formula (III).

[Chemical formula 23] (However, in the above formula, M represents an alkali metal, ammonium or an organic amine, m is 1 to 4, n is 0 to 3
Is. )

The fourth feature of the present invention is that it contains at least one pigment selected from acidic carbon black, neutral carbon black and basic carbon black as a coloring material for the black ink. To do.
Here, as the acidic carbon black, for example, MA
7, MA8, # 2200B (Made by Mitsubishi Kasei), RAV
EN1255 (made in Colombia), REGAL400R,
MOGUL L (made by Cabot), Color Bla
ck FW1, Color Black FW18, C
color Black S170, Color Bla
ck S150, Printex U and the like.
Further, examples of the neutral and basic carbon black include NO. 2300, NO. 900, MCF88, N
O. 33, NO. 4000B, NO. 40, NO. Four
5, NO. 52, CF9, NO. 10B (Made by Mitsubishi Kasei), Regal 660R, Rrgal 330R
(Made by Cabot), PRINTEX35 (Made by Tegutsusa)
Etc.

Specific examples of the dye used in the present invention as described above include the followings. In the formulas shown below, the sulfonic acid group and the carboxyl group are shown as alkali metal salts, but it goes without saying that any other ammonium salt, amine salt or the like may be used.

Magenta dye

[Chemical formula 24]

[0013]

[Chemical 25]

[0014]

[Chemical formula 26]

Yellow dye

[Chemical 27]

[0016]

[Chemical 28]

[0017]

[Chemical 29]

Cyan dye

[Chemical 30]

[0019]

[Chemical 31]

Each of the magenta, cyan, and yellow water-based inks used in the present invention contains one or more of the dyes listed above as a coloring material, and therefore a plurality of dyes of the same color listed above. Of course, when including multiple,
Other dyes not included in the above dyes may be contained. That is, the above dyes may be used alone or in combination of two or more kinds, or other dyes such as other direct dyes and acid dyes may be used in combination with the dye as an essential component. Further, the black ink can be prepared from any of the black pigments described above. Magenta, cyan used in the present invention,
In the yellow dye ink, the content of each of the above-mentioned specific dyes in each ink is the type of liquid medium component,
Although it is determined depending on the properties required for the ink, etc., it is generally 0.
The range is 1 to 20%, preferably 0.5 to 15%, more preferably 1 to 10%. The dyes can of course be used alone or in combination of two or more, or other various dyes such as direct dyes and acid dyes can be used in combination with the dye as an essential component.

The content of the pigment used in the black ink used in the present invention varies depending on the kind of the pigment, but is generally 3 to 20% by weight, preferably 3 to 20% by weight relative to the ink. Used in the range of 12%. As the dispersant, a water-soluble resin used for dispersing a pigment can be used. As such a water-soluble resin, the water-soluble resin is soluble in an aqueous solution in which an amine or a base is dissolved and has a weight average molecular weight of 3,000 to. It should be in the range of 30,000. More preferably, any one in the range of 5,000 to 15,000 can be used. Specifically, natural polymers such as lignin sulfonate and shellac, styrene-acrylic acid-alkyl acrylate such as polyacrylic acid, styrene-acrylic acid copolymer, styrene-acrylic acid-ethyl acrylate copolymer, etc. S copolymer, styrene-maleic acid copolymer,
Styrene-maleic acid-acrylic acid alkyl ester copolymer, styrene-methacrylic acid copolymer, styrene-
Methacrylic acid-acrylic acid alkyl ester copolymer,
Styrene-maleic acid half ester copolymer, vinylnaphthalene-acrylic acid copolymer, vinylnaphthalene-
Examples thereof include maleic acid copolymer, styrene-maleic acid half ester-maleic anhydride copolymer, and salts thereof. The content of these water-soluble resins is such that the weight ratio of the pigment to the water-soluble resin is 10: 3 to 10: 0.1,
It is desirable to be in the range of 10: 3 to 10: 0.2, more preferably the amount of the water-soluble resin dissolved in the ink is 2% or less, preferably 1% of the total weight of the ink.
The following is desirable. When the amount of the pigment is more than the above range, the dispersion stability is deteriorated and the sedimentation of the pigment occurs. On the contrary, when the amount of the pigment is less than the above range, the foaming property of the ink is deteriorated and the thin film resistor on the pulse application is applied. Stable discharge cannot be obtained for a long period of time because insoluble matter accumulates in it.

A suitable aqueous medium in the ink used in the present invention is a mixed solvent of water and a water-soluble organic solvent.
Water is not ordinary water containing various ions,
It is preferable to use ion-exchanged water (deionized water),
The content is 10 to 60% by weight, more preferably 10 to
It is in the range of 50% by weight. In addition, a water-soluble organic solvent used by mixing with water can be used as an optional solvent component that can be used in combination. Examples of the aliphatic monohydric alcohol include alkyl alcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol and tert-butyl alcohol. To be Of these, ethyl alcohol and isopropyl alcohol are particularly preferable because they greatly improve the ejection stability of the ink. The content of the aliphatic monohydric alcohol is in the range of 3 to 15% by weight, more preferably 3 to 10% by weight. If the content is less than 3% by weight, it is not possible to always obtain stable ejection against changes in the driving conditions of the printer, and if it exceeds 15% by weight, the print quality of the printed matter tends to be impaired.

Examples of the polyhydric alcohol and / or its alkyl ether used in the present invention include polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol,
1,2,6-hexanetriol, thiodiglycol,
Alkylene glycols in which the alkylene group such as hexylene glycol and diethylene glycol contains 2 to 6 carbon atoms; glycerin; ethylene glycol monomethyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) Lower alkyl ethers of polyhydric alcohols such as ethers may be mentioned. The content of these polyhydric alcohols and / or their alkyl ethers is 10-
It is 50% by weight, more preferably in the range of 20 to 40% by weight, and if the content is less than 10% by weight, it is not sufficient to prevent clogging at the nozzle tip, and if it exceeds 50% by weight, the printed matter is The quality deteriorates.

The main components constituting the ink used in the present invention are as described above, but if necessary, a water-soluble organic solvent, a surfactant, a pH adjusting agent, a defoaming agent, a preservative, etc. may be used. May be. As water-soluble organic solvent that can be used,
Amides such as dimethylformamide and dimethylacetamide; ketones or keto alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; N-methyl-2-pyrrolidone, 1,3-
Examples thereof include dimethyl-2-imidazolidinone.

As the surfactant, anionic surfactants such as fatty acid salts, higher alcohol sulfate ester salts, liquid fatty oil sulfate ester salts and alkylallyl sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters , Nonionic surfactants such as polyoxyethylene sorbitan alkyl esters, and one or more of these can be appropriately selected and used. The amount used is preferably 0.01 to 5% by weight with respect to the total amount of ink. At this time, it is preferable to determine the amount of the surfactant added so that the surface tension of the ink becomes 35 dyne / cm or more. This is because the surface tension of the ink shows a value smaller than this, in the ink jet recording system such as the present invention, printing deviation due to wetting of the nozzle tip (deviation of ink droplet landing point), etc.
This is because it causes an unfavorable situation.
Examples of the pH adjuster include various organic amines such as diethanolamine and triethanolamine, inorganic alkali agents such as alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide, organic acids and minerals. An acid is mentioned.

An example of the method for producing the ink used in the present invention is as follows. In the case of a dye ink, the above dye is mixed with water and a water-soluble organic solvent, and then pressure filtration is performed with a Teflon filter having an average pore diameter of 0.45 μm, followed by deaeration treatment to obtain an ink. In the case of a pigment ink, first, an aqueous solution containing at least a water-soluble resin, an amine or a base, and water is heated to 70 ° C. to completely dissolve the resin component. At this time, if the concentration of the resin to be dissolved is low, the resin may not be completely dissolved. Therefore, when dissolving the resin, a high-concentration solution may be prepared in advance and diluted to prepare a desired resin solution. A pigment and an aliphatic monohydric alcohol (ethanol or the like) are added to this solution, premixing is performed, and then a dispersion treatment is performed. The disperser used for the dispersion treatment may be any disperser generally used, and examples thereof include a ball mill using ceramic balls and steel balls, a roll mill, and a sand mill using glass beads and ceramic beads. To be Among these, a high speed type sand mill is preferable, and examples thereof include a super mill, a sand grinder, a bead mill, an agitator mill, a grain mill, a dyno mill, a pearl mill and a cobol mill (all are trade names). As the beads used in the sand mill, glass beads, ceramic beads, zirconium beads, etc. having a diameter of 1 mm to 1.5 mm are used.

An example of the conditions for preparing the dispersion liquid for the ink used in the present invention is shown below.・ Disperser: Sand grinder (Igarashi Machinery) ・ Grinding media: Glass beads or zirconium beads 1 mm diameter ・ Grinding media filling rate: 50% (volume) ・ Grinding time: 3 to 4 hours Further centrifugal separation treatment (12, 000 RPM, 15-20
Minute) to remove coarse particles to obtain a particle size of 100 nm
Make a 200 nm dispersion. As a disperser, other than this, a pearl mill (manufactured by Ashizawa, discharge rate: 100 ml /
Minutes) may be used.

It is desirable that the total amount of the pigment and the water-soluble resin in the dispersion liquid is 5 to 30% or more, preferably 10 to 30% or less by weight. The reason is that if the pigment and the water-soluble resin having a certain concentration or more do not exist in the dispersion liquid, the dispersion cannot be performed efficiently and the optimum dispersion state cannot be obtained. Next, a water-soluble organic solvent, ion-exchanged water and the like are mixed with this dispersion, and the mixture is stirred for 1 hour to obtain an ink. As a method for obtaining a pigment having a desired particle size distribution, the size of the grinding media of the disperser may be reduced, the packing ratio of the grinding media may be increased, the treatment time may be lengthened, the discharge speed may be slowed, a filter after grinding or A method such as classification with a centrifuge or the like is used. Or the combination of those methods is mentioned.

(Second Invention) A second invention of the present invention is a method of forming a color image by an ink jet system using yellow, magenta, cyan and black aqueous inks. First, the color of the magenta ink A material containing one or more dyes represented by the following general formula (IV) is used.

[Chemical 32] [Wherein R represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower acylamino group, a nitro group or a halogen atom, and X represents an acetyl group, a benzoyl group, a paratoluenesulfonyl group, 4-chloro- Represents any of a 6-hydroxy-1,3,5-triazin-2-yl group, M represents an alkali metal, ammonium or an organic amine, l represents 0 to 2, m or n represents 0 or 1. . ]

Specific examples of the magenta dye represented by the above general formula (IV) include those shown below.
Magenta dye

[Chemical 33]

[0031]

[Chemical 34]

[0032]

[Chemical 35]

The second invention of the present invention, like the first invention of the present invention, contains at least one dye represented by the following general formula (II) as a coloring material for the yellow ink. Is used as a second characteristic, and the third characteristic is that a color material of the cyan ink containing one or more kinds of dyes represented by the following general formula (III) is used. .
Furthermore, the second invention of the present invention is, like the first invention of the present invention, at least one kind selected from acidic carbon black, neutral carbon black and basic carbon black as the coloring material of the black ink. The fourth characteristic is that the pigment of the present invention is contained.

[0034]

[Chemical 36]

[0035]

[Chemical 37] The symbols in the above formulas (II) and (III) have the same meanings as explained in the first invention. In addition, formulas (II) and (II
As specific compounds of I), any of the exemplified compounds of Y1 to Y3 and Cy1 and Cy2 mentioned in the first invention of the present invention can be preferably used. Further, a dispersant, an aqueous medium, a surfactant, a water-soluble organic solvent, a pH adjusting agent, etc., contained in the ink used in the color image forming method of the present invention were also used in the first invention of the present invention. The same as that of is used.

The inks used in the above-described first and second inventions of the present invention are particularly preferably used in an ink jet recording system in which droplets are ejected by the action of thermal energy for recording. Needless to say, it can also be used as a writing instrument. The present invention forms a color image by an inkjet method using at least three colors of ink as described above. As the ink jet method used in the present invention, any conventionally known method can be used, but a particularly preferable method is a method utilizing heat energy. According to this method, ejection stability is satisfied and excellent. It is possible to perform a color image recording.

A recording apparatus suitable for use in the present invention is an apparatus for applying thermal energy corresponding to a recording signal to ink in a chamber of a recording head and generating droplets by the energy. An example of the head configuration, which is the main part, is shown in FIGS. 1, 2 and 3. The head 13 is a glass, ceramics, or plastic plate having a groove 14 through which ink passes, and a heating head 14 used for thermal recording.
(Thin film head is shown in the figure, but not limited to this). Heating head 1
Reference numeral 5 denotes a protective film 16 made of silicon oxide or the like, aluminum electrodes 17-1 and 17-2, a heating resistor layer 18 made of nichrome or the like, a heat storage layer 19, and a substrate 20 having good heat dissipation such as alumina. Made of The ink 21 reaches the ejection orifice (fine hole) 22, and the pressure P forms a meniscus 23. Now electrodes 17-1, 1
When an electric signal is applied to 7-2, the area indicated by n of the heating head 15 rapidly generates heat, and the ink 2 in contact therewith
A bubble is generated at 1, the pressure causes the meniscus 23 to project, the ink 21 is ejected, and the recording droplet 25 is ejected from the orifice 22 toward the recording medium 25. FIG. 3 shows an external view of a multi-head in which many heads shown in FIG. 1 are arranged. The multi-head includes a glass plate 27 having a multi-groove 26 and a heating head 2 similar to that described in FIG.
It is made by gluing 8. 1 is a cross-sectional view of the head 13 along the ink flow path, and FIG. 2 is a tangential cross-section taken along the line AB of FIG.

An example of an ink jet recording apparatus incorporating the head according to FIG. 4 is shown. In FIG. 4, reference numeral 61 is a blade as a wiping member, and one end of the blade is held by a blade holding member to become a fixed end, which is in the form of a cantilever. The blade 61 is arranged at a position adjacent to the recording area of the recording head, and in the case of this example, is held in a protruding form in the moving path of the recording head. 6
Reference numeral 2 denotes a cap, which is disposed 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. Further, 63 is an ink absorber provided adjacent to the blade 61, and like the blade 61, is held in a form protruding in the moving path of the recording head. The blade 61, the cap 62, and the absorber 63 constitute an ejection recovery unit 64, and the blade 61 and the absorber 63 remove water, dust, and dust on the ink ejection port surface. Reference numeral 65 denotes a recording head which has an ejection energy generating means and ejects ink to a recording material facing the ejection port surface where the ejection ports are arranged for recording, and 66 denotes a recording head 65 mounted to move the recording head 65. It is a carriage for performing.
The carriage 66 is movably engaged with the guide shaft 67, and a part of the carriage 66 is connected (not shown) to a belt 69 driven by a motor 68. This allows the carriage 66 to move along the guide shaft 67,
The recording area can be moved by the recording head 65 and its adjacent area. Reference numeral 51 is a paper feed unit 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 the position facing the ejection opening surface of the recording head, and is ejected to the ejection portion provided with the ejection roller 53 as the recording progresses. In the above configuration, when the recording head 65 returns to the home position after recording is completed, the carriage 62 of the head recovery unit 64 is retracted from the movement path of the recording head 65, but the blade 61 is projected in the movement 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. Recording head 65
Is moving from the home position to the recording start position,
The cap 62 and the blade 61 are in the same position as the above-described position during wyoing. As a result, even during this movement, the ejection port surface of the recording head 65 is wiped. The above-described 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. However, with this movement, the above wiping is performed.

FIG. 5 is a diagram showing an example of an ink cartridge 45 containing the ink to be supplied to the head through the ink supply tube. Here, 40 is an ink bag containing the supply ink, 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 discharged 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 separate from each other as described above, and the one in which they are integrated as shown in FIG. 6 is also preferably used.

In FIG. 6, an ink jet cartridge 70 contains an ink absorber impregnated with ink, and the ink in the ink absorber has a head portion 71 having a plurality of orifices. It is configured to be ejected as an ink droplet from. Reference numeral 72 is an atmosphere communication port for communicating the inside of the cartridge with the atmosphere. This inkjet cartridge 70 is used in place of the recording head 65 shown in FIG.
It is detachable from the carriage 66.

In the method of forming a color image of the present invention,
As a recording material that can be used when forming an image, not only various types of inkjet recording papers that have been proposed in the past or plastic sheets for OHP but also plain paper (usually used in offices) paper)
Naturally, excellent recording is possible by using. Further, the image is excellent in print quality and chromaticity regardless of the recording material.

[0042]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. (First Invention) Example 1 using the material constitution shown below
The inks used in Example 3, Comparative Example 1 and Comparative Example 2 were
It was created by the method described in the text. A color image was prepared using these inks by an inkjet method, and the images were evaluated as follows. The evaluation results are shown in Table 2.

(1) Printing Quality BJC440 (made by Canon) was used as a printer and printing was performed on two papers, NP-DRY copy paper (made by Canon) and XEROX4024 copy paper, as plain papers to be printed. The obtained image was visually observed, and the bleeding and color property of the boundary portion of each ink were evaluated according to the following criteria. (Bleeding at the border) ○: There is almost no bleeding at the border. B: Bleeding at the boundary occurred in the overprinted area. X: Severe bleeding at the boundary between single colors. (Color property of printed matter) ○: clear image Δ: slightly dull image ×: dull image

Example 1 (black ink) -Carbon black (MCF-88, manufactured by Mitsubishi Kasei) 3 parts-Resin A 0.8 part-Monoethanolamine 0.3 part-Glycerin 8 parts-Ethylene glycol 13 parts-Diethylene glycol 3 parts-Ethanol 4.9 parts-Ion exchanged water 67.0 parts (yellow ink) -Exemplified dye Y-1 3 parts-Diethylene glycol 28 parts-Acetylenol EH 0.2 parts-Ion exchanged water 68.8 parts (magenta ink) ) ・ Exemplified dye M-1 3 parts ・ Diethylene glycol 28 parts ・ Acetylene alcohol EH 0.2 part ・ Ion-exchanged water 68.8 parts (cyan ink) ・ Exemplified dye Cy-1 3 parts ・ Diethylene glycol 28 parts ・ Acetylenol EH 0.2 Part ・ Ion-exchanged water 68.8 parts

Example 2 (Black ink) -Carbon black (# 1000 manufactured by Mitsubishi Kasei) 3 parts-Resin A 0.3 parts-Aminomethyl propanol 0.5 parts-Glycerin 10 parts-Ethylene glycol 7 parts-Diethylene glycol 3 parts -Ethanol 4.2 parts-Ion exchanged water 72.0 parts (yellow ink) -Exemplary dye Y-2 2 parts-Diethylene glycol 25 parts-N-methylpyrrolidone 3 parts-Acetylenol EH 0.2 parts-Ion exchanged water 69. 8 parts (magenta ink) -Exemplary dye M-2 3 parts-Diethylene glycol 28 parts-Acetylenol EH 0.2 part-Ion-exchanged water 68.8 parts (cyan ink) -Exemplary dye Cy-2 3 parts-Diethylene glycol 28 parts- Acetylenol EH 0.2 part ・ Ion-exchanged water 68.8 parts

Example 3 (black ink) ・ Carbon black (manufactured by SB6 Tegusa) 3 parts ・ Resin C 0.8 part ・ Aminomethyl propanol 0.8 part ・ Glycerin 6 parts ・ Ethylene glycol 12 parts ・ Diethylene glycol 3 parts ・ Ethanol 5.4 parts-Ion-exchanged water 69.0 parts (yellow ink) -Exemplary dye Y-3 3 parts-Diethylene glycol 28 parts-Acetylenol EH 0.2 part-Ion-exchanged water 68.8 parts (magenta ink) -Exemplified dye M-3 3 parts-Diethylene glycol 28 parts-Acetylenol EH 0.2 part-Ion exchanged water 68.8 parts (cyan ink) -Exemplified dye Cy-2 3 parts-Diethylene glycol 28 parts-Acetylenol EH 0.2 parts-Ion exchange 68.8 parts of water

Comparative Example 1 (Black Ink) -Carbon Black (CIAcid Black 1) 5 parts-Diethylene glycol 28 parts-Acetylenol EH 0.2 parts-Ion-exchanged water 66.8 parts (yellow ink) -CIAcid Yellow 233 Part-diethylene glycol 28 parts-acetylenol EH 0.2 part-ion exchanged water 68.8 parts (magenta ink) -CIAcid Red 92 2 parts-diethylene glycol 28 parts-acetylenol EH 0.2 parts-ion exchanged water 69.8 parts (Cyan ink) -CIAcid Blue 9 4 parts-Diethylene glycol 28 parts-Acetylenol EH 0.2 parts-Ion-exchanged water 67.8 parts

Comparative Example 2 (Black Ink) -Carbon Black (CIAcid Black 1) 5 parts-Diethylene glycol 28 parts-Acetylenol EH 0.2 part-Ion-exchanged water 66.8 parts (yellow ink) -CI Pigment Yellow 43 Parts-Resin A 0.8 parts-Monoethanolamine 0.4 parts-Glycerin 6 parts-Ethylene glycol 12 parts-Diethylene glycol 3 parts-Ethanol 4.8 parts-Ion-exchanged water 70.0 parts (magenta ink) -CIPigment red 49 3 parts-Resin C 0.1 part-Monoethanolamine 0.3 part-Glycerin 10 parts-Ethylene glycol 12 parts-Diethylene glycol 3 parts-Ethanol 4.6 parts-Ion-exchanged water 67.0 parts (cyan ink) -CI Pigment Blue 17 3 parts-Resin B 0.7 part-Aminomethyl propanol 0. Parts Glycerin 10 parts Ethylene glycol 12 parts Diethylene glycol 3 parts Ethanol 4.9 parts Deionized water 66.0 parts

Resin A used in the above Examples and Comparative Examples
C has the properties shown in Table 1.

[Table 1]

[0050]

[Table 2] Robustness

(Second invention) The inks used in Examples 4 to 6, Comparative Example 3 and Comparative Example 4 were prepared by the method described in the text using the material constitution shown below. A color image was prepared using these inks by an inkjet method, and the images were evaluated as follows. Table 4 shows the evaluation results
Shown in.

(1) Printing Quality BJC440 (manufactured by Canon) was used as a printer, and two plain papers, NP-DRY copy paper (manufactured by Canon) and XEROX4024 copy paper, were used for printing. The obtained image was visually observed, and the bleeding and color property of the boundary portion of each ink were evaluated according to the following criteria. (Bleeding at the border) ○: There is almost no bleeding at the border. B: Bleeding at the boundary occurred in the overprinted area. X: Severe bleeding at the boundary between single colors. (Color property of printed matter) ○: clear image Δ: slightly dull image ×: dull image

Example 4 (Black ink) -Carbon black (MCF-88, manufactured by Mitsubishi Kasei) 3 parts-Resin A 0.8 part-Monoethanolamine 0.3 part-Glycerin 8 parts-Ethylene glycol 13 parts-Diethylene glycol 3 parts-Ethanol 4.9 parts-Ion exchanged water 67.0 parts (yellow ink) -Exemplified dye Y-1 3 parts-Diethylene glycol 28 parts-Acetylenol EH 0.2 parts-Ion exchanged water 68.8 parts (magenta ink) ) ・ Exemplified dye M-4 3 parts ・ Diethylene glycol 28 parts ・ Acetylene alcohol EH 0.2 part ・ Ion-exchanged water 68.8 parts (cyan ink) ・ Exemplified dye Cy-1 3 parts ・ Diethylene glycol 28 parts ・ Acetylenol EH 0.2 Part ・ Ion-exchanged water 68.8 parts

Example 5 (black ink) -Carbon black (# 1000 manufactured by Mitsubishi Kasei) 3 parts-Resin A 0.3 parts-Aminomethyl propanol 0.5 parts-Glycerin 10 parts-Ethylene glycol 7 parts-Diethylene glycol 3 parts -Ethanol 4.2 parts-Ion-exchanged water 72.0 parts (yellow ink) -Exemplary dye Y-2 2 parts-Diethylene glycol 25 parts-N-methylpyrrolidone 3 parts-Acetylenol EH 0.2 parts-Ion-exchanged water 69. 8 parts (magenta ink) -Exemplary dye M-5 3 parts-Diethylene glycol 28 parts-Acetylenol EH 0.2 part-Ion-exchanged water 68.8 parts (cyan ink) -Exemplary dye Cy-2 3 parts-Diethylene glycol 28 parts- Acetylenol EH 0.2 part ・ Ion-exchanged water 68.8 parts

Example 6 (black ink) ・ Carbon black (manufactured by SB6 Tegusa) 3 parts ・ Resin C 0.8 part ・ Aminomethyl propanol 0.8 part ・ Glycerin 6 parts ・ Ethylene glycol 12 parts ・ Diethylene glycol 3 parts ・ Ethanol 5.4 parts-Ion-exchanged water 69.0 parts (yellow ink) -Exemplary dye Y-3 3 parts-Diethylene glycol 28 parts-Acetylenol EH 0.2 part-Ion-exchanged water 68.8 parts (magenta ink) -Exemplified dye M-6 3 parts-Diethylene glycol 28 parts-Acetylenol EH 0.2 parts-Ion exchanged water 68.8 parts (cyan ink) -Exemplified dye Cy-2 3 parts-Diethylene glycol 28 parts-Acetylenol EH 0.2 parts-Ion exchange 68.8 parts of water

Comparative Example 3 (Black Ink) -Carbon Black (CIAcid Black 1) 5 parts-Diethylene glycol 28 parts-Acetylenol EH 0.2 part-Ion-exchanged water 66.8 parts (yellow ink) -CIAcid Yellow 23 3 Part-diethylene glycol 28 parts-acetylenol EH 0.2 part-ion exchanged water 68.8 parts (magenta ink) -CIAcid Red 92 2 parts-diethylene glycol 28 parts-acetylenol EH 0.2 parts-ion exchanged water 69.8 parts (Cyan ink) -CIAcid Blue 9 4 parts-Diethylene glycol 28 parts-Acetylenol EH 0.2 parts-Ion exchange water 67.8 parts

Comparative Example 4 (Black Ink) -Carbon Black (CIAcid Black 1) 5 parts-Diethylene glycol 28 parts-Acetylenol EH 0.2 part-Ion-exchanged water 66.8 parts (yellow ink) -CIPigment Yellow 43 Parts-Resin A 0.8 parts-Monoethanolamine 0.4 parts-Glycerin 6 parts-Ethylene glycol 12 parts-Diethylene glycol 3 parts-Ethanol 4.8 parts-Ion-exchanged water 70.0 parts (magenta ink) -CIPigment red 49 3 parts-Resin C 0.1 part-Monoethanolamine 0.3 part-Glycerin 10 parts-Ethylene glycol 12 parts-Diethylene glycol 3 parts-Ethanol 4.6 parts-Ion-exchanged water 67.0 parts (cyan ink)・ CIPigment Blue 17 3 parts ・ Resin B 0.7 parts ・ Aminomethyl propanol 0.4 parts・ Glycerin 10 parts ・ Ethylene glycol 12 parts ・ Diethylene glycol 3 parts ・ Ethanol 4.9 parts ・ Ion-exchanged water 66.0 parts

Resin A used in the above Examples and Comparative Examples
C has the properties shown in Table 1.

[Table 3]

[0059]

[Table 4] Robustness

[0060]

[Effects] According to the present invention as described above, since the coloring materials used in the present invention are at the same level and have excellent storage stability in a solvate, suitability as a general inkjet type aqueous ink, In particular, since it has a jetting property in the bubble jet system, it can provide not only coated paper but also plain paper with well-balanced and excellent performance, and it is possible to provide a high-quality color image.

[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 in which the head shown in FIG. 1 is multi-headed.

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.

[Explanation of symbols]

 61: Wiping member 62: Cap 63: Ink absorber 64: Ejection recovery section 65: Recording head 66: Carriage

Claims (3)

[Claims] 1. A method for forming a color image by an ink jet method using each of yellow, magenta, cyan and black aqueous inks, wherein a dye represented by the following general formula (I) is added as a coloring material in magenta ink. A dye containing at least one kind and containing at least one kind of dye represented by the following general formula (II) as a coloring material in the yellow ink, and containing as a coloring material in the cyan ink represented by the following general formula (III) And at least one pigment selected from the group consisting of acidic carbon black, neutral carbon black and basic carbon black as a coloring material of the black ink. . [Chemical 1] [However, Q _{1 to} Q ₄ in the above formula are each a sulfonic acid group,
A benzene ring or a naphthalene ring which may be substituted with a carboxyl group, an amino group, an anilino group or an acetylamino group, a hydroxyl group, a chloro group, an alkyl group or an alkoxyl group, and X is -NHCONH-, -NH-, -O. -Or (R ₁ and R ₂ are a hydrogen atom or a hydroxyethyl group), n is 0 or 1, and the sulfonic acid group and the carboxyl group are any of an alkali metal atom, ammonia and an organic amine. It is salted with that base. ] [Chemical 3] (However, Q in the above formula is -NHCONH- or Represents a bond, X ₁ and X ₂ are a hydrogen atom, —SO ₃ M, —
COOM or a phenyl group substituted with a hydroxyl group and a naphthyl group, R represents a methyl group or a methoxy group, and n
Represents 0 or 1, and M represents an alkali metal, ammonium or an organic amine. ) [Chemical 5] (However, in the above formula, M represents an alkali metal, ammonium or an organic amine, m is 1 to 4, n is 0 to 3
Is. ) 2. A method for forming a color image by an ink jet method using each of yellow, magenta, cyan and black aqueous inks, wherein a dye represented by the following general formula (I) is added as a coloring material to the magenta ink. A dye containing at least one kind and containing at least one kind of dye represented by the following general formula (II) as a coloring material in the yellow ink, and containing as a coloring material in the cyan ink represented by the following general formula (III) And at least one pigment selected from the group consisting of acidic carbon black, neutral carbon black and basic carbon black as a coloring material of the black ink. . [Chemical 6] [Wherein R represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower acylamino group, a nitro group or a halogen atom, and X represents an acetyl group, a benzoyl group, a paratoluenesulfonyl group, 4-chloro- Represents any of a 6-hydroxy-1,3,5-triazin-2-yl group, M represents an alkali metal, ammonium or an organic amine, l represents 0 to 2, m or n represents 0 or 1. . ] [Chemical 7] (However, Q in the above formula is -NHCONH- or Represents a bond, X ₁ and X ₂ are a hydrogen atom, —SO ₃ M, —
COOM or a phenyl group substituted with a hydroxyl group and a naphthyl group, R represents a methyl group or a methoxy group, and n
Represents 0 or 1, and M represents an alkali metal, ammonium or an organic amine. ) [Chemical 9] (However, in the above formula, M represents an alkali metal, ammonium or an organic amine, m is 1 to 4, n is 0 to 3
Is. ) 3. The method for forming a color image according to claim 1, wherein the ink jet method is a method using heat energy.