JP2000256587A - Aqueous ink set, coloring method and colored item - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous ink set capable of enriching the color in the wide visible region, excellent in clarity, light resistance and safety, and suitable for inkjet printing or the like by including each specific cyan ink, magenta ink and yellow ink. SOLUTION: This ink set consists of an yellow ink, a magenta ink and. a cyan ink usable for color image formation. The cyan ink contains a coloring matter having a phthalocyanine skeleton, and the magenta ink contains a sulfone derivative of an anthrapyridone skeleton represented by formula I (R1' is an alkoxycarbonyl, carboxy or benzoyl; R2 is H or an alkyl; R3 and R4 are each H, a halogen, an alkyl or the like), or an anthrapyridone-based coloring matter of formula II (R1 is an alkoxycarbonyl, 3-sulfobenzoyl or the like; n is 1-2). The inkjet coloring is preferably carried out by using the ink of the aqueous ink set.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an ink set and a colored body.

[0002]

2. Description of the Related Art Digitization of characters and images is expected to progress rapidly in the coming multimedia age. In order to make these advances, printers are needed,
In particular, ink jet printers are expected to be the center. Various ink ejection methods have been developed as a recording method using an ink jet printer. In each case, a small droplet of ink is generated, and this is used for various recording materials (paper, paper, etc.).
(Film, cloth, etc.).
This is quiet because there is no sound because the recording head does not come in contact with the recording material, and it has been rapidly spreading in recent years because of its features of miniaturization, high speed, and easy colorization. Growth is expected. In order to record the image or character information on a color display of a computer in color by an ink jet printer, generally, yellow (Y), magenta (M), cyan (C), and black (K) are used. It is expressed by subtractive color mixture using color inks. In order to reproduce an additive color mixture image by R, G, B of a CRT display or the like as faithfully as possible with a subtractive color mixture image, the dye used, especially the dye used in the YMC ink, has a hue as close to the ideal color of each YMC as possible. And sharpness is desired. or,
The ink composition is required to be stable for long-term storage, to have a high density of a printed image, and to have excellent fastness such as water fastness and light fastness. For water resistance,
Improvements have been made in recording materials, but no effective method has been found for improving light resistance.

[0003]

In order to display a hard copy of a computer color display as faithfully as possible to the original, the pigments used in the inks for ink jet color printers need to be vivid. Among them, magenta, which has a hue suitable for obtaining a wide range of compound colors and has a sharp color, has a problem that the light fastness level is low. Further, if the degree of fading of each of the yellow, magenta, and cyan colors and the respective compound colors has a large variation, there is a problem that not only the image becomes lighter, but also the color changes. Even if fading occurs, it is better to fading each color equally. Further, the inventors of the present invention have found that there is a problem that even if the lightfastness level of each ink is high, there is a combination in which the lightfastness level suddenly drops when a compounded color is obtained. INDUSTRIAL APPLICABILITY The present invention has a hue and clarity suitable for obtaining a wide range of compound colors used for recording of colors including ink jet prints, and the light fastness and other various fastnesses of a single color or compound color of a recorded matter thereby. It is an object of the present invention to provide an ink set comprising a magenta / cyan water-based ink composition which is strong and safe.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have accomplished the present invention. That is, the present invention provides (1) an aqueous ink set including a yellow ink, a magenta ink, and a cyan ink used for forming a color image, wherein the cyan ink contains a dye having a phthalocyanine skeleton, and the magenta ink has the formula (1) )

[0005]

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(Wherein R ₁ ′ is an alkoxycarbonyl group, a carboxy group or a benzoyl group, R ₂ is a hydrogen atom or an alkyl group, R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group or An aqueous ink set comprising a dye which is a sulfonic acid derivative of an anthrapyridone compound represented by an alkoxy group), and (2) a yellow ink, a magenta ink and a cyan ink used for forming a color image. An aqueous ink set, wherein the cyan ink contains a dye having a phthalocyanine skeleton, and the magenta ink has a formula (2)

[0007]

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Wherein R ₁ is an alkoxycarbonyl group,
A carboxy group, a benzoyl group or a 3-sulfobenzoyl group, R ₂ is a hydrogen atom or an alkyl group, R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and n is 1 to 2 Represents an integer. (3) wherein R ₁ is an alkoxycarbonyl group, a carboxy group, a benzoyl group or a 3-sulfobenzoyl group, and R ₂ is a hydrogen atom or methyl R ₃ represents a hydrogen atom, a methyl group or a chloro group bonded to the 3-position, R ₄ represents a hydrogen atom, and n represents 1-2.
Wherein the sulfonic acid group is bonded to the 4-position or 4-position and 6-position, (2) the aqueous ink set, (4) R ₁ represents an alkoxycarbonyl group or a carboxy group, and R ₂ represents a hydrogen atom or methyl R ₃ represents a hydrogen atom or a methyl group bonded to the 3-position, R ₄ represents a hydrogen atom, n is 2, and a sulfonic acid group is bonded to the 4- and 6-positions. A water-based ink set, (5) a colored body colored with the ink of the water-based ink set of (1) to (4), (6) a colored body of (5), wherein the coloring is performed by a printer, (7)
An ink-jet coloring method in which a recording material is colored by discharging ink droplets from an orifice according to a recording signal, wherein the ink is an ink of the ink set described in (1) to (4). (8) The ink jet coloring method according to (7), wherein the material to be colored is an information transmission sheet, (9) the ink jet coloring method according to (8), wherein the information transmission sheet is a surface-treated sheet, (10) (7) The inkjet coloring method according to (7), wherein the material to be colored is a polyamide-based fiber material, and the fiber material is subjected to a heat treatment after the ink is applied. 5. The recording unit according to claim 1, further comprising a head unit for discharging the ink as ink droplets, wherein the recording unit includes an ink container. (12) An ink jet recording apparatus comprising: a recording unit including a set of inks; (12) an ink storage unit containing the ink; and a recording unit including a head unit for discharging the ink as ink droplets. The present invention relates to an ink jet recording apparatus characterized in that the container contains the ink of the ink set according to any one of claims 1 to 4.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The ink set of the present invention has a hue and sharpness suitable for obtaining a wide range of compound colors used for color printing such as ink-jet printing, and a single color or a single color of a recorded matter thereby. This is a set of a water-soluble cyan ink and a water-based magenta ink having high lightfastness of compounding colors and other various fastnesses. As the cyan dye having a phthalocyanine skeleton used in the present invention,
For example, C.I. I. Direct Blue 86, C.I. I. Direct Blue 87, C.I. I. Direct Blue 199,
C. I. Acid Blue 249, C.I. I. Acid Blue 279, C.I. I. Acid blue 289, C.I. I. Reactive Blue 7, C.I. I. Reactive Blue 2
1, C.I. I. Reactive Blue 71 and the like.

The cyan dye having a phthalocyanine skeleton used in the present invention may be a salt. The salt is a salt at a sulfonic acid group or a carboxyl group, and examples thereof include an alkali metal salt such as a sodium salt, a potassium salt, and a lithium salt, an ammonium salt, and an ammonium salt including substituted ammonium. Examples of ammonium salts including substituted ammonium include mono-, di-, tri- or quaternary-substituted or unsubstituted alkyl ammonium or mono-, di-, tri- or quaternary-substituted or unsubstituted alkylammonium. Alkanol ammonium.

The magenta dye having an anthrapyridone skeleton used in the present invention includes, for example, compounds represented by the above formula (1) or (2).

R ₁ ′ in the above formula (1) is an alkoxycarbonyl group, a carboxy group or a benzoyl group;
R ₁ is an alkoxycarbonyl group, a carboxy group, a benzoyl group or a 3-sulfobenzoyl group. R ₁ ',
Examples of the alkoxycarbonyl group for R ₁ include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group, a t-
C1 to C6 alkoxycarbonyl groups such as butoxycarbonyl groups. In the above formulas (1) and (2), R ₂ is a hydrogen atom or an alkyl group. Examples of the alkyl group for R ₂ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. And a C1-C10 alkyl group such as a decyl group.

In the above formulas (1) and (2), R ₃ and R
₄ independently represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group include C1 to C4 alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group. Examples of the alkoxy group include a C1 to C6 alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group. R ₃ , R
The bonding position of _4, when the 1-position to the bonding position of the imino group,
R ₃ is at the 2- or 3-position and R ₄ is at the 3- or 4-position.
In the above formula (2), n is an integer of 0 to 3. n is 1
When it is an integer of 3 to 3, the sulfonic acid group is bonded to any of the 2-, 4-, and 6-positions when the bonding position of the imino group is the first position.

In the above formulas (1) and (2), R ₁ ′
Or, as a preferable combination of R ₁ , R ₂ , R ₃ , R ₄ and n in the formula (2), for example, R ₁ ′ or R ₁ is an alkoxycarbonyl group, a carboxy group, a benzoyl group or a 3-sulfobenzoyl group; ₂ is a hydrogen atom or a methyl group, R ₃ is a hydrogen atom bonded to the 3-position, a methyl group or a chloro group, R ₄ is a hydrogen atom, n is an integer of 1-2, and the sulfonic acid group is at the 4-position or 4 This is the case where it is bonded to the 6th and 6th positions. More preferably, R ₁ ′ or R ₁ is an alkoxycarbonyl group or a carboxy group, R ₂ is a hydrogen atom or a methyl group, R ₃ is a hydrogen atom or a methyl group bonded to the 3-position, R
₄ is a hydrogen atom, n is 2 and a sulfonic acid group is bonded to the 4- and 6-positions. More preferably, R ₁ ′ or R ₁ is an ethoxycarbonyl group or a carboxy group, R ₂
Is a methyl group, R ₃ is a hydrogen atom or methyl group bonded to the 3-position, R ₄ is a hydrogen atom, n is 2, and a sulfonic acid group is bonded to the 4- and 6-positions.

In the present invention, examples of the sulfonic acid derivative of the compound of the formula (1) include free sulfonic acid and salts thereof. Further, the anthrapyridone dye represented by the formula (2) may be a salt in a sulfonic acid group. Examples of the salt of the sulfonic acid derivative of the formula (1) (specifically, for example, the compound represented by the formula (2)) include alkali metal salts such as sodium salt, potassium salt, and lithium salt; ammonium salts; And salts with amines. Examples of the various amines include C1-C4 alkanolamines such as monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, and tripropanolamine. .

In order to obtain each of the above-mentioned salts of the magenta dye or the cyan dye, for example, the obtained sodium salt crystals are dissolved in water, acidified by adding an acid, and optionally filtered. The resulting cake is again dissolved in water, and an amine such as potassium hydroxide, lithium hydroxide, aqueous ammonia, diethanolamine or triethanolamine is added, thereby obtaining a potassium salt, lithium salt, ammonium salt, diethanolamine salt or triethanolamine, respectively. It can be an amine salt such as a salt. Next, specific examples of the compounds represented by the formulas (1) and (2) are shown below.

(Table 1) Table 1 Compound R 1 R 2 R 3 R 4 n Salt No. or R 1 ′ 01 -COOC 2 H 5 -CH 3 HH 0 21 -COOC 2 H 5 -CH 3 HH 2 (4th, 6th) Na 02 -COOC 2 H 5 -CH 3 H -CH 3 (3rd position) 0 22 -COOC2H5 HH -CH3 (3rd position) Na 03 -COOC2H5 HH -CH3 (3rd position) 023 -COOC2H5 HH -CH3 (3rd position) 2 (4, 6th) Na 04 -COOC2H5 HHH 0 24 -COOC2H5 HHH 2 (4th and 6th) Na 34 -COOH HHH 2 (4th and 6th) Na 05 -COPh HH -CH3 (3rd) 0 25 -COPh HH -CH3 (3rd) 2 (4,6th) Na 35 -3S-BENZOYL HH -CH3 (3rd) 2 (4,6th) Na 06 -COPh -CH3 HH 0 26 -COPh -CH3 HH 2 (2,4 Na 36 -3S-BENZOYL -CH3 HH 2 (2,4) Na

Compound R1 R2 R3 R4 n Salt No. or R1 ′ 07 -COPh HHH 027 -COPh HHH 2 (2,4 position) Na 37 -3S-BENZOYL HHH 2 (2,4 position) Na 08 -COPh − CH3 H -CH3 (3rd position) 0 28 -COPh -CH3 H -CH3 (3rd position) 2 (4,6th position) Na 31 -COOH -CH3 HH 2 (4,6th position) Na 09 -COOC2H5 -CH3 H- CH3 (4th position) 0 29 -COOC2H5 -CH3H -CH3 (4th position) 1 (2nd position) Na 010 -COOC2H5 -CH3H -CH3 (2nd position) 0 210 -COOC2H5 -CH3H -CH3 1 (4th position) Na 011 -COOC2H5 -CH3 H -Cl (3rd) 0 211 -COOC2H5 -CH3 H -Cl (3rd) 2 (4,6th) Na

Compound R1 R2 R3 R4 n Salt No. or R1 ′ 012 -COOC2H5 -CH3 H -Cl (4th position) 0 212 -COOC2H5 -CH3 H -Cl (4th position) 1 (2nd position) Na 013 -COOC2H5- CH3 H -OCH3 (4th) 0 213 -COOC2H5 -CH3 H -OCH3 (4th) 1 (2nd) Na 014 -COOC2H5 -CH3 H -OCH3 (2nd) 0 214 -COOC2H5 -CH3 H -OCH3 (2 1) (4) Na 015 -COOC2H5-CH3 -CH3 (2) -CH3 (6) 0 215 -COOC2H5 -CH3 -CH3 (2) -CH3 (6) 1 (4) Na 016 -COOC2H5 -CH3 H -C4H9 (4th) 0 216 -COOC2H5 -CH3 H -C4H9 (4th) 1 (2nd) Na 017 -COOC2H5 -C2H5 HH 0 217 -COOC2H5 -C2H5 HH 2 (2nd, 4th) Na 018 -COOC2H5 -C4H9 HH 0 218 -COOC2H5 -C4H9 HH 2 (2nd, 4th) Na

Compound R1 R2 R3 R4 n Salt No. or R1 ′ 019 -COOC2H5 HH -CH3 (4th position) 0 219 -COOC2H5 HH -CH3 (4th position) 1 (2nd position) Na 319 -COOC2H5 HH -CH3 (4 2) (2nd, 6th) Na 020 -COOC2H5 HH -CH3 (2nd) 0 220 -COOC2H5 HH -CH3 (2nd) 1 (4th) Na 021 -COOC2H5 HH -Cl (3rd) 0 221- COOC2H5 HH -Cl (3rd) 2 (4,6th) Na 022 -COOC2H5 HH -Cl (4th) 0 222 -COOC2H5 HH -Cl (4th) 1 (2nd) Na 023 -COOC2H5 HH -OCH3 ( 4th) 0 223 -COOC2H5 HH -OCH3 (4th) 1 (2nd) Na 024 -COOC2H5 HH -CH3 (2nd) 0 224 -COOC2H5 HH -CH3 (2nd) 1 (4th) Na 025 -COOC2H5 HH -C4H9-n (4th) 0 225 -COOC2H5 HH -C4H9-n (4th) 1 (2nd) Na

Compound R1 R2 R3 R4 n Salt No. or R1 ′ 026 -COOCH3 HHH0 226 -COOCH3 HHH 2 (2,4 position) Na 027 -COOC4H9 HHH 0 227 -COOC4H9 HHH 2 (2,4 position) Na 028 -COPh -CH3 H -CH3 (4th) 0 228 -COPh -CH3 H -CH3 (4th) 1 (2nd) Na 029 -COPh -CH3 H -CH3 (2nd) 0 229 -COPh -CH3 H- CH3 (2nd) 2 (4,6) Na 030 -COPh -CH3 H -Cl (3rd) 0 230 -COPh -CH3 H -Cl (3rd) 2 (4,6) Na 031 -COPh- CH3 H -Cl (4th) 0 231 -COPh -CH3 H -Cl (4th) 1 (2nd) Na 032 -COPh -CH3 H -OCH3 (4th) 0 232 -COPh -CH3 H -OCH3 (4 1) (2nd) Na

Compound R1 R2 R3 R4 n Salt No. or R1 '033 -COPh -CH3 H -OCH3 (2nd) 0 233 -COPh -CH3 H -OCH3 (2nd) 1 (4th) Na 03 -COPh- CH3-CH3 (2nd position) -CH3 (6th position) 0 234 -COPh -CH3 -CH3 (2nd position) -CH3 (6th position) 1 (4th position) Na 035 -COPh -CH3 H -C4H9-n (4th position) ) 0 235 -COPh -CH3 H -C4H9-n (4th) 1 (2nd) Na 036 -COPh -C2H5 HH 0 236 -COPh -C2H5 HH 2 (2,4th) Na 037 -COPh -C4H9 HH 0 237 -COPh -C4H9 HH 2 (2nd, 4th) Na 038 -COPh HH -CH3 (4th) 0 238 -COPh HH -CH3 (4th) 1 (2nd) Na 039 -COPh HH -CH3 (2nd) ) 0 239 -COPh HH -CH3 (2nd) 2 (2,4th) Na

Compound R1 R2 R3 R4 n Salt No. or R1 ′ 040 -COPh HH -Cl (3rd position) 0 240 -COPh HH -Cl (3rd position) 2 (4,6th position) Na 041 -COPh HH -Cl (4th) 0 241 -COPh HH -Cl (4th) 1 (2nd) Na 042 -COPh HH -OCH3 (4th) 0 242 -COPh HH -OCH3 (4th) 1 (2nd) Na 043- COPh HH -OCH3 (2nd) 0 243 -COPh HH -OCH3 (2nd) 1 (4th) Na 044 -COPh H -CH3 (2nd) -CH3 (6th) 0 244 -COPh H -CH3 (2 -CH3 (6th) 1 (4th) Na 045 -COPh HH -C4H9-n (4th) 0 245 -COPh HH -C4H9-n (4th) 1 (2nd) Na 046 -COOC2H5 -C2H5 HH 0 246 -COOC2H5 -C2H5 HH 2 (4th and 6th) Na

Compound R1 R2 R3 R4 n Salt No. or R1 ′ 047 -COOC2H5 -C3H7-n HH 0247 -COOC2H5 -C3H7-n HH 2 (4,6-position) Na 048 -COOC2H5 -C4H9-n HH 0 248 -COOC2H5 -C4H9-n HH 2 (position 4,6) Na 049 -COOC2H5 -CH (CH3) C2H5 HH 0 249 -COOC2H5 -CH (CH3) C2H5 HH 2 (position 4,6) Na 050 -COOC2H5 -C ( CH3) 3 HH 0 250 -COOC2H5 -C (CH3) 3 HH 2 (position 4,6) Na 051 -COOC2H5 -C6H13-n HH 0 251 -COOC2H5 -C6H13-n HH 2 (position 4,6) Na 052- COOC2H5 -C8H17-n HH 0 252 -COOC2H5 -C8H17-n HH 2 (4th and 6th positions) Na 053 -COOC2H5 -2EH HH 0 253 -COOC2H5 -2EH HH 2 (4th and 6th positions) Na 054 -COOC2H5 -2EH H -CH3 (3rd position) 0 254 -COOC2H5 -2EH H -CH3 (3rd position) 2 (4,6th position) Na 055 -COOC2H5 -C10H21-n HH 0 255 -COOC2H5 -C10H21-n HH 2 (4,6th position ) Na (Note) “Ph” in the table indicates a phenyl group. In addition, 01 to 09 and 010 to 055 are intermediates for producing the compound of the present invention. "2EH" is a 2-ethylhexyl group (-CH2CH (C
2H5) C4H9-n), "3S-BENZOYL" indicates a 3-sulfobenzoyl group, and "-n" indicates a linear.

The magenta dye used in the present invention is, for example, a compound represented by the following general formula (3)

[0026]

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(Wherein R ₂ , R ₃ and R ₄ have the same meanings as described above), and a compound represented by the general formula (4):

[0028]

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(Wherein R ₁ ′ has the same meaning as described above;
R ₅ represents an alkyl group. ) To give a compound of the above formula (1), which is obtained by sulfonating this compound.

The reaction of the compound of the general formula (3) with the compound of the general formula (4) is carried out, for example, in the presence of a base such as sodium carbonate or potassium carbonate as a catalyst in the presence of orthodichlorobenzene, monochlorobenzene, nitrobenzene, xylene or the like. What is necessary is just to carry out at 100-200 degreeC in a solvent. After completion of the reaction, the reaction mixture is cooled, diluted with a solvent such as methanol, ethanol or propanol and filtered, and then, if necessary, washed with an alcohol such as methanol, ethanol or propanol and dried to obtain the above-mentioned formula (1). Is obtained.

The sulfonation reaction is carried out using the compound of the above formula (1) as a raw material in sulfuric acid containing fuming sulfuric acid. The concentration of fuming sulfuric acid in sulfuric acid is preferably 2 to 20% by weight, more preferably 5 to 15% by weight, and still more preferably 7 to 12% by weight.
% By weight. The reaction temperature is generally 0-100 ° C, preferably 10-50 ° C. The reaction time varies depending on the reaction temperature, but is usually about 5 minutes to 20 hours, preferably about 15 minutes to 5 hours. After completion of the reaction, the reaction solution is poured into ice water, salted out, filtered, and dried to obtain a sulfonic acid derivative of the general formula (1) (specifically, for example, a compound in which n is 1 to 2 in the general formula (2)) ) Is obtained. Examples of the compound represented by the general formula (3) used for producing the compound of the present invention include the following.

(Table 2) Table 2 Compound No. R2 R3 R4 2-1 -CH3 HH 2-2 -CH3 H -CH3 (3rd position) 2-3 -CH3 H -CH3 (4th position) 2-4- -CH3 -CH3 (2nd position) H 2-5 -CH3 H -Cl (3rd position) 2-6 -CH3 H -Cl (4th position) 2-7 -CH3 H -OCH3 (4th position) 2-8 -CH3 -OCH3 (2nd position) H 2-9 -CH3 -CH3 (2nd position) -CH3 (6th position) 2-10 -CH3 H -C4H9-n (4th position) 2-11 -C2H5 HH 2-12 -C4H9-n HH 2-13 HHH 2-14 HH -CH3 (3rd) 2-15 H -CH3 (2nd) H

Compound No. R2 R3 R4 2-16 HH-Cl (3rd position) 2-17 HH-Cl (4th position) 2-18 HH-OCH3 (4th position) 2-19 H-OCH3 (2nd position) H 2-20 H -CH3 (2nd position) -CH3 (6th position) 2-21 HH -C4H9-n (4th position) 2-22 -CH (CH3) C2H5 HH 2-23 -C (CH3) 3 HH 2- 24 -C6H13-n HH 2-25 -C8H17-n HH 2-26 -CH2CH (C2H5) C4H9-n HH 2-27 -C10H21-n HH (Note) "-n" in the table is linear Is shown.

Examples of the compound represented by the general formula (4) used for producing the compound of the present invention include the following.

(Table 3) Table 3 Compound No. R1 'R5 3-1 -COOC2H5-C2H5 3-2-COOCH3 -CH3 3-3 -COOC4H9 -C4H9 3-4-COPh -C2H5 3-5 -COPh -CH3 Note) "Ph" in the table indicates a phenyl group.

The magenta dye used in the present invention can be synthesized as follows. That is, first, 1-alkylamino-
Reacting 4-bromo-anthraquinone or 1-amino-4-bromo-anthraquinone with a dialkyl malonate or an alkyl benzoylacetate to obtain an anthrapyridone compound having a bromo group at the 4-position of the anthraquinone nucleus; For example, aniline, m
-Condensation reaction with anilines such as toluidine and p-toluidine to obtain a compound of formula (1). Then, it is obtained by sulfonation in the same manner as described above. This method is represented by the following reaction route.

[0037]

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Each ink in the aqueous ink set of the present invention is obtained by dissolving a phthalocyanine dye and an anthrapyridone dye in water and / or a water-soluble organic solvent, respectively. When these aqueous ink compositions are used as inks for ink jet printers, it is preferable to use, as the coloring matter, those having a low content of inorganic substances such as chlorides and sulfates of metal cations. For example, it is about 1% or less. In order to produce the dye of the present invention containing less inorganic substances, desalting may be carried out by a usual method using, for example, a reverse osmosis membrane.

The ink used in the present invention is prepared using water as a medium, and the pigment component used in the present invention is preferably 0.1 to 20% by weight, more preferably 1 to 20% by weight.
The content is about 10% by weight, more preferably about 2 to 8% by weight. The ink used in the present invention may further contain a water-soluble organic solvent, preferably 0 to 30% by weight, and an ink preparation agent, preferably 0 to 5% by weight.

The ink used in the present invention can be obtained by dissolving a pigment having a low content of an inorganic substance in water and / or a water-soluble organic solvent together with an ink preparation as required. The pH of the composition is preferably between pH 6 and
About 11 is good. This ink is prepared by adding and mixing a dye and, if necessary, the above-mentioned water-soluble organic solvent, ink preparation agent and the like to water containing no impurities such as distilled water and ion-exchanged water. Further, the dye of the present invention may be added and dissolved in a mixture of water, the above-mentioned water-soluble solvent, and an ink preparation agent. If necessary, filtration may be performed after obtaining the ink composition to remove impurities.

Examples of the water-soluble organic solvent include C 1 -C 4 alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol and tert-butanol, N, N-dimethylformamide and N, N- Carboxylic acid amides such as dimethylacetamide, lactams such as ε-caprolactam, N-methylpyrrolidin-2-one, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2- Cyclic ureas such as on, acetone,
Ketones or keto alcohols such as methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one, ethers such as tetrahydrofuran and dioxane, mono-, oligo- or polyalkylene glycols having C2-C6 alkylene units or thioglycols such as ethylene glycol; 1,2- or 1,3-propylene glycol, 1,2- or 1,4-butylene glycol, 1,6
Mono-, oligo- or polyalkylene glycols having C2 -C6 alkylene units such as hexylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, polypropylene glycol, etc. or thioglycol, glycerin, hexane-1. 2.6 polyols (triols) such as 6-triol, C1 -C4 alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl or monoethyl ether, diethylene glycol monomethyl or monoethyl ether or triethylene glycol monomethyl or monoethyl ether, .gamma. Butyrolactone or dimethyl sulfoxide.

Two or more of these organic solvents may be used in combination. Among these organic solvents, preferred are
For example, N-methylpyrrolidin-2-one, mono-, di- or trialkylene glycols having a C2-C6 alkylene unit, preferably mono-, di- or triethylene glycol, dipropylene glycol, dimethyl sulfoxide, etc. Methylpyrrolidin-2-one,
The use of diethylene glycol, dimethylsulfoxide is preferred.

Examples of the ink preparation agent include an antiseptic / antifungal agent, a pH adjuster, a chelating reagent, a rust inhibitor, a water-soluble ultraviolet absorber, a water-soluble polymer compound, a dye dissolving agent, a surfactant and the like. Examples of the antiseptic / antifungal agent include sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate, sodium pentachlorophenol and the like. pH
As the adjusting agent, any substance can be used as long as it can control the pH of the ink in the range of 6 to 11 without adversely affecting the ink to be prepared. Examples thereof include ammonia, alkylamines such as monomethylamine, dimethylamine and dibutylamine, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide. And alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate. Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxytylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate,
And sodium uramil diacetate. As a rust inhibitor, for example, acid sulfite, sodium thiosulfate,
Examples thereof include ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

The ink set of the present invention is obtained by putting the yellow ink, cyan ink and magenta ink obtained as described above in separate containers.

Examples of the recording material of the ink jet recording method of the present invention include, for example, information transmission sheets such as paper and film, fibers and leather. As the information transmission sheet, those subjected to a surface treatment, specifically, those provided with an ink receiving layer on these substrates are preferable. The ink receiving layer is formed, for example, by impregnating or coating the above-described base material with a cationic polymer, or by disposing inorganic fine particles capable of adsorbing a dye in the ink such as porous silica, alumina sol or special ceramics to polyvinyl alcohol or polyvinyl pyrrolidone. It is provided by coating on the surface of the base material together with the hydrophilic polymer.

The fibers are preferably polyamide fibers such as nylon, silk and wool, and nonwoven fabrics and cloths are preferred. For these fibers, after applying the ink set of the present invention to the fibers, preferably after applying the ink set by an ink jet method, the wet heat (for example, about 80 to 12) is applied.
By adding a fixing step of 0 ° C.) or dry heat (for example, about 150 ° C. to 180 ° C.), a dye can be dyed inside the fiber, and a dyed article having excellent clarity, light fastness and washing resistance can be obtained. be able to.

To record on a recording material by the ink jet recording method of the present invention, for example, a container containing each of the above inks is set in an ink jet printer, and the ink is discharged onto the recording material by a usual method. I just need. Examples of the ink jet printer include a piezo printer using mechanical vibration and a bubble jet printer using bubbles generated by heating.

The recording unit of the present invention comprises an ink container for storing the ink of the water-based ink set described above, and a head for discharging the ink as ink droplets. The recording unit of the present invention containing the ink of this aqueous ink set is set in an ink tank portion. Further, the colored body of the present invention is colored with the ink of the ink set of the present invention.

The ink of the aqueous ink set of the present invention is a vivid and nearly ideal magenta ink and a cyan ink. By using the yellow ink together, it is possible to output a color tone in a wide visible region. This is useful as a recording ink composition for ink jet recording, writing implements and the like.

[0050]

EXAMPLES Synthesis Example 1-1 (1) 14.6 parts of 1-methylamino-4-anilinoanthraquinone, 0.75 part of sodium carbonate, 30.0 parts of malonic acid diethyl ester and orthodichlorobenzene 7
5 parts are charged into a reactor, heated to 170 to 175 ° C, and reacted for 10 hours. The reaction is performed while expelling ethanol and water generated during the reaction from the reaction system. After confirming the completion of the reaction by HPLC (high performance liquid chromatography), the reaction solution was cooled, 150 parts of methanol was added, and the mixture was stirred for 1 hour, filtered,
Wash with 100 parts of methanol and then with 300 parts of hot water,
Drying gives 25.2 parts of compound No. 01 as purple-red crystals.

(2) Next, 26.0 parts of 96% sulfuric acid was charged into a reactor, and 36.2 parts of 30% fuming sulfuric acid was added thereto under ice cooling to give 1 part.
Prepare 0% fuming sulfuric acid. Next, 8.5 parts of the above No. 01 compound was added at 20 ° C. or less under ice cooling, and the mixture was heated to 40 to 4
The sulfonation reaction is performed at a temperature of 5 ° C. for 3 hours. Ice water 400
The above reaction solution was added to the mixture, and sodium chloride 3
0 parts were added for salting out, stirred for 2 hours, filtered and dried to obtain a sodium salt of a sulfonic acid derivative of the compound of No. 01 (10.3 parts of the compound of No. 21 and
12.0 parts (comprising 1.7 parts of No. 31 compound) were obtained as a red powder. The λ max of the sulfonic acid derivative used in the present invention is 527 nm (in an aqueous solution). (3) The sulfonic acid derivative of the compound No. 01 used in the present invention obtained above is dissolved in water, acidified by adding an acid, and the cake obtained by filtration is again dissolved in water. , Potassium hydroxide, lithium hydroxide, aqueous ammonia, diethanolamine or triethanolamine to add potassium salt, lithium salt, ammonium salt, diethanolamine salt instead of the sodium salt of the sulfonic acid derivative of the compound No. 01, respectively. Alternatively, a compound which is a triethanolamine salt is obtained.

Synthesis Example 1-2 In the sulfonation reaction of Synthesis Example 1-1, the temperature was 40 to 45 ° C.
At a temperature of 3 hours instead of the reaction for 15 to 2 hours.
The same procedure as in Synthesis Example 1-1 was carried out except that the reaction was carried out at a temperature of 0 ° C. for 4 hours to obtain a sodium salt of a sulfonic acid derivative of the compound of No. 01 (Compound 12 of No. 21) used in the present invention. 12.3 parts (comprising 1 part and 0.2 part of the compound of No. 31) were obtained as a red powder. The .lambda.max of the sulfonic acid derivative used in the present invention is 528 nm.
(In aqueous solution).

Synthesis Example 2 15.7 parts of 1-methylamino-4- (3-methyl-anilino) anthraquinone, 0.75 part of sodium carbonate, 30.0 parts of malonic acid diethyl ester and 45 parts of orthodichlorobenzene were placed in a reactor. Charge, heat to 175-180 ° C and react for 5 hours. The reaction is performed while expelling ethanol and water generated during the reaction from the reaction system. After confirming the completion of the reaction by HPLC, the mixture was cooled with water, 135 parts of methanol was added, and the mixture was further stirred under ice cooling for 1 hour. The precipitated crystals were filtered, washed with 180 parts of methanol, washed with 180 parts of hot water, and dried. 26.3 parts of compound No. 02 used in the present invention are obtained as purple-red crystals.

Next, 31.0 parts of 96% sulfuric acid is charged into a reactor, and 33.4 parts of 30% fuming sulfuric acid is added under ice cooling to prepare 7% fuming sulfuric acid. Then, at 20 ° C or less under ice cooling, the above No.
8.8 parts of Compound No. 02 at room temperature of 20 to 25 ° C.
Perform the sulfonation reaction for hours. The above reaction solution was added to 400 parts of ice water, and while stirring, 60 parts of sodium chloride was added for salting out. After stirring for 2 hours, the mixture was filtered and dried, and the compound of No. 22 (the dye used in the present invention) ) Sodium salt 1
2.2 parts were obtained as a red powder. Λmax of the compound
Is 533 nm (in an aqueous solution). Also obtained above
After dissolving the compound of No. 22 in water and adding acid to make it acidic, the cake obtained by filtration was dissolved again in water,
By adding potassium hydroxide, lithium hydroxide, aqueous ammonia, diethanolamine or triethanolamine, potassium salt, lithium salt, ammonium salt, diethanolamine salt or triethanolamine salt is used instead of the sodium salt of No. 22 respectively. A compound is obtained.

Synthesis Example 3 14.6 parts of 1-amino-4- (3-methyl-anilino) anthraquinone, 0.75 part of sodium carbonate, 30.0 parts of malonic acid diethyl ester and 75 parts of orthodichlorobenzene were charged into a reactor. , Heated to 160-170 ° C and reacted for 2 hours. The reaction is performed while expelling ethanol and water generated during the reaction from the reaction system. Water cooled methanol 1
After adding 50 parts and stirring for 2 hours, filtration, methanol 100
No., then wash with 300 parts of hot water and dry.
25.3 parts of compound 03 are obtained as red crystals.

Next, 31.0 parts of 96% sulfuric acid is charged into a reactor, and 33.4 parts of 30% fuming sulfuric acid is added under ice cooling to prepare 7% fuming sulfuric acid. Then, at 20 ° C or less under ice cooling, the above No.
8.5 parts of Compound No. 03 and 1 at a temperature of 40-45 ° C.
Perform the sulfonation reaction for hours. The above reaction solution was added to 400 parts of ice water, and a 25% aqueous sodium hydroxide solution 200 was added with stirring.
To 100 parts of sodium chloride for salting out, and after stirring for 2 hours, 60 to 6 parts.
The mixture was heated and stirred at 5 ° C. for 1 hour, filtered and dried, and the sodium salt of the compound No. 23 (dye used in the present invention) 1
1.0 part is obtained as a red powder. Λmax of the compound
Is 534 nm (in an aqueous solution). Also obtained above
After dissolving the compound of No. 23 in water and adding acid to make it acidic, the cake obtained by filtration was dissolved again in water,
By adding potassium hydroxide, lithium hydroxide, aqueous ammonia, diethanolamine or triethanolamine, potassium salt, lithium salt, ammonium salt, diethanolamine salt or triethanolamine salt is used instead of the sodium salt of No. 23, respectively. A compound is obtained.

Synthesis Example 4 13.6 parts of 1-amino-4-anilinoanthraquinone
0.75 parts of sodium carbonate, 30.0 parts of malonic acid diethyl ester and 75 parts of orthodichlorobenzene are charged into a reactor and heated to 160 to 170 ° C. to react for 2 hours. The reaction is performed while expelling methanol and water generated during the reaction from the reaction system. After cooling with water, add 150 parts of methanol and add 1 part.
After stirring for an hour, the mixture was filtered, washed with 100 parts of methanol, then with 300 parts of hot water, and dried.
3 parts are obtained as red crystals.

Next, 26.0 parts of 96% sulfuric acid is charged into a reactor, and 36.2 parts of 30% fuming sulfuric acid is added under ice cooling to prepare 10% fuming sulfuric acid. Then, the above-mentioned N
Add 8.5 parts of o.04 compound and carry out sulfonation at 40-45 ° C. for 1 hour. The above reaction solution was added to 400 parts of ice water, and 100 parts of sodium chloride was added with stirring to carry out salting out. After stirring for 2 hours, 1 part was added at 60 to 65 ° C.
Heat and stir for hours, filter, dry and use N
o. The sodium salt of the sulfonic acid derivative of the compound of No. 04 (N
o. 6.7 parts of the compound of 24 and 5.0 of the compound of No. 34
11.7 parts were obtained as a red powder. The λ max of the sulfonic acid derivative used in the present invention is 52
2 nm (in aqueous solution). Further, the sulfonic acid derivative of the compound of No. 04 used in the present invention obtained above is dissolved in water, acidified by adding an acid, and the cake obtained by filtration is again dissolved in water, By adding potassium hydroxide, lithium hydroxide, aqueous ammonia, diethanolamine or triethanolamine, respectively, N
o. A compound which is a potassium salt, a lithium salt, an ammonium salt, a diethanolamine salt or a triethanolamine salt in place of the sodium salt of the sulfonic acid derivative of the compound of Compound 04 is obtained.

Synthesis Example 5 Instead of orthodichlorobenzene used in Synthesis Example 1-1 (1), 75 parts of monochlorobenzene was used at a reaction temperature of 130 to 135 ° C. while passing nitrogen gas slowly.
The reaction was carried out for 0 hour, and the others were treated in the same manner as in Synthesis Example 1-1 (1). The same compound 25.2 as the compound No. 01 used in the present invention obtained in Synthesis Example 1-1 (1) was used. Part is obtained as red crystals.

Synthesis Example 6 14.6 parts of 1-amino-4- (3-methyl-anilino) anthraquinone, 0.75 part of sodium carbonate, 36.0 parts of ethyl benzoylacetate and 75 parts of orthodichlorobenzene were charged into a reactor. , 170-175 ° C and react for 3 hours. The reaction is performed while expelling ethanol and water generated during the reaction from the reaction system. Complete the reaction with H
After confirmation by PLC, the mixture was cooled with water, and 150 parts of methanol was added to precipitate crystals. After stirring for 1 hour, the mixture was filtered, washed with 200 parts of methanol, washed with water and dried to obtain No. 05 compound 29.
4 parts are obtained as red crystals.

Next, 31.0 parts of 96% sulfuric acid is charged into a reactor, and 33.4 parts of 30% fuming sulfuric acid is added under ice cooling to prepare 7% fuming sulfuric acid. Then, at 20 ° C or less under ice cooling, the above No.
9.1 parts of Compound No. 05 at room temperature of 40-45 ° C.
Perform the sulfonation reaction for hours. The above reaction solution was added to 400 parts of ice water, and 40 parts of sodium chloride was added with stirring to carry out salting out. After stirring for 2 hours, the mixture was filtered and dried to obtain N of the present invention.
o. The sodium salt of the sulfonic acid derivative of compound 05 (N
o. Compound 12.0 parts of 25 and Compound 0 of No. 35.
12.9 parts were obtained as a red powder.
The λ max of the sulfonic acid derivative used in the present invention is 5
34 nm (in an aqueous solution). Further, the sulfonic acid derivative of No. 05 used in the present invention obtained above is dissolved in water, acidified by adding acid, and the cake obtained by filtration is again dissolved in water, No. 05 by adding potassium, lithium hydroxide, aqueous ammonia, diethanolamine or triethanolamine, respectively.
The compound which is a potassium salt, a lithium salt, an ammonium salt, a diethanolamine salt or a triethanolamine salt instead of the sodium salt of the sulfonic acid derivative is obtained.

Synthesis Example 7 1-methylamino-4-anilinoanthraquinone
6 parts, sodium carbonate 0.75 part, benzoyl acetic acid ethyl ester 36.0 parts and orthodichlorobenzene 75
The reactor is charged to a reactor, heated to 170 to 170 ° C., and reacted for 3 hours. The reaction is performed while expelling ethanol and water generated during the reaction from the reaction system. After completion of the reaction was confirmed by HPLC, the mixture was cooled with water and 150 parts of methanol was added to precipitate crystals. One hour later, the mixture was filtered, washed with 200 parts of methanol, washed with water and dried to obtain a compound of No. 06 (used in the present invention). 28.8 parts of dye) are obtained as red crystals.

Next, 24.0 parts of 96% sulfuric acid is charged into a reactor, and 39.6 parts of 30% fuming sulfuric acid is added under ice cooling to prepare 12% fuming sulfuric acid. Then, the above-mentioned N
Add 8.8 parts of the compound of o.06 and carry out the sulfonation reaction at a temperature of 40-45 ° C. for 5 hours. The above reaction solution was added to 400 parts of ice water, and 80 parts of sodium chloride was added with stirring to carry out salting out. After stirring for 2 hours, the mixture was filtered and dried to obtain a sulfone of the compound of No. 06 used in the present invention. 12.3 parts of the sodium salt of the acid derivative (consisting of 9.1 parts of the compound of No. 36 and 3.2 parts of the compound of N0.26) were obtained as a red powder. Λmax of this compound is 532 nm (in aqueous solution)
It is. In addition, No. 0 used in the present invention obtained above.
After dissolving the sulfonic acid derivative of compound 6 in water and adding acid to make it acidic, the cake obtained by filtration is again dissolved in water, and potassium hydroxide, lithium hydroxide, aqueous ammonia, diethanolamine or By adding triethanolamine, instead of the sodium salt of the sulfonic acid derivative of the compound of No. 06, a potassium salt,
Compounds that are lithium, ammonium, diethanolamine or triethanolamine salts are obtained.

Synthesis Example 8 14.6 parts of 1-amino-4-anilinoanthraquinone
0.75 parts of sodium carbonate, 36.0 parts of benzoyl acetic acid ethyl ester and 75 parts of orthodichlorobenzene are charged into a reactor, heated to 170 to 170 ° C., and reacted for 3 hours. The reaction is performed while expelling ethanol and water generated during the reaction from the reaction system. After confirming the completion of the reaction by HPLC, the mixture was cooled with water and 150 parts of methanol was added to precipitate crystals.
After an hour, the mixture is filtered, washed with 200 parts of methanol, then washed with water and dried to obtain 29.5 parts of the dye used in the present invention as red crystals.

Next, 26.0 parts of 96% sulfuric acid is charged into a reactor, and 36.2 parts of 30% fuming sulfuric acid is added under ice cooling to prepare 10% fuming sulfuric acid. Then, the above-mentioned N
o. Add 9.1 parts of 07 compound and carry out sulfonation at 40-45 ° C for 3 hours. The above reaction solution was added to 400 parts of ice water, and 80 parts of sodium chloride was added with stirring to carry out salting out. After stirring for 2 hours, the mixture was filtered and dried to obtain a sulfone of the compound of No. 07 used in the present invention. Sodium salt of acid derivative (12.2 parts of compound of No. 37 and No. 27
14.9 parts were obtained as a red powder. The λmax of this compound is 532 nm (in an aqueous solution). Also, the N used in the present invention obtained above
o. dissolving the sulfonic acid derivative of the compound 07 in water,
After acidification by adding an acid, the cake obtained by filtration was dissolved again in water, and potassium hydroxide, lithium hydroxide,
By adding aqueous ammonia, diethanolamine and triethanolamine, compounds which are potassium salt, lithium salt, ammonium salt, diethanolamine salt and triethanolamine salt instead of the sodium salt of the sulfonic acid derivative of the compound of No. 07, respectively, can get.

Synthesis Example 9 15.7 parts of 1-methylamino-4- (3-methyl-anilino) anthraquinone, 0.75 part of sodium carbonate, 36.0 parts of ethyl benzoylacetate and 75 parts of orthodichlorobenzene were placed in a reactor. Preparation, 170-170
Heat to 0 ° C and react for 4 hours. The reaction is performed while expelling ethanol and water generated during the reaction from the reaction system. After confirming the completion of the reaction by HPLC, the mixture was cooled with water and 150 parts of methanol was added to precipitate crystals.
After washing with 00 parts, then washing with water and drying, 27.1 parts of compound No. 08 (dye used in the present invention) are obtained as red crystals.

Next, 31.0 parts of 96% sulfuric acid is charged into a reactor, and 33.4 parts of 30% fuming sulfuric acid is added under ice cooling to prepare 7% fuming sulfuric acid. Next, the above No.
9.4 parts of Compound No. 08 at room temperature of 20 to 25 ° C.
Perform the sulfonation reaction for hours. The above reaction solution was added to 400 parts of ice water, and 100 parts of 25% caustic soda was added dropwise to the mixture to make it slightly alkaline with stirring. Then, 80 parts of sodium chloride was added for salting out, followed by stirring for 2 hours, followed by filtration and drying. Then N
o. 9.2 parts of the sodium salt of compound 28 (the dye used in the present invention) were obtained as a red powder. The λmax of this compound is 536 nm (in an aqueous solution). Further, the compound of No. 28 obtained above was dissolved in water, acidified by adding an acid, and the cake obtained by filtration was again dissolved in water, and potassium hydroxide, lithium hydroxide, ammonia By adding water, diethanolamine or triethanolamine, a compound is obtained which is a potassium salt, a lithium salt, an ammonium salt, a diethanolamine salt or a triethanolamine salt instead of the sodium salt of No. 28, respectively.

Example 1 Preparation of (A) Ink A liquid having the following composition was prepared and filtered with a 0.45 μm membrane filter (manufactured by Toyo Roshi Kaisha, Ltd.) to obtain an aqueous ink composition for inkjet. <Magenta ink composition> Dye of compound No. 21 in Table 1 4.5 parts (use a desalted one) Water 77.5 parts N-methylpyrrolidin-2-one 5.0 parts Glycerin 5.0 Part Urea 5.0 parts Isopropanol 3.0 parts <Cyan ink composition> I. Direct Blue 199 2.0 parts (Use desalted one) Water 80.0 parts N-methylpyrrolidin-2-one 5.0 parts Glycerin 5.0 parts Urea 5.0 parts Isopropanol 3.0 parts

(B) Inkjet printing Inkjet printer (trade name, manufactured by Canon)
BJC-610JW), plain paper (Canon Printer Paper A4 (TLB5A4S)), dedicated glossy film (Color BJ Photosheet Film CA)
-101 (manufactured by Canon Inc.)) was subjected to inkjet recording on two types of paper and film. The recorded image has three colors of magenta, cyan, and blue (a mixed color of magenta and cyan).
Color. (C) Hue and sharpness of the recorded image The hue of the recorded image is measured by a colorimeter (GRETAG SPM50:
GRETAG), L ^* , a ^* , b ^*
Calculate the value. Clearness is ^{C * = ((a *)} 2 + (b *) 2) 1/2
Was evaluated. The results are shown in Table 4. (D) Light fastness test of recorded image The recording paper was irradiated for 50 hours using an accelerated xenon arc fade meter (manufactured by Wacom). Next, the hue of the recorded image before and after the light resistance test was measured using a colorimeter (GRETAGSPM5).
0: manufactured by GRETAG Co.) and color difference (ΔE)
(JIS No.L0843). In addition, the film was irradiated with sunlight for one month through the glass, and similarly, the color difference (ΔE) of the recorded image before and after the light resistance test was determined. The results are shown in Table 5.

Comparative Example 1 An ink jet printer BJC-
The test was performed according to (B), (C) and (D) described in Example 1 except that the ink for 610 JW (manufactured by Canon) was used. The results are shown in Table 5.

Comparative Example 2 C.I. I. Direct Blue 199
As magenta ink. I. Acid Red 37
A test was performed in the same manner as in Comparative Example 1 except that the ink was prepared and used according to (A) described in Example 1. The results are shown in Table 5.

The results of the hue of the recorded image printed on the film are shown in Table 4 below.

(Table 4) Table 4 Hue Sharpness L * a * b * (C *) Example 1 Magenta 61.9 69.9-21.7 73.2 Blue 48.0-10.8-54. 555.6 Cyan 63.8-45.2-44.3 63.3 Comparative Example 1 Magenta 62.2 75.6-21.3 63.6 Blue 47.8-7.7-55.7 56. 2 Cyan 64.1-45.5-44.5 63.6 Comparative Example 2 Magenta 55.3 74.7 6.7 75.0 Blue 40.8-2.3-49.1 49.1 Cyan 63. 5-45.8-45.3 64.4

Table 5 shows the results of evaluating the light fastness of recorded images printed on plain paper and special films.

(Table 5) Table 5 Light fastness: color difference (ΔE) Plain paper dedicated film Accelerated xenon / natural light Accelerated xenon / natural light Example 1 Magenta 14.2.6.8 25.6.6.4 Blue 13. 2.5.5 18.2.5.9 Cyan 7.1.2.6 8.2.2.7 Comparative Example 1 Magenta 40.8.7.8 74.3.6.7 blue 24.6. 10.7 30.4-5.8 Cyan 7.2-3.2 9.1-2.8 Comparative Example 2 Magenta 3.5-1.5 31.3-15.3 Blue 9.1-7. 6 32.6 ・ 26.5 Cyan 7.1 ・ 2.7 7.8 ・ 2.8

From Table 4, it can be seen that the combination of Example 1 of the present invention has a clear hue equivalent to that of Comparative Example 1. In Comparative Example 2, in the hue of magenta single color, b
^{* Indicates a} positive value, indicating that the product is considerably yellowish. Blue, which is a combination of magenta and cyan, also has a small negative absolute value and is slightly yellowish.
Also, from Table 5, the combination of Example 1 of the present invention has a smaller color difference in monochromatic magenta and compound blue than that of Comparative Example 1. That is, light fastness is strong. Further, there is little variation in the color difference between the colors. This tendency is remarkable in a special film which is often used when printing a photographic image. In other words, it is shown that the image printed with the combination of the inks of Example 1 becomes even thinner than the combination of the inks of the comparative example without greatly disturbing the image of the image even if the image is faded. I have. Further, with regard to the compounded blue color, in Comparative Example 1, the natural light of plain paper increased, and in Comparative Example 2, the accelerated xenon and natural light of plain paper / glossy film showed a greater color difference than magenta alone or cyan alone. On the other hand, the compounding color blue using the ink set of the present invention of Example 1 has a single intermediate value. In other words, when the magenta dye is used as a reference, the degree of discoloration is large and the light fastness is significantly reduced in the compound color blue in which the magenta dye and the metal phthalocyanine cyan dye are used in combination in the comparative example. On the contrary, it can be seen that the compounded blue using the compound has a small degree of discoloration and has improved light fastness. This means that in the comparative example, the magenta dye was significantly reduced in light resistance due to the action considered to be catalytic when used in combination with the metal phthalocyanine cyan dye, whereas in Example 1 of the present invention, the magenta dye had an anthrapyridone skeleton. It appears that the magenta dye is not affected.

[0077]

The ink set of the present invention is a combination of a magenta color and a cyan color which is close to ideal, and can produce a color tone in a wide visible region. In addition, it has excellent light fastness even in a combination color in which only a single color is used. Further, the printed matter can express clear and nearly ideal magenta, cyan and blue colors, and by using both yellow and black inks, it is possible to colorize a wide visible region. Therefore, the ink set of the present invention is highly valuable as a recording ink composition for ink jet recording, writing implements and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J039 BA29 BC05 BC07 BC12 BC33 BC50 BC54 BC60 BC69 BC74 BC75 BC79 BE01 BE02 CA03 CA06 EA15 EA16 EA17 EA19 EA34 EA35 EA42 EA45 FA02 FA03 FA07 GA24

Claims (12)

[Claims] 1. A yellow ink used for forming a color image,
An aqueous ink set including a magenta ink and a cyan ink, wherein the cyan ink contains a dye having a phthalocyanine skeleton, and the magenta ink has a formula (1): (Wherein R ₁ ′ represents an alkoxycarbonyl group, a carboxy group or a benzoyl group, R ₂ represents a hydrogen atom or an alkyl group, and R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. A water-based ink set comprising a dye which is a sulfonic acid derivative of an anthrapyridone compound represented by the following formula: 2. A yellow ink used for forming a color image,
An aqueous ink set comprising a magenta ink and a cyan ink, wherein the cyan ink contains a dye having a phthalocyanine skeleton, and the magenta ink has a formula (2): (In the formula, R ₁ is an alkoxycarbonyl group, a carboxy group, a benzoyl group or 3-sulfobenzoyl group, R ₂
Represents a hydrogen atom or an alkyl group, R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and n represents an integer of 1-2. A water-based ink set comprising an anthrapyridone dye represented by the formula (1): (3) R ₁ is an alkoxycarbonyl group, a carboxy group, a benzoyl group or a 3-sulfobenzoyl group;
R ₂ represents a hydrogen atom or a methyl group; R ₃ represents a hydrogen atom bonded to the 3-position, a methyl group or a chloro group; R ₄ represents a hydrogen atom; n is an integer of 1 to 2; The water-based ink set according to claim 2, wherein the water-based ink set is bonded to the 4-position or the 4-position and the 6-position. R ₁ represents an alkoxycarbonyl group or a carboxy group; R ₂ represents a hydrogen atom or a methyl group; R ₃ represents a hydrogen atom or a methyl group bonded to the 3-position; R ₄ represents a hydrogen atom; 3. The aqueous ink set according to claim 2, wherein n is 2 and a sulfonic acid group is bonded to the 4- and 6-positions. 5. A colored body which is colored with the ink of the aqueous ink set according to any one of claims 1 to 4. 6. The colored body according to claim 5, wherein the coloring is performed by a printer. 7. An ink-jet coloring method in which a recording material is colored by discharging ink droplets from an orifice according to a recording signal, wherein the ink is an ink of the ink set according to any one of claims 1 to 4. An ink-jet coloring method, comprising: 8. The coloring material is an information transmission sheet.
3. The ink-jet coloring method according to 1. 9. The ink jet coloring method according to claim 8, wherein the information transmission sheet is a surface-treated sheet. 10. The ink-jet coloring method according to claim 7, wherein the material to be colored is a polyamide fiber material, and the fiber material is heat-treated after the ink is applied. 11. A recording unit comprising an ink storage section for storing ink and a head section for discharging the ink as ink droplets, wherein the ink storage section is provided in the ink storage section.
A recording unit comprising the ink of the ink set according to any one of the above. 12. An ink jet recording apparatus comprising: a recording unit having an ink container containing ink and a head for discharging the ink as ink droplets.
An ink jet recording apparatus comprising: an ink set containing the ink of the ink set according to any one of claims 1 to 4 in an ink container.