JP2002241652A - Ink set for inkjet and black ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink set for inkjet, capable of providing an image having excellent light resistance and bleeding resistance regardless of having excellent density and chroma, and having excellent jetting stability, and further to provide a black ink in the ink set. SOLUTION: This ink set for the inkjet is characterized in that the black ink contains a reactive dye in the ink set for the inkjet for forming a full-color image by using plural colors of the inks for the inkjet containing at least a water-soluble dye, a water-soluble organic solvent and water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink set for ink jet and a black ink in the ink set, and more particularly to an ink jet set which can provide an excellent image used for proofreading of printing using a dye ink and can stably discharge. The present invention relates to an ink jet ink set having excellent properties and a black ink of the ink set.

[0002]

2. Description of the Related Art The ink jet recording method is a non-contact recording method, and can be used in a wide range of applications from personal use to industrial use, because it is applicable to small to large-sized apparatuses and is easy to colorize. .

[0003] Ink jet recording is roughly classified into a continuous jet type and an on-demand type. The former has been used for industrial printers, and the latter has been mainly used for personal to OA use. In recent years, on-demand type droplets and high-speed printing performance have been improved, and the on-demand type has been used for industrial purposes.

[0004] Solvent-type and water-based inks have been proposed as recording liquids, but water-based inks are widely used except for some industrial uses.

[0005] Dye-based inks and pigment-based inks have been proposed as water-based inks. Dye-based inks are widely used in the market from the viewpoints of ejection stability, color reproducibility, and image fixability.

[0006] With the improvement of image quality in recent years, application of such a system using a water-based dye ink to applications for photography, color proofing, and the like has been studied. In addition, the accuracy of related technologies such as color matching has been improved, and it has been used as an outside school for proofing applications that require a strict color reproduction range. Is being requested.

[0007] The first characteristic required for ink-jet inks is ejection stability, followed by image quality. The image quality includes density, a wide color gamut, light resistance, bleeding resistance at high humidity, and the like, and a wide variety of extremely strict requirements are imposed.

Therefore, conventionally, a water-soluble organic solvent having a high boiling point and a low vapor pressure has been added to ink for the purpose of improving the ejection stability. Although the addition of a solvent in this manner is preferable because it can prevent the head surface from drying, the presence of the slow-volatile solvent for a long time adversely affects image bleeding and storage stability. Was.

The water-soluble dyes to be used include direct dyes, acid dyes, basic dyes and reactive dyes. Among the direct dyes, those having few vivid color tones and insufficient water solubility are available. Many, basic dyes have poor lightfastness, reactive dyes gradually hydrolyze, pH of ink liquid
However, there is a problem in that the dye is easily precipitated, and an acidic dye having a clear color tone, excellent light fastness, and good solubility is generally used. However, the acid dye has a problem in that the dyeability on plain paper or the like is lower than that of the reactive dye.

On the other hand, JP-A-53-49113, JP-A-58-49113, JP-A-61-61887,
JP-A-63-224998, JP-A-63-30797
No. 9 and the like disclose a paper dedicated to ink-jet image receiving containing a compound having a cationic group in a recording material, which greatly improves the dyeing property of an acid dye and has such an ink-jet image-receiving layer. By using special paper, it is possible to output in the form of inkjet coated paper or inkjet mat paper with a color tone and texture similar to printing paper without using printing paper that essentially does not accept any aqueous solvent at all, which is a very favorable situation It has become.

However, such ink-jet paper cannot hold dye indefinitely, and cannot hold dye in image output with excellent density and chroma required for print proofing in recent years. The problem has arisen. Dyes that cannot be retained cause deterioration of bleeding resistance and light resistance under high humidity, and it is difficult to achieve both image quality and image durability.

As a countermeasure for this, Hewlett-Packard Company has proposed and put into practical use a pigment ink using a black ink capable of giving the highest density as a pigment. Although such a correspondence is a preferable method, the density, light resistance, and bleeding resistance have a favorable effect, but have a problem in ejection stability, image fixability, and the like by using a black ink as a pigment ink. Not enough.

On the other hand, a method for forming an image using a reactive dye is disclosed in JP-A-56-143271 and JP-A-56-143271.
No. 161479 discloses a problem that the stability of the ink liquid is not sufficient. In order to improve the liquid stability of the reactive dye, an attempt has been made to use a hydrolysis product of the reactive dye as an ink dye in JP-A-59-19.
No. 9781. According to the present invention, it is considered that the liquid stability of the reactive dye was significantly improved and reached a practical level. However, in the case of the ink jet dedicated paper similar to the above-described printing paper, although the density is obtained, the saturation is insufficient, and the YMC (yellow, magenta, cyan)
Is not sufficiently satisfactory.

[0014]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to obtain an image which is excellent in light resistance and bleeding resistance while being an image having excellent density and saturation. Another object of the present invention is to provide an ink-jet ink set having excellent ejection stability and a black ink of the ink set.

[0015]

The above object of the present invention is achieved by the following constitution.

1. An inkjet ink set for forming a full-color image using a plurality of colors of an inkjet ink containing at least a water-soluble dye, a water-soluble organic solvent, and water, wherein the black ink contains a reactive dye. Ink set.

2. In an ink-jet ink set for forming a full-color image using a plurality of colors of an ink-jet ink containing at least a water-soluble dye, a water-soluble organic solvent, and water, the black ink contains a dye obtained by hydrolyzing a reactive dye. An ink set for ink jet, characterized by the following.

3. 3. The inkjet ink set according to 1 or 2, wherein the amount of the water-soluble organic solvent added to the black ink is 30 to 65% by mass.

4. The reactive dye is represented by the general formula (1),
(2) The ink set for inkjet according to (1), (2) or (3), which is a reactive dye represented by (3) or (4).

[5] The ink set for inkjet according to any one of claims 1 to 4, wherein the black ink further contains an acid dye.

6. The acid dye is C.I. I. Acid Yellow 42, C.I. I. Acid Red 106, C.I. I. Acid Red 249 or C.I. I. The ink set for inkjet according to 5, wherein the ink set is Acid Blue 249.

7. A black ink comprising a reactive dye represented by the general formula (1), (2), (3) or (4).

8. A black ink comprising a dye obtained by hydrolyzing a reactive dye represented by the general formula (1), (2), (3) or (4).

9. 9. The black ink according to 7 or 8, further comprising an acid dye.

10. The acid dye is C.I. I. Acid Yellow 42, C.I. I. Acid Red 106, C.I. I. Acid Red 249 or C.I. I. Acid Blue 249
10. The black ink according to 9, wherein

That is, in the present invention, the fixing means other than the cationic sites in the ink jet image receiving layer is provided to the black ink by using only the black ink as the reactive dye. Thus, it is possible to improve the bleeding of the high dye density portion and the light fastness while maintaining the high chroma image quality.

By using the hydrolyzate of the reactive dye only in the black ink as in claim 2, it is possible to improve the ejection stability while maintaining the same bleeding and light resistance as in claim 1. .

By increasing the amount of the water-soluble organic solvent added to the black ink, the fluctuation of pH, which is a problem with reactive dyes, can be reduced.
Furthermore, by using a combination in which the solubility of the water-soluble organic solvent and the dye is sufficiently high, the storage stability of the black ink can be increased without depending on water.

As described in claim 4, it has been found that a black ink containing a reactive dye of an azo dye having a specific structure is excellent in terms of bleeding, light resistance and storage stability. Furthermore, a black ink composed only of these combinations is particularly excellent in the above performance.

The present invention has been found that the output density can be further increased without deteriorating the discharge stability by additionally using an acid dye as in claims 5 and 6.

Hereinafter, the present invention will be described in detail. [Inkjet Ink Set] The inkjet ink set of the present invention has a basic configuration of four color inks of three primary colors YMC (yellow, magenta, cyan) and K (black) in printing. In a preferred embodiment, these are ink sets using two or more inks having different densities, which are conventionally known, for smooth gradation reproduction. In addition, from the viewpoint of improving spot color reproducibility and storage stability, YMC
It is also preferable to form an ink set using the color ink which is the secondary color of the above as a special color.

In any of the above combinations, in the present invention, the color ink other than the black ink is composed of a water-soluble dye other than the reactive dye, and is preferably composed mainly of an acid dye. Is preferable in terms of density and saturation, and it is particularly preferable that the color filter is composed of only an acid dye.

[Black Ink] The black ink of the present invention is characterized by containing at least a reactive dye and / or a hydrolyzate of the reactive dye and a water-soluble organic solvent.

Reactive Dye The reactive dye of the present invention is appropriately selected as required and dissolved in a solvent to be used. The typical ones are listed below. Of course, these are representative, and other dyes having structures similar to these may be used.

C. I. Reactive Yellow 1, 2,
3, 13, 14, 15, 17, 37, 42, 76, 8
5, 95, 168, 175; C.I. I. Reactive Red 2, 6, 11, 21, 22, 23, 24, 33, 4
5, 111, 112, 114, 180, 218, 22
6, 228, 235; I. Reactive Blue 7,
14, 15, 18, 19, 21, 25, 38, 49, 7
2, 77, 176, 203, 220, 230, 235;
C. I. Reactive Orange 5, 12, 13, 35,
95; I. Reactive Brown 7, 11, 33,
37, 46; I. Reactive green 8, 19;
C. I. Reactive Violet 2, 4, 6, 8, 2
1, 22, 25; C.I. I. Reactive Black 5,
8, 31, 39 The amount of the reactive dye used in the black ink of the present invention is preferably 1 to 20% by mass, based on the total mass of the black ink, as the solid content of the dye.

Any of the above reactive dyes can be preferably used, and in the present invention, these reactive dyes can be used in the form of a black ink by appropriately combining these reactive dyes.

It is also possible to use a mixture of an acidic dye or a known direct dye or basic dye described below. Above all, it is preferable to mix an acidic dye having good coloring properties, and conventionally known dyes can be mixed and used without any particular limitation.

The reactive dye preferably used in the black ink of the present invention includes azo dyes, which are reactive dyes represented by the above general formulas (1) to (4).

In the general formulas (1) to (4), T represents a linking group, and X represents a reactive group. M represents a hydrogen atom, an alkali metal or a substituted or unsubstituted ammonium group.

In the general formulas (1) to (4), T represents a linking group (group for bonding the reactive group X to the residue of the azo dye molecule), and X represents a reactive group. Preferably as a group, for example,

[0041]

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(Wherein R 'and R "are each
A hydrogen atom or a substituent). R ',
As the substituent represented by R ″, an alkyl group (for example, a methyl group, an ethyl group, a 2-hydroxyethyl group, a 2- (2-
(Hydroxyethyl) ethyl group, etc.), aryl group (phenyl group, p-sulfophenyl group, etc.), heterocyclic group (pyridyl group, etc.), hydroxyl group, azo dye molecule residue, etc. Among them, an alkyl group is preferable, and a 2-hydroxyethyl group and a 2- (2-hydroxyethyl) ethyl group are particularly preferable.

M is a hydrogen atom, an alkali metal or a substituent;
It represents an unsubstituted ammonium group, and examples of the alkali metal include a sodium atom, a potassium atom, and a lithium atom. As a substituted or unsubstituted ammonium group,
Examples include an ammonium group, a dimethyl ammonium group, a triethylammonium group, a triethanolammonium group, and the like.

Hereinafter, specific examples of the reactive dyes represented by formulas (1) to (4) which are preferably used for the black ink of the present invention will be described, but the present invention is not limited thereto.

[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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When these reactive dyes are appropriately combined and prepared into a black ink and used, a black ink having a particularly high concentration and excellent light resistance and bleeding resistance can be formed.

In the present invention, these reactive dyes are preferably used after being hydrolyzed, whereby the liquid stability can be improved and the discharge stability can be achieved.

The hydrolysis is carried out by a conventionally known method (JP-A-59-197781, "Preparation Example" on page 6).
Can be used without particular limitation.

Water-Soluble Organic Solvent The ink of the present invention contains water and a water-soluble organic solvent as main liquid medium components. The water-soluble organic solvent of the present invention has 1 to 1 carbon atoms.
4 alkyl alcohols (eg, methyl alcohol,
Ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, etc., amides (eg, dimethylformamide, dimethylacetamide, etc.), ketones or keto alcohols (eg, Acetone, diacetone alcohol, etc.), ethers (eg, tetrahydrofuran, dioxane, etc.), polyalkylene glycols (eg, polyethylene glycol, polypropylene glycol, etc.), alkylene glycols having an alkylene group containing 2 to 6 carbon atoms (eg, ethylene Glycol, propylene glycol, butylene glycol, triethylene glycol, 1,5 pentanediol, 1,2,6 hexanetriol, thiodiglycol Glycerin, lower alkyl ethers of polyhydric alcohols (such as ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, and triethylene glycol monomethyl (or ethyl) ether). .

Among these many water-soluble organic solvents,
Polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or ethyl) ether are preferred.

The content of the water-soluble organic solvent in each color ink is preferably from 10 to 70% by mass, more preferably from 30 to 65% by mass, particularly preferably from 45 to 60% by mass, based on the total amount of the ink. % Range.

When used in the above-mentioned range, the black ink, in particular, has a pH over time which is a problem of the reactive dye.
It is possible to emit light stably without causing deterioration of discharge stability due to precipitation due to fluctuation.

Acidic Dyes Specific examples of the acid dyes preferably used in combination with the black ink of the present invention are shown below, but the present invention is not limited thereto.

<Acid dye> C.I. I. Acid Yellow 2, 3, 7, 17, 19, 23, 25, 29, 38, 4
2, 49, 59, 61, 72, 99; I. Acid orange 56, 64; I. Acid Red 1, 8,
14, 18, 26, 32, 37, 42, 52, 57, 7
2, 74, 80, 87, 106, 115, 119, 13
1, 133, 134, 143, 154, 186, 24
9, 254, 256; C.I. I. Acid Violet 1
1, 34, 75; I. Acid Blue 1, 7, 9,
29, 87, 126, 138, 171, 175, 18
3, 234, 236, 249; I. Acid green 9, 12, 19, 27, 41; I. Acid Black 1, 2, 7, 24, 26, 48, 52, 58, 6
0, 94, 107, 109, 110, 119, 131,
155 These compounds can be used by being appropriately mixed with the above reactive dye. As the acid dye particularly preferably used in combination with the reactive dye in the black ink of the present invention,
C. having the following structure: I. Acid Yellow 42, C.I.
I. Acid Red 106, C.I. I. Acid Red 2
49, C.I. I. Acid Blue 249.

[0062]

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Additives The black ink of the present invention may contain a surfactant, a viscosity adjuster, etc. in accordance with the purpose of improving the ejection stability, compatibility with a print head or ink cartridge, storage stability, image storability, and other various properties. Agents, resistivity adjusters, film-forming agents, ultraviolet absorbers, antioxidants, discoloration inhibitors, rust inhibitors, preservatives, and the like.

In the black ink of the present invention, a surfactant can be used in order to accelerate the penetration of the ink droplets after ejection into the medium. As the surfactant to be used, conventionally known surfactants can be used without any particular limitation as long as they do not adversely affect the storage stability of the ink and the like. Specifically, for example, any of the following cationic, anionic, amphoteric, and nonionic types can be used.

Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts and the like.

Examples of the anionic surfactant include fatty acid soap, N-acyl-N-methylglycine salt, N-acyl-
N-methyl-β-alanine salt, N-acyl glutamate, acylated peptide, alkyl sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl sulfo acetate, α-olefin sulfone Acid salt, N
-Acylmethyl taurine, sulfated oil, higher alcohol sulfate, secondary higher alcohol sulfate,
Alkyl ether sulfate, secondary higher alcohol ethoxy sulfate, polyoxyethylene alkylphenyl ether sulfate, monoglycol sulfate, fatty acid alkylolamide sulfate, alkyl ether phosphate, alkyl phosphate, and the like. .

Examples of the amphoteric surfactant include carboxybetaine type, sulfobetaine type, aminocarboxylate, imidazolinium betaine and the like.

Examples of the nonionic activator include polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene glycerin fatty acid. Ester, polyoxyethylene, castor oil, hydrogenated castor oil, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, fatty acid alkanolamide , Polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, alkylamine oxide Id, acetylene glycol, acetylene alcohol, and the like.

[Other color inks other than black ink] The color inks other than the black ink among the inks of the ink-jet ink set of the present invention contain at least a water-soluble dye other than the reactive dye and a water-soluble organic solvent. .

As the dye, conventionally known dyes are used without any particular limitation, and examples thereof include direct dyes, acid dyes and basic dyes.

The following are representative dyes, but the present invention is not limited thereto. <Direct dye> C.I. I. Direct Yellow 1, 4, 8,
11, 12, 24, 26, 27, 28, 33, 39, 4
4, 50, 58, 85, 86, 100, 110, 12
0, 132, 142, 144; I. Direct Red 1, 2, 4, 9, 11, 13, 17, 20, 23, 2
4, 28, 31, 33, 37, 39, 44, 47, 4
8, 51, 62, 63, 75, 79, 80, 81, 8
3, 89, 90, 94, 95, 99, 220, 224,
227, 243; I. Direct Blue 1, 2,
6, 8, 15, 22, 25, 71, 76, 78, 80,
86, 87, 90, 98, 106, 108, 120, 1
23, 163, 165, 192, 193, 194, 19
5, 196, 199, 200, 201, 202, 20
3, 207, 236, 237; I. Direct Black 2, 3, 7, 17, 19, 22, 32, 38, 5
1, 56, 62, 71, 74, 75, 77, 105, 1
08, 112, 117, 154 <Acid dye> C.I. I. Acid Yellow 2, 3, 7, 1
7, 19, 23, 25, 29, 38, 42, 49, 5
9, 61, 72, 99; C.I. I. Acid Orange 5
6, 64; I. Acid Red 1, 8, 14, 1
8, 26, 32, 37, 42, 52, 57, 72, 7
4, 80, 87, 106, 115, 119, 131, 1
33, 134, 143, 154, 186, 249, 25
4, 256; I. Acid violet 11, 3
4, 75; I. Acid Blue 1, 7, 9, 29,
87, 126, 138, 171, 175, 183, 23
4, 236, 249; I. Acid Green 9, 1
2, 19, 27, 41; I. Acid Black 1,
2, 7, 24, 26, 48, 52, 58, 60, 94,
107, 109, 110, 119, 131, 155 <Basic dye> I. Basic Yellow 11, 1
4, 21, 32; C.I. I. Basic Red 1, 2,
9, 12, 13; I. Basic Violet 3,
7, 14; I. Basic Blue 3, 9, 24, 2
5. Dyes that can be used in addition to the above dyes include chelate dyes and azo dyes used for so-called silver dye bleaching photographic materials (for example, Cibachrome manufactured by Ciba Geigy).

As for the water-soluble organic solvent, surfactant and other additives, the same ones as in the case of the black ink can be used.

[Recording Method, Image Receiving Material] The ink of the present invention is not particularly limited with respect to the recording method used, and can be used in any ink jet recording method. It is preferable to use as an ink composition of an ink jet recording system for performing recording by ink. As the ink jet recording system, there are a continuous system and an on-demand system, and both systems can be used. Examples of the on-demand type system include an electro-mechanical conversion system (for example, a single cavity type, a double cavity type, a bender type, a piston type, a shared mode type, a shared wall type, etc.), and an electro-thermal conversion system (for example, thermal type). Inkjet type, bubble jet (registered trademark) type, etc.), electrostatic suction type (for example, electric field control type,
Specific examples include a slit jet type and the like, and a discharge method (for example, a spark jet type and the like).

As the ink jet recording medium, various recording media conventionally used are used. For example, various coated papers (art paper, coated paper, cast coated paper, etc.) in which a layer composed of a hydrophilic binder and an inorganic pigment is coated on a paper support, and further, these papers, various transparent or opaque papers A recording medium is used in which an ink absorbing layer is applied as a recording layer on a plastic film support or various supports in which both surfaces of paper are coated with a plastic resin.

The ink absorbing layer is roughly classified into a so-called swelling type ink absorbing layer mainly composed of a hydrophilic binder and a void type ink absorbing layer having a void layer in a recording layer. Is effectively used for a recording medium having both ink absorbing layers.

The ink of the present invention is particularly effective when the above-mentioned ink absorbing layer is thin.

[0077]

EXAMPLES The present invention will now be described specifically with reference to examples, but the embodiments of the present invention are not limited to these examples.

Example 1 <Preparation of Black Ink> After sufficiently stirring the following composition, a 0.8 μm filter (DISMIC-25C) was used.
S: Toyo Roshi Kaisha LTD) to obtain black inks K-1 (present invention), K-2 (present invention), and K-3 (comparative).

Dyes for black ink (described in Table 1) Amount described in Table 1 Proxel GXL (D) (manufactured by Zeneca, 20% by mass aqueous solution) 0.2% by mass ethylene glycol 12% by mass Diethylene glycol 13% by mass ion-exchanged water Amount to make the total mass 100 g <Preparation of yellow ink, magenta ink, and cyan ink> Acid dye C.I.
I. Acid yellow 42, 5% by mass of acid dye C.I.
I. Acid red 106, 3% by mass, acid dye C.I.
I. 3.8% by mass of Acid Blue 249 (described in Table 1)
A yellow ink Y-1, a magenta ink M-1, and a cyan ink C-1 were prepared in the same manner as in the preparation of the black ink, except that they were used.

<Preparation of Ink Set> Black Ink K
-1, yellow ink Y-1, magenta ink M-1,
An ink set combining the cyan ink C-1 is referred to as an ink set 1-1 (the present invention).

Black ink K-2, yellow ink Y
-1, magenta ink M-1, and cyan ink C-1 are referred to as ink set 1-2 (the present invention).

Black ink K-3, yellow ink Y
-1, magenta ink M-1 and cyan ink C-1 are combined with ink set 1-3 (comparison)
And

[0083]

[Table 1]

* ¹ : BASF Basacid Bla
ck X34, BASF, 33% by mass aqueous solution of solid content * ² : Kayacion Black P-NBR l
iq. 40, manufactured by Nippon Kayaku Co., Ltd., 40% by mass solid solution aqueous solution * ³ : Reactive dye Kayacion Black P-
NBR liq. 40 Hydrolyzate Reactive Dyes Kayacion Black P-NBR
liq. Preparation of hydrolyzate (* ³ ) of No. 40: The hydrolysis of the reactive dye is carried out according to a conventionally known hydrolysis method (Japanese Unexamined Patent Publication (Kokai) No. 59-197781, the description of "Preparation Example" on page 6). The procedure was as follows.

Reactive dye Kayacion Black
P-NBR liq. 40 (manufactured by Nippon Kayaku Co., Ltd .: solid content 4)
400 parts of distilled water with respect to 4 parts of 0 mass% aqueous solution)
Stir at 30 ° C. until homogeneously dissolved. Next, 1 part of sodium hydroxide was dissolved in 100 parts of distilled water, added to the aqueous dye solution prepared above, and stirred at 30 ° C. for 2.5 hours to complete the hydrolysis (the hydrolysis reaction was completed). Was confirmed by thin-layer chromatography).

Thereafter, a saturated aqueous solution of sodium acetate was added to the reaction solution to carry out salting out, and the resulting solution was collected by filtration.
A hydrolyzate of NBR was obtained. This was dissolved in water to form a 40% by mass aqueous solution, and the target Kayac having a solid content of 40% by mass was used.
A hydrolyzate of ion Black P-NBR was obtained.

The ink set prepared above was evaluated as follows. << Evaluation Method >> [Paper Only for Inkjet] The following paper was purchased and used as inkjet image receiving paper.

Coated paper: IJ-PR-SG127 (manufactured by Mitsubishi Paper Mills, average opening 127 g / m ² , semi-gross
s type) Photo Silky Paper: Konica Inkjet Paper QP
-Pro (Konica Corporation, Photosilky Thin) [Output] Inkjet printer (MachJet M
(J-810C, manufactured by Seiko Epson Corporation).

The target density of each color was set as follows, and the transport evaluation and the image quality evaluation at the target density were performed.

Y (yellow); 1.04 M (magenta); 1.53 C (cyan); 1.48 K (black); 1.83 The colorimetry is performed by a colorimeter (Gretag Macbeth; spectr).
(olino, keywizard) under the following conditions.

Light source; D50 visual field; 2 ° visual field density; ANSI T white standard; abs filter; no filter used <Evaluation item> [Bleed resistance] The above inkjet printer (Machjet MJ-810C, Seiko (Epson Corp.), 8 points each color-extracted character was output at the target density, and the image left for one week in an environment room at 25 ° C. and 80% was visually observed and observed with a 100-power loupe.

◎: No bleeding at all ○: Very slight bleeding with loupe ○ △: Bleeding can be confirmed with loupe △: Very slight bleeding with visual inspection △ ×: Bleeding with visual inspection X: A solid image is output at the target density on the purchased photo-silky paper by the above-mentioned inkjet printer, and a Xe fade meter (C: 65, manufactured by Atlas Co., Ltd.) can be confirmed. 70,000 lu using a xenon weather meter
x, 25 ° C., 80% relative humidity for 3 days, the solid images before and after that were measured with a colorimeter to determine the color difference ΔE.

◎ ・ ・ ・ ΔE is 0 or more and less than 2 ○ ・ ・ ・ ΔE is 2 or more and less than 3 ○ △ ・ ・ ΔE is 3 or more and less than 5 △ ・ ・ ・ ΔE is 5 or more and less than 7 △ × ・ ・ ΔE is 7 Not less than 10 × · ΔE is not less than 10 and less than 20 [Ejection stability]
After leaving for 1 day in an environment at a temperature of 20 ° C. and a relative humidity of 20%, it was confirmed by normal operation of the ink jet printer whether or not ejection was possible without any problem.

・ ・ ・: Discharge can be performed without any problem. △: Discharge requires one cleaning. ・ ・ ・: Discharge requires two or three cleanings. ×: Discharge cannot be performed. Seal the prepared ink liquid, and store at
The sample was placed in a thermostat in which the setting of ° C. was repeated every other day, left for a certain period described below, and taken out to check for the presence of sediment.

◎ ・ ・ ・ Precipitate precipitates after more than 3 months ○ ・ ・ ・ Precipitate precipitates after more than 1 month ○ △ ・ ・ Precipitate precipitates after more than 2 weeks △ ・ ・ ・ 1 A precipitate is deposited after more than one week. Δ ×: A precipitate is deposited after more than three days.... A precipitate is deposited after more than one day. The above results are shown in Table 2.

[0096]

[Table 2]

From Table 2, it can be seen that Black Ink 1-3 (Comparative)
As compared with the black ink 1-1 of the present invention containing the reactive dye of the present invention (the constitution of the first aspect of the present invention).
It can be seen that is excellent in light fastness, particularly, bleeding resistance.
When the reactive dye is a hydrolyzed dye (the structure of the invention of claim 2 of the present invention), it can be seen that the liquid dye is excellent in liquid preservability and is very preferable.

In each of the ink sets prepared in Example 1, a standard chart specified in ISO 1264 was output, and color measurement was performed 10 minutes after the output was completed. Color gamut mapping in a three-dimensional color space was performed from the 928 L ^* a ^* b ^* data, and it was confirmed that the color gamut reproducible from the ink set of the comparative acid dye did not change at all. It turns out that it can respond to output.

Example 2 For the black ink K-1 of the ink set 1-1 of the present invention of Example 1, the solvent (type and amount) was as follows.
Was changed in the same manner except that the black ink K-
4 to K-6 were produced.

[0100] Kayacion Black P-NBR liq. 40 (manufactured by Nippon Kayaku Co., Ltd., solid content 40% by mass aqueous solution) 25% by mass Proxel GXL (D) (manufactured by Zeneca Corporation, 20% by mass aqueous solution) 0.2% by mass Solvent: ethylene glycol Amount described in Table 3 Propylene glycol Table 3. Amount described in 3 Ion-exchanged water An amount that makes the total mass 100 g The black inks K-4 to K-6 of the present invention prepared above.
Are combined with the yellow ink Y-1, the magenta ink M-1, and the cyan ink C-1 in the same manner as in Example 1 to obtain ink sets 2-1 to 2-3 of the present invention. Was evaluated.

Table 3 shows the above progress, and Table 4 shows the results.

[0102]

[Table 3]

[0103]

[Table 4]

From Tables 3 and 4, it can be seen that the black inks of the present invention are all excellent in light resistance and bleeding resistance.

When the amount of the water-soluble organic solvent added to the black ink of the present invention is small, a precipitate is liable to be generated during long-term storage of the ink liquid. On the other hand, when the amount of addition is large, the viscosity of the liquid is increased, and ejection bending or the like is likely to occur. Further, since a large amount of solvent remains on the recording medium, the storage stability of the image tends to deteriorate. From the above, it can be seen that use within the more preferable range of the present invention (the structure of the invention of claim 3 of the present invention) is particularly preferable.

Example 3 Black inks K-7 to K-12 of the present invention having the following compositions
Was produced in the same manner as in Example 1.

<Composition of Black Ink> Dye for Black Ink (described in Table 5) Amount described in Table 5 Proxel GXL (D) [manufactured by Zeneca: 20% by mass aqueous solution] 0.2% by mass ethylene glycol 24% by mass propylene Glycol 22% by mass Ion-exchanged water Amount of the total mass to be 100 g Black inks K-7 to K-1 of the present invention prepared above.
2 was combined with yellow ink Y-1, magenta ink M-1, and cyan ink C-1 in the same manner as in Example 1 to form ink sets 3-1 to 3-6 of the present invention. It evaluated similarly.

Table 5 shows the above progress, and Table 6 shows the results.

[0109]

[Table 5]

[0110]

[Table 6]

* ¹¹ : Dystar Remazol B
black liq50, manufactured by Dystar Japan, 50% by weight solid content aqueous solution * ¹² : Cibacron Black P-GR-01
L40%, Ciba Specialty Chemicals, 40% by mass aqueous solution of solid content * ¹³ : Kayakron Black PN Liq
uid 40, manufactured by Nippon Kayaku Co., Ltd., aqueous solution of 40% by mass of solid content * ¹⁴ : Cibacron Black P-GR-01
L40% hydrolyzate (reactive dye Kayakion Black P-NBRliq.4 in Example 1)
The hydrolyzate was prepared in the same manner as in the preparation of the hydrolyzate of No. 0 (according to a conventionally known hydrolysis method (described in "Preparation Examples" on page 6, JP-A-59-197781)). ) * ¹⁵ : Cibacron Orange P-2R F
40% hydrolyzate (reactive dye Ka in Example 1)
yacion Black P-NBR liq. 40
(* ³ ) in the same manner as in the preparation of the hydrolyzate (* ³ ) described in
(Preparation Example) on page 6). Tables 5 and 6 show that the black inks of the present invention are all excellent in light resistance and bleeding resistance.

Further, when the dye constituting the black ink of the present invention is a reactive dye, the bleeding resistance is particularly good.
It can be seen that the solution has excellent storage stability. Further, it can be seen that the use of a hydrolyzate of a reactive dye or the combined use with an acid dye further improves the respective performances, and is particularly effective for improving the liquid storage stability.

[0113]

Industrial Applicability According to the present invention, an ink jet ink set which can obtain an image having excellent light fastness and bleeding resistance while having an image excellent in density and saturation and excellent in ejection stability, and an ink set of the ink set. Black ink could be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09B 62/245 C09B 62/25 62/25 62/33 62/33 62/51 C 62/51 62/513 62/513 B41J 3/04 101Y F-term (reference) 2C056 EA13 FC01 2H086 BA52 BA53 BA56 BA57 4H056 FA01 JA02 JA06 JB02 JB03 JC05 JC09 JC13 4J039 BA29 BC05 BC07 BC12 BC29 BC33 BC37 BC40 BC41 BC47 BC04 BC73 BC66 BC66 BC66 BC66 BE12 CA03 CA06 EA15 EA16 EA17 EA19 EA35 EA45 EA47 GA24

Claims (10)

[Claims] 1. A black ink containing a reactive dye in an ink-jet ink set for forming a full-color image using a plurality of colors of an ink-jet ink containing at least a water-soluble dye, a water-soluble organic solvent, and water. An ink set for ink jet, characterized by the following. 2. In an ink-jet ink set for forming a full-color image using a plurality of colors of an ink-jet ink containing at least a water-soluble dye, a water-soluble organic solvent, and water, the black ink hydrolyzes the reactive dye. An ink set for inkjet, comprising a dye. 3. The ink-jet ink set according to claim 1, wherein the amount of the water-soluble organic solvent added to the black ink is 30 to 65% by mass. 4. The reactive dye represented by the following general formula (1):
The inkjet ink set according to claim 1, 2 or 3, wherein the reactive dye is a reactive dye represented by (2), (3) or (4). Embedded image [Wherein, T represents a linking group, and X represents a reactive group. M represents a hydrogen atom, an alkali metal or a substituted or unsubstituted ammonium group. ] 5. The ink-jet ink set according to claim 1, wherein the black ink further contains an acid dye. 6. The method according to claim 1, wherein the acid dye is C.I. I. Acid Yellow 4
2, C.I. I. Acid Red 106, C.I. I. Acid Red 249 or C.I. I. The ink set for inkjet according to claim 5, wherein the ink set is Acid Blue 249. 7. A black ink comprising a reactive dye represented by the general formula (1), (2), (3) or (4). 8. A black ink containing a dye obtained by hydrolyzing a reactive dye represented by the general formula (1), (2), (3) or (4). 9. The black ink according to claim 7, further comprising an acid dye. 10. The method according to claim 10, wherein the acid dye is C.I. I. Acid Yellow 42, C.I. I. Acid Red 106, C.I. I. Acid Red 249 or C.I. I. The black ink according to claim 9, wherein the black ink is Acid Blue 249.