JP2000303009A - Water-base ink composition and ink jet recording process - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink composition which can give a recording having high fastness to light and water by using a tetrasulfocopper phthalocyanine as the colorant. SOLUTION: This composition contains a compound of the formula as the colorant. In the formula, M is H, an alkali (alkaline earth) metal, an alkylamine or alkanolamine cation, or ammonium; and (a), (b), (c) and (d) each 0 or 1; provided that their sum is 1-4. If necessary, the composition may further contain Direct Blue 86 (R) and/or Direct Blue 87 (R) and/or Direct Blue 199 (R) and/or Acid Blue 9 (R). The composition is a water-base one in which the medium is water optiotrally containing at most 1 wt.% water-soluble organic solvent and/or inorganic salt. The colorant is produced, for example, by reacting 4- sulfophthalic acid or both 4-sulfophthalic acid and phthalic anhydride in a desired ratio under heating in the presence of a catalyst and a copper compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an aqueous ink composition and a recording method. More specifically, the present invention relates to a cyan-based aqueous ink composition containing a specific compound and an inkjet recording method.

[0002]

2. Description of the Related Art Various types of ink ejection methods have been developed as recording methods using an ink jet printer, but all of them generate small ink droplets and attach them to various recording materials (paper, film, cloth, etc.). Alternatively, it is dyed and recorded. The recording method using an ink jet printer is characterized in that the recording head and the recording material do not come into contact with each other, so that there is no sound and the recording is quiet, and that printing can be performed anywhere, such as uneven surfaces, flexible materials, and fragile products. . In addition, printers have been rapidly spread in recent years due to their features of miniaturization, high speed, and easy colorization, and great growth is expected in the future. Image or character information on a color display of a computer is colorized by an ink jet printer.
In general, recording is performed by subtractive color mixing using four inks in which black (K) is added to three primary colors of yellow (Y), magenta (M), and cyan (C). In order to reproduce the additive color image of red (R), green (G), and blue (B) as faithfully as possible on a CRT display or the like, the dyes used, especially the dyes used in the YMC ink, are as YMC each as possible. It is desirable to have a hue close to the standard and to be sharp. Further, the ink composition is required to be stable for long-term storage, to have a high density of a printed image, and to be excellent in fastness such as water fastness and light fastness. In the future, when used in exhibitions such as advertisements in order to expand the field of use, exposure to light (electric lamps, fluorescent lamps, sunlight, etc.) will increase in many cases, and ink compositions with particularly excellent light resistance are required. ing. Among them, many of the cyan inks are Direct Blue 86 or Di
A phthalocyanine-based dye such as Rect Blue 199 is used, and these dyes are characterized by having superior light fastness compared to magenta and yellow. However, Direct Blue 86 or Direct Blue 86
Phthalocyanine dyes such as Blue 199 have a greenish hue under acidic conditions and are unsuitable for cyan ink. Therefore, when these dyes are used as cyan ink, it is most suitable to use them under neutral to alkaline conditions. However, even if the ink is neutral to alkaline, the hue of the printed matter may significantly change when the recording material to be used is acidic paper. Further, the color changes to green due to oxidizing gases such as nitrogen oxide gas and ozone, which are often taken up as an environmental problem these days.
From the above, it has not yet been possible to provide a product which sufficiently satisfies the market requirements even with the aqueous cyan ink.

[0003]

The applications of ink jet printers have been expanded from small printers for office automation to large printers for industrial use, and the opportunities for exposing printed matter outdoors have increased, so that the ink jet printer has a robustness such as water resistance and light resistance. Sex is more demanding than ever. Regarding water resistance, inorganic fine particles such as porous silica, cationic polymer, alumina sol or special ceramics that can adsorb the dye in the ink are used.
It is greatly improved by coating the surface of paper together with VA resin. Further, with respect to light resistance, phthalocyanine dyes used for cyan are superior to other magenta and yellow, and studies for improving light resistance have not been conducted as much as magenta and yellow. However, cyan currently used has problems such as discoloration and fading under acidic conditions and oxidizing gas. In the midst of environmental problems such as acid rain or nitric oxide gas, it is important to develop an ink with less discoloration and fading under acidic conditions and under oxidizing gas in order to maintain print quality even outdoors. It has become.

As a cyan dye skeleton used in an aqueous ink for ink jet recording, a phthalocyanine type and a triphenylmethane type are typical. However, for the phthalocyanine dyes currently used, hue, water resistance,
Although excellent in light resistance, there are problems such as discoloration and fading under acidic conditions. Further, the triphenylmethane type has good hue, but is very poor in light resistance and water resistance. An object of the present invention is to provide a cyan ink composition which has a hue and sharpness suitable for ink jet recording, has strong light fastness and water fastness of a recorded matter, and has less discoloration and fading even under acidic conditions. And

[0005]

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) a dye component represented by the formula (1):

[0006]

Embedded image

Wherein M represents a hydrogen atom, a cation of an alkali metal, an alkaline earth metal, an alkylamine, an alkanolamine or ammonium. A, b, c, d
Is 0 or 1, and the sum is an integer of 1 to 4. )
(2) a compound represented by the formula (1) described in (1) and Direct Blue 86 and / or Dir.
ect Blue 87 and / or Direct Bl
aqueous ink composition according to (1) or (2), which contains water 199 and / or Acid Blue 9; and (3) the aqueous ink composition according to (1) or (2), which contains water and a water-soluble organic solvent. The aqueous ink composition according to any one of (1) to (3), wherein the content of the inorganic salt is 1% by weight or less,
(5) For inkjet recording (1) to (4)
The aqueous ink composition according to any one of the above,

(6) The aqueous ink composition according to any one of (1) to (5), wherein the ink is an ink jet recording method in which ink droplets are ejected in accordance with a recording signal to perform recording on a recording material. (7) The inkjet recording method according to (6), wherein the recording material is an information transmission sheet,
(8) The ink jet recording method according to (6), wherein the recording material is an information transmission sheet surface-treated with an inorganic material and / or a polymer, and (9) the recording material is a porous silica and / or alumina sol as an inorganic material. And / or (10) the ink jet recording method according to (6), wherein the recording medium is a hydrophilic polymer and / or an acrylic polymer and / or a polyurethane polymer. The ink jet recording method according to (6), wherein the information transmission sheet is a surface-treated information transmission sheet, and (11) the information transmission sheet is a surface-treated information recording material which is treated with a polyvinyl alcohol and / or polyvinyl pyrrolidone as a hydrophilic polymer. The inkjet recording method according to (6), wherein (12) any one of (1) to (5) (13) An inkjet printer having the container according to (12), (14) tetrasulfocopper obtained by reacting 4-sulfophthalic acid in the presence of a copper compound Aqueous ink composition containing phthalocyanine,
(15) An aqueous ink composition containing copper phthalocyanine obtained by reacting 4-sulfophthalic acid and phthalic acid in the presence of a copper compound.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail. The aqueous ink composition of the present invention is characterized by containing a cyan compound represented by the formula (1) as a pigment component, and contains another cyan compound (DirectBlue 8).
6, Direct Blue 87, Direct B
lue 199, Acid Blue 9).

The cyan dye component used in the present invention is usually produced using phthalic anhydride and 4-sulfophthalic acid as raw materials. The number of sulfone groups can be adjusted by changing the molar ratio of the reaction between 4-sulfophthalic acid and phthalic anhydride. However, since mono or disulfone phthalocyanine has low solubility, it is preferable that the content thereof is small when used as an ink. The content thereof is determined by, for example, mass spectrometry (ESI-MS = electrospray-ionization measurement) or elemental analysis, and the content of mono- and disulfone-copper phthalocyanine is 50% or less, preferably 40% or less, more preferably 30% or less, particularly Preferably it is about 20% or less. The compound of the formula (1) is described in JH Weber,
Inorganic Chemistry, Vol 4,
469 (1965).

The dye component used in the present invention can be produced, for example, by subjecting 4-sulfophthalic acid or 4-sulfophthalic acid and phthalic anhydride in a desired ratio to a heat reaction in the presence of a catalyst and a copper compound. can get. The reaction temperature is usually 150 to 290 ° C. at normal pressure, preferably 170 to 290 ° C.
270 ° C. The reaction time varies depending on the reaction temperature, but is usually 1 to 8 hours. After completion of the reaction, the compound of formula (1) is obtained by filtration, salting out (or aciding out), and drying. Note that a, b, c, and d in the formula (1) are 0 or 1 and
Depending on the usage ratio of sulfophthalic acids and phthalic anhydrides,
The sum is an average value of 4 or less. Examples of the copper compound include copper chloride.

The compound synthesized by the above method is usually obtained in the form of a free acid or a salt thereof. In order to obtain a free acid, for example, acid precipitation may be performed. In addition, in order to form a salt, for example, a conventional salt exchange method in which a desired organic or inorganic base is added to a free acid may be applied.

M of the compound of the above formula (1) thus obtained is a hydrogen atom, an alkali metal, an alkaline earth metal, a cation of an alkylamine or an alkanolamine or ammonium. Examples of the alkali metal include sodium, potassium and Examples of lithium and the like and alkaline earth metals include calcium and magnesium. Examples of the alkylamine include methylamine and ethylamine, and examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine. Preferred M is
For example, hydrogen ion, ammonium ion, sodium ion, potassium ion, alkali metal ion such as lithium ion, monoethanolamine ion, diethanolamine ion, triethanolamine ion, monoisopropanolamine ion, diisopropanolamine ion, triisopropanolamine ion, etc. Alkanolamine ions and the like.

In the above formula (1), a, b, c, d are 0 or 1, and the sum is an integer of 4 or less. Usually, as long as phthalocyanine is not synthesized using only 4-sulfophthalic acid, it is obtained as a mixture of compounds in which the sum of a, b, c, and d is 0 to 4. However, when the sum of a, b, c, and d is 0 or 1, the solubility is low, so that it is preferable to adjust the mixing amount as described above in the process of filtration or purification. Note that a, b,
The sum of c and d is determined by mass spectrometry (ESI-MS), elemental analysis,
It can be measured by a method such as neutralization titration.

The dye component in the aqueous ink composition of the present invention may be a compound of the above formula (1) alone or a compound of the above formula (1) and another cyan compound (Direct Blue).
86, Direct Blue 87, Direct
Used as a mixture with Blue 199, Acid Blue 9). When mixed and used, the mixing ratio of the latter is 0 to 60%, preferably 0 to 50%, more preferably 0 to 40%, particularly preferably 0 to 30%, and this is added to water or a water-soluble organic solvent. It is dissolved. The pH of the ink is preferably about 6 to 11. When using this aqueous ink composition in an inkjet recording printer,
Metal cation chloride (eg, sodium chloride), sulfate (eg, sodium sulfate) contained in the ink composition
It is preferable that the content of the inorganic salt is small, and the content is preferably 1% by weight or less as the total content of the inorganic salt. To produce an ink composition with less inorganic salts,
For example, desalting may be carried out by a conventional method using a reverse osmosis membrane or a method of stirring a dried product or a wet cake of the other dye component of formula (1) in a mixed solvent of methanol and water, followed by filtration and drying.

The aqueous ink composition of the present invention is prepared using water as a medium, and the compound of the formula (1) is preferably 0.1 to 20% by weight, more preferably 0.1 to 20% by weight in the aqueous ink composition. The content is 1 to 10% by weight, more preferably 0.5 to 8% by weight. The aqueous ink composition of the present invention may further contain a water-soluble organic solvent or an ink preparation. The content of the water-soluble organic solvent is 0 to 30% by weight, preferably 1 to 30% by weight.
0 to 30% by weight, and the ink preparation is 0 to 5% by weight, preferably 0 to 2% by weight.

The ink composition of the present invention is prepared by adding the above-mentioned compound and, if necessary, the following water-soluble organic solvent, ink preparation agent, etc. to water from which impurities such as distilled water and ion-exchanged water have been removed. You. Further, a pigment component (dye) may be added to and dissolved in a mixture of water and the following water-soluble organic solvent, ink preparation agent and the like. If necessary, filtration may be performed after obtaining the ink composition to remove impurities. If desired, dye components other than those described above may be added within a range not departing from the object of the present invention.

Examples of usable water-soluble organic solvents include, for example,
Methanol, ethanol, propanol, isopropa
Knol, butanol, isobutanol, secondary butanol
C such as tertiary butanol₁ ~ C_Four Alkanol, N,
N-dimethylformamide or N, N-dimethylaceto
Carboxylic acid amides such as amides, ε-caprolactam, N
Lactams such as -methylpyrrolidin-2-one, urea,
1,3-dimethylimidazolidin-2-one or 1,3
-Cyclic urine such as dimethylhexahydropyrimid-2-one
Element, acetone, methyl ethyl ketone, 2-methyl-2-
Ketones or ketoals such as hydroxypentan-4-one
Ethers such as coal, tetrahydrofuran and dioxane
, Ethylene glycol, 1,2- or 1,3-propyl
Len glycol, 1,2- or 1,4-butylene glyco
, 1,6-hexylene glycol, diethylene glycol
Coal, triethylene glycol, dipropylene glycol
Tool, thiodiglycol, polyethylene glycol,
C such as propylene glycol _Two ~ C₆ Alkylene unit
A mono-, oligo- or polyalkylene glycol having
Or thioglycol, glycerin, hexane-1.
2.6 polyols (triols) such as triol,
Tylene glycol monomethyl ether, ethylene glycol
Coal monoethyl ether, diethylene glycol mono
Methyl ether, diethylene glycol monoethyl acetate
Ter, triethylene glycol monomethyl ether,
Polyvalent alcohols such as ethylene glycol monoethyl ether
Call C₁~ C_Four Alkyl ether, γ-butyrolact
And dimethyl sulfoxide. these
May be used in combination of two or more.

Preferred water-soluble organic solvents include N-methyl
Rupyrrolidin-2-one, C_Two ~ C ₆ Alkylene units
Having mono, di or trialkylene glycol, preferred
Or mono, di or triethylene glycol, dipropylene
Glycol, dimethyl sulfoxide, etc.
N-methylpyrrolidin-2-one, diethyleneglycol
The use of coal, dimethyl sulfoxide is preferred.

Examples of the ink preparation agent include an antiseptic / antifungal agent, a pH adjuster, a chelating agent, a rust inhibitor, a water-soluble ultraviolet absorber, a water-soluble polymer compound, a dye dissolving agent, a surfactant and the like.

Examples of preservatives and fungicides include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1
-Sodium oxide, sodium benzoate, sodium pentachlorophenol and the like.

As the pH adjuster, any substance can be used as long as it can control the pH of the ink within the range of 6 to 11 without adversely affecting the prepared ink. Examples thereof include alkanolamines such as diethanolamine and triethanolamine, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, and lithium carbonate, sodium carbonate, and potassium carbonate. Examples thereof include carbonates of alkali metals.

Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate,
Examples include sodium hydroxytylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uramildiacetate. Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, and the like. Examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamine, polyimine and the like.
Examples of the water-soluble ultraviolet absorber include sulfonated benzophenone and sulfonated benzotriazole. Examples of the dye dissolving agent include ε-caprolactam, ethylene carbonate, urea and the like.
As the surfactant, for example, anionic, cationic,
Known surfactants such as nonionic surfactants can be used.

Examples of the recording material in the ink jet recording method of the present invention include, for example, an information transmitting sheet such as paper and film, fiber 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. An ink receiving layer provided with an ink receiving layer is usually called a special paper (film) for ink jet or a glossy paper (film) for ink jet. For example, Pictorico (manufactured by Asahi Glass Co., Ltd.), color BJ paper, color BJ photo film sheet (both from Canon Inc.) ), Color image jet paper (manufactured by Sharp Corporation), glossy film for Super Fine (manufactured by Seiko Epson Corporation), Pictafine (manufactured by Hitachi Maxell), and the like. As an example of the ink receiving layer, for example, inorganic fine particles capable of adsorbing the dye in the ink such as porous silica, alumina sol, and special ceramics are coated on the surface of the base material together with a hydrophilic polymer such as polyvinyl alcohol or polyvinylpyrrolidone. It is provided by doing. Of course, it can be used for plain paper.

The aqueous ink composition according to the present invention has high solubility in water and does not cause separation of precipitate during storage. Further, when the aqueous ink composition of the present invention is used in an ink jet printer, the injection nozzle is not clogged and stored for a long time (use under constant recirculation or use under intermittent interruption). Even so, the aqueous ink composition of the present invention does not cause any change in physical properties.

The container of the present invention contains the above-mentioned aqueous ink composition. Further, the ink jet printer of the present invention,
The container of the present invention containing the aqueous ink composition is set in an ink tank portion. When the ink composition of the present invention is applied to a paper or film manufactured for inkjet, such as an inkjet paper (film) or an inkjet glossy paper (film) provided with an ink receiving layer as described above. It is preferable because the effects of the present invention are more exhibited.

The aqueous ink composition of the present invention has a sharp,
It is an ideal cyan color similar to the standard cyan color of the NC (Japan Printing Machinery Association), and can be used with other magenta and yellow inks to produce a wide visible color tone. . Also, when used with existing magenta, yellow, and black, which are excellent in light resistance and water resistance, and are resistant to use under acidic conditions, it is possible to obtain recorded materials that have excellent light resistance and water resistance, and are resistant to use under acidic conditions. Can be.

[0028]

The present invention will be described in more detail with reference to the following examples. In the text, “parts” and “%” are based on weight unless otherwise specified.

Synthesis Example 1 40 parts of sulfolane were added to a four-necked flask equipped with a cooling tube, and the temperature was raised to 180 ° C. in 1 hour. Thereto, 40 parts of 4-sulfophthalic acid, 4.5 parts of ammonium chloride, and 55 parts of urea were added.
Part, ammonium molybdate 0.5 part, copper (II) chloride
6 parts were added and stirred at the same temperature for 6 hours. Reaction solution at 40 ° C
After cooling, the target substance was filtered through Nutsche and 400
Washed with part of methanol. Subsequently, 300 parts of water was added to the obtained wet cake, and the resulting wet cake was adjusted to pH 1 with a 48% aqueous caustic solution.
Adjust to 0 and stir at 80 ° C. for 1 hour. While stirring, a 35% aqueous hydrochloric acid solution was added to adjust the pH to 3, and 80 parts of sodium chloride was gradually added thereto. The precipitated crystals are collected by filtration and
The resultant was washed with 150 parts of a sodium chloride solution to obtain 90 parts of a wet cake. Subsequently, 210 parts of methanol was added and stirred for 1 hour.
The precipitated crystals are separated by filtration, and a 70% aqueous methanol solution 300
22. After washing with a part, drying is performed, and sulfo copper phthalocyanine having a total of four sulfone groups at the 4-position (4, 4 ′, 4 ″, 4 ″ ′) of each benzene nucleus in the formula (1).
9 parts were obtained as blue crystals. λmax: 629 nm (in aqueous solution).

Synthesis Example 2 Nitrobenzene 40 was placed in a four-necked flask equipped with a cooling tube.
Then, the temperature was raised to 180 ° C. in 1 hour, and then 32 parts of 4-sulfophthalic acid, 6 parts of phthalic anhydride, 4.5 parts of ammonium chloride, 55 parts of urea, 0.5 part of ammonium molybdate, 0.5 part of copper chloride ( II) 6 parts were added and stirred at the same temperature for 6 hours. After the reaction solution was cooled to 40 ° C., the target substance was filtered with a Nutsche and washed with 400 parts of methanol. Subsequently, 300 parts of water was added to the obtained wet cake, and 4
Adjust to pH 10 with 8% aqueous caustic and stir at 80 ° C. for 1 hour. While stirring, a 35% aqueous hydrochloric acid solution was added to adjust the pH to 3, and 80 parts of sodium chloride was gradually added thereto. The precipitated crystals were collected by filtration and washed with 150 parts of a 20% saline solution to obtain 90 parts of a wet cake. Subsequently, 210 parts of methanol was added and the mixture was stirred for 1 hour. The precipitated crystals were separated by filtration, washed with 300 parts of a 70% aqueous methanol solution and dried, and in formula (1), a sulfone group at the 4-position was averaged in one molecule. Copper phthalocyanine (3: 4: 3: 2)
27.9 parts (3: 10: 3, from ESI-MS) were obtained as blue crystals. (Ratio of two sulfone groups 18.8
%) Λmax: 629 nm (in aqueous solution).

Example 1 (A) Preparation of Ink The components shown in Table 1 below were mixed and dissolved, and the mixture was filtered through a 0.45 μm membrane filter to obtain an aqueous ink composition for ink jet.

[0032]

[Table 1] 2.0 parts of each coloring matter component obtained in the above synthesis example (using a desalted material) 79.0 parts of water 5.0 parts of glycerin 5.0 parts of urea 5.0 parts of N-methyl-2-pyrrolidone 4 3.0 parts IPA 3.0 parts Butyl carbitol 2.0 parts Total 100.0 parts

An existing ink blended with a cyan dye is the same as the dye component obtained in Synthesis Example 1 and Direct Blue.
86, Direct Blue 87, Direct
Blue 199 and Acid Blue 9 were mixed at a weight ratio of 9: 1, respectively, and adjusted so that the above-mentioned ink composition and the optical density matched.

(B) Inkjet printing Inkjet printer (brand name: NEC Corporation, Picty)
80L) using plain paper (printer paper A4T)
LB5A4S (manufactured by Canon Inc.) and three types of commercially available processed paper surface-treated with an inorganic substance and / or a polymer. Special paper (coated paper for color image jet STX73A4)
(Manufactured by Sharp Corporation)), glossy film A (color BJ photosheet film CA-101 (manufactured by Canon)), glossy film B (special glossy film MJA4SP6 (manufactured by Seiko Epson)) Was subjected to inkjet recording. Tables 2 and 3 show the results of the hue, sharpness, light resistance test, water resistance test, nitric oxide gas discoloration test and acid drop discoloration test of the recorded image of the aqueous ink composition of the present invention.

As a comparative object, Direct Blue, which is actually used as a cyan dye for inkjet, is used.
86 (Comparative Example 1), Direct Blue 87 (Comparative Example 2), Direct Blue 199 (Comparative Example 3), and Acid Blue 9 (Comparative Example 4) with the same ink composition and the same optical density as the ink composition of the present invention. Hue, sharpness of the recorded image of the ink composition adjusted as described above,
Table 4 shows the results of the light resistance test, water resistance test, nitric oxide gas discoloration test and acid drop discoloration test. Further, as a material for comparison with the hue and sharpness of the ink composition of the present invention, J
Table 5 shows the hues and clarity of NC Japan Color standard cyan color samples.

(C) Evaluation of recorded image Hue evaluation Hue and clarity of recorded image: Gretag SP
Measure color using M50 (manufactured by GRETAG), L *,
Calculate a * and b * values. Hue is JAPAN C of JNC
The comparison with the color standard cyan color sample and the sharpness were evaluated by C * = ((a *) ² + (b *) ² ) ^1/2 . Light resistance test The recorded images were irradiated with carbon arc for 40 hours using a carbon arc fade meter (manufactured by Suga Test Instruments Co., Ltd.).
The judgment grade was determined according to the blue scale grade specified in JIS L-0841, and the color difference (ΔE) before and after the test was measured using the above colorimetric system. Water resistance test Put the recording paper in a beaker filled with water, stir for 2 minutes, take out and air-dry. Determine the change before and after the test by JIS discoloration gray scale, and use the above colorimetric system to determine the color difference before and after the test. Was measured. Nitrogen oxide gas discoloration test Based on the dyeing fastness test method (L0855) for dyed textiles to nitric oxide according to JIS standards, a strong test (three times weak test) and a stronger test (one test in nitric oxide gas)
), And perform the above measurements together with the visual judgment (◎ Hue change is extremely small, ○ Hue change is small, △ Hue change is slightly large, × Hue change is large, G discolors to green, B discolors to blue or navy). The color difference before and after the test was measured using a color system. Acid dripping test A 10% hydrochloric acid aqueous solution is dropped on the printed matter, and the discoloration is visually determined (◎ Hue change is extremely small, ○ Hue change is small, △ Hue change is slightly large, × Hue change is large, G turns green) The color difference before and after the test was measured using the above colorimetric system.

Tables 2 and 3 below show data on the hue, sharpness, light resistance, water resistance, nitrogen oxide gas resistance, and acid discoloration resistance of the aqueous ink of the present invention. Dyes (Direct Blue 86 (Comparative Example 1), Direct
ct Blue 87 (Comparative Example 2), DirectBl
ue 199 (Comparative Example 3) and Acid Blue 9
Table 4 shows the data of (Comparative Example 4).

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

When the results in Table 2 were compared with those in Table 4 of Comparative Examples, it was found that the printed matter using the ink of the present invention had good light fastness and water fastness, and showed no discoloration even in the tests of nitrogen oxide gas resistance and acid discoloration resistance. Almost never seen. On the other hand, the commonly used Direct Blue 86, Direct
In Blue 87, Direct Blue 199 and Acid Blue 9, the color changes to green (a phthalocyanine dye) or blue (a triphenylmethane dye). In particular, a large difference was observed in printed matter (special paper, glossy film A, glossy film B) on an information transmission sheet surface-treated with an inorganic substance and / or a polymer. Also, from the results in Table 3, when these commonly used cyan dyes are also used in combination with a copper phthalocyanine dye having a sulfone group, discoloration under nitrogen oxide gas and acidic conditions is suppressed as compared with the case where they are used alone. I understand.

As a material for comparison of hue and sharpness, JN
Table 5 shows the hues and clarity of C Japan Color standard cyan color samples.

Table 5 Hue Sharpness L * a * b * (C *) JNC standard cyan 53.9 -35.9 -50.4 61.9

From the comparison of Tables 2 and 3 with Table 5, the ink of the present invention is similar to the standard cyan hue of JNC and is suitable as a cyan ink for ink jet.

From the above, it can be seen that the ink of the present invention is a very excellent cyan ink for inkjet which has a small discoloration even under acidic conditions and has a wide use range.

[0046]

The ink composition of the present invention is capable of high-concentration ink-jet printing as an ink-jet ink, has no crystal precipitation, physical property change, color change, etc. after long-term storage, and has good storage stability. . Printed matter using the ink composition of the present invention as a cyan ink for inkjet recording is excellent in light resistance and water resistance, and can be used in combination with magenta, yellow, and black dyes to enable inkjet recording excellent in light resistance and water resistance. It is. Furthermore, discoloration is small even under an oxidizing gas such as nitrogen oxide gas or ozone, and a drop test of a 10% hydrochloric acid aqueous solution is also good. In particular, excellent results are obtained in printed matter on an information transmission sheet surface-treated with an inorganic substance and / or a polymer. From these results, the ink composition of the present invention enables application of print recording by the inkjet method to a wider use than ever, such as outdoor use and printing on acidic paper. Since the printed surface of the ink composition of the present invention is a clear and preferable cyan color, by using it together with other magenta and yellow inks, a color tone in a wide visible region can be obtained.

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Claims (15)

[Claims] (1) A dye component represented by the formula (1): (Wherein, M represents a hydrogen atom, an alkali metal, an alkaline earth metal, a cation of an alkylamine or an alkanolamine or ammonium. A, b, c, and d are 0 or 1)
And the sum is an integer from 1 to 4. A water-based ink composition comprising a compound represented by the formula: 2. The compound represented by the formula (1) according to claim 1 and Direct Blue 86 and / or Dir.
ect Blue 87 and / or DirectBlue
e 199 and / or Acid Blue 9, which is an aqueous ink composition. 3. The method according to claim 1, wherein the composition contains water and a water-soluble organic solvent.
Or the aqueous ink composition according to 2. 4. The aqueous ink composition according to claim 1, wherein the content of the inorganic salt is 1% by weight or less. 5. The aqueous ink composition according to claim 1, which is for inkjet recording. 6. An ink jet recording method for recording on a recording material by discharging ink droplets according to a recording signal,
An ink-jet recording method using the aqueous ink composition according to claim 1 as an ink. 7. The ink jet recording method according to claim 6, wherein the recording material is an information transmission sheet. 8. The ink jet recording method according to claim 6, wherein the recording material is an information transmitting sheet surface-treated with an inorganic substance and / or a polymer. 9. The ink jet recording method according to claim 6, wherein the recording material is an information transmitting sheet surface-treated with a porous silica and / or alumina sol and / or a special ceramic as an inorganic substance. 10. The ink jet recording method according to claim 6, wherein the recording material is an information transmitting sheet surface-treated with a hydrophilic polymer and / or an acrylic polymer and / or a polyurethane polymer as a polymer. 11. The ink jet recording method according to claim 6, wherein the recording material is an information transmitting sheet surface-treated with polyvinyl alcohol and / or polyvinyl pyrrolidone as a hydrophilic polymer. 12. A container containing the aqueous ink composition according to any one of claims 1 to 5. 13. An ink jet printer having the container according to claim 12. 14. An aqueous ink composition containing tetrasulfocopper phthalocyanine obtained by reacting 4-sulfophthalic acid in the presence of a copper compound. 15. An aqueous ink composition containing copper phthalocyanine obtained by reacting 4-sulfophthalic acid and phthalic acid in the presence of a copper compound.