JP2006057062A - Ink set, method for improving ozone fastness of multiple order color and method of inkjet-recording - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink set having a high ejection stability, without having an defect in points of hue, weather resistance, waterproof property and image quality, especially excellent in an image fastness of yellow in a mixed color part, and a method for improving the ozone fastness of the multiple order color by using the ink set. <P>SOLUTION: This ink set is characterized by containing at least a yellow ink and a cyan ink having ≤5.0x10<SP>-4</SP>/(hr x ppm) discoloration rate against the ozone gas. The method for improving the ozone fastness of the multiple order color is provided by improving the discoloration property of the yellow ink in the multiple order color formed by using at least the cyan ink and yellow ink, against the ozone gas. The method for inkjet-recording for forming a color image by using the ink set is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an ink set composed of an ink having high quality of a recorded image, excellent ejection stability, and excellent storage stability of the obtained image, a method for improving multi-color ozone fastness, and an ink jet recording method. .

In recent years, with the spread of computers, ink jet printers are widely used for printing on paper, film, cloth and the like not only in offices but also at home.
Ink jet recording methods include a method in which droplets are ejected by applying pressure with a piezo element, a method in which bubbles are generated in heat by generating bubbles in the ink, a method using ultrasonic waves, or a droplet by electrostatic force. There is a method of sucking and discharging. As these inks for inkjet recording, water-based inks, oil-based inks, or solid (melting type) inks are used. Among these inks, water-based inks are mainly used from the viewpoints of production, handleability, odor, safety, and the like.

For the colorant used in these inks for ink jet recording, it has high solubility in solvents, high density recording is possible, hue is good, light, heat, air, ozone, water, Excellent fastness to chemicals, good fixability to image-receiving materials, low bleeding, excellent storage stability as ink, no toxicity, high purity, and low cost It is required to be able to do it. However, it is extremely difficult to search for colorants that meet these requirements at a high level.
Various dyes and pigments have already been proposed and actually used for inkjet, but no colorant that satisfies all the requirements has yet been discovered. Conventionally well-known dyes and pigments having a color index (CI) number are difficult to achieve both hue and fastness required for ink jet recording inks.

As dyes for improving fastness, azo dyes derived from aromatic amines and 5-membered heterocyclic amines described in Patent Document 1 below have been proposed. However, these dyes have a problem of deteriorating color reproducibility because they have undesirable hues in the yellow and cyan regions.
The following Patent Document 2 and Patent Document 3 disclose inks for inkjet recording aimed at achieving both hue and light fastness. However, the dye used in each publication has insufficient solubility in water when used as a water-soluble ink. In addition, when the coloring matter described in each publication is used as a water-soluble ink for inkjet, a problem arises in wet heat fastness.
As means for solving these problems, compounds and ink compositions described in Patent Document 4 below have been proposed. Further, it describes an ink for ink jet recording using a pyrazolylaniline azo dye for further improving the hue and light fastness (Patent Document 5 below). However, these inks for ink jet recording are insufficient in both color reproducibility and output image fastness.
Furthermore, it has been found that there is a case where the image storability is remarkably poor when recorded on glossy paper dedicated to inkjet for photographic quality and pasted indoors. The inventor presumes that this phenomenon is caused by some kind of oxidizing gas in the air such as ozone. Moreover, although it becomes difficult to occur when the air flow is cut off by a measure such as putting it in a glass forehead, the use conditions are restricted.
This phenomenon is particularly prominent in glossy paper dedicated to inkjet for photographic image quality, and is a major problem for current inkjet recording systems in which photographic image quality is one of the important features.

  In ink jet recording, an image is formed by directly ejecting ink droplets onto image receiving paper. Therefore, many colors are formed by directly mixing ink droplets of a plurality of colors. In recent years, there has been reported an example in which fastness is greatly reduced in a secondary color and tertiary color portion in which a plurality of inks are mixed even if the ink alone has high fastness.

According to Patent Document 6, the applicants have proposed yellow ink for inkjet having high fastness and good hue. However, when a color image is formed using these yellow inks, It was found that the fastness of yellow was greatly reduced compared to the single yellow color in the mixed color parts, especially the green and gray parts mixed with the phthalocyanine dye.
Therefore, in order to obtain high image fastness, an ink set having high fastness in mixed colors as well as ink alone is required.

  On the other hand, in order to stably obtain a high-quality print image, it is also important that the ink has a stable ejection suitability.

JP-A-55-161856 JP 61-36362 A Japanese Patent Laid-Open No. 2-212566 Japanese National Patent Publication No. 11-504958 JP 2003-231850 A JP 2003-277661 A

  The problem to be solved by the present invention is to provide an ink set which has high ejection stability and has no defects in hue, weather resistance, water resistance and image quality, and in particular, yellow image fastness in a mixed color portion. It is to provide an excellent ink set. Another object of the present invention is to provide a method for improving ozone fastness of multi-order colors using the ink set, and further, an ink jet recording method capable of high quality recording using the ink set for ink jet recording. Is to provide.

Means for solving the above problems are as follows.
1) An ink set comprising at least a yellow ink and a cyan ink having a fading speed with respect to ozone gas of 5.0 × 10 ⁻⁴ / (hr · ppm) or less.
2) The ink set according to 1), wherein the cyan ink contains a phthalocyanine dye having an oxidation potential nobler than 1.0 V (vs SCE).
3) The ink set according to 2) above, wherein the phthalocyanine dye has an aza group.
4) The ink set according to any one of claims 1 to 3, wherein the cyan ink contains a compound represented by the following general formula (I).

In general formula (I), X < ₁ > -X < ₄ > and Y < ₁ > -Y < ₄ > represent a carbon atom or a nitrogen atom each independently.
A _{1 to} A ₄ are each independently required to form an aromatic ring or a heterocycle (may further form a condensed ring with another ring) together with X _{1 to} X ₄ and Y _{1 to} Y _4. Represents an atomic group. A _{1 to} A ₄ may have a substituent. At least one of A ₁ to A ₄ may alternatively at least one of the substituents of A ₁ to A ₄ has as a substituent an ionic hydrophilic group.
M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
5) The ink set of 4) above, wherein the compound represented by the general formula (I) has 2 to 4 ionic hydrophilic groups.
6) The ink set according to 4) or 5) above, wherein the ionic hydrophilic group is located at the β-position of the compound represented by the general formula (I).
7) The ink set according to any one of 1) to 6) above, wherein the yellow ink contains an azo dye.
8) The ink set described in any one of 1) to 6) above, wherein the yellow ink contains a dye represented by the following general formula (1).
General formula (1) (AN = NB) nL
In the formula, A and B each independently represent an optionally substituted heterocyclic group. L represents a hydrogen atom, a simple bond or a divalent linking group. n represents 1 or 2. However, when n is 1, L represents a hydrogen atom, and both A and B are monovalent heterocyclic groups. When n is 2, L represents a simple bond or a divalent linking group, one of A and B is a monovalent heterocyclic group, and the other is a divalent heterocyclic group. When n is 2, A may be the same or different, and B may be the same or different.
9) The ink set according to any one of 1) to 8) above, wherein the cyan ink comprises two or more kinds of inks having different dye contents.
10) The ink set as described in any one of 1) to 9) above, which comprises black ink.
11) The ink set as described in any one of 1) to 10) above, which is used for inkjet recording.
12) A multi-order ozone that improves the fading to the ozone gas of a yellow ink in a multi-color formed by using at least a cyan ink and a yellow ink of the ink set described in 1) to 11) above. A method of improving robustness.
13) An ink jet recording method comprising forming a color image using the ink set according to any one of 1) to 11) above.
14) The image receiving material having an image receiving layer containing white inorganic pigment particles on a support, ink droplets of an ink set are ejected in accordance with a recording signal, and a full color image is recorded on the image receiving material. The ink jet recording method according to 13).

  The present invention can provide an ink set that is particularly excellent in fastness of a yellow image in a mixed color portion by using a cyan ink excellent in ozone resistance, and has high ejection stability, hue, weather resistance, and water resistance. It is possible to provide an ink set that is free from defects in image quality and image quality.

The ink set of the present invention includes at least a yellow ink and a cyan ink, and the cyan ink has a fading speed with respect to ozone gas of 5.0 × 10 ⁻⁴ / (hr · ppm) or less (preferably 4.0 × 10 ^{−). 4} / (hr · ppm) or less, more preferably 2.0 × 10 ⁻⁴ / (hr · ppm) or less).

In the present invention, the fading speed of cyan ink with respect to ozone gas (hereinafter also referred to as “fading speed Ov”) refers to a value obtained as follows.
After printing cyan ink single color on a reflective medium, the reflection density is measured through a status A filter, and one point where the reflection density (D _B ) in the yellow region is 0.90 to 1.10 is the initial density of the ink. The printed matter is forcibly faded using an ozone fading tester that can always be generated so that the ozone concentration is constant, and the reflection density becomes 80% (residual rate) of the initial density. The forced fading rate constant (k) is obtained from the time (t) until the time and the value obtained by dividing the constant by the ozone concentration is taken as the fading rate. Here, the ozone concentration is selected from 0.1 to 20 ppm.
Here, the reflection density is a value measured by a status A filter (blue) using a reflection densitometer (X-Rite 310TR). The forced fading rate constant (k) is a value obtained from the remaining rate = exp (−kt), that is, k = (− ln 0.8) / t.

In the ink set of the present invention, the cyan ink having the specific fading speed Ov is used, so that the ink set is more than the case where the cyan ink having the fading speed Ov exceeding 5.0 × 10 ⁻⁴ / (hr · ppm) is used. The fading property of the yellow ink in the next color with respect to ozone gas can be improved.
That is, the present invention can improve the fastness of ozone of the multi-order color, and thus improve the temporal stability of the hue of the multi-order color.
In the present invention, the multi-order color whose ozone fastness is improved is a mixture of cyan (C) ink and yellow (Y) ink showing a specific fading speed Ov, or ink containing magenta (M) ink. Displayed colors, that is, colors including green (G) and gray (Gr). Multi-order colors include B (blue) (mixed color of C and M) and R (mixed color of Y and M), G (mixed color of C and Y) and R (red) (mixed color of Y and M) ) Mixed with Y, G (mixed color of C and Y), and C mixed with B (mixed color of C and M).

The cyan ink used in the present invention preferably contains a phthalocyanine dye having an oxidation potential nobler than 1.0 V (vs SCE).
The oxidation potential is more preferably noble than 1.1 V (vs SCE), and particularly preferably nobler than 1.15 V (vs SCE).
Further, the dyes of other inks used in the ink set preferably have the above oxidation potential.
The yellow ink is preferably an azo dye, and more preferably a compound represented by the general formula (1). Details of the compound represented by the general formula (1) will be described later.
The oxidation potential of the azo dye is particularly preferably nobler than 1.2 V (vs SCE).

  The cyan ink used in the present invention is preferably composed of two or more inks having different dye contents. In general, an ink having a low dye concentration is called a light cyan ink.

The ink set of the present invention preferably contains black ink. In the present invention, the dye concentration of the black ink is preferably the highest as the dye concentration of the ink from the viewpoint of the image quality of the mixed droplet ejection portion.
Further, it is preferable that the black ink includes an ink made of a pigment dispersion in addition to an ink made of a dye from the viewpoint of improving durability and improving character quality. In the present invention, as a black ink, an ink made of a pigment dispersion may be used in combination with a black ink made of a dye, or may be used alone.

  The oxidation potential value (Eox) of the dye used in the present invention can be easily measured by those skilled in the art. Regarding this method, for example Delahay, “New Instrumental Methods in Electrochemistry” (published by Interscience Publishers, 1954) J. et al. "Electrochemical Methods" by Bard et al. (Published by John Wiley & Sons in 1980) and "Electrochemical Measurement Method" by Akira Fujishima et al. (Published by Gihodo Publishing Co., Ltd. in 1984).

Specifically, the oxidation potential is 1 × 10 ⁻² to 1 × 10 ⁻⁶ mol / min in a solvent such as dimethylformamide or acetonitrile containing a supporting electrolyte such as sodium perchlorate or tetrapropylammonium perchlorate. Dissolve in 1 liter and measure as a value relative to SCE (standard saturated calomel electrode) using cyclic voltammetry or the like. Although this value may be deviated by several tens of mil volts due to the influence of the liquid potential difference or the liquid resistance of the sample solution, the reproducibility of the potential can be guaranteed by inserting a standard sample (for example, hydroquinone).
In order to uniquely define the potential, in the present invention, the measurement was performed in dimethylformamide containing 0.1 mol / liter of tetrapropylammonium perchlorate as a supporting electrolyte (the concentration of the dye was 0.001 mol / liter). The value obtained (vs SCE) is taken as the oxidation potential of the dye.

  The value of Eox represents the ease of transfer of electrons from the sample to the electrode, and the larger the value (the higher the oxidation potential), the less transfer of electrons from the sample to the electrode, in other words, less oxidation. In relation to the structure of the compound, the oxidation potential becomes more noble by introducing an electron withdrawing group, and the oxidation potential becomes lower by introducing an electron donating group. In the present invention, in order to lower the reactivity with ozone which is an electrophile, it is desirable to introduce an electron withdrawing group into the phthalocyanine skeleton to make the oxidation potential more noble. Therefore, by using Hammett's substituent constant σp value, which is a measure of the electron withdrawing property and electron donating property of a substituent, by introducing a substituent having a large σp value such as a sulfinyl group, a sulfonyl group, and a sulfamoyl group. It can be said that the oxidation potential can be made more noble.

  The dye used for cyan ink is preferably a compound represented by the above general formula (I).

  The phthalocyanine compound represented by the general formula (I) of the present invention includes a compound, a salt thereof, and a hydrate thereof.

In the general formula (I), X _{1 to} X ₄ and Y _{1 to} Y ₄ are each independently preferably a carbon atom or a nitrogen atom, and more preferably a carbon atom. The bond of X ₁ -Y ₁ , X ₂ -Y ₂ , X ₃ -Y ₃ , and X ₄ -Y ₄ may be a single bond or a double bond depending on the respective atomic species and the following A _{1 to} A ₄ heterocyclic species. It can be taken with a double bond.

In the above general formula (I), A _{1 to} A ₄ are each independently an aromatic ring or a heterocycle together with X _{1 to} X ₄ and Y _{1 to} Y ₄ (even if they form a condensed ring with another ring). Represents a group of atoms necessary to form (good). Unless otherwise specified, the aromatic ring refers to an aromatic ring in which the atoms constituting the ring are only carbon atoms, and specific examples include a benzene ring. The aromatic ring may further be condensed with other aromatic rings, hetero rings, and aliphatic rings. When forming a heterocyclic ring, the atomic group is preferably composed of at least two selected from a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom.
Among the heterocyclic rings composed of A _{1 to} A ₄ , X _{1 to} X ₄ and Y _{1 to} Y ₄ , a 5- or 6-membered heterocyclic ring is particularly preferable. Preferred examples of the heterocyclic ring composed of A _{1 to} A ₄ , X _{1 to} X ₄ and Y _{1 to} Y ₄ include imidazole, pyrazole, thiazole, isothiazole, oxazole, pyrrole, pyrazolone, indole, isoxazole, thiophene, Furan, pyran, penthiophene, quinoline, isoquinoline, pyridazine, pyrimidine, pyridone and the like are included.

A _{1 to} A ₄ may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, and a hydroxyl group. Group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, Carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, Sulfinyl group, phosphoryl group, Sill group or an ionic hydrophilic group. These groups may further have a substituent.

  Among them, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amide group, ureido group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfonyl group And an alkoxycarbonyl group or an ionic hydrophilic group are preferable, and in particular, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a carbamoyl group, a sulfamoyl group, and a sulfonyl group And an alkoxycarbonyl group or an ionic hydrophilic group are preferable, and a sulfamoyl group, a sulfonyl group, and an ionic hydrophilic group are most preferable.

At least one of A ₁ to A ₄ may alternatively at least one of the substituents of A ₁ to A ₄ has as a substituent an ionic hydrophilic group.

  Examples of the ionic hydrophilic group as a substituent include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable.

  The carboxyl group, phosphono group, and sulfo group may be in a salt state, and examples of the counter ion that forms the salt include alkali metal ions (eg, lithium ions, sodium ions, potassium ions) and organic cations (eg, Tetramethylguanidinium ion).

Examples of the substituent that A _{1 to} A ₄ can have include the following substituents.

  A linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched aralkyl group having 7 to 18 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, and a linear chain having 2 to 12 carbon atoms Or a branched alkynyl group, a linear or branched cycloalkyl group having 3 to 12 carbon atoms, a linear or branched cycloalkenyl group having 3 to 12 carbon atoms (the above groups having a branched chain are dissolved in the dye) Preferred are those having an asymmetric carbon, for example, methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, Trifluoromethyl, cyclopentyl), halogen atom (for example, chlorine atom, bromine atom), aryl group (for example, phenyl, 4-t-butylpheny) , 2,4-di-t-amylphenyl), heterocyclic groups (eg imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro Group, amino group, alkyloxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitro Phenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino groups (eg acetamide, benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide), alkylamino groups (eg methyl Amino, butylamino, die Ruamino, methylbutylamino), arylamino groups (eg, phenylamino, 2-chloroanilino, ureido groups (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino groups (eg, N, N) -Dipropylsulfamoylamino), alkylthio groups (eg methylthio, octylthio, 2-phenoxyethylthio), arylthio groups (eg phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), An alkyloxycarbonylamino group (for example, methoxycarbonylamino), a sulfonamide group (for example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), a carbamoyl group (for example, N-ethylcarbamoyl, N, -Dibutylcarbamoyl), sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl) ), An alkyloxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl), a heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4- Methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (for example, acetoxy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-fluoro) Phenylcarbamoyloxy), silyloxy groups (eg trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino groups (eg phenoxycarbonylamino), imide groups (eg N-succinimide, N-phthalimide), heterocyclic thio groups (For example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (for example, 3-phenoxypropylsulfinyl), phosphonyl group ( For example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic group ( Eg to a carboxyl group, a sulfo group, a phosphono group and a quaternary ammonium group).

  Among them, halogen atom, hetero group, cyano group, carboxyl group, acylamino group, sulfonamido group, sulfamoyl group, carbamoyl group, sulfonyl group, imide group, acyl group, sulfo group, quaternary ammonium group are preferable, cyano group, carboxyl group More preferred are sulfamoyl group, carbamoyl group, sulfonyl group, imide group, acyl group, sulfo group, and quaternary ammonium group.

The alkyl group represented by the substituent that A _{1 to} A ₄ can have includes an alkyl group having a substituent and an unsubstituted alkyl group. As the alkyl group, an alkyl group having 1 to 20 carbon atoms when a substituent is removed is preferable. Among these, an alkyl group having 1 to 12 carbon atoms is particularly preferable. In particular, a linear alkyl group having 1 to 8 carbon atoms and / or a branched alkyl group is preferable for solubility reasons, and particularly a case where it has an asymmetric carbon (use in racemic form). Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom and an ionic hydrophilic group. Examples of the alkyl group include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl.

The cycloalkyl group represented by the substituent that A _{1 to} A ₄ can have includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms when a substituent is removed. Among them, a cycloalkyl group having 5 to 12 carbon atoms is particularly preferable. In particular, a branched cycloalkyl group having 4 to 8 carbon atoms is preferable for reasons of solubility, and the case of having an asymmetric carbon (use in racemic form) is particularly preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The alkenyl group represented by the substituent that A _{1 to} A ₄ can have includes an alkenyl group having a substituent and an unsubstituted alkenyl group. The alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms when a substituent is removed. Among them, an alkenyl group having 2 to 12 carbon atoms is particularly preferable. In particular, a branched alkenyl group having 3 to 12 carbon atoms is preferable from the viewpoint of solubility, and a case of having an asymmetric carbon (use in a racemate) is particularly preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkenyl group include a vinyl group and an allyl group.

The alkynyl group represented by the substituent that A _{1 to} A ₄ can have includes an alkynyl group having a substituent and an unsubstituted alkynyl group. The alkynyl group is preferably an alkynyl group having 2 to 20 carbon atoms when a substituent is removed. Among them, an alkynyl group having 2 to 12 carbon atoms is particularly preferable. In particular, for reasons of solubility, a branched alkynyl group having 4 to 12 carbon atoms is preferred, and a case having an asymmetric carbon (use in racemic form) is particularly preferred. Examples of the substituent include an ionic hydrophilic group.

The aralkyl group represented by the substituent that A _{1 to} A ₄ can have includes an aralkyl group having a substituent and an unsubstituted aralkyl group. As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms when a substituent is removed is preferable. Among them, an aralkyl group having 7 to 12 carbon atoms is particularly preferable. In particular, from the viewpoint of solubility, a branched aralkyl group having 9 to 12 carbon atoms is preferable, and a case having an asymmetric carbon (use in racemic form) is particularly preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group.

The aryl group represented by the substituent that A _{1 to} A ₄ can have includes an aryl group having a substituent and an unsubstituted aryl group. The aryl group is preferably an aryl group having 6 to 40 carbon atoms. Among them, an aryl group having 6 to 12 carbon atoms is particularly preferable. As an example of a particularly preferred substituent, a branched aralkyl group having 7 to 12 carbon atoms is preferred for solubility reasons, and particularly preferred is a case having an asymmetric carbon (use in racemic form). Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl, m-sulfophenyl.

The heterocyclic group represented by the substituent that A _{1 to} A ₄ can have includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group, and forms a condensed ring with another ring. Also good. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Further, it may be an aromatic heterocyclic group or a non-aromatic heterocyclic group.

In the following, the heterocyclic group represented by A _{1 to} A ₄ is exemplified in the form of a heterocyclic ring by omitting the substitution position, but the substitution position is not limited. Substitution at the 3rd and 4th positions is possible. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole Benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like.

  Among them, an aromatic hetero group is preferable, and preferable examples thereof are exemplified in the same manner as described above. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole, Thiadiazole is mentioned.

Examples of the halogen atom represented by the substituent that A _{1 to} A ₄ can have include a fluorine atom, a chlorine atom, and a bromine atom.

The alkylamino group represented by the substituent that A _{1 to} A ₄ can have includes an alkylamino group having a substituent and an unsubstituted alkylamino group. The alkylamino group is preferably an alkylamino group having 1 to 6 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.

The alkyloxy group represented by the substituent that A _{1 to} A ₄ can have includes an alkyloxy group having a substituent and an unsubstituted alkyloxy group. As the alkyloxy group excluding the substituent, an alkyloxy group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an alkyloxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkyloxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

The aryloxy group represented by the substituent that A _{1 to} A ₄ can have includes an aryloxy group having a substituent and an unsubstituted aryloxy group. As the aryloxy group, an aryloxy group having 6 to 30 carbon atoms is preferable. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.

The acylamino group represented by the substituent that A _{1 to} A ₄ can have includes an amide group having a substituent and an unsubstituted amide group. The acylamino group is preferably an acylamino group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the acylamino group include an acetamide group, a propionamide group, a benzamide group, and a 3,5-disulfobenzamide group.

The arylamino group represented by the substituent that A _{1 to} A ₄ can have includes an arylamino group having a substituent and an unsubstituted arylamino group. The arylamino group is preferably an arylamino group having 6 to 30 carbon atoms. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include an anilino group and a 2-chloroanilino group.

The ureido group represented by the substituent that A _{1 to} A ₄ can have includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.

The sulfamoylamino group represented by the substituent that A _{1 to} A ₄ can have includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino group.

The alkylthio group represented by the substituent that A _{1 to} A ₄ can have includes an alkylthio group having a substituent and an unsubstituted alkylthio group. The alkylthio group is preferably an alkylthio group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylthio group include a methylthio group and an ethylthio group.

The arylthio group represented by the substituent that A _{1 to} A ₄ can have includes an arylthio group having a substituent and an unsubstituted arylthio group. As the arylthio group, an arylthio group having 6 to 30 carbon atoms is preferable. Examples of the substituent include an alkyl group and an ionic hydrophilic group. Examples of the arylthio group include a phenylthio group and a p-tolylthio group.

The alkyloxycarbonylamino group represented by the substituent that A _{1 to} A ₄ can have includes an alkyloxycarbonylamino group having a substituent and an unsubstituted alkyloxycarbonylamino group. The alkyloxycarbonylamino group is preferably an alkyloxycarbonylamino group having 2 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkyloxycarbonylamino group include an ethoxycarbonylamino group.

The sulfonamide group represented by the substituent that A _{1 to} A ₄ can have includes a sulfonamide group having a substituent and an unsubstituted sulfonamide group. The sulfonamide group is preferably a sulfonamide group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonamide group include methanesulfonamide, benzenesulfonamide, and 3-carboxybenzenesulfonamide.

The carbamoyl group represented by the substituent that A _{1 to} A ₄ can have includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.

The sulfamoyl group represented by the substituent that A _{1 to} A ₄ can have includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group and an aryl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group, a di- (2-hydroxyethyl) sulfamoyl group, and a phenylsulfamoyl group.

The sulfonyl group represented by the substituent that A _{1 to} A ₄ can have includes an alkylsulfonyl group and an arylsulfonyl group. Examples of the sulfonyl group include a 3-sulfopropylsulfonyl group and a 3-carboxypropylsulfonyl group.

The alkoxycarbonyl group represented by the substituent that A _{1 to} A ₄ can have includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

The heterocyclic oxy group represented by the substituent that A _{1 to} A ₄ can have includes a heterocyclic oxy group having a substituent and an unsubstituted heterocyclic oxy group. The heterocyclic oxy group is preferably a heterocyclic oxy group having a 5-membered or 6-membered heterocyclic ring. Examples of the substituent include a hydroxyl group and an ionic hydrophilic group. Examples of the heterocyclic oxy group include a 2-tetrahydropyranyloxy group.

The azo group represented by the substituent that A _{1 to} A ₄ can have includes an azo group having a substituent and an unsubstituted azo group. Examples of the azo group include a p-nitrophenylazo group.

The acyloxy group represented by the substituent that A _{1 to} A ₄ can have includes an acyloxy group having a substituent and an unsubstituted acyloxy group. The acyloxy group is preferably an acyloxy group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

The carbamoyloxy group represented by the substituent that A _{1 to} A ₄ can have includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

The silyloxy group represented by the substituent that A _{1 to} A ₄ can have includes a silyloxy group having a substituent and an unsubstituted silyloxy group. Examples of the substituent include an alkyl group. Examples of the silyloxy group include a trimethylsilyloxy group.

The aryloxycarbonyl group represented by the substituent that A _{1 to} A ₄ can have includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. As the aryloxycarbonyl group, an aryloxycarbonyl group having 7 to 30 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

The aryloxycarbonylamino group represented by the substituent that A _{1 to} A ₄ can have includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

The imide group represented by the substituent that A _{1 to} A ₄ can have includes an imide group having a substituent and an unsubstituted imide group. Examples of the imide group include an N-phthalimide group and an N-succinimide group.

The heterocyclic thio group represented by the substituent that A _{1 to} A ₄ can have includes a heterocyclic thio group having a substituent and an unsubstituted heterocyclic thio group. The heterocyclic thio group preferably has a 5-membered or 6-membered heterocyclic ring. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic thio group include a 2-pyridylthio group.

The sulfinyl group represented by the substituent that A _{1 to} A ₄ can have includes an alkylsulfinyl group and an arylsulfinyl group. Examples of the sulfinyl group include a 3-sulfopropylsulfinyl group and a 3-carboxypropylsulfinyl group.

The phosphoryl group represented by the substituent that A _{1 to} A ₄ can have includes a phosphoryl group having a substituent and an unsubstituted phosphoryl group. Examples of the phosphoryl group include a phenoxyphosphoryl group and a phenylphosphoryl group.

The acyl group represented by the substituent that A _{1 to} A ₄ can have includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

The ionic hydrophilic group represented by the substituent that A _{1 to} A ₄ can have includes a sulfo group, a carboxyl group, a quaternary ammonium group, and the like. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.

  The substituted phthalocyanine compound represented by the general formula (I) preferably has an ionic hydrophilic group. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, phosphono group, and sulfo group may be in the form of a salt. Examples of counter ions that form a salt include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions), and organic cations. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, an alkali metal salt is preferable, and a lithium salt is particularly preferable because it increases the solubility of the compound and improves the ink stability. As the number of ionic hydrophilic groups, those having at least two in one molecule of the substituted phthalocyanine compound are preferable, and those having at least two sulfo groups and / or carboxyl groups are particularly preferable.

M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
In addition to hydrogen atoms, preferable as M are metal elements such as Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi and the like can be mentioned. Of these, Cu, Ni, Zn, and Al are particularly preferable, and Cu is most preferable.

Preferred examples of the metal oxide include VO and GeO. Further, preferred examples of the metal hydroxide include Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) _{2 and the} like. Further, as the metal _{halide, AlCl, SiCl 2, VCl,} VCl 2, VOCl, FeCl 2, GaCl, ZrCl , and the like.

  In the phthalocyanine compound represented by the general formula (I), Pc (phthalocyanine ring) is a dimer (for example, Pc-MLMMM-Pc) or 3 via L (a divalent linking group). A monomer may be formed, and a plurality of M present at that time may be the same or different.

The divalent linking group represented by L includes an oxy group —O—, a thio group —S—, a carbonyl group —CO—, a sulfonyl group —SO ₂ —, an imino group —NH—, a methylene group —CH ₂ —, And a group formed by combining them is preferred.

  In addition, with respect to a preferable combination of substituents of the compound represented by the general formula (I), a compound in which at least one of various substituents is the above preferable group is preferable, and more various substituents are the above preferable groups. Are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

  Among the phthalocyanine compounds represented by the general formula (I), a phthalocyanine compound having a structure represented by the following general formula (II) is more preferable. Hereinafter, the phthalocyanine compound represented by the general formula (II) of the present invention will be described in detail.

In the general formula (II), Q _{1 to} Q ₄ and R _{1 to} R ₄ each independently represent a carbon atom, a nitrogen atom, a sulfur atom, an oxygen atom, or a phosphorus atom. E _{1 to} E ₄ are each independently required to form an aromatic ring or a hetero ring (which may form a condensed ring with another ring) together with Q _{1 to} Q ₄ and R _{1 to} R _4. Represents an atomic group. E _{1 to} E ₄ may have a substituent. Provided that at least one of E ₁ to E ₄ are, or at least one of substituents E ₁ to E ₄ has as a substituent an ionic hydrophilic group. M has the same meaning as in the general formula (I).
In the general formula (II), Q _{1 to} Q ₄ and R _{1 to} R ₄ each independently represent a carbon atom, a nitrogen atom, a sulfur atom, an oxygen atom, or a phosphorus atom, and among them, a carbon atom, a sulfur atom, or nitrogen It preferably represents an atom or an oxygen atom.

E _{1 to} E ₄ represent an atomic group necessary for forming an aromatic ring or a heterocyclic ring (which may further form a condensed ring with another ring) together with Q _{1 to} Q ₄ and R _{1 to} R _4. To express. When forming a heterocycle, the atomic group is preferably composed of at least two selected from a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. In addition, preferred examples of the heterocyclic ring constituted with E _{1 to} E ₄ , Q _{1 to} Q ₄ , and R _{1 to} R ₄ are A _{1 to} A ₄ , X _{1 to} X _4, and Y _{1 of the} general formula (I). it is similar to the example of a heterodimeric ring to Y _4.

E _{1 to} E ₄ may have a substituent, and the substituent is synonymous with the substituent that A _{1 to} A ₄ represented by formula (I) can have, and preferred examples are also included. It is the same. These groups may further have a substituent. Provided that at least one of E ₁ to E ₄ are, E ₁ to E ₄ has as a substituent a good ionic hydrophilic group which may have a substituent.

  When the phthalocyanine compound represented by the general formula (II) is water-soluble, it preferably has an ionic hydrophilic group. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, phosphono group, and sulfo group may be in the form of a salt. Examples of counter ions that form a salt include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions), and organic cations. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, an alkali metal salt is preferable, and a lithium salt is particularly preferable because it increases the solubility of the compound and improves the ink stability. As the number of ionic hydrophilic groups, those having at least two phthalocyanine compounds in one molecule are preferable, and those having at least two sulfo groups and / or carboxyl groups are particularly preferable.

  Among the phthalocyanine compounds represented by the general formula (II), particularly preferable combinations of substituents are the same as the particularly preferable combinations of substituents in the general formula (I).

  In addition, as for the preferable combination of substituents of the compound represented by the general formula (II), a compound in which at least one of various substituents is the above-mentioned preferable group is preferable, and more various substituents are preferable as described above. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups described above.

  Among the phthalocyanine compounds represented by the general formula (II), a phthalocyanine compound having a structure represented by the following general formula (III) is more preferable. Hereinafter, the phthalocyanine compound represented by the general formula (III) of the present invention will be described in detail.

In the general formula (III), Q _{1 to} Q ₄ , P _{1 to} P ₄ , W _{1 to} W ₄ , R _{1 to} R ₄ are each independently (= C (J ₁ ) − and / or —N =). , (= C (J ₂ )-and / or -N =), (= C (J ₃ )-and / or -N =), (= C (J ₄ )-and / or -N =). J _{1 to} J ₄ each independently represents a hydrogen atom and / or a substituent. Also, if J ₁ through J ₄ each represents a substituent, the substituent may further have a substituent. At least one of J ₁ through J _4, at least one of the substituents that have J ₁ through J ₄ has has as a substituent an ionic hydrophilic group. M is synonymous with the case of general formula (II), and its preferable examples are also the same.

In particular, (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ) at least one of rings {A ring: (A), B ring: (B), C ring: (C), D ring: (D)} is a nitrogen-containing heterocycle Or the ring {A ring: (A), B ring: (B), C ring: (C), D ring: (D)} are all aromatic rings.
More preferably, (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ) ring {A ring: (A), B ring: (B), C ring: (C), D ring: (D)} represents at least one aromatic ring In addition, it is preferable that at least one represents a pyridine ring and / or a pyrazine ring.

In addition, (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ) at least one of rings {A ring: (A), B ring: (B), C ring: (C), D ring: (D)} is represented by the following general formula (IV) The phthalocyanine compound which represents the aromatic ring represented by these is preferable.

In general formula (IV), G represents —SO—Z ₁ , —SO ₂ —Z ₁ , —SO ₂ NZ ₁ Z ₂ , —CONZ ₁ Z ₂ , —CO ₂ Z ₁ or —COZ ₁ , or a sulfo group. .

In particular, —SO ₂ —Z ₁ , —SO ₂ NZ ₁ Z ₂ , —CONZ ₁ Z ₂ and a sulfo group are preferable, and among them, —SO ₂ —Z ₁ , —SO ₂ NZ ₁ Z ₂ and a sulfo group are preferable, -SO ₂ -Z ₁ is most preferred.

Z ₁ may be the same or different and is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted total carbon. C2-C20 alkenyl group, substituted or unsubstituted C2-C12 alkynyl group, substituted or unsubstituted C7-20 aralkyl group, substituted or unsubstituted C6-C20 total carbon number An aryl group, a substituted or unsubstituted C4-C20 heterocyclic group having a total carbon number is preferable, and among them, a substituted or unsubstituted C1-C12 alkyl group having a total carbon number, or a substituted or unsubstituted aryl group having a total carbon number of C6-C18 A substituted or unsubstituted heterocyclic group having a total carbon number of C4 to C12 is preferable, and a substituted total carbon number of C1 to C12 alkyl group is most preferable.

Z ₂ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted An alkenyl group having a total carbon number of C2 to C20, a substituted or unsubstituted alkynyl group having a total carbon number of C2 to 12, a substituted or unsubstituted aralkyl group having a total carbon number of C7 to 20, a substituted or unsubstituted total carbon number of C6 Preferred is a C20 aryl group, a substituted or unsubstituted total carbon number C4 to C20 heterocyclic group, and among them, a hydrogen atom, a substituted or unsubstituted total carbon number C1 to C12 alkyl group, a substituted or unsubstituted total carbon number A C6-C18 aryl group, a substituted or unsubstituted heterocyclic group having a total carbon number of C4-C12 is preferred, and further a hydrogen atom, a substituted carbon number of C1-C12 Preferably 12 alkyl group, most preferably a hydrogen atom.

In addition, when Z < ₁ >, Z < ₂ > is a group which can have a substituent further, you may further have a substituent as quoted in the substituent which said A < ₁ > -A < ₄ > can have. .

  t represents an integer of 0 to 4, particularly preferably 1 to 2, and most preferably 1.

  Among the aromatic rings represented by the general formula (IV), an aromatic ring represented by the following general formula (V) is particularly preferable.

In general formula (V), Z < ₁ > and t are synonymous with Z < ₁ > and t in the said general formula (IV), and its preferable example is also the same.

Particularly preferred combinations as the phthalocyanine compound represented by the general formula (III) are as follows.
(A) (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ) a phthalocyanine compound in which at least one of rings {A ring: (A), B ring: (B), C ring: (C), D ring: (D)} represents a heterocycle .

(B) (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ) at least one of the rings {A ring: (A), B ring: (B), C ring: (C), D ring: (D)} is a nitrogen-containing 6-membered heterocycle A phthalocyanine compound representing
(C) (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ) at least one of rings {A ring: (A), B ring: (B), C ring: (C), D ring: (D)} represents an aromatic ring, And at least one represents a pyridine ring and / or a pyrazine ring. Among these, (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , At least one of the rings {ring A: (A), ring B: (B), ring C: (C), ring D: (D)} consisting of P ₄ , W ₄ , R ₄ ) is ionic hydrophilic A phthalocyanine compound which represents an aromatic ring substituted with a sulfinyl group, a sulfonyl group or a sulfamoyl group having a group as a substituent is preferable, and (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₁ ) ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ) ring {ring A: (A), ring B: (B), C ring: (C), D ring: (D)} A phthalocyanine which represents an aromatic ring substituted with a sulfonyl group or a sulfamoyl group having an ionic hydrophilic group as a substituent. Compounds are preferred.
(D) (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ) Rings {A ring: (A), B ring: (B), C ring: (C), D ring: (D)} all represent aromatic rings. Among these, (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , At least one of the rings {ring A: (A), ring B: (B), ring C: (C), ring D: (D)} consisting of P ₄ , W ₄ , R ₄ ) is ionic hydrophilic A group substituted with a sulfinyl group, a sulfonyl group or a sulfamoyl group having a group as a substituent is preferred, and (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ) ring {A ring: (A), B ring: (B), C ring : (C), D ring: (D)} is preferably substituted with a sulfonyl group or a sulfamoyl group having an ionic hydrophilic group as a substituent. In particular, it is preferable that the group having the above ionic hydrophilic group as a substituent has 2 to 4 groups in one molecule, and the group includes P _{1 to} P ₄ and / or W _{1 to} W ₄ (β position). It is preferred that the group is substituted.

(E) M is preferably a hydrogen atom, a metal atom, or an oxide, hydroxide, or halide thereof, among which Cu, Ni, Zn, Al or the like is preferable, and Cu is most preferable.

(F) The molecular weight (average) of the phthalocyanine compound is preferably in the range of 995 to 2500, more preferably in the range of 995 to 2000, of which the molecular weight in the range of 995 to 1800 is preferable, and the molecular weight in the range of 995 to 1600 is particularly preferable. Is most preferred.

(G) Among the ionic hydrophilic groups contained in one molecule of the phthalocyanine compound represented by the general formula (III), a sulfo group, a carboxyl group, and a phosphono group are preferable, and a sulfo group is particularly preferable. The sulfo group, carboxyl group, and phosphono group may be in the form of a salt. Examples of counter ions that form a salt include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions), and organic ions. Cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium) are included. Among the counter ions, an alkali metal salt is preferable, and a lithium salt is particularly preferable because it increases the solubility of the compound and improves the ink stability.

  Among the phthalocyanine compounds represented by the general formula (III), those having at least one ionic hydrophilic group are preferable, and the ionic hydrophilic group is particularly preferably a sulfo group. Most preferred are those having 2 or more, preferably 2 to 4 groups.

  Since the phthalocyanine compound represented by the general formula (III) has at least one ionic hydrophilic group in the molecule, it has good solubility or dispersibility in an aqueous medium.

Examples of the phthalocyanine dye used in the present invention include “Phthalocyanine—Chemistry and Function” (P. 1-62), C.I. C. Leznoff-A. B. P. Lever co-authored, published by VCH, “Phthalogicanes-Properties and Applications” (P. 1-54), etc., can be synthesized by combining quoted or similar methods.
Examples of the substituted phthalocyanine compound represented by the general formula (III) of the present invention include a dicarbonitrile derivative (compound a) and / or a 1,3-diiminoisoindoline derivative (compound b) represented by the following formula. It can be induced by reacting with a metal derivative represented by the formula (VII). In the synthesis of the water-soluble substituted phthalocyanine compound, a method in which an ionic hydrophilic group is previously introduced into the compound a and / or the compound b is used as a raw material, and after obtaining the substituted phthalocyanine compound, the ionic hydrophilic group is introduced to obtain a water-soluble compound. There is a way to make it.

In the above formulas, Q, P, W, and R correspond to Q _{1 to} Q ₄ , P _{1 to} P ₄ , W _{1 to} W ₄ , and R _{1 to} R ₄ in the general formula (III), respectively.

  Examples of the metal derivative represented by the general formula (VII) to be added to the reaction of the present invention include metals, metal hydroxides, metal chlorides, metal acetates, and complexes for the metal or metal oxide to be introduced. For example, a metal aco complex or an ammine complex can be used.

  In the above general formula (VII), preferable examples of M include a metal atom or an oxide, hydroxide, and halide thereof.

  As metal atoms, Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu , Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, and the like.

  Examples of the oxide include VO and GeO.

Examples of the hydroxide include Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) _{2 and the} like.

The _{halides, AlCl, SiCl 2, VCl,} VCl 2, VOCl, FeCl, GaCl, ZrCl , and the like.

  Among these, as M, Cu, Ni, Zn, Al, and the like are preferable, and Cu is most preferable.

  In the general formula (VII), Z represents a monovalent or divalent ligand such as a halogen atom, acetate anion, acetylacetonate, oxygen, and d represents an integer of 1 to 4.

  Specific examples of the metal derivative {metal derivative represented by the general formula (VII)} include Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ru, Rh, Pd, In , Halides such as Sn, Pt, and Pb, carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds, oxides, complexes, and the like. More specifically, copper chloride, copper bromide, copper iodide, copper acetate, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, cobalt bromide, cobalt acetate, iron chloride, zinc chloride, zinc bromide, Zinc iodide, zinc acetate, vanadium chloride, vanadium oxytrichloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate, acetylacetone manganese, manganese chloride, lead chloride, lead acetate, indium chloride, titanium chloride, tin chloride Etc.

Among these, cupric chloride (CuCl ₂ ) and copper acetate are particularly preferable, and cupric chloride (CuCl ₂ ) is particularly preferable.

  Hereinafter, although the specific example (dyes 1-25) of the substituted phthalocyanine compound of this invention represented by general formula (III) is given, this invention is not necessarily limited to these specific examples.

  In the table, examples of the substituents of the four rings (A), (B), (C), and (D) of the substituted phthalocyanine mother nucleus are dicarbonitrile derivatives (compound a) during the condensation reaction in the synthesis of the substituted phthalocyanine compound of the present invention. ) And / or 1,3-diiminoisoindoline derivative (compound b) charge ratio (eq./eq.), Which represents an average value of the mixing ratio of the obtained substituted phthalocyanine compounds.

  Specific examples (example compounds I-1 to I-12 and 101 to 190) of phthalocyanine dyes other than the above used in the present invention are shown below, but the phthalocyanine dyes used in the present invention are limited to the following examples. It is not a thing. Of the following examples, compounds satisfying the general formula (III) are preferred.

  In addition, the structure of the phthalocyanine compound shown by compound No.146-190 is as follows. Note that m and n indicate the number of substitutions.

  The phthalocyanine dye can be synthesized according to the aforementioned patent. In addition to the synthesis method described above, the synthesis can be performed by the methods described in JP-A Nos. 2001-226275, 2001-96610, 2001-47013, and 2001-193638. Further, the starting material, the dye intermediate and the synthesis route are not limited to these.

Next, the yellow ink will be described.
The yellow ink is more preferably a compound represented by the general formula (1).

In formula (1), A and B each independently represents an optionally substituted heterocyclic group. The heterocycle is preferably a 5-membered or 6-membered heterocycle, which may be a monocyclic structure or a polycyclic structure in which two or more rings are condensed. It may be a ring or a non-aromatic heterocyclic ring. As the hetero atom constituting the heterocyclic ring, N, O and S atoms are preferable.
L represents a hydrogen atom, a simple bond or a divalent linking group. n represents 1 or 2. However, when n is 1, L represents a hydrogen atom, and both A and B are monovalent heterocyclic groups. When n is 2, L represents a simple bond or a divalent linking group, one of A and B is a monovalent heterocyclic group, and the other is a divalent heterocyclic group. When n is 2, A may be the same or different, and B may be the same or different.

  In the general formula (1), the heterocyclic ring represented by A includes 5-pyrazolone, pyrazole, triazole, oxazolone, isoxazolone, barbituric acid, pyridone, pyridine, rhodanine, pyrazolidinedione, pyrazolopyridone, meldrum acid In addition, a condensed heterocyclic ring obtained by further condensing a hydrocarbon aromatic ring or a heterocyclic ring to these heterocyclic rings is preferable. Among them, 5-pyrazolone, 5-aminopyrazole, pyridone, 2,6-diaminopyridine, and pyrazoloazoles are preferable, and 5-aminopyrazole, 2-hydroxy-6-pyridone, and pyrazolotriazole are particularly preferable.

  The heterocyclic ring represented by B includes pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzo Examples include imidazole, triazole, oxazole, isoxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzoisothiazole, thiadiazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. Of these, pyridine, quinoline, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, isoxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzoisothiazole, thiadiazole, and benzoisoxazole are preferable, and quinoline, thiophene , Pyrazole, thiazole, benzoxazole, benzisoxazole, isothiazole, imidazole, benzothiazole, thiadiazole are more preferable, and pyrazole, benzothiazole, benzoxazole, imidazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole Is particularly preferred.

The substituents substituted for A and B are halogen atoms, alkyl groups, cycloalkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxy groups, nitro groups, alkoxy groups, aryloxy Group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfo group Famoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group Examples include acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, silyl groups, or the following ionic hydrophilic groups. It is done.
Examples of the divalent linking group represented by L include an alkylene group, an arylene group, a heterocyclic residue, -CO-, -SOn- (n is 0, 1, 2), -NR- (R is a hydrogen atom, an alkyl group). , Represents an aryl group), —O—, and a divalent group obtained by combining these linking groups, and further, these are the substituents mentioned in the substituents substituted for A and B, or the following ionic hydrophilic groups You may have.

  When the dye of the general formula (1) is used as a water-soluble dye, it preferably has at least one ionic hydrophilic group in the molecule. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and among them, a carboxyl group and a sulfo group are preferable. In particular, at least one is most preferably a carboxyl group. The carboxyl group, phosphono group, and sulfo group may be in the form of a salt. Examples of counter ions that form a salt include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions), and organic cations. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, alkali metal salts are preferable.

  Among the dyes represented by the general formula (1), dyes in which A—N═NB corresponds to the general formulas (1-A), (1-B), and (1-C) are preferable.

Formula (1-A)

  In general formula (1-A), R1 and R3 represent a hydrogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, an aryl group or an ionic hydrophilic group, R2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, a carbamoyl group, an acyl group, an aryl group or a heterocyclic group, and R4 represents a heterocyclic group.

Formula (1-B)

  In general formula (1-B), R5 represents a hydrogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, an aryl group, or an ionic hydrophilic group, and Za is -N =, -NH-, or -C (R11) =, Zb and Zc each independently represent -N = or -C (R11) =, and R11 represents a hydrogen atom or a nonmetallic substituent. R6 represents a heterocyclic group.

Formula (1-C)

  In the general formula (1-C), R7 and R9 are each independently a hydrogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, Or an ionic hydrophilic group, wherein R8 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, an acylamino group, a sulfonylamino group, an alkoxycarbonylamino group, a ureido group, or an alkylthio group. Represents an arylthio group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, an alkylamino group, an arylamino group, a hydroxy group, or an ionic hydrophilic group, and R10 represents a heterocyclic group.

  In the general formulas (1-A), (1-B), and (1-C), the alkyl group represented by R1, R2, R3, R5, R7, R8, and R9 includes an alkyl group having a substituent and none. Substituted alkyl groups are included. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms. Examples of the substituent include a hydroxy group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group. Examples of the alkyl group include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, and 4-sulfobutyl.

  The cycloalkyl group represented by R1, R2, R3, R5, R7, R8 and R9 includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include cyclohexyl. The aralkyl group represented by R1, R2, R3, R5, R7, R8 and R9 includes an aralkyl group having a substituent and an unsubstituted aralkyl group. The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include benzyl and 2-phenethyl.

  The aryl group represented by R1, R2, R3, R5, R7, and R9 includes an aryl group having a substituent and an unsubstituted aryl group. The aryl group is preferably an aryl group having 6 to 20 carbon atoms. Examples of the substituent include a hydroxy group, an alkyl group, an alkoxy group, a halogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, an alkylamino group, an acylamino group, and an ionic hydrophilic group. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl, and m- (3-sulfopropylamino) phenyl.

  The alkylthio group represented by R1, R2, R3, R5, R7, R8 and R9 includes an alkylthio group having a substituent and an unsubstituted alkylthio group. The alkylthio group is preferably an alkylthio group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylthio group include methylthio and ethylthio. The arylthio group represented by R1, R2, R3, R5, R7, R8 and R9 includes an arylthio group having a substituent and an unsubstituted arylthio group. The arylthio group is preferably an arylthio group having 6 to 20 carbon atoms. Examples of the substituent include the same substituents as the aryl group described above. Examples of the arylthio group include a phenylthio group and p-tolylthio.

  The heterocyclic group represented by R2 is preferably a 5- or 6-membered heterocyclic ring, which may be further condensed. As the hetero atom constituting the heterocyclic ring, N, S, and O are preferable. Further, it may be an aromatic heterocyclic ring or a non-aromatic heterocyclic ring. The heterocyclic ring may be further substituted, and examples of the substituent include the same substituents as the aryl group described above. Preferred heterocycles are 6-membered nitrogen-containing aromatic heterocycles, and triazine, pyrimidine and phthalazine can be mentioned as preferred examples.

  Examples of the halogen atom represented by R8 include a fluorine atom, a chlorine atom, and a bromine atom. The alkoxy group represented by R1, R3, R5 and R8 includes an alkoxy group having a substituent and an unsubstituted alkoxy group. The alkoxy group is preferably an alkoxy group having 1 to 20 carbon atoms. Examples of the substituent include a hydroxy group and an ionic hydrophilic group. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

  The aryloxy group represented by R8 includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 20 carbon atoms. Examples of the substituent include the same substituents as the aryl group described above. Examples of the aryloxy group include phenoxy, p-methoxyphenoxy and o-methoxyphenoxy. The acylamino group represented by R8 includes an acylamino group having a substituent and an unsubstituted acylamino group. The acylamino group is preferably an acylamino group having 2 to 20 carbon atoms. Examples of the substituent include the same substituents as the aryl group described above. Examples of the acylamino group include acetamide, propionamide, benzamide and 3,5-disulfobenzamide.

  The sulfonylamino group represented by R8 includes an alkylsulfonylamino group, an arylsulfonylamino group, and a heterocyclic sulfonylamino group, and each alkyl group part, aryl group part, and heterocyclic part may have a substituent. good. Examples of the substituent include the same substituents as the aryl group described above. The sulfonylamino group is preferably a sulfonylamino group having 1 to 20 carbon atoms. Examples of the sulfonylamino group include methylsulfonylamino and ethylsulfonylamino. The alkoxycarbonylamino group represented by R8 includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include ethoxycarbonylamino.

The ureido group represented by R8 includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 20 carbon atoms. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include 3-methylureido, 3,3-dimethylureido, and 3-phenylureido.
The alkoxycarbonyl group represented by R7, R8 and R9 includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl.

The carbamoyl group represented by R2, R7, R8 and R9 includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.
The sulfamoyl group having a substituent represented by R8 and the unsubstituted sulfamoyl group are included. Examples of the substituent include an alkyl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.

The sulfonyl group represented by R8 includes an alkylsulfonyl group, an arylsulfonyl group or a heterocyclic sulfonyl group, which may further have a substituent. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonyl group include methylsulfonyl and phenylsulfonyl.
The acyl group represented by R2 and R8 includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include acetyl and benzoyl.

  The amino group represented by R8 includes an amino group having a substituent and an unsubstituted amino group. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group. Examples of the amino group include methylamino, diethylamino, anilino and 2-chloroanilino.

  The heterocyclic group represented by R4, R6, and R10 is the same as the optionally substituted heterocyclic group represented by B in the general formula (1), and preferred examples, more preferred examples, and particularly preferred examples are also included. Same as above. Examples of the substituent include an ionic hydrophilic group, an alkyl group having 1 to 12 carbon atoms, an aryl group, an alkyl or arylthio group, a halogen atom, a cyano group, a sulfamoyl group, a sulfoneamino group, a carbamoyl group, and an acylamino group. And the alkyl group and aryl group may further have a substituent.

  In the general formula (1-B), Za represents —N═, —NH—, or —C (R11) ═, and Zb and Zc each independently represent —N═ or —C (R11) ═. R11 represents a hydrogen atom or a nonmetallic substituent. As the nonmetallic substituent represented by R11, a cyano group, a cycloalkyl group, an aralkyl group, an aryl group, an alkylthio group, an arylthio group, or an ionic hydrophilic group is preferable. Each of the substituents is synonymous with each substituent represented by R 1, and preferred examples are also the same. Examples of the heterocyclic skeleton composed of two 5-membered rings included in the general formula (1-B) are shown below.

  Examples of the substituent when each substituent described above may further have a substituent include the substituents that may be substituted on the heterocyclic rings A and B in the general formula (1) described above. I can do it.

  Among the above general formulas (1-A), (1-B) and (1-C), preferred is the general formula (1-A), and among them, those represented by the following general formula (1-A1) are preferred. Particularly preferred.

General formula (1-A1)

In General Formula (1-A1), R ²¹ and R ²³ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, or an aryl group. R ²² represents a hydrogen atom, an aryl group or a heterocyclic group. X and Y, one represents a nitrogen atom and the other represents -CR ^24. R ²⁴ is a hydrogen atom, halogen atom, cyano group, alkyl group, alkylthio group, alkylsulfonyl group, alkylsulfinyl group, alkyloxycarbonyl group, carbamoyl group, alkoxy group, aryl group, arylthio group, arylsulfonyl group, arylsulfinyl Represents a group, an aryloxy group or an acylamino group. Of these, a hydrogen atom, an alkyl group, an alkyl and arylthio group and an aryl group are preferable, and a hydrogen atom, an alkylthio group and an aryl group are particularly preferable. Each substituent may be further substituted.

  Examples of the dye used in the present invention include those described in Japanese Patent Application No. 2003-286844, Japanese Patent Application No. 2002-211683, Japanese Patent Application No. 2002-124832, Japanese Patent Application Laid-Open No. 2003-128953, and Japanese Patent Application Laid-Open No. 2003-41160. Can be mentioned. In addition, the dye which can be used for this invention is not limited to these. These compounds can be synthesized with reference to JP-A-2-24191 and JP-A-2001-279145 in addition to the above patents.

  The present invention preferably contains 0.2 to 20% by mass of the dye represented by the general formula (I) or the general formula (1) in the cyan ink or the yellow ink, more preferably 0.5. Contains ~ 15% by mass.

  Examples of dyes that can be used in the ink set of the present invention include the following in addition to those described above. A single dye is used in combination in order to adjust the color tone.

  Examples of yellow dyes include phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components; for example, open-chain active methylene compounds as coupling components. Azomethine dyes; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dye species such as quinophthalone dyes, nitro-nitroso dyes And dyes, acridine dyes, acridinone dyes and the like. These dyes may be those that exhibit yellow only after a part of the chromophore is dissociated, in which case the counter cation may be an alkali metal or an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, and further may be a polymer cation having them in a partial structure.

  Examples of magenta dyes include aryl or heteryl azo dyes having phenols, naphthols, and anilines as coupling components; azomethine dyes having pyrazolones and pyrazolotriazoles as coupling components; for example, arylidene dyes, styryl dyes, and merocyanine Dyes, methine dyes such as oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc. And ring dyes. These dyes may exhibit magenta only after part of the chromophore is dissociated, and the counter cation in that case may be an alkali metal or an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, and further may be a polymer cation having them in a partial structure.

  Examples of cyan dyes include azomethine dyes such as indoaniline dyes and indophenol dyes; polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; phthalocyanine Dyes; anthraquinone dyes; For example, aryl or heteryl azo dyes having phenols, naphthols and anilines as coupling components, and indigo / thioindigo dyes can be mentioned. These dyes may exhibit cyan only after a part of the chromophore is dissociated, and the counter cation in that case may be an alkali metal or an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, and further may be a polymer cation having them in a partial structure.

Further, water-soluble dyes such as direct dyes, acid dyes, food dyes, basic dyes and reactive dyes can also be used. Among them, preferred is
CI Direct Red 2, 4, 9, 23, 26, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184, 207 , 211, 212, 214, 218, 21, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247
CI Direct Violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101
CI Direct Yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 58, 59, 68, 86, 87, 93, 95, 96, 98, 100 106, 108, 109, 110, 130, 132, 142, 144, 161, 163
CI Direct Blue 1, 10, 15, 22, 25, 55, 67, 68, 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 108, 109, 151, 156, 158 , 159, 160, 168, 189, 192, 193, 194, 199, 200, 201, 202, 203, 207, 211, 213, 214, 218, 225, 229, 236, 237, 244, 248, 249, 251 252 264 270 280 288 289 291
CI Direct Black 9, 17, 19, 22, 32, 51, 56, 62, 69, 77, 80, 91, 94, 97, 108, 112, 113, 114, 117, 118, 121, 122, 125, 132 , 146, 154, 166, 168, 173, 199
CI Acid Red 35, 42, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 151, 154, 158, 249, 254, 257, 261, 263, 266 , 289, 299, 301, 305, 336, 337, 361, 396, 397
CI Acid Violet 5, 34, 43, 47, 48, 90, 103, 126
CI Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195 , 196, 197, 199, 218, 219, 222, 227
CI Acid Blue 9, 25, 40, 41, 62, 72, 76, 78, 80, 82, 92, 106, 112, 113, 120, 127: 1, 129, 138, 143, 175, 181, 205, 207 220, 221, 230, 232, 247, 258, 260, 264, 271, 277, 278, 279, 280, 288, 290, 326
CI Acid Black 7, 24, 29, 48, 52: 1, 172
CI Reactive Red 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55
CI Reactive Violet 1, 3, 4, 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26, 27, 33, 34
CI Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42
CI Reactive Blue 2, 3, 5, 8, 10, 13, 14, 15, 17, 18, 19, 21, 25, 26, 27, 28, 29, 38
CI Reactive Black 4, 5, 8, 14, 21, 23, 26, 31, 32, 34
CI Basic Red 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, 46
CI Basic Violet 1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48
CI Basic Yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40
CI Basic Blue 1, 3, 5, 7, 9, 22, 26, 41, 45, 46, 47, 54, 57, 60, 62, 65, 66, 69, 71
CI Basic Black 8, etc.

Furthermore, the present invention can also use an ink in which a pigment is used in combination with a dye.
As the pigment that can be used in the present invention, commercially available pigments and known pigments described in various documents can be used. Regarding the literature, the Color Index (Edited by The Society of Dyers and Colorists), "Revised New Edition Pigment Handbook" edited by Japan Pigment Technology Association (1989), "Latest Pigment Applied Technology" CMC Publishing (1986), "Printing Ink Technology" CMC Publication (1984), Industrial Organic Pigments by V. Herbst and K. Hunger (VCH Verlagsgesellschaft, 1993). Specifically, as organic pigments, azo pigments (azo lake pigments, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, indigo pigments, quinacridone Pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dyed lake pigments (acid or basic dye lake pigments), azine pigments, etc. CI Pigment Yellow 34, 37, 42, 53 of yellow pigment, CI Pigment Red 101, 108 of red pigment, CI Pigment Blue 27, 29, 17: 1 of blue pigment, CI Pigment Black of black pigment, etc. 7, white pigment CI Pigment White 4,6,18,21 and the like.

  As a pigment having a preferable color tone for image formation, a phthalocyanine pigment, an anthraquinone-based indanthrone pigment (for example, CI Pigment Blue 60), a dyed lake pigment-based triarylcarbonium pigment are preferable for blue to cyan pigments, and in particular phthalocyanine. Pigments (preferred examples include copper phthalocyanine such as CI Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, and 15: 6, monochloro or low chlorinated copper phthalocyanine, and arnium phthalocyanine. Pigment described in European Patent No. 860475, metal-free phthalocyanine which is CI Pigment Blue 16, phthalocyanine whose central metal is Zn, Ni, Ti, etc., among which CI Pigment Blue 15: 3, 15: 4, aluminum phthalocyanine ) Is most preferred.

  For red to violet pigments, azo pigments (preferred examples include CI Pigment Red 3, 5, 11, 22, 38, 48: 1, 48: 2, 48: 3, 48: 3, 48: 3, 48: 3). 4, 49: 1, 52: 1, 53: 1, 57: 1, 63: 2, 144, 146, 184), etc. 146, 184), quinacridone pigments (preferred examples include CI Pigment Red 122, 192, 202, 207, 209, CI Pigment Violet 19, 42, and among them, CI Pigment Red 122). Dye-attached lake pigment triarylcarbonium pigments (preferred examples include xanthene CI Pigment Red 81: 1, CI Pigment Violet 1, 2, 3, 27, 39), dioxazine pigments (for example, CI Pigment Violet 23, 37), diketopyrrolopyrrole pigment (eg CI Pigment Red 254), perylene pigment (eg CI Pigment Violet 29), anthraquinone Fee (e.g., C. I. Pigment Violet 5: 1, the 31, the 33), thioindigo (e.g. C. I. Pigment Red 38, the 88) is preferably used.

  As yellow pigments, azo pigments (preferred examples include monoazo pigment-based CI Pigment Yellow 1, 3, 74, 98, disazo pigment-based CI Pigment Yellow 12, 13, 14, 16, 17, 83, CI Pigment Yellow 93, 94, 95, 128, 155, benzimidazolone-based CI Pigment Yellow 120, 151, 154, 156, 180, etc., among which preferable ones do not use benzidine-based compounds), iso Indoline / isoindolinone pigments (preferred examples include CI Pigment Yellow 109, 110, 137, 139), quinophthalone pigments (preferred examples include CI Pigment Yellow 138), and furapantron pigments (for example, CI Pigment Yellow 24) Is preferably used.

Preferred examples of the black pigment include inorganic pigments (preferably carbon black and magnetite as examples) and aniline black.
In addition, an orange pigment (CI Pigment Orange 13, 16, etc.) or a green pigment (CI Pigment Green 7, etc.) may be used.

The pigment that can be used in the present invention may be the above-mentioned bare pigment or a surface-treated pigment. Surface treatment methods include resin or wax surface coating, surfactant deposition, reactive substances (eg radicals derived from silane coupling agents, epoxy compounds, polyisocyanates, diazonium salts, etc.) pigments A method of bonding to the surface is conceivable and is described in the following documents and patents.
(1) Properties and applications of metal soap (Sachishobo)
(2) Printing ink printing (CMC Publishing 1984)
(3) Latest pigment application technology (CMC Publishing 1986)
(4) US Pat. Nos. 5,554,739 and 5,571,311 (5) JP-A Nos. 9-151342, 10-140065, 10-292143 and 11-166145 The self-dispersing pigment prepared by allowing the diazonium salt to act on carbon black and the encapsulated pigment prepared by the method described in the Japanese patent (5) above use an extra dispersant in the ink. This is particularly effective because dispersion stability can be obtained without any problems.

In the present invention, the pigment may be further dispersed using a dispersant. Various known dispersants can be used in accordance with the pigment to be used, for example, a surfactant-type low-molecular dispersant or a polymer-type dispersant. Examples of the dispersant include those described in JP-A-3-69949, European Patent 549486 and the like. In addition, when a dispersant is used, a pigment derivative called a synergist may be added to promote adsorption of the dispersant to the pigment.
The particle size of the pigment that can be used in the present invention is preferably in the range of 0.01 to 10 μm after dispersion, and more preferably 0.05 to 1 μm.
As a method for dispersing the pigment, a known dispersion technique used in ink production or toner production can be used. Examples of the dispersing machine include vertical or horizontal agitator mills, attritors, colloid mills, ball mills, three roll mills, pearl mills, super mills, impellers, dispersers, KD mills, dynatrons, and pressure kneaders. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

  Examples of water-soluble dyes used in the present invention include magenta dyes described in JP-A No. 2002-371214, phthalocyanine dyes described in JP-A No. 2002-309118, JP-A Nos. 2003-12952 and 2003-12956. It is also preferable to use the dyes described in water-soluble phthalocyanine dyes.

  Ink compositions such as cyan ink and yellow ink used in the ink set of the present invention (hereinafter also referred to as “ink composition of the present invention”) mean those comprising at least a dye as a basic component. The ink composition of the present invention can contain a medium, but when a solvent is used as the medium, it is particularly suitable as an ink for inkjet recording. The ink composition of the present invention can be prepared by dissolving and / or dispersing the dye of the present invention in a lipophilic medium or an aqueous medium as a medium. Preferably, an aqueous medium is used. The ink composition of the present invention includes an ink composition excluding a medium. If necessary, other additives are contained within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned. These various additives are directly added to the ink liquid in the case of a water-soluble ink composition. When an oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.

  The ink composition of the present invention can be preferably prepared by incorporating a dye in an aqueous medium. As a means for containing the dye, it is preferable to dissolve and / or disperse the dye. The “aqueous medium” in the present invention means water or a water-added solvent such as a water-miscible organic solvent as necessary.

  The water-miscible organic solvent that can be used in the present invention is a material having functions such as an anti-drying agent, a penetration accelerator, and a wetting agent for inkjet recording inks in the field, and is mainly a high-boiling water-miscible material. An organic solvent is used. Such compounds include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols (eg, , Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg, ethylene glycol monomethyl) Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether Diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol Monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine) , Reethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2- Pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). In addition, the said water miscible organic solvent may use 2 or more types together.

Among these, alcohol solvents are particularly preferable. The ink composition of the present invention preferably contains a water-miscible organic solvent having a boiling point of 150 ° C. or higher, and examples thereof include 2-pyrrolidone selected from the above.
These water-miscible organic solvents are preferably contained in the ink in a total amount of 5 to 60% by mass, particularly preferably 10 to 45% by mass.

When the ink used in the present invention is prepared, when the dye is water-soluble, it is preferably dissolved in water first. Thereafter, various solvents and additives are added, dissolved and mixed to obtain a uniform ink solution.
As the dissolution method at this time, various methods such as dissolution by stirring, dissolution by ultrasonic irradiation, and dissolution by shaking can be used. Of these, the stirring method is particularly preferably used. In the case of stirring, various methods such as fluidized stirring known in the art and stirring using shearing force using an inverted agitator or dissolver can be used. On the other hand, a stirring method using a shearing force with the bottom surface of the container, such as a magnetic stirrer, can also be preferably used.

By including a surfactant in the ink composition of the present invention and adjusting the liquid physical properties of the ink, the ink ejection stability is improved, and the water resistance of the image is improved and the bleeding of the printed ink is excellent. Can have the same effect.
Examples of the surfactant include anionic surfactants such as sodium dodecyl sulfate, sodium dodecyloxysulfonate, and sodium alkylbenzene sulfonate, and cationic surfactants such as cetyl pyridinium chloride, trimethyl cetyl ammonium chloride, and tetrabutyl ammonium chloride. And nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene naphthyl ether, polyoxyethylene octylphenyl ether, and the like. Among these, nonionic surfactants are particularly preferably used.

  The content of the surfactant is 0.001 to 20% by mass, preferably 0.005 to 10% by mass, and more preferably 0.01 to 5% by mass with respect to the ink.

When the dye is an oil-soluble dye, it can be prepared by dissolving the oil-soluble dye in a high-boiling organic solvent and emulsifying and dispersing it in an aqueous medium.
The boiling point of the high-boiling organic solvent used in the present invention is 150 ° C. or higher, preferably 170 ° C. or higher.
For example, phthalic acid esters (for example, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1, 1-diethylpropyl) phthalate), esters of phosphoric acid or phosphones (eg diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate , Tridodecyl phosphate, di-2-ethylhexylphenyl phosphate), benzoic acid esters (eg 2-ethylhexyl benzoate, 2,4-dicarbonate) Lobenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecanamide, N, N-diethyllaurylamide), alcohols or phenols (isostearyl alcohol, 2, 4-di-tert-amylphenol), aliphatic esters (eg, dibutoxyethyl succinate, di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate , Trioctyl citrate), aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), chlorinated paraffins (paraffins having a chlorine content of 10% to 80%), trimesic acid esters Kind (for example, Tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols (eg, 2,4-di-tert-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4- (4-dodecyloxyphenylsulfonyl)) Phenol), carboxylic acids (eg, 2- (2,4-di-tert-amylphenoxybutyric acid, 2-ethoxyoctanedecanoic acid), alkylphosphoric acids (eg, di-2 (ethylhexyl) phosphoric acid, diphenylphosphoric acid) The high-boiling organic solvent can be used in an amount of 0.01 to 3 times, preferably 0.01 to 1.0 times the mass ratio of the oil-soluble dye.
These high-boiling organic solvents may be used alone or in a mixture of several types (eg tricresyl phosphate and dibutyl phthalate, trioctyl phosphate and di (2-ethylhexyl) sebacate, dibutyl phthalate and poly (Nt-butyl). Acrylamide)].

Examples of other high boiling point organic solvents used in the present invention and / or methods for synthesizing these high boiling point organic solvents are disclosed in, for example, US Pat. Nos. 2,322,027, 2,533,514, and 2 772,163, 2,835,579, 3,594,171, 3,676,137, 3,689,271, 3,700,454 3,748,141, 3,764,336, 3,765,897, 3,912,515, 3,936,303, 4, No. 004,928, No. 4,080,209, No. 4,127,413, No. 4,193,802, No. 4,207,393, No. 4,220,711, No. 4,239,851, No. 4,278,757, No. 4 353,979, 4,363,873, 4,430,421, 4,430,422, 4,464,464, 4,483,918, 4,540,657, 4,684,606, 4,728,599, 4,745,049, 4,935,321, 5,013 , 639, European Patent Nos. 276,319A, 286,253A, 289,820A, 309,158A, 309,159A, 309,160A, 509 No. 311A, No. 510,576A, East German Patent No. 147,009, No. 157,147, No. 159,573, No. 225,240A, British Patent No. 2,091,124A, JP-A-48-47335, 50 No. 26530, No. 51-25133, No. 51-26036, No. 51-27921, No. 51-27922, No. 51-149028, No. 52-46816, No. 53-1520, No. 53-1521 53-15127, 53-146622, 54-91325, 54-106228, 54-118246, 55-59464, 56-64333, 56-81836, 59-204041, 61-86441, 62-118345, 62-247364, 63-167357, 63-214744, 63-301941, 63-94552, 64-945 9454, 64-68745, JP-A-1-101543, 1-102454, 2-792, and 2 No.-4239, No. 2-43541, No. 4-29237, No. 4-30165, No. 4-232946, No. 4-346338 and the like.
The high boiling point organic solvent is used in an amount of 0.01 to 3.0 times, preferably 0.01 to 1.0 times the mass ratio of the oil-soluble dye.

  In the present invention, the oil-soluble dye and the high boiling point organic solvent are emulsified and dispersed in an aqueous medium. In the emulsification dispersion, a low boiling organic solvent can be used depending on the case from the viewpoint of emulsification. The low boiling point organic solvent is an organic solvent having a boiling point of about 30 ° C. or higher and 150 ° C. or lower at normal pressure. For example, esters (eg ethyl acetate, butyl acetate, ethyl propionate, β-ethoxyethyl acetate, methyl cellosolve acetate), alcohols (eg isopropyl alcohol, n-butyl alcohol, secondary butyl alcohol), ketones (eg methyl isobutyl) Ketones, methyl ethyl ketone, cyclohexanone), amides (for example, dimethylformamide, N-methylpyrrolidone), ethers (for example, tetrahydrofuran, dioxane) and the like are preferably used, but are not limited thereto.

The emulsification dispersion is used to disperse an oil phase in which a dye is dissolved in a mixed solvent of a high-boiling organic solvent and, optionally, a low-boiling organic solvent, in an aqueous phase mainly composed of water to form fine oil droplets in the oil phase. Done. At this time, components such as a surfactant, a wetting agent, a dye stabilizer, an emulsion stabilizer, an antiseptic, and an antifungal agent can be added to either or both of the aqueous phase and the oil phase as necessary. .
As an emulsification method, a method of adding an oil phase to an aqueous phase is common, but a so-called phase inversion emulsification method in which an aqueous phase is dropped into an oil phase can also be preferably used. The emulsification method can also be applied when the dye is water-soluble and the component is oil-soluble.

  When emulsifying and dispersing, various surfactants can be used. Anionic interfaces such as fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates, etc. Activator, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethyleneoxypropylene block copolymer Nonionic surfactants such as Further, SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred. Further, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.

For the purpose of stabilization immediately after emulsification, a water-soluble polymer can be added in combination with the surfactant. As the water-soluble polymer, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, polyacrylic acid, polyacrylamide or a copolymer thereof is preferably used. It is also preferable to use natural water-soluble polymers such as polysaccharides, casein, and gelatin. Furthermore, for stabilization of the dye dispersion, acrylic acid esters, methacrylic acid esters, vinyl esters, acrylamides, methacrylamides, olefins, styrenes, vinyl ethers that are substantially insoluble in an aqueous medium, Polyvinyl, polyurethane, polyester, polyamide, polyurea, polycarbonate and the like obtained by polymerization of acrylonitrile can also be used in combination. These polymers preferably contain —SO ₃ — and —COO ^— . When these polymers that do not substantially dissolve in an aqueous medium are used in combination, it is preferably used in an amount of 20% by mass or less, more preferably 10% by mass or less of the high boiling point organic solvent.

When an oil-soluble dye or a high-boiling organic solvent is dispersed by emulsification to obtain a water-based ink, control of the particle size is particularly important. In order to increase color purity and density when an image is formed by inkjet, it is essential to reduce the average particle size. Preferably it is 1 micrometer or less by volume average particle diameter, More preferably, it is 5-100 nm.
In addition to static light scattering, dynamic light scattering, and centrifugal sedimentation, the methods for measuring the volume average particle size and particle size distribution of the dispersed particles are described in pages 417 to 418 of Experimental Chemistry Course 4th edition. It can be easily measured by a known method such as using a method. For example, after dilution with distilled water so that the particle concentration in the ink is 0.1 to 1% by mass, it is easy with a commercially available volume average particle size measuring device (for example, Microtrac UPA (Nikkiso Co., Ltd.)) Can be measured. Furthermore, the dynamic light scattering method using the laser Doppler effect is particularly preferable because it can measure the particle size up to a small size.
The volume average particle diameter is an average particle diameter weighted by the particle volume, and is the sum of the diameter of each particle multiplied by the volume of the particle divided by the total volume of the particles. The volume average particle diameter is described on page 119 of “Chemistry of Polymer Latex (by Soichi Muroi, Polymer Press Society)”.

It was also found that the presence of coarse particles also plays a very important role in printing performance. That is, it has been found that the coarse particles clog the nozzles of the head, or even if they are not clogged, the ink is not ejected or the ink is not ejected, resulting in a serious influence on the printing performance. In order to prevent this, it is important to limit the number of particles of 5 μm or more to 10 or less and 1 μm or more to 1000 or less in 1 μl of ink.
As a method for removing these coarse particles, a known centrifugal separation method, microfiltration method, or the like can be used. These separation means may be performed immediately after the emulsification dispersion, or may be performed immediately after filling the ink dispersion after adding various components such as a wetting agent and a surfactant to the emulsification dispersion.
A mechanical emulsifier can be used as an effective means for reducing the average particle size and eliminating coarse particles.

As the emulsifying device, known devices such as a simple stirrer, impeller stirring method, in-line stirring method, mill method such as colloid mill, and ultrasonic method can be used, but the use of a high-pressure homogenizer is particularly preferable.
The high-pressure homogenizer is described in detail in US Pat. No. 4,533,254, JP-A-6-47264, etc., but as a commercially available apparatus, a Gorin homogenizer (APV GAULIN INC.), A microfluidizer ( MICROFLUIDEX INC.), Optimizer (Sugino Machine Co., Ltd.) and the like.
In addition, a high-pressure homogenizer equipped with a mechanism for atomizing in an ultrahigh-pressure jet stream as described in US Pat. No. 5,720,551 in recent years is particularly effective for the emulsification dispersion of the present invention. An example of an emulsifying apparatus using this ultra-high pressure jet flow is DeBEE2000 (BEE INTERNIONAL LTD.).

The pressure at the time of emulsification with a high-pressure emulsifying dispersion device is 50 MPa or more, preferably 60 MPa or more, more preferably 180 MPa or more.
For example, it is a particularly preferable method that two or more types of emulsifiers are used together by a method such as emulsification with a stirring emulsifier and then passing through a high-pressure homogenizer. In addition, a method of once emulsifying and dispersing with these emulsifiers, adding components such as a wetting agent and a surfactant, and then passing the high-pressure homogenizer again while filling the cartridge with ink is also a preferable method.
When a low boiling point organic solvent is contained in addition to the high boiling point organic solvent, it is preferable to remove the low boiling point solvent from the viewpoint of the stability of the emulsion and safety and health. Various known methods can be used as the method for removing the low boiling point solvent depending on the type of the solvent. That is, an evaporation method, a vacuum evaporation method, an ultrafiltration method, and the like. This step of removing the low-boiling organic solvent is preferably performed as soon as possible immediately after emulsification.

  Ink preparation methods are described in detail in JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, and 7-118584. It can also be used to prepare the ink composition of the present invention.

  The ink composition of the present invention can contain a functional component for imparting various functions to the ink. For example, as the functional component, the above-mentioned various solvents, a drying preventive agent for preventing clogging due to dry operation at the ink ejection port, a penetration enhancer for allowing the ink to permeate the paper better, an ultraviolet absorber, Antioxidants, viscosity modifiers, surface tension modifiers, dispersants, dispersion stabilizers, antifungal agents, rust inhibitors, pH adjusters, antifoaming agents, chelating agents and the like can be mentioned, and the ink composition of the present invention is These can be appropriately selected and used in appropriate amounts. These functional components include a single compound that can exhibit one or more functions. Therefore, in the following blending ratio of the functional component, the handling of the functional component in the case where the function is duplicated shall include the compound in each functional component independently.

  The drying inhibitor used in the present invention is preferably a water-soluble organic solvent having a vapor pressure lower than that of water. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin. Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. Moreover, said drying inhibitor may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.

  Examples of penetration enhancers used in the present invention include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic surfactants. Etc. can be used. If these are contained in the ink in an amount of 10 to 30% by mass, the effect is sufficient, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding and paper loss (print through).

  Examples of the ultraviolet absorber used for improving the storability of the image in the present invention include JP-A Nos. 58-185677, 61-190537, JP-A-2-782, and JP-A-5-97075. Benzotriazole compounds described in JP-A-9-34057, etc., benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194443, US Pat. No. 3,214,463, etc. 48-30492, 56-21114, and cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, and 8-239368. And triazine compounds described in JP-A-10-182621, JP-A-8-501291, etc. Jar No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based compounds and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

  In the present invention, various organic and metal complex anti-fading agents can be used as the antioxidant used to improve image storage stability. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, No. VII, I to J, ibid. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of the representative compounds described in pages 127 to 137 of JP-A-62-215272 can be used.

Antifungal agents used in the present invention include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and its salts. Can be mentioned. These are preferably used in the ink in an amount of 0.02 to 5.00% by mass.
Details of these are described in “Encyclopedia of Antibacterial and Antifungal Agents” (edited by the Japanese Association of Antimicrobial and Antifungal Society).
Examples of the rust preventive include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropyl ammonium nitrite, pentaerythritol tetranitrate, dicyclohexyl ammonium nitrite, and benzotriazole. These are preferably used in the ink in an amount of 0.02 to 5.00% by mass.

The pH adjuster used in the present invention can be suitably used in terms of adjusting pH, imparting dispersion stability, etc., and the pH of the ink at 25 ° C. is preferably adjusted to 8-11. When the pH is less than 8, the solubility of the dye is lowered and the nozzle is easily clogged, and when it exceeds 11, the water resistance tends to deteriorate. Examples of the pH adjuster include basic organic bases and inorganic alkalis, and acidic ones such as organic acids and inorganic acids.
Basic compounds include inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium phosphate, sodium hydrogen phosphate, aqueous ammonia, Use organic bases such as methylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, piperidine, diazabicyclooctane, diazabicycloundecene, pyridine, quinoline, picoline, lutidine, collidine Is also possible.
Examples of acidic compounds include inorganic compounds such as hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, sodium hydrogen sulfate, potassium hydrogen sulfate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, acetic acid, tartaric acid, benzoic acid, trifluoroacetic acid. Organic compounds such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, saccharic acid, phthalic acid, picolinic acid and quinolinic acid can also be used.

The conductivity of the ink composition of the present invention is in the range of 0.01 to 10 S / m. Among these, a preferable range is a conductivity of 0.05 to 5 S / m.
The conductivity can be measured by an electrode method using commercially available saturated potassium chloride.
The conductivity can be controlled mainly by the ion concentration in the aqueous solution. When the salt concentration is high, desalting can be performed using an ultrafiltration membrane or the like. Moreover, when adjusting conductivity by adding salt etc., it can adjust by adding various organic substance salt and inorganic substance salt.
Inorganic salts include potassium halide, sodium halide, sodium sulfate, potassium sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, sodium nitrate, potassium nitrate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, sodium monohydrogen phosphate, Inorganic compounds such as boric acid, potassium dihydrogen phosphate, sodium dihydrogen phosphate, sodium acetate, potassium acetate, potassium tartrate, sodium tartrate, sodium benzoate, potassium benzoate, sodium p-toluenesulfonate, potassium saccharinate Organic compounds such as potassium phthalate and sodium picolinate can also be used.
The conductivity can also be adjusted by selecting the components of the aqueous medium described later.

The viscosity of the ink composition of the present invention is preferably 1 to 30 mPa · s at 25 ° C. More preferably, it is 2-15 mPa * s, Most preferably, it is 2-10 mPa * s. If it exceeds 30 mPa · s, the fixing speed of the recorded image becomes slow, and the discharge performance also deteriorates. If it is less than 1 mPa · s, the recorded image is blurred and the quality is lowered.
The viscosity can be arbitrarily adjusted by adding the ink solvent. Examples of the ink solvent include glycerin, diethylene glycol, triethanolamine, 2-pyrrolidone, diethylene glycol monobutyl ether, and triethylene glycol monobutyl ether.
A viscosity modifier may be used. Examples of the viscosity modifier include water-soluble polymers such as celluloses and polyvinyl alcohol, and nonionic surfactants. For more details, see Chapter 9 of “Viscosity Preparation Technology” (Technical Information Association, 1999), and “Chemicals for Inkjet Printers (98 Supplement)-Material Development Trends and Perspective Survey” (CMC, 1997) 162- Page 174.

  The method for measuring the viscosity of the liquid is described in detail in JIS Z8803, but can be easily measured with a commercially available viscometer. For example, the rotary type includes Tokyo Keiki B-type viscometer and E-type viscometer. In this invention, it measured at 25 degreeC by the vibration type VM-100AL type of Yamaichi Electric. The unit of viscosity is Pascal second (Pa · s), but millipascal second (mPa · s) is usually used.

The surface tension of the ink used in the present invention is preferably 20 to 50 mN / m, more preferably 20 to 40 mN / m at 25 ° C. for both dynamic and static surface tension. When the surface tension exceeds 50 mN / m, the discharge stability, the bleeding at the time of color mixing, the print quality such as the whiskers are remarkably lowered. Further, when the surface tension of the ink is set to 20 mN / m or less, there may be a case where printing failure occurs due to adhesion of ink to the hard surface during ejection.
For the purpose of adjusting the surface tension, various cations, anions, nonionic surfactants and betaine surfactants can be added. Two or more surfactants can be used in combination.

As a static surface tension measuring method, a capillary rising method, a dropping method, a hanging ring method and the like are known. In the present invention, a vertical plate method is used as a static surface tension measuring method.
When a thin plate of glass or platinum is partially immersed in the liquid and suspended vertically, the surface tension of the liquid acts downward along the length of contact between the liquid and the plate. The surface tension can be measured by balancing this force with an upward force.

  Examples of the dynamic surface tension measurement method include “New Experimental Chemistry Course, Vol. 18, Interface and Colloid” [Maruzen Co., Ltd., p. 69-90 (1977)], the vibration jet method, the meniscus dropping method, the maximum bubble pressure method and the like are known, and further, the liquid film breakage as described in JP-A-3-2064 is known. In the present invention, a bubble pressure differential pressure method is used as a dynamic surface tension measurement method. The measurement principle and method will be described below.

  When bubbles are generated in the solution that has become homogeneous by stirring, a new gas-liquid interface is generated, and the surfactant molecules in the solution gather on the surface of the water at a constant rate. When the bubble rate (bubble generation rate) is changed, if the generation rate slows down, more surfactant molecules gather on the surface of the bubble, so the maximum bubble pressure just before the bubble pops is reduced, The maximum bubble pressure (surface tension) relative to the bubble rate can be detected. As a preferable dynamic surface tension measurement, a method is used in which bubbles are generated in a solution using two large and small probes, the differential pressure in the maximum bubble pressure state of the two probes is measured, and the dynamic surface tension is calculated. Can be mentioned.

The non-volatile component in the ink composition of the present invention is 10 to 70% by mass of the total amount of the ink. The ejection stability of the ink, the print image quality, various image fastnesses, the bleeding of the image after printing, and the printing surface It is preferable from the viewpoint of reducing stickiness, and is more preferably 20 to 60% by mass from the viewpoint of ink ejection stability and reduction of image bleeding after printing.
Here, the non-volatile component means a liquid, a solid component or a high molecular weight component having a boiling point of 150 ° C. or higher under 1 atm. Non-volatile components of the ink are dyes, high boiling point solvents, polymer latex added as necessary, surfactants, dye stabilizers, antifungal agents, buffering agents, etc., and many of these non-volatile components are dye-stable. Other than the agent, the dispersion stability of the ink is reduced, and it remains on the ink-jet image receiving paper after printing, so the stabilization due to the association of dyes on the image receiving paper is inhibited, and various fastness and high humidity conditions of the image area It has the property of exacerbating image blurring.

  In the present invention, a high molecular weight compound can also be contained. Here, the high molecular weight compound means all high molecular compounds having a number average molecular weight of 5000 or more contained in the ink. These polymer compounds are soluble in water-soluble polymer compounds that are substantially soluble in aqueous media, water-dispersible polymer compounds such as polymer latex and polymer emulsion, and polyhydric alcohols that are used as auxiliary solvents. Alcohol-soluble polymer compounds and the like can be mentioned, but any compound that substantially dissolves or disperses uniformly in the ink liquid is included in the high molecular weight compound in the present invention.

Specific examples of the water-soluble polymer compound include polyvinyl alcohol, silanol-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone, polyethylene oxide, water-soluble polymers such as polyoxyalkylene oxide such as polypropylene oxide, polysaccharides, starch, cationized starch, casein, natural water-soluble polymers such as gelatin, polyacrylic acid, polyacrylamide or aqueous acrylic resins such as a copolymer thereof, aqueous alkyd resins, -SO in the molecule ₃ ^-, Examples thereof include water-soluble polymer compounds having a —COO 2 ^— group and substantially soluble in an aqueous medium.
Examples of the polymer latex include styrene-butadiene latex, styrene-acrylic latex, and polyurethane latex. Furthermore, an acrylic emulsion etc. are mentioned as a polymer emulsion.
These water-soluble polymer compounds can be used alone or in combination of two or more.

As described above, the water-soluble polymer compound is used as a viscosity adjusting agent to adjust the viscosity of the ink in a viscosity region having good ejection characteristics. As a result, the ejection stability of the ink liquid is lowered, and the nozzle is easily clogged by the precipitate when the ink is aged.
The addition amount of the polymer compound of the viscosity modifier depends on the molecular weight of the compound to be added (the higher the molecular weight, the smaller the addition amount may be), but the addition amount is 0 to 5% by mass with respect to the total amount of ink, preferably Is 0 to 3% by mass, more preferably 0 to 1% by mass.

  Further, in the present invention, the above-mentioned cation, anion, nonionic and betaine surfactants are necessary as a dispersant and dispersion stabilizer, and fluorine-based, silicone-based compounds and chelating agents represented by EDTA are required as an antifoaming agent. Can be used according to.

The reflection type medium that is a printing medium preferably used in the present invention will be further described. Examples of the reflective media include recording paper and recording film. Supports for recording paper and recording film are made of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP, CGP, and waste paper pulp such as DIP. Additives such as known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc. can be mixed and used in various devices such as long net paper machines and circular net paper machines. is there. In addition to these supports, any of synthetic paper and plastic film sheet may be used as the support. The thickness of the support is preferably 10 to 250 μm and the basis weight is preferably 10 to 250 g / m 2.
An image receiving layer and a back coat layer may be provided on the support as they are to provide an image receiving material for the ink composition and ink set of the present invention, or after a size press or anchor coat layer is provided with starch, polyvinyl alcohol, A back coat layer may be provided as an image receiving material. Further, the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar.
As the support, paper and plastic film laminated on both sides with polyolefin (eg, polyethylene, polystyrene, polybutene and their copolymers) or polyethylene terephthalate are more preferably used. It is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a tinting dye (eg, cobalt blue, ultramarine blue, neodymium oxide) to the polyolefin.

  The image receiving layer provided on the support contains a porous material and an aqueous binder. The image receiving layer preferably contains a pigment, and the pigment is preferably a white pigment. White pigments include calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, barium sulfate, calcium sulfate, titanium dioxide, Examples thereof include inorganic white pigments such as zinc sulfide and zinc carbonate, organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. A porous white inorganic pigment is particularly preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, either anhydrous silicic acid obtained by a dry production method (gas phase method) or hydrous silicic acid obtained by a wet production method can be used.

  Specific examples of the recording paper containing the pigment in the image receiving layer include JP-A Nos. 10-81064, 10-119423, 10-157277, 10-217601, 11-348409, and JP-A-2001-138621. 2000-43401, 2000-2111235, 2000-309157, 2001-96897, 2001-138627, JP-A-11-91242, 8-2087, 8-2090, 8-2091, 8-9. 2093, 8-174992, 11-192777, JP-A-2001-301314, and the like can be used.

  As the aqueous binder contained in the image receiving layer, water-soluble polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, polyalkylene oxide derivatives, etc. Examples thereof include water-dispersible polymers such as polymers, styrene butadiene latexes, and acrylic emulsions. These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and resistance to peeling of the ink receiving layer.

  The image receiving layer can contain a mordant, a water resistance agent, a light resistance improver, a gas resistance improver, a surfactant, a hardener and other additives in addition to the pigment and the aqueous binder.

The mordant added to the image receiving layer is preferably immobilized. For that purpose, a polymer mordant is preferably used.
For the polymer mordant, JP-A-48-28325, 54-74430, 54-124726, 55-22766, 55-142339, 60-23850, 60-23835, 60-23852, 60-23853, 60-57836, 60-60643, 60-118834, 60-122940, 60-122941, 60-122294, 60- No. 235134, Japanese Patent Application Laid-Open No. 1-161236, U.S. Pat. It is described in each specification of the same No. 4450224. An image receiving material containing a polymer mordant described in JP-A-1-161236, pages 212 to 215 is particularly preferred. When the polymer mordant described in the publication is used, an image with excellent image quality is obtained and the light resistance of the image is improved.

  The water-proofing agent is effective for making the image water-resistant. As these water-proofing agents, cationic resins are particularly desirable. Examples of such a cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, and cationic polyacrylamide. The content of these cationic resins is preferably 1 to 15% by mass, particularly 3 to 10% by mass, based on the total solid content of the ink receiving layer.

Examples of the light resistance improver and gas resistance improver include phenol compounds, hindered phenol compounds, thioether compounds, thiourea compounds, thiocyanate compounds, amine compounds, hindered amine compounds, TEMPO compounds, hydrazine compounds, hydrazide compounds, amidine compounds, Vinyl group-containing compounds, ester compounds, amide compounds, ether compounds, alcohol compounds, sulfinic acid compounds, saccharides, water-soluble reducing compounds, organic acids, inorganic acids, hydroxy group-containing organic acids, benzotriazole compounds, benzophenone compounds, triazine compounds , Heterocyclic compounds, water-soluble metal salts, organometallic compounds, metal complexes, and the like.
Specific examples of these compounds include JP-A-10-182621, JP-A-2001-260519, JP-A-2000-260519, JP-B-4-34953, JP-B-4-34513, and JP-B-4-34512. , JP-A-11-170686, JP-A-60-67190, JP-A-7-276808, JP-A-2000-94829, JP-T 8-512258, JP-A-11-321090, etc. Can be given.

The surfactant functions as a coating aid, a peelability improver, a slippage improver or an antistatic agent. The surfactant is described in JP-A Nos. 62-173463 and 62-183457.
An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of organic fluoro compounds include fluorine-based surfactants, oily fluorine-based compounds (eg, fluorine oil), and solid fluorine compound resins (eg, tetrafluoroethylene resin). The organic fluoro compounds are described in JP-B-57-9053 (columns 8 to 17), JP-A-61-20994, and 62-135826.

  As the hardener, materials described in JP-A-1-161236, page 222, JP-A-9-263036, JP-A-10-119423, and JP-A-2001-310547 can be used.

  Examples of other additives to be added to the image receiving layer include pigment dispersants, thickeners, antifoaming agents, dyes, fluorescent whitening agents, preservatives, pH adjusters, and matting agents. The ink receiving layer may be one layer or two layers.

The recording paper and the recording film can be provided with a back coat layer, and examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components.
Examples of white pigments contained in the backcoat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. , Diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide, white inorganic pigment, styrene And organic pigments such as polyethylene plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, urea resins, and melamine resins.

  As the aqueous binder contained in the backcoat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose Water-soluble polymers such as hydroxyethyl cellulose and polyvinyl pyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the backcoat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-proofing agent.

  A polymer fine particle dispersion may be added to the constituent layers (including the back layer) of the inkjet recording paper and recording film. The polymer fine particle dispersion is used for the purpose of improving the physical properties of the film such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. The polymer fine particle dispersion is described in JP-A Nos. 62-245258, 62-136648, and 62-110066. When a polymer fine particle dispersion having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. Further, even when a polymer fine particle dispersion having a high glass transition temperature is added to the back layer, curling can be prevented.

  The ink composition of the present invention can also be used for purposes other than inkjet recording. For example, it can be used for display image materials, image forming materials for interior decoration materials, and image forming materials for outdoor decoration materials.

  Display image materials include posters, wallpaper, small decorative items (such as figurines and dolls), commercial flyers, wrapping paper, wrapping materials, paper bags, plastic bags, packaging materials, signs, transportation (automobiles, buses, trains, etc.) ) Refers to various things such as images drawn and attached to the side, clothes with logos, and so on. When the dye of the present invention is used as a material for forming a display image, the image includes all patterns of dyes that can be recognized by humans, such as abstract designs, characters, and geometric patterns, in addition to images in a narrow sense.

  The interior decoration material refers to various items such as wallpaper, decorative accessories (such as figurines and dolls), lighting fixture members, furniture members, floor and ceiling design members. When the dye of the present invention is used as an image forming material, the image includes all patterns of dyes that can be recognized by humans such as abstract designs, characters, and geometric patterns in addition to images in a narrow sense.

  The outdoor decoration material refers to various materials such as wall materials, roofing materials, signboards, gardening materials, outdoor decoration accessories (such as figurines and dolls), and members of outdoor lighting equipment. When the dye of the present invention is used as an image forming material, the image includes not only images in a narrow sense but also all patterns of dyes that can be recognized by humans, such as abstract designs, characters, and geometric patterns.

  In the above applications, examples of media on which a pattern is formed include various materials such as paper, fiber, cloth (including non-woven fabric), plastic, metal, and ceramics. As the dyeing form, the dye can be fixed in the form of mordanting, printing, or a reactive dye having a reactive group introduced. Among these, it is preferable that the mordanting is performed.

In the production of ink, ultrasonic vibration can be applied to the dissolution process of additives such as dyes.
Ultrasonic vibration refers to bubbles generated by applying ultrasonic energy equal to or higher than the energy received by the recording head in advance during the ink manufacturing process in order to prevent ink from generating bubbles due to the pressure applied by the recording head. Is to be removed.
The ultrasonic vibration is usually an ultrasonic wave having a frequency of 20 kHz or higher, preferably 40 kHz or higher, more preferably 50 kHz. The energy applied to the liquid by ultrasonic vibration is usually 2 × 10 ⁷ J / m ³ or more, preferably 5 × 10 ⁷ J / m ³ or more, more preferably 1 × 10 ⁸ J / m ³ or more. . Further, the application time of ultrasonic vibration is usually about 10 minutes to 1 hour.
The step of applying ultrasonic vibration shows an effect at any time after the dye is put into the medium. The effect is exhibited even if ultrasonic vibration is applied after the completed ink is once stored. However, adding ultrasonic vibration when the dye is dissolved and / or dispersed in the medium has a greater effect of removing bubbles, and the ultrasonic vibration promotes dissolution and / or dispersion of the dye in the medium. This is preferable.
That is, the step of applying at least ultrasonic vibration can be performed in any case, either during or after the step of dissolving and / or dispersing the dye in the medium. In other words, the step of applying at least ultrasonic vibration can be arbitrarily performed once or more after the ink preparation until it becomes a product.
As an embodiment, the step of dissolving and / or dispersing in the medium preferably includes a step of dissolving the dye in a medium of a part of the whole medium and a step of mixing the remaining medium, and at least one of the above It is preferable to apply ultrasonic vibration to this step, and it is more preferable to apply at least ultrasonic vibration to the step of dissolving the dye in a part of the medium.
The step of mixing the remaining solvent may be a single step or a plurality of steps.
In addition, it is preferable to use heat degassing or vacuum degassing in combination with the ink production according to the present invention because the effect of removing bubbles in the ink is improved. The heat degassing step or the vacuum degassing step is preferably performed simultaneously with or after the step of mixing the remaining medium.
Examples of the ultrasonic vibration generating means in the step of applying ultrasonic vibration include known devices such as an ultrasonic disperser.

When preparing the ink composition of the present invention, a step of removing dust that is a solid content by filtration, which is performed after further preparation of liquid, is important. A filtration filter is used for this work. The filtration filter at this time is a filter having an effective diameter of 1 μm or less, preferably 0.3 μm or less and 0.05 μm or more, particularly preferably 0.3 μm or less and 0.25 μm or more. Use. Various materials can be used as the filter material, but in the case of water-soluble dye ink, it is preferable to use a filter prepared for an aqueous solvent. Among them, it is particularly preferable to use a filter made of a polymer material that hardly generates dust. As a filtration method, a filter may be passed by liquid feeding, and either pressure filtration or vacuum filtration can be used.
After this filtration, air is often taken into the solution. Since bubbles caused by air often cause image disturbance in ink jet recording, it is preferable to separately provide the aforementioned defoaming step. As the defoaming method, the solution after filtration may be allowed to stand, or various methods such as ultrasonic defoaming and vacuum defoaming using a commercially available apparatus can be used. In the case of defoaming by ultrasonic waves, the defoaming operation is preferably performed for about 30 seconds to 2 hours, more preferably about 5 minutes to 1 hour.
These operations are preferably performed using a space such as a clean room or a clean bench in order to prevent dust from entering during the operation. In the present invention, it is particularly preferable to perform this operation in a space of class 1000 or less as the cleanliness. Here, “cleanness” refers to a value measured by a dust counter.

  In the present invention, the ink droplet volume on the recording material is from 0.1 pl to 100 pl. A preferable range of the droplet ejection volume is 0.5 pl or more and 50 pl or less, and a particularly preferable range is 2 pl or more and 50 pl or less.

In the present invention, there is no limitation on the ink jet recording method as long as the image recording is performed by the ink jet printer using the ink composition or ink set of the present invention, and a known method such as electrostatic attraction is used. Charge control method for ejecting ink, drop-on-demand method (pressure pulse method) using the vibration pressure of the piezo element, and changing the electrical signal to an acoustic beam and irradiating the ink to eject the ink using the radiation pressure It is used for an acoustic ink jet method, a thermal ink jet (bubble jet) method in which bubbles are formed by heating ink and the generated pressure is used.
Inkjet recording methods use a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving the image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included. The ink droplet volume is controlled mainly by the print head.

For example, in the case of the thermal ink jet method, the droplet ejection volume can be controlled by the structure of the print head. That is, droplets can be ejected in a desired size by changing the sizes of the ink chamber, the heating unit, and the nozzle. Even in the case of the thermal ink jet method, it is possible to realize droplet ejection of a plurality of sizes by providing a plurality of print heads having different sizes of heating units and nozzles.
In the case of the drop-on-demand method using a piezo element, the droplet ejection volume can be changed due to the structure of the print head as in the thermal ink jet method, but the waveform of the drive signal that drives the piezo element is controlled as described later. By doing so, droplets of a plurality of sizes can be ejected with a print head having the same structure.

The ejection frequency when the ink composition of the present invention is ejected onto a recording material is preferably 1 kHz or more.
In order to record a high-quality image like a photograph, it is necessary to set the droplet ejection density to 600 dpi (number of dots per inch) or more in order to reproduce a sharp image with small ink droplets.
On the other hand, when ink is ejected by a head having a plurality of nozzles, the number of heads that can be driven simultaneously is about several tens to 200 in the type in which the recording paper and the head move in a direction orthogonal to each other, and the line head There is a restriction that there are several hundreds even if the head is called a fixed type. This is because the drive power is limited, and heat generated by the head affects the image, so that a large number of head nozzles cannot be driven simultaneously.
Here, the recording speed can be increased by increasing the drive frequency.
In the case of the thermal ink jet method, the droplet ejection frequency can be controlled by controlling the frequency of the head drive signal for heating the head.
In the case of the piezo method, this is possible by controlling the frequency of a signal for driving the piezo.
The driving of the piezo head will be described. For the image signal to be printed, the droplet size, droplet ejection speed, and droplet ejection frequency are determined by the printer control unit, and a signal for driving the print head is created. The drive signal is supplied to the print head. The droplet ejection size, droplet ejection speed, and droplet ejection frequency are controlled by a signal for driving the piezo. Here, the droplet ejection size and droplet ejection speed are determined by the shape and amplitude of the drive waveform, and the frequency is determined by the signal repetition period.
When this droplet ejection frequency is set to 10 kHz, the head is driven every 100 microseconds, and recording of one line is completed in 400 microseconds. By setting the moving speed of the recording paper to move 1/600 inch in 400 microseconds, that is, approximately 42 microns, it is possible to print at a speed of one sheet in 1.2 seconds.

With respect to the configuration of the printing apparatus and the printer used in the present invention, for example, a mode as disclosed in JP-A-11-170527 is preferable. As the ink cartridge, for example, the one disclosed in JP-A-5-229133 is suitable. With respect to the suction and the configuration of a cap or the like that covers the print head at that time, for example, the one disclosed in JP-A-7-276671 is suitable. Further, it is preferable that a filter for eliminating bubbles as disclosed in JP-A-9-277552 is provided in the vicinity of the head.
The surface of the nozzle is preferably subjected to water repellent treatment as described in JP-A-2002-292878. The application may be a printer connected to a computer or an apparatus specialized for printing photographs.
In the ink jet recording method applied to the present invention, it is preferable that the average droplet ejection speed when ejecting ink onto a recording material is 2 m / sec or more, preferably 5 m / sec or more.
The droplet ejection speed is controlled by controlling the shape and amplitude of the waveform for driving the head.
Further, by using a plurality of driving waveforms properly, it is possible to perform droplet ejection of a plurality of sizes with the same head.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.
The following dyes were used.

Example 1
(Production of yellow ink)
Yellow dye (Dye1) 0.8g
7.2g deionized water
The liquid having the above composition is heated at 60 ° C. to dissolve uniformly, and cooled to room temperature. Next, the following components are added sequentially.
Triethylene glycol monobutyl ether 2g
Glycerin 2g
Triethylene glycol 2g
Surfynol STG 0.2g
Triethanolamine 0.03g
Water was added using deionized water to 20 cc, and the mixture was stirred for 1 minute, and then filtered under reduced pressure through a microfilter having an average pore size of 0.2 μm to prepare yellow ink 1Y.

(Cyan ink production)
Cyan dye (Compound No. 164) 1.3 g
Deionized water 11.7g
The liquid having the above composition is heated at 60 ° C. to dissolve uniformly, and cooled to room temperature. Next, the following components are added sequentially.
Triethylene glycol monobutyl ether 2.2g
Glycerin 2g
1.6 g of triethylene glycol
0.1g of urea
Surfynol STG (Nissin Chemical) 0.2g
Triethanolamine 0.13g
Water was added using deionized water to 20 cc, and the mixture was stirred for 1 minute, and then filtered under reduced pressure through a microfilter having an average pore size of 0.2 μm to prepare cyan ink 1C.

(Production of light cyan ink)
Cyan dye (Compound No. 164) 0.3 g
9g of deionized water
The liquid having the above composition is heated at 60 ° C. to dissolve uniformly, and cooled to room temperature. Next, the following components are added sequentially.
Triethylene glycol monobutyl ether 2.2g
Glycerin 2g
2-pyrrolidone 0.6g
Triethylene glycol 2g
0.05g urea
Surfynol STG (Nissin Chemical) 0.2g
Triethanolamine 0.13g
Water was added using deionized water to 20 cc, and the mixture was stirred for 1 minute, and then filtered under reduced pressure through a microfilter having an average pore diameter of 0.2 μm to prepare a light cyan ink 1LC.

(Preparation of print sample)
Yellow ink 1Y, cyan ink 1C, and light cyan ink 1LC are packed in the yellow, cyan, and light cyan portions of the color cartridge of the ink jet printer PM920C (manufactured by EPSON). A solid image of monochrome, green and gray was printed. In addition, magenta ink, light magenta ink, dark yellow ink, and black ink other than those described above were genuine inks of an inkjet printer PM920C manufactured by EPSON.

(Evaluation of image robustness)
Regarding the image storability, solid image print samples of yellow single color (image Y), cyan single color (image C), green (image G), and gray (image Gr) were prepared and evaluated as follows.
The print density is adjusted so that the yellow density in images Y, G, and Gr and the cyan density in images C, G, and Gr become 1 when the image density Ci before exposure to ozone gas is measured by X-rite. I went there.

  The photographic paper (glossy) on which the images Y, C, G and Gr are formed is left in a box where the ozone gas concentration is set to 5 ppm for 7 days, and the image density before and after being left under the ozone gas is measured by a reflection densitometer (X-Rite310TR). ) And evaluated as a dye residual ratio. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.

(Example 2)
In Example 1, the cyan dye was replaced with Compound No. A cyan ink 2C and a light cyan ink 2LC were produced in the same manner as in Example 1 except that the compound 1 was changed to 164. Preparation of print samples and evaluation of image fastness were performed in the same manner as in Example 1.

(Example 3)
In Example 1, the cyan dye was replaced with Compound No. A cyan ink 3C and a light cyan ink 3LC were produced in the same manner as in Example 1 except that the compound 2 was changed from 164 to Compound 2. Preparation of print samples and evaluation of image fastness were performed in the same manner as in Example 1.

(Comparative Example 1)
In Example 1, in place of the cyan ink 1C and the light cyan ink 1LC, except for using genuine cyan ink and light cyan ink of PM-920C manufactured by EPSON Co., Ltd. Evaluation was performed.

  The results obtained are shown in Table 6.

  From the results of Table 6 above, it can be seen that the ink set of the present invention improves the ozone resistance of yellow dyes in green and gray images in which cyan ink and yellow ink are mixed.

Claims (14)

An ink set comprising at least a yellow ink and a cyan ink having a fading speed with respect to ozone gas of 5.0 × 10 ⁻⁴ / (hr · ppm) or less.   The ink set according to claim 1, wherein the cyan ink includes a phthalocyanine dye having an oxidation potential nobler than 1.0 V (vs SCE).   The ink set according to claim 2, wherein the phthalocyanine dye has an aza group. The ink set according to claim 1, wherein the cyan ink contains a compound represented by the following general formula (I).

In general formula (I), X < ₁ > -X < ₄ > and Y < ₁ > -Y < ₄ > represent a carbon atom or a nitrogen atom each independently.
A _{1 to} A ₄ are each independently required to form an aromatic ring or a heterocycle (may further form a condensed ring with another ring) together with X _{1 to} X ₄ and Y _{1 to} Y _4. Represents an atomic group. A _{1 to} A ₄ may have a substituent. At least one of A ₁ to A ₄ may alternatively at least one of the substituents of A ₁ to A ₄ has as a substituent an ionic hydrophilic group.
M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.   The ink set according to claim 4, wherein the compound represented by the general formula (I) has 2 to 4 ionic hydrophilic groups.   The ink set according to claim 4 or 5, wherein the ionic hydrophilic group is located at the β-position of the compound represented by the general formula (I).   The ink set according to claim 1, wherein the yellow ink contains an azo dye. The ink set according to claim 1, wherein the yellow ink contains a dye represented by the following general formula (1).
General formula (1) (AN = NB) nL
In the formula, A and B each independently represent an optionally substituted heterocyclic group. L represents a hydrogen atom, a simple bond or a divalent linking group. n represents 1 or 2. However, when n is 1, L represents a hydrogen atom, and both A and B are monovalent heterocyclic groups. When n is 2, L represents a simple bond or a divalent linking group, one of A and B is a monovalent heterocyclic group, and the other is a divalent heterocyclic group. When n is 2, A may be the same or different, and B may be the same or different.   The ink set according to claim 1, wherein the cyan ink is composed of two or more inks having different dye contents.   The ink set according to claim 1, further comprising a black ink.   The ink set according to claim 1, wherein the ink set is used for ink jet recording.   The fastness of ozone of a multi-order color, which improves the fading to the ozone gas of a yellow ink in a multi-order color formed using at least a cyan ink and a yellow ink of the ink set according to claim 1. Improvement method.   A color image is formed using the ink set according to claim 1.   14. A full color image is recorded on an image receiving material by ejecting ink droplets of an ink set onto an image receiving material having an image receiving layer containing white inorganic pigment particles on a support in accordance with a recording signal. The ink jet recording method described in 1.