JP2002264490A - Imaging method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an imaging method by which an image showing high ink discharge stability, excellent hue and superb resistance to light and water without defects of an image quality such as fine line blot and outstanding preservability under severe conditions, is formed on an image receiving paper containing a porous image receiving material, especially, a white inorganic pigment, in the imaging method by an ink jet recording process with the use of an aqueous ink having advantages in terms of handling ease, smell and safety. SOLUTION: In the imaging method by an ink jet recording process by which an ink group using an ink composition for ink jet recording containing at least a water-soluble dye or an oil-soluble dye and further, a polymer fine particle dispersion, is discharged in accordance with a recording signal to record an image on an image receiving material, the image receiving material contains the porous image receiving material in the image receiving layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an ink-jet recording ink composition having excellent ejection stability and storage stability.
The present invention relates to an image forming method using an inkjet recording method capable of obtaining an image having high quality and excellent fastness.

[0002]

2. Description of the Related Art In recent years, with the spread of computers, ink jet printers have been used not only in offices but also at home in paper,
It is widely used for printing on films, cloths and the like.
Ink jet recording methods include a method in which pressure is applied by a piezo element to eject droplets, a method in which bubbles are generated in ink by heat to eject droplets, a method using ultrasonic waves, or a method in which droplets are applied by electrostatic force. There is a method of sucking and discharging. As these inkjet recording inks,
Water-based ink, oil-based ink, or solid (melt-type) ink is used. Among these inks, aqueous inks are predominant in terms of production, handling, odor, safety, and the like.

The colorants (dyes and pigments) used in these inks for ink jet recording have high solubility in solvents, enable high-density recording, have good hue, It has excellent fastness to heat, air, water and chemicals, has good fixability to the image receiving material and does not spread easily, has excellent storage stability as ink, has no toxicity, has high purity, Furthermore, it is required to be available at a low price, and various dyes and pigments have already been proposed and actually used for inkjet. However, at present, a colorant satisfying all requirements has not been found yet. With well-known dyes and pigments to which a color index (CI) number is assigned, it is difficult to achieve both the hue and the fastness required for an ink jet recording ink. Japanese Unexamined Patent Publication (Kokai) No. 55-55 as a dye for improving fastness
An azo dye derived from an aromatic amine and a 5-membered heterocyclic amine described in JP-A-161856 has been proposed. However, these dyes have unfavorable hues in the yellow and cyan regions, and thus have a problem of deteriorating color reproducibility. JP-A-61-36362 and JP-A-2-212566 disclose ink jet recording inks containing a water-soluble pyrazolylazo dye for the purpose of achieving both hue and light fastness. However, the dyes used in each publication have insufficient improvement in hue, and when used as a water-soluble ink, have insufficient solubility in water. Further, when the dyes described in the respective publications are used as water-soluble inks for ink jet, there is a problem in fastness to wet heat. As means for solving these problems, JP-A-11-504958 proposes, in addition to the same dye structure as described above, a compound containing an interactive group and an ink composition.

[0004]

However, these inks for ink-jet recording all have poor hue, and the resulting images also have problems with weatherability such as light and heat fastness. It has been found that under severe conditions, image degradation may occur.
The deterioration of the image under such severe conditions is particularly remarkable in a porous image receiving material, particularly in an image receiving paper containing a white inorganic pigment in an image receiving layer, and an image having excellent storability even under severe conditions such as weather resistance and severe conditions. A way to obtain it is desired.

Accordingly, an object of the present invention is to provide an ink jet recording method using an aqueous ink which has advantages in handleability, odor, safety, etc., in which the ink ejection stability is high, and The resulting image is excellent in hue, light resistance, heat resistance and water resistance, has no defects in image quality such as blurring of fine lines, and has excellent storage stability under severe conditions. An object of the present invention is to provide an image forming method for forming an image on an image receiving paper containing a pigment in an image receiving layer.

[0006]

The above object has been attained by the following inventions. (1) An image forming method by an ink jet recording method in which an ink liquid using an ink composition for ink jet recording containing at least a colorant and further containing a polymer fine particle dispersion is ejected in accordance with a recording signal and recorded on an image receiving material. 2. The image forming method according to claim 1, wherein the image receiving material includes a porous material in an image receiving layer. (2) The image forming method according to (1), wherein the colorant is a water-soluble dye. (3) The image forming method according to (1), wherein the colorant is an oil-soluble dye. (4) The image forming method according to (3), further comprising a high boiling point organic solvent. (5) The image forming method according to any one of (1) to (4), wherein the porous material is a white inorganic pigment.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. Here, the Hammett's substituent constant σ _p value used in the present specification will be described. The Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of a benzene derivative, and is widely accepted today. The substituent constants determined by Hammett's rule include σ _p and σ _m values, and these values can be found in many general books. For example, JADean, “Lange's Ha
ndbook of Chemistry, 12th Edition, 1979 (Mc Graw
-Hill) and "Chemistry", No.122, 96-10
See page 3, 1979 (Nankodo). In the present invention, each substituent is limited or described by Hammett's substituent constant σ _p, but this is limited to only those substituents having a value known in the literature, which can be found in the above-mentioned books. Not to mention the meaning, but it goes without saying that even if the value is unknown in the literature, it also includes a substituent that would be included in the range when measured based on the Hammett rule. Although the compound represented by the general formula of the present invention is not a benzene derivative, as a measure of the electronic effect of the substituent, σ
_{Use p-} value. Hereinafter, in the present invention, the σ _p value is used in such a meaning.

The coloring agent contained in the ink composition for ink jet recording used in the present invention is preferably a dye. Either an oil-soluble dye or a water-soluble dye can be used, and a yellow dye, a magenta dye, a cyan dye, etc. Is mentioned.

Examples of the yellow dye include phenols, naphthols, anilines, pyrazolones, pyridones, and open-chain active methylene compounds having a phenol, naphthol, open-chain active methylene compound as a coupling component; Azomethine dyes having compounds; for example, methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes, anthraquinone dyes and the like; other dyes include quinophthalone dyes; Examples include nitro / nitroso dyes, acridine dyes, and acridinone dyes. These dyes may be those that exhibit a yellow color only after a part of the chromophore dissociates, in which case the counter cation may be an alkali metal or an inorganic cation such as ammonium, pyridinium, Organic cations such as quaternary ammonium salts may be used, and further, polymer cations having these in a partial structure may be used.

The magenta dyes include, for example, aryl or hetenylazo dyes having phenols, naphthols and anilines as coupling components; azomethine dyes having pyrazolones and pyrazolotriazoles as coupling components; for example, arylidene dyes, styryl Methine dyes such as dyes, merocyanine dyes and oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone, and anthrapyridone; And condensed polycyclic dyes. These dyes may be those that exhibit magenta only after a part of the chromophore dissociates, in which case the counter cation may be an alkali metal or an inorganic cation such as ammonium, pyridinium, Organic cations such as quaternary ammonium salts may be used, and further, polymer cations having these in a partial structure may be used.

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; and carbonium dyes such as diphenylmethane dye, triphenylmethane dye and xanthene dye. Dyes; Phthalocyanine dyes; Anthraquinone dyes; Examples of the coupling component include aryl or hetenylazo dyes having phenols, naphthols, and anilines, and indigo / thioindigo dyes. These dyes may be those that exhibit cyan only when a part of the chromophore dissociates, and in that 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, or may be a polymer cation having them in a partial structure. Also, a black dye such as a polyazo dye can be used.

Examples of the water-soluble dye include direct dyes, acid dyes, food dyes, basic dyes, reactive dyes and the like. Preferred are CI Direct Red 2, 4, 9, 23, 26, 31, 39, 62,
63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 11
1, 173, 184, 207, 211, 212, 214, 218, 21, 223, 22
4, 225, 226, 227, 232, 233, 240, 241, 242, 243, 24
7 CI Direct Violet 7, 9, 47, 48, 51, 6
6, 90, 93, 94, 95, 98, 100, 101 CI Direct Yellow 8, 9, 11, 12, 27, 28, 2
9, 33, 35, 39, 41, 44, 50, 53, 58, 59, 68, 86, 8
7, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 1
32, 142, 144, 161, 163 CI Direct Blue 1, 10, 15, 22, 25, 55, 67, 6
8, 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 10
8, 109, 151, 156, 158, 159, 160, 168, 189, 192, 19
3, 194, 199, 200, 201, 202, 203, 207, 211, 213, 21
4,218,225,229,236,237,244,248,249,251,25
2, 264, 270, 280, 288, 289, 291 CI Direct Black 9, 17, 19, 22, 32, 51, 5
6, 62, 69, 77, 80, 91, 94, 97, 108, 112, 113, 11
4, 117, 118, 121, 122, 125, 132, 146, 154, 166, 16
8, 173, 199 CI Acid Red 35, 42, 52, 57, 62, 80, 82, 11
1, 114, 118, 119, 127, 128, 131, 143, 151, 154, 15
8, 249, 254, 257, 261, 263, 266, 289, 299, 301, 30
5, 336, 337, 361, 396, 397 CI Acid Violet 5, 34, 43, 47, 48, 90, 10
3, 126 CI Acid Yellow 17, 19, 23, 25, 39, 40, 42, 4
4, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 15
1, 159, 169, 174, 190, 195, 196, 197, 199, 218, 21
9, 222, 227 CI Acid Blue 9, 25, 40, 41, 62, 72, 76, 78,
80, 82, 92, 106, 112, 113, 120, 127: 1, 129, 13
8,143,175,181,205,207,220,221,230,232,24
7, 258, 260, 264, 271, 277, 278, 279, 280, 288, 29
0, 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, 17, 1
8, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42 CI Reactive Blue 2, 3, 5, 8, 10, 13, 14, 1
5, 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, 2
4, 25, 27, 29, 35, 36, 38, 39, 45, 46 CI Basic Violet 1, 2, 3, 7, 10, 15, 1
6, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48 CI Basic Yellow 1, 2, 4, 11, 13, 14, 15, 1
9, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40 CI Basic Blue 1, 3, 5, 7, 9, 22, 26, 41, 4
5, 46, 47, 54, 57, 60, 62, 65, 66, 69, 71 CI Basic Black 8, and the like.

As the water-soluble dye used in the present invention, an azo dye represented by the following formula (AI) is particularly preferred. Hereinafter, the azo dye represented by formula (AI) of the present invention will be described in detail. General formula (AI)

[0014]

Embedded image

In the general formula (AI), X is an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. Preferably, it is a 0.30 to 1.0 electron-withdrawing group. Specific examples of X which is an electron-withdrawing group having a σ _p value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkyl phosphono group. Group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl, arylsulfinyl group,
Alkylsulfonyl, arylsulfonyl, sulfonyloxy, acylthio, sulfamoyl, thiocyanate, thiocarbonyl, halogenated alkyl, halogenated alkyloxy, halogenated aryloxy, halogenated alkylamino, halogenated Examples include an alkylthio group, an aryl group substituted with another electron-withdrawing group having a σ _p value of 0.20 or more, a heterocyclic group, a halogen atom, an azo group, or a selenocyanate group.

The group in which X can further have a substituent may further have the following substituents. Halogen atom (for example, chlorine atom, bromine atom), carbon number 1
~ 12 linear or branched alkyl groups (e.g. methyl,
Ethyl, propyl, isopropyl, t-butyl), an aralkyl group having 7 to 18 carbon atoms (eg, benzyl, phenethyl), an alkenyl group having 2 to 12 carbon atoms (eg, vinyl, allyl), A chain or branched alkynyl group (e.g., ethynyl, 1-butynyl), a linear or branched cycloalkyl group having 3 to 12 carbon atoms (e.g., cyclopropyl, cyclohexyl), a carbon number of 3 to 1
Two linear or branched cycloalkenyl groups (eg, cyclopentenyl, cyclohexenyl), aryl groups (eg, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl), heterocyclic groups ( For example, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-
Thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxyl group, amino group, alkyloxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy), aryloxy Groups (eg, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino groups (eg, acetamido, benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide), an alkylamino group (eg, methylamino, butylamino, diethylamino, methylbutylamino), an anilino group (eg, phenylamino,
-Chloroanilino, a ureido group (e.g., phenylureido, methylureido, N, N-dibutylureido),
Sulfamoylamino group (eg, N, N-dipropylsulfamoylamino), alkylthio group (eg, methylthio, octylthio, 2-phenoxyethylthio), arylthio group (eg, phenylthio, 2-butoxy-5-t-) Octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino group (eg, methoxycarbonylamino), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), sulfamoyl group (for example, N-
Ethylsulfamoyl, N, N-dipropylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl,
Benzenesulfonyl, toluenesulfonyl), alkyloxycarbonyl groups (eg, methoxycarbonyl, butyloxycarbonyl), heterocyclic oxy groups (eg,
1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo) , An acyloxy group (eg, acetoxy),
A carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), an aryloxycarbonylamino group (eg, phenoxycarbonylamino), an imide group (eg, , N-succinimide, N-phthalimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl Groups (e.g., 3-phenoxypropylsulfinyl), phosphonyl groups (e.g., phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl groups (e.g., phenoxycarbonyl),
Acyl groups (eg, acetyl, 3-phenylpropanoyl, benzoyl) and the like.

X As a preferable one, a compound having 2 to 2 carbon atoms
An acyl group having 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, an aryloxycarbonyl group having 7 to 18 carbon atoms, a cyano group, and a nitro group , Having 1 to 1 carbon atoms
2, an alkylsulfinyl group having 6 to 18 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, a sulfamoyl group having 0 to 12 carbon atoms, carbon A halogenated alkyl group having 1 to 12 carbon atoms, a halogenated alkyloxy group having 1 to 12 carbon atoms, a halogenated alkylthio group having 1 to 12 carbon atoms, a halogenated aryloxy group having 7 to 18 carbon atoms, 2
An aryl group having 7 to 18 carbon atoms substituted with one or more σ _p values of 0.20 or more and another electron-withdrawing group, and a nitrogen atom,
Examples thereof include a 5- to 8-membered heterocyclic group having an oxygen atom or a sulfur atom and having 1 to 18 carbon atoms. More preferably, an alkyloxycarbonyl group having 2 to 12 carbon atoms, a nitro group, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms,
A carbamoyl group having 1 to 12 carbon atoms and a halogenated alkyl group having 1 to 12 carbon atoms. Particularly preferred as X are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, and an arylsulfonyl group having 6 to 18 carbon atoms, and the most preferred is a cyano group.

In the general formula (AI), R ₁ , R ₂ ,
R ₃ , R ₄ , R ₅ , R ₆ and Y each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group,
Aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl 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 , An aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphoryl group, an acyl group, or an ionic hydrophilic group.

Among them, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, an ureido group, an alkoxycarbonylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group and an alkoxycarbonyl group are particularly preferred. .

The halogen atom represented by R _{1 to} R ₆ and Y includes a fluorine atom, a chlorine atom and a bromine atom.

The alkyl groups represented by R _{1 to} R ₆ and Y include an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group has 1 to 1 carbon atoms.
Twelve alkyl groups are preferred. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group. Examples of alkyl groups include methyl, ethyl, butyl, isopropyl, t
-Butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl.

Examples of the cycloalkyl group represented by R _{1 to} R ₆ and Y include a substituted cycloalkyl group 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 a cyclohexyl group.

The aralkyl group represented by R _{1 to} R ₆ and Y includes an aralkyl group having a substituent and an unsubstituted aralkyl group. The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms. 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 R _{1 to} R ₆ and Y includes:
Examples include an aryl group having a substituent and an unsubstituted aryl group. The aryl group has 7 carbon atoms.
~ 12 aryl groups are preferred. Examples of the substituent include:
Examples include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group. Examples of the aryl groups include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.

The heterocyclic groups represented by R _{1 to} R ₆ and Y include:
Examples include a substituted heterocyclic group and an unsubstituted heterocyclic group. The heterocyclic group is preferably a 5- or 6-membered heterocyclic group. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic group include:
A 2-pyridyl group, a 2-thienyl group and a 2-furyl group.

The alkylamino group represented by R _{1 to} R ₆ and Y 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. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.

The alkoxy groups represented by R _{1 to} R ₆ and Y include an alkoxy group having a substituent and an unsubstituted alkoxy group. The alkoxy group is preferably an alkoxy group having 1 to 12 carbon atoms. Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy 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 R _{1 to} R ₆ and Y includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms. 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 amide group represented by R _{1 to} R ₆ and Y includes an amide group having a substituent and an unsubstituted amide group. The amide group is preferably an amide group having 2 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the amide group include an acetamido group, a propionamido group, a benzamido group, and a 3,5-disulfobenzamido group.

The arylamino groups represented by R _{1 to} R ₆ and Y include an arylamino group having a substituent and an unsubstituted arylamino group. The arylamino group is preferably an arylamino group having 6 to 12 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 groups represented by R _{1 to} R ₆ and Y include:
Examples include a ureido group having a substituent and an unsubstituted ureido group. The ureido group has 1 carbon atom.
~ 12 ureido groups are preferred. Examples of the substituent include:
Examples 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 R _{1 to} R ₆ and Y 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.

The alkylthio group represented by R _{1 to} R ₆ and Y includes an alkylthio group having a substituent and an unsubstituted alkylthio group. As the alkylthio group,
An alkylthio group having 1 to 12 carbon atoms is preferred. 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 R _{1 to} R ₆ and Y includes an arylthio group having a substituent and an unsubstituted arylthio group. The arylthio group is preferably an arylthio group having 6 to 12 carbon atoms. Examples of the substituent include an alkyl group and an ionic hydrophilic group. Examples of the arylthio group include:
Examples include a phenylthio group and a p-tolylthio group.

The alkoxycarbonylamino group represented by R _{1 to} R ₆ and Y includes a substituted alkoxycarbonylamino group and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

The sulfonamide groups represented by R _{1 to} R ₆ and Y include 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. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonamide groups include methanesulfonamide, benzenesulfonamide, and 3-carboxybenzenesulfonamide.

The carbamoyl group represented by R _{1 to} R ₆ and Y 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 groups represented by R _{1 to} R ₆ and Y include a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include:
And an alkyl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.

The sulfonyl group represented by R _{1 to} R ₆ and Y includes a methanesulfonyl group and a phenylsulfonyl group.

The alkoxycarbonyl group represented by R _{1 to} R ₆ and Y includes a substituted alkoxycarbonyl group and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group has 2 to 2 carbon atoms.
Twelve alkoxycarbonyl groups are preferred. 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 R _{1 to} R ₆ and Y includes a substituted heterocyclic oxy group and an unsubstituted heterocyclic oxy group. The heterocyclic oxy group is preferably a heterocyclic oxy group having a 5- 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 groups represented by R _{1 to} R ₆ and Y include an azo group having a substituent and an unsubstituted azo group. Examples of the azo group include a p-nitrophenylazo group.

The acyloxy groups represented by R _{1 to} R ₆ and Y include 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.
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 R _{1 to} R ₆ and Y 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 R _{1 to} R ₆ and Y 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 R _{1 to} R ₆ and Y includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. As the aryloxycarbonyl group,
An aryloxycarbonyl group having 7 to 12 carbon atoms is preferred. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include:
A phenoxycarbonyl group.

The aryloxycarbonylamino group represented by R _{1 to} R ₆ and Y 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. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

The imide groups represented by R _{1 to} R ₆ and Y include an imide group having a substituent and an unsubstituted imide group. Examples of the imide group include an N-phthalimido group and an N-succinimido group.

The heterocyclic thio group represented by R _{1 to} R ₆ and Y includes a substituted heterocyclic thio group and an unsubstituted heterocyclic thio group. The heterocyclic thio group preferably has a 5- 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 R _{1 to} R ₆ and Y includes a substituted sulfinyl group and an unsubstituted sulfinyl group. Examples of the sulfinyl group include phenylsulfinyl.

The phosphoryl group represented by R _{1 to} R ₆ and Y 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 groups represented by R _{1 to} R ₆ and Y include an acyl group having a substituent and an unsubstituted acyl group. As the acyl group, an acyl group having 1 to 12 carbon atoms is preferable. 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 groups represented by R _{1 to} R ₆ and Y include a carboxyl group, a sulfo group, and a quaternary ammonium group. As the ionic hydrophilic group,
A carboxyl group and a sulfo group are preferred, and a sulfo group is particularly preferred. The carboxyl group and the sulfo group may be in the form of a salt. Examples of the counter ion forming the salt include an alkali metal ion (eg, sodium ion, potassium ion) and an organic cation (eg, tetramethylguanidinium ion). ).

In the general formula (AI), R ₁ and R ₂ ,
R ₃ and R ₁ , and R ₅ and R ₂ may form a ring. Preferred examples for forming a ring are shown below.

[0055]

Embedded image

In the general formula (AI), A is 5 to
Represents a group of non-metallic atoms necessary for forming an 8-membered ring (hereinafter, the ring represented by A may be referred to as "ring A").
Ring A may be a saturated ring or may have an unsaturated bond. The non-metallic atom group is preferably a group of one or more selected from a nitrogen atom, an oxygen atom, a sulfur atom and a carbon atom, and particularly preferably only a carbon atom.

The ring A includes, for example, a benzene ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a pyridine ring, a piperazine ring, an oxane ring, and a thiane ring. Among them, the group which can have a substituent may be further substituted with the groups exemplified as the substituents R _{1 to} R ₆ , Y and Z _{1 to} Z ₂ .

At least three of the non-metallic atoms forming the ring A are N atoms of the pyrazole ring, Z ₁ and Z ₂
And the atom substituted by the N atom of the pyrazole ring is adjacent to both the Z ₁ and Z ₂ substituted atoms.

The ring A is preferably a benzene ring,
In particular, a benzene ring substituted with an ionic hydrophilic group (which may be substituted with the aforementioned substituent) at the 4-position to the N atom of the pyrazole ring other than the N atom of the pyrazole ring and Z ₁ and Z ₂ is particularly preferable. preferable.

In the general formula (AI), Z ₁ and Z
₂ is each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group,
Heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxy Carbonylamino 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, It represents an imide group, a heterocyclic thio group, a sulfinyl group, a phosphoryl group, an acyl group, or an ionic hydrophilic group.

Among them, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group and ionic hydrophilic group Are particularly preferable, and a halogen atom, an alkyl group and an alkoxy group are particularly preferable, and a halogen atom is most preferable.

For each group represented by Z ₁ and Z ₂ , R ₁
And the same as the respective groups represented by R ₆ and Y, and the preferred ranges are also the same.

Among the azo dyes represented by the general formula (AI), azo dyes having a structure represented by the following general formula (A-II) are preferable. Hereinafter, the azo dye represented by the general formula (A-II) will be described in detail. General formula (A-II)

[0064]

Embedded image

In the general formula (A-II), X, Y, Z
₁, Z_Two, R₁, R_Two, R_Three, R_Four, R_Five, R₆Is the general formula
X, Y, Z in (A-I)₁, Z_Two, R₁, R_Two, R_Three, R_Four,
R_Five, R₆Synonymous with X, Y, and Z₁, Z_Two, R
₁, R_Two, R_Three, R_Four, R_Five, R ₆Is the same.

In the general formula (A-II), Z ₃ , Z ₄ and Z ₅ each independently represent a hydrogen atom, a halogen atom,
Alkyl group, cycloalkyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl 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 Represents an aryloxycarbonyl group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphoryl group, an acyl group, or an ionic hydrophilic group.

Among them, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, an ureido group, an alkoxycarbonylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group and an ionic group Hydrophilic groups are particularly preferred.

Specific examples of Z ₃ , Z ₄ and Z ₅ include the substituents R _{1 to} R ₆ in the general formula (AI) and the groups described above for Y.

More preferably, Z ₃ and Z ₅ are a hydrogen atom, a halogen atom and an alkyl group, of which a hydrogen atom is particularly preferred.

More preferably, Z ₄ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group and an ionic group. A hydrophilic group is particularly preferable, and among them, a hydrogen atom, an alkyl group, and an ionic hydrophilic group are particularly preferable, and an ionic hydrophilic group is most preferable.

Azo Dye Represented by General Formula (A-II) of the Invention
X is particularly preferably a combination of substituents
Group, an alkylsulfonyl group having 1 to 12 carbon atoms, carbon number
6-18 arylsulfonyl groups, particularly preferred
What is a cyano group. Y is a hydrogen atom, an alkyl group,
An aryl group, particularly a hydrogen atom. R ₁
And R_TwoIs an alkyl group (an ionic hydrophilic group is a substituent
Or an aryl group (a
(It may have an on hydrophilic group as a substituent). R
_Three, R_FourAnd R_FiveIs a hydrogen atom, R₆Is an amide group.
(It may have an on hydrophilic group as a substituent). Z
₁And Z_TwoIs a halogen atom or an alkyl group.
Z_ThreeAnd Z_FiveRepresents a hydrogen atom, a halogen atom, an alkyl group
And among them, particularly a hydrogen atom. Z_FourIs hydrogen
Atom, halogen atom, sulfonamide group, carbamoyl
Group, sulfamoyl group, alkoxycarbonyl group and
It is an ionic hydrophilic group.
Sex groups are preferred.

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

However, in the general formula (AI),
At least _{one of} R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , X, Y, Z ₁ , Z ₂ and A. In the general formula (A-II), R ₁ , R _{2, R 3, R 4,} R 5, R 6, X, Y, Z 1,
At least one of Z ₂ , Z ₃ , Z ₄ and Z ₅ represents an ionic hydrophilic group or has an ionic hydrophilic group as a substituent. The general formula (AI) and the general formula (AI
Since the azo dye represented by I) has at least one ionic hydrophilic group in the molecule, it has good solubility or dispersibility in an aqueous medium. R _{1 to} R ₆ , X, Y
And the ionic hydrophilic group as a substituent of Z _{1 to} Z ₅ includes a sulfo group, a carboxyl group and a quaternary ammonium. Among them, a sulfo group and a carboxyl group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may be in the form of a salt, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg,
Tetramethylguanidinium ion).

The azo dye represented by the general formula (A-II) is more preferably a structure represented by the following general formula (A-III). General formula (A-III)

[0075]

Embedded image

In the general formula (A-III), X, Y, Z ₁ , Z
₂ , Z ₄ , R ₁ , R ₂ and R ₆ have the same meanings as X, Y, Z ₁ , Z ₂ , Z ₄ , R ₁ , R ₂ and R _{6 in} formula (A-II), respectively. The same applies to preferred examples.

Among the azo dyes represented by formula (A-III), particularly preferred combinations of substituents include:
X is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, or an arylsulfonyl group having 6 to 18 carbon atoms, and particularly preferably a cyano group. Y is a hydrogen atom, an alkyl group or an aryl group, and among them, a hydrogen atom is particularly preferred. R ₁ and R _{2 each} represent an alkyl group (which may have an ionic hydrophilic group as a substituent) or an aryl group (which may have an ionic hydrophilic group as a substituent)
It is. R ₆ is an amide group (which may have an ionic hydrophilic group as a substituent). Z ₁ and Z ₂ are a halogen atom or an alkyl group. Z ₄ is a hydrogen atom,
They are a halogen atom, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group and an ionic hydrophilic group, and among them, an ionic hydrophilic group is particularly preferable.

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

Formula (AI), Formula (A-II)
Specific examples of the azo dye represented by (Exemplified Compounds 101 to 14)
3) is shown below, and the azo dye used in the present invention includes:
It is not limited to the following example.

[0080]

Embedded image

[0081]

Embedded image

[0082]

Embedded image

[0083]

Embedded image

[0084]

Embedded image

[0085]

Embedded image

[0086]

Embedded image

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

The ink composition for ink-jet recording using a water-soluble dye can be prepared by dissolving and / or dispersing the above-mentioned water-soluble dye in an aqueous medium. The “aqueous medium” in the present invention means water or a mixture of water and a small amount of a water-soluble organic solvent to which additives such as a wetting agent, a stabilizer, and a preservative are added as necessary. A method for preparing an aqueous ink composition for inkjet recording is described in JP-A-5-148436, 5-2.
No. 95312, No. 7-97541, No. 7-82515
And JP-A-7-118584, which can be used for adjusting the ink composition for inkjet recording used in the present invention.

Examples of water-soluble organic solvents that can be used in the present invention include alcohols (eg, methanol,
Ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, Propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (for example,
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- ethyl diethanolamine,
Morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine,
Polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide,
N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-
2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). The water-miscible organic solvent may be used in combination of two or more.

The solubility of the oil-soluble dye used in the present invention in water is not particularly limited. Although not limited thereto, preferred specific examples include, for example, CI Solvent Black 3, 7, 27, 29 and 34;
Yellows 14, 16, 19, 29, 30, 56, 82, 93 and 162; CI Solvent Red 1, 3, 8, 18, 24, 27, 43, 49, 51, 72, 73, 109, 122,
132 and 218; CI Solvent Violet 3; CI Solvent Blue 2, 11, 25, 35, 38, 67 and 70; CI Solvent Greens 3 and 7; Particularly preferred among these are Nubian Black PC-0850, Oil Black HBB, Oil Yell
ow 129, Oil Yellow 105, Oil Pink 312, Oil Red 5B,
Oil Scarlet 308, Vali Fast Blue 2606, Oil Blue BOS
(Orient Chemical Co., Ltd.), Aizen Spilon Blue GNH
(Hodogaya Chemical Co., Ltd.), NeopenYellow 075, Neopen M
azenta SE1378, Neopen Blue 808, Neopen Blue FF401
2, Neopen Cyan FF4238 (manufactured by BASF) and the like.

In the present invention, a disperse dye can be used within a range that dissolves in a water-immiscible organic solvent.
Preferred examples thereof include CI Disperse Yellow 5,42,54,64,79,82,83,93,99,100,119,122,124,126,16.
0,184: 1,186,198,199,201,204,224 and 237; CI Disperse Orange 13,29,31: 1,33,49,54,55,66,73,118,119
And 163; CI Disperse Red 54,60,72,73,86,88,9
1,92,93,111,126,127,134,135,143,145,152,153,154,15
9,164,167: 1,177,181,204,206,207,221,239,240,258,27
7,278,283,311,323,343,348,356 and 362; CI Disperse Violet 33; CI Disperse Blue 56,60,7
3,87,113,128,143,148,154,158,165,165: 1,165: 2,176,1
83,185,197,198,201,214,224,225,257,266,267,287,35
4,358,365 and 368; and CI Disperse Green 6:
1 and 9 and the like.

Particularly preferred oil-soluble dyes include azo and azomethine dyes represented by the following formulas (BI) and (B-II). Dyes of general formula (B-II) are known as dyes formed from couplers and developing agents by oxidation in photographic materials.

[0096]

Embedded image

In the general formulas (BI) and (B-II), R ¹ ,
R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group,
Hydroxy, nitro, amino, alkylamino, alkoxy, aryloxy, amide, arylamino, ureido, sulfamoylamino,
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 , An aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphoryl group, an acyl group, a carboxyl group or a sulfo group. A
Represents -NR ⁵ R ⁶ or a hydroxy group, an R ⁵ and R ⁶ are independently a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. A is preferably -NR ⁵ R ^6. R ⁵ and R ⁶ may combine with each other to form a ring. B ¹ represents = C (R ³ )-or = N-,
B ² is -C (R ⁴⁾ = or represent -N =. Preferably if B ^1, B ² does not become -N = simultaneously, B ¹ is = C
It is more preferred that (R ³ )-and B ² be -C (R ⁴ ) =. R ¹ and R ⁵ , R ³ and R ⁶ , and / or R ¹ and R ² may combine with each other to form an aromatic ring or a heterocyclic ring. X represents a residue of a color photographic coupler, and Y represents an unsaturated heterocyclic group.

R ⁵ and R ⁶ are each independently preferably a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, preferably a hydrogen atom, an alkyl group or a substituted alkyl group, an aryl group, or a substituted aryl group. More preferably,
Most preferably, they are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a substituted alkyl group having 1 to 18 carbon atoms. R ² is a hydrogen atom, a halogen atom, an aliphatic group, an alkoxy group, an aryloxy group,
It is preferably an amide group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, or a sulfonamide group.

In the present specification, the aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group and a substituted aralkyl group. The aliphatic group may have a branch and may form a ring. The aliphatic group preferably has 1 to 20 carbon atoms,
More preferably, it is 18. The aryl part of the aralkyl group and the substituted aralkyl group is preferably phenyl or naphthyl, and phenyl is particularly preferable.
Examples of the substituent of the alkyl moiety of the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group and the substituted aralkyl group include the substituents described for R ¹ , R ² , R ³ and R ⁴ . Examples of the substituent of the aryl portion of the substituted aralkyl group are the same as the following examples of the substituent of the substituted aryl group.

In the present specification, an aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably phenyl or naphthyl, and phenyl is particularly preferred. The aryl part of the substituted aryl group is the same as the above-mentioned aryl group. Examples of the substituent of the substituted aryl group include the substituents described for R ¹ , R ² , R ³ and R ⁴ .

The unsaturated heterocyclic group represented by Y in the formula (BI) is preferably a 5- or 6-membered unsaturated heterocyclic ring.
An aliphatic ring, an aromatic ring or another hetero ring may be condensed to the hetero ring. Examples of heteroatoms in the heterocycle include N, O,
And S. Examples of saturated heterocycles include:
Examples include a pyrrolidine ring and a morpholine ring. Examples of unsaturated heterocycles include a pyrazole ring, an imidazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a thiophene ring, a benzothiazole ring, a benzoxazole ring, a benzoisothiazole ring, a pyrimidine ring, a pyridine ring, and a quinoline ring. Is mentioned. The heterocyclic group is represented by R ^{1 to} R ⁴ described above.
May have the substituents mentioned above.

The couplers represented by X in the formula (B-II) are preferably the following couplers. Yellow coupler: U.S. Pat.Nos. 3,933,501, 4,022,620
No. 4,326,024, No. 4,401,752, No. 4,248,961,
Japanese Patent Publication No. 58-10739, British Patent 1,425,020, 1,476,760
No. 3,973,968, 4,314,023, 4,511,64
No. 9, European Patents 249,473A and 502,424A, Formulas (I) and (II)
A coupler represented by formulas (1) and (2) of 513,496A (especially Y-28 on page 18), a coupler represented by formula (I) of claim 1 of 568,037A, U.S.A. Patent 5,06
No. 6,576, column 1, lines 45 to 55, a coupler represented by the general formula (I), a coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-274425, and EP-A-498,381 A1, page 40. Couplers described in claim 1 (particularly D-35 on page 18);
Couplers represented by the formula (Y) on page 4 of 69A1 (especially Y-1
(P. 17), Y-54 (p. 41)), U.S. Pat.
Of the formulas (II) to (IV) on lines 36 to 58 (particularly
II-17, 19 (column 17), II-24 (column 19)).

Magenta coupler; US Pat. No. 4,310,619,
4,351,897, European Patent 73,636, U.S. Patent 3,061,432
No. 3,725,067, Research Disclosure No.
No. 24220 (June 1984), No. 24230 (June 1984),
33552, 60-43659, 61-72238, 60-35730
No. 55-118034, No. 60-185951, U.S. Patent 4,500,63
No. 0, 4,540,654, 4,556,630, International Publication WO88 / 04
No. 795, JP-A-3-39737 (L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13), European Patent 456,257 (A-4) -63
(P. 134), (A-4) -73, -75 (p. 139), M-4, -6 of No. 486,965
(P. 26), M-7 (p. 27), M-45 of P. 571,959A (p. 19),
(M-1) of 5-204106 (p. 6), M- of paragraph 0237 of
22, U.S. Pat. Nos. 3,061,432 and 3,725,067.

Cyan coupler: US Pat. No. 4,052,212,
No. 4,146,396, No. 4,228,233, No. 4,296,200, European Patent 73,636, CX-1,3,4,5,11,12,14,15 of JP-A-4-04843
(Pages 14 to 16); C-7,10 (p. 35), 34, 35 (37
Page 1), (I-1), (I-17) (pages 42 to 43);
A coupler represented by the general formula (Ia) or (Ib):

In addition, JP-A-62-215272 (page 91), JP-A-2-33144 (pages 3 and 30), EP355,660A (pages 4, 5 and 45)
Pp. 47) are also useful.

Among the dyes represented by the general formula (BI), a dye represented by the following formula (B-III) is particularly preferably used as the magenta dye. Formula (B-III)

[0107]

Embedded image

In the formula, Z ¹ represents an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. Z ¹ has a σ _p value of 0.
The number of the electron-withdrawing groups is preferably 30 or more and 1.0 or less. Preferred specific substituents include the electron-withdrawing substituents described below.
Acyl group having 12 to 12 carbon atoms, alkyloxycarbonyl group having 2 to 12 carbon atoms, nitro group, cyano group, alkylsulfonyl group having 1 to 12 carbon atoms, arylsulfonyl group having 6 to 18 carbon atoms, carbamoyl having 1 to 12 carbon atoms Group and carbon number 1
~ 12 halogenated alkyl groups are preferred. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, and an arylsulfonyl group having 6 to 18 carbon atoms, and most preferred is a cyano group. R ^{1 to} R ⁶ have the same meaning as in formula (BI). Z ² is a hydrogen atom, an aliphatic group,
Alternatively, it represents an aromatic group. Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Among them, Q is preferably a group consisting of a nonmetallic atom group necessary for forming a 5- to 8-membered ring. Among them, an aromatic group and a heterocyclic group are particularly preferable. The 5- to 8-membered ring may be substituted, may be a saturated ring, or may have an unsaturated bond. Preferred non-metallic atoms include nitrogen, oxygen, sulfur or carbon. Specific examples of such a ring structure include, for example, benzene ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring,
Pyridazine ring, triazine ring, imidazole ring, benzimidazole ring, oxazole ring, benzoxazole ring, oxane ring, sulfolane ring, thiane ring, and the like.If these rings further have a substituent, as the substituent, The groups exemplified for the above substituents R ^{1 to} R ⁴ can be mentioned. The preferred dye structure represented by formula (B-III) is described in Japanese Patent Application No. 2000-80733.

Among the dyes represented by the formula (B-II), a dye represented by the following formula (B-IV) is particularly preferably used as the magenta dye. Formula (B-IV)

[0110]

Embedded image

In the formula, G is a hydrogen atom, an aliphatic group, an aromatic group,
Heterocyclic group, cyano group, alkoxy group, aryloxy
Group, alkylthio group, arylthio group, ester group,
Mino group, carbamoyl group, sulfonyl group, sulfamoi
Group, ureido group, urethane group, acyl group, amide group,
Or a sulfonamide group. Also R¹, R^Two, A, B
¹And B^TwoIs synonymous with formula (B-II) and their preference
The same is true for the range. L is an aliphatic group, an aromatic group, a heterocyclic ring
Group, cyano group, alkoxy group, aryloxy group,
Killthio, arylthio, ester, amino,
Carbamoyl, sulfonyl, sulfamoyl, c
Raid group, urethane group, acyl group, amide group, or
It may be substituted with at least one of the sulfonamide groups
A group of atoms that form a 5- or 6-membered nitrogen-containing heterocycle
This heterocyclic ring may form a condensed ring with another ring.
Good.

Among the compounds represented by the formula (B-IV), A
-NR ⁵ R ⁶ is preferably, L is preferably formed a nitrogen-containing heterocyclic 5-membered. Examples of the 5-membered nitrogen-containing heterocycle include an imidazole ring, a triazole ring, and a tetrazole ring. Examples of the magenta dyes represented by the formulas (BI) and (B-II) are described below, but they are for describing the present invention in detail, and the present invention is not limited thereto.

[0113]

Embedded image

[0114]

Embedded image

[0115]

Embedded image

[0116]

Embedded image

[0117]

Embedded image

[0118]

Embedded image

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

[0123]

Embedded image

[0124]

Embedded image

[0125]

Embedded image

[0126]

Embedded image

[0127]

Embedded image

[0128]

Embedded image

Examples of the compounds of the present invention are described in Japanese Patent Application No.
No. 65187, No. 11-365190, and Japanese Patent Application No. 2000-80733, but are not limited thereto.

The dye represented by the formula (B-III) of the present invention can be synthesized with reference to, for example, the methods described in Japanese Patent Application No. 2000-80733 and JP-A-55-161856. The dye represented by the formula (B-IV) of the present invention is described in, for example, JP-A-4-126772.
The compound can be synthesized with reference to the methods described in Japanese Patent Application Publication No. 7-94180 and Japanese Patent Application No. 11-365187.

Among the dyes represented by the general formula (B-II), a pyrrolotriazoleazomethine dye represented by the following formula (BV) is particularly preferably used as a cyan dye. Expression (BV)

[0132]

Embedded image

In the formula (BV), A, R ¹ , R ² , B ¹ and B
² has the same meaning as in formula (B-II), and their preferred ranges are also the same. Z ³ and Z ⁴ are each independently a group represented by the formula (B-IV)
Is synonymous with G in Z ³ and Z ⁴ are bonded to each other,
A ring structure may be formed. M is an atomic group capable of forming a 1,2,4-triazole ring fused to the 6-membered ring of the formula (BV), and one of two atoms B ³ and B ⁴ of the condensed portion is a nitrogen atom, The other is a carbon atom.

Further, in the pyrrolotriazoleazomethine compound represented by the formula (BV), Z ³ is an electron-withdrawing group having a Hammett substituent constant σ _p value of 0.30 or more:
Absorption is sharp and more preferred. Furthermore, Z ³
Is preferably an electron-withdrawing group having a Hammett substituent constant σ _p value of 0.45 or more, and most preferably an electron-withdrawing group having a Hammett substituent constant σ _p value of 0.60 or more. And Z ³ and Z ⁴
Those having a Hammett substituent constant σ _p value of 0.70 or more exhibit excellent hue as a cyan color, and are more preferable.

The pyrrolotriazoleazomethine compound represented by the formula (BV) of the present invention is preferably used as a cyan dye, but may be used as a magenta dye by changing the substituent.

Examples of the electron-withdrawing group having a Hammett substituent constant σ _p value of 0.60 or more include a cyano group, a nitro group and an alkylsulfonyl group (for example, a methanesulfonyl group and an arylsulfonyl group (for example, a benzenesulfonyl group)). Examples of the electron-withdrawing group having a Hammett σ _p value of 0.45 or more include an acyl group (eg, acetyl group), an alkoxycarbonyl group (eg, dodecyloxycarbonyl group), and an aryloxycarbonyl group (eg, , M-chlorophenoxycarbonyl), an alkylsulfinyl group (eg, n-propylsulfinyl), an arylsulfinyl group (eg, phenylsulfinyl), a sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dimethylsulfamoyl) A halogenated alkyl group (eg, , Trifluoromethyl) having a Hammett substituent constant σ _p value of 0.30.
Examples of the electron-withdrawing group include, in addition to the above, an acyloxy group (eg, acetoxy), a carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), a halogenated alkoxy group (eg, trifluoromethyloxy). ), A halogenated aryloxy group (for example, pentafluorophenyloxy), a sulfonyloxy group (for example, methylsulfonyloxy group), a halogenated alkylthio group (for example, difluoromethylthio), and two or more σ _p values of 0.15 or more. An aryl group (for example, 2,4-dinitrophenyl, pentachlorophenyl) and a heterocyclic ring (for example, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benz) substituted with the above electron-withdrawing group. Imidazolyl).

Specific examples of the electron-withdrawing group having a σ _p value of 0.20 or more include a halogen atom and the like in addition to the above.

The following are specific examples of the cyan dye used in the present invention, but these are for describing the present invention in detail, and the present invention is not limited thereto.

[0139]

Embedded image

[0140]

Embedded image

[0141]

Embedded image

The compounds usable in the present invention include, but are not limited to, the compounds described in Japanese Patent Application No. 11-365188.

It is preferable that 100 parts by mass of the ink for ink jet recording used in the present invention contains 0.2 to 20 parts by mass of a water-soluble dye or an oil-soluble dye. Further, the ink for inkjet recording used in the present invention may be used in combination with the azo dye, in order to obtain a full-color image or to adjust the color tone.

An ink composition for ink-jet recording using an oil-soluble dye 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.
That is all. For example, phthalate 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 phosphon (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-dichlorobenzoate, dodecyl benzoate, 2-ethylhexyl- p-hydroxybenzoate), amides (eg, N, N-diethyldodecaneamide, N, N-diethyllaurylamide), alcohols Or phenols (e.g., isostearyl alcohol, 2,4-di-tert-amylphenol), and aliphatic esters (e.g., 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-octyl aniline, etc.), chlorinated paraffins (chlorine content 10%) ~ 80%
Paraffins), trimesic esters (for example,
Tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols (for example, 2,4-
Di-tert-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4- (4-dodecyloxyphenylsulfonyl) phenol), carboxylic acids (for example, 2- (2,4-di-tert-amyl) Phenoxybutyric acid, 2-ethoxyoctanedecanoic acid), alkyl phosphoric acids (for example, di-2
(Ethylhexyl) phosphoric acid, diphenyl phosphoric acid) and the like. The high boiling organic solvent can be used in a mass ratio of 0.01 to 3 times, preferably 0.01 to 1.0 times the mass of the oil-soluble dye. These high-boiling organic solvents may be used alone or in a mixture of several kinds [for example, tricresyl phosphate and dibutyl phthalate, trioctyl phosphate and di (2-ethylhexyl) sebacate, dibutyl phthalate and poly (N-t-butyl). Acrylamide)].

Other examples of the high-boiling point organic solvent used in the present invention and / or methods for synthesizing these high-boiling point organic solvents are described in, for example, US Pat. Nos. 2,322,027 and 2,5.
No. 33,514, No. 2,772,163, No. 2,835,579, No. 3,
No. 594,171, No. 3,676,137, No. 3,689,271, No.
No. 3,700,454, No. 3,748,141, No. 3,764,336, No. 3,765,897, No. 3,912,515, No. 3,936,303,
No. 4,004,928, No. 4,080,209, No. 4,127,413
No. 4,193,802, No. 4,207,393, No. 4,220,71
No. 1, No. 4,239,851, No. 4,278,757, No. 4,353,9
No. 79, No. 4,363,873, No. 4,430,421, No. 4,430,
No. 422, No. 4,464,464, No. 4,483,918, No. 4,54
No. 0,657, No. 4,684,606, No. 4,728,599, No. 4,7
No. 45,049, No. 4,935,321, No. 5,013,639, European Patent No.276,319A, No. 286,253A, No. 289,820A, No. 309,158A, No. 309,159A, No. 309,160A, Same
No. 509,311A, 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, No. 50-26530
Nos. 51-25133, 51-26036, 51-27921, 51
-27922, 51-149028, 52-46816, 53-1520
Nos. 53-1521, 53-15127, 53-146622, 54
-91325, 54-106228, 54-118246, 55-59464
Nos. 56-64333, 56-81836, 59-204041, 6
1-84641, 62-118345, 62-247364, 63-1673
No. 57, No. 63-214744, No. 63-301941, No. 64-9452,
Nos. 64-9454, 64-68745, JP-A-1-101543, 1-1
02454, 2-792, 2-4239, 2-43541, 4-2
Nos. 9237, 4-30165, 4-232946, 4-346338, etc. The high-boiling organic solvent is used in an amount of 0 to 3 times, preferably 0 to 1 time, by mass of the oil-soluble dye.

In the present invention, the oil-soluble dye and the high-boiling organic solvent are used by emulsifying and dispersing in an aqueous medium. At the time of emulsification and dispersion, a low-boiling organic solvent can be used in some cases from the viewpoint of emulsification. The low-boiling organic solvent is an organic solvent having a boiling point of about 30 ° C. or more and 150 ° C. or less 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 (eg, dimethylformamide, N-methylpyrrolidone), ethers (eg, tetrahydrofuran, dioxane) and the like are preferably used, but are not limited thereto.

In the emulsification dispersion, an oil phase in which a dye is dissolved in a mixed solvent of a high-boiling organic solvent and a low-boiling organic solvent in some cases is dispersed in an aqueous phase mainly composed of water, and fine oil droplets of the oil phase are dispersed. Done to make. At this time, an additive such as a surfactant, a wetting agent, a dye stabilizer, an emulsion stabilizer, a preservative, and a fungicide described below is added to one or both of the aqueous phase and the oil phase as necessary. be able to. As the emulsification method, a method of adding an oil phase to an aqueous phase is generally used. However, a so-called phase inversion emulsification method in which an aqueous phase is dropped into an oil phase can also be preferably used.

For emulsification and dispersion of the present invention, various surfactants can be used. For example, anionic interfaces such as fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonic acid formalin condensates, and polyoxyethylene alkyl sulfate salts. 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, oxyethylene oxypropylene block copolymer And the like are preferable. Also, SURFYNOLS (A, an acetylene-based polyoxyethylene oxide surfactant)
irProducts & Chemicals) is also preferably used. Further, amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide are also preferable. Further, JP-A-59-157,63
No. 6, pages 37-38, Research Disclosure No. 6; 308119 (1989) can also be used.

For the purpose of stabilization immediately after emulsification, a water-soluble polymer may be added in combination with the above surfactant. As the water-soluble polymer, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, polyacrylic acid, polyacrylamide, and copolymers thereof are preferably used. Also polysaccharides, casein,
It is also preferable to use a natural water-soluble polymer such as gelatin. Further, for stabilizing the dye dispersion, acrylates, methacrylates, vinyl esters, acrylamides which are substantially insoluble in an aqueous medium,
Polyvinyl, polyurethane, polyester, polyamide, polyurea, polycarbonate and the like obtained by polymerization of methacrylamides, olefins, styrenes, vinyl ethers, and acrylonitriles can also be used in combination. These polymers -SO ^2-, -COO ^- preferred to contain. When these polymers which are substantially insoluble in an aqueous medium are used in combination, they are preferably used in an amount of 20% by mass or less of the high boiling point organic solvent, more preferably 10% by mass or less.

In the case where an oil-soluble dye or a high boiling point organic solvent is dispersed by emulsification and dispersion to obtain an aqueous ink, a particularly important control is the particle size. In order to increase color purity and density when an image is formed by inkjet, it is essential to reduce the average particle size. The volume average particle size is preferably 1 μm or less, more preferably 5 to 100 nm. It was also found that the presence of coarse particles plays a very important role in printing performance. That is, it has been found that coarse particles clog the nozzles of the head or form dirt even if they are not clogged, causing non-ejection of ink or ejection distortion, which has a significant effect on printing performance. To prevent this,
It is important to suppress the number of particles having a size of 5 μm or more to 10 or less in 1 μl of the ink to 1000 or less in 1 μl of the ink. As a method for removing these coarse particles, a known centrifugal separation method, a microfiltration method, or the like can be used. These separation means may be performed immediately after emulsification and dispersion, or may be performed immediately before filling the ink cartridge after adding various additives such as a wetting agent and a surfactant to the emulsified dispersion. As an effective means for reducing the average particle size and eliminating coarse particles, a mechanical emulsifying device can be used.

As the emulsifying apparatus, known apparatuses such as a simple stirrer, an impeller stirring method, an in-line stirring method, a mill method such as a colloid mill, and an ultrasonic method can be used, but the use of a high-pressure homogenizer is particularly preferable. is there. High pressure homogenizer is US-45332
No. 54, Japanese Patent Application Laid-Open No. 6-47264, etc. describe a detailed mechanism, and commercially available devices include a Gorin homogenizer (APV GAULIN INC.) And a microfluidizer (MICROFLUIDEX IN).
C. ), And Ultimate (Sugino Machine Co., Ltd.). Further, a high-pressure homogenizer provided with a mechanism for forming fine particles in an ultrahigh-pressure jet stream, as described in US Pat. No. 5,720,551, is particularly effective for the emulsification and dispersion of the present invention. DeBEE2000 (BEE IN) is an example of an emulsifying apparatus using this ultrahigh-pressure jet stream.
TERNATIONAL LTD. ).

The pressure when emulsifying with a high-pressure emulsifying and dispersing apparatus is 5
It is 0 MPa or more, preferably 60 MPa or more, and more preferably 180 MPa or more. For example, it is a particularly preferable method to use two or more emulsifiers in combination, for example, by emulsifying with a stirring emulsifier and then passing through a high-pressure homogenizer. Also, once emulsified and dispersed in these emulsifiers,
A preferred method is to add an additive such as a wetting agent or a surfactant, and then pass the ink through the high-pressure homogenizer again while filling the cartridge with the ink. When a low-boiling organic solvent is contained in addition to the high-boiling organic solvent, it is preferable to remove the low-boiling solvent from the viewpoint of the stability of the emulsion and safety and health. Various known methods can be used to remove the low-boiling solvent depending on the type of the solvent. That is, there are 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.

As the pigment used in the present technology, commercially available pigments and known pigments described in various documents can be used. For literature, see Color Index (The Socie
ly of Dyers and Colorists), `` Revised New Edition Pigment Handbook '' edited by Japan Pigment Technology Association (1989), `` Latest Pigment Application Technology '' CMC Publishing (1986), `` Printing Ink Technology '' CMC Publishing (1
Industrial, co-authored by W. Herbst, K. Hunger
Organic Pigments (VCHVerlagsgesellschaft, 1993) and the like. Specifically, organic pigments include 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, quinacridones). Pigments, dioxazine-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, diketopyrrolopyrrole-based pigments, etc., dyeing lake pigments (lake pigments of acidic or basic dyes), azine pigments, and the like. CI Pigment Yellow 3
CI Pigment Red 10, a red pigment such as 4, 37, 42, 53
CI Pigment Blue 27, 29,1
CI Pigment White 7, 6, 18, 21 and the like of white pigments such as CI Pigment Black 7, magnetite and the like, such as 7: 1.

Examples of pigments having a preferable color tone for image formation include phthalocyanine pigments for blue or cyan pigments and anthraquinone-based indanthrone pigments (for example, CI
Pigment Blue 60), and dyed lake pigment based triarylcarbonium pigments are preferred, and particularly phthalocyanine pigments (preferred examples are CI Pigment Blue 1
5: 1, 15: 2, 15: 3, 15: 4, 15: 6, etc., copper phthalocyanine, monochloro or low chlorinated copper phthalocyanine,
Alnium phthalocyanine is a pigment described in European Patent No.860475, a metal-free phthalocyanine having CI Pigment Blue 16, a phthalocyanine having a central metal of Zn, Ni, or Ti, among which CI Pigment Blue 15: 3, and the like are preferred.
15: 4, aluminum phthalocyanine).

As the red to purple pigments, azo pigments (preferable examples include CI Pigment Red 3, 5 and 11, and
22, 22, 38: 48, 48: 2, 48: 3, 48: 4, 49:
1, 52: 1, 53: 1, 57: 1, 63: 2, 144, 146,
Preferred is CI Pigment Red.
57: 1, 146, 184), quinacridone pigments (preferable examples are CI Pigment Red 122, 192, 202,
207, 209, CI Pigment Violet 19, 42, and particularly preferred are CI Pigment Red 122), dyed lake pigment-based triarylcarbonium pigments (preferable xanthene-based CI Pigment Red 81:
1, CI Pigment Violet 1, 2, 3, 27, 27
9), dioxazine-based pigments (for example, CI Pigment Viole
t23, 37), diketopyrrolopyrrole pigments (for example, C.I.
I. Pigment Red 254), perylene pigments (eg, CI P
igment Violet 29), anthraquinone pigments (for example, C.I.
I. Pigment Violet 5: 1, 31 and 33) and thioindigo (for example, CI Pigment Red 38 and 88) are preferably used.

As the yellow pigment, an azo pigment (preferably a monoazo pigment CI Pigment Yellow 1, 3,
74, 98, disazo pigment CI Pigment Yellow 12,
13,14, 16, 17, 83, CI Pigment Yello
w 93, 94, 95, 128, 155, benzimidazolone C.
Pigment Yellow 120, 151, 154, 156, 180, etc., among which preferred are those which do not use benzidine-based compounds as raw materials), isoindoline / isoindolinone-based pigments (preferred examples are CI Pigment Yellow 109, 110,
137, 139), quinophthalone pigments (preferably CI Pigment Yellow 138, etc.) and flapantron pigments (eg CI Pigment Yellow 24, etc.) are preferably used.

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

The pigment that can be used in the present technology may be the above-described naked pigment or a pigment that has been subjected to a surface treatment. Surface treatment methods include a method of surface-coating a resin or wax, a method of attaching a surfactant, and the use of a reactive substance (for example, a silane coupling agent, an epoxy compound, a polyisocyanate, or a radical generated from a diazonium salt) as a pigment. A method of bonding to the surface is considered, and is described in the following documents and patents. Properties and application of metal soap (Koshobo) Printing ink printing (CMC Publishing 1984) Latest pigment application technology (CMC Publishing 1986) US Patents 5,554,739 and 5,571,311 JP-A-9-151342, 10-140065, and 10 -292143
No. 11-166145, in particular, self-dispersible pigments prepared by acting carbon black on diazonium salts described in the above-mentioned U.S. Patents, and encapsulation prepared by the method described in the above-mentioned Japanese patents Pigments are particularly effective because dispersion stability can be obtained without using an extra dispersant in the ink.

In the present invention, the pigment may be further dispersed using a dispersant. As the dispersant, various known dispersants may be used according to the pigment to be used, for example, a surfactant type low molecular dispersant or a high molecular dispersant. Examples of the dispersant include those described in JP-A-3-69949, EP 549486 and the like. 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 technology is 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 at the time of ink production or toner production can be used. Examples of the dispersing machine include a vertical or horizontal agitator mill, an attritor, a colloid mill, a ball mill, a three-roll mill, a pearl mill, a super mill, an impeller, a disperser, a KD mill, a dynatron, and a pressure kneader. See “Latest Pigment Application Technology” for details
(CMC Publishing, 1986).

The ink composition for ink jet recording used in the present invention contains a polymer fine particle dispersion. The polymer fine particle dispersion is a product prepared by a so-called emulsion polymerization method using a vinyl monomer and in which a polymer is dispersed in a fine particle state in an aqueous medium (sometimes called a polymer latex). In order to improve the hue when forming an image by the inkjet recording method and to improve the printing performance (prevention of nozzle clogging and ejection distortion), the particle diameter of the dispersed particles is preferably 1 μm or less in volume average particle diameter. , More preferably from 0.001 to 1 μm, particularly preferably from 0.01 to 0.5 μm.

The methods for measuring the volume average particle diameter and the particle size distribution of the dispersed particles include static light scattering, dynamic light scattering, centrifugal sedimentation, and the methods described in Experimental Chemistry Course, 4th edition, pp. 417-418. It can be easily measured by a known method, for example, by using a known method. For example, by diluting with distilled water so that the particle concentration in the ink becomes 0.1 to 1% by mass,
It can be easily measured with a commercially available volume average particle size measuring device (for example, Microtrac UPA (manufactured by Nikkiso Co., Ltd.)). Further, the dynamic light scattering method using the laser Doppler effect is particularly preferable because the particle size can be measured down to a small size. The volume average particle size is an average particle size weighted by the particle volume, and is a value obtained by dividing the sum of the diameters of individual particles multiplied by the volume of the particles in the set of particles and dividing the total volume of the particles. The volume average particle size is described in “Chemistry of Polymer Latex” (published by Soichi Muroi, Polymer Publishing Association), page 119.

The structure of the polymer constituting the polymer latex can be a homopolymer of any monomer selected from the group of monomers shown below as typical examples or a copolymer of any combination thereof. There is no particular limitation on the monomer unit that can be used, and any monomer unit can be used as long as it can be polymerized by a usual radical polymerization method.

Monomer group (a) Olefins: ethylene, propylene, isoprene, butadiene, vinyl chloride, vinylidene chloride, 6-hydroxy-1-hexene, cyclopentadiene, 4-pentenoic acid, methyl 8-nonenoate, vinyl sulfonic acid , Trimethylvinylsilane, trimethoxyvinylsilane, butadiene, pentadiene, isoprene, 1,4-divinylcyclohexane, 1,2,5-trivinylcyclohexane and the like.

(B) α, β-unsaturated carboxylic acids and salts thereof: acrylic acid, methacrylic acid, itaconic acid, maleic acid, sodium acrylate, ammonium methacrylate, potassium itaconate and the like.

(C) Derivatives of α, β-unsaturated carboxylic acid: alkyl acrylate (for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-dodecyl acrylate, etc.), substituted alkyl Acrylates (eg, 2-chloroethyl acrylate, benzyl acrylate, 2-cyanoethyl acrylate, allyl acrylate, etc.), alkyl methacrylates (eg, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, n
-Dodecyl methacrylate, etc.), substituted alkyl methacrylates (for example, 2-hydroxyethyl methacrylate, glycidyl methacrylate, glycerin monomethacrylate, 2-acetoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methoxyethyl methacrylate, ω-methoxy polyethylene glycol methacrylate (poly Number of moles of oxyethylene added =
2 to 100), polyethylene glycol monomethacrylate (addition mole number of polyoxyethylene = 2 to 1)
00), polypropylene glycol monomethacrylate (addition mole number of polyoxypropylene = 2 to 10)
0), 2-carboxyethyl methacrylate, 3
-Sulfopropyl methacrylate, 4-oxysulfobutyl methacrylate, 3-trimethoxysilylpropyl methacrylate, allyl methacrylate, etc., derivatives of unsaturated dicarboxylic acids (for example, monobutyl maleate, dimethyl maleate, monomethyl itaconate, dibutyl itaconate, etc.) ), Polyfunctional esters (eg, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-cyclohexane diacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, dipenta Erythritol pentamethacrylate, dipentaerythritol hexaacrylate,
1,2,4-cyclohexanetrimethacrylate, etc.)
Such.

(D) Amides of α, β-unsaturated carboxylic acids: for example, acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-methyl-N-hydroxyethylmethacrylamide, N-tert -Butylacrylamide, N-ter
t-octyl methacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (2
-Acetoacetoxyethyl) acrylamide, N-acryloylmorpholine, diacetoneacrylamide, itaconic acid diamide, N-methylmaleimide, 2-acrylamido-2-methylpropanesulfonic acid, methylenebisacrylamide, dimethacryloylpiperazine and the like.

(E) Styrene and its derivatives: styrene, vinyltoluene, p-tert-butylstyrene,
Vinylbenzoic acid, methyl vinylbenzoate, α-methylstyrene, p-chloromethylstyrene, vinylnaphthalene, p-hydroxymethylstyrene, sodium p-styrenesulfonate, potassium p-styrenesulfinate, 1,4-divinyl Benzene, 4-vinylbenzoic acid-2-acryloylethyl ester and the like.

(F) Vinyl ethers: methyl vinyl ether, butyl vinyl ether, methoxyethyl vinyl ether and the like. (G) Vinyl esters: vinyl acetate, vinyl propionate, vinyl benzoate, vinyl salicylate, vinyl chloroacetate and the like. (H) Other polymerizable monomers: N-vinylpyrrolidone,
2-vinyloxazoline, 2-isopropenyloxazoline, divinylsulfone and the like.

The polymer which is synthesized by copolymerization of these monomers and which is preferably selected in the polymer fine particle dispersion used in the present invention is mainly composed of acrylic resin.
A methacrylic resin, a styrene resin, a conjugated diene resin, a vinyl acetate resin, a homopolymer or a copolymer of a polyolefin resin and the like. Dienes or polymers having at least two non-conjugated ethylenically unsaturated groups, and more preferably a polymer having at least one monomer having a different polymerizability of each unsaturated group as a constituent monomer component, more preferably a conjugated diene Is particularly preferable.

The above-mentioned preferred monomers having at least two non-conjugated ethylenically unsaturated groups, and monomers having different polymerizabilities of the respective unsaturated groups include allyl acrylate, allyl methacrylate, N-allyl acrylamide, N-allyl methacrylamide and the like can be mentioned. Specific examples of conjugated diene monomers that are particularly preferred monomers include 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, and 2-n-propyl-1,3-diene. Butadiene, 2,
3-dimethyl-1,3-butadiene, 2-methyl-1,
3-pentadiene, 1-phenyl-1,3-butadiene, 1-α-naphthyl-1,3-butadiene, 1-β-
Naphthyl-1,3-butadiene, 2-chloro-1,3-
Butadiene, 1-bromo-1,3-butadiene, 1-chlorobutadiene, 2-fluoro-1,3-butadiene,
2,3-dichloro-1,3-butadiene, 1,1,2-
Trichloro-1,3-butadiene and 2-cyano-1,
Examples thereof include 3-butadiene, 1,4-hexadiene, cyclopentadiene, and ethylidene norbornene.

Preferred examples of the polymer fine particle dispersion used in the present invention are shown below, but the present invention is not limited to these. Here, unless otherwise specified, the numerical value indicating the composition ratio of each monomer represents a mass percentage.

[0172]

[Table 1]

These polymer fine particle dispersions may be used alone or, if necessary, in combination of two or more.

The emulsion polymerization method used for synthesizing the polymer fine particle dispersion of the present invention will be described below.
The emulsion polymerization method uses at least one emulsifier in water or a mixed solvent of water and a water-miscible organic solvent (e.g., methanol, ethanol, acetone, etc.) in an amount of 5 to 150% by mass based on the dispersion medium. Of the monomers is emulsified using 0.1 to 20% by weight of an emulsifier with respect to the monomers, and 0.02 to 5% by weight of the radical polymerization initiator with respect to the monomers is used. C., preferably at a temperature of 40.degree. C. to 90.degree. C., with stirring. The amount of the organic solvent miscible with water is from 0 to 100 by volume relative to water.
%, Preferably 0 to 50%.

Examples of the polymerization initiator include azobis compounds, peroxides, hydroperoxides, redox catalysts, and the like. For example, inorganic peroxides such as potassium persulfate and ammonium persulfate, t-butyl peroctoate,
Organic peroxides such as benzoyl peroxide, isopropyl percarbonate, 2,4-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dicumyl peroxide, 2,2′-azobisisobutyrate, 2, Sodium salt of 2′-azobiscyanovaleric acid, 2,2′-azobis (2-amidinopropane) hydrochloride,
2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] hydrochloride, 2,2'-azobis {2-methyl-N- [1,1'-bis (hydroxymethyl)- Azo compounds such as [2-hydroxyethyl] propionamide}. Among them, potassium persulfate,
Ammonium persulfate is particularly preferred.

As the emulsifier, anionic, cationic and
In addition to amphoteric and nonionic surfactants, there are water-soluble polymers and the like. Specific examples thereof include sodium laurate, sodium dodecyl sulfate, sodium 1-octoxycarbonylmethyl-1-octoxycarbonylmethanesulfonate, sodium laurylnaphthalenesulfonate, sodium laurylbenzenesulfonate, sodium laurylphosphate, cetyl Examples thereof include trimethylammonium chloride, N-2-ethylpyridinium chloride, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan lauryl ester, polyvinyl alcohol, emulsifiers described in JP-B-53-6190, and water-soluble polymers.

In emulsion polymerization, depending on the purpose,
Wide range of polymerization initiator, concentration, polymerization temperature, reaction time, etc.
Needless to say, it can be easily changed. In addition, the emulsion polymerization reaction may be carried out by putting a monomer, a surfactant, and an aqueous medium in advance in a reaction vessel in a total amount, and adding an initiator, or, if necessary, any of a monomer and an initiator solution,
Alternatively, it may be carried out while dropping part or all of the two. The fine particle dispersion of the present invention can be easily synthesized by using a usual emulsion polymerization method. The general method of emulsion polymerization is detailed in the following books.
"Synthetic Resin Emulsion (edited by Tadashi Okuda and Hiroshi Inagaki, published by Polymer Publishing Association (1978))", "Application of Synthetic Latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara, Published by Polymer Publishing Association (1993)" ) ”,“ Synthesis of Synthetic Latex (Souichi Muroi, Published by The Society of Polymer Publishing (1970)) ”. Particularly, those known as soap-free latex can also be preferably used.

Another example of the water-dispersible polymer fine particles that can be used in the present invention is a water-insoluble polymer having a dissociating group. The water-insoluble polymer containing a dissociating group refers to a polymer having an ionic dissociating group. The ionic dissociating group includes a cationic dissociating group such as a tertiary amino group and a quaternary ammonium group, and an anionic dissociating group such as carboxylic acid, sulfonic acid and phosphoric acid. Examples of the dissociative group-containing polymer include a vinyl polymer and a condensation polymer (polyurethane, polyester, polyamide, polyurea, polycarbonate). The water-insoluble polymer having a dissociating group is preferably a polymer having water dispersibility, that is, self-emulsifying property.

Examples of the dissociating group contained in the dissociating group-containing vinyl polymer include a carboxyl group, a sulfonic acid group, a sulfuric acid monoester group, —OPO (OH) ₂ , a sulfinic acid group, and salts thereof (for example, Na, K, etc.). Alkali metal salts, or ammonia, dimethylamine, ethanolamine, diethanolamine, triethanolamine,
Anionic groups such as ammonium salts such as trimethylamine, or primary, secondary, tertiary amines, or salts thereof (eg, organic acids (eg, acetic acid, propionic acid,
Examples thereof include cationic groups such as methanesulfonic acid), inorganic acids (such as hydrochloric acid and sulfuric acid), and quaternary ammonium salts. Of these, anionic groups are preferable, and carboxyl groups are particularly preferable.

Examples of the monomer containing the carboxylic acid as a dissociating group include acrylic acid, methacrylic acid,
Itaconic acid, maleic acid, fumaric acid, citraconic acid, crotonic acid, itaconic acid monoalkyl ester (for example,
Monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc., and monoalkyl maleate (eg, monomethyl maleate, monoethyl maleate, monobutyl maleate, etc.).

Examples of the monomer containing sulfonic acid as a dissociating group include styrene sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid (for example, acryloyloxyethyl sulfonic acid, acryloyloxypropyl sulfonic acid, etc.), methacryloyloxy Alkylsulfonic acid (for example, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.), acrylamidoalkylsulfonic acid (for example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2 -Acrylamide-2-methylbutanesulfonic acid, etc.), methacrylamidoalkylsulfonic acid (for example, 2-methacrylamido-2-methylethanesulfonic acid, 2-meth Riruamido -2, methyl propane sulfonic acid) and the like.

Examples of the monomer containing phosphoric acid as a dissociating group include monoacryloyloxyethyl phosphate and monomethacryloyloxyethyl phosphate.

Of these, acrylic acid, methacrylic acid, styrene sulfonic acid, vinyl sulfonic acid, acrylamide alkyl sulfonic acid and methacrylamido alkyl sulfonic acid are preferable, and acrylic acid, methacrylic acid, styrene sulfonic acid, 2-acrylamide-2-acrylic acid are preferable. Methylpropanesulfonic acid and 2-acrylamido-2-methylbutanesulfonic acid are particularly preferred.

Examples of the monomer having a cationic dissociating group include dialkylaminoethyl methacrylate and dialkylaminoethyl acrylate.
Monomers having a quaternary ammonium group, and monomers having a quaternary ammonium group such as N-2-acryloyloxyethyl-N, N, N-trimethylammonium chloride and N-vinylbenzyl-N, N, N-triethylammonium chloride. No.

The above-mentioned monomer containing a dissociating group may be copolymerized with a monomer having no dissociating group, and the following monomers can be used as the monomer. That is, acrylic acid esters, specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl Acrylate,
tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, 2-acetoxyethyl acrylate, benzyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2-hydroxy Ethyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, Glycidyl acrylate, 1-bromo-2-methoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, 1 , IH, 2H, 2H-perfluoro-decyl acrylate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, and the like.

Methacrylic esters, specifically, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n
-Butyl methacrylate, isobutyl methacrylate,
sec-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate,
Lauryl methacrylate, stearyl methacrylate,
Furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate,
Dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-ethoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl Methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, allyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate,
Examples include 1H, 1H, 2H, 2H-perfluorodecyl methacrylate, dioctyl-2-methacryloyloxyethyl phosphate, and the like.

Vinyl esters, specifically, vinyl acetate, vinyl propionate, vinyl butyrate,
Examples include vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, and vinyl salicylate.

Acrylamides, specifically, acrylamide, methylacrylamide, ethylacrylamide, isopropylacrylamide, n-butylacrylamide, tert-butylacrylamide, tert-
Octylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxymethylacrylamide, butoxymethylacrylamide, methoxyethylacrylamide,
Examples include phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, diacetoneacrylamide, and the like.

Methacrylamides, specifically, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, n-butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacryl Amide, methoxyethyl methacrylamide, phenyl methacrylamide, β
-Cyanoethyl methacrylamide, N- (2-acetoacetoxyethyl) methacrylamide and the like.

Olefins, specifically, styrenes such as dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene; For example, styrene, methyl styrene,
Examples include dimethylstyrene, trimethylstyrene, ethylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, and methyl vinylbenzoate.

Vinyl ethers, specifically, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and the like can be mentioned.

Other monomers include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl Ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, N
-Vinyloxazolidone, N-vinylpyrrolidone, vinylidene chloride, methylenemalonnitrile, vinylidene and the like.

It is also preferable to copolymerize a monomer containing a nonionic dispersing group as described below. Examples of such a monomer include an ester of a polyethylene glycol monoalkyl ether and a carboxylic acid monomer, Contains an ester of polyethylene glycol monoalkyl ether and sulfonic acid monomer, an ester of polyethylene glycol monoalkyl ether and phosphoric acid monomer, a vinyl group-containing urethane formed from polyethylene glycol monoalkyl ether and isocyanate group-containing monomer, and a polyvinyl alcohol structure Macromonomer and the like. The repeating number of the ethyleneoxy moiety of the polyethylene glycol monoalkyl ether is preferably from 8 to 50, and more preferably from 10 to 30. The number of carbon atoms in the alkyl group of the polyethylene glycol monoalkyl ether is preferably from 1 to 20, and more preferably from 1 to 12.

Next, the above-mentioned condensation group-containing condensation polymer will be described in detail. The dissociative group-containing polyurethane is basically synthesized by a polyaddition reaction using a diol compound and a diisocyanate compound as raw materials. Specific examples of the diol compound include, as non-dissociable diols, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 2,2-dimethyl -1,3-propanediol, 1,4-pentanediol, 2,4-pentanediol, 3,3-dimethyl-1,2-butanediol,
-Ethyl-2-methyl-1,3-propanediol,
1,6-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,2-
Diethyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2,5-dimethyl-
2,5-hexanediol, 2-ethyl-1,3-hexanediol, 1,2-octanediol, 2,2,4
Trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol (average molecular weight = 200 to 4000), polypropylene glycol (average molecular weight = 200) ~ 1000), polyester polyol, 4,4'-dihydroxydiphenyl-2,2
-Propane, 4,4'-dihydroxyphenylsulfone and the like.

Preferred specific examples of the diisocyanate include ethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,4-toluene diisocyanate, 1,3-xylylene diisocyanate,
1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate,
3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 3,3′-dimethylbiphenylene diisocyanate, dicyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate)
And the like.

The polyurethane having a dissociable group can be obtained, for example, by using a diol having a dissociable group at the time of synthesizing the polyurethane. In that case, the dissociating group is introduced into the polyurethane as a substituent from the polymer backbone. As a diol having a dissociation group, particularly an anionic group,
2,2-bis (hydroxymethyl) propionic acid, 2,2
-Bis (hydroxymethyl) butanoic acid, 2,5,6-trimethoxy-3,4-dihydroxyhexanoic acid, 2,3-
Dihydroxy-4,5-dimethoxypentanoic acid, 3,5
-Di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid and salts thereof,
It is not particularly limited to these.

Examples of the dissociating group contained in the dissociating group-containing polyurethane include a carboxyl group, a sulfonic acid group, a sulfuric acid monoester group, -OPO (OH) ₂ , a sulfinic acid group, and salts thereof (for example, Na, K and the like). Alkali metal salts,
Or an anionic group such as ammonium, dimethylamine, ethanolamine, diethanolamine, triethanolamine, and trimethylamine, or a cationic group such as primary, secondary, tertiary amine, and quaternary ammonium salts. Among them, an anionic group is preferable, and a carboxyl group is particularly preferable.

The polyester is basically synthesized by a condensation reaction between a diol compound and a dicarboxylic acid compound. Specific examples of dicarboxylic acid compounds include oxalic acid, malonic acid, succinic acid, glutaric acid, dimethylmalonic acid, adipic acid, pimelic acid, α, α-dimethylsuccinic acid, acetone dicarboxylic acid, sebacic acid, 9-nonanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid,
Citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, 2-butylterephthalic acid, tetrachloroterephthalic acid, acetylenedicarboxylic acid, poly (ethylene terephthalate) dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid , Ω-poly (ethylene oxide) dicarboxylic acid, p-xylylene dicarboxylic acid and the like. These compounds may be used in the form of an alkyl ester of a dicarboxylic acid (for example, dimethyl ester) or an acid chloride of a dicarboxylic acid when performing a polycondensation reaction with a diol compound,
It may be used in the form of an acid anhydride such as maleic anhydride, succinic anhydride, and phthalic anhydride.

Dissociative group-containing polyesters include, in addition to carboxylic acids, sulfonic acid groups, sulfuric acid monoester groups, -OPO
(OH) ₂ , a sulfinic acid group, or an anion such as a salt thereof (for example, an alkali metal salt such as Na or K, or an ammonium salt such as ammonia, dimethylamine, ethanolamine, diethanolamine, triethanolamine, or trimethylamine). Or a cationic group such as a tertiary amine or a salt thereof (eg, a salt of an organic acid (eg, acetic acid, propionic acid, methanesulfonic acid) or an inorganic acid (eg, hydrochloric acid, sulfuric acid)) or a quaternary ammonium salt It is obtained by synthesizing using a dicarboxylic acid compound having a dissociating group as described above. As the dissociating group other than the carboxylic acid contained in the dissociating group-containing polyester, an anionic group is preferable, and a sulfonic acid group is particularly preferable.

A dicarboxylic acid having a sulfonic acid group,
Preferred examples of the diol raw materials include sulfophthalic acids (3-sulfophthalic acid, 4-sulfophthalic acid, 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, and 2-sulfoterephthalic acid), sulfosuccinic acid, and sulfonaphthalenedicarboxylic acids (4- Sulfo-1,8-naphthalenedicarboxylic acid, 7-sulfo-1,5-naphthalenedicarboxylic acid, etc.), 3,5-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid, and salts thereof.

As the diol compound, a compound selected from the same group as the diols described in the above polyurethane can be used. A typical synthesis method of the polyester is a condensation reaction of the above diol compound with a dicarboxylic acid or a derivative thereof, and is obtained by condensing a hydroxycarboxylic acid such as a hydroxycarboxylic acid (for example, 12-hydroxystearic acid). And ring-opening polymerization of cyclic ethers and lactones.
Polyesters obtained by a method such as ring-opening polymerization (I) written by Takeo Saegusa (detailed in Kagaku Dojin, 1971) can also be suitably used in the present invention.

The polyamide can be obtained by polycondensation of a diamine compound and a dicarboxylic acid compound, polycondensation of an aminocarboxylic acid compound, or ring-opening polymerization of lactams. Examples of the diamine compound include ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, hexamethylenediamine, octamethylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, piperazine, and 2,5-diamine. Examples thereof include dimethylpiperazine, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylsulfone, xylylenediamine, and the like. Examples of the aminocarboxylic acid include glycine, alanine, phenylalanine, and ω-.
Examples include aminohexanoic acid, ω-aminodecanoic acid, ω-aminoundecanoic acid, and anthranilic acid. Examples of the monomer that can be used for ring-opening polymerization include ε-caprolactam, azetidinone, and pyrrolidone. As the dicarboxylic acid compound, a compound selected from the same group as the dicarboxylic acids described in the polyester can be used.

The polyurea can be obtained basically by polyaddition of a diamine compound and a diisocyanate compound or deammonification reaction of a diamine compound and urea. Compounds selected from the same group as the diisocyanates described in the above polyurethane can be used.

The polycarbonate can be basically obtained by reacting a diol compound with a phosgene or a carbonate derivative (eg, an aromatic ester such as diphenyl carbonate). Compounds from the same group as the diols can be used.

The dissociating group can be introduced into each of the polymers by various methods. For example, in the case of polyurethane, as described above, a diol containing a dissociating group can be used during synthesis and introduced as a substituent from the polymer main chain. Further, as in the case of using a polyester as the oil-soluble polymer, it can be introduced by leaving a dicarboxylic acid unreacted terminal at the terminal of the polymer. Furthermore, after the polymerization of each of the above polymers, a compound capable of introducing a dissociating group by a reaction such as an acid anhydride (for example, maleic anhydride) may be allowed to act on a reactive group such as a hydroxy group or an amino group. .

For the above-mentioned polymer containing a dissociating group, both the vinyl polymer and the condensed polymer may use the necessary constituent materials one by one, or may be used for various purposes (for example, adjustment of the glass transition temperature (Tg) of the polymer). And the solubility, the compatibility with the dye, and the stability of the dispersion) can be used in an arbitrary ratio of two or more.

Further, among the polymers having a dissociating group,
Those having at least one of a carboxyl group and a sulfonic acid group as the dissociable group are preferred, and those having a carboxyl group as the dissociable group are particularly preferred.

The content of the dissociative group in the dissociative group-containing polymer is preferably from 0.1 to 3.0 mmol / g, more preferably from 0.2 to 2.0 mmol / g. When the content of the dissociable group is too small or too large, the self-emulsifying property of the dissociative group-containing polymer tends to be small, and the effect of stabilizing the fine particle dispersion of the dye tends to be small.

The anionic dissociating group may further include an alkali metal (for example, Na,
K) or a salt of an ammonium ion. The tertiary amine serving as the cationic dissociating group may further include an organic acid (eg, acetic acid, propionic acid, methanesulfonic acid) or an inorganic acid (hydrochloric acid, Salt).

In consideration of the excellent dispersing stability imparting and the ease of dissociating group introduction, etc.
More preferred are vinyl polymers, polyurethanes and polyesters, particularly preferred are vinyl polymers.

Specific examples of the dissociative group-containing vinyl polymer are listed below. The ratio in parentheses means the mass ratio. Note that the present invention is not limited to these specific examples.

[0212]

[Table 2]

Specific examples of the condensation polymer among the polymers having a dissociating group are listed below, but the present invention is not limited thereto. All acidic groups in each polymer are shown in non-dissociated form. Also polyester,
For those produced by condensation reaction such as polyamide,
The components are all dicarboxylic acids, regardless of the raw materials,
It is represented by diol, diamine, hydroxycarboxylic acid, aminocarboxylic acid and the like. The ratio in parentheses means the molar percentage ratio of each component.

[0214]

[Table 3]

With respect to the synthesis of the condensation polymer containing a dissociating group, “Polymer Experiments (Vol. 5) Polycondensation and Polyaddition (Edited by Shu Kanbara, published by Kyoritsu Shuppan Co., Ltd. (1980))” and “Polyester Resin Handbook (Eiichiro Takiyama, published by Nikkan Kogyo Shimbun (1988)), "Polyurethane Resin Handbook (edited by Keiji Iwata, published by Nikkan Kogyo Shimbun (1987))", "Experimental method for polymer synthesis (Takayuki Otsu and Kinoshita) Masaetsu, co-authored by Kagaku Doujin (19
72)) ”, JP-B No. 33-1141, 37-7641
Nos. 39-5989, 40-27349, 4
Nos. 2-5118, 42-24194, 45-10
No. 957, No. 48-25435, No. 49-36942
No. 52-81344, JP-A-56-88454.
And known methods described in each gazette such as JP-A-6-340835.

As the polymer fine particle dispersion used in the present invention, those having a glass transition point of -40 to 160 ° C. can be used. If the film formation is insufficient after printing, post-heating treatment can be performed.

When the ink composition for ink jet recording obtained in the present invention is used as an ink for ink jet recording, a drying inhibitor for preventing clogging due to a dry operation at an ink ejection port, and an ink using paper. Penetration enhancers, UV absorbers, antioxidants, viscosity modifiers, surface tension regulators, dispersants, dispersion stabilizers, fungicides, rust inhibitors, pH regulators, defoamers, chelates for good penetration An additive such as an agent can be appropriately selected and used in an appropriate amount.

As the drying inhibitor used in the present invention, a water-soluble organic solvent having a lower vapor pressure than water is preferable. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol,
Thiodiglycol, dithiodiglycol, 2-methyl-
Polyhydric alcohols represented by 1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin, trimethylolpropane, etc., ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl)
Lower alkyl ethers of polyhydric alcohols such as ether and triethylene glycol monoethyl (or butyl) ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethylmorpholine And the like, sulfur-containing compounds such as sulfolane, dimethyl sulfoxide and 3-sulfolene, polyfunctional compounds such as diacetone alcohol and diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. The above-mentioned drying inhibitors may be used alone or in combination of two or more. These anti-drying agents are preferably contained in the ink in an amount of 10 to 50% by mass.

Examples of the penetration enhancer used in the present invention include ethanol, isopropanol, butanol and di (tri) triol.
Alcohols such as ethylene glycol monobutyl ether and 1,2-hexanediol, sodium lauryl sulfate, sodium oleate and nonionic surfactants can be used. These have sufficient effects when contained in the ink in an amount of 10 to 30% by mass, and are preferably used within the range of an addition amount that does not cause printing bleeding or paper loss (print-through).

The ultraviolet absorber used in the present invention to improve the image storability is described in JP-A-58-1856.
Nos. 77, 61-90537 and JP-A-2-
No. 782, No. 5-1970075, No. 9-34
Benzotriazole compounds described in JP-A-557 / 057, JP-A-46-2784, JP-A-5-1944
No. 83, U.S. Pat. No. 3,214,463, benzophenone-based compounds described in JP-B-48-30492, JP-B-56-21141, and JP-A-10-881.
No. 06, etc., cinnamic acid-based compounds,
298503, 8-53427 and 8-
Nos. 339368, 10-182621, and JP-A-8-501291, and the like. 2423
Compounds described in No. 9 and compounds that absorb ultraviolet rays and emit fluorescence, typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent whitening agents can also be used.

As the antioxidant used for improving the storability of an image in the present invention, various organic and metal complex antifading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, heterocycles, and the like. Complexes and zinc complexes. More specifically, Research Disclosure No. VI of 17643
Nos. I through J of I. 15162; 18
No. 716, page 650, left column, ibid. 527 of 36544
Page, the same No. No. 307105, page 872; 151
Compounds described in the patents cited in JP-A-6-62
The compounds included in the general formulas and examples of the typical compounds described on pages 127 to 137 of JP-A-215272 can be used.

The fungicides used in the present invention include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazoline-3-
And its salts. These are preferably used in the ink in an amount of 0.02 to 5.00% by mass. still,
Details of these are described in "Encyclopedia of Bacterial and Fungicides" (edited by the Japanese Society of Bacteria and Fungi). Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, benzotriazole and the like. 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 pH adjustment, dispersion stability imparting, etc., and is preferably added so as to have a pH of 4.5 to 10.0. More preferably, it is added so as to have a pH of 6 to 10.0. As the pH adjuster, organic bases as basic ones, inorganic alkalis and the like, organic acids as acidic ones,
And inorganic acids. Examples of the organic base include triethanolamine, diethanolamine, N-methyldiethanolamine, dimethylethanolamine and the like. Examples of the inorganic alkali include hydroxides of alkali metals (eg, sodium hydroxide, lithium hydroxide, potassium hydroxide, etc.), carbonates (eg, sodium carbonate, sodium hydrogen carbonate, etc.), and ammonia. In addition, examples of the organic acid include acetic acid, propionic acid, trifluoroacetic acid, and alkylsulfonic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid.

Examples of the surface tension modifier used in the present invention include nonionic, cationic and anionic surfactants. For example, anionic surfactants include fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl sulfates Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene. Examples thereof include alkylamine, glycerin fatty acid ester, and oxyethyleneoxypropylene block copolymer. SUR, an acetylene-based polyoxyethylene oxide surfactant
FYNOLS (Air Products & Chemic
als) is also preferably used. Further, amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide are also preferable. Further, Japanese Unexamined Patent Publication No.
No. 9-157,636, pages (37) to (38), Research Disclosure No. 308119 (1989) can also be used.
The surface tension of the ink of the present invention is preferably 20 to 60 mN / m with or without using them. Further, it is preferably 25 to 45 mN / m.

The viscosity of the ink used in the present invention is 30 m
Pa · s or less is preferable. Since it is more preferable to adjust the viscosity to 20 mPa · s or less, a viscosity modifier may be used for the purpose of adjusting the viscosity. 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 Adjusting Technology" (Technical Information Association, 1999) and "Chemicals for Inkjet Printers (98 Supplement)-Material Development Trend and Outlook Survey-"
(CMC, 1997) at pages 162-174.

In the present invention, the above-mentioned various cationic, anionic and nonionic surfactants are used as dispersants and dispersion stabilizers, and fluorine-containing, silicone-based compounds and EDs are used as defoamers.
A chelating agent represented by TA and the like can be used as needed.

The recording paper and recording film used in the image recording method of the present invention will be described. Supports for recording paper and recording film are chemical pulp such as LBKP and NBKP, GP, PGW, RMP, TMP, CTMP, CM
It consists of mechanical pulp such as P and CGP, waste paper pulp such as DIP, etc., and if necessary, mixes known additives such as pigments, binders, sizing agents, fixing agents, cationic agents, and paper strength agents. And those manufactured by various devices such as a fourdrinier paper machine and a round paper machine can be used. In addition to these supports, any of synthetic paper and plastic film sheets may be used. The support has a thickness of 10 to 250 μm and a basis weight of 1
0-250 g / m < ² > is desirable. The image receiving material may be provided by directly providing an image receiving layer and a back coat layer on the support, or after providing a size press or an anchor coat layer with starch, polyvinyl alcohol, or the like, and then providing the image receiving layer and the back coat layer as an image receiving material. Good. Further, the support may be subjected to a flattening treatment using a calender such as a machine calender, a TG calender, and a soft calender. In the present invention, as the support, paper and plastic films laminated on both sides with a polyolefin (eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used. It is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a coloring dye (eg, cobalt blue, ultramarine blue, neodymium oxide) to the polyolefin 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. As the pigment, a white pigment is preferable. White pigments include calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite,
Examples thereof include inorganic white pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, and zinc carbonate; and organic pigments such as styrene pigment, acrylic pigment, urea resin, and melamine resin. Particularly preferred is a porous white inorganic pigment, and particularly preferred is synthetic amorphous silica having a large pore area. As the synthetic amorphous silica, both silicic anhydride obtained by a dry production method and hydrous silicic acid obtained by a wet production method can be used, and it is particularly preferable to use hydrous silicic acid. Two or more of these pigments may be used in combination.

Examples of the aqueous binder contained in the image receiving layer include polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, polyalkylene oxide derivative and the like. And a water-dispersible polymer such as styrene-butadiene latex and acrylic emulsion.
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 peel resistance of the ink receiving layer.

The image-receiving layer may contain a mordant, a water-proofing agent, a light-fastness 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 this purpose, a polymer mordant is preferably used. Polymer mordants are described in JP-A-48-28325, JP-A-54-74430,
Nos. 4-124726, 55-22766, 55-
Nos. 142339, 60-23850, 60-23
No. 851, No. 60-23852, No. 60-23853
No. 60-57836, No. 60-60643, No. 60-118834, No. 60-122940, No. 6
Nos. 0-122941, 60-122942, 60
-235134, JP-A-1-161236, U.S. Pat. Nos. 2,484,430 and 2,548,564,
No. 3148061, No. 3309690, No. 4115
No. 124, No. 4124386, No. 4193800,
No. 4238353, No. 4282305, No. 4450
No. 224 is described in each specification. JP-A-1-16112
An image receiving material containing a polymer mordant described on pages 212 to 215 of JP-A No. 36 is particularly preferred. By using the polymer mordant described in the publication, an image with excellent image quality is obtained, and the light fastness of the image is improved.

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

Examples of the light resistance improver include zinc sulfate, zinc oxide, hinderamine antioxidants, and benzotriazole-based ultraviolet absorbers such as benzophenone.
Of these, zinc sulfate is particularly preferred.

Surfactants include coating aids, release improvers,
It functions as a slipperiness improver or an antistatic agent. The surfactants are described in JP-A Nos. 62-173463 and 62-183457. An organic fluoro compound may be used instead of the surfactant. Preferably, the organic fluoro compound is hydrophobic. Examples of the organic fluoro compound include a fluorinated surfactant, an oily fluorinated compound (eg, fluorinated oil), and a solid fluorinated compound resin (eg, an ethylene tetrafluoride resin).
About the organic fluoro compound, Japanese Patent Publication No. 57-9053
No. (columns 8 to 17), JP-A No. 61-20994, 6
It is described in each gazette of 2-135826.

As the hardener, the materials described on page 222 of JP-A-1-161236 can be used.

Other additives to be added to the image receiving layer include a pigment dispersant, a thickener, a defoamer, a dye, a fluorescent brightener,
Preservatives, pH adjusters, matting agents, hardening agents and the like can be mentioned. The ink receiving layer may be a single layer or two layers.

The recording paper and the recording film may be provided with a back coat layer. 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 back coat 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,
Examples include white inorganic pigments such as hydrohaloysite, magnesium carbonate, and magnesium hydroxide, and organic pigments such as styrene-based plastic pigments, acrylic-based plastic pigments, polyethylene, microcapsules, urea resins, and melamine resins.

As the aqueous binder contained in the back coat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin And water-soluble polymers such as carboxymethylcellulose, hydroxyethylcellulose and polyvinylpyrrolidone, and water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion. Other components contained in the back coat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent whitening agent, a preservative, and a waterproofing agent.

A polymer fine particle dispersion may be added to the constituent layers (including the back layer) of the ink jet recording paper and the recording film. The polymer fine particle dispersion is used for the purpose of improving film properties such as dimensional stabilization, curl prevention, adhesion prevention, and film crack prevention. Polymer fine particle dispersions are described in JP-A-62-245258 and JP-A-62-1.
It is described in the respective publications of 316648 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. Also, curling can be prevented by adding a polymer fine particle dispersion having a high glass transition temperature to the back layer.

In the present invention, there is no limitation on the ink jet recording method, and a known method, for example, a charge control method for discharging ink by using electrostatic attraction, a drop-on-demand method using a vibration pressure of a piezo element (pressure Pulse method), an acoustic ink jet method in which an electric signal is converted into an acoustic beam, and the ink is radiated to the ink to discharge the ink using a radiation pressure. Bubble jet (registered trademark)) system. The ink jet recording method uses 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 by using a plurality of inks having substantially the same hue and different densities, or a colorless transparent ink. The method is included.

[0241]

The present invention will be described below with reference to examples.
The present invention is not limited to this.

Example 1 The following components were mixed with deionized water to make 1 liter, and then heated at 30 to 40 ° C. for 1 liter.
Stir for hours. Then, at 10 mol / l of KOH, p
H was adjusted to 9 and filtered under reduced pressure through a micro filter having an average pore diameter of 0.25 μm to prepare an ink liquid for light magenta. Magenta dye in the specification (101) 3.75 g Diethylene glycol 150 g Urea 37 g Glycerin 130 g Triethylene glycol monobutyl ether 130 g Surfynol 465 (Air Products & Chemicals) 10.5 g Compound of the present invention Polymer fine particle dispersion P-1 30 g (as solid) Tri Ethanolamine 6.9 g Benzotriazole 0.08 g PROXEL XL2 3.5 g Magenta ink, light cyan ink, cyan ink, yellow ink, and black ink are prepared by changing the dye type and additives, and ink set 101 shown in Table 2 is made. did.

[0243]

[Table 4]

[0244]

Embedded image

[0245]

Embedded image

Next, for each of the light magenta, magenta, light cyan, cyan, yellow, and black inks of the ink set 101, the dye type and the type and amount of the polymer fine particle dispersion of the present invention were changed according to Table 5, and the ink set was changed. 102-110 were created. When the dyes were used in combination, they were used in equimolar amounts, and when the polymer fine particle dispersion of the present invention was used in combination, they were used in equal amounts. The volume average particle size of the polymer fine particle dispersion is determined by Microtrack UP.
A was 1.0 μm or less as measured by A (manufactured by Nikkiso Co., Ltd.).

[0247]

[Table 5]

[0248]

Embedded image

Next, these ink sets 101-110
To the inkjet printer PM770C (EPSON
The product was packed in a cartridge manufactured by Fuji Photo Film Co., Ltd., and an image was printed on inkjet paper photo glossy paper EX and Xerox copy paper manufactured by Fuji Photo Film Co., Ltd., and the following evaluation was performed.

1) Regarding the printing performance, after setting the cartridge in the printer and confirming that the ink protruded from all the nozzles, 20 sheets of A4 paper were output, and the printing disorder was evaluated. A: There is no printing disturbance from the start to the end of printing. B: Output with disturbance of the printing occurs. C: There is the printing disturbance from the start to the end of printing. 2) The printing performance is as follows. Disorder of printing was evaluated by the same method as the printing performance. 3) Immediately after printing, the dryness was evaluated by visual inspection of the stain when touched with a finger. 4) Regarding bleeding of fine lines, yellow, magenta, cyan and black fine line patterns were printed and evaluated visually. As for black, after printing solid magenta ink, a black thin line was printed, and bleeding due to contact between two colors was also evaluated. 5) Regarding water resistance, the obtained image was immersed in deionized water for 5 seconds, and then the blur of the image was visually evaluated. 6) Regarding image storability, print samples of yellow, magenta, cyan and black were prepared and evaluated as follows. The light fastness was measured by measuring the image density Ci immediately after printing with an X-rite 310, irradiating the image with xenon light (85,000 lux) using an Atlas Weather Meter for 9 days, and then re-evaluating the image density Cf. Was measured to determine the residual dye ratio Cf / Ci * 100, and evaluated. Regarding the dye remaining ratio, the reflection density was 1,1.5,
Evaluation was made at 3 points, and the residual dye rate was 7 at any concentration.
A was 0% or more, A was 2 points less than 70%, and B was less than 70% at all concentrations. Regarding the heat fastness, the density before and after the sample was stored for 9 days under the condition of 80 ° C. was measured with an X-rite 310 to obtain and evaluate the residual ratio of the dye. Regarding the dye remaining rate, the reflection density is 1, 1.5, 2
And the dye remaining rate was 80 at all concentrations.
% Or more, and B when two points were less than 80%, and C when less than 80% at all concentrations.

[0251]

[Table 6]

[0252]

[Table 7]

Example 2 8 g of the dye (A-1) and 40 g of a surfactant (trade name: Emal 20C, manufactured by Kao Corporation) were mixed with 6 g of a high-boiling organic solvent (S-1) and a high-boiling organic solvent (S-2). )
It was dissolved at 70 ° C. in 10 g and 50 ml of ethyl acetate. 500 ml of deionized water was added to this solution while stirring with a magnetic stirrer to prepare an oil-in-water type coarse particle dispersion. Next, the coarse particle dispersion was passed through a micro flodizer (MICROFLUIDEXINC) five times at a pressure of 60 MPa to form fine particles. The solvent was removed from the resulting emulsion using a rotary evaporator until the odor of ethyl acetate disappeared. 140 g of diethylene glycol and 64 g of glycerin were added to the fine emulsion of the oil-soluble dye obtained as described above.
After adding additives such as urea and urea, 20 g of the polymer fine particle dispersion P-1 of the present invention in solid content is added, and deionized water is added so as to make the whole 1 liter.
By adjusting the pH to 9 at ol / l, a light magenta ink according to Table 8 was produced. The volume average particle size of the obtained emulsified dispersion ink was determined by using Microtrac UPA.
It was 51 nm when measured using (manufactured by Nikkiso Co., Ltd.). Further, by changing the type and amount of the dye used, the amount of the high boiling point organic solvent, and the type and amount of various additives, the magenta ink, light cyan ink, cyan ink, yellow ink, and black ink of the ink set 201 shown in Table 8 were prepared. did. Table 8 shows the composition of the final composition after evaporation of the solvent.

[0254]

[Table 8]

[0255]

Embedded image

[0256]

Embedded image

Similarly, according to Table 9, the ink sets 202 to
205 was created. The two types of polymer fine particle dispersions were combined at an equal mass ratio.

[0258]

[Table 9]

Next, these ink sets 201 to 20
5 with an inkjet printer PM670C (EPSO
N Co., Ltd.), and an image was printed on inkjet paper photo glossy paper EX and Xerox copy paper manufactured by Fuji Photo Film Co., Ltd. using the same machine, and the same evaluation as in Example 1 was performed. However, regarding the printing performance, after the cartridge was left at 50 ° C. for 2 days, printing disorder was evaluated in the same manner as the printing performance.

[0260]

[Table 10]

[0261]

[Table 11]

It can be seen that when the image forming method according to the ink jet image recording method of the present invention is used, an image excellent in water resistance and light / heat fastness can be obtained. In addition, the ink ejection stability during printing and the performance when outputting fine lines are excellent without bleeding.

Example 3 An ink set 301 was prepared by changing the dye of the ink set 101 to the following pigment. The dispersion of the pigment was performed by a sand grinder mill (manufactured by IMEX Co., Ltd.) using zirconia beads and using the following B-1 as a dispersant at 40% of the pigment.

[0264]

[Table 12]

[0265]

Embedded image

Further, for comparison, the polymer fine particle dispersion of the present invention was removed from the ink set 301 and the ink set 30 was removed.
2 was created. These ink sets 301 and 302 are packed in cartridges of an inkjet printer PM670C (manufactured by EPSON), and images are printed on inkjet photo gloss paper EX manufactured by Fuji Photo Film and Xerox copy paper by the same machine. An evaluation was performed.

[0267]

[Table 13]

[0268]

[Table 14]

As described above, even when the pigment was used, the effect of the present invention was obtained although the amount was small.

[0270]

According to the present invention, ink-jet recording (excellent in weather resistance) capable of forming an image having excellent ejection stability, high light and heat fastness, little bleeding, and little deterioration even under severe conditions. An image forming method according to the method can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2C056 EA05 EA13 FC01 FC02 FC06 2H086 BA54 BA56 BA59 4J039 AD01 AD05 AD07 AD08 AD09 AD10 AD12 AD15 AD22 AD23 BA04 BE01 BE02 BE06 BE07 BE12 BE22 CA03 EA34 EA35 EA42 EA44 EA46 GA24

Claims (5)

[Claims] An ink liquid using an ink composition for inkjet recording containing at least a colorant and further containing a polymer fine particle dispersion is ejected in accordance with a recording signal,
An image forming method using an ink jet recording method for recording on an image receiving material, wherein the image receiving material contains a porous material in an image receiving layer. 2. The image forming method according to claim 1, wherein the colorant is a water-soluble dye. 3. The image forming method according to claim 1, wherein the colorant is an oil-soluble dye. 4. The image forming method according to claim 3, further comprising a high boiling organic solvent. 5. The image forming method according to claim 1, wherein the porous material is a white inorganic pigment.