JP2002060658A - Inkjet ink and inkjet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inkjet ink having excellent image quality, water resistance, and image fastness. SOLUTION: The inkjet ink is obtained by dispersing an oil-soluble dye dissolved in a high boiling point organic solvent into an aqueous medium, and contains a compound represented by formula (I) (wherein X is N-Rd, O or S; Y is C-Re or N; and Ra, Rb, Rc, Rd, and Re are each independently hydrogen or a substituent, and each of Ra and Rb, Rb and Re, Re and Rc, Rc and Rd, and Rd and Ra may be bonded to each other to form a ring) or by formula (II) (wherein X is N-Rd, O or S; and Ra, Rb, Rc, Rd, and Re are each independently hydrogen or a substituent and each of Ra and Rb, Rb and Re, Re and Rc, Rc and Rd, and Rd and Ra may be bonded to each other to form a ring).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet ink excellent in image quality, water resistance and image fastness, and an ink jet recording method using the ink.

[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 as paper,
It is widely used for printing on films, cloths and the like.
Oil-based, water-based, and solid inks are known as ink-jet inks, but water-based inks are mainly used in terms of manufacturing, handling, odor, safety, and the like. However,
Many water-based inks have the advantage of high transparency and color density because they use water-soluble dyes that dissolve in a molecular state, but have poor water resistance and cause bleeding when printed on so-called plain paper. It has the drawbacks that the quality is deteriorated and that the light resistance is extremely poor.

Various aqueous inks using pigments or disperse dyes have been proposed to improve the above disadvantages. For example, JP-A-56-157468, JP-A-4-18468, JP-A-10-110126, and JP-A-10-110126
It is described in 195355. Although the water resistance is improved by these methods, it is not perfect.In particular, in the case of pigment inks, color development is inferior to dye inks, and the storage stability of the dispersion is liable to cause clogging at the discharge port due to lack of storage stability. Had disadvantages.

Japanese Patent Application Laid-Open No. 58-45272 proposes a method of enclosing a dye in urethane polymer latex particles. However, when the dye is encapsulated at a desired concentration, colored particles having excellent dispersion stability can be obtained. It had the disadvantage of being difficult to obtain. Further, JP-A-10-279873 discloses a method in which an acrylic polymer and an oil-soluble dye are dissolved in an organic solvent, and after dispersion, the organic solvent is removed to produce colored polymer fine particles. ,
In particular, there was a problem in quality when recording on a paper medium for photographic quality and stability in continuous recording.

On the other hand, Japanese Patent Publication No. 5-76977 discloses that
An ink composition in which an oil-soluble dye is dissolved and dispersed in an organic solvent is disclosed.However, the organic solvent defined here generally has a low recording density due to insufficient compatibility with the oil-soluble dye. It was clarified that some dyes precipitated during storage and caused clogging of nozzles. Further, the disclosed oil-soluble dyes did not have sufficient color reproducibility based on insufficient color tone and storage stability of images obtained. JP-A-1-170674 discloses an inkjet recording liquid containing an ultraviolet absorber and / or an antioxidant in order to improve the storage stability. I couldn't say. In order to prevent the precipitation of the dye, secure the ejection stability, and obtain higher recorded image quality, it is necessary to reduce the average particle size of the colored particles, but under such conditions, the image stability is further increased. It was desired to improve.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, an object of the present invention is to provide an inkjet ink excellent in image quality, water resistance, and image fastness, and an inkjet recording method using the same.

[0007]

Means for solving the above problems are as follows. That is, <1> an inkjet ink characterized in that an oil-soluble dye dissolved in a high boiling point solvent is dispersed in an aqueous medium and contains a compound represented by the following general formula (I).

Embedded image In (formula (I), X represents N-R _d, O or S, Y represents C-R _e or _{N .R a, R b, R} c, R d
And R _e each independently represent a hydrogen atom or a substituent, and R _a and R _b , R _b and R _e , R _e and R _c , R _c and R _d and R
_d and _Ra may be bonded to each other to form a ring. <2> The inkjet ink according to <1>, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II).

Embedded image In (general formula (II), X represents N-R _d, O or S, represents R _a, R _b, R _c, a hydrogen atom or a substituent each R _d and R _e independently, and R _a R _b , R _b and R _e , R _e
And R _c , R _c and R _d, and R _d and R _a may be connected to each other to form a condensed ring. <3> The inkjet ink according to <1> or <2>, wherein the volume average particle size of the dispersed particles in the dye dispersion is 5 to 100 nm. <4> The inkjet according to any one of <1> to <3>, wherein the compound represented by Formula (I) or Formula (II) is contained in substantially the same particles as the oil-soluble dye. It is ink for use. <5> The inkjet ink according to any one of <1> to <4>, wherein the oil-soluble dye is represented by the following general formula (III). General formula (III)

[0008]

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(In the general formula (III), X is a color image
Represents the residue of a true coupler, where A is -NR^FourR^FiveOr hydroxy
Represents a group, R^FourAnd R^FiveAre each independently a hydrogen atom,
Represents an aliphatic group, an aromatic group, or a heterocyclic group. B¹Is = C
(R⁶)-Or = N-, B ^TwoIs -C (R⁷) = Again
Represents -N =, R^Two, R^Three, R⁶And R⁷Are independent
Hydrogen atom, halogen atom, aliphatic group, aromatic group,
Ring group, cyano, -OR⁵¹, -SR⁵², -CO_TwoR⁵³,
-OCOR⁵⁴, -NR⁵⁵R⁵⁶, -CONR⁵⁷R⁵⁸, -S
O_TwoR⁵⁹, -SO_TwoNR⁶⁰R⁶¹, -NR⁶²CONR
⁶³R⁶⁴, -NR⁶⁵CO_TwoR⁶⁶, -COR⁶⁷, -NR⁶⁸C
OR⁶⁹Or -NR⁷⁰SO_TwoR⁷¹And R⁵¹, R⁵², R
⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹, R⁶⁰,
R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷, R⁶⁸, R
⁶⁹, R⁷⁰And R⁷¹Is independently a hydrogen atom or an aliphatic group
Or represents an aromatic group. R^TwoAnd R^Three, R^ThreeAnd R^Four, R^FourWhen
R^Five, R^FiveAnd R⁶And R⁶And R⁷Combine with each other to form a ring
May be. <6> The ink according to any one of <1> to <5>.
White inorganic pigment particles on support using jet ink
Recording on an image receiving material having an image receiving layer containing
Characteristic ink jet recording method.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an ink-jet ink and an ink-jet recording method of the present invention will be described.

(Ink for Ink Jet) The ink for ink jet of the present invention is obtained by dispersing an oil-soluble dye dissolved in a high-boiling organic solvent in an aqueous medium.
Or it contains the compound represented by the general formula (II). The ink-jet ink of the present invention is in a so-called emulsified dispersion state in which an oil-soluble dye and a high-boiling organic solvent are dispersed as fine oil droplets (hereinafter referred to as “dispersed particles”) in an aqueous medium. Is what it is. The "aqueous medium" in the present invention is water or a mixture of water and a small amount of a water-miscible organic solvent, if necessary, to which additives such as a surfactant, a wetting agent, a stabilizer, and a preservative are added. Means The solubility of the oil-soluble dye used in the present invention in water is not particularly limited.

<Compound represented by Formula (I) or (II)> The compound represented by Formula (I) will be described. _Ra , _Rb , _Rc , _Rd and _Re each independently represent a hydrogen atom or a substituent. Preferred examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, and an iodine atom), a linear, branched, or cyclic substituted or unsubstituted alkyl group or alkenyl group having 1 to 30 carbon atoms.
A substituted or unsubstituted aryl group having 6 to 30 carbon atoms,
5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, carbon number A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a silyloxy group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, a substituted or unsubstituted alkyl having 2 to 30 carbon atoms A carbonyloxy group, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, A substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, an amino group, A substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, 6 carbon atoms To 30 substituted or unsubstituted arylcarbonylamino groups, 1 to 30 substituted or unsubstituted aminocarbonylamino groups, 2 to 30 substituted or unsubstituted alkoxycarbonylamino groups, 7 to 30 carbon atoms substituted Or an unsubstituted aryloxycarbonylamino group, a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, a substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted with 6 to 30 carbon atoms, or Unsubstituted arylsulfonylamino, mercapto group, 1 carbon atom 30 substituted or unsubstituted alkylthio groups, substituted or unsubstituted arylthio groups having 6 to 30 carbon atoms, heterocyclic thio group, substituted or unsubstituted sulfamoyl groups having 0 to 30 carbon atoms, substituted with 1 to 30 carbon atoms Or an unsubstituted alkylsulfinyl group, a substituted or unsubstituted 6 to 30 substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, formyl A substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, or a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms bonded to the carbonyl group A substituted or unsubstituted aryloxy group having 7 to 30 carbon atoms Xycarbonyl group, substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, imide group, substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, carbon A substituted or unsubstituted phosphinyl group of the formulas 2 to 30,
A substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms; a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms; and a substituted or unsubstituted silyl group having 3 to 30 carbon atoms. Among the above functional groups, those having a hydrogen atom may be removed, and further substituted with the above group. Examples of such functional groups include
Examples thereof include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

Among them, more preferred substituents include a halogen atom, a linear, branched or cyclic, substituted or unsubstituted alkyl or alkenyl group having 1 to 30 carbon atoms, a substituted or unsubstituted group having 6 to 30 carbon atoms. Aryl group, 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group, cyano group, hydroxyl group, carbon number 1
A substituted or unsubstituted alkoxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms,
A substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, 1 to 3 carbon atoms
0 substituted or unsubstituted alkylcarbonylamino group, 6 to 30 substituted or unsubstituted arylcarbonylamino group, 1 to 30 substituted or unsubstituted aminocarbonylamino, 2 to 30 carbon substituted Or an unsubstituted alkoxycarbonylamino group, a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, substituted with 1 to 30 carbon atoms, or Unsubstituted alkylsulfonylamino, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, mercapto group, substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, substituted or unsubstituted having 6 to 30 carbon atoms Arylthio group, heterocyclic thio group, substitution of 0 to 30 carbon atoms Or an unsubstituted sulfamoyl group, a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, A substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, and having 4 to 30 carbon atoms
A heterocyclic carbonyl group having a substituted or unsubstituted carbon atom bonded to a carbonyl group, a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms And a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms and an imide group.

R _a and R _b , R _b and R _e , R _e and R _c , R _c and R _d
And R _d and R _a may be connected to each other to form a condensed ring. The ring formed by these is 3 to 1
A 0-membered carbocyclic or heterocyclic ring is preferable, and a 5- or 6-membered carbocyclic or heterocyclic ring is more preferable. When a condensed ring is formed, the condensed ring portion may have a substituent, and the substituent has the same meaning as described above.

R in the general formula (II)_a, R_b, R_c, R_das well as
R_eIs R in the general formula (I)_a, R_b, R _c, R_dAnd R_eSame as
It is like.

The compound represented by the general formula (I) or the general formula (II) can be obtained by the procedure described in New Experimental Chemistry, Vol. 14, Synthesis and Reaction of Organic Compounds [IV] (edited by The Chemical Society of Japan, Maruzen, 1978).
1879-2002, and 2191-225
It can be synthesized by the method described on page 3.

Specific examples of the compound represented by formula (I) or (II) are shown below, but the present invention is not limited thereto.

[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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The content of the compound represented by the general formula (I) or (II) is 10 to the oil-soluble dye.
５００500 mol%, preferably 10-200 mol%. Further, two or more compounds represented by the above general formula (I) or general formula (II) may be contained.

The compound represented by the general formula (I) or (II) may be present in a high boiling point solvent or an aqueous medium as in the case of the oil-soluble dye. It may be present in both the high boiling point solvent and the aqueous medium. Further, the compound represented by the general formula (I) or the general formula (II) is more preferably present in a high boiling point solvent as in the case of the oil-soluble dye.
Alternatively, the compound represented by the general formula (II) preferably has high hydrophobicity and high solubility in a high-boiling organic solvent.

<Oil-Soluble Dye> The oil-soluble dye used in the present invention is not particularly limited, and a conventionally known oil-soluble dye can be used. Examples of the yellow dye include phenols, naphthols, anilines, pyrazolones, pyridones, aryl or hetarylazo dyes having open-chain active methylene compounds as coupling components; for example, open-chain active methylene compounds as coupling components. Azomethine dyes; for example, methine dyes such as benzylidene dyes and monomethine oxonol dyes; and quinone dyes such as naphthoquinone dyes and anthraquinone dyes. Other types of dyes include quinophthalone dyes and nitro / nitroso dyes. dye,
Acridine dyes and acridinone dyes can be exemplified.

Examples of magenta dyes include 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 and 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, anthrapyridone; and dioxazine dyes And condensed polycyclic dyes.

Examples of cyan dyes include indoaniline dyes, indophenol dyes and azomethine dyes having pyrrolotriazoles as coupling components; polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes; diphenylmethane dyes and triphenylmethane dyes Phthalocyanine dyes; anthraquinone dyes; for example, aryl or hetenylazo dyes having phenols, naphthols, and anilines as coupling components, and indigo / thioindigo dyes.

Each of the oil-soluble dyes described above may exhibit each color of yellow, magenta and cyan only after a part of the chromophore is dissociated. In this case, the counter cation may be an alkali metal or ammonium. It may be an inorganic cation, an organic cation such as a pyridinium or quaternary ammonium salt, or a polymer cation having such a partial structure.

Although not limited to the following, preferred specific examples of the oil-soluble dye include C.I. I. Solvent
Black 3, 7, 27, 29 and 34; I. Solvent Yellow 14, 16, 19, 29, 30, 56,
82, 93 and 162; I. Solvent Red 1,3,8,18,24,27,43,49,51,7
2, 73, 109, 122, 132 and 218;
I. Solvent Violet 3; C.I. I. Solvent Blue 2, 11, 25, 35 and 70; C.I. I. Solvent Green 3 and 7; and C.I. I. Solvent Orange 2 and the like. Of these, particularly preferred are Nubian Black PC-0850, Oil Black HBB, O
il Yellow 129, Oil Yellow 105, Oil Pink 312, Oil R
ed 5B, Oil Sarcret 308, Vali Fast Blue 2606, Oil B
lue BOS (manufactured by Orient Chemical Co., Ltd.), Neopen Yellow 0
75, Neopen Mazenta SE1378, Neopen Blue 808, Neopen
BlueFF4012, 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. I. Disperse Yellow 5, 42, 54, 64, 79, 82, 83, 93,
99, 100, 119, 122, 124, 126, 16
0,184: 1,186,198,199,201,2
04, 224 and 237; I. Disperse Orange 13, 29, 31: 1, 33, 49, 54, 55, 6
6, 73, 118, 119 and 163; I. Disperse Red 54, 60, 72, 73, 86, 88, 9
1,92,93,111,126,127,134,1
35,143,145,152,153,154,15
9,164,167,177,181,204,20
6,207,221,239,240,258,27
7,278,283,311,323,343,34
8, 356 and 362; I. Disperse Violet 33; I. 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, 22
4,225,257,266,267,287,35
4,358,365 and 368; I. Disperse Green 6: 1 and 9;

Among the above oil-soluble dyes, those represented by the general formula (II)
It is preferably a compound represented by I). In the above general formula (III), X represents the residue of a color photographic coupler, A represents an -NR ⁴ R ⁵ or a hydroxyl group, R ⁴ and R ⁵ are each independently a hydrogen atom, an aliphatic group, Represents an aromatic group or a heterocyclic group. A is preferably -NR ⁴ R ^5. R ⁴ and R ⁵ are preferably each independently a hydrogen atom or an aliphatic group, more preferably a hydrogen atom, an alkyl group or a substituted alkyl group, and more preferably have 1 to 18 carbon atoms. Most preferably, the alkyl group is a substituted alkyl group having 1 to 18 carbon atoms.

In the general formula (III), B ¹ is ＝ C (R
⁶⁾ - or = N- and represents, B ² is -C (R ⁷⁾ = or -
N =. It is preferred that B ¹ and B ² do not simultaneously become -N =, more preferably B ¹ becomes = C (R ⁶ )-and B ² becomes -C (R ⁷ ) =. In this case, in the general formula (III), R ² , R ³ , R ⁶ and R ⁷ each independently represent a logen atom, an aliphatic group, an aromatic group, a heterocyclic group, cyano, —O
R ⁵¹ , -SR ⁵² , -CO ₂ R ⁵³ , -OCOR ⁵⁴ , -NR
⁵⁵ R ⁵⁶ , -CONR ⁵⁷ R ⁵⁸ , -SO ₂ R ⁵⁹ , -SO ₂ NR
⁶⁰ R ⁶¹ , -NR ⁶² CONR ⁶³ R ⁶⁴ , -NR ⁶⁵ CO
₂ R ⁶⁶ , -COR ⁶⁷ , -NR ⁶⁸ COR ⁶⁹ or -NR ⁷⁰ S
O ₂ R ⁷¹ , wherein R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R
⁵⁶ , ^R57 , ^R58 , ^R59 , ^R60 , ^R61 , ^R62 , ^R63 ,
R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ and R
¹ is each independently a hydrogen atom, an aliphatic group or an aromatic group.

The above R^TwoAnd R⁷Are, independently of each other,
Hydrogen atom, halogen atom, aliphatic group, -OR⁵¹, -N
R⁶²CONR⁶³R⁶⁴, -NR⁶⁵CO_TwoR⁶⁶, -NR⁶⁸C
OR^{6 9}Or -NR⁷⁰SO_TwoR⁷¹Is preferably
Hydrogen atom, fluorine atom, chlorine atom, alkyl group,
Alkyl group, -NR⁶²CONR⁶³R⁶⁴Or -NR⁶⁸COR
⁶⁹And more preferably a hydrogen atom, a chlorine atom,
An alkyl group having 1 to 10 carbon atoms or 1 to 1 carbon atoms
More preferably, it is a substituted alkyl group of 0.
, An alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
Is most preferably a substituted alkyl group.

R ³ and R ⁶ are each independently preferably a hydrogen atom, a halogen atom or an aliphatic group, preferably a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group or a substituted alkyl group. Is more preferable, a hydrogen atom, a chlorine atom, an alkyl group having 1 to 10 carbon atoms, further preferably a substituted alkyl group having 1 to 10 carbon atoms, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, Most preferably, it is a substituted alkyl group having 1 to 4 carbon atoms.

In the general formula (III), R ² and R ³ , R ³
And R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ^6, and R ⁶ and R ⁷ can be bonded to each other to form a ring. The combination forming a ring is preferably R ³ and R ⁴ , R ⁴ and R ⁵ or R ⁵ and R ⁶ . The ring formed by combining R ² and R ³ , or R ⁶ and R ⁷ , is preferably a 5- or 6-membered ring.
The ring is preferably an aromatic ring (eg, benzene ring) or an unsaturated heterocyclic ring (eg, pyridine ring, imidazole ring, thiazole ring, pyrimidine ring, pyrrole ring, furan ring). The ring formed by combining R ³ and R ⁴ or R ⁵ and R ⁶ with each other is preferably a 5- or 6-membered ring.
Examples of the ring include a tetrahydroquinoline ring and a dihydroindole ring. The ring formed by combining R ⁴ and R ⁵ with each other is preferably a 5- or 6-membered ring. Examples of the ring include a pyrrolidine ring, a piperidine ring and a morpholine ring.

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 alkyl group may have a branch or may form a ring. The alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 18 carbon atoms. The alkyl part of the substituted alkyl group is the same as the above-mentioned alkyl group. The alkenyl group may have a branch or may form a ring. The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 18 carbon atoms. The alkenyl part of the substituted alkenyl group is the same as the above alkenyl group. The alkynyl group may have a branch or may form a ring. The alkynyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 18 carbon atoms. The alkynyl part of the substituted alkynyl group is the same as the alkynyl group.

The alkyl part of the aralkyl group and the substituted aralkyl group is the same as the above-mentioned alkyl group. The aryl part of the aralkyl group and the substituted aralkyl group is the same as the following aryl group. Examples of the substituent of the alkyl portion of the substituted alkyl group, substituted alkenyl group, substituted alkynyl group and substituted aralkyl group include a halogen atom, cyano,
Nitro, heterocyclic group, -OR ¹¹¹ , -SR ¹¹² , -CO ₂ R
^{113, -NR 114 R 115, -CONR} 116 R 1 17, -SO 2 R
¹¹⁸ and -SO ₂ NR ¹¹⁹ R ¹²⁰ include. R ¹¹¹ ,
^R112 , ^R113 , ^R114 , ^R115 , ^R116 , ^R117 , ^R118 ,
R ¹¹⁹ and R ¹²⁰ are each independently a hydrogen atom, an aliphatic group or an aromatic group. 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, the 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 moiety of the substituted aryl group is
The same as the above aryl group. The examples of the halogen atom of the substituents of the substituted aryl group, cyano, nitro, aliphatic group, heterocyclic ^{group, -OR 121, -SR 122, -CO} 2 R 123,
—NR ¹²⁴ R ¹²⁵ , —CONR ¹²⁶ R ¹²⁷ , —SO ₂ R ¹²⁸ and —SO ₂ NR ¹²⁹ R ¹³⁰ are included. R ^121, R ^{12 2,} R
¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ and R ¹³⁰ are each independently a hydrogen atom, an aliphatic group or an aromatic group.

In the present specification, the heterocyclic group preferably contains a 5- or 6-membered saturated or 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 B,
N, O, S, Se and Te are included. N, O and S are preferred as heteroatoms. The heterocyclic ring preferably has a free valence (monovalent) at a carbon atom (the heterocyclic group is bonded at the carbon atom). Examples of saturated heterocycles include:
A pyrrolidine ring, a morpholine ring, a 2-bora-1,3-dioxolane ring and a 1,3-thiazolidine ring are included. Examples of the unsaturated heterocyclic ring include an imidazole ring, a thiazole ring,
It includes a benzothiazole ring, a benzoxazole ring, a benzotriazole ring, a benzoselenazole ring, a pyridine ring, a pyrimidine ring and a quinoline ring. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, cyano, nitro, an aliphatic group, an aromatic group, a heterocyclic group,
-OR ¹³¹ , -SR ¹³² , -CO ₂ R ¹³³ , -NR
¹³⁴ R ¹³⁵ , -CONR ¹³⁶ R ¹³⁷ , -SO ₂ R ¹³⁸ and -S
O ₂ NR ^{13 9} R ¹⁴⁰ are included. R ¹³¹ , R ¹³² , R ¹³³ , R
¹³⁴ , R ¹³⁵ , R ¹³⁶ , R ¹³⁷ , R ¹³⁸ , R ¹³⁹ and R
¹⁴⁰ is each independently a hydrogen atom, an aliphatic group or an aromatic group.

In the general formula (III), the coupler represented by X is preferably the following coupler. 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, EP-A-498,381 A1, p. 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)) and couplers represented by formulas (II) to (IV) in columns 7 to 36 of column 7 of U.S. Pat. No. 4,476,219 (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),
-4, -6 (p. 26), M-7 (p. 27), and M-45 (19
(M-1) (page 6) of JP-A-5-204106, M-22 of paragraph 0237 of JP-A-4-36631, U.S. Pat.Nos. 3,061,432 and 3,725,067.
issue.

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); JP-A-4-43345, C-7,10 (page 35), 34, 35 (37
(Ip), (I-1), (I-17) (pages 42 to 43); a coupler represented by the general formula (Ia) or (Ib) of claim 1 of JP-A-6-67385.

In addition, JP-A-62-215272 (page 91), JP-A-2-33144 (pages 3 and 30), EP355,660A (pages 4, 5, 45 and 47)
The couplers described on p.) Are also useful.

As the magenta dye, a compound represented by the following general formula (IV) is particularly preferably used.
General formula (IV)

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In the general formula (IV), R¹Is hydrogen
Atom, aliphatic group, aromatic group, heterocyclic group, cyano, -OR
¹¹, -SR¹², -CO_TwoR¹³, -OCOR¹⁴, -NR^Fifteen
R¹⁶, -CONR¹⁷R¹⁸, -SO_TwoR¹⁹, -SO_TwoNR²⁰
R^{twenty one}, -NR^{twenty two}CONR^{twenty three}R ^{twenty four}, -NR^{twenty five}CO_TwoR²⁶,
-COR²⁷, -NR²⁸COR²⁹Or -NR³⁰SO_TwoR³¹
And R¹¹, R¹², R¹³, R¹⁴, R^Fifteen, R¹⁶,
R¹⁷, R¹⁸, R¹⁹, R²⁰, R ^{twenty one}, R^{twenty two}, R^{twenty three}, R^{twenty four}, R
^{twenty five}, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰And R³¹Is German
Specifically, it is a hydrogen atom, an aliphatic group or an aromatic group. Also,
R^Two, R^Three, A, B¹And B^TwoAre each represented by the general formula (II
Is the same as I), and their preferred ranges are also the same.
You.

In the general formula (IV), Z represents an aliphatic group, an aromatic group, a heterocyclic group, cyano, -OR ⁸¹ , -S
_{^{R 82, -CO 2 R 83,}} -OCOR 84, -NR 85 R 86, -
_{^{CONR 8 7 R 88, -SO 2}} R 89, -SO 2 NR 90 R 91, -
NR ⁹² CONR ⁹³ R ⁹⁴ , -NR ⁹⁵ CO ₂ R ⁹⁶ , -COR
⁹⁷ , —NR ⁹⁸ COR ⁹⁹ or —NR ¹⁰⁰ SO ₂ R ¹⁰¹ represents a group of atoms forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may be substituted with at least one of these heterocyclic rings. And a fused ring may be formed. Where R ⁸¹ , R ⁸² ,
^R83 , ^R84 , ^R85 , ^R86 , ^R87 , ^R88 , ^R89 , ^R90 , R
^{91, R 92, R 93,} R 94, R 95, R 96, R 97, R 98,
R ⁹⁹ , R ¹⁰⁰ and R ¹⁰¹ are each independently a hydrogen atom, an aliphatic group or an aromatic group.

Of the compounds represented by formula (IV), those in which A is -NR ⁴ R ⁵ are more preferred.

Next, the compound represented by formula (IV) will be described in more detail. R ¹ is a hydrogen atom, an aliphatic group, an aromatic group, —OR ¹¹ , —SR ¹² ,
-NR ¹⁵ R ¹⁶ , -SO ₂ R ¹⁹ , -NR ²² CONR
²³ R ²⁴ , -NR ²⁵ CO ₂ R ²⁶ , -NR ²⁸ COR ²⁹ or-
It is preferably NR ³⁰ SO ₂ R ³¹ , more preferably a hydrogen atom, an aliphatic group, an aromatic group, —OR ¹¹ or —NR ¹⁵ R ¹⁶ , and a hydrogen atom, an alkyl group, a substituted alkyl group, or an aryl Group, a substituted aryl group, an alkoxy group, a substituted alkoxy group, a phenoxy group, a substituted phenoxy group, a dialkylamino group, or a substituted dialkylamino group, more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, A substituted alkyl group having 1 to 10 atoms, an aryl group having 6 to 10 carbon atoms or 6 to 10 carbon atoms
Is more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a carbon atom having 1 to 6 carbon atoms.
Most preferably, it is 6 substituted alkyl groups.

The above Z preferably forms a 5-membered nitrogen-containing heterocyclic ring, and examples of the 5-membered nitrogen-containing heterocyclic ring include an imidazole ring, a triazole ring and a tetrazole ring.

Of the compounds represented by the general formula (IV), an oil-soluble pyrazolotriazole azomethine compound represented by the following general formula (V) is particularly preferred. General formula (V)

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In the general formula (V), R ¹ , R ² ,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have the same meaning as in the above formula (III). In the above general formula (V), X ¹ and X
^2, each independently, -C (R ⁸⁾ = or represents -N =, R
⁸ represents a hydrogen atom, an aliphatic group or an aromatic group, and X ¹ and X ²
Is always -N =, and X ¹ and X ² are simultaneously -N
= Does not occur.

At this time, R ⁸ is preferably a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and is preferably a hydrogen atom, a substituted alkyl group having 1 to 150 carbon atoms, And more preferably a substituted alkyl group having 1 to 100 carbon atoms and a substituted aryl group having 1 to 100 carbon atoms.

In the general formula (V), a pyrazolotriazole azomethine compound in which X ¹ is -N = and X ² is -C (R ⁸ ) = is more preferable.

Examples of the pyrazolotriazole azomethine compounds represented by the formula (IV) will be described below.
Although (M-16) is shown, the present invention is not limited to these.

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The compound examples of the present invention are further described in Japanese Patent Application No.
No. 65189, but is not limited thereto.

The dye represented by the general formula (IV) is described in, for example, JP-A-4-126772, JP-B-7-9418.
No. 0 and Japanese Patent Application No. 11-365187 can be synthesized.

As the cyan dye, pyrrolotriazoleazomethine compounds represented by the following formulas (V-1) to (V-4) are particularly preferably used.

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In the general formulas (V-1) to (V-4), A, R ² , R ³ , B ¹ and B ² have the same meanings as in the general formula (III), and their preferred ranges are also the same. It is. In the general formulas (V-1) to (V-4), R ²⁰¹ , R ²⁰² and R ²⁰³ each independently represent R ¹ in the general formula (IV)
Is synonymous with R ²⁰¹ and R ²⁰² may combine with each other to form a ring structure.

Further, R ²⁰¹ of the pyrrolotriazole azomethine compound represented by the above general formulas (V-1) to (V-4)
Is an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.30 or more, which has sharp absorption and is more preferable. And, R of the pyrrolotriazole azomethine compound
The sum of Hammett substituent constant σ _p values of ²⁰¹ and R ²⁰² is 0.
Those having a value of 70 or more exhibit excellent hue as a cyan color, and are more preferable.

The hue will be described in more detail. The pyrrolotriazole azomethine compounds represented by the general formulas (V-1) to (V-4) are R ²⁰¹ , R ²⁰² , R ²⁰³ and R ² , R
Depending on the selection of ³ , A, B ¹ and B ² , various hues can be obtained. The pyrrolotriazole azomethine compound is preferred when R ²⁰¹ is an electron-withdrawing substituent, since the absorption waveform becomes sharper as compared with the case where R ²⁰¹ is not. The stronger the degree of electron withdrawing, the sharper the absorption waveform becomes. From this point, R ²⁰¹ has a Hammett substitution constant σ _p value of 0.3 more than an alkyl group or an aryl group.
It is preferably 0 or more electron-withdrawing groups. Further, an electron withdrawing group having a Hammett substitution constant σ _p value of 0.45 or more is more preferable, and an electron withdrawing group of 0.60 or more is most preferable.

The pyrrolotriazole azomethine compound is more preferably used as a cyan dye than as a magenta dye. In addition, the general formulas (V-1) and (V-2)
The pyrrolotriazole azomethine compound represented by the formula (1) can be used as a magenta dye. In order to make the dye of the present invention a cyan dye, the sum of Hammett substituent constant σ _p values of R ²⁰¹ and R ²⁰² is preferably 0.70 or more. If the sum of the σ _p values is less than 0.70, the absorption maximum wavelength is a short wavelength for a cyan dye and looks blue to human eyes, which is not preferable. Among them, those having a Hammett substituent constant σ _p value of R ²⁰² of 0.30 or more are preferable. The sum of Hammett substituent constant σ _p values of R ²⁰¹ and R ²⁰² is preferably 2.0 or less.

Examples of the electron-withdrawing group having a Hammett substituent constant σ _p value of 0.30 or more include an acyl group, an acyloxy group,
Carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, halogenated alkyl group, halogenated alkoxy group, aryl halide Oxy group, halogenated alkylthio group, 2
An aryl group substituted with one or more electron-withdrawing groups having a σ _p value of 0.15 or more, and a heterocyclic ring can be given.
More specifically, an acyl group (for example, acetyl, 3-phenylpropanoyl), an acyloxy group (for example, acetoxy), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) ) Carbamoyl, N-methyl-N-dodecylcarbamoyl), alkoxycarbonyl groups (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), aryloxycarbonyl groups (eg, phenoxycarbonyl), cyano group, nitro Group, alkylsulfinyl group (eg, 3-phenoxypropylsulfinyl), arylsulfinyl group (eg, 3-pentadecylphenylsulfinyl), alkylsulfonyl group (eg, methanesulfonyl) Le, C1-12alkyl), an arylsulfonyl group (e.g., benzenesulfonyl), a sulfamoyl group (e.g., N- ethylsulfamoyl,
N, N-dipropylsulfamoyl), a halogenated alkyl group (eg, trifluoromethyl, heptafluoropropyl), a halogenated alkoxy group (eg, trifluoromethyloxy), a halogenated aryloxy group (eg,
Pentafluorophenyloxy), a halogenated alkylthio group (eg, difluoromethylthio), two or more σ _p
An aryl group substituted with another electron-withdrawing group having a value of 0.15 or more (for example, 2,4-dinitrophenyl, 2,4,4)
6-trichlorophenyl, pentachlorophenyl), a heterocyclic group (for example, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl,
5-chloro-1-tetrazolyl, 1-pyrrolyl).

Examples of the electron-withdrawing group having a Hammett σ _p value of 0.45 or more include an acyl group (eg, acetyl, 3-phenylpropanoyl), an alkoxycarbonyl group (eg, methoxycarbonyl), and an aryloxycarbonyl group (eg, methoxycarbonyl). , M-chlorophenoxycarbonyl), a cyano group, a nitro group, an alkylsulfinyl group (for example, n
-Propylsulfinyl), arylsulfinyl group (eg, phenylsulfinyl), alkylsulfonyl group (eg, methanesulfonyl, n-octanesulfonyl), arylsulfonyl group (eg, benzenesulfonyl), sulfamoyl group (eg, N-ethylsulfamoyl) , N, N-dimethylsulfamoyl) and a halogenated alkyl group (eg, trifluoromethyl). Examples of the electron-withdrawing group having a Hammett substituent constant σ _p value of 0.60 or more include a cyano group (0.66), a nitro group (0.78), and a methanesulfonyl group (0.72).
Can be mentioned as an example.

The sum of the σ _p values of R ²⁰¹ and R ²⁰² is 0.7
Examples of the combination of 0 or more, R ^{20 1} is a cyano group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, selected from halogenated alkyl radical, R
²⁰² is an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
A combination selected from a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, and a halogenated alkyl group is preferred.

The pyrrolotriazole compound used in the present invention
The preferred structure of the zomethine compound is represented by the following general formula (V-1)
a) a structure represented by a)^TwoIs hydrogen atom, carbon number
An alkyl group having 1 to 4, a substituted alkyl group having 1 to 4 carbon atoms,
An alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine,
Chlorine, bromine), acylamino group having 1 to 5 carbon atoms, carbon number
1 to 5 aminocarbonylamino groups or 1 to 5 carbon atoms
R is an alkoxycarbonylamino group;^FourAnd R
^FiveAre each independently a hydrogen atom, an alkyl having 1 to 18 carbon atoms.
Or a substituted alkyl group having 1 to 18 carbon atoms;
²⁰¹And R²⁰²Is independently the Hammett substituent constant σ_p
An electron-withdrawing group having a value of 0.30 or more;^{Two 03}Is carbon
An alkyl group having 1 to 18 carbon atoms and a substituted alkyl having 1 to 18 carbon atoms
A substituted or unsubstituted aryl group having 6 to 20 carbon atoms
is there. And cyandyeWhen used as
R among the²⁰¹And R²⁰²Substituent constant σ of_pValue of
It is preferable that the sum is 0.70 or more._pSum of values
Is preferably 1.00 or more. Pyrrolotori of the present invention
The most preferred azole azomethine compounds are as follows:
A structure represented by the general formula (V-1a);^TwoIs a hydrogen source
R or a methyl group; R ^FourAnd R^FiveAre each independently charcoal
An alkyl group having a prime number of 1 to 5;²⁰¹Is a cyano group
R; R²⁰²Is an alkoxycarbonyl group; R²⁰³But
It is a reel base.

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Here, the Hammett's substituent constant used in this specification is described in Japanese Patent Application No. 11-365188, and the σ _p value and σ _m value of the present invention are also determined therein. Are identical.

Hereinafter, specific examples (Cy-1) to (Cy-1) of the pyrrolotriazole azomethine compound used in the present invention will be described.
-9), but these are for describing the present invention in detail, and the present invention is not limited by these.

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The above compound examples are disclosed in Japanese Patent Application No. 11-36518.
No. 8, but not limited thereto.

The pyrrolotriazole azomethine dyes represented by the general formulas (V-1) to (V-4) are disclosed in JP-A-5-17.
No. 7959, No. 9-292679, No. 10-6292
No. 6 and Japanese Patent Application No. 11-365188 can be synthesized with reference to the methods described therein.

The content of the oil-soluble dye used in the present invention is 0.05 to 50% by weight, preferably 0.1 to 10% by weight, based on the ink.

<High-boiling point organic solvent> The high-boiling point organic solvent used in the present invention preferably has a boiling point of 150 ° C or higher, more preferably 170 ° C or higher. As the high boiling organic solvent used in the present invention, phthalic acid esters (for example,
Dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-tert-
Amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or 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-ethylhexyl phenyl 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) Phenoxy) butyric acid, 2-ethoxyoctanedecanoic acid), alkyl phosphoric acids (for example, di-2
(Ethylhexyl) phosphoric acid, diphenyl phosphoric acid) and the like. These high-boiling organic solvents may be used alone or in combination of two or more, for example,
A combination of tricresyl phosphate and dibutyl phthalate, a combination of trioctyl phosphate and di (2-ethylhexyl) sebacate, and a combination of dibutyl phthalate and poly (Nt-butylacrylamide) are exemplified.

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, 2,533,514, and 2,772,163. Same 2,835,579
No. 3,594,171, No. 3,676,137, No. 3,689,
No. 271, No. 3,700,454, No. 3,748,141, No. 3,
764,336, 3,765,897, 3,912,515, 3,936,303, 4,004,928, 4,080,209
Nos. 4,127,413, 4,193,802, 4,20
No. 7,393, No. 4,220,711, No. 4,239,851, No.
4,278,757, 4,353,979, 4,363,873,
No.4,430,421, No.4,430,422, No.4,464,464
No. 4,483,918, No. 4,540,657, No. 4,684,
Nos. 606, 4,728,599, 4,745,049, 4,
935,321, 5,013,639, EP 276,319A
No. 286,253A, No. 289,820A, No. 309,158A
No. 309,159A, No. 309,160A, No. 509,311A
No. 510,576A, East German Patent No. 147,009, No. 157,
No. 147, No. 159,573, No. 225,240A, UK Patent No.
2,091,124A, JP-A-48-47335, JP-A-50-26530, JP-A-51
-25133, 51-26036, 51-27921, 51-27922
No. 51-149028, No. 52-46816, No. 53-1520, No.
53-1521, 53-15127, 53-146622, 54-913
No. 25, No. 54-106228, No. 54-118246, No. 55-59464
No. 56-64333, No. 56-81836, No. 59-204041, No.
61-84641, 62-118345, 62-247364, 63-1
67357, 63-214744, 63-301941, 64-945
No. 2, No. 64-9454, No. 64-68745, JP-A-1-101543
No. 1-102454, No. 2-792, No. 2-4239, No. 2-4354
No. 1, No. 4-29237, No. 4-30165, No. 4-232946, No. 4
-346338 and the like.

The upper limit of the weight ratio of the total amount of the high boiling organic solvent to the oil-soluble dye used in the present invention is 0.01 to 1
The amount is preferably 0 times, more preferably 0.05 to 5 times.

<Other Components> In the present invention, from the viewpoint of emulsifiability, a low-boiling organic solvent can be used in combination with the high-boiling organic solvent. The low-boiling organic solvent is an organic solvent having a boiling point of about 160 ° C. or less (usually about 30 ° C. or more) at normal pressure, and includes, for example, esters (eg, ethyl acetate, butyl acetate, ethyl propionate, β-
Ethoxyethyl acetate, methyl cellosolve acetate), alcohols (eg, isopropyl alcohol,
n-butyl alcohol, sec-butyl alcohol),
Ketones (e.g., methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone), amides (e.g., dimethylformamide, N-methylpyrrolidone), ethers (e.g., tetrahydrofuran, dioxane) and the like are preferably used, but are not limited thereto.

The emulsification and dispersion are performed by dissolving the oil phase obtained by dissolving the oil-soluble dye in the high-boiling organic solvent or, in some cases, in a mixed solvent of the high-boiling organic solvent and the low-boiling organic solvent, by adding water to the aqueous medium. It is performed by dispersing in a phase to form micro oil droplets (the dispersed particles) of the oil phase. The method of adding the oil phase to the aqueous phase is generally used to form the fine oil droplets (the dispersed particles) of the oil phase. However, the aqueous phase is dropped into the oil phase. A so-called phase inversion emulsification method can also be preferably used.

At the time of the emulsification and dispersion, one or both of the water phase and the oil phase may contain a surfactant, a wetting agent,
Additives such as dye stabilizers, emulsion stabilizers, preservatives and fungicides can be added as necessary.

Examples of the surfactant include fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonic acid formalin condensates, Anionic surfactants such as oxyethylene alkyl sulfates,
Nonionics such as 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, and oxyethylene oxypropylene block copolymer Surfactants are preferred. SURFYNO, an acetylene-based polyoxyethylene oxide surfactant,
LS (Air Products & Chemicals)
Is also preferably used. Also, N, N-dimethyl-
Amine oxide type amphoteric surfactants such as N-alkylamine oxide are also preferable. Further, Japanese Unexamined Patent Publication No.
No. 57,636, pages (37) to (38), Research Disclosure No. 308119 (1989) may be used as the surfactant.

In the present invention, 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, for example, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, polyacrylic acid, polyacrylamide, and copolymers thereof are preferably used. It is also preferable to use natural water-soluble polymers such as polysaccharides, casein and gelatin. Further, for stabilizing the dye dispersion, acrylic acid, ester, methacrylic ester, vinyl ester, acrylamide, methacrylamide, olefin, styrene, which are substantially insoluble in an aqueous medium.
Compounds obtained by polymerization of vinyl ether and acrylonitrile derivatives can also be used. These polymers desirably contain SO ₂ and COO. When these polymers that are substantially insoluble in an aqueous medium are used in combination, 0.1 to 20 of the high boiling organic solvent may be used.
%, Preferably 0.1 to 10% by weight.
More preferably, it is used in% by weight.

In the case of dispersing the oil-soluble dye into an aqueous ink by the emulsification and dispersion, what is particularly important is its particle size control. In order to increase the color purity and density when an image is formed by the inkjet recording method, it is preferable to reduce the average particle size of the dispersed particles, and specifically, the volume average particle size is 5 to 10
It is preferably in the range of 0 nm, and most preferably in the range of 1 to 50 nm. The volume average particle size is the average particle size weighted by the particle volume, and is obtained by dividing the sum of the diameters of the individual particles multiplied by the volume of the particles in the aggregate of the particles by the total volume of the particles. For the volume average particle size, see "Chemistry of Polymer Latex" (by Soichi Muroi)
Polymer Publishing Association) ”on page 119. Methods for measuring the volume average particle size and the particle size distribution of the dispersed particles include static light scattering method, dynamic light scattering method, and centrifugal sedimentation method, and are described in Experimental Chemistry Course, 4th edition, pp. 417-418. It can be easily measured by a known method such as using a method. For example, when the dye concentration in the ink is 0.1 to 1% by weight.
, And easily measured with a commercially available volume average particle size analyzer (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.

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 the coarse particles clog the nozzles of the head or form dirt even if they are not clogged, thereby causing non-ejection of the inkjet ink and / or skew of the ejection, which has a significant effect on printing performance. In order to prevent this, it is preferable to suppress the number of particles having a size of 5 μm or more to 10 or less and the number of particles having a size of 1 μm or more 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 the emulsification and dispersion, or may be performed immediately after filling the ink cartridge after adding various additives such as a wetting agent and a surfactant to the emulsification and dispersion. As an effective means for reducing the average particle size of the dispersed particles and eliminating coarse particles, an emulsifying and dispersing apparatus that performs mechanical stirring can be suitably used.

As the emulsifying and dispersing 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. Dispersing devices are preferred, and among them, a high-pressure homogenizer is particularly preferred.

The high-pressure homogenizer is US-453.
No. 3,254, JP-A-6-47264, etc., a detailed mechanism is described, but as a commercially available device, a Gaulin homogenizer (APV GAULIN INC.),
Microfluidizer (MICROFLUIDEX
INC. ), Ultimateizer (Sugino Machine Co., Ltd.) and the like.

In recent years, US Pat.
The high-pressure homogenizer having a mechanism for atomization in an ultra-high-pressure jet stream as described in the above item is particularly effective for the emulsification and dispersion of the present invention. DeBEE2000 (BEE) is an example of an emulsifying apparatus using this ultrahigh-pressure jet stream.
INTERNATIONAL LTD. ).

The pressure for emulsifying and dispersing using the high-pressure emulsifying and dispersing apparatus is preferably 50 MPa or more (500 bar or more), and 60 MPa or more (600 bar or more).
Is more preferable, and 180 Mpa or more (1800 bar or more) is still more preferable. In the present invention, it is particularly preferable to use two or more emulsifiers in combination during the emulsification and dispersion, for example, by emulsifying with a stirring emulsifier and then passing through a high-pressure homogenizer. Further, it is also preferable that the emulsion is once emulsified and dispersed by these emulsifying apparatuses, and then an additive such as a wetting agent or a surfactant is added. Then, the ink is passed through a high-pressure homogenizer again while the ink-jet ink is filled in the cartridge.

When the low-boiling organic solvent is contained in addition to the high-boiling organic solvent during the emulsification and dispersion, the low-boiling solvent is substantially removed from the viewpoint of stability and safety and health of the emulsion. Is preferred. As a method for substantially removing the low-boiling solvent, various known methods can be employed depending on the type of the low-boiling organic solvent, for example, an evaporation method, a vacuum evaporation method, an ultrafiltration method, and the like. . The step of removing the low-boiling organic solvent is preferably performed as soon as possible immediately after emulsification.

The ink-jet ink of the present invention can be suitably used as an aqueous ink for writing, an aqueous printing ink, an ink for information recording and the like. The ink-jet ink of the present invention may further contain other components, if necessary, in addition to the above components. The other components include a drying inhibitor, a penetration enhancer, an ultraviolet absorber, an antioxidant, a fungicide, a pH regulator, a surface tension regulator, a defoamer, a viscosity regulator, a dispersant, and a dispersion stabilizer. And known additives such as a rust preventive and a chelating agent.

The above-mentioned anti-drying agent is suitably used for the purpose of preventing clogging due to drying of the ink at the ink ejection port of the nozzle used in the ink jet recording method. As the drying inhibitor, a water-soluble organic solvent having a lower vapor pressure than water is preferable. Specific examples of the drying inhibitor 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, a sulfur-containing compound such as sulfolane, dimethylsulfoxide and 3-sulfolene, a polyfunctional compound such as diacetone alcohol and diethanolamine, and a urea derivative. 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 inkjet ink in an amount of 10 to 50% by weight.

Examples of the penetration enhancer include alcohols such as ethanol, isopropanol, butanol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether and 1,2-hexanediol, sodium lauryl sulfate, sodium oleate and the above-mentioned emulsified dispersion. Nonionic surfactants listed as surfactants for use. These have sufficient effects when added in an amount of 10 to 30% by weight to the ink for inkjet, and are preferably used within a range that does not cause bleeding of prints or paper missing (print-through).

The above-mentioned ultraviolet absorber is used for improving the storability of an image, for example, as 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 emitting fluorescent light by absorbing ultraviolet light represented by stilbene-based and benzoxazole-based compounds, so-called fluorescent whitening agents, and the like are also included.

The antioxidant is used for the purpose of improving the storability of an image, and examples thereof include various organic and metal complex antifading agents. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, heterocycles, and the like. . Examples of the metal complex-based anti-fading agent include a nickel complex, a zinc complex, and the like. 17643, VII I to J
No., the same No. 15162; 650 of 18716
No. in the left column of the page. No. 36544, page 527; 30
No. 7105, page 872; Compounds described in the patent cited in US Pat. No. 15,162, and the compounds represented by the general formulas and examples of the typical compounds described on pages 127 to 137 of JP-A-62-215272 are preferred.

Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethion-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof. Is mentioned. These are present in the ink at a concentration of 0.
It is preferred to use from 02 to 1.00% by weight.

Examples of the pH adjuster include hydroxides of alkali metals such as lithium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and sodium hydrogen carbonate, and the like.
Inorganic bases such as potassium acetate, sodium silicate and disodium phosphate, and organic bases such as N-methyldiethanolamine and triethanolamine are exemplified. The pH of the inkjet ink is preferably from 6 to 10, and more preferably from 7 to 10, from the viewpoint of improving storage stability.

Examples of the surface tension modifier include nonionic, cationic and anionic surfactants. For example, the surfactant used for the above emulsification and dispersion can be used.
Those having a solubility in water at 5 ° C. of 0.5% or more are preferred. The surface tension of the inkjet ink of the present invention is:
2-6 × 10 ⁻² N / m is preferred. More preferably, 2.
5 to 4.5 × 10 ⁻² N / m.

As the dispersant and the dispersion stabilizer,
Preferable examples include the above-mentioned cations, anions, and various nonionic surfactants. Examples of the defoaming agent include chelating agents represented by fluorine-based and silicone-based compounds and EDTA.

Examples of the viscosity modifier include water-soluble polymers such as celluloses and polyvinyl alcohol, and nonionic surfactants. More specifically,
"Viscosity Control Technology" (Technical Information Association, 1999) Chapter 9 and "Chemicals for Inkjet Printers (98 Supplement)-
Survey on Material Development Trends and Prospects ”(CMC, 1997
Year) pp. 162-174. The viscosity of the inkjet ink of the present invention is preferably 3 × 10 ⁻² Pa · s or less, and more preferably 2 × 10 ⁻² Pa · s or less.

These various additives are generally added to the emulsified dispersion after emulsification of the hydrophobic dye. However, they may be added to the oil phase or the aqueous phase during emulsification and dispersion, so-called co-emulsification.

The ink-jet ink of the present invention is suitably used in the following ink-jet recording method of the present invention.

(Inkjet Recording Method) In the inkjet recording method of the present invention, recording is performed on an image receiving material using the inkjet ink of the present invention. The ink nozzles and the like used at that time are not particularly limited, and can be appropriately selected according to the purpose.

<Image-Receiving Material> The image-receiving material is not particularly limited, and is a known recording material, that is, plain paper or resin-coated paper, for example, JP-A-8-169172, JP-A-8-2.
Nos. 7693, 2-276670, 7-2
No. 76789, No. 9-323475, Japanese Unexamined Patent Publication No. Sho 62-238783, Japanese Unexamined Patent Publication No. Hei 10-1538989
JP-A-10-217473 and JP-A-10-235
Nos. 995, 10-337947 and 10-337.
JP-A Nos. 217597 and 10-337947, and the like, papers exclusively for inkjet, films, electrophotographic common paper, fabrics, glass, metals, ceramics, and the like.

In the present invention, among the above-mentioned image receiving materials, a recording paper and a recording film having an image receiving layer on a support are particularly preferable.

As the support, LBKP, NBKP
Chemical pulp, GP, PGW, RMP, TMP, CT
It consists of mechanical pulp such as MP, CMP and CGP, waste paper pulp such as DIP and the like, and if necessary, a conventionally known pigment,
Additives such as a binder, a sizing agent, a fixing agent, a cationic agent, and a paper strength enhancer may be mixed, and those manufactured by various apparatuses such as a fourdrinier paper machine and a circular net paper machine may be used. In addition to these, any of synthetic paper and plastic film sheet may be used. The thickness of the support is 10
２５０250 μm, and its basis weight is 10-2
50 g / m ² is preferred.

On the support, the image receiving layer may be provided as it is, or a back coat layer may be further provided. Further, after providing a size press or an anchor coat layer with starch, polyvinyl alcohol or the like, An image receiving layer and a back coat layer may be provided. Further, the support may be subjected to a flattening process using a calender such as a machine calender, a TG calender, and a soft calender.

Among the above-mentioned supports, paper and plastic films laminated on both sides with a polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used. It is preferable to add a white pigment (for example, titanium oxide, zinc oxide) or a coloring dye (for example, cobalt blue, ultramarine, neodymium oxide) to the polyolefin.

The image receiving layer is provided on the support,
Contains a pigment and an aqueous binder. As the pigment, a white pigment is preferable.Examples of the white pigment include calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, Inorganic white pigments such as lithopone, zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, zinc carbonate, styrene pigment, acrylic pigment,
Organic pigments such as urea resins and melamine resins are preferred. Among these white pigments, inorganic pigments are preferable, porous inorganic pigments are more preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, any of silicic anhydride obtained by a dry production method and hydrous silicic acid obtained by a wet production method can be used, but it is particularly preferable to use hydrous silicic acid.

Examples of the aqueous binder include water-soluble binders such as polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide derivatives. Polymers, water-dispersible polymers such as styrene-butadiene latex, acrylic emulsions, and the like are included. These aqueous binders may be used alone or in combination of two or more. 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, in addition to the pigment and the aqueous binder, a mordant, a waterproofing agent, a light fastness improving agent, a surfactant, and other additives.

It is preferable that the mordant is immobilized. For this purpose, a polymer mordant is preferably used. The polymer mordant is described in
No. 28325, No. 54-74430, No. 54-124
No. 726, No. 55-22766, No. 55-14233
No. 9, No. 60-23850, No. 60-23851,
No. 60-23852, No. 60-23853, No. 60
No.-57836, No. 60-60643, No. 60-11
No. 8834, No. 60-122940, No. 60-122
No. 941, No. 60-122942, No. 60-2351
No. 34, JP-A-1-161236, U.S. Pat. Nos. 2,484,430, 2,548,564 and 31,480.
No. 61, No. 3309690, No. 4115124, No. 4124386, No. 4193800, No. 42738
No. 53, No. 4,282,305, and No. 4,450,224. An image receiving material containing a polymer mordant described on pages 212 to 215 of JP-A-1-161236 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, and cationic resins are particularly preferred. Examples of the cationic resin, for example, polyamide polyamine epichlorohydrin, polyethylene imine, polyamine sulfone, dimethyl diallyl ammonium chloride polymer,
Examples thereof include cationic polyacrylamide and colloidal silica, and among these, polyamide polyamine epichlorohydrin is particularly preferable. The content of these cationic resins is 1 to 15 with respect to the total solid content of the image receiving layer.
% By weight, and particularly preferably 3 to 10% by weight.

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

The surfactant functions as a coating aid, a releasability improver, a slipperiness improver, or an antistatic agent. The surfactant is described in JP-A-62-1734.
Nos. 63 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). Regarding the organic fluoro compound, JP-B-57-9053 (columns 8 to 17) and JP-A-61-2
Nos. 0994 and 62-135826.

Examples of the other additives include a pigment dispersant, a thickener, a defoamer, a dye, a fluorescent brightener, a preservative, a pH adjuster, a matting agent, a hardener, and the like. .
The image receiving layer may be a single layer or two or more layers. The thickness of the image receiving layer is 10 to 50.
μm is preferred, and 20 to 40 μm is more preferred.

The image receiving material may be provided with a back coat layer. Examples of components that can be added to the back coat layer include a white pigment, an aqueous binder, and other additives.

Examples of the white pigment 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, and the like.
Satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrohaloisite, magnesium carbonate, magnesium hydroxide, etc. Examples include white inorganic pigments, styrene-based plastic pigments, acrylic-based plastic pigments, polyethylene, microcapsules, organic pigments such as 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,
Examples include water-soluble polymers such as cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, and polyvinylpyrrolidone, and water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion.

Other additives contained in the back coat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent whitening agent,
Preservatives, waterproofing agents, and the like.

A polymer latex may be added to the constituent layers (including the back coat layer) of the image receiving material. The polymer latex is used for the purpose of improving film physical properties such as dimensional stability, curl prevention, adhesion prevention, and film crack prevention. Regarding the polymer latex, JP-A Nos. 62-245258 and 62-131648,
It is described in each publication of JP-A-62-10066. When a polymer latex having a low glass transition temperature (40 ° C. or less) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. When a polymer latex having a high glass transition temperature is added to the back coat layer, the back coat layer can be prevented from curling.

The ink jet recording method of the present invention is not particularly limited, and is a known method, for example, a charge control method in which ink is ejected by using electrostatic attraction, a drop-on-demand method in which the vibration pressure of a piezo element is used. (Pressure pulse method), Acoustic ink jet method in which an electric signal is converted into an acoustic beam to irradiate ink to discharge ink using radiation pressure, and thermal ink that heats ink to form bubbles and uses the generated pressure Any of an inkjet method and the like may be used. The inkjet recording method includes a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue and different densities, and a method of colorless and transparent. A method using ink.

[0139]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1 [Preparation of Ink Set 101] 8 g of dye (M-6) and 5 g of dioctylsulfosuccinic acid were added to a high boiling organic solvent (s-
1)) It was dissolved at 70 ° C in 6 g, 10 g of a high boiling point organic solvent (s-2), 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 is subjected to 600 bar with a microfluidizer (MICROFLUIDEXINC).
The particles were made to pass through five times at a pressure of 5 μm 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, 64 g of glycerin, and SURFYNOL were added to the fine emulsion of the hydrophobic dye thus obtained.
465 (Air Products & Chemicals)
After adding 7 g and an additive such as urea, 900 ml of deionized water was added, and pH = 9 with 10 mol / l of KOH.
The light magenta ink according to Table 1 was produced by adjusting The volume average particle size of the obtained emulsified dispersion ink was measured using Microtrac UPA (Nikkiso Co., Ltd.) and found to be 51 nm.

Further, the kinds of the dyes to be used, the high-boiling organic solvents and the amounts of the various additives were changed, and the ink set 1 shown in Table 1 was used.
No. 01 magenta ink, light cyan ink, cyan ink, yellow ink, and black ink were prepared.

[0142]

[Table 1]

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[0144]

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Next, the dyes of the ink set 101 were changed to equimolar amounts to the dyes shown in Tables 2 and 3, and / or the compounds of the present invention (represented by the general formula (I) or (II)). The same ink set was prepared except that the compound (A) was added in an equimolar amount to the dye. Further, a comparative ink set 118 was prepared in which the volume average particle size was changed by changing the pressure during emulsification. Note that an ink set 119 according to Table 4 was prepared as a comparative ink set using a water-soluble dye.

Here, the compound of the present invention exists mainly in a high-boiling organic solvent.

[0147]

[Table 2]

[0148]

[Table 3]

[0149]

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[0150]

[Table 4]

[0151]

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[0152]

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Next, these ink sets 101 to 11
9 to an inkjet printer PM670C (EPSO
N Co., Ltd.), an image was printed on the inkjet paper photo glossy paper EX manufactured by Fuji Photo Film using the same machine, and the following evaluation was performed. 1) For printing performance, after setting the cartridge in the printer and confirming the ejection of ink from all nozzles,
0 sheets were output, and the disturbance of printing was evaluated. A: There is no printing disturbance from the start to the end of printing. B: An output with printing disturbance occurs. C: There is a printing disturbance from the printing start to the end.

2) The printing performance is as follows.
After leaving for 2 days in the same manner as the printing performance,
The printing disorder was evaluated. 3) The drying property was evaluated by visual observation of the stain when touched with a finger immediately after printing. 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 10 seconds, and then the bleeding of the image was visually evaluated.

6) Regarding the image storability, print samples of yellow, magenta, cyan and black were prepared.
The following evaluation was performed. Regarding dark heat preservation, 80 ° C 1
The ratio of the concentration before and after the sample was stored for 14 days under the condition of 5% RH was determined by the following method, and expressed as a fading rate (%). Fading rate = (density after standing at 80 ° C., 15% RH for 14 days) / density immediately after printing × 100 The results obtained are shown in Tables 5 and 6.

[0156]

[Table 5]

[0157]

[Table 6]

It can be seen that when the ink-jet ink of the present invention is used, excellent printing performance can be obtained, and that the ink exhibits excellent performance in terms of water resistance and fastness.
Further, when the inkjet ink of the present invention is used, there is no bleeding when outputting fine lines, and the image fastness is improved. Furthermore, when a compound having a structure of M-6 was used as a magenta dye and Cy-1 was used as a cyan dye, a particularly remarkable improvement effect was observed.

(Example 2) The same ink produced in Example 1 was applied to an ink jet printer BJ-F850 (CA
(Non Corporation) cartridge, the image was printed on Fuji Photo Film inkjet paper photo glossy paper EX by the same machine, and the same evaluation as in Example 1 was performed. The same result as in Example 1 was obtained. Was.

[0160]

According to the present invention, it is possible to provide an ink jet ink excellent in image quality, water resistance and image fastness, and an ink jet recording method using the same.

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[Procedure amendment]

[Submission date] December 1, 2000 (200.12.
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 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2C056 EA05 EA13 FC01 FC02 2H086 BA52 BA56 BA59 BA60 4J039 BC02 BC03 BC05 BC20 BC31 BC33 BC36 BC44 BC50 BC51 BC52 BC53 BC54 BC55 BC65 BC68 BC69 BC72 BC73 BC74 BC75 BC76 BC79 BD02 BE07 BE12 CA06 EA38 EA42 EA43 GA24

Claims (6)

[Claims] 1. An ink-jet ink comprising an oil-soluble dye dissolved in a high-boiling solvent in an aqueous medium and containing a compound represented by the following general formula (I). General formula (I) In (formula (I), X represents N-R _d, O or S, Y represents C-R _e or _{N .R a, R b, R} c, R d
And R _e each independently represent a hydrogen atom or a substituent, and R _a and R _b , R _b and R _e , R _e and R _c , R _c and R _d and R
_d and _Ra may be bonded to each other to form a ring. ) 2. The ink-jet ink according to claim 1, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II). General formula (II) In (general formula (II), X represents N-R _d, O or S, represents R _a, R _b, R _c, a hydrogen atom or a substituent each R _d and R _e independently, and R _a R _b , R _b and R _e , R _e
And R _c , R _c and R _d, and R _d and R _a may be bonded to each other to form a ring. ) 3. The ink-jet ink according to claim 1, wherein the volume average particle size of the dispersed particles in the dye dispersion is 5 to 100 nm. 4. The ink jet printer according to claim 1, wherein the compound represented by the formula (I) or (II) is contained in substantially the same particles as the oil-soluble dye. ink. 5. The method according to claim 1, wherein the oil-soluble dye is represented by the following general formula (III):
The ink jet according to any one of claims 1 to 4,
For ink. General formula (III)(In the general formula (III), X represents a color photographic coupler.
A represents a residue,^FourR^FiveOr represents a hydroxy group,
R^FourAnd R^FiveIs independently a hydrogen atom, an aliphatic group, an aromatic
Represents a group or a heterocyclic group. B¹Is = C (R⁶)-Or =
N-, B ^TwoIs -C (R⁷) = Or -N =,
 R^Two, R^Three, R⁶And R⁷Are each independently a hydrogen atom,
Logen atom, aliphatic group, aromatic group, heterocyclic group, cyano,
-OR⁵¹, -SR⁵², -CO_TwoR⁵³, -OCOR⁵⁴, −
NR⁵⁵R⁵⁶, -CONR⁵⁷R⁵⁸, -SO_TwoR⁵⁹, -SO_Two
NR⁶⁰R⁶¹, -NR⁶²CONR⁶³R⁶⁴, -NR⁶⁵CO_Two
R⁶⁶, -COR⁶⁷, -NR⁶⁸COR⁶⁹Or -NR⁷⁰SO
_TwoR⁷¹And R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶,
R⁵⁷, R⁵⁸, R⁵⁹, R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R
⁶⁵, R⁶⁶, R⁶⁷, R⁶⁸, R⁶⁹, R⁷⁰And R⁷¹Is German
In addition, it represents a hydrogen atom, an aliphatic group or an aromatic group. R^TwoWhen
R^Three, R^ThreeAnd R^Four, R^FourAnd R^Five, R^FiveAnd R⁶And R⁶And R⁷Are
They may combine together to form a ring. ) 6. An ink-jet recording method comprising using an ink-jet ink according to claim 1 for recording on an image-receiving material having an image-receiving layer containing white inorganic pigment particles on a support. Method.