JPH11116873A - Ink-jet ink and ink-jet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject product suitable for forming an image good in magenta hue and having high fastness by compounding a pigment having a specific structure. SOLUTION: This ink-jet ink contains a pigment of formula I [R1 to R3 are each H or a substituting group; X is hydroxy or NR4 R5 (R4 and R5 are each an aliphatic group or an aromatic group); (n)=0-4]. A compound in which R1 is an alkyl, an acylamino or the like, R2 is an alkyl, a halogen or the like, R3 is H, an alkyl or the like, and X is hydroxy or NR4 R5 (R4 and R5 are each an alkyl) is preferable. Further, when used as a water-soluble pigment, a compound in which at least one of R1 to R5 has sulfo is preferable. When used as an oil-soluble pigment, a compound having no sulfo is preferable. A pigment of formula I may be produced by subjecting a pyrazolone derivative of formula II (Y is H or a leaving group) and p-aminophenol derivative of formula III to oxidative coupling reaction. A pigment of formula I is compounded preferably in an amount of 0.2-10 pts.wt. based on 100 pts.wt. of an ink.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording method, which has an excellent hue,
The present invention relates to an inkjet ink for forming an image having high robustness against water, chemicals, and the like, and an inkjet recording method using the same.

[0002]

2. Description of the Related Art Ink jet recording systems have rapidly spread and are further developed due to low material costs, high-speed recording, low noise during recording, and easy color recording. It is a recording method that is going on. 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, and a method in which droplets are sucked and ejected by electrostatic force. There are water-based inks, oil-based inks, and solid (melt-type) inks as inkjet inks.

Dyes used in ink-jet inks have high solubility in solvents, enable high-density recording, good hue, light, heat, air,
Excellent fastness to water, chemicals, etc., good fixability to image receiving materials, low bleeding, excellent storage stability as ink, no toxicity, high purity, low cost It is necessary to have requirements such as availability. However, it is extremely difficult to select a dye that meets these requirements at a high level. In particular, dyes having a good magenta hue and excellent light fastness are strongly desired.

[0004] From such a viewpoint, various ink jet dyes and pigments have been proposed and examined, but none of them satisfy all the required performances at present. For example,
Known C.I. I. It is difficult to achieve both hue and fastness by using numbered dyes and pigments, and it is very difficult especially for magenta ink.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks, and particularly to an ink-jet ink which has a good magenta hue and is suitable for forming a fast image. An object of the present invention is to provide an ink jet recording method.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have achieved the above object effectively by using an ink jet ink containing a dye represented by the following general formula (I). It has been found that the disadvantages of the prior art can be improved. The present invention is as follows.

[0007] An ink-jet ink comprising a dye represented by the following general formula (I):

[0008]

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In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a substituent, and X represents a hydroxy group or —N (R ₄ ) (R ₅ ). R ₄ and R ₅ represent an aliphatic group or an aromatic group, may be bonded to each other to form a 5- to 8-membered ring, or may be bonded to an ortho-position of the benzene ring to which X is bonded to form a 5- to 8-membered ring; A ring may be formed. n represents an integer of 0 to 4; when n is 2 to 4, R ₂ may be the same or different; and when R ₂ is substituted at the ortho position, R ₂ is bonded to 5 to 8; It may form a member ring.

[0010]

When a group in the present specification contains an aliphatic moiety, the aliphatic moiety may be linear, branched or cyclic and saturated or unsaturated. Represents alkyl, alkenyl, cycloalkyl, or cycloalkenyl, which may be unsubstituted or have a substituent. When an aryl moiety is included, the aryl moiety may be a single ring or a condensed ring, and may be unsubstituted or have a substituent. When a heterocyclic moiety is included, the heterocyclic moiety has a hetero atom (for example, a nitrogen atom, a sulfur atom, or an oxygen atom) in the ring. May be a single ring or a condensed ring,
It may be unsubstituted or have a substituent.

The substituent in the present invention may be any substitutable group, for example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group, Heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group,
Heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, aryl Sulfonamide group, heterocyclic sulfonamide group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, aliphatic sulfinyl group, aryl Sulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryloxyamino group,
Examples include a carbamoylamino group, a sulfamoylamino group, a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a dialiphatic oxyphosphinyl group, and a diaryloxyphosphinyl group.

Hereinafter, the general formula (I) will be described in detail. R ₁ is a hydrogen atom, a substituent (for example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group, a heterocyclic oxy group, an aliphatic oxycarbonyl group , Aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, heterocyclic sulfonyloxy group, aliphatic sulfonamide group, arylsulfonamide group, heterocyclic sulfonamide group, amino Group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, aliphatic thio group, arylthio group,
A hydroxyl group, a cyano group, a carboxyl group, a carbamoylamino group, a sulfamoylamino group, a sulfamoylcarbamoyl group, etc., and R ₂ represents a hydrogen atom, a substituent (for example, an aliphatic group, an aryl group, a heterocyclic group, Acyl group,
Acyloxy group, acylamino group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic Cyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, aryl sulfonamide group, heterocyclic sulfonamide group, aliphatic amino group, arylamino group, Heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group,
Cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphos A phenyl group, a diaryloxyphosphinyl group or the like), R ₃ is a hydrogen atom, a substituent (for example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, Heterocyclic oxycarbonyl group, carbamoyl group,
Aliphatic sulfonyl, arylsulfonyl, heterocyclic sulfonyl, sulfamoyl, sulfamoylcarbamoyl, carbamoylsulfamoyl, dialiphatic oxyphosphinyl, diaryloxyphosphinyl, etc.).

X represents a hydroxy group or -N (R ₄ ) (R ₅ ). R ₄ and R ₅ are an aliphatic group (an optionally substituted alkyl group having 20 or less carbon atoms, such as a methyl group, an ethyl group, a 2-methanesulfonamidoethyl group, etc.)
An alkenyl group having 20 or less carbon atoms which may have a substituent, such as an allyl group or a vinyl group, or an aromatic group (an aryl group having 26 or less carbon atoms which may have a substituent). Represents, for example, a phenyl group) and the like;
May form a 5-membered ring (for example, an indole ring or the like together with the benzene ring) by bonding to the ortho-position of the benzene ring to which X is bonded. Is also good. n represents an integer of 0 to 4;
Is 2 to 4, R ₂ may be the same or different, and when R ₂ is substituted at the ortho position, they are bonded to each other to form a 5- to 8-membered ring (for example, a naphthalene ring, (An indanone ring).

The substituents for R ₁ , R ₂ and R ₃ will be described in more detail. As the aliphatic group, an alkyl group which may have a substituent and has 30 or less carbon atoms, preferably 20 or less carbon atoms (for example, A methyl group, an i-propyl group, a t-butyl group, a dodecyl group, etc.) or an optionally substituted alkenyl group having 30 or less carbon atoms, preferably 20 or less carbon atoms (eg, vinyl group, allyl group, etc.) Wherein the aryl group is an aryl group which may have a substituent and has 35 or less carbon atoms, preferably 25 or less carbon atoms, such as a phenyl group and a 4-sulfophenyl group; and the heterocyclic group includes a substituent Having 35 or less carbon atoms, and preferably 2
A heterocyclic group having 5 or less, for example, a piperidyl group, a pyridyl group, or the like; and an acyl group which may have a substituent has 30 or less, preferably 20 or less, carbon atoms and may be, for example, an acetyl group. , A phenoxyacetyl group or the like, and the acyloxy group is an acyloxy group having 30 or less, preferably 20 or less carbon atoms which may have a substituent, for example, an acetoxy group, a benzoyloxy group or the like, and an acylamino group is An acylamino group having 30 or less, preferably 20 or less carbon atoms which may have a substituent, for example, an acetylamino group, a benzoylamino group,
A butyroylamino group or the like, and the aliphatic oxy group may have a substituent and may be an alkoxy group having 30 or less carbon atoms, preferably 20 or less carbon atoms (eg, a methoxy group, i
-Butoxy group, 2-ethylhexyloxy group, dodecyloxy group, etc.) or an alkenoxy group optionally having 30 or less carbon atoms, preferably 20 or less carbon atoms (eg, vinyloxy group, allyloxy group, etc.). ,
The aryloxy group is an aryloxy group having 35 or less, preferably 25 or less carbon atoms which may have a substituent, such as a phenoxy group and a 4-sulfophenoxy group,

The heterocyclic oxy group is an aryl group which may have a substituent and has a carbon number of 35 or less, preferably 25 or less, such as a 2-pyridyloxy group and a 4-pyridyloxy group. As the oxycarbonyl group, an optionally substituted alkoxycarbonyl group having 30 or less carbon atoms, preferably 20 or less carbon atoms (for example, methoxycarbonyl group, phenoxyethoxycarbonyl group,
Dodecyloxycarbonyl group) or an alkenoxycarbonyl group (for example, allyloxycarbonyl group or the like) having 30 or less carbon atoms, and preferably having 20 or less carbon atoms which may have a substituent. An aryloxycarbonyl group which may have a substituent and has 35 or less carbon atoms, preferably 25 or less, such as a phenoxycarbonyl group, a 4-methoxycarbonyl group, or a 3-chlorophenoxycarbonyl group; The group may be a heterocyclic oxycarbonyl group having 35 or less, preferably 25 or less carbon atoms which may have a substituent, for example, a 2-piperidyloxycarbonyl group, a 2-pyridyloxycarbonyl group, and the like.
The carbamoyl group may be a carbamoyl group having 30 or less, preferably 20 or less carbon atoms which may have a substituent, such as a dimethylcarbamoyl group and an N-methyl-N-phenylcarbamoyl group. Is an optionally substituted carbon number of 30 or less,

An alkanesulfonyl group having 20 or less carbon atoms (eg, methanesulfonyl group, butanesulfonyl group, octanesulfonyl group, etc.) is preferred, and an arylsulfonyl group having 35 carbon atoms which may have a substituent is preferred.
It is preferably an arylsulfonyl group having 25 or less, for example, a benzenesulfonyl group or a 4-methoxybenzenesulfonyl group, and the heterocyclic sulfonyl group may have a substituent of 35 or less, preferably 25 or less.
The following heterocyclic sulfonyl groups, for example, a 2-pyridinesulfonyl group and the like, and an aliphatic sulfonyloxy group which may have a substituent and has 30 or less carbon atoms, preferably an alkane sulfonyl having 20 or less carbon atoms. An oxy group (for example, a methanesulfonyloxy group, a butanesulfonyloxy group, etc.), and the arylsulfonyloxy group is an arylsulfonyloxy group having 35 or less, preferably 25 or less carbon atoms which may have a substituent. Benzenesulfonyloxy group, 2-naphthalenesulfonyloxy group and the like, and the heterocyclic sulfonyloxy group may be a heterocyclic sulfonyloxy group having 35 or less, preferably 25 or less carbon atoms which may have a substituent, for example, 2-pyridinesulfonyloxy group and the like; Carbon atoms which may have a group 3
0 or less, preferably 20 or less sulfamoyl groups such as dimethylsulfamoyl group and N-methyl-N-phenylsulfamoyl group, and the aliphatic sulfonamide group may have a substituent. An alkane sulfonamide group having 30 or less carbon atoms, preferably 20 or less carbon atoms (for example, a methane sulfonamide group, a butane sulfonamide group, a dodecane sulfonamide group, etc.), and the aryl sulfonamide group has a substituent. And a good arylsulfonamide group having 35 or less carbon atoms, preferably 25 or less, such as a benzenesulfonamide group,
A 4-methoxybenzenesulfonamide group or the like, and the heterocyclic sulfonamide group is an optionally substituted heterocyclic sulfonamide group having 35 or less, preferably 25 or less carbon atoms, such as 2-pyridinesulfone Examples of the aliphatic amino group include an amide group and the like. The aliphatic amino group may have a substituent, and may have an alkylamino group having 30 or less carbon atoms, preferably 20 or less carbon atoms (eg, a methylamino group, an i-propylamino group, a t- Butylamino group, dodecylamino group, etc.)
Alternatively, it is an alkenylamino group (e.g., allylamino group or the like) having 30 or less carbon atoms, preferably 20 or less carbon atoms which may have a substituent, and the arylamino group may have a carbon atom which may have a substituent. 35 or less, preferably 2
5 or less arylamino groups such as anilino group,
3-acetylaminoanilino group and the like,

The heterocyclic amino group is a heterocyclic amino group which may have a substituent and has 35 or less carbon atoms, preferably 25 or less carbon atoms, such as 4-piperidylamino group or 2-piperidylamino group.
Examples of the aliphatic oxycarbonylamino group include a pyridylamino group and the like, and an optionally substituted alkoxycarbonylamino group having 30 or less carbon atoms, preferably 20 or less carbon atoms (for example, methoxycarbonylamino group, i-propyloxy group). A carbonylamino group, a dodecyloxycarbonylamino group, etc. or an alkenoxycarbonylamino group optionally having 30 or less carbon atoms, preferably 20 or less carbon atoms (eg, vinyloxycarbonylamino group, allyloxycarbonyl And the aryloxycarbonylamino group is an aryloxycarbonylamino group which may have a substituent and has 35 or less carbon atoms, preferably 25 or less carbon atoms, such as a phenoxycarbonylamino group or 4-chlorophenoxy group. Carbonylamino group And the heterocyclic oxycarbonylamino group is a heterocyclic oxycarbonylamino group which may have a substituent and has a carbon number of 35 or less, preferably 25 or less, such as a 2-pyridyloxycarbonylamino group. The aliphatic sulfinyl group may have a substituent and has 30 or less carbon atoms, preferably 2 carbon atoms.
0 or less alkanesulfinyl group (for example, methanesulfinyl group, butanesulfinyl group and the like), and the arylsulfinyl group is an arylsulfinyl group having 35 or less carbon atoms and preferably 25 or less carbon atoms which may have a substituent. A benzenesulfinyl group, a 4-methoxybenzenesulfinyl group or the like, and an aliphatic thio group which may have a substituent has 30 or less carbon atoms, and preferably an alkylthio group having 20 or less carbon atoms (eg, a methylthio group, i- A propylthio group, a t-butylthio group, a dodecylthio group, etc.) or an optionally substituted alkenylthio group having 30 or less carbon atoms, preferably 20 or less carbon atoms (eg, vinylthio group, allylthio group, etc.), and arylthio The group may have a substituent and the number of carbon atoms is preferably 35 or less. 25 or less arylthio groups such as a phenylthio group and a 4-methoxyphenylthio group, and the hydroxy group, cyano group, sulfo group, carboxyl group, and aliphatic oxyamino group may have a substituent. An alkoxyamino group having 30 or less carbon atoms, preferably 20 or less carbon atoms (for example, methoxyamino group, i-
Propyloxyamino group, dodecyloxyamino group, etc.)
Or an alkenoxyamino group (e.g., an allyloxyamino group or the like) having 30 or less carbon atoms, and preferably having 20 or less carbon atoms, which may have a substituent;

The aryloxyamino group may be a substituted or unsubstituted aryloxyamino group having a carbon number of 35 or less, preferably 25 or less, such as a phenoxyamino group or a 2-naphthyloxyamino group. The amino group may be a carbamoylamino group having 30 or less, preferably 20 or less carbon atoms, which may have a substituent, for example, an N, N-dimethylcarbamoylamino group,
N-methyl-N-phenylcarbamoylamino group and the like, and the sulfamoylamino group may be a sulfamoylamino group having 30 or less, preferably 20 or less carbon atoms which may have a substituent, for example, N, N-dimethylsulfamoylamino group, N-methyl-N-phenylsulfamoylamino group and the like, and halogen atom (for example, fluorine atom, chlorine atom, bromine atom) sulfamoylcarbamoyl group has a substituent. A sulfamoylcarbamoyl group having 30 or less, preferably 20 or less carbon atoms, which may be, for example, an N, N-dimethylsulfamoylcarbamoyl group or an N-methyl-N-phenylsulfamoylcarbamoyl group; As the sulfamoyl group, an optionally substituted substituent having 30 or less carbon atoms, preferably 20 or less carbon atoms. Bamoylsulfamoyl groups such as N, N-dimethylcarbamoylsulfamoyl group and N-methyl-N-phenylcarbamoylsulfamoyl group, and the dialiphatic oxyphosphinyl group has a substituent. May be a dialkoxyphosphinyl group having 30 or less carbon atoms, preferably 20 or less carbon atoms (for example, dimethoxyphosphinyl group, diethoxyphosphinyl group, etc.). A diaryloxyphosphinyl group having 35 or less, preferably 25 or less carbon atoms, which may have a substituent, such as diphenoxyphosphinyl group.

In terms of the effect of the present invention, R ₁ is a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an acylamino group, an aliphatic oxy group, an aryloxy group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, A carbamoyl group, an arylamino group, an aliphatic oxycarbonylamino group, an aryloxycarbonylamino group, a hydroxy group, a cyano group, a carboxyl group, a carbamoylamino group, and a sulfamoylamino group are preferable, and an aliphatic group and an acylamino group. , An aliphatic oxy group, an aliphatic oxycarbonyl group, a carbamoyl group, an arylamino group, an aliphatic oxycarbonylamino group, and a cyano group, more preferably an aliphatic group, an acylamino group, an arylamino group, and a cyano group. Is most preferred. From the viewpoint of the effect of the present invention, R ₂ is preferably an aliphatic group, a halogen atom, an acylamino group, a carbamoyl group, a sulfamoyl group, or an aliphatic oxycarbonyl group. In terms of the effect of the present invention, R ₃ is a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an arylsulfonyl group, It is preferably a sulfamoyl group, a sulfamoylcarbamoyl group, or a carbamoylsulfamoyl group, and more preferably a hydrogen atom, an aliphatic group, or an aryl group. From the viewpoint of the effect of the present invention, R ₄ and R ₅ are preferably an aliphatic group or a case where they are bonded to each other to form a 5- to 6-membered ring.

In terms of the effect of the present invention, R ₁ is an aliphatic group, an acylamino group, an aliphatic oxy group, an aliphatic oxycarbonyl group, a carbamoyl group, an arylamino group, an aliphatic oxycarbonylamino group, a cyano group. , R ₂ is an aliphatic group, a halogen atom, an acylamino group, a carbamoyl group,
A sulfamoyl group or an aliphatic oxycarbonyl group, wherein R ₃ is a hydrogen atom, an aliphatic group, an aryl group, or an acyl group, and X is a hydroxy group, —N (R ₄ ) (R ₅ ) (R ₄ , R
₅ is an aliphatic group), and R ₁
Is an alkyl group, an acylamino group, an arylamino group, an alkoxycarbonyl group, a cyano group, R ₂ is an alkyl group, a halogen atom, an acylamino group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, and R ₃ is hydrogen It is more preferable that X is a hydroxy group or —N (R ₄ ) (R ₅ ) (where R ₄ and R ₅ are alkyl groups), which is an atom, an alkyl group or an aryl group.

When the dye represented by the formula (I) is used as a water-soluble dye, at least one of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ has an ionic hydrophilic group. preferable. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, and a quaternary ammonium group. In particular, it preferably has one or more sulfo groups. When the dye represented by the general formula (I) is used as an oil-soluble dye, a dye having no sulfo group is preferable. Preferred specific examples of the dye represented by formula (I) used in the present invention are shown below, but the dye of the present invention is not limited thereto.

[0022]

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[0023]

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[0024]

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[0025]

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The dye represented by the general formula (I) comprises a pyrazolone derivative represented by the following general formula (II) and a dye represented by the following general formula (III)
Can be obtained by an oxidative coupling reaction with a p-aminophenol derivative represented by the following formula or a p-phenylenediamine derivative represented by the general formula (IV).

[0027]

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The ink-jet recording method includes a method using an oil-based ink, a method using an aqueous ink, a method using a solid ink at room temperature, and the like. Is also applicable. Hereinafter, the solvent used in the ink of the present invention and its use will be described.

The liquid medium of the oil-based ink of the present invention is used by appropriately selecting it from an ordinary organic solvent as needed. Specifically, for example, ethanol, pentanol,
Alcohols such as heptanol, octanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, anis alcohol, ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol diacetate, ethylene glycol monoethyl ether acetate, propylene glycol Diacetate, etc. Recall derivatives, benzyl methyl ketone and diacetone alcohol, cyclohexanone, butyl phenyl ether, benzyl ethyl ether, ethers such as hexyl ether, ethyl acetate, amyl acetate, benzyl acetate, phenyl ethyl acetate,
Phenoxyethyl acetate, ethyl phenylacetate, benzyl propionate, ethyl benzoate, butyl benzoate, ethyl laurate, butyl laurate, isopropyl myristate, isopropyl palmitate, triethyl phosphate, tributyl phosphate, diethyl phthalate, phthalic acid Dibutyl, diethyl malonate, dipropyl malonate, diethyl diethyl malonate, diethyl succinate, dibutyl succinate, diethyl glutarate, diethyl adipate, dibutyl adipate, di (2-methoxyethyl) adipate, diethyl sebacate, maleate Esters such as diethyl phosphate, dibutyl maleate, dioctyl maleate, diethyl fumarate, dioctyl fumarate, 3-hexenyl cinnamate, petroleum ether, petroleum benzyl, tetralin, delican, 1-A Rubenzen, hydrocarbon solvents such as dimethyl naphthalene, acetonitrile, formamide, N, N- dimethylformamide, N, N- dimethylacetamide, dimethyl sulfoxide, sulfolane, propylene carbonate, N- methyl-2-pyrrolidone,
And polar solvents such as N-vinyl-2-pyrrolidone and N, N-diethyldodecaneamide. These solvents may be used alone or as a mixture of two or more.

The dye of the present invention may be used by dissolving it in the above organic solvent, or may be used by dispersing it together with a suitable dispersant. For a specific method of adjusting the organic solvent used in such an ink for ink jet, refer to
Reference can be made to the methods described in JP-A-231975 and JP-T-5-508883.

The liquid medium of the aqueous ink of the present invention is used by appropriately selecting it from water and a water-soluble organic solvent as needed. Specifically, for example, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, ethylene glycol, diethylene glycol, triethylene Glycol,
Polyhydric alcohols such as polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, 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, tri Chi glycol monomethyl ether, triethylene glycol monoethyl ether, glycol derivatives such as ethylene glycol monophenyl ether, ethanolamine, diethanolamine, triethanolamine, N- methyldiethanolamine, N- ethyldiethanolamine, morpholine, N
Amines such as -ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine, 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, Examples include polar solvents such as acetone.
Two or more of these solvents may be used together with water.

The dye of the present invention may be used by dissolving the dye of the present invention in a mixed solvent of water and the above-mentioned water-soluble organic solvent. If the dye is insoluble as it is, various dispersers (for example,
Ball mill, sand mill, attritor, roll mill,
Fine particles may be formed using an agitator mill, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, jet mill, ang mill, etc., or dispersed using an appropriate dispersant or surfactant after dissolving the dye in an organic solvent. Can be used. Specific methods for adjusting the aqueous ink used for such an ink-jet ink are described in JP-A-5-148436 and 5-29.
No. 5312, No. 7-97541, No. 7-82515
And the methods described in JP-A No. 7-118584 can be referred to.

The liquid medium of the solid ink of the present invention uses a phase-change solvent which is solid at room temperature and is molten when the ink is heated and jetted. Specifically, for example,
Beeswax, carnauba wax, rice wax, wood wax, jojoba oil, whale wax, candelilla wax, lanolin, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, natural wax such as petrolactam, polyethylene wax, chlorine Hydrocarbon, palmitic acid, stearyl acid, behenic acid, tiglic acid, 2-acetonaphthobehenic acid, 12
-Organic acids such as hydroxystearic acid, dihydroxystearic acid, dodecanol, tetradecanol, hexadecanol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, dodecenol, myricyl alcohol, tetracenol, hexadecenol, eicosenol, dococenol , Pinene glycol, hinokiol, butynediol, nonanediol, isophthalyl alcohol, mesicerin, hexanediol, decanediol, tetradecanediol, hexadecanediol, docosandiol, tetracosandiol, televisionneol, phenylglycerin, eicosandiol, Alcohols such as octanediol, phenylpropylene glycol, bisphenol A, p-α-cum Phenols such as phenol, glycerol organic acids mentioned above, ethylene glycol,

Organic acid esters such as diethylene glycol, cholesterol stearate, cholesterol palmitate, cholesterol myristate, cholesterol behenate, cholesterol fatty acid esters such as cholesterol laurate, cholesterol melysinate, saccharose stearate, saccharose palmitate,
Saccharose behenate, saccharose laurate, saccharose melinate, lactose stearate, lactose palmitate, lactose behenate, lactose laurate, saccharide fatty acid esters such as lactose melicate, benzoylacetone, diacetbenzene, benzophenone, tricosanone, heptacosanone, Ketones such as heptatriacontanone, hentriacontanone, stearone, lauron, oleamide, lauric amide, stearamide, ricinoleamide, palmitamide, tetrahydrofuranamide, erucamide, myristic amide, 12-hydroxystearic acid amide, N-discarded allyl erucamide, N
Oleyl stearamide, N, N-ethylenebis stearamide, N, N-ethylenebisstearamide, N, N-ethylenebisbehenamide, N, N
-Xylylenebisstearic acid amide, N, N-butylenebisstearic acid amide, N, N-dioleyladipamide, N, N-dioleylsebacic acid amide,
Amides such as N, N-distearyl sebacic amide, N, N-distearyl terephthalic amide, phenacetin, toluamide, acetamide, and sulfonamides such as p-toluenesulfonamide, ethylbenzenesulfonamide, butylbenzenesulfonamide, etc. No.

The phase change temperature of the solid solvent is from 60 to 200 ° C., preferably from 80 to 150 ° C. The dye of the present invention may be used by dissolving the dye of the present invention in the above-mentioned solid solvent in a molten state by heating, or may be used by dispersing or dissolving it together with an appropriate dispersant or binder. For a specific method of adjusting such an ink for ink jet, see JP-A-5-18 / 1990.
6723 and 7-70490 can be referred to.

The dye of the present invention is preferably contained in an amount of 0.2 to 10 parts by weight per 100 parts by weight of the ink. A dye other than the dye of the present invention may be appropriately added to the ink used in the present invention as desired. Various additives may be appropriately added to the ink of the present invention as desired. Such additives include viscosity adjusters, surface tension adjusters, specific resistance adjusters, film adjusters, ultraviolet absorbers, antioxidants, anti-fading agents, fungicides, rust inhibitors, dispersants, interfaces Activators and the like.

The viscosity of the ink of the present invention is preferably adjusted to 40 cp or less in the case of an aqueous ink or an oil-based ink. The surface tension of the ink of the present invention is preferably adjusted to 20 dyn / cm to 100 dyn / cm in the case of an aqueous ink or an oil-based ink.

To form a full color image, the magenta tone inks of the present invention can be used with cyan and yellow tone inks. Further, it can be used together with a black color ink to adjust the color tone.

In the ink jet recording method of the present invention, the recording paper used is not particularly limited. However, it is desirable to use coated paper from the viewpoint of image quality and image storage durability. Hereinafter, desirable modes of the recording paper will be described.

In the ink jet recording method of the present invention, it is desirable to use a recording paper containing a polymer mordant. Examples of the polymer mordant include JP-A-48-28.
No. 325, No. 54-74430, No. 54-12472
No. 6, No. 55-22766, No. 55-142339
Nos. 55-23850, 60-23851, 60-23852, 60-23853, 60-
No. 57836, No. 60-60643, No. 60-118
No. 834, No. 60-60643, No. 60-11883
No. 4, No. 60-122940, No. 60-122941
No. 60-122942, No. 60-235134
No. JP-A-1-161236, U.S. Pat.
No. 430, No. 2,548,564, No. 3,148,0
No. 61, 3,309,690, 4,115,12
No. 4, 4,124,386, 4,193,800
Nos. 4,273,853, 4,282,305
No. 4,450,224 and the like. In particular, it is desirable to use a recording paper containing a polymer mordant described in JP-A-1-161236, pages 212 to 215. This polymer mordant provides excellent image quality and improves light fastness.

In the ink jet recording method of the present invention, a recording paper containing an inorganic pigment can be used.
The type of the inorganic pigment is not particularly limited, and any inorganic pigment can be used. For example, silica pigment, alumina pigment, titanium dioxide pigment, zinc oxide pigment,
Zirconium oxide pigment, mica-like iron oxide, lead white, lead oxide pigment, cobalt oxide pigment, strontium chromate, molybdenum-based pigment, smectite, magnesium oxide pigment, calcium oxide pigment, calcium carbonate pigment, mullite, etc. Alternatively, two or more kinds can be used.

In the ink jet recording method of the present invention, recording paper containing various hydrophilic binders can be used. As the hydrophilic binder, any compound including gelatin or a derivative thereof, polyvinyl alcohol or a derivative thereof, polyalkylene oxide or a derivative thereof, and other superabsorbent polymers can be used. An example is disclosed in Japanese Patent Application Laid-Open No. 1-16.
No. 1236, pages 215 to 222 can be used.

In the image forming method of the present invention, it is desirable to use a recording paper containing a matting agent. As the matting agent, conventionally known matting agents can be used, and for example, those described in JP-A-1-161236, pages 263 to 264, can be used.

In the ink jet recording method of the present invention, recording paper hardened with a hardener can be used. There are no particular restrictions on the type of hardener, and known hardeners, for example, those described on page 222 of JP-A-1-161236 can be used.

In the image forming method of the present invention, recording paper hardened with a hardener can be used. There are no particular restrictions on the type of hardener, and any known hardeners, for example,
What is described on page 222 of -161236 can be used.

In the constituent layers of the recording medium used in the image forming method of the present invention, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of slipperiness, antistatic and the like. Specific examples of the surfactant are described in JP-A-62-1.
No. 73463, 62-183457 and the like. Further, an organic fluoro compound may be included for the above purpose. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, and JP-A-61-20.
No. 994, No. 62-135826 and the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluoro oil or a solid fluorine compound resin such as ethylene tetrafluoride resin. No.

The constituent layers (including the back layer) of the recording medium may contain various polymer latexes for the purpose of improving film physical properties such as dimensional stability, curl prevention, adhesion prevention, and film crack prevention. . Specifically, Japanese Patent Application Laid-Open No. Sho 62
-245258, 62-136648, 62
Any of the polymer latexes described in JP-A-110066 can be used. In particular, when a polymer latex having a low glass point transition (40 ° C. or less) is used for the mordant layer, the mordant layer can be prevented from cracking and curl can be improved, and if a polymer latex having a high glass transition point is used for the back layer, An anti-curl effect is obtained.

In the ink jet recording method of the present invention, a fading inhibitor may be used in the constituent layers of the recording paper used. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes. As an example,
JP-A-1-161236, pages 225 to 247, can be used.

The recording medium may use a fluorescent whitening agent. In particular, it is preferable that a fluorescent whitening agent is incorporated in the recording medium, or it is contained in ink or the like and supplied from outside to the recording medium.

In the present invention, the support of the recording medium is not particularly limited, but is a polyolefin (for example, a homopolymer such as polyethylene, polystyrene, polyethylene terephthalate, polybutene, a copolymer of any combination thereof) on both sides. And a plastic support (however, it is preferable to include a white pigment such as titanium oxide and zinc oxide and a coloring dye such as cobalt blue, ultramarine blue and neodymium oxide) in the polyolefin.

The ink-jet recording method of the present invention is not particularly limited in the recording method used, and can be used regardless of a continuous method or an on-demand method. There is no limitation on the type of the ink jet head, and the ink jet head can be preferably used for any printer including a bubble jet type, a thermal jet type, and a type using ultrasonic waves.

Recent advances in ink-jet systems have been remarkable, for example, a method of ejecting a large number of low-density inks called photo inks in a small volume, and improving image quality by using a plurality of inks having substantially the same hue and different densities. Many new methods have been proposed and put into practical use, such as a method using a colorless and transparent ink. The image forming method of the present invention is preferably used for any of these methods, but the improvement effect is remarkable particularly in a printer that prints a large amount of low-density ink at a high print speed and forms an image close to a photograph. Be demonstrated.

[0053]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these embodiments. Examples of oil-based ink Example 1 Commercially available uncoated base paper (basis weight: 64 g / m ² ) was coated with hollow fine particles of styrene-acrylate copolymer (particle size: 0.3
43 parts (weight ratio of solid content, the same applies hereinafter), 17 parts of fumed anhydrous silica (particle diameter 12 mμ), 12 parts of styrene butadiene copolymer latex, 18 parts of polyvinyl acetate latex, fine particles of polymethyl methacrylate (Particle diameter: about 8 μ) A coating solution consisting of 10 parts was coated with a solid content of 10 g /
The composition was applied using a wire bar so as to obtain m ² , thereby preparing an ink jet recording paper. Ink jet recording was carried out on this recording paper at 8 dots / mm using an electrostatic acceleration type ink jet apparatus equipped with a head having a nozzle hole diameter of 50 μm.

[Ink Liquid A] Dye (3) of the present invention 6 parts by weight Diethyl phthalate 30 parts by weight Diisopropyl adipate 44 parts by weight N, N-diethyldodecaneamide 20 parts by weight The discharge property of this ink liquid is good. A clear, high-density magenta image was obtained. Even when the paper printed with this ink was immersed in water for 10 minutes, no bleeding or running of the image was observed.

Example 2 Ink liquids B to F having the following compositions were prepared. [Ink liquid B] 6 parts by weight of the dye (2) of the present invention 4 parts by weight of the anti-fading agent (A) 70 parts by weight of dibutyl adipate 20 parts by weight of benzyl alcohol [Ink liquid C] 6 parts by weight of the dye (15) of the present invention Anti-fading agent (B) 6 parts by weight Dibutyl maleate 61 parts by weight Diethyl phthalate 22 parts by weight N-methylpyrrolidone 5 parts by weight [Ink liquid D] Dye (19) of the present invention 6 parts by weight Anti-fading agent (C) 3 Parts by weight Diethyl adipate 41 parts by weight Diethyl phthalate 30 parts by weight Dipropylene glycol monomethyl ether 20 parts by weight [Ink liquid E] Dye (21) of the present invention 6 parts by weight Dibutyl maleate 54 parts by weight Diethyl phthalate 25 parts by weight Benzyl Alcohol 15 parts by weight [Ink Liquid F] (Comparative Example) Comparative Dye (A) 6 parts by weight Dibutyl maleate 54 parts by weight Diethyl Tal acid 25 parts by weight of benzyl alcohol 15 parts by weight

[0056]

Embedded image

[0057]

Embedded image

Each of these ink liquids was printed on Fuji Photo Film inkjet paper, Super Photo Grade (photo glossy paper) in the same manner as in Example 1. Although the ink liquids B to F showed good ejection properties, the ink liquids B to F
In the case of E, a clear magenta image was obtained, whereas in the case of the ink liquid F, the sharpness was somewhat lacking. The density reduction rate after leaving these printed images in room light for 3 months was 3% or less in each case, which was good. Further, when the paper printed with these inks was immersed in water for 10 minutes, bleeding and flow of the image were considerably recognized in the case of the ink liquid F, whereas bleeding and flowing were observed in the case of the ink liquids B to E. There was not much flow.

Example of aqueous ink Example 3 An ink liquid G having the following composition was prepared. [Ink liquid G] Dye (16) of the present invention 4 parts by weight Diethylene glycol 9 parts by weight Tetraethylene glycol monobutyl ether 9 parts by weight Glycerin 7 parts by weight Diethanolamine 1 part by weight Water 70 parts by weight

After stirring the above composition for 1 hour while heating at 30 to 40 ° C., the average pore diameter was 0.8 μm and the diameter was 47 mm.
The mixture was filtered under pressure using a microfilter of the formula (1) to obtain the desired ink. Ink G except that the dye was changed as shown in Table 1.
Ink liquids H to N were prepared in the same manner as described above. Inkjet printer PM-700 using the above ink liquids G to N
C (manufactured by Seiko Epson) was used to print on Fuji Photo Film inkjet paper, Super Photo Grade (photo glossy paper) to obtain an image sample.

Hue and light fastness were evaluated using the obtained image samples. (Hue) The images obtained from the ink liquids G to L of the present invention were clearer magenta images than the images obtained from the ink liquids M and N of the comparative examples. (Light fastness) Image samples were obtained from Atlas C.I. Using an I65 weather meter, irradiate with xenon light (85,000 lux) for 3 days, measure the image density before and after xenon irradiation using a reflection densitometer (X-Rite 310TR), and determine the light stability of the image. Evaluation was made based on the dye remaining rate. The reflection density before irradiation was evaluated at three points of 1, 1.5, and 2.0. At any of the densities, the case where the dye remaining rate was 80 or more was evaluated as good, and the other cases were evaluated as x.
Was evaluated. The results are shown in Table 1. It can be seen that in the case of the ink of the present invention, an image having excellent light fastness can be obtained.

[0062]

[Table 1]

[0063]

Embedded image

On the other hand, the inks G to N were used to print on a glossy paper (MJA4S3P) for exclusive use of Seiko Epson by an ink jet printer PM-700C (manufactured by Seiko Epson) to obtain an image sample in the same manner as described above. . Both the hue and the light fastness were almost the same as those in Table 1. However, better results were obtained when Fuji Photo Film inkjet paper and Super Photo Grade (photo glossy paper) were used.

[0065]

As described above, it can be seen that the ink-jet ink of the present invention is suitable for obtaining an ink-jet image excellent in hue, light fastness, water resistance and the like.

Claims (2)

[Claims] 1. An ink-jet ink comprising a dye represented by the following general formula (I). Embedded image In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a substituent, and X represents a hydroxy group or —N (R ₄ ) (R ₅ )
Represents R ₄ and R ₅ represent an aliphatic group or an aromatic group, may be bonded to each other to form a 5- to 8-membered ring, or may be bonded to an ortho-position of the benzene ring to which X is bonded to form a 5- to 8-membered ring; A ring may be formed. n represents an integer of 0 to 4;
In the case of to 4, R ₂ may be the same or different;
_{When two} are substituted in the ortho position, they may be bonded to each other to form a 5- to 8-membered ring. 2. An ink jet recording method for recording an image on an image receiving material by ejecting ink in the form of droplets, wherein the ink is the ink according to claim 1.