JP2001106945A - Inkjet-recording liquid and recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink jet-recording liquid containing a new water-soluble dyestuff having an excellent image fastness, and to provide a method for recording by using the above recording liquid. SOLUTION: This ink jet-recording liquid contains the water-soluble dyestuff expressed by the general formulae (1) or (2) [R1, R2, R5 R6 are each a substituting group having <=8 total number of carbon atoms; (l1) is 1-3 integer; (l2), (l4) are each 0-2 integer; R3, R4, R7, R8 are each an alkyl group, phenyl group and a heterocyclic group having <=8 total number of carbon atoms and allowed to have a substituting group; X, Y are each nitrogen atom or C(R) (R is hydrogen atom or a substituting group); Q is a group of atoms necessary for forming 5- or 6-membered carbon ring or heterocyclic ring; and also the water-soluble dyestuff expressed by the general formulae (1) or (2) has at least one substituting group expressed by SO3A (A is hydrogen atom or a counter cation)].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an ink jet recording liquid containing a novel water-soluble dye having excellent image fastness.

[0002]

2. Description of the Related Art Conventionally, dyes used for color ink jet recording are known, for example, C.I. I. It has been selected from the dyes listed in the index. For example, among cyan dyes, triphenylmethane dyes having high color saturation, such as Acid Blue 9, and sulfo copper phthalocyanine dyes having high light resistance, such as Direct Blue 1
99 has been used.

On the other hand, the recent improvement in image quality of ink-jet recording has been remarkable, and in particular, prints using dedicated media have image quality close to that of photographs. The improvement in image quality is largely due to the development of special media with excellent ink absorbency, as well as the improvement of printer technology. In particular, in order to improve the ink absorbency, the image quality is most improved in a dedicated medium having a void layer.
However, the image storability on a dedicated medium having the above-mentioned void layer is still lower than that of a photograph. Even when the above-mentioned sulfo copper phthalocyanine dye having generally high fastness is used, it is necessary to further improve the image storability. Japanese Patent Application Laid-Open No. 10-183038 discloses an ink jet recording liquid containing an indoaniline dye having a substituent having 10 or more carbon atoms. However, the image storability on a dedicated medium having a void layer is disclosed. Is not satisfactory.

[0004]

Accordingly, a first object of the present invention is to provide an ink jet recording liquid containing a novel water-soluble dye having excellent image fastness. A second object is to provide an ink jet recording liquid containing a novel water-soluble dye having excellent image fastness on a void-dedicated medium.

[0005]

The object of the present invention is to provide (1) an ink jet recording liquid comprising at least one water-soluble dye represented by the following general formula (1) or (2). .

[0006]

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In the general formula (1), R ₁ and R ₂ each represent a substituent having a total carbon number of 8 or less, l ₁ represents an integer of 1 to 3, and l ₂ represents an integer of 0 to 2. When each of l ₁ and l ₂ is 2 or more, R ₁ and R ₂ may be the same or different. R ₃ and R ₄ each represent an optionally substituted alkyl group, phenyl group or heterocyclic group having a total carbon number of 8 or less. X and Y each represent a nitrogen atom and C (R). R represents a hydrogen atom or a substituent. The water-soluble dye represented by the general formula (1) has at least one substituent represented by SO ₃ A in the molecule. A represents a hydrogen atom or a counter cation.

In the general formula (2), R ₅ and R ₆ each represent a substituent having a total carbon number of 8 or less, l ₃ represents an integer of 1 to 3, and l ₄ represents an integer of 0 to 2. When each of l ₃ and l ₄ is 2 or more, R ₅ and R ₆ may be the same or different. R ₇ and R ₈ each represent an optionally substituted alkyl group, phenyl group, or heterocyclic group having a total carbon number of 8 or less. Q represents an atomic group necessary for forming a 5- or 6-membered carbocyclic or heterocyclic ring. X and Y each represent a nitrogen atom and C (R). R represents a hydrogen atom or a substituent. The water-soluble dye represented by the general formula (2) has at least one substituent represented by SO ₃ A in the molecule.
A represents a hydrogen atom or a counter cation.

(2) An ink jet recording method comprising recording on an ink jet recording paper having a porous ink absorbing layer using the ink jet recording liquid described in (1). Is achieved by

Hereinafter, the present invention will be described in detail. First, the water-soluble dye represented by the general formula (1) will be described.

[0011]

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In the general formula (1), R ₁ and R ₂ each represent a substituent having a total carbon number of 8 or less, l ₁ represents an integer of 0 to 4, and l ₂ represents an integer of 0 to 2. When each of l ₁ and l ₂ is 2 or more, R ₁ and R ₂ may be the same or different. R ₃ and R ₄ each represent an optionally substituted alkyl group, phenyl group or heterocyclic group having a total carbon number of 8 or less. X and Y each represent a nitrogen atom and C (R). R represents a hydrogen atom or a substituent. The water-soluble dye represented by the general formula (1) has at least one substituent represented by SO ₃ A in the molecule. A represents a hydrogen atom or a counter cation.

As the substituent represented by R ₁ , for example,
An alkyl group (eg, a methyl group, an ethyl group, etc.), a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an acylamino group (eg, an acetylamino group, a propanoylamino group, an i-butanoylamino group, 2-carboxypropanoylamino group, 2-carboxy-1-
Sulfopropanoylamino group, 2-sulfobenzoylamino group, 3,5-disulfobenzoylamino group, etc., sulfonylamino group (for example, methanesulfonamide group, benzenesulfonamide group, 3-carboxybenzenesulfonamide group) Ureido group (eg, phenylureido group, 4-chloro-3-cyanophenylureido group, etc.), oxycarbonylamino group (eg, ethoxycarbonylamino group, butoxycarbonylamino group, etc.), carbamoyl group (eg, methyl) Carbamoyl group, dimethylcarbamoyl group, etc.). A particularly preferred substituent among the substituents represented by R ₁ is a ureido group.

As the substituent represented by R ₂ , for example,
Alkyl groups (eg, methyl group, ethyl group, etc.), alkoxy groups (eg, methoxy group, ethoxy group), halogen atoms (eg, fluorine atom, chlorine atom, bromine atom, etc.),
An acylamino group (for example, an acetylamino group, a benzoylamino group, etc.) is exemplified.

The substituents represented by R ₁ and R ₂ include those further having a substituent. Specific examples of these substituents include, for example, an alkyl group (eg, a methyl group, an ethyl group, etc.), an alkoxy group (eg, a methoxy group, an ethoxy group), a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom) And the like) and an acylamino group (eg, an acetylamino group).

Specific examples of the alkyl group which may have a substituent represented by R ₃ and R ₄ include, for example, an ethyl group, a propyl group, a 2-methanesulfonamidoethyl group, a 2-hydroxyethyl group, Examples thereof include a 2-sulfoethyl group, a 2-methoxyethyl group, and a 2-carboxyethyl group.
Specific examples of the phenyl group which may have a substituent represented by R ₃ and R ₄ include, for example, a phenyl group and a 3-sulfophenyl group. Specific examples of the heterocyclic group which may have a substituent represented by R ₃ and R ₄ include, for example, 3
-Pyridyl group, 2-furyl group, 2-thienyl group and the like. The total number of carbon atoms in the optionally substituted alkyl group, phenyl group and heterocyclic group represented by R ₃ and R ₄ is 8 or less.

X and Y each represent a nitrogen atom or C (R).
R represents a hydrogen atom or a substituent. Preferably, X, Y
Both are C (R) or X is C (R) and Y is a nitrogen atom, and most preferably X is C (R) and Y is a nitrogen atom. Examples of the substituent represented by R include the substituents described in the description of the substituent represented by R ₂ .

In the substituent represented by SO ₃ A in the molecule of the water-soluble dye represented by the general formula (1), A represents a hydrogen atom or a counter cation. Alternatively, divalent metal ions such as lithium, sodium, potassium and ammonium ions are preferred. Next, the water-soluble dye represented by the general formula (2) will be described.

[0019]

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In the general formula (2), R ₅ and R ₆ each represent a substituent having a total carbon number of 8 or less, l ₃ represents an integer of 1 to 3, and l ₄ represents an integer of 0 to 2. When each of l ₃ and l ₄ is 2 or more, R ₅ and R ₆ may be the same or different. R ₇ and R ₈ each represent an optionally substituted alkyl group, phenyl group, or heterocyclic group having a total carbon number of 8 or less. Q represents an atomic group necessary for forming a 5- or 6-membered carbocyclic or heterocyclic ring. X and Y each represent a nitrogen atom and C (R). R represents a hydrogen atom or a substituent. The water-soluble dye represented by the general formula (2) has at least one substituent represented by SO ₃ A in the molecule.
A represents a hydrogen atom or a counter cation.

As the substituent represented by R ₅ , for example,
An alkyl group (eg, a methyl group, an ethyl group, etc.), a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an acylamino group (eg, an acetylamino group, a propanoylamino group, an i-butanoylamino group, 2-carboxypropanoylamino group, 2-carboxy-1-
Sulfopropanoylamino group, 2-sulfobenzoylamino group, 3,5-disulfobenzoylamino group, etc., sulfonylamino group (for example, methanesulfonamide group, benzenesulfonamide group, 3-carboxybenzenesulfonamide group) Ureido group (eg, phenylureido group, 4-chloro-3-cyanophenylureido group, etc.), oxycarbonylamino group (eg, ethoxycarbonylamino group, propoxycarbonylamino group, etc.), carbamoyl group (eg, A methylcarbamoyl group, a 2-sulfoethylcarbamoyl group,
2,5-disulfophenylcarbamoyl group).

The substituent represented by R ₅ is particularly preferably a carbamoyl group, and more preferably a carbamoyl group having a carbamoyl group, an acylamino group or a sulfonylamino group.

As the substituent represented by R ₆ , for example,
Alkyl groups (eg, methyl group, ethyl group, etc.), alkoxy groups (eg, methoxy group, ethoxy group), halogen atoms (eg, fluorine atom, chlorine atom, bromine atom, etc.),
An acylamino group (for example, an acetylamino group, a benzoylamino group, etc.) is exemplified.

The substituents represented by R ₅ and R ₆ include those further having a substituent. Specific examples of these substituents include, for example, an alkyl group (eg, a methyl group, an ethyl group, etc.), a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an acylamino group (eg, an acetylamino group, Propanoylamino group, i-butanoylamino group, etc.), sulfonylamino group (for example, methanesulfonylamino group, benzenesulfonamide group, etc.),
Ureido group (eg, phenylureido group, 4-chloro-3-cyanophenylureido group, etc.), oxycarbonylamino group (eg, ethoxycarbonylamino group, propoxycarbonylamino group, etc.), carbamoyl group (eg, carbamoyl group, methyl Carbamoyl group, 2-sulfoethylcarbamoyl group, 2,5-disulfophenylcarbamoyl group).

Specific examples of the alkyl group which may have a substituent represented by R ₇ and R ₈ include, for example, an ethyl group, a propyl group, a 2-methanesulfonamidoethyl group, a 2-hydroxyethyl group, Examples thereof include a 2-sulfoethyl group, a 2-methoxyethyl group, and a 2-carboxyethyl group.
Specific examples of the phenyl group which may have a substituent represented by R ₇ and R ₈ include, for example, a phenyl group and a 3-sulfophenyl group. Specific examples of the heterocyclic group which may have a substituent represented by R ₇ and R ₈ include, for example, 3
-Pyridyl group, 2-furyl group, 2-thienyl group and the like. The total number of carbon atoms in the optionally substituted alkyl group, phenyl group and heterocyclic group represented by R ₇ and R ₈ is 8 or less.

X and Y each represent a nitrogen atom or C (R).
R represents a hydrogen atom or a substituent. Preferably, X, Y
Both are C (R) or X is C (R) and Y is a nitrogen atom, and most preferably X is C (R) and Y is a nitrogen atom. Examples of the substituent represented by R include the substituents described in the description of the substituent represented by R ₂ .

In the substituent represented by SO ₃ A in the molecule of the water-soluble dye represented by the general formula (2), A represents a hydrogen atom or a counter cation. Alternatively, divalent metal ions such as lithium, sodium, potassium and ammonium ions are preferred. Hereinafter, specific compounds of the water-soluble dye represented by the general formula (1) or (2) (hereinafter, sometimes referred to as the water-soluble dye of the present invention) will be described.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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The water-soluble dye represented by the general formula (1) or (2) is obtained by combining a phenol or naphthol derivative synthesized by a known method and a p-phenylenediamine derivative synthesized by a known method in an aqueous alkaline solution or with water. It can be easily synthesized by dissolving in a mixture with a water-miscible organic solvent (eg, methanol, ethanol, etc.) and oxidative coupling with an oxidizing agent (eg, peroxodisulfate).

Hereinafter, synthesis examples of the water-soluble dye of the present invention will be described. Synthesis of Exemplified Dye 13 4.2 g of Intermediate S1 and 10% of 2.9 g of Intermediate S2
Sodium carbonate aqueous solution 100ml, methanol 50ml
Into the solution, and then add ammonium peroxodisulfate 4.5
An aqueous solution of g / 50 ml of water was added dropwise. After the dropwise addition, the mixture was stirred for 2 hours, and 50 ml of saturated saline was added thereto, followed by stirring for 2 hours. The precipitated dye was obtained by filtration. The dye was washed with 10% saline and then with diisopropyl ether to obtain Exemplified Dye 13. Elemental analysis and mass spectrum confirmed that the product was the desired product.

[0039]

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Next, an ink jet recording liquid containing at least one water-soluble dye represented by the general formula (1) or (2) (hereinafter sometimes referred to as the ink jet recording liquid of the present invention) will be described. In the inkjet recording liquid of the present invention, it is preferable to use a solvent in which water and a water-soluble organic solvent are used in combination as the solvent of the dye of the present invention.

Examples of the water-soluble organic solvent include alcohols (eg, methanol, ethanol, propanol,
Isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc., polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene) Propylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, ethylene glycol monophenyl ether, Propylene glycol monophenyl ether, etc.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentane Min Polyethyleneimine, pentamethyldiethylenetriamine, tetramethylene chill propylenediamine, etc.), amides (e.g., formamide, N, N-dimethylformamide, N, N-
Dimethylacetamide, etc.), heterocycles (eg, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (eg, dimethyl Sulfoxides), sulfones (for example,
Sulfolane), urea, acetonitrile, acetone and the like. Preferred water-soluble organic solvents among these are
Polyhydric alcohols.

These water-soluble organic solvents may be used alone or in combination of two or more. The addition amount of the water-soluble organic solvent in the ink is 5 to 6 in total of the water-soluble organic solvent.
0% by weight, preferably 10 to 30% by weight.
In the ink jet recording liquid, if the dye to be used is soluble in the solvent system, it can be used by dissolving it as it is.

The viscosity of the ink jet recording liquid of the present invention during flight is preferably 40 cps or less, more preferably 30 cps or less. Also,
The inkjet recording liquid of the present invention preferably has a surface tension during flight of 20 dyn / cm or more.
More preferably, it is 0 dyn / cm. The dye concentration in the inkjet recording liquid of the present invention is preferably in the range of 0.1 to 25% by weight, more preferably 0.5 to 10% by weight, based on the total amount of the inkjet recording liquid.

In the ink jet recording liquid of the present invention, a viscosity adjusting agent and a surface tension adjusting agent are used for the purpose of improving ejection stability, compatibility with a print head or an ink cartridge, storage stability, image storability and other various properties. It is also possible to add a specific resistance adjusting agent, a film forming agent, a dispersant, a surfactant, an ultraviolet absorber, an antioxidant, an anti-fading agent, a sunscreen agent, a rust inhibitor and the like. There is no particular limitation on the recording method using the ink jet recording liquid of the present invention, and it can be preferably used as an ink jet recording liquid for continuous type and on-demand type ink jet printers. Examples of the on-demand type include an electro-mechanical conversion type (for example, a single-cavity type, a double-cavity type, a bender type, a piston type, a shared mode type, a shared wall type, etc.), and an electro-thermal conversion type (for example, thermal type). Specific examples include an ink jet type, a bubble jet type, and the like, an electrostatic suction type (for example, an electric field control type, a slit jet type, and the like), and a discharge type (for example, a spark jet type).

[0045]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 (Preparation of Ink)-Preparation of Ink Base-Preparation of Ink Base 1 22.8 g of diethylene glycol, 18.3 g of glycerin, 17.8 g of triethylene glycol butyl ether, 0.2 g of Surfinol 465 The ink base 1 was prepared by adding ion-exchanged water and finishing to 200 g.

-Preparation of Ink- The dyes shown in Table 1 were dissolved in the ink base 1 to prepare Inks 1 to 32. At this time, the dye concentration was adjusted such that the absorbance of the ink became 250. Here, the absorbance of the ink refers to a value obtained by measuring the absorbance of the ink at λmax in a cell having an optical path length of 1 cm.

[0048]

[Table 1] Comparative Dye 1: Direct Blue 199 Comparative Dye 2: Acid Blue 9 Comparative Dye 3: JP-A-10-183038

[0049]

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Example 2 -Formation of Inkjet Image- Using the inks 1 to 32 described in Example 1, a photojet paper QP was produced using an inkjet printer MJ-810C (manufactured by Seiko Epson Corporation, electro-mechanical conversion system). An image was recorded on a thick sheet (manufactured by Konica Corporation) to obtain an image sample.

-Evaluation of ink-jet image- (Evaluation of light fastness) The image sample having a reflection density of 1.0 obtained by the above method was subjected to a fluorescent lamp fading tester at 2000 Lux for 60 hours.
Irradiation was performed for one day, and the reflection density change rate was determined as described below, and the light resistance was evaluated. Reflection density change rate = (A / B) x 100 A: Reflection density after irradiation with a fluorescent lamp fading tester B: Reflection density before irradiation The reflection density change rate in the obtained image sample is 1
Table 1 shows the relative values of 00.

[0052]

According to the ink jet recording liquid of the present invention, an image having excellent image fastness can be obtained. Also,
This excellent image fastness can be obtained even on a void-based dedicated medium.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2C056 EA13 FC01 FC06 2H086 BA02 BA15 BA53 BA56 4J039 BA29 BC05 BC12 BC16 BC19 BC20 BC31 BC33 BC36 BC37 BC44 BC50 BC51 BC54 BC55 BC65 BC74 BE06 CA03 EA34 EA44 GA24

Claims (2)

[Claims] 1. An ink jet recording liquid comprising at least one water-soluble dye represented by the following general formula (1) or (2). Embedded image In the general formula (1), R ₁ and R ₂ each represent a substituent having a total carbon number of 8 or less, l ₁ represents an integer of 1 to 3, and l ₂ represents an integer of 0 to 2. When each of l ₁ and l ₂ is 2 or more, R ₁ and R ₂ may be the same or different. R
₃ and R ₄ each represent an optionally substituted alkyl group, phenyl group, or heterocyclic group having a total carbon number of 8 or less. X and Y each represent a nitrogen atom and C (R). R represents a hydrogen atom or a substituent. The water-soluble dye represented by the general formula (1) has at least one substituent represented by SO ₃ A in the molecule. A represents a hydrogen atom or a counter cation. In the general formula (2), R ₅ and R ₆ each have a total carbon number of 8
Represents the following substituent, and l ₃ represents an integer of 1 to 3,
l ₄ represents an integer of 0 to 2. When each of l ₃ and l ₄ is 2 or more, R ₅ and R ₆ may be the same or different. R ₇ and R ₈ each represent an optionally substituted alkyl group, phenyl group or heterocyclic group having a total carbon number of 8 or less. Q
Represents an atomic group necessary for forming a 5- or 6-membered carbocyclic or heterocyclic ring. X and Y are each a nitrogen atom, C
(R). R represents a hydrogen atom or a substituent. The water-soluble dye represented by the general formula (2) has at least one substituent represented by SO ₃ A in the molecule. A represents a hydrogen atom or a counter cation. 2. An ink jet recording method using the ink jet recording liquid according to claim 1 for recording on an ink jet recording paper having a porous ink absorbing layer.