JP2001311016A - Quinophthalone compound and water-based ink using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a quinophthalone compound having a high water solubility and excellent in light fastness and a water-based ink useful as a recording liquid for an ink jet recording method using the quinophthalone compound and excellent in light fastness and preservation stability. SOLUTION: This quinophthalone compound is represented by general formula (1) wherein, X1 to X9 denote each independently hydrogen atom, a halogen atom, carboxy group, an alkoxycarbonyl group, an aminocarbonyl group, an alkylaminocarbonyl group, a group SO3Y [wherein, Y denotes hydrogen atom, an alkali metal, an alkaline earth metal or an ammonium salt residue represented by general formula (2) (wherein, R1 to R4 denotes each independently hydrogen atom or a 1-8C alkyl group which may have a substituent group)] or a group Z(CH2)nSO3Y [wherein, n denotes an integer of 1-4; Y denotes hydrogen atom, an alkali metal, an alkaline earthy metal or an ammonium salt residue represented by general formula (2); and Z denotes oxygen atom or sulfur atom], with the proviso that at least one of X1 to X9 denotes the group Z(CH2)nSO3Y}.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a quinophthalone compound, a novel water-soluble yellow quinophthalone dye having a high light resistance, a variety of inks for dyeing textiles, particularly an ink jet recording system and a quinophthalone dye suitable for the recording liquid. The present invention relates to an aqueous ink using the same.

[0002]

2. Description of the Related Art A water-based ink used for recording such as a writing instrument or an ink jet recording system is basically composed of a dye, water and an organic solvent. Due to consideration, aqueous inks using water as a main solvent have become mainstream. As the dye, a water-soluble dye such as an acid dye, a basic dye, a reactive dye, and a direct dye is generally used.

[0003] These dyes and aqueous inks are required to have various properties. In particular, the aqueous ink used for the recording liquid of the ink jet recording system has various required characteristics shown below. That is, (1) the physical properties such as viscosity, surface tension, specific conductivity, density, and pH of the ink are appropriate; (2) the long-term storage stability of the ink is good; High dissolution stability, no clogging of nozzles, (4) good fast drying on the recording material, (5) clear recorded images, good light fastness and good water fastness , Etc. However, at present, all of these required characteristics have not yet been satisfied. In particular, a water-soluble azo dye is generally used as the yellow dye, but since the azo bond is unstable to light, the yellow light resistance after printing is poor.

[0004] In order to improve the light fastness of the ink, an ink using a pigment as a dye, an ink using an oil-soluble dye as a dye, and the like have been studied. However, when a pigment is used, there are problems such as poor dispersion stability, poor storage stability, and nozzle clogging.
Further, when an oil-soluble dye is used, there is a problem in environmental hygiene such as odor due to the use of an organic solvent. In particular, the characteristics of the ink used in the ink jet recording system are greatly affected by the characteristics inherent to the dye, and it is extremely important to create a dye satisfying these conditions.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a quinophthalone compound having excellent light fastness and water solubility, and a recording liquid of an ink jet recording system using the same which is excellent in storage stability and light fastness. It is to provide a safe aqueous ink.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, completed the present invention. That is, the present invention relates to a quinophthalone compound represented by the following general formula (1),
The present invention relates to a use of the quinophthalone compound as a dye and an aqueous ink containing the dye.

(1) General formula (1)

Embedded image中 where X₁~ X₉Are each independently a hydrogen atom, a halogen
Atom, carboxyl group, alkoxycarbonyl group,
Nocarbonyl group, alkylaminocarbonyl group, -SO
₃A group Y (where Y is a hydrogen atom, an alkali metal, an alkali
Lithium earth metal or ammonium represented by the following general formula (2)
Or -Z (CH ₂)_nSO₃
Y group [where n represents an integer of 1 to 4, and Y is a hydrogen atom
Element, alkali metal, alkaline earth metal or the following general formula
Represents an ammonium salt residue represented by (2), and Z represents oxygen
Represents｝ representing an atom or a sulfur atom. Where X₁~ X₉
At least one of -Z (CH₂)_nSO₃Y group
You. A quinophthalone compound represented by｝.

Embedded image (In the formula, R _{1 to} R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent.)

(2) -Z (CH) in the formula (1)
₂₎ In the _n SO ₃ Y group, Z is a sulfur atom, and, n is 2 or 3 (1) quinophthalone compound according to claim. (3) The quinophthalone compound according to the item (1), wherein at least one of X _{6 to} X _{9 in} the formula of the general formula (1) is a —SO ₃ Y group.

[0009] (4) _{X 3} in the formula of the general formula (1) is -
S (CH ₂ ) _n SO ₃ Y group (where n represents an integer of 1 to 4, Y is a hydrogen atom, an alkali metal, an alkaline earth metal, or an ammonium salt residue represented by the following general formula (2)) Represents a general formula (3)

Embedded image In the formula, X ₁ is a hydrogen atom or a halogen atom, and X ₂ to
X ₄ is a hydrogen atom, X _{6 to} X ₉ are a hydrogen atom or —SO ₃
Y represents a group (where Y represents a hydrogen atom, an alkali metal, an alkaline earth metal or an ammonium salt residue represented by the following general formula (2)), and n represents an integer of 1 to 4.
However, at least one of X _{6 to} X ₉ is a —SO ₃ Y group. } The quinophthalone compound according to the above item (1).

Embedded image (In the formula, R _{1 to} R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent.)

(5) General formula (1)

Embedded image中 where X₁~ X₉Are each independently a hydrogen atom, a halogen
Atom, carboxyl group, alkoxycarbonyl group,
Nocarbonyl group, alkylaminocarbonyl group, -SO
₃A group Y (where Y is a hydrogen atom, an alkali metal, an alkali
Lithium earth metal or ammonium represented by the following general formula (2)
Or -Z (CH ₂)_nSO₃
Y group [where n represents an integer of 1 to 4, and Y is a hydrogen atom
Element, alkali metal, alkaline earth metal or the following general formula
Represents an ammonium salt residue represented by (2), wherein Z is oxygen
Atom or sulfur atom]. Where X₁~ X₉
At least one of -Z (CH₂)_nSO₃Y group
You. } A water-soluble quinophthalone dye represented by}.

Embedded image (In the formula, R _{1 to} R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent.)

(6) -Z (CH) in the formula (1)
In _{2) n} SO ₃ Y group, Z is a sulfur atom, and, n is 2 or 3 (5) water-soluble quinophthalone dyes described in section. (7) The water-soluble quinophthalone dye according to item (5), wherein at least one of X _{6 to} X _{9 in} the formula of the general formula (1) is a —SO ₃ Y group.

(8) When X ₃ in the formula (1) is-
S (CH ₂ ) _n SO ₃ Y group (where n represents an integer of 1 to 4, Y is a hydrogen atom, an alkali metal, an alkaline earth metal, or an ammonium salt residue represented by the following general formula (2)) Represents a general formula (3)

Embedded image In the formula, X ₁ is a hydrogen atom or a halogen atom, and X ₂ to
X ₄ is a hydrogen atom, X _{6 to} X ₉ are a hydrogen atom or —SO ₃
Y represents a group (where Y represents a hydrogen atom, an alkali metal, an alkaline earth metal or an ammonium salt residue represented by the following general formula (2)), and n represents an integer of 1 to 4.
However, at least one of X _{6 to} X ₉ is a —SO ₃ Y group. } The water-soluble quinophthalone dye according to item (5),

Embedded image (In the formula, R _{1 to} R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent.)

(9) An aqueous ink containing the water-soluble quinophthalone dye according to the above (5) to (8). (10)
An inkjet recording ink comprising the water-soluble quinophthalone dye according to any one of (5) to (8).

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The quinophthalone compound of the present invention comprises
Wherein it is represented by the general formula (1), as a water-soluble substituent, having at least one _{-Z (CH 2) n SO 3} Y group. In the general formula (1), X _{1 to} X ₉ each independently represent a hydrogen atom, a halogen atom, a carboxyl group, an alkoxycarbonyl group, an aminocarbonyl group, an alkylaminocarbonyl group, a —SO ₃ Y group (where Y is A hydrogen atom, an alkali metal, an alkaline earth metal, or an ammonium salt residue represented by the general formula (2), or -Z (C
H ₂ ) _n SO ₃ Y group (where n represents an integer of 1 to 4, Y represents a hydrogen atom, an alkali metal, an alkaline earth metal,
Or Z represents an ammonium salt residue represented by the general formula (2), and Z represents an oxygen atom or a sulfur atom.
However, at least one of X _{1 to} X ₉ is -Z (CH ₂ )
_n SO ₃ Y group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkylcarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group and the like. Examples of the alkylaminocarbonyl group include a methylaminocarbonyl group, a dimethylaminocarbonyl group, an ethylaminocarbonyl group, a diethylaminocarbonyl group, a propylaminocarbonyl group, a dipropylaminocarbonyl group, a butylaminocarbonyl group, and a dibutylaminocarbonyl group.

The carboxyl group may be in the form of an alkali metal salt such as lithium, sodium or potassium, an alkaline earth metal salt such as calcium or magnesium, or an ammonium salt represented by the general formula (2). Examples of the alkali metal of Y include lithium, sodium, and potassium, and examples of the alkaline earth metal include calcium and magnesium.

In the ammonium salt residue represented by the general formula (2), the alkyl groups represented by R _{1 to} R ₄ are alkyl groups having 1 to 8 carbon atoms which may have a substituent. Examples are methyl, ethyl, n-propyl,
Isopropyl group, n-butyl group, isobutyl group, ter
t-butyl group, sec-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, sec-pentyl group, cyclopentyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3- Methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1,2-trimethylpropyl Group, 1,2,2-trimethylpropyl group,
1-ethylbutyl group, 2-ethylbutyl group, 1-ethyl-2-methylpropyl group, cyclohexyl group, methylcyclopentyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4
-Methylhexyl group, 5-methylhexyl group, 1,1-
Dimethylpentyl group, 1,2-dimethylpentyl group,
1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3, 4-dimethylpentyl group, 1-
Ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1,1,2-trimethylbutyl group, 1,
1,3-trimethylbutyl group, 1,2,3-trimethylbutyl group, 1,2,2-trimethylbutyl group, 1,3
3-trimethylbutyl group, 2,3,3-trimethylbutyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-
2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-3
-Methylbutyl group, 1-n-propylbutyl group, 1-i
so-propylbutyl group, 1-iso-propyl-2-
Methylpropyl group, methylcyclohexyl group, n-octyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5
-Methylheptyl group, 6-methylheptyl group, 1,1-
Dimethylhexyl group, 1,2-dimethylhexyl group,
1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,2-dimethylhexyl group, 2,3-dimethylhexyl group, 2,4-dimethylhexyl group, 2, 5-dimethylhexyl group, 3,
3-dimethylhexyl group, 3,4-dimethylhexyl group, 3,5-dimethylhexyl group, 4,4-dimethylhexyl group, 4,5-dimethylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3- Ethylhexyl group, 4-ethylhexyl group, 1-n-propylpentyl group, 2-n-propylpentyl group, 1-iso-propylpentyl group, 2-iso-propylpentyl group, 1-
Ethyl-1-methylpentyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, 1
-Ethyl-4-methylpentyl group, 2-ethyl-1-methylpentyl group, 2-ethyl-2-methylpentyl group,
2-ethyl-3-methylpentyl group, 2-ethyl-4-
Methylpentyl group, 3-ethyl-1-methylpentyl group, 3-ethyl-2-methylpentyl group, 3-ethyl-
3-methylpentyl group, 3-ethyl-4-methylpentyl group, 1,1,2-trimethylpentyl group, 1,1,3
-Trimethylpentyl, 1,1,4-trimethylpentyl, 1,2,2-trimethylpentyl, 1,2,2
3-trimethylpentyl group, 1,2,4-trimethylpentyl group, 1,3,4-trimethylpentyl group, 2,
2,3-trimethylpentyl group, 2,2,4-trimethylpentyl group, 2,3,4-trimethylpentyl group,
1,3,3-trimethylpentyl group, 2,3,3-trimethylpentyl group, 3,3,4-trimethylpentyl group, 1,4,4-trimethylpentyl group, 2,4,4-
Trimethylpentyl group, 3,4,4-trimethylpentyl group, 1-n-butylbutyl group, 1-iso-butylbutyl group, 1-sec-butylbutyl group, 1-tert-
Butylbutyl group, 2-tert-butylbutyl group, 1-
n-propyl-1-methylbutyl group, 1-n-propyl-2-methylbutyl group, 1-n-propyl-3-methylbutyl group, 1-iso-propyl-1-methylbutyl group, 1-iso-propyl-2- Methylbutyl group, 1-
iso-propyl-3-methylbutyl group, 1,1-diethylbutyl group, 1,2-diethylbutyl group, 1-ethyl-1,2-dimethylbutyl group, 1-ethyl-1,3-dimethylbutyl group, 1 -Ethyl-2,3-dimethylbutyl group, 2-ethyl-1,1-dimethylbutyl group, 2-ethyl-1,2-dimethylbutyl group, 2-ethyl-1,3-
Linear or branched such as dimethylbutyl, 2-ethyl-2,3-dimethylbutyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl, ethylcyclohexyl, etc. Or a cyclic alkyl group having 1 to 8 carbon atoms.

Further, a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, a fluoroethyl group, a chloroethyl group,
A bromoethyl group, a trifluoroethyl group, a pentafluoroethyl group, a tetrachloroethyl group, a halogenated alkyl group having a total of 1 to 8 carbon atoms substituted with 1 to 17 halogen atoms such as a hexafluoroisopropyl group, a hydroxymethyl group, A hydroxyalkyl group having a total of 1 to 8 carbon atoms substituted by a hydroxyl group such as a hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, and a 3-hydroxypropyl group, and a benzyl group And an aralkyl group having a total carbon number of 1 to 8, such as a 4-methylbenzyl group.

An ammonium salt residue represented by the general formula (2)
Preferred examples of the group include NH.₄, NH₃(C₄H₉),
NH₃(C₈H₁₇), NH₂(C₄H₉)₂, NH (C
₂H ₅)₃, NH (C₄H₉)₃, N (CH₃)₃CH₂
C₆H₅, N (C₄H₉)₄, NH₃CH₂OH, NH
₂(CH₂OH)₂, NH (CH₂OH)₃, NH₃C
₂H₄OH, NH₂(C₂H₄OH)₂, NH (C₂H
₄OH)₃, NH₃C₃H₆OH, NH₃CH₂-P
h, NH (C₂H₅)₂CH₂-Ph, NHCH₃(C
yclo-C₆H₁₁)₂, NH (CH₃)₂(Cyc
lo-C₆H₁₁) And the like. Note that C₄H
₉Is nC₄H₉, Iso-C₄H₉, Sec-C₄
H₉, Tert-C₄H₉Represents any of

Among the quinophthalone compounds of the present invention,
In the formula (1), -Z (CH₂)_nSO₃In group Y
Is preferably a compound wherein Z is a sulfur atom, and further n is
Compounds that are 2 or 3 are more preferred. Z is a sulfur atom
Makes the synthesis of the dye easy, and n is large.
Over time, the solubility in water tends to decrease accordingly.
That is because X in the general formula (1)₆~
X₉At least one of -SO₃A compound that is Y group
More preferably, X in the formula of the general formula (1)₃Is -S
(CH₂) _nSO₃A group represented by the following general formula (3),
Nophthalone compounds are particularly preferred.

Embedded image (In the formula, at least one of X _{6 to} X ₉ is a —SO ₃ Y group.)

The quinophthalone compound represented by the general formula (1) can have a structure represented by the following general formula (4) or (5) by tautomerization.

Embedded image

Embedded image

The quinophthalone compound of the present invention is, for example,
A halogenated quinophthalone compound and HZ (C
H ₂ ) _n SO ₃ Y (where Z, n and Y are the same as above).

Since the quinophthalone compound of the present invention has high water solubility and light resistance, it can be used for various fibers, paper, leather,
It can be used for dyeing or printing silk, resin, etc., and is useful as a water-soluble quinophthalone dye. In these applications, the quinophthalone compounds of the present invention can be used in the form of a mixture or in the form of a single compound.
Further, the quinophthalone compound of the present invention is useful as a dye for various inks, particularly for a recording liquid of an ink jet recording system. The quinophthalone compound of the present invention, as a dye,
It can be used as it is, and in particular, when used as a recording liquid for an ink jet recording method, in order to prevent clogging of a discharge nozzle of a recording apparatus due to an inorganic salt or the like contained in a dye, for example, an ion exchange resin or It can also be used after desalination by external filtration or purification by other desalination methods. Further, for example, as a dye for fibers, a product obtained by blending an auxiliary agent or an extender with the quinophthalone compound of the present invention and commercializing the same can be used.

The aqueous ink of the present invention contains the quinophthalone compound of the present invention, and contains the quinophthalone compound, water and, if necessary, an organic solvent. The quinophthalone compounds represented by the general formula (1) may be used alone or as a mixture of two or more. The amount used depends on the application, purpose, type of dye, ink composition, print density of ink, clogging property and the like. As the aqueous ink, a quinophthalone compound is used in an amount of 0.1.
5-20%, water 10-99.5%, organic solvent 0-8
0% is a preferable range. In order to adjust the color tone of the ink, other water-soluble dyes or known dyes or pigments that have been processed into an emulsion or finely dispersed state without impairing the ink properties may be added.

In the aqueous ink of the present invention, the solvent component is mainly water, but an organic solvent can be mixed with water for the purpose of preventing drying of the ink and improving the solubility of the dye. . In this case, as an organic solvent that can be used,
Polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, glycerin and thioglycol, ethylene glycol monoethyl ether,
Polyhydric alcohol ethers such as ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, acetone,
Ketones such as methyl ethyl ketone, N, N-dimethylformamide, N, N-diethylformamide, N, N-
Amides such as dimethylacetamide, 2-pyrrolidone,
Nitrogen-containing compounds such as N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ethers such as tetrahydrofuran and dioxane, methanol, ethanol, 1-propanol;
Alcohols such as 2-propanol, 1-butanol and 2-butanol are exemplified.

These organic solvents may be used alone or as a mixture of two or more kinds. The amount of the organic solvent used is preferably 0 to 80% of the aqueous ink, more preferably 5 to 50%.
%. In the aqueous ink of the present invention, in order to further improve the water resistance, a hydroxylamine such as ammonia, amines, and triethanolamine may be used in combination.
The amount used is preferably about 0.001 to 10% by weight based on the aqueous ink. These amines may be used by forming a counter ion with the quinophthalone compound of the present invention. Also, urea, thiourea and their derivatives may be used in combination. The amount used is preferably about 0.1 to 15% by weight based on the ink.

When the aqueous ink of the present invention is used as an ink for ink jet recording, if necessary,
Various additives conventionally used, for example, ultraviolet absorbers, antioxidants, chelating agents, water-soluble polymers, masking agents, fungicides, preservatives, viscosity modifiers, surfactants, surface tension modifiers , A pH adjuster, a specific resistance adjuster, a near infrared absorber, a penetrant, and the like. The aqueous ink of the present invention having the above composition is used as an ink for a writing instrument or an ink of an ink jet recording system, and has recording characteristics, storage stability, fixability to a recording material, clarity of a recorded image, and light resistance. And so on. The aqueous ink of the present invention is obtained by dissolving the quinophthalone compound of the present invention together with water, an organic solvent, and, if necessary, the additives and the like mentioned above, and removing insolubles. Produced by filtration. The aqueous ink produced in this manner is particularly useful as a recording liquid for an ink jet recording method,
In addition, it is also used as ink for writing utensils such as ballpoint pens, felt pens and fountain pens.

[0028]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. Parts and% are “parts by weight” and “% by weight”, respectively.
Represents Example 1 Synthesis of Quinophthalone Compound In a reaction vessel equipped with a stirrer and a thermometer, 10.18 parts of a halogenated quinophthalone represented by the following formula (a) [halogenated quinophthalone (a); , 2
-8.00 parts of sodium mercaptoethanesulfonate,
5.61 parts of sodium carbonate and 203.7 parts of N, N'-dimethylimidazolidinone (DMI) were charged, heated to 100 ° C. under a nitrogen gas stream, and stirred for 1 hour.
The mixture was further heated to 170 ° C. and stirred for 6 hours. After completion of the reaction, the mixture was cooled to 90 ° C., suction-filtered, and the filtrate was discharged into acetone (700 parts). The crystals precipitated from the acetone solution were suction filtered, washed with acetone, and dried to obtain 7.89 parts of a quinophthalone compound (b). The maximum absorption wavelength of this quinophthalone compound (b) in an aqueous solution was 432 nm.

Embedded image

Embedded image Preparation of Ink With the composition shown below, each compound was mixed and dissolved,
The ink was prepared by filtration through a Teflon (registered trademark) filter having a pore size of 0.45 μm. Quinophthalone compound (b) 4% Diethylene glycol 30% N-methyl-2-pyrrolidone 10% Ion-exchanged water 56% Evaluation of characteristics The ink prepared above is used as an ink cartridge for a bubble jet type inkjet printer BJC-35v (manufactured by Canon Inc.). And printing and image recording were performed by the same printer, and the light resistance and the storage stability of the ink were evaluated. As a result, (A) evaluation of light resistance: (B) evaluation of storage stability of ink: ○, which was good. The results are shown in Table 1 (Table 1). The evaluation criteria for each test item are as follows. (A) Light fastness evaluation: After irradiating the printed portion with a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.) for 100 hours,
The print density (OD value) was measured, and the light resistance was evaluated. (B) Evaluation of storage stability of ink: After storing the recording liquid at 40 ° C. for 3 months, continuous recording was performed for a long time with the above-mentioned printer, and the presence or absence of clogging was observed.

Example 2 Synthesis of quinophthalone compound The procedure of Example 1 was repeated, except that 8.00 parts of sodium 2-mercaptoethanesulfonate was replaced with 9.00 parts of sodium 3-mercapto-1-sulfonate. 1
A quinophthalone compound (c) was synthesized in the same manner as described above.
8.11 parts were obtained. The maximum absorption wavelength of the quinophthalone compound (c) in the aqueous solution was 430 nm.

Embedded image Preparation of Ink The compounds having the following composition were mixed and dissolved, and filtered with a Teflon filter having a pore size of 0.45 μm to prepare an ink. Quinophthalone compound (c) 4% Diethylene glycol 30% N-methyl-2-pyrrolidone 10% Ion-exchanged water 56% Evaluation of properties The ink prepared above was bubble-jet-jet inkjet printer BJC-35v as in Example 1.
The ink was filled into an ink cartridge (manufactured by Canon Inc.), printing and image recording were performed by the same printer, and the light resistance and the storage stability of the ink were evaluated. As a result, (A) evaluation of light resistance: (B) evaluation of storage stability of ink: ○, which was good. The results are shown in Table 1 (Table 1).

Example 3 Synthesis of Quinophthalone Compound In a reaction vessel equipped with a stirrer and a thermometer, 10.00 parts of a quinophthalone (d) halide, 12.20 parts of sodium 2-mercaptoethanesulfonate, and 8.20 parts of sodium carbonate.
00 parts and N, N'-dimethylimidazolidinone (D
MI), 400 parts were charged, and the mixture was heated to 100 ° C and stirred for 1 hour under a stream of nitrogen. Further heat to 180 ° C and 6
Stirred for hours. After completion of the reaction, the mixture was cooled to 90 ° C., suction filtered, and the residue was washed with acetone and dried to obtain 15.80 parts of a quinophthalone compound (e). The maximum absorption wavelength of the quinophthalone compound (e) in the aqueous solution was 440 nm.

Embedded image

Embedded image Preparation of Ink With the composition shown below, each compound was mixed and dissolved,
The ink was prepared by filtration through a Teflon filter having a pore size of 0.45 μm. Quinophthalone compound (e) 4% Diethylene glycol 30% N-methyl-2-pyrrolidone 10% Ion-exchanged water 56% Evaluation of properties The ink prepared above is used as an ink cartridge for a bubble jet inkjet printer BJC-35v (manufactured by Canon Inc.). And printing and image recording were performed by the same printer, and the light resistance and the storage stability of the ink were evaluated. As a result, (A) evaluation of light resistance: (B) evaluation of storage stability of ink: ○, which was good. The results are shown in Table 1 (Table 1).

Examples 4 to 19 Inks were prepared according to Example 1 using various quinophthalone compounds of the present invention described in Table 1 (Tables 1 and 2).
Light fastness and storage stability were evaluated. As a result, as shown in Table 1 (Tables 1 and 2), all the inks obtained by using the water-soluble quinophthalone compound of the present invention have long-term storage stability and excellent light fastness. It turned out to show.

Example 20 Synthesis of quinophthalone compound N, N'-dimethylimidazolidinone
-17.1 parts of sodium mercaptoethanesulfonate and 15.7 parts of potassium carbonate were added, the temperature was raised to 115 ° C, and 22.6 parts of potassium halogenated quinophthalonesulfonate represented by the following formula (f) were charged. . Temperature to 150 ° C,
After stirring for 6 hours, the mixture was cooled to 65 ° C. Methanol 14
While dropping 0 parts, the mixture was cooled to 35 ° C., stirred for 1 hour, and then filtered. The filter cake was washed with methanol and dried. To this, 284 parts of water was added, and the temperature was raised to 75 ° C.
Stirred for 0.5 hour. Hot filtration and washing with hot water as they were to remove insolubles gave 362.9 parts of a filtrate. To this, 301.4 parts of methanol was added dropwise over 2 hours, the mixture was stirred at room temperature for 0.5 hour, filtered, and washed with methanol to give a quinophthalone compound 2.1 represented by the following formula (g) 2.1
5 parts were obtained. The maximum absorption wavelength of this compound in an aqueous solution is 429 nm, and the gram extinction coefficient is 54600 ml / g.
Cm.

Embedded image

Embedded image Preparation of Ink With the composition shown below, each compound was mixed and dissolved,
The ink was prepared by filtration through a Teflon filter having a pore size of 0.45 μm. Quinophthalone compound [Formula (g)] 4% Diethylene glycol 30% N-methyl-2-pyrrolidone 10% Ion-exchanged water 56% Evaluation of characteristics The ink prepared above was used as a bubble jet type inkjet printer BJC-35v (manufactured by Canon Inc.). The ink was filled in an ink cartridge for printing, printing and image recording were performed by the same printer, and evaluation of light resistance and evaluation of storage stability of the ink were performed. As a result, (A) evaluation of light resistance: (B) evaluation of storage stability of ink: ○, which was good. The results are shown in Table 1 (Table 2).

Example 21 Synthesis of Quinophthalone Compound Strongly acidic cation exchange resin (Diaion PK manufactured by Mitsubishi Chemical Corporation)
212) 21.7 parts were immersed in ion-exchanged water and filled in a glass column tube. After washing with deionized water, 3.5
The solution was washed with aqueous hydrochloric acid and then again with ion-exchanged water. Separately, 5.5 parts of the quinophthalone compound of the formula (g) was dissolved in 94.5 parts of ion-exchanged water, and charged in a column. The colored distillate was collected, 15.6 parts of 28% aqueous ammonia was added, and the mixture was concentrated under reduced pressure to a liquid weight of 8.8 parts. Methanol 1
1.8 parts were added, sludged at room temperature and filtered,
Washed with methanol and dried. 2.61 parts of a quinophthalone compound represented by the following formula (h) were obtained. The maximum absorption wavelength of the aqueous solution of the compound was 427 nm, and the gram extinction coefficient was 65,300 ml / g · cm.

Embedded image Preparation of Ink The compounds having the following composition were mixed and dissolved, and filtered with a Teflon filter having a pore size of 0.45 μm to prepare an ink. Quinophthalone compound [Formula (h)] 4% Diethylene glycol 30% N-methyl-2-pyrrolidone 10% Ion-exchanged water 56% Evaluation of properties The ink prepared above was used as a bubble jet ink jet printer BJC-35v (manufactured by Canon Inc.). The ink was filled in an ink cartridge for printing, printing and image recording were performed by the same printer, and evaluation of light resistance and evaluation of storage stability of the ink were performed. As a result, (A) evaluation of light resistance: (B) evaluation of storage stability of ink: ○, which was good. The results are shown in Table 1 (Table 3).

Example 22 Synthesis of quinophthalone compound To 166 parts of N, N'-dimethylimizolidinone, 17.0 parts of sodium 2-mercaptoethanesulfonate and 16.2 parts of potassium carbonate were added, and the mixture was heated to 115 ° C. And 22.6 parts of potassium quinophthalonesulfonate represented by the following formula (i). The temperature was raised to 150 ° C., stirred for 6 hours, and then cooled to 65 ° C. While dropping 140 parts of methanol, the mixture was cooled to 35 ° C., stirred for 1 hour, and then filtered. The filter cake was washed with methanol and dried. To this, 284 parts of water was added, and the temperature was raised to 75 ° C.
Stirred for 0.5 hour. The resulting solution was subjected to hot filtration and hot water washing to remove insolubles, thereby obtaining 362.9 parts of a filtrate. To this, 300 parts of methanol was added dropwise over 2 hours.
After stirring at room temperature for 0.5 hour, filtration and washing with methanol yielded 3.4 parts of a quinophthalone compound represented by the following formula (j). The maximum absorption wavelength of this compound in an aqueous solution is 4
30 nm.

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Embedded image Preparation of Ink With the composition shown below, each compound was mixed and dissolved,
The ink was prepared by filtration through a Teflon filter having a pore size of 0.45 μm. Quinophthalone compound [Formula (j)] 4% Diethylene glycol 30% N-methyl-2-pyrrolidone 10% Ion-exchanged water 56% Evaluation of properties The ink prepared above was used as a bubble jet inkjet printer BJC-35v (manufactured by Canon Inc.). The ink was filled in an ink cartridge for printing, printing and image recording were performed by the same printer, and evaluation of light resistance and evaluation of storage stability of the ink were performed. As a result, (A) evaluation of light resistance: (B) evaluation of storage stability of ink: ○, which was good. The results are shown in Table 1 (Table 3).

Examples 23 to 44 Using the various water-soluble quinophthalone compounds of the present invention described in Table 1 (Tables 3, 4 and 5), inks were prepared according to Examples 20 to 22 to obtain lightfastness. The properties and storage stability were evaluated. As a result, as shown in Table 1 (Tables 3, 4 and 5), all the inks obtained using the water-soluble quinophthalone compound of the present invention exhibited excellent storage stability over a long period of time and excellent storage stability. It was found to exhibit light fastness.

Comparative Example In Example 1, the dye was changed to a yellow azo dye (CI A
An ink was prepared according to the method of preparing an ink in Example 1 except that cid Yellow 23) was used, and the characteristics were similarly evaluated.

Embedded image As a result, (A) evaluation of light fastness: × (B) evaluation of storage stability of ink: ○, indicating poor light fastness as compared to the quinophthalone compound of the present invention.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

[0041]

[Table 5]

[0042]

The quinophthalone compound of the present invention has high water solubility and excellent light fastness, and the aqueous ink of the present invention prepared using the quinophthalone compound also has excellent performance in light fastness and storage stability. Is shown. In particular, when the aqueous ink of the present invention is used as a recording liquid for an ink jet recording method, a recording liquid having high quality and excellent light resistance can be provided.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Osamu Takago 580-32 Takuji, Nagaura-shi, Sodegaura-shi, Chiba In-house Mitsui Chemicals, Inc. 32 Inside Mitsui Chemicals Co., Ltd. Chemical Co., Ltd. F term (reference) 2H086 BA04 BA53 BA56 4J039 BC50 BC54 BE02 CA06 EA35 GA24 GA26 GA27 GA28

Claims (10)

[Claims] 1. General formula (1):中 where X₁~ X₉Are each independently a hydrogen atom, a halogen
Atom, carboxyl group, alkoxycarbonyl group,
Nocarbonyl group, alkylaminocarbonyl group, -SO
₃A group Y (where Y is a hydrogen atom, an alkali metal, an alkali
Lithium earth metal or ammonium represented by the following general formula (2)
Or -Z (CH ₂)_nSO₃
Y group [where n represents an integer of 1 to 4, and Y is a hydrogen atom
Element, alkali metal, alkaline earth metal or the following general formula
Represents an ammonium salt residue represented by (2), wherein Z is oxygen
Atom or sulfur atom]. Where X₁~ X₉
At least one of -Z (CH₂)_nSO₃Y group
You. Quinophthalone compound represented by}. Embedded image(Where R₁~ R₄Are each independently a hydrogen atom or
Represents an alkyl group having 1 to 8 carbon atoms which may have a substituent
You. ) 2. -Z (CH ₂ ) _{n in} formula (1)
The quinophthalone compound according to claim 1, wherein in the SO ₃ Y group, Z is a sulfur atom, and n is 2 or 3. 3. The quinophthalone compound according to claim 1, wherein at least one of X _{6 to} X _{9 in} the formula (1) is a —SO ₃ Y group. 4. X ₃ in the general formula (1) is -S (C
H ₂ ) _n SO ₃ Y group (where n represents an integer of 1 to 4, Y represents a hydrogen atom, an alkali metal, an alkaline earth metal, or an ammonium salt residue represented by the following general formula (2)) ) Is a general formula (3) In the formula, X ₁ is a hydrogen atom or a halogen atom, and X ₂ to
X ₄ is a hydrogen atom, X _{6 to} X ₉ are a hydrogen atom or —SO ₃
Y represents a group (where Y represents a hydrogen atom, an alkali metal, an alkaline earth metal or an ammonium salt residue represented by the following general formula (2)), and n represents an integer of 1 to 4.
However, at least one of X _{6 to} X ₉ is a —SO ₃ Y group. The quinophthalone compound according to claim 1, wherein Embedded image (In the formula, R _{1 to} R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent.) 5. A compound of the general formula (1)中 where X₁~ X₉Are each independently a hydrogen atom, a halogen
Atom, carboxyl group, alkoxycarbonyl group,
Nocarbonyl group, alkylaminocarbonyl group, -SO
₃A group Y (where Y is a hydrogen atom, an alkali metal, an alkali
Ammonium represented by the following formula (2):
Or -Z (CH₂) _nSO₃Y group
[Where n represents an integer of 1 to 4, Y represents a hydrogen atom,
Lucari metal, alkaline earth metal or the following general formula (2)
Represents an ammonium salt residue represented by
Or a sulfur atom]. Where X₁~ X₉Few
At least one is -Z (CH₂)_nSO₃Y group. }so
The water-soluble quinophthalone dye represented. Embedded image(Where R₁~ R₄Are each independently a hydrogen atom or
Represents an alkyl group having 1 to 8 carbon atoms which may have a substituent
You. ) 6. —Z (CH ₂ ) _{n in the} formula (1)
In SO 3 _Y group, Z is a sulfur atom, and a water-soluble quinophthalone dye according to claim 5, wherein n is 2 or 3. 7. The water-soluble quinophthalone dye according to claim 5, wherein at least one of X _{6 to} X _{9 in} the formula of the general formula (1) is a —SO ₃ Y group. 8. X ₃ in the general formula (1) is -S (C
H ₂ ) _n SO ₃ Y group (where n represents an integer of 1 to 4, Y represents a hydrogen atom, an alkali metal, an alkaline earth metal, or an ammonium salt residue represented by the following general formula (2)) ) Is a general formula (3) In the formula, X ₁ is a hydrogen atom or a halogen atom, and X ₂ to
X ₄ is a hydrogen atom, X _{6 to} X ₉ are a hydrogen atom or —SO ₃
Y represents a group (where Y represents a hydrogen atom, an alkali metal, an alkaline earth metal or an ammonium salt residue represented by the following general formula (2)), and n represents an integer of 1 to 4.
However, at least one of X _{6 to} X ₉ is a —SO ₃ Y group. The water-soluble quinophthalone dye according to claim 5, wherein Embedded image (In the formula, R _{1 to} R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent.) 9. An aqueous ink containing the water-soluble quinophthalone dye according to claim 5. 10. An ink jet recording ink comprising the water-soluble quinophthalone dye according to claim 5.