JPH11130997A - Recording liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a recording liquid which is excellent in water resistance, light resistance, and storage stabilty and, when used for ink jet recording or in writing utensils, etc., provides high-quality prints and high-density record images by incorporating, into an aq. medium, a colorant of which the free acid type is represented by a specific formula. SOLUTION: The free acid type of this colorant is represented by the formula (wherein A is an optionally substd. benzene ring; R1 and R2 are each H, 1-4C alkyl, 1-8C alkoxy, 2-7C acylamino, amino, hydroxyl, or halogen; R3 and R4 are each H, 2-7C acylamino, 1-10C alkyl, 1-8C alkoxy, hydroxyl, or halogen; R5 and R6 are each H, 1-18C alkyl, or aryl; m is 0-2; and n is 0 or 1) and is contained pref. in an amt. of 0.5-10 wt.% of the amt. of the recording liquid. The aq. medium constituting the recording liquid pref. comprises water and a water-soluble org. solvent (e.g. etylene glycol). The recording liquid may further contain 0.1-10 wt.% urea or the like and 0.001-5 wt.% surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording liquid. Specifically, the present invention relates to a black recording liquid suitable for ink jet recording.

[0002]

2. Description of the Related Art An ink jet recording method is a method in which a recording liquid containing a water-soluble dye such as a direct dye or an acid dye is directly ejected from a fine discharge orifice to perform recording. This recording liquid can be stably ejected for a long time, and is widely used for general office work such as PPC (plain paper copier) paper such as electrophotographic paper and fan hold paper (continuous paper such as a computer). It is required that the fixation to the recording paper is fast and the print quality of the printed matter is good, that is, the print has no blur and the outline is clear, and the stability during storage as a recording liquid is also excellent. Therefore, the solvent that can be used for the recording liquid is significantly limited.

On the other hand, dyes for recording liquids have sufficient solubility in the above-mentioned limited solvents and are stable even when stored as recording liquids for a long time.
In addition, it is required that the density of the printed image is high, and that it is excellent in water resistance and light resistance. However, it has been difficult to satisfy many of these requirements at the same time. For this reason, various dyes and methods of use (for example, JP-A-55-14406)
7, JP-A-55-152747, JP-A-57-20
7660, JP-A-58-147470, JP-A-61
-62562, JP-A-61-101576, JP-A-61-261377, JP-A-62-190269,
JP-A-62-190271, JP-A-62-19027
No. 2, JP-A-62-250082, JP-A-62-24
No. 6975, JP-A-62-257971, JP-A-62-29771
No.-288659, JP-A-63-8463, JP-A-6-8663
JP-A-3-22867, JP-A-63-22874, JP-A-63-30567, JP-A-63-33484, JP-A-63-63764, JP-A-63-105079,
JP-A-64-31877, JP-A-1-93389,
JP-A-1-210464, JP-A-2-140270
JP-A-3-167270, JP-A-3-20088
No. 2, etc.) have been proposed, but in terms of performance, a dye which satisfies the requirements of the market sufficiently and which is easy to produce has not yet been developed. With the widespread use of ink jet recording methods, recording liquids are required to have better physical properties such as density, light resistance, storage stability, and water resistance of printed matter than conventional ones.

[0004]

DISCLOSURE OF THE INVENTION The present invention has a good print quality even when recorded on plain paper for ink jet recording and writing instruments, and has a high density of recorded images, water resistance and light resistance. It is an object of the present invention to provide a recording liquid which is excellent in stability when stored for a long time.

[0005]

The recording liquid according to the present invention comprises:
The free acid form contains a dye represented by the following general formula (1) in an aqueous medium.

[0006]

Embedded image

Wherein A represents a benzene ring which may have a substituent, and R ₁ and R ₂ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. ,
Represents a substituted or unsubstituted alkoxy group having 1 to 8 carbon atoms, an acylamino group having 2 to 7 carbon atoms, an amino group, a hydroxyl group or a halogen atom, and R ₃ and R ₄ each independently represent a hydrogen atom, 7 represents an acylamino group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, or a halogen atom, and R ₅ and R ₆ are each independently Represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group; m represents 0 to 2;
Represents 0 or 1. )

Hereinafter, the present invention will be described in detail. In the general formula (1), A is a benzene ring which may have a substituent other than that shown in the drawing, and as the substituent, a sulfone group, a carboxyl group, an acylamino group having 2 to 7 carbon atoms ( Examples thereof include an acetylamino group, a benzoylamino group, an n-hexanoylamino group, an n-heptanoylamino group, and the like, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, t-
C1-C18 such as butyl, octyl, dodecyl, etc.
A linear or branched alkyl group and a trifluoromethyl group, a fluorine atom such as a dimethylaminomethyl group,
Examples include an alkyl group substituted with a substituted amino group and the like. ), Substituted or unsubstituted alkoxy groups having 1 to 10 carbon atoms (for example, linear or branched alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, isopropoxy, n-butoxy and the like) A hydroxyl group such as a 2-hydroxyethoxy group, a 2-methoxyethoxy group or a benzyloxy group, an alkoxy group substituted with an alkoxy group or an aryl group), an amino group, a hydroxyl group or a halogen atom. Or you may have two or more.

R ₁ and R ₂ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl) , A linear or branched alkyl group having 1 to 4 carbon atoms such as a t-butyl group and a fluorine atom such as a trifluoromethyl group, a dimethylaminomethyl group, a 2-hydroxyethyl group and a carboxymethyl group; Examples thereof include an alkyl group substituted with an amino group, a hydroxyl group, a carboxy group and the like.), A substituted or unsubstituted alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group) , A pentyloxy group,
Substituted with a linear or branched alkoxy group having 1 to 8 carbon atoms such as a 2-ethylhexyloxy group, and a hydroxyl group such as a 2-hydroxyethoxy group or a 2-methoxyethoxy group, an alkoxy group, or an aryl group. An alkoxy group. ), An acylamino group having 2 to 7 carbon atoms (for example, acetylamino group, benzoylamino group, n-hexanoylamino group, n-heptanoylamino group, etc.), an amino group, a hydroxyl group or a halogen atom. R
Preferably, at least _one of R ₁ and R ₂ is a hydrogen atom.

R ₃ and R ₄ each independently represent a hydrogen atom, a substituted or unsubstituted acylamino group having 2 to 7 carbon atoms (eg, acetylamino, propionylamino, butyrylamino, benzoylamino, cyclohexanecarbonylamino, etc.) ), A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-octyl group, Examples thereof include a linear or branched alkyl group having 1 to 10 carbon atoms such as a t-octyl group and a fluorine atom such as a trifluoromethyl group and a dimethylaminomethyl group, and an alkyl group substituted with a substituted amino group and the like. Is substituted or unsubstituted.
8 alkoxy groups (for example, methoxy group, ethoxy group,
A linear or branched alkoxy group having 1 to 8 carbon atoms such as an isopropoxy group and an n-butoxy group, and a hydroxyl group and an alkoxy group such as a 2-hydroxyethoxy group, a 2-methoxyethoxy group and a benzyloxy group. And an alkoxy group substituted with an aryl group. ), A hydroxyl group or a halogen atom. R ₃ and R ₄ are preferably each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an acylamino group having 2 to 7 carbon atoms.

R ₅ and R ₆ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, t- -Butyl group, n-octyl group, t
A linear or branched alkyl group having 1 to 18 carbon atoms such as an octyl group and a fluorine atom such as a trifluoromethyl group, a dimethylaminomethyl group, a 2-hydroxyethyl group and a carboxymethyl group, and a substituted amino group , A hydroxyl group, an alkyl group substituted with a carboxy group and the like. ),
Substituted or unsubstituted aryl groups (for example, phenyl group, 1-naphthyl group, 3,5-dicarboxyphenyl group, 4-butylphenyl group, 4-carboxyphenyl group, 3-sulfophenyl group, 4-mesylphenyl Group,
Carboxyl group such as 7-sulfo-1-naphthyl group, alkyl group, alkylsulfonyl group, phenyl group and naphthyl group substituted with a sulfone group and the like).
At least one of R ₅ and R ₆ is preferably a hydrogen atom, an aryl group substituted with a carboxy group or a sulfone group, and more preferably a phenyl group substituted with a carboxy group or a sulfone group. m represents 0 to 2,
n represents 0 or 1.

The dye of the general formula (1) has, as a counter ion of an acidic group, an alkali metal such as lithium and sodium, an ammonium group, and an alkyl group having 1 to 4 carbon atoms in which a substituent may have a hydroxyl group; It has an organic amine base such as a mono-, di-, or tri-substituted amine which is a hydroxyalkoxy group having 1 to 4 carbon atoms. Specific examples of these dyes include those having a free acid type such as N in Table 1 below.
o. 1 to No. An azo dye having a structure represented by 47 is exemplified.

[0013]

[Table 1]

[0014]

[Table 2]

[0015]

[Table 3]

[0016]

[Table 4]

[0017]

[Table 5]

[0018]

[Table 6]

[0019]

[Table 7]

[0020]

[Table 8]

[0021]

[Table 9]

The dye represented by the general formula (1) used in the present invention can be prepared by a method known per se [for example, Yutaka Hosoda, "Shin-Dye Chemistry" (published by Gihodo on December 21, 1973, Gihodo) 409] and a diazotization and coupling step. The content of the dye represented by the general formula (1) in the recording liquid is preferably 0.5 to 10% by weight, particularly preferably about 2 to 8% by weight based on the total amount of the recording liquid. The dye represented by the general formula (1) is 1
The types may be used, or two or more types may be mixed and used.
Moreover, you may use together with another black (black) pigment | dye. Examples of this dye include Food Black 2, Direct Black 17, 19, 154, 163, 168, 171,
195, Acid Black 2, Reactive Black 3
1 (above, color index name), Pontamine Black SP Liquid (trade name, manufactured by Bayer AG), and Bath Acid Black X-34 (trade name, manufactured by BASF). Further, although the dye used in the present invention is black, bluish black, reddish black, or yellowish black, etc., in order to obtain a desired color tone, if necessary, a dye of another color tone,
For example, one or more red, yellow, or blue dyes may be used in combination.

The aqueous medium constituting the recording liquid of the present invention is preferably composed of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (# 200), and polyethylene glycol (# 4).
00), glycerin, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethylimidazolidinone, thiodiethanol, dimethylsulfoxide, ethylene glycol monoallyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, 2-pyrrolidone, sulfolane ,Ethyl alcohol,
It is preferable to use one or more selected from isopropanol, triethanolamine and the like. These water-soluble organic solvents are usually used in the range of 5 to 30% by weight based on the total amount of the recording liquid. On the other hand, water is 6% of the total volume of the recording liquid.
It is used in the range of 0 to 90% by weight.

The recording liquid of the present invention, based on the total amount thereof,
0.1 to 10% by weight, preferably 0.5 to 5% by weight of a compound selected from urea, thiourea, biuret and semicarbazide, and 0.001 to 5% by weight of a surfactant By doing so, quick drying after printing and print quality can be further improved. Furthermore, the recording liquid of the present invention is a black recording liquid, and can be used not only for producing a monochrome printer or a monochrome printed matter, but also as a full-color printer or as one color for producing a full-color printed matter. Is also good. In particular, in the case of full color printing, recording liquids of magenta, cyan, and yellow are used together. In that case, the recording liquid of each color is an aqueous recording liquid of each color tone, and for example, contains a water-soluble dye of each color tone, an aqueous medium, and, if necessary, an additive. The aqueous medium and the additive may be the same as those usually used in the above-described recording liquid of the present invention. As the water-soluble dye having the color tone, in magenta, for example, Acid Red 35, 52, or 289, Direct Red 227 and hydrolyzate of Reactive Red 180 can be used. For cyan, for example, Direct Blue 86 or 199, Acid Blue 9 and the like can be used.
Alternatively, 142, Acid Yellow 23 and the like can be used. (All are color index names)

The recording liquid of the present invention can be used in various recording methods, but is particularly suitable for use as a recording liquid for ink jet. The type of the ink jet printer is not particularly limited, and for example, the means for discharging the droplets can be preferably used for any of those using electric energy, those using thermal energy, and the like.

[0026]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist. Example 1 10 parts by weight of diethylene glycol, 3 parts by weight of isopropyl alcohol, and no. Water was added to 3 parts by weight of the first dye, the pH was adjusted to 9 with aqueous ammonia, and the total amount was 100
Parts by weight were used. This composition was sufficiently mixed and dissolved, filtered under pressure through a Teflon filter having a pore size of 1 μm, and then degassed with a vacuum pump and an ultrasonic cleaner to prepare a recording liquid.

Using the obtained recording liquid, ink jet recording was carried out on electrophotographic paper (manufactured by Fuji Xerox Co., Ltd.) using an ink jet printer (manufactured by BJ-10V Canon Inc.) to print a high density bluish black print. I got something. In addition, evaluation was performed by the following methods (a), (b), (c), and (d). (A) Density of recorded image; O of recorded image printed solid
The D value was measured with a Macbeth densitometer (trade name: TR-927). (B) Light fastness of recorded image; irradiating the recording paper for 100 hours using a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.) and applying it to a spectral colorimeter (trade name: SZ-80, manufactured by Nippon Denshoku Industries Co., Ltd.) The color difference (ΔE) of the recorded matter before and after the test was measured by using the following criteria.

[0028]

○: Discoloration / fading is ΔE of 10 or less Δ: Discoloration / fading is ΔE of 10 to 20 ×: Discoloration / fading is ΔE of 20 or more

(C) Water resistance of the recorded image; a) Bleeding of the image after immersing the recording paper in tap water for 5 seconds was visually judged according to the following criteria.

[0030]

○: There is no bleeding of the image. Δ: Image bleeding is small. X: The image blur is large.

B) The OD value of the solid printed portion before and after immersion was measured with a Macbeth densitometer (TR927), and the OD residual ratio was calculated by the following equation.

[0032]

OD residual ratio (%) = (OD value after immersion / O before immersion)
D value) x 100

(D) Storage stability of recording solution: The recording solution was sealed in a Teflon container and stored at 5 ° C. and 60 ° C. for one month, and the change was examined.

[0034]

[Table 12] ○: No change ×: Changed

Table 2 shows the results of these evaluation tests (a) to (d). Example 2 5 parts by weight of glycerin, 10 parts by weight of ethylene glycol,
No. of Table-1. Water was added to 2.5 parts by weight of the dye No. 11 and the pH was adjusted to 9 with aqueous ammonia to make the total amount 100 parts by weight. This composition was treated by the method described in Example 1 to prepare a recording liquid. . Printing was performed in the same manner as in Example 1 using this recording liquid, and as a result, a high-density black recorded matter was obtained. Various evaluations according to (a) to (d) of Example 1 were performed on the recorded matter. Table 2 shows the results.

Example 3 Diethylene glycol 10 parts by weight, N-methylpyrrolidone 5 parts by weight, isopropyl alcohol 3 parts by weight, Table 1
No. Water was added to 3 parts by weight of the dye No. 33, the pH was adjusted to 9 with aqueous ammonia to make the total amount 100 parts by weight, and this composition was treated by the method described in Example 1 to prepare a recording liquid. Printing was performed in the same manner as in Example 1 using this recording liquid, and as a result, a high-density black recorded matter was obtained. Various evaluations according to (a) to (d) of Example 1 were performed on the recorded matter. Table 2 shows the results.

[0037]

[Table 13]

[0038]

The recording liquid of the present invention is used as an ink jet recording and writing instrument, and when recorded on plain paper,
Black recordings can be obtained, and it is excellent not only for monochrome printed matter but also for full color printed matter, and has excellent printing density and light resistance and water resistance of the printed matter, as well as a recording liquid. Good storage stability.

Claims (1)

[Claims] The free acid form is represented by the general formula (1) in an aqueous medium.
A recording liquid comprising a dye represented by the formula: Embedded image (Wherein, A represents a benzene ring which may have a substituent, and R ₁ and R ₂ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group, Represents an unsubstituted alkoxy group having 1 to 8 carbon atoms, an acylamino group having 2 to 7 carbon atoms, an amino group, a hydroxyl group or a halogen atom, and R ₃ and R ₄ each independently represent a hydrogen atom,
An acylamino group having 1 to 1 carbon atoms, substituted or unsubstituted
Represents an alkyl group of 0, a substituted or unsubstituted alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, or a halogen atom,
R ₅ and R ₆ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group, m represents 0 to 2, and n represents 0 or 1. Represent. )