JP3504102B2 - Recording liquid - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a recording liquid and to it
It relates to the dye used . Specifically, it relates to a black recording liquid suitable for ink jet recording and a dye used therefor .

[0002]

2. Description of the Related Art A so-called ink jet recording method has been in practical use for a long time since recording is carried out by ejecting droplets of a recording liquid containing a water-soluble dye such as a direct dye or an acid dye from a minute ejection orifice. Regarding this recording liquid, it is fast to fix to general recording paper for general office work such as PPC (plain paper copier) paper such as electrophotographic paper, fan hold paper (continuous paper such as computers), and printing of printed matter It is required that the quality is good, that is, the print has no bleeding and the contour is clear, and it has excellent stability during storage as a recording liquid and is stably ejected from a minute ejection orifice. Therefore, the solvent that can be used is extremely 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 period of time. However, it is difficult to satisfy many of the requirements at the same time.

For this reason, various methods have been proposed (for example, JP-A-55-144067 and JP-A-55-152).
747, JP-A-57-207660, JP-A-59-
226072, JP-A-61-27776, JP-A-61
-57666, JP-A-62-190269, JP-A-62-190271, JP-A-62-190272,
JP-A-62-197476, JP-A-62-25008
2, JP-A-62-246975, JP-A-62-25
6974, JP-A-62-288659, JP-A-63.
-8463, JP-A-63-22867, JP-A-63
No. 22874, JP-A-63-117079, 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 and JP-A 1-240584.
No. 2-16171 and No. 2-140270.
JP-A-3-200882, JP-A-5-26299
No. 8, JP-A-7-34020, and JP-A-8-26934.
However, the fact is that the requirements of the market have not been fully satisfied.

[0004]

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

[0005]

The present inventor has accomplished the present invention by confirming that the above object can be achieved when a specific dye is used as a recording liquid component. That is, the gist of the present invention resides in a recording liquid which is characterized in that the aqueous medium and the free acid form contain a dye represented by the following general formula [I] or [II].

[0006]

[Chemical 3]

(In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, a carbon atom which may have a substituent. Represents an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, a sulfo group or an amino group which may have a substituent, and X and Y each independently represent an alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms. 4 represents an alkoxy group having 4 to 4 carbon atoms or an acylamino group having 2 to 9 carbon atoms, and R ⁴ and R ⁵ each independently have a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or a substituent. Represents an optionally substituted phenyl group or an optionally substituted acyl group having 2 to 9 carbon atoms, 1 represents a number of 1 or 2 and m represents a number of 0 or 1.)

[0008]

[Chemical 4]

(In the formula, R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, and a carbon which may have a substituent. An alkoxy group of formulas 1 to 4, a halogen atom, a sulfo group or an amino group which may have a substituent, Z and W each independently represent a hydrogen atom, a sulfo group or a carboxyl group, and R ⁹
And R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a carbon which may have a substituent. Number 2
~ 9 represents an acyl group, n represents a number of 1 or 2,
p represents a number of 0 or 1. ) Hereinafter, the present invention will be described in detail.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The dye used in the present invention is selected from those in which the free acid form is represented by the above general formula [I] or [II]. In the general formula [I], R ¹ , R ² and R
Examples of the alkyl group represented by ³ include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, and a substituent of the alkyl group includes a hydroxyl group and, for example, a methoxy group. , An alkoxy group having 1 to 4 carbon atoms such as an ethoxy group or a butoxy group, and examples of the alkoxy group include a methoxy group, an ethoxy group,
Examples thereof include an alkoxy group having 1 to 4 carbon atoms such as n-butoxy group, and examples of the substituent of the alkoxy group include 1 to 1 carbon atoms such as methoxy group, ethoxy group or butoxy group.
Examples of the substituent of the amino group include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group or a butyl group, or a carbon number 2 such as an acetyl group or a benzoyl group. The acyl group of 9 and the like can be mentioned.

X and Y are alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group or butyl group, 1 carbon atoms such as methoxy group, ethoxy group or propoxy group.
To 4 alkoxy groups or acetylamino groups, propionylamino groups or other C2-5 alkylcarbonylamino groups, benzoylamino groups or p-methoxybenzoylamino groups or other alkoxy groups or other substituents. And an acylamino group such as arylcarbonylamino group. When the above group contains an alkylene chain having 3 or more carbon atoms, the alkylene group may be linear or branched.

Examples of the alkyl group represented by R ⁴ and R ⁵ include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group and a butyl group, and a substituent of the alkyl group is
Examples thereof include a C1-C4 alkoxy group such as a methoxy group, an ethoxy group or a butoxy group, a carboxyl group or a C2-C4 hydroxyalkyl group such as a hydroxyethyl group or a hydroxypropyl group, and phenyl. Examples of the substituent of the group include a sulfo group, a carboxyl group, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group or a butoxy group, and the like, and an acyl group such as an acetyl group, a benzoyl group and a tosyl group. And a substituent of the acyl group includes, for example, a methoxy group, an ethoxy group or an alkoxy group having 1 to 4 carbon atoms such as butoxy group, a nitro group or an amino group. .

In the general formula [II], R ⁶ , R ⁷ and R
Examples of the alkyl group represented by ⁸ include a methyl group, an ethyl group, an alkyl group having 1 to 4 carbon atoms such as n-butyl group, and a substituent of the alkyl group is a hydroxyl group or a methoxy group, an ethoxy group or a butoxy group. Examples of the alkoxy group include an alkoxy group having 1 to 4 carbon atoms, and examples of the alkoxy group include an alkoxy group having 1 to 4 carbon atoms such as methoxy group, ethoxy group, and n-butoxy group. Examples thereof include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group or a butoxy group, and examples of the substituent of the amino group include those having a carbon number of 1 to 4 such as a methyl group, an ethyl group or a butyl group. Examples thereof include an alkyl group or an acyl group having 2 to 9 carbon atoms such as an acetyl group or a benzoyl group.

The alkyl group represented by R ⁹ and R ¹⁰ has a carbon number of 1 to 1 such as methyl group, ethyl group and n-butyl group.
Examples of the substituent of the alkyl group include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group or a butoxy group, a carboxyl group or a hydroxyethyl group or a hydroxypropyl group. And a hydroxyalkyl group having 2 to 4 carbon atoms, and the like. Examples of the substituent of the phenyl group include a sulfo group,
Examples thereof include a carboxyl group or an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group or a butoxy group, and the acyl group includes an acyl group having 2 to 9 carbon atoms such as an acetyl group, a benzoyl group or a tosyl group. ,
Examples of the substituent of the acyl group include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group or a butoxy group, a nitro group or an amino group.

The dye used in the present invention may be used as it is as a free acid represented by the general formula [I] or [II], but when it is obtained in the form of a salt during production, it may be used as it is. Alternatively, it may be converted into a desired salt form. Further, a part of the acid groups in the molecule may be in the form of a salt, and a salt form dye and a free acid form dye may be mixed. Examples of such salt forms include salts of alkali metals such as Na, Li and K, ammonium salts and salts of organic amines. Examples of organic amines include lower alkylamines, hydroxy-substituted lower alkylamines, carboxy-substituted lower alkylamines, polyamines having 2 to 10 alkyleneimine units having 2 to 4 carbon atoms, and the like. Form a substituted ammonium salt with a secondary or tertiary organic amine. In the case of these salt forms, the kind of the salt is not limited to one kind, and one kind of dye molecule may contain plural kinds of salt forms, or dyes having different salt forms may be mixed. May be. Specific examples of these dyes include, for example, Nos. I-1 to No. I-9 and N
o. II-1 to No. An azo dye having a structure shown in II-6 can be mentioned.

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

[Chemical 8]

The disazo dye represented by the general formula [I] or [II] used in the present invention can be prepared by a known method, for example, Yutaka Hosoda, "New Dye Chemistry" (December 21, 1973, published by Gihodo, 396). Up to page 409), a diazotization step and a coupling step can be performed. The content of the dye of the general formula [I] or [II] in the recording liquid is preferably 0.5 to 12% by weight, more preferably 2 to 8% by weight, based on the total amount of the recording liquid.

In the present invention, the dye represented by the general formula [I] or [II] is used alone or in combination. In the case of a plurality of types, a plurality of types having the respective general formulas may be used, but one or more types of the dyes having both the general formulas may be used. Further, other known black dyes may be used in combination, or dyes of other color tones (for example, magenta, cyan or yellow) may be used in combination for adjusting the color tone. When another dye is used in combination for adjusting the color tone, it is preferably used in combination with a yellow dye.

The aqueous medium used in the present invention includes water and water-soluble organic solvents such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (weight average molecular weight (Mw) = 190-4).
00), glycerin, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethylimidazolidinone, thiodiethanol, dimethylsulfoxide, ethylene glycol monoallyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethyl glycol. It preferably contains ethylene glycol monobutyl ether, 2-pyrrolidone, sulfolane, ethyl alcohol, isopropyl alcohol, triethanolamine and the like. These water-soluble organic solvents are usually used in the range of 1 to 50% by weight based on the total amount of the recording liquid. On the other hand, water is used in the range of 45 to 95% by weight with respect to the total amount of the recording liquid.

The recording liquid of the present invention contains 0.
1-10 wt% urea, preferably 0.5-5 wt% urea,
By adding a compound selected from thiourea, biuret, and semicarbazide, or by adding 0.001 to 5.0% by weight of a surfactant, the quick-drying property after printing and the printing quality can be further improved. it can. The recording liquid of the present invention itself is black and forms a black image, as well as a multi-color or full-color image.
It can be formed by using recording liquids of yellow, magenta and cyan in combination. Specifically, for yellow, for example, C.I. I. Direct Yellow 86 (C.I. Direct Yellow 8)
6), 142, or 132, or C.I. I. Acid Yellow 23 (CI Acid Yellow
23) and the like, and magenta, for example, C.I. I. Acid Red 35 (CI Acid
Red 35), 37, 52, 257 or 28.
9 or C.I. I. Direct Red 80 (C.
I. For at least one kind of cyan such as Direct Red 80) and cyan, for example, C.I. I. Direct Blue 86 (C.I. Direct Blue 86)
Or 199, or C.I. I. Acid Blue 9
It can be formed by using a recording liquid containing at least one kind of dye such as (CI Acid Blue 9) together with the recording liquid of the present invention. The recording liquid other than the black one preferably has the same composition as the recording liquid of the present invention except that the above dye is used. That is, it contains an aqueous medium and, if necessary, various additives in addition to the above dyes.

The recording liquid of the present invention is suitable for use in ink jet recording, writing instruments, etc., but is particularly suitable for ink jet recording. As the ejection means of the apparatus for inkjet recording, one using electric energy, thermal energy, or the like can be used.

[0025]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. Example 1 10 parts by weight of diethylene glycol, 3 parts by weight of isopropyl alcohol, Water was added to 3 parts by weight of the dye of I-1, and the pH was adjusted to 9 with aqueous ammonia to adjust the total amount to 100.
It was made into a weight part. The composition was thoroughly mixed and dissolved, filtered under pressure with a Teflon filter having a pore size of 1 μm, and then deaerated with a vacuum pump and an ultrasonic cleaner to prepare a recording liquid.

An ink jet printer (BJ-10V, product name of Canon Inc.) using the obtained recording liquid
Inkjet recording was carried out on an electrophotographic paper (product of Xerox Co., Ltd.) to obtain a high-density (1.35) reddish black printed matter. Further, various evaluations were performed by the following methods (a), (b), (c) and (d). The results are shown in Table-1.

(A) Light resistance of recorded image: Using a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.)
Irradiated for 0 hours. The discoloration and fading after irradiation was small. (B) Water resistance of recorded image: Water resistance test (1) Test method After the recorded image was immersed in tap water for 5 minutes, the bleeding of the image was visually examined. The OD value (printing density) of the solid printed portion before and after the immersion was measured with a Macbeth densitometer (TR927). (2) Test results As a result of the above, blurring of the image was slight. The density change of the solid print part before and after the immersion is calculated by the following formula: OD
The residual rate was 89.2%.

[0028]

[Formula 1] OD residual ratio (%) = (OD value after immersion / O before immersion)
D value) x 100

(C) Storage stability of recording liquid: When the recording liquid was sealed in a Teflon container and stored at 5 ° C. and 60 ° C. for 1 month, the change was examined and no precipitation of insoluble matter was observed. It was (D) Discharge stability: Stable discharge was possible for 3 hours continuously even in a room adjusted to an air temperature of 30 ° C. and a relative humidity of 20%. In the above evaluations of (a), (b), (c), and (d), the visual judgment was evaluated in three grades of ◯: good, Δ: somewhat inferior, and x: defective.

Examples 2 to 4 Nos. Used in Example 1 were used. Instead of the dye of I-1, the above-mentioned No. I-2, No. I-5 and No. II-
A recording liquid was prepared by the method of Example 1 except that each of the dyes 1 was used, and printing was performed using the recording liquid to obtain a reddish black recorded material. Furthermore, Example 1 was applied to this recorded matter.
Various evaluations according to (a) to (d) were performed. As a result, good results were obtained in the same manner as in Example 1. The OD residual rates were 88.8%, 94.1%, and 93.2%, respectively. The results are shown in Table 1 below.

Comparative Example 1 No. 1 in Example 1 C.I. instead of the dye of I-1.
I. A composition was prepared using Food Black 2 in the same manner as in Example 1 and then treated to obtain a recording liquid. Using this recording liquid, printing was performed in the same manner as in Example 1 to obtain a black recorded material. For the obtained recorded matter, (a) to (d) of Example 1
Various evaluations were performed. The results are shown in Table 1 below.

Comparative Example 2 No. 1 in Example 1. Instead of the dye No. I-1, the dye No. 1 described in JP-A-7-34020 is used.
Using the dye of (1) (the following structural formula * 1), a composition was prepared and treated in the same manner as in Example 1 to obtain a recording liquid.
Using this recording liquid, printing was performed in the same manner as in Example 1 to obtain a black recorded material. (A) of Example 1 for the obtained recorded matter
Various evaluations according to (d) were performed. The results are shown in Table 1 below.

[0033]

[Chemical 9]

Comparative Example 3 No. 1 in Example 1 The structural formula (l) described in JP-A-63-22874 instead of the dye of I-1
A composition was prepared in the same manner as in Example 1 using the dye of the following structural formula * 2, and then treated to obtain a recording liquid. Using this recording liquid, printing was carried out in the same manner as in Example 1 to obtain a reddish black recorded product. (A) of Example 1 to the obtained recorded matter
Various evaluations according to (d) were performed. The results are shown in Table 1 below.

[0035]

[Chemical 10]

[0036]

[Table 1]

Examples 5 to 20 Nos. Used in Example 1 were used. Instead of the dye of I-1, the above-mentioned No. I-3, No. I-4, No. I-6
~ I-10, No. Using each of the dyes II-2 to II-10, a recording liquid was prepared by the method of Example 1 and printing was performed to obtain a black recorded matter. Various evaluations according to (a) to (d) of Example 1 were performed on this recorded matter. As a result, as in Example 1, good results were obtained.

[0038]

INDUSTRIAL APPLICABILITY The recording liquid of the present invention is used for ink jet recording, writing instruments, etc., and when recorded on plain paper, a black recorded matter can be obtained, and its printing density, light resistance, and water resistance. In addition to excellent properties, it also has good storage stability and ejection stability as a recording liquid.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-6-329931 (JP, A) JP-A-63-22874 (JP, A) JP-A-7-331145 (JP, A) JP-A-1- 141966 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09D 11/00-11/20 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A recording liquid comprising an aqueous medium and a dye whose free acid form is represented by the following general formula [I] or [II]. [Chemical 1] (In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a carbon atom having 1 to 4 which may have a substituent. 4 represents an alkoxy group, a hydroxyl group, a halogen atom, a sulfo group or an amino group which may have a substituent, and X and Y each independently represent an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. An alkoxy group or an acylamino group having 2 to 9 carbon atoms, R ⁴ and R ⁵
Are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a carbon number 2 which may have a substituent. 9 represents an acyl group, 1 represents a number of 1 or 2, and m represents a number of 0 or 1. ) [Chemical 2] (In the formula, R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a carbon atom having 1 to 4 carbon atoms which may have a substituent. 4 represents an alkoxy group, a halogen atom, a sulfo group or an optionally substituted amino group, Z and W each independently represent a hydrogen atom, a sulfo group or a carboxyl group, and R ⁹ and R ¹⁰ are Each independently has a hydrogen atom or 1 carbon atom which may have a substituent.
To 4 alkyl group, a phenyl group which may have a substituent or an acyl group having a carbon number of 2 to 9 which may have a substituent, n represents a number of 1 or 2 and p represents 0. Or represents the number of 1. ) 2. The free acid form is represented by the following general formula [I] or [I]:
I] is a dye for a recording liquid. [Chemical 3] (In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a carbon atom having 1 to 4 which may have a substituent. 4 represents an alkoxy group, a hydroxyl group, a halogen atom, a sulfo group or an amino group which may have a substituent, and X and Y each independently represent an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. An alkoxy group or an acylamino group having 2 to 9 carbon atoms, R ⁴ and R ⁵
Are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a carbon number 2 which may have a substituent. 9 represents an acyl group, 1 represents a number of 1 or 2, and m represents a number of 0 or 1. ) [Chemical 4] (In the formula, R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a carbon atom having 1 to 4 carbon atoms which may have a substituent. 4 represents an alkoxy group, a halogen atom, a sulfo group or an optionally substituted amino group, Z and W each independently represent a hydrogen atom, a sulfo group or a carboxyl group, and R ⁹ and R ¹⁰ are Each independently has a hydrogen atom or 1 carbon atom which may have a substituent.
To 4 alkyl group, a phenyl group which may have a substituent or an acyl group having a carbon number of 2 to 9 which may have a substituent, n represents a number of 1 or 2 and p represents 0. Or represents the number of 1. )