JP3486982B2 - Recording liquid - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording liquid for ink jet recording and writing instruments.

[0002]

2. Description of the Related Art In an ink jet recording method, when plain paper such as electrophotographic paper, bond paper, and stock foam paper is used as recording paper, the water resistance after printing is inferior, or the density of printed matter (hereinafter referred to as " There is a problem that the storage stability of the ink tends to become unstable in addition to the problem that the "OD" is abbreviated). Therefore, by reducing the water solubility of the dye in order to improve the water resistance, or by introducing a hydrogen-bonding amino group or the like into the dye structure, the dye's association property (aggregation property) is increased, and The so-called "bronzing", in which the pigment aggregates have a metallic flaky luster
There is a problem in that the so-called phenomenon occurs and the OD of the printed matter decreases, or the dye aggregates and deposits during storage of the ink.

As one of the means for solving these problems, it has been proposed to incorporate a certain nitrogen-containing compound in the recording liquid. As an example of this, Japanese Patent Laid-Open No. 54-797
28, JP-A-55-120676, JP-A-2-41
No. 369, JP-A No. 62-119280, and JP-A No. 5-1.
No. 25311, JP-A-1-152176, and JP-A-64
The inventions described in JP-A-6072, JP-A-6-128515 and the like are known, but these recording liquids fail to obtain sufficient effects or fail to obtain the effects with respect to the above problems. Also has major defects such as easy clogging at the nozzle tip or bleeding of printing.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a recording liquid which has a high print OD even when recording on plain paper and is excellent in water resistance.

[0005]

The present invention provides a water-soluble dye,
The gist is a recording liquid containing an aqueous medium and the compound represented by the general formula [I] described in claim 1.
Hereinafter, the present invention will be described in detail. The water-soluble dye used in the present invention is not particularly limited, and azo-based, anthraquinone-based, quinophthalone-based, indigo-based and phthalocyanine-based direct dyes and acid dyes, and dyes developed for recording liquids can of course be used. For example, C.I. I. Direct B
rack-17, -19, -22, -32, -51,-
80, -91, -151 and -154, C.I. I. Dir
ect Blue-86 and -199, C.I. I. Dir
ect Red-80, C.I. I. Direct Yel
low-86 and -142, C.I. I. Acid Bla
ck-2, -24, -26, -48, -52, -63,
-172, -194 and -208, C.I. I. Acid
Blue-9, -185 and -254, C.I. I. Aci
d Red-8, -35, -37 and -257, C.I.
I. Acid Yellow-23 and -49 and C.I.
I. Food Black-2 etc. are mentioned.

The content of the above water-soluble dye is usually in the range of 0.2 to 12%, preferably in the range of 2 to 8% based on the total weight of the recording liquid. Examples of the aqueous medium used in the present invention include, in addition to water, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (# 200), polyethylene glycol (# 40).
0), glycols such as glycerin, N-methyl-pyrrolidone, N-ethyl-pyrrolidone, N-vinyl-pyrrolidone, 1,3-dimethyl-imidazolidinone, ethylene glycol monoallyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether. Ethers, ethers such as diethylene glycol monobutyl ether, 2-pyrrolidone, sulfolane, ethyl alcohol, alcohols such as isopropanol, diethanolamine, it is preferable to contain a water-soluble organic solvent such as alkanolamines such as triethanolamine, The content of these water-soluble organic solvents is in the range of 10 to 50% by weight based on the total weight of the recording liquid.
On the other hand, the amount of water used is in the range of 45 to 90% by weight with respect to the total amount of the recording liquid.

The recording liquid of the present invention is characterized by using the compound represented by the general formula [I]. Specifically, in the general formula [I], among the substituents represented by X, Y and Z, the alkyl group of the alkylamino group is preferably one having 1 to 18 carbon atoms, and the alkenyl group of the alkenylamino group is It preferably has 2 to 18 carbon atoms, the arylamino group and aryloxy group preferably have 5 to 10 carbon atoms, and the alkoxy group preferably has 1 to 18 carbon atoms.

Further, an amino group represented by X, Y and Z,
Examples of the substituent that the group other than the hydroxyl group may have include a hydroxyl group, a COOH group, a SO ₃ H group, a halogen atom such as a chlorine atom, an alkoxy group having 1 to 8 carbon atoms, and an alkylamino group having 1 to 8 carbon atoms. Group, a piperazinyl group optionally substituted with an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 8 carbon atoms substituted with an amino group optionally substituted with an alkyl group having 1 to 8 carbon atoms optionally substituted piperazinyl group, a morpholino group, a cyano group, an anilino group, an acylamino group, an amino group, an indolyl group, an imidazolyl group, O
Examples thereof include a octyl group and a phenyl group . However, the hydroxyl group
It does not bind to the arylamino group. The octyl group is
It binds only to the reel amino group, and the phenyl group is alkyl
It binds only to the mino group. When X, Y and Z are substituted amino groups such as alkylamino groups, they may be monoalkylamino groups, dialkylamino groups or the like, monosubstituted amino groups or disubstituted amino groups.

Specific examples of X, Y and Z include --NH
₂, -NHC₂H_Five, -N (C_FourH ₉(I))₂, -N
HC_FourH₉(T),

[0010]

[Chemical 2]

[0011]

[Chemical 3]

[0012]

[Chemical 4]

[0013]

[Table 1]

[0014]

[Table 2]

The content of the compound represented by the general formula [I] is 0.1 to 3% by weight, preferably 0.5 to 1.5% by weight based on the total weight of the recording liquid. To be The compound represented by the general formula [I] can be easily obtained, for example, by reacting trichlorotriazine with amines, alcohols or phenols corresponding to X, Y and Z according to a conventional method.

The pH of the recording liquid of the present invention is usually adjusted to 8 to 10 using alkali or the like. Further, the recording liquid of the present invention contains 0.1 to 10% by weight, preferably 0.5 to 5% by weight, of a compound selected from urea, thiourea, biuret and semicarbazide, or 0% by weight based on the total weight of the recording liquid. .0
By adding the surfactant in an amount of 01 to 0.5% by weight, the quick drying property after printing and the printing quality can be further improved.

[0017]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1

[0018]

[Table 3]           Composition of recording liquid Usage (% by weight)     C. I. Food Black-23     Diethylene glycol 10     The No. Compound of 1 1.5     Water balance   ─────────────────────────────               Total 100

The above components were sufficiently mixed and dissolved in a container, filtered under pressure with a Teflon filter having a pore size of 1 μm, and then deaerated using a vacuum pump to prepare a recording liquid.
The obtained recording liquid was used to perform inkjet recording with an inkjet printer (trade name: HG-3000, manufactured by Epson Corporation), and quick-drying property and print quality were evaluated according to the following methods (a) and (b). .

(A) Quick-drying: Printing is performed on electrophotographic paper (product of Xerox Co., Ltd.), bond paper and stock form paper (product of Lion Office Equipment Co., Ltd.), and after 30 seconds, the printing portion is rubbed with a finger to prevent misalignment of the image. The presence or absence was judged. All of them showed no deviation and showed excellent fixability. (B) Print quality: Each dot printed on the above recording paper was observed with a microscope, and the presence or absence of feathering (whisker-like bleeding) around the dot and the sharpness of the contour were visually evaluated. Both have no feathering,
The contour was also sharp.

Further, the inkjet recording was evaluated according to the following methods (c) to (f). (C) Long-term storability of recording liquid: Even after the recording liquid was sealed in a glass container and stored at 0 ° C. and 60 ° C. for 6 months, insoluble matter was not deposited, and the physical properties and color tone of the liquid did not change. There wasn't. (D) Ejection stability: Continuous ejection was performed for 24 hours in each of the atmospheres at room temperature, 5 ° C., and 40 ° C., and stable high-quality recording was always possible under any of the conditions. (E) Discharge responsiveness: Intermittent discharge every 2 seconds and discharge after being left for 2 months were examined, and in any case, stable and uniform recording was obtained without clogging at the orifice tip. (F) Quality of recorded image: The recorded image was high in density and clear. The rate of decrease in density after exposure to room light for 3 months was 10% or less, and image bleeding was very slight when immersed in water for 1 minute.

Comparative Example In Example 1, the No. Evaluation was carried out in the same manner as in Example 1 except that the compound No. 1 was not added, and as a result, when the formed image was immersed in water for 1 minute, the recorded image was remarkably bleeded and the density was remarkably low. . Example 2

[0023]

[Table 4]           Composition of recording liquid Usage (% by weight)     C. I. Direct Blue-86 3     Glycerin 10     Ethylene glycol 10     The No. Compound 1 of 2     Water balance   ─────────────────────────────               Total 100

A recording liquid having the above composition was prepared in the same manner as in Example 1, and the results of (a) to (f) were examined. As a result, good results were obtained. Examples 3 to 14 According to the method of Example 1, recording liquids having the compositions shown in Table 1 below were prepared, and (a) to (f) described in Example 1 were prepared.
As a result of evaluation according to the above method, all were good.

[0025]

[Table 5]

[0026]

[Table 6]

[0027]

[Table 7]

[0028]

[Table 8]

[0029]

[Table 9]

[0030]

INDUSTRIAL APPLICABILITY The recording liquid of the present invention is used for ink jet recording, writing instruments, etc., and is excellent in quick-drying property after recording and printing quality. No rubbing of the image even if rubbed, and
An image with no bleeding and a sharp contour can be obtained. When the recording liquid of the present invention is used for inkjet recording, in addition to the above effects, recording characteristics (signal responsiveness, droplet formation stability, ejection stability, long-term continuous recording property), storage stability Also, the OD of recorded images, light resistance, weather resistance, water resistance, etc. are all good.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toru Nishimura 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Mitsubishi Kasei Corp. Research Institute (72) Takashi Hirasa 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Mitsubishi Kasei Research Institute, Inc. (56) Reference JP-A-3-54268 (JP, A) JP-A-4-120180 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09D 11 / 00-11/20 B41J 2/01-2/01 B41M 5/00

Claims (3)

(57) [Claims] 1. A recording liquid containing a water-soluble dye, an aqueous medium and a compound represented by the following general formula [I]. [Chemical 1] (In the formula, X, Y and Z are independently of each other an amino group, a hydroxyl group, an alkylamino group, an alkenylamino group, an arylamino group, a pyridylamino group, a pyrrolidinyl group, a pyrrolidinylamino group, a piperazinyl group and a piperazinylamino group. group, pyrazinyl group, pyrazinylamino group, a cyclohexylamino group, an amino group, other than a hydroxyl group of representative. these groups an alkoxy group or an aryloxy group, further
Even if it has a substituent selected from the following substituent group
Good. In addition, at least one group of X, Y, and Z is
Location the free acid form of the acid group is -COOH or -SO ₃ H
It has as a substituent. Further , two or more of X, Y and Z are not hydroxyl groups. Substituent group; hydroxyl group, COOH group, SO ₃ H group, halogen atom, carbon
C1-8 alkoxy group, C1-8 alkylamido
May be substituted with an alkyl group having 1 to 8 carbon atoms
Substituted with a piperazinyl group or an alkyl group having 1 to 8 carbon atoms
An optionally substituted amino group having 1 to 8 carbon atoms
An optionally substituted piperazinyl group,
Holino group, cyano group, anilino group, acylamino group,
Mino group, indolyl group, imidazolyl group, octyl group,
And a phenyl group. However, the hydroxyl group is not the arylamino group
Do not combine. Also, the octyl group is only the arylamino group.
Bond, the phenyl group only binds to the alkylamino group
It ) 2. At least one of X, Y and Z is as follows:
An ant which may have a substituent selected from the substituent group bonded thereto
3. The record according to claim 1, which is an amino group.
Recording fluid. Substituent group; -SO ₃ H group, -COOH group, alkoxy group having 1 to 8 carbon atoms
Si group, acylamino group, halogen atom, hydroxyal
An optionally substituted amino group, and octyl
Basis 3. X, Y and Z independently of one another are alkyl
Amino group, hydroxyl group, alkoxy group, phenyl group, morpho
Reno group, indolyl group, imidazolyl group, alkyl group
An optionally substituted piperazinyl group, a -COOH group,
And -SO ₃ Substituted with a substituent selected from the group consisting of H groups
Optionally substituted alkylamino group; alkenylamino
Group; -COOH group, -SO ₃ Consisting of H and octyl groups
An aryl group optionally substituted with a group selected from the group
Mino group; ar which may be substituted with alkylamino group
Coxy group; aryl which may be substituted with -COOH group
Ruoxy group; Pyro optionally substituted with -COOH group
Lysyl group; Piperazi optionally substituted with alkyl group
Nyl group; hydroxyl group; pyridylamino group; or cyclohexyl
A compound according to claim 1, which represents a ruamino group.
Recording fluid.