JPS5922967A - Novel copper phthalocyanine dye and aqueous ink containing the same - Google Patents

Abstract

NEW MATERIAL:A dye of formula (CuPc is copper phthalocyanine residue, R1 is H, 1-3C alkyl or 1-3C hydroxyalkyl; R2 is 1-4C hydroxyalkyl; n is 3-4). USE:For aqueous ink for ink jet recording, giving high water resistance. PROCESS:Copper phthalocyanine is chlorosulfonated, using, for example, chlorosulfonic acid and thionyl chloride, followed by condensation with an amine having substituents R1 and R2.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel copper phthalocyanine dye and an aqueous ink containing the same, and particularly provides an aqueous ink with extremely good water resistance for use in inkjet recording.

The inkjet recording method is a method in which recording is performed by ejecting a recording medium liquid called ink as droplets from an ejection port provided in a recording head to form small stones on a recording paper, and does not require a specific fixing process. First, it has the advantage of generating less noise during recording.

Various methods have been proposed for such recording methods. For example, a recording device with a piezo vibrator that applies a recording signal to the throat and generates droplets of the recording medium liquid in accordance with the recording, or a recording medium that electrostatically attracts the recording medium liquid and collects the generated droplets. Recording is performed by controlling the electric field according to the recorded value, and by the continuous vibration generation method, a liquid controlled by J11 electrician or FM is generated, and the sample liquid drop is deflected by a deflection electrode to which a uniform electric field is applied. Many methods are known, including one in which recording is performed by flying between the lines.

However, no matter which method is used, the ejection orifice of this type of recording apparatus is a fine hole (generally about 50 mm in diameter) and is easily clogged by solids in the ink. In fact, even with a method that does not cause clogging, the generation of solid components may affect the stable flight of uniform droplets, resulting in a decrease in ejection stability, responsiveness, and continuous recording performance. Alternatively, if the constituent components of the recording liquid medium undergo chemical changes, the physical properties of the recording medium liquid, which were adjusted to the desired values at the time of compounding, deviate from the appropriate range, resulting in problems with ejection stability, responsiveness, continuous recording, etc. There may be adverse effects.

The recording medium liquid used for inkjet recording is.

It is usually a dye dissolved in water or an organic solvent.

However, when using an organic solvent, it is necessary to avoid those that are highly volatile, have a bad odor, or are toxic to the human body, so inks that use water as the main solvent are generally preferred.

Under these circumstances, it is desirable for the coloring material used in ink-sheet recording to be a dye with excellent solubility in water and high tinting power.

Generally, ink has three primary colors: yellow, magenta, and cyan, and in some cases, various hues are created by combining these four primary colors with the addition of plaque.

Conventionally, the hue of cyan color is C,1, Dairef I Blue 86 (C,1,74180) (formula [11:] below)
(% formula %) (formula [■] below) and C, 1, Asindo Blue 9 (C, 1,
42090) (formula [■] below), etc. are known.

CuPc(SO3Na)2
[mouth] Cu Pc -(SO3Na)i
[111': IC, 1, Direct Blue 86 is not sufficiently soluble in water, so a solubilizer is added to it as an auxiliary agent, but it is still a completely stable water-based ink. It was difficult to make. C,1, Acid Blue 249 has many sulfonic acid residues, and its solubility in water may be improved, or conversely, its solubility may cause the disadvantage that the water resistance of the ink after recording is poor. Similarly, C,I Acid Blue 9 has good solubility, but the water resistance of the ink after recording is poor.

As in the north, inkjet recording ink has very stable solubility to prevent clogging of the orifice until it is recorded on paper, and after being recorded on paper, it does not get wet with water. It must have the contradictory properties of being water resistant and not soluble. The present invention has been made in view of this point.

The inventors of the present invention have made intensive studies to create a stable ink for cyan inkjet recording.The dye represented by the general formula [■] can be used to improve storage stability, ejection stability, ejection response, and continuous recording. It has been found that a cyan inkjet recording ink can be obtained which has good properties and also shows excellent water resistance after being recorded on paper.

The present invention has the general formula CI) I Cu Pc-(5O2N-R2)n CI
) (in the formula, CuPc is a copper phthalocyanine residue,
R+ represents water R1c, ~3 alkyl group or C1-3 hydroxyalkyl group, R2 represents C1-4 hydroxyalkyl group, and n represents a number from 3 to 4. ) A new copper phthalocyanine dye and an inkjet recording ink containing it are also available.

The copper phthalocyanine dye represented by the general formula [■] is produced by subjecting copper phthalocyanine to a conventional method, for example, using thalosulfation conditions and thionyl chloride, and then converting it to a specific amine having substituents R, R2. Obtained by condensation.

When a copper phthalocyanine residue is thalosulfated, the number of sulfonyl chloride groups introduced can vary from 1 to 4 depending on the talosulfation conditions, but in the case of the present invention, 3 to 4 sulfonyl chloride groups are introduced. Sulfonyl chloride groups are susceptible to hydrolysis;
It is hydrolyzed into sulfonic acid, which becomes an alkali metal salt or amine salt of sulfonic acid. If too much of these salts are mixed in, the water resistance of the recorded image will deteriorate, so special care must be taken when handling sulfonyl chloride.

Preferred amines for use in the present invention include monoethanolamine, jetanolamine, monopropanolamine, dibrobanolamine, 2-aminopropanolamine, (N-hydroxymethyl)ethanolamine, 2-
Amino-2-methylpropatool, N-methylex/-
Luamine etc. are given.

The dye represented by the general formula [■] thus obtained dissolves well in water and exhibits a clear cyan color17, and exhibits a dark same color on paper.

The inkjet recording ink of the present invention is produced by dissolving the dye represented by general formula CI) in water.

The gold bias of the dye at this time is 1 to 20% relative to the ink composition.
Heavy consumption%, good performance is 2 to 10 @ (14%).

Indeed, polyhydric alcohols, ethers or esters thereof may be added to the ink of the present invention as solubilizing agents. Examples include ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethyl ether or methyl ether, diethylene glycol 7-methyl ether, ethyl ether or methyl ether, ethylene glycol i k Id methyl, edyl or gudyl ester of diethylene glycol. It will be done.

These solubilizing agents are used in an amount of 0 to 20% by weight, preferably 1 to 15% by weight, based on the ink composition.

The ink of the present invention can be appropriately added with a finishing agent, a preservative, a metal corrosion inhibitor, and the like.

The cyan inkjet of the present invention thus obtained)
The recording ink is extremely stable and does not cause crystal precipitation, so the orifice will not be clogged, and has good ejection stability, responsiveness, and continuous recording performance. Water resistance has been greatly improved.

Next, a method for synthesizing the novel dye of the present invention will be described, but the present invention is not limited thereto.

Example 1 (Synthesis of dye (1)) 58p of copper phthalocyanine was gradually added and mixed to 210y of talolsulfonic acid with stirring, and then 130 to 140
Heat to °C and stir for 3 hours. The mixture was then cooled at 90°C in a sieve, added with 100Yf:M'b of thionyl chloride, and stirred at 90°C for 3 hours, then cooled at 20°C in a sieve, and heated to 100% in water.
Pour into a mixture of 7 and 300 Y of water and precipitate copper phthalocyanine!・Rinse the rasulfonyl chloride from door to door and wash it with water at 5℃ to make it almost neutral. The paste of copper phthalocyanine tetrasulfonyl chloride thus obtained was mixed with 5 ml of water.
The mixture is stirred and dispersed in a mixture of 00y and 300 g of ice, then 30y of monoethanolamine is added, and then an aqueous sodium carbonate solution is added to adjust the pH to 8 to 9, and the mixture is stirred for 10 hours. Next, the temperature was raised to a humidity of 50'CK in 1 hour, and an aqueous sodium carbonate solution was added to maintain the pH at 8 to 9. When the pH no longer decreased, the product was taken from house to house, washed with water, and dried. 100y of internally dark colored powder (referred to as dye (1)) was obtained.

Examples 2 to 8 (Synthesis of dye Pl(2) to (8)) Example 1
Similarly, instead of monoethanolamine, jetanolamine 602, propanolamine 35g, cibrobanolamine 707.2-aminopropanol 35
y, <N~hydroxymedyl) elafuramine 3f y
, 2-Asanol 2-methylpropyl-40/', N
- Dye (2) using methylethanolamine 3512
~(8) was obtained.

・Elemental analysis values of dyes (1) to (8), maximum absorption wavelength (
aqueous solution) are shown in Table 1. The riJ visual area absorption waveform of dye (1) is shown in FIG. 1, and the infrared absorption waveform is shown in FIG.

\\ Next, examples of the inkjet recording ink of the present invention will be described in detail.

Examples 9-12. Comparative Examples 1 to 2 Each composition shown in Table 2 was thoroughly mixed and dissolved individually in a container, filtered under pressure using a Teflon filter with a pore size of 1 μm, and then degassed using a vacuum pump to form an ink. . stomach(
An on-demand recording head (discharge orifice diameter 50, ilm, piezo vibrator, drive voltage 6
The following tests (a) to (d) were conducted using a recording device having a frequency of 0V, 4KI, and the results are shown in Table 2. Good results were obtained in Examples 9 to 12, but problems occurred in Comparative Examples.

(B) Long-term storage stability of ink: Even after the ink was sealed in a glass container and stored at -30°C and 60°C for 6 months, no precipitation of major soluble components was observed in the inks of Examples 9 to 12. There was no change in the physical properties or color tone of the liquid. The ink of Comparative Example 1 caused precipitation.

(b) Discharge stability; Examples 9 to 12 were continuous discharges were performed for 24 hours in an atmosphere of room temperature, 5°C, and 40°C.
The ink provided stable, high-quality recording from beginning to end under all conditions. The ink of Comparative Example 1 caused clogging of the orifice after 1 hour at 5°C.

(c) Ejection response: intermittent ejection of 2 seconds and 4 n゛. The ejection after being left for 2 months was investigated. In all cases, the inks of Examples 9 to 12 were stable and uniform without clogging of the orifice. recorded. The ink of the comparative example caused clogging of the orifice.

(iv) Quality of recorded images: Images recorded using the inks of Examples 9 to 12 had high density and were clear. Unfortunately, when immersed in water for 1 minute, there was very little blurring of the image. The image using the ink of Comparative Example 2 ran out in water and was difficult to read.

Examples 13 to 16 In the same manner as in Example 9, dye (5) was used instead of dye (1),
Example 13.14.1 using (6), (7), and (8)
5.16 inks were prepared, and (a) to
(d) was considered. Excellent results were obtained in all testing experiments.

4 Simple diagram explanation Figure 1 shows the visible absorption waveform of dye (1) (C20mY/l water)
FIG. 2 shows the infrared absorption waveform of dye (1).

Patent applicant: Taoka Chemical Industry Co., Ltd.

Claims (1)

[Claims] (1) Copper phthalocyanine dye represented by -1 formula [■]・2゜Cu Pc (5O2N R2) n
[I:lI (where Cu Pc is copper phthalocyanine 31.
N, R7 is hydrogen, C1-3 alkyl group, or C1-. There is a nohytroxyalkyl group, and R2 is C1~
An aqueous ink comprising a copper phthalocyanine dye having 4 hydroxyalkyl groups, where n represents a number of ˜4 (2) general formula CI)].