JPS6330573A - Monoazo compound and recording fluid containing same - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention is directed to a novel metal-containing noazo compound and a so-called so-called recording device that is ejected from a fine nucleated ejection port (ejection orifice) and made to fly as a droplet. The present invention relates to a recording liquid suitable for an inkjet recording method.

(Prior Art) In the inkjet recording method, recording is performed by flying droplets of a recording liquid called ink and adhering them to a recording material. The basic components of such a recording liquid include a recording agent (dye or pigment is used) and a liquid medium for dissolving or dispersing it (water, various organic solvents, acids, or mixtures thereof are used), and as necessary. Depending on the situation, various additives are added.

Preferred characteristics of the recording liquid include (1) liquid physical properties (viscosity, surface tension, electrical conductivity, etc.) that match the ejection conditions (piezoelectric element drive voltage, drive frequency, orifice shape and material, orifice diameter, etc.); ), (11) It is stable for long-term storage and does not cause clogging; (■ The printed image must have excellent water resistance and light resistance, (Vl) The recording liquid must be small, tube,
(Sealing materials, etc.), and (VID) should be highly safe in terms of odor, toxicity, and flammability. In particular, clogging of nozzles should be avoided from the viewpoint of reliability of the recording method. is also a very important element, but it is quite difficult to satisfy all of the above characteristics at the same time.

Furthermore, since the recording liquid used for such recording purposes is basically composed of a dye and its solvent, the above-mentioned characteristics of the recording liquid are largely influenced by the inherent properties of the dye.

Therefore, selecting a dye so that the recording liquid has the above characteristics is an extremely important technique in this technical field.

Conventionally, as monoazo compounds used as magenta dyes for recording liquids, compounds represented by the following structural formula (%) are known, for example, and also,
Publication No. 30773 describes a complex salt dye represented by the following structural formula.

0130, Na SO3Na However, the above C0■, Acid Red-3! The recording liquid using the above-mentioned dye and -37 has extremely poor light resistance, and the recording liquid using the dye described in JP-A-57-30773 has a light resistance that is concentration dependent. Large, dark colors are good, but light colors are poor, and the tone is extremely dark yellowish or dark bluish magenta. Therefore, a color image is created using the primary color method using three colors: yellow, magenta, and cyan. When recording, problems such as not being able to obtain clear printed matter and insufficient color reproducibility occur.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a novel magenta-colored monoazo compound that satisfies the above-mentioned characteristics, and a recording liquid containing the compound.

[A precautionary measure to resolve the problem]

The present invention provides a novel monoazo compound represented by the following general formula CI] and a recording agent which is a component for forming a recorded image;
The gist of the recording liquid includes a liquid medium for dissolving or dispersing the recording agent, which contains at least seven types of monoazo compounds represented by the following general formula (1) as the recording agent. It is something.

(In the formula, M represents CU or co, n represents l or co, Q represents a naphthalene nucleus, and in Q, the 10-group exists in the ortho position with respect to the azo group. The dye of the monoazo compound represented by the general formula [1] of the present invention is described, for example, in Yutaka Hosoda's "New Dye Chemistry" (Showa 4L♂, 1999).
Published on February 27th) From Gihodo, No. 1! It can be manufactured by the following method according to the descriptions on page μ, page to page E, etc.

That is, 2-hydroxy-3-amino-y-sulfo-
After diazotizing benzoic acid with sodium nitrite or the like in a mineral acid such as hydrochloric acid or sulfuric acid, it is diazotized with sulfonic acid group-containing naphthols, such as 1-naphthol-3,6-disulfonic acid or 1-naphthol-J- By coupling with sulfonic acid, a monoazo compound represented by the following general formula [■] (where n, Q and W are the same as defined above) is produced. Treating the obtained monoazo compound with a copper salt such as copper acetate or steel sulfate, or a cobalt salt such as cobalt acetate or cobalt chloride in water and/or a water-soluble organic solvent such as alcohol or N-methylpyrolide 7. The dye represented by the general formula (1) of the present invention is produced by this method.

The content of dye in the recording liquid of the present invention is determined depending on the type of liquid medium components, the characteristics required of the recording liquid, etc.
Generally, the weight percentage is 0.0% based on the total weight of the recording liquid.
/ -20%, better < FiO, yo~/! The scratches are preferably in the range of 1 to 10 scratches. Of course, the dye can be used alone or in combination of two or more, or in combination with the dye as an essential component and various other dyes such as other direct dyes and acid dyes.

As the liquid medium component in the recording liquid of the present invention, water or a mixture of water and various water-soluble organic solvents is used. Examples of water-soluble organic solvents include methyl alcohol, ethyl alcohol, n-7' propyl alcohol, isopropyl alcohol, n-butyl alcohol, eec-butyl alcohol, tart-phthyl alcohol, imbutyl alcohol, etc. /, alkyl alcohol of e;
Amides such as dimethylformamide and dimethylacetamide; Ketones or ketone alcohols such as acetone and diacetone alcohol; Ethers such as tetrahydrofuran and dioxane; N-methyl-cobyrolidone, /, 3
-Dimethyl--Nitrogen-containing heterocyclic ketones such as imidazolidinone; Noboralkylene glycols such as polyethylene glycol, polypropylene glycol: ethylene glycol, globylene glycol, butylene glycol, triethylene glycol, 'I2,6- hexanetriol, thiodiglycol, hexylene glycol,
Alkylene glycols in which the alkylene group has 1 to 6 carbon atoms such as diethylene glycol; glycerin; polyhydric alcohols such as ethylene glycol methyl ether, diethylene glycol methyl (or H ethyl) ether, triethylene glycol monomethyl (or ethyl) ether, etc. Examples include lower alkyl ethers.

When a mixture of water and the above-mentioned water-soluble organic solvent is used as a liquid medium component, the content of the water-soluble organic solvent is generally 3% to 3% by weight, preferably 10% by weight, based on the total weight of the recording liquid. -10%, preferably in the range of -10%.

゛ The recording liquid of the present invention prepared from such components has excellent recording properties (signal response), storage stability, fixability to recording materials, or light resistance, weather resistance, and water resistance of recorded images. All of them are well-balanced and excellent. In order to further improve such properties, various conventionally known additives may be further added.

NLjtl'f, yj-'+7 Viscosity modifiers such as hinyl alcohol, celluloses, water-soluble resins, etc.: Various cationic, anionic or nonionic surfactants, surface tension modifiers such as jetanolamine, triethanolamine, etc. Examples include pH adjusters using buffers, antifungal agents, and the like.

In addition, in order to prepare the recording liquid used in the type of inkjet recording method that charges the recording liquid, lithium chloride,
A resistivity adjuster such as inorganic salts such as ammonium chloride and sodium chloride is added.

Note that when applied to an inkjet method in which recording liquid is ejected by the action of thermal energy, thermal properties (e.g., specific heat, coefficient of thermal expansion, thermal conductivity, etc.) may be adjusted. [Examples] The present invention will be explained in detail with reference to the following examples, but the present invention is not limited to these examples.

Production example/ (1) Diazotized 2-hydroxy-3-amino! -Sulfobenzoic acid co3
．． 32 was added to 2% hydrochloric acid≠70wt1, stirred for 3 hours to form a uniform slurry, and then 4tsoy of ice was added thereto and cooled to 3°C. 73d of water in this 2nd place! An aqueous solution in which 7.32% of sodium nitrite was dissolved was added thereto, and the mixture was stirred for a long time at 3°C to effect diazotization, and 39% of sulfamic acid was added to eliminate the remaining sodium nitrite to obtain a diazo solution.

(2) Coupling l-naphthol-3,6-disulfonic acid J (7,4C
After adding f to water/100m17, add ice rooy,
Adding the diazo solution and 100% 23% sodium hydroxide,
Coupling was carried out at pHr-10 and temperature j-10°C. After stirring for -tj hours at the same temperature and pH, salt!
30? was added to perform salting out. After filtering the precipitated compound, it was washed with 27% saline solution, dried, and
-hydroxy λ-(2-hydroxy-3-carboxylic acid-
yo-sulfonic acid phenyl aso)-naphthalene-3,6-
Disulfonic acid chloride sodium salt r 4Z,/f was obtained.

(3) Metal impregnation l-hydroxy 2-(2-human o) obtained in (2) above
=? Cj-carboxylic acid-monosulfonic acid phenyl aso)-naphthalene-3,6-disulfonic acid sodium salt 3/, r f 44! After melting in addition to Od, sulfuric acid steel/2. Add ≠5' and pHA~? , temperature evening 0-60℃
After stirring for 70 hours to coordinate the copper, salt/30t
Be sure to add salt for salting out. After filtering the precipitated compound, it was washed with 20% saline solution and wet cake/
I got 309. After desalting this wet cake,
Table 1 4/Dye (maximum absorption wavelength!Jrnm) which is dried and shown by the following structural formula
26.99 (yield 77.6%) was obtained.

Production Example λ Aλ~yaio described in Table 1 below in the same manner as Production Example 1
dye was produced.

Example 1 Ion exchange water (hereinafter abbreviated as water) 7/parts by weight diethylene glycol 2! 〃Production example/Dye
≠ I The above components were thoroughly mixed and dissolved in a container, passed through a Teflon filter with a pore size of lμ under pressure, and then degassed using a vacuum pump to obtain a recording liquid. Using the obtained recording liquid, an on-demand recording head (discharge orifice diameter: 104 m, piezo vibrator drive voltage: 6011, frequency≠
KH2) The following (Tl) is recorded by a recording device having
-(T,) were investigated, and good results were obtained in all cases.

(Ts) Long-term shelf life of recording liquid: Even after recording liquid was sealed in a glass container and stored at 60°C for 6 months, no precipitation of insoluble matter was observed, and the characteristics and color tone of the liquid were not affected. There was no change.

(T-discharge stability: Continuous dispensing was performed for 2≠ hours each in an atmosphere of 3℃, room temperature, t, and to℃ (Ts) Discharge response: Examined intermittent dispensing for 2 seconds and dispensing after being left for a month. However, in all cases, there was no clogging at the tip of the orifice, and stable and uniform recording was achieved.

(T4) Quality of recorded images: Recorded images have high density and are clear. The rate of decrease in density after exposure to indoor light was less than 7%, and there was very little smearing of the image when immersed in water for 1 minute.

(Ts) Fixability for various recording materials: Printing with the recording materials listed in Table 2 below/! After a few seconds, the printed area was rubbed with a finger to determine the presence or absence of image shift or bleeding, and in both cases, there was no image shift or bleeding, and excellent fixation was observed.9.

second garment However, in Table 2 above, the recording material base is a trade name.

Example 2 Water 6 parts by weight H-Metelukopyrrolidone lj Diethylene glycol/Ta I Dyes of Table 1 & 3
A recording liquid having the above composition was prepared in the same manner as in IAx Example 1, and an on-demand type multi-head (discharge orifice diameter 35μ , heating resistor resistance k'''Ω, driving voltage 30■, frequency a-2
(Tl) to (Ts) were investigated in the same manner as in Example 1 using a recording device having K) (z), and excellent results were obtained in all the investigation experiments.

Example 3 Water 4 Lj parts by weight Ethylene glycol 20 /, J dimethyl-coimidazolidinone A recording liquid having the above composition was prepared in the same manner as in Example 1, and the on-demand type multihead used in Example 1 was used. Similar to Example 1, K(Tl) to (Ts) were investigated using a recording device having the following properties, and excellent results were obtained in all the investigation experiments.

Example ≠ Water 60 parts by weight diethylene glycol 36 # Dye of the first draw U Hiroshi 〃 A liquid I& of the above composition was prepared in the same manner as in Example 1,
Using the on-demand type multi-head recording device used in Example 2, (Tl) to (
Ts), and excellent results were obtained in all experimental experiments.

Example: 6 parts by weight of water, 30 parts of diethylene glycol, 70% methyl ether, 30 s of dyes shown in Tables 1 & 2 ≠ A recording liquid having the above composition was prepared in the same manner as in Example 1, and mixed with the on-demand type multi-layer paint used in Example 2. Similarly to Example 1, (Ts) ~ (
Ts) was investigated, and excellent results were obtained in all the investigation experiments.

Examples 6 to 10 Recording liquids having the compositions shown below in 6 and 10K were prepared in the same manner as in Examples. These compositions were filled into felt-tip pens and written on medium-quality paper (white peony) to examine water resistance and writability after the cap was removed and left for an extended period of time.

The recording liquid of this example was excellent in both water resistance and writability after standing.

Comparative Examples 1 to 3 Light fastness and color tone were evaluated using the dyes listed in Table 3 below. The results are summarized in Table 3K.

Table 3 Continuation of Table 3 lf1 Example/: O, 1, Acid Red-3j0 Comparison row λ and 3: Dye described in JP-A-77-30773.

Lightfastness: Printed items with xenon fade meter C! 1Jj
(manufactured by Atlas, product name), irradiated for 20 hours,
The degree of discoloration and fading was evaluated by color difference (ΔE). The smaller the value, the better the light resistance.

Color tone: Printed using inkjet paper manufactured by Mitsubishi Paper Mills Co., Ltd., and judged visually.

Effects and Effects According to the recording liquid using the azo compound of the present invention, physical property values such as viscosity and surface tension are within appropriate ranges, and a recorded image of sufficiently high density can be produced without clogging the fine discharge orifice. It is possible to record on various materials without any change in physical properties or precipitation of solids during storage, without limiting the type of recording material, with high fixing speed, water resistance, abrasion resistance, and resolution. A recording liquid that gives images of excellent quality is obtained.

Further, the recording liquid of the present invention is not only excellent as the above inkjet recording ink, but also can be used as an ink for writing instruments.

Claims (3)

[Claims] (1) The following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼......[I] (In the formula, M represents Cu or Co, n represents 1 or 2, and Q represents a naphthalene nucleus. In the expression and Q -O-
The group is in the ortho position to the azo group. and W represents an alkali metal, ammonium or amines). (2) In a recording liquid containing a recording agent, which is a component for forming a recorded image, and a solvent for dissolving or dispersing this recording agent, the recording agent has the following general formula [I] ▲ Numerical formula, chemical formula, There are tables, etc.▼...[I] (In the formula, M represents Cu or Co, n represents 1 or 2, Q represents a naphthalene nucleus, and -O
The - group is in the ortho position to the azo group. Further, a recording liquid characterized in that it contains at least one monoazo compound represented by (W represents an alkali metal, ammonium, or amine). (3) The recording liquid according to claim 2, wherein the dye represented by the general formula [I] is contained in an amount of 0.1 to 20% by weight based on the total weight of the recording liquid.