JPS63117079A - Disazo compound and recording fluid containing same - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (wherein R is COOM, SO3M, nitro, acylamino or Cl; X is carbonyl, triazinyl, phthaloyl or a group of formula II; Y is carbonyl, triazinyl or phthaloyl; Me is Cu, Ni or Co; M is an alkali metal, ammonium or an amine). EXAMPLE:A compound of formula III. USE:A disazo compound useful for use in a recording fluid for writing utensils, such as a fountain pen and a felt pen, and for ink jet recording. PREPARATION:An amine of formula IV is diazotized in a mineral acid with sodium nitrite and then coupled with a naphthol of formula V, thus giving a disazo compound of formula VI. This compound and a metallic salt are heated in water.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel disazo compound and a recording liquid using the same, particularly a recording liquid for writing instruments (perpetual value, felt-tip pens, etc.), and a microscopic coating provided in a recording head. The present invention relates to a recording liquid suitable for a so-called inkjet recording method in which recording is performed by ejecting the liquid from an ejection port (ejection orifice) and flying it as droplets.

In the conventional inkjet recording method, recording is performed by causing droplets of a recording liquid called ink to fly and attaching the droplets 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. The preferable characteristics of the recording liquid include: (1) Ejection conditions (driving voltage of piezoelectric element, driving frequency, orifice shape and material, orifice diameter, etc.) K-matched liquid physical properties (viscosity, surface tension, conductivity, etc.) ), (11 Stable for long-term storage and does not cause clogging, +h+) Fast fixation to the recording material (paper, film, etc.) and smooth dot periphery without bleeding. (1v) The lines of the printed mental image are clear and have high density; (V) The printed mental image has excellent water resistance and light resistance. (tubing, sealing material, etc.), and (v+o) have excellent safety in terms of odor, toxicity, and flammability. Although this is a very important element from this point of view, it is quite difficult to satisfy all of the above characteristics at the same time.

1+ Since the recording liquid used for such recording purposes is basically composed of a dye and its solvent, the above-mentioned properties 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.

Recording liquids using conventionally known magenta dyes, such as azo dyes represented by the following structural formulas (1) to (3), have excellent water resistance, light resistance, long-term storage stability, ejection response, etc. It had unique characteristics.

(Direct Red-4t7) (Direct Red-?3) ・・・・・・(2)(
Reactive Red-6) Problems to be Solved by the Invention The purpose of the present invention is to provide a compound suitable for a magenta recording liquid that satisfies the above characteristics and a recording liquid using the compound. It is something to do.

Means for Solving the Problems The present invention is based on the general formula [I]...[I] (wherein R represents a C00M group, an 803M group, a nitro group, an acylamino group, or a chlorine atom, and represents a carbonyl group, a triazinyl group, a phthaloyl group, a carbonyl group, a triazinyl group, a phthaloyl group, and Me represents Cu, N
i, C○, and M represents an alkali metal, ammonium or amines. ), a recording agent which is a component for forming a recorded image, and a solvent for dissolving or dispersing this recording agent, in which the recording agent is represented by the general formula CD. The gist of the present invention is a recording liquid that does not contain a disazo compound.

In the compound of the general formula (Ill), M is Na
, K, alkali metals such as Li, NH4, ff (a
2a4oa),,NH(C!F!s)s,HE(C2
Examples include H3)3, etc. (7)7/monium and amines.

The dye of the general formula CI) contained in the present invention includes:
Specifically, those having the force structure formula shown in Table 1 can be mentioned.

The compound represented by the general formula (1) of the present invention can be used, for example, in "New Dye Chemistry" by Yutaka Hosoda,
It can be produced by the following method according to the description in Gihodo, page 4 to page 07 (published by Japan).

After diazotizing the amines represented by the general formula [■] (wherein R and M are the same as defined above) using sodium nitrite in a mineral acid such as hydrochloric acid or sulfuric acid, the following - general formula [■ ] (wherein, The shown disazo compound is obtained.

By heating the obtained disazo compound [■] with a metal salt in an aqueous solvent, the water-soluble metal complex dye of the present invention represented by the general formula [''I] is obtained.

The content of the dye of general formula [I] 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., but is generally based on the total weight of the recording liquid. 0.0% by weight. /~ko'%s preferably θ, j~/! It is preferably in the range of 7 to 10%. Of course, these dyes can be used alone or in combination of two or more, or in combination with various dyes such as other direct dyes and acid dyes, using the dye as an essential component.

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' lobil alcohol, isopropyl alcohol, n-butyl alcohol, 5ea-7'
alkyl alcohols such as dimethylformamide, dimethylformamide, dimethylacetamide; ketones or ketone alcohols such as acetone and diacetone alcohol; Ethers such as tetrahydrofuran and dioxane; Nitrogen-containing olefin ketones such as N-methyl-pyrrolidone and/or 3-dimethyl-imidazolidinone; Polyalkylene glycols such as polyethylene glycol and polypropylene glycol; Ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, /
, 2.6-hexandriol, thiocyclyl, hexylene glycol, diethylene glycol and other purkylene glycols in which the alkylene group contains 2 to 2 carbon atoms; gmetherin; ethylene glycol methyl ether, diethylene glycol methyl ( or lower alkyl ethers of polyhydric alcohols such as ethyl) ether and triethylene glycol monomethyl (or ethyl) ether.

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 expressed as a weight percent based on the total weight of the recording liquid. ~? ! H, preferably 10~roe4, preferably 20~! θ%
The range of

The recording liquid of the present invention prepared from these various components has recording properties (signal response, droplet formation stability, ejection stability, long-term continuous recording performance, and long-term record edge stability) by itself. Discharge stability), storage stability, fixation to recording materials, and light resistance, weather resistance, and water resistance of recorded images are all well-balanced and excellent, and these properties are further improved. To ensure this, various conventionally known additives may be added to Kf1.

fil, tha, ho IJ? Viscosity modifiers such as alcohol, cellulose, and water-soluble resins; Surface tension v4 modifiers such as cationic, anionic, or nonionic surfactants, jetanolamine, triethanolamine, etc.; and antifungal agents.

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 materials such as ammonium chloride and sodium chloride is added.

Note that when applied to an inkjet system in which recording liquid is ejected by the action of thermal energy, thermal physical property values (eg, specific heat, coefficient of thermal expansion, thermal conductivity, etc.) may be adjusted.

Functions and Effects Inkjet recording liquids are made by dissolving or dispersing dyes or pigments in a water-based liquid medium mainly from the standpoint of safety, and generally contain glycols or other wetting agents. A water-soluble organic solvent of low volatility is added. The solubility of dyes in these liquid media varies slightly depending on their structure, and generally the solubility in water and the solubility in glycols even tend to contradict each other. At the tip of the nozzle, as soon as water, which is the highly volatile component of the ink, evaporates, the concentration of glycols tends to be high in this area. Therefore, if a dye having low solubility in glycols is added to the recording liquid, there is a high risk that the dye will precipitate and cause nozzle clogging.

The dyes (1) to (3) listed above exhibit very good solubility in water, but are poor in solubility in glycols. On the other hand, the dye represented by the general formula CII used in the recording liquid of the present invention improves the solubility in glycols while maintaining the solubility in water within a practically sufficient range. It is extremely difficult to cause nozzle clogging.

According to the present invention, the physical property values such as viscosity and surface tension are kept within appropriate ranges, the fine ejection orifice is not clogged, a recorded image of sufficiently high density is provided, and the physical properties are maintained during storage. It can record on various materials without changing the value or precipitation of solids, without limiting the type of recording material, has a high fixing speed, and produces images with excellent water resistance, abrasion resistance, and resolution. A recording liquid 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.

EXAMPLES The present invention will be explained in further detail in the following production examples and examples.

Production example/ (Synthesis of dye shown in Table 1 Nh/) (1) Diazotization step Two-aminophenol-4t, 4-disulfonic acid Ho, 19 carp, 2 were added to 3% salt syrup and stirred. 200 f of ice was added and the mixture was cooled to 3°C. Then water 73
Dissolve 7.3t of sodium nitrite in - and add the required solution,
After diazotization by stirring at ℃ for 2 hours, sulfamic acid 3
2 to eliminate the remaining sodium nitrite and obtain a diazo solution.

(2) Cup link process The following compounds! , -1 was dissolved in 4 tOσd of aqueous sodium chloride solution, and the diazo solution obtained in step (1) above and the aqueous solution of 10 sodium chloride/rOd were added thereto, and the temperature was -20°C, pH 9~
After stirring and compiling for 0 hours at 10, salt = 0? was added to perform salting out. The precipitated disazo compound was filtered, washed with saline, and dried to obtain a disazo compound. Yield! It was a flathead.

(3) Azo compound obtained in complex salt formation step (2) 23. 4 tons of water! Dissolve in θ- and heat to 60-70°C. Water for this! 6. Cupric chloride dihydrate in Od. ? ? An aqueous solution containing 70% sodium chloride and a 70% aqueous sodium chloride solution were added, and the mixture was stirred at a temperature of 60 to 70°C for 7 hours to form a complex salt.After cooling, the solution was 70% sodium chloride. ff was added and salting out was performed. Precipitated complex chloride 't after filtration/!
- The wet cake was washed with brine, and the wet cake was desalted and dried to obtain the target compounds 7r and If below. Maximum absorption wavelength: 141 nm Production Example 2 (Synthesis of compounds shown in Table 1 Nn!) (1) Diazotization step = -Aminophenol 4t, t--) 3-Aminocohydroxy! in place of sulfonic acid! -Sulfobenzoic acid23. The diazo solution was drawn in the same manner as in Production Example 1, except that If was used. (2) Coupling step The following azo compound Geta, I looked at 7f.

(3) Complex chloride step: In place of cupric chloride dihydrate, nickel acetate tetrahydrate is added,
The following target compound λo, 4tt was prepared in the same manner as in Production Example except that t was used. Maximum absorption wavelength j 20 nm Production Example 3 Examples of compounds produced in the same manner as Production Example 2 are summarized in Table 1 below.

Example: The above components were thoroughly mixed and dissolved in a container, filtered under pressure through a Teflon filter with a pore size of /μ, and then degassed using a vacuum pump! A recording device having an on-demand recording head (discharge orifice diameter θμ, piezo oscillator drive voltage tOV, frequency kHz) that discharges the recording liquid using a piezoelectric vibrator, using a recording liquid that has been heated as a recording liquid. When the following studies (T1) to (T5) were conducted, good results were obtained in all cases.

(T1) Long-term storage stability of recording liquid: Even after recording liquid was sealed in a glass container and stored at -30℃ and 6θ℃ for g months, no precipitation of insoluble matter was observed, and there was no change in the characteristics or color tone of the liquid. There was no.

(T2) Discharge stability:! ℃, room temperature, and 0.degree. C. for a continuous period of time, and stable high-quality recording was possible from beginning to end under all conditions.

(T8) Discharge response We investigated intermittent dispensing for a knee second and dispensing after leaving it for a month, but in both cases, there was no clogging at the tip of the oriswiss, and recording was stable and uniform.

(T4) Quality of recorded image: The recorded image had high density and was clear. After being exposed to room light for 3 months, the rate of decrease in density was less than 10%, and when immersed in water for 7 minutes, there was very little blurring of the image.

(T5) 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 smearing, and both showed excellent fixing properties with no image shift or smearing.

Table 2 However, in the above Table 2, the recorded row name is the product name. Example 2 A recording liquid having the above composition was prepared in the same manner as in Example/, and the recording liquid in the recording head was heated On-demand type multi-head that generates droplets by applying energy and performs recording.
Discharge oriice diameter 3! μ, heating resistor resistance value/jOΩ,
Examinations (T1) to (T5) were conducted in the same manner as in Example 1 using a recording device having a drive voltage of 30v1 and a frequency of λKHz.

However, excellent results were obtained in all experiments.

Example 3 A recording liquid having the above composition was prepared in the same manner as in Example 1, and K (T+) to (
T5) was investigated, and excellent results were obtained in all the investigation experiments.

Example 4t-6 A recording liquid having the composition shown in D to T below was prepared in the same manner as in Example. Fill a feltben with these compositions,
Water resistance and writability after removing the cap and leaving it for λ hours were examined by writing on medium-quality paper (Hakubotan: Honshu Paper Industries).

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

Incidentally, in Example 2, 3.6 and 2 were used as the dye compound in Table 1, and in Example 2, dye compound Yin! Nodaishini floor? , /θ, /k were used to prepare the recording liquid, and tests (T1) to (Ts) were conducted in the same manner as in Example 1. Good results were obtained in all of the test experiments.

Claims (3)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・・・・[I] (In the formula, R represents a COOM group, SO_3M group, nitro group, acylamino group, or chlorine atom, X represents a carbonyl group, a triazinyl group, a phthaloyl group, or a ▲ group with mathematical formulas, chemical formulas, tables, etc.; Y represents a carbonyl group, triazinyl group, or phthaloyl group; Me represents Cu, Ni, Co; M represents Disazo compounds represented by alkali metals, ammonium or amines. (2) In a recording liquid that includes a recording agent, which is a component that forms a recorded image, and a solvent for dissolving or dispersing this recording agent, there are ▲ mathematical formulas, chemical formulas, tables, etc. as the recording agent ▼ ・...[I] (In the formula, R represents a COOM group, SO_3M group, nitro group, acylamino group, or chlorine atom, and X represents a carbonyl group, triazinyl group, phthaloyl group, or At least one compound represented by ▼ group, Y represents a carbonyl group, triazinyl group, or phthaloyl group, Me represents Cu, Ni, or Co, and M represents an alkali metal, ammonium, or amines) A recording liquid characterized by containing. (3) The recording liquid according to claim 2, wherein the compound 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.