JPS60243176A - Recording solution containing disazo dye - Google Patents

Abstract

PURPOSE:A novel recording solution that contains a specific dye as a recording agent, thus being suitable for use in ink jet printing from an orifice, because it has high stability in jetting and storage for a long period of time. CONSTITUTION:In a recording solution containing a recording agent as a component forming record images and a liquid medium which dissolves or disperses the recording agent, a dye of formula I [R<1>, R<2> are H, OH, SO3M (M is alkali metal, quanternary ammonium, amines), amino, mono or di-lower-alkylamino, anilino which may be substituted, acetylamino, benzoylamino which may be substituted; R<3>, R<4> are H, OH, SO3M, mono-lower-alkylamino which may be substituted; D is benzene ring or naphthalene ring which may be substituted with SO3M, OH, lower alkoxy or acetylamino) such as the dye of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION Object of the Invention (a) Field of Industrial Application The present invention relates to a recording liquid containing a black disazo dye.

More specifically, the present invention relates to a novel recording liquid, and particularly to a recording liquid suitable for a recording method in which recording is performed by ejecting the liquid from fine ejection ports (ejection orifices) provided in a print head and flying the liquid as droplets.

(B) Conventional technology Traditionally, writing instruments (fountain pens, feltbens, etc.) that record on recording materials such as paper have used ink made by dissolving various dyes in water or other organic solvents. There is.

In addition, the liquid (droplets called ink) inside the recording head is ejected from the ejection orifice due to vibrations caused by the piezo sensor or electrostatic attraction caused by the application of voltage, etc. to perform temperature recording. Inkjet recording methods are known, and these also use recording liquids in which various dyes are dissolved in water, organic solvents, or the like. but,
Compared to inks for stationery such as general fountain pens and felt-tip pens, recording liquids for inkjet use have many characteristics that require stricter conditions.

Such a recording liquid is a recording agent (a dye or a dye is used).
The basic components are a liquid medium (water, various organic solvents, or a mixture thereof) for dissolving or dispersing this, and various additives are added as necessary.

(c) Problems to be solved by the invention Preferred conditions for this type of inkjet recording liquid include: (1) Ejection conditions (driving voltage of piezoelectric element, driving frequency,
Orifice shape and material, orifice diameter, etc.) Ic Matching liquid physical properties (viscosity, surface tension, conductivity, etc.) f, (2) Stable for long-term storage and does not cause clogging (3) It fixes quickly on the recording material (paper, film, etc.), the dot periphery is smooth and there is little bleeding, and (4) the color tone of the printed image is clear and lli! (5) The water resistance and light resistance of the printed image are poor; (6) The recording liquid does not corrode surrounding materials (containers, connecting tubes, sealing materials, etc.); (7) ) It must be safe in terms of odor, toxicity, flammability, etc. However, it is quite difficult to satisfy all of these 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-mentioned properties is an extremely important technique in this technical field. Conventionally, as this type of recording liquid, for example,
No. 61, special public Shoyo l-da Oda g4, special public Sho 5 Koichi/
J/Koro-go, Tokuko Akira! 2-/J/27 and JP-A-Sho
- As shown in various publications of the Tsoog issue, dyes or pigments dissolved or dispersed in aqueous or non-aqueous solvents are known.
C, 1, Footblack-2 (C, 1, Core 7!A;
)'303Nm An object of the present invention is to provide a recording liquid that simultaneously satisfies the above characteristics (1) to (5).

Components of the Invention That is, the present invention provides a recording agent which is a component for forming recording itt, a liquid medium for dissolving or dispersing this recording agent, and a recording liquid containing gold, in which the recording agent has the following general formula [I ] (In the formula, R1 and R2 are a hydrogen atom, a hydroxyl group, an SO-returning group, an amino group, a mono-lower alkylamino group, a di-lower alkylamino group, an optionally substituted anilino group, an acetylamino group, or a mineral-substituted group) R3 and R4 represent a mono-lower alkylamino group, di-lower alkylamino group, acetylamino group, lower All alkyl groups, lower alkoxy groups, or chlorine atoms are represented; D represents a benzene ring or naphthalene ring which may be substituted with an SO3M group, a water fIt group, a lower alkoxy group, or an acetylamino group; M is an alkali metal, a quaternary The gist of the recording liquid is a recording liquid containing a disazo dye, which is characterized by being a dye represented by (representing ammonium or amines).

In the dye of general formula [1] contained in the recording liquid of the present invention, lower alkyl and lower alkoxy mean alkyl and alkoxy having l-da carbon atoms.

Further, examples of the substituents of the optionally substituted anilino group and the optionally substituted benzoylamino group include a lower alkyl group, a lower alkoxy group, a hydroxyl group, an amine group, a nitro group, and an 803M group.

M is Na, alkali gold such as Ll, NH4,
NH(C,H40H),, Nu(CH,)3, NH(C
zHs) + specialized quaternary ammoniums and amines.

The compound of the present invention can be obtained, for example, by the following method.

By coupling with an amine represented by the following general formula [111% formula %] (the formula is the same as the above electrode) general formula [lid] s, the following general formula [1v] 8 (formula, R3 and R4 are the same as those mentioned above).

The obtained monoazo compound is diazotized in a mineral acid such as hydrochloric acid or sulfuric acid using a nitrous acid nose, etc., and then a naphthol represented by the following general formula [V] (in which Bl and R2 are the same as defined above) is obtained. When coupled with and K, the water-soluble disazo compound of the present invention can be obtained from K.
(See page core line to page 391 lt line).

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.
/5-20%, preferably Q-75%, more preferably /-10. Of course, these dyes can be used alone, or in combination of these or more types, or in combination with various dyes such as other direct dyes and acid dyes, with the dye as an essential component.

The liquid medium components for forming the recording metal composition of the present invention include:
Water or a mixture of water and various water-bathable organic solvents is used. Examples of water-soluble organic solvents include methyl alcohol, ethyl alcohol, n-7'' propyl alcohol, isopropyl alcohol, n-7'' alcohol, see-7'' alcohol, tert-7'' alcohol, Alkyl alcohols with 7 or more carbon atoms such as inbutyl alcohol Amides such as dimethylformamide and dimethylacetamide; Ketones or ketone alcohols such as acetone and diacetone alcohol; Ethers such as tetrahydrofuran and dioxane: N-methyl- Nitrogen-containing heterocyclic ketones such as λ-pyrrolidone and i,3-dimethyl-coimidazolidinone; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, ethylene glycol, triethylene glycol,
/, 2. A-hexanetriol, thiodiglycol,
Alkylene glycol containing 2 to 6 carbon atoms such as hexylene glycol, diethylene glycol; Glycerin: ethylene glycol methyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, triethylene glycol monomethyl ether, Examples include lower alkyl ethers of polyhydric alcohols such as ethylene glycol monoethyl ether.

The content of the above-mentioned water-soluble organic solvent in the recording liquid is generally expressed in percent by weight based on the total weight of the recording liquid! ? -93%, preferably /0-f9%, more preferably co-O-S
The range is 0%.

The water content 1 at this time is determined within a wide range depending on the above-mentioned solvent component 41j, its composition, and the desired characteristics of the recording liquid, but is generally io to 9 based on the total weight of the recording liquid.
o%, preferably lθ~7θchi, more preferably koO~
It is considered to be within the range of 70.

The method for producing the recording liquid of the present invention does not require any particularly difficult treatment, and the necessary components may be mixed by a conventional method.

The recording liquid of the present invention has recording characteristics (signal response,
Stability of droplet formation, ejection stability, continuous recording performance of Nagatokiura,
It is well-balanced in terms of ejection stability (after a long period of recording interruption), storage stability, fixation to recording materials, and light resistance, weather resistance, and water resistance of recorded images. In order to further improve such properties, various conventionally known additives may be added.

Example tR, ho'! By using vinyl alcohol, cellulose, viscosity enhancing agents such as water-soluble viscosity enhancers, cationic, anionic, or nonionic surfactants, surface tension modifiers such as jetanolamine and triethanolamine, and buffers. Examples include pH regulators, 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 suppressing agent such as an inorganic base oil such as ammonium chloride or sodium chloride is added.

Note that when applied to an inkjet method in which recording liquid is ejected by the action of thermal energy, the thermal physical properties (if, for example, specific heat, coefficient of thermal expansion, thermal conductivity, etc.) may be adjusted. be.

According to the present invention, physical property values such as viscosity and surface tension are within appropriate ranges, do not clog the fine discharge orifice, provide a sufficiently preserved recorded image, and do not change physical property values during storage. It can record on a variety of materials without any precipitation of solids, has a high fixing speed, and has excellent water resistance, light resistance, abrasion resistance, and resolution. i- A recording liquid is obtained.

There are many types of inkjet recording methods, depending on the method of generating liquid gaps and the method of controlling the flying direction of droplets. An example of this is shown in the tgt diagram.

That is, the device shown in FIG.
It is assumed that recording is performed by generating k. In FIG. 1, l is a recording head, which includes a piezo vibrator Ja, a diaphragm b, a recording liquid inlet 3, a liquid outlet in the head, and an ejection opening (
It has a discharge orifice (discharge orifice) S. A recording liquid stored in a storage tank 6 is introduced into the liquid chamber through a supply pipe g. Depending on the location, an intermediate treatment means such as a pump or a filter may be provided in the middle of the supply pipe g. Then, the piezo vibrator-a is applied with a pulse-transformed signal from the recording signal S by a signal processing means (for example, a pulse converter) io, and pressure is applied to the recording liquid in the liquid chamber in accordance with the signal. Change occurs. As a result, recording liquid 7
is ejected from the ejection orifice 5 as droplets 11, and recording is performed on the surface of the recording material /2.

In addition to the above-mentioned devices, various types of devices are known, such as K as shown in No. 11.

As a modification of Fig. 1, there is a device in which the droplet is shaped like a nozzle and all cylindrical piezoelectric vibrators are installed on the outer periphery (the mechanism of droplet generation in this device is essentially
(This is the same as the device shown in Figure 1).It is also a device that generates electrically charged droplets in a series and uses some of the droplets for recording, or a device that applies recording signals to the recording liquid in the base circle of the recording head. There are also known devices that apply corresponding thermal energy and use the energy to generate enemy gamma.

Examples thereof are shown in Figures 3-&, Figures a-b, and Figure 9.

The head 13 is made of glass, ceramics, plastic plate, etc. that supports the m/II through which ink passes, and a heat generating head 15 used for thermal recording (a thin film head is shown in the figure, but it is not limited to this). It is obtained by connecting the heat-generating head/jh thermal membrane 16 formed of silicon oxide etc., aluminum electric lamp lcooler, /7-
Heat-generating resistor (formed of nichrome, etc.) fill, heat storage 1111119, substrate 20 with good heat dissipation such as alumina, etc.
It consists of

It has reached the ink/q discharge orifice, and the pressure P
A meniscus d3 is formed by this.

Now, if we add the '-air booster signal to electrodes /7-/ and /7-, we get
The area indicated by n of the heating head /S suddenly generates heat, and bubbles are generated in the ink 2 / that is in contact with this area, and the meniscus 3 protrudes due to the pressure, and the ink 21 is ejected from the orifice 22 to the recording droplet unit. The recording material 25 becomes a target and flies toward the recording material 25. Fig. 1 shows an external view of a multi-head in which a large number of heads shown in Fig. iJa are arranged. The multi-head is manufactured by connecting a glass plate 27 having a multi-coil 26 to a heating head 2gf similar to that described in FIG. 3-a.

In addition, FIG. J-a is a sectional view of the head/J along the Ike flow path, and FIG. MJ-b is a sectional view of the head/J according to the 31st embodiment. Table 1 shows specific examples of the dye according to the present invention.

In addition, the maximum absorption wavelength of each dye, 1lnaX (water), is
Shown in the table.

Example Coin exchange water (hereinafter referred to as water) 71? Diethylene glycol 2S? Table 1 Ji/dye Tei? Total: 100f The above components were thoroughly mixed and dissolved in a container, filtered under pressure through a Teflon filter with a pore size of 1μ, and then degassed using a vacuum pump to obtain a liquid recording liquid. Using the obtained recording liquid, an on-demand recording head (discharge orifice diameter !θμ, piezo vibrator drive voltage t, ov, frequency 4' KH*) f
: When the following (Ts) was investigated using the recording apparatus, good results were obtained in all cases.

(TI) Long-term storage stability of recording liquid: Even after recording liquid was sealed in a glass container and stored at -J17C and 4DC for 6 months, no precipitation of insoluble matter was observed, and no changes were observed in the physical properties or color tone of the liquid. There wasn't.

(T,) Discharge stability: room temperature 1. Continuous ejection was carried out for 2 q hours in an atmosphere of tC and 0°C, and stable high-quality recording was possible from beginning to end under both conditions.

In both cases, there was no clogging at the orifice tip, and the recording was stable and uniform.

(Quality of recorded images: The recorded images were clear and sharp.The rate of decrease in density was less than 1 inch after being exposed to indoor light for 3 months, and after being immersed in water for 1 minute. There was very little K stain in the image.

(Fixability for various recording materials: Printing with the recording materials listed in Table 2 below. After 1 second, rub the printed area with your finger to eliminate image shift and blurring. Excellent fixing properties without any stains Table 1 Example 3 Water 6η N-methyl-corbyrolidone /, 5-p diethylene glyco /I//qlil Table 1 Flea 6.!r dye
72 Total 1001f A recording liquid having the above composition was prepared in the same manner as in Example 1, and an on-demand type multi-head (on-demand type multi-head for recording by applying thermal energy to the recording liquid in the recording head to generate all droplets)
Discharge orifice diameter 35μ, heating resistor resistance lSOΩ,
(T,) to (T,) were investigated in the same manner as in Example 1 using a recording device having a drive voltage JOV and a frequency a2xnz), but in all the investigation experiments, we obtained inconsistent results. O 1 Example water 5z Ethylene glycol 20f t3-dimethyl-1-imidazolidinone 30f-7th
Dye of surface point g sy- Total 1ooy- A recording liquid with the above composition was prepared in the same manner as in Example 1.
On-demand type multi-head that performs recording by applying thermal energy to the recording liquid in the recording head to generate droplets (discharge orifice diameter 35μ, heating resistor resistance value izoΩ)
(T1) to (Ta) were stacked in the same manner as in Example 1 using a recording device having a driving voltage of 30 V and a frequency of - KHv, and excellent results were obtained in all the experimental experiments. .

Example 5 Water 60J Diethylene glycol 36g・Dye of Table 1 10 Gu? A total of 1001 il- A recording liquid having the above composition was manufactured by U4i in the same manner as in Example 1, and an on-demand type multi-head (discharge Orifice diameter 35μ, heating resistor resistance value iro
Ω, driving voltage 3θV, frequency 21cut,
(rl), but the results obtained in all cross-country experiments were negative.Example 6 Water 66L? Dieterene glycol monomether ether, 30fl
Dye of Table 1 A//Ko2 Total 100f A recording liquid with the above composition is prepared in the same manner as in Example A, and thermal energy is applied to the recording liquid in the recording head to generate droplets and perform recording. On-demand type multi-head (
Discharge orifice diameter 35μ1 heating resistor resistance value/30Ω,
Using a recording equipment with a driving voltage of 30V and a frequency of Obtained Results Examples 7 to 1 A recording liquid having the composition shown in Examples to/4t in Table 3 below was prepared according to the method described in Example 2.

These compositions were filled into felt-tip pens and written on medium-quality paper (manufactured by Hakubotan Nihonshu Paper Co., Ltd.) to examine water resistance and memorability after the cap was removed and left for 2'1 hour.

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

Table 3 Note that all the dyes shown in Table 7 showed good results in the present invention.

[Brief explanation of drawings]

Figure Td-1 and Figure 2 are schematic diagrams of an inkjet recording apparatus, respectively. Fig. 3-a and Fig. J-b are a vertical cross-sectional view and a horizontal cross-sectional view of a main part of another recording device. Fig. q is an external perspective view of the head in which all the heads shown in Figs. 3-& and s-b are multi-layered. However, in the figure, h...L...recording head 1.2m...piezo vibrator, b
...Vibration plate, 3...Inlet, t...Liquid chamber, S...
・Discharge orifice, 6...storage tank, ? ...Recording liquid, g...Supply pipe, D...Intermediate processing means, io...
・Dougo processing method, //...liquid? Hei, lko and 25...
・Small recording material, S...recording signal, /<4...e, chamber,
15... Heat generating head, 16... Protective layer, 17...
Electrode, 19... Heat generating resistor layer, 19... Heat storage layer, UO... Substrate, 26... Groove. Patent applicant: Canon Co., Ltd. (and 1 other person) Agent: Patent attorney Hase - (7 others) Figure 1 Figure % 2 Continued from Figure 1 page [Part] Inventor Tomio Yoneyama 1, Kamoshida-cho, Midori-ku, Yokohama City Skin area Mitsubishi Chemical Industries, Ltd. Research Center

Claims (1)

[Claims] (1) In a recording liquid containing a recording agent, which is a component for forming a recorded image, and a liquid medium for completely dissolving or dispersing this recording agent, the recording agent has the following general formula (wherein R1 and R2 are ,
Represents a hydrogen atom, hydroxyl group, 805MM, amine group, mono-lower alkylamino group, di-lower alkylamino group, optionally substituted anilino group, acetylamino group, or optionally substituted benzoylamino group, and R8 and R4 are ,
Hydrogen atom, hydroxyl group, 80. M group, amino group or 803M
represents a mono-lower flukylamino group, di-lower alkylamino group, acetylamino group, lower alkyl group, lower alkoxy group or chlorine atom which may be substituted with a group, and D is 50
8M group, a benzene ring or a naphthalene ring which may be substituted with a hydroxyl group, a lower alkoxy group or an acetylamino group, and M represents an alkali metal, quaternary ammonium or amines). A recording liquid containing a disazo dye. (2. A recording liquid according to claim 1, in which the disazo dye represented by the general formula (1) is contained in an amount of 0./-20% by weight based on the total weight of the recording liquid.