JPS58174461A - Recording solution - Google Patents

Abstract

PURPOSE:A novel recording solution useful for ink jetting recording method, having prolonged use life of recording head, extremely reduced trouble ratio of head, and raised reliability, containing a specific compound. CONSTITUTION:The desired recording solution containing 5wt% compound (e.g., compound shown by the formula II, formula III, etc.) shown by the formula I [Q1 and Q4 are (substituted)phenyl, or substituted naphthyl; Q2 and Q3 are (substituted)phenylene or substituted naphthylene; the substituent group is -NH2, -OH, -CH3, -C2H5, -Cl, -Br, -SO3M, -SO2NH2, -SO2NHCH3, -NO2, or -COOM' (M and M' are Na, K, Li, ammonium, or amine)] as a recording agent for forming a recorded image. For example, the compound shown by the formula I is dissolved in water or a mixture of water and 20-50wt% water-soluble organic solvnt (e.g., diethylene glycol, etc.) and used.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel recording liquid, particularly a novel recording liquid suitable for an inkjet recording method in which droplets are ejected from nine fine ejection orifices (orifices) provided in a print head and used for recording. related.

BACKGROUND ART Writing instruments (fountain pens, felt pens, etc.) that record on recording materials such as paper have traditionally used inks prepared by dissolving various dyes in water or other organic solvents.

In addition, in the so-called inkjet recording method, in which recording is performed by ejecting the liquid in the recording head from the ejection orifice using vibration by a piezo vibrator or electrostatic attraction due to the application of high voltage, various dyes are mixed with water, organic solvents, etc. It is known to use compositions dissolved in However, compared to general stationery inks such as fountain baskets and feltbens, inkjet recording liquids require more stringent conditions in terms of many characteristics.

The inkjet recording method does not generate noise and can perform high-speed recording or color recording on plain paper without special fixing treatment, and various types are being actively researched.

In such an inkjet recording method, recording is performed by causing droplets of a recording liquid called ink to fly and adhere to a recording surface. 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 or various organic abrasions or mixtures thereof are used);
Additionally, various additives are added as necessary.

There are various types of such recording methods depending on the method of generating droplets and the method of controlling the flight direction of the droplets. An example of this is shown in FIG.

That is, the apparatus shown in FIG. 1 applies a recording signal to a recording head section having a piezoelectric sensor, and performs recording by generating droplets of recording liquid in response to the signal. In Figure 1, 1I
In the fi recording head, PC vibrator 2, diaphragm
It has an inlet 3 for recording liquid, a liquid chamber 4 in the head, and an ejection port (ejection orifice) 5. A recording liquid 7 stored in a storage tank 6 is introduced into the liquid chamber 4 through a supply pipe 8 . Incidentally, an intermediate treatment means 9 such as a pump or a filter may be provided in the middle of the supply pipe 8 depending on the case. The piezo camera element 2a has a signal processing means (
For example, a signal converted into a pulse from the recording signal S by a pulse converter (pulse converter) 10 is applied to the liquid chamber 4 according to the mosquito signal.
Pressure changes occur in the recording liquid inside. As a result, the recording liquid 7 is discharged from the discharge orifice 5 in the form of droplets 11, and recording is performed on the surface of the recording material 12.

In addition to the above devices, various types of devices are known. For example, as shown in FIG. 2, as a modification of FIG. There is a device in which a piezoelectric vibrator is installed (the mechanism of droplet generation in this device is essentially the same as the device shown in Figure 1.
: Ru). A device that continuously generates electrically charged droplets and uses some of the droplets for recording, or a device that applies thermal energy corresponding to the recording signal for recording inside the recording head and uses this energy to generate a signal. Devices that generate droplets are also known.

One example is shown in Figure 3-a, Figure 3-b, and Figure @4.

A glass, ceramic, or plastic plate or the like having a 11114 through which the head 13t-t is passed, a heat generating head 15 used for thermal recording (a thin film head is shown in the figure, but is not limited to this), and Obtained by gluing. The heating head 15 includes a protective film 16 made of silicon oxide or the like, and aluminum electrodes 17-1, 17-2.
, a heating resistor layer 18 formed of Nicro A or the like. Heat storage layer 1
9. Made of a 2° substrate with good heat dissipation such as alumina.

The ink 21 comes from the discharge orifice 221 and the pressure P
K forms a meniscus 23. - Now, electrode 17-1. When the 17-24C electric signal is applied, the portion of the heating head 15 indicated by n suddenly generates heat.
Bubbles are generated in the ink 21 in contact with this, and the meniscus 23 is protruded by the pressure, and the ink 21 is ejected from the orifice 22 to form recording droplets 24, which fly toward the recording material 25. Figure 4 shows 3-a! ! An external view of a multi-head in which a large number of heads shown in FIG. The multi-head has a glass plate 27 having multi-grooves 26 and a third
a@K It is made by gluing a heat generating head 28 similar to the one described above.

In particular, the liquid jet recording method that uses thermal energy is useful for recording high-resolution, high-quality images at higher speeds for longer periods of time, or for dramatically increasing the service life of the device. is necessary to improve the repeated use life (durable life) of the recording head.

Factors that determine the service life of a recording head applied to the above-described recording method include, in addition to the life of the heat-generating head provided, the deposition of solid matter on its surface.

Because the recording liquid is exposed to high temperatures during the repeated generation and disappearance of bubbles, it is expected that the thermally unstable recording liquid will undergo chemical changes.

In fact, many experiments have shown that if the generation and disappearance of bubbles continues for a long time, insoluble matter is generated and deposited near the surface of the heat-generating head, making the head incapable of ejecting. , observed.

The present invention has been made especially to eliminate the above-mentioned disadvantages, and can significantly extend the service life of the recording head applied to the recording method described in the above-mentioned publication, and furthermore, The object of the present invention is to provide a recording liquid that can reduce the failure rate of the head by one and increase its reliability.

The recording liquid of the present invention that achieves the above object is characterized by containing a compound (dye) represented by the following general formula as a recording agent.

1:: QI N=N QI NHQl-N=N Q4 (However, in the above formula, Q, , Q are phenyl groups, substituted phenyl'
Q, Q, represents either phenylene M, s-phenylene 7 group, or substituted naphthylene group. And the substituent at this time is -NH,,
-OH, -CH,,-Hl.

-C/, -Br, -80,M, -80,N
)l, , -80,NHeH,.

-No, -COOM'. Note that the substituted naphthyl group has at least 1
−80,M. Moreover, the above M and M' are Na,
It is either Li, ammoniums, or amines.

) =N-) or imino bond (-NH-),
The decomposition products have sufficient solubility in the liquid medium. Therefore, even when bubbles are repeatedly generated and extinguished over a long period of time, no insoluble matter is generated or deposited on the surface of the heat-generating head, and the recording head does not become incapable of ejecting. Furthermore, as can be predicted from its molecular structure, the dye used as the dedication agent of the present invention has sufficiently satisfactory solubility in a liquid medium, and has particularly excellent solubility in water. This makes it possible to use it very effectively when preparing aqueous recording liquids.

Further, the recording liquid of the present invention contains water, water, and dye in addition to the recording agent.
By adding and blending a suitable solvent such as an organic solvent and, if necessary, additives such as a surface tension modifier and a viscosity modifier, a liquid composition called an ink is obtained.

child? If you use a recording liquid to record with a recording head like the one shown in Figure 1, the usable life of the recording head will be longer than that when a conventional recording liquid is used, as shown in the example below. It can be improved dramatically.

Specific examples of the recording agent used in the present invention include dyes having the following chemical structures.

(A61) (Rot 2) '(412) (Rot 13) (Rot 14) (/i6x5) (416) (t41g) (Maro 19) (A20) (421) (/I622) (423) (Shoulder 25) (26) (429) (,,430) The liquid medium component for composing the recording liquid of the present invention is water or a mixture of water and various water-soluble organic solvents.
Examples of the water-soluble organic solvents used include methyl alcohol, ethyl alcohol, n-propyl alcohol,
Alcohol, isopropyl alcohol, n-butyl
Charcoal IE such as alcohol, formula-7' chill alcohol, tert-butyl alcohol, isobutyl alcohol, etc.
a1-4 alkyl alcohols; amides such as dimethylformamide and dimethylacetamide; a7tone;
Ketones or ketone/alcohols such as diacetone/alcohol; ethers such as tetrahydrofurano, dioxane; N-methyl-2-pyrrolidone, l, 3^dimethyl-
Nitrogen-containing heterocyclic ketones such as 2-imidazolidino 7; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1, 2.6 hexa/triol, Alkylene glycols in which the alkylene group contains 2 to 6 carbon atoms such as thiodiglycol, hexylene glycol, diethylene glycol; glycerin; ethylene glycol methyl ether, diethylene glycol methyl (also ethyl) ether, triethylene glycol monomethyl (
or lower alkyl ethers of polyhydric alcohols such as ethyl ether.

Among these many water-soluble organic solvents, diethylene glycol, which is a polyhydric alcohol, and triethylene glycol monomethyl (or ethyl) ether, which is a lower alkyl ether of a polyhydric alcohol, are preferred.

The content of the water-soluble organic solvent in the recording liquid is generally in the range of 5 to 95X1, preferably 1O to 80N, and more preferably 20 to 50X in weight percent based on the total weight of the recording liquid.

The recording liquid of the present invention prepared from such components is as follows:
As a recording liquid for so-called inkjet placement, the recording liquid itself has recording characteristics (signal response, stability of droplet formation, and ejection stability).

Long-term continuous recording performance, ejection stability after long-term recording material is stopped) storage stability, and recording agent dissolution stability.

Adhesion to recording material or light resistance of recorded images.

Weather resistance, water resistance, alcohol resistance, etc. are all well-balanced and excellent. In order to further improve these properties, various conventionally known additives may be added to the composition.

Examples: Viscosity modifiers such as EVA, polyvinyl alcohol, celluloses, water-soluble resins, etc.; Various surfactants with cationic, anionic or nonionic groups, surface tension modifiers such as diylamine, triethanolamine, etc.; buffering agents. PH1 by
1, and the like.

In order to prepare the recording liquid used in the type of recording method that charges the recording liquid, lithium chloride, ammonium chloride,
Resistivity modifiers such as inorganic salts such as sodium chloride are used. Urea and thiourea are preferably used as water retention improvers at the tip of the ti discharge orifice. In addition, in the case of a type that discharges recording liquid by the action of thermal energy,
Thermal physical property values (side wind, 1.1. specific heat,
(thermal expansion coefficient, thermal conductivity, etc.) may be adjusted.

When the recording liquid of the present invention is used as a recording liquid for so-called chain marking tools, various viscosity and various materials are required for recording.

The invention will be explained in more detail in the following examples.

Example 1 A SiQ layer (lower layer) was formed on an alumina substrate to a thickness of 5 μm by sputtering, followed by Hf as a heating resistance layer.
B, with a thickness of 1000λ and aluminum as an electrode.
Laminated to ooλ thickness and selectively etched after death to 50μ
A heating resistor pattern of m×200 μm was formed. Next K
8i0. After laminating the layers as a protective film layer (upper layer) to a thickness of 3500λ by sputtering to form an electrical/thermal converter on the substrate, a glass plate with grooves of 50 μm wide x 50 μm deep was placed between the grooves and the heating resistor. They were joined so that they matched.

Subsequently, the distance between the tip of the heating resistor and the oriice is 250
A recording head was prepared by polishing the end face of the orifice so that it became ItmK. Using this recording head, ink having the liquid composition shown below was ejected.

1 structural formula/%7 dye 5 parts by weight In this case,
When the recording head was driven with a rectangular voltage pulse print signal of 10 μm and 4 QV at a cycle of 200 μm, the result was 160 μm.
It had a long enough lifespan to withstand continuous printing for hours.

Example 2 Structural formula of the liquid composition (I/R) mentioned in Example 1
The table below shows the durability of the recording head when various dyes having the structure shown in the table below are used in place of the I67 dye.

In addition, the rectangular pressure pulse printing signal of soy was carried out at a period of 200μ.

Example 3 Similar results to Example 1 were obtained when triethanolamine was used instead of N-methyl-2-pyrrolidone in the ink composition used in Example 1.

Example 4 Even when ethylene glycol was used in place of diethylene glycol in each ink composition used in Example 2, the same results as in Example 2 were obtained in all cases.

[Brief explanation of the drawing]

FIGS. 1 and 2 are schematic diagrams of an inkjet recording apparatus, respectively. @ Figure 3-a and Figure 3-b are a vertical cross-sectional view and a cross-sectional view of a main part of another recording device. Figure 4 shows the spatulas shown in Figures 3-a and 3-b)
-e? #f (Head spatula-11° external perspective view. There is a. However, in the figure, 1... recording head, 2... piezo loss element, 2b...
Vibration plate, 3... Inflow port, 4... Liquid chamber, 5... Discharge orifice, 6... Storage tank, 7... Recording liquid, 8
. . . Supply pipe, 9 . . . Intermediate processing means, 10 .・Liquid chamber, 15... Heat generating head, 16... Protective layer, 17... Electrode, 18...
・Heating resistance weight, 19... Heat storage layer, 20... Substrate,
26...Groove. Patent applicant Canon Co., Ltd.

Claims (1)

[Scope of Claims] A recording liquid characterized by containing a compound represented by the following general formula as a recording agent that forms a recording layer. Q, -N=N-Q, -NH-Q, -N=N-Q. (However, in the above formula, Q, , Q, ti, phenyl group, substituted phenyl group, substituted 7-tyl group, (4, Q,
ti represents any one of a phenylene group, a substituted stillylene group, and a substituted naphthylene group. And the substituent at this time is -
Na, -OH, -C, -C1. -cj, -Br, -80,M, -80,N
H,,-80,NHCH,. At least one selected from -NO,, -COOM'
It is one. Note that the substituted 7-tyl group has at least one -80,M group. Further, M and M' are any of Na, Li, ammoniums, and ammoniums. )