JPS58174459A - Recording solution - Google Patents

Abstract

PURPOSE:A novel recording solution useful for ink jetting recording method, having extremely prolonged life of recording head to reduce the trouble ratio of head, containing a compound having a specific structure. CONSTITUTION:A compound shown by the formula (Q1 and Q2 are phenyl, substituted phenyl, or substituted naphthyl, and the substituent group is NH2, OH, SO3M, COOM', CH3, C2H5, NO2, NHCOCH3, or halogen; R1 is H, SO3M, OCH3, CH3, or halogen; R2 is H, CH3, or OCH3; M and M' are Na, K, Li, ammonium, or amine) is blended with water and a water-soluble organic solvent (e.g., diethylene glycol, etc.) as liquid medium components, and, if necessary, properly a viscosity modifier (e.g., polyvinyl alcohol, etc.), surface active agent, surface tension adjustor (e.g., diethanolamine, etc.), to give the desired recording solution.

Description

Detailed Description of the Invention The present invention relates to an inkjet recording method in which a new recording liquid, 41, is ejected from fine ejection ports (ejection orifice) provided in a recording head, and recording is performed using the droplets. Concerning suitable recording fluids.

BACKGROUND ART Conventionally, ink made by dissolving various dyes in water or other six organic solvents has been used as ink for recording on paper-based recording materials (fountain pens, felt-tip pens, etc.).

Furthermore, in the so-called inkjet arrangement method, in which recording is performed by ejecting the liquid in the recording silver head from the ejection orifice using vibrations by a piezo vibrator or electrostatic attraction due to the application of high voltage, various dyes can be mixed with water, organic solvents, etc. It is known that a round part paraboloid is used when dissolved in However, compared to general inks for writing purposes such as perpetual line and felt-top paper, inkjet recording liquids require more stringent conditions in terms of many characteristics.

The inkjet notation method does not generate noise.

Various types of printers are being actively researched, allowing high-speed recording or color recording on plain paper without special fixing treatment.

In such an inkjet recording method, recording is performed by flying droplets of a recording liquid called ink and making them adhere to a recording material. The basic components of such a recording liquid include a recording agent (a dye or a pigment is used) and a liquid medium for dispersing it or a solvent (water or various organic abrasions or mixtures thereof are used), and the necessary Various additives are added depending on the situation.

There are various types of recording methods such as 111 depending on the method of generating droplets and the method of controlling the flight direction of the droplets. That-
An example is shown in Fig. 1. In other words, the apparatus shown in Fig. 1 performs recording by applying a recording signal to a recording head section having a piezoelectric vibrator, and generating droplets of recording liquid in response to the recording signal. In Figure 1, 1 is! ! With sickle head, piezo vibrator 2 & diaphragm 2 b J
It has an inlet 3 for the recording liquid, a liquid chamber 4 in the head, and a discharge port (discharge orifice) 5. Depending on the case, an intermediate processing means 9 such as a pump or a filter may be provided in the middle of the supply pipe 8.The piezo vibrator 2a may also be equipped with a signal processing means (for example, a pulse converter). 10 converts the recording signal S into a pulse and applies a good signal, and a pressure change occurs in the recording liquid in the liquid chamber 4 according to the # signal.As a result, the recording liquid 7
is ejected from the ejection orifice 5 as a droplet 11, and recording is performed on the surface of the recording material 12.

In addition to the above-mentioned devices, various types of devices are known, for example, as shown in FIG.

As a modification of FIG. 1, the liquid chamber 4 is shaped like a nozzle.

There is a device in which a cylindrical piezo vibrator is installed on the outer periphery (the mechanism of droplet generation in this device is essentially the same as the device shown in FIG. 1). Also, an apparatus that continuously generates electrically charged droplets and uses a portion of the droplets for recording;

There are also known devices that apply heat energy corresponding to a recording signal to a recording liquid in a chamber of a recording head and generate droplets using scissor energy.

An example thereof is shown in Fig. 3-a, Fig. 3-b, and Fig. 4.

The head 13 is made of glass, ceramics, or a plastic plate, etc., having a groove 14 through which the ink passes.

Heat generating head 15 used for thermal recording (a thin film head is shown in the figure, but is not limited to this)
Obtained by gluing. The heat generating head 15 is made of a protective film 16 made of silicon oxide or the like. Aluminum electrode 17-1
．． Heat generating resistor layer 18 formed of 17-2° nichrome
．． Heat storage layer 19. It is made of a substrate 20 having good heat dissipation properties such as alumina.

The ink 21 comes from the ejection orifice X221, and the pressure P
Now, an electric signal is applied to the electrode 17-1. The pressure causes the meniscus 23 to protrude, and the droplet 21 is ejected from the orifice 22 into a recording droplet 24, which flies toward the recording material 25. Fig. 4 shows an external view of a multi-head in which a large number of heads shown in Fig. 3-a are lined up. Heat generating head 28t - is made by bonding. - In particular, in the liquid jet recording method using thermal energy mentioned above, it is necessary to record high-resolution, high-quality images at higher speed for a longer period of time, or to dramatically improve the service life of the device. It is necessary to improve the repeated use life (durable life) of the recording head.

Factors that determine the service life of the recording head applied to the above recording method include the life of the heat-generating head provided, as well as the deposition of solid matter on its surface. Since the recording liquid is exposed to high temperatures during repeated extinction, it is expected that the thermally unstable recording liquid will undergo chemical changes.

In fact, if the generation and disappearance of bubbles continues for a long time.

As a result, it has been experienced and observed in many experiments that insoluble matter is formed and deposited near the surface of the heat-generating head, causing the head to become unable to eject.

The present invention has been made in order to eliminate the above-mentioned disadvantages, and it is possible to significantly extend the service life of the recording head applied to the recording method described in the above-mentioned Publication No. 9. 4. The purpose of this invention is to provide a recording liquid that can significantly reduce the failure rate of heads and increase their reliability.

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

(However, in the above formula, s Qt g Qt represents any one of a phenyl group, a substituted phenyl group, and a substituted 7-tyl group.

Bird indicates either H, C, OC, or M above.
, M' are each one selected from Na;, *Li, ammoniums, and amines. ) The recording agent of the present invention described above is particularly one in which the decomposition product has sufficient solubility in the liquid medium even when the azo bond (-N-N-) is broken when heated to 250° C. or higher. It is. 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. In addition, the dye used as the recording material of the present invention has the following molecular structure: [・, i', ・As can be predicted, the dye has a sufficiently satisfactory solubility in a liquid medium.
- Since it has particularly excellent solubility in water, it can be used very effectively when forming an aqueous recording liquid.

Furthermore, 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.

If this recording liquid is used for recording with a recording head as shown in Fig. 1, the usable life of the recording head will be longer than that when a conventional recording liquid is used, as shown in the following example. This can be dramatically improved.

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

aOs8 (Mu 5) (Mu 8) (nts) (employed 22) (445) (muso) ”': 0■ (shoulder 55) The liquid medium components for composing the recording liquid of the present invention include: 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-propyl alcohol, isopropyl alcohol, n-propyl alcohol, and n-propyl alcohol. -C1-4 alkyl alcohols such as butyl alcohol, 5ec-butyl alcohol, tert-butyl alcohol, and isobutyl alcohol; Amides such as dimethylformamide and dimethylacetamide; acetone, diacetone, Ketones or ketone/alcohols such as alcohol; ethers such as tetrahydrofuran and dioxane 2N-methyl-2-pyrrolidone, 1,3 dimethyl-2-
Nitrogen-containing heterocyclic ketones such as imidazolidinone; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, clopylene glycol, butylene glyconyl, triethylene glycol, 1,2.6 hexanetriol, thio diglycol.

Alkylene glycols containing 2 to 6 carbon atoms such as hexylene glycol and diethylene glycol; glycerin: ethylene glycol methyl ether, diethylene glycol methyl (also ethyl) ether, triethylene glycol monomethyl (also a ethyl)
Examples include lower alkyl ethers of polyhydric alcohols such as ethers.

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

The content of the above-mentioned water-soluble organic solvent in the recording liquid is generally in the range of 5 to 95% by weight based on the total weight of the recording liquid, preferably tIilo-80-1, preferably 20 to 20% by weight. considered to be within.

The recording liquid of the present invention prepared from such components has excellent recording properties (signal response, droplet formation stability, Ejection stability, long-term continuous recording performance, ejection stability after long-term recording cessation) storage stability, dissolution stability of the recording agent, fixation to the recording material, or light resistance of the placed image,
Weather resistance, water resistance, and alcohol resistance are all well-balanced and excellent. In order to further improve these characteristics, various conventionally known additives may be added. IJ Viscosity modifiers such as vinyl alcohol, celluloses, and water-soluble resins; Surface tension modifiers such as cationic, anionic, or nonionic surfactants, diethanolamine, triethanolamine, etc.; Pi (adjustment) using buffering agents; Agents, etc. can be mentioned.

In order to prepare a recording liquid used in a type of recording method in which the recording liquid is charged, resistivity adjusting agents such as inorganic salts such as lithium chloride, ammonium monide, and sodium chloride are used. Urea or thiourea is also preferably used as a water retention improver at the tip of the ejection orifice.In addition, in the case of a type that ejects the recording liquid by the action of thermal energy, the thermal property value (for example, specific heat , thermal expansion coefficient, thermal conductivity, etc.) may be adjusted.
It is necessary to use it as a recording liquid for recording instruments.

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

Example 1 An 8i01 layer (lower layer) was formed on an alumina substrate by sputtering to a thickness of 5 μm, and then Hr was applied as a heating resistance layer.
B, with a thickness of 100OA, and aluminum as an electrode.
After laminating to a thickness of 0.00A, selective etching
μm x 2005m heating resistor (turn-formed 0
Next, add 5iUz layer to 3500
It is laminated as a protective layer (upper layer) to a thickness of A and electrically conductive on the board.
After forming the heat converter, a glass plate with grooves of 50 μm width x 50 μm depth was joined so that the grooves and the heating resistor matched.Subsequently, the distance between the tip of the heating resistor and the orifice was 250 μm. I polished the orifice end to make it look like a metal head and created a log head. Using this recording head, ink having the liquid composition shown below was ejected.

In this case, when the recording head was driven for 10 .mu.sec and a 40 V rectangular voltage pulse print signal was applied at a cycle of 200 .mu.sec, the recording head had a life span sufficient to withstand 160 hours of continuous printing.

Example, 2 Structural formula of the ink with the liquid composition used in Example 1,
Table 1 shows the durability of the recording head when various dyes having the structural formula M listed in the table below are used for the amount of dye of %19. A voltage pulse printing signal was applied at a cycle of 200 μsec.

(Table 1) Example 3 The same results as in Example 1 were obtained when K, )-liethanolamine was used in place 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. Figures 3-a and 3-b are a longitudinal cross-sectional view and a cross-sectional view of main parts of another recording device.0 Figure 4 shows the head shown in Figures 3-1 and 3-b. O is an external perspective view of a multi-head. However, in the figure, 1...recording head, 2a...piezo vibrator, 2
b... Vibration plate, 3... Inlet, 4... Liquid chamber, 5
...Discharge oriice, 6...Storage tank, 7...
Recording liquid, 8... Supply pipe, 9... Intermediate processing means, 1
0...Signal processing means, 11...Droplet, 12・25
...recording material, S...recording signal, 14...liquid chamber,
15... Heat generating head, 16... Insulating layer, 17...
- Electrode, 18... Heat generating resistor layer, 19... Heat storage layer, 20... Substrate. 26...Groove. Patent applicant Canon Co., Ltd.

Claims (1)

[Scope of Claims] As a recording agent that forms a recording compound, a recording liquid characterized by containing a compound represented by the following general formula (provided that s Q+ @ Q2 in the above formula is a phenyl group, Represents either a substituted phenyl group or a substituted naphthyl group. R1 represents either H, CHs * OCHm. The above M and M' respectively represent %Na, K, Li, ammoniums, amines. It is a type selected from the following types.)