JPH025784B2 - - Google Patents

Description

[Detailed description of the invention]

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 orifices provided in a recording head and flying the liquid as droplets. BACKGROUND ART Writing instruments (fountain pens, felt-tip pens, etc.) for recording on recording materials such as paper have conventionally 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 vibrations by a piezo vibrator or electrostatic attraction due to the application of high voltage, various dyes are dissolved in water or organic solvents. It is known that compositions are used. However, compared to ink for stationery such as general fountain pens and felt pens, recording liquid for inkjet has many characteristics that require stricter conditions. This type of inkjet recording method involves flying droplets of recording liquid called ink.
Recording is performed by attaching this 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 or various organic solvents or mixtures thereof are used), and if necessary, Various additives are added. 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 is shown in FIG. That is, the apparatus shown in FIG. 1 applies a recording signal to a recording head section having a piezo vibrator, and performs recording by generating droplets of recording liquid in response to the signal.
In FIG. 1, reference numeral 1 denotes a recording head, which has a piezo vibrator 2a, a diaphragm 2b, 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. And in the piezo vibrator 2a,
A signal converted from the recording signal S into a pulse by the signal processing means (for example, a pulse converter) 10 is applied, and a pressure change occurs in the recording liquid in the liquid chamber 4 in accordance with the signal. As a result, the recording liquid 7 is ejected from the ejection orifice 5 as droplets 11, and the recording material 12 is
Recording is done on the surface of the In addition to the above devices, various types of devices are known. For example, as shown in FIG.
As a modification of the figure, there is a device in which the liquid chamber 4 is shaped like a nozzle and a cylindrical piezoelectric vibrator is installed around the outer periphery (the mechanism of droplet generation in this device is essentially the same as in FIG. 1). (same as the equipment shown). Also, a device that continuously generates charged droplets and uses a portion of the droplets for recording. Alternatively, there is also known an apparatus that applies thermal energy corresponding to a recording signal to the recording liquid in the chamber of a recording head, and generates droplets using the energy. An example thereof is shown in Fig. 3-a, Fig. 3-b, and Fig. 4. The head 13 is made of glass, ceramic, or plastic plate having grooves 14 through which ink passes, and a 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. Heat generating head 1
5 is made up of a protective film 16 made of silicon oxide or the like, aluminum electrodes 17-1, 17-2, a heating resistor layer 18 made of nichrome or the like, a heat storage layer 19, and a substrate 20 with good radioactivity such as alumina. There is. The ink 21 has reached the discharge orifice 22 and forms a meniscus 23 due to the pressure P. Now, when an electric signal is applied to the electrodes 17-1 and 17-2, the area indicated by n of the heating head 15 suddenly generates heat, bubbles are generated in the ink 21 in contact with this area, and the pressure causes the meniscus 23 to rise. protrudes, and the ink 21 is ejected from the orifice 22 into a recording droplet 2.
4 and flies toward the recording material 25. Fourth
The figure shows an external view of a multi-head in which a large number of heads shown in Figure 3-a are arranged. The multi-head is made by gluing together a glass plate 27 having multi-grooves 26 and a heating head 28 similar to that described in FIG. 3-a. Note that FIG. 3-a is a cross-sectional view of the head 13 along the ink flow path, and FIG. 3-b is a cross-sectional view taken along line AB in FIG. 3-a. Conventionally, as this type of recording liquid, for example,
No. 8361, Special Publication No. 51-40484, Special Publication No. 52-13126
As shown in Japanese Patent Publication No. 52-13127 and Japanese Patent Application Laid-Open No. 50-95008, various dyes and pigments are dissolved or dispersed in aqueous or non-aqueous solvents.
The preferred conditions for this type of recording liquid are (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.); have the following. (2) Stable for long-term storage and should not cause clogging of fine discharge ports or capillary pores. (3) Fixation is fast on the recording material (paper, film, etc.) and the dot periphery is smooth with little bleeding. (4) The color tone of the printed image is clear and the density is high. (5) The printed image must have excellent water resistance and light resistance. (6) Do not immerse materials surrounding the recording liquid (containers, connecting tubes, sealing materials, etc.). (7) It must be safe in terms of odor, toxicity, flammability, etc. etc. It is quite difficult to simultaneously satisfy the above characteristics. The prior art described above was unsatisfactory in this respect. Since the recording liquid used for recording for this purpose is basically composed of a dye and its solvent,
The above recording liquid characteristics are determined by matching the dye and its solvent. Therefore, matching the dye and its solvent composition so that the recording liquid has the above characteristics is an extremely important technique in this technical field. As a result of extensive research, the present invention was completed by finding a suitable combination of dye and solvent for the recording liquid used for this purpose. That is, the recording liquid of the present invention contains 0.1 to 20% by weight of CI Direct Blue 199 as a recording agent which is an image forming component, and the liquid medium for dissolving or dispersing this recording agent contains at least (a) 1 ~30% by weight of polyethylene glycol, polyethylene glycol monomethyl ether, or both; (b) 1-40% by weight of diethylene glycol, sulfolane, or both; (c) 1-40% by weight of N-methyl. -2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, or both, and (d) 10 to 90% by weight of water. According to the present invention, the change in viscosity is small with respect to changes in environmental temperature, and the viscosity changes with respect to changes in moisture content.
Since a recording liquid with small changes in surface tension is obtained, not only can a constant ejection condition be maintained even when the environmental temperature changes significantly, but the viscosity increases due to moisture evaporation from the nozzle tip, making it possible to re-eject after leaving the nozzle. There is no possibility that the characteristics will deteriorate or that clogging will occur resulting in non-ejection. In addition, recording can be performed on various materials without restricting the type of recording material without causing changes in physical property values or precipitation of solid content during storage, and the fixing speed is high.
A recording liquid that provides images with excellent water resistance, light resistance, abrasion resistance, and resolution can be obtained. The content of CI Direct Blue 199 is determined depending on the type of liquid medium components, the characteristics required of the recording liquid, etc., but in general, it is 0.1 to 20% by weight based on the total weight of the recording liquid. It is preferably in the range of 0.5 to 15%, more preferably 1 to 10%. Of course, the dye can be used alone or in combination with other dyes,
(In other words, using the dye as an essential ingredient and various other dyes such as other direct dyes and acid dyes)
can be used. The content of the liquid medium used in the present invention is generally 1 to 30% by weight based on the total weight of the recording liquid.
% polyethylene glycol and/or polyethylene glycol monomethyl ether, 1-40% diethylene glycol and/or sulfolane, 1-40% N
- Methyl-2-pyrrolidone and/or 1,3-dimethyl-2-imidazolidinone and 10 to 90% water, more preferably 5 to 20% polyethylene glycol or polyethylene glycol Monomethyl ether and/or 5-30% diethylene glycol and/or sulfolane, 5-30%
% N-methyl-2-pyrrolidone and/or 1,3-dimethyl-2-imidazolidinone and 10-70% water. The recording liquid of the present invention prepared from such components has excellent recording properties (signal response, stability of droplet formation, ejection stability, long-term continuous recording, and long-term recording pauses) by itself. Discharge Stability) The storage stability, fixing properties to recording materials, and the light resistance, weather resistance, and water resistance of recorded images are all well-balanced and excellent. In order to further improve such properties, various conventionally known additives may be added. For example, viscosity modifiers such as polyvinyl alcohol, celluloses, and water-soluble resins; various cationic, anionic, or nonionic surfactants; surface tension modifiers such as diethanolamine and triethanolamine; PH modifiers using buffer solutions, and mold prevention agents. Agents, etc. can be mentioned. Further, in order to prepare the recording liquid used in the type of inkjet recording method in which the recording liquid is charged, a resistivity adjusting agent such as inorganic salts such as lithium chloride, ammonium chloride, and sodium chloride is added. Note that when applied to an inkjet method in which the recording liquid is ejected by the action of thermal energy, the thermal properties (e.g., specific heat, coefficient of thermal expansion, thermal conductivity, etc.) may be adjusted. be. The invention will be explained in more detail in the following examples. Example 1 CI Direct Blue 199 3 parts by weight polyethylene glycol monomethyl ether (average molecular weight: 210-240) 15 〃 Diethylene glycol 15 〃 N-Methyl-2-pyrrolidone 15 〃 Water 52 〃 The above composition was thoroughly mixed in a container. Dissolve and pore size
After filtering under pressure through a 1μ Teflon (trade name) filter, it was degassed using a vacuum pump to obtain a recording liquid. Using the obtained recording liquid, the following ( When we investigated T ₁ ) to (T ₅ ), good results were obtained for all of them. (T ₁ ) Long-term storage stability of the recording liquid: Even after the recording liquid was sealed in a glass container and stored at -30℃ and 60℃ for 6 months, no precipitation of insoluble matter was observed, and the physical properties and color tone of the liquid remained unchanged. There was no change. (T ₂ ) Ejection stability: Continuous ejection was performed for 24 hours in an atmosphere of room temperature, 5° C., and 40° C. Under all conditions, stable high-quality recording was possible from beginning to end. (T ₃ ) Ejection response: Intermittent ejection every 2 seconds and ejection after being left for 2 months were investigated, and in both cases, stable and uniform recording was achieved without clogging at the orifice tip. (T ₄ ) Quality of recorded images: The recorded images had high density and were clear. After 3 months of exposure to room light, the density reduction rate was less than 1%, and when immersed in water for 1 minute, there was very little blurring of the image. (T ₅ ) Fixability on various recording materials: Printing was performed on the recording materials listed in the table below, and after 15 seconds, the printed area was rubbed with a finger to determine the presence or absence of image shift and bleeding. All of them exhibited excellent fixing properties with no image shift or blurring.

[Table] Example 2 Polyethylene glycol monomethyl ether (average molecular weight: 210-240)
10 parts by weight Sulfolane 10 N-methyl-2-pyrrolidone 20 CI Direct Blue 199 3 Water 57 A recording liquid having the above composition was prepared in the same manner as in Example 1, and thermal energy was applied to the recording liquid in the recording head. On-demand type multi-head that generates droplets and performs recording by giving
Similar to Example 1, (T ₁ ) to (T ₅ ) were examined using a recording device having a high frequency (Hz), and excellent results were obtained in all the examination experiments. Example 3 {CI Direct Blue 199 5 parts by weight polyethylene glycol (average molecular weight: 300)
10 〃 Sulfolane 15 〃 1,3-dimethyl-2-imidazolidinone
10 〃 Water 60 〃 } A recording liquid having the composition shown above was prepared in the same manner as in Example 1. This composition was filled into a felt pen and written on medium-quality paper to examine water resistance and writability after removing the cap and leaving it for 24 hours. The recording liquid of this example was excellent in both water resistance and writability after standing. Examples 4 to 13 Recording liquids having the compositions listed in Table 1 were prepared in the same manner as in Example 1, and (T ₁ ) to (T ₅ ) were examined in the same manner as in Example 1. Ta. In Table 1, the numbers in parentheses indicate the composition (weight) ratio. These recording liquids all gave good results in terms of long-term storage stability, recording performance, fixation of recorded images, clarity, etc.

【table】

[Table] Comparative Example A recording liquid having the composition listed in Table 2 below was prepared,
Further, in the same manner as in Example 1, T ₁ to T ₅ were investigated.
The results are shown in Table 3.

【table】

【table】

【table】

【table】

[Table] Comparative Example 14 Instead of CI Acid Blue 7 used in Comparative Example 12, CI Acid Blue 23, 41, 51, 8 was used.
0.145 was used, but the same results as Comparative Example 12 were obtained in both cases. In addition, Direct Blue 236 used in Comparative Example 8
Instead of CI Direct Blue 34, 75, 9
8,218 was used, but the same results as Comparative Example 8 were obtained in both cases. As explained above, by using the recording liquid of the present invention, (1) the liquid has good long-term storage stability and is less likely to clog the ejection port; (2) it is stable against fluctuations in temperature and driving conditions; Wide discharge allowance (3) Fast fixation on recording material and clear images (4) Good water resistance and light resistance of printed matter (5) High safety of recording liquid and surrounding materials It has the advantage of not soaking (container sealing material, etc.).

[Brief explanation of drawings]

1 and 2 are schematic diagrams of an inkjet recording apparatus, respectively. Figures 3-a and 3-b are a vertical sectional view and a horizontal sectional view of a main part of another recording device. FIG. 4 is an external perspective view of a multi-head head shown in FIGS. 3-a and 3-b. However, in the figure, 1... recording head, 2a... piezo vibrator, 2b... diaphragm, 3... inlet, 4... liquid chamber, 5... discharge orifice, 6... storage tank, 7...
Recording liquid, 8... Supply pipe, 9... Intermediate processing means, 10...
Signal processing means, 11... Droplet, 12, 25... Recording material, S... Recording signal, 14... Liquid chamber, 15... Heat generating head, 16... Protective layer, 17... Electrode, 18... Heat generating resistor layer, 19... Heat storage layer, 20...substrate, 26... groove.

Claims (1)

[Claims] 1. As a recording agent which is a component forming an image, 0.1
Contains ~20% by weight CI Direct Blue 199,
The liquid medium in which the recording agent is dissolved or dispersed contains at least (a) 1 to 30% by weight of polyethylene glycol, polyethylene glycol monomethyl ether, or both, and (b) 1 to 40% by weight of diethylene glycol or sulfolane. (c) 1 to 40% by weight of either or both of N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone; (d) 10 to 90% by weight A recording liquid characterized by consisting of water.