JPH03200882A - Recording fluid and ink jet recording method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a recording liquid. The details relate to recording liquid suitable for inkjet recording, and furthermore,
The present invention relates to an inkjet recording method using the recording liquid. [Prior Art 1] A so-called inkjet recording method has been put into practical use, in which recording is performed by ejecting droplets of a recording liquid containing a water-soluble dye such as a direct dye or an acidic dye from a minute ejection orifice. σ) Regarding the solvent of the recording liquid, use PP such as electrophotographic paper.
Fixation is fast on recording paper commonly used for general office use, such as C (plain paper copier) paper and fan-hold paper (continuous paper for computers, etc.), and the print quality is good, that is, there is no smearing in the print and the outline is clear. In addition to being required to have clear properties, it is also necessary to have excellent stability during storage, which severely limits the solvents that can be used. On the other hand, dyes for recording liquids have sufficient solubility in the limited solvents mentioned above, are stable even when stored for long periods of time, and provide high density printed images. Moreover, it is required to have excellent water resistance, light resistance, and ozone resistance, but it has been difficult to satisfy many of these requirements at the same time. In particular, with regard to light resistance and ozone resistance, the light resistance and ozone resistance of mechanical pigments or inorganic pigments used as colorants in other printing methods, such as electrophotography and heat-sensitive melt transfer methods, are particularly important. Therefore, there is an urgent need to develop a recording liquid containing a dye with excellent light resistance and ozone resistance to counter this problem.
+144065, JP-A-57-30773, JP-A-5
However, market demands have been has not yet been fully satisfied. [Problems to be Solved by the Invention] The present invention provides good print quality even when recorded on plain paper for inkjet recording, writing, etc.
The object of the present invention is to provide a recording liquid that provides a recorded image with high density, good stability during long-term storage, and excellent water resistance, light resistance, and ozone resistance. [Means for Solving the Problem 1] As a result of intensive studies to achieve the above object, the present inventors found that when a specific dye is used as a recording liquid component,
The present invention has been achieved by confirming that the above objects are achieved. That is, the gist of the present invention is that a solvent and the following general formula [
A recording liquid containing at least one dye represented by I] and a recording material having an ink receiving layer containing a silicon-containing pigment and a binder resin on a base material, using the recording liquid,
It consists in an inkjet recording method for recording using an inkjet recording method. (In the formula, A and B each represent a phenyl group, a phenylene group, a naphthyl group, or a naphthylene group which may have a substituent, C is any of the organic groups having the following structure, and M is an alkali group. It represents a metal, an ammonium group, or an organic amine salt, and n represents O or the number of 1.) C: The present invention will be described in detail below. The gist of the present invention is to use the dye of formula [I] above as a coloring component of the recording liquid. [In formula I1, substituents for the phenyl group, phenylene group, naphthyl group, or naphthylene group represented by A and B include lower alkylcarbonylamino groups such as -803M group, amino group, acetylamino group, and propionylamino group; Examples include a lower alkoxy group, a hydroxyl group, a halogen atom, a methyl group, and the like, and may have a plurality of these substituents. Examples of the organic amine salt represented by M in formula [I1 include a group in which three or four hydrogen atoms of an ammonium group are substituted with a lower alkyl group and a l or hydroxy lower alkyl group. As B, a group having the following structure is preferable. Among the groups mentioned above, the following groups are particularly preferable as C. Specific examples of these dyes include the following (a) to
Examples include azo dyes having the structure shown in (g). (M is the same as defined above) Particularly preferred are groups having the following structure. In addition, dyes represented by the following structural formulas (I) to (I) can also be preferably used. (ch) (su) (nu) (ru) (wherein, M is the same as defined above) [The azo dye represented by formula 11 can be prepared by a well-known method (
For example, Yutaka Hosoda, “New Dye Chemistry” (December 2, 1970)
(Published by Gihodo on the 1st) (see pages 396-409),
It can be produced through diazotization and coupling steps. In the recording liquid of the present invention, the dye represented by the general formula [I] may be used alone, but it is also possible to use a mixture of two or more kinds. The content of the dye of formula 11 in the recording liquid is 0.5 to 8% by weight, especially 2 to 5% by weight based on the total amount of the recording liquid.
degree is preferred. Examples of solvents used in the recording liquid of the present invention include water and water-soluble organic solvents such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (#200), and polyethylene glycol (#400).
), glycerin, N-methyl-pyrrolidone, N-ethyl-pyrrolidone, 1,3-dimethyl-imidazolidinone,
Preferably, it contains ethylene glycol monoallyl ether, ethylene glycol monomethyl ether, diethylene glycol 7-methyl ether, and the like. These water-soluble organic solvents usually contain 10 to 10% of the total amount of the recording liquid.
It is used within the range of 50% by weight σ). On the other hand, water is used in an amount of 45 to 89.5% by weight based on the total amount of the recording liquid. To the recording liquid of the present invention, 0.1 to 10% by weight, preferably 0.5 to 5% by weight of a compound selected from urea, thiourea, biuret, semicarbazide, based on the total amount thereof, may be added, or 0. By adding 0.001 to 5.0% by weight of a surfactant, the quick drying properties and print quality after printing can be further improved. Next, the inkjet recording method of the present invention will be explained in detail. That is, the present invention relates to an inkjet recording method in which recording is performed by an inkjet recording method using the above-mentioned recording liquid on a recording material having an ink receiving layer containing an ion pigment and a binder resin on a base material. be. The base material used for the recording material of the present invention is not particularly limited, but paper and plastic film are usually mentioned. As the paper, synthetic paper made from polyolefin, polystyrene, polyethylene terephthalate, etc., which is made from plain paper consisting of cellulose and filler, is used. As the plastic film, films of polyvinyl chloride, polyethylene terephthalate, poly(methyl meth)acrylate, polystyrene, polyvinylidene fluoride, etc. are used. The binder resin used in the coating layer as an ink-receiving layer formed on the above-mentioned base material is preferably a hydrophilic one, such as polyvinyl alcohol, starch, -1! Latin, carboxymethylcellulose, hydroxyethylcellulose, polyurethane, polyvinylpyrrolidone, etc. are used. In addition, vinyl acetate emulsion, acrylic emulsion, polyvinyl acetal, etc. can also be used in combination to improve the strength of the coating layer. As the silicon-containing pigment used in the ink receiving layer on the recording material of the present invention, silica, calcium silicate, aluminum silicate, etc. are used. It is also possible to use inorganic pigments such as light and heavy calcium carbonate, talc, aluminum hydroxide, titanium dioxide, etc., but the amount to be blended is 50% of the total amount of pigments to be blended.
% or less. The particle size of the silicon-containing pigment is usually 10 to 1100 nm, preferably 20 to 50 nm, and the particle size of titanium dioxide particles is 0.0 nm.
The thickness used is from 1 to 10 μm, preferably from 0.3 to 5 pm. An aqueous coating solution consisting of the above-mentioned components is prepared and coated on the substrate. At this time, the usage ratio (weight) of pigment and binder resin is in the range of 1011 to 2/3, The total solid content in the coating liquid is in the range of 10 to 40% (by weight). The solvent for preparing the coating solution is mainly water, and may also contain lower alcohols such as isopropyl alcohol and lower alkyl ketones such as methyl ethyl ketone. Additives such as a dispersant, an antifoaming agent, a surfactant, and a waterproofing agent may be added to this aqueous coating liquid. A recording material having an ink-receiving layer is formed by applying and drying the coating liquid onto the base material, and coating methods include a roll coater, a blade coater, an air knife coater, a bar coater, and a slit reverse coater. ,
A die coater etc. are mentioned. In addition, if the coating amount on the substrate is less than 5 g/m2, the ink absorbency tends to be insufficient, while if it is more than 50 g/m2, the surface color development tends to be insufficient, so it is usually 5 to 5 g/m2.
50 g/m2 is preferred. As such a recording material, commercially available products include ST-73A4 (trade name) manufactured by Sharp Corporation, BJ printer paper or color bubble jet copier-1 paper manufactured by Canon Corporation, and these can also be used. Using the recording liquid of the present invention, recording is performed on the recording material as described above by an inkjet method. There are various types of inkjet recording methods. For example, there is a continuous jet recording method (Sw
There are two types: the on-demand method, which ejects ink particles only when necessary (eet method, Hertz method), and the on-demand method, which ejects ink particles only when necessary.The latter method uses a piezoelectric element to eject ink from a nozzle (pulse jet method), and a method that uses heating to generate air bubbles. A method (bubble jet method) in which ink is jetted from a nozzle using pressure is known. Although the present invention is not limited to these inkjet methods, it is convenient to use an on-demand type device. For example, these inkjet methods are disclosed in Japanese Patent Application Laid-Open No. 54-51.
They are described in detail in No. 837 and Japanese Unexamined Patent Publication No. 55+75465, so they can be used. [Example J Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded. Example 1

[Example of synthesis of dye of formula (A)] (Step 1) 2-aminonaphthalene-4,8-disulfonic acid 30.3
g (0.1M) was mixed and dissolved in 500 ml of water and 80 g of a 10% aqueous sodium hydroxide solution. Add 35% HC to this solution.
Add 39.8 ml (0.45 M) of I and heat to 5 °C +
It was cooled down. Add this to 27-25g of NaNO (0,1
05M) was gradually added, stirring was continued while maintaining the temperature at 0 to 5°C for 1 hour, excess NaNO was removed with sulfamic acid, and a diazo liquid was synthesized. (Step 2) 15.3g of 2.5-dimethoxyaniline (0.1M
) with 300 ml of water and 8.8 ml of 35% HCI (0,
1M), stirred to dissolve, and cooled to 0-5°C. The diazo solution obtained in step 1 above was added to this, and the mixture was gradually neutralized with a 10% aqueous sodium hydroxide solution to pH 2-3.
Coupling was performed by stirring at 0 to 5°C for 3 hours. Then, the mixture was gradually neutralized with a 10% aqueous sodium hydroxide solution to a final pH of 8. (Step 3) 2-amino-8-naphthol-6-sulfonic acid 23.9
g (0.1M) was mixed and dissolved in 500 ml of water and 40 g of a 10% aqueous sodium hydroxide solution. Add 35% HC to this solution.
Add 30.9 ml (0.35 M) of 0-5
Cooled to °C. This stuff has 7.25 g of NaN0□ (0
, 105M) was gradually added, stirred at 0 to 5°C for 3 hours, and excess NaNO2 was eliminated with sulfamic acid to synthesize a diazo liquid. (Step 4) 10.9 g of 2.6-diamitupyridine was dissolved in 300 ml of water, and 10% HCI was gradually added thereto and stirred.
The pH was adjusted to 6-7 and cooled to 0-5°C. Add the diazo solution obtained in step 3 to this, and gradually neutralize with a 10% aqueous sodium hydroxide solution to adjust the pH to 2-3.
Coupling was performed by stirring at 5°C for 4 hours. Then,
The pH was finally adjusted to 9 by gradually neutralizing with a 10% aqueous sodium hydroxide solution. (Step 5) Add 39.9% of 35% HCl to the coupling liquid obtained in Step 2.
8 ml (0.45 M) was added and cooled to 0-5°C. Add this to 27.25g of NaNO (0-105M
) was gradually added and stirred for 3 hours at 0-5 °C to remove excess N.
ANO2 was removed with sulfamic acid to synthesize a diazo liquid. Add this diazo solution to the coupling solution obtained in step 4 for 10 minutes.
% aqueous sodium hydroxide solution while maintaining pH 8-9. After the coupling was completed, NaCl was added in an amount equal to 20% of the volume of the reaction solution, followed by salting out and filtration. The wet cake thus obtained was dissolved in water 1e at 60'C, and after returning to room temperature, 2-propertool 2e was added, crystallized, and filtered. Dry this and use the desired dye 5.
7.0g was obtained. The yield was 63.0%. [Preparation and evaluation of recording liquid and evaluation of recorded images J The above components were thoroughly mixed and dissolved, filtered under pressure through a Teflon filter with a pore size of 1 pm, and then degassed using a vacuum pump and an ultrasonic cleaner. A recording liquid was prepared. Using the obtained recording liquid, print it on an inkjet printer (
Inkjet recording was performed on electrophotographic paper (manufactured by Fuji Xerox Co., Ltd.) using HG-3000 (manufactured by Kopuson Co., Ltd.).
The results of various evaluations performed using methods (1), (2), and (3) below are shown. (1) Light resistance of recorded images: Using a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.),
The recording paper was irradiated for 100 hours. Discoloration and fading after irradiation was small. (2) Water resistance of recorded images: The bleeding of images after the recording paper was immersed in water for 24 hours was examined. There was little blurring of the image, and the decrease in density was also small. (3) Storage stability of recording liquid: The recording liquid was sealed in a Teflon container, and changes after storage at 5°C and 6°C for one month were examined. No precipitation of insoluble matter was observed. (4) 5T-73A4 (product name) manufactured by Sharp Corporation, where the ozone-resistant ink receiving layer of the recorded image (on coated paper) is mainly composed of polyvinyl alcohol and amorphous silica.
Inkjet recording was carried out using the recording liquid and inkjet printer described in 1. The printed matter was placed in air containing 12 ppm of ozone at 90°C.
When the value of discoloration and fading (ΔEI) upon exposure for minutes was calculated as the color difference before and after using JIS z8730, the value was as small as 6. Example 2 [Synthesis of dye of formula (b) above] (Step 1) 2-amino-5-acetylaminobenzenesulfonic acid (
Add 30.9 ml of 35% MCI to a solution of 0.1M (0.1M)
35M) was added and the solution was cooled to 0-5<0>C. 7-25 g of NaNO2 (0.105 M) was gradually added to this mixture, stirring was continued while maintaining the temperature at 0 to 5°C for 1 hour, and excess NaNO27 was removed with sulfamic acid to synthesize a diazo liquid. (Step 2) 2.5-dimethoxyaniline t5.3g (0.1M
) with 300 ml of water and 8.8 ml of 35% HCI (0,
1M), stirred to dissolve, and cooled to 0-5°C. The diazo solution obtained in the above process was added to this mixture, and the mixture was gradually neutralized with a 10% aqueous sodium hydroxide solution to a pH of 2 to 3.
Coupling was performed by stirring at 0 to 5°C for 5 hours. Then, the mixture was gradually neutralized with a 10% aqueous sodium hydroxide solution to a final pH of 8. (Step 3) 2-amino-8-naphthol-6-sulfonic acid 23.9
g (0.1 M) in 500 ml of water and 10% NaOH40
It was mixed with g and dissolved. Add 35% HCI to this solution 30.9
ml (0.35M) was added and cooled to 0-56C. This stuff has 27.25g of NaNO (0.105M)
was gradually added and stirred at 0-5°C for 3 hours to remove excess Na.
N0□ was removed with sulfamic acid to synthesize a diazo solution. (Step 4) 15.2 g (0.1 M) of 3.5-diaminobenzoic acid was dissolved in 300 ml of water and 40 ml of 10% aqueous sodium hydroxide solution, and the pH was adjusted to 6-7 with 10% aqueous hydrochloric acid to 0-5.
Cooled to °C. Add this &4 the diazo liquid obtained in step 3 above, gradually neutralize with 10% aqueous sodium hydroxide solution to adjust the pH to 2-3, and perform coupling by stirring at 0-5°C for 5 hours. Ta. After 5 hours, the mixture was gradually neutralized with a 10% aqueous sodium hydroxide solution until the pH was finally adjusted to 9. (Step 5) Add 35% MCl30 to the cup and ring liquid obtained in Step 2.
．． 9ml (0.35M) was added and cooled to 0-5°C. This stuff has 27.25 g of NaNO (0.105
M) was gradually added, stirred at 0-5°C for 3 hours, and excess NaNO2 was removed with sulfur-amic acid to synthesize the diazo liquid. Dwarf? Add 1 diazo solution to the coupling solution obtained in step 3.
The mixture was added while maintaining pH 8 to 9 with a 0% aqueous sodium hydroxide solution. After the coupling was completed, NaCl was added in an amount equal to 20% of the volume of the reaction solution, followed by salting out and filtration. The wet cake thus obtained was added to 1e of water at 60°C.
After dissolving with 4 and returning to room temperature, 2-propatool 2e
was added, crystallized, filtered, and dried. Since the obtained dye has a sodium salt type, the following steps are performed to convert it to a lithium type. (Step 6) The dye obtained in Step 5 was dissolved in water to make an aqueous solution, treated with a strongly acidic cation exchange resin, and then LiOH was added to the eluate to neutralize it. This product was concentrated, filtered and dried to obtain 45.5 g of the desired dye. The yield was 55.2%. [Preparation and evaluation of recording liquid and evaluation of recorded images 1 A recording liquid was prepared by treating each of the above components according to the method described in Example 1, and various evaluations according to (1) to (3) of Example 1 were carried out. went. As a result, similar to Example 1, good results were obtained in all cases. Further, in the same manner as in Example 1, the evaluation according to (4) was performed to determine the value of discoloration and fading (ΔE*), and the value was 4. The dyes used in the following Examples were prepared in the same manner as in Examples 1 and 2 above. Good results were obtained. In addition, evaluation was performed according to (4) of Example 1, and discoloration and fading (Δ
When the value of El) was determined, the value was IO. Examples 4 to 9 The recording liquid was prepared by the method of Example 1, except that the dyes of formulas (d) to (g) were used in place of the dye of formula (h) used in example 1. Prepared Example 1
Various evaluations were conducted according to (1) to (3). As a result, similar to Example 1, good results were obtained in all cases. Further, the ozone resistance results (ΔEl) of the recorded image (on coated paper) in (4) were as follows. Example No. Dye No.
Ozone Resistance (ΔEl) A recording liquid was prepared by treating each main culprit component by the method described in Example 1, and various evaluations according to (1) to (3) of Example 1 were performed. As a result, as in Example 1, all of the results showed good results.In place of the dye of the above formula (A) used in Example 1, dyes of the above formulas (H) and (S) in which M is Na were used, respectively. Except for the above, a recording liquid was prepared according to the method of Example 1, and the ozone resistance was evaluated according to (4) of Example 1. When a dye having a structure in which M is Na in the formula (H) above was used. The value of 68 lines is 5, and the above (
When a dye having a structure in which M is Na in the formula (2) was used, the value of 68 lines was 7. Comparative Examples 1 to 3 In Example 1, a recording liquid was prepared using each of the dyes having the structural formulas shown in the table below instead of the dye of the formula (A), and
Ozone resistance of recorded images (68
When I looked into the book, the results were as shown in the table below. Results of various evaluations according to (1) to (3) of Example 1 Example 1
Similarly, good results were obtained in both cases. [Effect of the invention 1 The recording liquid of the present invention is used for inkjet recording and writing instruments, and in addition to being excellent in light fastness, water resistance, and ozone resistance of recorded images when recorded on plain paper, the recording liquid of the present invention It also has good storage stability.

Claims (2)

[Claims] (1) A recording liquid characterized by containing a solvent and at least one dye represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, A and B each represent a phenyl group, a phenylene group, a naphthyl group, or a naphthylene group that may have a substituent, and C has the following structure. (M represents an alkali metal, ammonium group, or organic amine salt, and n represents a number of 0 or 1.) C; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲Mathematical formulas , chemical formulas, tables, etc.▼ (2) A recording material having an ink receiving layer containing a silicon-containing pigment and a binder resin on a base material is coated with a solvent and the following general formula [
An inkjet recording method characterized in that recording is performed by an inkjet recording method using a recording liquid containing at least one dye represented by [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, A and B each represent a phenyl group, a phenylene group, a naphthyl group, or a naphthylene group that may have a substituent, and C has the following structure. (M represents an alkali metal, ammonium group, or organic amine salt, and n represents a number of 0 or 1.) C: ▲There are mathematical formulas, chemical formulas, tables, etc.▼