JPS6072738A - Ink making apparatus - Google Patents

Abstract

PURPOSE:To form an ink having a quality ideal for use in inkjet recording and writing tools by removing inorganic salts and heavy metal ion contained in a dye solution by chromatography and ion exchange separation in the preparation thereof. CONSTITUTION:A producing section 1 produces a dye aqueous solution. The refining section 100 of the dye aqueous solution have a refining section 100A for removing inorganic salts from the dye aqueous solution by chromatography and a refining section 100B for removing heavy metal ion by ion exchange separation. An ink preparation section 200 prepares an ink from a the refined dye aqueous solution fed from the refining section 100. A control section 300 controls the driving of above-mentioned sections. The dye solution undergoes chromatography to eliminate inorganic salts contained therein and undergoes an ion exchange separation to remove heavy metal ion therein. Such a refined dye solution is used to prepare an ink. This enables the formation of an ink having the quality ideal for use in inkjet recording and writing tools.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to an ink manufacturing apparatus for continuously manufacturing a recording liquid (generally referred to as ink) particularly suitable for inkjet recording, writing instruments, and the like.

[Prior Art] Conventionally, ink used in the inkjet recording method, in which recording is performed by ejecting ink in a recording head from an ejection orifice using vibrations caused by a piezo vibrator, has been made by mixing various dyes and pigments with water or other organic solvents. It is known to be dissolved or dispersed in a liquid medium consisting of: It is also known that similar inks are used in writing instruments such as felt pens and fountain pens.

An example of a general basic composition of such an ink is one in which the main components are a water-soluble dye, water as its solvent, and glycols as a drying inhibitor.

Here, water-soluble dyes usually contain large amounts of inorganic salts such as sodium chloride and sodium sulfate, and heavy metal ions.

When recording inks are prepared using dyes containing such inorganic salts and heavy metal ions, the following disadvantages occur. That is, inorganic salts and heavy metal ions reduce the dye dissolution stability in the ink, leading to aggregation and precipitation of the dye. Furthermore, in inkjet recording heads and writing instruments, when ink is ejected near the ejection orifice and the liquid composition changes, this causes precipitation of inorganic salts and heavy metals. All of these causes clogging of the discharge orifice, which is most avoided.

Therefore, in order to eliminate such adverse effects, it is necessary to control the concentrations of inorganic salts and heavy metal ions to fall within predetermined ranges during ink production. This is essential when common commercially available dyes containing inorganic salts and heavy metal ions as impurities are used in the preparation of inkjet recording inks and writing instrument inks.

[Objective] In view of the above points, the object of the present invention is to remove inorganic salts and heavy metal ions contained in a dye solution by chromatography and ion exchange separation method when preparing ink, and thereby improve inkjet printing. An object of the present invention is to provide an ink manufacturing apparatus capable of manufacturing ink having a quality suitable for use in recording and writing instruments.

[Example] Hereinafter, the present invention will be described in detail with reference to the drawings.

FIG. 1 shows the overall configuration of an embodiment of the apparatus of the present invention.

Here, l is the manufacturing department that manufactures the dye aqueous solution, and 10
0 is a dye aqueous solution purification section, and a purification section 100 removes inorganic salts from the dye aqueous solution by the chroma I/graph method.
A and a purification section 100B that removes heavy metal ions by an ion exchange separation method. An ink preparation section 200 prepares ink using the purified dye aqueous solution supplied from the purification section 100.

Reference numeral 300 denotes a control section, which controls the driving of each section described above.

FIG. 2 shows the structure of the dye solution manufacturing section 1 shown in FIG.

Here, 3 is a dye supply section that stores dye powder 5,
The dye powder 5 is supplied to a mixing tank 9 via a dye valve 7. Further, pure water is supplied to the mixing tank 8 via a pure water supply pipe 13 into which a pure water valve 11 is inserted.

In this mixing tank 9, the supplied dye powder 5 and pure water are stirred in the mixing tank #! 15 to prepare an aqueous dye solution. The amount of the aqueous dye solution stored in the mixing tank θ is detected by a mixing tank liquid amount detector 17.

The aqueous dye solution obtained in the mixing tank contains particles of dye powder that were not dissolved in the pure water, and these are removed by the filter 18. For this filter 18, ordinary filter paper, Fluorobor (trade name), or the like can be used. The aqueous dye solution from which particles and the like have been removed by passing through the filter 19 is supplied to the supply tank 21 .

The aqueous dye solution supplied to the supply tank 21 is supplied to the purification section 100, which will be described next, via the supply pipe 23. Here, this supply tank 21 is provided with a valve 25 for controlling the liquid level,
To suppress the amount of dye aqueous solution stored in the supply tank to a certain amount or less.

FIG. 3 shows a purification section 100A for removing inorganic salts from the aqueous dye solution in the purification section 100 of FIG.

As shown in the figure, the purification unit 1OOA includes a plurality of salt reduction processing units 101 (101-1 to 101-N). In the salt reduction processing unit 101, 103 (103-
1 to 103-N) are supply valve opening/closing parts, 105 (1
05-1-105-N) is the salt-reducing filter section and 10
7 (107-1 to 107-N) are discharge valve opening/closing parts.

The supply valve opening/closing section 103 includes a dye aqueous solution supply pipe 109.
(108-1 to 109-N), pure water supply pipe 111 (1
1 to 111-N) and secondary solution supply pipe 113 (1 to 111-N)
13-1 to 1 l3-N) are communicated with each other. The aqueous dye solution is supplied from the supply tank 21 to the opening/closing section 103 via the supply pipes 23 and 108 sequentially, and the pure water is supplied to the opening/closing part 103 from the supply pipe 13.
and 111 sequentially. Furthermore, 2 described later
The secondary solution is supplied from the secondary solution storage tank 115 to the supply valve opening/closing unit 103 via the supply pipe 117 and +13 in sequence.

The supply valve opening/closing section 103 transfers the supplied dye aqueous solution, pure water, and secondary solution to the low-salt filter section! Controls whether or not to supply to 05.

The salt-reducing filter section 105 uses chromatography to remove S-sulfur salts from the dye aqueous solution and secondary solution supplied from the supply valve opening/closing section 103.

By controlling the discharge valve opening/closing section 107, this (salt reduction)
The aqueous dye solution whose inorganic salt concentration has been reduced to a predetermined value (for example, 5% by weight based on the dye) after purification is discharged into the discharge pipe +19 (
1113-1 to 111]-N) to the storage tank 121. Further, the aqueous solution discharged from the filter section 105 is transferred to the discharge pipe +23 (+23-) according to its component concentration.
1 to 123-N) to the inorganic salt solution discharge section 125.
, or discharged to the discharge pipe 127 (127-1 to 127-N).

One end of this discharge pipe 127 is connected to a suction boat of a circulation pump 129, and the aqueous dye solution discharged to the discharge pipe 127 is transferred to a secondary source by this pump 128 via a discharge pipe 131 connected to its discharge port. The solution is pumped to the solution storage tank 115. In this way, the dye aqueous solution refluxed from the discharge side of the purification section 100A is used as a secondary solution, and the dye solution is returned to the purification section I.
Supplied to QOA for purification (salt reduction).

Reference numerals 133 and 135 are discharge valves disposed in the storage tank 121 and the discharge tank 125, respectively.The dye aqueous solution is supplied to the purification section 100B through the valve 133, and the inorganic salt solution is discharged through the valve 135.

FIG. 4 shows the configuration of the salt reduction processing unit 101 shown in FIG.

In the figure, the first supply pulp 137 in the supply valve opening/closing section 103 is controlled to close, thereby controlling one item of pure water supplied to the salt reduction filter section 105 via the supply pipe 111.

Similarly, the second supply valve 138 and the third supply valve 14
1 is opened and closed to control the supply of the secondary solution and dye aqueous solution to the salt-reducing filter section 105, respectively.

Next, the salt-reducing filter section 105 separates inorganic salts from the dye aqueous solution by chromatography. That is, the aqueous dye solution is supplied to the upper end of the chromatography column 143 from the supply valve opening/closing section 103 . The supplied dye aqueous solution is transferred to column 1.
While descending through 43, each component in the aqueous solution is separated. By this developing operation (chromatography), the components with the weakest adsorption properties flow out first. Therefore, by detecting the component concentration of the effluent solution, it is possible to extract only the aqueous dye solution in which the concentration of inorganic salts is below a predetermined concentration from the effluent solution based on the detection result.

Inorganic salt concentration detector 145 and dye concentration detector 147
is for detecting the respective concentrations of inorganic salts and dyes in the solution flowing out from the column 143.
Placed within. As a method of detecting each component, there are a method of measuring conductivity, a method of using ionic current, a method of measuring spectrophotointensity, etc., and any of them may be used.

The chromatography column 143 is supplied with a dye solution in fixed amounts for purification (salt reduction), and for this purpose, a liquid level position detector 151 is installed at the upper end of the column to detect the dye solution. Based on the result, the amount of aqueous solution supplied from the supply valve opening/closing section 103 is controlled.

Here, the stationary phase filled in the column 143 generally includes ion exchange resins, chelate resins, etc.
In this example, an ion retardation resin, such as Retardion IIA, is used.
-8 (trade name: manufactured by Dow Chemical Company) is used. Ion retardation resins do not require regeneration agents, can be regenerated with pure water, and are nearly neutral, so they are advantageous for desalting substances that are unstable to acids and alkalis.

FIG. 5 shows an effluent curve, in which the concentration of each component of the effluent solution from the chromatographic column 143 is plotted against the time axis, that is, a fractionation characteristic. As shown, dye concentration (curve I)
peaks between hours 11 and 12, and the inorganic salt concentration (curve ■) peaks between hours 13 and 74. In this example,
Based on such classification characteristics, the inorganic salt concentration detector 14
5 and dye concentration detector 14? Based on the detected value, the effluent solution from the chromatography column 143 is fractionated and extracted as follows.

That is, when the dye concentration of the effluent solution is equal to or higher than the predetermined value C2 (effective dye concentration) and the inorganic salt concentration is less than the predetermined value C3 (allowable salt-free concentration) (between times 11 and 12), the effluent solution is led to the storage tank 121. However, after the inorganic salt concentration exceeds the value C3 and the dye concentration falls below the value C2, the effluent solution is directed to the inorganic salt solution discharge tank 125. Also, during the period from when the inorganic salt concentration reaches the value C3 or more until the dye concentration becomes the value C2 or lower (between time T2 and T3)
The effluent solution is refluxed to the secondary solution storage tank 115.

Referring again to FIG. 4, the discharge valve opening/closing section 107 is for separating the effluent solution as described above, and is connected to the discharge passage 14.
9 into three prongs, each branch pipe and discharge pipe 123, 127
and 119, respectively. They are communicated via second and third exhaust valves 153, 155 and 157. With this configuration, by opening the first discharge valve 153, the effluent solution can be discharged into the inorganic salt solution discharge tank 125, and similarly, by opening the second and third discharge valves 155 and 157, the effluent solution can be discharged into the inorganic salt solution discharge tank 125. The liquid can be led to the next solution storage tank 115 and storage tank 121.

FIG. 6 shows the configuration of a purification section 100B that removes heavy metal ions from the dye aqueous solution in the purification section 100 of FIG.

Here, the supply tank 161 is supplied with an aqueous dye solution from which inorganic salts have been removed in the purification section 100A. This supply tank 1
A supply tank liquid level detector 163 is disposed at 61, and the valve 133 is opened and closed based on the output of the sensor 163 to control the liquid level in the supply tank 161.

The purification section 100B includes a plurality of processing units, in this example, three first to third processing units 185-1, 185-2 and 185-3. Each processing unit 185 (185
-1 to 185-3), the dye aqueous solution in the supply tank 161 is supplied to the ion exchange resin column 16!3 (168-1-1) through the supply valve 187 (167-1-167-3).
68-3). The ion exchange resin column 188 separates heavy metal ions from the dye aqueous solution by so-called ion exchange separation. That is, due to ion exchange within the column, highly adsorbable heavy metal ions contained in the aqueous dye solution are captured by the ion exchange resin and remain within the column. Here, a valve 171 (171-1-171-3) for controlling the liquid level is provided in the column to control the amount of the dye aqueous solution supplied into the column. Further, this column 1θ9 is made detachable from the processing unit, and whether or not the column is attached is detected by a filter replacement end switch (not shown).

Next, heavy metal ion concentration detector 173 (173-1 to 17
3-3) is arranged in the outflow solution passage at the lower end of the column 168 to detect the heavy metal ion concentration in the outflow solution from the column 11 (9).As a method for detecting the heavy metal ion concentration, for example, a metal ion electrode A measurement method using atomic absorption spectroscopy and a measurement method using atomic absorption spectroscopy shall be used.A solution detector 175 (175-1 to 175-3) is also disposed in the outflow solution passage to detect the presence or absence of an outflow solution in the outflow solution passage. To detect.

The effluent solution from the column 168 is transferred to the first discharge valve 17?
(17?-1 to 17?-3) to the storage tank 178. In addition, the second discharge valve 181 (1811 to 11
N-3), it is refluxed to the supply tank 161 by the action of the circulation pump 183. Both valves 177 and 181
The opening/closing control of the heavy metal ion concentration detector 17 is performed as described below.
This is done based on the detection results in step 3.

The dye aqueous solution from which heavy metal ions have been removed obtained in the storage tank 17e is supplied to the ink preparation unit 2 via the supply valve 185.
Supply to 00.

FIG. 7 shows the configuration of the ink preparation section 200 shown in FIG. 1. Here, 201 is an ink preparation tank, and a dye aqueous solution purified as described above is supplied from the purification section 100 to a valve 185.
Supply via. In addition, the storage section 203 and the storage section 2
From 05 onwards, water-soluble organic solvents and additives are supplied to the mixing tank 201 via valves 207 and 208, respectively. Furthermore, pure water is also supplied via the valve 211. Each of these supplied materials is stirred by stirring 92.13 to prepare ink.

The amount of ink obtained in the mixing tank 201 is measured by the liquid amount detector 2.
Detected by 15. Further, the dye concentration, inorganic salt concentration, and heavy metal ion concentration in the ink prepared in the mixing tank 201 are measured by a dye concentration detector 217. Detection is performed by an inorganic salt concentration detector 219 and a heavy metal ion concentration detector 221. Based on the output of the 4"L detector, final property management (lot management) of the adjusted ink is performed as described below.The ink with each component adjusted to the desired value is then Then, it is discharged through the discharge valve 223.

Reference numeral 225 is an operation unit including various display units and drive switches, and 227 is a printer that prints out various data. In the display section of the operation section 225, 225-1, 225
-2 and 225-3 are a dye concentration indicator, an inorganic salt concentration indicator and a heavy metal ion concentration indicator, respectively;
dye concentration detector 217. Inorganic salt concentration detector 2
18 and the detection results of the heavy metal ion concentration detector 221 are displayed. That is, the display shows the ink preparation tank 201.
The dye concentration value in the ink as the final product obtained within
Inorganic salt concentration values and heavy metal ion concentration values are displayed. Based on this display result, the operator can manage the properties (lot management) of the manufactured ink.

Further, the printer 227 prints out the detection results of the detectors 217, 2111 and 221 at regular intervals. Based on this output result, the operator can monitor changes in the properties of the manufactured ink over time.

FIG. 8 shows a portion related to the purification section 100 in the control section 300 of the apparatus shown in FIG.

Here, 301 is a controller, which controls the drive of each part. A read-only memory (ROM) 302 stores control programs such as operating procedures shown in FIGS. 8 and 10. 303 is a random access memory (RAM)
), and performs temporary storage of various data. Reference numeral 3θ4 denotes various switches arranged in the operation section, and sends various command signals to the controller 301 via the input/output buffer circuit 305. Reference numeral 306 denotes a display device also disposed in the operation section, and as described later, first to third indicators indicate that column replacement is required in each processing unit of the purification section 100B.
It has a unit filter replacement indicator and first to third unit operation indicators to indicate that each processing unit is in operation for purifying the dye aqueous solution. A drive circuit 307 controls the display of the display 308 based on a drive signal from the controller 301.

In the purification section 100A, analog signals are output from the inorganic salt concentration detector 145 and the dye concentration detector 147, and are converted into digital signals via A/D converters 311 and 312, respectively, and then sent to the input buffer circuit 31.
3 to the controller 301. On the other hand, a digital signal is output from the liquid level position detector 151 and is supplied to the controller 301 via the input buffer circuit 313.

321 to 328 are the aforementioned valves 137, 139, 1
41.

153.155 and 15? This is a drive circuit for opening and closing, respectively, and is controlled to be turned on or off by a drive signal supplied from the controller 301 via the output buffer 7 circuit 327.

In addition, since the configurations of the salt reduction processing units) 101-1 to 101-H are the same, in the figure, the units) 101-
1 is shown, and the other units 101-2 to 101-N are omitted.

Next, in the purification section 100B, the supply liquid level detector 113
The detection output No. 3 is supplied to the controller 301 via the input buffer circuit 331. Drive circuits 332 and 33
3, each load (valve 1
85, pump 183) is on/off controlled.

Next, the detection signal from the heavy metal ion concentration detector 173-1 is digitized via the A/D converter 341 and then supplied to the controller 301 via the input buffer circuit 342. Further, a digital detection signal is output from the solution detector 175-1 and is supplied to the controller 3Q1 via the input buffer circuit 342. 343°344 and 345
are each of the above-mentioned valves 187-1, 177-1 and 18
This is a drive circuit for opening and closing 1-1, respectively.
On/off control is performed by a drive signal supplied from the controller 301 via the output buffer circuit 346.

Note that since the configurations of each processing unit 185-1 to 1135-3 are the same, the other units 185-1 to 1135-3 are shown in the figure.
5-2 and 185-3 shall be omitted.

FIG. 8 shows the purification section 100 of this embodiment configured as described above.
The operation of each processing unit in A is shown.

In the figure, when a start command is received from the operation unit in step STI, the program switch is set to OFF in step ST2. next. In step ST3, the second and third supply valves 138 and 141 are opened, and the dye aqueous solution in the supply tank 21 and the secondary solution storage tank 11 are
5 starts to be supplied into the chromatography column 143. This supply operation continues until the liquid level in the column 143 reaches the highest position H (see FIG. 84) according to the output of the liquid level position detector 151 in step ST4. When the liquid level reaches the highest level, that is, when a predetermined amount of aqueous solution has been supplied to the column, the process proceeds to step ST5, and both valves 138 and 141 are closed.

Next, in step ST6, the first exhaust valve 153
is opened, and the effluent solution from the chromatography column 143 begins to be discharged to the inorganic salt solution discharge tank 125.

In step ST7, it is determined whether the liquid level in the column is at the lowest position (see FIG. 4). Immediately after the aqueous dye solution and secondary solution are supplied, in the state 9, the liquid level is higher than the lowest position, so the determination is "NO" and the process proceeds to step ST8.

In step ST8, the first supply valve 137 is closed, and the process proceeds to step 5TIO. Here, as described above, the aqueous dye solution and the secondary solution are supplied to the column 1.
Immediately after the expansion operation is started in 43,
The concentration of each component in the effluent solution is in the state shown between time 0 and time 71 in FIG. 5. Therefore, in step 5TIO, the determination as to whether the density value detected by the dye density detector 147 is equal to or greater than the effective dye density value 02 is "NO".
Proceed to step 5TII. Furthermore, in step 5TII, the determination as to whether the concentration value detected by the inorganic salt concentration detector 145 is equal to or greater than the cleaning inorganic salt concentration value 01 is determined as "NO", and the process proceeds to step 5T12. In step 5T12, it is determined whether the program switch is in the on state. In the first loop, it is in the off state, so the determination is "NO", and step ST7
Return to. Such steps ST7→ST8→
The loop of 5TIO-9TII-3T12 is repeated until rYESJ is determined in step 0 to step 5TIO.

In addition, in step ST7, when it is determined that rYESJ, the process proceeds to step ST8, and the first supply valve 1
3? is opened, and pure water is supplied to the column 143. Therefore, in such a case, steps ST7→ST9→ST
A loop of 10→5TII→5T12 is executed.

In step 5TIO, when the dye concentration value of the solution flowing out from the column 143 becomes equal to or higher than the effective dye concentration value C2 (time 0I in FIG. 5), the process proceeds to step 5T13. In step 5T13, it is determined whether the inorganic salt concentration value detected by the inorganic salt concentration detector 145 is equal to or higher than the allowable S organic salt concentration value 03.

Here, due to the development operation of the chromatography column 143, the aqueous dye solution from which the inorganic salts have been separated flows out first (5th column).
(See Figure Time 1 to T2), and in step 5TI3, "N
It is determined as "O" and the process proceeds to step 5T14. In step 5T14, the first discharge valve 153 is closed, and in step 5T15, the third discharge/help 1
5? is opened, and the effluent solution from the chromatography column 143 is discharged to the storage tank 121 through the discharge pipe 1113. Next, in step 5T18, the program switch is turned on, and step ST? Return to Step ST like this? →ST8→5TIO→5T13→5T1
4→5T15→5T18 or step ST7→ST9
→s'rto+ 5T13→5T14→5T15→5T
The IEi loop is repeated, and an aqueous dye solution purified to an inorganic salt concentration of 03 or less is obtained in the storage tank 121.

Such a loop executes rYEsJ in step 5T13.
This will continue until it is determined that

As shown in FIG. 5, when the inorganic salts start flowing out and the inorganic salt concentration of the effluent solution increases and the value exceeds the allowable inorganic salt concentration value 03 (time 02 in FIG. 5), step 5T13 starts. Step STI? The third discharge valve 157 is closed, and the second discharge valve 155 is opened in step 5T18. As a result, the effluent solution is transferred to the storage tank 121.
The discharge to the discharge pipe 127 is stopped and discharged to the discharge pipe 127. Here, in this example, assuming that the circulation pump 129 is driven in synchronization with the opening operation of the valve 155, the outflow solution is discharged to the secondary solution storage tank 115 via the discharge pipes 129 and 131. This refluxing operation of the effluent solution is performed in step 5TIO.
The process continues until a "NO" determination is made in the step. The secondary solution recovered in this way will be purified again to reduce salt. Next, when the dye concentration of the effluent solution decreases and its value falls below the effective dye concentration value C2 (time T3 in Figure 5),
In step 5TIO, the determination is "NO" and the process proceeds to step 5TII. Now, since the inorganic salts are continuing to flow out, it is determined that rYEsJ is present in step 5TII, and the process proceeds to step 5T19, in which the second discharge valve 155 is closed, and furthermore, in step 5T20, the first discharge valve 153 is opened. It will be done. As a result, the flow of the outflow solution to the secondary solution storage tank 115 is stopped, and the outflow solution starts to be discharged to the inorganic salt solution storage tank 125 via the discharge pipe 127. This draining operation is continued until the inorganic salt concentration of the effluent solution falls below the cleaning inorganic salt concentration value C1.

When the inorganic salt concentration falls below the value CI (Time T4 in Figure 5)
, the determination in step 5TII is "NO" and the process proceeds to step 5T12. Here, since the program switch is set to ON in step 5T1B as described above, rYE is set in step 5TI2.
It is determined that sJ, and the process proceeds to step ST21, where the first discharge valve 153 is closed and the discharge of the outflow solution to the discharge tank 125 is completed.

Next, in step 5T22, the supply pulp 137 is closed, and the supply of pure water to the chromato column 143 is stopped. That is, in this example, the first supply valve 137 is controlled to open and close so that the liquid level of the aqueous solution in the chromatography column 143 is always at the lowest position (see FIG. 4), and pure water is supplied (Stella 7 'ST8,5TY). This pure water washes (regenerates) the stationary phase within the chromato column. As mentioned above, when the inorganic salt concentration of the effluent solution falls below the cleaning inorganic salt concentration value CI, cleaning (regeneration) is performed.
It is determined that this has occurred, and the supply of pure water is stopped.

After executing step 5T22, step STI is executed again.
Return to and wait for the start command.

4 As described above, one (salt reduction) purification operation is completed. In addition, in this embodiment, each processing unit) 101
Although the operations in -1 to 101-N are executed synchronously, they are not limited to this, and of course may be executed sequentially, for example.

Further, in this embodiment, the collected secondary solution is purified in each processing unit 101, but a separate processing unit exclusively for the secondary solution may be provided to perform the purification.

FIG. 10 shows the operation of each processing unit in the purification section 100B.

In the purification section 100B, each processing unit l = 185-1 to 1 based on the detection output of the heavy metal ion concentration sensor 173.
85-3 are replaced one after another to remove heavy metal ions from the dye aqueous solution supplied from the purification section 100A. That is, there is a limit to the ability of the ion exchange resin in the ion exchange resin column 169 to capture heavy metal ions, and once a certain amount of heavy metal ions have been adsorbed, ion exchange separation is no longer performed. As a result, the dye solution containing heavy metal ions is discharged as is, and the concentration of heavy metal ions in the solution flowing out from the column IH increases. By detecting A at this concentration, use of the ion exchange resin column is disabled, and subsequent purification of the dye solution is performed using either of the other two columns.

In addition, an ion exchange resin column that is no longer usable is replaced with a new column, or the ion exchange resin is regenerated so that it can be purified again in the processing unit. FIG. 10 shows the operation of each processing unit, and each flag in the figure is used to make the following determination.

Unit filter replacement flag: A flag that instructs to replace the filter in each processing unit, that is, the ion exchange resin column. When this flag is turned on, the corresponding unit filter replacement indicator will display that filter replacement is necessary. .

Unit change request flag: A flag that requests a change in the processing unit. When this flag is turned on, the processing unit specified by the unit selection counter is selected,
Dye purification operations are transferred to that processing unit.

Unit operation flag: A flag indicating that the corresponding processing unit has been selected.

Unit i/operating flag: This is a flag that indicates that the corresponding processing unit is in operation.

Unit discharge flag: A flag that is turned on when the concentration of heavy metal ions in the solution flowing out from the column in the corresponding processing unit exceeds a set value, and instructs the pump 183 to start refluxing the solution to the supply tank 161.

Next, each step shown in FIG. 810 will be explained.

In FIG. 10(A), in step 5TIOI, each display and data are initialized. In step 5iT102, the processing unit change request flag is turned on and the contents of the unit selection counter are set to "1". In step 5T103, the supply tank liquid level detector 113
Based on the detection output No. 3, it is determined whether a predetermined amount of dye aqueous solution is stored in the supply tank 161. When the predetermined amount is stored, the dye solution supply valve 133 is closed in step 5T104, and then the process proceeds to step 5T1013.

However, if the predetermined amount has not been reached, step 5T
At step 105, the supply valve 133 is opened to supply the aqueous dye solution to the supply tank.

Step 5 TIf) 8 is the first processing unit +135-
This is a processing step when there is a filter replacement request in step 1, and consists of steps 5T108-1 to 5T106-3.

First, when it is determined in step 5T106-1 that the first unit filter replacement flag is in the on state, the process proceeds to step 5T108-2, where it is determined whether the first unit filter replacement end switch is on.

If it is in the on state, proceed to step 5106-3;
The first unit filter replacement flag is turned off, and the display indicating that replacement is required, which was displayed on the first unit filter replacement display, is erased. After this, step 5T
IO? Proceed to. Note that when the filter replacement flag is off in step 8 S7108-1 and when the filter replacement end switch is off in step 5T108-2, step 5T10? Proceed to.

Step 5TIO? and step 5T108 are processing steps when there is a filter replacement request in the second processing unit 185-2 and third processing unit 1135-3, respectively, and the contents are the same as step 5T11)8, so the explanation thereof will be omitted. do.

Step 5TIO! 3, it is determined whether or not the unit change request flag is in the on state, and if the determination is affirmative, the process proceeds to step 57110, and if the determination is negative, the process proceeds to step 57110, and if the determination is negative, FIG.
Proceed to step 5T11B of B). Step 5TIIO
Then, the content of the unit selection counter is determined, and if the content is rlJ, the process advances to step '3T113, and "2
”, the process goes to step 5T114, and when it is “3”, the process goes to step 5T115.

Steps 5T113 to 5T115 are for each processing unit 18.
These are processing steps when 5-1 to 185-3 are selected. Since the contents of each of these steps 5T113 to 5T115 are the same, the contents of step 5T113 when the first processing unit 185-1 is selected will be explained. first,
In step 5T113-1, it is determined whether the first unit filter replacement flag is in the off state.

If the determination is negative, the process proceeds to step 5T113-5, and if the determination is affirmative, the process proceeds to step 5T113-2. In step STI 13-2, the first unit operating indicator is turned on to indicate that the first processing unit 165-1 is operating. In step 5T113-3, the supply valve +
87-1 and second discharge valve 181-1 are opened. Subsequently, in step 5T113-4, the first unit operation flag is turned on and the unit change request flag is turned off. Next, in step 5T113-5, after setting the content of the unit selection counter to "2", step 57
Proceed to 118. Here, the contents of the unit selection counter are "r2", r3, 1 . rl”.

It is a ring counter that changes in the order of "2", etc., and by executing step 5T114, its contents are changed to "3"
", and by executing step 5T115, the content changes to "1".

Next, steps 5711B and 5T1 in FIG. 10(B)
17 and 5T118 are discharge control steps for the effluent solution from the ion exchange resin column in each processing unit, respectively. The contents of each of these steps are similar, so
The contents of only step 5T118, which shows the control in step 165-1 (first processing unit), will be explained.

First, in step 5T118-1, it is determined whether the first unit operation flag is in the on state. If the determination is negative, the process jumps to step 5T118-5, and if the determination is affirmative, the process advances to step 5T118-2. Step 5T
1113-2, heavy metal ion concentration detector 173-1
It is determined whether the heavy metal ion concentration detected in the column outflow solution is below a set value. If the determination is negative, the process proceeds to step 5T11θ-5, and if the determination is affirmative, the process proceeds to step 5T118-3. Step 5T118-
3, the second discharge pulp 181-1 is closed, and the first discharge valve 17? Open -1. As a result, in the ion exchange resin column 189-1, the dye aqueous solution 1 from which the heavy metal ions have been removed to a concentration value below the set value is removed by the first discharge valve 17? -1 through storage tank 178
discharged inside. Next, in step 5TII6-4, the first unit operation flag is turned off, and the first unit operation flag is turned on, after which the process advances to step 5T1113-5.

In step 5T118-5, it is determined whether the first unit operating flag is in the on state.

If it is in the off state, the process advances to step 5T118-10, and if it is in the on state, the process advances to step 5T116-8. In step 5T118-6, the heavy metal ion concentration sensor 173-
1, it is determined whether the detected concentration exceeds the set value or not. If the set value is not exceeded, step 5
Proceed to T118-10, and if exceed, step 5T1
Proceed to 18-7. After turning off the first unit operating indicator in step 5T11f3-7, step 5T1
Proceed to 18-8 and supply valve 1B? -1 and the first discharge valve 17? -Close 1. In addition, 2nd discharge/Shun Rev 1
81-1 and drives the circulation pump 183,
The effluent solution from column 189-1 is transferred to second discharge valve 18.
A reflux 2 operation is started in which the reflux 2 is refluxed to the supply tank 181 via 11. Next, in step 5T109, the first unit operating flag is turned off and the first unit discharge flag is turned on, and then in step 5711B-10
Proceed to.

Next, in step 5T11B-10, it is determined whether or not the first unit discharge flag is in the on state. If it is in the off state, the process proceeds to step 5T117, and if it is in the on state, the process proceeds to step 5T11B-11. Step 5T1
18-11 determines whether the solution detector 175-1 disposed in the outflow solution passage of the column 169-1 is off, that is,
It is determined whether or not any effluent solution remains in the effluent solution passage. When it is not in the off state, that is, when a solution is detected, the process advances to step 5T117, and when it is in the off state, step! Proceed to 3T118-12. This off state means that all of the aqueous dye solution discharged from the column IH-1 whose heavy metal ion concentration value is higher than the set value has been refluxed to the supply tank 181. Step 5T
11f (-12, the first unit filter replacement indicator is turned on to indicate that the column of the first processing unit needs to be replaced. Next, in step 5T118-13, the second discharge valve tst-t is turned on. and close pump 1.
83 is stopped, and the reflux operation is stopped. Next, in step 5T118-14, the first unit discharge flag is turned off, the first unit filter replacement flag is turned on, and the unit change request flag is turned on. After this,
Proceed to step 5T117.

Next, step 5TII? and after passing through 5T11B,
Steps shown in Figure 1θ (A) again! Return to 3T103.

By executing each of the above-described steps, the aqueous dye solution is purified in each of the processing units 185-1 to 185-3, and a purified aqueous dye solution whose heavy metal ion concentration is below the set value is obtained in the storage tank 178.

In this way, a purified dye aqueous solution from which inorganic salts and heavy metal ions have been removed is obtained in the storage tank 179 by the purification sections 100A and 100B, and as described above, the ink production section 200 uses this purified dye aqueous solution to make ink. Preparation is made.

[Effects] As explained above, according to the present invention, chromatography is performed using a dye solution to eliminate inorganic salts contained in the dye solution, and ion exchange separation is performed to remove heavy metal ions in the dye solution. Since the purified dye solution is used to prepare ink, it is possible to produce ink having a quality suitable for use in inkjet recording and writing instruments.

Furthermore, according to the present invention, such a purified dye solution can be produced continuously and automatically, making it possible to mass produce high quality ink.

In the above examples, the dye solution was purified by removing inorganic salts by performing a chromatography method.
Although the heavy metal ions are removed by performing the ion exchange separation method, it goes without saying that the order of these steps may be reversed.

[Brief explanation of the drawing]

FIG. 1 is an overall configuration diagram showing an embodiment of the apparatus according to the present invention, FIG. 2 is a configuration diagram showing the dye solution production section of FIG. 1, and FIG. 3 is an inorganic salt purification section in the purification section of FIG. 1. 84 is a block diagram showing the salt reduction treatment unit in Figure 3, Figure 5 is a characteristic curve diagram showing the separation characteristics of the chromatography column, and Figure 6 is the heavy metal ion purification in the purification section of Figure 1. 7 is a block diagram showing the ink manufacturing section in FIG. 1, FIG. 8 is a block diagram showing a part of the control section in FIG. 1, and FIG. 8 is a block diagram showing the ink manufacturing section in FIG. 3. Flowchart showing the operation of the processing unit of the purification section. FIGS. 10(A) and 10(B) are flowcharts showing the operation of the processing unit of the heavy metal ion purification section of FIG. Dye solution manufacturing department 3...Dye supply department, 5...Dye powder, ? ... Dye valve, 9... Mixing tank, 11... Pure water valve, 13... Pure water supply pipe, 15... Mixing tank stirrer, 17... Mixing tank liquid level detector, 18... Filtration filter, 21... Supply tank, 23... Supply pipe. Pile - Jshi Nipo - Shigo (100A, 100 pick up 100A...
- Inorganic salt purification section lOl... Salt reduction processing unit, 103... Supply valve opening/closing section, +05... Salt reduction filter section, 107... Discharge valve opening/closing section, 108... Dye aqueous solution supply pipe. +11...Pure water supply pipe, 113...Secondary solution supply pipe, 115...Secondary solution storage tank, 117...Supply pipe, 119...Discharge pipe, 12+...Storage tank, 123...Discharge pipe, 125...Inorganic salt solution discharge tank, 127...Discharge pipe, 129...Circulation pump, 131...Discharge pipe, 133.135...Discharge valve, 13? , 1313.141...supply valve, 143
...Chromato column, 145...Inorganic salt concentration detector, 147...Dye concentration detector, 149...Outflow passage, 151...Liquid level position detector, 153.155,157... discharge valve. 100B... Heavy metal ion purification section 181... Supply tank, 183... Supply tank liquid level detector, 185... Processing unit, 187... Supply valve, 168... Ion exchange resin column, 171 ...Valve, 173...Heavy metal ion concentration detector, 175...Solution detector, 17? ...First discharge valve, 179...Storage tank, 181...Second discharge valve, +83...Circulation pump. Inlet preparation section 200 201... Ink preparation tank, 203... Storage section, 205... Storage section, 207... Valve, 209... Valve, 211... Valve, 213... - Stirrer, 9 215...Liquid level detector, 217...Dye concentration detector, 219...Inorganic salt concentration detector, 221...Heavy metal ion concentration detector, 223...Drain valve . Control unit 300 301... Controller, 302... Read only memory, 303... Random access memory, 304... Switch, 305... Input/output buffer circuit, 306... Display, 307 ...Drive circuit, 311.312...A/D converter, 313...Input buffer circuit, 321-326...Drive circuit, 327...Output 4777 circuit, 331...Input buffer circuit 0 332.333...Drive circuit, 334...Output buffer 7 circuit, 341...A/D converter, 342...Input buffer circuit, 343.344,345...Drive circuit, 346・
...Output buffer circuit. Patent applicant Canon Co., Ltd. Zuhei translation 2 Kayuno (Nifunko) 346 167-1 Rate translation Moraifu? Soma 1' Power Dairy Novel' Copper Yu+-71"Life' Treatment 1 177-1=F Circuit
)<lL7' TS through) - Yai,,, 345 ・+81-1■Road Valve" 334 332 183 Upper blade F life A min valve Circuit 9 333 185 .1 Drive Lube, Road 'l Road 302 303 pxl −Down Ox;

Claims (1)

[Scope of Claims] A means for producing a dye solution; a first solution treatment means for performing chromatography using the dye solution; and a second solution treatment means for performing ion exchange separation to capture heavy metal ions in the solution. and an ink preparation section that prepares ink using the dye solution purified by the first and second solution processing means. (Margin below)