JP5651369B2 - Automatic titration analyzer, automatic titration analysis method, processing liquid automatic analysis management system, and processing liquid automatic titration analysis method - Google Patents

Description

  The present invention relates to an automatic titration analysis apparatus, an automatic titration analysis method, an automatic analysis management system for a processing liquid, and an automatic titration analysis method for a processing liquid.

  Conventionally, as an automatic sample analysis method, for example, a method using an automatic burette is known as described in Patent Document 1. In this method, for example, a titrant is introduced into an automatic burette, the extrusion plate in the burette is raised by a stepping motor, and the titration standard solution in the burette is dropped into a titration cell containing a sample to be analyzed. Calculate the amount of titrant and analyze the sample.

  The automatic burette needs to supply the titrant to the sample in small portions for titration analysis. Therefore, a certain accuracy is required for the supply amount of the titrant supplied from the automatic burette.

  However, in the automatic burette described in Patent Document 1, if the sealability between the column inner wall and the extruded plate is insufficient, air may be mixed into the automatic burette. If air is mixed into the automatic burette, air is supplied when the titrant should be supplied to the titration cell. As described above, if air is supplied to the titration cell when the titrant is to be supplied, an error occurs in the supply amount of the titrant, and an error also occurs in the titration analysis value.

  A method of preventing the supply of air by turning the automatic burette upside down is also conceivable. However, even in this method, air accumulates in the upper portion of the automatic burette, and the supply of the titrant is delayed because the extrusion plate compresses the air, so the accuracy of the amount of titrant supplied decreases.

Utility Model Public Notice No. 1-295937

  The present invention has been proposed in view of such circumstances, an automatic titration analyzer that can accurately supply a titrant to a titration cell, an automatic titration analysis method, an automatic analysis management system for a processing liquid, and an automatic processing liquid An object is to provide a titration analysis method.

An automatic titration analyzer according to the present invention includes a titration cell in which a sample is collected and a burette that supplies a titrant to the titration cell, and the titrant supplied from the burette is applied to the sample in the titration cell. In the automatic titration analyzer for dropping and analyzing the sample, the automatic titration analyzer further includes an air discharge mechanism for discharging air contained in the titrant supplied from the burette, and the air discharge mechanism is supplied with the titrant supplied from the burette. A chamber for storing the air in the upper part, one end communicating with the lower part of the chamber, the other end connected to the titration cell via switching means, and the titration cell supplied from the burette A titrant solution delivery pipe for delivering to the air, one end communicating with the upper end of the chamber, the other end connected to the switching means, and an air feed for delivering air stored in the upper part of the chamber And the switching means includes a state in which one of the titrant solution delivery pipe and the air delivery pipe is communicated between the chamber and the titration cell, and the other is connected between the chamber and the titration cell. switching between the state in which the communication between.

  The processing liquid automatic analysis management system according to the present invention includes the automatic titration analyzer, a recording section for recording the analysis result of the processing liquid by the automatic titration analyzer, and a processing liquid from the analysis result recorded in the recording section. A calculation unit that calculates a supply amount of the supply component and instructs the sample supply unit to supply the processing liquid supply component;

  In the present invention, since the titration liquid can be accurately supplied to the titration cell by providing the air discharge mechanism, automatic titration analysis with high accuracy can be performed.

It is a figure which shows typically the automatic analysis management system which concerns on this Embodiment. It is a figure which shows typically the automatic titration analyzer which concerns on this Embodiment. It is a figure which shows typically the automatic titration analyzer which concerns on other embodiment.

Hereinafter, an example of an automatic titration analysis system to which the present invention is applied will be described in the following order with reference to the drawings.
1. Automatic analysis management system 1-1. Automatic titration analyzer 1-1-1. Analysis unit 1-1-2. Sample weighing mechanism 1-2. Recording unit 1-3. Calculation unit 2. Automatic titration analysis method 2-1. Washing step 2-2. Air discharge step in the sample delivery tube 2-3. Supply to titration cell 2-4. Neutralization titration step 2-5. 2. Air discharge step using air discharge mechanism Other embodiments

<1. Automatic analysis management system>
The automatic analysis management system 1 according to the present embodiment includes an automatic titration analyzer 3, a recording unit 5, and a calculation unit 7, for example, as shown in FIG.

<1-1. Automatic titration analyzer>
As shown in FIG. 1, the automatic titration analyzer 3 includes an analysis unit 10 and a sample weighing mechanism 12.

<1-1-1. Analysis Department>
The analysis unit 10 includes a reagent tank 20, an automatic burette (hereinafter simply referred to as “burette”) 22, an air discharge mechanism 24, and a titration cell 26.

  The reagent tank 20 is made of, for example, polyethylene, and stores a titrant for performing a titration analysis of a sample. For example, sulfuric acid is used as the titrant. One end 30 a of a titrant liquid collecting tube 30 is connected to the reagent tank 20. A three-way valve 34 is connected to the other end 30 b of the titrant liquid collecting tube 30.

  The three-way valve 34 is composed of, for example, a three-port electromagnetic valve, and the state in which the titrant liquid delivery pipe 32 and the titrant liquid delivery pipe 38 communicate with each other (hereinafter referred to as “the state where the three-way valve 34 is NC (normally closed)”); It functions as a switching means for switching between a state in which the titrant solution collecting tube 30 and the titrant solution delivery tube 38 communicate with each other (hereinafter referred to as “the three-way valve 34 is in a NO (normally open) state”).

  A titrant solution delivery pipe 38 is connected to the burette 22. The burette 22 has an extrusion plate 36 therein. In the burette 22, when the three-way valve 34 is in the NO state, the titration solution is introduced from the reagent tank 20 when the pushing plate 36 is lowered by a stepping motor (not shown). In the burette 22, when the push plate 36 is raised by the stepping motor while the three-way valve 34 is in the NC state, the titrant in the burette 22 is sent to the air discharge mechanism 24.

  The air discharge mechanism 24 includes a chamber 40, an air delivery pipe 42, a titrant feed pipe 44, and switching means 46.

  The chamber 40 is made of a material having chemical resistance to the titrant, for example, transparent PVC. The chamber 40 is airtight and receives the titrant sent from the burette 22. Moreover, the chamber 40 stores air bubbles (air) flowing together with the titrant sent from the burette 22 in the upper part, as will be described in detail later.

  The air delivery pipe 42 is formed of a material having chemical resistance, such as a PTFE (Polytetrafluoroethylene) pipe. The air delivery pipe 42 has one end 42 a communicating with the upper end of the chamber 40 and the other end 42 b connected to the switching means 46.

  The titrant solution delivery tube 44 is formed of a chemical resistant material, such as a PTFE tube, like the air delivery tube 42. One end 44 a of the titrant solution delivery tube 44 communicates with the lower portion of the chamber 40, and the other end 44 b is connected to the titration cell 26 via the switching means 46.

  The switching means 46 is composed of, for example, a three-port solenoid valve, and the air delivery pipe 42 is in communication between the chamber 40 and the titration cell 26 (hereinafter referred to as “the switching means 46 is in the NC (normally closed) state”). And the switching means for switching the state in which the titrant solution delivery pipe 44 communicates between the chamber 40 and the titration cell 26 (hereinafter referred to as “the switching means 46 is in a NO (normally open) state”). That is, the switching means 46 is configured such that the one end 42a of the air delivery pipe 42 and the other end 44b of the titrant liquid delivery pipe 44 communicate with each other (the switching means 46 is in the NC state), and the one end 44a of the titrant liquid delivery pipe 44 The state where the other end 44b of the delivery pipe 44 communicates is switched (the switching means 46 is in a NO state).

  The titration cell 26 is formed of a heat-resistant material, for example, Pyrex (registered trademark). A level sensor 47 for detecting the solution level in the titration cell 26 and a pH electrode 48 are inserted into the titration cell 26. The titration cell 26 is provided with a stirrer 50 for stirring the solution.

  A discharge pipe 27 for discharging the solution in the titration cell 26 to the drain is connected to the lower portion of the titration cell 26. The discharge pipe 27 is provided with an on-off valve 28 for switching between opening and closing of the discharge pipe 27 and a drainage pump 29.

  The analysis unit 10 also includes an ion exchange water tank 100. From the ion exchange water tank 100, ion exchange water is supplied into the titration cell 26 by a liquid feed pump 98.

  Here, it is preferable that the inner diameters of the titrant solution collecting tube 30, the titrant solution delivery tube 32, the titrant solution delivery tube 38, the air delivery tube 42, and the titrant solution delivery tube 44 are 0.5 to 3 mm. Thereby, the air in a pipe | tube can be efficiently discharged | emitted with the liquid (titration liquid) sent out using the burette 22. FIG.

  In the analysis unit 10 as described above, a stepping motor (not shown) measures the amount of titrant dropped from the titrant feed pipe 44 into the titration cell 26 according to the distance by which the extrusion plate 36 of the burette 22 is pushed. can do.

<1-1-2. Sample weighing mechanism>
The sample weighing mechanism 12 collects and measures an electroless copper plating solution as a sample from a sample supply unit outside the automatic titration analyzer that supplies a sample to be analyzed, for example, a plating tank 52, and puts the measured sample in the titration cell 26. Supply. The sample metering mechanism 12 includes an airtight container 54, a sample collection tube 56, a sample metering tube 58, an on-off valve 60, a first sample delivery tube 62, a second sample delivery tube 63, and a third sample. A delivery pipe 64, a three-way valve 66, an on-off valve 68, a pressure increasing / decreasing means 70, a level sensor 72, and a level sensor 74 are provided.

  The airtight container 54 is formed of, for example, Pyrex (registered trademark), and has an airtight structure in order to accurately measure the sample. The airtight container 54 is supplied with a sample from the plating tank 52 via a sampling tube 56.

  The sample collection tube 56 is formed of, for example, a fluororesin tube (FEP tube). One end 56 a communicates with the airtight container 54, and the other end 56 b communicates with the plating tank 52.

  The sample measuring tube 58 is inserted substantially vertically into the airtight container 54 from the upper end of the airtight container 54.

  The sample measuring tube 58 is formed of, for example, an FEP tube, and has an opening 76 that communicates with the sample collection tube 56 at one end and communicates with the inside of the airtight container 54 at the other end. The position of the opening 76 is set to be the same as the liquid level in the airtight container 54 when the airtight container 54 and the first sample delivery pipe 62 are filled with the sample to be sent to the titration cell 26.

  The on-off valve 60 is constituted by, for example, a two-port solenoid valve, and controls the communication of the sample from the plating tank 52 to the airtight container 54 by switching the opening and closing of the sample collection tube 56. Specifically, the on-off valve 60 is in an opened state, that is, a state in which the plating tank 52 and the airtight container 54 communicate with each other, and a closed state, that is, a state in which the plating tank 52 and the airtight container 54 are blocked. Is switched.

  The first sample delivery tube 62 is formed of, for example, an FEP tube, and one end 62 a communicates with the airtight container 54 and the other end 62 b communicates with the three-way valve 66. One end 62 a of the first sample delivery pipe 62 communicates with the airtight container 54 at a position below the opening 76 of the sample measuring pipe 58.

  The second sample delivery tube 63 is formed of, for example, an FEP tube, and one end communicates with the three-way valve 66 and the other end communicates with the titration cell 26.

  The third sample delivery tube 64 is formed of, for example, an FEP tube, one end 64a communicates with the first sample delivery tube 62 via a three-way valve 66, and the other end 64b is outside the automatic titration analyzer 3. For example, it communicates with a drain (not shown).

  The three-way valve 66 is composed of, for example, a three-port solenoid valve, and the first sample delivery pipe 62 communicates with the second sample delivery pipe 63 (hereinafter referred to as “the three-way valve 66 is in an NC (normally closed) state”). ) And a state in which the first sample delivery tube 62 and the third sample delivery tube 64 communicate with each other (hereinafter referred to as “the three-way valve 66 is in a NO (normally open) state”). That is, the three-way valve 66 is in a state in which the titration cell 26 communicates with the airtight container 54 and the second sample delivery pipe 63 (the three-way valve 66 is in the NC state) and through the third sample delivery pipe 64. The state in which the airtight container 54 and the drain communicate with each other (the state where the three-way valve 66 is NO) is switched.

  Here, the sample collection tube 56, the sample metering tube 58, the first sample delivery tube 62, and the third sample delivery tube 64 preferably have an inner diameter of 0.5 to 3 mm. Thereby, the air in a pipe | tube can be efficiently discharged | emitted with the liquid (sample) sent out using the pressurization / decompression means 70 mentioned later.

  The pressurizing / depressurizing means 70 introduces a sample into the airtight container 54 from the plating tank 52 through the sample collection tube 56 by pressurizing or depressurizing the inside of the airtight container 54. Specifically, as shown in FIG. 1, the pressure-intensifying means 70 includes an air pump 80, an air delivery pipe 82 (82a, 82b, 82c) for supplying air from the outside to the air pump 80, an air column 84, and an air column. 84 and an air delivery pipe 86 for supplying air to the airtight container 54. The pressurizing / depressurizing means 70 includes a three-way valve 88 disposed in an air delivery pipe 82 that connects the air suction port and the air pump 80, and an air delivery pipe 90 (90a, 90b, 90c) that connects the air pump 80 and the air column 84. ) And an on-off valve 96 disposed on the air delivery pipe 94 that connects the air suction port and the air column 84.

  The three-way valve 88 is composed of, for example, a three-port solenoid valve, and a state in which the air delivery pipe 82a and the air delivery pipe 82b communicate with each other (hereinafter referred to as “the three-way valve 88 is in a NO state”), an air delivery pipe 82b, and an air It functions as a switching means for switching the state in which the delivery pipe 82c communicates (hereinafter referred to as “the three-way valve 88 is in the NC state”).

  The three-way valve 92 is composed of, for example, a three-port solenoid valve, and the air delivery pipe 90c and the air delivery pipe 90b communicate with each other (hereinafter referred to as “the three-way valve 92 is in the NO state”), the air delivery pipe 90c and the air. It functions as a switching means for switching the state in which the delivery pipe 90a is in communication (hereinafter referred to as “the state of the three-way valve 92 being NC”).

  The on-off valve 96 is composed of, for example, a two-port solenoid valve, and switches between opening and closing in the air delivery pipe 94. The on-off valve 96 also functions as a communication valve that reduces the pressure in the hermetic container 54 by communicating the hermetic container 54 with the outside of the hermetic container 54.

  The level sensor 72 is detection means for detecting the liquid level above the position of the opening 76 collected in the airtight container 54. The level sensor 74 detects the liquid level above the position where the level sensor 72 detects the liquid level.

  Here, the difference between the liquid volume detected by the level sensor 74 and the liquid volume detected by the level sensor 72 is set to be larger than the liquid volume in the first sample delivery tube 62. Thereby, in the air discharge step in the sample delivery tube to be described later, since all the air in the first sample delivery tube 62 can be discharged to the drain, the error of the sample supply amount supplied to the titration cell 26 is reduced. Can do.

  Next, a specific operation in the sample weighing mechanism 12 will be described. Here, a sample suction method and a sample discharge method in the sample weighing mechanism 12 will be described.

<Sample inhalation method>
The sample measuring mechanism 12 draws the sample from the plating tank 52 into the hermetic container 54 by setting the inside of the hermetic container 54 to a negative pressure state with the air pump 80 with the open / close valve 60 opened. When the sample liquid level in the hermetic container 54 reaches the detection level of the level sensor 74, the on-off valve 60 is closed and the inhalation of the sample from the plating tank 52 to the hermetic container 54 is completed.

<Sample discharge method>
The sample metering mechanism 12 discharges (injects) the sample in the airtight container 54 to the titration cell 26 by making the inside of the airtight container 54 pressurized by the air pump 80 while the three-way valve 66 is in the NC state.

<1-2. Recording section>
The recording unit 5 is composed of, for example, a ROM or a RAM. The recording unit 5 records the amount of titrant dropped from the inside of the burette 22 when a stepping motor (not shown) pushes the extrusion plate 36 of the burette 22. The recording unit 5 includes a calculation formula for calculating a standard concentration of sodium hydroxide in the electroless copper plating solution as a sample solution, a predetermined pH value, and a sodium hydroxide concentration in the electroless copper plating solution, The amount of electroless copper plating solution used for neutralization titration is recorded.

<1-3. Calculation unit>
The calculating part 7 is comprised by CPU, for example. The calculation unit 7 calculates the replenishment amount of the component to be replenished to the plating tank 52 (hereinafter referred to as “replenishment amount of the processing liquid replenishment component”) from the analysis result recorded by the recording unit 5. In addition, the calculation unit 7 instructs the plating tank 52 to replenish the processing liquid replenishment component based on the calculated replenishment amount of the processing liquid replenishment component. The instructed replenishment amount is recorded in the recording unit 5, and the operator can monitor whether there is an abnormality in the composition of the plating solution by referring to the past replenishment amount history.

  As an example, the calculation unit 7 calculates the water in the electroless copper plating solution from the amount of titrant recorded in the recording unit 5 and the standard concentration of sodium hydroxide in the electroless copper plating solution recorded in advance. Calculate the sodium oxide concentration. The calculating part 7 calculates the replenishment amount of the treatment liquid replenishment component, that is, the amount of sodium hydroxide to be replenished to the electroless copper plating solution, from the calculated sodium hydroxide concentration. The calculation unit 7 instructs the plating tank 52 that the calculated amount of sodium hydroxide should be replenished.

<2. Automatic titration analysis method>
Next, an example of an automatic titration analysis method using the automatic analysis management system 1 according to the present embodiment will be described. The automatic titration analysis method includes a washing step, a sample discharge pipe air discharge step, a sample supply step to the titration cell, a neutralization titration step, and an air discharge step using an air discharge mechanism.

<2-1. Tomo wash step>
The washing is performed to clean the inside of the sample collection tube 56, the sample metering tube 58, the airtight container 54, the first sample delivery tube 62, and the third sample delivery tube 64 with the sample in the plating tank 52. The washing step includes, for example, the following steps S1 to S6. Before and after washing, the on-off valve 60, the on-off valve 68, and the on-off valve 96 are all closed. The three-way valve 66, the three-way valve 88, and the three-way valve 92 are all in the NO state. The sample in the second sample delivery tube 63 is discharged to the titration cell 26 by a previous step (step S26 described later).

  In step S1, the automatic titration analyzer 3 operates the air pump 80, sets the three-way valve 88 to the NC state, and sets the three-way valve 92 to the NO state. Thereby, the inside of the airtight container 54 is brought into a reduced pressure state.

  In step S <b> 2, the automatic titration analyzer 3 opens the opening / closing valve 60, collects a sample from the plating tank 52 into the airtight container 54, and detects the liquid level of the sample by the level sensor 72 and the level sensor 74.

  In step S3, the automatic titration analyzer 3 closes the on-off valve 60, sets the three-way valve 88 to NO, and opens the on-off valve 96. Thereby, the inside of the airtight container 54 is brought into a normal pressure state.

  In step S4, the automatic titration analyzer 3 closes the on-off valve 96 and sets the three-way valve 92 to the NC state. Thereby, the inside of the airtight container 54 is brought into a pressurized state.

  In step S5, in the automatic titration analyzer 3, the three-way valve 66 is set to NO and the on-off valve 68 is opened, so that the inside of the airtight container 54, the first sample delivery pipe 62 and the third sample delivery pipe 64 is reached. Send all sample to drain.

  In step S6, the automatic titration analyzer 3 closes the on-off valve 68, sets the three-way valve 92 to NO, and opens the on-off valve 96. Thereby, the inside of the airtight container 54 is returned to a normal pressure state.

  As described above, in the automatic titration analyzer 3, the sample collection tube 56, the sample measuring tube 58, the airtight container 54, the first sample delivery tube 62, and the third sample delivery tube 64 are washed together. The inside can be cleaned. The washing may be performed a plurality of times.

<2-2. Air discharge step in sample delivery tube>
The air discharge step in the sample delivery tube is performed to exhaust the air in the first sample delivery tube 62 to the drain, and includes, for example, the following steps S10 to S15.

  In step S10, the three-way valve 88 is set to the NC state, and the three-way valve 92 is set to the NO state. Thereby, the inside of the airtight container 54 is brought into a reduced pressure state.

  In step S11, the opening / closing valve 60 is opened, a sample is collected from the plating tank 52 into the airtight container 54, and when the level sensor 72 and the level sensor 74 detect the liquid level of the sample, the opening / closing valve 60 is closed.

  In step S12, the three-way valve 88 is set to NO and the on-off valve 96 is opened. Thereby, the inside of the airtight container 54 is returned to a normal pressure state.

  In step S13, the on-off valve 96 is closed and the three-way valve 92 is set to the NC state. As a result, the inside of the airtight container 54 is pressurized.

  In step S14, the on-off valve 68 is opened, and the level sensor 72 detects the liquid level of the sample. Then, the on-off valve 68 is immediately closed, the three-way valve 92 is set to NO, and the on-off valve 96 is opened. Thereby, the inside of the airtight container 54 is returned to a normal pressure state.

  In step S15, the on-off valve 96 is closed.

  As described above, the sample metering mechanism 12 can discharge all the air in the first sample delivery pipe 62 to the drain, so that the error of the sample supply amount supplied to the titration cell 26 can be reduced. .

<2-3. Supplying step to titration cell>
The sample supply step to the titration cell includes, for example, the following steps S20 to S29.

  In step S20, in the automatic titration analyzer 3, the three-way valve 88 is set to the NC state, and the three-way valve 92 is set to the NO state. Thereby, the inside of the airtight container 54 is brought into a reduced pressure state.

  In step S21, the automatic titration analyzer 3 opens the on-off valve 60, collects a sample from the plating tank 52 into the airtight container 54, and closes the on-off valve 60 when the level sensor 74 detects the liquid level of the sample.

  In step S22, the automatic titration analyzer 3 sets the three-way valve 88 to NO and opens the on-off valve 96. Thereby, the inside of the airtight container 54 is returned to a normal pressure state.

  In step S23, the on-off valve 96 is closed and the three-way valve 92 is set to the NC state. As a result, the inside of the airtight container 54 is pressurized.

  In step S <b> 24, the automatic titration analyzer 3 opens the on-off valve 60 and returns the electroless copper plating solution in the airtight container 54 to the plating tank 52 from the opening 76 of the sample measuring tube 58. Here, when the liquid level of the electroless copper plating solution in the hermetic container 54 is lowered to the position of the opening 76, only air is returned to the plating tank 52 and the liquid level does not change. After this, by continuing to pressurize the inside of the airtight container 54, the plating solution in the sample measuring tube 58 and the sample collection tube 56 is returned to the plating tank 52. Therefore, due to the negative pressure in the airtight container 54, these It is possible to prevent the copper plating solution in the pipe from flowing into the airtight container 54 and causing an error in the sample collection amount.

  Here, the sample measuring mechanism 12 is designed so that the liquid level corresponding to the position of the opening 76 in the airtight container 54 is set to a predetermined sample volume (for example, 5 ml), that is, in the airtight container 54. The position of the opening 76 is set so that the sum of the amount of liquid up to the liquid level and the amount of liquid in the first sample delivery tube 62 is the sample volume. Thereby, the sample measuring mechanism 12 can accurately measure the sample.

  As a general sample measuring mechanism, there is one that closes the on-off valve when the level sensor detects the liquid level, but even after the on-off valve is closed, the liquid in the pipe is sucked, resulting in an error in measurement. Sometimes. On the other hand, the sample weighing mechanism 12 can measure more accurately than such a general mechanism.

  In step S25, the automatic titration analyzer 3 closes the on-off valve 60, opens the on-off valve 96, sets the three-way valve 66 to the NC state, and electroless copper in the airtight container 54 and the first sample delivery pipe 62. All the plating solution is delivered to the titration cell 26. Here, the automatic titration analyzer 3 pressurizes the inside of the hermetic container 54 and opens the on-off valve 96 so that the on-off valve 96 functions as a communication valve to reduce the pressure in the hermetic container 54. When the electroless copper plating solution is sent from the sample delivery pipe 63 to the titration cell 26, the electroless copper plating solution jumps in the titration cell 26 to contaminate the automatic titration analyzer 3, or the electroless copper plating solution jumps. Thus, it is possible to prevent an error from being generated in the analysis value due to a decrease from a predetermined amount used for neutralization titration.

  In step S26, the automatic titration analyzer 3 sets the three-way valve 66 to NO, closes the on-off valve 68, sets the three-way valve 92 to NO, and closes the on-off valve 96.

  In step S <b> 27, the automatic titration analyzer 3 operates the liquid feed pump 98, and ion exchange water from the ion exchange water tank 100 to the titration cell 26 until the level sensor 47 inserted in the titration cell 26 detects the solution. Supply.

  In step S <b> 28, the automatic titration analyzer 3 stops the operation of the liquid feed pump 98 and starts stirring the diluted sample in the titration cell 26 with the stirrer 50.

  In the sample supply step to the titration cell, the automatic titration analyzer 3 issues an alarm in a predetermined case and stops the subsequent operation when the sample is sent out from the airtight container 54 to the outside thereof. It is preferable to do this. Thereby, for example, even when there is a problem with a plurality of on-off valves, appropriate processing and accurate titration analysis can be performed. Specifically, in the predetermined case, for example, when the first level sensor 72 does not detect the liquid level after a lapse of a predetermined time after the level sensor 74 detects the liquid level, the sample is removed from the plating tank 52 to the airtight container 54. When the level sensor does not detect the liquid level 72 after the elapse of a predetermined time, or the level sensor 74 does not detect the liquid level after the elapse of the predetermined time after the level sensor 72 detects the liquid level. Say.

  As described above, the automatic titration analyzer 3 can accurately supply the sample from the sample weighing mechanism 12 to the titration cell 26.

<2-4. Neutralization titration step>
The neutralization titration step includes, for example, the following steps S30 to S37.

  In step S <b> 30, the automatic titration analyzer 3 sets the three-way valve 34 to NO, pulls the extrusion plate 36 of the burette 22, and sucks the titrant (sulfuric acid) in the reagent tank 20 into the burette 22.

  In step S31, in the automatic titration analyzer 3, the three-way valve 34 is set to the NC state, the switching means 46 is set to the NO state, and the burette is moved by a stepping motor (not shown) until the pH electrode 48 detects a predetermined pH. 22 extrusion plates 36 are extruded. As a result, the titrant in the burette 22 is dropped into the titration cell 26.

  In step S32, the automatic titration analyzer 3 stirs the electroless copper plating solution in the titration cell 26 with the stirrer 50 while the titration cell in the burette 22 is titrated until the pH electrode 48 detects a predetermined pH value. 26.

  In step S <b> 33, the recording unit 5 records the amount of titrant dropped from the burette 22 into the titration cell 26.

  In step S <b> 34, the calculation unit 7 calculates the concentration of sodium hydroxide in the electroless copper plating solution based on the amount of electroless copper plating and the amount of titrant liquid recorded in the recording unit 5.

  In step S35, the arithmetic unit 7 calculates the amount of sodium hydroxide to be replenished to the electroless copper plating solution in the plating tank 52 (replenishment amount of the treatment solution replenishment component) from the sodium hydroxide concentration calculated in step S34. The replenishment is instructed to the plating tank 52.

  In step S36, the automatic titration analyzer 3 sets the three-way valve 34 to NO and opens the on-off valve 28 to operate the drainage pump 29.

  In step S37, after all the electroless copper plating solution and titrant in the titration cell 26 are discharged to the drain, the operation of the drain pump 29 is stopped.

  As described above, the automatic analysis management system 1 can perform neutralization titration.

<2-5. Air discharge step using air discharge mechanism>
The air discharge step using the air discharge mechanism 24 is performed to discharge the air in the burette 22 when neutralization titration is not performed.

  Specifically, the air discharge step using the air discharge mechanism 24 includes, for example, the following steps S40 to S43.

  In step S <b> 40, the three-way valve 34 is set in the NO state, the push plate 36 of the burette 22 is pulled, and the titrant in the reagent tank 20 is sucked into the burette 22.

  In step S41, the three-way valve 34 is set to the NC state, the switching means 46 is set to the NC state, and the pushing plate 36 of the burette 22 is pushed out by a stepping motor (not shown) until all the air in the chamber 40 is discharged. At this time, air is discharged from the upper end of the chamber 40 to the titration cell 26 through the air delivery pipe 42 as shown in FIG.

  In step S42, the switching means 46 is set to NO, the three-way valve 34 is set to NO, and the on-off valve 28 is opened.

  In step S43, after all the titrant in the titration cell 26 is discharged by the drain pump 29, the on-off valve 28 is closed.

  As described above, in the air discharge step using the air discharge mechanism 24, the air flowing from the burette 22 to the chamber 40 can be discharged. By discharging air using the air discharge mechanism 24 in this manner, when the titrant is to be supplied to the titration cell 26, an error is caused in the supply amount of the titrant without supplying air to the titration cell 26. Therefore, the titration liquid can be accurately supplied to the titration cell, so that highly accurate automatic titration analysis can be performed.

<3. Other embodiments>
The analysis unit 10 may be configured as the analysis unit 108 illustrated in FIG. The analysis unit 108 shown in FIG. 3 includes an opening / closing valve 110 in the air delivery pipe 42 and an opening / closing valve 112 in the titrant liquid delivery pipe 44 in the air discharge mechanism 24. The on-off valve 110 switches between a state where the air delivery pipe 42 is communicated between the chamber 40 and the drain and a state where it is shut off. The on-off valve 112 switches between a state in which the titrant solution delivery pipe 44 is communicated between the chamber 40 and the titration cell 26 and a state in which it is shut off. In the analysis unit 108, the same components as those of the analysis unit 10 described above are denoted by the same reference numerals and description thereof is omitted. In this embodiment, the air delivery pipe 42 communicates with the drain, but the air delivery pipe 42 may communicate with the reagent tank 20 to return the reagent. Reagent consumption can be reduced.

  In the above description, the analysis unit 10 calculates the sodium hydroxide concentration in the electroless copper plating solution, but may similarly calculate the formalin concentration.

  In the above description, the sample metering mechanism 12 collects the electroless copper plating solution as a sample from one plating tank 52, but may collect samples from a plurality of plating tanks.

  In addition, the air discharge mechanism 24 may be operated for each titration analysis, or may be operated once after the titration analysis is performed a plurality of times.

  In the above description, the air pressure vessel 54 is pressurized and depressurized by the same pressurizing and depressurizing means (air pump). However, the present invention is not limited to this, and pressurization and depressurization are performed by separate pumps. May be.

  Further, a flow meter may be provided in the titrant solution delivery pipe 44 that is a pipe from the switching means 46 to the titration cell 26. Thereby, since an exact liquid amount can be measured, the titration analysis can be performed more accurately by using the result for titration analysis. As the flow meter, it is preferable to use a Coriolis flow meter capable of measuring a minute flow rate or an ultrasonic flow meter.

  In addition to the electroless copper plating solution, various processing solutions such as an electroless plating solution, an electroplating solution, an etching solution, a zincate solution, and an acid wash can be used as a sample to be subjected to titration analysis. .

  Further, as the titrant, a titrant other than sulfuric acid, for example, a sodium hydroxide aqueous solution or a potassium permanganate aqueous solution may be used depending on the sample.

  Further, in the automatic analysis management system 1, an ORP (Oxidation-Reduction Potential) electrode may be used instead of the pH electrode 48 described above.

  DESCRIPTION OF SYMBOLS 1 Automatic analysis management system, 3 Automatic titration analyzer, 5 Recording part, 7 Calculation part, 10,108 Analysis part, 12 Sample measuring mechanism, 20 Reagent tank, 22 Bullet, 24 Air discharge mechanism, 26 Titration cell, 27 Discharge pipe , 28 On-off valve, 29 Drain pump, 30 Titrant collection pipe, 34 Three-way valve, 36 Extrusion plate, 38 Titrant delivery pipe, 40 Chamber, 42 Air delivery pipe, 44 Titrant delivery pipe, 46 Three-way valve, 47 level Sensor, 48 pH electrode, 50 Stirrer, 52 Plating tank, 54 Airtight container, 56 Sample collection tube, 58 Sample metering tube, 60 On-off valve, 62 First sample delivery tube, 63 Second sample delivery tube, 64 3rd Sample delivery pipe, 66 three-way valve, 68 on-off valve, 70 pressure-inducing and decompressing means, 72 level sensor, 74 level sensor, 76 opening, 80 d Pump, 82 Air delivery pipe, 84 Air column, 86 Air delivery pipe, 88 Three-way valve, 90 Air delivery pipe, 92 Three-way valve, 94 Air delivery pipe, 96 Open / close valve, 98 Liquid feed pump, 100 Ion exchange water tank, 104 Open / close Valve, 110, 112 Open / close valve

Claims (2)

A titration cell in which a sample is collected and a burette for supplying a titrant to the titration cell, and the titration liquid supplied from the buret is dropped onto the sample in the titration cell and the sample is analyzed automatically. In the analyzer
An air discharge mechanism for discharging air contained in the titrant supplied from the burette ;
The air discharge mechanism is
A chamber for receiving the titrant supplied from the burette and storing the air in the upper part;
A titrant solution delivery tube for connecting one end to the lower part of the chamber and the other end connected to the titration cell via a switching means, and sending the titrant supplied from the burette to the titration cell;
One end communicates with the upper end of the chamber, the other end is connected to the switching means, and further comprises an air delivery pipe for delivering air stored in the upper part of the chamber,
The switching means is in a state in which one of the titrant solution delivery pipe and the air delivery pipe is communicated between the chamber and the titration cell, and the other is communicated between the chamber and the titration cell. automatic titration analysis apparatus according to claim to switch between and. An automatic titration analyzer according to claim 1 ;
A recording unit for recording the analysis result of the treatment liquid by the automatic titration analyzer;
A processing liquid automatic analysis management system comprising: an arithmetic unit that calculates a replenishment amount of the processing liquid replenishment component from the analysis result recorded in the recording unit and instructs the sample supply unit to replenish the processing liquid replenishment component.

Images