JPH02251762A - Method of automatically analyzing non-volatile component of liquid resin - Google Patents

Abstract

PURPOSE:To establish analytical technique reduced in an analytical error and having reproducibility by providing filter paper eliminating the liquid sump due to surface tension to the upper surface of a tray made of aluminum and dripping a sample to be inspected on the filter paper to develop the same uniformly and widely. CONSTITUTION:The measurement of a non-volatile component is performed according to the program of a computer and a lid is opened by a lid opening and closing mecha nism and a tray 503 is taken out of a tray container by an analytical robot 1 through a suction jig to be set on a balance 506 and subsequently closed. Subsequently, the lid is again opened and a sample to be inspected is dripped on the filter paper 509 on the tray 503 by the analytical robot 1 through a tip 50. The sample to be inspected is dripped from a place separated by a predetermined distance from the surface of the filter paper 509. The dripped liquid droplet 51 of the sample to be inspected forms a liquid sump 52 on the surface of the filter paper 509. Next, when the chip 50 is let fall so as to be brought into contact with said liquid sump 52, the liquid sump 52 penetrates and diffuses into the filter paper 509 and the liquid sump accumulated at the leading end of the chip 50 can also be eliminated.

Description

[Detailed Description of the Invention] [Industrial Field of Application J Unpublished] relates to an automatic analysis method for non-volatile content, which is an indicator for identifying the quality of liquid resin, using an analytical robot, and more specifically, to measuring a test sample in a weighing container. It relates to a method for automatically analyzing non-volatile components (hereinafter abbreviated as rNVJ as necessary) with good reproducibility by uniformly developing the same in a liquid.

[Prior Art] Manufacturers of liquid resin IFi (referred to as polymers when necessary) generally use the following methods to identify the quality of the chemical product:
Adopting Vis value, pH and N'/value as the indicators,
Manufacturers themselves analyze and determine index values.

Quality is often specified.

As an analysis method for determining the above index value, there is the JIS method.For example, the general test method for adhesives is JISKB833.
PH is defined as JISK8833.
B.2, the viscosity is defined in JIS K 88338.3, and the nonvolatile content is defined in JIS K 88338.4. but.

Since the quality of the liquid resin only needs to be regularly determined, index values obtained by simple analysis methods may be acceptable depending on the end user. Index values obtained by simple analytical methods are acceptable.

However, when looking at individual analyzes of the three index values, Via value, ΦpH, and NV value, which have been conventionally performed in the field of liquid resin production, the JIS method is the best.

Even if it is a simple method, most of it is done manually.
There were not many attempts at automation.

In recent years, attempts have been made to automate devices that individually analyze each of the ViS value, pH, and NV value. For example, p)1 measurement is described in J.K. Publication No. 81-28849.

[Problem to be solved by the invention] As mentioned above, in the field of liquid resin production, ViS
Automatic analysis of index values such as pH, pH, and NV value is extremely slow and most of the time relies on complicated manual operations, and although some index values have been automatically analyzed, it is still difficult There are many parts that require manipulation, and it cannot be said that the problems of complexity of work and high cost have been solved to a great extent.

In view of the above, the present inventors attempted to introduce an analytical robot for the purpose of completely automating liquid resin analysis.

The present invention is a technology that attempts to solve the unique problems found in the introduction of such analytical robots.

In other words, in measuring the NV value among multiple measurement items, the current JIS method or simple method uses a 50-layer flat weighing bottle with a stopper as a weighing container, or an aluminum foil plate formed into the same shape along its inner wall. is used (JIS K 8
8338.4), a test sample was smeared into this container using a clip, and the nonvolatile content was determined after drying with prescribed heat.

However, it is difficult to apply this method to analytical robots. In other words, analysis robots are not good at "smearing" work. In order to eliminate this drawback, the present inventor dropped the test sample liquid onto the above-mentioned scale bottle or aluminum foil plate, heated and dried it, weighed it, and measured the M.
The lJ value was determined.

However, it has been found that this method requires a long drying time and has the drawbacks of large analytical errors.

Therefore, an object of the present invention is to provide an analysis technique that has fewer analysis errors and more reproducibility when measuring NV values using an analysis robot.

[Means for Solving the Problems] The present inventors have made extensive studies to solve the above problems, and have arrived at the present invention.

That is, the NY automatic analysis method for liquid resin according to the present invention is a method in which a liquid resin test sample is taken into a weighing container via an analysis robot, and the non-volatile content is automatically analyzed by weighing it after drying. A syringe supporting a chip for collecting a test sample is attached to the syringe, and the weighing container is an aluminum plate.

The method is characterized in that a sheet is provided on the top surface of the aluminum plate to eliminate liquid accumulation due to surface tension, and a test sample is dropped onto the sheet from the tip of the analysis robot and spread uniformly over a wide area. That is, with this configuration, the test sample is spread thinly and widely, so reproducible analytical data can be obtained, and the drying time can be further shortened, contributing to speeding up of the overall analysis. In addition, since the weighing container is an aluminum type plate,
The weight of the container can be reduced, and the load on the analytical robot hand can be reduced.

Furthermore, when the sheet is a glass fiber filter paper, the test sample can be spread thinner and wider. In addition, by placing one drop of the test sample approximately in the center of the sheet and applying two or more drops around it, so-called discontinuous dropping, it is possible to further eliminate analysis errors.

In the method of the present invention, liquid resins are analyzed, and specifically, various resin compositions such as resin compositions for paints, resin compositions for adhesives, and resin compositions for paper processing.

The analysis items by the automatic analysis method of the present invention are at least N
However, if the viscosity (ViS) and pH are also analyzed, the quality of the liquid resin can be determined with certainty.

In the present invention, examples of the sheet that eliminates liquid retention due to surface tension include glass fiber filter paper, glass wool, cloth (including nonwoven fabric), and the like.

Among them, glass fiber filter paper is preferred because it can easily maintain a constant weight in weighing.

〔Example] The present invention will be explained below with reference to embodiments shown in the drawings.

This example describes a case where V's and pH are measured together with NY. First, Fig. 1 is a plan view showing an automatic analyzer according to an embodiment of the present invention, and Fig. 2 is a diagram showing the control system of the apparatus. Explanatory diagram showing, 3rd
The figure is a flowchart showing the automatic analysis system, and FIG. 4 is a perspective view showing the analysis robot and turntable device.

In the figure, reference numeral 1 denotes an analysis robot placed approximately in the middle of the analysis station 2. In the operating range around the analytical robot 1, there are a turntable device 31, an autometric robot hand station 4, an NV measurement device 5. Vacuum device6. Via measurement device W7, PH measurement device 8. Cleaning device 19. A storage device 10 and a barcode reader 11 are arranged.

Also, outside the operating range of the analysis robot 1.

A computer unit 12 is arranged.

The computer unit/) 12 mainly includes a CPU (central processing unit) 121. CRT (screen) 122, keyboard! 23, printer 124. Floppy disk device 12
5, and performs important functions such as barcode management, robot management, sequencer communication, real-time data check management, and public analysis data pass reanalysis management, as will be described later.

In this embodiment, as means for implementing the control system of the computer unit 12, an analysis robot controller 13, a power event controller 14, a network controller 15, and a sequencer 18 are provided as shown in FIG.

Examples of the analysis robot 1 include a cylindrical coordinate robot, a polar coordinate robot, a rectangular coordinate robot, and an articulated robot.

In this example, cylindrical coordinates are used.The analytical robot l used in this example has an arm length of 800 mm.
1. Operating radius 320■, vertical operation distance maximum 3401■
, the maximum operating speed is 76 fat layers l#ec, 90 degree rotation 73 seconds.

As shown in FIG. 4, the analytical robot l of this embodiment mainly consists of a platform 101. Two vertical axes 102. It is composed of an arm 103, a grip hand 104, and a finger portion 105.

The analytical robot 1 has an analytical robot controller 13.
The analytical robot controller 13
The specifications are that the maximum number of control axes is 3 at the same time, and the path control method is a servo motor method.

The control method uses a semi-closed loop method using a rotary encoder, the position setting is a teaching method, and the speed is variable in 10 steps from 0.1 to 1.0.

Input/output is input 8. The output is 8.

The analysis station 2 may be a commonly used laboratory analysis table, and is preferably configured such that the analysis robot and various peripheral devices can be set (fixed, etc.) therein.
In order to simplify the task of accurately arranging various devices in accordance with the operating range of the analysis robot, it is preferable that the analysis table is provided with set positions for the various devices in advance.

It is also preferable to process the surface of the analysis table to make it uneven, so that the device can be set in a removable manner.It is also preferable to set the entire system on the analysis stage 2 so that it can be treated as a system product. , therefore the first
It goes without saying that it is not necessary to arrange the computer units 12 separately as shown in the figure.

The turntable device t3 has a constant temperature bath 3 as shown in FIG.
01 and a turntable 302 rotatably provided within the constant temperature bath 301. Water is filled in the constant temperature bath 301, and the temperature is controlled at approximately 25°C.

Although the temperature control means is not particularly limited, it is convenient to use circulating hot water. The turntable 302 may have one stage, but it is preferable to have three stages spaced apart by a predetermined interval. In that case, the upper and middle turntables have transparent panels for setting the test sample containers 3 (13). A hole 304 is provided, and the through hole 304 is further provided with a positioning groove 305 for determining the setting position (direction) of the container 303.The lower turntable prevents the container 303 from falling when it is set. It is preferable that a small hole (not shown) is provided at a position in contact with the container 303.The direction of rotation of the turntable 302 is not particularly limited, but in this embodiment direction.

The MV measurement device 5 is a device that measures nonvolatile content. M
The V value is determined by heating and drying the test sample at a predetermined temperature with a heater until it reaches a constant weight.

In this example, this is intended to improve the certainty of analysis values.

Two measuring devices are provided. The details of the configuration of the device 5 will be described later.

The vacuum device 6 moves an aluminum weighing container (hereinafter simply referred to as a tray) into which a test sample is placed during MV measurement.
It consists of a suction device (for example, a vacuum cleaner) to be installed in the measuring device, a suction hose, and a tray mounting section in which unused and used trays are stored in a container.

The Vi*ill determination device 7 measures the Vis value based on the viscosity of a test sample by rotating a rotor, and consists of a device main body and a rotor for rotating the rotor. Since the viscosity varies depending on the type of test sample, it is desirable to select an appropriate rotor, and for this reason, rotor selection and attachment/detachment are performed automatically. Since the rotor is attached and detached by a robot, a one-touch type coupling (auto joint) is preferable, and it is preferable to interpose a universal coupling between the rotor and the device body to prevent rotor eccentricity.

For heavy and large rotors, it is preferable to make the rotor internally hollow to reduce weight in order to prevent it from falling off during robot transfer.

Since the viscosity changes depending on the temperature, it is necessary to measure the temperature at the same time as the rotor rotates, and a temperature sensor such as a thermocouple or thermistor is preferable as the temperature measuring means.

A commercially available PH sensor can be used as the pH measuring device 8.

The cleaning device 9 is a device for washing off test samples adhering to the surfaces of the p and H electrodes, the Vij measurement rotor, and the temperature sensor.

The cleaning means is not particularly limited, but if the viscosity of the test sample is high, a configuration using a pair of rotating brushes is preferred.

The storage device IO is a device for storing the Vis rotor and the PH electrode, and the PH electrode is preferably stored immersed in water at a predetermined temperature, and the rotor is preferably stored in an environment at a predetermined temperature. is to be stored together with the pH electrode. The storage temperature may be room temperature, but is preferably controlled to be equal to the analysis temperature (for example, 25°C). The configuration of the storage device is not particularly limited, but may include a rotor suspension mechanism and pH pH in a constant temperature water tank.
The rotor suspension mechanism, which preferably has an electrode immersion section, is preferably a one-touch coupling (auto joint) so that it can be easily attached and detached for analysis.

When the rotor is stored immersed in water, it is preferable to install a methanol cleaning device in order to remove water droplets adhering to the rotor in advance during the subsequent Via measurement.

Next, an example of an NV measuring device for carrying out the method of the present invention will be explained based on FIGS. 5 to 9.

FIG. 5 is a perspective view showing the external configuration of the MV measurement device according to the present example, FIG. 6 is a vt-v X-ray sectional view of FIG. 5, and FIG. 7 is a sectional view showing the state of the test sample when it is dropped. , FIG. 8 is a sectional view showing the movement of the chip after dropping the test sample, and FIG. 9 is an explanatory diagram showing the method of dropping the test sample.

The NY measuring device 5 has an approximately rectangular parallelepiped device main body 501, and a lid 502 is attached to the upper side of the device main body 501 via a hinge so that it can be opened and closed freely. A lid opening/closing mechanism 504 that automatically opens and closes is provided.

Further, a data display and operation panel 505 is integrally provided on the entire surface of the apparatus main body 501, and a balance 50B is arranged inside the apparatus main body 501. The balance 50B has a tray 503 containing a test sample placed on its tray holder 507.
The non-volatile content can be measured from the difference in weight before and after measurement. A spiral heater 508 is located behind the lid 502.
is attached to face the tray holder 507 of the balance 508 so that heat is radiated toward the tray 503 containing the test sample.

Measurement of nonvolatile content is performed through a series of operations according to a computer program. That is, the lid 502 is opened by the lid opening/closing mechanism 504.

Next, the analytical robot 1 takes out the tray 503 from the tray container via a suction tool, sets it on the balance 50B, and then closes the lid 502.

Next, as shown in FIG. 7, when the analytical robot 1 takes a test sample and drops it onto the filter paper 509 in the tray 503, the lid 502 is opened again and the analytical robot 1 takes the test sample through the chip 50. Drop it onto the filter paper 509 and leave it for a while after dropping. Then, the test sample is radiated with heat by the heater 508, and NY measurement is started.The measurement data is sent to the computer, processed, and displayed in real time. The measurement data is stored in memory within the computer as NV measurements.

Next, the test sample dropping method of the present invention will be explained. That is, as shown in FIG. 7, six test sample droplets 5 are dropped from a predetermined distance away from the surface of the filter paper 5H! A liquid pool 52 is formed on the surface of the filter paper.Then, the tip 50 is lowered so as to come into contact with this liquid pool 52 (see FIG. 8(A)).

By lowering the tip 50, the liquid pool 52 permeates and diffuses into the filter paper (see FIG. 8 CB), and the liquid pool accumulated at the tip of the chip 50 can also be eliminated.

The method of dropping the test sample is not particularly limited as long as it can be uniformly diffused and spread over a wide area, but a preferred example is the dropping method shown in FIG.

Next, in the present invention, an automatic analysis system for measuring pH and Vis as well as NV will be explained based on the drawings.

When the number n of test samples is entered into the computer, the program of the automatic system is started.

(Selection of robot hand for analysis) Robot hands for analysis (hereinafter referred to as rHANDJ as necessary) include GP HANDS and syringe HANDS.

GP HAND comes in sizes “Large” and “Medium” @ Small, but in this example, “Medium” and “Small” CPs are used.
) IAND and "Syringe 1 (ANDJ). First, select the "medium" (iP HAND). In FIG. 2, 50a is a tip rack on which the tip is placed.

(Check the number of specimens) If the number of specimens exceeds the number input from the computer 121, the process ends. If it is within the input number, proceed to the next step.

(Barcode Reading) The barcode (hereinafter referred to as rBCJ as necessary) reader 11 and Be sensor 110 read the barcode information of the test sample. If the reading on day 0 C, when the turntable automatically rotates by one test sample amount, is normal, proceed to the next step shown below; if abnormal, add 1 to n and return.

(Open the lid of the NY measurement MV measuring device 5, set the tray (aluminum plate) 503 using the vacuum device 6, and close the lid of the MV measuring device N5 (delete the tare on the aluminum plate).

Next, open the lid of the test sample container 303, and )! AND “
Change from "Medium" to "Syringe" (see Figure 7) and syringe H.
Attach a tip (a dropper-like thing for sucking a test sample) 50 to the AND loop, and suck up the test sample from the test sample container 303 to the tip.Next, open the lid of the NY device 5, and remove the glass fiber inside the aluminum tray 503. Drop onto filter paper 509. In this embodiment, the test sample amount is 1.
It is 2g.

Next, the lid of the MV measuring device 5 is closed, and the syringe 1 (AND tip) is discarded to start NVJIII determination. In FIG. 2, M1 and 82 are motors.

(Vis measurement) Change the OP HAND from "medium" to "small" and select a rotor suitable for the test sample from the rotor storage device W10 based on computer instructions.

Next, the rotor is immersed in a container 101 containing methanol to dry water droplets adhering to it, and dried at room temperature in a dryer 102 maintained at room temperature.Next, the rotor is automatically placed on the rotating shaft of a Via measuring device.

The temperature sensor is set near the viscometer included in the vi measuring device 7.

Next, the OP HAND is changed from "small" to "medium", the test sample container in the turntable N3 is set in the viscometer, and the viscosity is measured. In addition, in FIG. 2, 700 is a viscometer controller.

This viscosity and temperature are displayed graphically on the CR7 screen 122. At this time, data processing (data acquisition comparison) is performed.

(pH measurement) The pH sensor included in the pH measuring device 8 is set in the test sample container, and the measured value is displayed as a graph on the CR7 screen 122 (
pH and temperature), and at the same time data processing (data acquisition comparison).

(Cleaning number saved/end) The pH sensor is cleaned with the cleaning device 9. After setting the pH sensor in the cleaning device, the cleaning device automatically operates. That is, the rotating brush rotates and the cleaning liquid automatic supply and drainage system starts.

Next, return the test sample container 303 to the turntable 3,
Cover the test sample container 303.

Change the GP HAND from "Medium" to "Small", remove the rotor from the Via measurement device 7, wash the rotor with the cleaning device 9 to remove the attached test sample, and then return it to the storage device 10. Next, wash the temperature sensor. #! 9 and returned to the storage device lO.

Next, change the OP HAND from "small" to "medium".

Process data and check NV completion 0 then MV
Open the lid of the device and use vacuum device 6 to perform MV? T! The tray (aluminum plate) 503 in t5 is taken out and processed.

Next, the basic system employed in the present invention will be explained.

Barcode system In the present invention, test sample information (e.g. test sample name,
Adopt a system that manages standards) using barcodes. That is, information regarding the two test samples is input into a computer, the information is printed out as a bar code, and the bar code is set on the lid of a cylindrical test sample container. In the present invention, the barcode may be installed on the container body, but in order to reduce read errors and perform reproducible analysis, it is preferable to install the barcode on the lid with a flat top surface while maintaining flatness. This is because, in the method of displaying a bar code on the container body as in Japanese Patent Application Laid-open Nos. 61-275657 and 63-8557, reading errors are unavoidable due to bending of the label.

The positional relationship between the barcode and the league is not limited to that shown in FIG. 4, and if it is attached parallel to the top surface of the lid, the direction of the league may be directed to the barcode information on the container.

A feature of management using book barcodes is that it is possible to set analysis conditions according to the test sample, especially NY drying conditions.

Real-time data check In the present invention, real-time data check is performed to check whether the analysis value falls within the standard value of the test sample.

For example, in the case of test sample brand A mentioned above, standard value Analysis value Data check NY value 45.5 to 48.5 47 Passing NY value 4
5.5 - 48.5 50 Fail If the above check fails, re-analyze and reconfirm. 0 In the present invention, two measuring devices are used for NY in order to improve analysis accuracy. It is preferable.

Note that this real-time data check is available for p other than NY groups.
This is also done for H and Vi5, both of which are automatically determined based on information input into the computer.

[Effects of the Invention] According to the present invention, when measuring the MV value using an analytical robot, the test sample is spread thinly and widely, so reproducible analytical data can be obtained, the drying time can be further shortened, and the analysis It also contributes to speeding up the overall process. Further, when the weighing container is an aluminum plate, the weight of the container can be reduced, and the load on the analytical robot hand can be reduced. Furthermore, when the sheet is a glass fiber filter paper, the test sample can be spread thinner and wider.

In addition, analysis errors can be further reduced by dropping one drop of the test sample at the center of the sheet and then dropping two or more drops around it in what is called discontinuous dropping.

(Experiment example) Hereinafter, the effects of the present invention will be illustrated by experimental examples.

Test sample liquid resin A manufactured by Mitsui Toatsu Chemical Co., Ltd. was used.

Test sample 1.2 as shown in FIG. was dropped onto a filter paper held on an aluminum plate.

The dropping was carried out as shown in Section 9 (A), (B), and (C).

Figure 9 (A) shows the case where one drop is placed approximately in the center of the filter paper and eight drops are discontinuously placed around it. Figure 9 (B) shows the case where two drops are placed on the filter paper. w49 (C) The figure shows the case of continuous dripping onto filter paper as shown.

After the dropping was completed, the samples were heated and dried under heating conditions of first 120° C. and then 100° C. until a constant weight was reached (13 minutes on average), and after weighing, the NV value was determined for each test sample. Each measurement was performed five times, the average value was taken, and the analytical error (σ) was determined. The results are shown in Table 1.

Also, as a reference example, place the No. 9 plate directly on an aluminum plate without filter paper.
The NV value was determined in the same manner for the case where 9 drops were applied as shown in Figure (A). The results are shown in Table 1.

Table 1 As is clear from Table 1, when no filter paper is used as in the reference example, the NY analysis error is large.

On the other hand, according to the present invention, the analysis error of NY is small, and the analysis error is smaller in discontinuous dropping as shown in FIG. 9(B) than in continuous dropping as shown in FIG. 9(C). Furthermore, it can be seen that even when discontinuously dropping, in the case of 9-point dropping as shown in FIG. 9(A), more uniform dropping is possible and there are fewer analytical errors.

[Brief explanation of drawings]

Fig. 1 is a schematic plan view showing an example of an automatic analyzer of the present invention, Fig. 2 is a diagram showing a control system of the same device, Fig. 3 is a system flowchart of the same, and Fig. 4 is a diagram used in the above device. FIG. 5 is a perspective view showing the external configuration of the NY measuring device according to the present embodiment, FIG. 6 is a sectional view taken along the line VI-Vl in FIG. 5,
FIG. 7 is a sectional view showing the state when the test sample is dropped, FIGS. 8(A) and CB) are sectional views showing the movement of the tip after dropping the test sample, and FIGS. 9(A), (B), (C) is an explanatory diagram showing a method of dropping a test sample. l: Analytical robot 2 = Analysis station 3: Turntable device 4: Analytical robot hand station 5: NV measuring device 6: Vacuum device 7: Viscosity measuring device 8: pH measuring device 9: Cleaning device 10: Storage device 11: Barcode League 12: Computer Unit

Claims (1)

[Claims] 1. In a method of taking a liquid resin test sample into a weighing container via an analytical robot, weighing it after drying, and automatically analyzing the non-volatile content, the hand of the analytical robot is provided with a test sample collecting sample. A syringe supporting the chip is attached, the weighing container is an aluminum plate, a sheet is provided on the top surface of the aluminum plate to eliminate liquid accumulation due to surface tension, and the test is carried out from the tip of the analysis robot onto the sheet. An automatic non-volatile content analysis method for liquid resin, which is characterized by dropping a sample and spreading it uniformly over a wide area. 2. The automatic nonvolatile content analysis method for liquid resin according to claim 1, wherein the sheet is a glass fiber filter paper. 3. The automated method for non-volatile content of liquid resin according to claim 1 or 2, characterized in that one drop of the test sample is dropped approximately at the center of the sheet, and two or more drops are dropped around it to uniformly spread the test sample. Analysis method.