JPH0894512A - Measuring method for working life and its measuring device - Google Patents

Abstract

PURPOSE: To provide a method and its device by which the working life of a thermosetting resin is automatically measured. CONSTITUTION: A rotation body 2 is rotated in a curing agent-added thermosetting resin sample by a rotation type viscometer 3, and a time is clocked by a timer until the load torque of the rotation type viscometer 3 generated by the viscosity of the resin sample becomes a certain value. A vessel 1, containing the thermosetting resin sample, made of polyethylene, polypropylene, or polyacetal is used, and the rotation body 2 made of polyacetal, or polyethylene fluoride is used. With this working life measuring method, a numerical value approximately equivalent to a result by a conventional JIS method can be obtained so that no restricting time of an analyzer can be required during its measuring.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and apparatus for measuring the pot life of thermosetting resins. INDUSTRIAL APPLICABILITY The method and apparatus of the present invention are used to measure the pot life, which is the time after which a thermosetting resin is added with a curing agent and the usable state of the resin can be maintained.

[0002]

2. Description of the Related Art Pot life is also known as pot life or gelation time, and is a resin that cures a thermosetting resin such as unsaturated polyester resin, polyurethane resin, or epoxy resin with a curing agent or a catalyst. The maximum time that can be maintained in a usable state after adding and mixing a curing agent. The pot life varies depending on the type of resin, the type and amount of the curing agent, the solvent and other additives, and the storage temperature. When a thermosetting resin is manufactured, a user usually specifies a numerical range of the pot life, which is, for example, 2 to 5 minutes for short ones and 80 to 120 for long ones.
The range is very wide, such as minutes.

Conventionally, after measuring the pot life of a thermosetting resin after it has been manufactured, JIS K
The method described in 6901-1986 (hereinafter referred to as the JIS method)
It was done in. The JIS method is described below.・ JIS method Room temperature gelation time (Room temperature gelation time is as follows.) (1) Equipment and reagents (a) Beaker JIS R 3503 beaker 100 ml. (b) Glass rod JIS R 3645 (glass rod) glass rod with a diameter of 5 mm and a length of 120 mm with rounded ends. (c) Constant temperature bath A constant temperature water bath that can maintain a temperature of 25 ± 0.2 ° C. (d) Measuring pipette with 1 ml capacity. (e) Chemical balance Amount within 0.2 mg. (f) Upper plate weighing less than 100 mg. (g) Stopwatch (h) The type and amount of curing agent and accelerator are selected according to the type and application of the resin. (2) Operation Weigh 50 ± 1g of sample into a beaker with a pan balance, add a prescribed amount of accelerator to it, stir evenly with a glass rod, and place the sample surface in a constant temperature bath at 25 ± 0.2 ℃. About 1 below the bath surface
Fix it so that it is located at cm. Sample temperature is 25 ± 0.5 ° C
When it becomes, add the specified amount of curing agent and immediately start the stopwatch, and at the same time, stir well with a glass rod for 30 seconds while still immersed in the bath, mix evenly to dissolve. Stir the sample twice with a glass rod approximately every 1 minute, and pull up the glass rod. As the liquidity decreases,
This operation is continuously repeated to check the fluid state. When the sample attached to the glass rod does not lift up like a thread and is cut, stop the stopwatch and read the time, which is the room temperature gelation time. This operation is performed at least twice, the average value is shown in minutes, and is rounded to one decimal place. More than,
It is a method of measuring the pot life described in the JIS method.

Usually, the thermosetting resin, after being manufactured,
The pot life is measured several times, and after it is confirmed that the value is sufficiently within the standard, it is packed in a tank truck, a drum, a gallon can, or the like and shipped. After measuring the pot life, the solidified sample is usually taken out from the beaker, and the sample adhering to the glass rod is peeled off.The beaker and glass rod are then immersed in ethyl acetate or the like. Prepared for the next use by completely removing the adhesion of solidified substances.

When measuring the pot life,
Not only by the above-mentioned JIS method, but also some dedicated measuring instruments are commercially available, but many of them use expensive ceramics or polyimide for the sensor part that comes into contact with the resin, and the solidified sample after measurement is used as the sensor part. It is possible that the sensor part may be damaged when it is further removed or peeled off, and the cost for analysis tends to increase, so this is not a very preferable apparatus and method.

[0006]

In the conventional method of measuring the pot life by the JIS method, the measurer is restricted only to make the measurement almost completely. Moreover, in a thermosetting resin having a pot life of several tens of minutes to several hours, it is impossible to leave the place until the measurement is completed. Furthermore, if the thermosetting resin produced is out of the specified pot life range, the resin must be readjusted and the measurement must be repeated again from the beginning. It was often very painful.

According to the JIS method,
Even when the sample attached to the glass rod does not lift like a thread and is cut (hereinafter referred to as “end point”), there is a tendency for each measurer to make a difference, and long-term experience is required to obtain reliability. there were.

After the measurement is completed, the solidified sample is generally incinerated. However, at the time of disposal, the solidified sample may not be easily extracted from the beaker, and there is a risk of damage to the glass device and injury.

Therefore, in the present invention, when measuring the pot life of the thermosetting resin, there is no time bound by the analyst and individual differences, and it is possible to reproduce the same numerical value as the measurement result by the JIS method. Another object of the present invention is to provide a method for measuring the pot life and an apparatus for the same, which makes it possible to safely and easily reuse the device even in post-treatment after the measurement.

[0010]

Means for Solving the Problems When measuring the pot life of a thermosetting resin, the present inventor has noticed that the viscosity of the resin sample sharply increases near the end point, and I thought that the pot life could be automatically measured if the rise was detected by some method. As a result of further study, in order to detect the viscosity of the thermosetting resin, a rotary viscometer is used, and the load torque is detected by rotating the rotor in the resin sample with the viscometer. The inventors have found that the pot life of can be measured, and have completed the present invention.

That is, the first aspect of the present invention is to rotate a rotating body by a rotary viscometer in a thermosetting resin sample to which a curing agent has been added, and load torque of the rotary viscometer caused by the viscosity of the resin sample. Is a method for measuring the pot life, which is characterized by measuring the time until a predetermined value is reached by a timer, and the second is a container for containing a thermosetting resin sample, and a A rotating body, a rotary viscometer for rotating the rotating body, and a timer for counting the time until the load torque of the viscometer reaches a preset constant value. It is a time measuring device.

In the method and apparatus of the present invention, the kind of thermosetting resin for which the pot life is to be measured is not particularly limited, and for example, general polyesters such as unsaturated polyester resin, polyurethane resin and epoxy resin can be used. Can be widely used for thermosetting resins. The measurement time is also not limited, and it is possible to measure in a wide range, for example, from several minutes to several hours.

In the present invention, the container for containing the thermosetting resin sample may be one that does not react with the resin sample and can withstand a temperature of about 50 ° C., but the meat pressure is preferable. Is about 0.2 to 0.5 mm and is made of polyethylene, polypropylene, or polyacetal. Further, the shape of the container may be a single cylindrical shape with a bottom, but it is preferably a substantially cylindrical shape with a bottom whose diameter at the top is larger than the diameter at the bottom, and the side surface has a planar shape, The shape is wavy, polygonal, or substantially star-shaped. When a container having such a shape is used, a relatively large surface area can be obtained, the reaction heat of the thermosetting resin that is being cured can be dissipated, and the temperature can be made uniform. It is possible to measure the usage time.

The volume of the container is not constant depending on the shape and size of the rotating body used, but a container having a volume of about 10 to 150 ml is usually used. Here, in the container used in the present invention, it is preferable that the distance between the inner wall of the container at the time of pot life measurement and the outer surface of the rotating body described later is 2 to 20 mm, and more preferably 2 to It has a size of 15 mm. When a container having a size such that this distance is less than 2 mm or more than 20 mm is selected, it is often difficult to accurately measure the pot life of a wide range of thermosetting resins.

The rotating body used in the present invention is preferably a single cylinder or a thick taper upward. The material may be wood whose surface is finished smoothly, but more preferably it is made of polyacetal or a polyfluoroethylene-based material such as polytetrafluoroethylene. When a rotating body made of these materials is used, it is easy to pull out only the rotating body from the solidified resin after the pot life is measured, and it is easy to remove it, and it is not likely to break it. It's safe.

The length of the rotator is not particularly limited, but it is generally sufficient that the length is in the range of 50 to 100 mm.
The thickness may be such that the distance from the inner wall of the container is in the range described above, and normally, a thickness of about 3 to 50 mm can be preferably used.
The rotating body is attached to the rotating shaft of the rotary viscometer, but if a rotating chuck is equipped with a drill chuck or an auto joint (manufactured by Sunrise Trading Co., Ltd.), the rotating body can be easily attached and detached. Moreover, it is preferable because it can be performed quickly.

More specifically, examples of the shapes of the container and the rotating body include those shown in FIGS. 3 to 5 in the accompanying drawings. In these figures, a is a perspective view of the container, b is a front sectional view of the container and the rotating body, and c is a plan view thereof.
In FIG. 5, a container having a polygonal shape is used, and the shape of the rotating body is tapered corresponding to almost the same. When a rotating body having a shape as shown in FIG. 5 is used, the occupancy rate of the rotating body in the container is large, and it is possible to measure with a relatively small amount of sample, and the sample is pushed to the surroundings by the rotating body. The temperature change of the sample can be further prevented. The combination of the container shape and the rotating body shape shown in FIGS. 3 to 5 is not limited to those shown in each of them, and may be any combination.

By the way, when a container made of polyethylene, polypropylene, or polyacetal is used as the container and a rotating body made of polyacetal or polyfluorinated ethylene-based material is used, these are The container and the rotating body are very easy to remove or extract from the solidified thermosetting resin, and can be sufficiently reused. Therefore, JIS
Since the troublesome post-treatment and the risk of using a glass container and a stirring bar as in the method are eliminated, a particularly preferable method and apparatus can be provided.

In the present invention, the above-mentioned rotary body is attached to the rotary shaft of the rotary viscometer, and the rotary load torque is detected by rotating this rotary body in the thermosetting resin sample. The position of the rotator at the time of this detection should not be soaked in more than half of the depth of the sample and should not come into contact with the container. Usually, the distance is 1 to 5 mm from the bottom surface of the container.

In selecting the rotary viscometer, for example, when a rotating body having a size in the above range is used, the full scale torque is 330 μN · m or more, and more preferably
Those in the range of 330 to 1350 μN · m are preferable. Further, the rotation speed of the viscometer can be set within a range of about 1 to 30 rpm, and the O
It is preferable to select the one that can be turned on / off and can output the measured rotational load torque value to the outside.

Here, it is important to set the target value of the rotary viscometer load torque, which is the end point at the time of measurement, but according to the research conducted by the inventor of the present invention,
Generally, the setting of the target value is usually 50% or more, more preferably 70% or more, and further preferably 70 to 85% with respect to the full-scale torque of the rotary viscometer used. That is, to give an example, in the case of measuring with a rotational viscometer having a rotation speed of 12 rpm and a measurement range of 0 to 337 μN · m, it is preferable to measure 169 μN · m or more, more preferably 236 to 287 μN · m. The time point at which the range reaches is very well in agreement with the state of the end point at the time of measurement by the JIS method.
Also, when measuring at a rotation speed of 3 rpm with this model, the measurement range is 0 to 1348 μN · m, but the target value in this case is 674 μN · m or more, more preferably 944 to 1146 μN · m. Similarly, when the range reaches m, J
It is in good agreement with the state of the end point at the time of measurement by the IS method.
In any case, these target values are in the range of the above-mentioned "%" value, and if the target value to be the end point in the rotary viscometer is handled by the "%" value in the above-mentioned range, No operation is required to change the settings.

In order to measure the pot life of the thermosetting resin with the device having these constitutions, the timing is started from the time when the curing agent is added to the resin sample, and the rotating body is rotated in the sample. By doing so, the time until the load torque detected by the rotary viscometer falls within the above range is measured.

In the device of the present invention, the timekeeping of this time,
Furthermore, the operation of each device at the time of measurement is usually sufficiently possible by using a pre-programmable control means such as a personal computer. That is, most of the commercially available personal computers have a timer function, and the built-in timer allows the operation of each device according to the programmed contents as well as the execution of the above-mentioned timekeeping. Can be

With the device having the above-mentioned structure, by adding the curing agent to the thermosetting resin sample by hand and fixing the container containing the curing agent in the device, the programmed sequential operation is performed. Main operations and data processing related to measurement, such as descent and start of rotation of the rotary viscometer, measurement until the specified load torque value is reached, storage of the measured usable time measurement value, and further alarm transmission at the end of measurement. It is possible to automatically perform all of the above.

[0025]

Embodiments of the method and apparatus for measuring the pot life according to the present invention will be described below with reference to the drawings.
FIG. 1 is an explanatory view showing the configuration of an example of the device of the present invention, and FIG. 2 is a flow chart showing the operation and each operation when measuring the pot life using this device, except for the part shown as manual operation. The program is installed in the control device 6 shown in FIG.

In FIG. 1, reference numeral 1 denotes a container for containing a sample to be measured having a pot life, which is supported and fixed to a container base 10 in a constant temperature bath 11 kept at a constant temperature. Above the container 1, there is a main body 3 of a rotary viscometer which is automatically or manually moved up and down, and in this embodiment, ON / OFF of the device operation and rotation speed can be set from the outside, and measurement was performed. RC-200 type rotary viscometer (trade name; Toki Sangyo Co., Ltd.) capable of outputting the rotational load torque value to the outside.
Made, full scale torque = 67.4μN · m (at 60rpm), 3
The full scale torque at rpm is 1348 μN ・ m),
When measuring the pot life, the rotation shaft was set to rotate at a speed of 3 rpm. Further, the rotating body 2 is attached to the rotating shaft of the viscometer main body 3, and in this embodiment, a cylindrical body made of polyacetal having a thickness of 4 mm and a length of 90 mm was used.

The rotary viscometer body 3 is attached to an actuator 8 which moves up and down to a preset position in response to a signal from the actuator controller 7.
Further, a signal from the viscometer controller 4 is used to start or stop the rotation of the rotary shaft at a constant speed. Here, the viscometer controller 4
Then, the rotational reaction force detected by the rotary viscometer main body 3 is quantified and / or digitized and output to the outside. In this example, the end point of the sample when the pot life was measured was set at the time when it reached 70% of the full-scale torque of this rotary viscometer.

The sequencer 5 is a control device 6 above it.
According to the above, the viscometer controller 4 and the actuator controller 7 are controlled. The control device 6 is
The timing and the like of each operation of the rotary viscometer main body 3 and the actuator 8 are adjusted and controlled. Basically, a pre-programmed sequential operation is executed. In addition to this, the control device 6 has a function of storing the numerical value or outputting the numerical value based on the measurement result of the pot life of the sample.

The operating device 9 is composed of a switch for starting a program incorporated in the control device 6, an emergency stop switch in the event of an abnormality, and a switch for individually operating (manual operation) each device in this configuration. It is a thing.

Next, the operation of measuring the pot life using the apparatus of this embodiment and the operation of each device at each time point will be described in more detail. In addition, in the state before the operation of the apparatus, the rotary viscometer main body 3 is located at the upper side as shown in FIG. 1, and the rotary body 2 is attached to the rotary shaft thereof.

First, 50 g of a sample was sampled in a cup of about 100 ml different from the container described above, the sample temperature was adjusted to 25 ± 0.5 ° C., and if necessary, an accelerator was added, and a prescribed amount of the curing agent was added. At the same time, the program incorporated in the control device 6 is started. The timer built in the controller 6 is
The program starts to operate at the same time as this program starts, and the measurement of the pot life starts. Then, by manual operation, the sample in the cup is well stirred for 30 seconds according to the JIS method. Next, this sample is dispensed into the container 1 of the present apparatus and set on the container stand 10. The amount to be dispensed into the container 1 is 50 to 90%, and more preferably 70 to 80%, with respect to the total volume of the container 1 when the rotating body is lowered to a specified position in the container 1. .

The actuator 8 starts operating 2 minutes after the program is started, and lowers the rotary viscometer body 3. Here, the actuator 8 is set to start operating after 2 minutes because the sample is stirred for 30 seconds, the sample is dispensed into the container 20 seconds, and the container 1 is mounted on the container mount.
The time required for manual operation such as 10 seconds for setting to 10 and margin time is set in consideration of the margin, and it is not limited time, but the type of sample used or the type of curing agent It is the time that may be changed depending on the amount.

In this embodiment, the actuator 8
Has a two-stage descending manner, and the rotating body 2
Stops immediately before entering the sample in the container 1, slows its descending speed after receiving the second descending signal, and descends to the position where the lower end of the rotating body 2 is 2 mm above the bottom surface of the container 1. To do. The control device 6 searches for this second descending signal in communication with the sequencer 5, and after receiving this signal,
The rotary viscometer main body 3 controls the sequencer so as to rotate its rotary shaft and output the detected load torque. Here, it usually takes a little time for the rotary viscometer body 3 to start detecting the rotational load torque. That is, in the rotary viscometer main body 3, it is usual that the lock mechanism of the rotating portion is first removed, and the rotary viscometer main body 3 is slightly lowered before starting to detect the actual rotational load torque.

In the present embodiment, after the detection of the load torque in the rotary viscometer body 3 is started, the control device 6
On the screen attached to, the horizontal axis shows the elapsed time and the vertical axis shows the graph of 0 to 100% of load torque.
The ratio (%) of the load torque of the rotary viscometer main body 3 at the point of time elapsed is displayed in real time every second. Further, the control device 6 takes in the output value of this load torque, and also measures the time until this value reaches a preset constant value, that is, the time until it reaches 70%.

After the load torque output value reaches 70%, the control device 6 stops the rotation of the rotary shaft of the rotary viscometer main body 3 via the sequencer 5, and at the same time terminates the timing of the timer. Then, the end of measurement is displayed on the screen and a buzzer sound is emitted, and the timekeeping data and the load torque output data obtained at each output point are recorded on the flexible disk. After this operation is performed, all program operations by control device 6 are completed.
The time from the start of the operation of the timer to the end of the time measurement is the value of the pot life measured by this device.

After that, the rotary shaft of the rotary viscometer main body 3 and the rotary body 2 attached thereto are separated by manual operation, and the viscometer 3 is moved to the position before the start of measurement. Then, the container 1 containing the rotating body 2 and the sample is placed on the container stand 10
After removal, the rotor 2 and the container 1 are separated from the solidified sample, and post-treatment is performed to complete the measurement. Hereinafter, examples in which the pot life of various thermosetting resins is measured by the above-mentioned device of the present invention will be described.

Example 1 50 g of an unsaturated polyester resin as a thermosetting resin sample was placed in a cup having a capacity of 100 ml, and the temperature was adjusted to 25 ° C. Then, Permec N (55% methyl ethyl ketone peroxide; NOF CORPORATION) was used as a curing agent. ), A brand name) manufactured by the same company was added, and at the same time, the program of the control device 6 was started. Next, the above sample was put into a container (meat pressure) whose shape is shown in FIG.
It was made of polypropylene of 0.3mm, upper diameter 30mm, lower diameter 20mm, height 30mm, capacity 14cc) and then put up to 80% height, and then it was supported and fixed on the container stand 10 and made the program of the controller 6 below. Then, the pot life was measured. Figure 6
The graph output at the time of this measurement is shown in FIG. After the measurement, the solidified unsaturated polyester resin can be easily taken out from the container, and the rotating body can be pulled out from the resin, so that the container and the rotating body are not damaged or deformed. It could be used for measurement. Table 1 shows the measurement results. For this sample, JIS
The values measured according to the method are also shown.

Example 2 In Example 1, the type of unsaturated polyester resin was changed, and the shape of the container was as shown in FIG. 3 (made of polyethylene with a wall pressure of 0.3 mm, upper diameter 35 mm, lower diameter 25 mm, height). 30 mm,
The measurement was performed in exactly the same manner as in Example 1 except that the capacity was 20 cc. Even in this case, after the measurement, the solidified unsaturated polyester resin can be easily removed from the container, and the container is not damaged or deformed.
It could be used with the rotor for the next measurement. Table 1 shows the measurement results. In addition, the values measured according to the JIS method of this sample are also shown.

Example 3 In Example 1, the type of unsaturated polyester resin was changed, and the container had an octagonal side surface as shown in FIG. 5 (made of polypropylene with meat pressure of 0.3 mm, upper diameter). 41m
m, lower diameter 33 mm, height 38 mm, capacity 40 cc) were used, and the measurement was performed in exactly the same manner as in Example 1. Even in this case, the solidified unsaturated polyester resin can be easily removed from the container after the measurement, and the container is not damaged or deformed, and can be used for the next measurement together with the rotating body. It was possible. Table 1 shows the measurement results. In addition, the values measured according to the JIS method of this sample are also shown.

[0040]

[Table 1] As is clear from Examples 1 to 3, according to the measurement of the pot life using the device of the present invention, the results are very close to the values measured by the JIS method without being largely influenced by the size and shape of the container. You can see that

Examples 4 to 8 Using the same apparatus and the same container as in Example 1, the same operation was performed to measure the pot life of each of the five types of unsaturated polyester resins. For each of these, measurement by the JIS method was also performed for comparison. The results are shown in Table 2. In addition, as an example, a graph output in the fourth embodiment is shown in FIG.

[0042]

[Table 2] As is clear from the results of Examples 4 to 8, according to the measurement of the pot life using the apparatus of the present invention, various thermosetting resins were used, from short pot life to long pot life. It can be seen that a value extremely close to the measured value of JIS method can be obtained.

[0043]

According to the method and apparatus for measuring the pot life of the present invention, it is possible to obtain a numerical value almost equal to the result obtained by the conventional JIS method, and it is possible to eliminate the time when the analyst is restrained. Moreover, after the measurement, the container and the rotating body can be easily and safely removed from the solidified sample.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing a configuration of a pot life measuring device used in an embodiment of the present invention.

FIG. 2 is a flowchart showing an operation and each operation when measuring a pot life using the device of the present invention.

FIG. 3 is an example of a container and a rotating body used in the device of the present invention, a is a perspective view of the container, b is a front sectional view of the container and the rotating body, and c is a plan view thereof.

FIG. 4 is a diagram showing an example of another container and a rotating body,
Is a perspective view of the container, b is a front sectional view of the container and the rotating body, c
Shows the plan view.

FIG. 5 is a diagram showing another example of the container and the rotating body, wherein a is a perspective view of the container, b is a front sectional view of the container and the rotating body, and c is a plan view thereof.

FIG. 6 is a graph output when measuring the pot life by the device of the present invention in Example 1.

FIG. 7 is a graph output at the time of measuring the working time by the device of the present invention in Example 4.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Container 2 ... Rotating body 3 ... Rotational viscometer main body 4 ... Viscometer controller 5 ... Sequencer 6 ... Control device 7 ... Actuator controller 8 ... Actuator 9・ ・ ・ Operator 10 ・ ・ ・ Vessel base 11 ・ ・ ・ Constant bath

Claims (4)

[Claims] 1. A rotating viscometer rotates a rotating body in a thermosetting resin sample containing a curing agent, and the load torque of the rotating viscometer generated by the viscosity of the resin sample is a predetermined constant value. A method of measuring the pot life, which is characterized by measuring the time until it becomes a value. 2. A container made of polyethylene, polypropylene, or polyacetal is used as a container for containing the thermosetting resin sample, and a rotating body is made of polyacetal or polyfluorinated ethylene-based material. The method for measuring the pot life according to claim 1, which is used. 3. A container for containing a thermosetting resin sample, a rotating body rotating in the sample, a rotary viscometer for rotating the rotating body, and a load torque of the viscometer set in advance. A pot life measuring device, comprising a timer for measuring the time until the fixed value is reached. 4. The pot life measuring device according to claim 3, wherein the container is made of polyethylene, polypropylene, or polyacetal, and the rotating body is made of polyacetal or polyfluoroethylene-based material. .