JPH08122241A - Residence time distribution measuring method and device - Google Patents

Abstract

PURPOSE: To provide a device and a method for measuring the residence time distribution simply under the processing condition for resin of a resin melting and continuous kneading machine or a resin melting device. CONSTITUTION: A fluorescent is put into resin from a hopper 13, and the fluorescent mixed with resin is irradiated by light with a wavelength ranging from 250nm to 420nm emitted from an illuminating lamp 1. The light emitted by the flurorescent is transmitted through a filter 2 and an objective lens 3 and then received by a sensor 4. The sensor converts a light signal into an electric signal corresponding to brightness. An amplifier 5 amplifies the electric signal, and sends the signal to an A/D converter 6. The electric signal is converted into a digital signal, and CPU 7 conducts data processing for the digital signal according to a program to calculate the residence time distribution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a resin melt continuous kneader,
The present invention relates to an apparatus and method for measuring residence time distribution characteristics such as residence time distribution, average residence time or dimensionless residence time distribution function of resin in a resin melting device.

[0002]

2. Description of the Related Art The residence time distribution characteristics such as residence time distribution, average residence time or dimensionless residence time distribution function of resin in a resin melting continuous kneader or a resin melting apparatus are important factors for knowing the processing characteristics of the apparatus. Therefore, various technologies have been disclosed since the past.

An example of the continuous resin melt kneader is an extruder. Several techniques of residence time distribution measurement and tracer for investigating the residence time effective properties of molten resins in such equipment have been disclosed from the past. For example,
"Molding Processing Society of Japan 1992 Proceedings" B102 The apparatus and method of Toshiba Machine Co., Ltd. discloses a technique in which iron powder is used as a tracer, magnetic force is measured, and residence time distribution is measured. "Polymer Papers" Vol. 38, No.
4, p. The residence time distribution measurement technique disclosed in 279, 1981 uses the pigment cyanine blue as a tracer,
The pigment is irradiated with near infrared rays to measure the pigment concentration. T
odd et al., "Polymer Engineering"
and Science "Vol. 15, No. 6,
P. 437,1975 for measuring residence time distribution of extruder
Disclosed is a technique in which a radioisotope of ⁵⁶ Mn is used as a tracer, the tracer is put into a resin by an impulse method, and the intensity of radiation emitted from ⁵⁶ Mn is measured. Ch
en et al., “AIChEJornal” Vol. 39,
No. 9, 1993 discloses a technique in which aminoanthraquinone is used as a tocer, an ultraviolet absorption spectrum is measured, and a residence time distribution is measured.

It is known that the fluorescent agent has a property of absorbing a specific wavelength and emitting a specific wavelength. Several techniques using a fluorescent agent as a tracer utilizing this property have been disclosed. For example, Japanese Patent Laid-Open No. 2-93445
Japanese Patent Laid-Open Publication No. 2003-242242 discloses a technique of using a fluorescent whitening agent as a tracer for discriminating an image of an image forming apparatus. Ohmsha "Basics and Applications of Lightwave Sensing" P. At 326,
A technique using a fluorescent agent for detection of cancer cells and fundus examination is disclosed. The technique disclosed in Japanese Unexamined Patent Publication No. 4-376646 uses fluorescence brightness to obtain proper exposure of the fundus image. The technique disclosed in Japanese Patent Application Laid-Open No. 3-90292 uses a fluorescent agent in a solder paste and uses it for visual inspection of solder adhesion.

The technique of calculating the residence time distribution such as the average residence time and the dimensionless residence time distribution function from the measured residence time distribution is a known technique, and is described in Hashimoto's "Reaction Engineering" Baifukan and numerous technical books. It is disclosed.

[0006]

The residence time distribution of the resin in the resin melt continuous kneader or the resin melter, the average residence time, or the residence time distribution characteristics such as the dimensionless residence time distribution function are determined by the design and operation of the device. It is an important factor in setting the conditions. The measurement and method of the residence time distribution characteristics such as the residence time distribution of the resin, the average residence time or the dimensionless residence time distribution are performed under the operating conditions of processing the resin, that is, the temperature at which the resin melts, and the average shear rate of 30 sec ^-1 or more, There has been a demand for a residence time distribution measuring method and apparatus capable of measuring the average residence time under the condition of 1 second to 1 hour, and capable of accurately measuring the time when the tracer comes out by the residence time distribution measurement. However, it cannot be realized by the conventional technology.

"Forming Processing Society 1992 Proceedings" B
102 The equipment and method of Toshiba Machine Co., Ltd. is a method in which iron powder is used as a tracer and magnetic force is measured by a sensor.
It is measured under the operating conditions for processing the resin. However, this method and apparatus requires modification of a portion of the extruder to bypass the resin to the sensor for continuous flow. Therefore, the configuration of the screw combination is changed only for the residence time distribution measurement, that is, the extruder is disassembled and the reverse flow screw parts are incorporated to perform the measurement. In this method, the composition of the screw is substantially changed and the measurement is performed, so that the accurate residence time distribution is not measured. Also, since the sensor is iron powder, it can only be used with magnetic lines of force.

[Polymer Papers] Vol. 38, No.
4, p. 279, 1981, "Polymer Eng.
inering and Science "Vol.
15, No. 6, P. In the technique of 437, 1975, as a tracer, the pigment of Cyanine blue is irradiated with a pulse of near infrared rays to measure the concentration of cyanine blue.
However, in this method, a simulated liquid of silicone oil is used instead of the high-temperature melted polymer, and measurement can be performed only at a low temperature. Moreover, the residence time distribution of the extruder can be measured only under conditions far from the actual operating conditions. "Polymer Engine
ering and Science "Vol. 15,
No. 6, P. In the technology of 437 and 1975, the handling of the radioactive isotope ⁵⁶ Mn is regulated by the Radiation Hazard Prevention Law, and it is necessary to dispose of the radiation contained in the fluid.
There is a problem. "AIChE Journal" Vo
l. 39, no. In the technique of 9, 1993, the absorption UV spectrum of the tracer is discontinuous and the sample is sampled every time, and therefore the accurate residence time distribution cannot be measured. Moreover, since it takes a long time for sampling, only the residence time distribution far from the resin processing conditions of the extruder can be measured. The technique of Japanese Patent Laid-Open No. 02-93445 cannot measure the residence time distribution. Ohmsha "Basics and Applications of Lightwave Sensing" P. The technique of 326 cannot measure the residence time distribution.

Therefore, an object of the present invention is to provide a resin melting continuous kneader or a resin melting apparatus which has heretofore been impossible.
Operating conditions for processing the resin, that is, the temperature at which the resin melts,
A method and an apparatus for measuring a residence time distribution capable of measuring the average shear rate of 30 sec ^-1 or more and the average residence time of 1 second to 1 hour, and accurately measuring the time when the tracer comes out by the residence time distribution measurement. To provide.

[0010]

The residence time distribution measuring method according to the first solution of the present invention is a method in which a fluorescent agent as a tracer is charged into a molten resin by an impulse method, and the fluorescent agent is kneaded into the resin. Is irradiated with light having a wavelength of 250 nm to 420 nm, the brightness of the light emitted by the fluorescent agent is measured, the brightness of the light is converted into an electric signal, and the electric signal is subjected to data processing in accordance with a relationship determined in advance to obtain the data. It is characterized in that the change in the concentration of the fluorescent agent is obtained.

The residence time distribution measuring method according to the second solution of the present invention is the method according to the first solution, wherein the fluorescent agent absorbs light in a wavelength range of 250 nm to 420 nm and 380 nm to 550 nm. It is characterized by emitting light in the range.

A residence time distribution measuring method according to a third solving means of the present invention is the method according to the first solving means, wherein an area for measuring a change in luminance at which the fluorescent agent emits light is 0.0003 cm ² or less. It is characterized in that it is in the range of 4000 cm ² .

A residence time distribution measuring method according to a fourth solution means of the present invention is the method according to the first, second or third solution means, wherein the resin flow direction of the resin melt continuous kneader or the resin melt apparatus is It is characterized in that the brightness is measured downstream from the place where the fluorescent agent is charged.

A residence time distribution measuring method according to a fifth solving means of the present invention is the residence time distribution measuring method according to the first, second, third or fourth solving means, wherein the resin is continuously melted at a measuring place. The kneading machine is a multi-screw extruder including a single screw or a twin screw.

In the residence time distribution measuring method according to the sixth means of the present invention, the resin melting device at the measuring location is an injection molding machine or a resin flowing device in a resin melting mold.

In the method for measuring residence time according to the seventh means of the present invention, 2,5-bis (5'-) is used as the fluorescent agent.
It is characterized in that tertiary-butylbenzoxazolyl (2)) thiophene is used.

A residence time distribution measuring device according to an eighth solving means of the present invention is a device for measuring a residence time distribution by the method according to any one of the first to seventh solving means, wherein a fluorescent agent is used as a tracer. Charging mechanism for charging, 250
an irradiation mechanism for irradiating the fluorescent agent with light having a wavelength of nm to 420 nm, a light receiving mechanism for receiving light emitted by the fluorescent agent, and a luminance of light having a specific wavelength of the received light,
A brightness measuring mechanism for outputting a signal corresponding to the brightness, a calculating mechanism for inputting the brightness signal and calculating by the CPU of the data processing device, and a display mechanism for expressing an output signal of the CPU of the data processing device. It is characterized by having.

A residence time distribution measuring apparatus according to a ninth solving means of the present invention is the residence time distribution measuring apparatus according to the eighth solving means, wherein the light receiving mechanism has an area of 0.0003c.
It is characterized in that it receives light from a measurement area in the range of m ² to 4000 cm ² .

The residence time distribution measuring apparatus according to the tenth solving means of the present invention is the residence time distribution measuring apparatus according to the eighth solving means, wherein the luminance measuring mechanism has a luminance of light in a wavelength range of 380 nm to 550 nm. It is characterized by measuring.

A dwell time distribution measuring apparatus according to an eleventh solving means of the present invention is the dwell time distribution measuring apparatus according to the eighth solving means, wherein the calculating mechanism uses an input luminance signal to calculate an average dwell time or It is characterized in that the dimensionless residence time distribution function is calculated and the calculation result is output to the display mechanism.

The residence time distribution measuring apparatus according to the twelfth solution means of the present invention is the eighth, ninth, tenth or eleventh aspect.
In the residence time distribution measuring device according to the solving means, the measuring mechanism measures in a non-contact manner.

A resin melt continuous kneader according to the thirteenth solution means of the present invention is characterized by comprising a residence time distribution measuring device according to the eighth, ninth, tenth, eleventh or twelfth solution means. To do.

The resin melting apparatus according to the fourteenth solution means of the present invention is the eighth, ninth, tenth, eleventh or twelfth aspect.
It is characterized by comprising a residence time distribution measuring device according to the solution.

[0024]

According to the present invention, as described above, the residence time distribution of the resin is measured in a device such as a resin continuous melting and kneading machine or a resin melting device whose operation is accompanied by resin flow using the fluorescent agent mixed in the resin as a tracer. For 250 nm to 420
The light of the wavelength of nm is irradiated, the brightness of the light emitted by the fluorescent agent is measured, this is converted into an electric signal and data processing is performed. It seeks the distribution.

Of the continuous resin melt kneaders, the single-screw extruder is
It includes a single-screw special kneading extruder, a single-screw sheet extrusion molding machine, and a film extrusion molding machine of BUSS Co-Kneader. The twin-screw extruder includes multi-screw extruders such as a twin-screw co-direction extruder and a twin-screw different-direction extruder, which can perform sheet molding and film molding. Preferred is Warner & Friedler ZS
K series, Toshiba Machine Co., Ltd. TEM series, BUS
For example, a co-kneader of S company.

Among the resin melting devices, the injection molding machine includes one capable of molding a thermoplastic resin or a thermosetting resin. The resin device in the resin-melting mold of the resin-melting device is a device that causes a molten thermoplastic resin or thermosetting resin to flow into the cavity of the mold to perform molding.

The fluorescent agent is a substance that emits light upon stimulation with light of a certain wavelength. In particular, the fluorescent agent used in the present invention emits light sensitively even with a very small amount added, so when the tracer is used with a very small amount of fluorescent agent, the time when the tracer finishes leaving the device is accurately measured by the residence time distribution measurement. Can be measured. Further, the fluorescent agent used in the present invention absorbs only light having a wavelength shorter than visible light and emits light, and does not emit light under visible light, so that the resin containing this remains in the color of the resin itself. It has characteristics. The fluorescent agent may be in the form of powder, solid, or liquid dissolved in a solvent. A preferred fluorescent agent is a fluorescent agent that absorbs light having a wavelength in the range of 250 nm to 420 nm and emits light in the range of 380 to 550 nm, and includes a diaminostilbene disulfonic acid derivative, a quinacrine derivative, a pyrazoline derivative,
Examples thereof include a bisbenzoxazolyl derivative, a naphthylimide derivative, a cationic fluorescent dye, and a fluorescent pigment. As an example, 2,5-bis (5′-tert-butylbenzoxazolyl (2)) thiophene, 7
-Amino-4-methylcoumarin-3-acetic acid, Cascade Blue, 8-anilino-
1-naphthalenesulfonic acid Mg salt, coumarin maleimide, dimethylaminonaphthalene-5-sulfonic acid, dansyl chloride,
Dansyl hydrazine
e), Fluorescamine
e), Monochromobim
ane), o-phthalaldehyde, bisaminophenyloxadiazole-foilgen (bis-Amino)
-Phenyl-oxadiazole-Feul g
en), 4,6-diamidino-2-phenylindole HCl, Hoechst 33258, Hoechst 33342, Mithramycin, Quinacrine Mustard, Calcein Blue (Calcein Bluecrine Tetrace). ), Zinc sulfide, zinc silicate, zinc cadmium sulfide, calcium sulfide, strontium sulfide, and calcium tungstate. The inlet of the fluorescent agent may be the main hopper of the resin melting continuous kneader or the resin melting device, the atmospheric vent port, the degassing vent port, the runner, and the gate. Alternatively, the fluorescent agent may be charged using the measurement hole of the pressure gauge or the thermometer of the resin melting continuous kneader or the resin melting device.

In order to charge the fluorescent agent in an impulse, a person may instantaneously put it in from a hand together with a signal, or the fluorescent agent may be dissolved in a solvent and then injected instantaneously with a syringe, It may be injected instantaneously using a device such as a micro-quantitative pump for liquid chromatography, a gear pump or the like.

When measuring the change in the concentration of the above-mentioned fluorescent agent kneaded in the resin, the measurement location of the luminance is the location where the fluorescent agent is charged in the resin melt continuous kneader or the resin melting device in the resin flow direction. It is preferably further downstream, and examples thereof include the strand surface, the film surface, or the sheet surface of the resin discharged from the extruder die. Alternatively, the sensor and the irradiation device may be installed by modifying the die part or the barrel. In the molding machine, the sensor and the irradiation device may be installed in the nozzle, the barrel, the spool runner, or the mold cavity. How to install the sensor and irradiation device is a glass barrel, die, nozzle, cavity or barrel with glass,
The die, nozzle, and cavity are irradiated with the light beam with an irradiation lamp,
The brightness of the emitted light may be measured, or the barrel, die, nozzle, and cavity may be modified to install glass fiber and the light is emitted from one side with an illumination lamp, and the light emitted from the other side. The brightness of may be measured.

The brightness of the measured light is the luminous intensity (candelas) per unit area of the orthogonal projection of the light source in the direction toward the light source.

As a light source for irradiating a wavelength of 250 nm to 420 nm, there are a mercury lamp, a fluorescent lamp, a xenon lamp and the like.

The area of the measurement point (measurement site) at the measurement location for measuring the brightness change of the light emitted by the fluorescent agent is preferably in the range of 0.0003 cm ² to 4000 cm ² . The light receiving means has an objective lens group and can adjust the focal length within the above-mentioned area range. For example, a lens of a camera, a video camera, a luminance meter, a color luminance meter, a spectrophotometer, or the like. Alternatively, the glass fiber may be directly installed on the measurement surface, and the light emitted from the fluorescent agent may be measured through the glass fiber. If the area of the measurement point is smaller than 0.0003 cm ^2, the sensitivity of the measurement luminance is lowered, so that it becomes difficult to accurately measure the start time and the end time of the fluorescent agent. Diameter of measurement point is 4000 cm
^{If the value is} larger than ^2, the distance between the measuring point and the objective lens is too large, so that the residence time distribution device cannot be substantially installed.

The mechanism for measuring the luminance of a specific wavelength and outputting the luminance signal is a photomultiplier tube, a semiconductor or the like sensor capable of measuring the wavelengths of blue, green and red of the three primary colors of light. A preferred wavelength is a sensor capable of measuring the brightness of blue wavelengths from 380 nm to 550 nm. The change in the concentration of the fluorescent agent can be known by the change in the brightness. Preferred measuring sensors include a color luminance meter, a spectrophotometer,
A single-lens reflex camera equipped with the sensor and a luminance meter. The sensor is attached after the lens group and the glass fiber, and the brightness at the measurement point is continuously measured.

If the measurement surface is larger than the area of the measurement point,
It does not matter whether it is spherical or flat.

The CPU of the data processing device for processing the input signal of luminance is 4 bits, 8 bits, 16 bits, 32 bits.
It is a central processing unit of bits, 64 bits, etc. You can use either one.

The luminance signal is input and C of the data processing device is input.
The mechanism calculated by PU is a program (FIGS. 1 and 2) that outputs a signal input to the CPU to the display device.
This program includes Algorithm 1 (FIG. 1) and Algorithm 2 (FIG. 2) described below. Further, this program also includes a program for controlling the sensor, the signal amplifier, the A / D converter, the graphic display, the memory and the like.

Algorithm 1 When a start signal is sent to the CPU by an input means such as a keyboard (S1), the A / D converter outputs, for example, 0.
Digital data is input to a variable C (i) representing the concentration of the fluorescent agent every set time of 3 seconds (S2). Then, the variable C
The value of (i) is output to the graphic display device (S
3). The time ti of the variable C (i) is TD> 0, and ti
It is determined whether> TD is satisfied, that is, whether the tracer (fluorescent agent) start time has come (whether the tracer has already started) (S4). If it has not started yet (S4, N), C (i) / C (i-1) -1> 0.0
Calculate 5. Then, when this expression is satisfied, that is, the value of the variable C (i) representing the concentration data increases by 5 with respect to the variable C (i-1) immediately before (0.3 seconds before).
When it exceeds% (S5, Y), the time of ti at this time is set as the tracer start time TD (S6). The above-mentioned increase rate of 5% is an example, and may be appropriately set depending on the actual situation. If the above formula is not satisfied (S5, N), the process returns to S2,
This procedure is repeated until there is a 5% increase over the previous concentration. Next, AC is calculated by averaging C (i) from i = 0 to TD (S7). Tracer start time TD
0.3 seconds after ti when the above is determined, the relationship in S4 is satisfied (S4, Y), and this time, it is determined when the increase in the concentration C (i) with respect to the average concentration AC is less than 2%. Yes (S8). The above-mentioned increase rate of less than 2% is merely an example, and may be appropriately set according to the actual situation. When this becomes less than 2% (S8, Y), ti at this time is set as the tracer end time TF (S9). When 2% or more (S
8, Y) returns to S2 and repeats the procedure. Algorithm 2
followed by.

Algorithm 2 Using the data obtained in Algorithm 1 above, the average residence time TM is calculated according to the following equation (1) (S10).

[0039]

[Equation 1]

Further, according to the following equation (2), the ratio of ti to the average residence time TM is obtained, and the dimensionless time is calculated by converting θi from ti = 0 to TF into dimensionless (S11).

[0041]

[Equation 2] Infinite element time θ θi = ti / TM (2) Next, the residence time distribution function E (ti) is calculated according to the following equation (3).
Is recalculated from ti = 0 to TF.

[0042]

(Equation 3)

Further, the dimensionless residence time distribution function E (θi) is recalculated from ti = 0 to TF according to the following equation (4) (S12).

[0044]

[Equation 4] Dimensionless residence time distribution function E (θi) E (θi) = TM * E (ti) (4) The obtained values of θi and E (θi) are output to the graphic display device (S13). . When the dimensionless time θi is not equal to TF, the procedure is repeated (S14, N), and when they are equal (θi = TF), the procedure is terminated (S14,
Y).

The calculation mechanism integrates the data measured over time, calculates the average residence time or the dimensionless residence time distribution, and outputs the calculation result to the display device.

The display device may be a discharge light emitting diode, a liquid crystal display device, a cathode ray tube display device, or the like.

The non-contact type of the present invention means a method in which the resin containing the fluorescent agent in the resin melting continuous kneader or the resin melting device is not in direct contact with the light receiving mechanism for receiving a specific wavelength. Specifically, between the resin containing the fluorescent agent and the light receiving mechanism for receiving a specific wavelength, a colorless and transparent gas such as air or a colorless transparent gas such as glass and air that does not interfere with the wavelength emitted by the fluorescent agent. There is gas.

Resins processed by a resin melting continuous kneader or a resin melting device are polystyrene, HIPS (high
Impact polystyrene), acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylate and other polymers and copolymers, diene polymers and their copolymers, hydrogenated polymers and copolymers Coalesce, olefin polymers and copolymers thereof, phenylene ether polymers and copolymers thereof, amide polymers and copolymers thereof, ester polymers and copolymers, polyoxymethylene and copolymers thereof, etc., Processing methods include granulation, comonomer grafting reaction, physical blending of each polymer, alloying reaction with compatibilizer, composite formation with filler and fiber, dehydration reaction, degassing reaction, or styrene monomer. Polymerization reaction, acrylic monomer polymerization reaction, polyamide, polyester Le such condensation reactions, including polymerization reaction of olefin monomers.

[0049]

The present invention will be described in more detail with reference to the following examples with reference to the drawings, but it goes without saying that the present invention is not limited to these examples.

[Embodiment 1] In FIG. 3, a resin continuous melt-kneading device is a twin-screw co-direction extruder 20 (ZSK-40 manufactured by Werner & Pri of the Federal Republic of Germany), and has an adapter 20a at the tip thereof. 4m for 20a
A strand die 20b having mφ10 holes is attached. 250 nm in front of the strand die part 20b on the downstream side
An ultraviolet lamp (300 nm to 420 nm) is placed as a radiant lamp 1 that emits light in the range from 1 to 420 nm, and the light is emitted from the radiant lamp 1 to the resin strand 20c of about 4 mmφ that comes out from the hole of the strand die 20b. The wavelength of the light emitted from the resin strand 20c is measured by the residence time distribution measuring device 0. The residence time distribution measuring device 0
Wavelength of 380 nm to 550 emitted from the strand 20c
Filter 2 for transmitting only nm, strand 20c
Of the lens group including the objective lens 3 capable of changing the measurement point of from 0.1 mmφ to 380 mmφ and focusing the light of the wavelength of 380 nm to 550 nm that has passed through the filter 2 through the objective lens 3, the filter 2 and the objective lens 3. The sensor 4 is capable of measuring the brightness of a specific wavelength of 380 nm to 550 nm, and the signal amplifier 5 receives the electric signal of the brightness of 380 to 550 nm generated by the sensor 4 and amplifies the electric signal. The analog signal of brightness from the signal amplifier 5 is converted into a digital signal by the A / D converter 6, and the CPU 7 processes the digital signal of brightness sent from the A / D converter 6. The data processed by the CPU 7 is displayed on the graphic display device 8. CPU7
Data and program are written in the memory 9.
The calculation result data of the CPU 7 is stored in the external storage device 10.

In FIG. 4, a hopper 1 for supplying resin
1 is provided near the upstream end of the extruder (ZSK-40 manufactured by Werner & Pri of Germany),
The resin is supplied from the feeder 12 and the tracer is impulsively injected from the tracer injection device 13. The extruder operates by setting the screw rotation speed. The resin is supplied from the feeder 12 to the hopper 11 to start extrusion. Operating conditions for processing resin are extruder barrel temperature 23
0 ℃, die temperature 230 ℃, screw rotation speed 250rp
m, extrusion rate 60 kg / h (resin is Asahi Kasei polystyrene 666). After the operation is stabilized, 0.5 mg of the fluorescent agent (2,5-bis (5′-tert-butylbenzoxazolyl (2)) thiophene) as a tracer is supplied from the tracer injection device 13 at one time. CPU7 with the time when the tracer was thrown in as the start time
To start. It is possible to provide a signal transmission means capable of transmitting a tracer input signal to the CPU 7 in synchronization with the input of the tracer. With this start signal, the CPU 7 starts measuring the brightness of the fluorescent agent. The light emitted from the strand 20c passes through the filter 2 and the objective lens 3, is received by the sensor 4, and the brightness of the light is converted into an electric signal. This electric signal is amplified by the amplifier 5,
Converted to digital signal by A / D converter 6, CP
Input to U7. The digital signal input to the CPU 7 is sent to the display device and output. The CPU 7 repeatedly displays the residence time distribution until the tracer finishes to appear.

As shown in FIG. 5, the brightness (V) of the tracer is 35.7 seconds at the beginning (TD), 55.7 seconds at the peak (TP), and 178.8 seconds at the end (TF), and the brightness (V) is 0.25.
6V, 4.760V and 0.256V could be output with time. The CPU 7 automatically determines the end of the tracer, and according to the above algorithms 1 and 2, the following equations (1) to
(4)

[0053]

(Equation 5)

[0054]

(6) Infinite element time θ θi = ti / TM (2)

[0055]

(Equation 7)

[0056]

(8) Dimensionless residence time distribution function E (θi) E (θi) = TM * E (ti) (4)
To calculate the average residence time and the dimensionless residence time distribution function, and re-output to the graphic display device. The obtained results are shown in FIG. In this case, the average residence time (TM) is 7
It was 1.1 seconds.

[Embodiment 2] A description will be given below with reference to FIG.

The injection molding machine 29 has a nozzle 21 and is in communication with the cavity 23 of the mold 22. Molding machine nozzle 2
The injection pipe 2 in which the micro quantitative pump 24 for high performance liquid chromatography, which is opened in 2, is opened in the molding machine nozzle 22
A fluorescent agent as a tracer is added via 5. The mold cavity 23 is optically connected to the outside by glass fibers 26 and 27 having a diameter of 5 mm. The glass fiber 26 is optically connected to an irradiation lamp 28 that emits light of 250 nm to 420 nm. Glass fiber 27 is 380n
It is optically connected to a sensor 4 that receives light in the range of m to 550 nm and measures its brightness. Sensor 4 is 3
The brightness of light from 80 to 550 nm is converted into an electric signal and sent to the signal amplifier 5. The amplified analog signal of brightness from the signal amplifier 5 is sent to the A / D converter 6,
Converted to digital signal. This digital signal is the CPU
It is sent to 7 and processed. The data processed by the CPU 7 is sent to the display device 8 and displayed. Data and programs of the CPU 7 are written in the memory 9. The calculation result data of the CPU 7 is stored in the external storage device 10.

As the resin, Asahi Kasei Polystyrene 66
6. Using FANUC-50D (manufactured by FANUC) as a molding machine, barrel temperature 180 ° C to 240 ° C, nozzle temperature 240 ° C, injection time 15 seconds, measuring time 15 seconds, injection pressure 420 kg / cm ² , mold temperature Molding was carried out under molding conditions of 50 ° C.

After the injection molding machine 29 finishes the measurement, the metering pump 24 injects the solvent containing the fluorescent agent. The irradiation lamp 28 irradiates the inside of the mold cavity 23 from the glass fiber 26. Simultaneously with the start of molding, a start signal is sent to the CPU 7. When the molten resin enters the cavity 23 from the nozzle 21 and passes between the glass fibers 26 and 27 at the measurement point, the sensor 4 measures the brightness of the light emitted by the fluorescent agent as the tracer and converts it into an electric signal. The signal amplifier 5 amplifies this analog electric signal, and the A / D converter 6
Send to The A / D converter 6 converts the sent analog signal into a digital signal and inputs it to the CPU 7. C
The PU 7 periodically takes in a signal, for example, every 0.3 seconds,
Output to the display device 8. For the subsequent processing, the same operations as in Example 1 are repeated. FIG. 8 shows the results obtained. The average residence time was 2.3 seconds.

[0061]

INDUSTRIAL APPLICABILITY The method and apparatus for measuring the residence time distribution of the present invention comprises charging a fluorescent agent as a tracer by the impulse method and measuring the change in the concentration of the fluorescent agent by the change in the brightness of light having a wavelength of 250 to 420 nm. Since the residence time distribution of the resin is obtained by the above, it is possible to measure under the operating conditions for processing the resin, that is, the temperature at which the resin melts, the average shear rate of 30 seconds ^-1 or more, and the average residence time of 1 second to 1 hour. ,
In addition, since the time when the tracer finishes to be discharged can be accurately measured by measuring the residence time distribution, it is possible to optimize the design and operation of the resin melting continuous kneader or the resin melting device.

Further, the area for measuring the change in the luminance of the fluorescent agent that emits light is 0.0003 cm ² to 4000 cm.
By setting the range to be ^2, the residence time distribution can be accurately measured.

[Brief description of drawings]

FIG. 1 is a flowchart showing an example of an algorithm used in the present invention.

FIG. 2 is a flowchart showing an example of an algorithm used in the present invention.

FIG. 3 is a block diagram showing an example in which the present invention is applied to an extruder.

FIG. 4 is a block diagram showing an example in which the present invention is applied to an extruder.

FIG. 5 is a diagram showing a luminance change obtained in an example of the present invention.

FIG. 6 is a diagram showing a dimensionless residence time distribution function obtained in an example of the present invention.

FIG. 7 is a block diagram showing an example in which the present invention is applied to an injection molding machine.

FIG. 8 is a diagram showing a dimensionless residence time distribution function obtained in another example of the present invention.

[Explanation of symbols]

 0 Residence time distribution measuring device 1 Radiant lamp (ultraviolet lamp) 2 Filter 3 Objective lens 4 Sensor 5 Signal amplifier 6 A / D converter 7 CPU 8 Graphic display 9 Memory 10 External recording storage device 11 Hopper 12 Feeder 13 Tracer injection device 20 Extruder 20a Adapter 20b Die 20c (Resin) Strand 21 Nozzle 22 Mold 23 Mold cavity 24 Micro quantitative pump for high performance liquid chromatography 25 Injection pump 26, 27 Glass fiber 28 Irradiation lamp 29 Injection molding machine

Claims (14)

[Claims] 1. A fluorescent agent as a tracer is charged into a molten resin by an impulse method, and the fluorescent agent kneaded in the resin is 250 nm to 420 n.
m of light having a wavelength of m, the brightness of the light emitted by the fluorescent agent is measured, the brightness of the light is converted into an electric signal, and the electric signal is subjected to data processing in accordance with a relationship determined in advance to perform the data processing of the fluorescent agent. A method for measuring residence time distribution, characterized by obtaining a change in concentration. 2. The fluorescent agent is 250 nm to 420 nm.
Absorbs light in the wavelength range of 380 nm to 550 nm
The residence time distribution measuring method according to claim 1, wherein light in the range is emitted. 3. The residence time distribution measuring method according to claim 1, wherein an area for measuring a change in luminance of the fluorescent agent that emits light is in the range of 0.0003 cm ² to 4000 cm ² . 4. The retention according to claim 1, wherein the brightness is measured downstream of the place where the fluorescent agent is charged in the resin flow direction of the resin melting continuous kneader or the resin melting device. Time distribution measurement method. 5. The resin continuous melt kneader is a multi-screw extruder including a single screw or a twin screw.
The method for measuring the residence time distribution described. 6. The residence time distribution measuring method according to claim 4, wherein the resin melting device is an injection molding machine or a resin flowing device in a resin melting mold. 7. The fluorescent agent is 2,5-bis (5′-tert-butylbenzoxazolyl (2)) thiophene, and the brightness is measured in a continuous resin kneader. Item 4. A method for measuring residence time distribution according to item 4. 8. A charging mechanism for charging a fluorescent agent as a tracer, an irradiation mechanism for irradiating the fluorescent agent with light having a wavelength of 250 nm to 420 nm, and a light receiving mechanism for receiving light emitted by the fluorescent agent. A luminance measuring mechanism for measuring the luminance of light of a specific wavelength of the received light and outputting a signal corresponding to the luminance, and a calculating mechanism for inputting the luminance signal and calculating it in the CPU of the data processing device And a display mechanism for displaying an output signal of a CPU of the data processing device, wherein a residence time distribution for measuring a resin residence time distribution by the method according to any one of claims 1 to 7. measuring device. 9. The light receiving mechanism has an area of 0.0003 cm ²
9. The residence time distribution measuring device according to claim 8, which receives light from a measurement area in the range from 1 to 4000 cm ² . 10. The brightness measuring mechanism comprises:
9. The residence time distribution measuring device according to claim 8, which measures the luminance of light having a wavelength in the range of 50 nm. 11. The calculation mechanism calculates an average residence time or a non-dimensional residence time distribution function using the input luminance signal and outputs the calculation result to the display mechanism. 8. The residence time distribution measuring device described in 8. 12. The residence time distribution measuring device according to claim 8, 9, 10 or 11, wherein the measuring mechanism measures by a non-contact method. 13. The method according to claim 8, 9, 10, 11 or 12.
A resin melt continuous kneader comprising the residence time distribution measuring device according to the item. 14. The method according to claim 8, 9, 10, 11 or 12.
An apparatus for melting resin, comprising the residence time distribution measuring device according to the item.