JP2019181890A - Gas analysis method and device - Google Patents

Abstract

An object of the present invention is to understand the entire process of injection molding. A method for analyzing a gas generated when an injection molding machine 40 and a mold 50 are used to perform injection molding of a resin material 100, wherein the injection molding machine 40 and / or the mold 50 includes an injection molding machine. A step of collecting generated gas at two or more positions between a step of supplying the resin to the mold 40 and a step of taking out the molded product from the mold 50; Analyzing the collected gas quantitatively and / or qualitatively, respectively. [Selection diagram] Fig. 1

Description

  The present invention relates to a gas analysis method and apparatus for analyzing gas generated in an injection molding process.

  In the injection molding of a resin composition, the processing temperature is usually set within the range from the melting point (or flowable temperature) of the resin serving as the base of the resin composition to the thermal decomposition temperature so as not to deteriorate the resin. Yes. However, the resin composition may be decomposed in the molding machine due to various factors. The decomposition of the resin composition not only causes a problem of deterioration of physical properties due to deterioration of the resin itself, but also causes various problems such as deterioration of the appearance of the molded product and deterioration of workability due to generation of decomposition gas. Conventionally, in order to evaluate the decomposition gas of such a resin composition, a method of analyzing the generated gas by heating the resin composition itself in a pellet state or the like has been used. Moreover, in order to evaluate the state of the resin composition in the process of injection molding, a technique for collecting or analyzing gas generated from the resin composition during molding is provided.

  For example, Patent Document 1 describes that a gas amount measuring device is connected to a cavity of a mold, a material is injected into the mold, and the measured values are integrated. Patent Document 2 describes that the amount of a volatile substance contained in a gas generated from a synthetic resin filled in a molding die is measured. Patent Document 3 describes sucking a gaseous substance generated from a molding material through a material supply unit of a molding machine. Thus, conventional gas collection and analysis has been performed in one stage, such as the stage of injecting the material into the mold and the stage of supplying the material to the molding machine.

Japanese Patent Laid-Open No. 7-40390 JP 2011-247682 A JP 2010-23273 A

  In order to prevent the deterioration of the resin in injection molding, it is required to understand the gas generated in the process from the introduction of the material into the molding machine to the removal of the molded product from the mold and take appropriate measures. ing.

  The present invention has been proposed in view of the above-described circumstances, and an object thereof is to provide a gas analysis method and apparatus capable of grasping gas generated in an injection molding process as a whole.

  In order to solve the above-described problems, a gas analysis method according to the present application is a method for analyzing a gas generated when a resin is injection-molded using a molding machine and a mold, the molding machine and / or the mold. In the process of collecting the generated gas at two or more positions from the resin supply stage to the molding machine to the molded article removal stage from the mold, and at the two or more positions, respectively. Analyzing each collected gas quantitatively and / or qualitatively.

  You may further include the process of analyzing the deposit | attachment in the position which collects gas. The analyzing step may analyze changes over time for the gas collected at two or more positions. Furthermore, you may analyze the change with time of the generated gas at the time of continuous shaping | molding in each position which collects gas.

  The gas analyzer according to the present application is an analyzer for gas generated when a resin is injection-molded using a molding machine and a mold, and in the molding machine and / or the mold, a resin supply stage to the molding machine And collecting means for collecting the generated gas at two or more positions from the mold to the step of taking out the molded product from the mold.

  The collection means may further include an analysis means for quantitatively and / or qualitatively analyzing the gas respectively collected at two or more positions. The analysis means may be gas chromatography. As the collecting means, a simple container such as a bag or a bottle may be used, or a trap by chemical adsorption or physical adsorption such as porous or nonwoven fabric may be used.

  According to the present invention, it is possible to prevent deterioration of the resin in the injection molding by grasping the entire injection molding process and taking appropriate measures.

It is a figure which shows the example of a structure of the gas analyzer of this Embodiment. It is a figure which shows the example of a gas collection container. It is a flowchart which shows a series of processes of the gas analysis method of this Embodiment. It is a figure which shows the structure of the gas analyzer of a 1st modification. It is a figure which shows the structure of the gas analyzer of a 2nd modification. It is a figure which shows the structure of the gas analyzer of a 3rd modification. It is a figure which shows the structure of the gas analyzer of a comparative example. It is a graph which shows the time change of the exhaust gas of 1st Example. It is a graph which shows the time change of the exhaust gas of 2nd Example. It is a graph which shows the time change of the exhaust gas of 3rd Example. It is a graph which shows the weight of the deposit | attachment which generate | occur | produced in the metal mold | die of 4th Example.

  Hereinafter, embodiments of a gas analysis method and apparatus will be described in detail with reference to the drawings. FIG. 1 is a diagram illustrating an example of a schematic configuration of a gas analyzer according to the present embodiment. The gas analyzer of the present embodiment is configured to correspond to the injection molding machine 40 and the mold 50 of the present embodiment.

  The injection molding machine 40 according to the present embodiment is an inline screw type, and has a cylinder 41 extending in a substantially horizontal direction, a screw 46 built in the cylinder 41, and a drive mechanism (not shown) that rotationally drives the screw 46. is doing. The cylinder 41 is provided with a hopper 42, a band heater 47, a gas vent nozzle 43 and a nozzle 44. In the gas vent nozzle 43, a plurality of donut-shaped disks 48 are stacked in the direction in which the cylinder 41 extends, and a gap for discharging gas is formed.

  The mold 50 includes a fixed first mold 51 having a cavity 53 therein, and a movable second mold 52 corresponding to the first mold 51. The first mold 51 is provided with a sensor 55 that measures the temperature, pressure, and the like of the cavity 53. In addition, the cavity 53 as used in this specification means the whole area | region including the gate of the metal mold | die 50 through a sprue and a runner to a molded product main-body part (narrowly defined cavity). The second mold 52 is provided with a mold vent 54 that discharges gas from the cavity 53. The mold vent 54 is formed of a porous material or pores.

  In the injection molding machine 40, the pellet-shaped material 100 stored in the hopper 42 is dropped by its own weight and supplied to the cylinder 41 directly below the hopper 42. The cylinder 41 is heated to a predetermined temperature by a band heater 47. The material 100 supplied to the cylinder 41 is kneaded by the screw 46 while being melted by heating by the band heater 47 and shearing heat generated by the rotation of the screw 46 while being conveyed by the rotating screw 46, and further, the nozzle 44 is advanced by the advancement of the screw 46. And injected into the mold 50. The material 100 injected into the mold 50 is filled in the cavity 53 of the mold 50 and solidified, and then taken out from the mold 50 as a molded product.

  The material 100 supplied from the hopper 42 to the cylinder 41 generates gas when being melted in the cylinder 41. This gas is discharged from the cylinder 41 via the hopper 42. The hopper exhaust gas discharged to the hopper 42 is exhausted through the first exhaust path 21 extending from the hopper 42 to the first vacuum pump 31. Depending on the components of the gas discharged from the hopper 42, solid deposits may be generated in the hopper 42 and the first exhaust path 21.

  For collecting the hopper exhaust gas from the hopper 42, various degassing devices commercially available with names such as “reduced pressure plasticization” and “vacuum plasticization” may be used. As such an apparatus, for example, “Eco Mac” of Haruna Co., Ltd., “ALFIN II” of Sumitomo Heavy Industries, Ltd., “Baku Melta” of Meiki Seisakusho Co., Ltd., etc. are known. The hopper exhaust gas may flow from the hopper 42 to the first exhaust passage 21 through such a degassing device.

  The gas generated when the material 100 supplied from the hopper 42 to the cylinder 41 is melted in the cylinder 41 may be collected from the rear end portion of the cylinder 41 instead of the hopper 42. For example, when a vent is provided at the rear end of the cylinder 41, the gas may be collected through such a vent.

  Instead of connecting to the first vacuum pump 31, the first exhaust passage 21 for exhausting the hopper exhaust gas discharged from the hopper 42 may be sucked by connecting a syringe, for example. You may suck with pressure. Further, the first exhaust path 21 may passively trap the discharged one as it is, instead of actively suctioning it by vacuum or decompression. For the suction path connected with a syringe, suction with a negative pressure transferred from the Venturi effect, or passively trapping the exhausted air as it is, the exhaust paths are interchanged between them, or vacuum Pumps may be connected or combined. Such an aspect of the exhaust path is the same for the other exhaust paths of the first exhaust path 21.

  The material 100 conveyed in the cylinder 41 by the screw 46 gradually generates gas due to heat during melt kneading. This gas is discharged from the cylinder 41 through a gas vent nozzle 43 provided on the upstream side of the nozzle 44 in the cylinder 41. The nozzle exhaust gas discharged from the gas vent nozzle 43 is exhausted through the second exhaust path 22 extending from the gas vent nozzle 43 to the second vacuum pump 32. Depending on the components of the gas discharged from the gas vent nozzle 43, solid deposits 101 may be generated in the gas vent nozzle 43 and the second exhaust path 22.

  The material 100 injected from the injection molding machine 40 and injected into the mold 50 and filled in the cavity 53 of the mold 50 generates gas by shearing heat generation when passing through the gate part and the thin part of the cavity. This gas is discharged from the cavity 53 via a mold vent 54 formed in the mold 50. The mold exhaust gas discharged from the mold vent 54 is exhausted through the third exhaust path 23 extending from the mold vent 54 to the third vacuum pump 33. Depending on the components of the gas discharged from the mold vent 54, solid deposits 101 may be generated in the mold vent 54 and the third exhaust path 23.

  The gas analyzer of the present embodiment corresponds to the injection molding machine 40 and the mold 50 of the present embodiment, and collects the hopper exhaust gas discharged from the hopper 42 of the injection molding machine 40. In addition, a hopper exhaust gas collection pipe 11 provided in the first exhaust passage 21 through which the hopper exhaust gas flows may be provided. The hopper exhaust gas collection pipe 11 may be provided at the tip of the first exhaust path 21 or may be provided in the middle of the first exhaust path 21 from the hopper 42 to the first vacuum pump 31. The hopper exhaust gas collection tube 11 may be, for example, a glass tube, or a glass tube filled with a substance that physically or chemically adsorbs gas. For example, a porous or non-woven fabric may be used as the physically adsorbing substance.

  The gas analyzer also includes a nozzle exhaust gas collecting tube 12 provided in the second exhaust passage 22 through which the nozzle exhaust gas flows in order to collect the nozzle exhaust gas discharged from the gas vent nozzle 43 of the injection molding machine 40. You may have. The nozzle exhaust gas collecting tube 12 may also be, for example, a glass tube, or a glass tube filled with a substance that physically or chemically adsorbs gas. For example, a porous or non-woven fabric may be used as the physically adsorbing substance.

  Further, the gas analyzer collects the mold exhaust gas provided in the third exhaust passage 23 through which the mold exhaust gas flows in order to collect the mold exhaust gas discharged from the mold vent 54 of the mold 50. A tube 13 may be included. The mold exhaust gas collection tube 13 may also be, for example, a glass tube, or may be a glass tube filled with a substance that physically or chemically adsorbs gas. For example, a porous or non-woven fabric may be used as the physically adsorbing substance.

  FIG. 2 is a diagram illustrating an example of a gas collection container. In the gas analyzer of the present embodiment, the hopper exhaust gas collection pipe 11 for collecting the hopper exhaust gas, the nozzle exhaust gas collection pipe 12 for collecting the nozzle exhaust gas, and the mold exhaust gas are used. Although the mold exhaust gas collecting pipe 13 for collecting is used, other gas collecting containers may be used instead.

  Examples of the gas collection container include a vinyl fluoride gas collection bag shown in FIG. 2 (a), an aluminum bag with a cock shown in FIG. 2 (b), and a glass gas collection container shown in FIG. 2 (c). Either may be used. For example, any one, plural, or all of the hopper exhaust gas collection pipe 11, the nozzle exhaust gas collection pipe 12 and the mold exhaust gas collection pipe 13 may be replaced with any of these gas collection containers. . These gas collection containers may also be filled with a substance that physically or chemically adsorbs gas, similarly to the gas collection tube.

  In addition, in FIG.2 (d), the aspect which attached the gas collection tube employ | adopted by this Embodiment to the syringe is shown. The gas collection tube may collect gas by adsorbing the gas to a porous substance filled in the tube by flowing the gas stored in the syringe. Compared with the gas collection bag of FIG. 2A, the aluminum bag of FIG. 2B, and the gas collection container of FIG. 2C, the gas collection tube can collect gas most efficiently. .

  The gas analyzer according to the present embodiment qualitatively and / or quantitatively analyzes the gas collected by the hopper exhaust gas collection pipe 11, the nozzle exhaust gas collection pipe 12, and the mold exhaust gas collection pipe 13. It has an analyzer. As the analyzer, a known gas analyzer can be used. For example, gas chromatography, ion chromatography, or a Fourier transform infrared spectrometer (FT-IR) may be used. .

  Furthermore, each of the first exhaust path 21, the second exhaust path 22, and the third exhaust path 23 is replaced with the hopper exhaust gas collection pipe 11, the nozzle exhaust gas collection pipe 12, and the mold exhaust gas collection pipe 13, respectively. It is also possible to use a method of directly connecting to the various analyzers. For example, by directly connecting an analytical instrument using a so-called gas detection tube to each exhaust passage, the generated gas can be measured immediately at the molding site. As a gas detection tube, what is marketed, for example from Gastec Corporation etc. can be used.

  In the injection molding machine 40 of the present embodiment, the gas vent nozzle 43 is provided on the upstream side of the nozzle 44 in order to discharge the nozzle exhaust gas. However, a shutoff having a gas exhaust path instead of the gas vent nozzle 43 is provided. A nozzle may be used.

  Further, in the mold 50 of the present embodiment, a porous piece is installed at an arbitrary location such as the cavity 53 of the mold 50 in place of collecting the gas discharged from the mold vent 54. Alternatively, the protruding pin itself may be made of a porous material, and the gas may be collected from the back surface. Further, the gas may be collected from the gap at any location where the mold is broken, such as a parting portion, a slide structure portion, and a slot. Further, in the hot runner manifold and valve, gas may be collected in the same manner as the gas vent nozzle and the shut-off nozzle.

  FIG. 3 is a flowchart showing a series of steps of the gas analysis method of the present embodiment. The gas analysis method of the present embodiment may be performed using the gas analyzer of the present embodiment. In the first step S <b> 1, a gas collection tube is attached to the injection molding machine 40 and the mold 50, and the gas is collected from the location where the gas is discharged in the injection molding machine 40 and the mold 50.

  In the present embodiment, in order to collect the hopper exhaust gas discharged from the hopper 42 of the injection molding machine 40, the first evacuation gas from the hopper 42 flows from the hopper 42 to the first vacuum pump 31. A hopper exhaust gas collecting pipe 11 is provided in the exhaust passage 21. The hopper exhaust gas collection pipe 11 collects components of hopper exhaust gas flowing through the first exhaust passage 21.

  Further, in order to collect the nozzle exhaust gas exhausted from the gas vent nozzle 43 of the injection molding machine 40, the second exhaust path from the gas vent nozzle 43 to the second vacuum pump 32 and through which the gas exhausted from the gas vent nozzle 43 flows. A nozzle exhaust gas collecting pipe 12 is provided at 22. The nozzle exhaust gas collecting pipe 12 collects the component of the nozzle exhaust gas flowing through the second exhaust path 22.

  Further, in order to collect the mold exhaust gas discharged from the mold vent 54 of the mold 50, the gas reaches the third vacuum pump 33 from the mold vent 54 and flows the gas discharged from the mold vent 54. 3 A mold exhaust gas collecting pipe 13 is provided in the exhaust path 23. The mold exhaust gas collection pipe 13 collects the components of the mold exhaust gas flowing through the third exhaust passage 23.

  In the next step S2, the gas collected from the location where the gas is discharged in the injection molding machine 40 and the mold 50 in step S1 is analyzed. A hopper exhaust gas collection pipe 11 provided in the first exhaust path 21, a nozzle exhaust gas collection pipe 12 provided in the second exhaust path 22, and a mold exhaust gas collection pipe provided in the third exhaust path 23. 13 is taken out, and the gas collected in each gas collection tube is analyzed qualitatively and / or quantitatively. As described above, when a gas analyzer such as a gas detector tube is directly attached to the gas exhaust passage without using a gas collector tube, the gas analyzer also collects the gas in step S1. Is called.

  Gas qualitative and / or quantitative analysis can be performed by gas chromatography, ion chromatography, dispersive infrared spectroscopy, Fourier transform infrared spectroscopy (FT-IR), near infrared spectroscopy (NIRS), thermal infrared spectroscopy. (TIR), UV-visible spectroscopy (UV-Vis), Raman spectroscopy, optical rotation analysis, fluorescence analysis, X-ray fluorescence analysis (XRF), nuclear magnetic resonance (NMR), electron spin resonance (ESR), mass spectrometry, etc. You may implement by an analysis means.

  Further, in step S2, the deposits 101 generated on the hopper 42, gas vent nozzle 43, and mold vent 54 of the injection molding machine 40 may be collected, and the deposits 101 may be analyzed. The deposit 101 may be qualitatively and / or quantitatively analyzed by a known analysis means such as FT-IR. By analyzing the deposit 101 together with the collected gas, components generated from the material 100 may be grasped as a whole and appropriate measures may be taken. For example, feedback may be given to material development.

  Here, the hopper exhaust gas collection tube 11, the nozzle exhaust gas collection tube 12 and the mold exhaust gas collection tube 13 are taken out, and the deposit 101 generated on the hopper 42, the gas vent nozzle 43 and the mold vent 54 is captured. Collecting may be carried out at each collection point at predetermined time intervals such as the first shot, the 100th shot, and the 200th shot of injection molding, or a series of shots of the manufacturing process. You may implement after a batch is complete | finished. In addition, the collected gas and the deposit 101 may be observed over time as to how the components change in time for each location as described above, and the material 100 undergoes a molding process. You may observe over time according to progress of a process whether what kind of component gas and deposit 101 are generated every time. Furthermore, you may observe the temporal change when the gas after collection is left for a certain period of time.

  In the gas analysis method and apparatus of the present embodiment, in the injection molding machine 40 and the mold 50, the hopper exhaust gas discharged from the hopper 42, the vent exhaust gas discharged from the gas vent nozzle 43, and the mold vent 54 are used. It collects and analyzes the exhaust gas discharged from the mold. In other words, the gas generated in the step of supplying the material 100 to the cylinder 41 in the hopper 42, the step of melting and shearing the material 100 in the nozzle 44, and the step of injecting and filling the material 100 in the mold 50 are analyzed. Yes.

  The gas analysis method and apparatus according to the present embodiment is not limited to the gas collection and analysis only in such steps of supply, melting and shearing, injection and filling, and the hopper 42 of the injection molding machine 40 is used. What is necessary is just to collect gas generated at two or more positions from the step of supplying the material 100 to the step of taking out the molded product from the mold 50 and analyze the collected gas. The two or more locations may be any location in a series of stages from the material 100 supply step to the molded product removal step.

  In such a series of steps, for example, a supply process in which the material 100 is charged from the hopper 42 to the cylinder 41, melting / compression / shearing that melts the material 100 by heating of the cylinder 41 and heat generation by compression / shearing by the screw 46. Process, conveying / kneading step of feeding the material 100 to the nozzle 44 side while kneading for homogenization of the material 100 in the molten state, the amount of material 100 necessary for injection for one shot is transferred to the tip of the cylinder 41 (upstream side of the nozzle 44) ) May be included. Here, the melting / compression / shearing process may be collectively referred to as a plasticizing process, or may be referred to as a plasticizing process including a supplying process to a measuring process.

  In a series of steps, an injection process in which the measured resin is injected into the mold 50 from the nozzle 44, until the gate portion of the mold 50 is solidified so that the resin filled in the mold 50 does not flow backward to the cylinder 41 side. A pressure holding process is also included in which the pressure is maintained in the direction in which the material 100 is injected. In the pressure-holding step, normally, when the cavity 53 of the mold 50 is filled by about 80 to 90% by injection, the filling is switched from filling by injection to filling by pressure, and the pressure is kept until it is solidified.

  In a series of steps, if the material 100 is solidified at the gate portion of the mold 50, no reverse flow will occur. However, if the entire molded product is not solidified, there is a risk of deformation at the time of mold release. A cooling step of holding in the mold 50 is also included. In order to promote solidification of the material 100 in the cooling step, the mold 50 is usually provided with a temperature control circuit for circulating cooling water. In general, at the same time as the cooling step, the cylinder 41 measures the next injection shot.

  The series of steps includes an extraction process in which the mold 50 is opened and the molded product is released by a mechanism such as a protruding pin. In the extraction process, the molded product may be released using a robot arm having a suction cup or a vacuum suction mechanism. Note that two or more positions where gas is collected and analyzed may be applied to a desired process other than the above in a series of steps from the material 100 supply process to the molded product extraction process. The method may be applied to two or more positions in a specific process.

(First modification)
FIG. 4 is a view showing a gas analyzer of a first modification. The gas analyzer of the first modification is configured to correspond to the injection molding machine 40 and the mold 50 of the first modification.

  In the injection molding machine 40 of the first modification, a shutter 45 is provided in a hopper 42 so that the inside of the cylinder 41 is maintained in a vacuum or nitrogen atmosphere, and the amount of the material 100 sent from the hopper 42 to the cylinder 41 is controlled by a feeder 49. This is different from the injection molding machine 40 of the present embodiment in that it is a starvation supply. Other configurations are the same as those of the injection molding machine 40 of the present embodiment. In the injection molding machine 40 and the mold 50 according to the first modification, elements corresponding to those of the injection molding machine 40 and the mold 50 according to the present embodiment are denoted by the same reference numerals to indicate the correspondence.

  In the injection molding machine 40, the pellet-shaped material 100 stored in the hopper 42 is fed by a feeder 49, and a predetermined amount is supplied to a cylinder 41 maintained in a vacuum or nitrogen atmosphere. The cylinder 41 is heated to a predetermined temperature by a band heater 47. The material 100 supplied to the cylinder 41 is kneaded by the screw 46 while being melted by heating by the band heater 47 and shearing heat generated by the rotation of the screw 46 while being conveyed by the rotating screw 46, and further, the nozzle 44 is advanced by the advancement of the screw 46. And injected into the mold 50. The material 100 injected into the mold 50 is filled in the cavity 53 of the mold 50 and solidified, and then taken out from the mold 50 as a molded product.

  In the hopper 42 of the injection molding machine 40, the hopper exhaust gas is collected by a hopper exhaust gas collecting unit 15 provided adjacent to the hopper 42. The nozzle exhaust gas discharged from the gas vent nozzle 43 is exhausted by the second exhaust path 22 that joins the air flow from the air supply source 36 at the junction 28. At the junction 28 with the air flow, the hopper exhaust gas may be sucked from the second exhaust passage 22 by the venturi effect. The same applies to the following.

  A radiator 19 is attached to the nozzle exhaust gas collecting pipe 12 provided in the second exhaust path 22 to cool the nozzle exhaust gas collecting pipe 12. In the mold 50, the third exhaust path 23 through which the mold exhaust gas discharged from the mold vent 54 flows is connected to the syringe 14, and the mold exhaust gas is collected in the syringe 14.

  In the injection molding machine 40 and the mold 50 of the first modified example, the collecting means for collecting gas in the gas detection device of the present embodiment is a hopper exhaust gas collecting unit 15 for collecting hopper exhaust gas, You may comprise with the nozzle exhaust gas collection pipe | tube 12 which collects nozzle exhaust gas, and the syringe 14 which collects mold exhaust gas. Moreover, you may apply well-known analysis techniques, such as a gas chromatography which is not shown in figure, to the analysis means which analyzes the collected gas qualitatively and / or quantitatively.

  In the injection molding machine 40 and the mold 50 according to the first modification, the step of collecting gas in step S1 in the gas detection method of the present embodiment collects the hopper exhaust gas by the hopper exhaust gas collector 15. Alternatively, the nozzle exhaust gas may be collected by the nozzle exhaust gas collecting tube 12 and the mold exhaust gas may be collected by the syringe 14. Further, the gas analysis process in step S2 is performed by using known analysis means such as gas chromatography for the gas collected by the hopper exhaust gas collection unit 15, the nozzle exhaust gas collection pipe 12, and the syringe 14. You may analyze qualitatively and / or quantitatively. Further, the deposits 101 generated in the hopper 42, the gas vent nozzle 43, the mold vent 54, and the like may be collected and analyzed qualitatively and / or quantitatively.

(Second modification)
FIG. 5 is a view showing a gas analyzer of a second modified example. The gas analyzer of the second modification is configured to correspond to the injection molding machine 40 and the mold 50 of the second modification.

  The injection molding machine 40 of the second modified example is a starvation supply in which the shutter 45 is provided in the hopper 42 and the amount of the material 100 sent from the hopper 42 to the cylinder 41 is controlled by the feeder 49, and the gas is discharged to the cylinder 41. This is different from the injection molding machine 40 of the present embodiment in that a cylinder vent 39 is provided. Other configurations are the same as those of the injection molding machine 40 of the present embodiment. In the injection molding machine 40 and the mold 50 according to the second modified example, elements corresponding to those of the injection molding machine 40 and the mold 50 according to the present embodiment are denoted by the same reference numerals to indicate the correspondence.

  In the injection molding machine 40, the pellet-shaped material 100 stored in the hopper 42 is fed by the feeder 49, and a predetermined amount is supplied to the cylinder 41. The cylinder 41 is heated to a predetermined temperature by a band heater 47. The material 100 supplied to the cylinder 41 is kneaded by the screw 46 while being melted by heating by the band heater 47 and shearing heat generated by the rotation of the screw 46 while being conveyed by the rotating screw 46, and further from the nozzle 44 by the advancement of the screw 46. It is injected and injected into the mold 50. The material 100 injected into the mold 50 is filled in the cavity 53 of the mold 50 and solidified, and then taken out from the mold 50 as a molded product.

  In the hopper 42 of the injection molding machine 40, the hopper exhaust gas is collected by a hopper exhaust gas collecting unit 15 provided adjacent to the hopper 42. The gas discharged from the cylinder vent 39 is collected by a cylinder exhaust gas collecting unit 16 (not shown). The nozzle exhaust gas discharged from the gas vent nozzle 43 is exhausted by the second exhaust path 22 that joins the air flow from the air supply source 36 at the junction 28. A radiator 19 is attached to the nozzle exhaust gas collecting pipe 12 provided in the second exhaust path 22 to cool the nozzle exhaust gas collecting pipe 12. In the mold 50, the third exhaust path 23 through which the mold exhaust gas discharged from the mold vent 54 flows is connected to the syringe 14, and the mold exhaust gas is collected in the syringe 14.

  In the injection molding machine 40 and the mold 50 of the second modified example, the collecting means for collecting gas in the gas detection device of the present embodiment is the hopper exhaust gas collecting unit 15 for collecting hopper exhaust gas, You may comprise by the cylinder exhaust gas collection part 16 which collects cylinder exhaust gas, the nozzle exhaust gas collection pipe | tube 12 which collects nozzle exhaust gas, and the syringe 14 which collects mold exhaust gas. Moreover, you may apply well-known analysis means, such as a gas chromatography which is not shown in figure, to the analysis means which analyzes the collected gas qualitatively and / or quantitatively.

  In the injection molding machine 40 and the mold 50 of the second modified example, the step of collecting gas in step S1 in the gas analysis method of the present embodiment collects the hopper exhaust gas by the hopper exhaust gas collector 15. Alternatively, the cylinder exhaust gas may be collected by the cylinder exhaust gas collection unit 16, the nozzle exhaust gas may be collected by the nozzle exhaust gas collection pipe 12, and the mold exhaust gas may be collected by the syringe 14. The gas analysis process in step S2 includes gas chromatography for the gas collected by the hopper exhaust gas collection unit 15, the cylinder exhaust gas collection unit 16, the nozzle exhaust gas collection tube 12, and the syringe 14, respectively. The analysis may be performed qualitatively and / or quantitatively using known analysis means. Further, the deposits 101 generated in the hopper 42, the cylinder vent 39, the gas vent nozzle 43, the mold vent 54, and the like may be collected and analyzed qualitatively and / or quantitatively.

  Instead of the cylinder vent 39 provided in the injection molding machine 40 of the second embodiment, the gas injection path used for injecting gas into the cylinder 41 by foam molding or gas assist molding is used as the gas suction path. Also good. This gas injection path may be one in which a tube is arranged at the center of the cylinder 41.

(Third Modification)
FIG. 6 is a view showing a gas analyzer of a third modified example. The gas analyzer of the third modification is configured to correspond to the injection molding machine 40 and the mold 50 of the third modification.

  The injection molding machine 40 of the third modified example is a pre-plastic type, and is disposed obliquely with respect to the first cylinder 61 so as to communicate with the first cylinder 61 extending in a substantially horizontal direction and the first cylinder 61 at the tip. The second cylinder 71 is provided.

  The first cylinder 61 includes a plunger 62 built in the first cylinder 61, a driving mechanism (not shown) that drives the plunger 62 back and forth, a band heater 63, and a gas from the first cylinder 61 on the upstream side of the nozzle 66. A gas vent nozzle 65 is provided for discharging the gas. In the gas vent nozzle 65, a plurality of donut-shaped disks 68 are stacked in the direction in which the first cylinder 61 extends to form a gap through which gas passes. The second cylinder 71 includes a screw 73 built in the second cylinder 71, a drive mechanism (not shown) that rotationally drives the screw 73, a hopper 72, a band heater 74, and a second cylinder that discharges gas from the second cylinder 71. A vent 75 is provided. The hopper 72 is provided with a shutter 78 for maintaining the inside of the cylinder 41 in a nitrogen atmosphere or the like, and a feeder 79 for feeding a predetermined amount of material 100 from the hopper 72 to the second cylinder 71.

  In the mold 50, the third exhaust path 23 through which the mold exhaust gas discharged from the mold vent 54 flows is connected to the syringe 14, and the mold exhaust gas is collected in the syringe 14. Since other configurations are the same as those of the mold 50 of the present embodiment, the correspondence is clarified using the same reference numerals.

  In the injection molding machine 40, the pellet-shaped material 100 stored in the hopper 72 provided in the second cylinder 71 is fed by the feeder 79, and a predetermined amount is supplied to the second cylinder 71. The second cylinder 71 is heated to a predetermined temperature by a band heater 74. The material 100 supplied to the second cylinder 71 is kneaded by the screw 73 while being melted by heating by the band heater 74 and shearing heat generated by the rotation of the screw 73 while being conveyed by the rotating screw 73, and through the communication hole 64, the first cylinder is mixed. 61. The first cylinder 61 is also heated to a predetermined temperature by the band heater 63. The molten material 100 in the first cylinder 61 is injected by the advancement of the plunger 62 and injected into the mold 50. The material 100 injected into the mold 50 is filled in the cavity 53 of the mold 50 and solidified, and then taken out from the mold 50 as a molded product.

  In the hopper 72 of the second cylinder 71, the hopper exhaust gas is collected by a hopper exhaust gas collection unit 15 provided adjacent to the hopper 72. The gas discharged from the second cylinder vent 75 of the second cylinder 71 is collected by a cylinder exhaust gas collecting unit 16 (not shown). The nozzle exhaust gas discharged from the gas vent nozzle 65 of the first cylinder 61 is exhausted by the second exhaust path 22 that joins the air flow from the air supply source 36 at the junction 28. A radiator 19 is attached to the nozzle exhaust gas collecting pipe 12 provided in the second exhaust path 22 to cool the nozzle exhaust gas collecting pipe 12. In the mold 50, the third exhaust path 23 through which the mold exhaust gas discharged from the mold vent 54 flows is connected to the syringe 14, and the mold exhaust gas is collected in the syringe 14.

  In the injection molding machine 40 and the mold 50 of the third modified example, the collecting means for collecting gas in the gas detection device of the present embodiment is a hopper exhaust gas collecting unit 15 for collecting hopper exhaust gas, You may comprise by the cylinder exhaust gas collection part 16 which collects cylinder exhaust gas, the nozzle exhaust gas collection pipe | tube 12 which collects nozzle exhaust gas, and the syringe 14 which collects mold exhaust gas. Moreover, you may apply well-known analysis means, such as a gas chromatography which is not shown in figure, to the analysis means which analyzes the collected gas qualitatively and / or quantitatively.

  In the injection molding machine 40 and the mold 50 according to the third modification, the step of collecting gas in step S1 in the gas detection method of the present embodiment collects the hopper exhaust gas by the hopper exhaust gas collector 15. Alternatively, the cylinder exhaust gas may be collected by the cylinder exhaust gas collection unit 16, the nozzle exhaust gas may be collected by the nozzle exhaust gas collection pipe 12, and the mold exhaust gas may be collected by the syringe 14. The gas analysis process in step S2 includes gas chromatography for the gas collected by the hopper exhaust gas collection unit 15, the cylinder exhaust gas collection unit 16, the nozzle exhaust gas collection tube 12, and the syringe 14, respectively. The analysis may be performed qualitatively and / or quantitatively using known analysis means. Further, the deposits 101 generated in the hopper 42, the cylinder vent 39, the gas vent nozzle 43, the mold vent 54, and the like may be analyzed qualitatively and / or quantitatively.

(Comparative example)
FIG. 7 is a diagram showing a gas analyzer of a comparative example. The gas analyzer of the comparative example is configured to correspond to the injection molding machine 40 of the present embodiment. In the comparative example, only the nozzle exhaust gas discharged from the gas vent nozzle 43 of the injection molding machine 40 is analyzed.

  The nozzle exhaust gas discharged from the gas vent nozzle 43 of the injection molding machine 40 is exhausted by the second exhaust path 22 that joins the air flow from the air supply source 36 at the junction 28. A radiator 19 is attached to the nozzle exhaust gas collecting pipe 12 provided in the second exhaust path 22 to cool the nozzle exhaust gas collecting pipe 12.

  In the gas analyzer of the comparative example, the collecting means for collecting the gas is constituted only by the nozzle exhaust gas collecting pipe 12 for collecting the nozzle exhaust gas. Moreover, you may apply well-known analysis means, such as a gas chromatography which is not shown in figure, to the analysis means which analyzes the collected gas qualitatively and / or quantitatively.

  In the gas analysis method of the comparative example, the nozzle exhaust gas is collected by the nozzle exhaust gas collecting pipe 12 in the gas collecting step of Step S1. Further, in the gas analysis process of step S2, the gas collected by the nozzle exhaust gas collecting pipe 12 may be qualitatively and / or quantitatively analyzed using a known analysis means such as gas chromatography. Good. Further, the deposits 101 generated by the gas vent nozzle 43 may be collected and analyzed qualitatively and / or quantitatively.

  In the comparative example, only the nozzle exhaust gas is analyzed in the injection molding process. Therefore, it is different from the configuration of this embodiment in which the entire process of injection molding is grasped as a whole, and the mechanism of gas generation is clarified in order to provide feedback to material development and prevent resin deterioration. ing.

  In the examples, the results of carrying out the gas analysis method and apparatus of the present embodiment will be described. The gas analysis method of the example corresponds to the injection molding machine 40 and the mold 50 of the present embodiment as shown in FIG.

(First embodiment)
In the first example, polyphenyl sulfide (PPS) filled with 30% by weight of glass fiber was used as the material 100. After the injection molding machine 40 and the mold 50 shown in FIG. 1 are operated at a cylinder temperature of 310 ° C. for a predetermined time, the hopper exhaust gas collection pipe 11, the nozzle exhaust gas collection pipe 12 and the metal mold of the gas analyzer are used. The mold exhaust gas collecting pipes 13 were respectively taken out. The gas collected in these collecting tubes was analyzed by gas chromatography.

  FIG. 8 is a graph showing the results of the gas analysis of the first example. A curve a in the figure corresponds to the hopper exhaust gas collected by the hopper exhaust gas collection pipe 11. A curve b corresponds to the nozzle exhaust gas collected by the nozzle exhaust gas collecting pipe 12. A curve c corresponds to the mold exhaust gas collected by the mold exhaust gas collection pipe 13. With regard to the dwell time (minutes) on the horizontal axis, except for noise that appeared near 0 minutes and around 13 minutes, hopper-generated gas and mold exhaust gas were detected, but nozzle exhaust gas was not detected.

  Therefore, when polyphenyl sulfide (PPS) filled with 30% by weight of glass fiber is used as the material 100, the material 100 is injected from the hopper 42 of the injection molding machine 40 into the cylinder 41 and melted, and the mold It became clear that gas was generated from each material 100 in the process of filling the material 100 melted into 50. On the other hand, in the process of injecting the material 100 from the nozzle 44, it became clear that no gas was generated from the material 100.

(Second embodiment)
In the second example, PPS filled with 30% by weight of glass fiber, polybutylene terephthalate (PBT) filled with 30% by weight of glass fiber, and PBT filled with 30% by weight of glass fiber to which a flame retardant was added were used as the material 100. . After operating the injection molding machine 40 and the mold 50 shown in FIG. 1 for a predetermined time, the hopper exhaust gas collection pipe 11, the nozzle exhaust gas collection pipe 12 and the mold exhaust gas collection pipe of the gas analyzer. Each 13 was removed. Here, in the injection molding machine 40, the material 100 was heated at a cylinder temperature of 260 ° C. during the PBT molding and at a cylinder temperature of 310 ° C. during the PPS molding. The gas collected in these collecting tubes was analyzed by gas chromatography.

  FIG. 9 is a graph showing the results of gas analysis of the second example. A curve a in the figure corresponds to the mold exhaust gas collected by the mold exhaust gas collection tube 13 for PBT filled with 30% by weight of the glass fiber of the material 100. The curve b corresponds to the nozzle exhaust gas collected by the nozzle exhaust gas collecting pipe 12 for the same material as the curve a. A curve c corresponds to the mold exhaust gas collected by the mold exhaust gas collecting pipe 13 for PBT filled with 30% by weight of glass fiber to which the flame retardant of the material 100 is added. The curve d corresponds to the nozzle exhaust gas collected by the nozzle exhaust gas collecting pipe 12 for the same material as the curve c. A curve e corresponds to the nozzle exhaust gas collected by the nozzle exhaust gas collecting pipe 12 for PPS filled with 30% by weight of the glass fiber of the material 100.

  As can be seen from the curves a and b, when the PBT filled with 30% by weight of glass fiber is the material 100, when the material 100 is molded at a cylinder temperature of 260 ° C., the material 100 is removed from the nozzle 44 of the injection molding machine 40. It has been clarified that gas is generated from the material 100 in the injection process and in the process of filling the mold 50 with the molten material 100, respectively.

  As can be seen from the curves c and d, when the PBT filled with 30% by weight of glass fiber added with a flame retardant is used as the material 100, the material 100 is molded at a cylinder temperature of 260 ° C. as in the curves a and b. Even in this case, a relatively large amount of gas is generated from the material 100 in the step of injecting the material 100 from the nozzle 44 of the injection molding machine 40 and the step of filling the mold 50 with the molten material 100, respectively. Became clear.

  As can be seen from the curve e, when PPS filled with 30% by weight of glass fiber is used as the material 100, when the material 100 is molded at a cylinder temperature of 310 ° C., the mold 50 is filled with the molten material 100. It was revealed that only a small amount of gas was generated from the material 100.

  Here, since most of the components of the gas generated from the material 100 are the material 100 decomposed by heat, the step of injecting the material 100 from the nozzle 44 of the injection molding machine 40 and the material melted in the mold 50 In any of the steps of filling 100, PBT filled with 30% by weight of glass fiber added with a flame retardant that generates a larger amount of gas than PBT filled with 30% by weight of glass fiber may be relatively weak against heat. . Therefore, it can be said that PBT filled with 30% by weight of glass fiber to which a flame retardant is added is weak against retention in the cylinder 41.

(Third embodiment)
In the third embodiment, as the material 100, PPS filled with 30% by weight of glass fiber including an elastomer and PPS filled with 30% by weight of glass fiber not containing an elastomer were used. After operating the injection molding machine 40 and the mold 50 shown in FIG. 1 for a predetermined time, the hopper exhaust gas collection pipe 11, the nozzle exhaust gas collection pipe 12 and the mold exhaust gas collection pipe of the gas analyzer. Each 13 was removed. Here, in the injection molding machine 40, the cylinder temperature was set to 310 ° C., and the material 100 was heated to a predetermined temperature. The gas collected in these gas collection tubes was analyzed by gas chromatography.

  FIG. 10 is a graph showing the results of gas analysis of the third example. A curve a in the figure corresponds to the nozzle exhaust gas collected by the nozzle exhaust gas collecting tube 12 for PPS filled with 30% by weight of glass fiber not containing an elastomer of the material 100. Curve b corresponds to the nozzle exhaust gas collected in the same way for PPS filled with 30% by weight of glass fiber containing the material 100 elastomer. Curve c is the mold exhaust gas collected by the mold exhaust gas collecting tube 13 for PPS filled with 30% by weight of the glass fiber of the material 100 and the curve d is the glass fiber containing the elastomer of the material 100. This corresponds to the mold exhaust gas collected in the same manner for 30 wt% PPS.

  Curves a and c corresponding to the nozzle exhaust gas and mold exhaust gas of PPS filled with 30% by weight of glass fiber not containing elastomer of material 100, respectively, nozzle discharge of PPS filled with 30% by weight of glass fiber containing elastomer of material 100 When the curves b and d corresponding to the gas and the mold exhaust gas are compared, it is clear that the PPS containing the elastomer tends to generate more gas. That is, it has been clarified that the elastomer has lower heat resistance than PPS, and that when PPS containing the elastomer is injection-molded, gas derived from the elastomer is easily generated.

  The amount of nozzle exhaust gas is almost the same regardless of the presence or absence of elastomer, whereas the amount of mold exhaust gas is significantly higher in PPS containing elastomer. It was confirmed that the tendency of the occurrence of the difference in tendency varies depending on the molding stage. That is, in the conventional analysis method in which the generated gas analysis is performed only at one stage of the molding process, for example, when analyzing the material 100 of the third embodiment, only the nozzle exhaust gas is evaluated. The difference in generated gas due to the presence or absence of elastomer could not be grasped, but the analysis method of this specification clearly shows that the difference in generation amount of mold exhaust gas can be grasped became.

(Fourth embodiment)
In the fourth embodiment, as the material 100, PPS added with 30% by weight of glass fiber and an elastomer, and PPS added with 33% by weight of glass fiber and calcium carbonate were used. After the injection molding machine 40 and the mold 50 shown in FIG. 1 were operated at a cylinder temperature of 310 ° C. for a predetermined time, the deposit 101 generated on the mold 50 was collected. Further, the number of shots until the mold vent 54 of the mold 50 was closed was measured. Further, the hopper exhaust gas collection pipe 11, the nozzle exhaust gas collection pipe 12 and the mold exhaust gas collection pipe 13 of the gas analyzer are respectively taken out, and the gas collected in these collection pipes is obtained by gas chromatography. analyzed.

  Table 1 is a graph showing the number of shots until the mold vent 54 of the mold 50 is closed. In the case where PPS in which 30% by weight of glass fiber and an elastomer were added to the material 100 was used, the mold vent 54 was blocked by 45 shots. In the case of using PPS in which glass fiber and calcium carbonate were added by 33% by weight to the material 100, the mold vent 54 was not blocked even after 1000 shots.

  FIG. 11 is a graph showing the weight of deposits generated on the mold. The bar a in the figure corresponds to the weight of the deposit 101 generated in the cavity 53 of the mold 50 when using PPS in which 30% by weight of glass fiber and an elastomer are added to the material 100. The bar b in the figure corresponds to the weight of the deposit 101 generated in the cavity 53 of the mold 50 when PPS obtained by adding 33% by weight of glass fiber and calcium carbonate to the material 100 is used.

  Here, a rod a in the case of using PPS with 30% glass fiber and elastomer added to the material 100, and a rod b in which 33% by weight of glass fiber and calcium carbonate are added to the material 100 and PPS is used. In contrast, the mold vent 54 was blocked earlier when PPS in which 33% by weight of glass fiber and calcium carbonate were added to the material 100 in which the mold vent 54 did not block after 1000 shots was used. As a result, the weight of the deposit 101 generated in the mold cavity 53 was slightly smaller than that in the case of using PPS in which 30% by weight of glass fiber and an elastomer were added to the material 100.

  Table 2 shows the injection molding machine 40 when the material 100 is made of PPS added with 30% by weight of glass fiber and an elastomer, and the case of PPS added with 33% by weight of glass fiber and calcium carbonate. After the mold 50 is operated at a cylinder temperature of 310 ° C. for a predetermined time, the hopper exhaust gas collected from the hopper exhaust gas collection pipe 11 and the nozzle exhaust gas collection pipe 12 are used. The weights of the nozzle exhaust gas discharged from the collected gas vent nozzle 43 and the mold exhaust gas discharged from the mold vent 54 collected by the mold exhaust gas collection pipe 13 are shown.

  Table 3 shows the hopper exhaust gas collection when the PPS added with 30% by weight of glass fiber and an elastomer and the PPS added with 33% by weight of glass fiber and calcium carbonate are used as the material 100. In the hopper exhaust gas exhausted from the hopper 42 collected in the pipe 11, the nozzle exhaust gas exhausted from the gas vent nozzle 43 collected in the nozzle exhaust gas collection pipe 12, and the mold exhaust gas collection pipe 13 The results of gas chromatography analysis of the mold exhaust gas discharged from the collected mold vent 54 are shown. Table 3 shows the weights of major components detected.

  As shown in Table 3, when PPS containing 30% by weight of glass fiber and an elastomer was used for the material 100, a significant weight was observed in the component 1-butanol. On the other hand, 1-butanol was not detected when PPS in which glass fiber and calcium carbonate were added by 33% by weight to the material 100 was used. From this, 1-butanol is considered to be a gas derived from an elastomer. Here, since 1-butanol has a spontaneous ignition temperature close to the molding temperature of PPS, when the material 100 is PPS to which an elastomer having a high content of 1-butanol is added, gas burning is likely to occur. Thus, it was estimated that the mold vent 54 of the mold 50 was quickly closed.

  In the fourth embodiment, the hopper exhaust discharged from the hopper 42 of the injection molding machine 40 in the hopper exhaust gas collection pipe 11, the nozzle exhaust gas collection pipe 12 and the mold exhaust gas collection pipe 13 of the gas analyzer. The mold vent by collecting the gas and the nozzle exhaust gas discharged from the gas vent nozzle 43 and the mold exhaust gas discharged from the mold vent 54 of the mold 50, respectively, and grasping the entire injection molding process. The cause of 54 obstructions could be clarified.

  In Table 2, the amount of hopper exhaust gas is smaller in the case of 30% by weight of glass fiber and PPS added with an elastomer. The hopper exhaust gas is a result of measuring the generated gas when the material 100 supplied to the cylinder 41 is melted, and the result is close to the conventional analysis method for measuring the generated gas when the pellet of the resin composition is heated. It is considered to be. In other words, in the case of the conventional analysis method, PPS added with 30% by weight of glass fiber and an elastomer produces less gas and is advantageous, but this result tends to be opposite to the tendency of vent clogging in Table 1. It has become.

  On the other hand, in Table 2, the amount of mold exhaust gas is larger in PPS to which 30% by weight of glass fiber and elastomer are added, and this agrees with the tendency of vent clogging in Table 1 to occur easily. That is, 30% by weight of glass fiber, which can be considered advantageous in the conventional analysis method, and PPS added with an elastomer are disadvantageous in terms of vent clogging due to the large amount of gas generated in the mold part in actual molding. It is shown. Therefore, it was confirmed that by using the analysis method of the present specification, there is a possibility that the cause of the problem that could not be grasped by the conventional analysis method of generated gas could be investigated.

  Further, in FIG. 11, the amount of the deposit 101 on the mold cavity 53 is slightly higher in the PPS to which 30% by weight of the glass fiber and the elastomer, which are likely to cause the clogging of the vent in Table 1, are added. It was. In addition, since the difference in the amount of the adhering substance 101 was not so large, in the fourth embodiment, the vent clogging due to the difference in the material 100 is likely to occur only by evaluating the adhering substance 101 to the mold cavity 53. However, in the analysis method of this specification for analyzing the generated gas at two or more positions, the deposit 101 is analyzed at the position where the generated gas is collected. Thus, it is considered that the ease of vent blockage can be grasped more accurately.

  The present invention can be used in a process of molding a resin using an injection molding machine and a mold.

11 hopper exhaust gas collection pipe 12 nozzle exhaust gas collection pipe 13 mold exhaust gas collection pipe 15 hopper exhaust gas collection section 16 cylinder exhaust gas collection section 40 injection molding machine 41 cylinder 42 hopper 43 gas vent nozzle 44 nozzle 46 Screw 50 Die 54 Die vent 100 Material 101 Deposit

Claims (7)

A method for analyzing gas generated when a resin is injection-molded using a molding machine and a mold,
In the molding machine and / or mold, a process of collecting the generated gas at each of two or more positions from the resin supply stage to the molding machine to the molded article removal stage from the mold;
A step of quantitatively and / or qualitatively analyzing the gas collected at each of the two or more positions.   The method according to claim 1, further comprising analyzing deposits at the two or more positions.   The method according to claim 1 or 2, wherein the analyzing step analyzes changes over time for the gases collected at the two or more positions. An analyzer for gas generated when a resin is injection-molded using a molding machine and a mold,
In the molding machine and / or mold, a collecting means for collecting the generated gas at two or more positions from the resin supply stage to the molding machine to the molded article removal stage from the mold. Including the device.   The apparatus according to claim 4, further comprising analysis means for quantitatively and / or qualitatively analyzing the gas respectively collected at the two or more positions by the collection means.   The apparatus according to claim 5, wherein the analyzing means is gas chromatography.   The apparatus according to any one of claims 4 to 6, wherein the collecting means is a porous trap.

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