JP6086677B2 - Method and apparatus for measuring volatile components - Google Patents

Description

  The present invention relates to a method or apparatus related to a technique of combining or suppressing / deleting odor components and odor components essential for verifying so-called enhancement effects and masking effects of fragrance components and odor components.

  There is a feeling that aroma components contained in foods, fruits, etc. have been almost analyzed by the progress of GCMS and analytical techniques. “High impact Odourants”, that is, the most effective odorous substances in the product have been discovered, such as 3 mercaptohexanol of wine, as a representative. The aim of the development is shifting to the point of what effect is produced when a plurality of odor components or odor components are combined.

  Combining the original fragrance component with another fragrance component, and adding a substance that does not have its fragrance alone but interacts with it, the effect of improving the flavor of the food, that is, the enhancement effect, and conversely, the bad odor It has been attracting attention for its masking effect.

  In the world of food, it is known that a small amount of instant coffee is added to packed barley tea to reproduce the scent of roasting in the world of food. In the world of flavor, for example, 5- (3Z -Hexenyl) -3-methyl 4.5-dihydro-2 (3H) -furanone cis isomer is added to and used in a fruity floral fragrance, giving a strong and diffusible top note, and a clean fresh It is known to enhance the feeling. On the other hand, the masking effect is a sharp scent of ester flavors such as pineapples for salt of sports drinks and the bitter taste of amino acids, and the residue obtained by collecting flower essential oil from petals such as rose, jasmine, lavender, etc. It is known that water extracts do not feel an unpleasant odor.

  These aroma components are substances derived from existing animals and plants that are naturally found in nature, and have been obtained by extraction from animals and plants. In recent years, the same compounds are produced by chemical synthesis in terms of cost. In addition, substances with a very similar structure that produce a stronger aroma have been obtained by chemical synthesis. In such a case (such as ethyl vanillin), the structure of the substance itself must be determined and grasped, and it is an important technique to separate, isolate, and analyze the structure of the entire sample components.

The applicant of the present application has made a proposal on a fractionation technique for constituent components of a sample (Patent Document 1).
The present invention is suitable for the separation of samples such as foods and fragrances, prevents contamination of the sample separated by chromatography, reliably separates the target sample, and determines the liquefaction time of the collected sample. It is a method device that can be confirmed visually and accurately check the timing of sorting.

  In the method apparatus, the sorting apparatus 3 is provided with a high-temperature oven 12 and a medium-low temperature oven 11, and the high-temperature oven 12 is provided with two manifolds 22 and 23 capable of branching a plurality of flow paths. Yes. The sample components are separated for each component by the separation column, and the carrier gas is dissolved and guided to the detector, and the chromatogram is displayed on the recorder by the detection signal from the detector.

  The sample component moves through the transfer line 2 while being separated from the GC for each component, and is introduced into the manifolds 22 and 23 of the sorting apparatus. Here, when a component having a short retention time for the preparative target component is confirmed in the chromatogram, it is introduced into the collection tube through the low-boiling component preparative route. Thereafter, the separated components are sequentially introduced into the respective collecting tubes.

Although this technique is a technique that enables very accurate component sorting, it does not consider any combination of these components.
In addition, as a method for evaluating the scent, there are AEDA method and Charm Analysis method as a method using GC-O. Such a technique is introduced as an example in GROSCH H Trends in food Sciences & Technology 1993, 68-73.

The AEDA method is a method for specifying the odor key component. The odor component of the object is collected, extracted with an organic solvent, and the extract is diluted in order with GC-O. The component that can detect the odor even when the dilution increases is the key to the fragrance. This is a technique for judging as a component.
These methods are methods for measuring whether the component contributes most to the whole of the fragrance components, and cannot be measured for complex odors and enhancement effects.

In order to confirm these enhancement effects and masking effects, it is important how to efficiently and reliably combine scents, and how to efficiently switch between combined scents without leaving another scent.
In these known technologies, there is no suggestion of a method for accurately and efficiently combining a scent as described above, or switching between a combined scent and another scent without leaving a scent.

In the investigation of the characteristics of odor components through the nose of GC-O, since it takes too much time to specify each component, continuous supply evaluation of the sample has been proposed.
However, the characteristics of the components of the sample are extremely subtle, and it is extremely difficult to identify the difference between the components if the sample and the sample are continuous.In addition, in the sample evaluation where specific components such as masking and enhancement interact with each other. It is a difficult task to distinguish changes.

In examining the characteristics of the state in which specific components such as masking and enhancement interact, the state of isolation between samples is an absolute requirement.
This is because a method and an apparatus for isolating a sample from each other are required.
In particular, it is important that the mixing and residual of the sample and its odor are strictly excluded when introducing, selecting, mixing and delivering the sample components, and switching between them.

Japanese Patent No. 4559799

  The present invention makes it very easy and reliable to determine what kind of aroma and odor can be obtained or adjusted by combining a plurality of odors or odor components, and what kind of effect will be generated thereby. It is an object of the present invention to solve the problem of how to construct a method and a simple apparatus therefor.

  The present invention for solving the above problems includes a step of supplying a carrier gas to a plurality of vials, a step of selecting the vials by operating an on-off valve communicating with the vials, and sending out the generated volatile components. A process of delivering the delivered volatile component to the selective mixing section, a cleaning process of constantly flowing makeup gas downstream of the inflow section in the selective mixing section, and a single or a plurality of receiving processes in the selective mixing section. A method for measuring a volatile component comprising: a step of selecting or mixing a passed volatile component; and a step of sending the volatile component to a measuring unit by means of a carrier gas and a makeup gas.

  The vial is opened and closed by a solenoid valve connected to a switch.

  In the selective mixing unit, the volatile component of one vial is selected by operating one electromagnetic valve connected to one switch.

  In the selective mixing unit, the volatile components in a plurality of vials connected to the plurality of electromagnetic valves are simultaneously passed and combined by operating a plurality of switches.

  In addition, when the operation of the on-off valve communicating with the vial is externally output as a trigger signal, another measurement signal converted into data is simultaneously synchronized and output.

  In addition, the volatile component measuring method is characterized by heating a vial for generating a volatile component from a sample and a desired portion of a discharge pipe, a selective mixing section, a pipe, and a branch pipe.

  Further, when the blank gas is caused to flow through the carrier gas flow path and the selective mixing unit, both are directly communicated and the carrier gas is caused to flow through the selective mixing unit.

  In addition, a large number of vials are installed in parallel in the carrier gas flow path via on-off valves, and the discharge pipe connected to each vial is connected to each corresponding port of the selective mixing unit, and the port is connected to the discharge port, A volatile component measuring device characterized in that a branch pipe branched from a makeup gas port is connected to a pipe communicating with each port.

  The selective mixing unit is a volatile component measuring device characterized in that a port, a discharge port and a makeup gas port are installed on a single plate, and a pipe and a branch pipe are formed between the ports. .

  The selective mixing section has two manifolds. One manifold has a flow path from the port connecting the discharge pipe from the vial to the discharge port, and the other manifold has a branch pipe for the makeup gas flow path. Each of the volatile component measuring devices is connected to a discharge port.

  The volatile component measuring device is characterized in that when an operation of an on-off valve communicating with a vial is externally output as a trigger signal, other measurement signals converted into data are simultaneously synchronized and output.

  In addition, the measuring device for volatile components is characterized in that a heating unit is provided for heating desired portions of the vial, the discharge pipe, the selective mixing section, the piping, and the branch pipe installed in parallel.

  Further, the volatile component measuring apparatus is characterized in that when the carrier gas flow path and the selective mixing section are communicated with each other, a flow path is provided for direct communication between the carrier gas flow path and the selective mixing section.

  According to the claimed invention, it is extremely easy to select a desired component from a plurality of presented volatile components, or to select a desired plurality of components and try a combination thereof. Therefore, a combination of a plurality of fragrance components and odor components can be easily and easily implemented, and a trial of component combinations for achieving an enhancement effect and a masking effect can be performed very easily.

Brief description of the main part of one embodiment of the present invention Same as above. Side view explanatory drawing Same as above Main part outline explanatory drawing of this invention other Example Operational explanatory drawing of the main part of the other embodiment of the present invention Same as above Main part outline explanatory drawing of this invention other Example One embodiment of the present invention Arrangement state explanatory diagram Experiment execution data diagram of Daidai essential oil in one embodiment of the present invention Same as above Same as above Same as above Same as above Same as above Experimental data of vanillin in one embodiment of the present invention Same as above Same as above Same as above Same as above Same as above

The present invention is an apparatus and method for achieving them.
In the figure, reference numeral 1 denotes a gas supply path that communicates with a gas supply source 2 such as a gas cylinder of a carrier gas, and includes a pressure regulator 3 and a pressure gauge 4. A vial 5 communicates with the gas supply path 1 and is connected to the flow passage 7 through an electromagnetic valve 6 as an on-off valve. A proportional control valve can also be used as the on-off valve. The desired number of vials 5, 7 in the figure, 5 a to 5 g, are accommodated in the vial tray 8 in parallel. Naturally, the solenoid valves 6a to 6g and the flow passages 7a to 7g also correspond to the vials 5a to 5g. If necessary, a plurality of parallel vial trays can be provided. In this case, the electromagnetic valve 6 and the flow passage 7 are also installed correspondingly.

In each flow passage 7, a flow meter 9, a speed controller 10, and a joint 11 with a check valve are provided between the electromagnetic valve 6 and the vial 5.
Each vial 5 is provided with a discharge pipe 12, and a joint 13 is installed in the discharge pipe 12 as desired.

The vial tray 8 is provided with a heating mechanism such as a cartridge heater so that the temperature can be adjusted (not shown). Generation of gas in the vial 5 and gasification are promoted by this heating mechanism.
Each discharge pipe 12 from each vial 5 is connected to each port 16 of the selective mixing unit 15 housed in the oven 14.
Each port 16a-16g is connected to the discharge port 18 via a respective pipe 17a-17g. The discharge port 18 is provided with a transfer line 19. In front of the transfer line 19, an olfactory test section (smell section), a detector and other measuring section 25 are installed. It is also possible to branch 18 outlets, connect a transfer line and a pipe having the same resistance as the transfer line in parallel, and connect other detections to the tip of the transfer line.

A makeup gas supply path 20 has one end connected to the gas supply source 2 and the other end connected to the makeup gas port 21 of the selective mixing unit 15. The makeup gas supply path 20 is provided with a pressure regulator 22 and a pressure gauge 23.
Branch pipes 24 a to 24 g communicating with the makeup gas port 21 are connected to pipes 17 a to 17 g from the ports 16 a to 16 g to the discharge port 18. This connection is preferably a connection to a portion close to each port 16 .

  It is recommended that a filter made of an inert material be attached to the discharge pipe 12 attached to the vial 5. As a result, it is possible to prevent a solid or particle-shaped sample from entering the pipe and being contaminated.

  By providing the joints 11 and 13 in the pipes before and after the vial 5, that is, in the flow passage 7 and the discharge pipe 12, sample replacement and pipe maintenance can be facilitated.

  When the temperature of the vial tray 8 is set by the setting unit, the vial tray 8 is heated to a constant temperature by the control mechanism. This heating mechanism promotes the generation of volatile components from the sample. In this embodiment, heating up to 100 ° C. is possible.

  The exhaust pipe 12 and the joint 13 of the vial 5 in contact with the sample should be installed inactive. This makes it possible to handle active samples such as metal complexes.

The vial 5 is housed in a vial tray 8 having a heating part, an inert gas injection pipe is opened in the gas phase part of the vial, a joint 11 with a check valve is provided in the gas supply path 1, and a discharge pipe 12 is provided in the discharge pipe 12. By applying an inactive treatment and providing an external heating unit, it is possible to prevent residual components and component loss and improve maintainability.
By using an inert capillary tube for the transfer line 19 and being heated to a high temperature, for example, 280 ° C. including the oven 14, volatile components can reach the selective mixing unit 15 to the measurement unit 25 in a short time without any component loss. Thus, it is possible to shorten the time from mixing to presentation and to prevent the remaining of components and the loss of components.

  Inactivation treatment can be handled by existing methods such as pouring inorganic polysilazane and organic polysilazane into a stainless steel tube and heating them to a temperature suitable for the reagent at 300 ° C or higher for about 5-15 hours, followed by vitrification treatment. is there. After the treatment, put the vitrified stainless steel tube into the reaction tube, add disilazane or alkoxylane, fill the reaction tube with inert gas, and heat at 300 ° C or higher for about 5-15 hours to finish the inactivation process. Do.

  The sample discharged from the vial 5 is guided to the selective mixing unit 15 in the high temperature oven 14. By keeping the discharge pipe 12 through which the sample passes at a high temperature, it is possible to prevent the sample from aggregating due to the cold spot.

  In this case, the exhaust pipe 12 from the vial 5 to the selective mixing unit 15 in the oven 14 uses a stainless steel pipe having good heat conduction. The discharge pipe 12 passes through a heating mechanism 26 in which a cartridge heater and a temperature sensor are attached to an aluminum heat block, and is heated. Furthermore, a Kanthal wire heater is wrapped directly around the tube, and the area around the heater is kept warm with a heat insulating material to ensure heating. For example, a highly boiling component vanillin (boiling point: 285 ° C.) is very effective, and a response that has not been measured in the past was confirmed. It goes without saying that the heating mechanism 26 can be configured to heat only the desired number of vials 5.

  By changing the flow meter 9 and the speed controller 10 to flow controllers, the flow rate can be set arbitrarily. Specifically, a proportional control valve is arranged upstream or downstream of the sensor, the sensor value is read by the control circuit, a control signal is sent to the valve according to the sensor value, and the sensor value matches the set value. Use an electronic flow control system that controls.

By using the system, for example, it is possible to create a program for changing the flow rate with time, and to verify how the change in the amount of components accompanying the change affects the olfactory test and other measurement results. Further, the flow controller can be changed to a pressure controller.
When the carrier gas pressure and makeup gas pressure are constant, the flow rate setting value may be limited. By changing the pressure regulators 3 and 22 and the pressure gauges 4 and 23 to pressure controllers, An arbitrary flow rate can be set.

The pressure controller 33, the flow controller 36, the electromagnetic valve 6 and each heating unit can be arbitrarily controlled from a PC (personal computer) 38 through a dedicated interface to control the flow and pressure, and the conditions are on the PC. Can be saved as a file. As an example, since the vaporized components accumulate in the head space of the vial at the start of supply / measurement and the component concentration is high, the carrier gas pressure and flow rate supplied to the vial are kept low, and control is performed to automatically increase after a few seconds. It is conceivable to keep the odor component concentration constant.
In addition, the flow rate can be controlled by the operation of a physical controller or the like that can be actually touched and linked with the senses.

  In forming the selective mixing unit 15, the port 16 and the makeup gas port 21 are provided on the plate 15A, and the pipes 17 and the branch pipes 24 are connected to each other by connecting parts such as connecting units and joints.

  The selection mixing unit 15 actually selects the vial 5 by selecting the electromagnetic valve 6 which is a switching valve, and the sample flows through the discharge pipe 12 and flows into one of the ports 16. Alternatively, by selecting several vials 5, they are mixed at the discharge port 18 by flowing them simultaneously, and the transfer line 19 is flowed. Since the selection is performed by the electromagnetic valve 6, it is preferable to call it a mixing operation unit. However, since the sample actually flows, is selected and mixed, the selection mixing unit is used.

Reference numeral 29 denotes a switch, which is connected to a main body 27 housing the oven 14 by a cable 28. The flow path of the sample storage vial 5 is switched by performing the switching operation of the electromagnetic valve 6 described above. By pressing the changeover switch 29, the corresponding electromagnetic valve 6 is opened, and the carrier gas can be allowed to flow through the corresponding flow passage 7.
An electromagnetic valve 62 for pressure discharge is attached to the manifold 61 of the electromagnetic valve 6. When the power is turned off, the solenoid valve 62 for discharging pressure is opened as shown in black in FIG. 6, and the pressure of the entire system can be lowered to atmospheric pressure. The open / close state of the solenoid valve when the power is on and supplying / measuring is as shown in FIG. In this figure, a 5d vial is selected.

  As for the pressing time (time) of the switch 29, a trigger signal is output to the outside at the time of switching for each switch, and interlocked with other devices. In addition, by associating the measurement result of the measurement system of the present application with the switch switching signal of the sample and the generated gas, it is possible to easily confirm the state of smelling the sample gas. By installing the switch 29 so as not to be seen by the examiner, errors in the olfactory test due to preconception can be eliminated.

It is recommended that a computer (not shown) is connected to the main body 27 in the same manner as the switch 29 is connected via the cable 28 and these data are recorded and recorded.
At the same time, measurement values such as human physiological signals, other sensor values such as temperature, humidity, and odor sensor values are recorded and recorded. As a result, trigger signals for all external outputs such as vial switching operations are also converted into data, and transmitted and stored in the data logger so that all signals can be synchronized.
Therefore, it is possible to monitor and analyze the timing relationship with the mixing or removal of fragrance by selecting the vial in detail.

Next, the operation will be described.
The sample can be basically any material that can be stored in the sample vial. If it is a liquid fragrance component, the required amount is measured with a syringe or the like and placed in a vial and capped. In the case of solid materials (for example, fragrant wood, building materials), the weight is measured and placed in a vial. Preparative components separated and collected from the GC can also be introduced into the vial, so that it is possible to install a sample with excellent quantitativeness.

  While checking the pressure of the carrier gas with the pressure gauge 4, the pressure regulator 3 is turned to adjust the pressure to a predetermined pressure. The regulated carrier gas is sent to the manifold 61 of the electromagnetic valve 6. Seven solenoid valves 6 a to 6 g are attached to the manifold 61 of the solenoid valve 6. When a predetermined voltage is applied to the electromagnetic valve 6 corresponding to the vial 5 containing the sample to be generated, the electromagnetic valve 6 opens and gas flows.

A flow meter 9 and a speed controller 10 are attached to the downstream side of the electromagnetic valve 6 for each flow passage 7. Therefore, the flow rate of the carrier gas discharged from the electromagnetic valve 6 is adjusted by the speed controller 10 while checking the flow meter 9. The adjusted carrier gas is sent to the vial 5.
By disposing the solenoid valve 6 upstream of the sample, it is possible to prevent contamination, contamination, and sample adsorption from the solenoid valve 6.
One of the vials 5 is a blank gas containing no sample. Blank gas can serve as a reset function during an olfactory test. When the sample gas from the vial 5 is not flowing, the inside of the discharge pipe 12 can be kept clean by flowing the blank gas. In the case of blank gas, a method in which the carrier gas directly communicates with the selective mixing unit 15 without installing the vial 5 is also possible.

When one kind of sample gas is selected, the carrier gas is sent to the desired vial 5 through the desired electromagnetic valve 6 by pushing one button by the switch 29, and the generated or existing sample gas is discharged. This is sent to the selective mixing unit 15 via the pipe 12.
The sample gas does not enter the pipe 17 from the one port 16. At this time, makeup gas from the branch pipe 24 connected to the pipe 17 is constantly sent. The carrier gas is sent to the transfer line 19 from the discharge port 18 through the pipe 17 together with the makeup gas at the set pressure difference between the sample gas and the makeup gas.

  When two or more types of sample gases are selected and mixed, by pressing the desired number of switches 29 at the same time, several types of sample gases are sent to the selective mixing unit 15 and similarly mixed in the vicinity of the discharge port 18, It is sent to the transfer line 19.

In the formation of the selective mixing unit 15, an embodiment having the following configuration will be described.
As shown in FIGS. 2 to 4, grooves corresponding to the pipe 17 and the branch pipe 24 are formed on several plates, for example, five plates, and these plates 15A can be configured as a single plate by diffusion bonding. I can do it.
By configuring the selective mixing unit 15 on the plate 15A, the selective mixing unit 15 can be formed compactly and the heater capacity can be reduced.

Another embodiment of forming the selective mixing unit 15 will be described with reference to FIG.
The oven 14 that heats the sample sent from the vial 5 is provided with two manifolds 30 and 31 that can mix a plurality of flow paths constituting the selective mixing unit 15. One is configured as a 15-way manifold 31, and the other is configured as a 7-way manifold 30.
The seven-way manifold 30 is composed of one make-up gas port 21 and six outlets for extending a branch pipe 24 that branches the make-up gas into six directions.

  A pressure regulator 22 and a pressure gauge 23 are installed in the makeup gas supply path 20. While confirming the pressure with the pressure gauge 23, the pressure is adjusted with the pressure regulator 22. The adjusted makeup gas is connected to the three-way union 32. One of the three-way unions 32 is connected to the makeup gas port 21 of the seven-way manifold 30, and the other is connected to the makeup gas port 21 of the 15-way manifold 31.

  In the case of one type, the sample gas introduced into the 15-way manifold 31 through the discharge pipe 12 is introduced into the transfer line 19 from the discharge port 18 of the manifold 31 as one type of gas. When several kinds of sample gases are introduced from several kinds of vials 5 through the electromagnetic valves 6 and 6 by the switch 29, several kinds of sample gases are joined and mixed in the manifold 31. The mixed composite component gas is introduced into the transfer line 19 from the discharge port 18 of the manifold 31.

  In the manifold 31, a discharge port 18 communicating with the transfer line 19 and a branch pipe 24 extending from the manifold 30 are connected to a pipe 17 formed in communication with the discharge pipe 12 via the port 16.

  By installing the make-up gas pressure gauge 23 and the pressure regulator 22, the pressure is adjusted by the pressure regulator 22 while checking the pressure gauge 23. The gas whose pressure is adjusted is connected to the three-way union 32.

  Seven exhaust pipes 12 connected from the vial 5 are attached to the 15-way manifold 31. In the case of a single sample gas, only one type of sample gas passes through the manifold 31. When a plurality of sample gases are introduced into the manifold 31, the sample gases introduced in the manifold 31 are mixed and the mixed gas is discharged from the manifold 31.

  The makeup gas branch pipe 24 is disposed in the pipe 17 between the gas port 16 and the discharge port 18 of the 15-way manifold 31. For this reason, the piping 17 downstream of the port 16 is always pressurized from the makeup gas, so that the exhaust pipe 12 that does not flow the sample gas is in a state where the sample gas is covered with the makeup gas. At that time, the sample gas downstream from the makeup gas merge is always washed by the makeup gas. When flowing the sample gas, the sample gas and the make-up gas are merged and led to the discharge port 18 point.

  By always installing make-up gas, it was possible to prevent sample gas from leaking and remaining, and to switch the sample gas flow path with good sharpness.

  The gas discharged from the 15-way manifold 31 is introduced into the transfer line 19. The transfer line 19 is provided with a heating mechanism, and the sample can be guided to a measuring unit 25 such as an olfactory test unit without aggregating the sample.

A rapid and accurate response confirmation experiment for a sample using an olfactory test unit as a measurement unit in the present invention is shown below.
More specifically, the ON / OFF of the on-off valve in the flow path and the synchronization with the physiological index are confirmed and the temperature control effect is confirmed.
Explanation of FIGS. 10 to 21: The solid line of the rectangular waveform is ON / OFF of the flow path, and the broken line is ON / OFF of the hand switch (self-made) pressed when the odor is felt. When the on-off valve is turned on and opened, the solid line of the rectangular waveform rises, maintains the rise while it is on, and returns to the original 0 position when it is turned off. Similarly, the hand switch rises in the ON state when it feels odor, and returns to the original position because it turns OFF when it feels no. That is, it can be seen that the closer the rising of the solid line and the rising of the broken line are, the sooner the odor is felt when the flow path is opened.
10, 13, 16, and 19: No temperature control of the vial 5, the discharge pipe 12, the oven 14, and the transfer line 19 (room temperature)
11, 14, 17, and 20: Only vial 5 is heated to 60 ° C., and temperature of discharge pipe 12, oven 14, and transfer line 19 is not adjusted (room temperature).
12, 15, 18, and 21: Vials 5, oven 14, and transfer line 19 are all heated, 60 ° C, 280 ° C, and 280 ° C, respectively.
Sample Daidai Essential Oil
Carrier gas 100ml / min N2
Humidity control of sample part Aluminum block 60 ° C Heating line 180 ° C
Oven transfer line 280 ℃
The wavy solid line in the figure is a peripheral blood flow diagram in which fingertip blood flow is simultaneously recorded using a laser blood flow meter ALF21D.
The data is illustrated in FIGS.

It shows that the operation response of the hand switch is accelerated with respect to the supply of the die-dye, the termination of the olfactory response is accelerated by temperature control, and the situation where the scent of the fragrance is improved is synchronized and extracted as a signal. .
10 to 12 show the results of the same person, and FIGS. 13 to 15 show the results of the same person.
Daidai essential oil is a sample that generates mixed volatile component gas from low boiling point to high boiling point, and a sample that is assumed to contain a substance that is liable to be lost due to heating or metal contact.
・ If both the vial tray 8+ line (the oven 14 and the transfer line 19 downstream from the vial 5) are not heated, the cutting is bad and the odor is felt even when the flow path is closed. This is due to a component having a high boiling point and a low odor threshold (smell even in a small amount) in the mixed component.
・ Also, no odor alteration was observed during high-temperature heating of each line. This is considered to be the effect of inert gas, inert treatment of the flow path, and adoption of a capillary flow path (retention time at high temperature is extremely short).
Daidai Essential Oil: The olfactory response was accelerated by about 1 second by adjusting the temperature of the sample part with respect to the sample part OFF / other line OFF. Furthermore, by controlling the temperature of the other lines, the odor was cut off (end of olfactory response) after the ventilation to the sample part was blocked.

In the same manner as in Example 3, an experiment was conducted on a 10% ethanol solution of vanillin.
Results FIGS. 16 to 18 are results by the same person, and FIGS. 19 to 21 are results by another same person.
Since vanillin is a high boiling point (285 ° C.) component, it is a sample that is significantly affected by adsorption loss in the flow path due to cold spots.
-The vial tray 8+ line (the discharge pipe 12, the oven 14, and the transfer line 19 on the downstream side of the vial 5) is heated, and finally the odor is felt.
In the case of vanillin, the fingertip blood flow rate decreased due to heating in both the vial 5 and the subsequent lines because it smelled a little, and it may have been because of the sympathetic nerve superiority to try hard to smell. Physiological index (fingertip blood flow) can be considered as an example that demonstrates that measurement can be performed synchronously.
Vanillin 10% in EtOH: It was found that by applying temperature control to the sample part and all other lines, an olfactory response of vanillin, which is a high-boiling component, can be obtained, and there is no odor residue.

DESCRIPTION OF SYMBOLS 1 Gas supply path 2 Gas supply source 3 Pressure regulator 4 Pressure gauge 5 Vial 6 Switching valve 7 Flow path 8 Vial tray 9 Flowmeter 10 Speed controller 11 Joint 12 Discharge pipe 13 Joint 14 Oven 15 Selection mixing part 16 Port 17 Piping 18 Discharge Port 19 Transfer line 20 Makeup gas supply path 21 Makeup gas port 22 Pressure regulator 23 Pressure gauge 24 Branch pipe 25 Measuring unit 26 Heating mechanism 27 Main body 28 Cable 29 Switch 30 Manifold 31 Manifold 32 Three-way union 33 Pressure controller 34 Valve 35 Pressure sensor 36 Flow controller 37 Flow sensor 38 Personal computer

Claims (13)

A step of supplying a carrier gas to a plurality of vials; a step of selecting the vials by operating an on-off valve installed upstream of the vials and communicating with the vials; and sending out generated volatile components; A step of delivering components to the selective mixing unit, a step of constantly flowing makeup gas downstream of the inflow unit in the selective mixing unit to pressurize the downstream side of the inflow unit, and a single or a plurality of deliveries in the selective mixing unit A method for measuring a volatile component comprising: a step of selecting or mixing the volatile component, and a step of sending the volatile component to a measuring unit by means of a carrier gas and a makeup gas.   2. The method for measuring a volatile component according to claim 1, wherein the vial is opened and closed by an electromagnetic valve connected to a switch.   The method for measuring a volatile component according to claim 1 or 2, wherein in the selective mixing unit, the volatile component in one vial is selected by operating one electromagnetic valve linked to one switch.   The volatile property according to any one of claims 1 to 3, wherein in the selective mixing unit, the volatile components of a plurality of vials connected to a plurality of solenoid valves are simultaneously passed and combined by operating a plurality of switches. Ingredient measurement method.   The volatilization according to any one of claims 1 to 4, wherein when the operation of the on-off valve communicating with the vial is externally output as a trigger signal, other measurement signals converted into data are simultaneously synchronized and output. How to measure sex components.   The volatile component according to any one of claims 1 to 5, wherein a vial for generating a volatile component from a sample and a desired portion of a discharge pipe, a selective mixing section, a pipe, and a branch pipe are heated. Measurement method.   The volatilization according to any one of claims 1 to 6, wherein when the blank gas is caused to flow through the carrier gas flow path and the selective mixing unit, both are directly communicated to flow the carrier gas through the selective mixing unit. How to measure sex components.   A number of vials are installed in parallel in the carrier gas flow path via on-off valves, and the discharge pipes connected to the vials are connected to the corresponding ports of the selective mixing unit, and the ports are connected to the discharge ports. A measuring device for volatile components, wherein a branch pipe branched from a makeup gas port is connected to a pipe communicating with the pipe.   The volatile component according to claim 8, wherein the selective mixing unit has a port, a discharge port, and a makeup gas port installed on a single plate and forms a pipe and a branch pipe between the ports. Measuring device.   The selective mixing unit has two manifolds, one of which discharges the flow path from the port connecting the discharge pipe from the vial to the discharge port, and the other manifold discharges the branch pipe of the makeup gas flow path. The volatile component measuring device according to claim 8, wherein the volatile component measuring device is connected to a port.   The volatilization according to any one of claims 8 to 10, wherein when the operation of the on-off valve communicating with the vial is externally output as a trigger signal, other measurement signals converted into data are simultaneously synchronized and output. Sex component measuring device.  The volatile component according to any one of claims 8 to 11, further comprising a heating unit that heats each desired portion of the vial, the discharge pipe, the selective mixing unit, the pipe, and the branch pipe installed in parallel. Measuring device.   The volatilization according to any one of claims 8 to 12, wherein when the carrier gas channel and the selective mixing unit are communicated with each other, a channel is provided to directly connect the carrier gas channel and the selective mixing unit to flow the carrier gas to the selective mixing unit. Sex component measuring device.

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