JP2001153876A - Sample introducing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sample introducing device capable of measuring precisely a sample quantity introduced into a medium even when the quantity is a micro- quantity, and capable of compactifying the device. SOLUTION: This sample introducing device is formed by layering a base plate A 301, a base plate B 302, a base plate C 303 and a base plate D 304 to integrate valves and piping using them. An actuator A 316 and an actuator B 317 are sandwiched to be joined between the plate B 302 and the plate C 303 provided with diaphragm structure to drive a sample determination device in a saved space. A fixed amount of the sample of the micro-quantity is introduced when a flow passage A 313 is formed very finely by refining work.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for quantifying a small amount of sample with high accuracy when quantifying a fixed amount of sample in a chemical analyzer.

[0002]

2. Description of the Related Art As a method for measuring the amount of a specific component contained in a measurement sample, a method such as liquid chromatography or flow injection analysis is generally used. In either case: (1) A fixed amount of sample is introduced into a continuously flowing medium.

(2) The introduced sample is transferred to a column or a reaction tank for separation by moving the medium, where the sample is chemically and physically processed. (3) The sample after the treatment or the product generated after the treatment is transferred to a column or a detector connected to the outlet of the reaction tank. The detector can measure the amount of the substance contained in the original sample from the output electric signal. The measurement is performed according to the following procedure.

In such a measuring method, a sample introduction device for introducing a fixed amount of sample into a continuously flowing medium is required in the process (1). As an example of the device, as shown in FIG.
Three-way valves (3-way valve 1: 101, 3-way valve 2: 102,3
The three-way valve 3: 103 and the three-way valve 4: 104) are combined, and after the sample is introduced into the measuring pipe,
By switching the four three-way valves simultaneously, the sample filled in the metering pipe is introduced into the medium. In addition, as shown in FIG.
1 and the like have been widely and generally used.

[0005]

When the amount of a specific component contained in a sample is measured by liquid chromatography or flow injection analysis, the accuracy is significantly higher than the accuracy of the amount of the sample introduced into the medium. Dependent. Further, in some cases, it is assumed that a sufficient amount of sample cannot be obtained. Therefore, it is desirable to be able to cope with a small amount of sample introduced into the medium.

However, in the case of a conventional sample introduction device in which four three-way valves are combined, the four three-way valves are connected to each other by a pipe, so that the dead volume at the pipe connection becomes large.
There is a problem that the accuracy of the sample introduced into the medium is reduced. In addition, the measurement pipe has a large internal volume, and a sample amount larger than the internal volume of the measurement pipe is required. Therefore, it is very difficult to measure a sample of 1 μL or less with such a sample introduction device. . Furthermore, if the sample introduction is to be performed automatically,
Four actuators were required to simultaneously drive the direction valves, and it was difficult to reduce the size of the device.

On the other hand, in the case of a sample introduction device using a six-way valve, the volume of the pipe portion is reduced, so that the sample amount is smaller and the measurement accuracy is improved. Is manufactured by machining,
Since it is necessary to connect six pipes from the outside to the sample introduction device, there still remains a problem that it is difficult to reduce the size of the device.

[0008]

Accordingly, the sample introduction device of the present invention has the following structure to solve the above-mentioned problems. First, the sample introduction device of the present invention has a structure in which four substrates are stacked, and these are used to integrally form a valve and a pipe. Thereby, the size of the apparatus can be reduced as compared with a conventional sample introduction apparatus configured by combining mechanical parts. Further, by applying a fine processing technology such as a photolithography technology when processing the substrate, the volume of the entire piping portion can be reduced to 1 μL or less. Furthermore, by integrally forming the pipe and the valve, the number of connecting points of the pipe is minimized, and the ineffective volume at the connecting portion can be reduced.

The movable part (diaphragm) is provided on two of the four laminated substrates by thinning a part of the substrate, and the valve is operated by deforming the diaphragm with an actuator. . A total of four diaphragms are formed in two places on each substrate,
An actuator is sandwiched between two substrates, and two of the four diaphragms are simultaneously driven by one actuator. For this reason, four valves can be driven by two actuators, and the number of actuators required can be reduced as compared with the conventional sample introduction device. This is also advantageous for miniaturization of the device. .

[0010]

Embodiments of the present invention will be described below with reference to the drawings. (Embodiment Mode 1) In this embodiment mode, a glass substrate is used as a substrate A and a substrate D, and a substrate B is used to form a diaphragm.
An example in which a silicon substrate is used as the substrate C will be described.

FIG. 1 is a sectional view showing an example of the structure of the sample introduction device of the present invention, and FIG. 4 is a plan view. The substrate A301 is provided with a fluid A inlet 305 and a fluid A outlet 306,
By being joined to the substrate B302, the flow path A inlet 30
A flow path A 313 connecting the fluid A 5 and the fluid A outlet 306 is formed. On the substrate B302, a valve A309 and a valve B310 are formed, and the fluid A inlet 30
5 and the fluid A outlet 306 can be opened and closed.

Similarly, a fluid B inlet 30 is provided in the substrate D304.
7 and a fluid B outlet 308 are provided and joined to the substrate C303. A valve C311 and a valve D312 are formed on the substrate C303, and can open and close the fluid B inlet 307 and the fluid B outlet 308, respectively. Each valve is composed of a diaphragm formed by etching a part of the silicon substrate, a packing placed on the diaphragm, and an actuator for deforming the diaphragm, and the deformation of the diaphragm when a voltage is applied to the actuator Thus, the packing functions as a valve by opening and closing the fluid inlet / outlet.

The substrate B302 and the substrate C303 are each provided with an actuator A31 at two diaphragm positions.
6 and the actuator B 317 are bonded to each other with a spacer 318 interposed therebetween. When a voltage is applied to the actuator A 316, the open / close state of the valve B 310 and the valve D 312 is simultaneously switched. The actuator used here is
A unimorph type piezoelectric element, a laminated type piezoelectric element, an electrostatic actuator, a shape memory alloy array, and the like can be selected, but are not limited thereto. In the present embodiment, the actuator A316 and the actuator B3
A unimorph type piezoelectric element is used for the element 17, and in this case, the direction of displacement of the diaphragm can be changed depending on the polarity of the applied voltage.

Further, the fluid B inlet 307 and the channel A 313
B314 connecting the fluid, the fluid B outlet 308, and the flow path A
A flow path C315 connecting 313 is formed to penetrate the substrate B302 and the substrate C303, and the valve C311
When the valve D312 is in the open state, the fluid B inlet 307 leads to the flow path B314, the flow path A313, and the flow path C315.
, A flow path reaching the fluid B outlet 308 is formed.

Next, the operation of the sample introduction device of the present embodiment will be described. First, under normal conditions, the actuator A
No voltage is applied to the actuator 316 and the actuator B 317, and as shown in FIG.
The valve B310 is open, and the valve C311 and the valve D312 are closed. In this case, the fluid A flows from the fluid A inlet 305 through the flow path A313,
Although it is in a state of flowing to the fluid A outlet 306, the fluid B cannot enter the sample introduction device.

At the time of sample introduction, the actuator A316
5 and a voltage is applied to the actuator B317, and FIG.
As shown in (b), valve A309 and valve B3
Reference numeral 10 indicates a closed state, and the valve C311 and the valve D312 will be in an open state. At this time, at the same time as the flow of the fluid A is obstructed, the fluid B flows from the fluid B inlet 307 through the flow path B314, the flow path A313, and the flow path C315 to the fluid B outlet 30.
Start flowing from 8. In this state, a sufficient amount of the fluid B is introduced to fill the flow path B314, the flow path A313, and the flow path C315.

Finally, when the voltage applied to the actuator A 316 and the actuator B 317 is turned off, the valve A 309 is again turned on as shown in FIG.
And the valve B310 is opened, the valve C311 and the valve D312 are closed, and the fluid A
05 to the fluid A outlet 306 via the flow path A 313. At this time, the fluid B stored in the channel A 313 is taken out from the fluid A outlet 306. That is, the amount of the fluid B (sample) corresponding to the volume of the flow path A 313 is determined and introduced into the flow of the fluid A. When the flow path A313 is formed very finely by using anisotropic etching of silicon or the like, even a very small amount of sample can be introduced accurately. (Embodiment 2) In this embodiment, a silicon substrate is used as the substrate B302 and the substrate C303, and a sample of the present invention is used when a method shown in FIG. 6 is used as a method of forming a valve diaphragm on the substrate. An example of a method for manufacturing the introduction device will be described.

First, a silicon substrate 601 shown in FIG. 6 is thermally oxidized to form an oxide film 602 having a thickness of 0.3 μm. Next, after the oxide film is processed into a necessary pattern by a photolithography method, tetramethylammonium hydroxide (TMA) is used with the oxide film as a mask.
Using H), anisotropic etching of the silicon substrate 601 is performed. After that, the oxide film is removed with buffered hydrofluoric acid.

Next, the substrates A301 and B302, and the substrates C303 and D304 are bonded. In the present embodiment, an anodic bonding method is used as a bonding means, and a substrate A301 made of a glass material is replaced with a substrate B3 made of a silicon material.
02 were brought into close contact with each other and heated to 500 ° C., and a voltage of 500 V was applied between them to perform the bonding. Further, the substrate C303 and the substrate D304 can be similarly bonded.

Next, the substrate B3 is coated with an epoxy adhesive.
02 and the substrate C303, and the actuator is sandwiched between them to join them. Substrate A301, Substrate B3
02, the substrate C303, and the substrate D304, the channel B314 and the channel C315 are processed, respectively. Although the sand blast processing is used for the hole processing, it is also possible to use a processing method such as excimer laser processing or ultrasonic processing.

Subsequently, the fluid A inlet 3 of the substrate A301
The packing material is filled from 05, and then the packing material is cured to form a packing. An elastic material such as a silicone resin or an epoxy resin is used as a packing material, and as a means for curing, a method of leaving at room temperature, heating to a curing temperature, or irradiating ultraviolet rays can be used. For example, when using an ultraviolet curable resin, the packing material is filled, the packing material is cured by an ultraviolet lamp using a mask having a pattern according to the shape of the packing, and the packing is formed. It can be removed by using. Further, by using an ultraviolet laser light source and a scanner mirror to draw the filled packing material with an ultraviolet laser in a desired shape, the packing material can be selectively cured. (Embodiment 3) In this embodiment, a glass substrate is used as the substrate A and the substrate D, and a substrate B is used to form a diaphragm.
An example in which a silicon substrate is used as the substrate C will be described.

FIG. 7 is a sectional view showing an example of the structure of the sample introduction device of the present invention, and FIG. 8 is a plan view. The substrate A301 is provided with a fluid A inlet 305 and a fluid A outlet 306,
By being joined to the substrate B302, the flow path A inlet 30
A flow path A 313 connecting the fluid A 5 and the fluid A outlet 306 is formed. On the substrate B302, a valve A309 and a valve B310 are formed, and the fluid A inlet 30
5 and the fluid A outlet 306 can be opened and closed.

Similarly, the fluid D inlet 30 is provided in the substrate D304.
7 and a fluid B outlet 308 are provided and joined to the substrate C303. A valve C311 and a valve D312 are formed on the substrate C303, and can open and close the fluid B inlet 307 and the fluid B outlet 308, respectively. Each valve is composed of a diaphragm formed by etching a part of the silicon substrate, a packing placed on the diaphragm, and an actuator for deforming the diaphragm, and the deformation of the diaphragm when a voltage is applied to the actuator Thus, the packing functions as a valve by opening and closing the fluid inlet / outlet. Each valve is displaced by the deformation of the diaphragm,
By contacting and deforming the substrate A301 or the substrate D304, the substrate A301 or the substrate D304 is brought into close contact with the substrate A301 or the substrate D304, and pressure resistance can be obtained.

The substrate B302 and the substrate C303 are each provided with an actuator A31 at two diaphragm positions.
6 and the actuator B 317 are bonded to each other with a spacer 318 interposed therebetween. When a voltage is applied to the actuator A 316, the open / close state of the valve B 310 and the valve D 312 is simultaneously switched. The actuator used here is
A unimorph type piezoelectric element, a laminated type piezoelectric element, an electrostatic actuator, a shape memory alloy array, and the like can be selected, but are not limited thereto. In the present embodiment, the actuator A316 and the actuator B3
A unimorph type piezoelectric element is used for the element 17, and in this case, the direction of displacement of the diaphragm can be changed depending on the polarity of the applied voltage.

Further, the fluid B inlet 307 and the flow path A 313
B314 connecting the fluid, the fluid B outlet 308, and the flow path A
A flow path C315 connecting 313 is formed to penetrate the substrate B302 and the substrate C303, and the valve C311
When the valve D312 is in the open state, the fluid B inlet 307 leads to the flow path B314, the flow path A313, and the flow path C315.
, A flow path reaching the fluid B outlet 308 is formed.

Next, the operation of the sample introduction device of this embodiment will be described. First, under normal conditions, the actuator A
No voltage is applied to the valve A 316 and the actuator B 317, and as shown in FIG.
The valve B310 is open, and the valve C311 and the valve D312 are closed. In this case, the fluid A flows from the fluid A inlet 305 through the flow path A313,
Although it is in a state of flowing to the fluid A outlet 306, the fluid B cannot enter the sample introduction device.

At the time of sample introduction, the actuator A316
And a voltage is applied to the actuator B317, and FIG.
As shown in (b), valve A309 and valve B3
Reference numeral 10 indicates a closed state, and the valve C311 and the valve D312 will be in an open state. At this time, at the same time as the flow of the fluid A is obstructed, the fluid B flows from the fluid B inlet 307 through the flow path B314, the flow path A313, and the flow path C315 to the fluid B outlet 30.
Start flowing from 8. In this state, a sufficient amount of the fluid B is introduced to fill the flow path B314, the flow path A313, and the flow path C315.

Finally, when the voltage applied to the actuator A 316 and the actuator B 317 is turned off, as shown in FIG.
And the valve B310 is opened, the valve C311 and the valve D312 are closed, and the fluid A
05 to the fluid A outlet 306 via the flow path A 313. At this time, the fluid B stored in the channel A 313 is taken out from the fluid A outlet 306. That is, the amount of the fluid B (sample) corresponding to the volume of the flow path A 313 is determined and introduced into the flow of the fluid A. When the flow path A313 is formed very finely by using anisotropic etching of silicon or the like, even a very small amount of sample can be introduced accurately.

[0029]

According to the sample introduction device of the present invention, the following effects can be obtained. 1. In the quantification method using a three-way valve, it was necessary to drive four three-way valves with four actuators in order to quantify the sample.
Since two valve diaphragms can be driven by two actuators, the number of actuators can be reduced as compared with the conventional sample introduction device.

2. Since the silicon microfabrication technology is used, the conduit for quantification is narrow, the ineffective volume in the apparatus can be reduced, and a small amount of sample can be accurately measured. 3. In the sample introduction device according to the present invention, the device can be manufactured using the fine processing technology and the number of actuators can be reduced, so that the device can be downsized.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a sample introduction device according to a first embodiment of the present invention.

FIG. 2 is a schematic diagram showing a conventional sample introduction device using a three-way valve.

FIG. 3 is a schematic diagram showing a conventional sample introduction device using a six-way valve.

FIG. 4 is a plan view showing a sample introduction device according to the first embodiment of the present invention.

FIG. 5 is a schematic diagram showing an operation of the sample introduction device according to the first embodiment of the present invention.

FIG. 6 is a processing step diagram showing a silicon substrate according to a second embodiment of the present invention.

FIG. 7 is a cross-sectional view illustrating a sample introduction device according to a third embodiment of the present invention.

FIG. 8 is a plan view showing a sample introduction device according to a third embodiment of the present invention.

FIG. 9 is a schematic diagram showing an operation of the sample introduction device according to the third embodiment of the present invention.

[Explanation of symbols]

 101 Three-way valve 1 102 Three-way valve 2 103 Three-way valve 3 104 Three-way valve 4 201 Six-way valve 301 Substrate A 302 Substrate B 303 Substrate C 304 Substrate D 305 Fluid A inlet 306 Fluid A outlet 307 Fluid B inlet 308 Fluid B outlet 309 Valve A 310 Valve B 311 Valve C 312 Valve D 313 Channel A 314 Channel B 315 Channel C 316 Valve actuator A 317 Valve actuator B 318 Spacer 601 Silicon substrate 602 Silicon oxide film

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Jun Shinohara 1-8-1, Nakase, Mihama-ku, Chiba City, Chiba Prefecture Inside Seiko Instruments Inc. (72) Inventor Ichikichi Furuta 1-8-1, Nakase, Mihama-ku, Chiba City, Chiba Prefecture F-term (reference) in Seiko Instruments Inc. 2G042 HA10 2G058 EB00 EC07 3H067 AA02 AA32 BB02 BB12 CC32 DD05 DD13 DD32 EA24 EC04 EC07 FF01 FF11 GG25 GG26 GG27 GG28

Claims (3)

[Claims] 1. A sample introduction device for quantifying a certain amount of fluid B and injecting it into another fluid A, comprising a fluid A inlet, a fluid A outlet, a fluid B inlet, a fluid B outlet, and the fluid A A valve A installed near the inlet, a valve B installed near the fluid A outlet, a valve C installed near the fluid B inlet, a valve D installed near the fluid B outlet, and the fluid A inlet A flow path A connecting the fluid A outlet; a flow path B connecting the fluid B inlet and the fluid A outlet; and a flow path C connecting the flow path A and the fluid B outlet. When the valve A and the valve B are open and the valve C and the valve D are closed, the fluid A reaches the fluid A outlet from the fluid A inlet via the flow path A, and Fluid B is obstructed by valve C Therefore, when the sample is introduced, the valves A and B are closed.
With the valve C and the valve D open, the fluid B passes through the flow path B, the flow path A, and the flow path C,
By arriving at the outlet of the fluid B, a certain amount of the fluid B is stored in the flow channel A, and the fluid B stored in the flow channel A is taken out from the outlet of the fluid A by returning to the normal state again. Characteristic sample introduction device. 2. The sample introduction device according to claim 1, wherein the substrate A, the substrate B,
A substrate C and a substrate D are laminated, wherein the fluid A inlet and the fluid A outlet are formed on the substrate A, and the fluid B inlet and the fluid B outlet are formed on the substrate D; A is constituted by a gap between the substrate A and the substrate B. The valve A and the valve B are a diaphragm formed by making a part of the substrate B thinner than other parts, and a packing installed on the diaphragm. And a structure for switching the contact / non-contact state between the substrate A and the packing by the displacement of the diaphragm, and the diaphragm of the valve A and the valve C, and the valve B and the valve D. 2. The sample introduction device according to claim 1, wherein each of the sample introduction devices is simultaneously driven by the same actuator. 3. The sample introduction device according to claim 1, wherein the substrates A and D use glass plates, and the substrates B and C use silicon substrates.