JPH0435019B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Application of the Invention] The present invention relates to the injection form of a plurality of samples or the injection form and flow rate of sample liquids when two or more sample liquids are distributed and injected into an eluent in, for example, a flow injection analysis method. The present invention relates to a multifunctional liquid injection device that can selectively change the path change mode or the flow path change mode. [Background of the Invention] Liquid chromatography or flow injection analysis, which is generally known as a method for analyzing components in a sample solution, involves injecting a sample solution (hereinafter simply referred to as a sample) into a flow of eluent. Since the pressure applied to the system is high, a pressure-resistant liquid injection device is usually used to inject the sample. FIG. 1A schematically shows a typical liquid injection system using liquid chromatography as an example, and a well-known six-way valve 4 is used as the liquid injection device. To give an overview of this liquid injection system, the eluent tank 1
The eluent sent from the pump 2 to the channel 3 passes through one channel of the six-way valve 4, which is normally in communication as shown by the solid line in the figure, to the channel 5, the resin-filled column 6, and then to the detector 7. be done. On the other hand, the other two passages in the six-way valve 4 are connected to a liquid passage loop 8 (generally composed of a tube mounted on the valve, and simply referred to as a loop, hereinafter abbreviated as such) as a conduit. The sample in the sample container 9 is sucked by the pump 10 to fill the loop. Then, the passage in the six-way valve 4 is switched as shown by the broken line in the figure, and the sample is injected into the flow of the eluent as a "plug flow", thereby increasing the affinity of the resin in the column 6 with each component in the sample. Due to the differences, a predetermined separation is performed and analyzed using a detector. The six-way valve 4 has a pair of stator (fixed body) and rotor (rotating body) that have airtight opposing surfaces, the stator has a total of six small openings at each 60° rotation position, and the rotor has two adjacent It is well known as having three bridging grooves that communicate small openings, and the communication relationship can be switched as shown in the figure by rotating the rotor by 60 degrees. The mode of injection into the liquid is simple and can be performed by rotating the rotor, so it is now widely used. Figure 1B shows a typical system when multiple columns are selected and used in the liquid chromatography shown in Figure 1. The eluent is normally transferred to the six-way valve 1, which is in communication with the solid line shown in the figure.
The liquid is sent to the detector 7 through the flow paths shown in the solid line relationship indicated by 1 and 13. Therefore, the sample injected into the eluent is usually separated by the column 14. Furthermore, when the flow paths in the six-way valves 11 and 13 are switched as shown by the broken lines in the figure, the sample is transferred to column 1.
2. Flow-in injection analysis, which is attracting attention along with liquid chromatography, uses a reagent that reacts with specific components in the sample and measures the reaction products with a colorimeter, ion electrode, etc. This can be achieved by replacing the eluent with a reagent solution (hereinafter simply referred to as reagent) in the liquid injection system shown in FIG. 1, and by omitting the column 6. By the way, in liquid chromatography,
There is a growing need to separate and analyze specific components in samples by taking advantage of the mutual advantages of separation and reaction, such as pre- or post-column techniques. In addition, flow injection analysis uses only the reaction between a sample and a reagent without using a column.Recently, in these fields, research has been focused on how to control the reaction and how to effectively utilize a wide variety of analytical reactions to control the flow. The big challenge is how to plan the reaction inside. However, in the liquid injection device or flow path changing device based on the above-mentioned six-way valve, since the number of samples that can be carried into the sample injection device is one, the flow of eluent with different compositions such as sample and reagent is caused. cannot be injected into the Furthermore, the flow path changing device has serious drawbacks such as the inability to select from a large number of flow paths because the number of channels that can be changed in the flow path changing device is two. Further, as a method for injecting a fixed amount of a sample and a reagent into the flow of an eluent, a method has been proposed, for example, in Japanese Patent Application Laid-open No. 87464/1983. The above-mentioned publication describes a so-called "merging zone type" injection method in which sample S and reagent R are combined in parallel flow between eluent T as shown in FIG. 2A, using two sets of six-way valves. As shown in Figure B, a "Sandermansch type" injection method in which sample S is sandwiched between reagent R is disclosed, but both have the function of simultaneously injecting the sample and reagent into the flow of eluent. , as it is, it has only one function and is of limited use. Furthermore, when injecting multiple samples with different forms into the flow of eluent, (a) select one of the multiple sample liquids and inject it. (b) Selective injection of multiple liquid samples or injection of only some liquids. (c) Inject multiple liquid samples by selecting the forward or reverse injection order. The operation of selecting and performing two injection forms of a plurality of liquids only by rotating the rotor cannot be realized, and its uses are limited. [Object of the Invention] The object of the present invention is that when multiple liquids such as a sample and a reagent are injected into an eluent as described above, the plural liquids are, for example, (a) one of the plural liquid samples. Select one of the liquids to inject. (b) Select and perform simultaneous injection of multiple liquid samples or injection of only some liquids. (c) Select the forward or reverse order of injection of multiple liquid samples. It is possible to select and accurately perform different injection forms with simple operations.
Another object of the present invention is to provide a liquid injection system that enables accurate injection flow path change modes and various flow path change modes by changing only the piping. The goal is to provide equipment. [Summary of the Invention] In accordance with the above-mentioned object, the present invention is capable of selectively injecting two kinds of liquids into a steady flow of other liquids by only rotating a single rotor. The gist of this liquid injection device is that a pair of stator and rotor are combined to rotate relative to each other in an air-tight and liquid-tight state. One mutually opposing surface of the rotor is provided with a plurality of small liquid passage openings each belonging to n liquid systems (n is an integer of 3 or more), and a pair of mutually opposing surfaces of the stator and rotor are provided with is provided with a plurality of bridging grooves that are aligned to span two or more of the small openings to form a plurality of liquid passages, and the rotor is connected to the stator,
The liquid injection device is capable of switching from a neutral position, which is a liquid filling mode, to a forward rotation position and a reverse rotation position, which are a liquid injection mode rotated by a certain angle in the forward or reverse direction, and in each of these three positions ( a) The first liquid system among the n liquid systems has a pair of small openings, which are an inlet and an outlet for liquid passage, at the rotation center and eccentric position of the one mutually opposing surface, and these inlets and The outlet is directly communicated through the bridging groove at the center position, and the direct communication is interrupted at the forward and reverse rotation positions, respectively. (b) Each of the (n-1) other liquid systems other than the first liquid system has an external liquid passage circuit connected to the two small openings and a loop spanning the other two small openings. In the neutral position, each loop is connected to the respective liquid passage circuit via a bridging groove, and the positive,
In the reverse rotation position, part or all of each loop is connected to the inlet and outlet of the first liquid system in different ways in the forward and reverse rotation positions. The liquid passage is formed according to (a) and (b) above. In the present invention, the small opening is generally provided on the stator side, which is a fixed body, and the inlet (or outlet) of the first liquid system is provided at the rotation center position of the opposing surface, and other small openings are provided. are often provided at a predetermined angle on one circle or on two or more multiple circles on the mutually opposing surfaces. In addition, the bridging grooves provided on the opposing surfaces of the stator and rotor each have adjacent small openings on the same circle,
Small openings adjacent in the radial direction on different circles, and small openings located at the center of rotation of opposing surfaces as the inlet (or outlet) of the first liquid system and other small openings, respectively, communicated in a bridge manner. It is established as a. When the liquid injection device of the present invention is used, for example, to inject a minute amount of sample, reagent, etc. into the flow of eluent, the loop is used as a liquid measuring tube, and its filling volume is the injection amount. It is set appropriately (generally about 20 to 100μ) depending on the situation. Further, the liquid injection device of the present invention is configured as a liquid injection device that utilizes column operation by interposing a column filled with a predetermined adsorbent in at least one of the loops. The liquid injection device configured as described above can be designed in various ways depending on the conditions for forming the small opening and the bridging groove. This allows various types of different multifunctional liquid injection devices to be provided. Here, some representative types of multifunctional liquid injection devices formed according to the present invention are illustrated as follows. Selective injection function for multiple liquids In the neutral position, the first liquid system forms a steady flow of liquid through the liquid passage whose inlet and outlet are aligned by the bridging groove, while the other liquid system forms a steady liquid flow through the liquid metering tube. A liquid filling circuit is connected to the loop, and a certain amount of liquid determined by the length of the loop is filled into the loop. On the other hand, when the stator and rotor are moved relative to each other and switched to the forward rotation position, the bridging groove moves in the passage between the inlet and outlet of the first liquid system and becomes disconnected, while the second liquid system Communication between both ends and the liquid filling circuit is cut off, and both ends of this loop are communicated with the inlet and outlet of the first liquid system. Further, in the third liquid system, communication between both ends of the loop and the liquid filling circuit is cut off, but the inlet and outlet of the first liquid system are not communicated with each other. Therefore, the liquid passage formed between the pair of opposing surfaces of the stator and rotor becomes a flow path from the first liquid system inlet to the second liquid system loop to the first liquid system outlet, and as a result, the first liquid system The liquid of the second liquid system can be injected into the flow. Furthermore, when the stator and rotor are caused to slide relative to each other and are switched to the reverse rotation position, the bridging groove in the passage between the inlet and outlet of the first liquid system moves and becomes disconnected, while the second liquid system The communication between both ends of the liquid supply circuit and the liquid filling circuit is cut off, and there is no communication between the inlet and the outlet of the first liquid system. Further, communication between both ends of the third liquid system and the liquid filling circuit is cut off, and both ends of the loop are communicated with the inlet and outlet of the first liquid system. Therefore, the liquid passage formed between the pair of opposing surfaces of the stator and rotor becomes a flow path from the first liquid system inlet to the third liquid system loop to the first liquid system outlet, and as a result, the first liquid system The liquid of the third liquid system can be injected into the flow. It is clear that such a liquid injection device can be used as it is in the flow injection analysis method with the first liquid as the eluent and the second and third liquids as sample S ₁ and sample S ₂ . Furthermore, this type of liquid injection device can also be applied to multi-liquid injection of three or more liquids. Therefore, the three-position switching type liquid injection device has n
(n is an integer of 3 or more) each system belonging to each liquid system has a plurality of small openings, and one of the n (first liquid system) is rotated forward or backward from the neutral position. The other (n-1) liquid systems each have a set of small openings that connect both ends of the loop to the liquid filling system and the inlet and outlet. It is characterized by having
When these are on a single circle, the number of small openings required is given by 2 + 4 × (n-1) = 4n-2 (where n is an integer greater than or equal to 3 and represents the number of liquid systems). and the circumferential position of these small openings is on a radial line divided by an angle of 360° and 1+4(n-1) = 4n-3 and on the first liquid system of n liquid systems. The entrance or exit of a circle can be designed based on the fact that it is located at the center of the circle. In addition, if the necessary small openings are arranged on multiple concentric circles, m=
The number of small openings required is given by 2+4(n-1)=4n-2, and the number of small openings required is given by 2+4(n-1)=4n-2. The position on the circumference is at least on a radial line divided by an angle equal to 360° divided by 6, and the inlet or outlet of the first liquid system of the n liquid systems is located at the center of the circle. You can design based on what is given to you. Simultaneous injection of multiple liquids and injection of partial liquids In the neutral position, the first liquid system forms a steady flow of liquid through a liquid passage whose inlet and outlet are aligned by bridging grooves; In other liquid systems, a liquid filling circuit is connected to the loop, and a certain amount of liquid determined by the length of the loop is filled into the loop. On the other hand, when the stator and rotor are moved relative to each other and switched to the forward rotation position, the bridging groove moves in the passage between the inlet and outlet of the first liquid system and becomes disconnected, while the second and third liquid systems are in a non-communicating state. Communication between both ends of the loop and the liquid filling circuit is cut off, and both ends of the loop are communicated with the inlet and outlet of the first liquid system. Therefore, the liquid passage formed by the pair of opposing surfaces of the stator and rotor is On the way, the liquid passes through a bifurcated branch with each loop, and as a result, it becomes possible to inject two types of liquid into the liquid flow of the first liquid system as a "merging zone type." Furthermore, when the stator and rotor are moved relative to each other and switched to the reverse rotation position, the bridging grooves move between the inlet and outlet passages of the first liquid system, resulting in a disconnected state, while the second liquid system communicates with both ends of the passages. Communication of the liquid filling circuit is cut off and communicated with the inlet and outlet of the first liquid system. Furthermore, communication between both ends of the third liquid system and the liquid filling circuit is cut off, but there is no communication between the inlet and the outlet of the first liquid system. Therefore, the liquid passage formed between the pair of opposing surfaces of the stator and rotor becomes a flow path from the first liquid system inlet to the second liquid system loop and the first liquid system outlet. A liquid of the third liquid system can be injected into the flow. It is clear that such a liquid injection device can directly use the flow injection analysis method using the first liquid system as the eluent and the second and third liquids as sample S ₁ and sample S ₂ . Furthermore, this type of liquid injection device can also be applied to multi-liquid injection of three or more liquids. Therefore, a three-position switching type liquid injection device has a stator (or rotor) having a plurality of small openings for each system belonging to n liquid systems (n is an integer of 3 or more), and One (first liquid system) has small inlet and outlet openings that are communicated in the neutral position and are blocked in the forward and reverse rotation positions rotated forward or backward from the neutral position, and the other (n-
1) Each liquid system is characterized by having a set of small openings connecting both ends of each loop to the liquid filling system and the other liquid system, and when these are on one circle, the required small openings are The number of openings is given by 2+4×(n-1)=4n-2 (where n is an integer of 3 or more and represents the number of liquid systems), and the positions of these small openings on the circumference are 360 The inlet or outlet of the first liquid system among the n liquid systems is located at the center of the circle and given It can be designed based on what is possible. In addition, if the necessary small apertures are arranged on multiple concentric circles, the number of concentric circles is m, and m =
The number of small openings required is given by 2+4(n-1)=4n-2, and the number of small openings required is given by 2+4(n-1)=4n-2. The position on the circumference is located on a radial line divided by an angle equal to at least 360° divided by 6, and the inlet or outlet of the first liquid system of the n liquid systems is located at the center of the circle. It can be designed based on what is possible. Ability to change the injection order of multiple liquids back and forth At the central position, the inlet and outlet of the first liquid system form a steady flow of liquid through the liquid passage aligned by the bridging groove, while the other liquid In the system, a liquid filling circuit is connected to the loop, and the loop is filled with a certain amount of liquid determined by the length of the loop. On the other hand, when the stator and rotor are moved relative to each other and switched to the forward rotation position, the bridging groove moves in the passage between the inlet and outlet of the first liquid system and becomes disconnected, while the second liquid system Communication between both ends of the loop and the liquid filling circuit is cut off, and both ends of this loop are connected to the first liquid system inlet and the third liquid system, and communication between both ends of the loop and the liquid filling circuit is cut off. At the same time, both ends of this loop are communicated with the first liquid system outlet and the second liquid system. Therefore, the liquid passage formed between the pair of opposing surfaces of the stator and rotor becomes a flow path of first liquid system inlet → second liquid system loop ↓ first liquid system outlet ← third liquid system loop, As a result, the second and third liquid systems can be injected in series into the flow of the first liquid system. Furthermore, when the stator and rotor are moved relative to each other and switched to the reverse rotation position, the bridging groove moves in the passage between the inlet and outlet of the first liquid system and becomes disconnected, while the second liquid system Communication between both ends of the loop and the liquid filling circuit is cut off, and both ends of this loop are connected to the first liquid system outlet and the third liquid system, and the third liquid system is connected to both ends of the loop and the liquid filling circuit. is blocked, and both ends of this loop are communicated with the first liquid system inlet and the second liquid system. Therefore, the liquid passage formed between the pair of opposing surfaces of the stator and rotor becomes a flow path of first liquid inlet → third liquid system loop ↓ first liquid outlet ← second liquid system loop, and as a result, This means that the third and second liquids are injected in series into the flow of the first liquid in the reverse order of the forward rotation position. It is clear that such a liquid injection device can be used as is for flow injection analysis using the first liquid system as the eluent, the second liquid as the sample S, and the third liquid as the reagent R. Furthermore, this type of liquid injection device can also be applied to multi-liquid injection of three or more liquids. Therefore, the 3-position switching type liquid injection device has n
(n is an integer of 3 or more) each system has a plurality of small openings belonging to each liquid system, and one of the n (first liquid system) is communicated at the neutral position, and from the neutral position Having small inlet and outlet openings that are blocked in the forward and reverse rotation positions, and other (n-
1) The liquid system is characterized by having a set of small openings that communicate with the filling liquid system and other liquid systems at both ends of each loop, and when there are small openings on one circle, the necessary The number of small openings is given by 2+4×(n-1)=4n-2 (where n is an integer of 3 or more and represents the number of liquid systems), and the positions of these small openings on the circumference are , 360° divided by 1+(4n-1)=4n-3, and the inlet or outlet of the first liquid system among the n liquid systems is located at the center of the circle. It can be designed based on what is given. In addition, if the necessary small openings are arranged on multiple concentric circles, m = n
-1 (n is an integer greater than or equal to 3 and represents the number of liquid systems), and the number of required small openings is given by 2+4(n-1)=4n-2, and the number of small openings on the circumference of these small openings is The position of is located on a radial line divided by an angle equal to at least 360° divided by 6, and the inlet or outlet of the first liquid system of the n liquid systems is located at the center of the circle. You can design based on things. (Embodiments of the invention and their effects) The present invention will be described below based on embodiments shown in the drawings. Example 1 The example shown in Figs. 3 to 5 has two modes: one mode in which sample S ₁ (second liquid) is injected, and another mode in which sample S ₂ (third liquid) is injected with respect to the flow of the first liquid. This figure shows a three-liquid type multifunctional liquid injection device used for sample analysis, which can be selected by forward and reverse rotation of the rotor. FIG. 3 is a sectional view showing the outline of the configuration of the liquid injection device of this example. In the figure, 21 is a disc-shaped stator, and at its peripheral edge there is an annular flange of a rotor case 22 having a U-shaped cross section. The tips are engaged, and the stator 21 and rotor case 22 are firmly connected by the bottle 23. In the center surrounded by the stator 21 and the rotor case 22, there is a rotor 2 which is in air (liquid) tight contact with the inner surface of the stator 21 under a predetermined pressure.
4, and a drive disk 25 that rotates this rotor 24.
A spring 26 that applies a pressing force to the stator 21 of the rotor 24 is housed therein, and a rotary drive shaft 27 extends from the back surface of the drive disk 25 to the outside of the rotor case 22 . Reference numeral 28 denotes an operating handle that projects from the extending end of the rotary drive shaft 27 in the radial direction. The hollow inner surface of the stator 21 has a fourth
As shown in the figure, a plurality of small openings a to j are formed,
These small openings are connected and communicated with various external pipes through through holes penetrating the stator 21 in the thickness direction. Note that the small openings a to j are arranged so that j is located at the center of the circumference, and each of the nine small openings a to i are arranged on the circumference in a positional relationship divided into equal angles as shown in the figure. ing. Furthermore, grooves a to a', e to e', and f to f' extending slightly toward the center are successively provided in the small openings a, e, and f. Further, as shown in FIGS. 5A and 5B, on the surface of the rotor 24 facing the stator 21, adjacent small openings on the circumference on the stator side are formed at positions in the radial direction where the small openings a to j face. A plurality of circumferential bridging grooves D to G on the circumference that selectively communicate the circumferentially separated portions (for example, a and c for b), and the small central opening j and grooves a to the stator side a', e~
Radially extending bridging grooves A to C are formed to connect e', f to f' in a bridging manner. In this example, these bridging grooves are formed by providing recesses on the surface of the rotor, but they may be formed by opening only at both end portions of the groove on the surface of the rotor, and drilling inside the groove in the middle. Also, for convenience, the grooves are emphasized and drawn thick in the drawings, but in reality, fine line-like grooves are sufficient. The stator 21 and rotor 24 having the above configuration are connected to each other through the small openings a to j and the grooves a to a', e to the stator side.
Assemble the liquid injection device so that e', f to f' and bridging grooves A to G on the rotor side face each other in an airtight and liquid-tight manner as shown in FIG. By slidingly rotating the rotor 24, the sixth
Alignment is made possible in the states shown in Figures A to C. These figures schematically show a state in which liquid passages for the eluent, sample S ₁ (), and sample S ₂ () are formed by alignment of the small openings and the grooves. In this example, the above-mentioned small openings a to j are as follows in relation to external attachment devices and the like. j is an eluent outlet, which is connected so as to be able to selectively communicate with a flow injection analysis method and a liquid chromatography analysis system. a is the eluent inlet, pump P
is connected to an eluent tank (none of which is shown). b and e are connected to both ends of the loop 30 of sample _S1 . Further, f and i at symmetrical positions are connected to both ends of the loop 31 of the sample _S2 . c and d
constitute two points in the sample S ₁ filling circuit, one of which is connected to the sample container 32, and the other, d, is connected to a suction pump (not shown). Similarly, h and g at symmetrical positions are connected to the sample container 33 in the sample S filling circuit, and g to a suction pump (not shown). FIG. 6A shows a state in which the stator and rotor are aligned in the neutral position, which is the liquid filling mode, and this is the reference position of the liquid injection device. In this state, the small openings a and j are arranged so that the radial bridging groove A on the rotor side is aligned with the grooves a to a' on the stator side, so that a liquid passage from a to a' → A → j is formed. , the eluent is supplied with a steady flow by the pump P. In addition, the small openings b, c, d, and e of the sample S ₁ system are c→D→b→loop 30 due to the circumferential bridging grooves D and E.
→ e → E → d liquid passage is formed, sample S ₁ container 3
2, the loop 30 is filled with the sample _S1 . Similarly, liquid path h → G → i → loop 3 of sample S ₂ system
S ₂ is filled into the loop 31 by 1→f→F→g. Figure 6B shows the rotor 24 in Figure 6A as the stator 2.
1, slide and rotate by a certain angle (360°/9) in the clockwise direction in the figure (hereinafter, counterclockwise rotation in the figure is referred to as reverse rotation, and clockwise rotation is referred to as forward rotation), and switch to the forward rotation position. This rotation changes the liquid path as follows. That is, the radial bridging groove A is out of alignment with the grooves a to a' on the stator side, and the radial bridging groove C is out of alignment with the grooves f to f' on the stator side, and the circumferential bridging grooves D and E are out of alignment. , F change the communication relationship between the small apertures b to f of the sample _S1 system as follows according to their respective rotations. That is, D is the small openings a and b on the stator side,
E communicates small openings c and d, F communicates small openings e and f, and G communicates small openings g and h, respectively. Therefore, this liquid passage has an inlet a and an outlet j for the eluent.
In between, a → D → b → loop 30 → e → F ↓ j ← C ← f′ ~ f ↓ (occlusion) i ← loop 31. In short, in the injection mode at the forward rotation position, the eluent Sample S ₁ in loop 30
Only ( ) is injected, and injection of the sample S ₁ into the eluent as a "plug flow" (see FIG. 6 D) is realized. Figure 6C shows the rotor 24 in Figure 6A as the stator 2.
1, sliding rotation counterclockwise in the figure (reverse rotation)
This shows another injection mode in which these are switched to the reverse rotation position, and by this rotation, the liquid passage is changed similar to the case in FIG. 6B. That is, the direct communication of the eluent via the bridging groove A is blocked, and the communication of the liquid is between the eluent inlet a and the outlet j as follows: a→G→i→loop 31→f ↓ j←B←e ′〜e←E↓ (occlusion)←b←loop 30 In other words, in the injection mode at the reverse rotation position, the sample S ₂ in the loop 31 with respect to the eluent
Only ( ) is injected, and injection of sample S ₂ into the eluent as a "plug flow" (see Figure 6 E) is realized. In the above description, the length of the bridge grooves A to G, the arrangement of the small openings a to j, the length of the stator groove,
Furthermore, it goes without saying that the switching angles of the rotor from the neutral position to the normal rotation position and the reverse rotation position are set to correspond to the respective operations described above. According to this embodiment described above, by selecting and rotating the rotor in the forward or reverse direction from the neutral position in the liquid filling mode (switching the combined positional relationship of the stator and rotor to the forward rotation position or the reverse rotation position). Although the operation is extremely simple, it is possible to inject only one sample S ₁ or only the other sample S ₂ into the eluent. It has an excellent function of being able to select the mode of injection, and the structure of the device itself is only a single valve machine, so its usefulness is extremely great. Figures 6 to 6 show the case where the columns 12 and 14 are inserted and installed in the loop part, and the eluent is conveyed from the eluent tank to the small opening a through the pump, and then passes through the small opening j. It communicates with a detector (not shown). FIG. 6 is a neutral position, where a liquid path from a to a'→A→j is formed, and the eluent flows without passing through either column. In Figure 6, the rotor 24 in Figure 6 is connected to the stator 2.
The figure shows a state in which the liquid has been rotated 40° in the normal direction relative to column 1, and due to this rotation, the liquid communication is from a → D → b → column 12.
→e→F→f~f'→C→j, and the flow of the eluent selected in column 12 is as shown in FIG. Furthermore, FIG. 6 H shows a state in which the rotor 24 in FIG.
4→f→E→e~e'→B→j, and the flow of the eluent is as shown in FIG. 6, with column 14 selected as the column. Note that in the neutral position shown in Figure 6 above, column 1 is
A predetermined buffer solution is passed through 2 and 14. Embodiment 2, 3 Figure 7 A and B show an example when the number n of liquids is 4 (Example 2), and Figure 9 A and B show the same case when the number n of liquids is 4. (Embodiment 3), and the structure shown in FIGS. 7A and 7B is slightly modified to change the liquid injection mode. In Embodiment 2 of FIG. 7, the number n of liquids used is increased by one compared to Embodiment 1, and the liquid to be injected as a "plug flow" is selected between , and . The structure is basically the same as that of Example 1, except that the number of openings and bridging grooves are increased (the following examples are also the same). The liquid filling mode and liquid injection mode consisting of the combination of the stator and rotor shown in FIGS. 7A and 7B are as follows, respectively. (Neutral position; Liquid filling mode) First liquid () system a~a'→A→n Other liquid systems (,,) Fill each loop (See Figure 8 A) (Forward rotation position; Liquid injection mode, Rotate the rotor clockwise by 27.7 degrees) (Refer to Figure B) (Reverse rotation position; liquid injection mode, rotate the rotor 27.7 degrees counterclockwise) a〜a′→→m→R〓→j→G→i〜i′ ↓ n←B←f〜f ′←R〓 ↓ (Occluded) ←b←R〓←e←E (See Figure 8 C) In these cases, the mode of liquid injection is as shown in Figure 8 D in the forward rotation position and Figure 8 H in the reverse rotation position. becomes. In Embodiment 3 shown in FIG. 9, the liquid filling mode is set in 3 positions as in Embodiment 2 shown in FIG. The liquid injection mode is shown below. (Neutral position; Liquid filling mode) First liquid () system; a~a'→A→n Other liquid systems (,,); Fill each loop (See Figure 10 A) (Forward rotation position; Liquid injection mode, rotate the rotor 27.7° clockwise) a～a′→D→b→R〓→e→F→f ↓ n←C←i′～i←R〓 ↓ (occlusion)←m←R〓← i←H (Refer to Figure 10 B) (Reverse rotation position; liquid injection mode, rotor rotated 27.7° counterclockwise) a〜a′→→m→R〓→j→G ↓ n←B←i′ ~i ↓ (occlusion) ← b ← R ← e ← E ← f ← R (see Figure 10 C) In these cases, the liquid injection mode is as shown in Figure 10 D in the forward rotation position and as shown in Figure 10 D in the reverse rotation position. Figure 10 shows E. Examples 1, 2, and 3 shown in FIGS. 4 to 8 above
This is a case where the small openings formed in the stator (or rotor) are provided on a single circle. Example 4 The example shown in FIGS. 11 and 12 shows a case where small openings are formed on two concentric circles, and the formation of each liquid passage at three positions is as follows. . (Neutral position; liquid filling mode) First liquid system; 60° clockwise) f→E→H→k→R〓→h→F ↓ m←A←a′〜a〜g ↓ (occlusion)←e←R〓←b←C (Fig. 12 (Refer to b) (Reverse rotation position; liquid injection mode, rotor rotated 60° counterclockwise)

[Table] m←B←a′〜a←g←H k
↓
(occlusion)← G
(See FIG. 12C) In the cases shown in FIGS. 11A and 11B, the liquid injection mode is as shown in FIG. 12D in forward rotation and as shown in FIG. 12E in reverse rotation. Example 5 The example shown in FIGS. 13 and 14 shows the case where the small openings on the stator are formed on three concentric circles, and the formation of the liquid passages at the three positions is as follows. That's right. (Neutral position; Liquid filling mode) First liquid () system; f~f'→B→S Other liquid systems (,,); Fill each loop (See Figure 14 A) (Forward rotation position; Liquid injection mode, rotate the rotor 60° clockwise) (Refer to Figure 14 B) (Reverse rotation position; liquid injection mode, rotor rotated 60° counterclockwise) (See FIG. 14C) In the case of FIGS. 13A and 13B, the liquid injection mode is as shown in FIG. 14D in forward rotation and as shown in FIG. 14E in reverse rotation. Example 6 The example shown in FIGS. 15 and 16 includes a mode in which only the sample S (second liquid ()) is injected into the flow of the first liquid ( This example shows a sample analysis type liquid injection device in which the mode for simultaneously injecting liquid ()) can be selected by rotating the rotor forward or backward. Figure 15A shows the stator, and Figure 15B shows the rotor, which are the same as those in the previous example, and the sample injection mode (forward rotation position) and the sample and reagent injection into the "merging zone" type. The mode (reverse rotation position) is shown below. (Neutral position; liquid filling mode) 1st liquid system; a~a'→A→j Other liquid systems (,); Fill each loop (see Figure 16 A) (Forward rotation position; sample injection mode, rotor 32.7° clockwise) a～a″→H→i→R〓→f～f′ (occlusion) ↓ D ↓ b→R〓→e～e′→C→j (See Figure 16 B) (Reverse rotation position; sample and reagent injection mode, rotor rotated 32.7° counterclockwise)

[Table] ↓ ↓
H→b→R →e〜e′→B→j

(See Figure 16 C) Therefore, in the forward rotation position, only the sample is injected as shown in Figure 16 D, and in the reverse rotation position, the sample and reagent are injected in a "merging zone type" as shown in Figure 16 E. Ru. Example 7 The example shown in FIGS. 17 and 18 is
The liquid passages for the four liquids are formed as follows by switching between three positions. (Neutral position; Liquid filling mode) 1st liquid system; a~a'→A→n Other liquid systems (,,); Fill each loop (See Figure 18 A) (Forward rotation position; Liquid injection mode, Rotate the rotor 34 degrees clockwise) a～a″→J→m→R〓→j→H→(Closed) ↓ D ↓ b→R〓→e→F→f→R〓→i～i′ ↓ C ↓ n (Refer to Figure 18 B) (Reverse rotation position; liquid injection mode, rotor rotated 34° counterclockwise)

[Table] ↓ ↑
b→R →e→E→f→R →i〜i'

Therefore, in the cases shown in FIGS. 17A and 17B, the liquid injection mode is as shown in FIG. 18D in the forward rotation and as shown in FIG. 18E in the reverse rotation. Example 8 The example shown in Figs. 19 and 20 shows the case where the small openings of the stator are formed on two concentric circles, and the liquid passages are formed in each of the three positions as follows. It is. (Neutral position; liquid filling mode) First liquid system: l → J → g ~ a ~ a' → A → m Other liquid systems (,): Fill each loop (see Figure 20 A) (Forward rotation position ;Liquid injection mode, rotated 60° clockwise) (Refer to Figure 20B) (Reverse rotation position; liquid injection mode, 60° counterclockwise)
rotate)

【table】 ~
E←e←R ←b←F←a〜a′

↓ ↓
(occlusion) m←C
(See Fig. 20 C) Therefore, in the cases shown in Fig. 19 A and B, the liquid injection mode is as shown in Fig. 20 D for forward rotation and as shown in Fig. 20 D for reverse rotation.
Figure 0 becomes E. Example 9 The example shown in FIGS. 21 and 22 shows the case where the small openings of the stator are formed on three concentric circles, and the formation of the liquid passages at the three positions is as follows. It is. (Neutral position; liquid filling mode) First liquid system: S→N→K→G→a~a'→A→t Other liquid systems (,,): Fill each loop (see Figure 22 A) ( Forward rotation position; liquid injection mode, rotor rotated 60° clockwise)

[Table] ↓ ~
K→j→k→R →h→H→g

↓ ~
G→F→e→R →b→D→a~a'

↓
B→t
(Refer to Figure 22 B) (Reverse rotation position; liquid injection mode, rotor rotated 60° counterclockwise) (See FIG. 22C) Therefore, in the cases shown in FIGS. 21A and 21B, the liquid injection mode is as shown in FIG. 22D in forward rotation and as shown in FIG. 22E in reverse rotation. Example 10 In the example shown in FIGS. 23 and 24, the order of injection of sample S ₁ (second liquid) and sample S ₂ (third liquid), which are simultaneously injected into the flow of the first liquid, is as follows:
This shows a sample analysis type injection device that can be changed between forward rotational position and reverse rotational position.
The formation of each liquid passage in the three positions is as follows. In this example, the small opening of the stator is provided on a double circle. (Neutral position; liquid filling mode) 1st liquid system; 60° clockwise) f→D→l→G→k→R〓→h→E ↓ e'〜e←R〓←b←B←a〜g ↓ A→m (See Figure 24 B) ) (Reverse rotation position; liquid injection mode, rotor rotated 60° counterclockwise) f→C→e→R〓→b→D→h ↓ m←A←l′〜l←F←k←R〓 (See FIG. 24C) Therefore, in the case of FIGS. 23A and 23B, the liquid injection mode is as shown in FIG. 24D in the forward rotation and as shown in FIG. 24E in the reverse rotation. Example 11 The example shown in FIGS. 25 and 26 is
This figure shows a case in which the number of liquid systems in Example 10 is further increased by one (n=4), and the small openings of the stator are provided on three circles. The formation of each liquid passage in the three positions is as follows. (Neutral position; liquid filling mode) 1st liquid system; c~a'→A→S Other liquid systems (,,); Fill each loop (see Figure 26 A) (Forward rotation position; liquid injection mode, Rotate the rotor 60° clockwise)

[Table] ↓
h →F→g〜b→C→C→R

↓
S←A←f'～f
(Refer to Figure 26 B) (Reverse rotation position; liquid injection mode, rotor rotated 60° counterclockwise)

【table】
↓
R →n→K←m〜m′→A→S

(See FIG. 26C) Therefore, in the case of FIGS. 25A and 25B, the liquid injection mode is as shown in FIG. 26D in forward rotation and as shown in FIG. 26E in reverse rotation. (Modifications and Applications of the Invention and Their Effects) The present invention is not limited to the embodiments described above, and various embodiments can be considered. For example, as already stated, as shown in FIGS. Regarding the liquid injection device shown in FIG. 6, if only the position switching between FIG. 6 A and FIG. 6 B is made possible, and the position switching to FIG. 6 C is disabled by an appropriate blocking means, The device can be used as a normal liquid injection device. In addition, the grooves formed in the stator and rotor are actually fine linear grooves, and the rotor, which is usually made of polyimide, Teflon, etc., is pressed against the stator with a sufficiently large pressing force. Therefore, it is possible and easy to draw various grooves geometrically as long as there is no hindrance to liquid flow. A multifunctional liquid injection device that selectively injects two liquids can also be designed with various groove shapes and small opening arrangements. Furthermore, the liquid injection device of the present invention is not only applicable to sample analysis such as flow-in injection analysis and liquid chromatography analysis, but also to mixing three or more liquids (or a combination of three or more liquids) in addition to analysis operations. It may also be suitably used as a device for mixing two liquids, etc.). For example, it can be used to appropriately supply necessary reagents in a reaction system that performs a reaction using a fed reagent. A specific example is the delivery of a reagent to a reaction tank in the usual chemical industry or a fermentation tank in microbial fermentation. Furthermore, regarding the column operation shown in FIGS. It is possible. (Effects of the Invention) As described above, the liquid injection device according to the present invention is suitable for injecting a plurality of liquids in a number of ways, and can select functions with a simple operation, and can realize these functions. The rotor and stator can be rotated very easily, the structure is simple, and injection can be performed accurately at the same time. Moreover, by replacing the loop with a column, etc., it is possible to use a flow path changing device. It also has the added effect of being applicable to column switching devices, etc., and its applicability is extremely great.

[Brief explanation of drawings]

Figures 1A and 2B show an example of the use of a liquid injection device using a known six-way valve, Figures 2A and 2B show liquid injection modes, and Figure 3 is an embodiment of the present invention. Figure 4A is a front view of the stator, and Figure 4A is a schematic cross-sectional view of the liquid injection device in Figure 1.
5A is a front view of the rotor, FIG.
5 is a diagram showing the state of liquid passage formation accompanying the switching of the positions of the stator and rotor in the embodiment shown in FIG. 5,
FIGS. 6D and 6E are diagrams showing the state of liquid injection. FIGS. 6-6 are diagrams for explaining an example of column operation. 7 to 26 are diagrams showing Examples 2 to 11, among which the 7th, 9th, 11th, and 1st
3, 15th, 17th, 19th, 21st, 23rd,
Figure 25A shows a front view of the stator of each embodiment, Figure 25B shows a front view of the rotor of each embodiment, and 8th, 10th, 12th, 14th, 1st
6, 18th, 20th, 22nd, 24th, and 26th figures A, B, and C are diagrams showing the state of liquid passage formation accompanying the switching of the positions of the stator and rotor of the respective embodiments. Each figure (d) and (e) is a diagram showing the state of liquid injection in each embodiment.

Claims (1)

[Claims] 1. A pair of stators and rotors that are combined to rotate relative to each other in an air-tight and liquid-tight state, and n (n is an integer of 3 or more ), each of which has a plurality of small openings for passage of liquid, each belonging to the liquid system of The rotor is provided with a plurality of bridging grooves forming liquid paths, and the rotor is rotated by a certain angle in the forward or reverse direction with respect to the stator from a neutral position, which is a liquid filling mode, to a forward rotation position and a reverse rotation position, which are a liquid injection mode. 1. A liquid injection device capable of switching between three positions, wherein the liquid passage is formed in each of the three positions according to (a) and (b) below. (a) The first liquid system among the n liquid systems has a pair of small openings, which are an inlet and an outlet for liquid passage, at the rotation center and eccentric position of the one mutually opposing surface, and these inlets and the outlet are in direct communication via the bridging groove at the neutral position, and the direct communication is interrupted at the forward and reverse rotation positions, respectively. (b) Each of the (n-1) other liquid systems other than the first liquid system has an external liquid passage circuit connected to the two small openings and a loop spanning the other two small openings. In the neutral position, each loop is connected to the respective liquid passage circuit through a bridging groove, and in the normal and reverse rotation positions, a part or all of each loop is connected to the liquid passage circuit in a different manner in the normal and reverse rotation positions. Connected to the inlet and outlet of a single-liquid system. 2. The liquid injection device according to claim 1, wherein the loop is a measuring tube for filling liquid. 3. The liquid injection device according to claim 1, wherein at least a portion of the loop has a column inserted therein. 4. Claim 1, characterized in that in at least one of the forward and reverse rotation positions, two or more loops of the other liquid system are connected in series between the inlets of the first liquid system. The liquid injection device according to any one of items 1 to 3. 5. Claim No. 5, characterized in that in at least one of the forward and reverse rotation positions, two or more loops of the other liquid system are connected in parallel between the inlet and outlet of the first liquid system. The liquid injection device according to any one of Items 1 to 3. 6 In one of the forward and reverse rotation positions, only a portion of the other liquid system is connected between the inlet and the outlet of the first liquid system, and in the other of the forward and reverse rotation positions, the first part of the other liquid system is connected between the inlet and the outlet of the first liquid system. The liquid injection device according to any one of claims 1 to 3, wherein the remaining liquid system except for a part is connected between an inlet and an outlet of the first liquid system. 7 In the normal rotation position and the reverse rotation position, all of the other liquid systems are connected in series between the inlet and the outlet of the first liquid system, and the order of the other liquid systems is reversed in the normal rotation position and the reverse rotation position, respectively. A liquid injection device according to any one of claims 1 to 3, characterized in that: