JP6746395B2 - Metal laminate with internal space - Google Patents

Description

The present invention relates to a metal laminate in which a plurality of plate-shaped metal plates having through holes are stacked, and an internal space is formed by communicating the through holes, and a column having the internal space as a flow path. Regarding

In recent years, the downsizing of reactors, gas-related devices, gas cylinders, and other devices requiring pressure resistance has progressed, and the parts used in these devices and the molds used to form them require highly precise microfabrication. It has become to. However, it is said that the limit of the aspect ratio of the depth to the hole diameter is 10 to 20 times in the mechanical processing in the fine processing. Further, in order to realize such a limit value, the skill level of the processor has a great influence, so that the product becomes expensive and it is not suitable for a general-purpose product. In laser processing or electric discharge processing, a high aspect ratio of several thousand times is possible in the case of synthetic resin, but it is said that the limit is about 50 times in the case of metal. Further, the processing accuracy of these has a certain limit. Further, all of these processing techniques require handling from the outside of the workpiece, and it is difficult to perform internal processing such as increasing the diameter of the tip of the workpiece.

Therefore, a metal plate whose surface has been finely processed by etching is subjected to press processing by stacking two metal plates with their processed surfaces facing each other, and a component having a fine space inside is also made.

On the other hand, in recent years, 3D printers for producing structural parts having a space having a function inside while stacking have been provided, and in the case of synthetic resin, it has become possible to perform fine processing inside, but for metal, It has become a large-scale device and it has not yet been possible to make highly accurate products. Further, the 3D printer is manufactured in dot units, and is suitable for manufacturing a single component at the study stage, but is not suitable for a component that needs to be commercialized and needs to be mass-produced.

From the above, it can be said that a component manufactured by using the MEMS technology capable of utilizing a micromachined space is suitable for a product of a structural component having a space having a function inside.

Proposed is a component or column in which two or three corrosion-resistant plates or metal plates are provided with concave grooves or through holes on the surface, and these plates are stacked to form a flow path on the plate stacking direction and the plate plane. Has been done.

For example, a column in which a groove is finely processed in one substrate to form a separation channel (Patent Document 1), and an eluent mixing device in which a channel is formed by a groove formed in a thin metal plate (Patent Document 2) , A gas chromatograph flow passage assembly (Patent Document 3) in which thin plates having flow passage channels are stacked to form a gas flow passage, for gas chromatography in which a flow passage is formed by through holes or concave grooves on the surface of a metal substrate A gas separation metal column and its manufacturing method (Patent Document 4) have been proposed.

Further, there has been proposed a gas separation unit in which two plates each having a groove on the surface are stacked as a pair to form a flow path, and a plurality of pairs of plates are stacked to communicate the flow paths formed in each pair. (Patent Document 5). Further, there has been proposed a liquid chromatography component (Patent Document 6) in which two substrates are laminated and a fine channel and a liquid chromatography column portion are formed between the substrates. In addition, flat metal plates having a plurality of through holes are stacked, the holes communicate with each other in the vertical direction to form a flow path, and the flow path has a step portion, that is, a metal plate that is in contact with the top and bottom. There is proposed a porous metal body (Patent Document 7) in which the layers are laminated while being laterally displaced.

Various methods such as etching and electric discharge machining are used to form these grooves, and well-known adhesive fixing methods such as ultrasonic bonding, heat welding and diffusion bonding are used to bond these plates. ing.

JP, 2008-232799, A JP, 2003-156481, A JP, 2003-43022, A JP, 2008-241543, A JP, 2006-90806, A JP, 2005-241456, A Japanese Patent No. 5079586

However, the techniques described in Patent Documents 1 to 6 use an internal space formed on the surface of the plate by a groove formed by extending in the surface direction of the plate as a functional structure such as a flow path. Although a configuration provided with holes perforated in the stacking direction of the plates is also disclosed, those holes are used as a connecting portion between the internal spaces extending in the surface direction of the plates as described above or with other spaces. It only has a function. The number of stacked plates including the holes drilled in the stacking direction of the plates is 1 to 3.

That is, a technology is proposed in which a space formed in the stacking direction works functionally with respect to a stacked body completed by stacking the plates only by utilizing a minute space formed between the processed plates. Was not done.

When the internal space is considered to be a flow path, the fluid flows more uniformly when the distance from the center to the side surface of the flow path, which is the resistance, is constant, so in order to achieve this, the cross section of the internal space should be It is better to have a circular shape. However, in the above-mentioned conventional technique, there is also one in which a groove having a semicircular cross-section or the like is formed on the surface of the plate, and two of the grooves are laminated to form an internal space whose cross section is close to a circle. As shown in FIG. 41, a groove is formed on the surface of the plate, but it is difficult to process the cross section of the groove into a perfect semi-circular shape. It was difficult to make a perfect circle. Therefore, since the pressure in the circular direction acts along the mating surface B, it becomes necessary to strengthen the joint surface, and it becomes necessary to secure a sufficient joint distance A between the groove and the side surface of the plate. Although it depends on the material, the pressure used, the diameter of the groove, the joining method, the joining state, etc., in order to have a pressure resistance of 10 kgf/cm ^{2 in} the case where the major axis of the groove is 0.3 mm and diffusion joining is used with stainless steel, It was necessary to set the joining distance A between the side surfaces of the plate to be 3 mm or more, which is 10 times or more the major axis of the groove.

Therefore, the joining distance for joining the plates with respect to the size of the internal space becomes large, and it is inevitable that the parts become large in size, and the device cannot be made compact.

Furthermore, in such a method of forming the internal space, scratches parallel to the flow are generated, and when the internal space is considered to be the flow path, the flow of the fluid flowing in the flow path is uniform and clean across the cross section. I couldn't keep it in the flow. If the fluid flow cannot be kept clean as described above, it cannot be used as a part of an analyzer such as a column.

Further, the technique described in Patent Document 7 is a component in which holes punched in the plates communicate with each other in the stacking direction and work functionally, but the flow path thus formed has a step portion. The center of the flow channel was not coaxial. When the internal space is considered to be the flow path, it is desirable that the distance from the center of the flow path to the side surface of the flow path, which is the resistance, is constant in order to allow the fluid to flow uniformly. Due to the step, the fluid could not flow uniformly. If the fluid flow cannot be kept uniform as described above, it cannot be used as a part of an analyzer such as a column.

Therefore, it is an object of the present invention to reduce the size of parts and devices having an internal space.

Another object is to keep the flow of fluid in the internal space of the device or the device having the internal space clean.

The present invention as a means for solving the above problems is a metal laminated body formed by laminating a plurality of plate-shaped metal plates having through holes formed therein, the through holes communicating with each other The metal laminate is characterized in that a space is formed, and an opening communicating with the internal space is formed on one end face of the metal laminate in the laminating direction.

Further, in the above metal laminated body, a through hole having the same shape or a similar shape is formed in a metal plate to be laminated, and the center or the center of gravity of the through hole is located coaxially.

Further, in the above metal laminated body, the through hole is formed in a circular shape, and the center of the circular through hole is coaxially located.

Further, in the above-mentioned metal laminate, the internal space is a columnar metal laminate.

Further, the above metal laminated body is provided with two cylindrical inner spaces and a communication hole formed by a groove or a hole formed in the metal plate, which connects the two inner spaces. The space is a metal laminated body having an opening at one end surface of the metal laminated body.

In the above metal laminated body, a plurality of plate-shaped metal plates having two through holes formed therein are laminated, the through holes communicate with each other in the laminating direction to form two vertical holes, and two through holes are formed. Formed by stacking plate-shaped metal plates having horizontal holes that connect two vertical holes in succession to the metal plate at one end of the plate-shaped metal plates formed with In the metal laminated body, two openings communicating with the vertical holes are formed on one end face in the laminating direction of the formed metal laminated body.

Further, in the above metal laminated body, the through hole is formed in a circular shape, the center of the circular through hole is coaxially located, and the vertical hole is a columnar shape.

Further, in the above-mentioned metal laminated body, the lateral hole is a metal laminated body formed by a groove or a hole formed in a metal plate.

In the metal laminate, a third flow path communicating with the horizontal hole is provided, and the third flow path is openably and closably opened at the other end surface opposite to the one end surface where the opening of the vertical hole is formed. It is a metal laminate.

In addition, the above metal laminated body is a metal laminated body having a pressure resistance of 40 MPa or more.

In addition, the above-mentioned metal laminate is a metal laminate in which the inner surface of the through hole is treated.

Further, in the above metal laminate, the diameter of the through hole is 60 μm to 3 mm.

Further, in the above-mentioned metal laminate, the deviation of the laminate with respect to the inner diameter of the through hole is 6% or less.

Further, in the above metal laminated body, the metal laminated body is a metal laminated body which is a reaction column or an analytical column in which the vertical holes and/or the horizontal holes are filled with a filler.

Further, in the above-mentioned metal laminate, one vertical hole is filled with a filler, and the other one vertical hole and the horizontal hole are HPLC columns each having a flow path.

In addition, in the above-mentioned metal laminated body, a concave portion for forming a filter is formed on the metal plate.

Further, in the above-mentioned metal laminated body, it is a metal laminated body in which 33 to 2600 metal plates are laminated.

Further, in the above metal laminate, the filler is a metal laminate which is a particle having a particle diameter of 1 μm to 10 μm or a monolith having a pore diameter of 0.01 μm to 10 μm.

Further, in the above-mentioned metal laminated body, the metal laminated body has a quadrangular prism structure, and the surface thereof is a metal laminated body provided with a guide groove for setting in a holder.

According to the present invention as described above, it becomes possible to functionally operate the space formed in the stacking direction with respect to the stacked body completed by stacking the plates.

Further, it becomes possible to reduce the joining distance for joining the plates, and it becomes possible to miniaturize the components that require pressure resistance and thus the device using those components.

Further, when the internal space is considered as the flow path, it is possible to keep the flow of the fluid flowing in the flow path clean and to flow the fluid uniformly in the cross section.

In the present invention, it is possible to realize a component having pressure resistance and durability, which is an important element in a metal processed product, by performing the above-mentioned processing and laminating and forming the metal plate. It was Further, it becomes possible to simultaneously perform processing that can be performed by conventional machining and formation of a fine processing space that cannot be performed by conventional machining.

FIG. 3 is a perspective view of the embodiment of the present invention and a component diagram. Plan view of metal plate Perspective view of the embodiment of the present invention Perspective view of the embodiment of the present invention Plan view of metal plate Partially enlarged plan view of the metal plate Partially enlarged plan view of the metal plate Partially enlarged plan view of the metal plate Perspective view of the embodiment of the present invention Conceptual partial perspective view of metal plate Plan view of a metal plate constituting the metal laminate FIG. 3 is a perspective view of the embodiment of the present invention and a component diagram. Plan view of a metal plate constituting the metal laminate FIG. 3 is a perspective view of the embodiment of the present invention and a component diagram. Pressure fluctuation plot for metal laminate flow rate of the present invention Column holder perspective view holding a metal laminate Side view of the metal part of the present invention Enlarged view of metal parts Enlarged view of metal parts Column holder perspective view holding a metal laminate Chromatogram according to an example of the present invention Chromatogram according to an example of the present invention Side view of the metal part of the present invention The metal part perspective view of the present invention Chromatogram according to an example of the present invention Chromatogram by comparative example Chromatogram according to an example of the present invention Diagram showing an example of a holder Diagram showing an example of a holder Chromatogram according to an example of the present invention Chromatogram by comparative example Chromatogram according to an example of the present invention Chromatogram according to an example of the present invention Chromatogram by comparative example Plan view of a metal plate constituting the metal laminate FIG. 3 is a perspective view of the embodiment of the present invention and a component diagram. Chromatogram according to an example of the present invention Plan view of a metal plate constituting the metal laminate FIG. 3 is a perspective view of the embodiment of the present invention and a component diagram. Chromatogram according to an example of the present invention A prior art metal plate and its laminated conceptual partial perspective view

Embodiments of the present invention will be described below with reference to the drawings. The present invention is a metal laminated body formed by laminating a plurality of plate-shaped metal plates having through holes formed therein, wherein the through holes communicate with each other to form an internal space, It is a metal laminated body in which an opening communicating with the internal space is formed on one end surface. In addition, a plurality of plate-shaped metal plates having two through holes are stacked, the through holes communicate with each other in the stacking direction to form two vertical holes, and a plate shape having two through holes is formed. Of the metal plates, a plate-shaped metal plate having a horizontal hole connecting two vertical holes is continuously formed, and the metal plate is formed by stacking the metal plates. A metal laminated body in which two openings communicating with the vertical holes are formed on one end face in the laminating direction.

Since the metal plates with the through holes are laminated and the through holes communicate with each other to form the internal space, it is possible to reduce the bonding distance for bonding the metal plates to the size of the internal space. It is possible to reduce the size of parts and devices. Further, since the two openings communicating with the vertical holes are formed on one end surface of the metal laminated body, it is possible to reduce the size of the component and the device.

As one embodiment of the metal laminate 1, as shown in FIGS. 1 and 2, the metal laminate 1 is configured by laminating a plurality of thin metal plates 2 having the same outer shape. The metal plate 28 in which the through hole 3 forming the internal space 101 or the metal plate 27 in which the lateral hole 4 is formed and the metal plate 29 in which the through hole and the lateral hole are not formed are combined and laminated. ing. The size, shape, and arrangement of the through holes 3 or the communication holes 4 formed in the metal plate 2 are determined according to the purpose of use of the metal laminate 1, and the through holes 3 or the horizontal holes are formed in the stacked metal plates 2. The metal plate 29 in which the holes 4 are not formed is also included.

As another embodiment of the metal laminate 1, as shown in FIG. 3, a through hole that is configured by laminating a plurality of thin metal plates 2 having the same outer shape to form an internal space 101 of the metal laminate 1. The metal plate 26 in which 3 is formed and the metal plate 29 in which the through hole is not formed are combined and laminated. The size, shape, and arrangement of the through holes 3 formed in the metal plate 26 are determined according to the purpose of use of the metal laminate 1.

The metal plates 2 to be stacked have the same shape, and further, through holes having the same shape or a similar shape are formed in the metal plates 2, and the centers or the centers of gravity of the through holes are coaxially located at the time of stacking. With such a configuration, the internal space formed by the through holes is formed in a linear shape, and when the internal space is considered to be the flow path, the fluid can flow uniformly.

As a processing method for forming the through holes 3 and the lateral holes 4 of the metal plate 2, conventional techniques such as etching and machining can be used. Further, for the adhesion of the laminated metal plates 2 to each other, a known adhesion method such as diffusion bonding, heat welding, ultrasonic bonding or the like can be used.

When the internal space formed in the metal laminate 1 is considered to be a fluid flow path, the fluid flows uniformly if the distance from the center to the side surface of the flow path serving as resistance is constant. It is preferable that the through hole be circular, and that the center of the circular through hole is coaxially located when the metal plates are laminated. Further, when the metal laminated body is used as a tank, a mold or the like as shown in FIG. 3, the pressure can be increased by uniformly applying pressure to the surface, so that the inner space is preferably close to a spherical shape. As described above, it is desirable that the internal space has a circular cross section to form a columnar or spherical space in the component.

As in the present invention, by forming a through hole in one metal plate and stacking the through holes in the through direction, it is possible to form an internal space having a very small aspect ratio of the diameter and the length of the through hole. It is possible to machine holes of several tens of μm in a metal plate having a thickness of 0.2 mm, and finer holes can be formed by using etching or the like. Also, machining on a perfect circle can be done easily. The length of the internal space can be freely changed by changing the number of stacked metal plates.

Conventionally, in the case of machining pipes, tubes, etc., which are fluid passages having a circular cross section, they have been manufactured by rolling metal, extruding press, welding or the like. However, it is well known that inner surfaces of pipes, tubes and the like have scratches extending in the manufacturing process thereof, which are perpendicular to the cross section of the circular elongated channel, in other words, extend in the longitudinal direction of the channel. Therefore, processing such as inner surface polishing is performed after fabrication.

However, it is difficult to polish the inner surface of a thin pipe or tube having an inner diameter of 3 mm or less. On the other hand, a flaw in the direction perpendicular to the cross section orthogonal to the longitudinal direction of the pipe or tube is present in parallel to the fluid flow, and the fluid flows along the flaw, so that there is no effect on the fluid flow. growing.

For example, in the case of a column of liquid chromatography, the influence of the scratch occurs on the separation/analysis when the length is 10 times or more the inner diameter. Since a hole diameter of 2 mm, which is often used as a separation field, will be affected by 20 mm or more. Therefore, in the case of a column of such a size, by stacking 100 or more metal plates 2 having a plate thickness of 0.2 mm, It is preferable because it has higher performance than the conventionally machined pipes and tubes.

The details of the embodiment of the metal laminated body will be described below. When the metal laminate 1 is used as a pressure resistant component having a fluid flow path, for example, an analytical column for liquid chromatography, the metal laminate 1 has two identical shapes as shown in FIG. A plurality of metal plates 28, each having a circular through hole 3 perforated at equal distances from the longitudinal end and the lateral end of the metal plate 2, are provided at one end portion of the metal laminate, that is, the uppermost step portion in FIG. 1. A metal plate 27 that is laminated and is continuous with the metal plate 28 at one end of the metal plates 28, and has a horizontal hole 4 having a length between the upper two through holes 3 formed below the metal plate 28 in FIG. One of the metal plates 27, which is continuous with the metal plate 27 at one end thereof and has no hole formed in the lowermost step below the metal plate 27 in FIG. ing. The through holes 3 communicate with each other in the stacking direction to form two vertical holes, the two vertical holes 61 are connected by the communication hole 62 constituted by the horizontal holes 4, and the two vertical holes 61 are arranged in the stacking direction. An opening is formed on one end surface, that is, the upper surface 150 in the figure.

In addition, in the metal laminated body 100 according to another embodiment, as shown in FIGS. 4 and 5, two circular through holes 31 and 32 having different diameters are provided from the lateral end of the metal plate 2, respectively. A plurality of metal plates 200 perforated at equal distances to the center of the circle are stacked at one end portion of the metal laminate, that is, the uppermost step in FIG. In FIG. 4, a metal plate 220 having a horizontal hole 4 having a length between the upper two through holes 31 and 32 is laminated below the metal plate 220 and is continuous with the metal plate 220 at one end of the metal plate 220. In FIG. 4, the metal plate 230 below which is not formed with a hole in the lowermost step is formed by laminating one sheet to a predetermined plurality of sheets. The through holes 3 communicate with each other in the stacking direction to form two vertical holes 61, the two vertical holes 61 are connected by the communication holes 62, and the two vertical holes 61 are one end face in the stacking direction, that is, the upper surface in the figure. An opening 150 is formed in the.

The lateral hole 4 formed in the metal plate 220 may be a hole that penetrates the metal plate 220, or may be a groove that does not penetrate. The communication hole formed by the lateral holes 4 may be a single metal plate 220 having a hole penetrating the metal plate 220, or may be a plurality of metal plates 220.

The diameter of the vertical hole 61 may be changed in the middle of the stacking direction of the metal plates. For example, the two circular through holes 3 may be formed to have a diameter smaller than that of the other through hole that connects one or both of the through holes of the metal plate in the lowermost part of the metal plate in which the two through holes 3 are punched.

Further, the change of the diameter of the vertical hole 61 in the middle of the laminating direction of the metal plates may be achieved by laminating the metal plates having the through holes having different diameters, but as shown in FIG. In the sheet of metal plate 2, a small-diameter circular through hole 292 may be formed at the center of the large-diameter circular groove 291. Then, as shown in FIG. 7, by forming the large-diameter circular groove 291 in a tapered shape 295, it is possible to reduce the retention of the fluid, which is preferable.

In this way, by stacking the metal plates having the horizontal holes 4 formed therein, it is possible to form cylindrical internal spaces (vertical holes 61) that are connected to each other inside the metal, which cannot be obtained by conventional machining. The number of holes formed in the metal plate and the hole diameter can be freely selected.

Further, as shown in FIG. 8, eight kinds of metal plates each having circular through holes with different diameters are formed, and the number of each of the five metal plates is changed from small to large, then to small, and finally to small. A total of 25 sheets, 100 sheets in total, were laminated and diffusion-bonded to each other to produce a metal component 71 having a spherical internal space 101 as shown in FIG. Such a metal laminated body can be used as a mold, and as shown in FIG. 3, as the internal space 101 of the metal laminated body 71, a spherical cavity 21 forming a spherical molded article and a raw material of the molded article are used as a cavity. A columnar runner 23 for injecting into 21 is provided. The metal plate 2 forming the runner 23 has through holes of the same shape formed at the same position, and the metal plate forming the cavity 21 has a circular through hole centered coaxially with a small diameter in the stacking direction. To a large diameter, and a through hole that changes from a large diameter to a small diameter is formed. The number of laminated metal plates of the same type is not limited to five, and can be increased or decreased as appropriate.

Further, by combining the quadrangular through holes and the circular through holes, it is possible to manufacture the metal component 72 in which the rectangular parallelepiped space 119 is connected to the cylindrical space 118 as shown in FIG. Such a metal laminate can be used as a mold, and as shown in FIG. 9, a rectangular parallelepiped cavity 210 for forming a rectangular parallelepiped molded product and a cylindrical runner for injecting the raw material of the molded product into the cavity 210. 230 will be provided. A rectangular through hole is formed in the metal plate forming the cavity 210.

The material of the metal plate forming the metal laminate is not particularly limited, but stainless steel can be used. The thickness of the metal plate is not particularly limited, but the thinnest plate thickness that can be photo-etched is about 0.005 mm, and considering the ease of making a laminate, about 0.2 mm is preferable. When the body is used as an HPLC column, when the thickness of the metal plate itself becomes the flow path diameter of the HPLC, considering the effect of dead volume, about 0.75 mm is preferable, so 0.005 mm or more and 0.75 mm or less Preferably.

As described above, the present invention is a metal component that has a component part that vertically stacks metal plates partially provided with circular through holes and that has a cylindrical space in the vertical direction with respect to the stacking. The shape and the like of the laminate are not limited to the above shapes. The metal laminate is a mechanical component, an optical component, a sensor component, a liquid/gas flow channel, or a solid that has a function by laminating metal plates that have been cut, pressed, or etched and bonded by diffusion bonding, adhesion, or close contact. It can be used as a molded part, a biofunctional part, or a mold part for a biofunctional material. In addition, a vertical hole is formed by high-aspect through-holes, and it can have a flow path with a complicated shape such as a perfect circle or a honeycomb structure. The combination of these parts will provide a composite part that has a function for the first time. It is possible.

As described above, by laminating the metal plates having circular holes, it is possible to eliminate scratches parallel to the flow, and it is possible to form a clean flow in the metal component. Further, the conventional method of forming a space close to a circle by laminating two plates having a groove having a semicircular cross section on the surface is used to produce a metal plate having a circular hole according to the present invention. The space created by stacking can form a more durable space.

Also, conventionally, as shown in FIG. 41, two plates each having a groove having a semicircular cross section on the surface of the plate are overlapped to form a space close to a circle, and the groove is completely semicircular. It is difficult to process into a circular shape, and when they are overlapped, the cross section is limited to an elliptical shape and it is difficult to form a perfect circle. Therefore, since the pressure in the circular direction acts along the mating surface B, it is necessary to strengthen the welding surface, and it is necessary to secure a sufficient distance A between the groove and the side surface of the plate. Increasing the size of parts is inevitable.

However, in the present invention, since the circular through holes are formed in the metal plate, it is possible to easily make a cross section in a direction orthogonal to the stacking direction of the metal plates in the internal space such as the flow path, to be a perfect circle. The force is evenly applied in the direction, and a large welding surface is not necessary for the diameter of the circle of the through hole. Therefore, as shown in FIG. 10, the distance A between the through hole and the side surface of the plate and the distance between the through holes may be much shorter than the distance shown in FIG. 41 of the conventional example. Although it depends on the welding method, if diffusion bonding is used, they will be integrated, so that the distance from the through hole to the side surface of the plate can be formed with a numerical value similar to the thickness of a normal metal pipe. For example, in the case where the material is SUS316 and the diameter of the through hole is 2 mm, when the pressure resistance of 50 MPa is required, the distance A from the through hole to the side surface of the plate is 0.7 mm. Even with a pressure resistance of 100 MPa, a distance half the diameter of the through hole is sufficient.

Further, when two plates having a groove having a semicircular cross section are stacked on the surface of the plate, not only the distance between the groove and the side surface of the plate but also the thickness X of the plate to be joined is the diameter of the hole. It is necessary to make it about twice as wide. Further, when two plates each having a groove having a semicircular cross section on the surface of the plate are stacked to form a cylinder, a line along the direction B, that is, the flow direction of the fluid is formed. Further, in order to form a long groove, the parallelism of the plate is required, and in order to realize it, the thickness that can withstand the stress is required, and the metal portion is increased in the space. As a result, the size increases, the amount of metal material increases, and the parts become heavier.

On the other hand, in the present invention, a large number of thin plates having through holes, for example 100 or more, are formed by laminating and joining, so that even if the joining state of one sheet and one sheet is partially poor, the entire joining is uniform. If it is, there is little influence on the breakdown voltage. Of course, it is desirable that one sheet and one sheet are completely joined together, but even if the sheets are not completely joined together, it is possible to improve the withstand voltage by performing a known surface treatment on the defective portion. That is, it suffices to repair only the poorly joined portion. As the inner surface treatment for surface-treating the inner surface of the through hole, a method of applying or bonding a chemical substance to the inner surface of the through hole such as chromite treatment or polysilazane treatment can be used.

As described above, in the present invention, since the size of the component can be made smaller than the internal space, the temperature responsiveness becomes high, and the component can be suitably used for a separation column for chromatography or a reaction column. The application of the metal laminate of the present invention to a separation column for chromatography will be described in detail below.

Since a separation column for chromatography requires temperature control and pressure resistance, a metal pipe is used. The particle size of the filler used in HPLC is generally 1 μm to 10 μm. As described above, in the machined metal pipe, streaks (scratches) are formed in the channel direction, and the peak shape of the chromatogram becomes poor. In particular, a pipe with an inner diameter of less than 3 mm, which is difficult to perform a process such as polishing to remove the scratch, is likely to be affected. A packing material such as a separating agent and a catalyst are packed in such a pipe, and a filter is attached before and after the filling material to form a separation column or a reaction column. In order to fix the filter, it has been devised to attach joints before and after the pipe and to make the flow from the filter uniform. In some cases, such as the cartridge type, the holder is separated from the column body and processed, but in either case, it is a separate part such as a filter holder that holds those filters or a separate part such as a diffusion plate that makes the flow uniform. Is used.

On the other hand, in the present invention, since metal plates having circular through holes are laminated to create a space inside the metal laminate, the metal plates are laminated before or/and after the filling section for filling the filler in the internal space. In order to install the filter on the metal plate to be formed, a concave portion composed of a circular through hole or groove matching the filter diameter is formed, and further, a through hole or groove is provided with a taper or a hole having a reduced diameter is formed. By providing and stacking them in order or individually, an integrated type column that does not require a separate part for attaching a filter is formed. Further, instead of the filter, a metal plate having pores smaller than the diameter of solid or powder filled in the internal space of the metal laminate may be used.

In the conventional column, 1. Pipe manufacturing, 2. Pipe cutting, 3. Internal polishing, 4. Processing for joint connection to pipes, 5. Joint production, 6. Install a filter on the outlet side, 7. Tighten, 8. Filling, 9. Install a filter on the entrance side, 10. Tighten. Therefore, at least 10 steps or more are required, and manual work such as tightening is absolutely necessary, and each piece is manufactured.

However, in the present invention, 1. 1. Production of metal plate with perforations (depending on size, 50 or more can be produced on one surface) 2. Stack them and diffusion bond them, 3. 3. Form multiple columns by cutting at once. Filter in, 5. Filling,6. Filter installation. And it can be completed in 6 steps. Up to 3 steps, depending on the size of the device, it is possible to produce 50 or more column parts in one process. , Manual work can be greatly reduced. If the steps 4, 5, and 6 are performed before the cutting of step 3, it is possible to produce 50 or more packed columns at one time.

In an HPLC column, the conventional manufacturing method requires a step of using various pipes having different inner diameters, lengths, and the like, and attaching a machined joint connection portion to each of them. The pipes are machined one by one and the metal joints are machined one by one, which causes variations in machining. In particular, since the liquid leaks from the connection seal portion of the connection joint even if the damage is a little, the post-processing for each part is indispensable. That is, shaving work is required, resulting in different finishes.

On the other hand, in the present invention, by using the MEMS technology, it becomes possible to manufacture many columns of various types by one diffusion bonding. The parts that go out such as the connection part are all metal surface parts, which makes it easy to process and there are no scratches in the flow path direction on the column part, so there is no need for post-processing and it is a metal part that can withstand high withstand pressure. An HPLC column can be prepared.

Another feature of the MEMS technology is that it is possible to use a pattern mask in which various master plates are combined, so that it is possible to easily fabricate a large number of metal plates having the same pattern, and by diffusion bonding them, Depending on the size of the diffusion bonding apparatus, several types of columns can be easily manufactured at one time by several diffusion bonding at one time. And, since the same master plate is used, it is obvious that the variation between products is significantly reduced as compared with the conventional parts processed one by one.

How many pieces are produced at one time depends on the size of the diffusion bonding apparatus, but the effective part that is often used experimentally is that the inner diameter of the diffusion bonding apparatus is 25 cm in length, 25 cm in width, and 25 cm in height. With a 1 mm column, several hundreds of columns can be manufactured at once. For example, in the case of two columns having an inner diameter of 2.1 mm connected to each other, in the method of the present invention in which metal plates having perfectly circular through holes are stacked, if one diffusion bonding portion is 0.7 mm or more, 50 MPa or more. A sufficient pressure resistance will be obtained, and it is sufficient if the size is 2.1 mm × 2 + 0.7 mm × 2 + 0.7 mm + 0.7 mm = 7 mm in length and 2.1 mm + 0.7 mm × 2 = 3.5 mm in width. It is possible to obtain 1250 lines from one diffusion bonding. In practice, 550 columns can be manufactured into a column having an inner diameter of 2.1 mm and a length of 5 cm because of its easy handling.

The length of an HPLC column having an inner diameter of 2.1 mm and a particle diameter of 3 μm, which requires high pressure resistance, is 150 mm at maximum due to the pressure resistance of the apparatus used, and 20 mm to 100 mm is often used.

Since it is easier to connect the columns only on one side of the metal laminate, the two vertical holes 61 are opened at one end face in the stacking direction, that is, the top face in the figure, and the column length is 100 mm. It is preferable to form two internal spaces (vertical holes) as a column portion (height in the stacking direction) of 50 mm. With such a configuration, a height of 60 mm is sufficient even if a laminated portion of metal plates that constitutes a vertical hole connecting portion (communication hole) is inserted.

The number of stacked metal plates may be any as long as the diffusion bonding apparatus allows it. Further, not only all the through holes have the same hole diameter but also different hole diameters are appropriately combined to form different column parts at a time according to the purpose of use.

In the present invention, the plates having the through holes are laminated, but compared with the column made of the conventional pipe, the number of laminated column space parts, that is, the lamination height is the length of the pipe, and the diameter of the through hole is the inner diameter. Corresponds to. For example, in the case of producing a column having a length of 10 cm, if a 10 cm pipe is used and a joint part is inserted, the total length becomes 13 cm or more.

In the present invention, for example, by connecting two vertical holes having a height of 5 cm, which is a space (filling portion) for filling a filler having a height of 5 cm, with the communicating holes, even if a portion for inserting a filter is inserted, It can be formed with a size of 6 cm. If two packed parts are made and communicated inside the metal laminate, a column having a length of 10 cm will be obtained. If three packed parts are made to communicate with each other, a column having a length of 15 cm will be obtained. The length can be adjusted freely.

In the case of a separation column, the communication holes that connect the vertical holes have a dead volume, so the volume of the communication holes must be 1/10 or less of the space volume after the packing material is filled in the packing portion. is there. The actual volume of the communication hole varies depending on the type of filler used, and for example, in the case of filling a space having an inner diameter of 2.1 mm and a length of 5 cm with the filler, the space of the filling portion for filling the filler is 0. 0.17 mL. When the monolith body having the highest porosity is packed therein, the packing density is about 0.4, and the space volume after packing the column is 100 μL. Therefore, the space other than the filling portion needs to have a volume of 10 μL or less, which is one-tenth or less of the space volume after column filling. Further, in the case where fine particles having the highest packing density of 1.5 μm octadecyl group-bonded silica gel are packed, the packing density is about 0.8, and the space volume after packing is 35 μL. The space other than the filling portion needs to have a volume of 3.5 μL or less, which is 1/10 or less. Assuming that the length of the communication hole that connects the vertical holes is 8 mm, the maximum diameter of the allowed horizontal holes is 0.75 mm (0.75 mm ID×8 mm≈3.5 μL).

When the cross section is circular, the diameter of the communication part, which connects the columns composed of vertical holes, and the communication part composed of communication holes, if the cross section is rectangular, the vertical and horizontal lengths should be less than 0.75 mm. A configuration in which a lateral hole is formed by a through hole using a metal plate of 0.75 mm or less is suitable. In the case of a HPLC column with a column length of 20 mm, it can be configured by combining 3 pieces in the joint part, 27 pieces in the filling part, 1 piece in the filter driving part, 1 connecting part, and 1 bottom plate part, with a minimum of 33 pieces or more. Can be formed by stacking.

The thinnest plate thickness that can be photo-etched is said to be 0.005 mm, but from the viewpoint of the accuracy of the current diffusion bonding apparatus, when about 100 sheets are stacked, a maximum of 0. Since it is said that a shift of 030 mm occurs, it is necessary to form the filling internal space (filling portion) and other vertical holes with a diameter larger than 60 μm so that the through hole is never blocked.

For example, in the case of a plate thickness of 60 μm, two circular through holes with a diameter of the through hole of 0.1 mm are formed, and a thickness of a joint portion for driving a filter with a thickness of 0.2 mm is 0.3 mm. 2500 pieces in the filled portion 150 mm with two 60 μm perfect circular through holes, 4 pieces in the embedded portion of the 0.2 mm filter, 1 communicating portion (transverse hole) that penetrated, 80 μm filling solvent through hole processing The height is 1 mm, and the total number of layers is 17, which is about 2,600 in total. It is possible to manufacture a column having an inner diameter of 0.1 mm and a length of 300 mm and high pressure resistance. This is the maximum number of stacks for the HPLC column.

Actually, considering the required size as a column and the ease of making, the 0.2mm plate thickness that reduces the dead volume is good, and the joint part is 9 pieces + the filling part is 30mm, 150 pieces, the filter driving part is 1 piece, and the penetration is There is a total of 162 sheets, one communicating portion (lateral hole) and one bottom plate portion. As the HPLC column, it is recommended to stack several hundred sheets.

The positional deviation of the through-holes due to stacking basically causes no problem if the through-holes penetrate through after stacking, but as a column for chromatographic separation, it affects the analysis result during actual use. The variation in the actual elution time in HPLC is preferably as small as possible, but in the gradient elution used in the high pressure HPLC, about 12% is an allowable variation with respect to the good elution time. That is, by suppressing the deviation of the lamination with respect to the inner diameter of the through hole to 6% or less, it is possible to suppress the variation in the elution time to about 12%. In the current technology, it is said that the maximum deviation width in the diffusion bonding of about 100 metal plates is about 30 μm. Although accuracy may increase in the future, stacking through-holes with a diameter of 0.5 mm or more is suitable for the HPLC column as a packing part in view of the current dispersion of stacking. Even with a maximum deviation of 30 μm from the diameter of 500 μm, the variation in elution time can be suppressed to 12% or less, and the column can be used as a separation column for chromatography. That is, for the HPLC column, it is necessary to suppress the stacking variation to 6% or less of the inner diameter.

As described above, the component according to the present invention can be applied to an HPLC column, which has the most required specifications such as accuracy, pressure resistance, dead volume among metal components. When the metal part according to the present invention is used for a column, the conventional connection joint is unnecessary, and the joint is possible without tightening. As the joint, the surface of the laminated plates is exposed at the connection surface, so that the surface is clean and face sealing can be easily performed without processing.

Inside the metal laminate having two vertical holes, it is possible to form a liquid passing portion that connects the vertical holes and is not affected by dead volume. Therefore, configure the column injection side and outlet side in the same direction. It is possible to easily seal by pressing from one side from the outside.

In addition, the discharge passage necessary for discharging the liquid to be injected at the time of filling the particle type filler other than the monolith type is connected to the communication hole as the third flow passage, and the third flow passage is formed with a vertical hole. It is also possible to open on the other end surface opposite to the one end surface and to open and close by closing the discharge passage with a plug that can be inserted and removed after filling. The discharge path can be formed by forming a through hole and laminating one or more metal plates.

When two vertical holes and a communication hole that connects the vertical holes to each other are formed in the metal laminate, the filling portion may be formed only in one vertical hole or in only two vertical holes. The hole and the communication hole may be filled with the filler, or the two vertical holes and the communication hole may be filled with the filler, or only the communication hole may be filled with the filler to form the filling portion.

The filler that fills the communication holes of the metal laminate must be in the form of particles, but the filler that fills the vertical holes is in the form of particles, as well as a monolith with an integral shape, and a glass film is formed on the surface of the monolith. The glass clad monolith body can be used.

The metal laminate of the present invention can be used for machine parts, optical parts, sensor parts, liquid/gas flow paths, solid molded parts and the like.

A column tube having an inner diameter of 2.0 mm and a length of 31.4 mm (metal plate thickness 0.2 mm×157 sheets) was formed as follows. 11A to 11F are plan views of the metal plate. Each of the metal plates is made of a plurality of metal plates, and the metal plates are laminated and adhered to each other to form a plurality of metal laminated bodies, which are then cut and manufactured. It

A metal plate 201 (FIG. 11(a)) in which a cylindrical through hole 301 having a diameter of 3 mm for connecting another flow channel and a column and a cylindrical through hole 302 forming a flow channel outlet is formed, as a filling portion. A metal plate 202 in which a cylindrical through hole 303 having a diameter of 2 mm for filling a filler and a cylindrical through hole 304 forming a cylindrical space having a diameter of 0.2 mm of the second vertical hole are formed (FIG. 11B). ), a metal plate 203 having a groove 305 for creating a space for holding a circular diameter filter for holding a filler, a cylindrical through hole 306, and a cylindrical through hole 307 forming a second vertical hole (FIG. 11(c)). )) Metal plate 204 (FIG. 11(d)) for forming two cylindrical through holes 308 and 309 having a diameter of 0.2 mm and a lateral hole constituted by a through hole 310 having a depth of 0.2 mm. A pattern mask made of glass for producing a plurality of metal plates 205 (FIG. 11E) for forming and a plurality of metal plates 206 (FIG. 11F) adjacent to the lateral holes and defining one surface of the lateral holes. Was produced.

Using this pattern mask, a resist was applied, and 60 patterns of 15×4 rows were transferred by printing onto a metal plate surface having a plurality of metal plate surface areas. The resist at the portion exposed to the transmitted light was cured, and then developed to remove the uncured resist. A portion where no resist remains is etched, then the resist is removed and washed to obtain a metal plate having a thickness of 0.2 mm provided with patterned through holes for a plurality of metal plates having the same shape. .. By repeating this process continuously, nine metal plates 201 shown in FIG. 11A, 157 metal plates 202 shown in FIG. 11B, and one metal plate 203 shown in FIG. One metal plate 204 shown in FIG. 11(d), one metal plate 205 shown in FIG. 11(e), and 131 metal plates 206 shown in FIG. 11(f) were obtained. These 300 metal plates were laminated and diffusion-bonded to obtain a laminate in which a plurality of metal plates were integrally formed.

After the diffusion bonding, the stacked metal plates 3 were cut in the stacking direction to obtain 60 metal components 10 including a metal stack having a cylindrical internal space 101 shown in FIG.

A column tube having an inner diameter of 2.0 mm and a length of 51.4 mm (metal plate thickness: 0.2 mm×257 sheets) was connected to form two column tubes as follows. 13A to 13F are plan views of the metal plate. Each of the metal plates is made of a plurality of metal plates, and the metal plates are laminated and adhered to each other to form a plurality of metal laminated bodies, which are then cut and manufactured. R.

A metal plate 201 (FIG. 13(a)) for forming cylindrical through holes 331 having a diameter of 3 mm at two locations for connecting another flow path and the column, and two locations for filling a filler as a filling portion. A metal plate 212 (FIG. 13B) for forming a cylindrical through hole 332 having a diameter of 2 mm, a groove 335 for creating two spaces for holding a circular diameter filter for holding a filler, and a cylindrical through hole 336. A metal plate 213 (FIG. 13(c)) in which two holes are formed, and a metal plate 214 (FIG. 13(d)) for forming two cylindrical through holes 336 having a diameter of 0.2 mm, a through hole having a depth of 0.2 mm. A metal plate 215 (FIG. 13E) for forming a lateral hole constituted by the hole 337, a cylindrical through hole 338 having a diameter of 0.8 mm for discharging the solvent at the time of filling the filler (the discharge passage, the third A patterned mask made of glass for producing a plurality of metal plates 216 (FIG. 13(f)) for forming the flow paths was produced.

Using this pattern mask, a resist was applied, and 60 patterns of 15×4 rows were transferred by printing onto a metal plate surface having a plurality of metal plate surface areas. The resist at the portion exposed to the transmitted light was cured, and then developed to remove the uncured resist. A portion where no resist remains is etched, then the resist is removed and washed to obtain a metal plate having a thickness of 0.2 mm provided with patterned through holes for a plurality of metal plates having the same shape. .. By continuously repeating this step, nine metal plates 211 shown in FIG. 13A, 257 metal plates 212 shown in FIG. 13B, and one metal plate 213 shown in FIG. One metal plate 214 shown in FIG. 13(d), one metal plate 215 shown in FIG. 13(e), and 31 metal plates 216 shown in FIG. 13(f) were obtained. These 300 metal plates were laminated and diffusion-bonded to obtain a laminate in which a plurality of metal plates were integrally formed.

After the diffusion bonding, the stacked metal plates were cut in the stacking direction to obtain 60 metal components 11 composed of a metal stack having a cylindrical internal space 101 shown in FIG. There is also a metal plate omitted in FIG. 14(b).

There was no problem even if the pattern mask of Example 1 and the pattern mask of Example 2 were combined and two or more different types were patterned.

A variation test of withstand voltage was performed by diffusion bonding of the metal components of Example 1. Diffusion bonding is a bonding method in which bonded interface portions are integrated by heating and pressing, and is used for bonding various metal parts. However, with respect to general metal parts, variations in pressure resistance when liquids or gasses are put in have not been confirmed or studied. However, in order to increase the breakdown voltage, since metal plates having through-holes with a perfect circular cross section are laminated, the influence on the breakdown voltage of the diffusion bonding is important.

With respect to the metal laminate having the structure of Example 1, the pressure resistance of a metal component in which 300 metal plates of 0.2 mm thickness using SUS316L were laminated was examined. Three types of diffusion-bonded metal parts A, B, and C were obtained by changing the diffusion-bonding conditions. The metal component A has a laminated height of 60.101 mm, the metal component B has a laminated height of 59.497 mm, and the metal component C has a laminated height of 58.615 mm.

The metal parts A, B, and C were installed in the column holder 80 of Example 4, a stainless tube having an inner diameter of 0.13 mm and a length of 3 m was attached to the outlet as a resistance tube, and chloroform was often used for filling with a pump. The pressure resistance was examined by changing the flow rate from 1 mL/min to 20 mL/min. A pressure fluctuation plot with respect to the flow rate is shown in FIG.

The metal part A did not rise above about 20 MPa, and liquid oozes out on the surface. The metal parts B and C increased to 80 MPa and 100 MPa in proportion to the flow rate, and no leakage occurred. However, in the metal part C, since the diffusion bonding conditions were too strong, it was considered that the flow path in the metal part was partially filled with metal and narrowed. For metal parts such as HPLC columns and reaction tubes used with high pressure resistance, a clear difference in pressure resistance was observed depending on the pressure conditions of the diffusion bonding method.

Using a metal plate of SUS316L, by a diffusion bonding method for the metal part B, a column having 10 columns having the configuration of Example 1 and 40 columns having the configuration of Example 2 was prepared in a mask pattern, and diffusion bonding was performed. After that, a total of 50 metal parts were obtained by cutting. As a result of measuring the stack height, it was confirmed that the average was 59.483 mm, the standard deviation was 0.03 mm, and the CV (coefficient of variation) was 0.05%, showing high reproducibility and no variation. Two columns were randomly picked up from the column having the constitution of Example 1, 10 were randomly picked from the column having the constitution of Example 2, and when the liquid was fed at 8 mL/min with 100% of water, the pressure was 44 MPa. It was demonstrated that the reaction tube has sufficient pressure resistance.

If a withstand voltage test is performed once and diffusion bonding conditions with a withstand voltage of 40 MPa or more are used, it is possible to obtain several tens of metal parts having a withstand voltage of 40 MPa or more with good reproducibility.

As in Examples 1 to 3, it was verified whether or not a component obtained by laminating metal plates provided with through holes having a perfect circular cross section could be used as an HPLC column. In the metal part of the present invention, since it is unnecessary to use a conventional pipe, it is not necessary to connect a ferrule, an cine, a screw, or the like. Further, since the flow path can be provided inside the metal part, the flow path can be folded back inside the metal part, and the connection part of the column can be gathered in one direction. In the conventional pipe type column, it is necessary to connect the columns and the packer while tightening them with a spanner so that they can withstand high pressure.

In the metal component of the present invention, as shown in FIG. 17, the portion 91 to be stopped by the filter which is the connection seal surface or the connection portion 92 with the chromatography device is a metal plate surface, which is a clean and smooth surface, and the packer 82 as it is. By simply applying a force to the metal component 10 of the present invention in the vertical direction, the metal component 10 can be easily connected to have a high withstand voltage. Although the filling jig is not limited to this shape, the filling jig 80 of FIG. 16 was prepared and used for this verification. The packer 82 and the metal component 10 can be easily sealed by applying a force in the vertical direction at the connection seal portion 85. As a method of applying the force in the vertical direction, the lever principle may be used as in the column holder of Example 8 to be described later, but in the filling of the present example, the hexagonal screw 83 was turned to suppress the vertical direction.

17 is a side view of the metal component 10 shown in FIG. 12 in the first embodiment inside the metal component of the present embodiment. When the metal part 10 is used as an HPLC column, a filter driving part 94, a communication part 93 composed of lateral holes, a filling part 99 for filling a packing material, a filter setting part 91 after filling, and a connection part 92 with the device. Become.

When used as an HPLC column, high withstand pressure is required. Therefore, as shown in FIG. 18, the tip portion 931 of the communicating portion 93 is processed so that its cross section is close to a circle, and the lateral hole has a diameter of 0.2 mm. With respect to the groove processing of No. 3, the end portion is subjected to circular processing with a diameter of 0.3 mm, and is configured to withstand deformation when the filter is driven. Further, as shown in FIG. 19, the vertical cross section of the filter driving part 94 is half-etched so that the fluid flows through the entire filter even when the filter holding the filler is driven. When used at a flow rate of 50 μL/min or more, if there is no half-etched portion 95, there is no space between the filter and the punched surface, so the inner diameter becomes sharply sharp, and salts and the like easily precipitate. It is preferable to form the half-etched portion 95. However, if the flow rate is less than 50 μL/min, the influence of dead volume due to the filter driving part 94 becomes large, the flow rate becomes slow, and the filter flows throughout the filter, so the importance of this half etching diminishes.

In practice, it is necessary to select the optimum shape while checking the chromatographic data after packing, but in the case of an HPLC column having an inner diameter of 1 mm or more, it is preferable to incorporate a half-etched part.

The HPLC column using the metal part 10 manufactured in Example 1 has an inner diameter of 2.0 mm and a length of 31.4 mm. In this example, the inner diameter was 2.0 mm and the inner diameter was 1 mm or more, so a half-etched metal plate was incorporated.

First, a sintered metal filter having an outer diameter of 2 mm, a thickness of 1 mm, and made of SUS316 and having 0.2 μm holes was inserted into a metal part, and was punched and fixed. The filter can be fixed with an adhesive that has solvent resistance, but it can also be stopped by just driving because the part where the filter is stopped is half-etched.

As shown in FIG. 16, the metal component 10 was set in the packer 82 and fixed with hexagonal screws 83. Seals obtained by punching out a PEEK sheet having a thickness of 50 μm were used for the device connecting portions 91 and 92. The packer 82 used had an inner diameter of 3 mm and a length of 30 cm. Octadecyl group-bonded silica gel packing material for HPLC Inertsil ODS-3 3 μm (manufactured by GL Science Co., Ltd.) 0.3 g is weighed into a beaker, added with 3 mL of hexanol, and ultrasonically added with an ultrasonic cleaner to thoroughly mix and fill. An agent slurry was prepared. The slurry was put in from the upper part of the packer 82, connected to a high pressure pump, and was filled with a pressurized solvent dichloromethane at a flow rate of 1 mL/min at a constant flow rate. The pressure increased up to 60 MPa and became constant at 40 MPa. Next, the pressurized solvent was changed to methanol, and the solution was fed at a constant pressure of 50 MPa for 2 hours. During this filling, no liquid leakage was observed from the metal parts and the connecting portion, demonstrating that the HPLC column has sufficient pressure resistance.

In Example 4, an HPLC column in which Inertsil ODS-3 3 μm was packed in the metal part of Example 1 was used, and the packer part used for packing in Example 4 had an inner diameter of 0. A stainless steel pipe 79 having a length of 25 mm and a length of 10 cm was used, and it was set on a high performance liquid chromatograph LC800 (manufactured by GL Sciences Inc.) for analysis and evaluation.

Eluent 35% acetonitrile aqueous solution, oven temperature 45° C., detection UV254 nm (MU701, cell optical path length 5 mm, cell volume 1 μL), sample 1. Uracil, 2. Acetophenone, 3. Benzene, 4. Toluene, 5. The evaluation was performed by changing the flow rate with naphthalene. The respective results show that the flow rate of 0.4 mL/min is shown in FIG. 21(a), 0.8 mL/min is shown in FIG. 21(b), 1 mL/min is shown in FIG. 21(c), and 1.5 mL/min. min is shown in FIG.
The analytical pressures changed to 7.4 MPa, 17.5 MPa, 24 MPa, and 40 MPa, respectively, but neither the leak nor the column deteriorated, and it was confirmed that the metal part of the present invention is effective as a high pressure HPLC column. Was done.

Furthermore, it was evaluated by a gradient analysis which is often used as an HPLC analysis. As a result of performing a linear gradient from 40% acetonitrile aqueous solution to 100% acetonitrile for 1.5 minutes at a flow rate of 0.2 mL/min and other conditions as above, as shown in FIG. 22, at all peaks, A tailing-free peak having a peak symmetry of 1.2 or less was obtained, and it was verified that the inner wall surface of the stacked column tubes had a uniform flow in the HPLC analysis.

It was verified whether a metal plate having a through-hole having a perfect circular cross section was laminated and a component having two packing portions for packing a packing material could be used as an actual HPLC column. Since the direction of the flow path can be folded back by providing the communication part (lateral hole) as in Example 5, it is possible to provide a space to be the packing part at any number of places, but as a particle packing type HPLC column, packing is performed. Since steps are required, it is preferable to provide two filling portions as shown in this embodiment.

23 is a side view of the metal part 11 shown in FIG. 14 in the second embodiment. Two column tubes having an inner diameter of 2.0 mm and a length of 51.4 mm (metal plate thickness: 0.2 mm×257 sheets) are connected to each other. When the metal part 11 is used as an HPLC column having two packing parts, there are two filter driving parts 94, communication holes 93 for communicating the packing parts 99, 99, and a discharge path 95 for discharging the slurry solvent at the time of packing ( (3rd flow path), a filter is installed after filling, and there are two connecting portions 91 for connecting to the device.

The same filling jig as in Example 4 was used to fill the filler in the same manner as in Example 4. As the filter driving part 94, as shown in FIG. 13C, a part in which holes on both sides were half-etched was used. A sintered metal filter having an outer diameter of 2 mm, a thickness of 1 mm, and a 0.2 μm hole made of SUS316 having a diameter of 2 μm was inserted into two places of the filter driving portion 94, and was fixed by driving. As the packer, one having an inner diameter of 3 mm and a length of 50 cm was used, and the packer was set at two places of the filling portion 99. The liquid sent from one pump may be branched into two locations and filled at the same time, but this time, each packer was filled with a separate pump. Although it is possible to change the filling condition or the type of the filler for each filling part, in the present example, the same filling agent was used and the filling was performed under the same filling condition.

Octadecyl group-bonded silica gel filler for HPLC Inertsil ODS-3 4 μm (manufactured by GL Sciences Inc.) 1 g was weighed into a beaker, 10 mL of hexanol was added, and ultrasonic waves were added with an ultrasonic cleaner to mix well, and the filler slurry 10 mL was made. From the top of each packer, the slurry was divided into 5 mL portions, each was connected to a high-pressure pump, and a constant flow rate filling was performed with a pressurized solvent dichloromethane at a flow rate of 1 mL/min. The solvent waste liquid was discharged from the slurry solvent discharge passage 95 (third passage). The pressure increased up to 70 MPa and became constant at 50 MPa. Both filling parts 99 showed the same pressure rise. Since the pressure rise is the same, it is clear that the filling parts on both sides are the same, and the filling can be performed with good reproducibility.

Next, the pressurized solvent was changed to methanol, and the solution was fed at a constant pressure of 50 MPa for 3 hours. During this filling, no liquid leakage was observed from the metal parts and the connecting portion, demonstrating that the HPLC column has sufficient pressure resistance.

After the filling, as shown in FIG. 24, a solid rod 951 of SUS316 having an outer diameter of 0.82 mm and a length of 6 mm was press-fitted into the slurry solvent discharge passage 95 (third passage). Since the metal plates are laminated, there is a line in the hole in the direction perpendicular to the indentation, so it was possible to seal even by press fitting. Of course, an organic solvent resistant adhesive may be used.

In Example 6, the HPLC column of the present invention having an inner diameter of 2.0 mm and a length of 102.8 mm (two 51.4 mm packed portions communicated) packed with Inertsil ODS-3 4 μm was evaluated.
In the same manner as in Example 5, the packer portion was changed to a stainless steel pipe having an inner diameter of 0.25 mm and a length of 10 cm, which was set in a high performance liquid chromatograph LC800 (manufactured by GL Sciences Inc.) for analysis and evaluation.

Eluent 65% acetonitrile aqueous solution, oven temperature 45° C., detection UV254 nm (MU701, cell optical path length 5 mm, cell volume 1 μL), sample 1. Uracil, 2. Acetophenone, 3. Benzene, 4. Toluene, 5. The results of isocratic analysis with naphthalene at a flow rate of 0.3 mL/min are shown in FIG. The pressure was 4.8 MPa.

As a comparative example, a conventional HPLC column having an inner diameter of 2.1 mm and a length of 50 mm (Inertsil ODS-3 4 μm (manufactured by GL Science)) was analyzed by connecting it with a peak tube having an inner diameter of 0.13 mm and a length of 15 cm. 26. In the comparative example, the peak eluting at about 1 minute is thick due to the dead volume at the connection part, but the tailing of the peak after about 2 minutes is also observed by the conventional method. This is because when a column tube is manufactured using a stainless tube, streaks (scratches) are formed along the flow. It is considered that the thin column having an inner diameter of 2.1 mm has not been completely improved by the inner surface polishing. Compared to this comparative example, in the metal component of the present invention in which metal plates are laminated, since a flaw parallel to the flow is not formed, a peak with good symmetry is obtained as shown in FIG. There is.

Next, FIG. 27 shows the analysis result of linear gradient from 40% acetonitrile aqueous solution to 100% acetonitrile for 4 minutes under the other conditions same as above, and the pressure is from 5 MPa to 3. MPa according to the eluent composition. It changed to 7 MPa. At the time of filling, the pressure is 40 MPa or more, but at the time of HPLC analysis, the pressure is 10 MPa or less, depending on the analysis conditions, the liquid passing part is crushed by the driving of the filter, and the connection part (lateral hole) by the filling pressure. It was clarified that the deformation of No. 1 and the deformation of the connection part due to the press-fitting of the plug into the discharge path (third flow path) of the slurry solvent did not occur. The peak symmetry is also good, and there is no dead volume of the pipe that is usually seen when two columns are connected by pipes, and it was verified that the column has better peak symmetry than the conventional column connection. As in Example 6, the flow rate was changed and the pressure was raised to 50 MPa, but there was no leakage from the column, plug part, or connection part, and it was also proved that the column was sufficiently effective as a high-voltage column.

In the same manner as in Example 6, InertSustain C18 3 μm (manufactured by GL Sciences Inc.) of the present invention having an inner diameter of 2.0 mm and a length of 102.8 mm (two filled portions having a length of 51.4 mm communicate with each other) according to the present invention. The stack was packed in a HPLC column. A columnar column can be produced inside a square-shaped metal laminate, the entrance and exit of the column can be formed on the same surface of the metal laminate, and since it has a high withstand voltage, it can be easily attached and detached. Since the outer shape is not a columnar shape like a conventional column but a quadrangular prism structure, the entire six faces are flat parts and can be easily set in a holder. In order to make it easier to set, as shown in FIG. 24, a groove 111 serving as a guide is provided on the surface of the metal component 11.

By stacking metal plates with through-holes with a perfect circle in cross section and performing diffusion bonding, it is possible to form a cylindrical space (vertical hole) and a communication hole (horizontal hole). The connection portion) can be formed on the same surface. That is, by simply pressing the connecting portion in the vertical direction, it is possible to seal up to a high pressure resistance of 40 MPa or more. Since the sealing surface is the surface of the metal plate and is not machined, there is no unevenness such as scratches, and it is easy to seal with a smooth surface. Even when packing is used, the verticality of the etched part where the packing is inserted is high, and when the packing is pressed, there is no escape part and sealing becomes easy. In the column of the present invention having such a characteristic, the holder can be easily sealed by simply pressing it down and the holder can be easily made.

An example of the holder is shown in FIG. In the holder 600, by tilting the arm 69 to the right, the column 68 of the present invention is pushed rightward by the holding portion 68, and the entrance and exit of the column 11 is easily sealed. Further, since the column 11 has a square prism shape, it can be easily set in the holder 600 and can move in parallel along a plane, so that the seal portion does not shift. That is, the column is sealed only by pressing it and can be easily removed by loosening it. In the holder 601 shown in FIG. 29, the column 11 can be held by the holding portion 681 by turning the knurl 691 instead of the arm. In either case, since the column main body is a quadrangular prism, the guide 111 is provided so that it can be easily set in the holder and further easily set.

Using the holder 601 of FIG. 29, InertSustain C18 3 μm (manufactured by GL Sciences) was filled in the same manner as in Example 6, and the inner diameter was 2.0 mm and the length was 102.8 mm (the length of the filling portion 2 was 51.4 mm). Using the HPLC column of the present invention in which the points are in communication), it was set in a high performance liquid chromatograph LC800 (manufactured by GL Sciences) and HPLC analysis was carried out for evaluation.

Eluent 40% acetonitrile aqueous solution, oven temperature 40°C, sample 1. Thioolea, 2. Acetanilide, 3. Acetophenone, 4. Propiophenone, 5. Butyrophenone, 6. Benzophenone, 7. Naphthalene, 8. Hexanophenone, 9. Heptanophenone, 10. The results of isocratic analysis with octanophenone at a flow rate of 0.3 mL/min are shown in FIG. Adsorption does not occur even with phenones containing a polar group, and a peak with good symmetry of less than 1.2 is obtained.

As a comparative example, a conventional HPLC column having an inner diameter of 2.1 mm and a length of 5 cm (Inert Sustain C18 3 μm (manufactured by GL Sciences)) was connected with a peak tube having an inner diameter of 0.13 mm and a length of 15 cm to analyze the results. Show. Adsorption does not occur even with phenones containing polar groups, and a symmetric peak of less than 1.2 is obtained. In the conventional stainless steel column, since the inner surface is polished, there is no adsorption and the peak after 10 minutes elutes sharply without adsorption. Tailing is seen in peaks earlier than 10 minutes. It is considered that the components that elute quickly are tailed because they flow along the longitudinal stripes extending in the column longitudinal direction on the inner surface of the column before being distributed to the packing material. Furthermore, it is considered that, in the peak within 2 minutes of elution, the effect of vertical stripes, which could not be separated, and the effect of diffusion due to dead volume are exerted. Further, a significant difference between the column using the metal laminate of the present invention and the column of the comparative example compared to Example 7 is that the particle size is 3 μm, which is smaller, and the inside of the vertical stripes. This is because it is easy for particles to get into. On the other hand, in the column using the metal laminate of the present invention, since there are only stripes in the direction perpendicular to the flow direction, a peak with good symmetry is obtained.

In Example 3, leakage occurred at 20 MPa or higher, and the metal part A, which could not be used as an HPLC column, was modified so that it could be used as an HPLC column by treating the inner surface of the through hole. Since it is a stack of metal plates with through holes whose cross section is perfect circle, by filling the part where the liquid is soaked in with a surface treatment agent in the diffusion bonding, it becomes a high pressure resistant part and it can be used for HPLC column. Can be done.

When the inner surface of the through hole is treated, an organic solvent is used in HPLC, and therefore a resin polymer is not suitable as a surface treatment agent. The surface treatment agent that can enter the gap between the metal plates at first and finally becomes an inorganic solid is most suitable. Since polysilazane vitrifies in the presence of oxygen and water, it is used for various surface treatments. Using this polysilazane, modification was tried and it was proved that it can be used with an actual HPLC column. Note that the reagent is not limited to polysilazane, and any reagent that forms an SiO ₂ layer such as silicon tetrachloride, tetraethoxysilane, and silane gas can be used.

The metal part A was set in the holder 80 of FIG. 20 used in Example 5, a PEEK tube having an inner diameter of 0.13 mm and a length of 3 m was attached to the outlet side as a resistance tube, and 1 mL of a 4% perhydroxypolysilazane dichloromethane solution was attached. /Min for 1 hour. The liquid exuded from the surface of the metal part A, and the pressure became about 20 MPa. After that, the resistance tube was removed, and dichloromethane was sent at 5 mL/min for 10 minutes to wash the polysilazane reagent on the filling part inside the metal part A and on the surface of the flow path. Then it was left at 40° C. for 12 hours to evaporate the dichloromethane solvent. Then, the temperature was raised to 350° C. over 10 hours and left at 350° C. for 10 hours. The portion soaked with polysilazane was converted into an amorphous SiO ₂ layer, and the appearance color of the metal part A was changed.

Using this surface-treated part, Inertsil WP300C8 5 μm (manufactured by GL Sciences Inc.) was filled according to Example 4 and evaluated according to Example 5. As a resistance tube for column back pressure, a fused silica capillary tube having an inner diameter of 25 μm and a length of 15 cm was connected between the column outlet and the detector cell. The eluent was a 65% aqueous acetonitrile solution, the oven temperature was 40° C., and the sample was 1. Uracil, 2. Acetophenone, 3. Benzene, 4. Toluene, 5. The results of isocratic analysis with naphthalene at a flow rate of 0.2 mL/min are shown in FIG. The pressure was 45 MPa.

Even with the column that had leaked at a pressure of 20 MPa before the surface treatment as described above, the pressure resistance of 40 MPa or higher was improved by the polysilazane treatment. It was proved that it can be used as an HPLC column by performing the surface treatment on the inside of the diffusion-bonded metal parts.

Of the two filling parts 99 of the metal part 11 (FIG. 23) used in Example 6, one part on the inlet side of the metal part was filled with the monolith body. First, as disclosed in Japanese Patent No. 4714789, a monolith body having a diameter of 1.5 mm was produced by a known method and glass clad was performed to obtain a glass clad monolith body having an outer diameter of 2 mm and a length of 50.3 cm. .. Out of the two filling parts 99 of the metal part 11 (FIG. 23), the filter driving part 94 on the upstream side of the flow path at one place on the outlet side of the metal part has an outer diameter of 2 mm, a thickness of 1 mm, made of SUS316, 0. A sintered metal filter having a pore size of 2 μm was fixed with a ceramic adhesive.

0.5 g of a filler for HPLC InertSustain C18 2 μm (manufactured by GL Sciences Inc.) was weighed into a beaker, 5 mL of hexanol was added, and ultrasonic waves were added by an ultrasonic cleaner to mix well to prepare 5 mL of a filler slurry. A packer having an inner diameter of 3 mm and a length of 50 cm was used to fill one of the two filling portions 99 of the metal component 11 (FIG. 23) on the outlet side of the metal component. A high pressure pump was connected to the outlet side connection part of the metal part, and a constant flow rate filling was performed with a pressurized solvent dichloromethane at a flow rate of 0.5 mL/min. The solvent waste liquid was discharged from the slurry solvent discharge passage (third passage). The pressure increased up to 70 MPa and became constant at 50 MPa. Next, the pressurized solvent was changed to methanol, and the solution was fed at a constant pressure of 50 MPa for 3 hours. After the filling, a solid rod 951 of SUS316 having an outer diameter of 0.82 mm and a length of 6 mm was fixed to the slurry solvent discharge passage 95 (third passage) with a ceramic adhesive (FIG. 24). After the above filling, a sintered metal having an outer diameter of 2.2 mm, a thickness of 1 mm, made of SUS316, and 0.2 μm hole was press-fitted and fixed in the filter installation portion 91 on the outlet side of the metal part by using peak packing.

Of the two filling parts 99 of the metal part 11 (FIG. 23), the sintering filter is not inserted into the filter driving part 94 on the downstream side of the flow path at one position on the inlet side of the metal part, and the glass clad is used. I inserted a monolith. The communication hole side is sealed by the glass monolith end face and the half-etched end face. A 1.2 mm-thick peak packing was put and sealed in the filter installation part 91 on the connection side into which the eluent enters. That is, since the heights of the connecting portions of both the filling portions 99 are the same when pressed by the holder, they can be easily sealed.

Using the holder (FIG. 20) used in Example 8, the sample was set on a high performance liquid chromatograph LC800 (manufactured by GL Sciences Inc.) and HPLC analysis was performed to evaluate it. Eluent 65% acetonitril aqueous solution, oven temperature 65° C., detection UV254 nm (MU701, cell optical path length 5 mm, cell volume 1 μL), sample 1. Acetophenone, 2. Benzene, 3. Toluene, 4. The results of isocratic analysis with naphthalene at a flow rate of 0.60 mL/min are shown in FIG. The pressure was 56 MPa. It was demonstrated that the column of the present invention can be used even in a monolith body. Furthermore, since the filling portion 99 on the inlet side of the metal component contains the glass monolith clad body and has a seal at the end face, it can be taken out. That is, if the entrance side becomes dirty, it can be easily changed like a guard column. Further, the column of the present invention has a quadrangular prism shape, has high thermal conductivity, and a peak with good symmetry was obtained even at 65° C. analysis.

As a comparative example, a conventional commercial C18-modified silica monolith column inner diameter 3 mm×5 cm and a conventional packed column C18 2 μm, inner diameter 2.1 mm, length 5 cm are connected by a peak tube having inner diameter 0.13 mm, length 15 cm, and 65° C. 34 shows the result of the analysis. The thermal conductivity of the column itself and the connecting portion is low, and a temperature distribution is generated, so peak cracking may occur unless sufficient preheating is performed. On the other hand, in the column of the present invention, the two columnar packing portions and the communicating portions are inside the same metal, and the heat conduction is good and the temperature is constant, so that the peak shape is good.

In Example 6, a sintered metal filter was installed in order to retain the particulate filler in the filling portion produced by laminating metal plates provided with through holes having a perfect circular cross section. It is possible to use a metal plate having a flow path hole smaller than the particle size to replace the sintered metal filter. The number of flow passage holes may be one or more. If the pore size is smaller than the diameter of the particles to be filled, the particles will not come off, but if it is too small, the pores may be completely blocked. Therefore, it is recommended that the diameter is one third or more of the particle size. It For example, when filling a filler having a particle diameter of 3 μm, pores of 1 μm or more and less than 3 μm are suitable.

A metal plate of SUS316 having a thickness of 0.2 mm was produced by the same method as in Example 2. Nine metal plates 221 (FIG. 35(a)) provided with two through holes 321 having a diameter of 0.8 mm for forming a cylindrical space for connection, and a filling portion for filling a filler. 257 metal plates 222 (FIG. 35(b)) provided with two through holes 322 having a diameter of 0.5 mm for forming, and a metal plate 223 having through holes 324 having a diameter of 100 μm and subjected to half etching 323. (FIG. 35(c)) 1 sheet, a metal plate 224 (FIG. 35(d)) having a through hole 324 having a diameter of 0.1 mm, and a 1.9 μm diameter plate having an aspect ratio of 200 for holding particles. One metal plate 225 (FIG. 35(e)) in which the through holes 325 were perforated with a laser, two filling spaces, and a metal plate 226 having a groove with a semicircular cross section and a diameter of 0.1 mm connecting the through holes 325 ( 35(f)) One sheet, a metal plate 227 provided with a through hole 327 having a diameter of 0.8 mm for forming a cylindrical discharge path 379 (third flow path) for discharging the solvent at the time of filling the filler. (FIG. 35(g)) 30 sheets were produced. These 300 metal plates were stacked, diffusion bonding was performed, and the respective metal plates were adhered to each other to obtain a metal component 181 having an inner cylindrical space 119 as shown in FIG. Two packed parts 909 having an inner diameter of 0.1 mm and a length of 51.4 cm are connected inside the metal part to form an HPLC empty column capable of retaining a packing material of 2 μm or more.

In the same manner as in Example 6, InertCore C18 2 μm (manufactured by GL Sciences Inc.) was weighed in a beaker (0.1 g), 10 mL of hexanol was added, and the ultrasonic cleaner ultrasonic waves were well mixed to prepare a filler slurry. .. From the upper part of each packer connected to the inlet and outlet of the metal laminate, 5 mL each of the filler slurry was put, and each was connected to a high pressure pump, and a constant flow rate filling was performed with a pressurized solvent dichloromethane at a flow rate of 1 mL/min. I did. The solvent waste liquid was discharged from the slurry solvent discharge passage 379 (third passage). The maximum pressure increased to 70 MPa, and the pressure became constant at 50 MPa. Both filled parts showed the same pressure rise. Since the pressure rise is the same, it is clear that the filling parts on both sides are the same and the filling can be performed with good reproducibility.

Next, the pressurized solvent was changed to methanol, and the solution was fed at a low pressure of 50 MPa for 3 hours. During the filling, no liquid leakage was observed from the metal parts and the connection part, demonstrating that the HPLC column has sufficient pressure resistance. After the filling, a solid rod of SUS316 having an outer diameter of 0.82 mm and a length of 6 mm was press-fitted into the slurry solvent discharge passage. Since they are laminated, there is a line in the hole in the direction perpendicular to the indentation, so it was possible to seal only by press fitting. Of course, an organic solvent resistant adhesive may be used.

Using the holder used in Example 8 (FIG. 20), eluent 65% acetonitrile aqueous solution, oven temperature 40° C., sample 1. Uracil, 2. Acetophenone, 3. Benzene, 4. Toluene, 5. The results of isocratic analysis with naphthalene at 0.1 μL injection and a flow rate of 25 μL/min are shown in FIG. 37. The pressure was 40 MPa, but there was no leakage from the column, and a peak with good symmetry was obtained even if the inner diameter was small.

In order to confirm that the filler slurry is sent from one place and branched inside the metal parts to fill the two filled parts cleanly, the metal plate with through holes is used instead of the sintered filter. In order to confirm that, through the reverse of the above, using a metal plate of SUS316 having a thickness of 0.2 mm, a through hole 331 (diameter 0.8 mm) for forming the opening 908 for filling the filler. 38 (FIG. 38(a)), and a metal plate 232 (FIG. 38(b) having a through hole 332 having a diameter of 0.5 mm for forming a portion 907 for dividing the filling slurry into two directions. )) 1 sheet, 257 sheets of metal plate 233 (FIG. 38(c)) provided with two through holes 333 (diameter 0.5 mm) for forming the filling portion 906 for filling the filler, One metal plate 234 (FIG. 38(d)), which has a through hole 334 (diameter 0.8 mm) smaller than the diameter of the above, instead of the sintered filter for retaining the particles, and a portion to be connected to the analyzer at the time of analysis. Nine metal plates 235 (FIG. 38(e)) provided with through holes 335 for forming were produced and laminated as shown in FIG. 39 to obtain a metal component 171.

The metal part 171 was set in the holder (FIG. 20), and the filling packer was connected to the lower part of the holder (FIG. 20). In the eleventh embodiment, the packer is connected to the discharge flow path that is connected to the third flow path for discharging the solvent when the filler is filled. In this case, the channels to which the packers were connected in Example 11 were two channels for discharging the solvent at the time of filling the filler. The same slurry as in Example 11 was filled from the opening 908. The filling slurry is evenly divided and filled in the filling portion 906, and the gel is retained in the through holes 334. During the filling, there was no leakage of particles from the through holes 335, and it was confirmed that the particles were stopped by the metal plate 234 and the through holes 334. After completion of the filling, the metal part 171 was removed from the holder, a monolith capillary column having an outer diameter of 0.8 mm was put in from above, and the end was plugged with an inorganic adhesive. After that, the metal part 171 was set in the holder again and evaluated under the same conditions as in Example 11, and as a result, the data in FIG. 40 was obtained, and a sharp peak with a good peak shape was obtained. Although the retention was larger than that in FIG. 37, it was found that the portion where the filler was branched at the time of filling (FIG. 38(b)) was also filled.

According to the present invention, by laminating and welding metal plates provided with through-holes having a perfect circular cross section, it is possible to form a metal laminated body having an accurate columnar or spherical space. The size of the metal plate can be freely selected depending on the thickness and the number of stacked layers. Therefore, it is possible to provide a metal part having a space inside, which is impossible by conventional machining. Further, since the holes are formed in the stacking direction, the welded surface between the metal plates can be made small, and the durability can be improved. Since fine processing is possible by combining with etching technology, it becomes possible to manufacture a compact metal part having a fine cylindrical or spherical space inside. Therefore, it is possible to reduce the size of an apparatus or the like using such components. Furthermore, it can be applied to small cylinders, small reaction tubes, cartridge columns, etc., which require pressure resistance. Further, since a large amount can be produced by one production, mass production is possible, and it is possible to apply to a new technology by suppressing the price.

1 Metal Laminated Body 101 Internal Space 2 Metal Plate 3 Through Hole 4 Horizontal Hole 61 Vertical Hole 62 Communication Hole

Claims (16)

A metal laminated body formed by laminating a plurality of plate-shaped metal plates having through-holes formed therein, wherein the through-holes communicate with each other to form two cylindrical internal spaces. A metal which is provided with a communication hole formed by a groove or a hole formed in a metal plate and which connects the internal spaces, and the two internal spaces are open at one end face in the stacking direction of the metal laminate. Laminate. A metal laminate in which a plurality of plate-shaped metal plates having through-holes are laminated, and the through-holes communicate with each other to form an internal space, which is a plate having two through-holes formed therein. -Shaped metal plates are stacked, the through holes communicate with each other in the stacking direction to form two vertical holes, and one of the plate-shaped metal plates having the two through holes is continuous with the metal plate at one end. Then, plate-shaped metal plates having horizontal holes connecting the two vertical holes are stacked, and the vertical hole is communicated with one end face in the stacking direction of the metal stack formed by stacking the metal plates. A metal laminate having two openings formed therein. The metal laminated body according to claim 2, wherein through holes having the same shape or similar shapes are formed in the metal plates to be laminated, and the center or the center of gravity of the through holes is coaxially located. The metal laminated body according to claim 3, wherein the through hole is formed in a circular shape, the center of the circular through hole is located on the same axis, and the vertical hole is cylindrical. The metal laminate according to any one of claims 2 to 4, wherein the lateral hole is formed by a groove or a hole formed in a metal plate. A third flow path communicating with the lateral hole is provided, and the third flow path is openably and closably open at the other end surface opposite to the one end surface where the opening of the vertical hole is formed. Item 6. The metal laminate according to any one of items 2 to 5. The pressure resistance is 40 MPa or more, and the metal laminate according to any one of claims 2 to 6. The metal laminate according to any one of claims 2 to 7, wherein the inner surface of the through hole is treated. The metal laminate according to any one of claims 2 to 8, wherein the through hole has a diameter of 60 µm to 3 mm. The metal layered product according to any one of claims 2 to 9, wherein the displacement of the lamination with respect to the inner diameter of the through hole is 6% or less. The metal laminate according to any one of claims 2 to 10, wherein the metal laminate is a reaction column or an analytical column in which the vertical holes and/or the horizontal holes are filled with a filler. Laminate. The metal laminate according to claim 11, wherein one vertical hole is filled with a packing material, and the other one vertical hole and the horizontal hole are HPLC columns having channels. The metal laminated body according to claim 11 or 12, wherein a recess for installing a filter is formed in the metal plate. The metal laminate according to any one of claims 10 to 13, wherein 33 or more and 2600 or less of the metal plates are laminated. The metal filler according to any one of claims 11 to 14, wherein the filler is a particle having a particle diameter of 1 µm to 10 µm or a monolith body having a pore diameter of 0.01 µm to 10 µm. The metal laminate according to any one of claims 11 to 15, wherein the metal laminate has a quadrangular prism structure, and a guide groove for setting in a holder is provided on a surface of the metal laminate.

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