Method for sampling organic deposits on metal plates and method for identifying organic compounds

Abstract

To provide a sampling method reducing contamination in recovering a minute organic deposit adhering to the surface of a plate-like metal material, and to provide a method for identifying the organic deposit using the sampling method.SOLUTION: Under microscopic observation, an organic deposit is dissolved by ejecting an organic solvent with a tubular member having an opening diameter of 25 μm or less on the surface of the minute organic deposit, and then the organic solvent containing the dissolved organic deposit is evaporated to dryness at a solvent volatilized part subjected to a liquid repellent treatment, or a droplet controlled to 600 μm or less in the long diameter is formed at the solvent volatilized part not subjected to the liquid repellent treatment and evaporated to dryness to prepare a sample for microscopic FT-IR measurement.SELECTED DRAWING: Figure 6

Description

[Technical Field]

[0001] The present invention relates to a method for sampling organic deposits containing trace amounts of organic compounds as foreign matter adhering to the surface of a metal plate, and a method for identifying the organic compounds as foreign matter. [Background technology]

[0002] In order to improve the quality of metal products, it is important to identify the components of trace amounts of organic substances (hereinafter referred to as organic deposits), which are foreign bodies that adhere to the surface of metal materials during the manufacturing process.In particular, in the case of metal sheets such as copper sheets and steel sheets, and surface-treated metal sheets that have been subjected to surface treatment, the manufacturing process involves a complex process that includes multiple steps, so it is necessary to identify the components of the organic deposits in order to identify the process that caused the contamination.

[0003] The organic deposits are often found on the surface of metal plates in the form of tiny spots or lines. Conventional methods for identifying trace amounts of organic matter or organic matter in minute regions include microscopic Fourier transform infrared spectroscopy (hereinafter referred to as microscopic FT-IR) and microscopic Raman spectroscopy, as disclosed in, for example, Non-Patent Document 1. In microscopic FT-IR measurements, a plate or other material with organic matter attached thereto is typically placed under a microscope, and measurements are performed using a reflection method such as a microscopic reflection method or a high-sensitivity microscopic reflection method. However, in the case of reflection FT-IR measurements, if the thickness of the organic deposit is thin, sufficient infrared absorption intensity cannot be obtained. Furthermore, if the surface roughness of the metal to which the organic deposit is attached is high, diffuse reflection of infrared light occurs on the metal surface. Therefore, a clear infrared absorption spectrum cannot be obtained, making it difficult to identify the components of the organic deposits.

[0004] In such cases, it is necessary to sample and concentrate the organic deposits prior to microscopic FT-IR measurement. Patent Document 1 discloses a technique in which an organic solvent in which the organic matter of the measurement sample has been dissolved is dropped onto a thin film of fluororesin attached to the surface of an infrared reflecting member, and the organic solvent is evaporated to concentrate the organic matter before performing microscopic FT-IR measurement. However, Patent Document 1 does not disclose a method for sampling organic deposits, which are foreign matter, from the surface of a metal material. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 4-348256 [Non-patent literature]

[0006] [Non-Patent Document 1] Journal of the Japanese Society of Infrared Science, Vol. 5, No. 2, pp. 49-61 (1995) Summary of the Invention [Problem to be solved by the invention]

[0007] Conventionally, sampling of minute organic deposits on metal materials has involved manually dropping an organic solvent onto the organic deposits using a general-purpose microsyringe to dissolve or disperse the organic deposits. The organic deposits are then extracted into the organic solvent, and the organic solvent containing the organic deposits is then recovered using an organic solvent recovery device. Furthermore, when the organic solvent droplets spread, they also collect organic contaminants (hereinafter sometimes referred to as "contamination") other than the organic deposits being collected, resulting in a problem of reduced accuracy in identifying the organic deposits. While methods for identifying organic deposits include microscopic reflection FT-IR measurement and mass spectrometry (MS), these methods also suffer from the problem of contamination when sampling the organic deposits used as the measurement sample.

[0008] The technical problem to be solved by the present invention is to provide a sampling method that reduces contamination when recovering minute organic deposits (small in size when viewed from above) attached to the surface of a metal material, particularly a plate-shaped metal material, and a method for identifying the organic deposits using the sampling method. [Means for solving the problem]

[0009] As a result of extensive research, the present inventors have found that the deterioration in the accuracy of identifying organic deposits due to the wetting and spreading of droplets of the organic solvent can be improved by dissolving the organic deposits under microscope observation using a tubular member, which is the organic solvent recovery means, with a member having a very small diameter opening. Based on the above findings, the present inventors have completed the present invention described below.

[0010] That is, in order to achieve the above object, the present invention provides: (1) A method for sampling organic deposits on a metal plate using an apparatus for dissolving organic deposits containing organic compounds deposited on a metal plate with an organic solvent and then aspirating them, the apparatus comprising: a sample stage provided with a solvent volatilizing section that has been subjected to a liquid-repellent treatment; a microscope observation system; and a thin tubular member that can eject and aspirate an organic solvent using a pressurization-depressurization mechanism, wherein the sample stage and the thin tubular member are relatively movable by a transport mechanism under observation by the microscope observation system, the thin tubular member is a single member having an opening for discharging and suctioning the organic solvent, the diameter of the opening being 25 μm or less, and the thin tubular member into which the organic solvent has been injected is moved to the vicinity of organic deposits on the surface of a metal plate placed on a sample stage under microscope observation; By applying pressure, the organic solvent in the tubular member is discharged onto the surface of the organic deposit to form a film of the organic solvent and dissolve the organic deposit, and then the inside of the tubular member is depressurized to suck the organic solvent containing the dissolved organic deposits through the opening; The method for sampling organic deposits on a metal plate includes moving the tubular member containing the organic solvent containing the dissolved organic deposits above the solvent volatilization section, applying pressure to eject the organic solvent containing the dissolved organic deposits to form droplets on the solvent volatilization section, and volatilizing the organic solvent from the droplets to concentrate the organic deposits.

[0011] In the present invention, (2) There is provided a sampling method according to (1) above, in which organic deposits are dissolved while the opening of the tubular member is in contact with the droplet of organic solvent.

[0012] In the present invention, (3) A method for sampling organic deposits on a metal plate using an apparatus for dissolving organic deposits containing organic compounds deposited on a metal plate with an organic solvent and then sucking them up, the apparatus comprising: a sample stage provided with a solvent volatilizing section that has been subjected to a liquid-repellent treatment; a microscope observation system; and a thin tubular member that can eject or suck an organic solvent, wherein the sample stage and the thin tubular member are relatively movable by a transport mechanism under observation by the microscope observation system, the thin tubular members are a pair of members consisting of a discharge member having an opening for discharging an organic solvent onto organic deposits and a suction member having an opening for suctioning the discharged organic solvent, the diameter of the opening of the discharge member being 25 μm or less, and the pair of thin tubular members are moved near the organic deposits on the surface of a metal plate placed on a sample stage under microscope observation; applying pressure by a pressure mechanism to discharge the organic solvent from the discharge member into which the organic solvent has been injected onto the surface of the organic deposit, and at the same time, sucking the discharged organic solvent by the suction member to form a flow of the organic solvent on the surface of the organic deposit, thereby dissolving the organic deposit; The organic solvent containing the dissolved organic deposits is sucked by the suction member, The method for sampling organic deposits on a metal plate includes moving the suction member above the solvent volatilization section, applying pressure to the organic solvent containing the dissolved organic deposits inside the suction member, thereby ejecting the organic solvent containing the dissolved organic deposits to form droplets on the solvent volatilization section, and volatilizing the organic solvent in the droplets to concentrate the organic deposits.

[0013] In the present invention, (4) A method for sampling organic deposits on a metal plate using an apparatus 1 for dissolving organic deposits containing organic compounds adhered to a metal plate with an organic solvent and then aspirating them, the apparatus 1 comprising a sample stage provided with a solvent volatilizing section that has not been treated for liquid repellency, a microscope observation system, and a capillary member that can discharge and aspirate an organic solvent by a pressurization-depressurization mechanism, and the sample stage and the capillary member are relatively movable by a transport mechanism under observation by the microscope observation system; or an apparatus 2 for dissolving organic deposits containing organic compounds adhered to a metal plate with an organic solvent and then aspirating them, the apparatus 2 comprising a sample stage provided with a solvent volatilizing section that has not been treated for liquid repellency, a microscope observation system, and a capillary member that can discharge or aspirate an organic solvent, and the sample stage and the capillary member are relatively movable by a transport mechanism under observation by the microscope observation system, When the device 1 is used, the device 1the capillary member is a single member having an opening for discharging and sucking the organic solvent, the diameter of the opening being 25 μm or less; the capillary member into which the organic solvent has been injected is moved under microscope observation to the vicinity of organic deposits on the surface of a metal plate placed on a sample stage; pressure is applied to discharge the organic solvent inside the capillary member onto the surface of the organic deposits to form a film of organic solvent and dissolve the organic deposits; the pressure inside the capillary member is reduced to suck the organic solvent containing the dissolved organic deposits through the opening; the capillary member containing the organic solvent containing the dissolved organic deposits is moved above the solvent volatilization section; pressure is applied to discharge the organic solvent containing the dissolved organic deposits to form droplets on the solvent volatilization section with a major axis controlled to 600 μm or less; and the organic solvent in the droplets is volatilized to concentrate the organic deposits; When the device 2 is used, the device 2 The thin tubular members are a pair of members consisting of a discharge member having an opening for discharging the organic solvent onto the organic attachment and a suction member having an opening for sucking up the discharged organic solvent, the diameter of the opening of the discharge member being 25 μm or less, the pair of thin tubular members are moved to the vicinity of the organic attachment on the surface of the metal plate placed on a sample stage under microscope observation, and pressure is applied by a pressure mechanism, whereby the organic solvent inside the discharge member into which the organic solvent has been injected is discharged onto the surface of the organic attachment, and the discharged organic solvent is sucked up by the suction member, and the organic solvent is removed. The present invention provides a method for sampling organic attachments on a metal plate, comprising the steps of: forming a flow of organic solvent on the surface of the attachments to dissolve the organic attachments; sucking the organic solvent containing the dissolved organic attachments with the suction member; moving the suction member above the solvent volatilization section; applying pressure to the organic solvent containing the dissolved organic attachments inside the suction member to discharge the organic solvent containing the dissolved organic attachments to form droplets on the solvent volatilization section with a major axis controlled to 600 μm or less; and volatilizing the organic solvent from the droplets to concentrate the organic attachments.

[0014] In the present invention, (5) There is provided a method for identifying organic compounds constituting the organic attachment, which comprises using the method for sampling organic attachment on a metal plate described in any one of (1) to (4) above and measuring the condensed organic attachment formed in the solvent volatilization area on the sample stage by microscopic reflection Fourier transform infrared spectroscopy. [Effects of the Invention]

[0015] By using the sampling method of the present invention, it becomes possible to identify minute organic deposits adhering to the surface of a plate-shaped metal material. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 1 is a schematic diagram showing an extraction operation of organic deposits in a first embodiment of the present invention. [Figure 2] FIG. 4 is a schematic diagram showing an extraction procedure for organic deposits in a second embodiment of the present invention. [Figure 3] 1 is a photograph showing a part of an apparatus used in carrying out the present invention and an operating state thereof. [Figure 4] 1 shows infrared absorption spectra obtained by microscopic FT-IR measurement for artificial blemishes 1 to 4 in Example 1. [Figure 5] 1 shows infrared absorption spectra obtained by microscopic FT-IR measurement of the evaporated, dried product obtained by dissolving and extracting organic deposits from artificial stains 3 and 4 in Example 1 using the sampling method of the present invention. [Figure 6] 10 shows infrared absorption spectra obtained in Example 2 for pseudo stain 4-2 with a fingerprint attached nearby when the method for extracting organic deposits was changed. [Figure 7] 10 is an infrared absorption spectrum obtained when the organic deposits on the pseudo stains were replaced with polycarbonate in Example 3. [Figure 8] 10 is an infrared absorption spectrum obtained when the organic deposits on the pseudo stains were replaced with polymethyl methacrylate in Example 3. [Figure 9]FIG. 10 is a diagram showing changes in infrared absorption spectrum due to re-extraction in Example 4. [Figure 10] This is an infrared absorption spectrum obtained for a sample of unknown components in Example 5. [Figure 11] This is an infrared absorption spectrum obtained for a sample of unknown components in Example 6. [Figure 12] FIG. 10 is a diagram showing changes in infrared absorption spectrum due to re-extraction in Example 6. [Figure 13] 10 is an infrared absorption spectrum obtained for a concentrate formed using a solvent volatilization part that has not been subjected to liquid repellent treatment in Example 7. DETAILED DESCRIPTION OF THE INVENTION

[0017] [Sample to be sampled] The target sample of the organic adhesion sampling method of the present invention is a metal plate with organic matter attached. The organic adhesion may be composed solely of organic compounds or a mixture with inorganic substances. The organic compound may be one type or a mixture of multiple types. The material constituting the metal plate is not particularly limited, but the effects of the present invention are preferably achieved when the metal is insoluble in the organic solvent used to dissolve the organic adhesion and has high wettability with the organic solvent. If the metal plate is a metal laminate such as a plated product, the type of metal on the surface to which the organic adhesion is attached is important. Examples of the material constituting the metal plate (or the surface metal layer in the case of a laminate) include copper, copper alloy, silver, and tin.

[0018] The organic deposit sampling method of the present invention can be applied to organic deposits of any size, but the effects of the invention are most pronounced when applied to minute organic deposits, such as minute spot-like organic deposits with a diameter (diameter of the circumscribed circle) of 3 mm or less, or narrow linear organic deposits with a width of 3,000 μm or less. The width is the minimum length of the normal to each point on the outline of the planar shape formed by the organic deposit on the metal plate (a straight line perpendicular to the tangent at each point on the outline) that passes through the planar shape.

[0019] [Sample stage] In the organic adhesion sampling method of the present invention, a solvent volatilization section with a liquid-repellent surface, as described below, is provided on the sample stage. When using microscopic FT-IR as a method for identifying organic adhesions, it is preferable to use a sample stage made of an infrared-reflecting material, since the stage used in the sampling method of the present invention can be directly subjected to the microscopic reflection FT-IR. During sampling, it is preferable from the viewpoint of operability to place the sample to be sampled, which has minute organic matter adhering thereto, near the solvent volatilization section. While not particularly limited in the sampling method of the present invention, it is preferable from the viewpoint of operability to place a container containing an organic solvent used to dissolve the organic adhesions near the solvent volatilization section and the sample to be sampled. The sample stage must be movable relative to the capillary member described below. If the sample stage is movable, it should be movable in at least two directions.

[0020] [Microscope observation system] In the organic adhesion sampling method of the present invention, the movement of the capillary tubular member, the discharge of the organic solvent from the capillary tubular member, and the suction of the organic solvent containing the dissolved organic adhesion are performed under observation by a microscope observation system. In this case, an image within the field of view of the microscope may be displayed on a display device such as a CRT display. Conventionally, the relative positioning of the organic adhesion and the capillary tubular member has been performed visually and manually. However, when the organic adhesion is minute, the accuracy of the relative positioning is poor when visually inspecting, which increases the possibility of sampling contaminants near the organic adhesion to be measured.

[0021] Furthermore, the microscope observation system preferably includes an arm for setting a capillary member (described below) and enabling precise control of the operation of the member. Furthermore, if the microscope observation system has a position memory function and a function for moving to the stored position, it is more preferable from the viewpoint of operability to store in advance the coordinates of a container containing an organic solvent to be injected into the capillary member, a location for sampling organic deposits, and a solvent volatilization portion, and to move the capillary member and the stage based on these coordinates.

[0022] When microscopic FT-IR is used to identify organic deposits, the microscope used for the measurement may be included in the microscope observation system.

[0023] [Thin tubular member] In the organic deposit sampling method of the present invention, a thin tubular member capable of discharging and / or sucking an organic solvent by a pressure-decompression mechanism is used to dissolve and recover minute organic deposits with an organic solvent. The thin tubular member may be a micropipette with a piston, which is used for microinjection in the field of biotechnology. The micropipette may be equipped with a rubber bulb as a pressure adjustment mechanism.

[0024] Here, a micropipette is a glass tube with an outer diameter of about 1 mm, one end of which is tapered outward, and the diameter of the opening at the tip, which serves as a discharge or suction port (hereinafter also referred to as the opening diameter), is usually 25 μm or less. From the viewpoint of preventing contamination by discharging fine droplets and from the viewpoint of the cost of the micropipette, the opening diameter is preferably 2 to 18 μm, more preferably 5 to 12 μm. The opening shape of the opening is preferably circular. In the method for sampling organic deposits of the present invention, if the amount of solvent is too small, it will volatilize during operation, so a volume of 5×10 -4 When a micropipette is used as the thin tubular member, the upper limit of its volume is not particularly specified in the present invention, but it is preferable to use one with a volume of 50 μL or less, since even trace amounts of impurities in the solvent may remain as spots and be detected by microscopic FT-IR.

[0025] A capillary member having such a small opening is used to move it near the organic attachment, and the organic solvent is then dispensed onto the organic attachment. The "nearby" may refer to a position where the dispensed organic solvent comes into contact with the organic attachment, and the opening may come into contact with the organic attachment. Even if the organic attachment does not dissolve in the organic solvent, it can be sucked up by a capillary member for suction (hereinafter also referred to as a suction member) if it is dispersed in the organic solvent into particles smaller than the opening diameter of the capillary member. Hereinafter, in this specification, such dissolution or dispersion will be referred to simply as "dissolution."

[0026] In the sampling method of the present invention, the sample stage and the capillary tubular member must be moved relative to each other. In this case, the capillary tubular member may be movable and the sample stage may be fixed, or the capillary tubular member may be fixed and the sample stage may be movable. In either case, to improve the positional accuracy of sampling, the movable capillary tubular member or the sample stage is mechanically moved using a transport mechanism. Any known transport means may be used as the transport means.

[0027] [Solvent evaporation part] In the organic adhesion sampling method of the present invention, a capillary member that has sucked in an organic solvent containing dissolved organic adhesion is moved above a solvent volatilization section, and the organic solvent is ejected into the solvent volatilization section, causing the organic solvent to volatilize from the formed droplets, thereby evaporating and solidifying (concentrating) the organic adhesion. As described below, the solvent volatilization section can be a sample stage surface that has not been treated with a liquid repellent coating. However, when rapid operation is required, it is preferable to use a surface that has been treated with a liquid repellent coating. For ease of operation, it is preferable that the solvent volatilization section be located near the position where the metal plate is placed on the sample stage.

[0028] The liquid-repellent treatment refers to a treatment for repelling organic solvents that dissolve organic deposits. Examples of liquid-repellent treatment methods include the method disclosed in Patent Document 1 and the method disclosed in Japanese Patent Application Laid-Open No. 2008-203020, which involves forming a thin film of fluorine-based resin on a substrate (the thin film exhibits liquid repellency). Furthermore, rather than directly applying the liquid-repellent treatment to the surface of the sample stage, it is possible to alternatively place a commercially available liquid-repellent plate on the sample stage. An example of such a liquid-repellent plate is the pinpoint concentration plate (2020-01) manufactured by Toray Research, Inc.

[0029] The liquid-repellent treatment is applied to the solvent volatilization portion to reduce the wettability of the solvent volatilization portion to the organic solvent, so that droplets of organic solvent containing dissolved organic deposits formed on the solvent volatilization portion do not wet and spread, and the organic solvent is volatilized while remaining in the form of small droplets. If the organic solvent is volatilized in this state, the spot diameter of the evaporated dried product (concentrated spot) of the organic deposits remaining after volatilization becomes smaller, and the thickness of the evaporated dried product increases, resulting in an increase in the infrared absorption intensity when, for example, microscopic FT-IR measurement is performed.

[0030] In the present invention, a thin tubular member with a small opening diameter is used as a means for discharging the organic solvent onto the organic deposits, as described above. If the organic solvent dissolving the organic deposits is discharged little by little using this thin tubular member, the droplets formed by the discharge will not be very large, even if the area to which the organic solvent is discharged is not treated with a liquid repellent treatment like the solvent volatilization area. Specifically, the major axis of the droplet (the diameter of the circumscribed circle) can be controlled to approximately 600 μm or less (usually 30 μm or more).

[0031] By volatilizing such small droplets of organic solvent, a concentrate of organic deposits is obtained that is thick enough to identify the substance by microscopic FT-IR analysis, although not as thick as when volatilization is performed using a liquid-repellent treated solvent volatilization section. This embodiment is advantageous in that it does not require an expensive liquid-repellent treated solvent volatilization section. Furthermore, even when a liquid-repellent treated solvent volatilization section is used, if the droplets are controlled to be small as described above, the sampling method of the present invention can be performed multiple times using a single solvent volatilization section (plate) by changing the location where the droplets are formed.

[0032] The organic fouling sampling method of the present invention can take the following two embodiments according to the method of using the tubular member described above. However, the present invention is not limited to the two embodiments described below.

[0033] [First embodiment] In a first embodiment of the organic deposit sampling method of the present invention, a single capillary member is used that serves both to dispense and to suction the organic solvent. In this embodiment, the capillary member, into which an organic solvent for dissolving the organic deposits has been previously injected, is moved to the vicinity of the organic deposits using a transport means under microscope observation, and then a pressurization-depressurization mechanism is used to apply pressure to dispense the organic solvent onto the surface of the organic deposits, thereby forming a film of droplets of the organic solvent. Note that, even without using the pressurization-depressurization mechanism, it may be possible to dispense the organic solvent from the capillary member by increasing the internal pressure due to evaporation of the organic solvent; in such cases, the pressurization-depressurization mechanism is also considered to have been used.

[0034] After forming a film of organic solvent on the surface of the organic deposit, the organic deposit is preferably dissolved in the film of organic solvent while maintaining contact between the film of organic solvent and the opening, which is the outlet of the capillary member. Maintaining contact between the film of organic solvent and the outlet of the capillary member prevents the organic substance film from spreading and allows it to remain in a droplet state for a long time. In carrying out the sampling method of the present invention, the type of organic deposit is unknown, and multiple types of organic solvents with different physical properties such as polarity are used to test whether the organic deposit can be dissolved by these solvents. Examples of organic solvents that can be used in the present invention include toluene, acetonitrile, acetone, isopropanol, etc.

[0035] After dissolving the organic deposits for a predetermined time, the pressure inside the tubular member is reduced using a pressure-vacuum mechanism, and the organic solvent containing the dissolved organic deposits is sucked into the tubular member through the discharge port, in this case the suction port. The time required to dissolve the organic deposits varies depending on the surface condition of the metal material, the properties of the organic deposits, and the type of organic solvent used for dissolution. For typical metal materials, the time from when the organic solvent is discharged to when it is sucked in (dissolution time) is about 0.5 to 5 seconds.

[0036] After sucking up the organic solvent containing the dissolved organic deposits, the capillary member is moved above the solvent volatilization section, pressure is applied to the inside of the capillary member, and the organic solvent containing the dissolved organic deposits is ejected into the solvent volatilization section to form droplets on the solvent volatilization section, and the organic solvent is volatilized to obtain an evaporated, solidified organic deposit (concentrated spot). If the amount of organic deposits obtained in this way is insufficient for identification or if the organic deposits are linear, the extraction operation is repeated while changing the sampling position. FIG. 1 shows a schematic diagram of the extraction procedure in the first embodiment.

[0037] [Second embodiment] A second embodiment of the organic deposit sampling method of the present invention uses two capillary members: a capillary member (hereinafter also referred to as a discharge member) that discharges an organic solvent for dissolving the organic deposits, and a suction member that sucks up the organic solvent containing the dissolved organic deposits. In this embodiment, the discharge member, into which the organic solvent for dissolving the organic deposits has been previously injected, and the suction member are moved to the vicinity of the organic deposits using a conveying means under microscopic observation. Then, the interior of the discharge member is pressurized to discharge the organic solvent from the discharge port of the discharge member onto the surface of the organic deposits. At the same time, the interior of the suction member is depressurized to suck up the organic solvent dispensed onto the surface of the organic deposits through the suction port. This creates a continuous flow of organic solvent on the surface of the organic deposits from the discharge port of the discharge member to the suction port of the suction member. The organic deposits are extracted by dissolving them in the organic solvent flow. In this case, the small diameter of the opening in the discharge member allows the droplets to be formed, and the simultaneous dispensing and suction of the organic solvent further effectively prevents the organic solvent from spreading. In order to form the continuous flow and to provide a place for dissolving the organic deposits, the distance between the discharge port of the discharge member and the suction port of the suction member is preferably in the range of 5 to 500 μm.

[0038] Regarding suction by the suction member, the discharged organic solvent can be sucked for several seconds by capillary action without reducing the pressure. When continuously extracting organic deposits, as described below, the suction will continue for a longer period, and therefore reduced pressure is necessary. Furthermore, the opening diameter of the suction port of the suction member is preferably about 50 to 200% of the opening diameter of the discharge port of the discharge member, from the viewpoint of facilitating simultaneous discharge and suction of the organic solvent.

[0039] Furthermore, even without using a pressurizing mechanism, it may be possible to eject the organic solvent from the ejection member by increasing the internal pressure due to evaporation of the organic solvent, and in this case, it is also considered that a pressurizing mechanism is used.

[0040] After dissolving the organic deposits for a predetermined time, the suction member that has sucked in the organic solvent containing the dissolved organic deposits is moved above the solvent volatilization section, pressure is applied to the inside of the suction member, and the organic solvent containing the dissolved organic deposits is ejected into the solvent volatilization section, forming droplets on the solvent volatilization section, and the organic solvent is volatilized to obtain an evaporated, solidified organic deposit (concentrated spot). Note that, as a general rule, the solvent volatilization section is one that has been treated with a liquid repellent coating. However, as in the first embodiment, if a suction member with an opening diameter similar to that of the ejection member is used, the organic solvent containing the dissolved organic deposits is ejected little by little from the suction member, and the major diameter of the formed droplets is controlled to approximately 600 μm or less (usually 30 μm or more), the solvent volatilization section does not need to be treated with a liquid repellent coating.

[0041] In this case, the movement to the solvent volatilization section may be performed by the suction member alone, or by a pair of the suction member and the discharge member simultaneously. The time required to dissolve the organic deposits varies depending on the surface condition of the metal material, the properties of the organic deposits, and the type of organic solvent used for dissolution, but can be set appropriately by observing the dissolution status of the organic deposits under a microscope.

[0042] The advantage of the second embodiment is that by moving the discharge member and the suction member as a pair while discharging and suctioning the organic solvent, it is possible to continuously extract, for example, linear organic deposits along their length. FIG. 2 shows a schematic diagram of the extraction procedure in the second embodiment.

[0043] [Identification of organic compounds in organic deposits] By using the evaporated, dried product obtained by the above-described organic attachment sampling method as a measurement sample, it becomes possible to qualitatively analyze the components (organic compounds) of trace amounts of organic attachment. Microanalysis methods (microanalysis) such as micro-FT-IR, micro-Raman spectroscopy, micro-area X-ray photoelectron spectroscopy (μ-XPS), and micro-sampling mass spectrometry (μ-MS) can be used to identify the components of trace amounts of organic attachment. Among these, micro-FT-IR measurement is preferred because it can be performed in air, requires inexpensive measurement equipment, and provides information on organic functional groups, making it easy to identify the chemical structure of organic attachments.

[0044] In a preferred embodiment of the present invention, an infrared reflective member with a liquid-repellent surface is used as the solvent volatilization section, and the components of the organic deposits are identified by microscopic FT-IR measurement, but any material, such as a metal, may be used as the infrared reflective member as long as it does not absorb infrared rays. Furthermore, if a material transparent to infrared rays is used as the solvent volatilization section, transmission-type microscopic FT-IR measurement can also be performed.

[0045] [Operation of the sampling and identification methods of the present invention] An example of a specific implementation of the sampling method and identification method of the present invention described above will now be described.

[0046] The sampling method of the present invention is performed on a metal plate to which a target substance, whether a single substance or a mixture of multiple substances, is attached. A standard organic solvent is determined in advance, and if the target substance dissolves in this, the next step, discharge into the solvent volatilization section, is performed. On the other hand, if at least a portion of the target substance does not dissolve, various organic solvents with different polarities are used to attempt to dissolve the remaining material. If, after this trial and error process, at least a portion of the target substance does not dissolve in the organic solvent, the undissolved substance is considered to be an organic or inorganic substance that is insoluble in organic solvents. By determining approximately two types of organic solvents with different polarities as standard substances, it is possible to accommodate a wide range of target substances for sampling.

[0047] Next, when at least a portion of the target substance has dissolved, organic solvent A containing the dissolved substance is discharged into a solvent volatilizing section to volatilize the organic solvent, yielding concentrate 1. An attempt is made to dissolve concentrate 1 in organic solvent B, which has a different polarity from organic solvent A. If some of concentrate 1 remains and some dissolves, this means that concentrate 1 contains multiple organic compounds, and organic compounds can be identified for both the residue and concentrate 2 produced from the residue dissolved in organic solvent B. It is preferable to dissolve the residue in organic solvent A, discharge it into a solvent volatilizing section, and volatilize the solvent to form a concentrate, thereby increasing its thickness and providing it for identification.

[0048] On the other hand, if concentrate 1 is completely dissolved in organic solvent B, organic solvent B is discharged to volatilize the solvent and return it to concentrate 1, and dissolution is then attempted with organic solvent C, which has a different polarity from both organic solvents A and B. If part of concentrate 1 remains and part dissolves, this means that concentrate 1 contains multiple types of organic compounds, and organic compounds can be identified for both the residue and concentrate 3 produced from the residue dissolved in organic solvent C. It is preferable to dissolve the residue in organic solvent B, discharge it into a solvent volatilization section, and volatilize the solvent to form a concentrate, thereby increasing its thickness and providing it for identification.

[0049] On the other hand, if the concentrate 1 is completely dissolved by the organic solvent C, the organic solvent C that has dissolved the concentrate 1 can be discharged to volatilize the solvent and return it to the concentrate 1, and then the organic matter can be identified. If the organic matter cannot be identified by this identification, an attempt can be made to dissolve a portion of the concentrate 1 using another organic solvent D and separate it into a residue and a dissolved matter.

[0050] As the organic solvent A used initially in the above operation, a mixed solvent of organic solvents B and C (the mass ratio of organic solvents B and C is about 40:60 to 60:40) can be used. [Example]

[0051] [Microscopic FT-IR measurement] For the microscopic FT-IR measurements, a Thermo Fisher Scientific infrared spectrometer infrared microscope system (Nicolet 4700, Continuμm) was used. A Micro Support Axis Pro SS microscope-integrated manipulator was used as the sample stage, and a Toray Research pinpoint concentration plate (2020-01) (liquid-repellent treated) was placed on the sample stage to serve as the solvent volatilization area. A 10μm diameter circular micropipette (Micro Support micropipette, tip inner diameter 10μm (10 pieces), model: MP-010, capacity 10μL, hereinafter also referred to as a 10μm micropipette) was used as the thin tube component. Figure 3 shows a portion of the device used in carrying out the present invention and its operation.

[0052] [Example 1] A copper plate (1 mm thick) manufactured by Taiho Trading Co., Ltd. was cut into 2-3 cm squares, ultrasonically treated for 2 minutes in Kanto Chemical Co., Inc.'s Primepure toluene (purity of 99.9% by mass or higher), dried with a blower, and then a pseudo-organic deposit (hereafter referred to as a pseudo-stain) was formed on the surface to serve as the test material. The pseudo-stain formation method is as follows.

[0053] 10 mg of powdered stearic acid amide (Grade 1, purity 90% by mass or more) manufactured by Kanto Chemical Co., Inc. was weighed using a precision balance and dissolved in 100 mL of the toluene using an ultrasonic cleaner to prepare solution 1. Subsequently, 10 mL of toluene was added to 10 mL of solution 1 to prepare solution 2. Furthermore, 10 mL of toluene was added to 10 mL of solution 2 to prepare solution 3, and 10 mL of toluene was added to 10 mL of solution 3 to prepare solution 4.

[0054] Solutions 1 to 4 prepared by the above method were dropped onto the surface of the Cu plate using a 10 μL syringe (inner diameter 170 μm, hereinafter referred to as a 170 μm syringe) manufactured by SGE Analytical Science Pty., and then air-dried to obtain annular pseudo-stains 1 to 4 made of stearic acid amide. The annular pseudo-stains had a diameter of about 10 mm and a ring (outline) width of about 50 to 200 μm.

[0055] FIG. 4 shows the infrared absorption spectra obtained by conventional microscopic FT-IR measurement for the artificial spots 1 to 4 obtained by the above method. -1 The absorption peaks appearing near the center are due to the absorption of atmospheric CO2. The figure also shows a standard spectrum (reference spectrum) of stearic acid amide from the library stored in the computer attached to the microscope FT-IR spectrometer. The vertical axis indicates the reflectance of the standard spectrum. For example, the reflectance of pseudo-stain 4 is not approximately 115 across the entire wavenumber range shown in Figure 4 (the same applies below). The results in Figure 4 qualitatively demonstrate that, in the case of pseudo-stains formed using the above-mentioned method, the components of the deposits on pseudo-stains 3 and 4 cannot be identified using conventional microscope FT-IR measurements.

[0056] For artificial stains 3 and 4, high-sensitivity microscopic FT-IR measurements were also performed using infrared light at a low angle of incidence, but due to the surface roughness of the Cu sample plate, a clear infrared absorption spectrum could not be obtained.

[0057] Next, the extraction operation of the organic deposits on the pseudo stains 3 and 4 was carried out using two 10 μm micropipettes according to the second embodiment of the present invention. The organic solvent used to extract the organic deposits was toluene, and the extraction operation was carried out by moving along the circular ring (outline portion) of the stain over a length of approximately 1 / 8 of the circular ring.

[0058] A Cu plate with a pseudo-stain attached and a Thermo Fisher Scientific Au-coated plate with the pinpoint concentration plate and an Al pan for containing organic solvents attached with carbon tape were placed side by side on the sample stage of the manipulator. To ensure rapid operation (solvent intake, extraction, and concentration), the coordinates of the sample, Al pan, and solvent evaporation area were entered into the operation computer in advance, and the stage was moved based on these coordinates. The following operations were then performed while observing the operation area with the microscope on the manipulator at a magnification of 200x.

[0059] Two 10 μm micropipettes (manufactured by Micro Support) with pressure adjustment mechanisms were attached to both arms of the manipulator. The 10 μm micropipette 1 used as the dispensing component was used to aspirate toluene from an aluminum pan. Then, a pair of capillary tubes was moved to the location where the organic deposits were to be extracted. The nozzle of the 10 μm micropipette 1 was brought into contact with the simulated stain. The organic solvent evaporated, causing the internal pressure to rise, allowing the organic solvent inside the 10 μm micropipette 1 to spontaneously dispense. At the same time, the 10 μm micropipette 2 used for aspirating was brought into contact with the dispensed solvent. The syringe attached to the microinjector was used to create negative pressure within the 10 μm micropipette 2, allowing the organic solvent to be aspirated. This created a flow of organic solvent on the surface of the organic deposits. While the above dispensing and aspirating processes were performed continuously, the sample stage was moved to change the extraction location, allowing the organic deposits to be continuously dissolved and aspirated. The distance between the discharge port of the 10 μm micropipette 1 and the intake port of the 10 μm micropipette 2 was set to approximately 20 μm.

[0060] After completing the extraction procedure, the capillary element was moved onto the pinpoint concentration plate, and the suction port of the 10 μm micropipette 2 of the suction element was brought into contact with the pinpoint concentration plate. Using the rubber ball attached to the microinjector, the organic solvent in the 10 μm micropipette 2 was ejected onto the pinpoint concentration plate, volatilizing the organic solvent to obtain an evaporated, dry product (concentrated spot) of the organic deposits. The maximum diameter of the droplets that spread onto the concentration plate during ejection was approximately 1 mm. The diameter of the resulting concentrated spots was approximately 100 μm for both pseudo-stains 3 and 4. Microscopic FT-IR measurements were performed on the concentrated spots using the FT-IR measurement device described above. Figure 5 shows the infrared absorption spectra obtained for pseudo-stains 3 and 4. As can be seen from the figure, the obtained infrared absorption spectra were roughly consistent with those of stearic acid amide. Using the organic deposit sampling method of the present invention, it became possible to identify organic deposits, which was previously impossible using conventional microscopic FT-IR measurements.

[0061] [Example 2] Using the above solution 4, a circular pseudo-blemish was formed on a Cu plate using the same procedure as in Example 1, and three fingerprints were attached near the pseudo-blemish, designated pseudo-blemish 4-2. Microscopic observation revealed that the distance between the attached fingerprint and the circular ring was approximately 500 μm to 1 mm. The pseudo-blemish was subjected to the following procedures near the attached fingerprint: (1) visual and manual extraction of organic deposits using one 170 μm syringe; (2) extraction of organic deposits using one 10 μm micropipette according to the first embodiment; and (3) extraction of organic deposits using two 10 μm micropipettes according to the second embodiment. After evaporating the organic deposits to dryness (concentrated spots), microscopic FT-IR analysis was performed. Note that all extraction procedures were performed using the above toluene. The concentrated spots obtained in procedure (1) were approximately 300 μm in diameter, and the concentrated spots obtained in procedures (2) and (3) were approximately 100 μm in diameter. FIG. 6 shows the results of microscopic FT-IR measurement of the obtained evaporated to dryness product.

[0062] In the case of the visual and manual extraction described in (1) above, the extraction was performed using a single 170 μm syringe that served as both a discharge member and a suction member, and no microscopic observation was performed during the extraction. The procedure for extracting organic deposits according to the second embodiment described in (3) above was the same as that described in Example 1, and was performed while moving over a length of approximately 1 / 8 of the ring. The extraction of organic deposits according to the first embodiment of the present invention described in (2) above was performed according to the following procedure.

[0063] First, a Cu plate with a pseudo-stain attached and a Thermo Fisher Scientific Au-coated plate with the pinpoint concentration plate and an Al pan for containing organic solvents attached with carbon tape were placed side by side on the sample stage of the manipulator. To ensure rapid operation (solvent intake, extraction, and concentration), the coordinates of the sample, Al pan, and solvent evaporation area were entered into the operation computer in advance, and the stage was moved based on these coordinates. The following operations were then performed while observing the operation area with the microscope on the manipulator at a magnification of 200x.

[0064] A 10 μm micropipette (Micro Support, Inc.) with a pressure adjustment mechanism was attached to one arm of the manipulator. After aspirating toluene from an Al pan with the 10 μm micropipette, the 10 μm micropipette was moved to the location where the organic deposits were to be extracted. The nozzle of the 10 μm micropipette was then brought into contact with the simulated stain 4-2. The rubber ball attached to the microinjector was then squeezed to eject a portion of the organic solvent from the 10 μm micropipette. The rubber ball was then released, and the organic solvent was sucked into the 10 μm micropipette under negative pressure. The process took approximately 1 second from ejection to aspiration. The operation was performed while the nozzle of the 10 μm micropipette was still in contact with the droplet. The ejection volume was adjusted so that the droplet spread on the Cu plate had a maximum diameter of approximately 400 μm. The area of ​​this droplet spread can be considered the extraction area.

[0065] After the extraction operation was completed, the capillary element was moved onto the pinpoint concentration plate, and the nozzle of the 10 μm micropipette, which was the capillary element, was brought into contact with the pinpoint concentration plate. Using a rubber ball, the organic solvent inside the 10 μm micropipette was ejected onto the pinpoint concentration plate, volatilizing the organic solvent and obtaining a dried product (concentrated spot) of the organic deposits. The droplets that spread onto the concentration plate during ejection had a maximum diameter of approximately 1 mm. The droplets that spread onto the concentration plate were larger than those that spread onto the Cu plate because, unlike the ejection during the extraction operation, all of the solvent previously drawn into the pipette was ejected onto the concentration plate.

[0066] In Figure 6, in addition to the absorption peak due to stearic acid amide, multiple absorption peaks were observed in the infrared absorption spectrum obtained when extraction was performed visually and manually using a 170 μm syringe. Microscopic observation after the extraction operation showed that the dropped organic solvent had spread to a diameter of approximately 3000 μm, wetting the ring with a width of approximately 200 μm. This suggests that contamination from fingerprints attached near the ring was also extracted.

[0067] In contrast, when the extraction operation was carried out in the first and second embodiments, only the absorption peak due to stearic acid amide was observed, demonstrating the effectiveness of the organic deposit sampling method of the present invention.

[0068] [Example 3] Approximately 10 mg of commercially available rod-shaped polycarbonate (manufactured by AS ONE Corporation) was cut into small pieces with a cutter and weighed on a precision balance. This was dissolved in 100 mL of the toluene using an ultrasonic cleaner to prepare solution 5. 10 mL of toluene was added to 10 mL of solution 5 to prepare solution 6. 10 mL of toluene was added to 10 mL of solution 6 to prepare solution 7, and 10 mL of toluene was added to 10 mL of solution 7 to prepare solution 8. Approximately 10 mg of powdered polymethyl methacrylate (Technovit 4004 Powder, manufactured by KULZER, purity 95% by mass) was weighed on a precision balance and dissolved in 100 mL of acetone (manufactured by Kanto Chemical Co., Inc., Primepure purity (purity 99.9% by mass or higher)) using an ultrasonic cleaner to prepare solution 9. 10 mL of acetone was added to 10 mL of solution 9 to prepare solution 10. Furthermore, 10 mL of acetone was added to 10 mL of solution 10 to prepare solution 11, and 10 mL of acetone was added to 10 mL of solution 11 to prepare solution 12. Using solutions 8 and 12, circular pseudo-stains 5 and 6 were formed using the same procedure as in Example 1. In this case, the circular pseudo-stains 5 and 6 each had a diameter of approximately 10 mm and a ring (outline) width of approximately 200 μm, but were not continuous, resulting in scattered island-like stains approximately 100 μm in diameter. The resulting pseudo-stains 5 and 6 were subjected to extraction using the procedure of the second embodiment described in Example 1, using toluene as the organic solvent for pseudo-stain 5 and acetone as the organic solvent for pseudo-stain 6. In both cases, evaporated, dried organic deposits (concentrated spots) approximately 100 μm in diameter were obtained. The extraction procedure was performed while moving along the ring of the stain, approximately 1 / 4 of the length of the ring. Figure 7 shows the results of microscopic FT-IR measurements performed on the evaporated and dried material obtained when the organic attachment type was polycarbonate (in the case of pseudo stain 5), and Figure 8 shows the results when the organic attachment type was polymethyl methacrylate (in the case of pseudo stain 6). Figures 7 and 8 also show the infrared absorption spectra obtained when microscopic FT-IR measurements were performed directly on the pseudo stains without performing an extraction procedure.

[0069] [Example 4] Approximately 10 mg of commercially available rod-shaped ABS resin (manufactured by AS ONE Corporation) was cut into small pieces using a cutter and weighed on a precision balance. The pieces were then dissolved in 100 mL of acetonitrile (manufactured by Kanto Chemical Co., Inc., for LC / MC, purity 99.9% by mass or higher) using an ultrasonic cleaner to prepare solution 13. 10 mL of acetonitrile was added to 10 mL of solution 13 to prepare solution 14. 10 mL of acetonitrile was added to 10 mL of solution 14 to prepare solution 15. Equal amounts of solution 3 (a toluene solution of stearic acid amide) prepared in Example 1 and solution 15 were mixed to prepare solution 16, and then annular pseudo-stain 7 was formed using solution 16 according to the same procedure as in Example 1. The annular pseudo-stain had a diameter of approximately 10 mm and a ring (outline) width of approximately 100 μm.

[0070] For the pseudo stain 7, a continuous extraction operation was performed along the ring over approximately one-quarter of the length of the ring using the same procedure as the extraction operation described in Example 1, except that acetonitrile was used as the organic solvent for dissolving the organic deposits, and an evaporated, dried product of the organic deposits with a diameter of approximately 200 μm (hereinafter referred to as concentrated spot 1) was obtained in the solvent evaporation area. Note that the spot where the extraction operation for pseudo stain 7 was performed had disappeared, so it is believed that all of the organic deposits present in that area were extracted (dissolved in acetonitrile).

[0071] Subsequently, the organic solvent was changed to toluene for concentrated spot 1, and an extraction operation was performed using the same procedure as the extraction operation described in Example 1. The organic solvent containing the organic deposits was discharged at a different location in the solvent volatilization section, and then the organic solvent was volatilized to obtain a second evaporated to dryness product with a diameter of about 200 μm (hereinafter referred to as concentrated spot 2). Furthermore, the organic deposits remaining in concentrated spot 1 that were not extracted with toluene were extracted using acetonitrile as the organic solvent using the same procedure as the extraction operation described in Example 1, and a third evaporated to dryness product with a diameter of about 100 μm (hereinafter referred to as concentrated spot 3) was obtained at a different location in the solvent volatilization section.

[0072] Microscopic FT-IR measurements were performed on concentrated spot 2 and concentrated spot 3, and the infrared absorption spectrum obtained was roughly consistent with that of stearic acid amide for concentrated spot 2, and with that of ABS resin for concentrated spot 3 (Figure 9). The vertical axis in Figure 9 indicates the reflectance of the reference spectrum of ABS resin.

[0073] These measurement results for concentrated spots 2 and 3 were obtained because acetonitrile, which is close to the hydrophilic side, elutes both stearic acid amide and ABS resin, while hydrophobic toluene elutes ABS resin less easily than stearic acid amide. As a result, re-extraction with toluene resulted in separation into two components. Similarly, even if a stain contains two components, if the extraction amounts differ due to differences in solvent polarity, it is possible to separate each component by combining solvents of different polarity and performing extraction and re-extraction. However, since it is not known what components are actually present in a stain, or whether there are multiple components, it is possible to separate the two components by, for example, preparing two solvents of different polarity and performing extraction and re-extraction in advance. However, it is important to note that the separated components may also contain multiple components with equal extraction amounts per solvent.

[0074] [Example 5] The sample used for the measurement was a metal plate with stain-like contamination of an organic substance of unknown composition, sampled at an actual factory. The stain was linear, approximately 1 cm long and 200-300 μm wide.

[0075] The above sample was extracted using toluene as a solvent to dissolve the organic deposits. Extraction was performed using the single-micropipette extraction method described in Example 2 and the dual-micropipette extraction method described in Example 1. After forming a concentrated spot (concentrated spot) of unknown composition (approximately 100 μm in diameter), microscopic FT-IR measurements were performed. When using dual-micropipette extraction, the extraction was performed while moving the pipette over a range of approximately 500 μm along the length of the stain and 200 μm in width. Figure 10 shows the infrared absorption spectra obtained. Clear absorption spectra were obtained for both concentrated spots. Searching the library built into the data processing computer revealed that the infrared absorption spectra generally matched the reference spectrum of an amide compound (erucic acid amide). Furthermore, in both the single-micropipette and dual-micropipette extractions, the stain color disappeared at the extraction site, suggesting that the toluene had completely dissolved the stain components.

[0076] [Example 6] Sampling and identification method for organic deposits using mixed solvents <Example 6-1> The same sample as in Example 5 (a metal plate contaminated with organic stains of unknown composition) was used as the measurement sample.

[0077] For the sample, an equal-volume mixed solvent of toluene and acetonitrile was used as the solvent to dissolve the organic deposits. Using the extraction method using two micropipettes described in Example 1, an evaporated, dried product of the organic deposits with unknown components, approximately 100 μm in diameter (hereafter referred to as concentrated spot 4), was formed. The extraction operation was performed while moving within a range of approximately 500 μm in the length direction and 200 μm in width of the stain. Furthermore, since the color of the stain disappeared at the extraction site, it is believed that all of the stain components were dissolved by the equal-volume mixed solvent of toluene and acetonitrile.

[0078] Next, the organic solvent was changed to acetonitrile for concentrated spot 4, and an extraction operation was performed using the same procedure as that described in Example 1. The organic solvent containing the organic deposits was ejected at a different location in the solvent volatilization section, and then the organic solvent was volatilized to obtain a second evaporated, dried product with a diameter of approximately 100 μm (hereinafter referred to as concentrated spot 5). At this time, no residue that remained insoluble in acetonitrile was observed.

[0079] Next, the organic solvent was changed to toluene for concentrated spot 5, and an extraction operation was performed using the same procedure as the extraction operation described in Example 1. The organic solvent containing the organic deposits was discharged at a different location in the solvent volatilization section, and then the organic solvent was volatilized to obtain a third evaporated, dried product with a diameter of about 100 μm (hereinafter referred to as concentrated spot 6). At this time, no residue that remained insoluble in toluene was confirmed.

[0080] Microscopic FT-IR measurement of concentrated spot 6 yielded a clear absorption spectrum. When the data was searched using the library built into the computer used for data processing, the infrared absorption spectrum was found to be roughly consistent with the reference spectrum of an amide compound (erucic acid amide) (Figure 11).

[0081] This procedure was performed because it was assumed that stains might be composed of multiple components, and the aim was to first use a mixed solvent of different polarities for extraction in order to extract as many components as possible, and then to separate each component using a single solvent.

[0082] <Example 6-2> The sample to be measured was the same as in Example 4 (annular pseudo stain 7 on a Cu plate (a stain formed using a solution obtained by mixing equal amounts of an acetonitrile solution of ABS resin and a toluene solution of stearic acid amide)). For the sample, an equal-volume mixed solvent of toluene and acetonitrile was used as the solvent to dissolve the organic deposits. Using the extraction method described in Example 1 using two 10 μm micropipettes, an evaporated, dried product of the organic deposits with a diameter of approximately 200 μm (hereafter referred to as concentrated spot 7) was formed. The extraction procedure was performed by moving along the stain ring for approximately 1 / 4 of the length of the ring. Since the color of the stain disappeared at the extraction site, it is believed that the stain components were dissolved by the equal-volume mixed solvent of toluene and acetonitrile.

[0083] Next, the organic solvent was changed to acetonitrile and an extraction operation was performed on concentrated spot 7 using the same procedure as in Example 1. The organic solvent containing the organic deposits was ejected at a different location in the solvent volatilization section, and then the organic solvent was volatilized to obtain a second evaporated, dried product with a diameter of about 200 μm (hereinafter referred to as concentrated spot 8). At this time, no residue that remained insoluble in acetonitrile was observed.

[0084] Next, the organic solvent was changed to toluene for concentrated spot 8, and an extraction operation was performed using the same procedure as the extraction operation described in Example 1 above. The organic solvent containing the organic attachments was discharged at a different location in the solvent volatilization section, and the organic solvent was then volatilized to obtain a third evaporated dry product with a diameter of approximately 200 μm (hereinafter referred to as concentrated spot 9). Furthermore, since residual matter that was not extracted with toluene was confirmed in concentrated spot 8, an extraction operation was performed using acetonitrile as the organic solvent using the same procedure as the extraction operation described in Example 1 above, and a fourth evaporated dry product with a diameter of approximately 100 μm was obtained at a different location in the solvent volatilization section (hereinafter referred to as concentrated spot 10).

[0085] Microscopic FT-IR measurements were performed on concentrated spots 9 and 10, and the infrared absorption spectrum obtained for concentrated spot 9 was roughly consistent with that of stearic acid amide, and the infrared absorption spectrum obtained for concentrated spot 10 was roughly consistent with that of ABS resin (Figure 12).

[0086] [Example 7] The same sample as in Example 5 (a metal plate contaminated with organic stains of unknown composition) was used as the measurement sample.

[0087] Toluene was used as a solvent for dissolving the organic deposits on the sample, and (1) extraction of the organic deposits was performed using one micropipette according to the first embodiment, and (2) extraction of the organic deposits was performed using two micropipettes according to the second embodiment.

[0088] Extraction of organic deposits according to the first embodiment was carried out according to the following procedure. First, a stained metal plate, an aluminum pan for containing the organic solvent, and a 2-3 cm square piece of untreated copper plate (1 mm thick) manufactured by Taiho Trading Co., Ltd., cut into pieces, were placed side by side on the sample stage of the manipulator. To ensure rapid operation (solvent intake, extraction, and concentration), the coordinates of the sample, aluminum pan, and solvent volatilization area were entered into the operation computer beforehand, and the stage was moved based on these coordinates. The following operations were then performed while observing the operation area with the microscope on the manipulator at a magnification of 200x.

[0089] A 10 μm micropipette (Micro Support, Inc.) with a pressure adjustment mechanism was attached to one arm of the manipulator. After aspirating toluene from an Al pan with the 10 μm micropipette, the 10 μm micropipette was moved to the area where the organic deposits were to be extracted. The nozzle of the 10 μm micropipette was then brought into contact with the stain. The rubber ball attached to the microinjector was then squeezed to eject a portion of the organic solvent from the 10 μm micropipette. The rubber ball was then released, and the organic solvent was sucked into the 10 μm micropipette under negative pressure. The process took approximately 1 second from ejection to aspiration. The operation was performed while the nozzle of the 10 μm micropipette was still in contact with the droplet. The ejection volume was adjusted so that the droplet spread on the Cu plate had a maximum diameter of approximately 400 μm. The area of ​​this droplet spread can be considered the extraction area.

[0090] After the extraction procedure was completed, the capillary element was moved onto a Cu plate, and the nozzle of the 10 μm micropipette of the capillary element was brought into contact with the Cu plate. Using a rubber ball, the organic solvent in the micropipette was ejected onto the Cu plate, and the organic solvent was evaporated to obtain an evaporated, solidified product. The solvent was ejected in small amounts so that the droplets on the Cu plate were approximately 500 μm in diameter or less. The evaporated, solidified product was circular. The above extraction operation was also performed at two other locations on the stain on the metal plate, for a total of three locations, and each time a small amount was ejected onto the same location on the Cu plate to accumulate the stain components, ultimately yielding a circular ring-shaped concentrate 1 with a diameter of approximately 500 μm.

[0091] The extraction of organic deposits according to the second embodiment was carried out according to the following procedure. First, the stained metal plate, an Al pan for containing the organic solvent, and the same Cu plate as above were placed side by side on the sample stage of the manipulator. To ensure rapid operation (solvent intake, extraction, and concentration) during the extraction procedure, the coordinates of the sample, Al pan, and solvent evaporation area were entered into the operation computer in advance, and the stage was moved based on these coordinates. The following operations were then performed while observing the operation area with the microscope on the manipulator at a magnification of 200x.

[0092] Two 10 μm micropipettes (manufactured by Micro Support) with pressure adjustment mechanisms were attached to both arms of the manipulator. The 10 μm micropipette used as the dispensing component aspirated toluene from an aluminum pan. Then, a pair of capillary tubes was moved to the location where the organic deposits were to be extracted. The discharge nozzle of 10 μm micropipette 1 of the dispensing component was brought into contact with the stain. The organic solvent evaporated, causing the internal pressure to increase, allowing the organic solvent to be spontaneously dispensed from 10 μm micropipette 1. At the same time, 10 μm micropipette 2, used for aspirating, was brought into contact with the dispensed solvent. A syringe attached to the microinjector was used to create negative pressure within 10 μm micropipette 2, allowing the organic solvent to be aspirated. While the above dispensing and aspirating processes were performed continuously, the sample stage was moved two-dimensionally to change the extraction location, continuously dissolving and extracting the organic deposits. The distance between the discharge nozzle of 10 μm micropipette 1 and the intake nozzle of 10 μm micropipette 2 was approximately 20 μm. The extraction operation was carried out while moving within a range of approximately 500 μm in the length direction and 200 μm in width of the stain.

[0093] After the extraction operation was completed, the capillary member was moved onto the Cu plate, the suction nozzle of the 10 μm micropipette of the suction member was brought into contact with the Cu plate, and the organic solvent in the 10 μm micropipette was ejected onto the Cu plate using a rubber ball attached to the microinjector. The organic solvent was then evaporated, yielding a ring-shaped concentrate 2 with a diameter of approximately 400 μm. At this time, the solvent was ejected in small amounts so that the spread (droplets) on the Cu plate were approximately 500 μm in diameter or less.

[0094] Microscopic FT-IR measurements were performed on the annular portions of the resulting annular concentrates 1 and 2. Figure 13 shows the infrared absorption spectra obtained. Clear absorption spectra were obtained for both stains, and when a search was performed using the library built into the data processing computer, the infrared absorption spectra generally matched the reference spectrum of an amide compound (erucic acid amide).

[0095] The above measurement results show that the location where the solvent is evaporated after extraction of organic adhesions does not necessarily have to be a solvent evaporation area with a liquid-repellent surface treatment, and that if the solvent is evaporated by ejecting small amounts over a narrow area so that the solvent does not spread, the extracted components will accumulate in a circular shape, for example, and a concentrated substance (stain) that is thicker than the original stain will be reformed, thereby obtaining a clear spectrum.

Claims

1. A method for sampling organic deposits on a metal plate using an apparatus for dissolving organic deposits containing organic compounds deposited on a metal plate with an organic solvent and then aspirating them, the apparatus comprising: a sample stage provided with a solvent volatilizing section that has been subjected to a liquid-repellent treatment; a microscope observation system; and a thin tubular member that is capable of discharging and aspirating an organic solvent by a pressure-depressurization mechanism, wherein the sample stage and the thin tubular member are relatively movable by a transport mechanism under observation by the microscope observation system, the thin tubular member is a single member having an opening for discharging and suctioning the organic solvent, the diameter of the opening being 25 μm or less, and the thin tubular member into which the organic solvent has been injected is moved to the vicinity of organic deposits on the surface of a metal plate placed on a sample stage under microscope observation; By applying pressure, the organic solvent in the tubular member is discharged onto the surface of the organic deposit to form a film of the organic solvent and dissolve the organic deposit, and then the inside of the tubular member is depressurized to suck the organic solvent containing the dissolved organic deposits through the opening; a capillary member containing an organic solvent containing the dissolved organic deposits being moved above the solvent volatilization section, and pressure being applied to eject the organic solvent containing the dissolved organic deposits to form droplets on the solvent volatilization section; and the organic solvent in the droplets is volatilized to concentrate the organic deposits.

2. 2. The sampling method according to claim 1, wherein the organic deposits are dissolved while the opening of the tubular member is in contact with the droplet of the organic solvent.

3. A method for sampling organic deposits on a metal plate using an apparatus for dissolving organic deposits containing organic compounds deposited on a metal plate with an organic solvent and then aspirating them, the apparatus comprising: a sample stage provided with a solvent volatilizing section that has been subjected to a liquid-repellent treatment; a microscope observation system; and a thin tubular member that can eject or aspirate an organic solvent, wherein the sample stage and the thin tubular member are relatively movable by a transport mechanism under observation by the microscope observation system, the thin tubular members are a pair of members consisting of a discharge member having an opening for discharging an organic solvent onto organic deposits and a suction member having an opening for suctioning the discharged organic solvent, the diameter of the opening of the discharge member being 25 μm or less, and the pair of thin tubular members are moved near the organic deposits on the surface of a metal plate placed on a sample stage under microscope observation; applying pressure by a pressure mechanism to discharge the organic solvent from the discharge member into which the organic solvent has been injected onto the surface of the organic deposit, and at the same time, sucking the discharged organic solvent by the suction member to form a flow of the organic solvent on the surface of the organic deposit, thereby dissolving the organic deposit; The organic solvent containing the dissolved organic deposits is sucked by the suction member, A method for sampling organic attachments on a metal plate, comprising: moving the suction member above the solvent volatilization section; applying pressure to the organic solvent containing the dissolved organic attachments inside the suction member, thereby ejecting the organic solvent containing the dissolved organic attachments to form droplets on the solvent volatilization section; and concentrating the organic attachments by volatilizing the organic solvent in the droplets.

4. a sample stage provided with a solvent volatilizing section that has not been treated for liquid repellency, a microscope observation system, and a capillary member that can discharge and aspirate an organic solvent by means of a pressurization-depressurization mechanism, wherein the sample stage and the capillary member are relatively movable by a transport mechanism under observation by the microscope observation system; and an apparatus 1 for dissolving organic deposits containing organic compounds that have been deposited on a metal plate with an organic solvent and then aspirating the organic deposits; or a sample stage provided with a solvent volatilizing section that has not been treated for liquid repellency, a microscope observation system, and a capillary member that can discharge or aspirate an organic solvent, wherein the sample stage and the capillary member are relatively movable by a transport mechanism under observation by the microscope observation system; and an apparatus 2 for dissolving organic deposits containing organic compounds that have been deposited on a metal plate with an organic solvent and then aspirating the organic deposits; When the apparatus 1 is used, the capillary member of the apparatus 1 is a single member having an opening for discharging and sucking the organic solvent, the diameter of the opening being 25 μm or less, the capillary member into which the organic solvent has been injected is moved under microscope observation to the vicinity of organic deposits on the surface of a metal plate placed on a sample stage, and pressure is applied to discharge the organic solvent inside the capillary member onto the surface of the organic deposits to form a film of organic solvent and dissolve the organic deposits, and then the pressure inside the capillary member is reduced to suck the organic solvent containing the dissolved organic deposits through the opening, the capillary member containing the organic solvent containing the dissolved organic deposits is moved above the solvent volatilization section, and pressure is applied to discharge the organic solvent containing the dissolved organic deposits to form droplets on the solvent volatilization section with a major axis controlled to 600 μm or less, and the organic solvent in the droplets is volatilized to concentrate the organic deposits, When the device 2 is used, the thin tubular members of the device 2 are a pair of members consisting of a discharge member having an opening for discharging the organic solvent onto the organic attachment and a suction member having an opening for sucking up the discharged organic solvent, the diameter of the opening of the discharge member being 25 μm or less, and the pair of thin tubular members are moved to the vicinity of the organic attachment on the surface of the metal plate placed on the sample stage under microscope observation, and pressure is applied by a pressure mechanism, whereby the organic solvent inside the discharge member into which the organic solvent has been injected is discharged onto the surface of the organic attachment, and the discharged organic solvent is sucked up by the suction member. a solvent is sucked, and a flow of the organic solvent is formed on the surface of the organic attachment, thereby dissolving the organic attachment; the organic solvent containing the dissolved organic attachment is sucked by the suction member; the suction member is moved above the solvent volatilization section; pressure is applied to the organic solvent containing the dissolved organic attachment inside the suction member, thereby discharging the organic solvent containing the dissolved organic attachment to form droplets on the solvent volatilization section, the major axis of which is controlled to be 600 μm or less; and the organic solvent of the droplets is volatilized, thereby concentrating the organic attachment.

5. A method for identifying organic compounds constituting the organic attachment, comprising using the sampling method for organic attachment on a metal plate according to any one of claims 1 to 4, and measuring the concentrated organic attachment formed in the solvent volatilization area on the sample stage by microscopic reflection Fourier transform infrared spectroscopy.

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