JP6901846B2 - Morphological observation method by spectroscopic method - Google Patents

Description

The present invention relates to a novel analytical method for measuring the morphology of a substance from a spectroscopic method.

The spectroscopic method irradiates a measurement object with measurement light, measures a change in the spectrum of the measurement light due to the interaction between the measurement light and the measurement object, and analyzes the measurement object. It is a method for qualitatively or quantitatively analyzing the morphology of an object. In the spectroscopic method, since the morphology of the measurement object does not change depending on the measurement itself, it is possible to observe the morphology of an extremely unstable measurement object (see, for example, Non-Patent Document 1). In Non-Patent Document 1, Raman spectroscopy, which is a kind of spectroscopic method, is used to observe the morphology of electrodes in a charged lithium-ion battery.

Since the extremely unstable measurement object as described above is oxidized by contact with the atmosphere and deteriorates into a form different from the original one, the measurement object is sealed in a non-atmospheric exposure cell. After that, measurement is performed (see Non-Patent Document 2). By sealing, it is possible to suppress the contact of the measurement object with the atmosphere and observe the original morphology.

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The present inventors have attempted to observe the morphology of various substances by a spectroscopic method. Then, mainly, in a substance whose morphology is changed by water, in the conventional measurement method, the morphology is changed by water vapor in the atmosphere during the measurement, and the original morphology cannot be measured. In particular, it has been found that the original morphology cannot be observed with a substance whose morphology changes when exposed to the atmosphere in a humidity region of 20 to 100% RH.

Therefore, an object of the present invention is to provide a method for observing the original morphology of a measurement object without changing the morphology of the measurement object when analyzing the measurement object by a spectroscopic method.

The present inventors have conducted diligent studies in order to solve the above problems. Then, at least a part of the outer periphery of the surface to be measured of the object to be measured is covered with a brazing material, and the brazing material is used to bring a permeate into close contact with the surface to be measured. We have found that analysis can be performed with little change in the state of the surface to be measured), and have completed the present invention.

That is, the first invention is
(1) In a method of exposing the surface to be measured of the object to be measured by grinding the object to be measured and then analyzing the surface to be measured by a spectroscopic method.
Adhesion material attachment step in which a brazing material is attached to at least a part of the outer periphery of the measurement object when the measurement surface of the measurement object is exposed.
A preparatory step in which a transmitter that transmits the measurement light of the spectroscopic method is brought into close contact with the surface to be measured of the object to be measured obtained in the adhesive material adhesion step, and an object obtained in the preparatory step. of to said measurement surface, the measurement light, by applying through the transparent member, seen containing an analysis step for analyzing a該被measurement surface,
In the preparatory step, the brazing material adhering to the outer periphery of the surface to be measured is softened, and the permeate is brought into close contact with the surface to be measured by the softened brazing material.

The first invention can take the following aspects.

(2) The adhesive material adhering step is
The first coating step of coating the brazing material so as to include at least a part of the surface of the object to be measured, which is the outer periphery of the surface to be measured, and the first coating obtained in the first coating step. Analysis of (1) including a grinding step of grinding an object together with a coated brazing material to expose the surface to be measured so that the brazing material is attached to at least a part of the outer periphery of the surface to be measured. Method.

(3) In the adhesion material adhering step, a high softening point material having a softening point higher than that of the brazing material by 20 ° C. or more is further adhered to the surface of the brazing material adhering to the outer periphery of the surface to be measured ( Analysis method of 1).

(4) The adhesive material adhering step is
The first coating step of coating the brazing material so as to include at least a part of the surface of the object to be measured, which is the outer periphery of the surface to be measured.
A second coating step of coating at least the surface of the brazing material of the first coating obtained in the first coating step with a high softening point material having a softening point higher than that of the brazing material by 20 ° C. or more, and the first coating step. (Ii) The second coating obtained in the coating step is ground together with the coated brazing material and the coated high softening point material to expose the surface to be measured, thereby adhering to the outer periphery of the surface to be measured. The analysis method of (3), which further includes a grinding step in which the high softening point material is attached to the surface of the material.

(5) The analysis method according to any one of (1) to (4), wherein the brazing material adheres to the entire outer periphery of the surface to be measured in the adhesion material adhering step.

(6) The analysis method according to (1) to (5) , wherein the waxing material has a softening point of 200 ° C. or lower.

(7) The analysis method according to any one of (1) to (6) , wherein the transmittance of the permeate becomes 0.01 to 1.0 when analyzed by the corresponding spectroscopic method.

(8) The analysis method according to any one of (1) to (7 ), wherein the measurement object contains a substance whose morphology is changed by water.

(9) The analysis method according to any one of (1) to (8) , wherein the spectroscopic method analyzes with infrared rays, visible rays, and ultraviolet rays.

According to the present invention, the object to be measured can be analyzed by a spectroscopic method. Therefore, in particular, even a substance whose morphology is changed by water, for example, a substance whose morphology is changed by water vapor in the atmosphere when exposed to the atmosphere, can be analyzed without changing its morphology. As a result, the original morphology of the measurement object whose morphology is changed by water can be analyzed in detail, and feedback can be given to the manufacturing method, purification method, etc. of the measurement object.

In the present invention, the first coating step of coating the surface of the object to be measured with a brazing material, the second coating step of coating the surface of the first coating obtained in the first coating step with a high softening point material, the first. (Ii) It is a schematic diagram of the grinding process for grinding the second coating material obtained in the coating process, and the preparatory process for bringing the permeate into close contact with the surface to be measured of the ground product obtained in the grinding process. It is a microscopic Raman measurement result for the measurement object of an Example. It is a microscopic Raman measurement result for the measurement object of the comparative example.

The present invention is a method of exposing a surface to be measured of the object to be measured by grinding the object to be measured and then analyzing the surface to be measured by a spectroscopic method. And
Adhesion material attachment step in which a brazing material is attached to at least a part of the outer periphery of the measurement object when the measurement surface of the measurement object is exposed.
A preparatory step in which a transmitter that transmits the measurement light of the spectroscopic method is brought into close contact with the surface to be measured of the object to be measured obtained in the adhesive material adhesion step, and an object obtained in the preparatory step. This is an analysis method including an analysis step of analyzing the surface to be measured by irradiating the surface to be measured with the measurement light through the transmitter. Hereinafter, the description will be given step by step.

(Measurement target)
In the present invention, the object to be measured is not particularly limited and may be an inorganic substance or an organic substance. According to the method of the present invention, even if the morphology is changed by water, the original morphology can be analyzed without changing the morphology of the object to be measured. Therefore, it is particularly suitable for a measurement object whose morphology changes due to water vapor in the atmosphere when exposed to the atmosphere. Therefore, the present invention is suitable for measuring a substance having high hygroscopicity and a substance whose structure is changed by water. Specifically, it is suitable for measuring organic substances such as APIs.

In the measurement object, the humidity at which the morphological change occurs is not particularly limited. Specifically, the humidity is preferably 20 to 100% RH, more preferably 40 to 60% RH. According to the present invention, even the measurement object whose morphology changes in this humidity range can be analyzed by a spectroscopic technique with little morphological change. The humidity is a value measured by a thermo-hygrometer (testo 608-H2) manufactured by Testo.

Further, since the object to be measured may be heated above the softening point of the brazing material used, it is preferable that the substance is a substance whose morphology does not change due to the heating. The object to be measured is a solid (lump) that can be ground. However, even if it is a powder, if it can be made into a lump by compression or the like, it can be made into the object to be measured. Above all, in order to facilitate the coating of the brazing material on the object to be measured, the object to be measured is a substantially quadrangular prism having a bottom side length of 0.5 to 1 mm and a height of 1 to 5 mm. It is preferable to make it. It is preferable to process the object to be measured into the shape before the adhesion material adhering step described in detail below.

(Blazed material)
In the present invention, the brazing material that covers at least a part of the surface of the object to be measured (the surface including at least a part of the outer periphery of the surface to be measured) is not particularly limited, and may be an inorganic substance or an organic substance. May be good. Above all, in the preferred method of the present invention, since the brazing material may be softened by heating, it is preferable that the brazing material has a softening point. In the present invention, the softening point is the glass transition start temperature or the melting start temperature measured by a differential scanning calorimetry device (DSC8230 manufactured by Rigaku Co., Ltd.). When a brazing material made of an organic material having no crystallinity is used, the softening point of the brazing material is set to the glass dislocation start temperature. When a crystalline organic material or an inorganic brazing material having a glass dislocation point of less than −20 ° C. is used, the softening point of the brazing material is set to the melting start temperature.

The glass transition start temperature or the melting start temperature is a value measured by the measuring device under the following conditions.
-Sample amount (wax material amount): 3 mg.
-Rising rate: 10 ° C / min.
-Measurement atmosphere: N2 gas.
-N2 gas flow rate: 50 cc / min.

The softening point of the brazing material measured by the above method may be heated or the like when the object to be measured is coated or when the permeate is brought into close contact with the object, but the influence of the heating on the object to be measured is reduced. In order to do so, the temperature is preferably as follows. For example, the softening point of the brazing material is preferably 200 ° C. or lower. The softening point of the brazing material is preferably as close to room temperature (about 25 ° C.), and above all, the softening of the brazing material is taken into consideration in consideration of prevention of deterioration and maintenance of the state of the object to be measured, coating and adhesion operation with the permeable material. The point is particularly preferably -20 to 50 ° C.

Specific examples of brazing materials include organic substances such as wax and petroleum resin, and inorganic substances such as low melting point solder.

Next, each step in the present invention will be described.

(Adhesion material adhesion process)
First, in the present invention, when the surface to be measured of the object to be measured is exposed, an adhesive material attachment step is carried out in which the brazing material is attached to at least a part of the outer periphery of the surface to be measured.

In the adhesion material adhering step, the brazing material may be adhered to at least a part of the outer periphery of the surface to be measured exposed by grinding. In order to do so, a method in which the object to be measured itself (at least a part of the side surface to be the surface to be measured of the object to be measured) is previously coated with a brazing material and then ground together with the brazing material to expose the surface to be measured. Alternatively, a method can be adopted in which the object to be measured is first ground to expose the surface to be measured, and then a brazing material is attached to at least a part of the outer periphery of the surface to be measured.

However, in the method of adhering the brazing material after grinding, especially when the shape of the object to be measured changes even with a small amount of water, the steps of grinding, adhering the brazing material, and adhering the permeable material are performed. It is necessary to carry out in an inert gas atmosphere, etc., and advanced equipment may be required. Therefore, in order to analyze by a spectroscopic method without changing the morphology of the object to be measured with a simple device and method as much as possible, the side surface of the object to be measured is coated with a brazing material in advance and then coated. It is preferable to grind the entire brazing material to expose the surface to be measured. By doing so, it is possible to suppress the morphological change of the object to be measured without using an advanced device. Therefore, it is preferable that the adhesive material adhering step specifically includes the following steps.

That is, the adhesive material adhering step is
The first coating step of coating the brazing material so as to include at least a part of the surface of the object to be measured, which is the outer periphery of the surface to be measured, and the first coating obtained in the first coating step. It is preferable to include a grinding step in which the material is ground together with the coated brazing material to expose the surface to be measured so that the brazing material is attached to at least a part of the outer periphery of the surface to be measured. Next, the first coating process and the grinding process will be described.

(Adhesion material adhesion process; first coating process)
In the present invention, it is preferable to cover the side surface of the object to be measured with a brazing material in advance. The region covered with the brazing material may be a range in which the brazing material adheres to at least a part of the outer periphery of the surface to be measured exposed by grinding the object to be measured. The presence of the brazing material on at least a part of the outer periphery of the surface to be measured makes it possible to improve the adhesion of the transmissive body described in detail below. Above all, in order to further improve the adhesion of the transmissive material, it is preferable that the brazing material adheres to the entire outer periphery of the surface to be measured. Further, in consideration of operability, it is preferable to cover all the side surfaces of the measurement object with a brazing material. When the shape of the object to be measured is easily changed by moisture, it is possible to prevent the moisture from coming into contact with the object to be measured by covering all the sides of the object to be measured with a brazing material. It is possible to carry out a more stable analysis.

The method of attaching (coating) the brazing material to at least a part of the side surface of the object to be measured is not particularly limited. For example, a solution of the brazing material dissolved in an organic solvent or the like can be applied to the side surface of the object to be measured, but it is preferable to adopt a method of heating the brazing material above the softening point to cover the side surface. Specifically, for example, an object to be measured, a brazing material, and a heatable container are prepared. Then, a method of putting the measurement object in the container, then arranging a brazing material around the measurement object, heating the container to soften the brazing material, and covering the side surface thereof can be mentioned. (Finally cool the container). Further, a method of first putting a brazing material in the container, heating the container to soften the brazing material, putting an object to be measured in the container, and cooling the container to cover the side surface. Can be mentioned.

The thickness of the coated brazing material is not particularly limited. Above all, in order to grind more stably, the thickness of the brazing material is 0.5 to 2.0 mm in the thinnest part covering the object to be measured (see the thickness part in FIG. 1 brazing material thickness (W1)). It is preferably 0.5 to 1.0 mm. The thickness of the brazing material can be confirmed with a microscope or the like when the surface to be measured is exposed by grinding.

In the present invention, the object to be measured (that is, the first coating) coated with the brazing material can be ground as it is. However, the brazing material is very brittle and may be crushed during grinding and peeled off from the side surface of the object to be measured. Therefore, in the present invention, it is preferable to further coat at least the surface of the coated brazing material with a highly softening point material having a softening point higher than that of the brazing material by 20 ° C. or more. That is, it is preferable that a high softening point material having a softening point higher than that of the brazing material by 20 ° C. or more is further attached to the surface of the brazing material adhering to the outer periphery of the surface to be measured. Next, a method of coating with this high softening point material (second coating step) will be described.

(Adhesion material adhesion process; second coating process)
In the present invention, at least the surface of the brazing material of the first coating obtained in the first coating step is further coated with a high softening point material having a softening point higher than that of the brazing material by 20 ° C. or more. It is preferable to carry out the step (preferably preparing a second coating).
The high softening point material has a softening point, and the softening point is preferably 20 ° C. or more higher than the softening point of the brazing material 3. By covering the brazing material portion with such a high softening point material having a high softening point, it is possible to prevent the brazing material from being damaged in the grinding process described in detail below. Therefore, the softening point of the high softening point material is more preferably 20 to 60 ° C. higher than the softening point of the brazing material for use.

Such a high softening point material may be determined according to the brazing material used. Therefore, although not particularly limited, it is preferable to use a resin that is chemically stable with respect to the object to be measured and the brazing material and is easy to handle. Specific examples thereof include an epoxy resin, an acrylic resin, and a polyester resin. This resin can also be applied to the surface of the brazing material in the form of a monomer, and the applied monomer can be cured to obtain a resin. When a monomer is used, the temperature at which it is cured is preferably less than the softening point of the brazing material. The softening point of these high softening point materials is preferably 20 ° C. or higher higher than the softening point of the brazing material. However, the softening point of the high softening point material itself is preferably 0 to 110 ° C., more preferably 20 to 50 ° C. in consideration of normal operation. The softening point of this high softening point material can be measured by the same method as the softening point of the brazing material.

The region covered by the high softening point material may be at least the surface of the brazing material in the first coating. Therefore, as a preferred embodiment, it is preferable to be present on the entire surface of the brazing material, and it is preferable to cover the entire surface of the brazing material covering the entire side surface of the object to be measured. By doing so, it is difficult to change the form of the object to be measured, and the operability can be improved.

The coating thickness of the high softening point material is not particularly limited. Above all, in order to grind more stably, it is preferably 0.5 to 2.0 mm, and more preferably 0.5 to 1.0 mm. The thickness of the high softening point material can be confirmed by cutting the second coating and using a microscope or the like.

In the present invention, a known method can be adopted as a method for coating the surface of the brazing material with a high softening point material. For example, a method of applying a highly softened material diluted with a solvent to the surface of the brazing material, and a method of applying a monomer diluted with a solvent to the surface of the brazing material and then curing the monomer can be mentioned. The method of applying the monomer and the high softening point material is not particularly limited, and examples thereof include a method of spraying, a method of immersing the first coating material in the monomer or a solvent in which the high softening point material is dissolved, and the like. Be done.

(Preferable method of adhering adhesive material)
In the present invention, the first coating or the second coating to be ground in the grinding step is preferably prepared by the following method. This will be described with reference to FIG. FIG. 1 is a schematic view showing each step of the present invention. The object to be measured is a cross-sectional view for easy understanding. The object to be measured 1 has a surface to be measured 2 and an outer circumference 2a of the surface to be measured 2 to which a brazing material is attached.

First, the object to be measured 1 is placed in a heatable container. Then, the brazing material 3 is packed in the container so that the entire side surface of the measurement object 1 is covered with the brazing material 3. Then, the container is heated to a temperature equal to or higher than the softening point of the brazing material 3 to soften the brazing material 3, so that the brazing material 3 covers the entire side surface of the object to be measured 1. After that, by setting the container to be equal to or lower than the softening point of the brazing material 3, the first coating material 4 having the brazing material thickness W1 (thickness of the brazing material 3 adhering to the outer periphery of the surface to be measured 2) can be obtained ( First coating step). In FIG. 1, the first covering 4 is also shown in a cross-sectional view. In this case, the brazing material 3 covers the entire outer circumference of the surface to be measured 2, and further, the brazing material 3 covers the entire side surface of the object to be measured 1.

Although the first coating material 4 can be ground, it is preferable to coat the surface of the brazing material 3 with the high softening point material 5 next because the brazing material 3 may be peeled off during grinding. For example, the first coating 4 is placed in a container, and the monomer forming the high softening point material 5 is placed in the container. Then, the monomer is polymerized and cured to obtain a second coating material 6 in which the entire surface of the brazing material 3 is coated with the high softening point material 5 (second coating step). FIG. 1 shows a cross-sectional view of a second coating material 6 in which the surface of a brazing material 3 existing on the outer periphery of the surface to be measured 2 is coated with a high softening point material 5 having a thickness of W2.

In the present invention, it is preferable that the adhesion material adhering step includes the first coating step and the second coating step. The adhesion material adhering step further includes a grinding step. Next, the grinding process will be described.

(Adhesion material adhesion process; grinding process)
In the present invention, the coating material obtained in the process of adhering the amount of the adhesive material is ground together with the material covering the object to be measured to expose the surface to be measured. As described above, the coating material to be ground is the first coating material coated only with the brazing material or the second coating material in which the surface of the brazing material is coated with the high softening point material (hereinafter, the first coating material). The cover and the second cover may be collectively referred to as a "coat"). In order to stably expose the surface to be measured by grinding, it is preferable to target the second coating.

The method for grinding the covering is not particularly limited, and a known method can be adopted. Above all, grinding with a cutting tool is preferable so that the brazing material and the high softening point material are not heated during grinding. In particular, grinding with a microtome device is preferable because a smooth cross section can be obtained. The procedure for grinding with a microtome device (Leica EM UC7 manufactured by Leica Microsystems) is shown below, but the embodiment in the grinding process of the present invention is not limited to the grinding method with the following microtome device.

First, the covering and the glass knife are fixed using the fixing device attached to the microtome device. At this time, the covering and the glass knife are fixed so that the surface portion to be ground in the covering comes into contact with the blade of the glass knife. Next, under the following conditions, the covering is cut to expose the cross section of the object to be measured in the covering (roughing).
-FEED amount: 1000 to 3000 nm.
-Cutting speed: 0.6 to 1.5 mm / s.

Finally, the glass knife is moved under the following conditions to further cut the cross section of the exposed object to be measured and smooth the cross section (finishing).
-FEED amount: 100 to 500 nm.
-Cutting speed: 0.1 to 0.5 mm / s.

FIG. 1 shows a schematic view of the grinding process. In the object to be measured 1, the first covering 4, and the second covering 6, the portion indicated by the diagonal line in the object 1 to be measured is removed in this grinding step. As described above, in this grinding step, the brazing material 3 and the high softening point material 5 are ground together to expose the surface to be measured 2. When the surface to be measured 2 is exposed by grinding the object 1 to be measured together with the brazing material 3 covering the entire side surface of the object 1 to be measured and the high softening point material 5 covering the entire surface of the brazing material 3, the measuring object 1 is exposed. The brazing material 3 adheres to the outer periphery of the surface to be measured 2, and the surface of the brazing material 3 can be covered with a high softening point material. Hereinafter, what is obtained in this grinding step may be simply referred to as a ground product 7.

In the present invention, the transparent body 8 is brought into close contact with the surface 2 to be measured of the ground object 7 obtained in the adhesion material adhesion step to prepare the object 9 (preparation step). Next, this preparatory step will be described.

(Preparation process)
In the preparatory step of the present invention, the transmissive body 8 is brought into close contact with the surface 2 to be measured of the ground object 7. First, the transparent body will be described.

(Preparation process; transparent body)
This will be described with reference to FIG. In the present invention, the transmissive body 8 that is brought into close contact with the surface to be measured 2 of the ground object 7 is made of a substance that is transparent to the measurement light used in the analysis step. Above all, it is preferable to use a material having a transmittance of 0.01 or more calculated by the following method with respect to the measurement light. The higher the transmittance, the more preferable, but by definition, the upper limit of the transmittance is 1.0. A transmissive material made of a material having a transmittance of less than 0.01 can be used, but in the analysis step, the signal / noise ratio (S / N ratio) of the spectrum obtained from the surface to be measured is lowered, and the transmittance is reduced. The accuracy of the analysis may decrease.

The material of the transmissive material having a transmittance of 0.01 or more is not particularly limited, and may be selected from known materials. Further, the thickness of the transmissive body is not particularly limited, but it is preferable to set the thickness so that the transmittance is 0.01 or more with respect to the measuring instep. Although it depends on the spectroscopic method, borosilicate glass and quartz glass are preferable because of their high transmittance.

The transmittance of the transmitter with respect to the measurement light is calculated by the following method. First, the surface to be measured of the object to be measured is measured with an analyzer to obtain a spectrum (spectrum without a transmitter) of the object to be measured alone. Next, a permeator is brought into close contact with the surface of the object to be measured by the procedure described later, and the object to be measured is measured through the permeator to obtain a spectrum (spectrum with the permeator). Finally, the spectra with and without the transmitter are compared and the intensity ratio of the same peak in both spectra is calculated. This peak intensity ratio (peak with a transmitter / peak without a transmitter) is defined as the transmittance of the transmitter with respect to the measurement light. At this time, as the peak used for calculating the transmittance, the peak having the highest intensity in the spectrum of the measurement object is selected.

The shape of the transparent body is not particularly limited as long as it can cover the surface to be measured. Above all, the shape is preferably plate-shaped in order to facilitate measurement in the analysis step. At this time, it is preferable that the thickness of the plate-shaped transmissive body is such that the transmittance is 0.01 or more as described above. Although not particularly limited, the thickness and the transmittance are inversely proportional to each other, so that the thickness is preferably 1 mm or less, and more preferably 0.2 mm or less. In consideration of operability, the lower limit of the thickness of the transparent body is 0.05 mm.

Further, the area of the transmissive body (the area of the surface to be brought into close contact with the surface to be measured) is preferably equal to or larger than the area of the surface to be measured, and particularly preferably twice or more. If the area of the permeator is smaller than the area of the surface to be measured, the entire surface to be measured cannot be covered, and the surface to be measured may be exposed to the atmosphere.

The procedure of the preparation process will be described with reference to FIG. In the present invention, it is preferable that the transmissive body 8 is brought into close contact with the surface 2 to be measured of the ground object 7 by the following procedure. After the ground product 8 is heated to the softening point or higher of the brazing material 3, the transparent body 8 can be brought into close contact with the brazing material 3 and the transparent body 8 can be brought into close contact with the surface to be measured 2. However, in order not to change the form of the object to be measured 1 as much as possible, it is preferable to bring the transparent body 8 into close contact by the following method. That is, first, the permeator 8 is heated above the softening point of the brazing material 3. At this time, the method used for heating is not limited, and a known method can be adopted. It is preferable to use a hot plate or the like to facilitate the coating work. Next, the heated transmission body 8 and the surface to be measured 2 of the ground object 7 are adhered to each other, and the surface to be measured 2 and the transmission body 8 are brought into close contact with each other. At this time, the brazing material 3 existing on the outer periphery of the surface to be measured 2 is softened, and the softened brazing material 3 adheres the surface to be measured 2 and the transmissive body 8 in close contact with each other. Finally, the ground product 7 in which the transmission body 8 is in close contact with the surface to be measured 2 is cooled to room temperature (the transmission body 8 is cooled to room temperature), and the brazing material 3 is cured to be an object to be measured. Get thing 9. Next, a method (analysis step) of analyzing the object 9 obtained in this preparatory step by a spectroscopic method will be described.

(Analysis process)
In the present invention, the surface to be measured of the object produced by the above method is analyzed by a spectroscopic method. The analysis method is not limited, and known conditions of known methods can be adopted. For example, if the transmitter 8 is adjusted, the analysis can be performed by infrared rays, visible rays, and ultraviolet rays. Specific analysis methods include Raman spectroscopy, ultraviolet / visible / near-infrared spectroscopy, and infrared absorption spectroscopy.

In addition, the method of the present invention is suitable for analysis of substances whose state may change over time. That is, the surface to be measured is analyzed through the transparent body, and if there is a surface to be measured for comparison, it can be confirmed that the state has not changed with respect to the surface to be measured.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples.

Example 1
(Measurement target)
From a commercially available preparation (a preparation consisting of a composition containing about 10% by mass of ezetimibe Form H1 in which crystal transition occurs at a humidity of 45% RH or more at 25 ° C.) with a razor, a square columnar (bottom surface □ 0.5 mm, An object to be measured (height 1 mm) was cut out.

(Blazed material)
A mounting wax manufactured by JEOL Ltd. was used as the brazing material. The mounting wax is hereinafter referred to as wax. From the above method, the softening point of the wax was measured to be 15 ° C. (glass transition point).

(Adhesion material adhesion process)
(First coating process)
An aluminum container was placed on a hot plate (HP300 manufactured by AS ONE Corporation), 0.5 g of a brazing material (wax) was placed in the container, and the mixture was heated to 100 ° C. to soften it. The softened wax material was applied to the entire surface of the object to be measured (square columnar object), and then cured at room temperature. By doing so, a measurement object having wax applied to the entire surface was obtained (the first coating was obtained).

(Second coating process)
In addition, 2 g of liquid epoxy resin and 1 g of liquid curing agent for curing epoxy resin (53 type manufactured by Bernox Co., Ltd.) are placed in a paper cup, mixed, and then vacuum degassed to form a composition for a high softening point material. I prepared things. Next, the composition for the high softening point material and the first coating material whose entire surface is coated with a brazing material (wax) are placed in a mold (5 mm × 10 mm × 3 mm) and left for 72 hours to allow the epoxy resin to be applied. It was cured. By doing so, a second coating was prepared in which the entire surface of the brazing material (wax) of the first coating was coated with a high softening point material. Only the composition for the high softening point material was placed in a mold having the same shape as above, and the epoxy resin was cured to obtain a high softening point material. When the softening point of the high softening point material was measured by the same method as that for measuring the brazing material (wax), the softening point was 37 ° C. (glass transition point).

(Grinding process)
The second coating was ground using a microtome device (Leica EM UC7 manufactured by Leica Microsystems) to obtain a ground product in which the cross section (measured surface) of the object to be measured was exposed. When confirmed from the upper surface, the brazing material (wax) adheres (coats) to the entire outer circumference of the surface to be measured, and the high softening point material adheres (coats) to the surface of the brazing material (wax). I confirmed that.

(Preparation process)
(Transparent body)
As a transparent body, a cover glass (Matsunami Glass Ind. No. 1 thickness: 0.15 mm, size: □ 10 mm) was used. The transmittance of this cover glass (transmittance in microscopic Raman measurement) was 0.19 ± 0.06.

The transmittance was determined as follows.

(Measurement of transmittance of transmissive material)
^{The intensities of the peaks of 1399 cm -1} (peaks indicated by * in FIG. 3) in the spectra of ezetimibe Form H1 measured in Example 1 and Comparative Example 1 described below were compared (measured 5 times. The results are shown in the table. Shown in 1.). The transmittance was determined from these intensity ratios.

Next, the permeate was placed on a hot plate and heated to 100 ° C. Next, the surface of the heated permeator is pressed against the surface to be measured of the ground product obtained in the second coating step (adhesion material adhesion step), and the brazing material (wax) on the outer periphery of the surface to be measured is applied. By softening, the surface to be measured and the permeator were brought into close contact with each other. Further, the ground product in which the permeable material was in close contact was cooled at room temperature, and the brazing material (wax) was cured to obtain an object.

(Analysis process)
The object immediately after production is installed in a microscopic Raman measuring device (NRS-7100 manufactured by JASCO Corporation), and the surface to be measured is irradiated with measurement light from the side where the transmitter is in close contact to obtain Ezetimibu Form H1 in the object to be measured. Measured (see FIG. 2). The measurement conditions are shown below.
-Measurement light wavelength: 735 nm
・ Exposure time: 60s x 2 times ・ Grating: 600 lines / mm
・ Aperture: 4000 μm
・ Dimmer: Open ・ Objective lens: 100x ・ Slit: φ100μm
Further, the object was left in a laboratory (temperature: 25 ° C., humidity 50%) for 1 week, and then the same measurement was performed. As a result, the spectrum of ezetimibe in the object left for 1 week was consistent with that immediately after sample preparation (see FIG. 2). In other words, the morphology of ezetimibe in the object has not changed. It was Form H1. Therefore, from this example, it was confirmed that even a substance whose morphology is changed by water can be observed in its original morphology without changing its morphology.

Comparative Example 1
The preparatory step was carried out using the same commercially available formulation used in Example 1 (a composition containing about 10% by mass of ezetimibe Form H1 in which crystal transition occurs at 25 ° C. under the condition of humidity of 45% RH or more). The same operation as in Example 1 was performed except that the operation was not performed, and a ground product was obtained. Further, the surface to be measured of the ground product was observed under the same conditions as in Example 1. The measurement results are shown in FIG.

In the object immediately after preparation, only the peak peculiar to ezetimibe Form H1 (dotted line arrow) was observed, but after 1 hour, the peak peculiar to ezetimibe Form I (solid line arrow) appeared at the position indicated by the arrow. .. Furthermore, in the spectra after 2 hours and 4 hours, the peak intensity ratio of both (peak intensity of solid arrow / peak intensity of dotted arrow) increased with the passage of time. Therefore, ezetimibe changed from Form H1 to Form I by absorbing water vapor in the atmosphere.

1 Object to be measured 2 Measured surface 2a Outer circumference of the surface to be measured 3 Brazing material W1 Brazing material thickness 4 First covering material 5 High softening point material W2 High softening point material thickness 6 Second covering material 7 Grinded material 8 Transmitter 9 Object

Claims (9)

In a method of exposing the surface to be measured of the object to be measured by grinding the object to be measured and then analyzing the surface to be measured by a spectroscopic method.
Adhesion material attachment step in which a brazing material is attached to at least a part of the outer periphery of the measurement object when the measurement surface of the measurement object is exposed.
A preparatory step in which a transmitter that transmits the measurement light of the spectroscopic method is brought into close contact with the surface to be measured of the object to be measured obtained in the adhesive material adhesion step, and an object obtained in the preparatory step. of to said measurement surface, the measurement light, by applying through the transparent member, seen containing an analysis step for analyzing a該被measurement surface,
An analytical method in which a brazing material adhering to the outer periphery of the surface to be measured is softened in the preparatory step, and the permeate is brought into close contact with the surface to be measured by the softened brazing material. The adhesive material adhesion process
The first coating step of coating the brazing material so as to include at least a part of the surface of the object to be measured, which is the outer periphery of the surface to be measured, and the first coating obtained in the first coating step. It is characterized by including a grinding step of grinding an object together with a coated brazing material to expose the surface to be measured so that the brazing material is attached to at least a part of the outer periphery of the surface to be measured. The analysis method according to claim 1. In the adhesion material adhering step, a high softening point material having a softening point higher than that of the brazing material by 20 ° C. or more is further adhered to the surface of the brazing material adhering to the outer periphery of the surface to be measured. The analysis method according to claim 1. The adhesive material adhesion process
The first coating step of coating the brazing material so as to include at least a part of the surface of the object to be measured, which is the outer periphery of the surface to be measured.
A second coating step of coating at least the surface of the brazing material of the first coating obtained in the first coating step with a high softening point material having a softening point higher than that of the brazing material by 20 ° C. or more, and the first coating step. (Ii) The second coating obtained in the coating step is ground together with the coated brazing material and the coated high softening point material to expose the surface to be measured, thereby adhering to the outer periphery of the surface to be measured. The analysis method according to claim 3, further comprising a grinding step in which the highly softened point material is attached to the surface of the material. The analysis method according to any one of claims 1 to 4, wherein in the adhesion material adhering step, the brazing material is in a state of adhering to the entire outer periphery of the surface to be measured. The analysis method according to any one of claims 1 to 5 , wherein the waxing material has a softening point of 200 ° C. or lower. The analysis method according to any one of claims 1 to 6 , wherein the transmittance of the permeate is 0.01 to 1.0 when analyzed by the corresponding spectroscopic method. The analysis method according to any one of claims 1 to 7 , wherein the measurement object contains a substance whose morphology is changed by water. The analysis method according to any one of claims 1 to 8 , wherein the spectroscopic method performs analysis by infrared rays, visible rays, and ultraviolet rays.

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