JP2005127938A - Method for obtaining cut face information of sample - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent a chemical reaction on cut faces of a sample and a cut piece while a sample is cut, and conveniently, accurately and rapidly observe and evaluate data about a continuous or gradual periphery in depth from a surface layer to an inner layer of the sample in a bulk state of a composition structure and a composition frame different from the surface layer. <P>SOLUTION: The cutting apparatus has a cutting blade and is used for cutting the sample in a taper form from a surface to an inner face at an arbitrary angle under cutting conditions of the sample. Cut face information in three axes directions of X, Y and Z axes about coating states, distribution states and infiltration states in depth of a coating liquid and an additional chemical of coated paper on the cut faces of sample and the cut piece formed by cutting, a transition state, a distribution state and an infiltration state in depth of ink on a printed material and an interface state between a substrate, is observed by a means for two-dimensionally developing and displaying the information. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for forming a cut surface by designating a cutting position of a sample and displaying or outputting the formed cut surface. More specifically, the data on the depth direction from the surface layer to the inner layer of the sample and its surroundings is simply, continuously, or stepwise with respect to the cut surface of the cut piece or the cut surface that accompanies cutting. The present invention relates to an image information acquisition method that can be obtained accurately and quickly over a long distance.

  Conventional analysis methods for obtaining information about the depth direction of the sample and its periphery include a secondary ion mass spectrometer (SIMS), an Auger electron spectrometer (AES), and an X-ray photoelectron spectrometer (XPS). Each of these analysis methods uses a beam of ions, electrons, X-rays or the like, and takes information on the depth method of the sample by measuring the sample while sputtering. In these methods, information on the composition of the sample and the binding fragment can be obtained (for example, see Non-Patent Document 1).

  In addition, using a focused ion beam (FIB) device, which has been used for local processing of several μm thick, cuts out a cross section of paper or printed matter with a thickness of around 100 μm, cutting with a blade, resin embedding, freezing Compared to cross-section preparation methods such as embedding method, freeze cleaving method, ion etching method, etc., it becomes possible to produce cross-sections of paper or printed matter with incomparable accuracy, and materials with different hardness and brittleness, That is, it has become possible to produce a sharp cross-section by irradiating a focused ion beam in an amount necessary for producing a cross-section of paper or printed matter. In addition, since the paper as the base material can be cut together with the ink transfer layer, the method for directly observing the cross section of the ink layer transferred to the paper of printing ink that could not be observed so far, and the influence of the paper layer structure on the ink transfer are analyzed. It has been proposed as a method (for example, see Patent Document 1).

  In addition, as a method of observing the distribution of the binder component of the ink in the ink transfer product transferred to paper, osmium tetroxide or bromine is selectively added to the unsaturated double bond portion of the binder component, and then focused. By irradiating the ion beam with an ion beam device, the structure of the paper is produced without breaking, and the ink transfer material containing the binder subjected to the addition reaction is irradiated with an electron beam, and the generated signal is converted into an electron beam microanalysis ( EPMA) proposes a method for mapping each element (for example, see Patent Document 2).

Surface Chemistry Society of Japan “Surface Science Fundamentals and Basics and Applications of Surface / Interface Analysis”, 1998, p. 219-376 Japanese Patent No. 3044298 JP 2000-171420 A

  In the conventional secondary ion mass spectrometer (SIMS), Auger electron spectrometer (AES), and X-ray photoelectron spectroscopy (XPS), the data in the depth direction is affected by the sputtering rate, so the measurement efficiency Is low, and it is difficult to obtain data in the deep part of the sample. In addition, since the obtained data is limited to the number of surface layers to several hundreds of nanometers, it is generally widely recognized as a surface analysis method. Specifically, the data of the cut surface of the sample is measured while cutting the sample. Has been proposed as a method for accurately measuring the data in the depth direction of the sample, but the internal structure of the paper, the distribution state in the thickness direction of the additive chemicals, and the pigments and binders of the coated paper The distribution state, the ink penetration state, and the ink transfer are not intended to analyze the effect of the paper layer structure while cutting. Furthermore, in the secondary ion mass spectrometer (SIMS), Auger electron spectrometer (AES), and X-ray photoelectron spectroscopy (XPS), the sample must be sputtered in a high vacuum. It takes a lot of time and effort to prepare for exhaust.

  In addition, since a focused ion beam (FIB) apparatus is extremely expensive as an apparatus for preparing a sample, it is not a stage where it is generally widely used, and the cross-section preparation processing time requires several hours. In the sample where the depth direction (Z direction) is planar, but the planar direction (XY direction) is linear, so in the sample in which minute regions with different states or compositions are distributed in the planar direction (XY direction) Since a cutting surface can be formed only up to about 250 μm at a time in the width direction, it is necessary to prepare and observe a large number of sample cross sections for each minute region portion having a different state or composition in the plane direction (XY direction).

  In addition, as a method of observing the distribution state of the binder component of the ink in the ink transfer product transferred to the paper, osmium tetroxide or bromine is selectively added to the unsaturated double bond portion of the binder component, and the paper is fed by the FIB apparatus. When the binder component of the ink in the section of the paper having a thickness of about 100 μm penetrates only about 30 μm from the surface, the penetration depth of the binder component However, since the analysis must be performed in a narrow range of about 30 μm or so, an effective image information acquisition site is narrowed.

  The present invention aims to solve the above-described problems. Specifically, it prevents chemical changes in the cutting surface of the sample and the cutting surface of the cutting piece that accompanies cutting, and the composition structure and composition skeleton are the surface layer. The purpose is to easily and accurately observe and evaluate data on continuous or stepwise surroundings in the depth direction from the surface layer to the inner layer of the sample in different bulk states.

  The method for acquiring cutting surface information of a sample according to the present invention is a method of cutting a taper at a predetermined angle by a cutting blade from the surface of the sample toward the inside, and the cutting surface of the sample formed by the cutting, and the cutting piece accompanying the cutting. Three-dimensional image information in the Z-axis direction, X-axis direction, and Y-axis direction on the cutting surface is acquired two-dimensionally when viewed from the surface direction of the sample before cutting by the image acquisition means, and an image is displayed using the image information. And / or outputting an image.

  The cutting surface information acquisition method for a sample of the present invention is a method in which the cutting edge is cut into a tapered shape at a predetermined angle from the surface of the sample toward the inside by the cutting edge, and after the cutting edge reaches a preset cutting depth, the cutting edge is moved to the sample. By moving in parallel to the surface and cutting to form a cutting surface, further changing the setting conditions of the cutting depth, cutting at a predetermined angle until the cutting depth is reached, and performing cutting step by step The three-dimensional image information in the Z-axis direction, X-axis direction, and Y-axis direction on the cutting surface of the sample to be formed and the cutting surface of the cutting piece accompanying cutting is viewed from the surface direction of the sample before cutting by the image acquisition means. The image information is displayed and / or output using the image information.

  The cutting surface information acquisition method of the sample of the present invention is characterized in that the cutting surface of the sample and the cutting surface of the cutting piece accompanying the cutting are enlarged by the image acquisition means.

  The cutting surface information acquisition method for a sample according to the present invention is characterized in that element mapping is performed by an element analyzer on the cutting surface of the sample and the cutting surface of a cutting piece accompanying cutting.

  According to the present invention, although related to the material and size of the sample, the depth of the sample from the surface layer of the sample to the inner surface layer is determined by setting the angle when cutting the cutting edge from the surface layer of the sample to the inner layer. It is possible to acquire cutting surface information in a desired range with respect to the length direction and its surroundings with one observation sample. As a result, the paper layer structure and coating layer structure acquired as cutting surface information, and the transfer, distribution state and penetration state of ink, etc. can be observed in a bulk state in which the composition structure and composition skeleton are different from those of the surface layer. Therefore, its convenience and applicability are great.

  Ink penetration into paper is a major factor that affects printing or image quality in ink jet printers that use low-viscosity inks. The fact that it can be acquired as image information by dividing it in the direction is a great merit and greatly contributes to paper development and ink development.

  FIG. 1 shows the overall configuration of the cutting apparatus. The sample (1) is fixed to a cutting apparatus including cutting condition setting means, means for detecting displacement and pressure, sample fixing means, sample cutting means, and means for pressing the cutting blade of the cutting means to the sample. Then, cutting is performed from the surface of the sample toward the inside by the movement of the cutting blade (2) which is a cutting means. The cutting state is taken by the camera (3), and the image from the camera is confirmed in real time by the monitor (4). The sample can be fixed by placing the sample directly on the sample stage and fixing the sample end with a clamp, fixing the sample to the plate with double-sided tape in advance, or fixing the sample in vacuum from the back of the sample. These may be considered, and may be appropriately selected according to the form of the sample.

  The method for forming a continuous cutting surface of a sample according to the present invention is as follows. First, a cutting width (2) for forming a cutting surface of a sample and a cutting edge shape having a cutting angle (2) ) And specify the cutting position of the sample. Next, cutting conditions such as the cutting edge vertical movement speed, the cutting depth (5), and the cutting edge horizontal movement speed necessary for forming the cutting surface of the sample are set in advance. Next, as shown in FIG. 2, the cutting surface (6) is set as a precondition, and based on the cutting edge horizontal movement speed and cutting edge vertical movement speed, the surface of the sample is cut by the cutting edge (2). Cutting is started diagonally from (1) to the inside, and cutting is continued until the cutting edge (2) reaches a preset cutting distance (6), thereby cutting along the cutting surface (7) of the sample and cutting. A cut surface (11) of the piece is formed.

  The stepwise cutting surface forming method of a sample according to the present invention is a cutting blade (2) having a blade angle, a rake angle, and a burr angle for a cutting width and a cutting edge shape necessary for forming a cutting surface of a sample. ) And specify the cutting position of the sample. Next, as shown in FIG. 3, the cutting surface (12) is set as a precondition, and the surface of the sample is cut by the cutting edge (2) based on the preset cutting edge horizontal movement speed and cutting edge vertical movement speed. Cutting is started from (1) to the inside, and after the cutting edge (2) reaches a preset cutting distance (12), based on the set horizontal cutting speed, the surface (1) of the sample is And cut in parallel. Furthermore, the cutting edge horizontal movement speed, the cutting edge vertical movement speed, and the cutting distance are reset, and based on the reset conditions, the cutting edge (2) further repeats cutting to a desired depth to obtain a sample stage. The cutting surface (7) as well as the stepwise cutting surface (11) of the cut piece accompanying the cutting are formed.

  The sample used in the present invention is a material such as paper, printed matter, plastic, rubber, and sheet, but the material and shape are not limited. Further, the image information of the cut surface can be displayed and the image information can be output for the deposited film and the laminated thin film sample.

  When the cutting surface of the sample is formed by the cutting blade, for example, a known cutting blade such as a knife or a metallic cutter can be used as the cutting blade, but hopefully it is found in Japanese Patent Publication No. 7-26908. It is desirable to form the cutting surface using a precise cutting device. In addition, the cutting blade of precision cutting equipment is required to be a sharp and hard cutting blade, so it has a high hardness, excellent wear resistance, durability and heat resistance, and a material with little spillage. Although a single crystal diamond blade is particularly preferable, the material and surface treatment of the cutting blade are not limited.

  Further, as cutting conditions when forming a continuous cutting surface of the sample, the cutting edge width 0.3 to 4 mm, the cutting time 10 to 3600 sec, the cutting edge vertical moving speed 0.002 to 5 μm / sec, When the cutting depth is 0 to 1000 μm, the horizontal movement speed of the cutting edge is 0.02 to 50 μm / sec, and the cutting edge forms a continuous oblique cutting section from the surface of the sample to the inside, the cutting speed ratio (cutting) The blade vertical movement speed / cutting blade horizontal movement speed) is preferably 1/5 to 1/20, and can be adjusted by the type, hardness, and elasticity of the sample, but is not limited thereto.

  Moreover, as cutting conditions when forming the stepped cutting surface of the sample, the cutting edge width 0.3 to 4 mm, the cutting time 10 to 3600 sec, the cutting edge vertical moving speed 0.002 to 5 μm / sec, When the cutting depth is 0 to 1000 μm, the horizontal movement speed of the cutting edge is 0.02 to 50 μm / sec, and the cutting edge forms a continuous oblique cutting section from the surface of the sample to the inside, the cutting speed ratio (cutting) The blade vertical movement speed / cutting blade horizontal movement speed) is preferably 1/5 to 1/20, and can be adjusted by the type, hardness, and elasticity of the sample, but is not limited thereto. In addition, the cutting speed ratio is not limited to this condition ratio when the cutting surface is formed by moving the cutting blade in the direction parallel to the sample surface during cutting and cutting.

  Furthermore, the optimum conditions for cutting the sample can be changed and cut according to the material of the sample.

  The term “tapered” as used in the present invention means that the taper is cut in a tapered state such as a cone or the like.

  The three-dimensional image information in the Z-axis direction, X-axis direction, and Y-axis direction referred to in the present invention is acquired two-dimensionally when viewed from the surface of the sample before cutting by the image acquisition means. Direction) and XY axis direction (longitudinal and lateral directions), three-dimensional cutting surface image information is acquired as planar two-dimensional cutting surface image information from the surface direction of the sample before cutting by an image acquisition means such as an electron microscope. That is.

  The cutting surface of the formed sample, and the cutting surface of the cut piece accompanying cutting, the depth direction inside the ink film, the transfer state of ink and additive chemicals in the depth direction of the paper, the interface state with the substrate, and the penetration There may be some deviation in the observation time of the paper layer structure and the coating layer structure of the state and distribution state, the cut surface of the sample, and the cut surface of the cut piece accompanying the cutting, but among them, the penetration into the sample When observing the state of dispersion and penetration of ink, etc., which has high diffusibility and diffusibility to the surface, reduce the chemical change on the cutting surface and reduce the influence of temperature and humidity from the cutting environment as much as possible so that the form does not differ However, since it is preferable that the composition structure and the composition skeleton are in a bulk state different from that of the surface layer, image information is acquired immediately after cutting, or chemistry with osmium tetroxide or bromine is used. It is desirable to perform the processing.

  As an example of chemical treatment, when the observed substance contained in the cut surface or cut piece of the sample contains double bonds, the method of selectively adding osmium tetroxide or bromine is simple and effective. It is. When the sample is porous, it may be added to the inside of the sample by gas phase treatment before cutting, or after the chemical substance is added after cutting, the sample is left in vacuum and physically adsorbed. May be removed.

  In the image information acquisition means of the cut surface of the formed sample and the cut surface of the cutting piece accompanying the cutting, an optical microscope, an electron microscope or an elemental analysis device is used. Observe or visualize the penetration and distribution state, the depth direction inside the ink film, the paper layer structure of the paper, and the coating layer structure.

  Regarding the method of observing the cut surface of the formed sample and the cut surface of the cutting piece that accompanies the cutting, a cutting surface is formed in an oblique direction from the surface to form a cut surface, and in some cases a chemical treatment is performed, and an optical microscope or Enlarged observation with SEM (electron microscope), element mapping with elemental analyzers such as EDX (energy dispersive X-ray fluorescence analysis) and EPMA (electron beam microanalyzer), and penetration of coating liquids and internal chemicals The state and distribution state are displayed on a monitor, and the monitor image is output by an output device such as a printer to obtain a visualized image for analysis.

  As for the observation method of the cut surface of the formed sample and the cut surface of the cut piece in the printed material, the cut surface is cut inwardly from the surface to form the cut surface, and the ink component is unsaturated double bond or terminal double. In some cases, it contains a binder component with a heavy bond, and is subjected to chemical modification treatment, magnified observation with an optical microscope or SEM (electron microscope), EDX (energy dispersive X-ray fluorescence analysis) and EPMA (electron beam microanalyzer). ) Etc. by elemental analysis with an elemental analyzer, the surface state of the printed matter, the state in the ink film and the distribution of the ink constituents such as the varnish component and the pigment component at the depth position inside the printing substrate. The reaction state is also displayed on the monitor, and the monitor image is output by an output device such as a printer to obtain a visualized image. Subjected to analysis.

  In the drying of the ink, there is no restriction even if it has a crosslinking effect at room temperature as well as forced heating drying such as hot air drying, far-infrared drying, etc., and the binder component of the printing ink is intended for two-dimensional or three-dimensional crosslinking As a forced drying method, there is a method using an electron beam or ultraviolet rays, and it is more desirable to cut the paper or printed matter in a frozen state in order to prevent a reaction including chemical modification of the formed cutting surface.

  In the sample used in the present invention, when cutting a material such as ultra-thin or soft paper, humidity is adjusted with a medium such as water that does not dissolve the substance to be observed and does not affect the distribution state, etc. Then, after the immersion, cutting is performed in a state where the medium is frozen with liquid nitrogen or the like, and then lyophilization or the like is performed to further facilitate cutting and provide a cutting surface of a sample suitable for observation.

  The material to be printed and ink are important factors relating to troubles such as print-through of penetrating ink as well as quality of printed matter such as density and uniformity of printed matter. Obtaining this information easily and accurately can greatly contribute to the development of inks with controlled penetration, including the development of coating materials, the study of coating methods, and the study of calendar conditions. In particular, information that cannot be determined by visual inspection inside the paper can be visualized and further acquired as an enlarged image, and the fields in which the present invention can be used are wide.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to a following example. In this example and comparative example, high-quality paper and coated paper were used, water-based gravure ink (Dick Safe WH507 primary color: manufactured by Dainippon Ink & Chemicals, Inc.) was used, and the number of lines was 250 and the plate depth was 24 μm. Ink was filled in the image area of the gravure printing plate, and a printing pressure of 490 N / cm was applied to print on fine paper and coated paper.

  After printing under the above conditions, the cut surfaces of the fine paper and the coated paper are formed by a continuous cutting surface forming method as shown in FIG. In this case, the cutting surface was formed by using a surface / interface physical property analyzer (Daipura Wintis Co., Ltd.), the blade width of the cutting blade (2), the cutting blade horizontal movement speed of 0.5 μm / sec, and the cutting blade. At a vertical moving speed of 0.05 μm / sec, an oblique cutting surface (7) extending over a long distance up to a depth of 60 μm at a cutting angle of about 6 ° with respect to the sample surface is developed to 600 μm and formed on the printed material. Cutting was performed with a cutting time of about 2 minutes.

  FIG. 4 is a photograph in which the cut surface (7) of the fine paper formed under the above conditions is enlarged 80 times. First, images of the surface (1) and the cut surface (7) of the sample of the printed matter were copied on a monitor using an optical microscope on the cut surface of the fine paper on which printing was performed, and further printed out, observed, and evaluated. As a result, the quality of the high quality paper is inferior in smoothness of the paper surface, and irregularities formed between the fibers (8) intertwined on the cutting surface exist up to the surface and inside of the paper, and the state of ink transfer to the concave portion (10) In addition, the ink permeation state (9), which was observed slightly, could be observed.

  FIG. 5 is a photograph in which the cut surface (7) of the coated paper formed under the above conditions is magnified 80 times. First, using an optical microscope on the cut surface of the coated paper on which printing was performed, images of the surface (1) and the cut surface (7) of the printed matter were copied on a monitor, printed out, observed, and evaluated. As a result, in the coated paper, the paper surface had a smooth coated surface, and fibers were not observed near the surface layer. In addition, a blue dot indicating the ink permeation state (9) was observed from the surface to the inside, and the distribution of the blue dot decreased with increasing depth. In the coated paper, since the coating agent covers the paper surface, it can be seen that the inside of the paper penetrates from the pores of the coating layer into the inside by capillary action.

  FIG. 6 shows a composition image when the cut surface (7) of the coated paper formed under the above conditions is observed with a low vacuum SEM. In the composition image, fibers mainly composed of organic substances and permeated ink were observed darker than the coating layer. In the coating layer, the entangled state of the exposed base paper fibers can be observed in the depth direction.

(Comparative example)
FIG. 7 shows a method for forming a cross section of paper or printed matter. The cross section of the printed matter formed in the example was formed by the focused ion beam method, but the pores scattered in a plane were not observed in the cross section, and the ink layer, the coat layer, and the paper layer structure existing on the surface portion of the coat layer The observation method according to the present invention, in particular, is characterized by a thin layer to be observed having a small thickness in the depth direction, and features scattered in a dotted pattern on a plane. It was found that two observation samples are suitable for simple observation.

An overall view of a cutting device is shown. The continuous cutting surface formation state of a sample is shown. The intermittent cutting surface formation state of a sample is shown. The photograph of the cutting surface of the quality paper in this invention is shown (x80 times). The photograph of the cut surface of the coated paper in this invention is shown (x80 times). The photograph of the composition image by the low vacuum SEM of the cutting surface of the coated paper in this invention is shown (x80 times). The cross-section formation method of paper or printed matter is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Sample surface 2 Cutting edge 3 Camera 4 Monitor 5 Cutting depth 6 Cutting distance 7 Cutting surface 8 Fiber 9 Ink penetration state 10 Ink transfer state 11 Cutting surface 12 Cutting distance

Claims (4)

Cutting from the surface of the sample into a taper at a predetermined angle with a cutting blade from the surface to the inside, the Z-axis direction, the X-axis direction, and the Y-axis on the cutting surface of the sample formed by cutting, and the cutting surface of the cutting piece that accompanies the cutting The three-dimensional image information in the axial direction is acquired two-dimensionally when viewed from the surface direction of the sample before cutting by the image acquisition means, and the image information is displayed and / or output as an image by the image generation means. A method for obtaining cutting surface information of a sample. Cutting from the surface of the sample to the inside with a cutting edge in a tapered shape at a predetermined angle, and after the cutting blade has reached a predetermined cutting depth, the cutting blade is moved in a direction parallel to the sample surface for cutting. Then, the cutting surface is formed by cutting the tape to a predetermined angle at a predetermined angle until the predetermined cutting depth is reached, and the cutting surface of the sample formed by performing the cutting stepwise, and the cutting of the cutting piece accompanying the cutting. Three-dimensional image information in the Z-axis direction, X-axis direction, and Y-axis direction on the surface is obtained two-dimensionally when viewed from the surface direction of the sample before cutting by the image acquisition means, and the image information is obtained by the image generation means. A method for acquiring cutting surface information of a sample, characterized by displaying an image and / or outputting an image. 3. The image of the cutting surface of the sample acquired by the image acquisition unit and the cutting surface of the cutting piece resulting from the cutting are enlarged and / or output by the image generation unit. The cutting surface information acquisition method of the sample of description. The cutting of the sample according to claim 1 or 2, wherein element mapping is performed on the cutting surface of the sample acquired by the image acquisition means and the cutting surface of the cutting piece accompanying the cutting by an element analyzer. Surface information acquisition method.

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