JP2008281528A - Pretreatment method and pretreatment apparatus of thin film laminated material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pretreatment method of thin film laminated material for expanding and exposing a smooth intermediate layer having no crack, nipping, or the like in an interface so that the composition of the intermediate layer of the thin film laminated material whose thickness is controlled in a range from several μm to nm level can be analyzed. <P>SOLUTION: In the pretreatment method of the thin film laminated material, the thin film laminated material is cut in the cross section direction and the intermediate layer is exposed in order to analyze the composition of the intermediate layer of the thin film laminated material having the intermediate layer. When the thin film laminated material 10 is cut using a cutting edge 1 driven relatively in the horizontal direction and perpendicular direction with respect to the surface of the thin film laminated material 10, the perpendicular cutting velocity is set to be 0.01 nm/s or higher and lower than 1 nm/s, and the cross section is cut in a diagonal direction. The cutting direction by the cutting edge 1 is set at ≥0.05° and ≤5° with respect to the surface of the thin film laminated material 10. The thin film laminated material 10 is formed of at least three or more layers, and the thickness of the intermediate layer 10b is ≤10 μm. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  In order to analyze the composition of the intermediate layer of the thin film laminate material having the intermediate layer, the present invention provides a thin film laminate material pretreatment method in which the intermediate layer is exposed by cutting the thin film laminate material in the cross-sectional direction, and before the method is used The present invention relates to a processing apparatus.

  In general, thin film laminate materials using polymers and metals with ductility tend to be thinned while imparting various properties such as durability and optical properties. It is thought to strengthen. As such a thin film laminated material, there are many types such as a multilayer film having a printing layer as an intermediate layer. In order to analyze the composition of the intermediate layer, it is necessary to cut the thin film laminated material in the cross-sectional direction to expose the intermediate layer and observe it with an analytical instrument or the like.

  However, if the thickness of the thin film laminated material is reduced and the intermediate layer is 10 μm or less, it becomes difficult to directly analyze the composition due to the limitations of the spatial resolution, detection sensitivity, or sampling technology of existing analytical instruments. . Therefore, at present, it is conceivable to expose the intermediate layer by physically peeling the surface layer at the thin film interface of the thin film laminate material, but it is difficult to expose the intermediate layer well, and analysis and evaluation are not always possible. is not. Therefore, the situation has to be relied on by chance, and the efficiency is poor.

  On the other hand, the following patent documents 1, 2, 3 and the like are known as techniques for obtaining depth data, peel strength, and shear strength of a multilayer film of a thin film laminated material. Patent Document 1 discloses an analysis method for measuring data other than mechanical data (measured using infrared rays, visible light, laser light, etc.) while cutting a sample (claims). As a specific example, it is described that a sample obtained by sputtering copper on a silicon wafer and applying and curing a polyimide (thickness 2 μm) thereon was cut at an incident angle of 1 degree using a diamond cutter ( Paragraph 0014).

  Patent Document 2 includes a sample mounting table that performs linear displacement, a cutting blade support that performs perpendicular displacement, and a pressure detector that detects a repulsive force generated on the cutting blade, and measures adhesion force and shear force of a coating film. An apparatus is disclosed (claims). Specifically, using a coated plate having a thickness of 8 mm, a part of the coating film is peeled off by about 2 cm to expose the material, and the cutting blade is pressed against the exposed surface and pressed. Next, the coated plate is moved at a speed of 1 mm / min, and the resistance force of the cutting blade is detected by the load cell (second page, lower left column and lower right column).

  Patent Document 3 discloses an apparatus for measuring the adhesion strength and shear strength of a coating film adhered to a sample. This apparatus has a cutting blade that can move in two directions, a direction perpendicular to the coating film surface and a direction parallel to the sample surface, and is driven by a parallel movement motor and a vertical movement motor, respectively. The coating film is cut by cutting the cutting blade into the coating film.

JP 2002-365183 A JP-A 61-169745 JP 2003-254894 A

  According to the methods disclosed in these Patent Documents 2 and 3, the composition of the intermediate layer of the thin film laminated material is not analyzed, but mainly the peel strength and shear strength of the coating film on the surface are analyzed. The movement of the cutting blade is also moved in the horizontal direction to measure the peel strength of the material. Therefore, there is no teaching or suggestion on how to expose the intermediate layer when it is analyzed and evaluated.

  Patent Document 1 discloses a method of performing analysis while cutting a material in an oblique direction. It is considered that the surface area of the exposed surface can be increased by cutting the thin film laminated material in an oblique direction as compared with cutting in the vertical direction. Patent Document 1 does not describe what speed to cut, but if a thin film laminated material having an intermediate layer of about 10 μm is cut obliquely, if the cutting speed is too high, the intermediate layer In many cases, cracks and cracks are generated at the interface, and it is difficult to obtain an exposed surface suitable for analysis. Therefore, in the present situation, a technique for expanding and exposing an intermediate layer having a thickness of 10 μm or less, particularly a thickness of several μm to a nano level, to an analyzable level has not been established.

  The present invention has been made in view of the above circumstances, and the problem is that the composition of the intermediate layer of the thin film laminated material having the intermediate layer controlled to a thickness of several μm to nm (nanometer) level can be analyzed. Furthermore, it is to provide a pretreatment method of a thin film laminated material that expands and exposes a smooth intermediate layer having no cracks or peeling at the interface, and a pretreatment apparatus used for this.

In order to solve the above problems, a pretreatment method for a thin film laminated material according to the present invention
In order to analyze the composition of an intermediate layer of a thin film laminate material having an intermediate layer, a thin film laminate material pretreatment method in which the intermediate layer is exposed by cutting the thin film laminate material in a cross-sectional direction. On the other hand, when the thin film laminated material is cut using a cutting blade that is driven relatively in the parallel direction and the vertical direction, the cutting speed in the vertical direction is 0.01 nm (10 ⁻¹¹ m) / s to 1 nm (10 ^−9). m) It is set to be less than / s, and the cross section is cut obliquely.

  According to this configuration, since the cutting blade is driven relatively in the direction parallel to and perpendicular to the surface of the thin film laminate material, the thin film laminate material can be cut obliquely by the cutting blade. Thereby, since an intermediate | middle layer will also be cut in the diagonal direction, a exposed surface can be taken larger compared with the case where it cuts perpendicularly. However, it is necessary to suppress an increase in the force acting between the cutting blade and the material, particularly the shearing force, when cutting in an oblique direction. In other words, if the increase in the shearing force acting between the cutting blade and the material is large, when the cutting blade reaches the vicinity of the interface of the intermediate layer, cracking or peeling occurs in that part, the intermediate layer is missing, This will cause the roughness of the exposed surface to increase.

  Therefore, the present inventors have found that it is effective to reduce the speed when cutting in an oblique direction in order to suppress an increase in shearing force. In particular, by setting the cutting speed in the vertical direction of the cutting blade to be not less than 0.01 nm / s and less than 1 nm / s, the increase in shear force acting near the interface of the intermediate layer can be reduced by the effect of stress relaxation. It can be made small, cracking and peeling are less likely to occur, and a smooth enlarged exposed surface can be obtained. Furthermore, by setting this speed, there is also an effect that an apparent high temperature state is formed between the material and the cutting blade, and thereby it is possible to impart free-cutting properties to the material. If the speed is too slow, the cutting time becomes too long, so the vertical cutting speed should be 0.01 nm / s or more. As a result, a thin film that expands and exposes a smooth intermediate layer that does not have cracks or peeling at the interface so that the composition of the intermediate layer of the thin film laminate material having an intermediate layer controlled to a thickness of several μm to the nm level can be analyzed A method for pre-processing a laminated material can be provided.

  The vertical cutting speed according to the present invention is preferably set to be 0.6 nm / s or less. More preferably, it is 0.2 nm / s or less, and particularly preferably 0.1 nm / s or less. The lower limit value of the cutting speed is more preferably 0.05 nm / s or more. By setting this speed, the increase in shearing force acting near the interface of the intermediate layer can be made smaller, and as a result, a smooth enlarged exposed surface can be obtained.

  The cutting direction by the cutting blade according to the present invention is preferably set to be 0.03 ° or more and 5 ° or less with respect to the surface of the thin film laminated material. More preferably, it is 0.05 degree or more and 3 degrees or less, More preferably, it is 0.05 degree or more and 1 degree or less. When the angle is 5 ° or more, the area of the exposed surface after cutting is not large enough to perform analysis, and analysis evaluation becomes difficult.

  In the present invention, the thin film laminate material is preferably composed of at least three layers or more, and the thickness of the intermediate layer is preferably 10 μm or less. In the case of such a thickness, since the exposed width is 10 μm or less when cut vertically, the composition is directly analyzed depending on the spatial resolution and detection sensitivity limit of existing analytical instruments or the sampling technology limit. It becomes difficult. Therefore, by setting the cutting speed range as in the present invention, an intermediate layer having a size of 10 μm or less is particularly exposed and analysis of the intermediate layer becomes possible.

The pretreatment apparatus used in the pretreatment method of the thin film laminate material according to the present invention is
A first piezoelectric element capable of driving the cutting blade in a direction perpendicular to the surface of the thin film laminated material;
A second piezoelectric element capable of driving the cutting blade in a direction parallel to the surface of the thin film laminate material,
The cutting speed in the vertical direction of the cutting blade is set to be 0.01 nm / s or more and less than 1 nm / s, and the cross section of the thin film laminated material can be cut obliquely. .

  By setting the cutting speed in the vertical direction of the cutting blade as described above, the increase in shear force acting near the interface of the intermediate layer can be reduced by the effect of stress relaxation, as described above, and cracking In addition, it is difficult for peeling to occur, and a smooth enlarged exposed surface can be obtained. In addition, a piezoelectric element is used when driving the cutting blade, which makes it possible to achieve a cutting speed in the above range.

  A preferred embodiment of a pretreatment method for a thin film laminate material according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic diagram illustrating a configuration of a pretreatment device (cutting device). The target thin film laminate material is composed of a polymer or a ductile metal component, and examples thereof include a laminate film composed of a multilayer film, a coating laminate product, and a vapor deposition product. Is not limited to a particular material.

  A cutting blade 1 is provided so as to face a mounting surface A on which a material to be cut is mounted. The cutting blade 1 is held by a parallel pressure detector 2, and the parallel pressure detector 2 is held by a vertical pressure detector 4 via a connector 3. Further, the vertical pressure detector 4 is connected to the first piezoelectric element 6 and the second piezoelectric element 7 via a connector 5, thereby enabling the cutting blade 1 to be driven horizontally and vertically. The first piezoelectric element 6 drives the cutting blade 1 in the vertical direction, and the second piezoelectric element 7 drives the cutting blade 1 in the horizontal direction. By using a piezoelectric element as a drive source, the cutting blade 1 can be finely moved. By simultaneously driving the first and second piezoelectric elements 6 and 7, the cutting blade 1 can be driven in an oblique direction. In addition, you may install the 2nd piezoelectric element 7 in the sample stand side.

  The structure shown in FIG. 1 is an integral structure with no sliding parts or rotating parts, and no gears or stages are used at each connecting part. The parallel pressure detector 2 and the vertical pressure detector 4 detect the pressure in the horizontal direction and the vertical direction, respectively. Even if the pressure detectors 2 and 4 are deformed by the pressure, the cutting blade 1 is driven by the principle of the parallelogram. The set angle is always kept constant. A capacitance-type displacement meter 8 is provided below the placement surface A. The placement surface A is formed above the placement surface A, and the cutting depth in the vertical direction of the cutting blade 1 can be measured. Yes.

  FIG. 2 shows a perspective view and a side view of the cutting blade 1 actually used. The specifications of the cutting blade 1 are a rake angle of 20 °, a blade angle of 60 °, a clearance angle of 10 °, and a blade width of 1 mm.

  In the present invention, the thin film laminated material having the intermediate layer is cut in an oblique direction when cutting. FIG. 3 shows a model diagram when cutting in an oblique direction. Here, a thin film laminated material 10 having a three-layer structure of a surface layer 10a, an intermediate layer 10b, and a back surface layer 10c is shown. If the thickness of the intermediate layer 10b is 50 nm, the intermediate layer 10b having a length of 50 nm is exposed when it is cut vertically, but this size is considered in consideration of the spatial resolution of the analytical instrument, the limit of detection sensitivity, and the like. Now, it becomes difficult to directly analyze the composition.

  Therefore, cutting is performed in an oblique direction as shown in FIG. Assuming that the cutting angle is set to 0.05 °, as shown in FIG. 3 (b), when viewed from the direction perpendicular to the exposed surface, the exposed length of the intermediate layer 10b is 50 μm and cut vertically. Compared to the case, the length is 1000 times longer. Therefore, an exposed surface capable of composition analysis is obtained.

However, even when cutting in an oblique direction, if the cutting speed is too high, cracking and peeling often occur at the interface of the intermediate layer 10b, making it difficult to obtain an exposed surface suitable for analysis. Therefore, it is considered that there is an appropriate cutting speed range even when cutting in an oblique direction. Specifically, the cutting speed is divided into a vertical component and a horizontal component, and in particular, the cutting speed V _Y of the cutting blade 1 in the vertical direction is preferably set as follows.

0.01 nm / s ≦ V _Y <1 nm / s
In particular, by setting it to less than 1 nm / s, the increase in shearing force acting near the interface of the intermediate layer 10b can be reduced due to the effect of stress relaxation, cracking and peeling are less likely to occur, and smoothness And a continuous expansion exposure surface can be obtained. This makes it possible to perform a composition analysis of the intermediate layer 10b. The cutting speed in the vertical direction is more preferably 0.6 nm / s or less, further preferably 0.2 nm / s or less, and particularly preferably 0.1 nm / s or less. By setting the speed smaller, the increase in shearing force acting near the interface of the intermediate layer can be made smaller, and as a result, it becomes easier to obtain a smooth enlarged exposed surface.

  If the cutting speed is too low, the cutting time becomes too long. Therefore, it is preferable to set it to 0.01 nm / s or more in consideration of the overall efficiency. Furthermore, by slowing down the speed, there is also an effect of apparently increasing the temperature between the thin film laminated material 10 and the cutting blade 1, and this also produces a secondary effect of imparting free machinability to the material.

  In addition, the cutting angle θ when cutting in an oblique direction is preferably set so that 0.03 ° ≦ θ ≦ 5 ° or less. More preferably, 0.05 ° ≦ θ ≦ 3 °, and still more preferably 0.05 ° ≦ θ ≦ 1 °. This is because if the angle is 5 ° or more, the area of the exposed surface after cutting is not large enough for analysis, and analysis evaluation becomes difficult. Further, when the angle is small, such as less than 0.05 °, it approaches a state almost parallel to the surface of the thin film laminated material, and it becomes difficult to cut.

  By performing the setting as described above, a smooth expanded exposed surface having a width of about 10 to 1000 times the thickness of the intermediate layer can be obtained, and the composition can be formed using existing analytical equipment on the surface. Can be analyzed.

Further, the surface roughness R of the enlarged exposed surface of the intermediate layer obtained by oblique cutting is preferably R <1 μm, more preferably 100 nm ≦ R ≦ 500 nm, further preferably 10 nm ≦ R ≦ 50 nm, and R < 10 nm is particularly preferable. This is because, when the surface roughness R is 1 μm or more, it is difficult to analyze the composition using the existing analytical equipment because the convex portions on the surface make a shadow. By setting the vertical cutting speed V _Y and the cutting angle θ as described above, it is possible to obtain an enlarged exposed surface having a surface roughness in a preferable range as described above. By obtaining a smooth exposed surface in this way, analysis by an analytical instrument can be performed accurately.

  In the present invention, it is preferable that the atmosphere in which cutting is performed is a room temperature that does not change the physical properties of the target thin film laminated material. If it is set to a temperature higher than room temperature, it is related to the glass transition temperature of the thin film laminate material, etc., but generally it has fluidity, and the cutting itself is performed well, but the characteristics of the material change, An analysis of an appropriate composition cannot be performed.

<Experimental result>
An experiment was conducted to see how the surface roughness changes when cutting in an oblique direction.

First, the surface of PMMA (polymethyl methacrylate resin) was cut obliquely using the apparatus shown in FIG. As shown in Table 1, the experiment was conducted while changing the speed in the vertical direction from 0.1 nm / s to 10 nm / s. As shown in Table 1, the horizontal cutting speed V _X is 500 times the vertical cutting speed V _Y (for example, when V _Y is 0.1 nm / s, V _X is 50 nm). / S) was set. The measurement result of the surface roughness R is as shown in Table 1. The surface roughness was measured using an AFM Nanoscope V + D3100 manufactured by Veeco Digital Digital Instruments. The measurement conditions were tapping mode, the probe was NCH-10V made of silicon single crystal, and the measurement area was 1 μm × 0. The thickness was 5 μm.

  FIG. 4 shows a photograph of the surface taken from the direction orthogonal to the exposed surface at each cutting speed, and a graph of Table 1. As can be seen from this graph, when the cutting speed in the vertical direction is particularly less than 1 nm / s, the surface roughness becomes considerably small, and it becomes easy to analyze the composition with the existing analytical instrument.

Next, experimental results when the surface of a spectacle lens with an HC (hard coat) layer is cut are shown. The cutting apparatus is the same as in the first embodiment, and the relationship between the horizontal cutting speed V _X and the vertical cutting speed V _Y is the same as in the first embodiment. The measurement results of the surface roughness are as shown in Table 2. The apparatus used for the measurement of the surface roughness is the same as in Example 1, but the measurement area was 10 μm × 1 μm.

  FIG. 5 shows a photograph of the surface taken from a direction orthogonal to the exposed surface at each cutting speed, and a graph of Table 2. As can be seen from this graph, when the cutting speed in the vertical direction is set to 2 nm / s or less, particularly less than 1 nm / s, the surface roughness is considerably reduced, and it becomes easy to analyze the composition with the existing analytical instrument.

Next, experimental results when a thin film laminated material (laminated film) having a three-layer structure is cut will be shown. Specifically, it is a laminated film composed of polyimide layer / adhesive layer / PET layer. The horizontal cutting speed V _X was set to be 100 times the vertical cutting speed V _Y. The measurement results of the surface roughness are as shown in Table 3. The apparatus used for the measurement of the surface roughness is the same as in Example 1, but the measurement area was 1 μm × 1 μm.

  FIG. 6 shows a photograph of the surface taken from the direction orthogonal to the exposed surface at each cutting speed and a graph of Table 3. As can be seen from this graph, when the cutting speed in the vertical direction is particularly less than 1 nm / s, the surface roughness becomes considerably small, and it becomes easy to analyze the composition with the existing analytical instrument. Moreover, FIG. 7 is a figure which shows the SEM image of the cross section before intermediate layer cutting, in the middle of cutting, and after cutting. The exposed portion of the intermediate layer is indicated by an arrow, and it can be seen that a sufficient length is exposed as compared with the thickness of the intermediate layer.

  Next, FIG. 8 shows composition analysis data of an adhesive with an undercoat layer (corresponding to an intermediate layer). This object corresponds to a thin film laminate material, but is applied on a PET (polyethylene terephthalate) base material with a methacrylic polymer containing an oxazoline group as a primer at a thickness of 40 nm, and then a butyl acrylate type. An adhesive tape having an adhesive transferred by gravure printing was prepared. A cross-sectional TEM photograph near the undercoat layer is shown in the upper left of FIG.

  Since the adhesive cannot be cut in an oblique direction at room temperature, it was first subjected to an electronic dyeing process (vapor dyeing with a 0.5% Ru acid aqueous solution: room temperature for 1.5 hours), and then cut in an oblique direction. . The cutting speed at this time was 0.5 nm / s in the vertical direction and 250 nm / s in the horizontal direction. An optical micrograph after obliquely cutting the material is shown in the upper right of FIG. As a result of cutting in the oblique direction, an enlarged exposed surface estimated to be an undercoat layer having a width of about 20 μm could be obtained.

As a result of analyzing the exposed surface using TOF-SIMS (TRIFT-2 manufactured by ULVAC-PHI), an ion mapping image obtained is shown in the lower right of FIG. As a result of analysis by TOF-SIMS, C ₄ H ₇ O ⁻ (M / Z 71) and C ₄ H ₉ O ⁻ (M / Z 73) derived from butyl acrylate were detected from the pressure-sensitive adhesive layer. Further, C ₄ H ₅ O ₂ ⁻ (M / Z 85) derived from methacrylic polymer was detected from the undercoat layer. In addition, CN ⁻ (M / Z 26) and CNO ⁻ (M / Z 42) ions presumed to originate from the amide bond reacted with the oxazoline ring of the crosslinking agent were also detected, and the components as designed could be identified. .

Comparative example

  Next, as a comparative example, FIG. 9 shows an experimental result when the cutting speed is set to 2 nm / s in the vertical direction and 1000 nm / s in the horizontal direction in Example 4. It was found that when the cutting speed was used, the undercoat layer (intermediate layer) was not exposed, and the interface was peeled off and became non-uniform. Further, a peak derived from the pressure-sensitive adhesive layer is also detected in a portion corresponding to the undercoat layer.

  As described above, the effect of the present invention could be experimentally confirmed.

Schematic showing the configuration of the thin film laminated material pretreatment equipment Diagram showing the configuration of the cutting blade Model diagram when cutting in an oblique direction The figure which shows the experimental result at the time of cutting PMMA The figure which shows the experimental result at the time of cutting spectacle lens with HC layer The figure which shows the experimental result when the laminated film is cut The figure which shows the SEM image of the cross section after the intermediate | middle layer cutting of a laminated | multilayer film, in the middle of cutting, and after cutting The figure which shows the data of the compositional analysis of the thin film laminated material which has the adhesive with undercoat The figure which shows the experimental result of a comparative example

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Cutting blade 2 Parallel pressure detector 3 Connecting tool 4 Vertical pressure detector 5 Connecting tool 6 1st piezoelectric element 7 2nd piezoelectric element 10 Thin film laminated material 10a Surface layer 10b Intermediate | middle layer 10c Back surface layer

Claims (5)

In order to analyze the composition of the intermediate layer of the thin film laminated material having the intermediate layer, the thin film laminated material is pre-processed by cutting the thin film laminated material in the cross-sectional direction to expose the intermediate layer,
When cutting a thin film laminated material using a cutting blade driven relatively in a direction parallel to and perpendicular to the surface of the thin film laminated material, the cutting speed in the vertical direction is 0.01 nm / s or more and less than 1 nm / s. A thin film laminated material pretreatment method, characterized in that the cross section is cut obliquely.   The pretreatment method for a thin film laminated material according to claim 1, wherein the cutting speed in the vertical direction is set to 0.6 nm / s or less.   The thin film laminated material pretreatment method according to claim 1 or 2, wherein a cutting direction by the cutting blade is set to be 0.05 ° or more and 5 ° or less with respect to a surface of the thin film laminated material.   The thin film laminate material pretreatment method according to any one of claims 1 to 3, wherein the thin film laminate material comprises at least three layers and the intermediate layer has a thickness of 10 µm or less. A pretreatment device used in the thin film laminate material pretreatment method according to any one of claims 1 to 4,
A first piezoelectric element capable of driving the cutting blade in a direction perpendicular to the surface of the thin film laminated material;
A second piezoelectric element capable of driving the cutting blade in a direction parallel to the surface of the thin film laminate material,
A thin film stack characterized in that the cutting speed in the vertical direction of the cutting blade is set to be 0.01 nm / s or more and less than 1 nm / s, and the cross section of the thin film stack material can be cut obliquely. Material pretreatment equipment.

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