JP2011169763A - Measurement method and evaluation method for phase separation state of polymer material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a measurement method and an evaluation method for a phase separation state of a polymer material which simply evaluate a phase separation state of the polymer material having two kinds or more mixed macromolecular materials without use of an expensive apparatus. <P>SOLUTION: In the measurement method for phase separation state of the polymer material having two kinds or more mixed macromolecular materials, a polymer specimen is formed by the macromolecular materials, exposed to a gaseous or aqueous solution-like electronic dyeing agent, and formed with an electronic dyeing layer. An electronic dyeing layer thickness changed in response to an exposure time is measured, and converted into a data with regard to the exposure time. The electronic dyeing layer thickness converted into the data with regard to the exposure time as a correlation line of a phase separation tendency of the polymer material is displayed on a screen of a data processor at a coordinate by considering one axis as the exposure time, and considering the other axis as the electronic dyeing layer thickness. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for measuring a phase separation state of a polymer material and a method for evaluating a phase separation state, and more particularly to a method for measuring and evaluating a phase separation state of a polymer material formed by mixing a plurality of polymer materials. is there.

  A polymer material that must satisfy a plurality of required properties may be made by blending two or more polymer materials. In such polymer materials, the phase separation structure of the blended polymeric material affects the material properties. For this reason, it is very important to control and evaluate the phase separation structure of a plurality of polymer materials used in the polymer material in order to optimize the polymer material and perform quality control.

  For example, Patent Document 1 describes a polymer material in which a crosslinked rubber and a crystalline resin are mixed. In Patent Document 1, it has been confirmed with a transmission electron microscope that a crystalline resin has a continuous phase and a crosslinked rubber has a dispersed phase by dynamically cross-linking rubber during kneading.

  Non-Patent Document 1 describes an example of observation. An example of the observation described in Non-Patent Document 1 is shown in FIG. Non-Patent Document 1 describes that by using a crystalline resin as a continuous phase, high mechanical strength can be imparted during use (room temperature), and high fluidity can be imparted during processing (above the melting point of the crystalline resin). Yes. Conversely, when a phase separation structure in which the crosslinked rubber is a continuous phase is taken, mechanical strength and recyclability (thermoplasticity) are impaired.

  A transmission electron microscope used for evaluating a phase separation structure of a polymer material is an observation means for forming an image with a transmitted electron beam by making an electron beam incident on a sample sliced to a thickness of about 100 nanometers. . Here, the transmittance of the electron beam used in the transmission electron microscope depends on the elemental composition of the sample. For this reason, in the case of a polymer material mainly composed of light polymer materials, there is no significant difference in the elemental composition of each phase separated, and it is very difficult to identify the phase structure by observing the sample as it is. . For this reason, an electron stain containing heavy metal is used in such a polymer material, and means for imparting contrast by the difference in the amount of heavy metal absorbed in each phase by utilizing the difference in reactivity between the electron stain and each phase. Used.

  In Patent Document 2, when a transmission electron microscope sample is stained by individually acting one or a plurality of stains on a sample block prepared in a shape that can be set in a microtome (sample thinning device). Describes a method for preparing a sample for a transmission electron microscope in which at least one staining is performed in a heated state, and an apparatus used in the method.

  Further, in Patent Document 3, when a resin mixture composed of two or more polymer material components is observed using a transmission electron microscope, it is above and below the glass transition temperature range of the contained polymer material components. A method for preparing a sample for observation with a transmission electron microscope in which electron staining is performed in a wide temperature range by 20 ° C. is described.

  As another evaluation method of a polymer material, Non-Patent Document 2 discloses a scanning probe microscope (SPM) that scans the surface of a sample while vibrating the probe with a piezoelectric element, and an input signal for vibrating the probe. An example is described in which dynamic force mode (DFM) is used to obtain a hardness distribution image of the sample surface by mapping the phase difference between the probe and the output signal of the detector at the tip position of the probe. That is, the soft phase has a large phase difference, and the hard phase has a small phase difference, whereby the phase is identified. Non-Patent Document 2 is a material system in which rubber and crystalline resin are kneaded at a ratio of 70:30. When kneaded simply, rubber is in a continuous phase and resin is in a dispersed phase, whereas rubber is kneaded during kneading. It is shown that when dynamic crosslinking is performed by kneading while crosslinking, the rubber is finely dispersed and the crystalline resin becomes a continuous phase.

JP 2008-31354 A Japanese Patent Laid-Open No. 06-288882 JP 07-318470 A

“Hitachi Cable” No. 27 (2008), p. 5 The 19th Annual Meeting of the Chemical Society of Japan Kanto Branch Ibaraki Area Research Exchange Proceedings (2008), p. 39

  The polymer material can measure the phase separation structure by electron-staining the sample and observing with a transmission electron microscope. However, transmission electron microscope observation has the following problems.

  First, in transmission electron microscope observation, it is necessary to prepare an extremely thin sample piece of about 100 nanometers so that an electron beam can be transmitted. Expensive laboratory equipment such as a microtome is required. Above all, the transmission electron microscope itself is very expensive.

  In addition, it is necessary to use appropriate reaction conditions in order to react a thin sample of a polymer material sample cut out for transmission electron microscope observation with an electron staining agent. Observation of a phase separation structure using a transmission electron microscope Requires proficiency. If the electron staining conditions (exposure time) are not appropriate, clear contrast cannot be obtained, and it is necessary to repeat sample preparation and measurement for optimization. The same applies to the method described in Patent Document 3 in which electron staining is performed while heating within a temperature range wider than the glass transition temperature of the polymer material constituting the polymer material.

  Furthermore, an experimenter determines which component is a continuous phase or a dispersed phase from the obtained transmission image, but since the information on the entire thickness of the sample overlaps, the structure is compared with the film thickness (about 100 nanometers). If it is fine, the boundary will be blurred, making judgment difficult. Further, in order to extract quantitative parameters, it is necessary to perform complicated image analysis.

  As described above, the evaluation of the phase separation structure using a transmission electron microscope is expensive, requires skill (experience) in its operation, decreases in resolution when the phase separation structure is fine, and quantifies There are problems such as difficult parameter extraction.

  On the other hand, in the case of an observation method using a scanning probe microscope, the unevenness of the observation surface also affects the phase difference, so that an extremely smooth observation surface must be formed in order to accurately identify the phases. Actually, when a polymer material in which phases having different hardnesses are dispersed by phase separation is cut, a step is likely to occur at the boundary between different phases, and the phase identification accuracy is lowered. Furthermore, as with the transmission electron microscope, it is necessary to perform advanced image analysis in order to extract quantitative parameters.

  Based on the above problems, the present invention is a method for measuring the phase separation state of a polymer material in which a phase separation state can be easily evaluated without using an expensive apparatus for a polymer material obtained by mixing two or more types of polymer materials. It is an object to provide a method and a phase separation state evaluation method.

  In order to achieve the above object, the present invention provides a method for measuring a phase separation state of a polymer material in which two or more kinds of polymer materials are mixed, wherein a polymer test piece is formed from the polymer material, and the polymer test piece is gaseous. Alternatively, an electron staining layer is formed on the polymer test piece by exposure to an aqueous electron staining agent, and the thickness of the electron staining layer changed corresponding to the exposure time is measured, and the thickness of the electron staining layer relative to the exposure time is A phase of a polymer material characterized by measuring a phase separation state of the polymer material by a correlation line of a phase separation tendency of the polymer material derived based on the thickness of the electron dye layer with respect to the exposure time that is converted into data and data. A separation state measurement method is provided.

  In addition, the present invention provides a method for measuring a phase separation state of a polymer material, wherein the saturation value of the thickness of the electron staining layer with respect to the exposure time obtained based on the correlation line is used as a saturation value parameter.

  In addition, the present invention provides a method for measuring a phase separation state of a polymer material, wherein an index representing a slope of the correlation line obtained based on the correlation line is used as a slope parameter.

  Further, the present invention provides a saturation value parameter consisting of a saturation value of the thickness of the electron staining layer with respect to the exposure time obtained based on the correlation line, and a slope about the correlation line obtained based on the correlation line. A method for measuring a phase separation state of a polymer material is provided, in which a slope parameter index composed of indices representing the parameters is fitted to the following equation.

（ただし、ここでｄは電子染色層厚さ（μｍ）、ｔは曝露時間（分）、ｃは電子染色剤がガス状化または水溶液化するまでの遅れ時間、Ａは飽和値パラメータ、Ｂは傾きパラメータ指数、Ｄは曝露時間の累乗を示すパラメータ）

(Where d is the thickness of the electron staining layer (μm), t is the exposure time (minutes), c is the delay time until the electron staining agent becomes gaseous or aqueous, A is the saturation value parameter, and B is Slope parameter index, D is a parameter indicating the power of exposure time)

  In the present invention, the electron staining layer thickness with respect to the exposure time converted into the data is processed by the following formula, and a parameter (X in the following formula) indicating an increase rate of the electron staining layer thickness with respect to the exposure time is used. A method for measuring a phase separation state of a polymer material, comprising measuring a phase separation state of a polymer.

  The present invention is also directed to the polymer material phase separation state evaluation method using the polymer material phase separation state measurement method, wherein the data processing device stores in the database the phase separation state of the polymer material, the exposure time, and the electron staining layer. The correlation line of the polymer material phase separation tendency with respect to the thickness is stored in advance as correlation data, and the correlation line displayed on the screen is compared with the correlation line stored in the database, and the approximate correlation stored in the database is stored. Provided is a method for evaluating a phase separation state of a polymer material, wherein a phase separation state of the polymer material is specified from a line.

  According to the present invention, for a polymer material obtained by mixing a plurality of polymer materials of two or more types, a phase separation state measuring method and a phase separation state of a polymer material can be easily evaluated without using an expensive device. An evaluation method is obtained.

It is a flowchart which shows the phase-separation state measurement procedure which concerns on embodiment of this invention. It is the image which observed what the sample 5 (rubber ratio 70%, no dynamic bridge | crosslinking) exposed to the electron dye for 60 minutes, and sliced the cross section with the optical microscope. The sample 6 (rubber ratio 70%, with dynamic crosslinking) is exposed to an electron stain for 60 minutes, and a cross-sectional slice is observed through an optical microscope. Electronic stains of raw material 1 (crystalline resin), raw material 2 (rubber), sample 1 (rubber ratio 30%), sample 3 (rubber ratio 50%), and sample 5 (rubber ratio 70%) This is a plot of the relationship between exposure time and the thickness of the electron staining layer. Raw material 1 (crystalline resin), raw material 2 (rubber) and dynamically crosslinked sample 2 (rubber ratio 30%), sample 4 (rubber ratio 50%), and sample 6 (rubber ratio 70%) were added to the electronic stain. The relationship between the exposure time and the thickness of the electron staining layer is plotted. It is the result of plotting the fitting value of the parameter A when the relationship between the exposure time of the raw material 1, raw material 2, and samples 1 to 6 to the electronic staining agent and the thickness of the electronic staining layer was fitted with the formula 1 against the rubber ratio. . The fitting result of the parameter B when the relationship between the exposure time of the raw material 1, the raw material 2, and the samples 1 to 6 to the electronic stain and the thickness of the electronic stain layer is fitted by the equation 1 is plotted against the rubber ratio. . The fitting result of the parameter D when the relationship between the exposure time of the raw material 1, the raw material 2, and the samples 1 to 6 to the electronic staining agent and the thickness of the electronic staining layer is fitted by the equation 1 is plotted against the rubber ratio. . The result of the parameter X calculated by Formula 2 from the relationship between the exposure time of the raw material 1, raw material 2, and samples 1 to 6 to the electronic stain and the thickness of the electronic stain layer is plotted against the rubber ratio. This is an example in which a phase separation structure of a polymer material composed of a crosslinked rubber and a crystalline resin is observed with a transmission electron microscope.

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings.

  FIG. 1 shows a procedure for measuring the phase separation state of the polymer material according to the embodiment of the present invention. In S101 shown in FIG. 1, the polymer material is cut out as a test piece. It is desirable that the surface of the cut specimen is smooth to some extent. This is because the electron dyeing proceeds from the surface of the test piece, and in this embodiment, after the polymer material is electron dyed, the film thickness of the electron dye layer is measured and evaluated.

  The size of the test piece may be any size as long as it fits into a reaction vessel for electronic staining, but considering the workability during cutting and observation, the size of the test piece is several mm to several cm. The order is good. When it is desired to confirm the anisotropy of the sample, the surfaces to be compared may be cut out and compared. If the polymer material is in a pellet form or the like and has an appropriate size from the beginning, it may be used as it is as a test piece.

  In the present embodiment, the polymer material is more preferably composed of rubber and crystalline resin.

  As the rubber used in the present embodiment, an ethylene vinyl acetate copolymer, an ethylene-propylene-diene copolymer, or the like is preferable.

  Examples of the crystalline resin used in this embodiment include polypropylene, high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer, and ethylene. -Crystalline polyolefin resin containing at least one selected from octene-1 copolymer, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer, used alone or in a blend of two or more Is preferred.

  Here, as a polypropylene used in the present embodiment, a rubber component typified by a block copolymer or random copolymer obtained by copolymerizing an α-olefin typified by ethylene in addition to a homopolymer, and ethylene propylene rubber. Is included in the polymerization stage. As the ethylene-vinyl acetate copolymer, those having a crystalline vinyl acetate content of less than 30 wt% are suitable. In addition, low density polyethylene, polybutene, poly-4-methyl-pentene-1, ethylene-butene-hexene terpolymer, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-glycidyl A methacrylate copolymer or the like is preferable.

  Next, in S102, the test piece is exposed to an electronic stain and subjected to electronic staining. As the electron staining agent used in this embodiment, ruthenium tetroxide and osmium tetroxide are suitable. Since ruthenium tetroxide has a strong oxidizing power and reacts with most polymer materials, it has a wide range of applicable materials. On the contrary, other electronic stains such as osmium tetroxide have a large difference between those that react and those that do not react depending on the type of polymer material, so the difference due to the difference in phase separation structure may be obtained extremely, It is good to use properly depending on the target material.

  Since these electron dyes sublime at room temperature, the surface of the test piece is electronically stained by putting the test piece and the crystal of the electron dye into a glass container or metal container, and taking out after sealing for a predetermined exposure time.

  In addition, since these electron stains are also water-soluble, they may be dissolved in water, and the sample may be immersed therein, and the immersion time may be used as the exposure time. In the case of using an aqueous solution in which an electron stain is dissolved in water, since the entry of the electron stain into the test piece becomes slow, it is necessary to increase the exposure time accordingly.

  In addition to these, there are uranyl acetate, phosphotungstic acid and the like as electron staining agents that can be used in the solution.

  In S102, electronic staining is performed for a plurality of exposure times. Here, in order to grasp the tendency of electronic staining, it is desirable to carry out with an exposure time of 3 points or more. The exposure time should be set at equal intervals or times in consideration of the balance when plotting the change in the thickness of the electron staining layer. Since the electron staining reaction tends to proceed in a shorter time when the concentration and temperature of the electron staining agent are higher, it should be considered that these conditions do not change greatly between samples to be compared.

  Next, in S103, the electron-stained test piece is cut, and the slice is sliced to produce a slice piece. In the present embodiment, the thickness of the slice piece may be about 10 to 100 micrometers. For this reason, a processing machine such as a general microtome or a tool such as a razor may be used for slicing the cross section of the test piece in the present embodiment instead of an ultramicrotome. If the slice piece is too thin, the electron-stained layer will be difficult to see, and handling will be poor. On the other hand, if it is too thick, the boundary of the electron staining layer appears to spread in the thickness direction, and the measurement accuracy may deteriorate. Therefore, it is preferable to slice a slice perpendicular to the dyeing surface.

  Next, in S104, the slice piece obtained in S103 is observed, and the thickness of the electronic staining layer is estimated. As a means for estimating the thickness of the electronic staining layer, the thickness of the electronic staining layer may be obtained by, for example, reading with a light microscope with a scale or taking a photograph and estimating the magnification from the observation conditions. Further, it is more preferable that the transmission image or reflection image of the slice piece is taken into a computer by an image pickup device such as a digital microscope, and the thickness of the electronic staining layer is calculated, thereby improving workability.

  Next, in S105, the correlation of the electron dye layer thickness with the exposure time is examined. Plot changes in the thickness of the electron-stained layer with respect to exposure time, grasp the rough tendency, apply the model function and perform fitting, and determine quantitative parameters to determine the phase separation structure of the polymer material It is to do.

  In the present embodiment, the phase separation structure of the polymer material can be determined by taking the correlation of the thickness of the electron dye layer with respect to the exposure time for the following reason. In other words, in the case of polymer materials, the diffusion rate and reaction rate of the electron stain differ depending on the type of polymer material, and the amount of penetration and deposition of the electron stain differs. This is because a difference occurs in the dependency of the change in the staining time on the staining time.

  For example, when the polymer and rubber as the polymer material constituting the polymer material are each electron-dyed individually, the electron dye layer is thicker than rubber than the crystalline resin. The increase tends to reach a peak (saturation). On the contrary, the crystalline resin tends to reach the saturation later than the rubber, although the initial increase in the thickness of the electron dye layer is slow.

  When polymer materials blended with these materials are compared, in the case of a polymer material in which the continuous phase is rubber, as in the case of the rubber alone, the electron dyeing layer becomes thick at an early point and reaches saturation quickly. On the other hand, in the polymer material in which the continuous phase is a crystalline resin, as in the case of the crystalline resin alone, the increase in the thickness of the electron-stained layer at an early time is slow, but the saturation tends to be slow. It can be seen.

  In this way, by examining the exposure time dependence of the change in the thickness of the electron staining layer, a material for determining the phase separation structure of which polymer material is in the continuous phase can be obtained. In S106, the phase separation state of the polymer material is evaluated and determined.

  In this embodiment, when the polymer material has anisotropy, it can be easily estimated that the exposure time dependency of the change in the thickness of the electron staining layer differs depending on the surface exposed to the electron staining agent. Is also considered applicable.

  In addition, the rate of change may be used as a criterion for determination, for example, by taking a ratio or difference between measured values.

  Examples of the present invention will be specifically described below.

  As a sample for evaluation, a sample having a composition shown in Table 1 was used. A silane graft copolymerized ethylene-vinyl acetate copolymer (vinyl acetate content 42 wt%) was used as a rubber component, and an ethylene-vinyl acetate copolymer (vinyl acetate content 14 wt%) was used as a raw material as a crystalline resin component. These were put into a 37 mm twin screw extruder (L / D = 60) and kneaded. Samples 1, 3, and 5 are only kneaded, but samples 2, 4, and 6 are subjected to the action of the added dibutyltin dilacrate, and a silane crosslinking reaction occurs during kneading and dynamic crosslinking proceeds.

  Table 2 shows the results of observing the prepared samples with SPM phase contrast images and the results of evaluating the tensile strength and the flexural modulus. The SPM phase contrast image was observed by measuring a cross section obtained by cutting a cooled sample piece with a microtome.

  From the SPM phase difference image shown in Table 2, it can be seen that Sample 1 and Sample 2 having a large raw material ratio of the crystalline resin have a continuous phase of the crystalline resin. Samples 3 and 5 with a rubber ratio exceeding 50% have a rubber phase as a continuous phase, but samples 4 and 6 that are dynamically crosslinked have a crystalline resin as a continuous phase.

  Sample 2, Sample 4, and Sample 6, which are dynamically crosslinked as a whole, have a smaller dispersion size of the rubber phase compared to Sample 1, Sample 3 and Sample 5 having the same rubber ratio, and the continuity of the crystalline resin. Is high.

  When the mechanical properties are compared, the bending strength shows almost the same strength if the rubber ratio is the same, but the tensile strength shows a large numerical value for Sample 2, Sample 4 and Sample 6 where the continuity of the crystalline resin is high. ing.

Thus, there is a correlation between the phase dispersion structure evaluated by the SPM phase contrast image and the tensile strength. However, contrast due to the unevenness of the sample surface is also superimposed on the SPM phase difference image as shown in Table 2, and it is not easy to extract quantitative parameters from this two-dimensional image.

［実施例１］
次にこれらの試料を本発明の実施の形態に係る方法で評価した。

[Example 1]
Next, these samples were evaluated by the method according to the embodiment of the present invention.

  First, a 2 mm square test piece was cut out from each sample with a razor and placed in a sealable 50 cc glass bottle. Here, 40 mg of ruthenium tetroxide crystal frozen as an electron stain was added, sealed, and left at 25 ° C. for a predetermined exposure time. In this example, three stages of 10 minutes, 60 minutes, and 360 minutes were used as the predetermined exposure time.

  After elapse of a predetermined exposure time, the glass bottle was opened and the test piece was taken out. This work was carried out in a draft with local exhaust function. The sample taken out was allowed to stand for half a day, and then divided into two with a razor, and the cut surface was cut (sliced) with a microtome to cut out a sliced piece having a thickness of 20 μm.

  Next, the slice piece was observed with an optical microscope, and a photograph was taken. An example of the result of photographing is shown in FIGS. FIG. 2 shows sample 5 (rubber 70%, without dynamic crosslinking), and FIG. 3 shows sample 6 (rubber 70%, with dynamic crosslinking) exposed to the dye for 60 minutes and sliced in cross section. A scale for calibrating magnification was taken in advance, and the scale was put in reference to it. 1a shown in FIG. 2 and 1b shown in FIG. 3 represent an electron staining layer on the sample surface side. 2a shown in FIG. 2 and 2b shown in FIG. 3 represent sample layers inside the sample.

  As shown in FIGS. 2 and 3, dyeing with an electron stain progresses with a substantially constant film thickness, and a boundary is recognized between the electron stain layer and the sample layer. The electron dye layer thickness 1a in FIG. 2 was 198 μm, and the electron dye layer thickness 1b in FIG. 3 was 157 μm.

  A plot of the correlation between the thickness of the electron-stained layer and the exposure time of each sample thus observed is shown in FIGS. The thickness of the electron staining layer on the vertical axis is plotted linearly, but the exposure time on the horizontal axis is logarithmic.

  4 and 5, Equation 1 is assumed as an approximate expression of the correlation between the electron dye layer thickness d and the exposure time t, and the results of parameter fitting are indicated by a solid line and a dotted line.

ここで、ｄは電子染色層厚さ（μｍ）、ｔは曝露時間（分）、Ａ〜Ｄはフィッティングパラメータであり、Ａは飽和値パラメータ、Ｂは傾きパラメータ指数、Ｄは曝露時間の累乗を示すパラメータを示す。この中でＣは、凍結した電子染色剤である四酸化ルテニウム結晶が室温放置で昇温し、昇華してガス化するまでの遅れ時間を想定しており、本実施例では１．５分としている。実際の実験でも電子染色剤が昇華して、ガスの褐色が顕著になるまで１〜２分を要していた。

Here, d is the electron staining layer thickness (μm), t is the exposure time (minutes), A to D are fitting parameters, A is a saturation value parameter, B is a slope parameter index, and D is a power of the exposure time. Indicates the parameter shown. Among them, C assumes a delay time until the frozen ruthenium tetroxide crystal, which is an electron stain, is allowed to stand at room temperature, sublimates and gasifies, and in this example, 1.5 minutes. Yes. In actual experiments, it took 1-2 minutes for the electron stain to sublimate and the brown color of the gas to become noticeable.

  The correlation between the parameters A, B, D obtained by parameter fitting and the rubber ratio is shown in FIGS. 6, 7, and 8, respectively. Here, the parameter A is the saturation point of the thickness of the electronic staining layer, and the parameters B and C represent the slopes of the graphs described in FIGS.

  Here, in the fitting result of the parameter B in FIG. 7, when the continuous phase is the group 11 of crystalline resin and the continuous phase is the rubber group 12 and the continuous phase is rubber, the parameter B tends to be large. I understand.

  Further, Sample 1 and Sample 2, Sample 3 and Sample 4, and Sample 5 and Sample 6 having the same rubber ratio but different phase separation structures have large differences in parameter A and parameter D.

  Compared with Table 2, when the continuous phase is a crystalline resin and the rubber is finely dispersed, the parameter A tends to increase and the parameters B and D tend to decrease.

In this way, information on the phase separation structure is obtained from the correlation between the electron dye layer thickness d and the exposure time t, and the phase separation state of the polymer material can be measured.
[Example 2]

  As an example of the present invention, a parameter extracted from the correlation between the exposure time and the electron staining layer thickness may be the parameter X shown in Equation 2. The parameter X shown in Equation 2 is the difference between the change rate of the electron staining layer thickness from the exposure time of 60 minutes to the exposure time of 360 minutes to the change rate of the electron staining layer thickness from the exposure time of 10 minutes to the exposure time of 60 minutes. Is.

本実施例で用いられる試料からパラメータＸを抽出した結果を図９に示す。図９に示すようにパラメータＸは、曝露時間が増えたときに電子染色層厚さの増加率が大きく減少しているものほど大きくなり、電子染色層厚さの増加率の減少が少ないほど小さくなることが分かる。表２と図９の比較から、パラメータＸは、連続相が結晶性樹脂で、ゴムが微細分散すると小さくなる傾向があることが分かる。

FIG. 9 shows the result of extracting the parameter X from the sample used in this example. As shown in FIG. 9, the parameter X increases as the increase rate of the electron staining layer thickness decreases as the exposure time increases, and decreases as the decrease in the increase rate of the electron staining layer thickness decreases. I understand that From comparison between Table 2 and FIG. 9, it can be seen that the parameter X tends to be smaller when the continuous phase is a crystalline resin and the rubber is finely dispersed.

  In this way, in this embodiment, information on the phase separation structure is obtained from the correlation between the electron staining layer thickness d and the exposure time t, and the phase separation state of the polymer material can be measured.

  As described above, the numerical parameters are extracted by the formulas 1 and 2 as examples of the present invention. However, as an example of the present invention, the expression for extracting the numerical parameters from the measurement data group of the electron staining layer thickness and the exposure time is not limited to Expression 1 and Expression 2.

  As described above, in the present invention, in a polymer material obtained by mixing two or more types of polymer materials as raw materials, the material reacts with at least one of the raw polymer materials to form a heavy metal compound. Expose the test piece of polymer material to the dyeing gas or dyeing solution for electron staining at multiple times, then slice the cross section and measure the change in the thickness of the electron staining layer with respect to the exposure time. Information on the phase separation structure can be obtained from the correlation of the exposure time.

  According to the present invention, it is possible to extract numerical parameters about the phase separation structure of a polymer material by simple observation and calculation without using an expensive observation device, and a method for measuring a phase separation state of a polymer material and a phase separation state evaluation method are provided. can get.

  DESCRIPTION OF SYMBOLS 1a, 1b ... Electro dyeing | staining layer, 2a, 2b ... Sample layer, 11 ... Sample group whose continuous phase is crystalline resin, 21 ... Sample group whose continuous phase is rubber | gum.

Claims (6)

In a method for measuring a phase separation state of a polymer material in which two or more kinds of polymer materials are mixed,
Forming a polymer specimen with the polymeric material;
Exposing the polymer test piece to an electron staining agent in the form of a gas or an aqueous solution to form an electron staining layer on the polymer test piece,
The thickness of the electron staining layer changed corresponding to the exposure time is measured and the electron staining layer thickness with respect to the exposure time is converted into data,
A method for measuring a phase separation state of a polymer material, comprising: measuring a layer separation state of the polymer material based on a correlation line of a phase separation tendency of the polymer material derived based on an electron-stained layer thickness with respect to a data exposure time. . The method for measuring a phase separation state of a polymer material according to claim 1, wherein the saturation value of the thickness of the electron staining layer with respect to the exposure time obtained based on the correlation line is used as a saturation value parameter. The method for measuring a phase separation state of a polymer material according to claim 1, wherein an index representing a slope of the correlation line obtained based on the correlation line is used as a slope parameter. In Claim 1, the saturation value parameter obtained from the saturation value of the electron staining layer thickness with respect to the exposure time obtained based on the correlation line and the inclination of the correlation line obtained based on the correlation line are represented. A method for measuring a layer separation state of a polymer material, characterized in that a slope parameter index composed of an index is parameter-fitted into the following equation.

(Where d is the thickness of the electron staining layer (μm), t is the exposure time (minutes), C is the delay time until the electron staining agent becomes gaseous or aqueous, A is the saturation parameter, and B is Slope parameter index, D is a parameter indicating the power of exposure time) The electron-stained layer thickness according to claim 1 for the data-exposed exposure time.

(Where X is a parameter indicating the rate of increase in the thickness of the electron staining layer with respect to the exposure time),
A method for measuring a phase separation state of a polymer material, wherein a total separation state of the polymer is measured using a parameter indicating an increase rate of the thickness of the electron staining layer with respect to the exposure time. In the polymer material phase separation state evaluation method using the polymer material phase separation state measurement method according to claim 1,
The data processing device stores in a database the phase separation state of the polymer material and the correlation line of the phase separation tendency of the polymer material with respect to the exposure time and the electron dye layer thickness as correlation data in advance, and the correlation displayed on the screen A phase separation state evaluation method for a polymer material, wherein a line is compared with a correlation line stored in the database, and a phase separation state of the polymer material is specified from an approximate correlation line stored in the database.

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