JP6908069B2 - A method for analyzing an organic component in a metal material having an organic-inorganic composite film, and a method for producing a metal material having an organic-inorganic composite film. - Google Patents

Description

The present invention relates to a method for analyzing an organic component in an organic-inorganic composite film applied to the surface of a metal material, and more particularly to a method for analyzing the content of a polymer compound which is an organic component. The present invention also relates to a method for producing a metal material having an organic-inorganic composite film using this analytical method.

Metal materials are often surface-treated with inorganic compounds such as metal plating, anodizing treatment, and chemical conversion treatment for the purpose of improving corrosion resistance, design property, wear resistance, and insulating property. In recent years, in addition to further enhancing the above functions by complexly dispersing organic compounds (organic components) in the surface treatment film, new functions such as lubricity, water repellency, hydrophilicity, adsorptivity, and chemical resistance have been added. For the purpose of this, surface treatment materials having an organic-inorganic surface treatment film (referred to as an organic-inorganic composite film) are being actively developed. For example, in Patent Document 1 and Patent Document 2, a zinc-based plated steel sheet is immersed in an acidic solution containing an organic component, fluororesin or polyethylene, so that Zn, fluororesin, oxide or water is formed on the surface of the plating layer. A surface-treated steel sheet on which an oxide film is formed is disclosed. In Patent Documents 1 and 2, by allowing the fluororesin, which is a solid lubricant, to be dispersed and present in the film, the lubricity at the time of press molding is greatly improved.

In the development of metal materials (surface treatment materials) having an organic-inorganic composite film, it is important to control the film composition for the efficient expression of functionality. For that purpose, it is necessary to accurately grasp the distribution and content of organic components in the film. The distribution of organic components in the film is generally grasped by observing from the surface and cross section using a scanning electron microscope (SEM) having an acceleration voltage of 5 kV or less and X-ray analysis in combination.

On the other hand, the content of the organic component in the film is calculated by obtaining the area ratio of the organic component in the film from the observation result of SEM, and when the organic component is in the form of particles, the number density and the average particle size are obtained and organic. Calculate the content of the ingredients. In addition, a method of measuring the characteristic X-ray intensity derived from carbon by fluorescent X-ray analysis (XRF) and determining the content of organic components by a calibration curve method may be used.

Japanese Unexamined Patent Publication No. 2016-98380 JP-A-2017-206715

However, when determining the content of organic components from the SEM observation results, it is necessary to pay close attention so that the adhesion (contamination) of hydrocarbons, etc. to the sample due to electron beam irradiation does not occur, which complicates the work. Requires a high degree of skill. Further, when the amount of the organic component charged is small, the quantitative result varies greatly depending on the observation field of view, so it is necessary to observe a large number of fields of view. When the amount of the organic component charged is large, if there is uneven distribution of the organic component in the film thickness direction, there is a problem that it cannot be quantified correctly by surface observation by SEM. Further, when XRF is used, an error tends to occur due to absorption of characteristic X-rays of C into the film and detection of characteristic X-rays derived from carbon contamination other than the main component.

The present invention has been made in view of such circumstances, and has an analytical method capable of quantifying organic components in a metal material having an organic-inorganic composite film, and an organic-inorganic composite film. It is an object of the present invention to provide a method for producing a metal material.

The present inventors have conducted intensive studies to solve the above problems. As a result, we focused on the fact that organic components are generally resistant to acids. Specifically, a metal material having an organic-inorganic composite film is dissolved in an acidic solution, the organic component existing as a residue is filtered to recover the entire amount, and then mass spectrometry is performed to accurately determine the type and amount of the organic component. We found that it can be quantified. Furthermore, when the organic component is a polymer compound, paying attention to the fact that the composition ratio of the fragment, which is a decomposition product, is reproduced if the heating pattern is the same, the recovered organic component is thermally decomposed and gasified, and then gas chromatography is performed. When analyzed by chromatographic mass spectrometry, it was found that even a small amount of organic components can be quantified with high accuracy.

The present invention has been completed based on the above findings, and the gist thereof is as follows.
[1] A method for analyzing an organic component in a metal material having an organic-inorganic composite film.
A dissolution step of dissolving the metal material with an acidic solution,
An extraction step of filtering an acidic solution in which the metal material is dissolved to extract organic components in the film, and
An analysis process for analyzing the extracted organic components and
A method for analyzing an organic component in a film in a metal material having an organic-inorganic composite film.
[2] The method for analyzing an organic component in a film of a metal material having an organic-inorganic composite film according to [1], wherein the extracted organic component is analyzed by using a mass spectrometry method in the analysis step.
[3] Further provided with a heating vaporization step of heating the organic components extracted in the extraction step to decompose and gasify them, and analyzing the decomposition gas obtained by the heating vaporization step in the analysis step [1] or [2]. The method for analyzing an organic component in a film in a metal material having an organic-inorganic composite film according to.
[4] In the heating vaporization step, when the decomposition temperature of the organic component is T (° C.), the heating start temperature is (T-100) ° C. or 30 ° C., whichever is higher or lower. The method for analyzing an organic component in a film of a metal material having an organic-inorganic composite film according to [3], wherein the heating end temperature is (T + 150) ° C. or higher.
[5] The method for analyzing an organic component in a metal material having an organic-inorganic composite film according to [3] or [4], wherein the heating rate is 5 to 30 ° C./min in the heating vaporization step. ..
[6] In the analysis step, in the film of the metal material having the organic-inorganic composite film according to any one of [3] to [5], which analyzes the decomposed gas by using gas chromatography-mass spectrometry. Analytical method of organic components.
[7] The method for analyzing an organic component in a metal material having an organic-inorganic composite film according to any one of [1] to [6], wherein the acidic solution is filtered by suction filtration in the extraction step. ..
[8] Analysis of organic components in a metal material having an organic-inorganic composite film according to any one of [1] to [7], which is filtered using an inorganic glass filter in the extraction step. Method.
[9] Analysis of organic components in a metal material having an organic-inorganic composite film according to any one of [1] to [8], wherein a corrosion inhibitor is added to the acidic solution in the dissolution step. Method.
[10] The method for analyzing an organic component in a metal material having an organic-inorganic composite film according to any one of [1] to [9], wherein the organic component is a polymer compound.
[11] The method for analyzing an organic component in a metal material having an organic-inorganic composite film according to any one of [1] to [10], wherein the metal material is a steel plate or a plated steel sheet.
[12] A method for producing a metal material having an organic-inorganic composite film. After forming an organic-inorganic composite film on the surface of the metal material, the organic components in the film after the film formation are [1] to [11]. It has an organic-inorganic composite film that is analyzed by the method for analyzing an organic component in a film according to any one of the above, and when the content of the organic component in the film is within a predetermined range, it is judged to be good and shipped. Method of manufacturing metal material.

According to the present invention, in a metal material having an organic-inorganic composite film, the amount of organic components present in the film can be quantified with high accuracy.

FIG. 1 is a diagram showing a temperature-total MS profile when polyethylene particles (0.16 mg) are heated from room temperature to 650 ° C. at a heating rate of 10 ° C./min. FIG. 2 is a diagram showing a temperature-MS profile for each fragment of m / z = 41, 55, 69, 83, 97 and 111. FIG. 3 is a calibration curve of polyethylene prepared from a temperature-MS profile of m / z = 41, which is one of the decomposition products of polyethylene. FIG. 4 is a calibration curve of PTFE prepared from a temperature-MS profile of m / z = 100, which is one of the decomposition products of polytetrafluoroethylene (PTFE).

Hereinafter, embodiments of the present invention will be described. The present invention comprises a dissolution step of dissolving a metal material (base metal) with an acidic solution, an extraction step of filtering an acidic solution obtained by dissolving the metal material obtained by the dissolution step, and extracting an organic component in a film. It is characterized by including an analysis step for analyzing an organic component.

The metal material is not particularly limited, but the present invention is suitable as a method for analyzing an organic component of an organic-inorganic composite film applied to the surface of a steel sheet or a plated steel sheet. Further, the organic-inorganic composite film is not particularly limited, but is suitable as a method for analyzing a polymer compound having excellent acid resistance as an organic component. The organic compound and the polymer compound having excellent acid resistance are not particularly limited, and examples thereof include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polycarbonate, and phenol resin. In particular, the present invention is more suitable as a method for analyzing polyethylene particles as an organic component.

Dissolution step In the dissolution step, a metal material having an organic-inorganic composite film is immersed in an acidic solution to dissolve the metal material. As the organic component in the organic-inorganic composite film, for example, an organic component such as polyethylene is generally excellent in acid resistance. Therefore, the inorganic component and the metal material in the film are dissolved by immersing in an acidic solution, and only the organic component is used. Can be left in the acidic solution.

As the acidic solution, any acid may be used as long as only the organic component can be left. From the viewpoint of versatility and the like, aqueous solutions of sulfuric acid, nitric acid, hydrofluoric acid and hydrochloric acid can be used. Further, the type and pH of the acidic solution may be selected according to the base metal and the inorganic component in the film. For example, in the case of a steel sheet to which a hydroxide such as iron or zinc is attached as an inorganic component, hydrochloric acid prepared so that pH <2 may be used.

Moreover, a corrosion inhibitor (inhibitor) can be added to the acidic solution. In particular, when the metal material is a plated steel sheet, by adding an inhibitor to the acidic solution, only the plated layer can be selectively dissolved and the film is separated from the base. Therefore, since the end point of the reaction can be known (melting of the steel sheet can be suppressed), elution of inclusions and the like in the steel sheet can be suppressed. Therefore, when the metal material is a plated steel sheet, it is acidic. It is more preferable to add the inhibitor to the solution.

When the base is a Zn-based plated steel sheet, if the acidic solution is hydrochloric acid and an inhibitor is added, excessive dissolution of the base steel sheet can be suppressed and the upper layer portion can be selectively dissolved above the plating. As the inhibitor at this time, an adsorption film type inhibitor such as a surfactant is suitable. Examples of the adsorption film type inhibitor that can be used in hydrochloric acid include amines, imidazoles, quaternary ammonium salts, thiols, and sulfides.

^{The size (dissolved area) of the test piece is preferably 500 mm 2} or more in order to suppress the influence of accuracy deterioration due to location unevenness during film formation, but it is appropriately adjusted according to the analysis method and the detection sensitivity of the analyzer. I do not care.

Further, when the metal material is not completely dissolved in the acidic solution (for example, when the steel sheet is immersed as the metal material in the acidic solution to which the inhibitor is added), the metal material may be appropriately recovered.

Extraction step After dissolving the metal material that is the base metal with an acidic solution, the organic component is extracted by filtering the acidic solution containing the organic component exfoliated from the base metal. When the organic component is in the form of particles, the filter used for filtration has a hole diameter equal to or smaller than the particle size. The material of the filter is not particularly limited as long as it is a material different from the organic component of the test sample, and a general polycarbonate-based filter can be used. As will be described later, when quantifying an organic component by gas chromatography-mass spectrometry, it is necessary to heat-decompose and vaporize the organic component together with the filter, so a filter having a higher decomposition temperature than the organic component is used. For example, when the organic component is polyethylene particles, the decomposition temperature of general polyethylene is about 300 to 500 ° C (depending on the atmosphere), so an inorganic glass filter (decomposition temperature: about 680 ° C) is used. Is preferable. The filtration method is not particularly limited, but suction filtration using an aspirator is preferable from the viewpoint of filtration rate.

Analysis step Next, the organic components extracted in the extraction step are analyzed in the analysis step. The extracted organic component may be analyzed together with the filter. The analysis of the organic component may be any method as long as it can detect the organic substance, and infrared absorption spectroscopy (FT-IR), nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), mass spectrometry, etc. are used. be able to. Among these, a mass spectrometry method having high detection sensitivity is preferable.

In the case of mass spectrometry, liquid, gas, or solid may be selected depending on the method of introducing the test sample, but it is better to use gas chromatography-mass spectrometry (GC / MS) having high resolution and detection sensitivity. preferable. Here, it is preferable to further include a heating vaporization step of heating the organic components extracted in the above-mentioned extraction step to decompose and gasify them, and a gas chromatography mass analysis method is used in the analysis step to analyze the decomposed gas obtained by the heating vaporization step. It is preferable to use and analyze. In the heat vaporization step, the test sample is heated together with the filter to thermally decompose and vaporize the organic components. Therefore, the decomposed gas obtained by vaporization is introduced into an analysis column for mass spectrometry.

In the heat vaporization step, the heating start temperature when the organic component, that is, the test sample extracted on the filter is thermally decomposed, is (T-100) with respect to the decomposition temperature T (° C.) of the organic component to be analyzed. ) ° C or lower or 30 ° C, whichever is higher, is preferable. The heating end temperature is preferably (T + 150) ° C. or higher.

The reason why the heating start temperature is set to (T-100) ° C. or lower is that, in addition to improving the efficiency of measurement, it suppresses rapid decomposition of organic components, reduces the variation in the generation ratio of decomposition-generated fragments, and improves quantification accuracy. This is to raise it. However, when (T-100) ° C. is lower than 30 ° C., heating may be performed from 30 ° C. On the other hand, the heating end temperature is preferably (T + 150) ° C. or higher. When the heating end temperature is (T + 150) ° C. or higher, most of the organic components of interest are decomposed.

The rate of temperature rise is preferably 5 to 30 ° C./min. The reason why the temperature rising rate is preferably 5 to 30 ° C./min is that it is easy to detect the peak of the decomposition product and the variation in the fragment formation ratio due to the temperature unevenness in the measurement system is suppressed.

Next, a method for quantifying the extracted organic component will be specifically described. As an example, polyethylene particles in a Zn-based galvanized steel sheet having an organic-inorganic composite film in which polyethylene particles (average particle size: 500 nm) are dispersed as organic components in an oxide film containing Zn on a Zn-based galvanized steel sheet. The quantification method of

First, the calibration curve used for quantification was examined. An aqueous dispersion of polyethylene (manufactured by Mitsui Kagaku Co., Ltd .: Chemipearl W4005 stock solution) was weighed so that the equivalent amount of polyethylene was 0.16 mg, extracted with an inorganic glass filter (pore size: 300 nm), and the inorganic type on which polyethylene particles were placed. The glass filter was heated from 50 ° C. to 650 ° C. at a heating rate of 10 ° C./min. The decomposition gas generated at this time was introduced into the analysis column of GC-MS and analyzed. FIG. 1 shows the temperature-total MS profile. Here, the temperature (Temp.) Refers to the temperature of the pyrolyzer (pyrolyzer). From FIG. 1, it can be seen that polyethylene is thermally decomposed from around 400 to 550 ° C with the pyrolyzer temperature peaking at about 480 ° C. The decomposition temperature of the polyethylene particles was determined by thermogravimetric-differential thermal analysis (TG-DTA) and found to be about 450 ° C. From this, it can be said that the peak in FIG. 1 is caused by the decomposition product of polyethylene. Therefore, as a result of analyzing the MS spectrum at the peak position in FIG. 1, the thermal decomposition product (fragment) of polyethylene has a mass-to-charge ratio m / z derived from 3 to 7 carbon chains (where m is a unified atom). It was found that the relative mass of the ion expressed as a ratio to the mass unit, z indicates the number of charges of the ion) is mainly molecular ions of 41, 55, 69, 83, 97 and 111. Next, the temperature-MS profile for each fragment of m / z = 41, 55, 69, 83, 97 and 111 was examined. The results are shown in FIG.

The peak intensity (peak height) of each fragment in FIG. 2 was determined, and the standardized intensity was determined by standardizing with a peak intensity of m / z = 41. Further, the aqueous dispersion of polyethylene was weighed so that the polyethylene equivalent was 0.04 mg and 0.08 mg, and the temperature-total MS profile of these samples was also measured by GC / MS in the same manner for each fragment. The normalized strength was determined from the temperature-MS profile of. The results are shown in Table 1.

The normalized strength with respect to m / z = 41 was almost constant in all the samples. Therefore, it was found that if the heating process is the same, the composition ratio of the fragments generated by the thermal decomposition of polyethylene is constant, and the thermal decomposition behavior with good reproducibility is exhibited.

From the above, the GC / MS spectrum can be measured in a temperature range including the thermal decomposition temperature of polyethylene, and a polyethylene calibration curve can be prepared from the temperature-MS profile of any one or more of each fragment. Therefore, the content of the organic component can be quantified based on the obtained calibration curve.

For example, FIG. 3 is a calibration curve of polyethylene prepared from a temperature-MS profile of m / z = 41, which is one of the decomposition products of polyethylene. The polyethylene contained in the test sample is extracted on a filter, and the filter is heated and decomposed with the same heat pattern as this calibration curve, and the GC / MS spectrum is measured to measure the temperature of the fragment of m / z = 41-MS. Measure the peak intensity (peak height) of the profile. By reading the horizontal axis of FIG. 3 corresponding to this peak intensity, the amount of polyethylene contained in this test sample can be quantified. The m / z of the fragment used for quantification is preferably low if there is no interfering peak because the detection sensitivity is high. When the organic component is polyethylene, the peak intensity (peak height or integrated intensity) of the temperature-MS profile of m / z = 41 derived from the number of carbon chains 3 or m / z = 55 derived from the number of carbon chains 4 is determined. It is preferable to use it.

From the above, according to the analysis method of the present invention, it is possible to quantify the amount of the organic component present in the film in the metal material having the organic-inorganic composite film with high accuracy.

Further, a metal material having an organic-inorganic composite film can also be produced by using the analysis method of the present invention. For example, when an organic-inorganic composite film is formed on the surface of a metal material, the organic components in the film after film formation are analyzed by the analysis method of the present invention, and the content of the organic components in the film is within a predetermined range. , It should be judged as good and shipped. That is, the characteristic values of the metal material (mechanical characteristics, film characteristics, etc.) and the threshold value of the content of the organic component (predetermined range of the content of the organic component) are examined in advance, and the content of the organic component is within the predetermined range. If it meets the requirements, it can be shipped as good. For example, when the organic component is polyethylene, it is known that if the content of polyethylene in the film is 30 mg / m ² or more, the sliding characteristics are excellent. Therefore, when the content of polyethylene in the film is 30 mg / m ² or more, the sliding characteristics may be good (passed) and the product may be shipped. As described above, by feeding back the content of the organic component obtained by the analysis method of the present invention to the production method, a metal material having desired properties can be obtained.

Hereinafter, the effects of the present invention will be described with reference to Examples. However, the effect of the present invention is not limited to this example.
(Invention Examples 1 to 3)
Polyethylene having an average particle size of 500 nm (manufactured by Mitsui Chemicals, Inc .: Chemipearl W4005) was charged in an amount of 10 mg / m ² (Invention Example 1), 50 mg / m ² (Invention Example 2), and 250 mg / m ² (Invention Example 3). An organic-inorganic composite film was formed on one side by contacting an acidic solution of zinc sulfate heptahydrate containing zinc sulfate with an electrogalvanized steel sheet. The decomposition temperature of the polyethylene particles (in a nitrogen atmosphere) was determined by thermogravimetric differential thermal analysis and found to be about 450 ° C.

Each sample was cut into a size of 30 mm square and immersed in an acidic solution containing 3.5 g / l of hexamethylenetetramine as an inhibitor in 30 ml of an aqueous solution of hydrochloric acid (1 + 1), and contained in a zinc plating layer and an organic-inorganic composite film. Inorganic components were dissolved. The aqueous hydrochloric acid solution containing the polyethylene particles in the organic-inorganic composite film was suction-filtered using a glass filter having a pore size of 300 nm, and all the polyethylene particles in the film were recovered in the glass filter.

Further, as a sample for the analytical calibration curve, the chemipearl W4005 stock solution, which is an aqueous dispersion of polyethylene, was weighed so that the polyethylene equivalent was 0.04 mg, 0.08 mg, and 0.16 mg, and the pore size was 300 nm, which was the same as the actual measurement. It was collected in a glass filter and dried.

For the analysis of the content of polyethylene particles, a gas chromatograph mass spectrometer (6890N manufactured by Agilent) equipped with a pyrolyzer (multi-spot pyrolizer manufactured by FRONTIER LAB) was used in the gas introduction section. The glass filter was introduced into a pyrolyzer maintained at 50 ° C., and the temperature was raised from 50 ° C. to 650 ° C. at a rate of 10 ° C./min to thermally decompose polyethylene. The generated decomposition gas was introduced into a gas chromatograph mass spectrometer having a column temperature of 300 ° C. together with helium (carrier gas) having a flow rate of 1 ml / min, and the temperature-total MS profile was measured. Next, a temperature-MS profile with m / z = 41 was determined.

Similarly, for the sample for the calibration curve, the temperature-MS profile of m / z = 41 was obtained, and the calibration curve shown in FIG. 3 was prepared. The content of polyethylene particles in the organic-inorganic composite film on the galvanized steel sheet was quantified using the calibration curve shown in FIG.
(Comparative Examples 1 to 3)
As a comparative example, each sample of Invention Examples 1 to 3 was separately cut into a size of 15 mm square, polyethylene in the film was observed using SEM (LEO1530 manufactured by Carl Zeiss), and the content was calculated. The observation conditions were an acceleration voltage of 3 kV, an operating distance (distance between the objective lens and the sample): 8.5 mm, and a magnification of Polaroid (registered trademark) photograph of 5000 times, and 5 randomly selected visual fields were observed. The number of polyethylene particles in one field of view and the particle size (major axis) are visually counted to obtain the total volume of polyethylene, which is multiplied by the density of polyethylene and converted into the amount of polyethylene adhered (weight per unit area) in the observation field of view. Then, the average value of the five fields of view was calculated.

Table 2 shows the results of the polyethylene particle content determined by the analysis method of the present invention and the polyethylene particle content determined by SEM as a comparative example.

The content of the polyethylene particles determined by the analysis method of the present invention was almost the same as the charged amount. On the other hand, the content of polyethylene particles determined by SEM was less than the charged amount, except for the charged amount of ^{50 mg / m 2.} When the amount charged is 10 mg / m ² , in the comparative example, the influence of the uneven distribution of the polyethylene particles is large, and it is considered necessary to increase the number of observation fields (n) by n, which requires enormous labor. In addition, when the charge amount was 250 mg / m ² , only the polyethylene particles existing on the outermost surface could be measured in the comparative example, so that the evaluation was underestimated due to the presence of uneven distribution of polyethylene particles overlapping in the thickness direction. Conceivable.
(Invention Examples 4 and 5)
Polytetrafluoroethylene (PTFE, manufactured by Okuno Pharmaceutical Co., Ltd .: Top Disper NTF, decomposition temperature: 350 ° C.) with an average particle size of 200 nm is charged on an electrogalvanized steel sheet with a thickness of 0.8 mm at a charge rate of 40 mg / m. ² (Invention Example 4) and 110 mg / m ² (Invention Example 5) are contained so that an acidic solution of zinc sulfate / heptahydrate is brought into contact with an electrogalvanized steel sheet to form an organic-inorganic composite film on one side. The film was formed on.

Each sample was cut into a size of 30 mm square and immersed in an acidic solution containing 3.5 g / l of hexamethylenetetramine as an inhibitor in 30 ml of an aqueous hydrochloric acid (1 + 1) solution to dissolve the galvanized layer. The aqueous hydrochloric acid solution containing PTFE in the organic-inorganic composite film was suction-filtered using a polycarbonate membrane filter having a pore size of 100 nm, and all the PTFE in the film was recovered in the membrane filter.

Further, as a sample for an analytical calibration curve, a stock solution in which PTFE having a particle size of 200 nm was suspended was weighed so that the PTFE equivalent was 0.05 mg, 0.25 mg, or 0.50 mg, and the pore size was the same as that of the actual measurement. It was collected on a 100 nm membrane filter and dried.

A gas chromatograph mass spectrometer (6890N manufactured by Agilent) equipped with a pyrolyzer (multi-spot pyrolizer manufactured by FRONTIER LAB) was used for the analysis of the content of PTFE. PTFE was introduced together with the membrane filter into a pyrolyzer maintained at 300 ° C., and the temperature was raised from 200 ° C. to 600 ° C. at a rate of 10 ° C./min to thermally decompose the PTFE. The generated decomposition gas was introduced into a gas chromatograph mass spectrometer having a column temperature of 300 ° C. together with helium (carrier gas) having a flow rate of 1 ml / min, and the temperature-total MS profile was measured. Next, a temperature-MS profile of m / z = 100, which is a monomer of PTFE, was determined. Similarly, for the sample for the calibration curve, the temperature-MS profile of m / z = 100 was obtained, and the calibration curve shown in FIG. 4 was prepared.

The content of PTFE in the organic-inorganic composite film on the galvanized steel sheet was quantified using the calibration curve shown in FIG. ^{As a result, 38 mg / m 2} and 107 ^{mg / m 2} were obtained as the content of PTFE for each sample having the charged amounts of 40 mg / m ² and 110 mg / m ^{2 of PTFE, respectively.}

Claims (11)

A method for analyzing organic components in a metal material having an organic-inorganic composite film.
A dissolution step of dissolving the metal material with an acidic solution,
An extraction step of filtering an acidic solution in which the metal material is dissolved to extract organic components in the film, and
An analysis process for analyzing the extracted organic components and
Equipped with a,
In the analysis step, a method for analyzing an organic component in a film of a metal material having an organic-inorganic composite film for analyzing the extracted organic component using a mass spectrometry method. The organic-inorganic composite according to claim 1, further comprising a heating vaporization step of heating the organic components extracted in the extraction step to decompose and gasify them, and analyzing the decomposition gas obtained by the heating vaporization step in the analysis step. A method for analyzing an organic component in a film in a metal material having a film. In the heating vaporization step, when the decomposition temperature of the organic component is T (° C.), the heating start temperature is (T-100) ° C. or 30 ° C., whichever is higher or lower.
The method for analyzing an organic component in a film of a metal material having an organic-inorganic composite film according to claim 2 , wherein the heating end temperature is (T + 150) ° C. or higher. The method for analyzing an organic component in a metal material having an organic-inorganic composite film according to claim 2 or 3 , wherein the heating rate is 5 to 30 ° C./min in the heat vaporization step. In the analysis step, analysis of an organic component in a metal material having an organic-inorganic composite film according to any one of claims 2 to 4 for analyzing the decomposed gas using a gas chromatography-mass spectrometry method. Method. The method for analyzing an organic component in a metal material having an organic-inorganic composite film according to any one of claims 1 to 5 , wherein the acidic solution is filtered by suction filtration in the extraction step. The method for analyzing an organic component in a metal material having an organic-inorganic composite film according to any one of claims 1 to 6 , which is filtered using an inorganic glass filter in the extraction step. The method for analyzing an organic component in a metal material having an organic-inorganic composite film according to any one of claims 1 to 7 , wherein a corrosion inhibitor is added to the acidic solution in the dissolution step. The method for analyzing an organic component in a metal material having an organic-inorganic composite film according to any one of claims 1 to 8 , wherein the organic component is a polymer compound. The method for analyzing an organic component in a metal material having an organic-inorganic composite film according to any one of claims 1 to 9 , wherein the metal material is a steel sheet or a plated steel sheet. A method for producing a metal material having an organic-inorganic composite film, wherein an organic-inorganic composite film is formed on the surface of the metal material, and then the organic component in the film after the film is formed is any one of claims 1 to 10. A method for producing a metal material having an organic-inorganic composite film, which is analyzed by the method for analyzing an organic component in a film according to the above, and when the content of the organic component in the film is within a predetermined range, it is judged to be good and shipped. ..

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