WO2016093179A1 - Method for evaluating fluororesin paint or fluororesin coating film, evaluation-information calculation device, evaluation-information presentation system, and terminal device - Google Patents

Method for evaluating fluororesin paint or fluororesin coating film, evaluation-information calculation device, evaluation-information presentation system, and terminal device Download PDF

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Publication number
WO2016093179A1
WO2016093179A1 PCT/JP2015/084208 JP2015084208W WO2016093179A1 WO 2016093179 A1 WO2016093179 A1 WO 2016093179A1 JP 2015084208 W JP2015084208 W JP 2015084208W WO 2016093179 A1 WO2016093179 A1 WO 2016093179A1
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WIPO (PCT)
Prior art keywords
sample
fluororesin
measurement data
peak
coating film
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PCT/JP2015/084208
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French (fr)
Japanese (ja)
Inventor
陽司 中島
直文 大島
佐藤　秀一
雄介 菅原
一裕 新田
豪明 荒井
潔 笠原
俊 齋藤
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旭硝子株式会社
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Publication of WO2016093179A1 publication Critical patent/WO2016093179A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/86—Signal analysis
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/44—Resins; Plastics; Rubber; Leather

Definitions

  • the present invention relates to a fluororesin paint or fluororesin coating film evaluation method, an evaluation information calculation device, an evaluation information presentation system, and a terminal device.
  • fluororesin coating films are superior in weather resistance compared to other resin coating films. For this reason, a fluororesin paint is sometimes used as a paint for road bridges.
  • the fluororesin paint and the fluororesin coating film differ in the weather resistance obtained depending on the composition. Therefore, not all fluororesin paints are suitable as road bridge paints.
  • the component of the fluororesin coating film is a pyrolysis gas chromatography method (hereinafter also referred to as pyrolysis GC method, GC is an abbreviation for Gas Chromatography) or pyrolysis gas chromatography mass spectrometry (hereinafter pyrolysis GC / MS). MS is an abbreviation for Mass Spectrometry).
  • pyrolysis GC method a pyrolysis gas chromatography method
  • MS pyrolysis gas chromatography mass spectrometry
  • MS mass Spectrometry
  • Patent Document 1 discloses a method of identifying a thermal decomposition product of a sample polymer using a database that stores a retention index related to a known polymer.
  • the retention index obtained by pyrolysis gas chromatography or pyrolysis gas chromatography mass spectrometry does not necessarily match the retention index recorded in the database.
  • the identification support system disclosed in Patent Document 1 supports the identification of a sample polymer by calculating the degree of match between the sample polymer and the known polymer. Therefore, when a degree of matching that can be confident that the fluororesin paint or fluororesin coating film is a known paint or coating film is not obtained, depending on the method disclosed in Patent Document 1, the fluororesin paint or fluorine It is not possible to evaluate whether a resin coating is suitable as a paint or coating for road bridges.
  • the object of the present invention is to determine whether or not the fluororesin paint or the fluororesin paint film is suitable as a road bridge paint or paint film even when it is difficult to identify the fluororesin paint or the fluororesin paint film.
  • An evaluation method, an evaluation information calculation device, an evaluation information presentation system, and a terminal device that can be evaluated are provided.
  • a 1st aspect acquires the measurement data by the pyrolysis gas chromatography method or pyrolysis gas chromatography mass spectrometry of the sample which is the fluororesin coating material applied to a road bridge, or the fluororesin coating film provided in the road bridge
  • the data relating to the peak of the thermal decomposition product derived from the structural unit based on at least one of vinyl ester and vinyl ether recorded in the storage device and the measurement data, vinyl ester and vinyl ether are added to the sample.
  • a specific monomer estimation step for estimating at least one of the presence and amount of a structural unit based on at least one of the above, and data relating to a peak of a thermal decomposition product derived from a structural unit based on a monomer having a fluorine atom recorded in a storage device; Based on the measurement data, fluorine of the sample Fluorine resin paint or fluororesin coating film evaluation method, comprising: fluorine atom content estimation step for estimating the content of the monomer; and evaluation step for evaluating the sample based on the estimation result of the specific monomer estimation step and the fluorine atom content It is.
  • the second aspect is the spectral data obtained by spectroscopically analyzing the light absorbed or emitted by the known fluororesin paint or the known fluororesin coating film recorded in the storage device in the first aspect or Measurement data of fluororesin paint or known fluororesin coating film by pyrolysis gas chromatography or pyrolysis gas chromatography mass spectrometry, spectral data obtained by spectroscopic analysis of light absorbed or emitted by the sample, or acquisition of measurement data
  • a similarity specifying step for specifying a similarity with the measurement data acquired in the step, and in the evaluation step, an estimation result of the specific monomer estimation step, a specification result of the similarity specification step, and a fluorine atom content Evaluation method of fluororesin paint or fluororesin coating film to evaluate the sample based on It is.
  • the third aspect further includes a similar paint specifying step for specifying the known fluororesin paint or the known fluororesin coating film having the highest degree of similarity specified in the similarity specifying step in the second aspect. And having the estimation result of the specific monomer estimation step and the fluorine atom content in the evaluation step, the known fluororesin paint specified by the similar paint specification step or the vinyl ester and vinyl ether of the known fluororesin coating film.
  • a fluororesin paint or a fluororesin coating film evaluation method for evaluating the sample by comparing the presence / absence and / or amount of a structural unit based on at least one of the above and the fluorine atom content.
  • a fourth aspect is any one of the first to third aspects, wherein the measurement data is measurement data obtained by pyrolysis gas chromatography mass spectrometry of the sample, and the data relating to the peak includes a peak.
  • This is a method for evaluating a fluororesin paint or a fluororesin coating film including a physical quantity related to the mass of the pyrolysis product to be produced and a threshold of peak intensity.
  • a fifth aspect is any one of the first to third aspects, wherein the measurement data is measurement data obtained by pyrolysis gas chromatography of the sample, and the data related to the peak is heat that causes a peak.
  • This is a method for evaluating a fluororesin paint or a fluororesin coating film including the time at which a decomposition product is detected and a threshold of peak intensity.
  • a sixth aspect is a peak of a thermal decomposition product derived from a structural unit based on a monomer having the fluorine atom in the measurement data in the fluorine atom content estimation step. This is a method for evaluating a fluororesin coating material or a fluororesin coating film, which estimates the fluorine atom content of the sample based on an intensity threshold.
  • a seventh aspect is the fluororesin paint or fluororesin coating according to any one of the first to sixth aspects, wherein the fluorine atom-containing monomer is at least one of tetrafluoroethylene and chlorotrifluoroethylene. This is a film evaluation method.
  • the eighth aspect is the measurement data obtained by pyrolysis gas chromatography or pyrolysis gas chromatography mass spectrometry of a sample that is a fluororesin paint applied to a road bridge or a fluororesin coating film provided on a road bridge.
  • Measurement data acquisition unit to acquire, specific monomer peak storage device that stores data related to the peak of thermal decomposition products derived from structural units based on at least one of vinyl ester and vinyl ether, and derived from structural units based on monomers having fluorine atoms
  • a fluorine peak storage device for storing data relating to the peak of the thermal decomposition product of the product, and a peak of the thermal decomposition product derived from a structural unit based on at least one of vinyl ester and vinyl ether recorded in the specific monomer peak storage device Based on the data and the measurement data, A specific monomer estimator for estimating at least one of the presence and amount of a structural unit based on at least one of nyl ester and vinyl ether, and a thermal decomposition product derived from the structural unit based on a monomer having a fluorine atom recorded in the fluorine peak storage device
  • the evaluation information calculation device includes a fluorine atom content estimation unit that estimates the fluorine atom content of the sample based
  • a ninth aspect is the recording section according to the eighth aspect, wherein the specific monomer peak storage device records new data relating to a peak of a thermal decomposition product derived from a structural unit based on at least one of vinyl ester and vinyl ether. It is the information calculation device for evaluation further provided with.
  • a tenth aspect includes the evaluation information calculation device according to the eighth or ninth aspect and a terminal device, and the terminal device is configured to measure the sample by pyrolysis gas chromatography or pyrolysis gas chromatography mass spectrometry.
  • a measurement data generation unit that generates measurement data, a transmission unit that transmits the measurement data to the evaluation information calculation device, and a structural unit based on at least one of vinyl ester and vinyl ether from the evaluation information calculation device
  • a receiving unit that receives information on the estimation result of at least one of the presence / absence and amount and the fluorine atom content, and a presentation unit that presents information used for evaluation of the sample based on the information received by the receiving unit It is the information presentation system for evaluation with which it is provided.
  • An eleventh aspect includes a measurement data generation unit that generates measurement data of a sample that is a fluororesin paint or a fluororesin coating film by pyrolysis gas chromatography or pyrolysis gas chromatography mass spectrometry, and the measurement data From the transmitter for transmitting to the evaluation information calculation device and the evaluation information calculation device according to the eighth or ninth aspect, at least one of the presence and the amount of the structural unit based on at least one of vinyl ester and vinyl ether in the sample.
  • the terminal device includes a receiving unit that receives information on an estimation result and a fluorine atom content, and a presentation unit that presents information used for evaluating the sample based on the information received by the receiving unit.
  • a twelfth aspect includes a measurement data generation step for generating measurement data of a sample that is a fluororesin paint or a fluororesin coating film by pyrolysis gas chromatography or pyrolysis gas chromatography mass spectrometry, and the measurement data From the transmitting step for transmitting to the evaluation information calculation device, and from the evaluation information calculation device of the eighth or ninth aspect, at least one of the presence and amount and the amount of the structural unit based on at least one of vinyl ester and vinyl ether in the sample
  • An evaluation method for a fluororesin paint or a fluororesin coating film comprising: a reception step for receiving information on an estimation result and a fluorine atom content; and an evaluation step for evaluating the sample based on the received information.
  • the fluororesin paint or the fluororesin paint film is suitable as a road bridge paint or paint film even when it is difficult to identify the fluororesin paint or the fluororesin paint film. It can be evaluated whether or not.
  • FIG. 1 is a schematic diagram illustrating a configuration of an evaluation information presentation system 1 according to the first embodiment.
  • the information presentation system for evaluation 1 is a sample S that is a fluororesin paint applied to a road bridge or a fluororesin coating film provided on the road bridge based on Raman spectroscopy and pyrolysis GC / MS method. Provides information used to evaluate Specifically, the information presentation system for evaluation 1 is similar to a known fluororesin paint or fluororesin coating film and the sample S, vinyl ester, vinyl ether, tetrafluoroethylene (hereinafter also referred to as TFE) of the sample S. And the presence or absence of chlorotrifluoroethylene (hereinafter also referred to as CTFE), and the content of vinyl ester, vinyl ether, TFE, CTFE, and fluorine atoms in Sample S.
  • TFE tetrafluoroethylene
  • the evaluation information presentation system 1 includes a terminal device 10 and an evaluation information calculation device 20.
  • the terminal device 10 and the evaluation information calculation device 20 are connected via a network N.
  • An example of the network N is the Internet.
  • the terminal device 10 performs an analysis process related to the Raman spectroscopy and an analysis process related to the pyrolysis GC / MS method on the sample S. Further, the terminal device 10 displays information used for the evaluation of the sample S generated by the evaluation information calculation device 20.
  • the evaluator E who evaluates the sample S evaluates whether or not the sample S is appropriate as a paint or a coating film for a road bridge based on the information displayed on the terminal device 10.
  • the terminal device 10 Since the evaluator E evaluates the sample S collected at the site where the fluororesin paint is used, the terminal device 10 is preferably portable.
  • the evaluation information calculation device 20 calculates information used for the evaluation of the sample S based on the measurement data generated by the terminal device 10.
  • FIG. 2 is a schematic diagram illustrating a configuration of the terminal device 10 according to the first embodiment.
  • the terminal device 10 includes a storage space 101, a Raman spectroscopic device 102, a pyrolysis GC / MS device 103, a calculation device 104, a communication device 105, and a display device 106.
  • the storage space 101 is a space for storing the sample S.
  • the Raman spectroscopic device 102 measures scattered light of the sample S due to Raman scattering.
  • the Raman spectroscopic device 102 passes through a laser device 121 that irradiates a sample S accommodated in the accommodation space 101 with laser light, a filter 122 that allows light scattered by Raman scattering out of light scattered by the sample S of the laser light, and a filter 122.
  • a detector 124 for detecting the intensity of the light dispersed by the monochromator 123.
  • the Raman spectroscopic device 102 is an example of a measurement data generation unit.
  • the filter 122 May cut scattered light due to Rayleigh scattering.
  • the pyrolysis GC / MS apparatus 103 generates a mass chromatogram of the sample S.
  • the pyrolysis GC / MS device 103 includes a pyrolysis device 131, a gas chromatograph 132, and a mass spectrometer 133.
  • the thermal decomposition apparatus 131 thermally decomposes the sample S by heating the sample S accommodated in the accommodation space 101.
  • the gas chromatograph 132 separates the thermal decomposition product of the sample S.
  • the mass spectrometer 133 ionizes the thermal decomposition product eluted from the gas chromatograph 132 and measures the peak intensity for each m / z value.
  • the m / z value is an example of a physical quantity related to mass.
  • the pyrolysis GC / MS device 103 is an example of a measurement data generation unit.
  • the computing device 104 generates measurement data based on the measurement results of the Raman spectroscopic device 102 and the pyrolysis GC / MS device 103.
  • the communication device 105 transmits the measurement data generated by the arithmetic device 104 to the evaluation information calculation device 20 via the network N. Further, the communication device 105 receives the evaluation information from the evaluation information calculation device 20 via the network N.
  • the communication device 105 is an example of a transmission unit and a reception unit.
  • the display device 106 displays the evaluation information received by the communication device 105.
  • the display device 106 is an example of a presentation unit.
  • FIG. 3 is a schematic diagram illustrating a configuration of the evaluation information calculation apparatus 20 according to the first embodiment.
  • the evaluation information calculation apparatus 20 includes a measurement data acquisition unit 201, a database 202, a recording unit 203, an identification unit 204, an ester estimation unit 205, an ether estimation unit 206, a fluoroolefin estimation unit 207, and an evaluation information output unit 208.
  • the measurement data acquisition unit 201 acquires measurement data of the sample S measured by the Raman spectroscopy method and pyrolysis GC / MS method measured by the terminal device 10 via the network N.
  • the database 202 stores a paint table 221, an ester peak table 222, an ether peak table 223, and a fluorine peak table 224.
  • the paint table 221 includes Raman spectra data of known fluororesin paints and fluororesin paint films that are recognized as being suitable as road bridge paints or paint films, the presence or absence of vinyl esters, vinyl ethers, TFE and CTFE, vinyl esters, Stores the content of vinyl ether, TFE, CTFE and fluorine atoms and the weather resistance rank.
  • the ester peak table 222 stores data relating to peaks of thermal decomposition products derived from structural units based on vinyl esters.
  • the database 202 is an example of an ester peak storage device that stores data relating to the peak of the thermal decomposition product derived from the structural unit based on the vinyl ester.
  • the ether peak table 223 stores data relating to peaks of thermal decomposition products derived from structural units based on vinyl ether. That is, the database 202 is an example of an ether peak storage device that stores data related to the peak of the thermal decomposition product derived from the structural unit based on vinyl ether.
  • the ester peak table 222 and the ether peak table 223 are both examples of specific monomer peak storage devices.
  • the fluorine peak table 224 stores data relating to the peak of the thermal decomposition product derived from the structural unit based on the fluoroolefin (monomer having a fluorine atom). That is, the database 202 is an example of a fluorine peak storage device that stores data relating to the peak of the thermal decomposition product derived from the structural unit based on the monomer having a fluorine atom. In the present embodiment, the data relating to the peak of the thermal decomposition product is data in which the m / z value of the thermal decomposition product is associated with the threshold value of the peak intensity.
  • the database 202 is an example of a storage device.
  • the peak intensity threshold is a threshold for determining whether or not a peak exists in the mass chromatogram by comparing with the intensity appearing in the mass chromatogram.
  • the peak intensity threshold is represented by a ratio with respect to a reference peak, for example.
  • the recording unit 203 includes a Raman spectrum data of a fluororesin paint or a fluororesin coating newly recognized as being suitable as a paint or a coating on a road bridge, presence / absence of vinyl ester, vinyl ether, TFE and CTFE, vinyl ester, vinyl ether. , TFE, CTFE, fluorine atom content, and weather resistance rank are received, and the data is recorded in the paint table 221.
  • the recording unit 203 receives input of new data related to the peak of the thermal decomposition product derived from the structural unit based on the vinyl ester, and records the data in the ester peak table 222.
  • the recording unit 203 receives input of new data related to the peak of the thermal decomposition product derived from the structural unit based on vinyl ether, and records the data in the ether peak table 223.
  • the identification unit 204 compares the measurement data of the sample S obtained by the Raman spectroscopy obtained by the measurement data acquisition unit 201 with the Raman spectrum data stored in the paint table 221, and the sample S is a known fluororesin paint or fluororesin coating. It is determined whether or not it is a film.
  • the ester estimation unit 205 uses the measurement data of the sample S obtained by the pyrolysis GC / MS method acquired by the measurement data acquisition unit 201 and the peak of the pyrolysis product derived from the structural unit based on the vinyl ester stored in the ester peak table 222. It is compared with such data, and it is determined whether or not the sample S contains a structural unit based on vinyl ester.
  • the ester estimation unit 205 estimates the content of the structural unit based on the vinyl ester in the sample S.
  • the ether estimation unit 206 relates to the measurement data of the sample S by the pyrolysis GC / MS method acquired by the measurement data acquisition unit 201 and the peak of the pyrolysis product derived from the structural unit based on vinyl ether stored in the ether peak table 223. The data is compared to determine whether or not the sample S contains a structural unit based on vinyl ether.
  • the ether estimation unit 206 estimates the content of the structural unit based on vinyl ether in the sample S. That is, the ester estimation unit 205 and the ether estimation unit 206 are both examples of the specific monomer estimation unit.
  • the fluoroolefin estimation unit 207 uses the measurement data of the sample S obtained by the pyrolysis GC / MS method acquired by the measurement data acquisition unit 201 and the peak of the pyrolysis product derived from the structural unit based on TFE stored in the fluorine peak table 224. This data is compared with the data, and it is determined whether or not the sample S includes a structural unit based on TFE. In addition, the fluoroolefin estimation unit 207 estimates the content of the structural unit based on TFE in the sample S.
  • the fluoroolefin estimation unit 207 includes the measurement data of the sample S obtained by the pyrolysis GC / MS method acquired by the measurement data acquisition unit 201 and the pyrolysis product derived from the structural unit based on CTFE stored in the fluorine peak table 224. It is compared with the data concerning the peak, and it is determined whether or not the sample S includes a structural unit based on CTFE. In addition, the fluoroolefin estimation unit 207 estimates the content of the structural unit based on CTFE in the sample S.
  • the fluoroolefin estimation unit 207 uses the measurement data of the sample S obtained by the pyrolysis GC / MS method acquired by the measurement data acquisition unit 201 and the data related to the peak of the pyrolysis product derived from the structural unit based on TFE and CTFE. Based on this, the fluorine atom content of sample S is estimated.
  • the evaluation information output unit 208 transmits the calculation results of the identification unit 204, ester estimation unit 205, ether estimation unit 206, and fluoroolefin estimation unit 207 to the terminal device 10 via the network N.
  • FIG. 4 is a flowchart showing the operation of the terminal device 10 according to the first embodiment.
  • 5, 6 and 7 are flowcharts showing the operation of the evaluation information calculation apparatus 20 according to the first embodiment.
  • the evaluator E goes to the site where the fluororesin paint is used with the terminal device 10 and collects a sample S that is a fluororesin paint or a fluororesin coating film.
  • the evaluator E stores the collected sample S in the storage space 101 of the terminal device 10.
  • the evaluator E activates the terminal device 10 when the sample S is accommodated in the accommodation space 101.
  • the laser device 121 irradiates the sample S accommodated in the accommodation space 101 with laser light (step S101 in FIG. 4). At this time, as the sample S accommodated in the accommodating space 101, the accuracy of the obtained spectrum data is improved by using the sample S from which at least one of the solvent, the pigment, and other additives has been previously removed by the component separation process. Can be made.
  • the terminal device 10 may generate spectrum data for both the sample S from which the additive has been removed and the sample S from which the additive has not been removed. When the sample S is irradiated with laser light, a plurality of types of scattered light are generated from the sample S.
  • the sample S is irradiated with laser light to generate scattered light due to Rayleigh scattering, scattered light due to Raman scattering, and other scattered light.
  • the scattered light enters the monochromator 123 through the filter 122.
  • the filter 122 passes the scattered light due to the Raman scattering among the scattered light, the scattered light due to the Raman scattering is incident on the monochromator 123.
  • the light incident on the monochromator 123 is split for each wavelength. The split light enters the detector.
  • the detector 124 detects the intensity of the light incident from the monochromator 123, and generates spectral data indicating the relationship between the wavelength and the light intensity (step S102).
  • the arithmetic device 104 acquires spectrum data that is measurement data from the detector 124, and transmits the spectrum data to the evaluation information calculation device 20 via the communication device 105 (step S103).
  • the measurement data acquisition unit 201 of the evaluation information calculation device 20 receives the spectrum data (step S201 in FIG. 5).
  • the identifying unit 204 calculates the similarity between the received spectrum data and each of the plurality of spectrum data recorded in the paint table 221 (step S202).
  • the similarity of spectrum data can be obtained, for example, by a peak position difference and a peak intensity ratio.
  • the identification unit 204 refers to the paint table 221 and identifies a known paint or paint film having the highest degree of similarity in spectrum data (step S204).
  • the identification unit 204 determines whether or not the similarity of the spectrum data with the specified known paint or coating film is within a predetermined doubt range (step S204).
  • the doubt range is a range of values that are equal to or less than the maximum value of similarity and greater than a threshold value that determines that the sample S does not match any known paint or coating film.
  • the doubt range is a range of similarity in which the sample S may match a known paint or coating film.
  • the evaluation information output unit 208 determines the highest similarity among the spectrum data. The higher one is transmitted to the terminal device 10 (step S205).
  • the evaluation information output unit 208 determines the similarity of the spectrum data. The highest one of them and an instruction to acquire the chromatogram of the sample S are transmitted to the terminal device 10 (step S206).
  • the communication device 105 of the terminal device 10 receives the similarity (step S104 in FIG. 4).
  • the arithmetic device 104 displays the similarity received by the communication device 105 on the display device 106 (step S105).
  • the evaluator E evaluates based on the similarity displayed on the display device 106 whether or not the sample S is appropriate as a paint or coating film for a road bridge. Specifically, the evaluator E, when the similarity is out of the doubt range (below the threshold value), does not use any of the known paints and coatings for which the sample S is recognized as being suitable as a road bridge paint or coating.
  • the evaluator E suspends the evaluation of whether or not the sample S is suitable as a paint or coating film for a road bridge.
  • the arithmetic device 104 determines whether or not the communication device 105 has received an instruction to acquire chromatograms of the standard agent and the sample S together with the similarity of the spectrum data (step S106).
  • the standard agent for example, substances containing structural units based on TFE, CTFE, specific vinyl ester, and specific vinyl ether, and the contents of which are known, and known compounds such as specific monomers can be used. If the arithmetic unit 104 determines that an instruction to acquire chromatograms of the standard agent and the sample S has not been received (step S106: NO), the processing ends. This is because the similarity is not within the suspicion range, and the evaluator E can evaluate whether or not the sample S is appropriate as a paint or a coating on the road bridge only by displaying the similarity.
  • step S106 determines that the instruction to acquire the chromatogram of the standard agent and the sample S has been received (step S106: YES)
  • the thermal decomposition apparatus 131 is activated and the standard agent accommodated in the accommodating space 101 is removed.
  • Heat step S107).
  • the standard agent is thermally decomposed by heating and introduced into the gas chromatograph 132.
  • the gas chromatograph 132 separates the thermal decomposition products of the standard agent.
  • the mass spectrometer 133 ionizes the thermal decomposition product eluted from the gas chromatograph 132 and measures the peak intensity for each m / z value.
  • the mass spectrometer 133 produces
  • the arithmetic unit 104 acquires a mass chromatogram that is measurement data from the mass spectrometer 133 and transmits the mass chromatogram to the evaluation information calculation unit 20 via the communication unit 105 (step S109).
  • the evaluator E takes out the standard agent from the storage space 101 and puts the sample S into the storage space 101.
  • the arithmetic unit 104 activates the thermal decomposition apparatus 131 and heats the sample S stored in the storage space 101 (step S110).
  • the accuracy of the obtained chromatogram is improved by using the sample S from which at least one of the solvent, the pigment, and other additives has been previously removed by the component separation process.
  • the terminal device 10 may generate chromatograms for both the sample S from which the additive has been removed and the sample S from which the additive has not been removed.
  • the sample S is thermally decomposed by heating and introduced into the gas chromatograph 132.
  • the gas chromatograph 132 separates the thermal decomposition product of the sample S.
  • the mass spectrometer 133 ionizes the thermal decomposition product eluted from the gas chromatograph 132 and measures the peak intensity for each m / z value. Thereby, the mass spectrometer 133 produces
  • the m / z range to be measured by the mass spectrometer 133 is, for example, in the range of 10 to 1000.
  • the arithmetic unit 104 acquires a mass chromatogram that is measurement data from the mass spectrometer 133, and transmits the mass chromatogram to the evaluation information calculation unit 20 via the communication unit 105 (step S112).
  • the measurement data acquisition unit 201 of the evaluation information calculation device 20 receives the mass chromatogram (step S207 in FIG. 5).
  • the fluoroolefin estimation unit 207 specifies the m / z value and peak intensity threshold of the specific compound from the fluorine peak table 224.
  • the fluoroolefin estimating unit 207 specifies the peak intensity of the mass chromatogram of the standard agent associated with the m / z value at which the specific compound appears (step S208). That is, the fluoroolefin estimation unit 207 specifies the intensity of a specific peak (for example, a peak related to TFE and CTFE) in the standard agent.
  • the fluoroolefin estimation unit 207 creates a calibration curve of the peak position and peak intensity of the specific compound (step S209). That is, the fluoroolefin estimation unit 207 derives a sensitivity correction coefficient for correcting the detection sensitivity for each analysis of the pyrolysis GC / MS apparatus 103.
  • the measurement data acquisition unit 201 corrects the mass chromatogram by multiplying the peak intensity of the acquired mass chromatogram of the sample S by the sensitivity correction coefficient derived by the fluoroolefin estimation unit 207.
  • the ester estimation unit 205 specifies the m / z value (peak position) and the peak intensity threshold value for each thermal decomposition product derived from the vinyl ester-based structural unit from the ester peak table 222 (FIG. 6). Step S210).
  • the ester estimation unit 205 determines whether or not there is a peak exceeding the specified peak intensity threshold in the mass chromatogram associated with the m / z value for each specified thermal decomposition product. (Step S211).
  • step S211: YES the sample estimation unit 205 determines that the sample S includes a structural unit based on vinyl ester.
  • step S212 determines that there is no one kind of thermal decomposition product having a peak exceeding the peak intensity threshold.
  • step S211: NO the ester estimation unit 205 determines that there is no one kind of thermal decomposition product having a peak exceeding the peak intensity threshold. It is determined that there is not (step S213).
  • the ether estimation unit 206 specifies the m / z value and the peak intensity threshold value for each thermal decomposition product derived from the structural unit based on vinyl ether from the ether peak table 223 (step S214).
  • the ether estimation unit 206 determines whether or not a peak exceeding the specified peak intensity threshold exists in the mass chromatogram associated with the m / z value for each specified thermal decomposition product. (Step S215).
  • step S215 determines that one or more types of thermal decomposition products having peaks exceeding the peak intensity threshold are present (step S215: YES)
  • the ether estimation unit 206 determines that the structural unit based on vinyl ether is included in the sample S ( Step S215).
  • the sample S does not include a structural unit based on vinyl ether. Is determined (step S217).
  • the fluoroolefin estimation unit 207 specifies the threshold value of the m / z value and the peak intensity for each thermal decomposition product derived from the structural unit based on TFE from the fluorine peak table 224 (step S218).
  • the fluoroolefin estimating unit 207 determines whether or not there is a peak exceeding the specified peak intensity threshold in the mass chromatogram associated with the m / z value for each specified thermal decomposition product. (Step S219).
  • step S219: YES When the fluoroolefin estimating unit 207 determines that there is a thermal decomposition product having a peak exceeding the threshold value of the peak intensity (step S219: YES), the fluoroolefin estimating unit 207 determines that the structural unit based on TFE is included in the sample S (step S220). ). On the other hand, when the fluoroolefin estimating unit 207 determines that there is no thermal decomposition product having a peak exceeding the peak intensity threshold value (step S219: NO), the sample S determines that the structural unit based on TFE is not included. (Step S221).
  • the fluoroolefin estimating unit 207 specifies the m / z value and the peak intensity threshold value for each thermal decomposition product derived from the structural unit based on CTFE from the fluorine peak table 224 (step S222).
  • the fluoroolefin estimating unit 207 determines whether or not there is a peak exceeding the specified peak intensity threshold in the mass chromatogram associated with the m / z value for each specified thermal decomposition product. (Step S223).
  • the fluoroolefin estimation unit 207 determines that there is a thermal decomposition product having a peak exceeding the threshold value of the peak intensity (step S223: YES).
  • the fluoroolefin estimation unit 207 determines that the structural unit based on CTFE is included in the sample S (step S224).
  • the fluoroolefin estimating unit 207 determines that there is no pyrolysis product having a peak exceeding the peak intensity threshold value (step S223: NO)
  • the sample S determines that the constituent unit based on CTFE is not included. (Step S225).
  • the evaluation information output unit 208 outputs the estimated presence / absence of each structural unit, the presence / absence of each known structural unit, and the name of the known paint or coating film having the highest degree of similarity to the terminal device 10 (step S10). S226).
  • the fluoroolefin estimation unit 207 determines the peak intensity of the mass chromatogram of the sample S associated with the m / z value specified in steps S218 and S222 and the peak intensity of the mass chromatogram of the standard agent specified in step S208. Based on the ratio, the constituent unit based on TFE and CTFE of the sample S and the content of fluorine atoms are estimated (step S227 in FIG. 7). Specifically, for example, the fluoroolefin estimating unit 207 multiplies the TFE and CTFE contents of the standard agent by the ratio of the peak intensity of the mass chromatogram of the standard agent and the peak intensity of the mass chromatogram of the sample S. The contents of TFE and CTFE of sample S are estimated. In addition, the fluoroolefin estimating unit 207 estimates the fluorine atom content by multiplying the specified TFE content and CTFE content by a predetermined coefficient and adding them together.
  • the ester estimation unit 205 determines the vinyl of the sample S based on the ratio between the peak intensity specified in step S210 and the intensity of a specific peak (for example, a specific vinyl ester monomer) in the standard agent specified in step S208.
  • the content of the structural unit based on the ester is estimated (step S228).
  • the ether estimation unit 206 is based on the vinyl ether of the sample S based on the ratio between the peak intensity specified in step S214 and the intensity of a specific peak (for example, a specific vinyl ether monomer) in the standard agent specified in step S208.
  • the content of the structural unit is estimated (step S229).
  • the evaluation information output unit 208 transmits the estimation results obtained by the ester estimation unit 205, the ether estimation unit 206, and the fluoroolefin estimation unit 207 to the terminal device 10 as evaluation information (step S230).
  • the communication device 105 of the terminal device 10 receives the evaluation information (step S114 in FIG. 4).
  • the arithmetic device 104 displays the evaluation information received by the communication device 105 on the display device 106 (step S115), and ends the processing.
  • the evaluator E evaluates based on the evaluation information displayed on the display device 106 whether or not the sample S is appropriate as a paint or coating film for a road bridge.
  • the evaluator E matches the presence or absence of vinyl ester, vinyl ether, TFE, and CTFE in the sample S and the known paint or coating film most similar to the sample S, and the vinyl ester, vinyl ether, When the errors in the contents of TFE, CTFE and fluorine atoms are within a certain value, it is evaluated that the sample S is suitable as a paint or coating film for a road bridge.
  • the evaluator E also evaluates the weather resistance of the sample S based on the weather resistance rank of the sample S.
  • sample S and the known paint or coating film most similar to sample S have the same or no vinyl ester, vinyl ether, TFE, and CTFE, or vinyl ester, vinyl ether, TFE, CTFE, and fluorine atoms If the content error is greater than a certain value, it is evaluated that the sample S is not suitable as a paint or coating for a road bridge.
  • the weather resistance rank will be described below.
  • the weather resistance of the fluororesin coating material and the fluororesin coating film is obtained when the C—F bond energy of the fluoroolefin is greater than the ultraviolet energy. Accordingly, the greater the fluorine atom content of the sample S, the better the weather resistance, and the smaller the fluorine atom content of the sample S, the poorer the weather resistance.
  • the fluorine atom content in the fluororesin coating and the fluororesin coating is preferably 20% by mass or more based on the solid content (100% by mass) of the fluororesin coating from the point that a fluororesin coating having excellent weather resistance can be formed. 22 mass% or more is more preferable, and 24 mass% or more is further more preferable.
  • the fluororesin paint or fluororesin coating film has a structural unit based on vinyl ether and does not have a structural unit based on vinyl ester
  • the structural unit based on fluoroolefin and vinyl ether The structural units based on are regularly arranged alternately. Therefore, a structural unit based on vinyl ether that is weak against ultraviolet rays is sandwiched between and hidden from structural units based on fluoroolefins that are resistant to ultraviolet rays, and the structural units based on vinyl ether are not easily hit by ultraviolet rays. Therefore, the fluororesin paint and fluororesin coating film having a structural unit based on vinyl ether have a relatively high weather resistance rank.
  • the fluororesin paint or fluororesin coating film has a structural unit based on vinyl ester
  • the structural unit based on fluoroolefin and the structural unit based on vinyl ester are randomly selected in the fluororesin paint or fluororesin coating film. Arranged in close proximity. Therefore, a structural unit based on a vinyl ester that is weak against ultraviolet rays is easily exposed to ultraviolet light, and a bond portion between the structural units based on vinyl ester is likely to be cut. Therefore, the fluororesin paint and fluororesin coating film having a structural unit based on vinyl ester have a relatively low weather resistance rank.
  • the fluororesin paint or fluororesin coating film evaluation method determines whether or not the sample S contains a structural unit based on at least one of vinyl ester and vinyl ether, and the fluorine atom of the sample S Sample S is evaluated based on the content.
  • the evaluator E evaluates whether or not the sample S has an appropriate weather resistance as a paint or coating film for a road bridge even when it is difficult to identify the fluororesin coating material or the fluororesin coating film. Can do.
  • the fluororesin paint or fluororesin coating film evaluation method when it is difficult to identify the sample S based on the scattered light due to Raman scattering, the sample S has at least one of vinyl ester and vinyl ether.
  • the sample S is evaluated on the basis of whether or not the constituent unit is included and the fluorine atom content of the sample S.
  • the evaluator E evaluates whether or not the sample S has an appropriate weather resistance as a road bridge paint or coating film based on the identification result. be able to.
  • FIG. 8 is a schematic block diagram illustrating a configuration of the terminal device 10 according to the second embodiment.
  • the terminal device 10 according to the present embodiment includes a detector 134 instead of the mass spectrometer 133 according to the first embodiment.
  • the detector 134 detects the time-series intensity of the thermal decomposition product eluted from the gas chromatograph 132. That is, the detector 134 generates a chromatograph of the sample S.
  • FIG. 9 is a schematic block diagram showing the configuration of the evaluation information calculation apparatus 20 according to the second embodiment.
  • the evaluation information calculation apparatus 20 according to the present embodiment further includes a reference specifying unit 209 in addition to the configuration of the first embodiment.
  • the information stored in the ester peak table 222, the ether peak table 223, and the fluorine peak table 224 according to the present embodiment is different from that of the first embodiment.
  • the operations of the ester estimation unit 205, the ether estimation unit 206, and the fluoroolefin estimation unit 207 according to this embodiment are different from those of the first embodiment.
  • the ester peak table 222 stores data related to peaks of thermal decomposition products derived from structural units based on vinyl esters.
  • the ether peak table 223 stores data relating to peaks of thermal decomposition products derived from structural units based on vinyl ether.
  • the fluorine peak table 224 stores data relating to the peak of the thermal decomposition product derived from the structural unit based on the fluoroolefin.
  • the data relating to the peak of the thermal decomposition product is data in which the time at which the peak of the thermal decomposition product appears and the threshold value of the peak intensity are associated with each other.
  • the time at which the peak of the pyrolysis product appears is represented by the elapsed time from the time when the pyrolysis product of the sample S is introduced into the gas chromatograph, for example.
  • the reference specifying unit 209 obtains a chromatogram related to the standard agent whose peak time is known from the terminal device 10, and the time when the peak actually appears in the chromatogram and the peak recorded in the database 202 are obtained. Identify the difference from the time of appearance.
  • the standard agent for example, any monomer stored in the ester peak table 222, the ether peak table 223 or the fluorine peak table 224 can be used. Other molecules not stored in the ester peak table 222, the ether peak table 223, and the fluorine peak table 224 may be used as the standard agent.
  • the database 202 needs to store in advance the time at which the peak of the standard agent appears.
  • the ester estimating unit 205 corrects the time when the peak of the thermal decomposition product derived from the structural unit based on the vinyl ester stored in the ester peak table 222 appears based on the time specified by the reference specifying unit 209.
  • the ester estimation unit 205 determines whether or not there is a peak between a predetermined time before and after the time obtained by the correction in the chromatogram acquired by the measurement data acquisition unit 201, so that the vinyl ester is present in the sample S. Whether or not a structural unit based on the formula is included, and the amount of the structural unit based on the vinyl ester is estimated.
  • the ether estimation unit 206 corrects the time at which the peak of the thermal decomposition product derived from the structural unit based on vinyl ether stored in the ether peak table 223 appears based on the time specified by the reference specification unit 209.
  • the ether estimation unit 206 determines whether or not there is a peak between a predetermined time before and after the time obtained by the correction in the chromatogram acquired by the measurement data acquisition unit 201, so that the sample S has vinyl ether. Estimate whether or not a constituent unit based is included and the amount of constituent unit based on vinyl ether.
  • the fluoroolefin estimating unit 207 corrects the time when the peak of the thermal decomposition product derived from the structural unit based on the fluoroolefin stored in the fluorine peak table 224 appears based on the time specified by the reference specifying unit 209.
  • the fluoroolefin estimation unit 207 determines the TFE, CTFE, and fluorine of the sample S based on the intensity of the peak existing between a predetermined time before and after the time obtained by the correction in the chromatogram acquired by the measurement data acquisition unit 201. Estimate the presence and content of atoms.
  • the same effects as those of the first embodiment can be obtained based on the Raman spectroscopy and the pyrolysis GC method.
  • FIG. 10 is a schematic block diagram illustrating a configuration of the terminal device 10 according to the third embodiment.
  • the terminal device 10 according to the present embodiment does not include the Raman spectroscopic device 102 according to the first embodiment.
  • the computing device 104 according to the present embodiment identifies the sample S and a known paint or coating film based on the mass chromatogram output from the pyrolysis GC / MS device 103.
  • the configuration of the arithmetic device 104 according to the present embodiment is the same as that of the first embodiment.
  • the information stored in the paint table 221 and the operation of the identification unit 204 are different from those in the first embodiment.
  • the paint table 221 shows the mass chromatogram of a known paint or coating film, the presence or absence of vinyl ester, vinyl ether, TFE and CTFE, the content of vinyl ester, vinyl ether, TFE, CTFE and fluorine atoms, and the weather resistance rank.
  • the identification unit 204 specifies the similarity between the mass chromatogram stored in the paint table 221 and the mass chromatogram acquired by the measurement data acquisition unit 201, and based on the similarity, the sample S is a known paint or It is judged whether it is a coating film.
  • the similarity between the mass chromatograms can be determined, for example, by the similarity of the ratios of peak intensities when a certain peak included in a known mass chromatogram is taken as a reference. Further, for example, the similarity between mass chromatograms may be calculated based on a multivariate analysis method such as a PCA score plot method, a Volcano Plot analysis, or a hierarchical cluster analysis.
  • the same effects as those of the first embodiment can be obtained without using spectral analysis such as Raman spectroscopy.
  • the evaluation information presentation system 1 according to the present embodiment is based on the chromatogram according to the pyrolysis GC method as in the second embodiment, instead of the identification based on the mass chromatogram according to the pyrolysis GC / MS method. Identification may be performed.
  • the evaluation information presentation system 1 according to another embodiment may perform identification by spectroscopic analysis as in the first embodiment or the second embodiment, and may further perform identification according to a chromatograph. Further, the evaluation information presentation system 1 according to another embodiment may evaluate the sample S based only on identification based on the chromatogram, and may not compare the presence or absence or amount of each structural unit. .
  • the information presentation system 1 for evaluation replaces Raman spectroscopy with infrared spectroscopy, near infrared spectroscopy, ultraviolet spectroscopy, visible spectroscopy, laser induced breakdown spectroscopy (LIBS).
  • Sample S may be identified based on a spectrum obtained from Laser-Induced Breakdown Spectroscopy. Further, the sample S may be identified based on a combination of a plurality of spectra obtained by a plurality of the spectroscopic methods.
  • the Raman spectroscopic device 102 described above is an example of a spectroscopic unit that generates spectral data by splitting light absorbed or emitted by the sample S. That is, the Raman spectroscopic device 102 described above is an example of an identification information generation unit that generates identification information used for identifying the sample S.
  • the evaluation information presentation system 1 does not perform spectroscopic analysis, and does not perform structural analysis based on a chromatogram obtained by pyrolysis GC method or pyrolysis GC / MS method.
  • the sample S may be evaluated by estimating at least one of presence / absence and amount. In this case, since the evaluation information presentation system 1 cannot identify the known paint or coating film having the highest similarity, the sample S is compared with all the known paints or coating films to obtain the sample. Evaluate S.
  • the evaluation information presentation system 1 sequentially performs identification by spectroscopic analysis, determination of the presence / absence of each structural unit, and determination of the amount of each structural unit, but is not limited thereto.
  • the evaluation information presentation system 1 according to another embodiment performs a parallel analysis of identification by spectroscopic analysis, determination of the presence / absence of each structural unit, and determination of the amount of each structural unit, and a sample obtained by each analysis.
  • the sample S may be evaluated by comprehensively considering the similarity between S and a known paint or coating film.
  • Comprehensive evaluation refers to, for example, determining whether or not the value obtained by adding each similarity is greater than or equal to a threshold, and determining whether or not the value obtained by multiplying each similarity is greater than or equal to the threshold. A determination as to whether or not all the similarities are equal to or greater than a predetermined threshold can be given. Further, for example, the evaluation information presentation system 1 according to another embodiment may generate multidimensional data combining a chromatogram and a spectrum, and calculate a similarity based on the multidimensional data.
  • the evaluation information presentation system 1 is derived from trace components in addition to the presence / absence of vinyl ester, vinyl ether, TFE and CTFE, and the content of vinyl ester, vinyl ether, TFE, CTFE and fluorine atom.
  • the sample S may be evaluated in consideration of the presence or absence of the peak or the content.
  • the evaluation information presentation system 1 may include an evaluation unit that evaluates the sample S in the evaluation information calculation device 20, and the evaluation information calculation device 20 may evaluate the sample S.
  • the terminal device 10 displays the evaluation result by the evaluation unit instead of the evaluation information.
  • the terminal device 10 and the evaluation information calculation device 20 may be directly connected without going through the network N.
  • the evaluation information calculation device 20 by mounting the evaluation information calculation device 20 on a notebook PC, the sample S can be analyzed and evaluated even in an area where connection to the network N is not possible.
  • the terminal device 10 may present the evaluation information not by display by the display device 106 but by printing, voice, or other output means.
  • the evaluation information presentation system 1 includes, as evaluation information, a weather resistance index value of the sample S, whether the sample S satisfies a predetermined standard, or whether the sample S is a paint or paint for a road bridge. You may present the determination result of whether it is suitable as a film
  • the evaluator E does not evaluate whether or not the sample S is suitable as a paint or a coating film for a road bridge, but the weather resistance index value of the sample S or the sample S satisfies a predetermined standard. It may be evaluated whether or not.
  • the evaluation information presentation system 1 may not present the determination result as to whether or not the sample S includes a structural unit based on vinyl ether as evaluation information.
  • the fluororesin paint and the fluororesin coating film generally contain at least one of a structural unit based on vinyl ester and a structural unit based on vinyl ether. Therefore, it can be estimated that the determination result that the structural unit based on vinyl ester is not included in the sample S is equivalent to the determination result that the structural unit based on vinyl ether is included in the sample S. Therefore, the evaluator E can also use the sample S as a paint or coating film for the road bridge even when the evaluation information presentation system 1 does not present the determination result as to whether the structural unit based on vinyl ether is included in the sample S.
  • the evaluation information presentation system 1 may not present the determination result as to whether or not the sample S includes a structural unit based on vinyl ester as evaluation information.
  • the fluororesin paint and the fluororesin coating film may include a structural unit based on vinyl ester and a structural unit based on vinyl ether
  • the evaluation information presentation system 1 includes a structural unit based on vinyl ester in the sample S. It is preferable to present a determination result of whether or not it is included.
  • the evaluation information calculation apparatus 20 is derived from the structural unit derived from the monomer having a fluorine atom and the data related to the peak of the thermal decomposition product derived from the structural unit based on the vinyl ester, instead of the database 202.
  • Another storage device that stores data relating to the peak of the thermal decomposition product of may be provided. That is, the storage device may be one in which data is managed by a file system that does not have a data operation function.
  • the recording unit 203, the identification unit 204, the ester estimation unit 205, the ether estimation unit 206, and the fluoroolefin estimation unit 207 which are applications for processing data, need to have a data operation function.
  • the above-described evaluation information calculation device 20 is mounted on a computer having a CPU, a main storage device, an auxiliary storage device, and an interface.
  • the operation of each processing unit described above is stored in the auxiliary storage device in the form of a program.
  • the CPU reads the program from the auxiliary storage device, develops it in the main storage device, and executes the above processing according to the program.
  • the CPU constructs the above-described database 202 in the auxiliary storage device when the program is executed for the first time.
  • the auxiliary storage device is an example of a tangible medium that is not temporary.
  • Other examples of the non-temporary tangible medium include a magnetic disk, a magneto-optical disk, a CD-ROM, a DVD-ROM, and a semiconductor memory connected via an interface.
  • the program may be for realizing a part of the functions described above. Further, the program may be a so-called difference file (difference program) that realizes the above-described function in combination with another program already stored in the auxiliary storage device.
  • difference file difference program
  • the fluororesin paint to be evaluated contains a fluororesin (A).
  • the fluororesin paint may contain an organic solvent (B) and other paint blending components (C) as necessary.
  • Fluororesin (A) As a fluororesin (A), what is necessary is just a fluororesin used for a well-known fluororesin coating material.
  • a fluororesin coating film having excellent weather resistance can be formed, a structural unit based on the fluoroolefin (a1), a structural unit based on the monomer (a2) having a crosslinkable group, a fluorine atom and A fluoroolefin copolymer (A1) comprising a structural unit based on the monomer (a3) having no crosslinkable group is preferred.
  • Fluoroolefin (a1) The number of fluorine atoms contained in the fluoroolefin (a1) is preferably 2 or more, more preferably 2 to 6, and further preferably 3 to 4. When the number of fluorine atoms is 2 or more, a fluororesin coating film having excellent weather resistance can be formed.
  • fluoroolefin (a1) examples include TFE, CTFE, vinylidene fluoride, hexafluoropropylene and the like, and TFE or CTFE is preferable from the viewpoint that a fluororesin coating film having excellent weather resistance can be formed. That is, the database 202 which concerns on embodiment mentioned above memorize
  • a fluoroolefin (a1) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the monomer (a2) is a monomer having a crosslinkable group.
  • a functional group having active hydrogen hydroxyl group, carboxyl group, amino group, etc.
  • hydrolyzable silyl group alkoxysilyl group, etc.
  • a monomer (a21) represented by the following formula is preferable because a fluororesin coating film having excellent weather resistance can be formed.
  • CH 2 CX 1 (CH 2 ) n1 -Q 1 -R 1 -Y X 1 is a hydrogen atom or a methyl group, n1 is 0 or 1, Q 1 is an oxygen atom, —C (O) O— or —O (O) C—, and R 1 Is an alkylene group having 2 to 20 carbon atoms which may have a branched structure or a ring structure, and Y is a crosslinkable functional group.
  • Y is preferably a hydroxyl group, a carboxyl group or an amino group, more preferably a hydroxyl group.
  • R 1 is preferably a linear alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • Q 1 is preferably an oxygen atom.
  • the monomer (a21) is roughly classified into a monomer having an ether bond and a monomer having an ester bond.
  • Examples of the monomer having an ether bond include hydroxyalkyl vinyl ethers and hydroxyalkyl allyl ethers.
  • Examples of the monomer having an ester bond include vinyl hydroxyalkanoates, allyl hydroxyalkanoates, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, and the like.
  • hydroxyalkyl vinyl ethers examples include 2-hydroxyethyl vinyl ether, hydroxymethyl vinyl ether, 4-hydroxybutyl vinyl ether (hereinafter also referred to as HBVE), and the like.
  • hydroxyalkyl allyl ethers examples include hydroxyethyl allyl ether.
  • hydroxyalkyl acrylates and hydroxyalkyl methacrylates include hydroxyethyl acrylate and hydroxyethyl methacrylate.
  • the monomer (a21) is preferably a monomer having an ether bond, more preferably a hydroxyalkyl vinyl ether, and particularly preferably HBVE from the viewpoint that a fluororesin coating film having excellent weather resistance can be formed.
  • a monomer (a2) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • a monomer (a3) is a monomer which does not have a fluorine atom and a crosslinkable group.
  • a monomer (a31) represented by the following formula is preferable because a fluororesin coating film having excellent weather resistance can be formed.
  • CH 2 CX 2 (CH 2 ) n2 -Q 2 -R 2 Where X 2 is a hydrogen atom or a methyl group, n2 is 0 or 1, Q 2 is an oxygen atom, —C (O) O— or —O (O) C—, and R 2 Is an alkyl group having 2 to 20 carbon atoms which may have a branched structure or a ring structure.
  • the monomer (a31) is roughly classified into a monomer having an ether bond and a monomer having an ester bond.
  • Examples of the monomer having an ether bond include alkyl vinyl ethers and alkyl allyl ethers.
  • Examples of the monomer having an ester bond include vinyl alkanoates, vinyl arylcarboxylates, allyl alkanoates, alkyl acrylates, alkyl methacrylates, and the like.
  • alkyl vinyl ethers examples include ethyl vinyl ether (hereinafter also referred to as EVE), cyclohexyl vinyl ether (hereinafter also referred to as CHVE), 2-ethylhexyl vinyl ether, and the like.
  • EVE ethyl vinyl ether
  • CHVE cyclohexyl vinyl ether
  • 2-ethylhexyl vinyl ether examples include vinyl alkanoates.
  • vinyl arylcarboxylates examples include vinyl benzoate.
  • a monomer (a3) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Composition unit ratio The proportion of the structural unit based on the fluoroolefin (a1) is preferably from 30 to 70 mol%, more preferably from 40 to 60 mol%, based on the total structural units (100 mol%) of the fluoroolefin copolymer (A1). 45 to 55 mol% is more preferable. If the ratio of the structural unit based on fluoroolefin (a1) is 30 mol% or more, a fluororesin coating film having excellent weather resistance can be formed. If the ratio of the structural unit based on fluoroolefin (a1) is 70 mol% or less, it is excellent in the solubility to an organic solvent or a diluent.
  • the total proportion of the structural unit based on the monomer (a2) and the structural unit based on the monomer (a3) is 70 to 30 mol% of all the structural units (100 mol%) of the fluoroolefin copolymer (A1). 60 to 40 mol% is more preferable, and 55 to 45 mol% is more preferable.
  • the proportion of the structural unit based on the monomer (a21) is preferably 5 to 40 mol%, more preferably 8 to 35 mol%, of all the structural units (100 mol%) of the fluoroolefin copolymer (A1).
  • the proportion of the structural unit based on the monomer (a21) is 5 mol% or more, a sufficient amount of crosslinkable groups are introduced into the fluoroolefin copolymer (A1) to obtain a highly hard fluororesin coating film.
  • the ratio of the structural unit based on the monomer (a21) is 40 mol% or less, even if it is a high solid content type, a sufficiently low viscosity can be maintained as a solution of the fluoroolefin copolymer (A1).
  • the proportion of the structural unit based on the monomer (a31) is preferably more than 0 mol% and 45 mol% or less, and preferably 3 to 35 mol% in the total structural units (100 mol%) of the fluoroolefin copolymer (A1). More preferred is 5 to 30 mol%.
  • the proportion of the structural unit based on the monomer (a31) is 45 mol% or less, a sufficient amount of crosslinkable groups for obtaining a fluororesin coating film having excellent weather resistance and high hardness is contained in the fluoroolefin copolymer (A1). ) Introduced in.
  • the ratio of the structural unit based on the other monomer is Of the total structural units (100 mol%) of the fluoroolefin copolymer (A1), 20 mol% or less is preferable, and 10 mol% or less is more preferable.
  • fluoro olefin copolymer (A1) As a commercial item of a fluoro olefin copolymer (A1), the following are mentioned, for example. Lumiflon (registered trademark) series (LF200, LF100, LF710, etc.) manufactured by Asahi Glass Co., Ltd. Zaffle (registered trademark) GK series (GK-500, GK-510, GK-550, GK-570, GK-580, etc.) manufactured by Daikin Industries, Ltd.
  • Lumiflon (registered trademark) series LF200, LF100, LF710, etc.
  • Zaffle registered trademark
  • GK series GK-500, GK-510, GK-550, GK-570, GK-580, etc.
  • Zeffle® GK-570 is a TFE / hydroxyethyl allyl ether / vinyl versatate / vinyl benzoate / vinyl acetate copolymer
  • Zeffle® GK-580 is TFE / hydroxyethyl allyl.
  • Fluorate (registered trademark) series manufactured by DIC K-700, K-702, K-703, K-704, K-705, K-707, etc.
  • Fluonate® K-705 is a CTFE / HBVE / EVE / vinyl versatate copolymer.
  • ETERFLON series (E-4101, E-41011, E-4102, E-41021, E-4261A, E-4262A, E-42631, E-4102A, E-41041, E-41111, E-, manufactured by Eternal Chemical 4261A etc.).
  • ETERFLON E-4101 is a CTFE / HBVE / CHVE / EVE copolymer.
  • Organic solvent (B) examples include aromatic hydrocarbon solvents, ketone solvents, ester solvents, third organic solvents in the Industrial Safety and Health Act, alcohol solvents, ether ester solvents, and the like.
  • the organic solvent (B) a solvent corresponding to the PRTR method and HAPs regulations, that is, an organic solvent having no aromatic ring is preferable from the viewpoint of reducing the environmental load.
  • category of the organic solvent by the occupational safety and health law is also preferable.
  • ketone solvents, ether ester solvents that do not comply with the PRTR method and HAPs regulations; paraffinic solvents or naphthenic solvents classified as the third organic solvents in the Industrial Safety and Health Act are preferable.
  • aromatic hydrocarbon solvent examples include toluene, xylene, ethylbenzene, aromatic petroleum naphtha, tetralin, turpentine oil, Solvesso (registered trademark) # 100 (manufactured by Exxon Chemical), Solvesso (registered trademark) # 150 (Exxon Chemical) Product).
  • ketone solvent acetone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and isophorone are preferable.
  • ester solvent methyl acetate, ethyl acetate, n-propyl acetate, isobutyl acetate, and tert-butyl acetate are preferable.
  • the Class III organic solvents in the Industrial Safety and Health Act are gasoline, coal tar naphtha (including solvent naphtha), petroleum ether, petroleum naphtha, petroleum benzine, turpentine oil, mineral spirit (mineral thinner, petroleum spirit, white spirit and A solvent consisting of one or more selected from the group consisting of mineral terpenes).
  • mineral spirits including mineral thinner, petrolium spirit, white spirit and mineral turpentine
  • the flash point is room temperature or higher.
  • alcohol solvent those having 4 or less carbon atoms are preferable, and specifically, ethanol, tert-butyl alcohol, and iso-propyl alcohol are preferable.
  • ether ester solvent ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, and methoxybutyl acetate are preferable.
  • An organic solvent (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the amount of the organic solvent (B) is preferably such that the solid content concentration of the fluororesin coating is 20 to 100% by mass, and more preferably 40 to 100% by mass.
  • paint ingredients (C) examples include curing agents, colorants, resins other than the fluororesin (A), silane coupling agents, ultraviolet absorbers, curing accelerators, light stabilizers, matting agents, and the like. It is done. Two or more of these may be used in combination.
  • the curing agent is preferably at least one selected from the group consisting of isocyanate curing agents, blocked isocyanate curing agents, and amino resin curing agents.
  • non-yellowing isocyanates hexamethylene diisocyanate, isophorone diisocyanate, etc.
  • blocked isocyanate curing agent those obtained by blocking the isocyanate group of the isocyanate curing agent with caprolactam, isophorone, ⁇ -diketone or the like are preferable.
  • the amino resin curing agent is a curing agent obtained by polycondensation of amines (melamine, methylolmelamine, guanamine, urea, etc.) and aldehydes (formaldehyde, etc.).
  • amino resin-based curing agents include melamine resin-based curing agents, guanamine resin-based curing agents, urea resin-based curing agents, sulfoamide resin-based curing agents, and aniline resin-based curing agents.
  • the amount of the curing agent is preferably 1 to 100 parts by mass and more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the fluororesin (A) in the fluororesin paint. If a hardening
  • Colorant examples include inorganic pigments (carbon black, titanium oxide, etc.) having good weather resistance, organic pigments (phthalocyanine blue, phthalocyanine green, quinacridone red, indanthrene orange, isoindolinone yellow, etc.), dyes, and the like. .
  • resins As other resin, the well-known resin mix
  • the fluororesin coating film is formed by applying a fluororesin paint to the surface of an article and drying it.
  • the coating method include spray coating, air spray coating, brush coating, dipping method, roll coating, and flow coating.
  • Materials to be painted include inorganic substances (concrete, natural stone, glass, metal (iron, stainless steel, aluminum, copper, brass, titanium, etc.)), organic substances (plastic, rubber, adhesive, wood, etc.), organic Examples thereof include inorganic composite materials (fiber reinforced plastic, resin reinforced concrete, fiber reinforced concrete, and the like).
  • the article to be painted is a road bridge.
  • a road bridge is a bridge where a road is installed. In other words, even a bridge belonging to an overpass, an overland bridge or the like is included in the road bridge if the road is installed. Further, not only bridges on which roadways are installed, but also pedestrian bridges, which are bridges of roads through which people pass, are also included in road bridges. A composite bridge in which both a road and a railway are installed is also included in the road bridge.
  • the entire content of the specification, claims, abstract, and drawings of Japanese Patent Application No. 2014-252464 filed on December 12, 2014 is cited here as disclosure of the specification of the present invention, Incorporated.
  • Information presentation system for evaluation 10 terminal device, 20 information calculation device for evaluation, 101 storage space, 102 Raman spectroscopic device, 103 pyrolysis GC / MS device, 104 arithmetic device, 105 communication device, 106 display device, 121 laser device , 122 filter, 123 monochromator, 124 detector, 131 pyrolysis device, 132 gas chromatograph, 133 mass spectrometer, 134 detector, 201 measurement data acquisition unit, 202 database, 203 recording unit, 204 identification unit, 205 ester determination Part, 206 ether determination part, 207 fluorine atom content estimation part, 208 information output part for evaluation, 209 reference identification part, 221 spectrum table, 222 ester peak table, 223 ether peak table, 224 Fluorine Peak Table, S samples, N networks, E evaluator

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Abstract

The purpose of the present invention is to evaluate whether a fluororesin paint or a fluororesin coating film is suitable as a paint or a coating film for road bridges. An evaluation-information calculation device (20) acquires a chromatogram related to a sample (S). The evaluation-information calculation device (20) estimates, on the basis of the chromatogram and data related to peaks of thermal decomposition products derived from constituent units based on vinyl ester and/or vinyl ether, the presence and/or amount of the constituent units based on vinyl ester and/or vinyl ether in the sample (S). The evaluation-information calculation device (20) estimates the fluorine content of the sample (S) on the basis of the chromatogram and data related to peaks of thermal decomposition products derived from constituent units based on monomers including fluorine. An evaluator (E) evaluates the sample (S) on the basis of the fluorine content, and the presence and/or amount of the constituent units based on vinyl ester and/or vinyl ether.

Description

フッ素樹脂塗料またはフッ素樹脂塗膜の評価方法、評価用情報算出装置、評価用情報提示システム、および端末装置Evaluation method for fluororesin paint or fluororesin coating film, evaluation information calculation device, evaluation information presentation system, and terminal device
　本発明は、フッ素樹脂塗料またはフッ素樹脂塗膜の評価方法、評価用情報算出装置、評価用情報提示システム、および端末装置に関する。 The present invention relates to a fluororesin paint or fluororesin coating film evaluation method, an evaluation information calculation device, an evaluation information presentation system, and a terminal device.
　一般にフッ素樹脂塗膜は、他の樹脂塗膜に比べて耐候性に優れている。そのため道路橋の塗料としてフッ素樹脂塗料が採用されることがある。フッ素樹脂塗料およびフッ素樹脂塗膜は、組成によって得られる耐候性が異なる。そのため、必ずしもすべてのフッ素樹脂塗料が道路橋の塗料として適切であるとは限らない。 Generally, fluororesin coating films are superior in weather resistance compared to other resin coating films. For this reason, a fluororesin paint is sometimes used as a paint for road bridges. The fluororesin paint and the fluororesin coating film differ in the weather resistance obtained depending on the composition. Therefore, not all fluororesin paints are suitable as road bridge paints.
　フッ素樹脂塗膜の成分は、熱分解ガスクロマトグラフィ法（以下、熱分解ＧＣ法とも記す。ＧＣは、Ｇａｓ　Ｃｈｒｏｍａｔｏｇｒａｐｈｙの略である。）または熱分解ガスクロマトグラフィ質量分析法（以下、熱分解ＧＣ／ＭＳ法とも記す。ＭＳは、Ｍａｓｓ　Ｓｐｅｃｔｒｏｍｅｔｒｙの略である。）によって分析される。熱分解ＧＣ法および熱分解ＧＣ／ＭＳ法による成分分析は、クロマトグラム（熱分解ＧＣ／ＭＳ法においては、マスクロマトグラム。）に現れる複数のピークから、フッ素樹脂の成分を見出す必要がある。つまり、成分分析の経験の浅い者にとって、フッ素樹脂塗料またはフッ素樹脂塗膜の成分を分析することは困難である。そのため、道路橋の塗装に用いられているフッ素樹脂塗料が道路橋の塗料として適切であるか否かを塗装現場で評価することは困難である。 The component of the fluororesin coating film is a pyrolysis gas chromatography method (hereinafter also referred to as pyrolysis GC method, GC is an abbreviation for Gas Chromatography) or pyrolysis gas chromatography mass spectrometry (hereinafter pyrolysis GC / MS). MS is an abbreviation for Mass Spectrometry). In component analysis by the pyrolysis GC method and pyrolysis GC / MS method, it is necessary to find the components of the fluororesin from a plurality of peaks appearing in the chromatogram (in the pyrolysis GC / MS method, mass chromatogram). That is, it is difficult for those who have little experience in component analysis to analyze the components of the fluororesin paint or the fluororesin coating film. Therefore, it is difficult to evaluate at the painting site whether or not the fluororesin paint used for painting the road bridge is appropriate as the paint for the road bridge.
　特許文献１には、既知ポリマーに係る保持指標を記憶するデータベースを用いて、試料ポリマーの熱分解生成物を同定する方法が開示されている。 Patent Document 1 discloses a method of identifying a thermal decomposition product of a sample polymer using a database that stores a retention index related to a known polymer.
特開平５－９３７１９号公報Japanese Patent Laid-Open No. 5-93719
　熱分解ガスクロマトグラフィ法または熱分解ガスクロマトグラフィ質量分析法によって求められる保持指標は、必ずしもデータベースに記録された保持指標と一致するとは限らない。特許文献１に開示された同定支援システムは、試料ポリマーと既知ポリマーとのマッチ度を算出することで、試料ポリマーの同定を支援する。
　そのため、フッ素樹脂塗料またはフッ素樹脂塗膜が既知の塗料または塗膜であると確信できる程度のマッチ度が得られない場合、特許文献１に開示された方法によっては、該フッ素樹脂塗料または該フッ素樹脂塗膜が道路橋の塗料または塗膜として適切であるか否かを評価できない。
　本発明の目的は、フッ素樹脂塗料またはフッ素樹脂塗膜の同定が困難である場合にも、該フッ素樹脂塗料または該フッ素樹脂塗膜が道路橋の塗料または塗膜として適切であるか否かを評価できる、フッ素樹脂塗料またはフッ素樹脂塗膜の評価方法、評価用情報算出装置、評価用情報提示システム、および端末装置を提供する。 The retention index obtained by pyrolysis gas chromatography or pyrolysis gas chromatography mass spectrometry does not necessarily match the retention index recorded in the database. The identification support system disclosed in Patent Document 1 supports the identification of a sample polymer by calculating the degree of match between the sample polymer and the known polymer.
Therefore, when a degree of matching that can be confident that the fluororesin paint or fluororesin coating film is a known paint or coating film is not obtained, depending on the method disclosed in Patent Document 1, the fluororesin paint or fluorine It is not possible to evaluate whether a resin coating is suitable as a paint or coating for road bridges.
The object of the present invention is to determine whether or not the fluororesin paint or the fluororesin paint film is suitable as a road bridge paint or paint film even when it is difficult to identify the fluororesin paint or the fluororesin paint film. An evaluation method, an evaluation information calculation device, an evaluation information presentation system, and a terminal device that can be evaluated are provided.
　第１の態様は、道路橋に塗布されるフッ素樹脂塗料または道路橋に設けられたフッ素樹脂塗膜である試料の、熱分解ガスクロマトグラフィ法または熱分解ガスクロマトグラフィ質量分析法による計測データを取得する計測データ取得ステップと、記憶装置に記録されたビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位由来の熱分解生成物のピークに係るデータと前記計測データとに基づいて、前記試料にビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位の有無および量の少なくとも一方を推定する特定モノマー推定ステップと、記憶装置に記録されたフッ素原子を有するモノマーに基づく構成単位由来の熱分解生成物のピークに係るデータと前記計測データとに基づいて、前記試料のフッ素原子含量を推定するフッ素原子含量推定ステップと、前記特定モノマー推定ステップの推定結果と前記フッ素原子含量とに基づいて前記試料を評価する評価ステップとを有するフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法である。 A 1st aspect acquires the measurement data by the pyrolysis gas chromatography method or pyrolysis gas chromatography mass spectrometry of the sample which is the fluororesin coating material applied to a road bridge, or the fluororesin coating film provided in the road bridge Based on the measurement data acquisition step, the data relating to the peak of the thermal decomposition product derived from the structural unit based on at least one of vinyl ester and vinyl ether recorded in the storage device, and the measurement data, vinyl ester and vinyl ether are added to the sample. A specific monomer estimation step for estimating at least one of the presence and amount of a structural unit based on at least one of the above, and data relating to a peak of a thermal decomposition product derived from a structural unit based on a monomer having a fluorine atom recorded in a storage device; Based on the measurement data, fluorine of the sample Fluorine resin paint or fluororesin coating film evaluation method, comprising: fluorine atom content estimation step for estimating the content of the monomer; and evaluation step for evaluating the sample based on the estimation result of the specific monomer estimation step and the fluorine atom content It is.
　また、第２の態様は、第１の態様において、記憶装置に記録された、既知のフッ素樹脂塗料または既知のフッ素樹脂塗膜が吸収または放射する光を分光して得られるスペクトルデータまたは既知のフッ素樹脂塗料または既知のフッ素樹脂塗膜の熱分解ガスクロマトグラフィ法または熱分解ガスクロマトグラフィ質量分析法による計測データと、前記試料が吸収または放射する光を分光して得られるスペクトルデータまたは前記計測データ取得ステップで取得した前記計測データとの類似度を特定する類似度特定ステップをさらに有し、前記評価ステップで、前記特定モノマー推定ステップの推定結果と前記類似度特定ステップの特定結果と前記フッ素原子含量とに基づいて前記試料を評価するフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法である。 Further, the second aspect is the spectral data obtained by spectroscopically analyzing the light absorbed or emitted by the known fluororesin paint or the known fluororesin coating film recorded in the storage device in the first aspect or Measurement data of fluororesin paint or known fluororesin coating film by pyrolysis gas chromatography or pyrolysis gas chromatography mass spectrometry, spectral data obtained by spectroscopic analysis of light absorbed or emitted by the sample, or acquisition of measurement data A similarity specifying step for specifying a similarity with the measurement data acquired in the step, and in the evaluation step, an estimation result of the specific monomer estimation step, a specification result of the similarity specification step, and a fluorine atom content Evaluation method of fluororesin paint or fluororesin coating film to evaluate the sample based on It is.
　また、第３の態様は、第２の態様において、前記類似度特定ステップで特定した類似度が最も高い前記既知のフッ素樹脂塗料または前記既知のフッ素樹脂塗膜を特定する類似塗料特定ステップをさらに有し、前記評価ステップで、前記特定モノマー推定ステップの推定結果および前記フッ素原子含量と、前記類似塗料特定ステップが特定した前記既知のフッ素樹脂塗料または前記既知のフッ素樹脂塗膜のビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位の有無および量の少なくとも一方、ならびにフッ素原子含量とを比較することで、前記試料を評価するフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法である。 The third aspect further includes a similar paint specifying step for specifying the known fluororesin paint or the known fluororesin coating film having the highest degree of similarity specified in the similarity specifying step in the second aspect. And having the estimation result of the specific monomer estimation step and the fluorine atom content in the evaluation step, the known fluororesin paint specified by the similar paint specification step or the vinyl ester and vinyl ether of the known fluororesin coating film This is a fluororesin paint or a fluororesin coating film evaluation method for evaluating the sample by comparing the presence / absence and / or amount of a structural unit based on at least one of the above and the fluorine atom content.
　また、第４の態様は、第１から第３の何れかの態様において、前記計測データが、前記試料の熱分解ガスクロマトグラフィ質量分析法による計測データであり、前記ピークに係るデータが、ピークを生じる熱分解生成物の質量に係る物理量とピーク強度の閾値を含むフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法である。 Further, a fourth aspect is any one of the first to third aspects, wherein the measurement data is measurement data obtained by pyrolysis gas chromatography mass spectrometry of the sample, and the data relating to the peak includes a peak. This is a method for evaluating a fluororesin paint or a fluororesin coating film including a physical quantity related to the mass of the pyrolysis product to be produced and a threshold of peak intensity.
　また、第５の態様は、第１から第３の何れかの態様において、前記計測データが、前記試料の熱分解ガスクロマトグラフィ法による計測データであり、前記ピークに係るデータが、ピークを生じる熱分解生成物が検出される時刻とピーク強度の閾値を含むフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法である。 Further, a fifth aspect is any one of the first to third aspects, wherein the measurement data is measurement data obtained by pyrolysis gas chromatography of the sample, and the data related to the peak is heat that causes a peak. This is a method for evaluating a fluororesin paint or a fluororesin coating film including the time at which a decomposition product is detected and a threshold of peak intensity.
　また、第６の態様は、第１から第５の何れかの態様において、前記フッ素原子含量推定ステップで、前記計測データにおける前記フッ素原子を有するモノマーに基づく構成単位由来の熱分解生成物のピーク強度の閾値に基づいて、前記試料のフッ素原子含量を推定するフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法である。 In addition, in any one of the first to fifth aspects, a sixth aspect is a peak of a thermal decomposition product derived from a structural unit based on a monomer having the fluorine atom in the measurement data in the fluorine atom content estimation step. This is a method for evaluating a fluororesin coating material or a fluororesin coating film, which estimates the fluorine atom content of the sample based on an intensity threshold.
　また、第７の態様は、第１から第６の何れかの態様において、前記フッ素原子を有するモノマーが、テトラフルオロエチレンまたはクロロトリフルオロエチレンの少なくとも何れか一方であるフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法である。 A seventh aspect is the fluororesin paint or fluororesin coating according to any one of the first to sixth aspects, wherein the fluorine atom-containing monomer is at least one of tetrafluoroethylene and chlorotrifluoroethylene. This is a film evaluation method.
　また、第８の態様は、道路橋に塗布されるフッ素樹脂塗料または道路橋に設けられたフッ素樹脂塗膜である試料の、熱分解ガスクロマトグラフィ法または熱分解ガスクロマトグラフィ質量分析法による計測データを取得する計測データ取得部と、ビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位由来の熱分解生成物のピークに係るデータを記憶する特定モノマーピーク記憶装置と、フッ素原子を有するモノマーに基づく構成単位由来の熱分解生成物のピークに係るデータを記憶するフッ素ピーク記憶装置と、前記特定モノマーピーク記憶装置に記録されたビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位由来の熱分解生成物のピークに係るデータと前記計測データとに基づいて、前記試料にビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位の有無および量の少なくとも一方を推定する特定モノマー推定部と、前記フッ素ピーク記憶装置に記録されたフッ素原子を有するモノマーに基づく構成単位由来の熱分解生成物のピークに係るデータと前記計測データとに基づいて、前記試料のフッ素原子含量を推定するフッ素原子含量推定部とを備える評価用情報算出装置である。 In addition, the eighth aspect is the measurement data obtained by pyrolysis gas chromatography or pyrolysis gas chromatography mass spectrometry of a sample that is a fluororesin paint applied to a road bridge or a fluororesin coating film provided on a road bridge. Measurement data acquisition unit to acquire, specific monomer peak storage device that stores data related to the peak of thermal decomposition products derived from structural units based on at least one of vinyl ester and vinyl ether, and derived from structural units based on monomers having fluorine atoms A fluorine peak storage device for storing data relating to the peak of the thermal decomposition product of the product, and a peak of the thermal decomposition product derived from a structural unit based on at least one of vinyl ester and vinyl ether recorded in the specific monomer peak storage device Based on the data and the measurement data, A specific monomer estimator for estimating at least one of the presence and amount of a structural unit based on at least one of nyl ester and vinyl ether, and a thermal decomposition product derived from the structural unit based on a monomer having a fluorine atom recorded in the fluorine peak storage device The evaluation information calculation device includes a fluorine atom content estimation unit that estimates the fluorine atom content of the sample based on the peak data and the measurement data.
　また、第９の態様は、第８の態様において、前記特定モノマーピーク記憶装置にビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位由来の熱分解生成物のピークに係る新たなデータを記録する記録部をさらに備える評価用情報算出装置である。 A ninth aspect is the recording section according to the eighth aspect, wherein the specific monomer peak storage device records new data relating to a peak of a thermal decomposition product derived from a structural unit based on at least one of vinyl ester and vinyl ether. It is the information calculation device for evaluation further provided with.
　また、第１０の態様は、第８または第９の態様の評価用情報算出装置と端末装置とを備え、前記端末装置が、熱分解ガスクロマトグラフィ法または熱分解ガスクロマトグラフィ質量分析法による前記試料の計測データを生成する計測データ生成部と、前記計測データを前記評価用情報算出装置に送信する送信部と、前記評価用情報算出装置から、前記試料にビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位の有無および量の少なくとも一方の推定結果およびフッ素原子含量とに関する情報を受信する受信部と、前記受信部が受信した情報に基づいて、前記試料の評価に用いられる情報を提示する提示部とを備える評価用情報提示システムである。 Further, a tenth aspect includes the evaluation information calculation device according to the eighth or ninth aspect and a terminal device, and the terminal device is configured to measure the sample by pyrolysis gas chromatography or pyrolysis gas chromatography mass spectrometry. A measurement data generation unit that generates measurement data, a transmission unit that transmits the measurement data to the evaluation information calculation device, and a structural unit based on at least one of vinyl ester and vinyl ether from the evaluation information calculation device A receiving unit that receives information on the estimation result of at least one of the presence / absence and amount and the fluorine atom content, and a presentation unit that presents information used for evaluation of the sample based on the information received by the receiving unit It is the information presentation system for evaluation with which it is provided.
　また、第１１の態様は、フッ素樹脂塗料またはフッ素樹脂塗膜である試料の、熱分解ガスクロマトグラフィ法または熱分解ガスクロマトグラフィ質量分析法による計測データを生成する計測データ生成部と、前記計測データを評価用情報算出装置に送信する送信部と、前記第８または第９の態様の評価用情報算出装置から、前記試料にビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位の有無および量の少なくとも一方の推定結果およびフッ素原子含量とに関する情報を受信する受信部と、前記受信部が受信した情報に基づいて、前記試料の評価に用いられる情報を提示する提示部とを備える端末装置である。 An eleventh aspect includes a measurement data generation unit that generates measurement data of a sample that is a fluororesin paint or a fluororesin coating film by pyrolysis gas chromatography or pyrolysis gas chromatography mass spectrometry, and the measurement data From the transmitter for transmitting to the evaluation information calculation device and the evaluation information calculation device according to the eighth or ninth aspect, at least one of the presence and the amount of the structural unit based on at least one of vinyl ester and vinyl ether in the sample. The terminal device includes a receiving unit that receives information on an estimation result and a fluorine atom content, and a presentation unit that presents information used for evaluating the sample based on the information received by the receiving unit.
　また、第１２の態様は、フッ素樹脂塗料またはフッ素樹脂塗膜である試料の、熱分解ガスクロマトグラフィ法または熱分解ガスクロマトグラフィ質量分析法による計測データを生成する計測データ生成ステップと、前記計測データを評価用情報算出装置に送信する送信ステップと、前記第８または第９の態様の評価用情報算出装置から、前記試料にビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位の有無および量の少なくとも一方の推定結果およびフッ素原子含量とに関する情報を受信する受信ステップと、受信した前記情報に基づいて前記試料を評価する評価ステップとを有するフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法である。 A twelfth aspect includes a measurement data generation step for generating measurement data of a sample that is a fluororesin paint or a fluororesin coating film by pyrolysis gas chromatography or pyrolysis gas chromatography mass spectrometry, and the measurement data From the transmitting step for transmitting to the evaluation information calculation device, and from the evaluation information calculation device of the eighth or ninth aspect, at least one of the presence and amount and the amount of the structural unit based on at least one of vinyl ester and vinyl ether in the sample An evaluation method for a fluororesin paint or a fluororesin coating film, comprising: a reception step for receiving information on an estimation result and a fluorine atom content; and an evaluation step for evaluating the sample based on the received information.
　上記態様のうち少なくとも１つの態様によれば、フッ素樹脂塗料またはフッ素樹脂塗膜の同定が困難である場合にも、該フッ素樹脂塗料または該フッ素樹脂塗膜が道路橋の塗料または塗膜として適切であるか否かを評価できる。 According to at least one of the above aspects, the fluororesin paint or the fluororesin paint film is suitable as a road bridge paint or paint film even when it is difficult to identify the fluororesin paint or the fluororesin paint film. It can be evaluated whether or not.
第１の実施形態に係る評価用情報提示システム１の構成を示す概略図である。It is the schematic which shows the structure of the information presentation system for evaluation 1 which concerns on 1st Embodiment. 第１の実施形態に係る端末装置１０の構成を示す概略図である。It is the schematic which shows the structure of the terminal device 10 which concerns on 1st Embodiment. 第１の実施形態に係る評価用情報算出装置２０の構成を示す概略図である。It is the schematic which shows the structure of the information calculation apparatus 20 for evaluation which concerns on 1st Embodiment. 第１の実施形態に係る端末装置１０の動作を示すフローチャートである。It is a flowchart which shows operation | movement of the terminal device 10 which concerns on 1st Embodiment. 第１の実施形態に係る評価用情報算出装置２０の動作を示すフローチャートである。It is a flowchart which shows operation | movement of the information calculation apparatus 20 for evaluation which concerns on 1st Embodiment. 第１の実施形態に係る評価用情報算出装置２０の動作を示すフローチャートである。It is a flowchart which shows operation | movement of the information calculation apparatus 20 for evaluation which concerns on 1st Embodiment. 第１の実施形態に係る評価用情報算出装置２０の動作を示すフローチャートである。It is a flowchart which shows operation | movement of the information calculation apparatus 20 for evaluation which concerns on 1st Embodiment. 第２の実施形態に係る端末装置１０の構成を示す概略ブロック図である。It is a schematic block diagram which shows the structure of the terminal device 10 which concerns on 2nd Embodiment. 第２の実施形態に係る評価用情報算出装置２０の構成を示す概略ブロック図である。It is a schematic block diagram which shows the structure of the information calculation apparatus 20 for evaluation which concerns on 2nd Embodiment. 第３の実施形態に係る端末装置１０の構成を示す概略ブロック図である。It is a schematic block diagram which shows the structure of the terminal device 10 which concerns on 3rd Embodiment.
　以下、図面を参照しながら実施形態について詳しく説明する。
《第１の実施形態》
　図１は、第１の実施形態に係る評価用情報提示システム１の構成を示す概略図である。
　本実施形態に係る評価用情報提示システム１は、ラマン分光法および熱分解ＧＣ／ＭＳ法に基づいて道路橋に塗布されるフッ素樹脂塗料または道路橋に設けられたフッ素樹脂塗膜である試料Ｓの評価に用いられる情報を提供する。具体的には、評価用情報提示システム１は、既知のフッ素樹脂塗料またはフッ素樹脂塗膜と試料Ｓとの類似度、試料Ｓのビニルエステル、ビニルエーテル、テトラフルオロエチレン（以下、ＴＦＥとも記す。）およびクロロトリフルオロエチレン（以下、ＣＴＦＥとも記す。）の有無、ならびに、試料Ｓのビニルエステル、ビニルエーテル、ＴＦＥ、ＣＴＦＥ、およびフッ素原子の含量を提示する。 Hereinafter, embodiments will be described in detail with reference to the drawings.
<< First Embodiment >>
FIG. 1 is a schematic diagram illustrating a configuration of an evaluation information presentation system 1 according to the first embodiment.
The information presentation system for evaluation 1 according to the present embodiment is a sample S that is a fluororesin paint applied to a road bridge or a fluororesin coating film provided on the road bridge based on Raman spectroscopy and pyrolysis GC / MS method. Provides information used to evaluate Specifically, the information presentation system for evaluation 1 is similar to a known fluororesin paint or fluororesin coating film and the sample S, vinyl ester, vinyl ether, tetrafluoroethylene (hereinafter also referred to as TFE) of the sample S. And the presence or absence of chlorotrifluoroethylene (hereinafter also referred to as CTFE), and the content of vinyl ester, vinyl ether, TFE, CTFE, and fluorine atoms in Sample S.
　評価用情報提示システム１は、端末装置１０と評価用情報算出装置２０とを備える。端末装置１０と評価用情報算出装置２０とは、ネットワークＮを介して接続される。ネットワークＮの例としては、インターネットが挙げられる。
　端末装置１０は、試料Ｓについてラマン分光法に係る分析処理および熱分解ＧＣ／ＭＳ法に係る分析処理を行う。また端末装置１０は、評価用情報算出装置２０が生成した、試料Ｓの評価に用いられる情報を表示する。試料Ｓを評価する評価者Ｅは、端末装置１０に表示された情報に基づいて、試料Ｓが道路橋の塗料または塗膜として適切であるか否かを評価する。評価者Ｅは、フッ素樹脂塗料が用いられる現場において採取された試料Ｓを評価するため、端末装置１０は、携帯可能であることが好ましい。評価用情報算出装置２０は、端末装置１０が生成した計測データに基づいて、試料Ｓの評価に用いられる情報を算出する。 The evaluation information presentation system 1 includes a terminal device 10 and an evaluation information calculation device 20. The terminal device 10 and the evaluation information calculation device 20 are connected via a network N. An example of the network N is the Internet.
The terminal device 10 performs an analysis process related to the Raman spectroscopy and an analysis process related to the pyrolysis GC / MS method on the sample S. Further, the terminal device 10 displays information used for the evaluation of the sample S generated by the evaluation information calculation device 20. The evaluator E who evaluates the sample S evaluates whether or not the sample S is appropriate as a paint or a coating film for a road bridge based on the information displayed on the terminal device 10. Since the evaluator E evaluates the sample S collected at the site where the fluororesin paint is used, the terminal device 10 is preferably portable. The evaluation information calculation device 20 calculates information used for the evaluation of the sample S based on the measurement data generated by the terminal device 10.
　図２は、第１の実施形態に係る端末装置１０の構成を示す概略図である。
　端末装置１０は、収容スペース１０１、ラマン分光装置１０２、熱分解ＧＣ／ＭＳ装置１０３、演算装置１０４、通信装置１０５、および表示装置１０６を備える。 FIG. 2 is a schematic diagram illustrating a configuration of the terminal device 10 according to the first embodiment.
The terminal device 10 includes a storage space 101, a Raman spectroscopic device 102, a pyrolysis GC / MS device 103, a calculation device 104, a communication device 105, and a display device 106.
　収容スペース１０１は、試料Ｓを収容する空間である。
　ラマン分光装置１０２は、試料Ｓのラマン散乱による散乱光を計測する。ラマン分光装置１０２は、収容スペース１０１に収容された試料Ｓにレーザ光を照射するレーザ装置１２１、レーザ光の試料Ｓによる散乱光のうちラマン散乱による散乱光を通過させるフィルタ１２２、フィルタ１２２を通過した散乱光を複数の周波数の光に分光するモノクロメータ１２３およびモノクロメータ１２３が分光した光の強度を検出する検出器１２４を備える。ラマン分光装置１０２は、計測データ生成部の一例である。
　レーザ光の試料Ｓによる散乱光のうちラマン散乱による散乱光およびレイリー散乱による散乱光以外の他の散乱光の強度が、ラマン散乱による散乱光の計測に影響を与えない程度に小さい場合、フィルタ１２２は、レイリー散乱による散乱光をカットするものであってもよい。 The storage space 101 is a space for storing the sample S.
The Raman spectroscopic device 102 measures scattered light of the sample S due to Raman scattering. The Raman spectroscopic device 102 passes through a laser device 121 that irradiates a sample S accommodated in the accommodation space 101 with laser light, a filter 122 that allows light scattered by Raman scattering out of light scattered by the sample S of the laser light, and a filter 122. And a detector 124 for detecting the intensity of the light dispersed by the monochromator 123. The Raman spectroscopic device 102 is an example of a measurement data generation unit.
When the intensity of the scattered light other than the scattered light due to the Raman scattering and the scattered light due to the Rayleigh scattering is small enough not to affect the measurement of the scattered light due to the Raman scattering, the filter 122 May cut scattered light due to Rayleigh scattering.
　熱分解ＧＣ／ＭＳ装置１０３は、試料Ｓのマスクロマトグラムを生成する。熱分解ＧＣ／ＭＳ装置１０３は、熱分解装置１３１、ガスクロマトグラフ１３２、および質量分析装置１３３を備える。熱分解装置１３１は、収容スペース１０１に収容された試料Ｓを加熱することで、試料Ｓを熱分解する。ガスクロマトグラフ１３２は、試料Ｓの熱分解生成物を分離する。質量分析装置１３３は、ガスクロマトグラフ１３２から溶出した熱分解生成物をイオン化し、ｍ／ｚ値ごとのピーク強度を計測する。ｍ／ｚ値は、質量に係る物理量の一例である。熱分解ＧＣ／ＭＳ装置１０３は、計測データ生成部の一例である。 The pyrolysis GC / MS apparatus 103 generates a mass chromatogram of the sample S. The pyrolysis GC / MS device 103 includes a pyrolysis device 131, a gas chromatograph 132, and a mass spectrometer 133. The thermal decomposition apparatus 131 thermally decomposes the sample S by heating the sample S accommodated in the accommodation space 101. The gas chromatograph 132 separates the thermal decomposition product of the sample S. The mass spectrometer 133 ionizes the thermal decomposition product eluted from the gas chromatograph 132 and measures the peak intensity for each m / z value. The m / z value is an example of a physical quantity related to mass. The pyrolysis GC / MS device 103 is an example of a measurement data generation unit.
　演算装置１０４は、ラマン分光装置１０２および熱分解ＧＣ／ＭＳ装置１０３の計測結果に基づいて計測データを生成する。
　通信装置１０５は、演算装置１０４によって生成された計測データを、ネットワークＮを介して評価用情報算出装置２０に送信する。また通信装置１０５は、ネットワークＮを介して評価用情報算出装置２０から評価用情報を受信する。通信装置１０５は、送信部および受信部の一例である。
　表示装置１０６は、通信装置１０５が受信した評価用情報を表示する。表示装置１０６は、提示部の一例である。 The computing device 104 generates measurement data based on the measurement results of the Raman spectroscopic device 102 and the pyrolysis GC / MS device 103.
The communication device 105 transmits the measurement data generated by the arithmetic device 104 to the evaluation information calculation device 20 via the network N. Further, the communication device 105 receives the evaluation information from the evaluation information calculation device 20 via the network N. The communication device 105 is an example of a transmission unit and a reception unit.
The display device 106 displays the evaluation information received by the communication device 105. The display device 106 is an example of a presentation unit.
　図３は、第１の実施形態に係る評価用情報算出装置２０の構成を示す概略図である。
　評価用情報算出装置２０は、計測データ取得部２０１、データベース２０２、記録部２０３、同定部２０４、エステル推定部２０５、エーテル推定部２０６、フルオロオレフィン推定部２０７、および評価用情報出力部２０８を備える。
　計測データ取得部２０１は、端末装置１０が計測したラマン分光法および熱分解ＧＣ／ＭＳ法による試料Ｓの計測データをネットワークＮを介して取得する。 FIG. 3 is a schematic diagram illustrating a configuration of the evaluation information calculation apparatus 20 according to the first embodiment.
The evaluation information calculation apparatus 20 includes a measurement data acquisition unit 201, a database 202, a recording unit 203, an identification unit 204, an ester estimation unit 205, an ether estimation unit 206, a fluoroolefin estimation unit 207, and an evaluation information output unit 208. .
The measurement data acquisition unit 201 acquires measurement data of the sample S measured by the Raman spectroscopy method and pyrolysis GC / MS method measured by the terminal device 10 via the network N.
　データベース２０２は、塗料テーブル２２１、エステルピークテーブル２２２、エーテルピークテーブル２２３、およびフッ素ピークテーブル２２４を記憶する。
　塗料テーブル２２１は、道路橋の塗料または塗膜として適切であると認められる既知のフッ素樹脂塗料およびフッ素樹脂塗膜のラマンスペクトルデータと、ビニルエステル、ビニルエーテル、ＴＦＥおよびＣＴＦＥの有無と、ビニルエステル、ビニルエーテル、ＴＦＥ、ＣＴＦＥおよびフッ素原子の含量と、耐候性のランクとを格納する。エステルピークテーブル２２２は、ビニルエステルに基づく構成単位由来の熱分解生成物のピークに係るデータを格納する。つまり、データベース２０２は、ビニルエステルに基づく構成単位由来の熱分解生成物のピークに係るデータを記憶するエステルピーク記憶装置の一例である。エーテルピークテーブル２２３は、ビニルエーテルに基づく構成単位由来の熱分解生成物のピークに係るデータを格納する。つまり、データベース２０２は、ビニルエーテルに基づく構成単位由来の熱分解生成物のピークに係るデータを記憶するエーテルピーク記憶装置の一例である。エステルピークテーブル２２２およびエーテルピークテーブル２２３は、いずれも特定モノマーピーク記憶装置の一例である。フッ素ピークテーブル２２４は、フルオロオレフィン（フッ素原子を有するモノマー）に基づく構成単位由来の熱分解生成物のピークに係るデータを格納する。つまり、データベース２０２は、フッ素原子を有するモノマーに基づく構成単位由来の熱分解生成物のピークに係るデータを記憶するフッ素ピーク記憶装置の一例である。本実施形態において熱分解生成物のピークに係るデータとは、熱分解生成物のｍ／ｚ値とピーク強度の閾値とを関連付けたデータである。データベース２０２は、記憶装置の一例である。ピーク強度の閾値とは、マスクロマトグラムに表れる強度との比較により該マスクロマトグラムにピークが存在するか否かを判定するための閾値である。ピーク強度の閾値は、たとえば、基準ピークに対する比によって表される。 The database 202 stores a paint table 221, an ester peak table 222, an ether peak table 223, and a fluorine peak table 224.
The paint table 221 includes Raman spectra data of known fluororesin paints and fluororesin paint films that are recognized as being suitable as road bridge paints or paint films, the presence or absence of vinyl esters, vinyl ethers, TFE and CTFE, vinyl esters, Stores the content of vinyl ether, TFE, CTFE and fluorine atoms and the weather resistance rank. The ester peak table 222 stores data relating to peaks of thermal decomposition products derived from structural units based on vinyl esters. That is, the database 202 is an example of an ester peak storage device that stores data relating to the peak of the thermal decomposition product derived from the structural unit based on the vinyl ester. The ether peak table 223 stores data relating to peaks of thermal decomposition products derived from structural units based on vinyl ether. That is, the database 202 is an example of an ether peak storage device that stores data related to the peak of the thermal decomposition product derived from the structural unit based on vinyl ether. The ester peak table 222 and the ether peak table 223 are both examples of specific monomer peak storage devices. The fluorine peak table 224 stores data relating to the peak of the thermal decomposition product derived from the structural unit based on the fluoroolefin (monomer having a fluorine atom). That is, the database 202 is an example of a fluorine peak storage device that stores data relating to the peak of the thermal decomposition product derived from the structural unit based on the monomer having a fluorine atom. In the present embodiment, the data relating to the peak of the thermal decomposition product is data in which the m / z value of the thermal decomposition product is associated with the threshold value of the peak intensity. The database 202 is an example of a storage device. The peak intensity threshold is a threshold for determining whether or not a peak exists in the mass chromatogram by comparing with the intensity appearing in the mass chromatogram. The peak intensity threshold is represented by a ratio with respect to a reference peak, for example.
　記録部２０３は、道路橋の塗料または塗膜として適切であると新たに認められたフッ素樹脂塗料またはフッ素樹脂塗膜のラマンスペクトルデータ、ビニルエステル、ビニルエーテル、ＴＦＥおよびＣＴＦＥの有無、ビニルエステル、ビニルエーテル、ＴＦＥ、ＣＴＦＥおよびフッ素原子の含量、ならびに耐候性のランクの入力を受け付け、該データを塗料テーブル２２１に記録する。記録部２０３は、ビニルエステルに基づく構成単位由来の熱分解生成物のピークに係る新たなデータの入力を受け付け、該データをエステルピークテーブル２２２に記録する。記録部２０３は、ビニルエーテルに基づく構成単位由来の熱分解生成物のピークに係る新たなデータの入力を受け付け、該データをエーテルピークテーブル２２３に記録する。 The recording unit 203 includes a Raman spectrum data of a fluororesin paint or a fluororesin coating newly recognized as being suitable as a paint or a coating on a road bridge, presence / absence of vinyl ester, vinyl ether, TFE and CTFE, vinyl ester, vinyl ether. , TFE, CTFE, fluorine atom content, and weather resistance rank are received, and the data is recorded in the paint table 221. The recording unit 203 receives input of new data related to the peak of the thermal decomposition product derived from the structural unit based on the vinyl ester, and records the data in the ester peak table 222. The recording unit 203 receives input of new data related to the peak of the thermal decomposition product derived from the structural unit based on vinyl ether, and records the data in the ether peak table 223.
　同定部２０４は、計測データ取得部２０１が取得したラマン分光法による試料Ｓの計測データと塗料テーブル２２１に格納されたラマンスペクトルデータとを比較し、試料Ｓが既知のフッ素樹脂塗料またはフッ素樹脂塗膜であるか否かを判定する。
　エステル推定部２０５は、計測データ取得部２０１が取得した熱分解ＧＣ／ＭＳ法による試料Ｓの計測データとエステルピークテーブル２２２に格納されたビニルエステルに基づく構成単位由来の熱分解生成物のピークに係るデータとを比較し、試料Ｓにビニルエステルに基づく構成単位が含まれるか否かを判定する。またエステル推定部２０５は、試料Ｓにおけるビニルエステルに基づく構成単位の含量を推定する。
　エーテル推定部２０６は、計測データ取得部２０１が取得した熱分解ＧＣ／ＭＳ法による試料Ｓの計測データとエーテルピークテーブル２２３に格納されたビニルエーテルに基づく構成単位由来の熱分解生成物のピークに係るデータとを比較し、試料Ｓにビニルエーテルに基づく構成単位が含まれるか否かを判定する。またエーテル推定部２０６は、試料Ｓにおけるビニルエーテルに基づく構成単位の含量を推定する。
　つまり、エステル推定部２０５およびエーテル推定部２０６は、いずれも特定モノマー推定部の一例である。 The identification unit 204 compares the measurement data of the sample S obtained by the Raman spectroscopy obtained by the measurement data acquisition unit 201 with the Raman spectrum data stored in the paint table 221, and the sample S is a known fluororesin paint or fluororesin coating. It is determined whether or not it is a film.
The ester estimation unit 205 uses the measurement data of the sample S obtained by the pyrolysis GC / MS method acquired by the measurement data acquisition unit 201 and the peak of the pyrolysis product derived from the structural unit based on the vinyl ester stored in the ester peak table 222. It is compared with such data, and it is determined whether or not the sample S contains a structural unit based on vinyl ester. Further, the ester estimation unit 205 estimates the content of the structural unit based on the vinyl ester in the sample S.
The ether estimation unit 206 relates to the measurement data of the sample S by the pyrolysis GC / MS method acquired by the measurement data acquisition unit 201 and the peak of the pyrolysis product derived from the structural unit based on vinyl ether stored in the ether peak table 223. The data is compared to determine whether or not the sample S contains a structural unit based on vinyl ether. The ether estimation unit 206 estimates the content of the structural unit based on vinyl ether in the sample S.
That is, the ester estimation unit 205 and the ether estimation unit 206 are both examples of the specific monomer estimation unit.
　フルオロオレフィン推定部２０７は、計測データ取得部２０１が取得した熱分解ＧＣ／ＭＳ法による試料Ｓの計測データとフッ素ピークテーブル２２４に格納されたＴＦＥに基づく構成単位由来の熱分解生成物のピークに係るデータとを比較し、試料ＳにＴＦＥに基づく構成単位が含まれるか否かを判定する。またフルオロオレフィン推定部２０７は、試料ＳにおけるＴＦＥに基づく構成単位の含量を推定する。
　また、フルオロオレフィン推定部２０７は、計測データ取得部２０１が取得した熱分解ＧＣ／ＭＳ法による試料Ｓの計測データとフッ素ピークテーブル２２４に格納されたＣＴＦＥに基づく構成単位由来の熱分解生成物のピークに係るデータとを比較し、試料ＳにＣＴＦＥに基づく構成単位が含まれるか否かを判定する。またフルオロオレフィン推定部２０７は、試料ＳにおけるＣＴＦＥに基づく構成単位の含量を推定する。
　また、フルオロオレフィン推定部２０７は、計測データ取得部２０１が取得した熱分解ＧＣ／ＭＳ法による試料Ｓの計測データとＴＦＥおよびＣＴＦＥに基づく構成単位由来の熱分解生成物のピークに係るデータとに基づいて、試料Ｓのフッ素原子含量を推定する。
　評価用情報出力部２０８は、同定部２０４、エステル推定部２０５、エーテル推定部２０６およびフルオロオレフィン推定部２０７の算出結果を、ネットワークＮを介して端末装置１０に送信する。 The fluoroolefin estimation unit 207 uses the measurement data of the sample S obtained by the pyrolysis GC / MS method acquired by the measurement data acquisition unit 201 and the peak of the pyrolysis product derived from the structural unit based on TFE stored in the fluorine peak table 224. This data is compared with the data, and it is determined whether or not the sample S includes a structural unit based on TFE. In addition, the fluoroolefin estimation unit 207 estimates the content of the structural unit based on TFE in the sample S.
In addition, the fluoroolefin estimation unit 207 includes the measurement data of the sample S obtained by the pyrolysis GC / MS method acquired by the measurement data acquisition unit 201 and the pyrolysis product derived from the structural unit based on CTFE stored in the fluorine peak table 224. It is compared with the data concerning the peak, and it is determined whether or not the sample S includes a structural unit based on CTFE. In addition, the fluoroolefin estimation unit 207 estimates the content of the structural unit based on CTFE in the sample S.
Further, the fluoroolefin estimation unit 207 uses the measurement data of the sample S obtained by the pyrolysis GC / MS method acquired by the measurement data acquisition unit 201 and the data related to the peak of the pyrolysis product derived from the structural unit based on TFE and CTFE. Based on this, the fluorine atom content of sample S is estimated.
The evaluation information output unit 208 transmits the calculation results of the identification unit 204, ester estimation unit 205, ether estimation unit 206, and fluoroolefin estimation unit 207 to the terminal device 10 via the network N.
　次に、本実施形態に係る評価用情報提示システム１を用いたフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法について説明する。
　図４は、第１の実施形態に係る端末装置１０の動作を示すフローチャートである。図５、図６および図７は、第１の実施形態に係る評価用情報算出装置２０の動作を示すフローチャートである。
　評価者Ｅは、端末装置１０を携えてフッ素樹脂塗料が用いられる現場に赴き、フッ素樹脂塗料またはフッ素樹脂塗膜である試料Ｓを採取する。評価者Ｅは、採取した試料Ｓを端末装置１０の収容スペース１０１に収容する。評価者Ｅは、試料Ｓを収容スペース１０１に収容すると、端末装置１０を起動させる。 Next, a fluororesin paint or a fluororesin coating film evaluation method using the evaluation information presentation system 1 according to the present embodiment will be described.
FIG. 4 is a flowchart showing the operation of the terminal device 10 according to the first embodiment. 5, 6 and 7 are flowcharts showing the operation of the evaluation information calculation apparatus 20 according to the first embodiment.
The evaluator E goes to the site where the fluororesin paint is used with the terminal device 10 and collects a sample S that is a fluororesin paint or a fluororesin coating film. The evaluator E stores the collected sample S in the storage space 101 of the terminal device 10. The evaluator E activates the terminal device 10 when the sample S is accommodated in the accommodation space 101.
　端末装置１０が起動すると、レーザ装置１２１は、収容スペース１０１に収容された試料Ｓにレーザ光を照射する（図４のステップＳ１０１）。このとき収容スペース１０１に収容される試料Ｓとして、予め成分分離処理により、溶媒、顔料、およびその他の添加物の少なくとも１つを除去されたものを用いることで、得られるスペクトルデータの精度を向上させることができる。また、端末装置１０は、添加物を除去した試料Ｓと除去しない試料Ｓの両方についてスペクトルデータを生成してもよい。レーザ光が試料Ｓに照射されると、試料Ｓから複数種類の散乱光が生じる。具体的には、試料Ｓへのレーザ光の照射によりレイリー散乱による散乱光、ラマン散乱による散乱光、およびその他の散乱光が生じる。散乱光は、フィルタ１２２を通ってモノクロメータ１２３へ入射する。このとき、フィルタ１２２は、散乱光のうちラマン散乱による散乱光を通過させるため、モノクロメータ１２３には、ラマン散乱による散乱光が入射する。モノクロメータ１２３に入射した光は波長ごとに分光される。分光された光は、検出器に入射する。 When the terminal device 10 is activated, the laser device 121 irradiates the sample S accommodated in the accommodation space 101 with laser light (step S101 in FIG. 4). At this time, as the sample S accommodated in the accommodating space 101, the accuracy of the obtained spectrum data is improved by using the sample S from which at least one of the solvent, the pigment, and other additives has been previously removed by the component separation process. Can be made. The terminal device 10 may generate spectrum data for both the sample S from which the additive has been removed and the sample S from which the additive has not been removed. When the sample S is irradiated with laser light, a plurality of types of scattered light are generated from the sample S. Specifically, the sample S is irradiated with laser light to generate scattered light due to Rayleigh scattering, scattered light due to Raman scattering, and other scattered light. The scattered light enters the monochromator 123 through the filter 122. At this time, since the filter 122 passes the scattered light due to the Raman scattering among the scattered light, the scattered light due to the Raman scattering is incident on the monochromator 123. The light incident on the monochromator 123 is split for each wavelength. The split light enters the detector.
　検出器１２４は、モノクロメータ１２３から入射した光の強度を検出し、波長と光の強度との関係を示すスペクトルデータを生成する（ステップＳ１０２）。次に、演算装置１０４は、検出器１２４から計測データであるスペクトルデータを取得し、通信装置１０５を介して該スペクトルデータを評価用情報算出装置２０に送信する（ステップＳ１０３）。 The detector 124 detects the intensity of the light incident from the monochromator 123, and generates spectral data indicating the relationship between the wavelength and the light intensity (step S102). Next, the arithmetic device 104 acquires spectrum data that is measurement data from the detector 124, and transmits the spectrum data to the evaluation information calculation device 20 via the communication device 105 (step S103).
　端末装置１０がスペクトルデータを送信すると、評価用情報算出装置２０の計測データ取得部２０１は、該スペクトルデータを受信する（図５のステップＳ２０１）。次に、同定部２０４は、受信したスペクトルデータと塗料テーブル２２１に記録された複数のスペクトルデータそれぞれとの類似度を算出する（ステップＳ２０２）。スペクトルデータの類似度は、たとえば、ピーク位置の差およびピーク強度の比によって求めることができる。 When the terminal device 10 transmits spectrum data, the measurement data acquisition unit 201 of the evaluation information calculation device 20 receives the spectrum data (step S201 in FIG. 5). Next, the identifying unit 204 calculates the similarity between the received spectrum data and each of the plurality of spectrum data recorded in the paint table 221 (step S202). The similarity of spectrum data can be obtained, for example, by a peak position difference and a peak intensity ratio.
　次に、同定部２０４は、塗料テーブル２２１を参照し、スペクトルデータの類似度が最も高い既知の塗料または塗膜を特定する（ステップＳ２０４）。次に、同定部２０４は、特定した既知の塗料または塗膜とのスペクトルデータの類似度が所定の疑義範囲内にあるか否かを判定する（ステップＳ２０４）。疑義範囲とは、類似度の最大値以下、かつ試料Ｓがいずれの既知の塗料および塗膜とも一致しないと判断する閾値より大きい値の範囲である。つまり、疑義範囲とは、試料Ｓが既知の塗料または塗膜と一致している可能性がある類似度の範囲である。 Next, the identification unit 204 refers to the paint table 221 and identifies a known paint or paint film having the highest degree of similarity in spectrum data (step S204). Next, the identification unit 204 determines whether or not the similarity of the spectrum data with the specified known paint or coating film is within a predetermined doubt range (step S204). The doubt range is a range of values that are equal to or less than the maximum value of similarity and greater than a threshold value that determines that the sample S does not match any known paint or coating film. In other words, the doubt range is a range of similarity in which the sample S may match a known paint or coating film.
　同定部２０４が、スペクトルデータの類似度のうち最も高いものが所定の疑義範囲内にないと判定した場合（ステップＳ２０４：ＮＯ）、評価用情報出力部２０８は、スペクトルデータの類似度のうち最も高いものを、端末装置１０に送信する（ステップＳ２０５）。
　他方、同定部２０４が、スペクトルデータの類似度のうち最も高いものが所定の疑義範囲内にあると判定した場合（ステップＳ２０４：ＹＥＳ）、評価用情報出力部２０８は、スペクトルデータの類似度のうち最も高いものと、試料Ｓのクロマトグラムの取得指示とを、端末装置１０に送信する（ステップＳ２０６）。 When the identification unit 204 determines that the highest similarity among the spectrum data is not within the predetermined suspicion range (step S204: NO), the evaluation information output unit 208 determines the highest similarity among the spectrum data. The higher one is transmitted to the terminal device 10 (step S205).
On the other hand, when the identifying unit 204 determines that the highest similarity among the spectrum data is within the predetermined doubt range (step S204: YES), the evaluation information output unit 208 determines the similarity of the spectrum data. The highest one of them and an instruction to acquire the chromatogram of the sample S are transmitted to the terminal device 10 (step S206).
　評価用情報算出装置２０がスペクトルデータの類似度を送信すると、端末装置１０の通信装置１０５は、該類似度を受信する（図４のステップＳ１０４）。次に、演算装置１０４は、通信装置１０５が受信した類似度を表示装置１０６に表示させる（ステップＳ１０５）。評価者Ｅは、表示装置１０６に表示された類似度に基づいて、試料Ｓが道路橋の塗料または塗膜として適切であるか否かを評価する。具体的には、評価者Ｅは、類似度が疑義範囲外（閾値以下）である場合、試料Ｓが道路橋の塗料または塗膜として適切であると認められる既知の塗料および塗膜のいずれとも一致しないため、試料Ｓが道路橋の塗料または塗膜として適切でないと評価する。評価者Ｅは、類似度が疑義範囲内である場合、試料Ｓが道路橋の塗料または塗膜として適切であるか否かの評価を保留する。 When the evaluation information calculation device 20 transmits the similarity of the spectrum data, the communication device 105 of the terminal device 10 receives the similarity (step S104 in FIG. 4). Next, the arithmetic device 104 displays the similarity received by the communication device 105 on the display device 106 (step S105). The evaluator E evaluates based on the similarity displayed on the display device 106 whether or not the sample S is appropriate as a paint or coating film for a road bridge. Specifically, the evaluator E, when the similarity is out of the doubt range (below the threshold value), does not use any of the known paints and coatings for which the sample S is recognized as being suitable as a road bridge paint or coating. Since they do not agree, it is evaluated that the sample S is not suitable as a paint or coating film for a road bridge. If the degree of similarity is within the doubt range, the evaluator E suspends the evaluation of whether or not the sample S is suitable as a paint or coating film for a road bridge.
　次に、演算装置１０４は、通信装置１０５がスペクトルデータの類似度とともにスタンダード剤と試料Ｓのクロマトグラムの取得指示を受信したか否かを判定する（ステップＳ１０６）。スタンダード剤としては、たとえばＴＦＥやＣＴＦＥ、特定ビニルエステル、特定ビニルエーテルに基づく構成単位を含み、かつこれらの含量が既知である物質や、特定のモノマーなどの既知化合物を用いることができる。演算装置１０４は、スタンダード剤と試料Ｓのクロマトグラムの取得指示を受信していないと判定した場合（ステップＳ１０６：ＮＯ）、処理を終了する。これは、類似度が疑義範囲にないため、類似度の表示のみにより評価者Ｅが試料Ｓが道路橋の塗料または塗膜として適切であるか否かを評価できるためである。 Next, the arithmetic device 104 determines whether or not the communication device 105 has received an instruction to acquire chromatograms of the standard agent and the sample S together with the similarity of the spectrum data (step S106). As the standard agent, for example, substances containing structural units based on TFE, CTFE, specific vinyl ester, and specific vinyl ether, and the contents of which are known, and known compounds such as specific monomers can be used. If the arithmetic unit 104 determines that an instruction to acquire chromatograms of the standard agent and the sample S has not been received (step S106: NO), the processing ends. This is because the similarity is not within the suspicion range, and the evaluator E can evaluate whether or not the sample S is appropriate as a paint or a coating on the road bridge only by displaying the similarity.
　他方、演算装置１０４は、スタンダード剤と試料Ｓのクロマトグラムの取得指示を受信したと判定した場合（ステップＳ１０６：ＹＥＳ）、熱分解装置１３１を起動させ、収容スペース１０１に収容されたスタンダード剤を加熱させる（ステップＳ１０７）。スタンダード剤は、加熱により熱分解され、ガスクロマトグラフ１３２に導入される。ガスクロマトグラフ１３２は、スタンダード剤の熱分解生成物を分離する。質量分析装置１３３は、ガスクロマトグラフ１３２から溶出した熱分解生成物をイオン化し、ｍ／ｚ値ごとのピーク強度を計測する。これにより、質量分析装置１３３は、ｍ／ｚ値ごとのマスクロマトグラムを生成する（ステップＳ１０８）。
　次に、演算装置１０４は、質量分析装置１３３から計測データであるマスクロマトグラムを取得し、通信装置１０５を介して該マスクロマトグラムを評価用情報算出装置２０に送信する（ステップＳ１０９）。 On the other hand, when the arithmetic unit 104 determines that the instruction to acquire the chromatogram of the standard agent and the sample S has been received (step S106: YES), the thermal decomposition apparatus 131 is activated and the standard agent accommodated in the accommodating space 101 is removed. Heat (step S107). The standard agent is thermally decomposed by heating and introduced into the gas chromatograph 132. The gas chromatograph 132 separates the thermal decomposition products of the standard agent. The mass spectrometer 133 ionizes the thermal decomposition product eluted from the gas chromatograph 132 and measures the peak intensity for each m / z value. Thereby, the mass spectrometer 133 produces | generates the mass chromatogram for every m / z value (step S108).
Next, the arithmetic unit 104 acquires a mass chromatogram that is measurement data from the mass spectrometer 133 and transmits the mass chromatogram to the evaluation information calculation unit 20 via the communication unit 105 (step S109).
　演算装置１０４がスタンダード剤のマスクロマトグラムを送信すると、評価者Ｅは、収容スペース１０１からスタンダード剤を取り出し、収容スペース１０１に試料Ｓを入れる。収容スペース１０１に試料Ｓが入れられると、演算装置１０４は、熱分解装置１３１を起動させ、収容スペース１０１に収容された試料Ｓを加熱させる（ステップＳ１１０）。このとき収容スペース１０１に収容される試料Ｓとして、予め成分分離処理により、溶媒、顔料、およびその他の添加物の少なくとも１つを除去されたものを用いることで、得られるクロマトグラムの精度を向上させることができる。また、端末装置１０は、添加物を除去した試料Ｓと除去しない試料Ｓの両方についてクロマトグラムを生成してもよい。試料Ｓは、加熱により熱分解され、ガスクロマトグラフ１３２に導入される。ガスクロマトグラフ１３２は、試料Ｓの熱分解生成物を分離する。質量分析装置１３３は、ガスクロマトグラフ１３２から溶出した熱分解生成物をイオン化し、ｍ／ｚ値ごとのピーク強度を計測する。これにより、質量分析装置１３３は、ｍ／ｚ値ごとのマスクロマトグラムを生成する（ステップＳ１１１）。質量分析装置１３３による計測の対象となるｍ／ｚの範囲は、たとえば１０以上１０００以下の範囲である。
　次に、演算装置１０４は、質量分析装置１３３から計測データであるマスクロマトグラムを取得し、通信装置１０５を介して該マスクロマトグラムを評価用情報算出装置２０に送信する（ステップＳ１１２）。 When the arithmetic unit 104 transmits the mass chromatogram of the standard agent, the evaluator E takes out the standard agent from the storage space 101 and puts the sample S into the storage space 101. When the sample S is placed in the storage space 101, the arithmetic unit 104 activates the thermal decomposition apparatus 131 and heats the sample S stored in the storage space 101 (step S110). At this time, as the sample S stored in the storage space 101, the accuracy of the obtained chromatogram is improved by using the sample S from which at least one of the solvent, the pigment, and other additives has been previously removed by the component separation process. Can be made. The terminal device 10 may generate chromatograms for both the sample S from which the additive has been removed and the sample S from which the additive has not been removed. The sample S is thermally decomposed by heating and introduced into the gas chromatograph 132. The gas chromatograph 132 separates the thermal decomposition product of the sample S. The mass spectrometer 133 ionizes the thermal decomposition product eluted from the gas chromatograph 132 and measures the peak intensity for each m / z value. Thereby, the mass spectrometer 133 produces | generates the mass chromatogram for every m / z value (step S111). The m / z range to be measured by the mass spectrometer 133 is, for example, in the range of 10 to 1000.
Next, the arithmetic unit 104 acquires a mass chromatogram that is measurement data from the mass spectrometer 133, and transmits the mass chromatogram to the evaluation information calculation unit 20 via the communication unit 105 (step S112).
　端末装置１０がスタンダード剤および試料Ｓのマスクロマトグラムを送信すると、評価用情報算出装置２０の計測データ取得部２０１は、該マスクロマトグラムを受信する（図５のステップＳ２０７）。次に、フルオロオレフィン推定部２０７は、フッ素ピークテーブル２２４から、特定化合物のｍ／ｚ値およびピーク強度の閾値を特定する。フルオロオレフィン推定部２０７は、特定化合物が出現するｍ／ｚ値に関連付けられたスタンダード剤のマスクロマトグラムのピーク強度を特定する（ステップＳ２０８）。つまり、フルオロオレフィン推定部２０７は、スタンダード剤における特定のピーク（例えばＴＦＥおよびＣＴＦＥに係るピーク）の強度を特定する。次に、フルオロオレフィン推定部２０７は、特定化合物のピーク位置およびピーク強度の検量線を作成する（ステップＳ２０９）。つまり、フルオロオレフィン推定部２０７は、熱分解ＧＣ／ＭＳ装置１０３の分析毎の検出感度を補正するための感度補正係数を導き出す。 When the terminal device 10 transmits the mass chromatogram of the standard agent and the sample S, the measurement data acquisition unit 201 of the evaluation information calculation device 20 receives the mass chromatogram (step S207 in FIG. 5). Next, the fluoroolefin estimation unit 207 specifies the m / z value and peak intensity threshold of the specific compound from the fluorine peak table 224. The fluoroolefin estimating unit 207 specifies the peak intensity of the mass chromatogram of the standard agent associated with the m / z value at which the specific compound appears (step S208). That is, the fluoroolefin estimation unit 207 specifies the intensity of a specific peak (for example, a peak related to TFE and CTFE) in the standard agent. Next, the fluoroolefin estimation unit 207 creates a calibration curve of the peak position and peak intensity of the specific compound (step S209). That is, the fluoroolefin estimation unit 207 derives a sensitivity correction coefficient for correcting the detection sensitivity for each analysis of the pyrolysis GC / MS apparatus 103.
　計測データ取得部２０１は、取得した試料Ｓのマスクロマトグラムのピーク強度に、フルオロオレフィン推定部２０７が導き出した感度補正係数を乗算することで、マスクロマトグラムを補正する。次に、エステル推定部２０５は、エステルピークテーブル２２２から、ビニルエステルに基づく構成単位由来の熱分解生成物毎の、ｍ／ｚ値（ピーク位置）およびピーク強度の閾値を特定する（図６のステップＳ２１０）。次に、エステル推定部２０５は、特定した熱分解生成物毎のｍ／ｚ値に関連付けられたマスクロマトグラムの中に、特定したピーク強度の閾値を超えるピークが存在するか否かを判定する（ステップＳ２１１）。 The measurement data acquisition unit 201 corrects the mass chromatogram by multiplying the peak intensity of the acquired mass chromatogram of the sample S by the sensitivity correction coefficient derived by the fluoroolefin estimation unit 207. Next, the ester estimation unit 205 specifies the m / z value (peak position) and the peak intensity threshold value for each thermal decomposition product derived from the vinyl ester-based structural unit from the ester peak table 222 (FIG. 6). Step S210). Next, the ester estimation unit 205 determines whether or not there is a peak exceeding the specified peak intensity threshold in the mass chromatogram associated with the m / z value for each specified thermal decomposition product. (Step S211).
　エステル推定部２０５は、ピーク強度の閾値を超えるピークを有する熱分解生成物が１種類以上存在すると判定した場合（ステップＳ２１１：ＹＥＳ）、試料Ｓにビニルエステルに基づく構成単位が含まれると判定する（ステップＳ２１２）。他方、エステル推定部２０５は、ピーク強度の閾値を超えるピークを有する熱分解生成物が１種類も存在しないと判定した場合（ステップＳ２１１：ＮＯ）、試料Ｓにビニルエステルに基づく構成単位が含まれないと判定する（ステップＳ２１３）。 When the ester estimation unit 205 determines that one or more types of thermal decomposition products having peaks exceeding the peak intensity threshold are present (step S211: YES), the sample estimation unit 205 determines that the sample S includes a structural unit based on vinyl ester. (Step S212). On the other hand, when the ester estimation unit 205 determines that there is no one kind of thermal decomposition product having a peak exceeding the peak intensity threshold (step S211: NO), the sample S includes a structural unit based on vinyl ester. It is determined that there is not (step S213).
　次に、エーテル推定部２０６は、エーテルピークテーブル２２３から、ビニルエーテルに基づく構成単位由来の熱分解生成物毎の、ｍ／ｚ値およびピーク強度の閾値を特定する（ステップＳ２１４）。次に、エーテル推定部２０６は、特定した熱分解生成物毎のｍ／ｚ値に関連付けられたマスクロマトグラムの中に、特定したピーク強度の閾値を超えるピークが存在するか否かを判定する（ステップＳ２１５）。 Next, the ether estimation unit 206 specifies the m / z value and the peak intensity threshold value for each thermal decomposition product derived from the structural unit based on vinyl ether from the ether peak table 223 (step S214). Next, the ether estimation unit 206 determines whether or not a peak exceeding the specified peak intensity threshold exists in the mass chromatogram associated with the m / z value for each specified thermal decomposition product. (Step S215).
　エーテル推定部２０６は、ピーク強度の閾値を超えるピークを有する熱分解生成物が１種類以上存在すると判定した場合（ステップＳ２１５：ＹＥＳ）、試料Ｓにビニルエーテルに基づく構成単位が含まれると判定する（ステップＳ２１５）。他方、エーテル推定部２０６は、ピーク強度の閾値を超えるピークを有する熱分解生成物が１種類も存在しないと判定した場合（ステップＳ２１５：ＮＯ）、試料Ｓにビニルエーテルに基づく構成単位が含まれないと判定する（ステップＳ２１７）。 When the ether estimation unit 206 determines that one or more types of thermal decomposition products having peaks exceeding the peak intensity threshold are present (step S215: YES), the ether estimation unit 206 determines that the structural unit based on vinyl ether is included in the sample S ( Step S215). On the other hand, when the ether estimation unit 206 determines that there is no one kind of thermal decomposition product having a peak exceeding the peak intensity threshold (step S215: NO), the sample S does not include a structural unit based on vinyl ether. Is determined (step S217).
　次に、フルオロオレフィン推定部２０７は、フッ素ピークテーブル２２４から、ＴＦＥに基づく構成単位由来の熱分解生成物毎の、ｍ／ｚ値およびピーク強度の閾値を特定する（ステップＳ２１８）。次に、フルオロオレフィン推定部２０７は、特定した熱分解生成物毎のｍ／ｚ値に関連付けられたマスクロマトグラムの中に、特定したピーク強度の閾値を超えるピークが存在するか否かを判定する（ステップＳ２１９）。 Next, the fluoroolefin estimation unit 207 specifies the threshold value of the m / z value and the peak intensity for each thermal decomposition product derived from the structural unit based on TFE from the fluorine peak table 224 (step S218). Next, the fluoroolefin estimating unit 207 determines whether or not there is a peak exceeding the specified peak intensity threshold in the mass chromatogram associated with the m / z value for each specified thermal decomposition product. (Step S219).
　フルオロオレフィン推定部２０７は、ピーク強度の閾値を超えるピークを有する熱分解生成物が存在すると判定した場合（ステップＳ２１９：ＹＥＳ）、試料ＳにＴＦＥに基づく構成単位が含まれると判定する（ステップＳ２２０）。他方、フルオロオレフィン推定部２０７は、ピーク強度の閾値を超えるピークを有する熱分解生成物が存在しないと判定した場合（ステップＳ２１９：ＮＯ）、試料ＳにＴＦＥに基づく構成単位が含まれないと判定する（ステップＳ２２１）。 When the fluoroolefin estimating unit 207 determines that there is a thermal decomposition product having a peak exceeding the threshold value of the peak intensity (step S219: YES), the fluoroolefin estimating unit 207 determines that the structural unit based on TFE is included in the sample S (step S220). ). On the other hand, when the fluoroolefin estimating unit 207 determines that there is no thermal decomposition product having a peak exceeding the peak intensity threshold value (step S219: NO), the sample S determines that the structural unit based on TFE is not included. (Step S221).
　次に、フルオロオレフィン推定部２０７は、フッ素ピークテーブル２２４から、ＣＴＦＥに基づく構成単位由来の熱分解生成物毎の、ｍ／ｚ値およびピーク強度の閾値を特定する（ステップＳ２２２）。次に、フルオロオレフィン推定部２０７は、特定した熱分解生成物毎のｍ／ｚ値に関連付けられたマスクロマトグラムの中に、特定したピーク強度の閾値を超えるピークが存在するか否かを判定する（ステップＳ２２３）。 Next, the fluoroolefin estimating unit 207 specifies the m / z value and the peak intensity threshold value for each thermal decomposition product derived from the structural unit based on CTFE from the fluorine peak table 224 (step S222). Next, the fluoroolefin estimating unit 207 determines whether or not there is a peak exceeding the specified peak intensity threshold in the mass chromatogram associated with the m / z value for each specified thermal decomposition product. (Step S223).
　フルオロオレフィン推定部２０７は、ピーク強度の閾値を超えるピークを有する熱分解生成物が存在すると判定した場合（ステップＳ２２３：ＹＥＳ）、試料ＳにＣＴＦＥに基づく構成単位が含まれると判定する（ステップＳ２２４）。他方、フルオロオレフィン推定部２０７は、ピーク強度の閾値を超えるピークを有する熱分解生成物が存在しないと判定した場合（ステップＳ２２３：ＮＯ）、試料ＳにＣＴＦＥに基づく構成単位が含まれないと判定する（ステップＳ２２５）。
　評価用情報出力部２０８は、推定した各構成単位の有無と、既知の各構成単位の有無と、類似度が最も高い既知の塗料または塗膜の名称とを、端末装置１０に出力する（ステップＳ２２６）。 When the fluoroolefin estimation unit 207 determines that there is a thermal decomposition product having a peak exceeding the threshold value of the peak intensity (step S223: YES), the fluoroolefin estimation unit 207 determines that the structural unit based on CTFE is included in the sample S (step S224). ). On the other hand, when the fluoroolefin estimating unit 207 determines that there is no pyrolysis product having a peak exceeding the peak intensity threshold value (step S223: NO), the sample S determines that the constituent unit based on CTFE is not included. (Step S225).
The evaluation information output unit 208 outputs the estimated presence / absence of each structural unit, the presence / absence of each known structural unit, and the name of the known paint or coating film having the highest degree of similarity to the terminal device 10 (step S10). S226).
　次に、フルオロオレフィン推定部２０７は、ステップＳ２１８およびＳ２２２で特定したｍ／ｚ値に関連付けられた試料Ｓのマスクロマトグラムのピーク強度と、ステップＳ２０８で特定したスタンダード剤のマスクロマトグラムのピーク強度の比に基づいて、試料ＳのＴＦＥおよびＣＴＦＥに基づく構成単位ならびにフッ素原子の含量を推定する（図７のステップＳ２２７）。具体的には、例えばフルオロオレフィン推定部２０７は、スタンダード剤のＴＦＥおよびＣＴＦＥの含量に、スタンダード剤のマスクロマトグラムのピーク強度と試料Ｓのマスクロマトグラムのピーク強度との比を乗算することで、試料ＳのＴＦＥ、ＣＴＦＥの含量を推定する。また、フルオロオレフィン推定部２０７は、特定したＴＦＥの含量とＣＴＦＥの含量に所定の係数を乗算して合算することで、フッ素原子の含量を推定する。 Next, the fluoroolefin estimation unit 207 determines the peak intensity of the mass chromatogram of the sample S associated with the m / z value specified in steps S218 and S222 and the peak intensity of the mass chromatogram of the standard agent specified in step S208. Based on the ratio, the constituent unit based on TFE and CTFE of the sample S and the content of fluorine atoms are estimated (step S227 in FIG. 7). Specifically, for example, the fluoroolefin estimating unit 207 multiplies the TFE and CTFE contents of the standard agent by the ratio of the peak intensity of the mass chromatogram of the standard agent and the peak intensity of the mass chromatogram of the sample S. The contents of TFE and CTFE of sample S are estimated. In addition, the fluoroolefin estimating unit 207 estimates the fluorine atom content by multiplying the specified TFE content and CTFE content by a predetermined coefficient and adding them together.
　次に、エステル推定部２０５は、ステップＳ２１０で特定したピーク強度と、ステップＳ２０８で特定したスタンダード剤における特定のピーク（例えば、特定ビニルエステルモノマー）の強度との比に基づいて、試料Ｓのビニルエステルに基づく構成単位の含量を推定する（ステップＳ２２８）。また、エーテル推定部２０６は、ステップＳ２１４で特定したピーク強度と、ステップＳ２０８で特定したスタンダード剤における特定のピーク（例えば、特定ビニルエーテルモノマー）の強度との比に基づいて、試料Ｓのビニルエーテルに基づく構成単位の含量を推定する（ステップＳ２２９）。そして、評価用情報出力部２０８は、エステル推定部２０５、エーテル推定部２０６およびフルオロオレフィン推定部２０７による推定結果を評価用情報として端末装置１０に送信する（ステップＳ２３０）。 Next, the ester estimation unit 205 determines the vinyl of the sample S based on the ratio between the peak intensity specified in step S210 and the intensity of a specific peak (for example, a specific vinyl ester monomer) in the standard agent specified in step S208. The content of the structural unit based on the ester is estimated (step S228). Further, the ether estimation unit 206 is based on the vinyl ether of the sample S based on the ratio between the peak intensity specified in step S214 and the intensity of a specific peak (for example, a specific vinyl ether monomer) in the standard agent specified in step S208. The content of the structural unit is estimated (step S229). Then, the evaluation information output unit 208 transmits the estimation results obtained by the ester estimation unit 205, the ether estimation unit 206, and the fluoroolefin estimation unit 207 to the terminal device 10 as evaluation information (step S230).
　ステップＳ２２７またはステップＳ２３０により評価用情報算出装置２０が評価用情報を送信すると、端末装置１０の通信装置１０５は、該評価用情報を受信する（図４のステップＳ１１４）。次に、演算装置１０４は、通信装置１０５が受信した評価用情報を表示装置１０６に表示させ（ステップＳ１１５）、処理を終了する。
　評価者Ｅは、表示装置１０６に表示された評価用情報に基づいて、試料Ｓが道路橋の塗料または塗膜として適切であるか否かを評価する。具体的には、評価者Ｅは、試料Ｓと、該試料Ｓと最も類似する既知の塗料または塗膜とで、ビニルエステル、ビニルエーテル、ＴＦＥおよびＣＴＦＥの有無が一致し、かつビニルエステル、ビニルエーテル、ＴＦＥ、ＣＴＦＥおよびフッ素原子の含量の誤差が一定値以内である場合に、試料Ｓが道路橋の塗料または塗膜として適切であると評価する。また、評価者Ｅは、試料Ｓの耐候性ランクに基づいて、該試料Ｓの耐候性についても評価する。他方、試料Ｓと、該試料Ｓと最も類似する既知の塗料または塗膜とで、ビニルエステル、ビニルエーテル、ＴＦＥおよびＣＴＦＥの有無が一致しない場合、またはビニルエステル、ビニルエーテル、ＴＦＥ、ＣＴＦＥおよびフッ素原子の含量の誤差が一定値より大きい場合に、試料Ｓが道路橋の塗料または塗膜として適切でないと評価する。 When the evaluation information calculation device 20 transmits the evaluation information in step S227 or step S230, the communication device 105 of the terminal device 10 receives the evaluation information (step S114 in FIG. 4). Next, the arithmetic device 104 displays the evaluation information received by the communication device 105 on the display device 106 (step S115), and ends the processing.
The evaluator E evaluates based on the evaluation information displayed on the display device 106 whether or not the sample S is appropriate as a paint or coating film for a road bridge. Specifically, the evaluator E matches the presence or absence of vinyl ester, vinyl ether, TFE, and CTFE in the sample S and the known paint or coating film most similar to the sample S, and the vinyl ester, vinyl ether, When the errors in the contents of TFE, CTFE and fluorine atoms are within a certain value, it is evaluated that the sample S is suitable as a paint or coating film for a road bridge. The evaluator E also evaluates the weather resistance of the sample S based on the weather resistance rank of the sample S. On the other hand, if sample S and the known paint or coating film most similar to sample S have the same or no vinyl ester, vinyl ether, TFE, and CTFE, or vinyl ester, vinyl ether, TFE, CTFE, and fluorine atoms If the content error is greater than a certain value, it is evaluated that the sample S is not suitable as a paint or coating for a road bridge.
　以下に、耐候性のランクについて説明する。
　フッ素樹脂塗料およびフッ素樹脂塗膜の耐候性は、フルオロオレフィンのＣ－Ｆ結合エネルギーの大きさが、紫外線エネルギーより大きいことで得られるものである。したがって、試料Ｓのフッ素原子含量が大きいほど耐候性に優れ、試料Ｓのフッ素原子含量が小さいほど耐候性に劣る。フッ素樹脂塗料およびフッ素樹脂塗膜中のフッ素原子含量は、耐候性に優れるフッ素樹脂塗膜を形成できる点から、フッ素樹脂塗料の固形分（１００質量％）に対して、２０質量％以上が好ましく、２２質量％以上がより好ましく、２４質量％以上がさらに好ましい。 The weather resistance rank will be described below.
The weather resistance of the fluororesin coating material and the fluororesin coating film is obtained when the C—F bond energy of the fluoroolefin is greater than the ultraviolet energy. Accordingly, the greater the fluorine atom content of the sample S, the better the weather resistance, and the smaller the fluorine atom content of the sample S, the poorer the weather resistance. The fluorine atom content in the fluororesin coating and the fluororesin coating is preferably 20% by mass or more based on the solid content (100% by mass) of the fluororesin coating from the point that a fluororesin coating having excellent weather resistance can be formed. 22 mass% or more is more preferable, and 24 mass% or more is further more preferable.
　フッ素樹脂塗料またはフッ素樹脂塗膜が、ビニルエーテルに基づく構成単位を有し、かつビニルエステルに基づく構成単位を有しない場合、フッ素樹脂塗料またはフッ素樹脂塗膜においては、フルオロオレフィンに基づく構成単位とビニルエーテルに基づく構成単位とが規則的に交互に配列している。そのため、紫外線にに弱いビニルエーテルに基づく構成単位が紫外線にに強いフルオロオレフィンに基づく構成単位に挟まれて隠れる形となり、ビニルエーテルに基づく構成単位に紫外線が当たりにくい。したがって、ビニルエーテルに基づく構成単位を有するフッ素樹脂塗料およびフッ素樹脂塗膜は、耐候性のランクが相対的に高くなる。
　一方、フッ素樹脂塗料またはフッ素樹脂塗膜が、ビニルエステルに基づく構成単位を有する場合、フッ素樹脂塗料またはフッ素樹脂塗膜においては、フルオロオレフィンに基づく構成単位とビニルエステルに基づく構成単位とがランダムに近い状態で配列している。そのため、紫外線に弱いビニルエステルに基づく構成単位が紫外線にさらされやすく、ビニルエステルに基づく構成単位同士の結合部分が切断されやすい。したがって、ビニルエステルに基づく構成単位を有するフッ素樹脂塗料およびフッ素樹脂塗膜は、耐候性のランクが相対的に低くなる。 When the fluororesin paint or fluororesin coating film has a structural unit based on vinyl ether and does not have a structural unit based on vinyl ester, in the fluororesin paint or fluororesin coating film, the structural unit based on fluoroolefin and vinyl ether The structural units based on are regularly arranged alternately. Therefore, a structural unit based on vinyl ether that is weak against ultraviolet rays is sandwiched between and hidden from structural units based on fluoroolefins that are resistant to ultraviolet rays, and the structural units based on vinyl ether are not easily hit by ultraviolet rays. Therefore, the fluororesin paint and fluororesin coating film having a structural unit based on vinyl ether have a relatively high weather resistance rank.
On the other hand, when the fluororesin paint or fluororesin coating film has a structural unit based on vinyl ester, the structural unit based on fluoroolefin and the structural unit based on vinyl ester are randomly selected in the fluororesin paint or fluororesin coating film. Arranged in close proximity. Therefore, a structural unit based on a vinyl ester that is weak against ultraviolet rays is easily exposed to ultraviolet light, and a bond portion between the structural units based on vinyl ester is likely to be cut. Therefore, the fluororesin paint and fluororesin coating film having a structural unit based on vinyl ester have a relatively low weather resistance rank.
　このように、本実施形態に係るフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法によれば、試料Ｓにビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位が含まれるか否かと、試料Ｓのフッ素原子含量とに基づいて試料Ｓを評価する。これにより、評価者Ｅは、フッ素樹脂塗料またはフッ素樹脂塗膜の同定が困難である場合にも、試料Ｓが道路橋の塗料または塗膜として適切な耐候性を有するか否かを評価することができる。 Thus, according to the fluororesin paint or fluororesin coating film evaluation method according to the present embodiment, whether or not the sample S contains a structural unit based on at least one of vinyl ester and vinyl ether, and the fluorine atom of the sample S Sample S is evaluated based on the content. Thereby, the evaluator E evaluates whether or not the sample S has an appropriate weather resistance as a paint or coating film for a road bridge even when it is difficult to identify the fluororesin coating material or the fluororesin coating film. Can do.
　また本実施形態に係るフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法によれば、ラマン散乱による散乱光に基づく試料Ｓの同定が困難である場合に、試料Ｓにビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位が含まれるか否かと、試料Ｓのフッ素原子含量とに基づいて試料Ｓを評価する。これにより、評価者Ｅは、フッ素樹脂塗料またはフッ素樹脂塗膜を同定できる場合、該同定結果に基づいて試料Ｓが道路橋の塗料または塗膜として適切な耐候性を有するか否かを評価することができる。 Further, according to the fluororesin paint or fluororesin coating film evaluation method according to the present embodiment, when it is difficult to identify the sample S based on the scattered light due to Raman scattering, the sample S has at least one of vinyl ester and vinyl ether. The sample S is evaluated on the basis of whether or not the constituent unit is included and the fluorine atom content of the sample S. Thereby, when the evaluator E can identify the fluororesin paint or the fluororesin coating film, the evaluator E evaluates whether or not the sample S has an appropriate weather resistance as a road bridge paint or coating film based on the identification result. be able to.
　《第２の実施形態》
　本実施形態に係る評価用情報提示システム１は、ラマン分光法および熱分解ＧＣ法に基づいてフッ素樹脂塗料またはフッ素樹脂塗膜である試料Ｓの評価に用いられる情報を提供する。
　図８は、第２の実施形態に係る端末装置１０の構成を示す概略ブロック図である。
　本実施形態に係る端末装置１０は、第１の実施形態の質量分析装置１３３に代えて検出器１３４を備える。検出器１３４は、ガスクロマトグラフ１３２から溶出する熱分解生成物の時系列の強度を検出する。つまり、検出器１３４は、試料Ｓのクロマトグラフを生成する。 << Second Embodiment >>
The information presentation system for evaluation 1 according to the present embodiment provides information used for evaluating the sample S that is a fluororesin paint or a fluororesin coating film based on Raman spectroscopy and pyrolysis GC.
FIG. 8 is a schematic block diagram illustrating a configuration of the terminal device 10 according to the second embodiment.
The terminal device 10 according to the present embodiment includes a detector 134 instead of the mass spectrometer 133 according to the first embodiment. The detector 134 detects the time-series intensity of the thermal decomposition product eluted from the gas chromatograph 132. That is, the detector 134 generates a chromatograph of the sample S.
　図９は、第２の実施形態に係る評価用情報算出装置２０の構成を示す概略ブロック図である。
　本実施形態に係る評価用情報算出装置２０は、第１の実施形態の構成に加え、基準特定部２０９をさらに備える。また、本実施形態に係るエステルピークテーブル２２２、エーテルピークテーブル２２３およびフッ素ピークテーブル２２４が格納する情報は、第１の実施形態と異なる。また、本実施形態に係るエステル推定部２０５、エーテル推定部２０６およびフルオロオレフィン推定部２０７の動作は、第１の実施形態と異なる。 FIG. 9 is a schematic block diagram showing the configuration of the evaluation information calculation apparatus 20 according to the second embodiment.
The evaluation information calculation apparatus 20 according to the present embodiment further includes a reference specifying unit 209 in addition to the configuration of the first embodiment. The information stored in the ester peak table 222, the ether peak table 223, and the fluorine peak table 224 according to the present embodiment is different from that of the first embodiment. The operations of the ester estimation unit 205, the ether estimation unit 206, and the fluoroolefin estimation unit 207 according to this embodiment are different from those of the first embodiment.
　エステルピークテーブル２２２は、ビニルエステルに基づく構成単位由来の熱分解生成物のピークに係るデータを格納する。エーテルピークテーブル２２３は、ビニルエーテルに基づく構成単位由来の熱分解生成物のピークに係るデータを格納する。フッ素ピークテーブル２２４は、フルオロオレフィンに基づく構成単位由来の熱分解生成物のピークに係るデータを格納する。本実施形態において熱分解生成物のピークに係るデータとは、熱分解生成物のピークが出現する時刻とピーク強度の閾値とを関連付けたデータである。熱分解生成物のピークが出現する時刻は、たとえば試料Ｓの熱分解生成物をガスクロマトグラフに導入した時刻からの経過時間によって表される。 The ester peak table 222 stores data related to peaks of thermal decomposition products derived from structural units based on vinyl esters. The ether peak table 223 stores data relating to peaks of thermal decomposition products derived from structural units based on vinyl ether. The fluorine peak table 224 stores data relating to the peak of the thermal decomposition product derived from the structural unit based on the fluoroolefin. In the present embodiment, the data relating to the peak of the thermal decomposition product is data in which the time at which the peak of the thermal decomposition product appears and the threshold value of the peak intensity are associated with each other. The time at which the peak of the pyrolysis product appears is represented by the elapsed time from the time when the pyrolysis product of the sample S is introduced into the gas chromatograph, for example.
　基準特定部２０９は、端末装置１０からピークが出現する時刻が既知のスタンダード剤に係るクロマトグラムを取得し、該クロマトグラムに実際にピークが出現している時刻とデータベース２０２に記録されたピークが出現する時刻との差を特定する。スタンダード剤としては、たとえばエステルピークテーブル２２２、エーテルピークテーブル２２３またはフッ素ピークテーブル２２４に格納された任意のモノマーを用いることができる。またエステルピークテーブル２２２、エーテルピークテーブル２２３およびフッ素ピークテーブル２２４に格納されない他の分子をスタンダード剤として用いても良い。この場合、データベース２０２は、該スタンダード剤のピークが出現する時刻を予め記憶しておく必要がある。 The reference specifying unit 209 obtains a chromatogram related to the standard agent whose peak time is known from the terminal device 10, and the time when the peak actually appears in the chromatogram and the peak recorded in the database 202 are obtained. Identify the difference from the time of appearance. As the standard agent, for example, any monomer stored in the ester peak table 222, the ether peak table 223 or the fluorine peak table 224 can be used. Other molecules not stored in the ester peak table 222, the ether peak table 223, and the fluorine peak table 224 may be used as the standard agent. In this case, the database 202 needs to store in advance the time at which the peak of the standard agent appears.
　エステル推定部２０５は、エステルピークテーブル２２２に格納されたビニルエステルに基づく構成単位由来の熱分解生成物のピークが出現する時刻を、基準特定部２０９が特定した時間に基づいて補正する。エステル推定部２０５は、計測データ取得部２０１が取得したクロマトグラムのうち、補正によって得られた時刻の前後所定時間の間にピークが存在するか否かを判定することで、試料Ｓにビニルエステルに基づく構成単位が含まれるか否か、およびビニルエステルに基づく構成単位の量を推定する。
　エーテル推定部２０６は、エーテルピークテーブル２２３に格納されたビニルエーテルに基づく構成単位由来の熱分解生成物のピークが出現する時刻を、基準特定部２０９が特定した時間に基づいて補正する。エーテル推定部２０６は、計測データ取得部２０１が取得したクロマトグラムのうち、補正によって得られた時刻の前後所定時間の間にピークが存在するか否かを判定することで、試料Ｓにビニルエーテルに基づく構成単位が含まれるか否か、およびビニルエーテルに基づく構成単位の量を推定する。
　フルオロオレフィン推定部２０７は、フッ素ピークテーブル２２４に格納されたフルオロオレフィンに基づく構成単位由来の熱分解生成物のピークが出現する時刻を、基準特定部２０９が特定した時間に基づいて補正する。フルオロオレフィン推定部２０７は、計測データ取得部２０１が取得したクロマトグラムのうち、補正によって得られた時刻の前後所定時間の間に存在するピークの強度に基づいて、試料ＳのＴＦＥ、ＣＴＦＥおよびフッ素原子の有無および含量を推定する。 The ester estimating unit 205 corrects the time when the peak of the thermal decomposition product derived from the structural unit based on the vinyl ester stored in the ester peak table 222 appears based on the time specified by the reference specifying unit 209. The ester estimation unit 205 determines whether or not there is a peak between a predetermined time before and after the time obtained by the correction in the chromatogram acquired by the measurement data acquisition unit 201, so that the vinyl ester is present in the sample S. Whether or not a structural unit based on the formula is included, and the amount of the structural unit based on the vinyl ester is estimated.
The ether estimation unit 206 corrects the time at which the peak of the thermal decomposition product derived from the structural unit based on vinyl ether stored in the ether peak table 223 appears based on the time specified by the reference specification unit 209. The ether estimation unit 206 determines whether or not there is a peak between a predetermined time before and after the time obtained by the correction in the chromatogram acquired by the measurement data acquisition unit 201, so that the sample S has vinyl ether. Estimate whether or not a constituent unit based is included and the amount of constituent unit based on vinyl ether.
The fluoroolefin estimating unit 207 corrects the time when the peak of the thermal decomposition product derived from the structural unit based on the fluoroolefin stored in the fluorine peak table 224 appears based on the time specified by the reference specifying unit 209. The fluoroolefin estimation unit 207 determines the TFE, CTFE, and fluorine of the sample S based on the intensity of the peak existing between a predetermined time before and after the time obtained by the correction in the chromatogram acquired by the measurement data acquisition unit 201. Estimate the presence and content of atoms.
　このように、本実施形態によれば、ラマン分光法および熱分解ＧＣ法に基づいて、第１の実施形態と同様の効果を奏することができる。 Thus, according to the present embodiment, the same effects as those of the first embodiment can be obtained based on the Raman spectroscopy and the pyrolysis GC method.
《第３の実施形態》
　本実施形態に係る評価用情報提示システム１は、分光分析を行わずに、熱分解ＧＣ／ＭＳ法に基づいてフッ素樹脂塗料またはフッ素樹脂塗膜である試料Ｓの評価に用いられる情報を提供する。
　図１０は、第３の実施形態に係る端末装置１０の構成を示す概略ブロック図である。
　本実施形態に係る端末装置１０は、第１の実施形態のラマン分光装置１０２を備えない。他方、本実施形態に係る演算装置１０４は、熱分解ＧＣ／ＭＳ装置１０３が出力するマスクロマトグラムに基づいて、試料Ｓと既知の塗料または塗膜との同定を行う。本実施形態に係る演算装置１０４の構成は、第１の実施形態と同じである。他方、塗料テーブル２２１に格納される情報および同定部２０４の動作が、第１の実施形態と異なる。 << Third Embodiment >>
The information presentation system for evaluation 1 according to the present embodiment provides information used for the evaluation of the sample S that is a fluororesin paint or a fluororesin coating film based on the pyrolysis GC / MS method without performing spectroscopic analysis. .
FIG. 10 is a schematic block diagram illustrating a configuration of the terminal device 10 according to the third embodiment.
The terminal device 10 according to the present embodiment does not include the Raman spectroscopic device 102 according to the first embodiment. On the other hand, the computing device 104 according to the present embodiment identifies the sample S and a known paint or coating film based on the mass chromatogram output from the pyrolysis GC / MS device 103. The configuration of the arithmetic device 104 according to the present embodiment is the same as that of the first embodiment. On the other hand, the information stored in the paint table 221 and the operation of the identification unit 204 are different from those in the first embodiment.
　塗料テーブル２２１は、既知の塗料または塗膜のマスクロマトグラムと、ビニルエステル、ビニルエーテル、ＴＦＥおよびＣＴＦＥの有無と、ビニルエステル、ビニルエーテル、ＴＦＥ、ＣＴＦＥおよびフッ素原子の含量と、耐候性のランクとを格納する。
　同定部２０４は、塗料テーブル２２１に格納されたマスクロマトグラムと、計測データ取得部２０１が取得したマスクロマトグラムとの類似度を特定し、該類似度に基づいて、試料Ｓが既知の塗料または塗膜であるか否かを判定する。マスクロマトグラム同士の類似度は、たとえば、既知のマスクロマトグラムに含まれるあるピークを基準にとったときのピーク強度の比の類似度によって判定することができる。またたとえば、ＰＣＡスコアプロット法、Ｖｏｌｃａｎｏ　Ｐｌｏｔ解析、階層的クラスター解析などの多変量解析法に基づいて、マスクロマトグラム同士の類似度を算出してもよい。 The paint table 221 shows the mass chromatogram of a known paint or coating film, the presence or absence of vinyl ester, vinyl ether, TFE and CTFE, the content of vinyl ester, vinyl ether, TFE, CTFE and fluorine atoms, and the weather resistance rank. Store.
The identification unit 204 specifies the similarity between the mass chromatogram stored in the paint table 221 and the mass chromatogram acquired by the measurement data acquisition unit 201, and based on the similarity, the sample S is a known paint or It is judged whether it is a coating film. The similarity between the mass chromatograms can be determined, for example, by the similarity of the ratios of peak intensities when a certain peak included in a known mass chromatogram is taken as a reference. Further, for example, the similarity between mass chromatograms may be calculated based on a multivariate analysis method such as a PCA score plot method, a Volcano Plot analysis, or a hierarchical cluster analysis.
　このように、本実施形態によれば、ラマン分光法などの分光分析を用いなくても、第１の実施形態と同様の効果を奏することができる。 Thus, according to the present embodiment, the same effects as those of the first embodiment can be obtained without using spectral analysis such as Raman spectroscopy.
　本実施形態に係る評価用情報提示システム１は、熱分解ＧＣ／ＭＳ法に係るマスクロマトグラムに基づく同定に代えて、第２の実施形態と同様に熱分解ＧＣ法に係るクロマトグラムに基づいて同定を行ってもよい。
　また、他の実施形態に係る評価用情報提示システム１は、第１の実施形態または第２の実施形態と同様に分光分析による同定を行い、さらにクロマトグラフに係る同定を行ってもよい。
　また、他の実施形態に係る評価用情報提示システム１は、クロマトグラムに基づく同定のみに基づいて試料Ｓの評価を行い、各構成単位の有無または量の比較を行わないものであってもよい。 The evaluation information presentation system 1 according to the present embodiment is based on the chromatogram according to the pyrolysis GC method as in the second embodiment, instead of the identification based on the mass chromatogram according to the pyrolysis GC / MS method. Identification may be performed.
In addition, the evaluation information presentation system 1 according to another embodiment may perform identification by spectroscopic analysis as in the first embodiment or the second embodiment, and may further perform identification according to a chromatograph.
Further, the evaluation information presentation system 1 according to another embodiment may evaluate the sample S based only on identification based on the chromatogram, and may not compare the presence or absence or amount of each structural unit. .
　以上、図面を参照して実施形態について詳しく説明してきたが、具体的な構成は上述のものに限られることはなく、様々な設計変更等をすることが可能である。
　たとえば、他の実施形態に係る評価用情報提示システム１は、ラマン分光法に代えて、赤外分光法、近赤外分光法、紫外分光法、可視分光法、レーザー誘起ブレークダウン分光法（ＬＩＢＳ、Ｌａｓｅｒ－Ｉｎｄｕｃｅｄ　Ｂｒｅａｋｄｏｗｎ　Ｓｐｅｃｔｒｏｓｃｏｐｙ）から得られるスペクトルに基づいて試料Ｓを同定してもよい。また、複数の上記分光法により得られる複数のスペクトルの組み合わせに基づいて試料Ｓを同定してもよい。つまり、上述したラマン分光装置１０２は、試料Ｓが吸収または放射する光を分光してスペクトルデータを生成する分光部の一例である。つまり、上述したラマン分光装置１０２は、試料Ｓの同定に用いる同定用情報を生成する同定用情報生成部の一例である。 The embodiment has been described in detail above with reference to the drawings, but the specific configuration is not limited to the above-described one, and various design changes and the like can be made.
For example, the information presentation system 1 for evaluation according to another embodiment replaces Raman spectroscopy with infrared spectroscopy, near infrared spectroscopy, ultraviolet spectroscopy, visible spectroscopy, laser induced breakdown spectroscopy (LIBS). Sample S may be identified based on a spectrum obtained from Laser-Induced Breakdown Spectroscopy. Further, the sample S may be identified based on a combination of a plurality of spectra obtained by a plurality of the spectroscopic methods. That is, the Raman spectroscopic device 102 described above is an example of a spectroscopic unit that generates spectral data by splitting light absorbed or emitted by the sample S. That is, the Raman spectroscopic device 102 described above is an example of an identification information generation unit that generates identification information used for identifying the sample S.
　また他の実施形態に係る評価用情報提示システム１は、分光分析を行わず、熱分解ＧＣ法または熱分解ＧＣ／ＭＳ法によるクロマトグラムに基づいてビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位の有無および量の少なくとも一方の推定によって、試料Ｓを評価しても良い。この場合、評価用情報提示システム１は、最も類似度が高い既知の塗料または塗膜を特定することができないため、試料Ｓと全ての既知の塗料または塗膜との比較を行うことで、試料Ｓを評価する。 In addition, the evaluation information presentation system 1 according to another embodiment does not perform spectroscopic analysis, and does not perform structural analysis based on a chromatogram obtained by pyrolysis GC method or pyrolysis GC / MS method. The sample S may be evaluated by estimating at least one of presence / absence and amount. In this case, since the evaluation information presentation system 1 cannot identify the known paint or coating film having the highest similarity, the sample S is compared with all the known paints or coating films to obtain the sample. Evaluate S.
　また上述した実施形態に係る評価用情報提示システム１は、分光分析による同定と、各構成単位の有無の判定と、各構成単位の量の判定とを、順番に行うが、これに限られない。たとえば、他の実施形態に係る評価用情報提示システム１は、分光分析による同定と、各構成単位の有無の判定と、各構成単位の量の判定とを並列実行し、各分析によって得られる試料Ｓと既知の塗料または塗膜との類似度を総合的に考慮して試料Ｓを評価してもよい。総合的な評価とは、たとえば、各類似度を加算して得られる値が閾値以上であるか否かの判断、各類似度を乗算して得られる値が閾値以上であるか否かの判断、各類似度が全て所定の閾値以上であるか否かの判断などが挙げられる。またたとえば、他の実施形態に係る評価用情報提示システム１は、クロマトグラムとスペクトルとを組み合わせた多次元データを生成し、当該多次元データに基づいて類似度を算出してもよい。 Further, the evaluation information presentation system 1 according to the above-described embodiment sequentially performs identification by spectroscopic analysis, determination of the presence / absence of each structural unit, and determination of the amount of each structural unit, but is not limited thereto. . For example, the evaluation information presentation system 1 according to another embodiment performs a parallel analysis of identification by spectroscopic analysis, determination of the presence / absence of each structural unit, and determination of the amount of each structural unit, and a sample obtained by each analysis. The sample S may be evaluated by comprehensively considering the similarity between S and a known paint or coating film. Comprehensive evaluation refers to, for example, determining whether or not the value obtained by adding each similarity is greater than or equal to a threshold, and determining whether or not the value obtained by multiplying each similarity is greater than or equal to the threshold. A determination as to whether or not all the similarities are equal to or greater than a predetermined threshold can be given. Further, for example, the evaluation information presentation system 1 according to another embodiment may generate multidimensional data combining a chromatogram and a spectrum, and calculate a similarity based on the multidimensional data.
　また他の実施形態に係る評価用情報提示システム１は、ビニルエステル、ビニルエーテル、ＴＦＥおよびＣＴＦＥの有無と、ビニルエステル、ビニルエーテル、ＴＦＥ、ＣＴＦＥおよびフッ素原子の含量とに加え、さらに微量成分に由来するピークの有無または含量を考慮して試料Ｓを評価しても良い。 In addition, the evaluation information presentation system 1 according to another embodiment is derived from trace components in addition to the presence / absence of vinyl ester, vinyl ether, TFE and CTFE, and the content of vinyl ester, vinyl ether, TFE, CTFE and fluorine atom. The sample S may be evaluated in consideration of the presence or absence of the peak or the content.
　また他の実施形態に係る評価用情報提示システム１は、評価用情報算出装置２０に試料Ｓを評価する評価部を備え、評価用情報算出装置２０が試料Ｓを評価しても良い。この場合、端末装置１０は、評価用情報に代えて、評価部による評価結果を表示する。 The evaluation information presentation system 1 according to another embodiment may include an evaluation unit that evaluates the sample S in the evaluation information calculation device 20, and the evaluation information calculation device 20 may evaluate the sample S. In this case, the terminal device 10 displays the evaluation result by the evaluation unit instead of the evaluation information.
　また他の実施形態に係る評価用情報提示システム１は、端末装置１０と評価用情報算出装置２０とがネットワークＮを介さずに直接接続されても良い。たとえば、評価用情報算出装置２０がノートＰＣに実装されることで、ネットワークＮへの接続ができない地域においても、試料Ｓを解析し、評価することができる。 In the evaluation information presentation system 1 according to another embodiment, the terminal device 10 and the evaluation information calculation device 20 may be directly connected without going through the network N. For example, by mounting the evaluation information calculation device 20 on a notebook PC, the sample S can be analyzed and evaluated even in an area where connection to the network N is not possible.
　また他の実施形態に係る端末装置１０は、表示装置１０６による表示ではなく、印刷、音声、またはその他の出力手段によって、評価用情報を提示してもよい。
　また他の実施形態に係る評価用情報提示システム１は、評価用情報として、試料Ｓの耐候性指標値、試料Ｓが所定の基準を満たすか否か、または試料Ｓが道路橋の塗料または塗膜として適切であるか否かの判定結果を提示しても良い。また他の実施形態に係る評価者Ｅは、試料Ｓが道路橋の塗料または塗膜として適切であるか否かの評価でなく、試料Ｓの耐候性指標値または試料Ｓが所定の基準を満たすか否かを評価しても良い。 Further, the terminal device 10 according to another embodiment may present the evaluation information not by display by the display device 106 but by printing, voice, or other output means.
In addition, the evaluation information presentation system 1 according to another embodiment includes, as evaluation information, a weather resistance index value of the sample S, whether the sample S satisfies a predetermined standard, or whether the sample S is a paint or paint for a road bridge. You may present the determination result of whether it is suitable as a film | membrane. In addition, the evaluator E according to another embodiment does not evaluate whether or not the sample S is suitable as a paint or a coating film for a road bridge, but the weather resistance index value of the sample S or the sample S satisfies a predetermined standard. It may be evaluated whether or not.
　また他の実施形態に係る評価用情報提示システム１は、試料Ｓにビニルエーテルに基づく構成単位が含まれるか否かの判定結果を、評価用情報として提示しなくてもよい。フッ素樹脂塗料およびフッ素樹脂塗膜は、一般的に、ビニルエステルに基づく構成単位およびビニルエーテルに基づく構成単位の少なくとも一方を含む。そのため、試料Ｓにビニルエステルに基づく構成単位が含まれないとの判定結果は、試料Ｓにビニルエーテルに基づく構成単位が含まれるとの判定結果と等価であると推定することができる。したがって、評価者Ｅは、評価用情報提示システム１が、試料Ｓにビニルエーテルに基づく構成単位が含まれるか否かの判定結果を提示しない場合にも、試料Ｓが道路橋の塗料または塗膜として適切であるか否かを評価できる。同様に、他の実施形態に係る評価用情報提示システム１は、試料Ｓにビニルエステルに基づく構成単位が含まれるか否かの判定結果を、評価用情報として提示しなくてもよい。なお、フッ素樹脂塗料およびフッ素樹脂塗膜は、ビニルエステルに基づく構成単位とビニルエーテルに基づく構成単位とを含む場合があるため、評価用情報提示システム１は、試料Ｓにビニルエステルに基づく構成単位が含まれるか否かの判定結果を提示することが好ましい。 Further, the evaluation information presentation system 1 according to another embodiment may not present the determination result as to whether or not the sample S includes a structural unit based on vinyl ether as evaluation information. The fluororesin paint and the fluororesin coating film generally contain at least one of a structural unit based on vinyl ester and a structural unit based on vinyl ether. Therefore, it can be estimated that the determination result that the structural unit based on vinyl ester is not included in the sample S is equivalent to the determination result that the structural unit based on vinyl ether is included in the sample S. Therefore, the evaluator E can also use the sample S as a paint or coating film for the road bridge even when the evaluation information presentation system 1 does not present the determination result as to whether the structural unit based on vinyl ether is included in the sample S. You can evaluate whether it is appropriate. Similarly, the evaluation information presentation system 1 according to another embodiment may not present the determination result as to whether or not the sample S includes a structural unit based on vinyl ester as evaluation information. In addition, since the fluororesin paint and the fluororesin coating film may include a structural unit based on vinyl ester and a structural unit based on vinyl ether, the evaluation information presentation system 1 includes a structural unit based on vinyl ester in the sample S. It is preferable to present a determination result of whether or not it is included.
　また他の実施形態に係る評価用情報算出装置２０は、データベース２０２に代えて、ビニルエステルに基づく構成単位由来の熱分解生成物のピークに係るデータと、フッ素原子を有するモノマーに基づく構成単位由来の熱分解生成物のピークに係るデータとを記憶する他の記憶装置を備えてもよい。つまり、記憶装置は、データの操作機能を有しないファイルシステムによってデータが管理されるものであってもよい。この場合、データを処理するアプリケーションである記録部２０３、同定部２０４、エステル推定部２０５、エーテル推定部２０６およびフルオロオレフィン推定部２０７が、データの操作機能を有する必要がある。 In addition, the evaluation information calculation apparatus 20 according to another embodiment is derived from the structural unit derived from the monomer having a fluorine atom and the data related to the peak of the thermal decomposition product derived from the structural unit based on the vinyl ester, instead of the database 202. Another storage device that stores data relating to the peak of the thermal decomposition product of may be provided. That is, the storage device may be one in which data is managed by a file system that does not have a data operation function. In this case, the recording unit 203, the identification unit 204, the ester estimation unit 205, the ether estimation unit 206, and the fluoroolefin estimation unit 207, which are applications for processing data, need to have a data operation function.
　上述の評価用情報算出装置２０は、ＣＰＵ、主記憶装置、補助記憶装置、インタフェースを備えるコンピュータに実装される。そして、上述した各処理部の動作は、プログラムの形式で補助記憶装置に記憶されている。ＣＰＵは、プログラムを補助記憶装置から読み出して主記憶装置に展開し、該プログラムに従って上記処理を実行する。ＣＰＵは、プログラムの初回実行時に、上述したデータベース２０２を補助記憶装置に構築する。 The above-described evaluation information calculation device 20 is mounted on a computer having a CPU, a main storage device, an auxiliary storage device, and an interface. The operation of each processing unit described above is stored in the auxiliary storage device in the form of a program. The CPU reads the program from the auxiliary storage device, develops it in the main storage device, and executes the above processing according to the program. The CPU constructs the above-described database 202 in the auxiliary storage device when the program is executed for the first time.
　少なくとも１つの実施形態において、補助記憶装置は、一時的でない有形の媒体の一例である。一時的でない有形の媒体の他の例としては、インタフェースを介して接続される磁気ディスク、光磁気ディスク、ＣＤ－ＲＯＭ、ＤＶＤ－ＲＯＭ、半導体メモリ等が挙げられる。また、このプログラムが通信回線によってコンピュータに配信される場合、配信を受けたコンピュータが該プログラムを主記憶装置に展開し、上記処理を実行しても良い。 In at least one embodiment, the auxiliary storage device is an example of a tangible medium that is not temporary. Other examples of the non-temporary tangible medium include a magnetic disk, a magneto-optical disk, a CD-ROM, a DVD-ROM, and a semiconductor memory connected via an interface. When this program is distributed to a computer via a communication line, the computer that has received the distribution may develop the program in a main storage device and execute the above processing.
　また、該プログラムは、前述した機能の一部を実現するためのものであっても良い。さらに、該プログラムは、前述した機能を補助記憶装置に既に記憶されている他のプログラムとの組み合わせで実現するもの、いわゆる差分ファイル（差分プログラム）であっても良い。 Further, the program may be for realizing a part of the functions described above. Further, the program may be a so-called difference file (difference program) that realizes the above-described function in combination with another program already stored in the auxiliary storage device.
《フッ素樹脂塗料》
　評価対象のフッ素樹脂塗料は、フッ素樹脂（Ａ）を含む。フッ素樹脂塗料は、必要に応じて、有機溶媒（Ｂ）、他の塗料配合成分（Ｃ）を含んでいてもよい。 《Fluorine resin paint》
The fluororesin paint to be evaluated contains a fluororesin (A). The fluororesin paint may contain an organic solvent (B) and other paint blending components (C) as necessary.
　（フッ素樹脂（Ａ））
　フッ素樹脂（Ａ）としては、公知のフッ素樹脂塗料に用いられるフッ素樹脂であればよい。
　フッ素樹脂（Ａ）としては、耐候性に優れるフッ素樹脂塗膜を形成できることから、フルオロオレフィン（ａ１）に基づく構成単位と、架橋性基を有するモノマー（ａ２）に基づく構成単位と、フッ素原子および架橋性基を有しないモノマー（ａ３）に基づく構成単位とからなるフルオロオレフィン共重合体（Ａ１）が好ましい。 (Fluororesin (A))
As a fluororesin (A), what is necessary is just a fluororesin used for a well-known fluororesin coating material.
As the fluororesin (A), since a fluororesin coating film having excellent weather resistance can be formed, a structural unit based on the fluoroolefin (a1), a structural unit based on the monomer (a2) having a crosslinkable group, a fluorine atom and A fluoroolefin copolymer (A1) comprising a structural unit based on the monomer (a3) having no crosslinkable group is preferred.
　フルオロオレフィン（ａ１）：
　フルオロオレフィン（ａ１）が有するフッ素原子数は、２以上が好ましく、２～６がより好ましく、３～４がさらに好ましい。該フッ素原子数が２以上であれば、耐候性に優れるフッ素樹脂塗膜を形成できる。 Fluoroolefin (a1):
The number of fluorine atoms contained in the fluoroolefin (a1) is preferably 2 or more, more preferably 2 to 6, and further preferably 3 to 4. When the number of fluorine atoms is 2 or more, a fluororesin coating film having excellent weather resistance can be formed.
　フルオロオレフィン（ａ１）としては、たとえば、ＴＦＥ、ＣＴＦＥ、フッ化ビニリデン、ヘキサフルオロプロピレン等が挙げられ、耐候性に優れるフッ素樹脂塗膜を形成できる点から、ＴＦＥまたはＣＴＦＥが好ましい。つまり、上述した実施形態に係るデータベース２０２は、少なくともＴＦＥおよびＣＴＦＥに基づく構成単位由来の熱分解生成物のピークに係るデータと前記計測データを記憶する。
　フルオロオレフィン（ａ１）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the fluoroolefin (a1) include TFE, CTFE, vinylidene fluoride, hexafluoropropylene and the like, and TFE or CTFE is preferable from the viewpoint that a fluororesin coating film having excellent weather resistance can be formed. That is, the database 202 which concerns on embodiment mentioned above memorize | stores the data regarding the peak of the thermal decomposition product derived from the structural unit based on at least TFE and CTFE, and the said measurement data.
A fluoroolefin (a1) may be used individually by 1 type, and may be used in combination of 2 or more type.
　モノマー（ａ２）：
　モノマー（ａ２）は、架橋性基を有するモノマーである。
　架橋性基としては、活性水素を有する官能基（水酸基、カルボキシル基、アミノ基等）、加水分解性シリル基（アルコキシシリル基等）等が好ましい。 Monomer (a2):
The monomer (a2) is a monomer having a crosslinkable group.
As the crosslinkable group, a functional group having active hydrogen (hydroxyl group, carboxyl group, amino group, etc.), hydrolyzable silyl group (alkoxysilyl group, etc.) and the like are preferable.
　モノマー（ａ２）としては、耐候性に優れるフッ素樹脂塗膜を形成できる点から、下式で表されるモノマー（ａ２１）が好ましい。
　ＣＨ２＝ＣＸ１（ＣＨ２）ｎ１－Ｑ１－Ｒ１－Ｙ
　ただし、Ｘ１は、水素原子またはメチル基であり、ｎ１は、０または１であり、Ｑ１は、酸素原子、－Ｃ（Ｏ）Ｏ－または－Ｏ（Ｏ）Ｃ－であり、Ｒ１は、分岐構造または環構造を有していてもよい炭素数２～２０のアルキレン基であり、Ｙは、架橋性官能基である。 As the monomer (a2), a monomer (a21) represented by the following formula is preferable because a fluororesin coating film having excellent weather resistance can be formed.
CH 2 = CX 1 (CH 2 ) n1 -Q 1 -R 1 -Y
X 1 is a hydrogen atom or a methyl group, n1 is 0 or 1, Q 1 is an oxygen atom, —C (O) O— or —O (O) C—, and R 1 Is an alkylene group having 2 to 20 carbon atoms which may have a branched structure or a ring structure, and Y is a crosslinkable functional group.
　Ｙとしては、水酸基、カルボキシル基またはアミノ基が好ましく、水酸基がより好ましい。
　Ｒ１としては、直鎖状のアルキレン基が好ましい。該アルキレン基の炭素数は、１～１０が好ましく、１～６がより好ましく、２～４がさらに好ましい。
　Ｑ１としては、酸素原子が好ましい。 Y is preferably a hydroxyl group, a carboxyl group or an amino group, more preferably a hydroxyl group.
R 1 is preferably a linear alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
Q 1 is preferably an oxygen atom.
　モノマー（ａ２１）は、エーテル結合を有するモノマーと、エステル結合を有するモノマーとに大別される。
　エーテル結合を有するモノマーとしては、ヒドロキシアルキルビニルエーテル類、ヒドロキシアルキルアリルエーテル類等が挙げられる。
　エステル結合を有するモノマーとしては、ヒドロキシアルカン酸ビニル類、ヒドロキシアルカン酸アリル類、ヒドロキシアルキルアクリレート類、ヒドロキシアルキルメタクリレート類等が挙げられる。 The monomer (a21) is roughly classified into a monomer having an ether bond and a monomer having an ester bond.
Examples of the monomer having an ether bond include hydroxyalkyl vinyl ethers and hydroxyalkyl allyl ethers.
Examples of the monomer having an ester bond include vinyl hydroxyalkanoates, allyl hydroxyalkanoates, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, and the like.
　ヒドロキシアルキルビニルエーテル類としては、２－ヒドロキシエチルビニルエーテル、ヒドロキシメチルビニルエーテル、４－ヒドロキシブチルビニルエーテル（以下、ＨＢＶＥとも記す。）等が挙げられる。
　ヒドロキシアルキルアリルエーテル類としては、ヒドロキシエチルアリルエーテル等が挙げられる。
　ヒドロキシアルキルアクリレート類やヒドロキシアルキルメタクリレート類としては、ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレート等が挙げられる。 Examples of hydroxyalkyl vinyl ethers include 2-hydroxyethyl vinyl ether, hydroxymethyl vinyl ether, 4-hydroxybutyl vinyl ether (hereinafter also referred to as HBVE), and the like.
Examples of hydroxyalkyl allyl ethers include hydroxyethyl allyl ether.
Examples of hydroxyalkyl acrylates and hydroxyalkyl methacrylates include hydroxyethyl acrylate and hydroxyethyl methacrylate.
　モノマー（ａ２１）としては、耐候性に優れるフッ素樹脂塗膜を形成できる点から、エーテル結合を有するモノマーが好ましく、ヒドロキシアルキルビニルエーテル類がより好ましいく、ＨＢＶＥが特に好ましい。
　モノマー（ａ２）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 The monomer (a21) is preferably a monomer having an ether bond, more preferably a hydroxyalkyl vinyl ether, and particularly preferably HBVE from the viewpoint that a fluororesin coating film having excellent weather resistance can be formed.
A monomer (a2) may be used individually by 1 type, and may be used in combination of 2 or more type.
　モノマー（ａ３）：
　モノマー（ａ３）は、フッ素原子および架橋性基を有しないモノマーである。
　モノマー（ａ３）としては、耐候性に優れるフッ素樹脂塗膜を形成できる点から、下式で表されるモノマー（ａ３１）が好ましい。
　ＣＨ２＝ＣＸ２（ＣＨ２）ｎ２－Ｑ２－Ｒ２
　ただし、Ｘ２は、水素原子またはメチル基であり、ｎ２は、０または１であり、Ｑ２は、酸素原子、－Ｃ（Ｏ）Ｏ－または－Ｏ（Ｏ）Ｃ－であり、Ｒ２は分岐構造または環構造を有していてもよい炭素数２～２０のアルキル基である。 Monomer (a3):
A monomer (a3) is a monomer which does not have a fluorine atom and a crosslinkable group.
As the monomer (a3), a monomer (a31) represented by the following formula is preferable because a fluororesin coating film having excellent weather resistance can be formed.
CH 2 = CX 2 (CH 2 ) n2 -Q 2 -R 2
Where X 2 is a hydrogen atom or a methyl group, n2 is 0 or 1, Q 2 is an oxygen atom, —C (O) O— or —O (O) C—, and R 2 Is an alkyl group having 2 to 20 carbon atoms which may have a branched structure or a ring structure.
　モノマー（ａ３１）は、エーテル結合を有するモノマーと、エステル結合を有するモノマーとに大別される。
　エーテル結合を有するモノマーとしては、アルキルビニルエーテル類、アルキルアリルエーテル類等が挙げられる。
　エステル結合を有するモノマーとしては、アルカン酸ビニル類、アリールカルボン酸ビニル類、アルカン酸アリル類、アルキルアクリレート類、アルキルメタクリレート類等が挙げられる。 The monomer (a31) is roughly classified into a monomer having an ether bond and a monomer having an ester bond.
Examples of the monomer having an ether bond include alkyl vinyl ethers and alkyl allyl ethers.
Examples of the monomer having an ester bond include vinyl alkanoates, vinyl arylcarboxylates, allyl alkanoates, alkyl acrylates, alkyl methacrylates, and the like.
　アルキルビニルエーテル類としては、エチルビニルエーテル（以下、ＥＶＥとも記す。）、シクロヘキシルビニルエーテル（以下、ＣＨＶＥとも記す。）、２－エチルへキシルビニルエーテル等が挙げられる。
　アルカン酸ビニル類としては、酢酸ビニル、ビニルバーサテート等が挙げられる。
　アリールカルボン酸ビニル類としては、安息香酸ビニル等が挙げられる。
　モノマー（ａ３１）としては、耐候性に優れるフッ素樹脂塗膜を形成できる点から、エーテル結合を有するモノマーが好ましく、アルキルビニルエーテル類がより好ましく、ＥＶＥ、ＣＨＶＥがさらに好ましく、ＣＨＶＥが特に好ましい。
　モノマー（ａ３）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the alkyl vinyl ethers include ethyl vinyl ether (hereinafter also referred to as EVE), cyclohexyl vinyl ether (hereinafter also referred to as CHVE), 2-ethylhexyl vinyl ether, and the like.
Examples of vinyl alkanoates include vinyl acetate and vinyl versatate.
Examples of vinyl arylcarboxylates include vinyl benzoate.
As the monomer (a31), a monomer having an ether bond is preferable, an alkyl vinyl ether is more preferable, EVE and CHVE are more preferable, and CHVE is particularly preferable because a fluororesin coating film having excellent weather resistance can be formed.
A monomer (a3) may be used individually by 1 type, and may be used in combination of 2 or more type.
　構成単位の割合：
　フルオロオレフィン（ａ１）に基づく構成単位の割合は、フルオロオレフィン共重合体（Ａ１）が有する全構成単位（１００モル％）のうち、３０～７０モル％が好ましく、４０～６０モル％がより好ましく、４５～５５モル％がさらに好ましい。フルオロオレフィン（ａ１）に基づく構成単位の割合が３０モル％以上であれば、耐候性に優れるフッ素樹脂塗膜を形成できる。フルオロオレフィン（ａ１）に基づく構成単位の割合が７０モル％以下であれば、有機溶媒や希釈剤への溶解性に優れる。 Composition unit ratio:
The proportion of the structural unit based on the fluoroolefin (a1) is preferably from 30 to 70 mol%, more preferably from 40 to 60 mol%, based on the total structural units (100 mol%) of the fluoroolefin copolymer (A1). 45 to 55 mol% is more preferable. If the ratio of the structural unit based on fluoroolefin (a1) is 30 mol% or more, a fluororesin coating film having excellent weather resistance can be formed. If the ratio of the structural unit based on fluoroolefin (a1) is 70 mol% or less, it is excellent in the solubility to an organic solvent or a diluent.
　モノマー（ａ２）に基づく構成単位およびモノマー（ａ３）に基づく構成単位の合計の割合は、フルオロオレフィン共重合体（Ａ１）が有する全構成単位（１００モル％）のうち、７０～３０モル％が好ましく、６０～４０モル％がより好ましく、５５～４５モル％がさらに好ましい。 The total proportion of the structural unit based on the monomer (a2) and the structural unit based on the monomer (a3) is 70 to 30 mol% of all the structural units (100 mol%) of the fluoroolefin copolymer (A1). 60 to 40 mol% is more preferable, and 55 to 45 mol% is more preferable.
　モノマー（ａ２１）に基づく構成単位の割合は、フルオロオレフィン共重合体（Ａ１）が有する全構成単位（１００モル％）のうち、５～４０モル％が好ましく、８～３５モル％がより好ましい。モノマー（ａ２１）に基づく構成単位の割合が５モル％以上であれば、硬度の高いフッ素樹脂塗膜を得るために充分な量の架橋性基がフルオロオレフィン共重合体（Ａ１）中に導入される。モノマー（ａ２１）に基づく構成単位の割合が４０モル％以下であれば、高固形分タイプであっても、フルオロオレフィン共重合体（Ａ１）溶液として充分な低粘度を維持できる。 The proportion of the structural unit based on the monomer (a21) is preferably 5 to 40 mol%, more preferably 8 to 35 mol%, of all the structural units (100 mol%) of the fluoroolefin copolymer (A1). When the proportion of the structural unit based on the monomer (a21) is 5 mol% or more, a sufficient amount of crosslinkable groups are introduced into the fluoroolefin copolymer (A1) to obtain a highly hard fluororesin coating film. The If the ratio of the structural unit based on the monomer (a21) is 40 mol% or less, even if it is a high solid content type, a sufficiently low viscosity can be maintained as a solution of the fluoroolefin copolymer (A1).
　モノマー（ａ３１）に基づく構成単位の割合は、フルオロオレフィン共重合体（Ａ１）が有する全構成単位（１００モル％）のうち、０モル％超４５モル％以下が好ましく、３～３５モル％がより好ましく、５～３０モル％がさらに好ましい。モノマー（ａ３１）に基づく構成単位を有することによって、得られるフッ素樹脂塗膜の硬度や柔軟性を適宜調整できる。モノマー（ａ３１）に基づく構成単位の割合が４５モル％以下であれば、耐候性に優れ、硬度の高いフッ素樹脂塗膜を得るために充分な量の架橋性基がフルオロオレフィン共重合体（Ａ１）中に導入される。 The proportion of the structural unit based on the monomer (a31) is preferably more than 0 mol% and 45 mol% or less, and preferably 3 to 35 mol% in the total structural units (100 mol%) of the fluoroolefin copolymer (A1). More preferred is 5 to 30 mol%. By having a structural unit based on the monomer (a31), the hardness and flexibility of the resulting fluororesin coating film can be adjusted as appropriate. When the proportion of the structural unit based on the monomer (a31) is 45 mol% or less, a sufficient amount of crosslinkable groups for obtaining a fluororesin coating film having excellent weather resistance and high hardness is contained in the fluoroolefin copolymer (A1). ) Introduced in.
　フルオロオレフィン（ａ１）に基づく構成単位、モノマー（ａ２１）に基づく構成単位およびモノマー（ａ３１）に基づく構成単位以外の他のモノマーに基づく構成単位を有する場合、他のモノマーに基づく構成単位の割合は、フルオロオレフィン共重合体（Ａ１）が有する全構成単位（１００モル％）のうち、２０モル％以下が好ましく、１０モル％以下がより好ましい。 In the case of having a structural unit based on another monomer other than the structural unit based on the fluoroolefin (a1), the structural unit based on the monomer (a21) and the structural unit based on the monomer (a31), the ratio of the structural unit based on the other monomer is Of the total structural units (100 mol%) of the fluoroolefin copolymer (A1), 20 mol% or less is preferable, and 10 mol% or less is more preferable.
　フルオロオレフィン共重合体（Ａ１）の市販品としては、たとえば、下記のものが挙げられる。
　旭硝子社製のルミフロン（登録商標）シリーズ（ＬＦ２００、ＬＦ１００、ＬＦ７１０等）。
　ダイキン工業社製のゼッフル（登録商標）ＧＫシリーズ（ＧＫ－５００、ＧＫ－５１０、ＧＫ－５５０、ＧＫ－５７０、ＧＫ－５８０等）。たとえば、ゼッフル（登録商標）ＧＫ－５７０は、ＴＦＥ／ヒドロキシエチルアリルエーテル／ビニルバーサテート／安息香酸ビニル／酢酸ビニル共重合体であり、ゼッフル（登録商標）ＧＫ－５８０は、ＴＦＥ／ヒドロキシエチルアリルエーテル／ビニルバーサテート／安息香酸ビニル共重合体である。
　ＤＩＣ社製のフルオネート（登録商標）シリーズ（Ｋ－７００、Ｋ－７０２、Ｋ－７０３、Ｋ－７０４、Ｋ－７０５、Ｋ－７０７等）。たとえば、フルオネート（登録商標）Ｋ－７０５は、ＣＴＦＥ／ＨＢＶＥ／ＥＶＥ／ビニルバーサテート共重合体である。
　Ｅｔｅｒｎａｌ　Ｃｈｅｍｉｃａｌ社製のＥＴＥＲＦＬＯＮシリーズ（Ｅ－４１０１、Ｅ－４１０１１、Ｅ－４１０２、Ｅ－４１０２１、Ｅ－４２６１Ａ、Ｅ－４２６２Ａ、Ｅ－４２６３１、Ｅ－４１０２Ａ、Ｅ－４１０４１、Ｅ－４１１１１、Ｅ－４２６１Ａ等）等が挙げられる。たとえば、ＥＴＥＲＦＬＯＮ　Ｅ－４１０１は、ＣＴＦＥ／ＨＢＶＥ／ＣＨＶＥ／ＥＶＥ共重合体である。 As a commercial item of a fluoro olefin copolymer (A1), the following are mentioned, for example.
Lumiflon (registered trademark) series (LF200, LF100, LF710, etc.) manufactured by Asahi Glass Co., Ltd.
Zaffle (registered trademark) GK series (GK-500, GK-510, GK-550, GK-570, GK-580, etc.) manufactured by Daikin Industries, Ltd. For example, Zeffle® GK-570 is a TFE / hydroxyethyl allyl ether / vinyl versatate / vinyl benzoate / vinyl acetate copolymer, and Zeffle® GK-580 is TFE / hydroxyethyl allyl. Ether / vinyl versatate / vinyl benzoate copolymer.
Fluorate (registered trademark) series manufactured by DIC (K-700, K-702, K-703, K-704, K-705, K-707, etc.). For example, Fluonate® K-705 is a CTFE / HBVE / EVE / vinyl versatate copolymer.
ETERFLON series (E-4101, E-41011, E-4102, E-41021, E-4261A, E-4262A, E-42631, E-4102A, E-41041, E-41111, E-, manufactured by Eternal Chemical 4261A etc.). For example, ETERFLON E-4101 is a CTFE / HBVE / CHVE / EVE copolymer.
　（有機溶媒（Ｂ））
　有機溶媒（Ｂ）としては、芳香族炭化水素系溶媒、ケトン系溶媒、エステル系溶媒、労働安全衛生法における第三種有機溶剤、アルコール系溶媒、エーテルエステル系溶媒等が挙げられる。 (Organic solvent (B))
Examples of the organic solvent (B) include aromatic hydrocarbon solvents, ketone solvents, ester solvents, third organic solvents in the Industrial Safety and Health Act, alcohol solvents, ether ester solvents, and the like.
　有機溶媒（Ｂ）としては、環境負荷低減の点からは、ＰＲＴＲ法、ＨＡＰｓ規制に対応した溶媒、すなわち、芳香族環を有しない有機溶媒が好ましい。また、労働安全衛生法による有機溶剤の分類において、第三種有機溶剤に分類されている有機溶媒も好ましい。具体的には、ＰＲＴＲ法、ＨＡＰｓ規制に該当しないケトン系溶媒、エーテルエステル系溶媒；労働安全衛生法において第三種有機溶剤に分類されているパラフィン系溶剤またはナフテン系溶剤が好ましい。 As the organic solvent (B), a solvent corresponding to the PRTR method and HAPs regulations, that is, an organic solvent having no aromatic ring is preferable from the viewpoint of reducing the environmental load. Moreover, the organic solvent classified into the 3rd type organic solvent in the classification | category of the organic solvent by the occupational safety and health law is also preferable. Specifically, ketone solvents, ether ester solvents that do not comply with the PRTR method and HAPs regulations; paraffinic solvents or naphthenic solvents classified as the third organic solvents in the Industrial Safety and Health Act are preferable.
　芳香族炭化水素系溶媒としては、トルエン、キシレン、エチルベンゼン、芳香族石油ナフサ、テトラリン、テレピン油、ソルベッソ（登録商標）♯１００（エクソン化学社製）、ソルベッソ（登録商標）♯１５０（エクソン化学社製）が好ましい。ケトン系溶媒としては、アセトン、メチルエチルケトン、メチルアミルケトン、メチルイソブチルケトン、エチルイソブチルケトン、ジイソブチルケトン、シクロヘキサノン、イソホロンが好ましい。エステル系溶媒としては、酢酸メチル、酢酸エチル、酢酸ｎ－プロピル、酢酸イソブチル、酢酸ｔｅｒｔ－ブチルが好ましい。 Examples of the aromatic hydrocarbon solvent include toluene, xylene, ethylbenzene, aromatic petroleum naphtha, tetralin, turpentine oil, Solvesso (registered trademark) # 100 (manufactured by Exxon Chemical), Solvesso (registered trademark) # 150 (Exxon Chemical) Product). As the ketone solvent, acetone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and isophorone are preferable. As the ester solvent, methyl acetate, ethyl acetate, n-propyl acetate, isobutyl acetate, and tert-butyl acetate are preferable.
　労働安全衛生法における第三種有機溶剤は、ガソリン、コールタールナフサ（ソルベントナフサを含む。）、石油エーテル、石油ナフサ、石油ベンジン、テレピン油、ミネラルスピリット（ミネラルシンナー、ペトロリウムスピリット、ホワイトスピリットおよびミネラルターペンを含む。）からなる群から選ばれる１種以上からなる溶剤である。
　労働安全衛生法における第三種有機溶剤としては、引火点が室温以上である点から、ミネラルスピリット（ミネラルシンナー、ペトロリウムスピリット、ホワイトスピリットおよびミネラルターペンを含む。）が好ましい。 The Class III organic solvents in the Industrial Safety and Health Act are gasoline, coal tar naphtha (including solvent naphtha), petroleum ether, petroleum naphtha, petroleum benzine, turpentine oil, mineral spirit (mineral thinner, petroleum spirit, white spirit and A solvent consisting of one or more selected from the group consisting of mineral terpenes).
As the third type organic solvent in the Industrial Safety and Health Law, mineral spirits (including mineral thinner, petrolium spirit, white spirit and mineral turpentine) are preferable because the flash point is room temperature or higher.
　アルコール系溶媒としては、炭素数４以下のものが好ましく、具体的には、エタノール、ｔｅｒｔ－ブチルアルコール、ｉｓｏ－プロピルアルコールが好ましい。
　エーテルエステル系溶媒としては、３－エトキシプロピオン酸エチル、プロピレングリコールモノメチルエーテルアセテート、酢酸メトキシブチルが好ましい。 As the alcohol solvent, those having 4 or less carbon atoms are preferable, and specifically, ethanol, tert-butyl alcohol, and iso-propyl alcohol are preferable.
As the ether ester solvent, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, and methoxybutyl acetate are preferable.
　有機溶媒（Ｂ）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　有機溶媒（Ｂ）の量は、フッ素樹脂塗料の固形分濃度が２０～１００質量％となる量が好ましく、４０～１００質量％となる量がより好ましい。 An organic solvent (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
The amount of the organic solvent (B) is preferably such that the solid content concentration of the fluororesin coating is 20 to 100% by mass, and more preferably 40 to 100% by mass.
　（他の塗料配合成分（Ｃ））
　他の塗料配合成分（Ｃ）としては、硬化剤、着色剤、フッ素樹脂（Ａ）以外の他の樹脂、シランカップリング剤、紫外線吸収剤、硬化促進剤、光安定剤、つや消し剤等が挙げられる。これらは２種以上を併用してもよい。 (Other paint ingredients (C))
Examples of the other paint blending component (C) include curing agents, colorants, resins other than the fluororesin (A), silane coupling agents, ultraviolet absorbers, curing accelerators, light stabilizers, matting agents, and the like. It is done. Two or more of these may be used in combination.
　硬化剤：
　硬化剤としては、イソシアネート系硬化剤、ブロック化イソシアネート系硬化剤およびアミノ樹脂系硬化剤からなる群から選ばれた少なくとも１種が好ましい。 Curing agent:
The curing agent is preferably at least one selected from the group consisting of isocyanate curing agents, blocked isocyanate curing agents, and amino resin curing agents.
　イソシアネート系硬化剤としては、無黄変イソシアネート類（ヘキサメチレンジイソシアネート、イソホロンジイソシアネート等）が好ましい。
　ブロック化イソシアネート系硬化剤としては、イソシアネート系硬化剤のイソシアネート基をカプロラクタム、イソホロン、β－ジケトン等でブロックしたものが好ましい。 As the isocyanate curing agent, non-yellowing isocyanates (hexamethylene diisocyanate, isophorone diisocyanate, etc.) are preferable.
As the blocked isocyanate curing agent, those obtained by blocking the isocyanate group of the isocyanate curing agent with caprolactam, isophorone, β-diketone or the like are preferable.
　アミノ樹脂系硬化剤は、アミン類（メラミン、メチロールメラミン、グアナミン、尿素等）と、アルデヒド類（ホルムアルデヒド等）とを重縮合して得られた硬化剤である。アミノ樹脂系硬化剤としては、メラミン樹脂系硬化剤、グアナミン樹脂系硬化剤、尿素樹脂系硬化剤、スルホアミド樹脂系硬化剤、アニリン樹脂系硬化剤等が挙げられる。 The amino resin curing agent is a curing agent obtained by polycondensation of amines (melamine, methylolmelamine, guanamine, urea, etc.) and aldehydes (formaldehyde, etc.). Examples of amino resin-based curing agents include melamine resin-based curing agents, guanamine resin-based curing agents, urea resin-based curing agents, sulfoamide resin-based curing agents, and aniline resin-based curing agents.
　硬化剤の量は、フッ素樹脂塗料中のフッ素樹脂（Ａ）の１００質量部に対して、１～１００質量部が好ましく、１～５０質量部がより好ましい。硬化剤が１質量部以上であれば、フッ素樹脂塗膜の耐溶剤性に優れ、硬度が充分である。硬化剤が１００質量部以下であれば、加工性に優れ、耐衝撃性に優れる。 The amount of the curing agent is preferably 1 to 100 parts by mass and more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the fluororesin (A) in the fluororesin paint. If a hardening | curing agent is 1 mass part or more, it is excellent in the solvent resistance of a fluororesin coating film, and hardness is enough. If a hardening | curing agent is 100 mass parts or less, it is excellent in workability and is excellent in impact resistance.
　着色剤：
　着色剤としては、耐候性のよい無機顔料（カーボンブラック、酸化チタン等）、有機顔料（フタロシアニンブルー、フタロシアニングリーン、キナクリドンレッド、インダンスレンオレンジ、イソインドリノン系イエロー等）、染料等が挙げられる。 Colorant:
Examples of the colorant include inorganic pigments (carbon black, titanium oxide, etc.) having good weather resistance, organic pigments (phthalocyanine blue, phthalocyanine green, quinacridone red, indanthrene orange, isoindolinone yellow, etc.), dyes, and the like. .
　他の樹脂：
　他の樹脂としては、塗料に配合される公知の樹脂が挙げられる。
　たとえば、塗膜の乾燥性を改善するために、セルロースアセテートブチレート、ニトロセルロース等を配合してもよい。また、塗膜の光沢、硬度、塗料の施工性を改良するために、アクリル酸やそのエステル、メタクリル酸やそのエステル等に基づく単位を有する重合体、ポリエステル等を配合してもよい。 Other resins:
As other resin, the well-known resin mix | blended with a coating material is mentioned.
For example, cellulose acetate butyrate, nitrocellulose, or the like may be blended in order to improve the drying properties of the coating film. In addition, in order to improve the gloss, hardness, and paint workability of the coating film, a polymer having units based on acrylic acid or an ester thereof, methacrylic acid or an ester thereof, or the like may be blended.
《フッ素樹脂塗膜》
　フッ素樹脂塗膜は、物品の表面にフッ素樹脂塗料を塗布し、乾燥させることによって形成される。
　塗装方法としては、スプレー塗装、エアスプレー塗装、はけ塗り、浸漬法、ロールコート、フローコート等の方法が挙げられる。 《Fluorine resin coating film》
The fluororesin coating film is formed by applying a fluororesin paint to the surface of an article and drying it.
Examples of the coating method include spray coating, air spray coating, brush coating, dipping method, roll coating, and flow coating.
　塗装される物品の材質としては、無機物（コンクリート、自然石、ガラス、金属（鉄、ステンレス、アルミニウム、銅、真鍮、チタン等）等）、有機物（プラスチック、ゴム、接着剤、木材等）、有機無機複合材（繊維強化プラスチック、樹脂強化コンクリート、繊維強化コンクリート等）が挙げられる。 Materials to be painted include inorganic substances (concrete, natural stone, glass, metal (iron, stainless steel, aluminum, copper, brass, titanium, etc.)), organic substances (plastic, rubber, adhesive, wood, etc.), organic Examples thereof include inorganic composite materials (fiber reinforced plastic, resin reinforced concrete, fiber reinforced concrete, and the like).
　塗装される物品は、道路橋である。道路橋とは、道路が設置される橋のことである。つまり、跨線橋や陸上橋等に属する橋であっても、道路が設置された橋であれば、道路橋に含まれる。また、車道が設置される橋のみならず、人が渡る道路の橋である歩道橋も、道路橋に含まれる。また、道路と鉄道との両方が設置された複合橋も、道路橋に含まれる。
　なお、２０１４年１２月１２日に出願された日本特許出願２０１４－２５２４６４号の明細書、特許請求の範囲、要約書および図面の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The article to be painted is a road bridge. A road bridge is a bridge where a road is installed. In other words, even a bridge belonging to an overpass, an overland bridge or the like is included in the road bridge if the road is installed. Further, not only bridges on which roadways are installed, but also pedestrian bridges, which are bridges of roads through which people pass, are also included in road bridges. A composite bridge in which both a road and a railway are installed is also included in the road bridge.
In addition, the entire content of the specification, claims, abstract, and drawings of Japanese Patent Application No. 2014-252464 filed on December 12, 2014 is cited here as disclosure of the specification of the present invention, Incorporated.
１　評価用情報提示システム、１０　端末装置、２０　評価用情報算出装置、１０１　収容スペース、１０２　ラマン分光装置、１０３　熱分解ＧＣ／ＭＳ装置、１０４　演算装置、１０５　通信装置、１０６　表示装置、１２１　レーザ装置、１２２　フィルタ、１２３　モノクロメータ、１２４　検出器、１３１　熱分解装置、１３２　ガスクロマトグラフ、１３３　質量分析装置、１３４　検出器、２０１　計測データ取得部、２０２　データベース、２０３　記録部、２０４　同定部、２０５　エステル判定部、２０６　エーテル判定部、２０７　フッ素原子含量推定部、２０８　評価用情報出力部、２０９　基準特定部、２２１　スペクトルテーブル、２２２　エステルピークテーブル、２２３　エーテルピークテーブル、２２４　フッ素ピークテーブル、Ｓ　試料、Ｎ　ネットワーク、Ｅ　評価者 1 Information presentation system for evaluation, 10 terminal device, 20 information calculation device for evaluation, 101 storage space, 102 Raman spectroscopic device, 103 pyrolysis GC / MS device, 104 arithmetic device, 105 communication device, 106 display device, 121 laser device , 122 filter, 123 monochromator, 124 detector, 131 pyrolysis device, 132 gas chromatograph, 133 mass spectrometer, 134 detector, 201 measurement data acquisition unit, 202 database, 203 recording unit, 204 identification unit, 205 ester determination Part, 206 ether determination part, 207 fluorine atom content estimation part, 208 information output part for evaluation, 209 reference identification part, 221 spectrum table, 222 ester peak table, 223 ether peak table, 224 Fluorine Peak Table, S samples, N networks, E evaluator

Claims (12)

  1. 　道路橋に塗布されるフッ素樹脂塗料または道路橋に設けられたフッ素樹脂塗膜である試料の、熱分解ガスクロマトグラフィ法または熱分解ガスクロマトグラフィ質量分析法による計測データを取得する計測データ取得ステップと、
    　記憶装置に記録されたビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位由来の熱分解生成物のピークに係るデータと前記計測データとに基づいて、前記試料にビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位の有無および量の少なくとも一方を推定する特定モノマー推定ステップと、
    　記憶装置に記録されたフッ素原子を有するモノマーに基づく構成単位由来の熱分解生成物のピークに係るデータと前記計測データとに基づいて、前記試料のフッ素原子含量を推定するフッ素原子含量推定ステップと、
    　前記特定モノマー推定ステップの推定結果と前記フッ素原子含量とに基づいて前記試料を評価する評価ステップと
    　を有するフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法。     A measurement data acquisition step for acquiring measurement data by pyrolysis gas chromatography or pyrolysis gas chromatography mass spectrometry of a sample which is a fluororesin paint applied to a road bridge or a fluororesin coating film provided on a road bridge;
    A configuration based on at least one of vinyl ester and vinyl ether in the sample based on the data related to the peak of the thermal decomposition product derived from the structural unit based on at least one of vinyl ester and vinyl ether recorded in the storage device and the measurement data A specific monomer estimation step for estimating at least one of the presence and amount of units; and
    A fluorine atom content estimation step for estimating the fluorine atom content of the sample based on the data related to the peak of the thermal decomposition product derived from the structural unit based on the monomer having a fluorine atom recorded in the storage device and the measurement data; ,
    An evaluation method for a fluororesin paint or a fluororesin coating film, comprising: an evaluation step for evaluating the sample based on the estimation result of the specific monomer estimation step and the fluorine atom content.
  2. 　記憶装置に記録された、既知のフッ素樹脂塗料または既知のフッ素樹脂塗膜が吸収または放射する光を分光して得られるスペクトルデータまたは既知のフッ素樹脂塗料または既知のフッ素樹脂塗膜の熱分解ガスクロマトグラフィ法または熱分解ガスクロマトグラフィ質量分析法による計測データと、前記試料が吸収または放射する光を分光して得られるスペクトルデータまたは前記計測データ取得ステップで取得した前記計測データとの類似度を特定する類似度特定ステップをさらに有し、
    　前記評価ステップで、前記特定モノマー推定ステップの推定結果と前記類似度特定ステップの特定結果と前記フッ素原子含量とに基づいて前記試料を評価する
    　請求項１に記載のフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法。     Spectral data obtained by spectroscopic analysis of light absorbed or emitted by a known fluororesin paint or known fluororesin coating film or pyrolysis gas of a known fluororesin paint or known fluororesin coating film recorded in a storage device Specify the similarity between the measurement data obtained by chromatography or pyrolysis gas chromatography mass spectrometry and the spectrum data obtained by spectroscopic analysis of the light absorbed or emitted by the sample or the measurement data acquired in the measurement data acquisition step And further comprising a similarity specifying step,
    The fluororesin paint or fluororesin coating film according to claim 1, wherein in the evaluation step, the sample is evaluated based on an estimation result of the specific monomer estimation step, a specification result of the similarity specification step, and the fluorine atom content. Evaluation method.
  3. 　前記類似度特定ステップで特定した類似度が最も高い前記既知のフッ素樹脂塗料または前記既知のフッ素樹脂塗膜を特定する類似塗料特定ステップをさらに有し、
    　前記評価ステップで、前記特定モノマー推定ステップの推定結果および前記フッ素原子含量と、前記類似塗料特定ステップが特定した前記既知のフッ素樹脂塗料または前記既知のフッ素樹脂塗膜のビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位の有無および量の少なくとも一方、ならびにフッ素原子含量とを比較することで、前記試料を評価する
    　請求項２に記載のフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法。     And further comprising a similar paint specifying step for specifying the known fluororesin paint or the known fluororesin coating film having the highest similarity specified in the similarity specifying step,
    In the evaluation step, the estimation result of the specific monomer estimation step and the fluorine atom content, and at least one of the known fluororesin paint or the known fluororesin coating film vinyl ester and vinyl ether specified by the similar paint specification step The method for evaluating a fluororesin paint or a fluororesin coating film according to claim 2, wherein the sample is evaluated by comparing at least one of the presence and amount and the fluorine atom content of the constituent unit based on.
  4. 　前記計測データが、前記試料の熱分解ガスクロマトグラフィ質量分析法による計測データであり、
    　前記ピークに係るデータが、ピークを生じる熱分解生成物の質量に係る物理量とピーク強度の閾値を含む
    　請求項１から請求項３の何れか１項に記載のフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法。     The measurement data is measurement data obtained by pyrolysis gas chromatography mass spectrometry of the sample,
    The data relating to the peak includes a physical quantity related to the mass of the pyrolysis product that generates the peak and a threshold value of the peak intensity. The fluororesin paint or the fluororesin coating film according to any one of claims 1 to 3. Evaluation methods.
  5. 　前記計測データが、前記試料の熱分解ガスクロマトグラフィ法による計測データであり、
    　前記ピークに係るデータが、ピークを生じる熱分解生成物が検出される時刻とピーク強度の閾値を含む
    　請求項１から請求項３の何れか１項に記載のフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法。     The measurement data is measurement data obtained by pyrolysis gas chromatography of the sample,
    The data relating to the peak includes a time at which a thermal decomposition product causing the peak is detected and a threshold value of the peak intensity. The fluororesin paint or the fluororesin coating film according to any one of claims 1 to 3. Evaluation methods.
  6. 　前記フッ素原子含量推定ステップで、前記計測データにおける前記フッ素原子を有するモノマーに基づく構成単位由来の熱分解生成物のピーク強度の閾値に基づいて、前記試料のフッ素原子含量を推定する
    　請求項１から請求項５の何れか１項に記載のフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法。     The fluorine atom content of the sample is estimated based on the threshold value of the peak intensity of the thermal decomposition product derived from the structural unit based on the monomer having the fluorine atom in the measurement data in the fluorine atom content estimation step. The evaluation method of the fluororesin coating material or fluororesin coating film of any one of Claim 5.
  7. 　前記フッ素原子を有するモノマーが、テトラフルオロエチレンまたはクロロトリフルオロエチレンの少なくとも何れか一方である
    　請求項１から請求項６の何れか１項に記載のフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法。     The method for evaluating a fluororesin paint or a fluororesin coating film according to any one of claims 1 to 6, wherein the monomer having a fluorine atom is at least one of tetrafluoroethylene and chlorotrifluoroethylene.
  8. 　道路橋に塗布されるフッ素樹脂塗料または道路橋に設けられたフッ素樹脂塗膜である試料の、熱分解ガスクロマトグラフィ法または熱分解ガスクロマトグラフィ質量分析法による計測データを取得する計測データ取得部と、
    　ビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位由来の熱分解生成物のピークに係るデータを記憶する特定モノマーピーク記憶装置と、
    　フッ素原子を有するモノマーに基づく構成単位由来の熱分解生成物のピークに係るデータを記憶するフッ素ピーク記憶装置と、
    　前記特定モノマーピーク記憶装置に記録されたビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位由来の熱分解生成物のピークに係るデータと前記計測データとに基づいて、前記試料にビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位の有無および量の少なくとも一方を推定する特定モノマー推定部と、
    　前記フッ素ピーク記憶装置に記録されたフッ素原子を有するモノマーに基づく構成単位由来の熱分解生成物のピークに係るデータと前記計測データとに基づいて、前記試料のフッ素原子含量を推定するフッ素原子含量推定部と
    　を備える評価用情報算出装置。     A measurement data acquisition unit for acquiring measurement data by a pyrolysis gas chromatography method or pyrolysis gas chromatography mass spectrometry of a sample which is a fluororesin paint applied to a road bridge or a fluororesin coating film provided on a road bridge;
    A specific monomer peak storage device for storing data relating to peaks of thermal decomposition products derived from structural units based on at least one of vinyl ester and vinyl ether;
    A fluorine peak storage device for storing data relating to peaks of thermal decomposition products derived from structural units based on monomers having fluorine atoms;
    Based on the data related to the peak of the thermal decomposition product derived from the structural unit based on at least one of vinyl ester and vinyl ether recorded in the specific monomer peak storage device and the measurement data, the sample contains at least vinyl ester and vinyl ether. A specific monomer estimator that estimates at least one of the presence and amount of a constituent unit based on one;
    Fluorine atom content for estimating the fluorine atom content of the sample based on the measurement data and the data related to the peak of the thermal decomposition product derived from the structural unit based on the monomer having fluorine atoms recorded in the fluorine peak storage device An evaluation information calculation apparatus comprising: an estimation unit.
  9. 　前記特定モノマーピーク記憶装置にビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位由来の熱分解生成物のピークに係る新たなデータを記録する記録部をさらに備える
    　請求項８に記載の評価用情報算出装置。     The evaluation information calculation apparatus according to claim 8, further comprising a recording unit that records new data relating to a peak of a thermal decomposition product derived from a structural unit based on at least one of vinyl ester and vinyl ether in the specific monomer peak storage device. .
  10. 　請求項８または請求項９に記載の評価用情報算出装置と端末装置とを備え、
    　前記端末装置が、
    　熱分解ガスクロマトグラフィ法または熱分解ガスクロマトグラフィ質量分析法による前記試料の計測データを生成する計測データ生成部と、
    　前記計測データを前記評価用情報算出装置に送信する送信部と、
    　前記評価用情報算出装置から、前記試料にビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位の有無および量の少なくとも一方の推定結果およびフッ素原子含量とに関する情報を受信する受信部と、
    　前記受信部が受信した情報に基づいて、前記試料の評価に用いられる情報を提示する提示部と
    　を備える評価用情報提示システム。     An evaluation information calculation device according to claim 8 or claim 9 and a terminal device,
    The terminal device is
    A measurement data generation unit for generating measurement data of the sample by pyrolysis gas chromatography or pyrolysis gas chromatography mass spectrometry;
    A transmission unit for transmitting the measurement data to the evaluation information calculation device;
    A receiving unit that receives information on the estimation result of at least one of the presence / absence and amount of a structural unit based on at least one of vinyl ester and vinyl ether and the fluorine atom content from the evaluation information calculation device;
    An evaluation information presentation system comprising: a presentation unit that presents information used for evaluating the sample based on information received by the reception unit.
  11. 　道路橋に塗布されるフッ素樹脂塗料または道路橋に設けられたフッ素樹脂塗膜である試料の、熱分解ガスクロマトグラフィ法または熱分解ガスクロマトグラフィ質量分析法による計測データを生成する計測データ生成部と、
    　前記計測データを請求項８または請求項９に記載の評価用情報算出装置に送信する送信部と、
    　前記評価用情報算出装置から、前記試料にビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位の有無および量の少なくとも一方の推定結果およびフッ素原子含量とに関する情報を受信する受信部と、
    　前記受信部が受信した情報に基づいて、前記試料の評価に用いられる情報を提示する提示部と
    　を備える端末装置。     A measurement data generation unit that generates measurement data by pyrolysis gas chromatography or pyrolysis gas chromatography mass spectrometry of a sample that is a fluororesin paint applied to a road bridge or a fluororesin coating film provided on a road bridge;
    A transmitter that transmits the measurement data to the evaluation information calculation device according to claim 8 or 9,
    A receiving unit that receives information on the estimation result of at least one of the presence / absence and amount of a structural unit based on at least one of vinyl ester and vinyl ether and the fluorine atom content from the evaluation information calculation device;
    And a presentation unit that presents information used for the evaluation of the sample based on the information received by the reception unit.
  12. 　道路橋に塗布されるフッ素樹脂塗料または道路橋に設けられたフッ素樹脂塗膜である試料の、熱分解ガスクロマトグラフィ法または熱分解ガスクロマトグラフィ質量分析法による計測データを生成する計測データ生成ステップと、
    　前記計測データを請求項８または請求項９に記載の評価用情報算出装置に送信する送信ステップと、
    　前記評価用情報算出装置から、前記試料にビニルエステルおよびビニルエーテルの少なくとも一方に基づく構成単位の有無および量の少なくとも一方の推定結果およびフッ素原子含量とに関する情報を受信する受信ステップと、
    　受信した前記情報に基づいて前記試料を評価する評価ステップと
    　を有するフッ素樹脂塗料またはフッ素樹脂塗膜の評価方法。     A measurement data generation step for generating measurement data by pyrolysis gas chromatography or pyrolysis gas chromatography mass spectrometry of a sample which is a fluororesin paint applied to a road bridge or a fluororesin coating film provided on a road bridge;
    A transmission step of transmitting the measurement data to the evaluation information calculation device according to claim 8 or 9,
    A receiving step of receiving information on the estimation result of at least one of the presence and amount of a constituent unit based on at least one of vinyl ester and vinyl ether and the fluorine atom content from the evaluation information calculation device;
    An evaluation method of a fluororesin paint or a fluororesin coating film, comprising: an evaluation step of evaluating the sample based on the received information.
PCT/JP2015/084208 2014-12-12 2015-12-04 Method for evaluating fluororesin paint or fluororesin coating film, evaluation-information calculation device, evaluation-information presentation system, and terminal device WO2016093179A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020531256A (en) * 2017-08-24 2020-11-05 カーハーエス・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング A method for controlling the amount of adhesive to be applied onto the substrate

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02240154A (en) * 1989-03-15 1990-09-25 Dainippon Ink & Chem Inc Aqueous dispersion of fluoroolefin copolymer
JPH02276808A (en) * 1988-12-29 1990-11-13 Tokuyama Soda Co Ltd Fluorine-containing random copolymer and production thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02276808A (en) * 1988-12-29 1990-11-13 Tokuyama Soda Co Ltd Fluorine-containing random copolymer and production thereof
JPH02240154A (en) * 1989-03-15 1990-09-25 Dainippon Ink & Chem Inc Aqueous dispersion of fluoroolefin copolymer

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHOI SUNG-SEEN ET AL.: "Analysis of pyrolysis products of poly(vinylidene fluoride- co-hexafluoropropylene) by pyrolysis-gas chromatography/mass spectrometry", JOURNAL OF FLUORINE CHEMISTRY, vol. 165, September 2014 (2014-09-01), pages 33 - 38, XP029014963, DOI: doi:10.1016/j.jfluchem.2014.06.004 *
T ISHIDA ET AL.: "Effect of monomer sequence on the polymer durability in the copolymers of chlorotrifluoroethylene with an alkyl vinyl ester or an alkyl vinyl ether", SURFACE COATINGS INTERNATIONAL PART B: COATINGS TRANSACTIONS, vol. 85, June 2002 (2002-06-01), pages 143 - 148 *
TSUGUHIDE ISEMURA ET AL.: "Netsu Bunkai Gas Chromatography ni yoru Ethylene-Tetrafluoroethylene Jushi no Sosei Bunseki", ABSTRACT OF THE FLUORINE CONFERENCE OF JAPAN, vol. 17, 1992, pages 29 - 30 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020531256A (en) * 2017-08-24 2020-11-05 カーハーエス・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング A method for controlling the amount of adhesive to be applied onto the substrate
JP7157139B2 (en) 2017-08-24 2022-10-19 カーハーエス・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング Method for controlling the amount of adhesive to be applied onto a substrate

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