WO2016093179A1 - Procédé d'évaluation de peinture à base de résine fluorée ou de film de revêtement à base de résine fluorée, dispositif de calcul d'informations d'évaluation, système de présentation d'informations d'évaluation, et dispositif terminal - Google Patents

Procédé d'évaluation de peinture à base de résine fluorée ou de film de revêtement à base de résine fluorée, dispositif de calcul d'informations d'évaluation, système de présentation d'informations d'évaluation, et dispositif terminal Download PDF

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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
Prior art date
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PCT/JP2015/084208
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English (en)
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/fr

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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

L'objet de la présente invention est d'évaluer si une peinture à base de résine fluorée ou un film de revêtement à base de résine fluorée est approprié(e) comme peinture ou film de revêtement destiné à un pont routier. Un dispositif (20) de calcul d'informations d'évaluation acquiert un chromatogramme se rapportant à un échantillon (S). Le dispositif (20) de calcul d'informations d'évaluation estime, sur la base du chromatogramme et des données se rapportant aux pics de produits de décomposition thermique dérivés de motifs constitutifs à base d'ester de vinyle et/ou d'éther de vinyle, la présence et/ou la quantité des motifs constitutifs à base d'ester de vinyle et/ou d'éther de vinyle dans l'échantillon (S). Le dispositif (20) de calcul d'informations d'évaluation estime la teneur en fluor de l'échantillon (S) sur la base du chromatogramme et des données se rapportant aux pics de produits de décomposition thermique dérivés de motifs constitutifs à base de monomères comprenant du fluor. Un évaluateur (E) évalue l'échantillon (S) sur la base de la teneur en fluor, et de la présence et/ou de la quantité des motifs constitutifs à base d'ester de vinyle et/ou d'éther de vinyle.
PCT/JP2015/084208 2014-12-12 2015-12-04 Procédé d'évaluation de peinture à base de résine fluorée ou de film de revêtement à base de résine fluorée, dispositif de calcul d'informations d'évaluation, système de présentation d'informations d'évaluation, et dispositif terminal WO2016093179A1 (fr)

Applications Claiming Priority (2)

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JP2014-252464 2014-12-12
JP2014252464A JP2018021757A (ja) 2014-12-12 2014-12-12 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

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JP2020531256A (ja) * 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 基体の上に塗布されるべき粘着剤の量の制御のための方法
CN114236013A (zh) * 2021-12-23 2022-03-25 广州合成材料研究院有限公司 一种测定水性氟树脂涂料基料中氟含量的方法

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Publication number Priority date Publication date Assignee Title
JP2020531256A (ja) * 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 基体の上に塗布されるべき粘着剤の量の制御のための方法
JP7157139B2 (ja) 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 基体の上に塗布されるべき粘着剤の量の制御のための方法
CN114236013A (zh) * 2021-12-23 2022-03-25 广州合成材料研究院有限公司 一种测定水性氟树脂涂料基料中氟含量的方法

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