JP6643611B2 - Fluoride detection agent, fluoride detection method, fluoride detection kit, and fluoride detection device - Google Patents

Description

  The present invention relates to a fluoride detection agent for detecting a fluoride of an unsaturated hydrocarbon, a fluoride detection method, a fluoride detection kit, and a fluoride detection device.

2. Description of the Related Art In recent years, in order to preserve the global environment and preserve many species and human beings, it has been required to reduce the use of fluorine-containing compounds that are global warming substances. In particular, the use of saturated fluorocarbons such as carbon tetrafluoride and octafluorocyclobutane, which have been used as dry etching gas, is limited due to their adverse effects on global warming. As these alternatives, fluorinated hydrocarbon compounds having an unsaturated bond of carbon in the molecule, such as octafluorocyclopentene (C ₅ F ₈ ) and hexafluorobutadiene (C ₄ F ₆ ), have been developed.

  Fluorohydrocarbon compounds having carbon unsaturated bonds (hereinafter sometimes referred to as “unsaturated hydrocarbon fluorides”) are known as high-performance compounds capable of finely processing silicon oxide with a high selectivity, and Partially used in the process. Although fluorides of unsaturated hydrocarbons have an improved global warming potential as compared with saturated fluorocarbons, there are regulations for preventing leakage and controlling environmental concentrations due to problems of high vapor pressure and toxicity. Therefore, there is a need for a technique for detecting fluorides of unsaturated hydrocarbons with high sensitivity.

Currently, techniques for detecting unsaturated hydrocarbon fluoride using permanganate or pyrolysis are being developed. A method for detecting the fluoride of an unsaturated hydrocarbon using permanganate utilizes the decolorization of permanganate due to the reaction of permanganate with C ₅ F ₈ or C ₄ F ₆ (Patent Document 1) ). However, in this method, (1) the reaction is slow and it is difficult to detect unless the concentration of fluoride is 50 ppm or more. (2) It takes 19 minutes or more on average to detect fluoride of unsaturated hydrocarbon having a concentration of 50 ppm. (3) Since permanganate is difficult to process, the form for detecting fluoride is limited. (4) Permanganate, which is a strong oxidizing agent, is a hydride or complex such as a boron derivative. However, there is a problem that erroneous detection may occur because the color is erased even when the reaction is performed.

In the detection method of fluoride of unsaturated hydrocarbon using pyrolysis, C ₅ F ₈ or C ₄ F ₆ present in a gas is pyrolyzed in a pyrolysis furnace, and acid gas HF generated at that time is optically converted. (Patent Document 2). However, this method (1) handles very dangerous acid gas HF, (2) consumes energy for thermal decomposition, and (3) performs thermal decomposition at a high temperature, so that it is used as a cleaning agent or an insulator material. There is a problem that the acid gas generated from the used fluorine-based liquid may be erroneously detected, and (4) if an acid gas having a structure similar to that of HF is mixed, it may be erroneously detected.

In order to solve these problems, a detection agent has been developed that selectively detects C ₅ F ₈ or C ₄ F ₆ near room temperature by utilizing characteristics of a reaction of an amidine derivative or the like (Patent Document 3). However, the life of this detection agent is shortened due to the influence of water vapor or acid gas in the air. As described above, there are various problems in the conventional method for detecting the fluoride of unsaturated hydrocarbon, and thus a new economical detection method with high performance, high durability, and long life is required.

JP 2001-324492 A JP 2001-324492 A International Publication No. WO2012 / 002239

  The present invention has been made in view of the above problems, and can be easily detected at around room temperature without using high-temperature pyrolysis or a strong oxidizing agent, and without interference of an interfering gas from a fluorine-based liquid or the like. It is an object of the present invention to provide an unsaturated hydrocarbon fluoride detecting agent which can be detected, can be rapidly detected with high sensitivity, is durable, and can be detected with a long life.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by utilizing the selective direct reaction of fluorides of unsaturated hydrocarbons such as C ₅ F ₈ and C ₄ F ₆ , The knowledge which can achieve the above-mentioned object was obtained. That is, they found that a certain sulfur compound group and an unsaturated hydrocarbon fluoride cause a selective color-forming reaction, and that even if the unsaturated hydrocarbon fluoride is at a low concentration, it can be optically detected with high sensitivity. Revealed.

  Furthermore, it has been found that the detection agent containing this sulfur compound group has excellent durability in air of high humidity and a longer life of the detection agent than the detection agent using an amidine derivative. In addition, the detection agent containing the sulfur compound group allows the fluorine containing hydrocarbon to have a first carbon bonded to hydrogen, and an anionic leaving group and a second carbon bonded to the first carbon. Was also found to be detectable. The present invention has been made based on these findings, and the following configurations are provided.

  The agent for detecting fluoride of the present invention comprises an inorganic sulfur compound containing a sulfur anion species as an active ingredient, and is a detecting agent for detecting fluoride, wherein the fluoride is (1) a fluoride of an unsaturated hydrocarbon. And (2) at least one of a hydrocarbon fluoride comprising a first carbon bonded to hydrogen, and an anionic leaving group and a second carbon bonded to the first carbon. .

  Another agent for detecting fluoride according to the present invention comprises an organic sulfur compound containing a sulfur anion species as an active ingredient, and is a detecting agent for detecting fluoride, wherein the fluoride is (1) an unsaturated hydrocarbon. At least one of fluoride, and (2) a hydrocarbon fluoride comprising a first carbon bonded to hydrogen and a second carbon bonded to the anionic leaving group and the first carbon. It is.

  The method for detecting a fluoride of the present invention includes a reaction step of reacting the detection agent of the present invention with a fluoride, and a measurement step of measuring a change in a property value before and after the reaction of the detection agent.

  The kit for detecting a fluoride of the present invention is a detection member including the detection agent of the present invention, and a determination member for determining the color of the detection agent after the reaction between the detection agent and the fluoride by colorimetry. And

  The fluoride detection device of the present invention includes a detection unit including the detection agent of the present invention, an introduction unit that guides a gas containing fluoride to the detection unit, a light source that irradiates the detection unit with light, and a light source of the detection unit. A measuring unit for measuring the reflectance.

  Another fluoride detection device of the present invention is a detection unit including a quartz oscillator provided with a surface of the detection agent of the present invention, an introduction unit that guides a gas containing fluoride to the detection unit, and a quartz oscillator. A measuring unit for measuring a resonance frequency.

  According to the present invention, the fluoride of the unsaturated hydrocarbon can be easily detected.

9 is a graph showing the detection time dependency of an optical change in Example 2. 21 is a graph showing the detection time dependency of the optical change in Example 11. FIG. 1 is a schematic diagram of a detection kit according to an embodiment of the present invention. FIG. 1 is a schematic diagram of a detection device according to an embodiment of the present invention. FIG. 6 is a schematic diagram of a detection device according to another embodiment of the present invention.

  Hereinafter, the fluoride detection agent, detection method, detection kit, and detection device of the present invention will be described in detail based on embodiments and examples. Duplicate description is omitted as appropriate. In addition, when "-" is described between two numerical values to indicate a numerical range, the two numerical values are also included in the numerical range.

  The detection agent according to the first embodiment of the present invention is a detection agent for detecting a fluoride, which contains an inorganic sulfur compound containing a sulfur anion species as an active ingredient, and wherein the fluoride comprises (1) an unsaturated carbon compound. A hydrogen fluoride, and (2) a hydrocarbon fluoride comprising a first carbon bonded to hydrogen, and a second carbon bonded to the anionic leaving group and the first carbon. At least one. The detection agent of the first embodiment may further include water and at least one of a base and a reducing agent.

  The detection agent according to the second embodiment of the present invention is a detection agent for detecting a fluoride, which contains an organic sulfur compound containing a sulfur anion species as an active ingredient, and wherein the fluoride comprises (1) unsaturated carbon A hydrogen fluoride, and (2) a hydrocarbon fluoride comprising a first carbon bonded to hydrogen, and a second carbon bonded to the anionic leaving group and the first carbon. At least one. The detection agent of the second embodiment may further include at least one of water, a base, a reducing agent, and a transition metal ion.

  The sulfur anion species refers to a chemical species containing sulfur having a negative charge or a chemical species containing sulfur in a state where electron density is high due to polarization. When a sulfur anion species is generated by a chemical reaction or the like, the sulfur anion species causes a nucleophilic reaction that is relatively stable and has high selectivity for a reaction target. On the other hand, chemical species such as hydroxide ions and alkoxides, which are oxygen anion species, are strongly alkaline, and the acidity of the chemical species in which a proton is bonded to the oxygen anion species is low. Oxygen anion species are unstable and cause a violent nucleophilic reaction with no selectivity for the target. On the other hand, the acidity of a chemical species in which a proton is bonded to a sulfur anion species is high.

  The stability of the sulfur anion species contributes to high durability and long life of the detection agent of the present embodiment. After the nucleophilic reaction of the sulfur anion species, a covalent bond of carbon and sulfur may be formed. At this time, the electron orbital of sulfur, particularly the electron of the sulfur lawn pair, forms a hybrid orbital that matches the electron orbital of the carbon skeleton, particularly the carbon π electron cloud, and exhibits an effect of enhancing aromaticity. For this reason, the sulfur anion species acts on the carbon skeleton, causing light absorption on the long wavelength side, that is, causing a change that is easily measured optically. Also, the sulfur anion species act on the carbon skeleton to cause changes other than optical changes. Due to such an effect of the sulfur anion species, the fluoride of the unsaturated hydrocarbon and the sulfur anion species cause a selective reaction, and the detection accompanying the change of the sulfur anion species becomes possible.

  In the detection agent of the first embodiment, the inorganic sulfur compound contains a sulfur anion species. Further, in the detection agent of the second embodiment, the organic sulfur compound contains a sulfur anion species. Here, “the inorganic sulfur compound or the organic sulfur compound contains a sulfur anion species” means that the sulfur anion species present in the inorganic sulfur compound or the organic sulfur compound can immediately react with the fluoride to be detected as it is. In addition, the inorganic sulfur compound or the organic sulfur compound cannot react with the fluoride to be detected as it is, but when the inorganic sulfur compound or the organic sulfur compound is chemically treated, a sulfur anion species is generated and can react with the fluoride to be detected. It means when it comes to.

  Reagents used in this chemical treatment include bases, reducing agents, or transition metal ions. The base is a substance exhibiting alkalinity such as hydride compounds such as hydroxides, alkoxides and sodium hydride; sodium acetate and potassium acetate which are weak alkalis; and nitrogen compounds such as ammonia and amines. The reducing agent is a substance that causes a reduction reaction, such as a simple metal such as sodium, potassium, and zinc, and a reducing reagent such as sodium borohydride, lithium aluminum hydride, and Rongalite. Transition metal ions increase the stability of the sulfur anion species and control the selectivity of the reaction. The type of the transition metal is not particularly limited.

Examples of the inorganic sulfur compound include a compound composed of an alkali metal, an alkaline earth metal, a transition metal, a cationic element of a typical element, and S ²⁻ . Chemically known polysulfur anion species (S _n ^2- : n ≧ 2) and phosphorus sulfide compounds are also inorganic sulfur compounds, but inorganic sulfur compounds other than these are preferred from the viewpoint of stability and reactivity. . From the viewpoints of reactivity, solubility and economy, inorganic sulfur compounds include sulfides of alkali metals such as sodium and lithium or sulfides having cations other than sodium, for example, sulfides of alkaline earth metals such as calcium and magnesium. Are more preferred. Among these, sodium sulfide and sodium hydrogen sulfide are particularly preferred.

  The organic sulfur compound is preferably at least one of thiol, disulfide, thioester, dithioester, thiocarboxylic acid, dithiocarboxylic acid, dithiocarbamic acid, and thiourea, and derivatives thereof. Thiols, disulfides, thioesters, and dithioesters can produce sulfur anion species by reaction with bases and reducing agents. Therefore, the thiol, disulfide, thioester, and dithioester derivatives have high reactivity with the fluoride to be detected, and the optical change before and after the reaction when the detection agent of the second embodiment has reacted with the fluoride. large.

  Further, thiocarboxylic acid, dithiocarboxylic acid, and dithiocarbamic acid have relatively high acidity, and their salts can be easily formed by a weak alkali. These salts inherently contain chemically stable sulfur anion species. Therefore, derivatives of thiocarboxylic acid, dithiocarboxylic acid, and dithiocarbamic acid are preferable as the organic sulfur compound of the detection agent of the second embodiment.

  In addition, thiourea contains a sulfur anion species through polarization of nitrogen and sulfur via carbon of thiocarbonyl in the molecule. Therefore, a thiourea derivative is preferable as the organic sulfur compound of the detection agent of the second embodiment. Among these, from the viewpoints of stability and reactivity, a derivative of dithiocarbamic acid is most preferable as the organic sulfur compound of the detection agent of the second embodiment. That is, since the derivative of dithiocarbamic acid is a stable compound, the detection agent containing the derivative of dithiocarbamic acid as an active ingredient has improved durability and longer life than the conventional detection agent containing a nitrogen compound or the like as an active ingredient. Is expected.

  Examples of the thiol derivative include alkanethiol, alkenethiol, alkynethiol, and π-electron-bonding aromatic thiol having a substituent that may contain a hetero atom. Thiol cannot be used for detection of a fluoride to be detected as it is, but when mixed with a base, a sulfur anion species (general formula RS: R is a substituent) capable of detecting a fluoride is generated by mixing with a base. .

  Derivatives of disulfides include alkane disulfides, alkene disulfides, alkyne disulfides, and aromatic disulfides that may contain heteroatoms, such as symmetric or asymmetric disulfides. The functional group bonded to the disulfide group may be a hetero atom and is not particularly limited. Disulfide cannot be used for detection of a fluoride to be detected as it is, but a sulfur anion species capable of detecting a fluoride by mixing with a reducing agent or a base (general formula RS: R is a substituent) Is generated.

  Examples of the thioester derivative include a compound in which H of thiol SH is substituted with an aliphatic or aromatic carbonyl. The aliphatic or aromatic carbonyl may contain a heteroatom. A thioester cannot be used for detection of a fluoride to be detected as it is, but when mixed with a base, a sulfur anion species (general formula RS: R is a substituent) capable of detecting a fluoride is generated by mixing with a base. .

  Examples of the dithioester derivative include compounds in which the carbonyl moiety of the thioester derivative has become thiocarbonyl. The dithioester may contain a heteroatom. Dithioester cannot be used for detection of a fluoride to be detected as it is, but when mixed with a base, a sulfur anion species (general formula RS: R is a substituent) capable of detecting a fluoride is generated by mixing with a base. I do.

  The thiocarboxylic acid is represented by R-COSH, and the substituent R is an aliphatic or aromatic derivative that may contain a hetero atom. For example, thiocarbamic acid in which nitrogen is bonded to carbon of thiocarboxylic acid is a derivative of thiocarboxylic acid. Since thiocarboxylic acid is a strong organic sulfur acid, it can be used as it is for the detection of fluoride to be detected. The thiocarboxylic acid is preferably used in the form of a thiocarboxylic acid salt, mixed with a base, especially a weak base.

  The dithiocarboxylic acid is represented by R-CSSH, and the substituent R is an aliphatic or aromatic derivative that may contain a hetero atom. For example, xanthic acid, which is a derivative of dithiocarbonic acid in which oxygen is bonded to carbon of dithiocarboxylic acid, is represented by R-OCSH and is a derivative of dithiocarboxylic acid. Derivatives of xanthogenic acid include potassium amyl xanthogenate, sodium ethyl xanthogenate, ammonium 1-pyrrolidinecarbodithioate, and the like, which can be used as it is for detection of the fluoride to be detected.

  Trithiocarbonic acid in which sulfur is further bonded to carbon of dithiocarboxylic acid is also a derivative of dithiocarboxylic acid. Since dithiocarboxylic acid is a strong organic sulfuric acid, it can be used as it is for the detection of fluoride to be detected. The dithiocarboxylic acid is preferably used in the form of a dithiocarboxylic acid salt, mixed with a base, especially a weak base. When the sulfur anion species is a salt, a counter cation is present. Counter cations include alkali metals, alkaline earth metals, transition metal ions, ammonium, or phosphonium, as well as polycations thereof.

  Examples of the dithiocarbamic acid derivative include an alkali metal salt, an alkaline earth metal salt, a transition metal salt, an ammonium salt, and a phosphonium salt of dithiocarbamic acid. The derivative of dithiocarbamic acid is preferably an alkali metal salt, an alkaline earth metal salt, an ammonium salt, or a phosphonium salt. Further, the molecular skeleton of the derivative of dithiocarbamic acid may have a hydrocarbon substituent which may contain a hetero atom. The alkali metal, alkaline earth metal, ammonium, or phosphonium salts of dithiocarbamic acid contain the sulfur anion species of the dithiocarbonyl moiety. In addition, these salts generally have adsorbed water and are in a state where water is already mixed.

  Examples of the counter cation of these salts include alkali metal ions, alkaline earth metal ions, transition metal ions of copper and iron, ammonium, phosphonium, and polycations thereof. Derivatives of dithiocarbamic acid that are readily available include sodium N, N-dimethyldithiocarbamate, hydrates of sodium N, N-diethyldithiocarbamate, and hydrates of potassium N, N-diethyldithiocarbamate.

  Other derivatives of dithiocarbamic acid, such as diethylammonium diethyldithiocarbamate, dimethylammonium dimethyldithiocarbamate, and hexamethyleneammonium hexamethylenedithiocarbamate, in which the counter cation is ammonium, and dimethyldithiocarbamic acid in which the counter cation is a transition metal ion Iron (III), copper (II) bis (2-hydroxyethyl) dithiocarbamate, copper (II) dimethyldithiocarbamate and the like. Among them, transition metal ions such as copper and iron are included as counter cations from the viewpoint of the stability of the derivative of dithiocarbamic acid, that is, the stability of the detection agent and the stability of the signal for detecting fluoride. Preferred dithiocarbamic acid derivatives are preferred.

  Thiourea contains a sulfur anion species due to the polarization of nitrogen and sulfur through the carbon of the thiocarbonyl in the molecule. In the thiourea derivative, the hydrogen bonded to the nitrogen is replaced by an aliphatic or aromatic derivative that may contain a heteroatom. Thiourea derivatives also include thioamide and N, N-dimethylthioformamide, but these have relatively low reactivity.

  The organic sulfur compound may have a hydrocarbon substituent which may contain a hetero atom. "Hydrocarbons which may contain a hetero atom" include, in addition to hydrocarbons consisting of carbon and hydrogen, oxygen, nitrogen, phosphorus, boron, aluminum, silicon, fluorine, chlorine, bromine, iodine, transition metals, alkali metals, alkalis A compound or composition in which a part of a hydrocarbon is substituted with a hetero atom such as an earth metal.

  Therefore, as a substituent of a hydrocarbon which may contain a hetero atom, for example, a methyl group (C1), an ethyl group (C2) to a stearyl group (C18), a trimethylphenyl (C19) group Alkyl group, alkene group, alkyne group, phenyl group, naphthyl group, anthracenyl group, hydroxy group, alkoxy group, aldehyde group, ketone group, ether group, crown ether group, alcohol group, ethylene glycol group, glycerin group, polyethylene Glycol group, carboxylate group, carboxylate, acetal group, epoxy group, amino group, amide group, imino group, nitro group, cyano group, isocyano group, thioisocyano group, azo group, azoxy group, porphyrin group, sulfinic acid Ester groups, sulfonic ester groups, salts of these acids, Jin group, a pyrrole group, a pyrrolidine group, piperidine group, morpholine group, piperazine group, a quinoline group, a thiophene group, a furan group. In addition, examples of the hydrocarbon that may contain a hetero atom include a heterocyclic compound, a transition metal complex, an organic oligomer, an organic polymer, and a complex thereof. Further, the organic sulfur compound may be present as a side chain of an oligomer or a polymer, or may be held on the substrate by a coordination bond or a bond by Coulomb force or Van der Waals force.

  The fluoride detected by the detection agent of the present embodiment includes (1) a fluoride of an unsaturated hydrocarbon (hereinafter sometimes referred to as a “first aspect of the fluoride”), and (2) a fluoride bonded to hydrogen. A hydrocarbon fluoride comprising one carbon and a second carbon bonded to the anionic leaving group and the first carbon (hereinafter sometimes referred to as the “fluoride of the second embodiment”. Together, the fluoride of one embodiment and the fluoride of the second embodiment may be referred to as “fluoride to be detected”. The fluoride according to the first embodiment and the fluoride according to the second embodiment, that is, the fluoride to be detected is a fluoride having two or more carbon atoms. The fluoride of the first embodiment has a structure in which some or all of the unsaturated hydrocarbons have been replaced with fluorine.

  The fluoride of the first aspect contains carbon and fluorine and has at least one of a carbon-carbon double bond and a carbon-carbon triple bond. The fluoride may be a gas or a liquid at normal temperature. A π-electron bond is present in a carbon-carbon double bond or a carbon-carbon triple bond of an unsaturated hydrocarbon, and the π-electron bond is often rich in electrons, that is, negative charges. However, since the fluoride of the first aspect detected by the detection agent of the present embodiment has a fluorine atom with a high electronegativity, the π-electron bond between carbon and carbon has a low electron density, that is, a negative electron bond. The charge is thin. Therefore, the π-electron bond between carbon and carbon of the fluoride of the first aspect undergoes a nucleophilic reaction of the sulfur anion species, and is detected by the detection agent of the present embodiment. Therefore, perfluoroalkanes, perfluoroethers, and the like having no π-electron bond are not detected by the detection agent of the present embodiment.

  The fluoride of the first embodiment may contain atoms other than carbon, hydrogen, and fluorine such as chlorine, bromine, iodine, oxygen, sulfur, or nitrogen, and carboxyl, alkoxy, and formyl groups. Some of the fluorocarbons, which are a series of gaseous compounds evaluated by the Kyoto Protocol, are included in the fluoride of the first embodiment.

As the fluoride of the first aspect, for example, _{C 2 F 4, C 3 F} 6, C 4 F 6, c-C 4 F 6, c-C 4 F 8, c-C 5 F 8, CF 3 OCF = CF ₂ , C ₂ F ₅ OCF = CF _{2 and the} like. In addition, "c-" represents cyclic (cyclo). Some of the fluorides of the first aspect may be used as refrigerants, blowing agents, cleaning agents, insulating liquids, or etching gases. Further, a part of the fluoride of the first embodiment is a kind of PFC (perfluorocarbon), and has a burden on the environment. Further, among the fluorides of the first embodiment, there is also a linear fluorine compound having an ether group, and there is a concern that the load on the environment and the effect on the human body may be apprehended. The detection agent of the present embodiment is applied to the detection of the fluoride of the first aspect, the check of the leakage of the fluoride to be detected, the detector, the alarm, the concentration measurement, the environmental measurement, the environmental management, and the like.

The reaction of the fluoride and sulfur anion species of the second embodiment is similar to the reaction of the fluoride and sulfur anion species of the first embodiment. For example, C ₅ F ₈ H ₂ causes a deprotonation reaction with a detection agent containing a base. Thereafter, the anionic leaving group is eliminated, and an unsaturated double bond is generated in the fluoride of the second embodiment, and the fluoride of the first embodiment is obtained. The fluoride of the first embodiment reacts with the inorganic sulfur compound or the organic sulfur compound. That is, since the fluoride of the second embodiment does not have a π-electron bond, it is difficult to react with the sulfur anion species as it is. However, it reacts with the base contained in the detection agent of the present embodiment to generate the fluoride of the first aspect.

  Examples of the anionic leaving group contained in the fluoride of the second embodiment include a halogen group such as fluorine and chlorine, an alkoxy group, an ether group, a chalcogen-containing group such as a sulfide group, a carboxylic acid group, and a sulfonic acid group. Is mentioned. The fluoride of the second embodiment may have, in addition to the anionic leaving group, atoms such as chlorine, bromine, iodine, oxygen, sulfur, and nitrogen, and functional groups such as a carboxyl group, an alkoxy group, and a formyl group. . Some of the fluorocarbons, which are a series of gaseous compounds evaluated by the Kyoto Protocol, are included in the fluoride of the second embodiment. Further, even if the fluoride of the second aspect is a liquid, it can be detected by the detection agent of the present embodiment.

As the fluoride of the second _{aspect, CF 3 CHF 2, CHF 2} CHF 2, CF 3 CHFCF 3, CF 3 CF 2 CHF 2, CHF 2 CF 2 CHF 2, CF 3 OCHFCF 3, c-C 5 F 8 H _{2 and the} like. The fluoride of the second embodiment is used as a refrigerant for air conditioners, refrigerators, or freezers for home use, business use, or for vehicles, as a foaming agent for forming heat insulating materials at construction sites, and as a cleaning agent for electronic devices. May be asked. Further, the fluoride of the second embodiment may be used as an etching gas, a cleaning agent, or a cooling agent in a semiconductor process. Among the fluorides of the second embodiment, there are those called HFC (hydrofluorocarbon) and HCFC (hydrochlorofluorocarbon) which are taken up in environmental issues.

  The fluoride of the second aspect also causes a color-forming reaction when brought into contact with the detection agent of the present embodiment, and can be detected using its optical change. The detection agent of the present embodiment is applied to the detection of fluoride of the second aspect, the check for leakage of fluoride to be detected, a detector, an alarm, a concentration measurement, an environmental measurement, an environmental management, and the like.

  The detection agent of the present embodiment may contain an organic substance other than the active ingredient. Examples of the organic substance include alcohols such as ethanol, ethylene glycol, and glycerin, amides such as dimethylformamide (DMF), N-methyl-pyrrolidone (NMP), and hexamethylphosphoramide (HMPA), and dimethyl sulfoxide (DMSO). ) And sulfolane, and common organic solvents such as ethers such as tetrahydrofuran (THF) and dioxane. Examples of the organic substance include amines such as diisopropylamine, triisobutylamine, dicyclohexylmethylamine, and pentamethylpiperidone, and 1,3-dimethyl-2-imidazolidinone and N, N-dimethylpropylene urea (DMPU And organic liquids such as ureas.

  Examples of the organic substance include organic ammonium salts, organic phosphonium salts, cellulose, polyethylene, polybutadiene, polyethylene acrylate, polyimide polybenzoic acid, organic oligomers such as poly (methyl methacrylate) (PMMA), organic polymers, pyridinium ions, and imidazole. Examples include ionic liquids including ions, nitrogen compounds such as polyamines, and phosphorus compounds. Since high-boiling organic substances, organic polymers, and ionic liquids have extremely low vapor pressures, the detection agent containing them can suppress a change in concentration and a change in overall mass. Furthermore, the detection agent containing a substance having an appropriate moisturizing property can suppress the influence of humidity, and can stably and accurately detect the fluoride of the first embodiment and the second embodiment.

  The detection agent of the present embodiment may include water and at least one of a base and a reducing agent. When the active ingredient is an inorganic sulfur compound, the inorganic sulfur compound can be dissolved in water. When the active ingredient is an inorganic sulfur compound or an organic sulfur compound, water contained in the detection agent is useful for suppressing the influence of the humidity of the detection environment. In the case where the active ingredient is a salt of dithiocarbamic acid, water may be contained in the detection agent in some cases due to the presence of adsorbed water in the salt of dithiocarbamic acid.

  Examples of the base include general hydroxides, alkoxide anions such as potassium t-butoxide and sodium methoxide, organic acid salts such as sodium acetate which is weakly alkaline, and amines. When acidic gases are present in the detection environment, the base contained in the detection agent reduces the influence of the acidic gases. Further, the base contained in the detection agent suppresses odors derived from inorganic sulfur compounds (especially sulfides) and organic sulfur compounds (especially thiols), and suppresses generation of hydrogen sulfide. Further, the base contained in the detecting agent generates a sulfur anion species from an organic sulfur compound, such as thiol, disulfide, thioester, dithioester, thiocarboxylic acid, dithiocarboxylic acid, or dithiocarbamic acid, and enhances the reactivity for detection.

Examples of the reducing agent include iron (II) ion, lithium aluminum hydride (LiAlH ₄ ), sodium amalgam, sodium borohydride (NaBH ₄ ), tin (II) ion, sulfite, sodium sulfite, sodium thiosulfate, Rongalit, Examples include formaldehyde, hydrazine, zinc amalgam, diisobutylaluminum hydride, oxalic acid, formic acid and the like. Among them, sodium borohydride is preferable from the viewpoint of safety and convenience. This is because sodium borohydride contributes to stabilization of the optical signal of the inorganic sulfur compound (particularly, sulfide). In addition, sodium borohydride can generate a sulfur anion species by performing reduction from disulfide, which is one of organic sulfur compounds, and mixing with a base. Either the base and the reducing agent may be mixed first, or they may be mixed simultaneously.

  Further, depending on the type of the sulfur compound as the active ingredient, only a base or only a reducing agent may be mixed. In addition, depending on the type of the sulfur compound as the active ingredient, at least one of a base and a reducing agent, and a mixing order and a mixing method of water and at least one of the base and the reducing agent can be appropriately selected. Further, the reducing agent contained in the detection agent can generate a sulfur anion species. Further, the reducing agent contained in the detecting agent can suppress deterioration and decomposition of sulfur anion species due to oxidation. For this reason, instability of the measurement of the change in the physical property value can be suppressed.

  The content of the active ingredient contained in the detection agent is preferably from 10% by mass to 50% by mass from the viewpoint of controlling the reactivity. In order to detect the fluoride to be detected, the sulfur compound may be brought into contact with the fluoride. The detection agent of the present embodiment can be dissolved in an organic solvent, placed in a container, and used as a liquid. The detection agent of the present embodiment can be used by applying a liquid dissolved in an organic solvent to a substrate or impregnating a porous material. The detection agent of the present embodiment can be used in a liquid, powder, string, rod, cylindrical, plate, cloth, tape, or cassette form. The detection agent of the present embodiment is obtained by applying a polymer containing an active ingredient to a substrate, impregnating the active ingredient into a base material, and ion-bonding the active ingredient to a surface of a base material composed of an oligomer or a polymer. It may be produced by a chemical bond such as a bond, Van der Waals bond, or a coordinate bond.

  The method for detecting a fluoride to be detected according to the embodiment of the present invention includes a reaction step of reacting the detection agent and the fluoride to be detected according to the embodiment, and a measurement step of measuring a change in a property value before and after the reaction of the detection agent. It has. The change in the physical property value includes an optical change and a mass change.

  In the reaction step, for example, (a) bubbling the detection target fluoride in the present embodiment, which is a liquid, with the detection target fluoride, and (b) spraying the detection target fluoride on the polymer film containing the detection agent in the present embodiment. (C) allowing the fluoride to be detected to pass through the cellulose containing the detection agent of the present embodiment; and (d) detecting the tape, sheet, or plate-like member containing the detection agent of the present embodiment. (E) powder containing the detection agent of the present embodiment, or (f) passing or spraying the fluoride of the detection target on a network tape or sheet containing the detection agent of the present embodiment. (G) powder, capsule, bead, which allows the fluoride to be detected to pass through a tube provided on the inner surface of each of a shape, a capsule, a bead, a particle, a string, a rod, and a cloth. Or particulate members (H) a book which is a liquid which is made to pass the fluoride to be detected on the surface of the fixed tape or spray the fluoride to be detected on the tape (in the case of a capsule-shaped member, it may be crushed immediately before detection); The detection agent of the embodiment can be detected in a tank, and the detection agent can be dropped or sprayed from the tank onto the fluoride to be detected.

  The flow rate of the detection gas when spraying the detection gas containing the fluoride to be detected onto the detection agent, passing through the detection member containing the detection agent, or bubbling the detection agent is not particularly limited, but accelerates the detection reaction. In view of this, a flow rate of 800 mL / min or more is preferable. For example, a flow rate of 1 to 10 L / min is employed. In addition, from the viewpoint of handling and setting of the detection device, 200 to 2000 mL / min is preferable. In addition, from the viewpoint of energy saving, 20 to 600 mL / min is preferable. When the detection agent of the present embodiment originally contains water or is mixed with water, it is hardly affected by the humidity of the environment in which the detection is performed. For this reason, stable detection is possible from dry air (humidity around 0%) to humid air (humidity of about 85%).

  In the measurement step, a change in physical property values of the detection agent before and after the reaction in the reaction step, for example, an optical change caused by a reaction proceeding near room temperature is measured. The temperature at the time of detection is preferably 80 ° C. or less from the viewpoint of practical use. From the viewpoint of the stability of the reaction temperature and, consequently, the stabilization of the signal, it is preferable to set the detection environment at a temperature of about 40 ° C. The optical change may be at least one of changes in absorbance, reflectance, infrared vibration, light emission, phosphorescence, refractive index, liquid crystal state, and photoelectron kinetic energy due to X-rays.

  The change in absorbance is caused by a change in the transmittance of light having a wavelength in the ultraviolet-visible light region.The ultraviolet-visible light region is defined as a range from the ultraviolet light region including vacuum ultraviolet rays to purple, blue, green, yellow, orange, and red. Means the region of light up to the visible light region. When measuring the change in absorbance in the measurement step, the measurement wavelength is preferably 200 to 800 nm. Further, from the viewpoint of selecting a light source used in the measurement step, the measurement wavelength is preferably 300 to 700 nm. The optical change may be measured by visual observation directly using a colorimetric method, or may be measured using an instrument. In the measurement step, it is possible to select a measurement wavelength that is not affected by the detection agent of the present embodiment or has little influence by the detection agent of the present embodiment.

  The change in reflectance is caused by a change in transmittance of light having a wavelength in the ultraviolet-visible light range and a change in scattering of light, and is related to a change in absorbance. The measurement wavelength is preferably from 250 to 600 nm from the viewpoint of easy determination of the color reaction of the sulfur compound. In the coloring reaction of a sulfur compound, a characteristic wavelength change is particularly at 300 to 450 nm. Therefore, the measurement wavelength is preferably 300 to 450 nm. In particular, in the case of a detection agent containing a dithiocarbamic acid derivative as an active ingredient, fluoride to be detected can be detected even in the presence of air for several days. This detection agent has characteristic reflection spectrum peaks at around 350 nm and around 425 nm. By measuring at least one signal change, it is possible to stably detect the fluoride to be detected.

  As a change in reflectivity, a converted value obtained by dividing the change in reflectivity at a wavelength at which the reflectivity changes before and after the reaction with the reference value at a wavelength at which the reflectivity does not change before and after the reaction by the reference value is used. be able to. The change in reflectance is measured by using only a single wavelength to be detected, setting a plurality of wavelengths to be detected, using an integrated value in a certain wavelength range, or using a change in the shape of the reflection spectrum curve as a numerical value. Any method useful for measuring the reflectance change by measuring the reflection spectrum can be used.

Changes in infrared vibration are caused by changes in expansion and contraction and vibration in each bond in the molecule in the infrared region.Infrared vibration is vibration in the near-infrared to infrared and further in the far-infrared region. is there. Measurement of changes in the infrared vibration is preferably 10~4000cm ^-1, particularly preferably 1000～1500Cm ^-1 in terms of the measurement ease. The change in fluorescence emission or phosphorescence emission is a change in light emitted when energy is transferred from an excited state of a molecule to a ground state, which changes with the reaction of the molecule, and the excited state is generated by the excitation light. Therefore, the region of the light used is the same as the region used for the change in the absorbance or the change in the reflectance. The change in fluorescence emission or phosphorescence emission may be increased or decreased.

  The change in the refractive index is caused by a change in the dielectric constant of a portion that changes with the reaction of the molecule. The measurement of the change in the refractive index is often performed in the air, and the light used is preferably in the ultraviolet-visible light range, and the refractive index is preferably changed in the range of 0.1 to 3.2. The change in the liquid crystal state is caused by a change in the orientation state of the molecule, which changes with the reaction of the molecule. In particular, the change between the isotropic liquid state and the nematic liquid crystal or the smectic liquid crystal is used. The change in the liquid crystal state is measured using polarized light in the ultraviolet-visible light region.

  The change in photoelectron kinetic energy due to X-rays is caused by a change in the atomic state in the molecule that changes with the reaction of the molecule, and measures the observed change in the photoelectron kinetic energy. It is preferable to use X-rays of MgKa or AlKa as a light source. From the viewpoint of the magnitude of the change due to the reaction, it is preferable to measure a change in the photoelectron kinetic energy of 200 to 800 eV. In addition, by combining two or more of the above and measuring the optical change, the fluoride to be detected can be detected with high sensitivity.

  In addition, the mass change before and after the reaction of the detection agent can be grasped by measuring the frequency change on the surface of the vibrating body provided with the detection agent or the frequency change on the surface of the crystal resonator for the crystal balance provided with the detection agent. You may. That is, a QCM (Quarts Crystal Microbalance: quartz balance) can be used to measure the change in mass before and after the reaction of the detection agent. Applying the QCM, the detection agent of the present embodiment is adsorbed on the surface of the vibrator or the surface of the crystal oscillator of the QCM, and the frequency of the surface of the vibrator is changed by the reaction between the surface and the fluoride to be detected. By measuring the change in the resonance frequency of the surface, the fluoride to be detected can be detected with high sensitivity. The mass change of the detection agent before and after the reaction may be grasped by measuring the mass change and the pattern change of the mass spectrum before and after the reaction by applying mass spectrum measurement.

  FIG. 3 schematically shows the detection kit 10 according to the embodiment of the present invention. The detection kit 10 includes a detection member 12 and a determination member 14. The detection member 12 is a powder containing the detection agent of the present embodiment. The detection member 12 is filled in a glass tube 20 so as to be sandwiched between the glass filters 16 and 18. The glass tube 20 is filled with a removing agent 24 for removing dust, moisture, and the like so as to be sandwiched between the glass filters 16 and 22. The gas containing fluoride to be detected is introduced into the glass tube 20 from the glass filter 22 side, passes through the glass filter 22, the removing agent 24, the glass filter 16, the detection member 12, and the glass filter 18, and passes through the glass tube 20. Is discharged outside. At this time, the color of the detection agent contained in the detection member 12 changes by reacting with the fluoride to be detected.

  The determination member 14 is for determining the color of the detection agent after the reaction between the detection agent and the fluoride to be detected by colorimetry. For example, as shown in FIG. This is a card displaying a color corresponding to the concentration of fluoride. Therefore, by comparing the color of the detection member 12 after the passage of the gas containing the fluoride to be detected with the color of the determination member 14, the concentration of the fluoride to be detected or whether the concentration exceeds the reference value or not. Can be determined. The detection member may be a cloth-like, plate-like, or tape-like member. For example, a gas containing fluoride to be detected is sprayed on the tape-like detection member, and the color of the detection member is determined by the determination member 14. The density and the like can be determined by comparing with the color. Thus, the use of the detection kit of the present invention makes it possible to detect the fluoride to be detected without performing high-temperature treatment or advanced separation treatment.

  FIG. 4 schematically shows the detection device 30 according to the embodiment of the present invention. The detection device 30 includes a detection unit 32, an introduction unit 34, a light source 36, and a measurement unit 38. The detection unit 32 includes a detection member 40 including the detection agent of the present embodiment. The introduction unit 34 guides the gas containing fluoride to be detected to the detection unit 32. The light source 36 irradiates the detection member 40 with light. The measurement unit 38 measures the light reflectance of the detection member 40. The detection member may include a porous material impregnated with the detection agent.

  Examples of the porous material include mesh-like cellulose, porous polymer, and porous alumina. Further, the detection member may include a polymer containing a detection agent. Further, the detection member 40 can be replaced or transported at any time in the form of a string, a rod, a tube, a plate, a cloth, a tape, or a cassette. The detection member 40 applies the polymer containing the active ingredient to the substrate, impregnates the base with the active ingredient, and attaches the active ingredient to the surface of the base made of oligomers, polymers, and the like by ionic bonding, hydrogen bonding, and foundation. It may be produced by making a chemical bond such as an Owarus bond or a coordination bond.

  FIG. 5 schematically shows a detection device 50 according to the embodiment of the present invention. The detection device 50 includes a detection unit 52, an introduction unit 54, and a measurement unit 56. The detection unit 52 includes a crystal oscillator 58 having the detection agent of the present embodiment provided on the surface. The introduction unit 54 guides the gas containing the fluoride to be detected to the detection unit 52. The measuring unit 56 measures the resonance frequency of the crystal unit 58. The crystal unit 58, which is a vibrator, is a cantilever or a rod-shaped member made of, for example, a metal oxide or a metal silicon material. By using the detection device 50, a low concentration of the fluoride to be detected can be detected with high sensitivity, for example, 2 ppm of the fluoride to be detected within one minute.

  Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Detector using ultraviolet-visible reflection spectrum (Ocean Optics, light source for reflectance measurement: DH-4000, detector for reflectance measurement: USB2000, reflection probe for guiding light (optical fiber): 727-733-2447 ) Was used to measure the optical change. The plate-like cellulose containing the detection agent of the present invention was set in a fluororesin cell serving as a detection portion. The gas containing the fluoride to be detected is sucked by a pump, passes through a dust filter, a detection unit, a flow meter, a temperature / humidity meter, activated carbon, and alkaline water in that order, and is then discharged into a fume hood.

  The change in mass was measured using a detection device (Quartz Crystal Analyzer QCA922, manufactured by SEIKO EG & G) capable of measuring the change in the resonance frequency of the power supply and the quartz oscillator. A quartz resonator provided with the detection agent of the present invention (gold-evaporated surface: QA-A9M (resonance frequency 9 MHz)) was set in a fluororesin cell serving as a detection unit. The gas containing the fluoride to be detected is sucked by the pump, passes through the dust filter and the detection unit in order, and is then directly discharged into the fume hood.

(Example 1)
First, about 1 g of sodium sulfide 9-hydrate (Merck) was dissolved in about 4 mL of water (MilliQ water), and about 1 mL of dimethylformamide was added and mixed to obtain a detection agent. Next, this detection agent was immersed in cellulose having a mesh diameter of about 3 μm, and dried with a dryer for about 1 minute to obtain cellulose for detection. Then, a detection gas containing C ₅ F ₈ at a concentration of 50 ppm in room air was sprayed onto the cellulose for detection at a flow rate of 600 mL / min. As a result, the reflectance in the ultraviolet and visible regions of the cellulose for detection before and after spraying changed from 250 nm to 600 nm. In particular 400 nm to 450 _nm, the signal changes in the characteristic reflectivity to detect the C 5 _{F 8} was observed.

On the other hand, four types containing fluorine compounds (perfluoroalkanes (Fluorinert FC-72 and Florinert FC-84 from 3M) and perfluoroethers (Galden HT70 and Galden HT90 from Solvay Specialty Polymers) in the indoor air, respectively. No such change in signal was observed even when the gas was sprayed on the cellulose for detection. From the above, it was confirmed that C ₅ F ₈ can be easily and selectively detected by optical change using a detection agent containing an inorganic sulfur compound containing a sulfur anion species as an active ingredient and further containing water and an organic substance. . C ₅ F ₈ is the fluoride of the first embodiment.

(Example 2)
First, about 170 mg of sodium sulfide nonahydrate was dissolved in 0.1 mL of water, and about 0.3 mL of hexamethylphosphoramide (HMPA, also known as hexamethylphosphoric triamide) was added and mixed. Next, about 100 mg of sodium borohydride as a reducing agent was further mixed to obtain a detecting agent. Then, the detection agent was soaked in cellulose having a mesh diameter of about 3 μm, and then dried with a dryer for about 1 minute to obtain cellulose for detection. Next, a detection gas containing C ₅ F ₈ at a concentration of 50 ppm in room air was sprayed on the cellulose for detection at a flow rate of 600 mL / min. As a result, the reflectance in the ultraviolet and visible regions of the cellulose for detection before and after spraying changed from 250 nm to 550 nm. In particular 400 nm to 450 _nm, the signal changes in the characteristic reflectivity to detect the C 5 _{F 8} was observed.

  FIG. 1 shows “change in reflectance” with the lapse of the spraying time. The “change in reflectance” is a converted value obtained by dividing the change in reflectance at 425 nm of cellulose for detection before and after spraying by the value of the reflectance at 550 nm of cellulose for detection (the same before and after spraying). As shown in FIG. 1, the change in the reflectance was proportional to the time change, and it became clear that the detection reaction was progressing quantitatively. As shown in FIG. 1, it is possible to detect 50 ppm of unsaturated hydrocarbon fluoride within one minute from the start of spraying.

  Even if a gas containing perfluoroalkane (Fluorinert FC-72 and Florinert FC-84 from 3M) was blown into the indoor air, such a signal change was not observed, and the base of the reflectance spectrum was not observed. The line was stable. In addition, a shift in the baseline was observed in the reflectance spectrum of the sample containing no sodium borohydride, that is, sodium sulfide nonahydrate, water, and a detection agent using HMPA. Therefore, it is considered that sodium borohydride is effective in stabilizing the baseline of the reflectance spectrum.

On the other hand, when a gas containing perfluoroether (Galden HT70 and Galden HT90 manufactured by Solvay Specialty Polymers, Inc.) is blown onto the cellulose for detection in the indoor air, the change in reflectance, which is considered to have been affected by the fluorine-based compound, changes from 400 nm to 450 nm. Was seen in _However, signal change in reflectance characteristic 400nm~450nm the detection of C 5 _{F 8} was observed. As described above, it is possible to easily and selectively detect C ₅ F ₈ by optical change using a detection agent containing an inorganic sulfur compound containing a sulfur anion species as an active ingredient, and further containing water, an organic substance, and a reducing agent. Was confirmed.

(Example 3)
First, after dissolving about 190 mg of sodium sulfide nonahydrate in 0.2 mL of water, about 0.5 mL of N-methyl-2-pyrrolidone (NMP) was added and mixed. Next, about 100 mg of a reducing agent, sodium borohydride, was further mixed. Then, while heating the mixture to about 60 ° C., 1 mL of an NMP solution of tetraoctyl ammonium bromide (concentration: about 98 mM) was further mixed. Next, 0.2 mL of organic and base dicyclohexylmethylamine was further slowly added and mixed to obtain a detection agent. Then, the detection agent was soaked in cellulose having a mesh diameter of about 3 μm, and then dried with a dryer for about 1 minute to obtain cellulose for detection.

Next, a detection gas containing C ₅ F ₈ at a concentration of 5 ppm in room air was sprayed onto the cellulose for detection at a flow rate of 600 mL / min. As a result, the reflectance in the ultraviolet and visible regions of the cellulose for detection before and after spraying changed from 250 nm to 600 nm. In particular 400 nm to 450 _nm, the signal changes in the characteristic reflectivity to detect the C 5 _{F 8} was observed. On the other hand, even if a gas containing a fluorine compound (Fluorinert FC-72 and Florinert FC-84 of 3M, and Galden HT70 and Galden HT90 of Solvay Specialty Polymers) is blown into the indoor air, the reflectance spectrum is obtained. Although there was a shift in the baseline, no such signal change was observed. As described above, it is possible to easily and selectively detect C ₅ F ₈ by optical change using a detection agent containing an inorganic sulfur compound containing a sulfur anion species as an active ingredient, and further containing water, an organic substance, and a reducing agent. Was confirmed.

(Example 4)
About 40 mg of hydrate of sodium hydrogen sulfide (also called sodium hydrosulfide) was dissolved in 0.5 mL of water, and about 0.5 mL of DMF was added and mixed to obtain a detection agent. Next, this detection agent was immersed in cellulose having a mesh diameter of about 3 μm, and dried with a dryer for about 1 minute to obtain cellulose for detection. Then, when a detection gas containing C ₅ F ₈ in a saturated state in room air was sprayed on the cellulose for detection, the color of the cellulose for detection changed from yellow to brown. From the above, it was confirmed that C ₅ F ₈ can be easily detected using a detection agent containing an inorganic sulfur compound containing a sulfur anion species as an active ingredient and further containing water and an organic substance.

(Example 5)
First, about 0.1 g of 2-aminoethanethiol was mixed with 0.1 mL of DMF containing water. Next, about 0.2 mL of organic and base dicyclohexylmethylamine and about 20 mg of potassium t-butoxide were further added and mixed to obtain a detection agent. Then, when the detection gas containing C ₅ F ₈ in the indoor air in a saturated state was bubbled to the liquid detection agent, the color of the liquid changed from yellow to brown. Even if only a liquid of perfluoroalkane (Fluorinert FC-84 of 3M) was added to this detection agent, the color did not change, but when a liquid of this fluorine-based compound in which C ₅ F ₈ was dissolved was added, the color changed from yellow to brown. Changed to As described above, C ₅ F ₈ is easily and selectively detected by colorimetry using a detection agent containing thiol, which is an organic sulfur compound containing a sulfur anion species, as an active ingredient and further containing water, an organic substance, and a base. It was confirmed that it was possible.

(Example 6)
First, about 0.1 g of 2-aminoethanethiol was mixed with about 0.1 mL of HMPA. Next, about 1 mL of organic and base dicyclohexylmethylamine was further added and mixed. Then, about 10 mg of glycerin was further added and mixed to obtain a detection agent. Next, this detection agent was immersed in cellulose having a mesh diameter of about 3 μm, and dried with a dryer for about 1 minute to obtain cellulose for detection. Then, a detection gas containing C ₅ F ₈ at a concentration of 5 ppm in the room air was sprayed onto the cellulose for detection at a flow rate of 800 mL / min. As a result, the reflectance in the ultraviolet and visible regions of the cellulose for detection before and after spraying changed from 250 nm to 500 nm. In particular 300 nm to 400 _nm, the signal changes in the characteristic reflectivity to detect the C 5 _{F 8} was observed.

Even if a gas containing perfluoroalkane (Fluorinert FC-72 and Florinert FC-84 from 3M) was blown into the indoor air, such a signal change was not observed, and the base of the reflectance spectrum was not observed. The line was also stable. On the other hand, when a gas containing perfluoroether (Galden HT70 and Galden HT90 from Solvay Specialty Polymers Co., Ltd.) is blown onto the cellulose for detection in the indoor air, the change in the reflectance, which is considered to have affected the fluorine-based compound, from 300 nm to 400 nm. However, it was not a big change. From the above, it was confirmed that C ₅ F ₈ can be easily and selectively detected by optical change using a detection agent containing an organic sulfur compound containing a sulfur anion species as an active ingredient and further containing an organic substance and a base. .

(Example 7)
First, about 40 mg of 4-bromobenzenethiol was added to about 1.5 mL of organic and basic dicyclohexylmethylamine and mixed. Next, about 10 mg of anhydrous magnesium sulfate was added and mixed to obtain a detection agent. Then, the detection agent was soaked in cellulose having a mesh diameter of about 3 μm, and then dried with a dryer for about 1 minute to obtain cellulose for detection. Next, a detection gas containing C ₅ F ₈ at a concentration of 5 ppm in room air was sprayed onto the cellulose for detection at a flow rate of 800 mL / min.

As a result, the reflectance in the ultraviolet and visible regions of the cellulose for detection before and after spraying changed from 250 nm to 500 nm. In particular 250 nm to 400 _nm, the signal changes in the characteristic reflectivity to detect the C 5 _{F 8} was observed. In addition, when a gas containing perfluoroether (Galden HT70 and Galden HT90 manufactured by Solvay Specialty Polymers Co., Ltd.) is blown onto the cellulose for detection in the indoor air, the change in the reflectance, which is considered to have influenced the fluorine-based compound, from 250 nm to 350 nm. Was seen. From the above, it was confirmed that C ₅ F ₈ can be easily and selectively detected by optical change using a detection agent containing an organic sulfur compound containing a sulfur anion species as an active ingredient and further containing an organic substance and a base. .

(Example 8)
First, about 30 mg of stearyl mercaptan (alias: n-octadecylthiol, carbon number 18) was mixed with about 0.4 mL of DMF containing water. Next, about 20 mg of base potassium t-butoxide was further added and mixed while heating to obtain a detection agent. Then, the detection agent was soaked in cellulose having a mesh diameter of about 3 μm, and then dried with a dryer for about 1 minute to obtain cellulose for detection. Next, when a detection gas containing C ₅ F ₈ in a saturated state in room air was sprayed on the cellulose for detection, the color of the cellulose for detection changed from yellow to brown. From the above, it was confirmed that C ₅ F ₈ can be easily detected by colorimetry using a detection agent containing an organic sulfur compound containing a sulfur anion species as an active ingredient and further containing an organic substance, water, and a base.

(Example 9)
First, about 30 mg of the synthesized triphenylmethanethiol (alias: triphenylmethylmercaptan, having 19 carbon atoms) was mixed and dissolved in about 0.3 mL of DMF containing water. Next, about 30 mg of potassium t-butoxide as a base was further added and mixed while heating to obtain a detection agent. Then, the detection agent was soaked in cellulose having a mesh diameter of about 3 μm, and then dried with a dryer for about 1 minute to obtain cellulose for detection. Next, when a detection gas containing C ₅ F ₈ in a saturated state in room air was sprayed on the cellulose for detection, the color of the cellulose for detection changed from yellow to brown. From the above, containing a sulfur anion species, containing a derivative of thiol, which is an organic sulfur compound having a bulky tertiary carbon, as an active ingredient, using an organic substance, water, and a detection agent further containing a base, colorimetrically It was confirmed that C ₅ F ₈ could be easily detected.

(Example 10)
First, about 100 mg of sodium N, N-diethyldithiocarbamate trihydrate was mixed with about 0.12 mL of HMPA containing water. Next, 0.2 mL of an NMP solution of tetraoctyl ammonium bromide (concentration: about 98 mM) was further added and mixed. Then, about 0.1 mL of base dicyclohexylmethylamine was further added and mixed to obtain a detection agent. Next, this detection agent was immersed in cellulose having a mesh diameter of about 3 μm, and dried with a dryer for about 1 minute to obtain cellulose for detection.

Then, a detection gas containing C ₅ F ₈ at a concentration of 50 ppm in room air was sprayed onto the cellulose for detection at a flow rate of 600 mL / min. As a result, the reflectance in the ultraviolet and visible regions of the cellulose for detection before and after spraying changed from 250 nm to 500 nm. In particular _{330Nm～450nm,} signal change characteristic reflectivity to detect the C 5 _{F 8} was observed. Further, the detection agent to the derivative of diethyldithiocarbamate as an active ingredient, there are characteristic peaks of a reflection spectrum in the vicinity of 350nm and around 425 nm, C ₅ F ₈ is detected by measuring these at least one of the signal change it can.

Even if a gas containing a fluorine compound (Fluorinert FC-72 and Fluorinert FC-84 of 3M, and Galden HT70 and Galden HT90 of Solvay Specialty Polymers) was blown into the indoor air, the reflectance spectrum was not changed. Although there was a shift in the baseline, there was no characteristic change in reflectance signal between 330 nm and 450 nm. As described above, C ₅ F ₈ is easily converted by optical change using a detection agent containing a derivative of dithiocarbamic acid, which is an organic sulfur compound containing a sulfur anion species, as an active ingredient and further containing an organic substance, water, and a base. It was confirmed that it could be detected selectively.

(Example 11)
First, about 150 mg of sodium N, N-diethyldithiocarbamate trihydrate was mixed with about 0.12 mL of HMPA containing water. Next, 0.2 mL of a heated NMP solution of tetraoctyl ammonium bromide (concentration: about 98 mM) was further added and mixed. Then, about 0.1 mL of base dicyclohexylmethylamine was further added and mixed to obtain a detection agent. Next, this detection agent was immersed in cellulose having a mesh diameter of about 3 μm, and dried with a dryer for about 1 minute to obtain cellulose for detection.

Then, the cellulose for detection was exposed to air under an environment of a temperature of 20 to 24 ° C and a humidity of 40 to 80% under a fluorescent lamp for 2 days. Then, a detection gas containing C ₅ F ₈ at a concentration of 50 ppm in the indoor air was sprayed onto the detection cellulose at a flow rate of 600 mL / min. As a result, the reflectance in the ultraviolet and visible regions of the cellulose for detection before and after spraying changed from 250 nm to 500 nm. In particular _{330Nm～450nm,} signal change characteristic reflectivity to detect the C 5 _{F 8} was observed. In addition, the detection agent containing a derivative of diethyldithiocarbamic acid as an active ingredient has characteristic reflection spectrum peaks at around 350 nm and around 425 nm, and C ₅ F ₈ is detected by measuring at least one of these signal changes. it can.

  FIG. 2 shows “change in reflectance” with the lapse of the spraying time. The “change in reflectance” is a converted value obtained by dividing the change in reflectance at 430 nm of cellulose for detection before and after spraying by the value of the reflectance at 550 nm of cellulose for detection (the same before and after spraying). As shown in FIG. 2, the change in the reflectance was proportional to the change with time, and it became clear that the detection reaction was progressing quantitatively. Further, as shown in FIG. 2, it is possible to detect 50 ppm of unsaturated hydrocarbon fluoride within one minute from the start of spraying.

A conventional detecting agent for acid gas or a detecting agent containing a nitrogen compound having at least two rings centering on an amidine skeleton as an active ingredient is exposed to the air under a fluorescent lamp for 2 days as in this embodiment. In many cases, signals cannot be observed. According to this example, it is considered that the detection agent containing a dithiocarbamic acid derivative as an active ingredient has excellent durability and long life. As described above, C ₅ F ₈ is easily converted by optical change using a detection agent containing a derivative of dithiocarbamic acid, which is an organic sulfur compound containing a sulfur anion species, as an active ingredient and further containing an organic substance, water, and a base. It was confirmed that it could be detected.

(Example 12)
First, about 150 mg of sodium N, N-diethyldithiocarbamate trihydrate was mixed with about 0.12 mL of HMPA containing water. Next, 0.2 mL of a heated NMP solution of tetraoctyl ammonium bromide (concentration: about 98 mM) was further added and mixed. Then, about 0.1 mL of base dicyclohexylmethylamine was further added and mixed to obtain a detection agent. Next, about 380 mg of a polymer having a polyamine compound (Araldite curing agent, manufactured by Huntsman Advanced Materials, Inc., 50520) was mixed and dissolved in about 1.5 mL of NMP.

Then, about 0.2 mL of the obtained solution and about 0.1 mL of the detection agent were mixed to obtain a detection member. Here, the amine group of the polymer having the polyamine compound is hydrogen-bonded to a part of sodium N, N-diethyldithiocarbamate. Further, the amine group of the polymer having the polyamine compound is bonded to sodium N, N-diethyldithiocarbamate by Coulomb force via sodium cation. Next, the detection member was immersed in cellulose having a mesh diameter of about 3 μm, and dried with a dryer for about 1 minute to obtain cellulose for detection. The cellulose for detection was exposed to air under a fluorescent lamp at a temperature of 20 to 24 ° C. and a humidity of 40 to 80% for 5 days. Then, a detection gas containing C ₅ F ₈ at a concentration of 0.4 ppm in room air was sprayed on the cellulose for detection at a flow rate of 600 mL / min. As a result, the reflectance in the ultraviolet and visible regions of the cellulose for detection before and after spraying changed from 250 nm to 500 nm.

In particular _{330Nm～450nm,} signal change characteristic reflectivity to detect the C 5 _{F 8} was observed. Even if a gas containing a fluorine compound (Fluorinert FC-72 and Fluorinert FC-84 of 3M, and Galden HT70 and Galden HT90 of Solvay Specialty Polymers) was blown into the indoor air, the reflectance spectrum was not changed. In a state where the baseline of was stable, there was no characteristic change in reflectance signal between 330 nm and 450 nm.

Therefore, it was found that the detection agent of the present example can selectively detect the fluoride to be detected, by selecting the fluoride to be detected and the fluoride to be detected having similar chemical structures. From the above, optical change using a polymer or oligomer comprising a detection agent containing a derivative of dithiocarbamic acid, which is an organic sulfur compound containing a sulfur anion species, as an active ingredient and further containing an organic solvent, an organic substance, water, and a base. As a result, it was confirmed that C ₅ F ₈ can be easily and selectively detected.

(Example 13)
First, about 800 mg of sodium N, N-diethyldithiocarbamate trihydrate was dissolved in about 1 mL of HMPA containing water to obtain a detection agent. Next, this detection agent was immersed in cellulose having a mesh diameter of about 3 μm, and dried with a dryer for about 1 minute to obtain cellulose for detection. Then, the inside of the fluororesin cell, which is the detecting section, was heated to about 40 ° C., and the cellulose for detection was set. Thereafter, a detection gas containing C ₅ F ₈ at a concentration of 40 ppm was blown into room air having a humidity of about 73% at a flow rate of about 1200 mL / min. As a result, the reflectance in the ultraviolet and visible regions of the cellulose for detection before and after spraying changed from 300 nm to 500 nm. Particularly in 300 nm to 450 _nm, the signal changes in the characteristic reflectivity to detect the C 5 _{F 8} was observed, detectable _C 5 _{F 8} is by measuring these signals change.

(Example 14)
First, about 800 mg of sodium N, N-diethyldithiocarbamate trihydrate was dissolved in about 1 mL of HMPA containing water. Next, 0.2 mL of a heated NMP solution of tetraoctyl ammonium bromide (concentration: about 98 mM) was further added and mixed to obtain a detection agent. After infiltrating this detection agent into cellulose having a mesh diameter of about 3 μm, cellulose for detection was obtained. Then, the inside of the fluororesin cell, which is the detecting section, was heated to about 40 ° C., and the cellulose for detection was set. Thereafter, a detection gas containing C ₅ F ₈ at a concentration of 2 ppm was blown into room air having a humidity of about 73% at a flow rate of about 1800 mL / min. As a result, the reflectance in the ultraviolet and visible regions of the cellulose for detection before and after spraying changed from 300 nm to 500 nm. Particularly in 300 nm to 450 _nm, the signal changes in the characteristic reflectivity to detect the C 5 _{F 8} was observed, detectable _C 5 _{F 8} is by measuring these signals change.

(Example 15)
First, about 800 mg of sodium N, N-diethyldithiocarbamate trihydrate was dissolved in about 1 mL of HMPA containing water, and 260 mg of calcium chloride was added thereto and mixed by heating. Next, 40 mg of tetraoctylammonium bromide and 60 mg of 4-bromophenylmethyltriphenylphosphonium bromide were added, and about 10 mg of glycerin as a humectant was added and mixed to obtain a translucent slurry-like detection agent having high viscosity. This detection agent was soaked in cellulose having a mesh diameter of about 3 μm, and excess detection agent was wiped off with a paper waste to obtain cellulose for detection. Then, the inside of the fluororesin cell serving as the detection unit was set at about 30 ° C., and the cellulose for detection was set. Thereafter, a humidity of about 65-69% of the detected gas concentration 2ppm in the indoor air include _C 5 _{F 8,} was sprayed on the detection cellulose at a flow rate of about 7L / min. As a result, the reflectance in the ultraviolet and visible regions of the cellulose for detection before and after spraying changed from 300 nm to 500 nm. In particular _{420Nm～430nm,} signal change characteristic reflectivity to detect the C 5 _{F 8} was observed.

It should be noted that a gas containing saturated fluorine-containing compounds (Fluorinert FC-72 and Florinert FC-84 from 3M, Galden HT70 and Galden HT90 from Solvay Specialty Polymers, Novec 7100 from 3M) in indoor air is detected. Even when sprayed on cellulose for use, there was a shift in the baseline of the reflectance spectrum, but there was no characteristic change in reflectance signal between 300 nm and 500 nm. As described above, by using an organic substance (HMPA glycerin) other than the dithiocarbamic acid derivative and a detecting agent containing an ammonium salt or a phosphonium salt, a change in the signal of the reflectance can be measured without interference or interference such as florinate, and C ₅ the F ₈ can be easily and stably detected.

(Example 16)
First, about 150 mg of sodium N, N-diethyldithiocarbamate trihydrate was mixed with about 0.12 mL of HMPA containing water. Next, 0.2 mL of a heated NMP solution of tetraoctyl ammonium bromide (concentration: about 98 mM) was further added and mixed. Then, about 30 mg of copper (II) chloride was further added and mixed to obtain a detection agent which was a brown solution. The solution turned brown because a part of sodium dithiocarbamate was bonded to copper ions. Next, this detection agent was immersed in cellulose having a mesh diameter of about 3 μm, and dried with a dryer for about 1 minute to obtain cellulose for detection. Then, a detection gas containing C ₅ F ₈ at a concentration of 1 ppm in the room air was sprayed onto the detection cellulose at a flow rate of 600 mL / min.

As a result, the reflectance of the cellulose for detection in the ultraviolet and visible regions before and after spraying changed from 250 nm to 500 nm with a relatively stable signal. In particular _{330Nm～450nm,} signal change characteristic reflectivity to detect the C 5 _{F 8} was observed. As described above, C ₅ F _{8 is obtained} by optical change using a detection agent containing a derivative of dithiocarbamic acid, which is an organic sulfur compound containing a sulfur anion species, as an active ingredient, and further containing an organic solvent, an organic substance, water, and a base. Was easily and selectively detected.

(Example 17)
First, about 800 mg of poly (methyl methacrylate) (PMMA, Mn: 4760, Mw: about 410,000) is mixed with about 15 mL of tetrahydrofuran (THF, dehydrated, containing 0.03% of a stabilizer (2,4,6-trialkylphenol)). And stirred for 3 hours to dissolve. Next, about 1.2 g of ethylenediamine and about 3 mg of p-toluenesulfonic acid as a catalyst were further added, and reacted at room temperature for 17 hours to obtain a reaction solution. This reaction introduces an aminoethylamide group into the side chain of PMMA. Then, water was added to the obtained reaction solution to precipitate a polymer, and the supernatant was removed by decantation.

  Next, THF was added to the liquid containing water in which the polymer was precipitated, to dissolve the polymer again. Then, a mixed solution of 80 μL of 36% hydrochloric acid containing hydrogen chloride corresponding to 0.1 equivalent of the number of polymer units, 80 μL of water, and 80 μL of THF was further added. Then, about 2 mL of a THF solution in which about 200 mg of sodium N, N-diethyldithiocarbamate dihydrate was dissolved was further added, and the mixture was heated at 50 ° C. for 10 minutes. Next, THF contained in this solution was evaporated to obtain a polymer. The polymer was dissolved in a mixed solvent of about 4 mL of HMPA and about 4 mL of THF to obtain a detection agent. This detection agent is a polymer containing, as an active ingredient, an organic sulfur compound having an N, N-diethyldithiocarbamoyl group in a side chain.

Next, this detection agent was immersed in cellulose having a mesh diameter of about 3 μm, and dried with a dryer for about 1 minute to obtain cellulose for detection. Then, when a detection gas containing C ₅ F ₈ in a saturated state in room air was sprayed on the cellulose for detection, the color of the cellulose for detection changed from yellow to brown. From the above, it was confirmed that C ₅ F ₈ can be easily detected by colorimetry using a detection agent containing an organic sulfur compound containing a sulfur anion species as an active ingredient and further containing an organic substance and water. This polymer has a polymer skeleton of about 10 units per one molecule of the derivative of dithiocarbamic acid due to its composition. This means that one molecule of the derivative of dithiocarbamic acid has a hydrocarbon substituent having about 60 carbon atoms in terms of atomic weight. As described above, it was found that the fluoride to be detected can be detected even when a large hydrocarbon substituent having about 60 carbon atoms exists.

(Example 18)
First, about 800 mg of PMMA (Mn: 4760, Mw: about 410,000) was added to about 15 mL of THF (dehydrated, containing a stabilizer), and dissolved by stirring for 3 hours. Next, about 1.2 g of ethylenediamine and about 3 mg of p-toluenesulfonic acid as a catalyst were further added, and reacted at room temperature for 17 hours to obtain a reaction solution. This reaction introduces an aminoethylamide group into the side chain of PMMA. Then, water was added to the obtained reaction solution to precipitate a polymer, and the supernatant was removed by decantation.

  Next, THF was added to the liquid containing water in which the polymer was precipitated, to dissolve the polymer again. Then, a mixed solution of 80 μL of 36% hydrochloric acid containing hydrogen chloride corresponding to 0.1 equivalent of the number of polymer units, 80 μL of water, and 80 μL of THF was further added. Then, about 2 mL of a THF solution in which about 200 mg of sodium N, N-diethyldithiocarbamate dihydrate was dissolved was further added, and the mixture was heated at 50 ° C. for 10 minutes. Next, THF contained in this solution was evaporated to obtain a polymer. Then, this polymer was dissolved in a mixed solvent of about 4 mL of HMPA and about 4 mL of THF. Then, 0.2 mL of a heated NMP solution of tetraoctyl ammonium bromide (concentration: about 98 mM) was further added and mixed to obtain a detection agent. This detection agent is a polymer containing, as an active ingredient, an organic sulfur compound having an N, N-diethyldithiocarbamoyl group in a side chain.

Next, this detection agent was immersed in cellulose having a mesh diameter of about 3 μm, and dried with a dryer for about 1 minute to obtain cellulose for detection. Then, a detection gas containing C ₅ F ₈ at a concentration of 1 ppm in the room air was sprayed onto the detection cellulose at a flow rate of 600 mL / min. As a result, the reflectance in the ultraviolet and visible regions of the cellulose for detection before and after spraying changed from 250 nm to 500 nm. In particular _{330Nm～450nm,} signal change characteristic reflectivity to detect the C 5 _{F 8} was observed. As described above, while having a large hydrocarbon substituent corresponding to about 60 carbon atoms, containing an organic sulfur compound containing a sulfur anion species as an active ingredient, and using a detection agent further containing an organic substance and water, the optical change As a result, it was confirmed that C ₅ F ₈ could be easily detected.

(Example 19)
First, about 80 mg of sodium N, N-dimethyldithiocarbamate dihydrate was mixed with about 0.1 mL of HMPA containing water to obtain a detection agent. Next, this detection agent was immersed in cellulose having a mesh diameter of about 3 μm, and dried with a dryer for about 1 minute to obtain cellulose for detection. Then, when a detection gas containing C ₅ F ₈ in a saturated state in room air was sprayed on the cellulose for detection, the color of the cellulose for detection changed from yellow to brown. From the above, it was confirmed that C ₅ F ₈ can be easily detected by colorimetry using a detection agent containing a derivative of dithiocarbamic acid, which is an organic sulfur compound containing a sulfur anion species, as an active ingredient and further containing an organic substance and water. Was done.

(Example 20)
First, about 0.1 g of thiobenzoic acid was mixed with about 0.3 mL of DMF containing water to obtain a detection agent. Next, this detection agent was immersed in cellulose having a mesh diameter of about 3 μm, and dried with a dryer for about 1 minute to obtain cellulose for detection. Then, when a detection gas containing C ₅ F ₈ in a saturated state in room air was sprayed on the cellulose for detection, the color of the cellulose for detection changed from yellow to brown. From the above, it is possible to easily detect C ₅ F ₈ by colorimetry using a detection agent containing thiobenzoic acid, which is an organic sulfur compound containing a sulfur anion species, as an active ingredient, and further containing an organic substance, water, and a base. Was confirmed.

(Example 21)
First, about 0.3 g of thiourea was mixed with about 0.5 mL of DMF containing water to obtain a detection agent. Next, this detection agent was immersed in cellulose having a mesh diameter of about 3 μm, and dried with a dryer for about 1 minute to obtain cellulose for detection. Then, when a detection gas containing C ₅ F ₈ in a saturated state in room air was sprayed on the cellulose for detection, the color of the cellulose for detection changed from yellow to brown. As described above, C ₅ F ₈ can be easily detected by colorimetry using a detection agent containing thiourea, which is an organic sulfur compound containing a sulfur anion species, as an active ingredient and further containing an organic substance, water, and a base. confirmed.

(Example 22)
First, about 190 mg of diphenyl disulfide (diphenyl disulfide) was mixed with about 0.12 mL of HMPA containing water. Next, about 100 mg of sodium borohydride as a reducing agent and about 20 mg of potassium t-butoxide were further added and mixed to obtain a detection agent. Then, the detection agent was soaked in cellulose having a mesh diameter of about 3 μm, and then dried with a dryer for about 1 minute to obtain cellulose for detection. Next, when a detection gas containing C ₅ F ₈ in a saturated state in room air was sprayed on the cellulose for detection, the color of the cellulose for detection changed from yellow to brown. From the above, it was confirmed that C ₅ F ₈ can be easily detected by colorimetry using a detection agent containing an organic sulfur compound containing a sulfur anion species as an active ingredient and further containing an organic substance, water, a base, and a reducing agent. Was done.

(Example 23)
First, about 190 mg of sodium sulfide nonahydrate was dissolved in 0.2 mL of water. Next, about 0.5 mL of NMP was further added and mixed. Then, about 100 mg of sodium borohydride as a reducing agent was further mixed. Next, 1 mL of an NMP solution of tetraoctyl ammonium bromide (concentration: about 98 mM) was further added and mixed while heating to about 60 ° C. Then, while heating to about 60 ° C., 0.2 mL of base dicyclohexylmethylamine and about 30 mg of potassium t-butoxy were further slowly added and mixed to obtain a detection agent. Next, this detection agent was immersed in cellulose having a mesh diameter of about 3 μm, and dried with a dryer for about 1 minute to obtain cellulose for detection.

Then, a detection gas in indoor air 1,2,3,3,4,4,5,5- octafluoro cyclopentane _{(c-C 5 F 8 H} 2) is contained in a saturated state in the detection cellulose Upon spraying, the color of the cellulose for detection changed from yellow to brown. From the above, sulfur containing anionic species sodium hydrogen sulfide is an inorganic sulfur compound containing as an active ingredient, organic, water, using a base, and a reducing agent further comprises a detectable agent, c-C ₅ F ₈ by colorimetry it was confirmed that the H ₂ can be easily detected. _{Incidentally, c-C 5 F 8 H} 2 is a fluoride of the second embodiment.

(Example 24)
First, about 100 mg of sodium N, N-diethyldithiocarbamate trihydrate was mixed with about 0.12 mL of HMPA containing water. Next, 0.2 mL of a heated NMP solution of tetraoctyl ammonium bromide (concentration: about 98 mM) was further added and mixed. Then, 50 μL of base dicyclohexylmethylamine and about 30 mg of potassium t-butoxy were further added and mixed to obtain a detection agent. Next, this detection agent was immersed in cellulose having a mesh diameter of about 3 μm, and then dried with a dryer for about 1 minute to obtain cellulose for detection.

When the blow detection gas c-C ₅ F ₈ H ₂ in room air is contained in a saturated state in the detection cellulose, color detection cellulose is changed to yellow to brown. From the above, comprises as active ingredient a derivative of the sulfur anion species dithiocarbamate is an organic sulfur compound containing, organic matter, water, and a base further with a detection agent comprising a, c-C ₅ F ₈ by colorimetric H ₂ Was easily detected.

(Example 25)
First, about 150 mg of sodium N, N-diethyldithiocarbamate trihydrate was mixed with about 0.12 mL of HMPA containing water. Next, 0.2 mL of a heated NMP solution of tetraoctyl ammonium bromide (concentration: about 98 mM) was further added and mixed. Then, about 0.1 mL of base dicyclohexylmethylamine was further added and mixed to obtain a detection agent.

  Next, 5 μL of a detection agent was dropped on the surface of a QCM crystal resonator (QA-A9M (resonance frequency 9 MHz)) in which gold was deposited on both sides, and the detection agent was spread over the entire gold surface by air blowing. Thereafter, the quartz oscillator was dried with hot air of about 60 ° C. for 5 minutes. Then, the quartz oscillator was set in a detection device, and five kinds of gases containing a fluorine-based compound in a saturated state in room air were sequentially blown to the quartz oscillator.

  Here, the five kinds of fluorine compounds are perfluoroalkanes (Fluorinert FC-72 and Florinert FC-84 from 3M), hydrofluoroethers (Novec 7100 from 3M), and perfluoroethers (from Solvay Specialty Polymers). Galden HT70 and Galden HT90). As a result, no significant change in the resonance frequency was observed in all of the five types of gases.

Next, when a detection gas containing C ₅ F ₈ in a saturated state in room air is blown onto this quartz resonator, a significant change of about 5000 Hz occurs at a resonance frequency of 9 MHz of the QCM due to a change in the mass of the detection agent provided in the QCM. Significant decrease was measured. As described above, C ₅ F ₈ is easily selected by mass change using a detection agent containing a derivative of dithiocarbamic acid, which is an organic sulfur compound containing a sulfur anion species, as an active ingredient, and further containing an organic substance, water, and a base. It was confirmed that it could be detected.

  ADVANTAGE OF THE INVENTION According to the detection agent of this invention, a detection method, a detection kit, and a detection apparatus, about 5 ppm of fluoride to be detected can be simply, rapidly, and economically detected near room temperature. Further, according to the detection agent, the detection method, the detection kit, and the detection device of the present invention, it is possible to detect a fluoride to be detected without receiving interference of an interfering gas generated from a fluorine-based liquid. Further, according to the detection agent of the present invention, durability against moisture and acidic gas is improved. Therefore, the life of the detection agent can be extended, and the running cost of the detection device can be reduced. Further, according to the detection method of the present invention, a fluoride to be detected can be easily detected by an optical change such as a colorimetric method or a change in mass.

Reference Signs List 10 detection kit 12 detection member 14 determination member 30, 50 detection device 32, 52 detection unit 34, 54 introduction unit 36 light source 38, 56 measurement unit

Claims (24)

An inorganic sulfur compound containing a sulfur anion species as an active ingredient, a detecting agent for detecting fluoride,
The fluoride comprises (1) a fluoride of an unsaturated hydrocarbon, and (2) a first carbon bonded to hydrogen and a second carbon bonded to an anionic leaving group and the first carbon. And a fluoride of a hydrocarbon comprising carbon.   The detection agent according to claim 1, wherein the inorganic sulfur compound is at least one of sodium sulfide, sodium hydrogen sulfide, and a sulfide having a cation other than sodium.   3. The detecting agent according to claim 1, further comprising water, at least one of a base and a reducing agent. An organic sulfur compound containing a sulfur anion species as an active ingredient, a detecting agent for detecting fluoride,
The fluoride comprises (1) a fluoride of an unsaturated hydrocarbon, and (2) a first carbon bonded to hydrogen and a second carbon bonded to an anionic leaving group and the first carbon. And a fluoride of a hydrocarbon comprising carbon.   The detection agent according to claim 4, wherein the organic sulfur compound is at least one of thiol, disulfide, thioester, dithioester, thiocarboxylic acid, dithiocarboxylic acid, dithiocarbamic acid, and thiourea, and derivatives thereof.   The detection agent according to claim 4 or 5, wherein the organic sulfur compound has a substituent of a hydrocarbon that may contain a hetero atom.   The detection agent according to claim 6, wherein the hydrocarbon has 1 to 60 carbon atoms.   The detection agent according to claim 5, wherein the organic sulfur compound is a derivative of dithiocarbamic acid.   The detection agent according to claim 8, wherein the derivative of dithiocarbamic acid is an alkali metal salt, an alkaline earth metal salt, a transition metal salt, an ammonium salt, or a phosphonium salt.   The detection agent according to any one of claims 4 to 9, further comprising at least one of water, a base, a reducing agent, and a transition metal ion. The _{fluoride, C 5 F 8, C 4} F 6, and detection agent according to any one of claims 1 to 10 _C 5 is at least one _F 8 _{H 2.} 1 SL and placing the detection agent according to claim (1) Fluoride unsaturated hydrocarbon, and (2) coupled with the first carbon bound to a hydrogen, an anionic leaving group and the first carbon A reaction step of reacting at least one of a hydrocarbon fluoride having a second carbon and
A measuring step of measuring a change in a physical property value before and after the reaction of the detection agent,
Off Tsu method of detecting the product that have a.   13. The detection method according to claim 12, wherein the physical property value change is an optical change.   14. The detection method according to claim 13, wherein the optical change is at least one of a change in absorbance, reflectance, infrared vibration, light emission, phosphorescence, refractive index, liquid crystal state, and photoelectron kinetic energy due to X-rays. The optical change is a change in absorbance or reflectance in the ultraviolet and visible light regions,
The method according to claim 13 for detecting the _C 5 _{F 8} concentration 0.4Ppm～50ppm.   14. The detection method according to claim 13, wherein the optical change is measured by a colorimetric method.   The detection method according to claim 12, wherein the change in the property value is a change in mass.   18. The detection method according to claim 17, wherein the mass change is measured by a change in the frequency of the surface of the vibrating body provided with the detection agent or a change in the frequency of a surface of the crystal unit for the quartz balance provided with the detection agent. A detecting member, including the claims 1 Symbol placement detection agent,
The detection agent , (1) a fluoride of an unsaturated hydrocarbon, and (2) a first carbon bonded to hydrogen, and a second carbon bonded to the anionic leaving group and the first carbon. A determination member for determining the color of the detection agent after the reaction when at least one of a fluoride of a hydrocarbon having carbon and the reaction is performed, by colorimetry,
A full Tsu product detection kit that Yusuke. A detection unit comprising a detection member including the claims 1 Symbol placement detection agent,
A carbon comprising (1) a fluoride of an unsaturated hydrocarbon, and (2) a first carbon bonded to hydrogen, and a second carbon bonded to the anionic leaving group and the first carbon. An introduction unit that guides a gas containing at least one of hydrogen fluoride and the gas to the detection unit;
A light source for irradiating the detection member with light,
A measuring unit for measuring the reflectance of light of the detection member,
Detection device off Tsu monster that have a.   The detection device according to claim 20, wherein the detection member includes a porous material impregnated with the detection agent.   22. The detection device according to claim 21, wherein the porous material is mesh-like cellulose, porous polymer, or porous alumina.   21. The detection device according to claim 20, wherein the detection member has a polymer containing the detection agent. A detecting section 1 Symbol placement detection agent according to claim comprises a crystal oscillator provided on the surface,
A carbon comprising (1) a fluoride of an unsaturated hydrocarbon, and (2) a first carbon bonded to hydrogen, and a second carbon bonded to the anionic leaving group and the first carbon. An introduction unit that guides a gas containing at least one of hydrogen fluoride and the gas to the detection unit;
A measuring unit for measuring a resonance frequency of the crystal unit,
Detection device off Tsu monster that have a.

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