Penetrant, developer, penetrant flaw detection product, and method used in penetrant flaw detection test method

Abstract

A penetrant solution being one embodiment of the present invention has, as essential components thereof, a dye and a volatile organic solvent and includes at least one type selected from the group consisting of hydrofluoro olefin, hydrofluoro ketone, and perfluoro ketone, as the volatile organic solvent. A penetrant solution being one embodiment of the present invention has a volatile organic solvent as an essential component thereof and includes, as the volatile organic solvent, at least one type selected from the group consisting of hydrofluoro olefin, hydrofluoro ketone, and perfluoro ketone. A developing agent as one embodiment of the present invention has as essential components thereof a powder and a volatile organic solvent and includes at least one type selected from the group consisting of hydrofluoro olefin, hydrofluoro ketone, and perfluoro ketone, as the volatile organic solvent.

Description

Technical Field

[0001] One embodiment of the present disclosure relates to a penetrant, a cleaning agent, and a developer used in a penetrant inspection method, which is characterized by containing at least one selected from the group consisting of hydrofluoroolefin, hydrofluoroketone, and perfluoroketone as a solvent component.

Background Art

[0002] The penetrant inspection method applied to the detection of surface opening defects such as fine cracks and pinholes existing on the surfaces of articles such as steel materials, machine parts, castings, and forgings (hereinafter also referred to as "defects" or "scratches") is standardized in the JIS Z 2343 standard group such as JIS Z 2343-1:2017.

[0003] In the solvent-removable penetrant inspection method, HCFC-225 has been used as a non-flammable solvent for diluting and dispersing dye and developer components in non-flammable penetrants (penetrant, cleaning agent, developer) (Patent Document 1). However, since HCFC-225 is an ozone-depleting substance (ODS), production was stopped at the end of 2019 based on the Ozone Layer Protection Law. Furthermore, hydrochlorofluorocarbon compounds (HCFCs) and hydrofluorocarbon compounds (HFCs) have a large global warming potential (GWP), and there are concerns about their impact on global warming.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Non-flammable flaw detection agents are used at sites where safety considerations for fire accidents are required, such as chemical plants and nuclear power plants. In addition, since the solvents contained in the flaw detection agents are released into the atmospheric environment during use, those having no impact on the global environment (zero ODP and low GWP) are desired. That is, one of the problems to be solved in the embodiments of the present disclosure is to provide a penetrant, a cleaning agent, and a developer used in a penetrant flaw detection test method that are non-flammable and environmentally friendly.

Means for Solving the Problems

[0006] The inventors have found that at least one selected from the group consisting of hydrofluoroolefins, hydrofluoroketones, and perfluoroketones is suitable as a solvent for a penetrant flaw detection agent. The embodiments of the present disclosure include the following [1] to

[26] . [1] A penetrant containing a dye or a coloring agent and a volatile organic solvent, The penetrant is characterized in that the volatile organic solvent contains at least one selected from the group consisting of hydrofluoroolefins, hydrofluoroketones, and perfluoroketones, and the penetrant is used in a penetrant flaw detection test. [2] The penetrant according to [1], wherein the hydrofluoroolefin is at least one selected from the group consisting of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, Z-1,2-dichloro-3,3,3-trifluoropropene, E-1,2-dichloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1,1,2-trichloro-3,3,3-trifluoropropene, Z-1,1,1,4,4,4-hexafluoro-2-butene, E-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, Z-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, Z-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene, E-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene, Z-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene, E-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene and methoxyperfluoroheptene. [3] The penetrant according to [1], wherein the hydrofluoroolefin has a boiling point of 30°C to 60°C 、[ The penetrant according to [1]. [4] The penetrant according to [1], wherein the hydrofluoroolefin is at least one selected from the group consisting of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene and Z-1,1,1,4,4,4-hexafluoro-2-butene. [5] The penetrant according to any one of [1] to [4], comprising at least one selected from the group consisting of nitrogen, carbon dioxide, compressed air, argon and fluorine-based gas as a propellant. [6] A cleaning agent containing at least one selected from the group consisting of hydrofluoroolefin, hydrofluoroketone and perfluoroketone as a volatile organic solvent, wherein the cleaning agent is used for a penetrant flaw detection test. [7] The cleaning agent according to [6], wherein the hydrofluoroolefin is at least one selected from the group consisting of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, Z-1,2-dichloro-3,3,3-trifluoropropene, E-1,2-dichloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1,1,2-trichloro-3,3,3-trifluoropropene, Z-1,1,1,4,4,4-hexafluoro-2-butene, E-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, Z-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, Z-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene, E-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene, Z-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene, E-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene, and methoxyperfluoroheptene. [8] The cleaning agent according to [6], wherein the hydrofluoroolefin has a boiling point of 30°C to 60°C. [9] The cleaning agent according to [6], wherein the hydrofluoroolefin is at least one selected from the group consisting of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, and Z-1,1,1,4,4,4-hexafluoro-2-butene.

[10] The cleaning agent according to any one of [4] or [6] to [8], which contains at least one selected from the group consisting of nitrogen, carbon dioxide, compressed air, argon, and fluorine-based gases as a propellant.

[11] It contains a powder and a volatile organic solvent, and is a developer containing at least one selected from the group consisting of hydrofluoroolefins, hydrofluoroketones, and perfluoroketones as the volatile organic solvent. The developer is characterized by being used in a penetrant flaw detection test, the developer.

[12] The hydrofluoroolefin is at least one selected from the group consisting of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, Z-1,2-dichloro-3,3,3-trifluoropropene, E-1,2-dichloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1,1,2-trichloro-3,3,3-trifluoropropene, Z-1,1,1,4,4,4-hexafluoro-2-butene, E-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, Z-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, Z-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene, E-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene, Z-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene, E-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene and methoxyperfluoroheptene, the developer according to

[11] .

[13] The hydrofluoroolefin has a boiling point of 30 °C to 60 °C, the developer according to

[11] .

[14] The hydrofluoroolefin is at least one selected from the group consisting of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene and Z-1,1,1,4,4,4-hexafluoro-2-butene, the developer according to

[11] .

[15] As the propellant, the developer according to any one of

[11] to

[14] contains at least one selected from the group consisting of nitrogen, carbon dioxide, compressed air, argon and fluorine-based gases.

[16] The hydrofluoroolefin is at least one selected from the group consisting of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene and Z-1,1,1,4,4,4-hexafluoro-2-butene, and the propellant is at least one of E-1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene, the developer according to

[11] .

[17] A solvent composition for a penetrant, comprising at least one selected from the group consisting of hydrofluoroolefins, hydrofluoroketones and perfluoroketones, said penetrant Using a solvent composition is characterized by being used in a penetrant test, a solvent for a penetrant Using a solvent composition.

[18] The hydrofluoroolefin is at least one selected from the group consisting of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, Z-1,2-dichloro-3,3,3-trifluoropropene, E-1,2-dichloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1,1,2-trichloro-3,3,3-trifluoropropene, Z-1,1,1,4,4,4-hexafluoro-2-butene, E-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, Z-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, Z-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene, E-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene, Z-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene, E-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene and methoxyperfluoroheptene, the solvent composition for a penetrant according to

[17] .

[19] The hydrofluoroolefin has a boiling point of 30°C to 60°C, the solvent composition for a penetrant according to

[17] .

[20] The solvent composition for penetrant inspection agent according to

[17] , wherein the hydrofluoroolefin is at least one selected from the group consisting of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene and Z-1,1,1,4,4,4-hexafluoro-2-butene.

[21] A penetrant inspection agent product comprising three components: a penetrant, a cleaner, and a developer, wherein the penetrant is the penetrant according to any one of [1] to [5], the cleaner is the cleaner according to any one of [6] to

[10] , and the developer is the developer according to any one of

[11] to

[16] .

[22] The penetrant inspection agent product according to

[21] , wherein the penetrant, the cleaner, and the developer contain at least one selected from the group consisting of the same type of hydrofluoroolefin, hydrofluoroketone, and perfluoroketone.

[23] A method for detecting an opening defect on the surface of an article using a penetrant inspection agent, wherein a penetrant containing at least one selected from the group consisting of hydrofluoroolefin, hydrofluoroketone, and perfluoroketone as a volatile organic solvent is infiltrated into the opening defect on the surface of the article, a cleaner containing at least one selected from the group consisting of hydrofluoroolefin, hydrofluoroketone, and perfluoroketone as a cleaning component is used to remove the excess penetrant on the surface of the article, and a developer containing at least one selected from the group consisting of hydrofluoroolefin, hydrofluoroketone, and perfluoroketone as a volatile organic solvent is used for development processing. The method comprising the above steps.

[24] The method according to

[23] , wherein the hydrofluoroolefin has a boiling point of 30°C to 60°C.

[25] The hydrofluoroolefin is at least one selected from the group consisting of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, and Z-1,1,1,4,4,4-hexafluoro-2-butene. 、[ 23 ] The method according to.

[26] The method according to

[23] , wherein the penetrant, the cleaner, and the developer contain at least one selected from the group consisting of the same type of hydrofluoroolefin, hydrofluoroketone, and perfluoroketone. [Advantages of the Invention]

[0007] According to the present disclosure, there are provided a penetrant, a cleaner, and a developer for use in a penetrant inspection test method, which are nonflammable and have a low environmental load. [Brief Description of the Drawings]

[0008]

Figure 1

[0009] Hereinafter, the method according to the embodiment of the present disclosure will be described. However, the embodiments of the present disclosure are not construed as being limited to the descriptions of the following embodiments and examples.

[0010] In this specification, for halogenated hydrocarbons (including hydrofluoroolefins, hydrofluoroketones, perfluoroketones, and hydrofluoroethers), the abbreviation of the compound is described in parentheses after the compound name, and the abbreviation is used instead of the compound name as necessary. In addition, (E) attached to the abbreviation of a compound having geometric isomers indicates the E-isomer (trans-isomer), and (Z) indicates the Z-isomer (cis-isomer). When the E-isomer and the Z-isomer are not specified in the name or abbreviation of the compound, the name or abbreviation means a general term including the E-isomer, the Z-isomer, and a mixture of the E-isomer and the Z-isomer.

[0011] In this specification, the dye penetrant refers to a penetrant containing a dye for staining (particularly a red dye), and the fluorescent penetrant refers to a penetrant containing a fluorescent dye. Note that the combination of the dye penetrant or fluorescent penetrant, cleaning agent, and developer used in the penetrant flaw detection test method may be collectively referred to as a "penetrant flaw detector". Further, the volatile organic solvent contained in the dye penetrant, fluorescent penetrant, cleaning agent, or developer may be referred to as a "solvent composition for penetrant flaw detector". In this specification and the like, the volatile organic solvent refers to an organic solvent having a boiling point of 150°C or lower at standard atmospheric pressure (1 atm) and being a liquid at 20°C.

[0012] The dye penetrant or fluorescent penetrant used in the penetrant flaw detection test method (hereinafter, a mixture containing both the dye penetrant and the fluorescent penetrant is also referred to as a "binary penetrant", and the dye penetrant, fluorescent penetrant, and binary penetrant are collectively simply referred to as a "penetrant"), the cleaning agent, and the developer will be described. Note that the modes of the penetrant flaw detection test method are generally as follows. (1) Step of attaching a penetrant to the surface of a test article and allowing the penetrant to penetrate into the defect portion of the article (penetration treatment) (2) Step of removing the excess penetrant remaining on the surface of the article using a cleaning agent for the article subjected to the penetration treatment (removal treatment) (3) Step of forming a thin layer of powder on the surface of the article using a developer and causing a defect indication pattern due to the penetrant that has penetrated into the defect portion to appear on the surface of the thin layer (development treatment) (4) Observing the article subjected to the development treatment , defect Step of detecting the presence and position of the defect portion based on the defect indication pattern

[0013] The observation in the above (4) is preferably performed under natural light or white light when the dye penetrant is used in the above (1), and is preferably performed under an ultraviolet lamp when the fluorescent penetrant is used.

[0014] 1. Penetrant The penetrant contains a dye and a volatile organic solvent as essential components.

[0015] As dyes, in the dye penetrant, generally oil-soluble red dyes such as azo red dyes are included. For example, Oil Red 5BN (manufactured by Shillad Chemical Co., Ltd.), Orient Oil Red 5B (manufactured by Orient Co., Ltd.), Rhodamine B (manufactured by Sumitomo Chemical Co., Ltd.), etc. can be mentioned, but it is not limited thereto. In the fluorescent penetrant, fluorescent dyes that emit yellow-green color under an ultraviolet lamp are included. For example, C.I. Solvent Yellow 43 (manufactured by Morton Co., USA), C.I. Fluorescent Brightening Agent 68 (manufactured by Nippon Kayaku Co., Ltd.), etc. can be mentioned, but it is not limited to these. The dual penetrant contains both red dyes and fluorescent dyes. In one embodiment, dyes other than red may be used as the dye of the dye penetrant, and fluorescent dyes that emit colors other than yellow-green may be used as the dye of the fluorescent penetrant. The content of the dye may be 40 parts by mass or less, preferably 20 parts by mass or less, based on 100 parts by mass of the total amount of the volatile organic solvent.

[0016] The volatile organic solvent contains at least one selected from the group consisting of hydrofluoroolefins, hydrofluoroketones, perfluoroketones, and hydrofluoroethers. The hydrofluoroolefin is an olefin compound containing a carbon-carbon double bond, a fluorine atom, and a hydrogen atom in the molecule, and may contain a chlorine atom and / or an oxygen atom.

[0017] Since hydrofluoroolefins have a carbon-carbon double bond in the molecule, they have a short atmospheric lifetime and have extremely little impact on ozone layer depletion and global warming. The number of carbon atoms is from 3 to 8, preferably from 3 to 6, and particularly preferably from 3 to 5.Hydrofluoroolefins include, for example, Z-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)), Z-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd(Z)), E-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd(E)), Z-1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd(Z)), E-1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd(E)), 1,1-dichloro-3,3,3-trifluoropropene (HCFO-1223za), 1,1,2-trichloro-3,3,3-trifluoropropene (HCFO-1213xa), Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz(Z)), E-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HCFO-1437dycc(E)), Z-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HCFO-1437dycc(Z)), Z-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (HFO-1429myz(Z)), E-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (HFO-1429myz(E)), Z-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (HFO-1429mzy(Z)), E-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (HFO-1429mzy(E)), Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), E-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), Z-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe(Z)), E-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe(E)), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), methoxyperfluoroheptene, and the like. These may be used alone or in combination of two or more thereof.Among these, from the viewpoint of industrial practicality, for example, having appropriate volatility as a volatile organic solvent in penetrant flaw detection (for example, having a boiling point of about 30°C to 60°C), Z-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)), Z-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd(Z)), E-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd(E)), Z-1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd(Z)), E-1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd(E)), 1,1-dichloro-3,3,3-trifluoropropene (HCFO-1223za), Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz(Z)), mixtures of two or more of these (for example, a mixture of Z-1-chloro-3,3,3-trifluoropropene and Z-1-chloro-2,3,3-trifluoro-1-propene, a mixture of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene and E-1-chloro-2,3,3-trifluoro-1-propene, a mixture of Z-1-chloro-3,3,3-trifluoropropene and Z-1,1,1,4,4,4-hexafluoro-2-butene, a mixture of Z-1-chloro-2,3,3-trifluoro-1-propene and Z-1,1,1,4,4,4-hexafluoro-2-butene, a mixture of Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene and Z-1,1,1,4,4,4-hexafluoro-2-butene) are preferably used as the main component.In one embodiment, these may be used as main components, and high-boiling compounds such as methoxyperfluoroheptene may be included as sub-components. For example, mixtures of Z-1-chloro-3,3,3-trifluoropropene and methoxyperfluoroheptene, mixtures of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene and methoxyperfluoroheptene, mixtures of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene and methoxyperfluoroheptene, mixtures of Z-1-chloro-3,3,3-trifluoropropene, Z-1,1,1,4,4,4-hexafluoro-2-butene and methoxyperfluoroheptene, mixtures of Z-1-chloro-2,3,3-trifluoro-1-propene, Z-1,1,1,4,4,4-hexafluoro-2-butene and methoxyperfluoroheptene, mixtures of Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, Z-1,1,1,4,4,4-hexafluoro-2-butene and methoxyperfluoroheptene, etc. may be mentioned.

[0018] Examples of commercially available hydrofluoroolefins include CELEFIN (registered trademark) 1233Z (manufactured by Central Glass Co., Ltd.), AMOLEA (registered trademark) AS-300 (manufactured by AGC Inc.), Opteon (registered trademark) SF10 (manufactured by Mitsui Chemicals Fluoro Products Co., Ltd.), Opteon (registered trademark) 1100 (manufactured by Mitsui Chemicals Fluoro Products Co., Ltd.), etc.

[0019] Hydrofluoro ketone is a ketone compound containing a carbon-oxygen double bond, a fluorine atom, and a hydrogen atom in the molecule, and may contain a chlorine atom. Since hydrofluoro ketone has a carbon-oxygen double bond in the molecule, its atmospheric lifetime is short, and its impact on ozone layer depletion and global warming is extremely small. Examples of hydrofluoro ketones include 3,3,4,4-tetrafluoro-2-butanone (HFK-354pc), 1,1,1,2,2-pentafluoro-3-pentanone (HFK-465mc), 3,3,4,4,5,5,5-heptafluoro-2-pentanone (HFK-447mcc), 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-2-butanone (HFK-447mmy), 3,3,4,4,5,5,6,6,6-nonafluoro-2-hexanone (HFK-549mccc), 3,3,4,4,5,5,6,6,7,7,7-undecafluoro-2-heptanone (HFK-64-11mcccc), and the like.

[0020] Perfluoro ketone is a ketone compound containing a carbon-oxygen double bond and a fluorine atom in the molecule. Since perfluoro ketone has a carbon-oxygen double bond in the molecule, its atmospheric lifetime is short, and its impact on ozone layer depletion and global warming is extremely small. Examples of perfluoro ketones include 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and the like. Examples of commercially available perfluoro ketones include Novec (registered trademark) 649 (manufactured by 3M) and the like.

[0021] Hydrofluoroether is an ether compound containing a fluorine atom and a hydrogen atom in the molecule, and may contain a chlorine atom. Examples of hydrofluoroether include heptafluoropropyl methyl ether, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (HFE-347pc-f), 1,1,1,3,3,3-hexafluoro-2-methoxypropane (HFE-356mmz), and the like. In one embodiment, since the volatile organic solvent has a small global warming potential (GWP), it preferably contains 1,1,1,3,3,3-hexafluoro-2-methoxypropane (HFE-356mmz). Commercially available products of hydrofluoroether include, for example, Novec (registered trademark) 7000 (manufactured by 3M), Novec (registered trademark) 7100 (manufactured by 3M), Novec (registered trademark) 7200 (manufactured by 3M), Novec (registered trademark) 7300 (manufactured by 3M), AE-3000 (manufactured by AGC), and the like.

[0022] The volatile organic solvent may contain hydrofluoroolefins, hydrofluoroketones, and volatile organic solvents other than perfluoroketones (hereinafter also referred to as "other organic solvents"). Examples of other organic solvents include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, pentafluoropropanol, etc.; hydrocarbons such as pentane, hexane, isopentane, n-heptane, cyclopentane, cyclohexane, etc.; petroleum paraffins; alkylbenzenes such as toluene, xylene, etc.; ketones such as acetone, methyl ethyl ketone, etc.; esters such as ethyl acetate, etc.; glycol ethers such as diethylene glycol monobutyl ether, etc.; naphthas such as light naphtha, heavy naphtha, petroleum naphtha, coal tar naphtha, etc.; chlorinated solvents such as methylene chloride, trichloroethane, trichloroethylene, tetrachloroethylene, E-1,2-dichloroethylene, etc.; hydrochlorofluorocarbons (HCFCs) such as dichlorofluoroethane, dichlorodifluoroethane, dichlorotrifluoroethane, chlorofluoropropane, chlorodifluoropropane, chlorotrifluoropropane, chlorotetrafluoropropane, dichlorofluoropropane, dichlorodifluoropropane, dichlorotrifluoropropane, dichlorotetrafluoropropane, dichloropentafluoropropane, trichlorofluoropropane, trichlorodifluoropropane, trichlorotrifluoropropane, etc.; hydrofluorocarbons (HFCs) such as fluoropropane, difluoropropane, trifluoropropane, tetrafluoropropane, pentafluoropropane, hexafluoropropane, heptafluoropropane, fluorobutane, difluorobutane, trifluorobutane, tetrafluorobutane, pentafluorobutane, hexafluorobutane, heptafluorobutane, octafluorobutane, nonafluorobutane, fluoropentane, difluoropentane, trifluoropentane, tetrafluoropentane, pentafluoropentane, hexafluoropentane, heptafluoropentane, octafluoropentane, nonafluoropentane, decafluoropentane, undecafluoropentane, etc.; and hydrofluoroethers (HFE).When the volatile organic solvent contains other organic solvents, the content thereof is preferably within a range that exhibits non-flammability as the entire volatile organic solvent. In one embodiment, the content of the other organic solvent may be 50 parts by mass or less, preferably 30 parts by mass or less, based on 100 parts by mass of the total amount of the volatile organic solvent.

[0023] In addition to the dye and the volatile organic solvent, the penetrant may contain, as other components, additives, surfactants, rust inhibitors, hydrocarbon oils, vegetable oils, stabilizers, and the like. Examples of the additives include, but are not limited to, phthalic acid esters such as bis(2-ethylhexyl) phthalate, phosphate esters such as tricresyl phosphate and tris(2-ethylhexyl) phosphate, and aliphatic acid esters. Examples of the surfactants include, but are not limited to, nonionic surfactants such as poly(oxyethylene) nonylphenyl ether and polyoxyalkylene ether. Examples of the rust inhibitors include, but are not limited to, nitromethane and ethylenediamine. In the production process or storage process of hydrofluoroolefin, "fluorine-based gas" may be by-produced, generated as decomposition products, or used as raw materials. When using hydrofluoroolefin as the volatile organic solvent, such "fluorine-based gas" may be entrained in the hydrofluoroolefin as impurities. For example, when using Z-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)) as the volatile organic solvent, E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)) may be mixed as an impurity. The penetrant may contain, as other components, fluorine-based gas that may be contained as an impurity of the volatile organic solvent. In this specification, the fluorine-based gas refers to a fluorine-containing hydrocarbon compound having a boiling point of less than 20 °C at standard atmospheric pressure (1 atm) and being a gas at 20 °C. The other components may be 40 parts by mass or less, preferably 30 parts by mass or less, based on 100 parts by mass of the dye and the volatile organic solvent.

[0024] The penetrant may be an aerosol composition containing a propellant.

[0025] Examples of the propellant include liquefied petroleum gas (LPG), dimethyl ether (DME), nitrogen, carbon dioxide, compressed air, argon, fluorine-based gases, etc. These may be used alone or as a mixture of two or more. Examples of the fluorine-based gas include hydrofluorocarbons such as difluoromethane (HFC-32), 1,1-difluoroethane (HFC-152a), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), etc., and hydrofluoroolefins such as E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)), Z-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), E-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), etc., but are not limited thereto. Among the fluorine-based gases, since the flammability is nonflammable or slightly flammable, difluoromethane, 1,1,1,2-tetrafluoroethane, 1,1,1,2,2-pentafluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)), Z-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), E-1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene are preferred. Since the global warming potential (GWP) is small and the toxicity is low, E-1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, and a mixture of E-1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene are particularly preferred.

[0026] When the penetrant is an aerosol composition, the content of the propellant may be 300 parts by mass or less, 100 parts by mass or less, or 50 parts by mass or less with respect to 100 parts by mass of the total amount of the dye, the volatile organic solvent, and the other components.

[0027] In one embodiment, the penetrant may be the following composition. [Table 1] [Table 2]

[0028] 2. Cleaner One of the embodiments of the present disclosure is a cleaner used in a penetrant inspection test method. This cleaner contains a volatile organic solvent as an essential component, and is characterized by containing at least one selected from the group consisting of hydrofluoroolefins, hydrofluoroketones, and perfluoroketones. Examples of the hydrofluoroolefins, hydrofluoroketones, and perfluoroketones include those exemplified for the penetrant.

[0029] The cleaner may contain other organic solvents in addition to at least one selected from the group consisting of hydrofluoroolefins, hydrofluoroketones, and perfluoroketones. Examples of the other organic solvents include those exemplified for the penetrant. The content of the other organic solvents may be 40 parts by mass or less, preferably 30 parts by mass or less, with respect to 100 parts by mass of the total amount of the volatile organic solvents. In one embodiment, the content of the other organic solvents may be 50 parts by mass or less, preferably 30 parts by mass or less, with respect to 100 parts by mass of the total amount of the volatile organic solvents. The volatile organic solvent contained in the cleaner may be the same component as the volatile organic solvent contained in the penetrant, or may contain different components.

[0030] In addition to the volatile organic solvent, the cleaning agent may contain, as other components, additives, surfactants, rust inhibitors, hydrocarbon oils, vegetable oils, stabilizers, etc. Examples of the additives, surfactants, rust inhibitors, hydrocarbon oils, vegetable oils, and stabilizers include those exemplified for the penetrant. Further, "fluorine-based gas" which may be contained as an impurity of the volatile organic solvent may be included as another component. The total content of these components may be 40 parts by mass or less, preferably 20 parts by mass or less, based on 100 parts by mass of the total amount of the volatile organic solvent.

[0031] The cleaning agent may be an aerosol composition containing a propellant.

[0032] Examples of the propellant include those exemplified for the penetrant.

[0033] When the cleaning agent is an aerosol composition, the content of the propellant may be 300 parts by mass or less, may be 100 parts by mass or less, or may be 50 parts by mass or less, based on 100 parts by mass of the total amount of the volatile organic solvent and the other components.

[0034] In one embodiment, the cleaning liquid may be the following composition.

Table 3

Table 4

[0035] 3. Developer One of the embodiments of the present disclosure is a developer used in a penetrant flaw detection test method. This developer contains a powder and a volatile organic solvent as essential components, and is characterized by containing at least one selected from the group consisting of hydrofluoroolefins, hydrofluoroketones, and perfluoroketones as the volatile organic solvent.

[0036] The powder may be, for example, inorganic powders (such as magnesium carbonate, calcium carbonate, aluminum oxide), white powders such as silica (such as hydrous silicic acid, anhydrous silicic acid, talc), etc., but is not limited thereto. In one embodiment, a white fine powder selected from inorganic powders, silica, etc. having a particle size of about 0.5 to 3 μm may be used. Commercially available products include, for example, Carplex #1120 (manufactured by Shionogi & Co., Ltd.), Siloid 244 (manufactured by Fuji Devson Co., Ltd.), a Aerosil #200 (manufactured by Nippon Aerosil Co., Ltd.), Orben (manufactured by Shiraishi Kogyo Co., Ltd.), etc. The content of the powder may be 30 parts by mass or less, preferably 20 parts by mass or less, based on 100 parts by mass of the total amount of the volatile organic solvent.

[0037] The volatile organic solvent contains at least one selected from the group consisting of hydrofluoroolefins, hydrofluoroketones, and perfluoroketones, which are non-flammable and environmentally friendly. Examples of the hydrofluoroolefins, hydrofluoroketones, and perfluoroketones include those exemplified for the penetrant. In the development process, after forming a powder layer (coating film) on the surface of the penetrant inspection article, the powder layer (coating film) is quickly dried. Therefore, Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, Z-1,2-dichloro-3,3,3-trifluoropropene, Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz(Z)), mixtures of two or more of these (for example, a mixture of Z-1-chloro-3,3,3-trifluoropropene and Z-1-chloro-2,3,3-trifluoro-1-propene, a mixture of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene and E-1-chloro-2,3,3-trifluoro-1-propene, a mixture of Z-1-chloro-3,3,3-trifluoropropene and Z-1,1,1,4,4,4-hexafluoro-2-butene, a mixture of Z-1-chloro-2,3,3-trifluoro-1-propene and Z-1,1,1,4,4,4-hexafluoro-2-butene, a mixture of Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene and Z-1,1,1,4,4,4-hexafluoro-2-butene) are preferably used as the main component.In one embodiment, these may be used as the main components, and high-boiling compounds such as methoxyperfluoroheptene may be included as sub-components. For example, mixtures of Z-1-chloro-3,3,3-trifluoropropene and methoxyperfluoroheptene, mixtures of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene and methoxyperfluoroheptene, mixtures of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene and methoxyperfluoroheptene, etc. may be mentioned.

[0038] The volatile organic solvent may contain other organic solvents in addition to hydrofluoroolefins, hydrofluoroketones, and perfluoroketones. Examples of the other organic solvents include the other organic solvents exemplified for the penetrant. The content of the other organic solvents may be 40 parts by mass or less, preferably 30 parts by mass or less, based on 100 parts by mass of the total amount of the volatile organic solvent. The volatile organic solvent contained in the developer may be the same component as the volatile organic solvent contained in the penetrant or the cleaning liquid, or may contain different components.

[0039] In addition to the powder and the volatile organic solvent, the developer may contain, as other components, additives, surfactants, rust inhibitors, hydrocarbon oils, vegetable oils, stabilizers, etc. Examples of the additives, surfactants, rust inhibitors, hydrocarbon oils, vegetable oils, and stabilizers include the additives, surfactants, rust inhibitors, hydrocarbon oils, vegetable oils, and stabilizers exemplified for the penetrant. Further, "fluorine-based gas", which may be contained as an impurity of the volatile organic solvent, may be included as another component. The total content of these components may be 40 parts by mass or less, preferably 20 parts by mass or less, based on 100 parts by mass of the total amount of the powder and the volatile organic solvent.

[0040] The developer may be an aerosol composition containing a propellant.

[0041] Examples of the propellant include the propellants exemplified as the penetration liquid. Among them, difluoromethane, 1,1-difluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,1,2,2-pentafluoroethane, 1,1,1-trifluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, Z-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), E-1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, and a mixture of E-1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene are preferable because they can form a uniform powder layer (coating film) on the surface of the penetrant flaw detection test article in the development process.

[0042] The fluorine-based gas is characterized by excellent compatibility with hydrofluoroolefins, hydrofluoroketones, and perfluoroketones used as volatile organic solvents of the flaw detector. Compressed gases such as nitrogen, compressed air, and argon are immiscible with the volatile organic solvent, so it is difficult to form a uniform powder layer (coating film) of the powder component of the developer on the surface of the penetrant flaw detection test article compared with the fluorine-based gas. On the other hand, when the volatile organic solvent and the fluorine-based gas are combined, the organic solvent component and the injection gas component are miscible, and the powder component can be uniformly dispersed in the liquid, so the powder component can be uniformly applied to the surface of the penetrant flaw detection test article. In the above combination, a combination of a volatile organic solvent as a hydrofluoroolefin and an injection gas as a hydrofluoroolefin is preferable from the viewpoints of uniform coating performance, non-flammability, and environmental impact. Among them, a combination of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz(Z)), or a mixture of two or more of them as the volatile organic solvent and E-1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, or a mixture of them as the injection gas is particularly preferable.

[0043] When the developer is an aerosol composition, the content of the propellant may be 300 parts by mass or less, 100 parts by mass or less, or 50 parts by mass or less with respect to 100 parts by mass of the total amount of the powder, the volatile organic solvent, and the other components.

[0044] In one embodiment, the developer may be the following composition.

Table 5

Table 6

[0045] 4. Method for detecting an open defect portion on the surface of an article using a penetrant One embodiment of the present disclosure is a method for detecting an open defect portion on the surface of an article using a penetrant, characterized by including at least one selected from the group consisting of hydrofluoroolefins, hydrofluoroketones, and perfluoroketones as components of the penetrant.

[0046] Articles to which this method is applied include, but are not limited to, metal members such as stainless steel, carbon steel, copper, aluminum, titanium, nickel, etc., and alloy materials such as Hastelloy and Inconel. In one embodiment, the article to which this method is applied may be a resin, or may be a composite material of two or more selected from resins, metal members, and alloy materials.

[0047] When the article to which this method is applied is contaminated with dirt such as scale, rust, oil and fat, grease, paint, etc., it is preferable to perform a pretreatment to remove the dirt in advance. For this pretreatment, various cleaning agents can be used, and a cleaning agent containing at least one selected from the group consisting of hydrofluoroolefins, hydrofluoroketones and perfluoroketones can also be used, and it is preferable to use a cleaning agent containing at least one selected from the group consisting of hydrofluoroolefins, hydrofluoroketones and perfluoroketones. Examples of the hydrofluoroolefin, hydrofluoroketone and perfluoroketone include the hydrofluoroolefin, hydrofluoroketone and perfluoroketone exemplified as the penetrant. Since it shows high cleaning performance for dirt such as scale, rust, oil and fat, grease, paint, etc., hydrofluoroolefin is preferable, and Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, Z-1,1,1,4,4,4-hexafluoro-2-butene and a mixture of two or more of them are particularly preferable. After removing the dirt from the article and drying the article when using a cleaning agent, a penetrant is applied to the article.

[0048] The application of the penetrant to the article is not particularly limited, and it can be carried out by methods such as a spray method, a brushing method, a pouring method, a partial immersion method or a total immersion method. Thereby, the penetrant is infiltrated into the inside of the defect.

[0049] The excess penetrant remaining on the surface without infiltrating into the defect of the article is removed using a cleaning agent. The application of the cleaning agent is generally carried out by wiping off the excess penetrant using a cloth or paper moistened with the cleaning agent so that the penetrant remains inside the defect, but is not limited thereto. After removing the excess penetrant from the article, a developer is applied. In one embodiment, the cleaning agent may be a general-purpose organic solvent that does not contain hydrofluoroolefins, hydrofluoroketones, and perfluoroketones.

[0050] The application of the developer to the article can be carried out, for example, but not limited to, by a spraying method. By applying the developer to the article, a coating film is formed, and a defect indication sweat-like pattern caused by the penetrant that has penetrated into the surface of the coating film and into the interior of the defect is revealed. By observing this, the presence and location of the defect in the article are detected.

[0051] The application of the developer to the article can be carried out, for example, by spraying the developer filled in an aerosol can. At this time, coating film components such as amorphous silica and carbonate must be uniformly applied to the surface of the article. If a fluorine-based liquefied gas is selected as the injection gas of the aerosol can, since it is compatible with the organic solvent which is an essential component of the developer, when spraying on the article, the fine droplets sprayed will spread well, and it is preferable because the coating film components can be uniformly applied to the surface of the article. The combination of the organic solvent and the injection gas is non-flammable, does not destroy the ozone layer, and has an extremely low impact on global warming. Therefore, a combination using hydrofluoroolefins such as Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, Z-1,1,1,4,4,4-hexafluoro-2-butene, or a mixture of two or more of them as the organic solvent and hydrofluoroolefins such as E-1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, or a mixture of them as the injection gas is particularly preferable.

[0052] In one embodiment, as shown in FIG. 1 , object A penetrant is applied to the surface of the article 1, and a penetration treatment is performed to allow the penetrant 10 to penetrate into the opening defect portion 5 of the article surface 3. An excess penetrant on the article surface is removed (however, the penetrant is left in the opening defect portion 5), and a removal treatment is performed. Subsequently, a development treatment is performed by applying a developer to the opening defect portion 5 or the opening defect portion 5 and its periphery to form a coating film 20 of the developer, and a defect indication sweat-like pattern 30 caused by the penetrant that has penetrated into the opening defect portion is revealed on the surface of the coating film. This is observed to detect the presence and location of the defect in the article.

[0053] The boiling point of Z-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)), which is used as a hydrofluoroolefin, is 39 °C, the boiling point of Z-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd(Z)) is about 54 °C, the boiling point of E-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd(E)) is 48 °C, and the boiling point of Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz(Z)) is about 33 °C. All of them are substances with excellent dryness. Also, even when these substances become vapor, for HCFO-1233zd(Z) it is 39 °C, for HCFO-1233yd(Z) it is about 54 °C, for HCFO-1233yd(E) it is 48 °C, and for HFO-1336mzz(Z) it is about 33 °C. Therefore, even for parts that are easily affected by heat such as resin parts, it is difficult to have an adverse effect. Further, HCFO-1233zd(Z), HCFO-1233yd, and HFO-1336mzz(Z) are non-flammable, have low surface tension and viscosity, and easily evaporate even at room temperature. They have excellent performance as penetrants, cleaning agents, and developers used in the penetrant flaw detection test method.

[0054] Here, in any of the penetrant, the cleaning agent, and the developer, it is preferable to contain the same type of hydrofluoroolefin, hydrofluoroketone, perfluoroketone, and hydrofluoroether. Thereby, each step of the penetration step, the removal step, and the development step in the penetrant flaw detection test can be facilitated. For example, when HCFO-1233zd(Z) is contained as a hydrofluoroolefin in the penetrant, it is preferable to contain HCFO-1233zd(Z) also in the cleaning agent and the developer.

[0055] In one embodiment, this method may be to apply this penetrant flaw detection agent to a penetrant flaw detection test standardized in the standard group of JIS Z 2343.

Explanation of Signs

[0056] 1... article, 3... surface of the article, 5... opening defect part, 10... penetrant, 20... coating film, 30... defect indication bleed pattern

Claims

1. A penetrant containing a dye and a volatile organic solvent, wherein the volatile organic solvent contains at least one selected from the group consisting of hydrofluoroolefins, hydrofluoroketones, and perfluoroketones, and the penetrant is characterized by being used in a penetrant inspection test.

2. The penetrant according to claim 1, wherein the hydrofluoroolefin is at least one selected from the group consisting of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, Z-1,2-dichloro-3,3,3-trifluoropropene, E-1,2-dichloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1,1,2-trichloro-3,3,3-trifluoropropene, Z-1,1,1,4,4,4-hexafluoro-2-butene, E-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, Z-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, Z-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene, E-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene, Z-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene, E-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene, and methoxyperfluoroheptene.

3. The penetrant according to claim 1, wherein the hydrofluoroolefin has a boiling point of 30°C to 60°C.

4. The penetrant according to claim 1, wherein the hydrofluoroolefin is at least one selected from the group consisting of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, and Z-1,1,1,4,4,4-hexafluoro-2-butene.

5. The penetrant according to claim 1, further containing at least one selected from the group consisting of nitrogen, carbon dioxide, compressed air, argon, and fluorine-based gases as a propellant.

6. The hydrofluoroolefin is at least one selected from the group consisting of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, and Z-1,1,1,4,4,4-hexafluoro-2-butene and The penetrant according to claim 1, wherein the propellant is at least one of E-1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene.

7. The penetrant according to claim 1, wherein the content of the dye is 40 parts by mass or less with respect to 100 parts by mass of the total amount of the volatile organic solvent.

8. The penetrant according to claim 1, further comprising at least one of an additive, a surfactant, a rust inhibitor, a hydrocarbon oil, a vegetable oil, and a stabilizer.

9. comprising a powder and a volatile organic solvent, a developer comprising at least one selected from the group consisting of hydrofluoroolefins, hydrofluoroketones, and perfluoroketones as the volatile organic solvent, The developer is characterized by being used in a penetrant flaw detection test.

10. The hydrofluoroolefin is at least one selected from the group consisting of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, Z-1,2-dichloro-3,3,3-trifluoropropene, E-1,2-dichloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1,1,2-trichloro-3,3,3-trifluoropropene, Z-1,1,1,4,4,4-hexafluoro-2-butene, E-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, Z-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, Z-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene, E-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene, Z-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene, E-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene, and methoxyperfluoroheptene. The developer according to claim 9.

11. The developer according to claim 9, wherein the hydrofluoroolefin has a boiling point of 30°C to 60°C.

12. The developer according to claim 9, wherein the hydrofluoroolefin is at least one selected from the group consisting of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, and Z-1,1,1,4,4,4-hexafluoro-2-butene.

13. The developer according to claim 9, comprising at least one selected from the group consisting of nitrogen, carbon dioxide, compressed air, argon, and fluorine-based gas as a propellant.

14. The developer according to claim 9, wherein the hydrofluoroolefin is at least one selected from the group consisting of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, and Z-1,1,1,4,4,4-hexafluoro-2-butene, and the propellant is at least one of E-1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene.

15. The developer according to claim 9, wherein the powder contains at least one of inorganic powder and silica.

16. The developer according to claim 9, wherein the content of the powder is 30 parts by mass or less with respect to 100 parts by mass of the total amount of the volatile organic solvent.

17. The developer according to claim 9, further comprising at least one of an additive, a surfactant, a rust inhibitor, a hydrocarbon oil, a vegetable oil, and a stabilizer.

18. A penetrant inspection agent product comprising a penetrant, a cleaning agent, and a developer as constituent elements, wherein the penetrant is the penetrant according to claim 1, the cleaning agent is a cleaning agent containing at least one selected from the group consisting of hydrofluoroolefin, hydrofluoroketone, and perfluoroketone as a volatile organic solvent, and the cleaning agent is characterized by being used in a penetrant inspection test, and the developer is the developer according to claim 9.

19. The penetrant inspection agent product according to claim 18, wherein the penetrant, the cleaning agent, and the developer contain at least one selected from the group consisting of the same type of hydrofluoroolefin, hydrofluoroketone, and perfluoroketone.

20. A method for detecting an open defect on the surface of an article using a penetrant inspection agent, comprising: penetrating a penetrant containing at least one selected from the group consisting of hydrofluoroolefins, hydrofluoroketones, and perfluoroketones as a volatile organic solvent into the open defect on the surface of the article; removing excess penetrant on the surface of the article using a cleaning agent containing at least one selected from the group consisting of hydrofluoroolefins, hydrofluoroketones, and perfluoroketones as a cleaning component; performing a developing process using a developer containing at least one selected from the group consisting of hydrofluoroolefins, hydrofluoroketones, and perfluoroketones as a volatile organic solvent; The method comprising the above steps.

21. The method according to claim 20, wherein the hydrofluoroolefin has a boiling point of 30°C to 60°C.

22. The method according to claim 20, wherein the hydrofluoroolefin is at least one selected from the group consisting of Z-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-2,3,3-trifluoro-1-propene, E-1-chloro-2,3,3-trifluoro-1-propene, and Z-1,1,1,4,4,4-hexafluoro-2-butene.

23. The method according to claim 20, wherein the penetrant, the cleaning agent, and the developer contain at least one selected from the group consisting of the same type of hydrofluoroolefins, hydrofluoroketones, and perfluoroketones.

24. The method according to claim 20, wherein the article contains at least one selected from stainless steel, carbon steel, copper, aluminum, titanium, nickel, Hastelloy, and Inconel.

25. The method according to claim 20, wherein the article is selected from any one of two or more composite materials selected from resin, metal members, and alloy materials, and resin.

26. The method according to claim 20, wherein a pretreatment for removing dirt is performed on the article before the penetrant is penetrated into the open defect on the surface of the article.

27. The method according to claim 20, wherein each of the penetrant, the cleaning agent, and the developer contains the same type of hydrofluoroolefin, hydrofluoroketone, or perfluoroketone.

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