Composition, cleaning agent, aerosol composition, draining agent, foaming agent or heat-transfer medium containing the composition, system using the heat-transfer medium, and method of cleaning articles

Abstract

To provide an aerosol composition, a draining agent, a foaming agent, or a heat-transfer medium containing a hydrochlorofluoroolefin-based composition.SOLUTION: A novel hydrochlorofluoroolefin-based composition contains Z-1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3,3-tetrafluoropropane, and water. In the composition, the proportions of Z-1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3,3-tetrafluoropropane, and water are 55.00 mass% to 99.98 mass%, 0.01 mass% to 44.99 mass%, and 0.01 mass% to 10.00 mass%, respectively, with respect to the total amount of Z-1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3,3-tetrafluoropropane, and water.SELECTED DRAWING: None

Description

[Technical field]

[0001] One embodiment of the present invention relates to a composition. Specifically, the present invention relates to a composition containing Z-1-chloro-3,3,3-trifluoropropene (hereinafter also referred to as HCFO-1233zd(Z) or 1233zd(Z)), 1-chloro-1,3,3,3-tetrafluoropropane (hereinafter also referred to as HCFC-244fa or 244fa), and water, or a composition containing 1233zd(Z), 244fa, dichlorotetrafluoropropene (hereinafter also referred to as HCFO-1214 or 1214), and water. Alternatively, one embodiment of the present invention relates to a cleaning agent, an aerosol composition, a draining agent, a foaming agent, or a heat transfer medium containing the above composition. Alternatively, one embodiment of the present invention relates to a system using the above heat transfer medium. [Background technology]

[0002] Fluorine-containing compounds such as hydrochlorofluoroolefins (HCFOs) and hydrochlorofluorocarbons (HCFCs) have a high ability to dissolve various solutes, and are therefore widely used as blowing agents, heat transfer media, solvents, cleaning agents, etc. In particular, hydrochlorofluoroolefins (HCFOs) have excellent environmental performance, such as a short lifespan in the atmosphere and a small global warming potential, and are therefore useful as one of the environmentally friendly functional solvents (see Patent Documents 1 to 6). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2018-039799 A [Patent Document 2] Patent No. 5477011 [Patent Document 3] Special Publication No. 2015-507039 [Patent Document 4] US Patent Application Publication No. 2006-0142173 [Patent Document 5] JP 2017-043742 A [Patent Document 6] JP 2013-087066 A Summary of the Invention [Problem to be solved by the invention]

[0004] One of the embodiments of the present invention has an objective to provide a novel hydrochlorofluoroolefin-based composition. Alternatively, one of the embodiments of the present invention has an objective to provide a cleaning agent containing a hydrochlorofluoroolefin-based composition having excellent properties. Alternatively, one of the embodiments of the present invention has an objective to provide an aerosol composition, a draining agent, a foaming agent, or a heat transfer medium containing a hydrochlorofluoroolefin-based composition. Alternatively, one of the embodiments of the present invention has an objective to provide a system using the above heat transfer medium. Alternatively, one of the embodiments of the present invention has an objective to provide a method for cleaning an article using a cleaning agent containing a hydrochlorofluoroolefin-based composition. [Means for solving the problem]

[0005] One embodiment of the present invention is a composition. The composition includes Z-1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3,3-tetrafluoropropane, and water. In the composition, the ratio of Z-1-chloro-3,3,3-trifluoropropene is 55.00% to 99.98% by mass, the ratio of 1-chloro-1,3,3,3-tetrafluoropropane is 0.01% to 44.99% by mass, and the ratio of water is 0.01% to 10.00% by mass, based on the total amount of Z-1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3,3-tetrafluoropropane, and water.

[0006] One embodiment of the present invention is a composition. The composition includes Z-1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3,3-tetrafluoropropane, dichlorotetrafluoropropene, and water. In the composition, the ratio of Z-1-chloro-3,3,3-trifluoropropene is 55.00000 mass% to 99.98989 mass%, the ratio of 1-chloro-1,3,3,3-tetrafluoropropane is 0.00010 mass% to 44.98999 mass%, the ratio of dichlorotetrafluoropropene is 0.00001 mass% to 5.00000 mass%, and the ratio of water is 0.01000 mass% to 10.00000 mass% based on the total amount of Z-1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3,3-tetrafluoropropane, dichlorotetrafluoropropene, and water.

[0007] One embodiment of the present invention is a method for forming a coating of a film-forming component on a surface of an article, comprising applying a solution containing any of the compositions described above and the film-forming component to the surface of the article, and allowing the composition to volatilize. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Hereinafter, embodiments of the present invention will be described. However, the embodiments of the present invention should not be construed as being limited to the description of the following embodiments and examples.

[0009] 1. Definitions "Azeotrope" refers to azeotropy in the strict thermodynamic sense. For example, in the case of water and ethanol, the composition of ethanol (96% by mass) and water (4% by mass) is an azeotropic mixture, and the vapor that exists in vapor-liquid equilibrium with this is also "ethanol (96% by mass): water (4% by mass)", which is completely consistent with the liquid composition. This phenomenon is called "azeotropy", and the azeotropic mixture is called an azeotropic composition. At a specific temperature and pressure, there is only one composition of the azeotropic composition. An azeotropic composition evaporates with the same composition as the liquid composition, making it a very desirable composition in which the liquid composition does not change during use.

[0010] "Azeotrope-like" refers to a phenomenon in which the composition of the liquid and the composition of the gas in equilibrium are substantially equal, although they do not completely match. Compositions that exhibit such a phenomenon can be treated in the same way as azeotropic compositions, so azeotropic compositions and compositions that exhibit azeotrope-like phenomena are sometimes collectively referred to as "azeotrope-like compositions". In this specification, "azeotrope-like composition" refers to a composition that is composed of n (n is a natural number of 2 or more) or more components (or compounds) and has a lower boiling point than a composition excluding the component with the highest boiling point from this composition (a single composition when n is 2). For example, if the boiling point of a composition consisting of three components, components A, B, and C (boiling points are C>B>A), is lower than the boiling point of a composition consisting of components A and B that does not contain component C with the highest boiling point, this composition consisting of the three components is an azeotrope-like composition. Azeotrope-like compositions include homogeneous azeotrope-like compositions that exist as a single liquid phase at a specified pressure, and heterogeneous azeotrope-like compositions that exist as two or more liquid phases at a specified pressure. An azeotrope-like composition consisting of n components is called an n-component azeotrope-like composition. For example, an azeotrope-like composition consisting of three components is called a ternary azeotrope-like composition, and an azeotrope-like composition consisting of four components is called a quaternary azeotrope-like composition. Note that the boiling point of a composition is the boiling point at 1 atmosphere (101.3 kPa), that is, the standard boiling point.

[0011] 2. Three-component composition One embodiment of the present invention is a composition comprising 1233zd(Z), 244fa, and water. In this ternary composition, the proportion of 1233zd(Z) is 55.00% to 99.98% by mass, the proportion of 244fa is 0.01% to 44.99% by mass, and the proportion of water is 0.01% to 10.00% by mass, based on the total amount of 1233zd(Z), 244fa, and water. The structural formulas of 1233zd(Z) and 244fa are as follows: [ka]

[0012] The boiling points of 1233zd(Z), 244fa, and water at 1 atmospheric pressure are 39°C, 42°C, and 100°C, respectively, with water showing the highest boiling point in this ternary composition. As shown in the examples, the boiling point of a ternary composition consisting of 1233zd(Z), 244fa, and water in the above ratios is lower than the boiling point of a binary composition consisting of 1233zd(Z) and 244fa in the same composition ratio. Therefore, this ternary composition exhibits an azeotrope-like phenomenon, and can also be called a ternary azeotrope-like composition.

[0013] In this ternary composition, the proportion of 1233zd(Z) may be 60.00% to 99.98% by mass, the proportion of 244fa may be 0.01% to 39.98% by mass, and the proportion of water may be 0.01% to 5.00% by mass, based on the total amounts of 1233zd(Z), 244fa, and water. Alternatively, in this ternary composition, the proportion of 1233zd(Z) may be 85.00% to 99.98% by mass, the proportion of 244fa may be 0.01% to 14.98% by mass, and the proportion of water may be 0.01% to 2.00% by mass, based on the total amounts of 1233zd(Z), 244fa, and water. Alternatively, in this three-component composition, the proportion of 1233zd(Z) may be 60.02000 mass% to 99.92000 mass%, the proportion of 244fa may be 0.03000 mass% to 39.38000 mass%, and the proportion of water may be 0.01000 mass% to 1.01000 mass%, based on the total amounts of 1233zd(Z), 244fa, and water.

[0014] 3. Four-component composition Another embodiment of the present invention is a four-component composition consisting of 1233zd(Z), 244fa, 1214, and water. In this four-component composition, the ratio of 1233zd(Z) is 55.00000% to 99.98989% by mass, the ratio of 244fa is 0.00010% to 44.98999% by mass, the ratio of 1214 is 0.00001% to 5.00000% by mass, and the ratio of water is 0.01000% to 10.00000% by mass, based on the total amount of 1233zd(Z), 244fa, 1214, and water. The structural formula of 1214 is as follows: [ka]

[0015] As shown in the above structural formula, 1214 refers to 1,1-dichloro-2,3,3,3-tetrafluoropropene (hereinafter also referred to as 1214ya), 1,2-dichloro-1,3,3,3-tetrafluoropropene (hereinafter also referred to as 1214xb), and 1,3-dichloro-1,2,3,3-tetrafluoropropene (hereinafter also referred to as 1214yb). 1214xb includes cis and trans isomers. Similarly, 1214yb also includes cis and trans isomers. Therefore, in this specification, 1214 is a collective term for five isomers. 1214 contained in the above four-component composition may include only one of the above isomers, may include multiple isomers, or may include all of them. When multiple isomers are included, the composition ratio is arbitrary. In addition, when 1214xb, which can be a cis- or trans-isomer, is contained, only one of the isomers may be contained, or both isomers may be contained in any composition ratio. Similarly, when 1214yb, which can be a cis- or trans-isomer, is contained, only one of the isomers may be contained, or both isomers may be contained in any composition ratio.

[0016] The boiling points of 1233zd(Z), 244fa, 1214, and water at 1 atmospheric pressure are 39°C, 42°C, 43 to 48°C, and 100°C, respectively, and water has the highest boiling point among the four-component composition. As shown in the examples, the boiling point of a four-component composition consisting of 1233zd(Z), 244fa, 1214, and water in the above ratio is lower than the boiling point of a composition consisting of 1233zd(Z), 244fa, and 1214 in the same composition ratio. Therefore, this four-component composition exhibits an azeotrope-like phenomenon and can also be called a four-component azeotrope-like composition.

[0017] In this four-component composition, the proportion of 1233zd(Z) may be 60.00000 mass% to 99.98989 mass%, the proportion of 244fa may be 0.00010 mass% to 39.98999 mass%, the proportion of 1214 may be 0.00001 mass% to 5.00000 mass%, and the proportion of water may be 0.01000 mass% to 5.00000 mass%, based on the total amounts of 1233zd(Z), 244fa, 1214, and water. Alternatively, in this four-component composition, the proportion of 1233zd(Z) may be 85.00000 mass% to 99.98989 mass%, the proportion of 244fa may be 0.00010 mass% to 14.98999 mass%, the proportion of 1214 may be 0.00001 mass% to 5.00000 mass%, and the proportion of water may be 0.01000 mass% to 2.00000 mass%, based on the total amounts of 1233zd(Z), 244fa, 1214, and water. Alternatively, in this four-component composition, the proportion of 1233zd(Z) may be 86.78000 mass% to 99.97699 mass%, the proportion of 244fa may be 0.00260 mass% to 9.34000 mass%, the proportion of 1214 may be 0.00001 mass% to 4.82000 mass%, and the proportion of water may be 0.01690 mass% to 1.14640 mass% based on the total amount of 1233zd(Z), 244fa, 1214, and water. From the viewpoint of stability, the proportion of 1214 is preferably 10 mass% or less, more preferably 5 mass% or less.

[0018] It is not always easy to predict the azeotropic properties of a composition containing multiple compounds that are liquid at room temperature. In particular, when compounds with significantly different boiling points are included, it is extremely difficult to predict whether the composition will form an azeotrope-like composition or to predict the composition ratio for forming an azeotrope-like composition. This tendency is particularly noticeable in compositions containing compounds that do not have hydrophilic substituents, such as hydrochlorofluoroolefins, contained in the present composition, and polar solvents such as water, and it is not possible to judge unless the composition is actually adjusted and its behavior is examined. In addition, this difficulty in prediction naturally increases as the number of compounds contained in the composition increases, and it is only after a considerable amount of trial and error that the azeotropic properties and the composition ratio for realizing it can be found. Therefore, the present invention has important technical significance in that it has been found that the present multi-component composition containing three or more compounds with significantly different polarities and boiling points exhibits an azeotrope-like phenomenon, and that the composition ratio for exhibiting the azeotrope-like phenomenon has been identified based on experimental results.

[0019] The 1233zd(Z), 244fa, 1214, and water that make up these three-component and four-component compositions (hereinafter, these compositions may be referred to as the present multi-component compositions, respectively) have extremely low ozone depletion potentials and global warming potentials (GWP), and are therefore less likely to have a negative impact on the global environment than compositions containing only conventional chlorofluorocarbons (CFCs) or hydrochlorofluorocarbons (HCFCs).

[0020] 4. Additives One embodiment of the present invention is a composition comprising the multi-component composition. The composition may comprise one or more other components in addition to the multi-component composition. As described below, the multi-component composition can be used in a variety of applications, and other components may be added as additives depending on the application. Examples of additives include, but are not limited to, lubricants, stabilizers, flame retardants, surfactants, metal passivators, organic solvents (except 1233zd(Z), 244fa, and 1214), propellant gases, and the like. The amount of additive added is appropriately adjusted depending on the application. Hereinafter, an embodiment including additives will be described.

[0021] 4-1.Lubricants One embodiment of the present invention is a composition comprising the multi-component composition and a lubricant. The lubricant may be, but is not limited to, mineral oil (paraffinic oil or naphthenic oil), synthetic oil alkylbenzene, poly(α-olefin), ester, polyol ester, polyalkylene glycol, polyvinyl ether, etc. A mixture of the lubricant and the multi-component composition may be used as a heat transfer composition such as a refrigerant for a high-temperature heat pump or a working medium for a Rankine cycle. The amount of the lubricant added may be, but is not limited to, 0.01% to 20% by weight, 0.01% to 10% by weight, or 0.01% to 5% by weight of the multi-component composition.

[0022] Examples of alkylbenzenes include n-octylbenzene, n-nonylbenzene, n-decylbenzene, n-undecylbenzene, n-dodecylbenzene, n-tridecylbenzene, 2-methyl-1-phenylheptane, 2-methyl-1-phenyloctane, 2-methyl-1-phenylnonane, 2-methyl-1-phenyldecane, 2-methyl-1-phenylundecane, 2-methyl-1-phenyldodecane, and 2-methyl-1-phenyltridecane.

[0023] Examples of the ester include aromatic esters such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and mixtures thereof, dibasic acid esters, polyol esters, complex esters, and carbonate esters.

[0024] Examples of alcohols that can be used as raw materials for polyol esters include polyhydric alcohols such as neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol, di(pentaerythritol), and tri(pentaerythritol). Examples of carboxylic acids that can be used as raw materials for polyol esters include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid.

[0025] Examples of polyalkylene glycols include compounds obtained by addition polymerization of alkylene oxides (e.g., ethylene oxide, propylene oxide, butylene oxide, etc.) with alcohols having 1 to 18 carbon atoms (e.g., aliphatic alcohols such as methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, and linear or branched hexanol).

[0026] Examples of the polyvinyl ether include polymethyl vinyl ether, polyethyl vinyl ether, poly n-propyl vinyl ether, and polyisopropyl vinyl ether.

[0027] 4-2. Stabilizers One embodiment of the present invention is a composition containing the multi-component composition and a stabilizer. The addition of a stabilizer can improve the thermal stability, oxidation resistance, and the like of the multi-component composition. Examples of such stabilizers include, but are not limited to, nitro compounds, epoxy compounds, phenols, imidazoles, amines, and hydrocarbons. These may be used alone or in combination of two or more. The amount of stabilizer added may be, for example, selected from the range of 0.01% to 20% by weight, 0.01% to 10% by weight, or 0.01% to 5% by weight relative to the multi-component composition, but is not limited thereto.

[0028] Examples of nitro compounds include aliphatic and / or aromatic derivatives. Examples of aliphatic nitro compounds include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, etc. Examples of aromatic nitro compounds include nitrobenzene, o-, m-, or p-dinitrobenzene, trinitrobenzene, o-, m-, or p-nitrotoluene, o-, m-, or p-ethylnitrobenzene, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-dimethylnitrobenzene, o-, m-, or p-nitroacetophenone, o-, m-, or p-nitrophenol, o-, m-, or p-nitroanisole, etc.

[0029] Examples of epoxy compounds include monoepoxy compounds such as ethylene oxide, 1,2-butylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, glycidol, epichlorohydrin, glycidyl methacrylate, phenyl glycidyl ether, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, and 2-ethylhexyl glycidyl ether; and polyepoxy compounds such as diepoxybutane, vinylcyclohexene dioxide, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin polyglycidyl ether, and trimethylolpropane tolglycidyl ether.

[0030] Examples of phenols include, in addition to phenol, aromatic compounds containing a phenolic hydroxyl group and a substituent such as an alkyl group, an alkenyl group, an alkoxy group, a carboxyl group, a carbonyl group, a halogen, etc. Examples of such aromatic compounds include monohydric phenols such as 2,6-di-t-butyl-p-cresol, o-cresol, m-cresol, p-cresol, thymol, pt-butylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, eugenol, isoeugenol, butylhydroxyanisole, phenol, and xylenol, and dihydric phenols such as t-butylcatechol, 2,5-di-t-aminohydroquinone, and 2,5-di-t-butylhydroquinone.

[0031] Examples of the imidazoles include 1-methylimidazole, 1-n-butylimidazole, 1-phenylimidazole, 1-benzylimidazole, 1-(β-oxyethyl)imidazole, 1-methyl-2-propylimidazole, 1-methyl-2-isobutylimidazole, 1-n-butyl-2-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethylimidazole, 1,5-dimethylimidazole, 1,2,5-trimethylimidazole, 1,4,5-trimethylimidazole, and 1-ethyl-2-methylimidazole, each of which has a linear or branched alkyl group, cycloalkyl group, or aryl group having 1 to 18 carbon atoms as a substituent at the N-position.

[0032] Examples of amines include pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine, diallylamine, triethylamine, N-methylaniline, pyridine, morpholine, N-methylmorpholine, triallylamine, allylamine, α-methylbenzylamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, dibutylamine, tributylamine, dipentylamine, tripentylamine, 2-ethylhexylamine, aniline, N,N-dimethylaniline, N,N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine, benzylamine, dibenzylamine, diphenylamine, and diethylhydroxylamine.

[0033] Examples of the hydrocarbon include α-methylstyrene, p-isopropenyltoluene, isoprenes, propadienes, and terpenes.

[0034] 4-3.Flame retardants One embodiment of the present invention is a composition comprising the multi-component composition and a flame retardant. The addition of a flame retardant can reduce the flammability of the multi-component composition, thereby improving safety. Examples of such flame retardants include, but are not limited to, phosphate esters, halogenated aromatic compounds, fluorinated iodocarbons, and fluorinated bromocarbons. The amount of the flame retardant added may be selected from the range of, for example, 0.01% to 20% by weight, 0.01% to 10% by weight, or 0.01% to 5% by weight relative to the multi-component composition, but is not limited thereto.

[0035] 4-4.Surfactants One embodiment of the present invention is a composition containing the multi-component composition and a surfactant. The addition of a surfactant can further improve the cleaning power, interfacial action, and the like. Examples of such surfactants include nonionic surfactants such as sorbitan aliphatic esters such as sorbitan monooleate and sorbitan trioleate; polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitol tetraoleate; polyethylene glycol fatty acid esters such as polyoxyethylene monolaurate; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonyl phenyl ether; and polyoxyethylene alkylamine fatty acid amides such as polyoxyethylene oleic acid amide. For the purpose of synergistically improving the cleaning power and interfacial action, the composition of the present invention may contain a cationic surfactant or an anionic surfactant together with these nonionic surfactants. The amount of surfactant added may be selected from the range of, for example, 0.01% by mass to 20% by mass, 0.01% by mass to 10% by mass, or 0.01% by mass to 5% by mass relative to the multi-component composition, but is not limited thereto.

[0036] 4-5.Metal passivators One embodiment of the present invention is a composition comprising the multi-component composition and a metal passivator. The metal passivator may comprise a corrosion inhibitor and / or a metal deactivator. The metal passivator may be useful for preventing corrosion of metals that may be included on the surface of an article with which the multi-component composition may come into contact. Various metal passivators are well known in the art, and any may be used as an additive to the multi-component composition. The amount of the metal passivator added may be selected from, for example, but not limited to, the range of 0.01% to 20% by weight, 0.01% to 10% by weight, or 0.01% to 5% by weight relative to the multi-component composition.

[0037] 4-6. Organic solvents One embodiment of the present invention is a composition containing the multi-component composition and an organic solvent. By adding an organic solvent, the cleaning power of the multi-component composition can be further improved. Examples of such organic solvents include, but are not limited to, the following. Alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, pentafluoropropanol; Hydrocarbons such as pentane, hexane, isopentane, n-heptane, cyclopentane, and cyclohexane; Petroleum paraffins; Alkylbenzenes such as toluene and xylene; Ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate; Glycol ethers such as diethylene glycol monobutyl ether; Naphthas such as light naphtha, heavy naphtha, petroleum naphtha, and coal tar naphtha; Chlorinated solvents such as methylene chloride, trichloroethane, trichloroethylene, tetrachloroethylene, and E-1,2-dichloroethylene; Hydrochlorofluorocarbons such as dichlorofluoroethane, dichlorodifluoroethane, dichlorotrifluoroethane, chlorofluoropropane, chlorodifluoropropane, chlorotrifluoropropane, chlorotetrafluoropropane (excluding 244fa), dichlorofluoropropane, dichlorodifluoropropane, dichlorotrifluoropropane, dichlorotetrafluoropropane, dichloropentafluoropropane, trichlorofluoropropane, trichlorodifluoropropane, and trichlorotrifluoropropane; hydrofluorocarbons such as fluoropropane, difluoropropane, trifluoropropane, tetrafluoropropane, pentafluoropropane, hexafluoropropane, fluorobutane, difluorobutane, trifluorobutane, tetrafluorobutane, pentafluorobutane, hexafluorobutane, heptafluorobutane, octafluorobutane, nonafluorobutane, fluoropentane, difluoropentane, trifluoropentane, tetrafluoropentane, pentafluoropentane, hexafluoropentane, heptafluoropentane, octafluoropentane, nonafluoropentane, decafluoropentane, and undecafluoropentane; 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 ( Hydrohaloolefins such as 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), and methoxyperfluoroheptene; hydrofluoroethers such as 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); Hydrofluoroketones such as 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); Perfluoroketones such as 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone. These may be used alone or in combination of two or more. The amount of the organic solvent added may be selected from the range of, for example, 0.01% by mass to 50% by mass, 0.01% by mass to 30% by mass, or 0.01% by mass to 10% by mass relative to the multi-component composition, but is not limited thereto.

[0038] 4-7. Propellant gas One embodiment of the present invention is a composition containing the multi-component composition and a propellant gas. By including a propellant gas, an aerosol composition containing the multi-component composition can be obtained. The propellant gas can be a liquefied gas or a compressed gas. Examples of the propellant gas include, but are not limited to, LPG (liquefied petroleum gas), DME (dimethyl ether), carbon dioxide, fluorine-based gas, nitrogen gas, compressed air, and other gases. These gases may be used alone or in the form of a mixture of two or more kinds. Here, the fluorine-based gas refers to a fluorine-containing hydrocarbon compound that has a boiling point of less than 20°C at 1 atmospheric pressure and is in a gaseous state at 20°C at 1 atmospheric pressure. Examples of fluorine-based gases 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), and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea). Examples of the propellant include, but are not limited to, carbon 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)), and 2,3,3,3-tetrafluoropropene (HFO-1234yf). The aerosol composition can be provided by filling a composition containing the multi-component composition and a propellant gas into a pressure-resistant can. When a propellant gas is included, for example, the volume ratio of the multi-component composition to the propellant may be, but is not limited to, 0.01:99.99 to 99.99:0.01, or 0.1:99.9 to 99.9:0.1.

[0039] 5.Applications Examples of uses of the present multi-component composition are given below. Similar to the present multi-component composition, compositions containing the present multi-component composition can also be used in the applications exemplified below.

[0040] 5-1. Cleaning applications The multi-component composition has excellent cleaning power and can be used as a cleaning agent. The field in which it is used as a cleaning agent is not particularly limited, but it is suitable for use in fields in which mixtures of CFC-113 (chlorotrifluoromethane), HCFC-141b (1,1-dichloro-1-fluoroethane), HCFC-225 (3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC-225ca), and 1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb) have been used as cleaning agents.

[0041] Specifically, the multi-component composition is suitable for removing foreign matter, oils and fats, grease, wax, flux, ink, and the like from articles to be cleaned, such as precision machine parts, electronic materials (printed circuit boards, liquid crystal displays, magnetic recording parts, semiconductor materials, etc.), resin-processed parts, optical lenses, and clothing. The multi-component composition has appropriate fluidity and dissolving power, so that contaminants such as foreign matter can be washed away or dissolved and removed. Examples of materials for the substrates constituting these articles to be cleaned include metals such as iron, stainless steel, magnesium, aluminum, zinc, silver, copper, copper alloys, tin, anodized aluminum sulfate, and titanium, metals whose surfaces are plated with copper, zinc, nickel, chromium, gold, and the like, plastic materials such as polypropylene and epoxy resin, polymer materials, and glass materials.

[0042] Although the type of contaminant is not limited, dirt that can be removed with CFC-113, HCFC-141b, or HCFC-225 can be removed by optimizing the composition ratio of the present multi-component composition, and examples of such contaminants include solid contaminants such as particles, and liquid contaminants such as oil, grease, wax, flux, ink, etc. In addition, since the present multi-component composition contains water, which is a highly polar substance, even if the contaminant contains a highly polar substance such as water-soluble oil or inorganic salt, these can be easily removed.

[0043] Alternatively, the present multi-component composition can be suitably used for cleaning various vehicles, conveyances, and transport engines, such as automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railroad vehicles, and ships (particularly, for cleaning the brakes of these engines). In cleaning vehicles, conveyances, and transport engines, a step of wetting and washing away contaminants may be required, and the present multi-component composition has a high affinity for contaminants, so that the contaminants can be wetted and washed away.

[0044] The cleaning method is not particularly limited, but may be any method that brings the multi-component composition into contact with the article to be cleaned. For example, the article to be cleaned may be immersed in the multi-component composition. Alternatively, the multi-component composition may be sprayed onto the article to be cleaned. Alternatively, contaminants on the article to be cleaned may be wiped off with a cloth soaked in the multi-component composition. When immersing, ultrasonic waves may be applied. When spraying, for example, an aerosol containing the multi-component composition and a propellant gas may be used.

[0045] As described above, the multi-component composition can exhibit an azeotrope-like phenomenon. Therefore, even if the multi-component composition is used in an open system, the composition hardly changes, and stable cleaning power can be exhibited without strict composition control. In addition, the multi-component composition can be recovered from the cleaning waste liquid after cleaning by purification such as distillation, and reused as a cleaning agent. In general, the cleaning agent obtained by distillation recovery from the cleaning waste liquid often has a different composition from the original cleaning liquid, which can be a cause of reduced cleaning power. On the other hand, since the multi-component composition exhibits an azeotrope-like phenomenon, the composition hardly changes even when distilled, and the reused product can exhibit stable cleaning power.

[0046] In addition, hydrochlorofluoroolefins and hydrochlorofluorocarbons such as 1233zd(Z), 244fa, and 1214 contained in this multi-component composition have a high ability to dissolve organic compounds, and are useful as cleaning agents for removing lipophilic contaminants attached to the surface of the article to be cleaned. However, when the polarity of the contaminants is high, for example, when the contaminants are highly polar substances such as water-soluble oils and inorganic salts, these are substances that are poorly soluble in hydrochlorofluoroolefins and hydrochlorofluorocarbons, so it is difficult to completely remove the contaminants with a cleaning agent composed only of hydrochlorofluoroolefins and / or hydrochlorofluorocarbons.

[0047] On the other hand, since the present multi-component composition contains water in addition to hydrochlorofluoroolefins and hydrochlorofluorocarbons, it is also effective in removing highly polar substances attached to the surface of the article to be cleaned. Furthermore, since the present multi-component composition remaining on the surface of the article to be cleaned after cleaning exhibits azeotropic properties, the water evaporates together with the hydrochlorofluoroolefins and hydrochlorofluorocarbons. Therefore, water does not remain on the surface of the article, and the occurrence of water drip points (water stains, water marks), which is an issue when using a composition containing water as a cleaning agent, can be prevented at the same time.

[0048] 5-2. Draining use The multi-component composition can be used as a draining agent. In the manufacturing process of articles used in various industrial fields such as automobiles, machinery, precision instruments, electricity, electronics, and optics, articles may be washed with water such as pure water, or washed with an aqueous cleaner, a semi-aqueous cleaner obtained by blending an aqueous cleaner with a water-soluble solvent, an alcohol cleaner, a glycol ether cleaner, or a hydrocarbon cleaner obtained by blending a surfactant with a hydrocarbon. When an aqueous cleaner or a semi-aqueous cleaner is used, water adheres to the article after washing, and a draining process is generally performed after the washing process to remove the water with a draining agent. The multi-component composition can also be suitably used as a draining agent for use in such a draining process.

[0049] The method for draining water is not particularly limited, and any method known in the art can be used, for example, a method in which the article to be drained is brought into contact with the multi-component composition and dried.

[0050] Since the multi-component composition exhibits a cleaning action as well as a draining action, the cleaning step and the draining step can be performed simultaneously. That is, by performing the cleaning step, contaminants attached to the object to be cleaned can be removed, and water that may adhere to the object to be cleaned can be removed. Therefore, it is not necessary to use the cleaning agent and draining agent separately in the cleaning step and the draining step, and productivity is improved. This does not prevent the cleaning agent and draining agent used in the cleaning step and the draining step from being used separately, and the multi-component composition may be used as a cleaning agent and / or draining agent in each step. As described above, since the multi-component composition contains water, it is suitable for cleaning an object to be cleaned to which water-containing contaminants such as water-soluble oil are attached, and water can be removed together with the contaminants attached to the object to be cleaned. In addition, the occurrence of water dripping points can also be prevented.

[0051] 5-3. Solvent (dispersant) applications Since the multi-component composition exhibits an azeotrope-like phenomenon, it can be used as a solvent or dispersant in the same way as a single-component composition. For example, the multi-component composition has excellent properties as a solvent or dispersant for silicone, polytetrafluoroethylene powder (PTFE powder), fluorine-based grease, etc., and can be used as a non-flammable, highly volatile solvent that can dissolve or disperse various silicones at will. Since the multi-component composition has a wide azeotrope-like composition range, the optimal composition can be selected according to various silicone compounds, PTFE powder, and fluorine-based grease.

[0052] The multi-component composition can be used as a solvent or dispersant for film-forming components such as silicone, PTFE powder, and fluorine-based grease to coat the surface of an article. Specifically, a solution containing the multi-component composition and film-forming components is applied to the surface of an article, and the multi-component composition is volatilized to form a film of the film-forming components on the surface of the article. Examples of materials for the surface of an article to which this method can be applied include metals, resins, ceramics, and glass. In particular, this method can be suitably applied to coating the needle tube of a syringe needle, the spring or spring part of a dispenser (a device for dispensing a fixed amount of liquid), and the like. For example, when forming a silicone coating on the needle tube of a syringe needle, the needle tube of the syringe needle may be immersed in a silicone coating solution, and then left at room temperature or under heating to evaporate the multi-component composition.

[0053] Various silicones can be used in the surface coating, for example, straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil having methyl groups, phenyl groups, and / or hydrogen atoms as substituents on silicon, reactive silicone oils having components derived from straight silicone oils, non-reactive silicone oils, and other modified silicone oils can be used.In addition, reactive silicones can be, for example, amino-modified, diamino-modified, epoxy-modified, carboxy-modified, carbinol-modified, methacryl-modified, mercapto-modified, phenol-modified, hydroxy-modified, heterofunctional group-modified silicones, and the like, but are not limited thereto.Non-reactive silicones can be, for example, polyether-modified, methylstyryl-modified, alkyl-modified, fatty acid ester-modified, hydrophilic special modified, fatty acid-containing, fluorine-modified, and the like, but are not limited thereto.

[0054] Other silicones include those mainly composed of a copolymer of aminoalkylsiloxane and dimethylsiloxane, those mainly composed of a reaction product of an amino group-containing silane and an epoxy group-containing silane, and a reaction product of a silanol group-containing polydiorganosiloxane, silicone mixtures consisting of a silicone containing an amino group in the side chain or at the end and a polydiorganosiloxane, and mixtures of a silicone obtained by reacting an amino group-containing alkoxysilane, an epoxy group-containing alkoxysilane, and a silicone having silanol groups at both ends with a non-reactive silicone, and the like.

[0055] The ratio of the coating film-forming components in a solution containing the present multi-component composition and the coating film-forming components may be from 0.1 to 20% by mass, and preferably from 0.5 to 10% by mass.

[0056] 5-4. Foaming agent applications The multi-component composition can be used as a blowing agent for producing rigid polyurethane foam or polyisocyanurate foam. That is, a composition (premix) containing the multi-component composition as a blowing agent, one or more polyols, a catalyst, a foam stabilizer, a flame retardant, etc., is used, and reacted with an isocyanate to produce a rigid polyurethane foam or polyisocyanurate foam. The premix may further contain an ultraviolet inhibitor, a scorch inhibitor, a premix storage stabilizer, etc., which can improve various physical properties of the rigid polyurethane foam or polyisocyanurate foam.

[0057] The isocyanate includes aromatic isocyanate, cyclic aliphatic isocyanate, and chain aliphatic isocyanate, and generally, bifunctional isocyanate is used. Specific examples include polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and dicyclohexylmethane isocyanate, as well as prepolymer-type modified products, nurate-modified products, or urea-modified products thereof. These isocyanates are used alone or as a mixture.

[0058] Examples of polyols include polyether polyols, polyester polyols, polyhydric alcohols, and hydroxyl group-containing diethylene polymers, but polyether polyols are generally used. In addition, polyester polyols and polyether polyols may be used as main components, or other polyols may be used.

[0059] Examples of polyester polyols include compounds derived from phthalic anhydride, waste polyester, and castor oil, as well as condensation polyester polyols, lactone polyester polyols, polycarbonate polyols, etc. From the viewpoints of compatibility with the present multi-component composition, foamability, foam physical properties, etc., it is preferable that the hydroxyl value (OH value) of the polyester polyol is 100 mgKOH / g or more and 400 mgKOH / g or less, and that the viscosity of the polyester polyol is 200 Pa·s / 25°C or more and 4000 mPa·s / 25°C or less.

[0060] Examples of polyether polyols include polypropylene glycol, polytetramethylene glycol, and modified versions of these, as well as sugars and polyhydric alcohols. Alternatively, those obtained by polymerizing cyclic ethers such as propylene oxide, ethylene oxide, epichlorohydrin, and butylene oxide using a compound containing active hydrogen such as alkanolamine as an initiator are preferably used. As the polyether polyol, those having a hydroxyl value of 400 mgKOH / g or more and 1000 mgKOH / g or less may be used.

[0061] Examples of the catalyst include organic metal catalysts and organic amine catalysts. As the organic metal catalyst, an organic tin compound is preferably used, and examples thereof include stannous octoate, stannous laurate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, and dioctyltin diacetate. As the organic amine catalyst, examples thereof include tertiary amines, such as triethylenediamine, N-ethylmorpholine, bis(2-dimethylaminoethyl)ether, and N,N',N'-triethylethanolamine.

[0062] As the foam stabilizer, an organosilicon compound surfactant can be used, such as SH-193, SH-195, SH-200, or SRX-253 manufactured by Toray Silicones Co., Ltd., F-230, F-305, F-341, or F-348 manufactured by Shin-Etsu Silicones Co., Ltd., L-544, L-5310, L-5320, L-5420, or L-5720 manufactured by Nippon Unicar Co., Ltd., or TFA-4200 or TFA-4202 manufactured by Toshiba Silicones Co., Ltd.

[0063] Flame retardants include phosphate esters used in rigid polyurethane foams or polyisocyanurate foams, such as tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, tris(butoxyethyl) phosphate, trismethyl phosphate, trisethyl phosphate, triphenyl phosphate, and tris(isopropylphenyl) phosphate.

[0064] 5-5.Heat transfer medium applications The multi-component composition is suitable as a heat transfer medium for refrigeration cycle systems, high temperature heat pump systems, organic Rankine cycle systems, etc. The multi-component composition is also suitable as a cleaning agent for cleaning these systems.

[0065] The refrigeration cycle system is a vapor compression type refrigeration cycle system including at least the component devices of an evaporator, a compressor, a condenser, and an expansion valve, and is a system mainly intended for cooling. The expansion valve is a device for throttling and expanding a heat transfer medium, and may be a capillary tube. In addition to the above component devices, the refrigeration cycle system may also include an internal heat exchanger, a dryer, a liquid separator, an oil recovery device, a non-condensable gas separator, and the like. The refrigeration cycle system can be used as a refrigerator, an air conditioning system, or a cooling device.

[0066] The high-temperature heat pump cycle system is a vapor compression type heat pump cycle system including at least an evaporator, a compressor, a condenser, and an expansion valve, and is a system mainly intended for heating. The expansion valve is a device for throttling and expanding a heat transfer medium, and may be a capillary tube. In addition to the above-mentioned components, the high-temperature heat pump cycle system may also include an internal heat exchanger, a dryer, a liquid separator, an oil recovery device, a non-condensable gas separator, and the like. The high-temperature heat pump cycle system may be used as a hot water supply system, a steam generation system, or a heating device. The high-temperature heat pump cycle system may also utilize solar thermal energy, factory waste heat, and the like as a heat source.

[0067] The organic Rankine cycle system is a system including at least the component devices of an evaporator, an expander, a condenser, and a booster pump, and is a system mainly intended to convert thermal energy into electrical energy. In addition to the above component devices, the organic Rankine cycle system may also include an internal heat exchanger, a dryer, a liquid separator, an oil recovery device, a non-condensable gas separator, and the like. The organic Rankine cycle system can be used as a power generation device that recovers low- and medium-temperature heat. The organic Rankine cycle system may also utilize solar thermal energy or factory waste heat as a heat source. EXAMPLES

[0068] The following describes the results of evaluating the properties of the multi-component composition according to the embodiment of the present invention, but the present invention is not limited to the following examples. In the following Examples 1 to 4, the results of confirming that a three-component composition consisting of 1233zd(Z), 244fa, and water forms an azeotrope-like composition are shown. In Examples 5 to 9, the results of confirming that a four-component composition consisting of 1233zd(Z), 244fa, 1214xb, and water forms an azeotrope-like composition are shown. In Example 10, the results of confirming that the three-component composition and the four-component composition according to the embodiment of the present invention exhibit a cleaning action as well as a water-draining action are described. The 1214xb used in Examples 5 to 10 had a cis:trans ratio of 57:43.

[0069] 1. Example 1 A high-precision thermometer (CHINO Corporation, main body type: CAB-F201-2, practical standard platinum resistance thermometer: R900-F25AD) was attached to a 300mL three-neck round-bottom flask equipped with a condenser at the top, and the internal pressure of the three-neck round-bottom flask was made equal to the external pressure while maintaining a state in which moisture from the outside air was not mixed in from the top of the condenser. Standard sample 1, prepared by mixing 60.62 mass% 1233zd(Z) and 39.38 mass% 244fa, was added to a 200mL flask, and standard sample 1 was heated while stirring thoroughly. The temperature at which standard sample 1 was sufficiently boiled and the sample temperature stabilized was measured as the "read boiling point," and the external pressure at this time was measured using a barometer (SANO Corporation, high-precision digital barometer VR-16NK). The read boiling point was converted to the standard boiling point based on the external pressure. The boiling point was converted by calculating a correction value using the Sidney Young equation described in the method for correcting thermometer readings to atmospheric pressure described in the Japanese Industrial Standards: JIS K2254 "Methods for distillation of petroleum products," and adding the correction value to the boiling point reading. As a result, the standard boiling point of standard sample 1 was 39.70°C. Standard sample 1 was prepared by adding a specified amount of water to samples 1 to 3, and the standard boiling points were calculated using the above method. The results are shown in Table 1. Standard sample 1 and samples 1 to 3 have the same composition ratio of 1233zd(Z) and 244fa.

[0070] [Table 1]

[0071] As shown in Table 1, Samples 1 to 3 were all observed to exhibit normal boiling points lower than that of Standard Sample 1. This suggests that each of Samples 1 to 3 forms a ternary azeotrope-like composition.

[0072] 2. Example 2 The normal boiling point of standard sample 2, which was prepared by mixing 90.91 mass% 1233zd(Z) and 9.09 mass% 244fa, was determined in the same manner as in Example 1 and was 39.31°C. The normal boiling points of samples 4 to 6, which were prepared by adding a specified amount of water to standard sample 2, were determined in the same manner as above. The results are shown in Table 2. Standard sample 2 and samples 4 to 6 have the same composition ratio of 1233zd(Z) and 244fa.

[0073] [Table 2]

[0074] As shown in Table 2, Samples 4 to 6 were all observed to exhibit normal boiling points lower than that of Standard Sample 2, suggesting that each of Samples 4 to 6 forms a ternary azeotrope-like composition.

[0075] 3. Example 3 The normal boiling point of standard sample 3, which was prepared by mixing 99.18 mass% 1233zd(Z) and 0.82 mass% 244fa, was determined in the same manner as in Example 1 and was 39.21°C. Standard sample 3 was prepared by adding a specified amount of water to samples 7 and 8, and the normal boiling points were determined in the same manner as above. The results are shown in Table 3. Standard sample 3 and samples 7 and 8 have the same composition ratio of 1233zd(Z) and 244fa.

[0076] [Table 3]

[0077] As shown in Table 3, Samples 7 and 8 were both observed to exhibit normal boiling points lower than that of Standard Sample 3, suggesting that Samples 7 and 8 each form a ternary azeotrope-like composition.

[0078] 4. Example 4 The normal boiling point of standard sample 4, which was prepared by mixing 99.97% by mass of 1233zd(Z) and 0.03% by mass of 244fa, was determined in the same manner as in Example 1 and was found to be 39.24°C. The normal boiling points of samples 9 and 10, which were prepared by adding a specified amount of water to standard sample 4, were determined in the same manner as above. The results are shown in Table 4. Standard sample 4 and samples 9 and 10 have the same composition ratio of 1233zd(Z) and 244fa.

[0079] [Table 4]

[0080] As shown in Table 4, Samples 9 and 10 were both observed to exhibit normal boiling points lower than that of Standard Sample 4, suggesting that Samples 9 and 10 each form a ternary azeotrope-like composition.

[0081] 5. Example 5 Standard sample 5, consisting of 99.9631% by mass of 1233zd(Z), 0.0044% by mass of 244fa, and 0.0325% by mass of 1214xb, was placed in a 50 mL three-neck round-bottom flask, and its normal boiling point was determined in the same manner as in Example 1, and was found to be 39.07°C. A specified amount of water was added to this standard sample 5 to prepare sample 11, which was then used to determine its normal boiling point in the same manner. The results are shown in Table 5. Standard sample 5 and sample 11 have the same composition ratio of 1233zd(Z), 244fa, and 1214xb.

[0082] [Table 5]

[0083] As shown in Table 5, Sample 11 was observed to exhibit a normal boiling point lower than that of Standard Sample 5, suggesting that Sample 11 forms a quaternary azeotrope-like composition.

[0084] 6. Example 6 The standard boiling point of standard sample 6, which was prepared by mixing 99.99389% by mass of 1233zd(Z), 0.00610% by mass of 244fa, and 0.00001% by mass of 1214xb, was determined in the same manner as in Example 5 and was found to be 39.07°C. Standard sample 6 was prepared by adding a specified amount of water to samples 12 and 13, and the standard boiling points were determined in the same manner as above. The results are shown in Table 6. Standard sample 6 and samples 12 and 13 have the same composition ratio of 1233zd(Z), 244fa, and 1214xb.

[0085] [Table 6]

[0086] As shown in Table 6, Samples 12 and 13 were both observed to exhibit normal boiling points lower than that of Standard Sample 6, suggesting that Samples 12 and 13 each form a quaternary azeotrope-like composition.

[0087] 7. Example 7 The standard boiling point of standard sample 7, which was prepared by mixing 99.9971% by mass of 1233zd(Z), 0.0026% by mass of 244fa, and 0.0001% by mass of 1214xb, was determined in the same manner as in Example 5, and was found to be 39.05°C. Standard sample 7 was prepared by adding a specified amount of water to samples 14 and 15, and the standard boiling points were determined in the same manner as above. The results are shown in Table 7. Standard sample 7 and samples 14 and 15 have the same composition ratio of 1233zd(Z), 244fa, and 1214xb.

[0088] [Table 7]

[0089] As shown in Table 7, Samples 14 and 15 were both observed to exhibit normal boiling points lower than that of Standard Sample 7, suggesting that Samples 14 and 15 each form a quaternary azeotrope-like composition.

[0090] 8. Example 8 The standard boiling point of standard sample 8, which was prepared by mixing 87.66% by mass of 1233zd(Z), 9.34% by mass of 244fa, and 3.00% by mass of 1214xb, was determined in the same manner as in Example 5, and was found to be 39.14°C. Standard sample 8 was prepared by adding a specified amount of water to samples 16 and 17, and the standard boiling points were determined in the same manner as above. The results are shown in Table 8. Standard sample 8 and samples 16 and 17 have the same composition ratio of 1233zd(Z), 244fa, and 1214xb.

[0091] [Table 8]

[0092] As shown in Table 8, Samples 16 and 17 were both observed to exhibit normal boiling points lower than that of Standard Sample 8, suggesting that Samples 16 and 17 each form a quaternary azeotrope-like composition.

[0093] 9. Example 9 The standard boiling point of standard sample 9, which was prepared by mixing 94.40% by mass of 1233zd(Z), 0.78% by mass of 244fa, and 4.82% by mass of 1214xb, was determined in the same manner as in Example 5, and was found to be 39.03°C. Standard sample 9 was prepared by adding a specified amount of water to samples 18 and 19, and the standard boiling points were determined in the same manner as above. The results are shown in Table 9. Standard sample 9 and samples 18 and 19 have the same composition ratio of 1233zd(Z), 244fa, and 1214xb.

[0094] [Table 9]

[0095] As shown in Table 9, Samples 18 and 19 were both observed to exhibit normal boiling points lower than that of Standard Sample 9, suggesting that Samples 18 and 19 each form a quaternary azeotrope-like composition.

[0096] 10. Example 10 A ternary composition was prepared by mixing 98.98% by weight of 1233zd(Z), 0.03% by weight of 244fa, and 0.99% by weight of water. Similarly, a quaternary composition was prepared by mixing 99.93293% by weight of 1233zd(Z), 0.00610% by weight of 244fa, 0.00001% by weight of 1214xb, and 0.06096% by weight of water.

[0097] A 5% by mass aqueous solution of water-soluble processing oil Unisoluble EM (manufactured by JX Nippon Oil & Energy) was applied to a SUS316 test piece having a width of 15 mm, a length of 30 mm, and a thickness of 2 mm. The test piece was immersed in the above three-component composition and ultrasonically cleaned for 2 minutes at 25°C using an ultrasonic oscillator (Neosonic manufactured by Alex Corporation, output 100 W, frequency 28 kHz. The same applies below). The test piece was removed and dried for 5 minutes at 80°C, and the surface of the test piece was visually observed. As a result, neither stains nor water drop points were confirmed, and it was found that the three-component composition exhibited good cleaning and draining properties. When a similar experiment was performed using the above four-component composition, the same results were obtained, and neither stains nor water drop points were confirmed, confirming that the four-component composition exhibited good cleaning and draining properties.

[0098] A similar experiment was carried out using oil as the contaminant. That is, the dry mass of a glass rod (diameter 7.2 mm, length 4 cm) was measured, and then it was immersed in the oil shown in Table 10 for 2 minutes. After that, the mass of the glass rod removed from the oil was measured, and the amount of oil attached to the surface of the glass rod was calculated. Cleaning was carried out by immersing the glass rod in a three-component composition or a four-component composition, and irradiating it with ultrasonic waves at 25°C for 2 minutes using an ultrasonic oscillator. After drying the glass rod after cleaning, it was visually observed with a magnifying glass and its mass was measured, and the mass of the oil remaining on the glass rod was calculated from the difference with the dry mass. The oil removal rate was calculated based on the following formula. Oil removal rate (%)= (Mass of remaining oil / Amount of oil attached to the surface of the glass rod) x 100

[0099] [Table 10]

[0100] As a result, the oil removal rate was nearly 100% for all oils listed in Table 10, and no residual oil was observed under a magnifying glass. This indicates that the multi-component composition according to one embodiment of the present invention exhibits good properties as a cleaning agent.

Claims

1. A composition comprising Z-1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3,3-tetrafluoropropane, water, and an additive; the additives are selected from lubricants, stabilizers, flame retardants, surfactants, metal passivators, propellant gases, film-forming components, and organic solvents other than Z-1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3,3-tetrafluoropropane, and dichlorotetrafluoropropene; When the additive is the lubricant, the stabilizer, the flame retardant, the surfactant, or the metal passivator, the amount of the additive is 0.01% by mass to 20% by mass based on the total amount of Z-1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3,3-tetrafluoropropane, and water; When the additive is the organic solvent, the amount of the additive is 0.01% by mass to 50% by mass based on the total amount of the additive; When the additive is the propellant gas, the volume ratio of the total amount to the additive is 0.01:99.99 to 99.99:0.01; When the additive is a coating film forming component, the additive is contained in the composition in an amount of 0.1% by mass or more and 20% by mass or less, The ratio of Z-1-chloro-3,3,3-trifluoropropene to the total amount is 55.00% by mass to 99.97% by mass, the ratio of 1-chloro-1,3,3,3-tetrafluoropropane is 0.01% by mass to 44.99% by mass, and the ratio of water is 0.02% by mass to 10.00% by mass.

2. The ratio of Z-1-chloro-3,3,3-trifluoropropene is 60.00% by mass to 99.97% by mass, the ratio of 1-chloro-1,3,3,3-tetrafluoropropane is 0.01% by mass to 39.98% by mass, and the ratio of water is 0.02% by mass to 5.00% by mass, based on the total amount. The composition according to claim 1.

3. The ratio of Z-1-chloro-3,3,3-trifluoropropene is 85.00% by mass to 99.97% by mass, the ratio of 1-chloro-1,3,3,3-tetrafluoropropane is 0.01% by mass to 14.98% by mass, and the ratio of water is 0.02% by mass to 2.00% by mass, based on the total amount. The composition according to claim 1.

4. The composition described in claim 1, wherein the proportion of Z-1-chloro-3,3,3-trifluoropropene relative to the total amount is 99.92 mass% or less, and the proportion of water is 0.06 mass% or more.

5. Z-1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3,3-tetrafluoropropane, dichlorotetrafluoropropene, water, and additives; the additives are selected from lubricants, stabilizers, flame retardants, surfactants, metal passivators, propellant gases, film-forming components, and organic solvents other than Z-1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3,3-tetrafluoropropane, and dichlorotetrafluoropropene; When the additive is the lubricant, the stabilizer, the flame retardant, the surfactant, or the metal passivator, the amount of the additive is 0.01% by mass to 20% by mass based on the total amount of Z-1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3,3-tetrafluoropropane, and water; When the additive is the organic solvent, the amount of the additive is 0.01% by mass to 50% by mass based on the total amount of the additive; When the additive is the propellant gas, the volume ratio of the total amount to the additive is 0.01:99.99 to 99.99:0.01; When the additive is a coating film forming component, the additive is contained in the composition in an amount of 0.1% by mass or more and 20% by mass or less, A composition, wherein the proportion of Z-1-chloro-3,3,3-trifluoropropene is 55.00000 mass% to 99.98989 mass%, the proportion of 1-chloro-1,3,3,3-tetrafluoropropane is 0.00010 mass% to 44.98999 mass%, the proportion of dichlorotetrafluoropropene is 0.00001 mass% to 5.00000 mass%, and the proportion of water is 0.01000 mass% to 10.00000 mass%, based on the total amount of Z-1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3,3-tetrafluoropropane, dichlorotetrafluoropropene, and water.

6. The ratio of Z-1-chloro-3,3,3-trifluoropropene is 60.00000% by mass to 99.98989% by mass, the ratio of 1-chloro-1,3,3,3-tetrafluoropropane is 0.00010% by mass to 39.98999% by mass, the ratio of dichlorotetrafluoropropene is 0.00001% by mass to 5.00000% by mass, and the ratio of water is 0.01000% by mass to 5.00000% by mass, based on the total amount. The composition according to claim 5.

7. The ratio of Z-1-chloro-3,3,3-trifluoropropene is 85.00000% by mass to 99.98989% by mass, the ratio of 1-chloro-1,3,3,3-tetrafluoropropane is 0.00010% by mass to 14.98999% by mass, the ratio of dichlorotetrafluoropropene is 0.00001% by mass to 5.00000% by mass, and the ratio of water is 0.01000% by mass to 2.00000% by mass, based on the total amount. The composition according to claim 5.

8. The composition of claim 5, wherein the dichlorotetrafluoropropene is 1,2-dichloro-1,3,3,3-tetrafluoropropene.

9. The composition of claim 1, wherein Z-1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3,3-tetrafluoropropane, and water in the composition comprise an azeotrope-like composition.

10. The composition of claim 5, wherein Z-1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3,3-tetrafluoropropane, dichlorotetrafluoropropene, and water in the composition constitute an azeotrope-like composition.

11. The composition described in claim 1 or 5, wherein the propellant gas is selected from carbon dioxide gas, nitrogen gas, and air.

12. The composition of claim 1 or 5, wherein the lubricant is selected from mineral oils and synthetic oils.

13. The composition according to claim 1 or 5, wherein the coating film forming component is selected from the group consisting of silicone oil, polytetrafluoroethylene powder, and fluorine-based grease.

14. A method for forming a coating on a surface of an article, comprising applying to the surface of the article a composition according to claim 1 or 5, wherein the additive is a coating-forming component.

15. A solvent, cleaning agent, draining agent, aerosol composition, foaming agent, or heat transfer medium comprising the composition of claim 1 or 5.

16. A high-temperature heat pump cycle system or a refrigeration cycle system using the heat transfer medium according to claim 15.

17. A method for cleaning an article, comprising contacting the article to be cleaned with the composition of claim 1 or 5.

18. The composition of claim 1 or 5, further comprising a contaminant.

19. The composition of claim 18, wherein the contaminants are selected from oils, greases, waxes, inks, and inorganic salts.