Azeotrope-like composition, aerosol composition, cleaning agent, lubricant solution, heat transfer medium, preparation method of composition, composition, cleaning method, and recovery method

Abstract

The invention provides an azeotrope-like composition containing (Z)-1-chloro-3, 3, 3-trifluoropropene and 1, 1, 1, 3, 3, 3-hexafluoroisopropyl methyl ether, an aerosol composition containing the azeotrope-like composition, a cleaning agent, a lubricant solution, a heat transfer medium, a preparation method of the composition, the composition, a cleaning method using the cleaning agent and a recovery method.

Description

Technical Field

[0001] This application relates to an azeotropic composition that has minimal impact on the Earth's environment and whose composition does not easily change even after repeated evaporation and condensation, as well as an aerosol composition containing the composition, a cleaning agent, a lubricant solution, a heat transfer medium, a method for preparing the composition, the composition, a cleaning method using the cleaning agent, and a method for recovering the cleaning agent. Background Technology

[0002] Previously, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs) were considered non-flammable and, due to their excellent stability and drying properties, were used in various applications such as cleaning agents, solvents, heat transfer media, foaming agents, and fire extinguishing agents. However, concerns have arisen regarding the impact of CFCs, HCFCs, and HFCs on the ozone layer and global warming.

[0003] Fluoroolefins have been proposed as alternatives to CFCs, HCFCs, and HFCs. Because fluoroolefins have carbon-carbon double bonds in their molecules, they have a shorter atmospheric lifetime and a smaller impact on the Earth's environment.

[0004] However, when fluoroolefins are used alone for the aforementioned applications, the required performance is sometimes not fully achieved. To address this issue, the combination of other components with fluoroolefins has been investigated, depending on the intended purpose.

[0005] For example, Patent Document 1 proposes a composition comprising monochlorotrifluoropropylene (HCFO-1233) and additional ingredients.

[0006] Furthermore, Patent Document 2 specifically discloses a composition comprising 40 to 70% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 30 to 60% by mass of 1,1,1,3,3,3-hexafluoroisopropylmethyl ether.

[0007] Existing technical documents Patent documents Patent Document 1: International Publication No. 2011 / 031697 Patent Document 2: Japanese Patent Application Publication No. 2020-132688 Summary of the Invention

[0008] (a) Technical problems to be solved However, when multiple components are used in combination, the composition may change during use due to the different boiling points of each component, thus failing to exhibit full performance.

[0009] The purpose of this application is to provide an azeotropic composition that has little impact on the Earth's environment and whose composition does not easily change even after repeated evaporation and condensation.

[0010] Furthermore, the purpose of this application is to provide an aerosol composition comprising an azeotropic composition, a cleaning agent, a lubricant solution, a heat transfer medium, and a method for preparing the composition, the composition, a cleaning method using the cleaning agent, and a recycling method.

[0011] (II) Technical Solution The inventors of this application conducted careful research and discovered that the above-mentioned technical problems can be solved by the following method.

[0012] [1] An azeotropic composition containing (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropylmethyl ether.

[0013] [2] The azeotropic composition according to [1] is composed of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropylmethyl ether.

[0014] [3] The azeotropic composition according to [1] or [2] comprises 70.01 to 99.99% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 0.01 to 29.99% by mass of 1,1,1,3,3,3-hexafluoroisopropylmethyl ether, or comprises 0.01 to 28.00% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 72.00 to 99.99% by mass of 1,1,1,3,3,3-hexafluoroisopropylmethyl ether.

[0015] [4] An azeotropic composition according to any one of [1] to [3], comprising 70.01 to 99.99% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 0.01 to 29.99% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether in total amount relative to (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

[0016] [5] An azeotropic composition according to any one of [1] to [3], comprising 0.01 to 28.00% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 72.00 to 99.99% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether in total amount relative to (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

[0017] [6] An azeotropic composition according to any one of [1] to [5], wherein the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropylmethyl ether is 80% by mass or more relative to the total amount of the composition.

[0018] [7] An azeotropic composition according to any one of [1] and [3] to [6], wherein the azeotropic composition further comprises water.

[0019] [8] According to the azeotropic composition of [7], wherein the azeotropic composition contains water in an amount of 0.0001 to 1.00% by mass relative to the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropylmethyl ether.

[0020] [9] An azeotropic composition according to [7] or [8], wherein the azeotropic composition comprises (Z)-1-chloro-3,3,3-trifluoropropene, 1,1,1,3,3,3-hexafluoroisopropylmethyl ether, and water.

[0021]

[10] A method for preparing a composition, comprising: A process for preparing an azeotropic composition containing (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropylmethyl ether; and The step of adding at least one selected from the group consisting of stabilizers, surfactants, flame retardants, metal passivators and rust inhibitors to the azeotropic composition.

[0022]

[11] A composition comprising any one of the azeotropic compositions described in [1] to [9] and at least one selected from the group consisting of stabilizers, surfactants, flame retardants, metal passivators and rust inhibitors.

[0023]

[12] An aerosol composition comprising any one of [1] to [9] an azeotropic composition and a jet gas.

[0024]

[13] A cleaning agent comprising any one of the azeotropic compositions described in any one of [1] to [9].

[0025]

[14] A cleaning agent comprising the aerosol composition described in

[12] .

[0026]

[15] The cleaning agent according to

[13] or

[14] is used to clean vehicles or to clean vehicles used for transportation.

[0027]

[16] A method for cleaning an article, comprising the step of bringing the cleaning agent described in

[13] or

[14] into contact with the article to be cleaned.

[0028]

[17] A method for recovering a cleaning agent, comprising: The process of cleaning articles using the cleaning agent described in

[13] or

[14] ; and The process of purifying the cleaning agent after cleaning.

[0029]

[18] A lubricant solution comprising any one of [1] to [9] an azeotropic composition and a lubricant.

[0030]

[19] A heat transfer medium comprising any one of [1] to [9] an azeotropic composition or

[12] an aerosol composition.

[0031] (III) Beneficial Effects This application provides an azeotropic composition that has minimal impact on the Earth's environment and whose composition does not easily change even after repeated evaporation and condensation.

[0032] Furthermore, this application can provide an aerosol composition comprising an azeotropic composition, a cleaning agent, a lubricant solution, a heat transfer medium, and a method for preparing the composition, the composition, a cleaning method using the cleaning agent, and a recovery method. Detailed Implementation

[0033] In this specification, for halogenated hydrocarbons, the abbreviation of the compound is indicated in parentheses after the compound name, and this abbreviation will be used in place of the compound name as needed. Additionally, sometimes only the number and lowercase Arabic numerals following the hyphen (-) are used as the abbreviation (e.g., "1233zd" in "HCFO-1233zd"). Furthermore, for compounds with geometric isomers, (E) indicates the E-isomer, and (Z) indicates the Z-isomer (e.g., "HCFO-1233zd(Z)" or "1233zd(Z)" in "(Z)-1-chloro-3,3,3-trifluoropropene"). Where the E-isomer and Z-isomer are not explicitly indicated in the compound name or abbreviation, the name or abbreviation refers to the collective term encompassing the E-isomer, Z-isomer, and mixtures of the E-isomer and Z-isomer.

[0034] In this specification, compounds in which a portion of the hydrogen atoms of a saturated hydrocarbon are replaced with fluorine atoms are called hydrofluorocarbons (HFCs); compounds in which a portion of the hydrogen atoms of a saturated hydrocarbon are replaced with fluorine and chlorine atoms are called hydrochlorofluorocarbons (HCFCs); compounds in which all the hydrogen atoms of a saturated hydrocarbon are replaced with fluorine and chlorine atoms are called chlorofluorocarbons (CFCs); compounds having carbon-carbon double bonds and composed of carbon atoms, fluorine atoms, and hydrogen atoms are called hydrofluoroolefins (HFOs); and compounds having carbon-carbon double bonds and composed of carbon atoms, chlorine atoms, fluorine atoms, and hydrogen atoms are called hydrochlorofluoroolefins (HCFOs).

[0035] In this specification, the numerical range represented by "~" refers to the range encompassed by the values ​​recorded before and after "~" as the lower and upper limits.

[0036] [Azeotropic or azeotropic compositions] Before describing the compositions of this application, azeotropic compositions and azeotropic-like compositions will be described.

[0037] Because fluorinated olefins have high compatibility with various solvents, homogeneous compositions can be easily formulated. However, even with such pure compositions, there is an inherent problem of "fluid composition variation." That is, even assuming that multiple liquids can be mixed and compatibility is ensured, the difference in volatility of each component makes it impossible to avoid the problem of fluid composition variation. For example, when a binary liquid composition is used as a cleaning agent in an ultrasonic cleaner, the lower-boiling-point component (component with higher vapor pressure) with higher volatility usually evaporates preferentially, while the higher-boiling-point component with lower volatility is concentrated in the cleaning tank. For example, in the case of a composition containing a lower-boiling-point component with higher cleaning power and a higher-boiling-point component with lower cleaning power, the concentration of the lower-boiling-point component in the cleaning solution decreases over time, which may lead to poor cleaning. Especially when a non-flammable composition is formulated by blending a non-flammable solvent into a flammable solvent, the cleaning solution may sometimes become a flammable composition if the non-flammable component evaporates preferentially.

[0038] Furthermore, although it is ideal to recover and reuse cleaning solvents after use through distillation and other operations, both from an environmental protection and economic perspective, in the case of a two-component liquid system, it is usually necessary to recover the two components with different boiling points separately, which can easily increase the operational burden in terms of recovery and reuse.

[0039] The same problem exists with working fluids used in thermodynamic cycles. That is, over a long period, the liquid composition can change when used as a working fluid in a thermodynamic cycle. If the liquid composition changes, the liquid's heat capacity, viscosity, or affinity for lubricants will change, and the performance of the thermodynamic cycle may sometimes decrease.

[0040] Therefore, when using binary (or multi-component) liquid compositions as cleaning agents or working fluids, it is necessary to frequently analyze the liquid composition, continuously adjust the appropriate ratios to maintain it within the suitable composition range, and replenish volatile components. However, such liquid composition management can constitute a significant operational burden.

[0041] In contrast, in the case of an azeotropic composition, since it evaporates with the same composition as the liquid, the liquid phase composition does not change during use, making it a highly preferred composition. In this specification, "azeotrope" refers to the thermodynamically defined azeotrope. For example, in the case of a water / ethanol mixture, a composition of ethanol (96% by mass) and water (4% by mass) is an azeotrope, and the vapor present in vapor-liquid equilibrium with this composition is also "ethanol (96% by mass): water (4% by mass)," completely consistent with the liquid composition. This phenomenon is called "azeotrope." At a specific temperature and pressure, the composition of an azeotropic composition is unique.

[0042] "Azeotropic-like" is also known as "pseudo-azeotropic." Although it is not a strictly thermodynamically defined azeotrope, for a certain range of liquid compositions, its liquid composition is substantially equal to its gaseous composition in equilibrium. "Azeotropic-like" refers to this phenomenon. Even if the compositions of the gas and liquid phases are not completely identical, if the compositions of the gas and liquid phases are substantially identical, those skilled in the art can operate in the same way as with azeotropic compositions. In this case, the smaller the difference in gas-liquid equilibrium composition between the gas and liquid phases, the better. For example, in a binary system composition, it is preferable that the difference in composition between the gas and liquid phases of one component is 8.00% by mass or less, more preferably 7.00% by mass or less, and particularly preferably 4.00% by mass or less. Therefore, the phenomenon where the gas-liquid equilibrium compositions of the gas and liquid phases are substantially identical is called azeotropic-like or pseudo-azeotropic, and this composition is called an azeotropic composition or pseudo-azeotropic composition. Furthermore, a composition having an azeotropic composition (or pseudo-azeotropic composition) is called an azeotropic composition (or pseudo-azeotropic composition).

[0043] "The gas-liquid equilibrium composition of the gas phase and the liquid phase need to be substantially the same" means that the difference in gas-liquid equilibrium composition between the gas phase and the liquid phase is small. In the case that the composition of this application is a binary system (or a ternary system or more), it means that the composition difference between the gas phase and the liquid phase of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropylmethyl ether contained in the composition of this application is 8.00% by mass or less, and preferably 7.00% by mass or less, and more preferably 4.00% by mass or less.

[0044] "Azeotropic-like composition" is not derived through theoretical deduction, but rather is determined by experimentally exploring the gas-liquid equilibrium of various liquids with different types and composition ratios. It can only be discovered when the composition of the gas phase and the composition of the liquid phase accidentally reach a substantial consistency. In this invention, when conducting gas-liquid equilibrium experiments on a mixture of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropylmethyl ether, it is possible to discover that the gas and liquid phases have substantially the same azeotropic composition.

[0045] Specifically, the gas-liquid balance experiment was conducted based on the <Determination of Gas-Liquid Balance> described in the examples.

[0046] [Composition] The composition of this application is an azeotropic composition containing 1,1,1,3,3,3-hexafluoroisopropylmethyl ether (hereinafter also referred to as HFE-356mmz) and (Z)-1-chloro-3,3,3-trifluoropropene (1233zd(Z)) (also referred to as "the azeotropic composition of this application").

[0047] The composition of this application may consist only of HFE-356mmz and 1233zd(Z).

[0048] In this specification, unless otherwise specified, "the composition of this application" refers to an azeotropic composition containing 1233zd(Z) and HFE-356mmz (described later).

[0049] Specifically, the composition comprises 70.01 to 99.99% by mass of 1233zd(Z) and 0.01 to 29.99% by mass of HFE-356mmz relative to the total amount of 1233zd(Z) and HFE-356mmz contained in the composition.

[0050] Because the compositions of the gas and liquid phases of the composition of 1233zd(Z) and HFE-356mmz are similar within this composition range, compositional variations are less likely to occur. More preferably, the composition comprises 85.00–99.99% by mass of 1233zd(Z) and 0.01–15.00% by mass of HFE-356mmz relative to the total amount of 1233zd(Z) and HFE-356mmz contained in the composition. More preferably, the composition comprises 90.00–99.99% by mass of 1233zd(Z) and 0.01–10.00% by mass of HFE-356mmz relative to the total amount of 1233zd(Z) and HFE-356mmz contained in the composition. Within this composition range, because the compositions of the gas and liquid phases are further similar, compositional variations are less likely to occur.

[0051] In addition, specifically, the composition comprises 0.01 to 28.00% by mass of 1233zd(Z) and 72.00 to 99.99% by mass of HFE-356mmz relative to the total amount of 1233zd(Z) and HFE-356mmz contained in the composition.

[0052] Because the compositions of the gas and liquid phases of the composition of 1233zd(Z) and HFE-356mmz are similar within this composition range, compositional variations are less likely to occur. More preferably, the composition comprises 0.01 to 15.00% by mass of 1233zd(Z) and 85.00 to 99.99% by mass of HFE-356mmz relative to the total amount of 1233zd(Z) and HFE-356mmz contained in the composition. More preferably, the composition comprises 0.01 to 11.00% by mass of 1233zd(Z) and 89.00 to 99.99% by mass of HFE-356mmz relative to the total amount of 1233zd(Z) and HFE-356mmz contained in the composition. Within this composition range, because the compositions of the gas and liquid phases are further similar, compositional variations are less likely to occur.

[0053] Relative to the total amount of the composition, the total amount of 1233zd(Z) and HFE-356mmz in the composition of this application is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. The composition of this application may substantially consist only of 1233zd(Z) and HFE-356mmz.

[0054] The statement "The composition of this application is substantially composed only of 1233zd(Z) and HFE-356mmz" indicates that in the composition of this application, the total amount of 1233zd(Z) and HFE-356mmz is 98% by mass or more relative to the total amount of the composition. Furthermore, as a preferred embodiment, the composition of this application preferably consists only of 1233zd(Z) and HFE-356mmz.

[0055] By including at least 80% by mass of 1233zd(Z) and HFE-356mmz in the composition of this application, the composition has a minimal impact on the global environment, and its composition remains largely unchanged even under repeated evaporation and condensation, allowing for operation substantially the same as the aforementioned azeotropic compositions. Therefore, when using the composition of this application in various applications such as cleaning agents, solvents, aerosols, and heat transfer media, it offers advantages such as the ability to obtain the same stable properties as the aforementioned azeotropic compositions.

[0056] [1233zd(Z)] Because 1233zd(Z) is an olefin with carbon-carbon double bonds, it has a short atmospheric lifetime and a small ozone depletion coefficient or global warming coefficient.

[0057] 1233zd(Z) has a boiling point of 39°C, making it suitable for use even in components susceptible to heat. Furthermore, due to its lack of a flash point, excellent drying properties, and low surface tension and viscosity, 1233zd(Z) exhibits excellent properties as a cleaning agent or solvent, including superior penetration.

[0058] Furthermore, due to the low viscosity of 1233zd(Z), it exhibits low resistance when passing through piping, excellent transport characteristics, and superior performance as a heat transfer medium.

[0059] 1233zd(Z) can be prepared, for example, according to the description in Japanese Patent Application Publication No. 2017-110020.

[0060] By including the above-mentioned amount of 1233zd(Z), the compositions of this application have a small impact on the Earth's environment and can exhibit performance suitable for various applications such as cleaning agents, solvents, aerosols, and heat transfer media.

[0061] [1,1,1,3,3,3-Hexafluoroisopropylmethyl ether] 1,1,1,3,3,3-Hexafluoroisopropylmethyl ether (HFE-356mmz) has a boiling point of approximately 51°C and can be used even in components susceptible to heat.

[0062] Furthermore, due to its excellent drying properties and low surface tension or viscosity, HFE-356mmz possesses excellent properties as a cleaning agent or solvent, such as excellent penetration.

[0063] Furthermore, due to the low viscosity of HFE-356mmz, it exhibits low resistance when passing through piping, excellent transport characteristics, and superior performance as a heat transfer medium.

[0064] In addition, HFE-356mmz has little effect on resin materials such as acrylonitrile-butadiene-styrene copolymer (hereinafter also known as ABS resin), polycarbonate (PC), and polystyrene resin (PS).

[0065] HFE-356mmz is a known compound, which can be obtained, for example, in the presence of a base by the reaction of 1,1,1,3,3,3-hexafluoroisopropanol with dimethylsulfuric acid (US Patent No. 3,346,448).

[0066] By including the aforementioned amount of HFE-356mmz, the composition of this application exhibits excellent various properties such as cleaning properties, solubility, and transport characteristics. Furthermore, although 1233zd(Z) may sometimes cause strong chemical erosion (corrosion) to resins when used alone, the simultaneous use of HFE-356mmz can reduce chemical erosion.

[0067] The compositions of this application may contain water. Even if water is contained, the compositions of this application are still capable of forming azeotropic-like compositions.

[0068] The water content is not particularly limited, but is preferably 0.0001 to 1.00% by mass relative to the total amount of 1233zd(Z) and HFE-356mmz, more preferably 0.0001 to 0.5% by mass, and even more preferably 0.0001 to 0.1% by mass.

[0069] By containing water, it has the effect of improving the cleaning performance of water-soluble processing oils.

[0070] As a preferred embodiment, the composition of this application is preferably an azeotropic composition consisting of (Z)-1-chloro-3,3,3-trifluoropropene, 1,1,1,3,3,3-hexafluoroisopropylmethyl ether, and water.

[0071] The compositions of this application may further contain other ingredients.

[0072] Other components may include, for example, hydrocarbons, alcohols, ketones, non-fluorinated ethers, esters, chlorinated hydrocarbons, HFCs, HFEs, etc., which are raw materials or byproducts used in the preparation or purification process of 1233zd(Z) or HFE-356mmz.

[0073] The hydrocarbon is preferably a hydrocarbon with 5 or more carbon atoms. The hydrocarbon can be chain-like or cyclic, and can be saturated or unsaturated.

[0074] As hydrocarbons, n-pentane, cyclopentane, n-hexane, and n-heptane are preferred.

[0075] Alcohols with 1 to 16 carbon atoms are preferred. Alcohols can be chain-like or cyclic, and can be saturated or unsaturated.

[0076] The preferred alcohols are methanol, ethanol, and isopropanol.

[0077] Ketones with 3 to 9 carbon atoms are preferred. Ketones can be chain-like or cyclic, and can be saturated or unsaturated.

[0078] As a ketone, acetone or methyl ethyl ketone is preferred.

[0079] As a non-fluorinated ether, it is preferred to have 2 to 8 carbon atoms. Non-fluorinated ethers can be chain-like or cyclic, and can be saturated or unsaturated.

[0080] The preferred ethers are diethyl ether, diisopropyl ether, and tetrahydrofuran.

[0081] As an ester, esters with 2 to 19 carbon atoms are preferred. Esters can be chain-like or cyclic, and can be saturated or unsaturated.

[0082] As an ester, methyl acetate or ethyl acetate are preferred.

[0083] As a chlorinated hydrocarbon, a chlorinated hydrocarbon with 1 to 3 carbon atoms is preferred. The chlorinated hydrocarbon can be in the form of a chain or a ring; in addition, it can be a saturated chlorinated hydrocarbon or an unsaturated chlorinated hydrocarbon.

[0084] As chlorinated hydrocarbons, dichloromethane, trans-1,2-dichloroethylene, and trichloroethylene are more preferred.

[0085] HFCs are preferably chain-like or cyclic HFCs with 4 to 8 carbon atoms, and more preferably HFCs in which the number of fluorine atoms in one molecule is more than the number of hydrogen atoms.

[0086] As HFCs, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,1,2,2,3,3,4,4-nonafluorohexane, and 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane are preferred.

[0087] As HFE, preferred HFEs are those other than 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, such as 1,1,2,2-tetrafluoroethoxy-1-(2,2,2-trifluoro)ethane (CF3CH2OCF2CF2H, hereinafter also called HFE-347pc-f), methoxynonafluorobutane (C4F9OCH3, hereinafter also called HFE-449s1), ethoxynonafluorobutane (C4F9OC2H5, hereinafter also called HFE-569sf), and methoxyheptafluoropropane. (C3F7OCH3, hereinafter also known as HFE-347mcc), methoxy-2-(trifluoromethyl)-3-methoxynonafluoropentane (C2F5CF(OCH3)CF(CF3)CF3, hereinafter also known as HFE-7300), 2-(trifluoromethyl)-3-ethoxydodecylfluorohexane (C3F7CF(OC2H5)CF(CF3)CF3, hereinafter also known as HFE-7500), 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec), etc.

[0088] In addition, as raw materials or byproducts used in the preparation or purification process of 1233zd(Z) or HFE-356mmz, examples include, for instance, chlorotrifluoropropene (e.g., (E)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E), or also referred to as "1233zd(E)"), dichlorotrifluoropropene (HCFO-1223), tetrachlorofluoropropane (HCFC-244), and pentachlorofluoropropane (HCFO-1223), other than 1233zd(Z)). The following are listed as compounds: FC-235, chlorotetrafluoropropylene (HCFO-1224), dichlorotetrafluoropropylene (HCFO-1214), pentafluoropropane (HFC-245), tetrafluoropropylene (HFO-1234), trifluoropropyne, water, hexafluoropropylene, tetrafluoroethylene, 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), dimethyl ether, halomethanes, methyl p-toluenesulfonate, p-toluenesulfonic acid, p-toluenesulfonate, compounds represented by C4H3F5O, and 2,2,2-trifluoroethyl methyl ether. In the presence of geometric or positional isomers among these components, they can be a single component or a mixture of any one isomer.

[0089] The content of other components relative to the total amount of the composition is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0090] [Compositions containing azeotropic-like compositions] Furthermore, this application also relates to a composition comprising the azeotropic composition of the present application described above and at least one selected from the group consisting of stabilizers, surfactants, flame retardants, metal passivators and rust inhibitors.

[0091] When a composition comprising the azeotropic composition described above and at least one of the additives described above is used for various applications, it has the advantage of being able to obtain the same stable properties as the azeotropic composition described above.

[0092] The content of at least one component selected from stabilizers, surfactants, flame retardants, metal passivators and rust inhibitors is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 1% by mass or less, relative to the total amount of the composition.

[0093] Examples of stabilizers include nitromethane, nitrobenzene, nitrobenzene, diethylamine, triethylamine, isopropylamine, diisopropylamine, butylamine, isobutylamine, tert-butylamine, α-methylpyridine, N-methylbenzylamine, diallylamine, N-methylmorpholine, phenol, o-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, o-methoxyphenol, p-methoxyphenol, 4,4'-dihydroxyphenyl-2,2-propane isoamyl ester, benzyl salicylate, methyl salicylate, and 2,6-di-tert-butyl-p-methoxyphenol. Cresol, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 1,2,3-benzotriazole, 1-[(N,N-bis-2-ethylhexyl)aminomethyl]benzotriazole, 1,2-epoxypropane, 1,2-epoxybutane, 1,4-dioxane, butyl glycidyl ether, phenyl glycidyl ether, isopentenene, octene, 2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-pentene, 2-methylpentene, etc. Preferably, 2,6-di-tert-butyl-p-cresol, p-methoxyphenol, 1,2-epoxybutane, isopentenene, octene, 2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-pentene, and 2-methylpentene are preferred.

[0094] As a stabilizer, one or more can be used.

[0095] As surfactants, the preferred types are nonionic surfactants such as sorbitan aliphatic esters like sorbitan monooleate and sorbitan trioleate; polyoxyethylene sorbitan fatty acid esters like polyoxyethylene sorbitan tetraoleate; polyethylene glycol fatty acid esters like polyoxyethylene monolaurate; polyoxyethylene alkyl ethers like polyoxyethylene lauryl ether; polyoxyethylene alkylphenyl ethers like polyoxyethylene nonylphenyl ether; and polyoxyethylene alkylamine fatty acid amides like polyoxyethylene oleamide.

[0096] One type or more can be used as a surfactant.

[0097] As flame retardants, phosphate esters, halogenated aromatic compounds, fluorinated iodinated hydrocarbons, and fluorinated brominated hydrocarbons are preferred.

[0098] As a flame retardant, one or more can be used.

[0099] The compositions of this application, as described above, have minimal impact on the Earth's environment and are not prone to compositional changes even after repeated evaporation and condensation. They exhibit excellent performance suitable for various applications such as cleaning agents, solvents, aerosols, and heat transfer media.

[0100] The compositions of this application are preferably used as cleaning agents, solvents, aerosols, heat transfer media, fire extinguishing agents, foaming agents, etc.

[0101] Materials to which the compositions of this application are applicable include resin materials, metals, plastics, elastomers, glass, ceramics, fibers, and composite materials of these materials. Among these, suitable materials include metals such as iron, copper, nickel, gold, silver, and platinum, sintered metal bodies, glass, fluoropolymers, polyimide, polyphenylene sulfide, liquid crystal polymers, and engineering plastics such as PEEK.

[0102] (Preparation method of the composition) This application also relates to a method for preparing a composition, comprising: A process for preparing an azeotropic composition containing (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropylmethyl ether; and The step of adding at least one selected from the group consisting of stabilizers, surfactants, flame retardants, metal passivators and rust inhibitors to the azeotropic composition.

[0103] The stabilizers, surfactants, flame retardants, metal passivators, and rust inhibitors mentioned above can be listed as stabilizers, surfactants, flame retardants, metal passivators, and rust inhibitors.

[0104] The content of the component selected from at least one of stabilizers, surfactants, flame retardants, metal passivators and rust inhibitors relative to the total amount of the composition is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 1% by mass or less.

[0105] [Aerosols and aerosol compositions] The composition of this application can be used as an aerosol by combining it with a jet gas. This application also relates to an aerosol composition comprising the above-described composition of this application and a jet gas. The jet gas used in this application is preferably at a pressure of atmospheric pressure (1.013 × 10⁻⁶) at 0°C. 5 Pa) or above.

[0106] Liquefied or compressed gases can be used as the jet gas. Examples include dimethyl ether (DME), propane, butane, isobutane, 1,1-difluoroethane (HFC-152a), 1,1,1,2-tetrafluoroethane (HFC-134a), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), nitrogen, carbon dioxide, nitrous oxide, and trifluoroiodomethane. One gas can be used alone or in combination with two or more gases. For example, air can be used appropriately.

[0107] The jet gas can be either liquefied gas or compressed gas, or a combination of liquefied gas and compressed gas.

[0108] The aerosol of this application is filled with the composition of this application and the jet gas. The composition of this application can be filled into a container together with the jet gas, or it can be filled into a container separately from the jet gas. The internal pressure of the jet gas contained in the aerosol when sealed in the sprayer is preferably 0.2~1MPa at 35°C.

[0109] The aerosol may be further filled with a solute. The solute may be dissolved in the composition of this application and filled into the aerosol, or it may be filled into the container separately from the composition of this application and the jet gas. Examples of solutes include surface treatment agents such as lubricants, rust inhibitors, moisture-proof coating agents, and antifouling coating agents.

[0110] When filling the solute, for example, relative to the total of the composition and the solute of this application, it is preferable to fill in such a way that the concentration of the solute is 0.01 to 50 by mass.

[0111] The aerosol of this application may contain stabilizers, other solvents, etc., as needed. Specific examples of stabilizers include the stabilizers described above. Other solvents include the solvent (A) described below.

[0112] Relative to the total composition and stabilizer of this application, the stabilizer content in the aerosol of this application is preferably 5% by mass or less, more preferably 1% by mass or less.

[0113] The proportion of other solvents in the aerosol of this application is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, relative to the total of the composition of this application and other solvents.

[0114] [Cleaning agent] The composition of this application exhibits excellent cleaning properties and can therefore be used as a cleaning agent for degreasing, flux cleaning, precision cleaning, dehydration cleaning, rinsing, dry cleaning, etc. It is preferable to use the aforementioned aerosol composition instead of the composition of this application.

[0115] This application also relates to a cleaning agent comprising the composition or aerosol composition described above.

[0116] Articles to which the cleaning agent of this application is applicable include optical components, medical devices, electrical machinery, precision machinery, fiber products, and components thereof. Examples of electrical machinery, precision machinery, optical articles, and components thereof include ICs, capacitors, printed circuit boards, micro motors, relays, bearings, optical lenses, and glass substrates. Examples of medical devices include catheters and injection needles.

[0117] Furthermore, the cleaning agent of this application can also be applied to various components such as brakes, wheels, and suspensions in various vehicles and transportation mechanisms, including automobiles, bicycles, construction machinery, airplanes, and rail vehicles, and can be used as a so-called brake cleaner or parts cleaner. That is, the cleaning agent of this application is also preferably used for cleaning vehicles or transportation mechanisms.

[0118] There are no particular limitations on the cleaning method, but as a method for cleaning articles, the following methods are applicable: contacting the cleaning agent of this application with the article to remove dirt adhering to it. This application also relates to a method for cleaning articles, which includes the step of contacting the cleaning agent of this application with the article to be cleaned.

[0119] Examples of methods include immersing the items to be cleaned in the cleaning agent of this application to remove dirt, wiping with a cloth, and spray cleaning, and these methods can also be used in combination. A particularly preferred method is to add the cleaning agent of this application into an ultrasonic cleaner, immerse the items to be cleaned in the liquid, and perform ultrasonic cleaning. In addition, spray cleaning, such as spraying a cleaning agent containing the above-described aerosol composition onto various items to be cleaned, is also a preferred method.

[0120] In open systems, it is assumed that the composition slowly incorporates water. The azeotropic compositions of this application still exhibit azeotropic properties even when water is present, thus achieving the aforementioned effects.

[0121] Examples of dirt adhering to objects include lubricating grease, processing oil, silicone oil, flux, wax, ink, mineral oil, release agents containing silicone oil, asphalt, tar and other greases, and dust. Examples of processing oils include cutting oil, quenching oil, rolling oil, lubricating oil, machine oil, stamping oil, blanking oil, drawing oil, assembly oil, and wire drawing oil.

[0122] The cleaning agent of this application has excellent cleaning properties, and is therefore particularly suitable for cleaning processing oils, asphalt, and tar.

[0123] In the above cleaning method, the contact time with the item, temperature, and other cleaning conditions can be appropriately selected according to the cleaning method. Furthermore, known cleaning devices can also be appropriately selected. The method and cleaning apparatus described in, for example, International Publication No. 2008 / 149907 can be used to implement the method.

[0124] As mentioned above, azeotropic compositions exhibit minimal compositional changes even when used in open systems. Therefore, cleaning agents using compositions of this application containing such azeotropic compositions can maintain stable cleaning power even without frequent composition management. This is a significant practical advantage.

[0125] The cleaning agent can be recycled through the following process.

[0126] There are no particular limitations on the method of recycling the cleaning agent, which includes the following steps: cleaning articles with the cleaning agent of this application; and purifying the cleaning agent after cleaning.

[0127] There are no particular limitations on the method of cleaning articles using the cleaning agent of this application. As mentioned above, there are methods such as: bringing the cleaning agent of this application into contact with the article to be cleaned and removing dirt attached to the article.

[0128] There are no particular limitations on the method for purifying the cleaning agent after cleaning; for example, the following distillation operation can be listed.

[0129] If distillation is performed, grease or foreign matter (particulate matter) can be separated and removed, and the cleaning agent of this application (as an example, an azeotropic composition constituting the cleaning agent) can be recovered. Since the distillation regeneration apparatus used for conventional cleaning agents is a single-stage distillation apparatus, the azeotropic composition composed of 1233zd(Z) and HFE-356mmz can be regenerated using a commercially available distillation regeneration apparatus in a manner with substantially no change in composition. This is particularly advantageous for azeotropic compositions, as their composition remains unchanged even when using a distillation column with a high theoretical plate number.

[0130] During distillation, the two liquid components, 1233zd(Z) and HFE-356mmz, maintain their azeotropic properties, allowing the recovered liquid to be reused as a cleaning solvent without extensive composition adjustments. Furthermore, when the aforementioned "other components" are used in the compositions of this application, since these "other components" may be removed during distillation, it is preferable to replenish them.

[0131] One of the substances removed (or reduced) by the cleaning agent is water. This method of removing (or reducing) water is also called dehydration cleaning.

[0132] The method for dehydration and cleaning is not particularly limited, and existing known methods can be used. For example, methods that involve contacting the article to be dehydrated with the composition of this application and then drying it can be listed. As mentioned above, it is also preferable to use the above-described aerosol composition instead of the composition of this application.

[0133] Furthermore, as a preferred embodiment, the cleaning agent can also be used as a rinsing agent to remove the high-boiling-point cleaning agent adhering to the article after the cleaning process based on the high-boiling-point cleaning agent. In this case, the cleaning agent is preferably a rinsing agent.

[0134] The composition of this application is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, relative to the total amount of the cleaning agent. An upper limit of 100% by mass can be listed.

[0135] When the cleaning agent contains an aerosol composition, it is preferable that the composition of this application contains, relative to the total amount of the cleaning agent components after the jet gas has been removed, within the range described above.

[0136] The cleaning agent of this application may include stabilizers, etc., as needed. The stabilizers described above may be used.

[0137] The stabilizer content in the cleaning agent of this application is preferably 5% by mass or less, and more preferably 1% by mass or less, relative to the total amount of the cleaning agent.

[0138] The cleaning agent of this application may contain other solvents (hereinafter also referred to as solvent (A)) as needed. Solvent (A) may be appropriately selected for various purposes such as improving solubility and adjusting evaporation rate. Examples of solvent (A) include hydrocarbons, alcohols, ketones, non-fluorinated ethers, esters, chlorinated hydrocarbons, HFCs, HFEs, etc. Relative to the total amount of the cleaning agent, the content of solvent (A) in the cleaning agent of this application is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 1% by mass or less.

[0139] The above-mentioned compounds can be used for hydrocarbons, alcohols, ketones, non-fluorinated ethers, esters, chlorinated hydrocarbons, HFCs, and HFEs.

[0140] Solvent (A) can be one or more. Furthermore, when two or more solvents (A) are included, the combination can be a combination of solvents from the same category or a combination of solvents from different categories. For example, it can be a combination of two components selected from hydrocarbons, or a combination of one component selected from hydrocarbons and one component selected from alcohols.

[0141] Solvent (A) is further preferably a solvent without a flash point. Examples of organic solvents without a flash point include HFCs such as 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,1,2,2,3,3,4,4-nonafluorohexane, and 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecylfluorohexane, and HFEs such as 1,1,2,2-tetrafluoroethoxy-1-(2,2,2-trifluoro)ethane, methoxynonafluorobutane, ethoxynonafluorobutane, methoxyheptafluoropropane, methoxy, 2-(trifluoromethyl)-3-methoxynonafluoropentane, and 2-(trifluoromethyl)-3-ethoxydodecylfluorohexane. When using a solvent with a flash point as solvent (A), it is preferable to use it as a cleaning agent within the range of solvents without a flash point.

[0142] [Dehydrating agent, rinsing agent] The composition of this application can be used as a dehydrating agent. In various industrial fields such as automotive, machinery, precision machinery, electrical, electronic, and optical manufacturing, articles are sometimes cleaned using water such as pure water, or using aqueous cleaning agents, quasi-aqueous cleaning agents (containing water-soluble solvents), alcohol-based cleaning agents, alcohol-ether-based cleaning agents, or hydrocarbon-based cleaning agents (containing surfactants). When using aqueous or quasi-aqueous cleaning agents, the cleaned articles are usually in a state with water adhering to them. After the cleaning process, a dehydration process using a dehydrating agent is usually performed to remove the water. The composition of this application is suitable for use as a dehydrating agent in such a dehydration process. Similarly, the composition of this application is suitable for use as a rinsing agent to remove the high-boiling-point cleaning agent adhering to articles after a cleaning process based on a high-boiling-point cleaning agent. It is also preferable to use the aforementioned aerosol composition instead of the composition of this application.

[0143] This application also relates to a dehydrating agent comprising the composition or aerosol composition described above.

[0144] Besides using the composition of this application as a dehydrating agent, the dehydration method is not particularly limited, and existing known methods can be used. For example, methods that involve contacting the article to be dehydrated with the composition of this application and then drying it can be listed.

[0145] In various embodiments, the composition of this application exhibits both cleaning and dehydrating effects, thus enabling the cleaning and dehydration processes to be performed simultaneously. That is, by performing the cleaning process, both dirt and moisture adhering to the cleaned object can be removed. Therefore, it is not necessary to distinguish between the cleaning agent and the dehydrating agent used in the cleaning and dehydration processes, making it more suitable for production. Furthermore, the above does not preclude the separate use of cleaning agents and dehydrating agents in the cleaning and dehydration processes; the composition of this application can be used as a cleaning agent and / or a dehydrating agent in each process as needed. In several embodiments, the composition of this application is suitable for cleaning articles (cleaned articles) to which moisture-containing dirt (e.g., water-soluble oil) adheres. By using the composition of this application, dirt and moisture adhering to the cleaned article can be removed simultaneously.

[0146] The composition of this application is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, relative to the total amount of the dehydrating agent or rinsing agent. An upper limit of 100% by mass can be listed.

[0147] When the dehydrating agent or rinsing agent contains an aerosol composition, the composition of this application is preferably set within the range described above relative to the total amount of the dehydrating agent or rinsing agent components excluding the jet gas.

[0148] The dehydrating agent or rinsing agent of this application may include stabilizers, other solvents, etc., as needed. Specific examples of stabilizers include the stabilizers described above. Other solvents include the solvent (A) described above.

[0149] The proportion of stabilizer in the dehydrating agent or rinsing agent of this application is preferably 5% by mass or less, more preferably 1% by mass or less, relative to the total amount of the dehydrating agent or rinsing agent.

[0150] The proportion of other solvents in the dehydrating agent or rinsing agent of this application is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, relative to the total amount of the dehydrating agent or rinsing agent.

[0151] [solvent] The solvents in this application include the compositions of this application.

[0152] The compositions of this application have excellent solubility for organic compounds, and therefore can be used as solvents for dissolving surface treatment agents such as lubricants, rust inhibitors, moisture-proof coating agents, and anti-fouling coating agents and applying them to the surface of articles.

[0153] As an item, for example, items that are the same as items that can be cleaned with a cleaning agent can be listed.

[0154] As a method for applying a surface treatment agent to the surface of an article, the following methods can be listed: after applying a surface treatment agent solution, which is obtained by dissolving the surface treatment agent in the solvent of this application, onto the surface of the article, the solvent is evaporated to form a coating film on the surface of the article.

[0155] When dissolving the surface treatment agent in the solvent of this application, it is preferable to dissolve it in a manner that gives the concentration of the surface treatment agent 0.01 to 50% by mass.

[0156] Examples of coating methods include brush-based coating, spray-based coating, and immersion-based coating. In the case of a tubular article, a method exists where a surface treatment agent solution obtained by dissolving the surface treatment agent in a solvent is drawn upwards and coated onto the inner wall. Furthermore, spray coating can also be performed in the form of an aerosol containing the surface treatment agent, the solvent of this application, liquefied gas, or compressed gas.

[0157] Evaporation methods for solvents include air drying and drying by heating. The preferred drying temperature is 20~100℃.

[0158] The proportion of the composition of this application in the solvent of this application is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and the upper limit can be listed as 100% by mass.

[0159] The solvent in this application may include stabilizers, other solvents, etc., as needed. Specific examples of stabilizers include the stabilizers described above. Other solvents include the solvent (A) described above.

[0160] The proportion of stabilizer in the solvent of this application is preferably 5% by mass or less, more preferably 1% by mass or less, relative to the total amount of solvent.

[0161] The proportion of other solvents in the solvent of this application is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, relative to the total amount of solvent.

[0162] [Lubricant solution] This application also relates to a lubricant solution comprising the composition of this application and a lubricant.

[0163] Lubricants are substances used to lubricate friction surfaces and improve their mechanical efficiency. They are substances used to reduce friction and prevent heat or wear damage when two moving components are in contact with each other. Lubricants require appropriate viscosity, physical and chemical stability, oiliness, and oxidation stability. Lubricants can be in the form of liquids (oils), semi-solids (greases), or solids. Types of lubricants include mineral oil-based lubricants, synthetic oil-based lubricants, fluorinated lubricants, and silicone-based lubricants.

[0164] Based on the excellent solubility or dispersibility of the compositions of this application, fluorine-based or silicone-based lubricants are preferred as lubricants.

[0165] Fluorine-based lubricants are lubricants that contain fluorine atoms in their molecules. Examples include fluorinated oils, fluorinated greases, and polytetrafluoroethylene resin powders, which are all fluorine-based solid lubricants.

[0166] As a fluorinated oil, perfluoropolyether (hereinafter also referred to as PFPE) or trifluorochloroethylene oligomers are preferred, such as products with the names "krytox (registered trademark) GPL102" (manufactured by DuPont de Nemours, Inc.), "Daifloil#1", "Daifloil#3", "Daifloil#10", "Daifloil#20", "Daifloil#50", "Daifloil#100", "DEMNUMS-65" (manufactured by DAIKIN INDUSTRIES, LTD.), "Fomblin (registered trademark) Y" series, "Fomblin (registered trademark) M" series, "Fomblin (registered trademark) W" series, and "Fomblin (registered trademark) Z" series (manufactured by Solvay Specialty Polymers Co., Ltd.).

[0167] As a fluorinated grease, it is preferred to use fluorinated oils such as PFPE or trifluorochloroethylene oligomers as the base oil and to incorporate polytetrafluoroethylene powder or other thickeners. Examples include products with names such as "krytox (registered trademark) GREASE 240AC" (manufactured by DuPont de Nemours, Inc.), "Daifloil GREASE DG-203", "DEMNUML65", "DEMNUML100", "DEMNUML200" (manufactured by DAIKIN INDUSTRIES, LTD.), "Sumitec F936" (manufactured by SUMICO LUBRICANT CO., LTD.), "MOLYKOTE (registered trademark) HP-300", "MOLYKOTE (registered trademark) HP-500", "MOLYKOTE (registered trademark) HP-870", and "MOLYKOTE (registered trademark) 6169" (manufactured by DowCorning Toray Co., Ltd.).

[0168] In addition, silicone-based lubricants refer to lubricants containing silicone, such as silicone oil or silicone grease.

[0169] Silicone oils can be categorized into straight-chain silicone oils, reactive silicone oils, non-reactive silicone oils, and other modified silicone oils. More specifically, straight-chain silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil, which are formed by bonding methyl, phenyl, and hydrogen atoms as substituents. Reactive silicone oils include those modified with amino groups, epoxy groups, carboxyl groups, methanol, methacrylic acid, phenol, and various functional groups. Non-reactive silicone oils include those modified with polyether, methylstyrene, alkyl, higher fatty acid esters, hydrophilic properties, and fluorine. These silicone oils can be one type or a mixture of two or more. Examples of silicone oils include "Shin-Etsu Silicone KF-96", "Shin-Etsu Silicone KF-965", "Shin-Etsu Silicone KF-968", "Shin-Etsu Silicone KF-99", "Shin-Etsu Silicone KF-50", "Shin-Etsu Silicone KF-54", "Shin-Etsu Silicone HIVACF-4", "Shin-Etsu Silicone HIVACF-5", "Shin-Etsu Silicone KF-56A", "Shin-Etsu Silicone KF-995" (manufactured by Shin-Etsu Chemical Co., Ltd.), "SH200" (manufactured by Dow Corning Toray Co., Ltd.), and "MDX4-4159" (manufactured by Dow Corning Corp.).

[0170] As a silicone grease, a preferred product is one made by using the various silicone oils listed above as base oils and incorporating thickeners such as metal soaps and various additives. Examples include products with names such as "Shin-Etsu Silicone G-30 series," "Shin-Etsu Silicone G-40 series," "Shin-Etsu Silicone FG-720 series," "Shin-EtsuSilicone G-411," "Shin-Etsu Silicone G-501," "Shin-Etsu Silicone G-6500," "Shin-Etsu Silicone G-330," "Shin-Etsu Silicone G-340," "Shin-Etsu Silicone G-350," and "Shin-Etsu Silicone G-630" (the above are from Shin-Etsu Chemical Co., Ltd.). The products manufactured by Dow Corning Toray Co., Ltd. include "MOLYKOTE SH33L", "MOLYKOTE 41", "MOLYKOTE 44", "MOLYKOTE 822M", "MOLYKOTE 111", "MOLYKOTE High Vacuum Grease", and "MOLYKOTE Thermally Conductive Composite Materials".

[0171] The lubricant solution may contain one or more lubricants.

[0172] The lubricant solution of this application is mild to the Earth's environment, has excellent solubility in lubricants, and is sufficiently quick-drying, thus making it suitable for forming a lubricant coating film.

[0173] In the lubricant solution of this application, the composition of the composition and the composition of the lubricant are not particularly limited, and can be appropriately selected as needed. For example, relative to 100% by mass of the lubricant solution of this application, the lubricant is set to 0.1% by mass or more and 50% by mass or less, but it is not limited thereto.

[0174] [Preparation method of articles with lubricant coating] One embodiment of the present invention is a method for preparing an article with a lubricant coating, which involves coating the aforementioned lubricant solution of the present application onto the surface of the article, and thereby forming a lubricant coating on the surface of the article by evaporating the volatile components of the aforementioned azeotropic composition of the present application.

[0175] As an article, it can be made of various materials such as metal, resin, elastomer, ceramic, and glass. Examples include industrial machines using fluorine-based lubricants, CD / DVD tray components in personal computers and audio equipment, and household and office machines such as printers, copiers, and flux machines. In addition, it can be suitable for use in injection needles or syringes of syringes using silicone-based lubricants, and medical catheter components.

[0176] The method of applying the lubricant solution of this application to the surface of an article is not particularly limited. Examples include brush-based application, spray-based application, and application by immersing the article in the composition of this lubricant.

[0177] The compositions of this application can also be used as reaction solvents, extractants, desiccants, refrigerants, etc.

[0178] [Heat transfer medium] The composition of this application can be used as a heat transfer medium for thermodynamic circulation systems. It is also preferable to use the above-described aerosol composition instead of the composition of this application.

[0179] This application also relates to a heat transfer medium comprising the composition or aerosol composition described above.

[0180] As thermodynamic cycle systems, examples include Rankine cycles, heat pump cycles, refrigeration cycles, heat transport systems, and secondary cooling systems. More specifically, examples include refrigeration and freezing machines, air conditioning machines, power generation systems, heat transport devices, and secondary coolers.

[0181] The following is an example of a thermodynamic cycle system, illustrating the refrigeration cycle system.

[0182] A refrigeration cycle system refers to a system in which heat energy is removed from the load fluid via a heat transfer medium in an evaporator, thereby cooling the load fluid to a lower temperature. A refrigeration cycle system consists of the following components: a compressor, which compresses the vapor of the heat transfer medium to form a high-temperature, high-pressure vapor of the heat transfer medium; a condenser, which cools the compressed vapor of the heat transfer medium to form a low-temperature, high-pressure liquid of the heat transfer medium; an expansion valve, which expands the liquid heat transfer medium discharged from the condenser to form a low-temperature, low-pressure liquid of the heat transfer medium; an evaporator, which heats the heat transfer medium discharged from the expansion valve to form a high-temperature, low-pressure vapor of the heat transfer medium; a pump, which supplies the load fluid to the evaporator; and a pump, which supplies the load fluid to the condenser.

[0183] The composition of this application is particularly preferred for use as a secondary refrigerant in a secondary circulation cooling system.

[0184] The secondary circulation cooling system comprises the following components: a primary cooling unit that cools a primary refrigerant composed of ammonia or hydrocarbon refrigerant; a secondary circulation cooling unit that circulates a secondary refrigerant within the secondary circulation cooling system to cool the object being cooled; and a heat exchanger that allows heat exchange between the primary and secondary refrigerants to cool the secondary refrigerant. This secondary circulation cooling system enables the cooling of the object being cooled.

[0185] The heat transfer medium of this application comprises the composition of this application. The content of the composition of this application in the heat transfer medium of this application is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, relative to the total amount of the heat transfer medium. An upper limit of 100% by mass can be listed.

[0186] When the heat transfer medium contains an aerosol composition, it is preferable that the composition of this application contains a proportion relative to the total amount of the heat transfer medium components after the jet gas has been removed within the range described above.

[0187] The heat transfer medium of this application may include stabilizers, other solvents, etc., as needed. Specific examples of stabilizers include the stabilizers described above. Other solvents include the solvent (A) described above.

[0188] The proportion of stabilizer in the heat transfer medium of this application is preferably 5% by mass or less, and more preferably 1% by mass or less, relative to the total amount of the heat transfer medium.

[0189] Relative to the total amount of the heat transfer medium, the content of other solvents in the heat transfer medium of this application is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0190] The heat transfer medium in this application is typically used as a heat transfer medium composition comprising a heat transfer medium and a refrigeration oil. Examples of refrigeration oils include polyalkylene glycols, polyol esters, and polyvinyl ethers.

[0191] The content of refrigeration oil in the heat transfer medium composition is preferably 10 to 100 parts by weight, more preferably 20 to 50 parts by weight, relative to 100 parts by weight of the heat transfer medium.

[0192] [Azeotropic-like composition] This application also relates to an azeotropic composition (hereinafter also referred to as "azeotropic composition A"), which consists of 70.01 to 99.99% by mass of (Z)-1-chloro-3,3,3-trifluoropropylene and 0.01 to 29.99% by mass of 1,1,1,3,3,3-hexafluoroisopropylmethyl ether.

[0193] The azeotropic composition A is a composition consisting of (Z)-1-chloro-3,3,3-trifluoropropene (1233zd(Z)) and 1,1,1,3,3,3-hexafluoroisopropylmethyl ether (hereinafter also referred to as HFE-356mmz), which can be formed by having a composition of 1233zd(Z) and HFE-356mmz present in an effective amount to form the azeotropic composition.

[0194] In addition, this application also relates to an azeotropic composition (hereinafter also referred to as "azeotropic composition B"), which consists of 0.01 to 28.00% by mass of (Z)-1-chloro-3,3,3-trifluoropropylene and 72.00 to 99.99% by mass of 1,1,1,3,3,3-hexafluoroisopropylmethyl ether.

[0195] The azeotropic composition B is a composition consisting of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropylmethyl ether, which can be formed by the presence of a composition of 1233zd(Z) and HFE-356mmz in an effective amount to form the azeotropic composition.

[0196] The azeotropic composition A of this application can be used to form an aerosol by combining it with a jet gas. A preferred embodiment of the aforementioned aerosol is an aerosol using the azeotropic composition A.

[0197] This application also relates to an aerosol composition (also referred to as aerosol composition A) comprising an azeotropic-like composition A and a jet gas. A preferred embodiment of the above-mentioned aerosol composition is an aerosol composition using the azeotropic-like composition A.

[0198] The azeotropic composition A of this application has excellent cleaning properties, and therefore can be used as a cleaning agent for degreasing cleaning, flux cleaning, precision cleaning, dehydration cleaning, rinsing cleaning, dry cleaning, etc.

[0199] Furthermore, it is preferable to use an aerosol composition (aerosol composition A) comprising the aforementioned azeotropic composition A and the injected gas instead of the azeotropic composition A of this application. This application also relates to a cleaning agent comprising the aforementioned azeotropic composition A or aerosol composition A.

[0200] A preferred embodiment of the use of the above-described compositions of this application as a cleaning agent is the use of the aforementioned azeotropic composition A as a cleaning agent. Furthermore, a preferred embodiment of the cleaning agent comprising an aerosol composition related to the above-described compositions of this application is a cleaning agent comprising the aforementioned azeotropic composition A or aerosol composition A.

[0201] The azeotropic composition A of this application exhibits excellent solubility for organic compounds, and therefore can be used as a solvent for dissolving and applying surface treatment agents such as lubricants, rust inhibitors, moisture-proof coating agents, and anti-fouling coating agents to the surface of articles. A preferred embodiment of using the composition of this application as a solvent is its use as a solvent for azeotropic composition A.

[0202] This application also relates to a lubricant solution comprising the aforementioned azeotropic composition A and a lubricant. A preferred embodiment of the lubricant solution comprising the aforementioned composition and lubricant is a lubricant solution comprising the aforementioned azeotropic composition A and a lubricant.

[0203] The azeotropic composition A of this application can be used as a heat transfer medium for thermodynamic circulation systems. It is also preferable to use the aforementioned aerosol composition A instead of the azeotropic composition A of this application.

[0204] This application also relates to a heat transfer medium comprising the aforementioned azeotropic composition A or aerosol composition A. A preferred embodiment of the heat transfer medium comprising the aforementioned composition is a heat transfer medium comprising the azeotropic composition A. Furthermore, a preferred embodiment of the heat transfer medium comprising the aforementioned aerosol composition is a heat transfer medium comprising the aforementioned aerosol composition A.

[0205] The azeotropic composition B of this application can be used to form an aerosol by combining it with a jet gas. A preferred embodiment of the aforementioned aerosol is an aerosol using the azeotropic composition B.

[0206] This application also relates to an aerosol composition (also referred to as aerosol composition B) comprising an azeotropic-like composition B and a jet gas. A preferred embodiment of the above-mentioned aerosol composition is an aerosol composition using the azeotropic-like composition B.

[0207] The azeotropic composition B of this application has excellent cleaning properties, and therefore can be used as a cleaning agent for degreasing cleaning, flux cleaning, precision cleaning, dehydration cleaning, rinsing cleaning, dry cleaning, etc.

[0208] Furthermore, it is preferable to use an aerosol composition (aerosol composition B) comprising the aforementioned azeotropic composition B and the injected gas instead of the azeotropic composition B of this application. This application also relates to a cleaning agent comprising the aforementioned azeotropic composition B or aerosol composition B.

[0209] A preferred embodiment of the use of the above-described compositions of this application as a cleaning agent is the use of the aforementioned azeotropic composition B as a cleaning agent. Furthermore, a preferred embodiment of the cleaning agent comprising an aerosol composition related to the above-described compositions of this application is a cleaning agent comprising aerosol composition B.

[0210] The azeotropic composition B of this application exhibits excellent solubility for organic compounds, and therefore can be used as a solvent for dissolving and applying surface treatment agents such as lubricants, rust inhibitors, moisture-proof coating agents, and anti-fouling coating agents to the surface of articles. A preferred embodiment of using the above-described composition of this application as a solvent is its use as a solvent for the azeotropic composition B.

[0211] This application also relates to a lubricant solution comprising the aforementioned azeotropic composition B and a lubricant. A preferred embodiment of the lubricant solution comprising the aforementioned composition and lubricant is a lubricant solution comprising the aforementioned azeotropic composition B and a lubricant.

[0212] The azeotropic composition B of this application can be used as a heat transfer medium for thermodynamic circulation systems. It is also preferable to use the aforementioned aerosol composition B instead of the azeotropic composition B of this application.

[0213] This application also relates to a heat transfer medium comprising the aforementioned azeotropic composition B or aerosol composition B. A preferred embodiment of the heat transfer medium comprising the aforementioned composition is a heat transfer medium comprising the azeotropic composition B. Furthermore, a preferred embodiment of the heat transfer medium comprising the aforementioned aerosol composition is a heat transfer medium comprising the aforementioned aerosol composition B.

[0214] In addition, a composition comprising the azeotropic composition A or B of this application and at least one selected from the group consisting of stabilizers, surfactants, flame retardants, metal passivators and rust inhibitors is also involved.

[0215] For stabilizers, surfactants, flame retardants, metal passivators, and rust inhibitors, the above-mentioned stabilizers, surfactants, flame retardants, metal passivators, and rust inhibitors can be listed respectively.

[0216] The content of at least one of the stabilizers, surfactants, flame retardants, metal passivators and rust inhibitors, relative to the total amount of the composition, is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 1% by mass or less.

[0217] Example The present application will now be described in detail with reference to the embodiments, but the present application is not limited to these embodiments. Compositions 1-5 and 8-11 are examples, and compositions 6-7 are comparative examples.

[0218] [Examples 1-1 to 1-9, Comparative Examples 1 to 2] <Preparation example of 1233zd(Z)> 1233zd(Z) was prepared according to the description in Japanese Patent Application Publication No. 2017-110020.

[0219] <Example of Preparation of 1,1,1,3,3,3-Hexafluoroisopropylmethyl ether> 1,1,1,3,3,3-Hexafluoroisopropylmethyl ether was prepared according to the description in U.S. Patent No. 3,346,448.

[0220] <Determination of Gas-Liquid Equilibrium> Compositions 1-11, obtained by mixing 250g of 1233zd(Z) and HFE-356mmz in various mass ratios, were placed in an Othmer gas-liquid equilibrium apparatus. When the temperatures of the gas and liquid phases reached equilibrium, liquid and gas phase samples were taken and placed in 10mL sample vials pre-cooled with ice water. The composition of 1233zd(Z) and HFE-356mmz was analyzed by gas chromatography. The results are shown in Table 1.

[0221] Compositions 1 to 11 were adjusted using 0.0026% by mass of 1233zd(Z) and 0.0359% by mass of HFE-356mmz, respectively, and the water content of each composition could be calculated from the content of 1233zd(Z) and HFE-356mmz. For example, in composition 2, it was 0.0043% by mass.

[0222] [Table 1] As shown in Table 1, within the range of 1233zd(Z) of 70.01–99.99% by mass, 0.01–28.00% by mass, and HFE-356mmz of 0.01–29.99% by mass, 72.00–99.99% by mass, the composition of the gas and liquid phases of the azeotropic composition remained substantially unchanged. Furthermore, azeotropy was maintained even when 0.0029–0.0356% by mass of water was included.

[0223] <Cleaning Test> [Example 2] 100g of cutting oil (RELIACUT AM30, manufactured by ENEOS Corporation) was added to a 200mL glass beaker. Next, a SUS316 test piece (30mm × 15mm × 2mm) was completely immersed in the cutting oil. The test piece was removed from the cutting oil, and it was visually confirmed that the cutting oil adhered to its surface. Then, 200g of cleaning agent was added to a 300mL glass beaker, and the SUS test piece with the cutting oil attached was completely immersed in it and ultrasonically cleaned at 25°C for 2 minutes (ultrasonic oscillator: neosonic manufactured by Alex Corporation, power 100W, frequency 28kHz). Here, the same cleaning agent as compositions 1-5 prepared in Examples 1-1 to 1-5 was used. The test piece was then removed, dried at 80°C for 5 minutes, and its surface was visually inspected. No dirt was observed on the surface of the test piece when any cleaning agent was used.

[0224] [Example 3] 100g of cutting oil (Daphne Magplus S, manufactured by Idemitsu Kosan Co., Ltd.) was added to a 200mL glass beaker. Next, a SUS316 test piece (30mm × 15mm × 2mm) was completely immersed in the cutting oil. The test piece was removed from the cutting oil, and it was visually confirmed that the cutting oil adhered to the surface of the test piece. Then, 200g of cleaning agent was added to a 300mL glass beaker, and the SUS test piece with the cutting oil attached was placed in the beaker and ultrasonically cleaned at 25°C for 2 minutes (ultrasonic oscillator: neosonic manufactured by Alex Corporation, power 100W, frequency 28kHz). Here, the cleaning agent is a cleaning agent prepared by replacing 1233zd(Z) in compositions 1-5 prepared in Examples 1-1 to 1-5 with 1233zd(Z) / 1233zd(E) = 90 / 10 (mass ratio). Then, the test piece was removed and dried at 80°C for 5 minutes. The surface of the test piece was then visually inspected. No dirt was found on the surface of the test piece when any cleaning agent was used.

[0225] In the compositions prepared in Examples 1-1 to 1-5, the composition difference between 1233zd(Z) and the gas phase and liquid phase of HFE-356mmz is 8.00% by mass or less.

[0226] Therefore, the above compositions are azeotropic-like compositions.

[0227] 1233zd(E) was prepared according to the description in Japanese Patent Application Publication No. 2017-110020.

[0228] [Example 4] The components were mixed in such a manner that 1233zd(Z) / HFE-356mmz / HFIP was 95.00% / 4.99% / 0.01% by mass to prepare a composition. A cleaning test was performed in the same manner as in Example 2. The results were the same as in Example 2, with no dirt detected on the surface of the test piece.

[0229] In the composition, the composition difference between the gas phase and liquid phase of 1233zd(Z) and HFE-356mmz is 8.00% by mass or less. Therefore, the composition is an azeotropic composition.

[0230] Industrial practicality The composition of this application has little impact on the Earth's environment, and its composition is not easily changed even if it is repeatedly evaporated and condensed. Therefore, it can be used in a wide range of applications such as cleaning agents, solvents, aerosols, and heat transfer media.

[0231] Although this application has been described in detail with reference to specific embodiments, those skilled in the art will understand that various changes and modifications can be made to this application without departing from the spirit and scope of this application.

[0232] Furthermore, the contents of Japanese Patent Application No. 2023-134119, filed on August 21, 2023, are incorporated herein by reference.

Claims

1. A quasi-azeotropic composition comprising (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

2. The quasi-azeotropic composition according to claim 1, consisting of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

3. The quasi-azeotropic composition according to claim 1 or 2, comprising 70.01 to 99.99 mass% of (Z)-1-chloro-3,3,3-trifluoropropene and 0.01 to 29.99 mass% of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, or comprising 0.01 to 28.00 mass% of (Z)-1-chloro-3,3,3-trifluoropropene and 72.00 to 99.99 mass% of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, relative to the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

4. The quasi-azeotropic composition according to claim 1 or 2, comprising 70.01 to 99.99 mass% of (Z)-1-chloro-3,3,3-trifluoropropene and 0.01 to 29.99 mass% of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, relative to the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

5. The quasi-azeotropic composition according to claim 1 or 2, comprising 0.01 to 28.00 mass% of (Z)-1-chloro-3,3,3-trifluoropropene and 72.00 to 99.99 mass% of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, relative to the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

6. The azeotrope-like composition of claim 1 wherein, The total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether is 80 mass% or more relative to the total amount of the composition.

7. The azeotrope-like composition of claim 1 wherein, The quasi-azeotropic composition further comprises water.

8. The azeotrope-like composition of claim 7 wherein, The quasi-azeotropic composition comprises 0.0001 to 1.00 mass% of water relative to the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

9. The azeotrope-like composition of claim 7 or 8 wherein, The quasi-azeotropic composition consists of (Z)-1-chloro-3,3,3-trifluoropropene, 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, and water.

10. A method for producing a composition, comprising: a step of preparing a quasi-azeotropic composition comprising (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether; and a step of adding at least one selected from the group consisting of a stabilizer, a surfactant, a flame retardant, a metal deactivator, and a rust preventive to the quasi-azeotropic composition.

11. A composition comprising the azeotrope-like composition of claim 1 and at least one selected from the group consisting of stabilizers, surfactants, flame retardants, metal deactivators, and rust preventives.

12. An aerosol composition comprising the azeotrope-like composition of claim 1 and a propellant gas.

13. A cleaning agent comprising the azeotrope-like composition of claim 1.

14. A cleaning agent comprising the aerosol composition of claim 12.

15. The cleaning agent according to claim 13 or 14 for use in cleaning a vehicle or a mechanism for transportation.

16. A method for cleaning an article, comprising the step of contacting the cleaning agent of claim 13 or 14 with an article to be cleaned.

17. A method for recycling a cleaning agent, comprising: the step of cleaning an article using the cleaning agent of claim 13 or 14; and the step of purifying the cleaning agent after cleaning.

18. A lubricant solution comprising the azeotrope-like composition of claim 1 and a lubricant.

19. A heat transfer medium comprising the azeotrope-like composition of claim 1 or the aerosol composition of claim 12. ​

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