Cleaning method and cleaning composition

Abstract

A cleaning method for cleaning, by using a cleaning composition, an article to be cleaned containing at least one selected from acrylic polymers, polycarbonates, acrylonitrile-butadiene-styrene resins, polystyrenes, polyurethanes, polyvinyl chlorides, and nitrile rubbers, wherein the cleaning composition contains (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoro isopropyl methyl ether, and the amount of the (Z)-1-chloro-3,3,3-trifluoropropene is 15.0-60.0 mass% and the amount of the 1,1,1,3,3,3-hexafluoro isopropyl methyl ether is 40.0-85.0 mass% with respect to the total amount of the (Z)-1-chloro-3,3,3-trifluoropropene and the 1,1,1,3,3,3-hexafluoro isopropyl methyl ether.

Description

Cleaning method and cleaning composition

[0001] This disclosure relates to a cleaning method that achieves both material compatibility with the object to be cleaned and cleaning performance, and to a cleaning composition that can be suitably used in said cleaning method.

[0002] Traditionally, chlorofluorocarbons (hereinafter referred to as "CFCs"), hydrochlorofluorocarbons (hereinafter referred to as "HCFCs"), and hydrofluorocarbons (hereinafter referred to as "HFCs") have been used in various applications such as detergents, solvents, heat transfer media, foaming agents, and fire extinguishing agents due to their non-flammability and excellent stability and drying properties. However, there are concerns about the impact of CFCs, HCFCs, and HFCs on the ozone layer and global warming. Fluoroolefins have been proposed as an alternative to CFCs, HCFCs, and HFCs. Because fluoroolefins have carbon-carbon double bonds in their molecules, they have a short lifetime in the atmosphere and therefore have a small impact on the global environment.

[0003] (Z)-1-chloro-3,3,3-trifluoropropene is known as one such fluoroolefin. (Z)-1-chloro-3,3,3-trifluoropropene is widely used industrially as a degreasing detergent because it dissolves various mineral oils well (for example, Patent Documents 1 and 2).

[0004] Japanese Patent Publication No. 2023-013565 Japanese Patent Publication No. 2014-181405

[0005] On the other hand, (Z)-1-chloro-3,3,3-trifluoropropene is invasive to resins such as acrylic polymers, polycarbonates, acrylonitrile-butadiene-styrene resin (ABS resin), polystyrene, polyurethane, polyvinyl chloride (PVC), and nitrile rubber (NBR). Therefore, when the object to be cleaned contains these resin components, it was sometimes difficult to use a cleaning agent containing (Z)-1-chloro-3,3,3-trifluoropropene.

[0006] Therefore, this disclosure aims to provide a cleaning method that achieves both material compatibility with the object to be cleaned and cleaning performance. Furthermore, this disclosure aims to provide a cleaning composition that can be suitably used in the above cleaning method.

[0007] As a result of diligent research, the inventors have found that the above problem can be solved as follows.

[0008] [1] A method for cleaning an object to be cleaned, comprising at least one selected from acrylic polymer, polycarbonate, acrylonitrile-butadiene-styrene resin, polystyrene, polyurethane, polyvinyl chloride, and nitrile rubber, using a cleaning composition, wherein the cleaning composition contains (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, comprising 15.0 to 60.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 40.0 to 85.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether. [2] The cleaning method according to [1], wherein the object to be cleaned comprises at least one selected from polycarbonate, acrylonitrile-butadiene-styrene resin, polystyrene, polyurethane, polyvinyl chloride, and nitrile rubber, and the cleaning composition comprises (Z)-1-chloro-3,3,3-trifluoropropene and 25.0 to 60.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 40.0 to 75.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether. [3] The cleaning method according to [1], wherein the object to be cleaned contains an acrylic polymer, and the cleaning composition comprises (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether in an amount of 15.0 to 35.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 65.0 to 85.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.[4] A cleaning composition for cleaning an object to be cleaned, comprising at least one selected from acrylic polymer, polycarbonate, acrylonitrile-butadiene-styrene resin, polystyrene, polyurethane, polyvinyl chloride, and nitrile rubber, wherein the composition contains (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, comprising 15.0 to 60.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 40.0 to 85.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether. [5] The cleaning composition according to [4], wherein the object to be cleaned comprises at least one selected from polycarbonate, acrylonitrile-butadiene-styrene resin, polystyrene, polyurethane, polyvinyl chloride, and nitrile rubber, and comprises (Z)-1-chloro-3,3,3-trifluoropropene and 25.0 to 60.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 40.0 to 75.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether. [6] The cleaning composition according to [4], wherein the object to be cleaned contains an acrylic polymer and comprises (Z)-1-chloro-3,3,3-trifluoropropene and 15.0 to 35.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 65.0 to 85.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

[0009] This disclosure can provide a cleaning method that achieves both material compatibility with the object to be cleaned and cleaning performance. Furthermore, this disclosure can provide a cleaning composition that can be suitably used in the above cleaning method.

[0010] In this specification, for halogenated hydrocarbons, the abbreviation of the compound is indicated in parentheses after the compound name, but in this specification, the abbreviation may be used instead of the compound name as needed. In addition, as an abbreviation, only the numbers and lowercase letters after the hyphen (-) may be used (for example, "1233zd" for "HCFO-1233zd"). Furthermore, (E) attached to the name and abbreviation of a compound having geometric isomers indicates the E-isomer, and (Z) indicates the Z-isomer (for example, "HCFO-1233zd(Z)" or "1233zd(Z)" may be used for "(Z)-1-chloro-3,3,3-trifluoropropene"). If the E-isomer or Z-isomer is not specified in the name or abbreviation of the compound, the name or abbreviation means a general term including the E-isomer, the Z-isomer, and mixtures of the E-isomer and Z-isomer.

[0011] In this specification, a compound obtained by replacing some of the hydrogen atoms of a saturated hydrocarbon compound with fluorine atoms is called a hydrofluorocarbon (HFC), a compound obtained by replacing some of the hydrogen atoms of a saturated hydrocarbon compound with fluorine and chlorine atoms is called a hydrochlorofluorocarbon (HCFC), a compound obtained by replacing all of the hydrogen atoms of a saturated hydrocarbon compound with fluorine and chlorine atoms is called a chlorofluorocarbon (CFC), a compound having a carbon-carbon double bond and composed of carbon atoms, fluorine atoms and hydrogen atoms is called a hydrofluoroolefin (HFO), and a compound having a carbon-carbon double bond and composed of carbon atoms, chlorine atoms, fluorine atoms and hydrogen atoms is called a hydrochlorofluoroolefin (HCFO).

[0012] In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively.

[0013] [Cleaning Method] The cleaning method of the present disclosure is a method for cleaning an object to be cleaned using a cleaning composition, the object comprising at least one selected from acrylic polymer, polycarbonate, acrylonitrile-butadiene-styrene resin (ABS resin), polystyrene, polyurethane, polyvinyl chloride (PVC), and nitrile rubber (NBR), The cleaning composition contains (Z)-1-chloro-3,3,3-trifluoropropene (1233zd(Z)) and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether (hereinafter also referred to as HFE-356mmz), comprising 15.0 to 60.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 40.0 to 85.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

[0014] <Cleaning Composition> The cleaning composition used in the cleaning method of this disclosure (hereinafter also referred to as the cleaning composition of this disclosure) will now be described. The cleaning composition of this disclosure contains 1233zd(Z) and HFE-356mmz, and comprises 1233zd(Z) and 15.0 to 60.0% by mass of 1233zd(Z) and 40.0 to 85.0% by mass of HFE-356mmz, based on the total amount of HFE-356mmz.

[0015] The cleaning composition of this disclosure preferably contains 80% by mass or more of 1233zd(Z) and HFE-356mmz in total, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total amount of the composition. The cleaning composition of this disclosure may consist substantially of only 1233zd(Z) and HFE-356mmz. "The cleaning composition of this disclosure consists substantially of only 1233zd(Z) and HFE-356mmz" means that in the cleaning composition of this disclosure, the total amount of 1233zd(Z) and HFE-356mmz is 98% by mass or more of the total amount of the composition. In a preferred embodiment, the cleaning composition of this disclosure is preferably composed of only 1233zd(Z) and HFE-356mmz.

[0016] The cleaning composition of this disclosure is preferable because it has a small impact on the global environment, by containing 80% by mass or more of the total amount of 1233zd(Z) and HFE-356mmz. In one preferred embodiment, the total amount of 1233zd(Z) and HFE-356mmz is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, and may be 98 to 100% by mass or 100% by mass, based on the total amount of the composition.

[0017] (1233zd(Z)) 1233zd(Z) is an olefin having a carbon-carbon double bond, and therefore has a short lifetime in the atmosphere and a low ozone depletion potential and global warming potential. 1233zd(Z) has a boiling point of 39°C and can be used on parts that are susceptible to heat. In addition, 1233zd(Z) has no flash point, excellent drying properties, and excellent penetration due to its low surface tension and viscosity, giving it excellent performance as a cleaning agent. 1233zd(Z) can be manufactured, for example, according to the description in Japanese Patent Application Publication No. 2017-110020.

[0018] The cleaning composition disclosed herein, by containing 1233zd(Z) in the above-mentioned amount, has a low impact on the global environment and exhibits performance suitable for cleaning agent applications.

[0019] (1,1,1,3,3,3-Hexafluoroisopropyl methyl ether) 1,1,1,3,3,3-Hexafluoroisopropyl methyl ether (HFE-356mmz) has a boiling point of approximately 51°C and can be used on parts that are susceptible to heat. Furthermore, HFE-356mmz has excellent cleaning properties, including excellent drying properties and excellent penetration due to its low surface tension and viscosity. In addition, HFE-356mmz has little effect on resin materials such as acrylic polymers, polycarbonate, ABS resin, polystyrene, polyurethane, PVC, and NBR. HFE-356mmz is a known compound and can be obtained, for example, by the reaction of 1,1,1,3,3,3-Hexafluoroisopropyl alcohol and dimethyl sulfuric acid in the presence of an alkali (US Patent No. 3346448).

[0020] The cleaning composition disclosed herein exhibits excellent cleaning properties due to the inclusion of HFE-356 mmZ in the above-mentioned amount. Furthermore, while 1233 zd (Z), when used alone, may cause strong chemical attack (corrosion) on resins, etc., the chemical attack can be reduced by using HFE-356 mmZ in combination.

[0021] One preferred embodiment of the cleaning composition of the present disclosure is an embodiment (Embodiment I) comprising 1233zd(Z) and 25.0 to 60.0% by mass of 1233zd(Z) and 40.0 to 75.0% by mass of HFE-356mmz, relative to the total amount of HFE-356mmz. In Embodiment I, chemical attack can be particularly reduced when the object to be cleaned contains at least one selected from polycarbonate, ABS resin, polystyrene, polyurethane, PVC, and NBR.

[0022] In other words, the cleaning method of the present disclosure preferably comprises at least one selected from polycarbonate, acrylonitrile-butadiene-styrene resin, polystyrene, polyurethane, polyvinyl chloride, and nitrile rubber, and the cleaning composition preferably contains (Z)-1-chloro-3,3,3-trifluoropropene in an amount of 25.0 to 60.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 40.0 to 75.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

[0023] In embodiment I, the cleaning composition more preferably contains 25.0 to 55.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 45.0 to 75.0% by 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, and more preferably 27.5 to 52 It is more preferable to contain 5% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 47.5 to 72.5% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, and it is particularly preferable to contain 30.0 to 50.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 50.0 to 70.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether. In one preferred embodiment, it is preferable to include 25.0 to 55.0 mass% of 1233zd(Z) and 45.0 to 75.0 mass% of HFE-356mmz with respect to the total amount of 1233zd(Z) and HFE-356mmz, more preferably 25.0 to 52.5 mass% of 1233zd(Z) and 47.5 to 75.0 mass% of HFE-356mmz, and even more preferably 25.0 to 50.0 mass% of 1233zd(Z) and 50.0 to 75.0 mass% of HFE-356mmz. In one preferred embodiment, it is preferable to include 27.5 to 60.0 mass% of 1233zd(Z) and 40.0 to 72.5 mass% of HFE-356mmz with respect to the total amount of 1233zd(Z) and HFE-356mmz, more preferably 27.5 to 55.0 mass% of 1233zd(Z) and 45.0 to 72.5 mass% of HFE-356mmz, even more preferably 27.5 to 52.5 mass% of 1233zd(Z) and 47.5 to 72.5 mass% of HFE-356mmz, and particularly preferably 27.5 to 50.0 mass% of 1233zd(Z) and 50.0 to 72.5 mass% of HFE-356mmz.In one preferred embodiment, it is preferable to include 30.0 to 60.0 mass% of 1233zd(Z) and 40.0 to 70.0 mass% of HFE-356mmz with respect to the total amount of 1233zd(Z) and HFE-356mmz; more preferably 30.0 to 55.0 mass% of 1233zd(Z) and 45.0 to 70.0 mass% of HFE-356mmz; even more preferably 30.0 to 52.5 mass% of 1233zd(Z) and 47.5 to 70.0 mass% of HFE-356mmz; and particularly preferably 30.0 to 50.0 mass% of 1233zd(Z) and 50.0 to 70.0 mass% of HFE-356mmz.

[0024] Another preferred embodiment of the cleaning composition of the present disclosure is an embodiment (Embodiment II) comprising 1233zd(Z) and 15.0 to 35.0% by mass of 1233zd(Z) and 65.0 to 85.0% by mass of HFE-356mmz, relative to the total amount of HFE-356mmz. In Embodiment II, chemical attack can be reduced in particular when the object to be cleaned contains an acrylic polymer.

[0025] In other words, the cleaning method of the present disclosure preferably includes an acrylic polymer in the object to be cleaned, and the cleaning composition preferably contains 15.0 to 35.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 65.0 to 85.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

[0026] In embodiment II, the cleaning composition more preferably contains 15.0 to 30.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 70.0 to 85.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, and more preferably 17.5 to 2 It is more preferable to contain 7.5% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 72.5 to 82.5% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, and it is particularly preferable to contain 20.0 to 25.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 75.0 to 80.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether. In one preferred embodiment, it is preferable that the total amount of 1233zd(Z) and HFE-356mmz contains 15.0 to 30.0 mass% of 1233zd(Z) and 70.0 to 85.0 mass% of HFE-356mmz, more preferably 15.0 to 27.5 mass% of 1233zd(Z) and 72.5 to 85.0 mass% of HFE-356mmz, and even more preferably 15.0 to 25.0 mass% of 1233zd(Z) and 75.0 to 85.0 mass% of HFE-356mmz. In one preferred embodiment, it is preferable to include 17.5 to 35.0 mass% of 1233zd(Z) and 65.0 to 82.5 mass% of HFE-356mmz with respect to the total amount of 1233zd(Z) and HFE-356mmz, more preferably 17.5 to 30.0 mass% of 1233zd(Z) and 70.0 to 82.5 mass% of HFE-356mmz, even more preferably 17.5 to 27.5 mass% of 1233zd(Z) and 72.5 to 82.5 mass% of HFE-356mmz, and particularly preferably 17.5 to 25.0 mass% of 1233zd(Z) and 75.0 to 82.5 mass% of HFE-356mmz.In one preferred embodiment, it is preferable to include 20.0 to 35.0 mass% of 1233zd(Z) and 65.0 to 80.0 mass% of HFE-356mmz with respect to the total amount of 1233zd(Z) and HFE-356mmz, more preferably 20.0 to 30.0 mass% of 1233zd(Z) and 70.0 to 80.0 mass% of HFE-356mmz, even more preferably 20.0 to 27.5 mass% of 1233zd(Z) and 72.5 to 80.0 mass% of HFE-356mmz, and particularly preferably 20.0 to 25.0 mass% of 1233zd(Z) and 75.0 to 80.0 mass% of HFE-356mmz.

[0027] The cleaning composition of this disclosure may contain water. The water content is not particularly limited, but is preferably 0.0001 to 1.00% by mass, more preferably 0.0001 to 0.5% by mass, and even more preferably 0.0001 to 0.2% by mass, relative to the total amount of 1233zd(Z) and HFE-356mmz. In a preferred embodiment, the water content is preferably 0.0001 to 0.1% by mass, relative to the total amount of 1233zd(Z) and HFE-356mmz. The inclusion of water has effects such as improving the cleaning performance against water-soluble processing oils.

[0028] In a preferred embodiment, the cleaning composition of the present disclosure is preferably a composition comprising (Z)-1-chloro-3,3,3-trifluoropropene, 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, and water.

[0029] The cleaning compositions of this disclosure may contain at least one selected from the group consisting of stabilizers, surfactants, flame retardants, metal passivators, and rust inhibitors.

[0030] 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, still more preferably 5% by mass or less, and particularly preferably 1% by mass or less, based on the total amount of the composition. In a preferred embodiment, the content of the above component is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, still more preferably 0 to 5% by mass, and particularly preferably 0 to 1% by mass, based on the total amount of the composition.

[0031] Examples of the stabilizer include nitromethane, nitroethane, nitropropane, nitrobenzene, diethylamine, triethylamine, isopropylamine, diisopropylamine, butylamine, isobutylamine, tert-butylamine, α-picoline, 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-propaneisoamyl, benzyl salicylate, methyl salicylate, 2,6-di-tert-butyl-p-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-propylene oxide, 1,2-butylene oxide, 1,4-dioxane, butyl glycidyl ether, phenyl glycidyl ether, isoamylene, octene, 2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-pentene, 2-methylpentene, etc. Among them, 2,6-di-tert-butyl-p-cresol, p-methoxyphenol, 1,2-butylene oxide, isoamylene, octene, 2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-pentene, 2-methylpentene are preferred. The stabilizer may be used alone or in combination of two or more.

[0032] As the surfactant, 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; nonionic surfactants such as polyoxyethylene alkyl amine fatty acid amides such as polyoxyethylene oleic acid amide are preferred. As the surfactant, one kind may be used, or two or more kinds may be used.

[0033] As the flame retardant, phosphates, halogenated aromatic compounds, fluorinated iodo-carbon, fluorinated bromo-carbon and the like are preferred. As the flame retardant, one kind may be used, or two or more kinds may be used.

[0034] The cleaning composition of the present disclosure may further contain other components. Examples of the other components include other solvents such as hydrocarbons, alcohols, ketones, non-fluorinated ethers, esters, chlorocarbons, HFCs, HFEs (hereinafter also referred to as solvent (A)), raw materials, materials, by-products, etc. used in the production process and purification process of 1233zd(Z) and HFE-356mmz. The solvent (A) is appropriately selected according to various purposes such as enhancing solubility and adjusting the evaporation rate.

[0035] As the hydrocarbon, a hydrocarbon having 5 or more carbon atoms is preferred. The hydrocarbon may be linear, cyclic, saturated or unsaturated. Preferred hydrocarbons include n-pentane, cyclopentane, n-hexane, cyclohexane, and n-heptane.

[0036] As the alcohol, an alcohol having 1 to 16 carbon atoms is preferred. The alcohol may be in a chain, a cyclic form, a saturated alcohol, or an unsaturated alcohol. Methanol, ethanol, and isopropyl alcohol are preferred as the alcohol.

[0037] Preferably, the ketone has 3 to 9 carbon atoms. The ketone may be linear, cyclic, saturated, or unsaturated. Preferably, the ketone is acetone or methyl ethyl ketone.

[0038] As non-fluorinated ethers, ethers having 2 to 8 carbon atoms are preferred. Non-fluorinated ethers may be linear, cyclic, saturated, or unsaturated. As ethers, diethyl ether, diisopropyl ether, and tetrahydrofuran are preferred.

[0039] As the ester, esters having 2 to 19 carbon atoms are preferred. The ester may be linear, cyclic, saturated, or unsaturated. Methyl acetate and ethyl acetate are preferred as the ester.

[0040] As the chlorocarbon, a chlorocarbon having 1 to 3 carbon atoms is preferred. The chlorocarbon may be in the form of a chain, a ring, a saturated chlorocarbon, or an unsaturated chlorocarbon. As the chlorocarbon, methylene chloride, trans-1,2-dichloroethylene, and trichloroethylene are more preferred.

[0041] Preferably, the HFC is a chain or cyclic HFC having 4 to 8 carbon atoms, and more preferably, an HFC in which the number of fluorine atoms in one molecule is equal to or greater than the number of hydrogen atoms. Preferred HFCs are 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.

[0042] As the HFE, HFEs other than 1,1,1,3,3,3 - hexafluoroisopropyl methyl ether are preferred. For example, 1,1,2,2 - tetrafluoroethoxy - 1 - (2,2,2 - trifluoro) ethane (CF ３ CH ２ OCF ２ CF ２ H, hereinafter also referred to as HFE - 347pc - f.), methoxynonafluorobutane (C ４ F ９ OCH ３ , hereinafter also referred to as HFE - 449s1.), ethoxynonafluorobutane (C ４ F ９ OC ２ H ５ , hereinafter also referred to as HFE - 569sf.), methoxyheptafluoropropane (C ３ F ７ OCH ３ , hereinafter also referred to as HFE - 347mcc.), methoxy - 2 - (trifluoromethyl) - 3 - methoxynonafluoropentane (C ２ F ５ CF(OCH ３ )CF(CF ３ )CF ３ , hereinafter also referred to as HFE - 7300.), 2 - (trifluoromethyl) - 3 - ethoxydodecafluorohexane (C ３ F ７ CF(OC ２ H ５ )CF(CF ３ )CF ３ , hereinafter also referred to as HFE - 7500.), 1,1,2,3,3,3 - hexafluoropropyl methyl ether (HFE - 356mec), etc. are preferred.

[0043] The solvent (A) may be one kind or two or more kinds. When two or more kinds of solvents (A) are included, their combinations may be combinations of solvents in the same category or combinations of solvents in different categories. For example, a combination of two kinds selected from hydrocarbons may be used, or a combination of one kind selected from hydrocarbons and one kind selected from alcohols may be used.

[0044] It is even more preferable that solvent (A) is 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-tridecafluorohexane, 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-ethoxidedodecafluorohexane. When a solvent with a flash point is used as solvent (A), it is preferable to use it as a cleaning agent within a range that does not have a flash point.

[0045] Furthermore, the raw materials, supplies, and by-products used in the manufacturing and purification processes of 1233zd(Z) and HFE-356mmz include, for example, chlorotrifluoropropene other than 1233zd(Z) (e.g., (E)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E), or also called "1233zd(E)")), dichlorotrifluoropropene (HCFO-1223), chlorotetrafluoropropane (HCFC-244), chloropentafluoropropane (HCFC-235), and chloro Rotetrafluoropropene (HCFO-1224), dichlorotetrafluoropropene (HCFO-1214), pentafluoropropane (HFC-245), tetrafluoropropene (HFO-1234), trifluoropropine, water, hexafluoropropene, tetrafluoroethylene, 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), dimethyl ether, halomethane, and methyl p-toluenesulfonate, p-toluenesulfonic acid, p-toluenesulfonate, C ４ H ３ F ５ Examples include compounds represented by O and 2,2,2-trifluoroethyl methyl ether. If geometric or positional isomers exist for these components, either a single component of one of the isomers or a mixture thereof may be used.

[0046] The content of other components is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on the total amount of the composition. In one preferred embodiment, the content of other components is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and even more preferably 0 to 5% by mass, based on the total amount of the composition.

[0047] The method for producing the cleaning composition of this disclosure is not particularly limited, but it can be produced by mixing 1233zd(Z), HFE-356mmz, and optionally other components besides 1233zd(Z) and HFE-356mmz. For example, it can be produced by preparing a composition containing 1233zd(Z) and HFE-356mmz, and adding at least one selected from the group consisting of stabilizers, surfactants, flame retardants, metal passivators, and rust inhibitors to the composition.

[0048] Because the cleaning method of this disclosure has excellent cleaning properties, it can be used for degreasing, flux cleaning, precision cleaning, water draining, rinsing, dry cleaning, and the like.

[0049] The cleaning method of this disclosure can be applied to the material to be cleaned, but is not particularly limited in that it includes at least one selected from acrylic polymer, polycarbonate, ABS resin, polystyrene, polyurethane, PVC, and NBR.

[0050] Furthermore, polyurethanes with particularly excellent elasticity are called urethane rubber. Specific examples of PVC include rigid polyvinyl chloride (rigid PVC) and flexible polyvinyl chloride (flexible PVC). Rigid PVC is PVC without plasticizers, while flexible PVC is PVC with plasticizers added. Flexible PVC is particularly preferred.

[0051] Specific articles (objects to be cleaned) to which the cleaning method of this disclosure can be applied include optical components, medical devices, electrical equipment, precision machinery, textile products, and their parts. Examples of electrical equipment, precision machinery, optical articles, and their parts include ICs, capacitors, printed circuit boards, micromotors, relays, bearings, optical lenses, and glass substrates. Examples of medical devices include catheters and hypodermic needles. Furthermore, the cleaning method of this disclosure can also be applied to cleaning various parts such as brakes, wheels, and suspensions in various vehicles and transportation equipment such as automobiles, bicycles, construction machinery, aircraft, and railway vehicles, and can be suitably used as a so-called brake cleaner or parts cleaner. In other words, the cleaning method of this disclosure is also preferably a cleaning method for vehicles or transportation equipment.

[0052] The specific cleaning method is not particularly limited, but one method involves bringing the cleaning composition of this disclosure into contact with the object to be cleaned to remove dirt adhering to the object. That is, the cleaning method of this disclosure preferably includes a step of bringing the cleaning composition of this disclosure into contact with the object to be cleaned. For example, methods include immersing the object to be cleaned in the cleaning composition of this disclosure to wash away the dirt, wiping it with a cloth, or performing spray cleaning, and these may be used in combination. One particularly preferred embodiment is to place the cleaning composition of this disclosure into an ultrasonic cleaner, immerse the article to be cleaned (object to be cleaned) in the liquid, and perform ultrasonic cleaning. Another preferred embodiment is spray cleaning, for example, a method of spraying an aerosol composition containing the cleaning composition of this disclosure and a propellant gas onto the object to be cleaned.

[0053] The cleaning composition of this disclosure can be used as an aerosol when combined with a propellant gas. The propellant gas used has a pressure at 0°C equal to atmospheric pressure (1.013 × 10⁻¹⁰). ５It is preferable that the pressure is Pa or higher. As the propellant gas, liquefied gas or compressed gas can be used. 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, trifluoroiodomethane, etc., which can be used individually or in combination of two or more, and air can also be suitably used, for example. The propellant gas may be either liquefied gas or compressed gas, or a combination of liquefied gas and compressed gas may be used.

[0054] The above aerosol is filled with the cleaning composition of the present disclosure and a propellant gas. The cleaning composition of the present disclosure may be filled in the container together with the propellant gas, or it may be filled in the container separately from the propellant gas. The propellant gas contained in the aerosol preferably has an internal pressure of 0.2 to 1 MPa at 35°C when sealed in a sprayer.

[0055] The aerosol may further contain a solute. The solute may be dissolved in the cleaning composition of the present disclosure and filled into the aerosol, or it may be filled into the container separately from the cleaning composition of the present disclosure and the propellant gas. Examples of solutes include surface treatment agents such as lubricants, rust inhibitors, moisture-proof coatings, and anti-fouling coatings. When filling with a solute, it is preferable to fill it so that the concentration of the solute is 0.01 to 50% by mass relative to the total amount of the cleaning composition of the present disclosure and the solute.

[0056] The above aerosol may contain stabilizers, other solvents, etc., as needed. Specific examples of stabilizers include the stabilizers mentioned above. Examples of other solvents include solvent (A) mentioned above. The content of the stabilizer in the above aerosol is preferably 5% by mass or less, and more preferably 1% by mass or less, relative to the total of the cleaning composition and the stabilizer of the present disclosure. In a preferred embodiment, the content of the stabilizer is preferably 0 to 5% by mass, and more preferably 0 to 1% by mass, relative to the total of the cleaning composition and the stabilizer of the present disclosure. The content of other solvents in the above aerosol 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 cleaning composition and the other solvents of the present disclosure. In a preferred embodiment, the content of other solvents is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and even more preferably 0 to 5% by mass, relative to the total of the cleaning composition and the other solvents of the present disclosure.

[0057] Examples of dirt adhering to the object to be cleaned include grease, processing oil, silicone oil, flux, wax, ink, mineral oil, mold release agents containing silicone oil, oils and fats such as pitch and asphalt, dust, sebum, and dirt. Examples of processing oils include cutting oil, quenching oil, rolling oil, lubricating oil, machine oil, press working oil, punching oil, drawing oil, assembly oil, and wire drawing oil. The cleaning method and cleaning composition of this disclosure have excellent cleaning properties and are therefore particularly suitable for cleaning processing oil, mineral oil, mold release agents, and sebum.

[0058] The cleaning conditions, such as the contact time and temperature between the object to be cleaned and the cleaning composition of this disclosure in the cleaning method of this disclosure, can be appropriately selected depending on the cleaning method. Furthermore, a known cleaning apparatus can also be appropriately selected. For example, the method and cleaning apparatus described in International Publication No. 2008 / 149907 can be used.

[0059] In a preferred embodiment, the cleaning temperature is preferably 5°C or higher, more preferably 10°C or higher, even more preferably 15°C or higher, particularly preferably 20°C or higher, and most preferably room temperature (25°C) or higher. Furthermore, the cleaning temperature is more preferably below the boiling point of the solvent component in the cleaning composition of this disclosure (a mixed solvent of 1233zd(Z), HFE-356mmz, and, if necessary, other solvent components such as the above-mentioned solvent (A)). For example, it may be 48°C or lower, 46°C or lower, or 45°C or lower. In a preferred embodiment, the cleaning temperature is 5°C or higher, below the boiling point of the solvent component in the cleaning composition of this disclosure, and may be 5 to 48°C, 5 to 46°C or 5 to 45°C. In a preferred embodiment, the cleaning temperature is 10°C or higher, below the boiling point of the solvent component in the cleaning composition of this disclosure, and may be 10 to 48°C, 10 to 46°C or 10 to 45°C. In one preferred embodiment, the washing temperature is 15°C or higher and below the boiling point of the solvent component in the washing composition of the disclosure, and may be 15 to 48°C, 15 to 46°C, or 15 to 45°C. In one preferred embodiment, the washing temperature is 20°C or higher and below the boiling point of the solvent component in the washing composition of the disclosure, and may be 20 to 48°C, 20 to 46°C, or 20 to 45°C. In one preferred embodiment, the washing temperature is 25°C or higher and below the boiling point of the solvent component in the washing composition of the disclosure, and may be 25 to 48°C, 25 to 46°C, or 25 to 45°C. The contact time between the object to be washed and the washing composition of the disclosure may be, for example, 1 minute or more, 5 minutes or more, or 10 minutes or more, from the viewpoint of the washing effect of the dirt adhering to the object to be washed. Furthermore, the contact time may be, for example, 90 minutes or less, or 30 minutes or less, from the viewpoint of minimizing chemical attack on the object to be cleaned. In a preferred embodiment, the contact time between the object to be cleaned and the cleaning composition of the present disclosure may be 1 to 90 minutes, or 1 to 30 minutes. In a preferred embodiment, the contact time between the object to be cleaned and the cleaning composition of the present disclosure may be 5 to 90 minutes, or 5 to 30 minutes.In a preferred embodiment, the contact time between the object to be cleaned and the cleaning composition of the present disclosure is 10 to 90 minutes, or may be 10 to 30 minutes.

[0060] When the cleaning method of this disclosure is used for degreasing, the cleaning temperature is preferably 5°C or higher, more preferably 10°C or higher, even more preferably 15°C or higher, particularly preferably 20°C or higher, and most preferably room temperature (25°C) or higher. The cleaning temperature is also, for example, 48°C or lower, may be 46°C or lower, or 45°C or lower. In one preferred embodiment, the cleaning temperature in degreasing is 5 to 48°C, may be 5 to 46°C, or may be 5 to 45°C. In one preferred embodiment, the cleaning temperature in degreasing is 10 to 48°C, may be 10 to 46°C, or may be 10 to 45°C. In one preferred embodiment, the cleaning temperature in degreasing is 15 to 48°C, may be 15 to 46°C, or may be 15 to 45°C. In one preferred embodiment, the cleaning temperature in degreasing is 20 to 48°C, may be 20 to 46°C, or may be 20 to 45°C. In a preferred embodiment, the cleaning temperature in degreasing cleaning is 25 to 48°C, may be 25 to 46°C, or 25 to 45°C. The contact time between the object to be cleaned and the cleaning composition of the Disclosure may be, for example, 1 minute or more, may be 5 minutes or more, or may be 10 minutes or more. The contact time may also be, for example, 30 minutes or less, or 20 minutes or less. In a preferred embodiment, the contact time between the object to be cleaned and the cleaning composition of the Disclosure may be 1 to 30 minutes, or 1 to 20 minutes. In a preferred embodiment, the contact time between the object to be cleaned and the cleaning composition of the Disclosure may be 5 to 30 minutes, or 5 to 20 minutes. In a preferred embodiment, the contact time between the object to be cleaned and the cleaning composition of the Disclosure may be 10 to 30 minutes, or 10 to 20 minutes.

[0061] When the cleaning method of this disclosure is used for degreasing, any cleaning composition of this disclosure may be used, but the cleaning composition of embodiment (I) described above is preferred. The object to be cleaned may be an object containing at least one selected from acrylic polymer, polycarbonate, ABS resin, polystyrene, polyurethane, PVC, and NBR, but it is preferred that the object to be cleaned contains at least one selected from polycarbonate, ABS resin, polystyrene, polyurethane, PVC, and NBR.

[0062] Furthermore, for example, when the cleaning method of this disclosure is used for dry cleaning, the cleaning temperature is preferably 10°C or higher, more preferably 15°C or higher, and even more preferably 20°C or higher. The cleaning temperature may also be, for example, 40°C or lower, 35°C or lower, or 30°C or lower. For example, it may be roughly around room temperature (25°C). In one preferred embodiment, the cleaning temperature in dry cleaning may be 10 to 40°C, 10 to 35°C, or 10 to 30°C. In one preferred embodiment, the cleaning temperature in dry cleaning may be 15 to 40°C, 15 to 35°C, or 15 to 30°C. In one preferred embodiment, the cleaning temperature in dry cleaning may be 20 to 40°C, 20 to 35°C, or 20 to 30°C. The contact time between the object to be cleaned and the cleaning composition of this disclosure may be, for example, 5 minutes or more, 10 minutes or more, or 30 minutes or more. Furthermore, the contact time may be, for example, 90 minutes or less, or 60 minutes or less. In a preferred embodiment, the contact time between the object to be cleaned and the cleaning composition of the Disclosure may be 5 to 90 minutes, or 5 to 60 minutes. In a preferred embodiment, the contact time between the object to be cleaned and the cleaning composition of the Disclosure may be 10 to 90 minutes, or 10 to 60 minutes. In a preferred embodiment, the contact time between the object to be cleaned and the cleaning composition of the Disclosure may be 30 to 90 minutes, or 30 to 60 minutes.

[0063] When the cleaning method of this disclosure is used for dry cleaning, any cleaning composition of this disclosure may be used, but the cleaning composition of embodiment (II) described above is preferred. When the cleaning method of this disclosure is used for dry cleaning, the cleaning composition may further preferably contain a surfactant. The type and content of the surfactant are as described above. The object to be cleaned may contain at least one selected from acrylic polymer, polycarbonate, ABS resin, polystyrene, polyurethane, PVC, and NBR, but an object containing acrylic polymer is preferred.

[0064] One of the substances removed (or reduced) by the cleaning composition of this disclosure is water. Removing (or reducing) water is also called water-draining cleaning. The method of water-draining cleaning is not particularly limited, and conventionally known methods can be employed. For example, one method is to bring the object to be cleaned (the article to be drained) into contact with the cleaning composition of this disclosure and dry it. As described above, it is also preferable to use the aerosol composition described above. In another preferred embodiment, the cleaning composition of this disclosure can be suitably used as a rinse agent to remove high-boiling point detergent adhering to an article after a cleaning process with a high-boiling point detergent.

[0065] [Cleaning Composition] The present disclosure also relates to a cleaning composition for cleaning an object to be cleaned, comprising at least one selected from acrylic polymer, polycarbonate, acrylonitrile-butadiene-styrene resin, polystyrene, polyurethane, polyvinyl chloride, and nitrile rubber, wherein the cleaning composition contains (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, and comprises 15.0 to 60.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 40.0 to 85.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether. Details of the cleaning composition of this disclosure can be directly referenced from the description of <cleaning composition> in the section on cleaning methods of this disclosure described above.

[0066] One preferred embodiment of the cleaning composition of the present disclosure is Embodiment I described above. In Embodiment I, when the object to be cleaned contains at least one selected from polycarbonate, ABS resin, polystyrene, polyurethane, PVC, and NBR, chemical attack can be reduced in particular.

[0067] In other words, the cleaning composition of the present disclosure preferably contains at least one selected from polycarbonate, acrylonitrile-butadiene-styrene resin, polystyrene, polyurethane, polyvinyl chloride, and nitrile rubber, and preferably contains (Z)-1-chloro-3,3,3-trifluoropropene in an amount of 25.0 to 60.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 40.0 to 75.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

[0068] In embodiment I, the cleaning composition more preferably contains 25.0 to 55.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 45.0 to 75.0% by 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, and more preferably 27.5 to 52 It is more preferable to contain 5% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 47.5 to 72.5% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, and it is particularly preferable to contain 30.0 to 50.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 50.0 to 70.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether. In one preferred embodiment, it is preferable to include 25.0 to 55.0 mass% of 1233zd(Z) and 45.0 to 75.0 mass% of HFE-356mmz with respect to the total amount of 1233zd(Z) and HFE-356mmz, more preferably 25.0 to 52.5 mass% of 1233zd(Z) and 47.5 to 75.0 mass% of HFE-356mmz, and even more preferably 25.0 to 50.0 mass% of 1233zd(Z) and 50.0 to 75.0 mass% of HFE-356mmz. In one preferred embodiment, it is preferable to include 27.5 to 60.0 mass% of 1233zd(Z) and 40.0 to 72.5 mass% of HFE-356mmz with respect to the total amount of 1233zd(Z) and HFE-356mmz, more preferably 27.5 to 55.0 mass% of 1233zd(Z) and 45.0 to 72.5 mass% of HFE-356mmz, even more preferably 27.5 to 52.5 mass% of 1233zd(Z) and 47.5 to 72.5 mass% of HFE-356mmz, and particularly preferably 27.5 to 50.0 mass% of 1233zd(Z) and 50.0 to 72.5 mass% of HFE-356mmz.In one preferred embodiment, it is preferable to include 30.0 to 60.0 mass% of 1233zd(Z) and 40.0 to 70.0 mass% of HFE-356mmz with respect to the total amount of 1233zd(Z) and HFE-356mmz; more preferably 30.0 to 55.0 mass% of 1233zd(Z) and 45.0 to 70.0 mass% of HFE-356mmz; even more preferably 30.0 to 52.5 mass% of 1233zd(Z) and 47.5 to 70.0 mass% of HFE-356mmz; and particularly preferably 30.0 to 50.0 mass% of 1233zd(Z) and 50.0 to 70.0 mass% of HFE-356mmz.

[0069] Another preferred embodiment of the cleaning composition of the present disclosure is Embodiment II described above. In Embodiment II, chemical attack can be reduced, especially when the object to be cleaned contains an acrylic polymer.

[0070] In other words, the cleaning composition of the present disclosure is also preferably such that the object to be cleaned contains an acrylic polymer and comprises 15.0 to 35.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 65.0 to 85.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

[0071] In embodiment II, the cleaning composition more preferably contains 15.0 to 30.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 70.0 to 85.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, and more preferably 17.5 to 2 It is more preferable to contain 7.5% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 72.5 to 82.5% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, and it is particularly preferable to contain 20.0 to 25.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 75.0 to 80.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether. In one preferred embodiment, it is preferable that the total amount of 1233zd(Z) and HFE-356mmz contains 15.0 to 30.0 mass% of 1233zd(Z) and 70.0 to 85.0 mass% of HFE-356mmz, more preferably 15.0 to 27.5 mass% of 1233zd(Z) and 72.5 to 85.0 mass% of HFE-356mmz, and even more preferably 15.0 to 25.0 mass% of 1233zd(Z) and 75.0 to 85.0 mass% of HFE-356mmz. In one preferred embodiment, it is preferable to include 17.5 to 35.0 mass% of 1233zd(Z) and 65.0 to 82.5 mass% of HFE-356mmz with respect to the total amount of 1233zd(Z) and HFE-356mmz, more preferably 17.5 to 30.0 mass% of 1233zd(Z) and 70.0 to 82.5 mass% of HFE-356mmz, even more preferably 17.5 to 27.5 mass% of 1233zd(Z) and 72.5 to 82.5 mass% of HFE-356mmz, and particularly preferably 17.5 to 25.0 mass% of 1233zd(Z) and 75.0 to 82.5 mass% of HFE-356mmz.In one preferred embodiment, it is preferable to include 20.0 to 35.0 mass% of 1233zd(Z) and 65.0 to 80.0 mass% of HFE-356mmz with respect to the total amount of 1233zd(Z) and HFE-356mmz, more preferably 20.0 to 30.0 mass% of 1233zd(Z) and 70.0 to 80.0 mass% of HFE-356mmz, even more preferably 20.0 to 27.5 mass% of 1233zd(Z) and 72.5 to 80.0 mass% of HFE-356mmz, and particularly preferably 20.0 to 25.0 mass% of 1233zd(Z) and 75.0 to 80.0 mass% of HFE-356mmz.

[0072] The present disclosure will be described in more detail below with reference to examples, but the disclosure is not limited thereto. Compositions 4 to 6 are examples, and compositions 1 to 3 are comparative examples.

[0073] <Example of 1233zd(Z) production> 1233zd(Z) was produced based on the description in Japanese Patent Publication No. 2017-110020. The purity was 99% or higher.

[0074] <Example of preparation of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether> 1,1,1,3,3,3-hexafluoroisopropyl methyl ether was prepared in accordance with the description in U.S. Patent No. 3346448. The purity was 99% or higher.

[0075] <Preparation of Cleaning Compositions> Compositions 1-6 were prepared by mixing 1233zd(Z) (Composition 1), HFE-356mmz (Composition 2), and 1233zd(Z) and HFE-356mmz in mass ratios of 7:3, 5:5, 3:7, and 2:8, respectively. Compositions 1-6 were prepared using 1233zd(Z) with a water content of 0.0026% by mass and HFE-356mmz with a water content of 0.0050% by mass, respectively. The water content of each composition can be calculated from the content of 1233zd(Z) and HFE-356mmz. For example, in composition 4, the water content is 0.0038% by mass.

[0076] The following tests were conducted assuming degreasing and cleaning. [Examples 1-1 to 1-2, Comparative Examples 1-1 to 1-3] <Mass Change Rate Test 1> Rectangular prism-shaped test pieces (dimensions: 30 mm x 15 mm x 5 mm) from the manufacturers and model numbers shown in Table 1 were prepared.

[0077]

[0078] After measuring the mass (mass I) of the test piece described above, the test piece was immersed in compositions 1 to 5 under the following conditions: • Immersion time: 10 minutes • Test temperature: Near the boiling point of each composition Composition 1 (1233 Hz) 40°C Composition 2 (HFE-356 Hz) 51°C Compositions 3-5 48°C

[0079] Test pieces were removed from each composition, vacuum-dried at room temperature (25°C) until no further mass change occurred, and the mass of the immersed test piece (mass II) was measured. The mass change rate was calculated using the following formula and evaluated based on the evaluation criteria below: Mass change rate (%) = {(mass II - mass I) / mass I} × 100

[0080] (Evaluation Criteria) A: Mass change rate of ±1.0% or less B: Mass change rate greater than ±1.0% and 1.5% or less C: Mass change rate greater than ±1.5% Note that A and B are usable under the above evaluation criteria. The evaluation results are shown in Table 2.

[0081] In the table below, the ratio of 1233zd(Z) to HFE-356mmz represents the mass ratio.

[0082]

[0083] The results in Table 2 show that compositions 4 and 5 in the examples have material compatibility with various resins. Compositions 1 and 3, which have a 1233zd(Z) content greater than the specified value, were found to have insufficient material compatibility.

[0084] When using the cleaning composition for degreasing purposes, the contact time between the cleaning composition and the object being cleaned is short, so the immersion time can be evaluated at 10 minutes. However, a long-term resistance test was also conducted with an immersion time of 7 days (168 hours). The test conditions other than the immersion time were the same as above, and the same evaluation criteria were used for evaluation. Composition 5 received an A rating for polycarbonate and polystyrene. Composition 4 received a B rating for flexible PVC. Thus, depending on the composition of the cleaning composition of this disclosure and the type of resin of the object being cleaned, long-term resistance was also achieved.

[0085] [Examples 2-1 to 2-2, Comparative Examples 1-1 to 1-2] <Cleaning Power Test 1> Various oils (mineral oils) from the manufacturers and model numbers shown in Table 3 were prepared. Commercially available kerosene was also prepared.

[0086]

[0087] To evaluate the cleaning power of the composition, its compatibility with various oils was confirmed. Specifically, the above-mentioned oils and the composition were mixed in a mass ratio of 1:9 and shaken well. After standing, the appearance was observed and evaluated according to the evaluation criteria below. The test temperature was room temperature (25°C).

[0088] (Evaluation Criteria) A: No bilayer separation was observed, and the samples were miscible. B: Bilayer separation was observed. Based on the above evaluation criteria, A is acceptable. Table 4 shows the evaluation results.

[0089]

[0090] The results in Table 4 show that compositions 4 and 5 in the examples have sufficient cleaning power against various oils. Composition 2, which has a higher HFE-356 MHz content than the specified value, was found to have insufficient cleaning power against many types of oils.

[0091] The results in Tables 2 and 4 show that compositions 4 and 5 of the examples have material compatibility with various resins and sufficient cleaning power with various oils.

[0092] The following tests were conducted simulating dry cleaning. [Examples 3-1 to 3-2, Comparative Examples 3-1 to 3-2] <Mass Change Rate Test 2> A cylindrical test piece with a diameter of 30 mm and a thickness of 5 mm (manufactured by Kuraray Co., Ltd., model number: Acrylic plate transparent Comoglass (extruded), plate thickness (5 mm)) was prepared. After measuring the mass (mass III) of the above test piece, the test piece was immersed in compositions 1, 2, 5, and 6 respectively under the following conditions. ・Immersion time: 5 minutes, 10 minutes, 60 minutes ・Test temperature: Room temperature (25°C)

[0093] Test pieces were taken from each composition, vacuum-dried at room temperature (25°C) for 1 minute, and the mass (mass IV) of the immersed test piece was measured. The mass change rate was calculated using the following formula and evaluated based on the evaluation criteria below: Mass change rate (%) = {(mass IV - mass III) / mass III} × 100

[0094] (Evaluation Criteria) A: Mass change rate of ±1.0% or less B: Mass change rate greater than ±1.0% and 1.5% or less C: Mass change rate greater than ±1.5% Note that A and B are acceptable under the above evaluation criteria.

[0095] Table 5 shows the evaluation results.

[0096]

[0097] Furthermore, after immersion for 60 minutes and drying, the test pieces were observed on the surface and evaluated as A for those that were not sticky and B for those that were sticky. Compositions 2, 5, and 6 were evaluated as A, while composition 1 was evaluated as B.

[0098] The results in Table 5 show that compositions 5 and 6 in the examples have material compatibility with the acrylic polymer. Composition 1, which has a 1233zd(Z) content greater than the specified value, was found to have insufficient material compatibility.

[0099] [Example 4-1, Comparative Examples 4-1 to 4-2] <Cleaning Power Test 2> Approximately 0.03 g of mayonnaise (commercially available) was applied as an oil component to a cut cloth (cotton, white, approximately 30 mm x 30 mm) to be used as the object to be washed. Two 20 mL vials were prepared, each containing 10 mL of the composition, to be used for washing and rinsing, respectively. The object to be washed was placed in the washing vial and shaken, and after ultrasonic irradiation for 1 minute, the object to be washed was transferred to the rinsing vial and shaken. The washed object was then removed and dried in a 40°C constant temperature bath for 5 minutes, and its appearance was visually observed and evaluated according to the evaluation criteria below. The test temperature during washing was room temperature (25°C).

[0100] (Evaluation Criteria) A: Almost no remaining dirt B: Some remaining dirt C: A lot of remaining dirt Note that A is usable according to the above evaluation criteria. The evaluation results are shown in Table 6.

[0101]

[0102] The results in Table 6 show that composition 5 of the example has sufficient cleaning power against oily components. Composition 2, which has an HFE-356 MHz content higher than the specified value, was found to have insufficient cleaning power against oily components.

[0103] From the results in Tables 5 and 6, it was found that composition 5 of the example has material compatibility with acrylic polymers and sufficient cleaning power against oily components.

[0104] This disclosure can provide a cleaning method that achieves both material compatibility with the object to be cleaned and cleaning performance. Furthermore, this disclosure can provide a cleaning composition that can be suitably used in the above cleaning method.

[0105] Although this disclosure has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of this disclosure. This application is based on Japanese Patent Application No. 2025-025905, filed on February 20, 2025, the contents of which are incorporated herein by reference.

Claims

1. A method for cleaning an object to be cleaned, comprising at least one selected from acrylic polymer, polycarbonate, acrylonitrile-butadiene-styrene resin, polystyrene, polyurethane, polyvinyl chloride, and nitrile rubber, using a cleaning composition, wherein the cleaning composition contains (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, and comprises 15.0 to 60.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 40.0 to 85.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

2. The cleaning method according to claim 1, wherein the object to be cleaned comprises at least one selected from polycarbonate, acrylonitrile-butadiene-styrene resin, polystyrene, polyurethane, polyvinyl chloride, and nitrile rubber, and the cleaning composition comprises (Z)-1-chloro-3,3,3-trifluoropropene and 25.0 to 60.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 40.0 to 75.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

3. The cleaning method according to claim 1, wherein the object to be cleaned contains an acrylic polymer, and the cleaning composition contains (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether in an amount of 15.0 to 35.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 65.0 to 85.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

4. A cleaning composition for cleaning an object to be cleaned, comprising at least one selected from acrylic polymer, polycarbonate, acrylonitrile-butadiene-styrene resin, polystyrene, polyurethane, polyvinyl chloride, and nitrile rubber, wherein the composition contains (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, and comprises 15.0 to 60.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 40.0 to 85.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

5. The cleaning composition according to claim 4, wherein the object to be cleaned comprises at least one selected from polycarbonate, acrylonitrile-butadiene-styrene resin, polystyrene, polyurethane, polyvinyl chloride, and nitrile rubber, and comprises (Z)-1-chloro-3,3,3-trifluoropropene, 25.0 to 60.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 40.0 to 75.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

6. The cleaning composition according to claim 4, wherein the object to be cleaned contains an acrylic polymer and comprises (Z)-1-chloro-3,3,3-trifluoropropene, 15.0 to 35.0% by mass of (Z)-1-chloro-3,3,3-trifluoropropene and 65.0 to 85.0% by mass of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, based on the total amount of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.

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