Azeotropic composition, azeotrope-like composition, composition, cleaning agent, solvent, heat transfer medium

Abstract

The present invention provides an azeotropic composition, a quasi-azeotropic composition, and a composition that have little impact on the global environment, are non-flammable, and are not prone to composition changes even after repeated evaporation and condensation, as well as a cleaning agent, a solvent, and a heat transfer medium containing the azeotropic composition, the quasi-azeotropic composition, or the composition. An azeotropic composition, which is composed of 34.5% by mass of (Z)-1-chloro-2,3,3-trifluoropropene and 65.5% by mass of trans-1,2-dichloroethylene; an azeotropic composition, which is composed of 28 to 41% by mass of (Z)-1-chloro-2,3,3-trifluoropropene and 59 to 72% by mass of trans-1,2-dichloroethylene.

Description

Technical Field

[0001] The present invention relates to azeotropic compositions, azeotrope-like compositions, and compositions that have little impact on the global environment, are non-flammable, and are unlikely to undergo compositional changes even after repeated evaporation and condensation, as well as cleaning agents, solvents, and heat transfer media containing the azeotropic compositions, azeotrope-like compositions, or compositions. Background Art

[0002] Chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs) have long been used in a variety of applications, including cleaning agents, solvents, heat transfer media, foaming agents, and fire extinguishers, due to their non-flammability, stability, and drying properties. However, there are concerns about the impact of CFCs, HCFCs, and HFCs on the ozone layer and the global warming effect.

[0003] Fluoroolefins have been proposed as a replacement for CFCs, HCFCs, and HFCs. Because fluoroolefins have carbon-carbon double bonds in their molecules, they have a short lifespan in the atmosphere and have little impact on the global environment.

[0004] However, when fluoroolefins are used alone for these applications, the desired performance may not be fully achieved. To address this issue, studies are underway to combine fluoroolefins with other components depending on the intended purpose.

[0005] For example, Patent Document 1 proposes a composition containing monochlorotrifluoropropene (HCFO-1233) and additional components.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: International Publication No. 2011 / 031697 Summary of the Invention

[0009] Technical problem to be solved by the invention

[0010] However, when using multiple ingredients in combination, the boiling points of each ingredient vary, causing the composition to change during use, sometimes preventing full performance. Furthermore, when adding ingredients with a flash point as an additional ingredient, safety measures must be taken.

[0011] An object of the present invention is to provide an azeotropic composition, an azeotrope-like composition, and a composition that have little impact on the global environment, are non-flammable, and are unlikely to undergo compositional changes even after repeated evaporation and condensation.

[0012] In addition, the present invention also aims to provide a cleaning agent, a solvent and a heat transfer medium comprising the azeotropic composition, the azeotrope-like composition or the composition.

[0013] Technical solutions used to solve technical problems

[0014] The present inventors have conducted diligent research and have completed the present invention. That is, the present invention is as follows [1] to

[17] .

[0015] [1] An azeotropic composition consisting of 34.5% by mass of (Z)-1-chloro-2,3,3-trifluoropropene and 65.5% by mass of trans-1,2-dichloroethylene.

[0016] [2] An azeotrope-like composition comprising 28 to 41 mass % of (Z)-1-chloro-2,3,3-trifluoropropene and 59 to 72 mass % of trans-1,2-dichloroethylene.

[0017] [3] The azeotrope-like composition as described in [2], which has a relative volatility of 1.00±0.10.

[0018] [4] A composition comprising (Z)-1-chloro-2,3,3-trifluoropropene and trans-1,2-dichloroethylene,

[0019] The total ratio of (Z)-1-chloro-2,3,3-trifluoropropene and trans-1,2-dichloroethylene in the composition is 90% by mass or more relative to the total amount of the composition.

[0020] The mass ratio of (Z)-1-chloro-2,3,3-trifluoropropene to trans-1,2-dichloroethylene is 28 / 72 to 41 / 59.

[0021] [5] The composition according to [4], further comprising (E)-1-chloro-2,3,3-trifluoropropene.

[0022] [6] A cleaning agent comprising the azeotropic composition described in [1].

[0023] [7] A cleaning agent comprising the azeotrope-like composition described in [2] or [3].

[0024] [8] A cleaning agent comprising the composition described in [4] or [5].

[0025] [9] A solvent comprising the azeotropic composition described in [1].

[0026]

[10] A solvent comprising the azeotrope-like composition described in [2] or [3].

[0027]

[11] A solvent comprising the composition described in [4] or [5].

[0028]

[12] An aerosol composition comprising the azeotropic composition described in [1].

[0029]

[13] An aerosol composition comprising the azeotrope-like composition described in [2] or [3].

[0030]

[14] An aerosol composition comprising the composition described in [4] or [5].

[0031]

[15] A heat transfer medium comprising the azeotropic composition described in [1].

[0032]

[16] A heat transfer medium comprising the azeotrope-like composition described in [2] or [3].

[0033]

[17] A heat transfer medium comprising the composition described in [4] or [5].

[0034] Effects of the Invention

[0035] The azeotropic composition, azeotrope-like composition and composition of the present invention have little impact on the global environment, are non-flammable, and are unlikely to undergo compositional changes even after repeated evaporation and condensation.

[0036] The cleaning agent, solvent and heat transfer medium of the present invention have little impact on the earth's environment, are non-flammable, and are unlikely to undergo component changes even after repeated evaporation and condensation. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 FIG2 is a schematic diagram showing an example of a cleaning apparatus for carrying out the cleaning method of the present invention. DETAILED DESCRIPTION

[0038] In this specification, the abbreviation of the halogenated hydrocarbon is recorded in the brackets after the compound name, but its abbreviation may be used instead of the compound name as needed in this specification. In addition, as an abbreviation, sometimes only the lowercase numerals and letters after the dash (-) are used (for example, only "1233yd" is used for "HCFO-1233yd"). In addition, the (E) in the name of the compound having geometric isomers and its abbreviation represents the E-form body, and (Z) represents the Z-form body. If the E-form body and the Z-form body are not clearly recorded in the name or abbreviation of the compound, the name or abbreviation refers to a general term including the E-form body, the Z-form body and the mixture of the E-form body and the Z-form body.

[0039] In this specification, compounds in which a portion of the hydrogen atoms of a saturated hydrocarbon compound are replaced by fluorine atoms are referred to as hydrofluorocarbons (HFCs), compounds in which a portion of the hydrogen atoms of a saturated hydrocarbon compound are replaced by fluorine atoms and chlorine atoms are referred to as hydrochlorofluorocarbons (HCFCs), compounds in which all the hydrogen atoms of a saturated hydrocarbon compound are replaced by fluorine atoms and chlorine atoms are referred to as chlorofluorocarbons (CFCs), compounds having a carbon-carbon double bond and consisting of carbon atoms, fluorine atoms, and hydrogen atoms are referred to as hydrofluoroolefins (HFOs), and compounds having a carbon-carbon double bond and consisting of carbon atoms, chlorine atoms, fluorine atoms, and hydrogen atoms are referred to as hydrochlorofluoroolefins (HCFOs).

[0040] In this specification, the numerical range expressed with "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0041] [Azeotropic composition]

[0042] The azeotropic composition of the present invention comprises 34.5 mass% of (Z)-1-chloro-2,3,3-trifluoropropene (HCFO-1233yd(Z)) and 65.5 mass% of trans-1,2-dichloroethylene (hereinafter referred to as "tDCE"). Specifically, in the azeotropic composition of the present invention, the content of 1233yd(Z) is 34.5 mass% relative to the total amount of the azeotropic composition of the present invention, and the content of tDCE is 65.5 mass% relative to the total amount of the azeotropic composition of the present invention.

[0043] The azeotropic composition of the present invention is at a pressure of 1.0×10 5 The boiling point under Pa is 46°C.

[0044] The azeotropic composition of the present invention has minimal impact on the global environment, is non-flammable, and maintains no compositional changes even after repeated evaporation and condensation. Therefore, it offers the advantage of achieving extremely stable performance in various applications, such as cleaning agents, solvents, and heat transfer media.

[0045] The azeotropic composition has a relative volatility of 1.00 as expressed by the following formula.

[0046] (Calculation formula for relative volatility)

[0047] Relative volatility = (mass % of 1233yd(Z) in the liquid phase / mass % of tDCE in the liquid phase) / (mass % of 1233yd(Z) in the gas phase / mass % of tDCE in the gas phase)

[0048] [Azeotrope-like composition]

[0049] The azeotrope-like composition of the present invention comprising 1233yd(Z) and tDCE is a composition having a 1233yd(Z) content ratio of 28 to 41% by mass and a tDCE content ratio of 59 to 72% by mass. Specifically, in the azeotrope-like composition of the present invention, the 1233yd(Z) content is 28 to 41% by mass, and the tDCE content is 59 to 72% by mass, relative to the total amount of the azeotrope-like composition of the present invention.

[0050] In this specification, an azeotrope-like composition refers to a composition having a relative volatility calculated from the above formula within the range of 1.00±0.10.

[0051] In addition, the azeotrope-like composition of the present invention is 5 The boiling point under Pa is 44-48°C.

[0052] The azeotrope-like composition of the present invention has minimal impact on the global environment, is non-flammable, and exhibits minimal compositional changes upon repeated evaporation and condensation, making it substantially equivalent to the aforementioned azeotropic composition of the present invention. Therefore, when used in various applications such as cleaning agents, solvents, and heat transfer media, it offers the advantage of achieving stable performance comparable to that of the aforementioned azeotropic composition.

[0053] [Composition]

[0054] The composition of the present invention comprises 1233yd(Z) and tDCE, wherein the total ratio of 1233yd(Z) and tDCE in the composition is 90% by mass or more relative to the total amount of the composition, and the mass ratio of 1233yd(Z) to tDCE (1233yd(Z) / tDCE) is 28 / 72 to 41 / 59.

[0055] That is, the composition of the present invention contains 1233yd(Z) and tDCE in an amount of 90% by mass or more in total based on the total amount of the composition.

[0056] The composition of the present invention may further contain components other than 1233yd(Z) and tDCE (hereinafter also referred to as "other components") in an amount of 10% by mass or less based on the total amount of the composition, within a range not impairing the effects of the present invention.

[0057] Examples of other components include (E)-1-chloro-2,3,3-trifluoropropene (HCFO-1233yd(E)), 1-chloro-2,2,3,3-tetrafluoropropane (HCFC-244ca), 1,1,2-trifluoro-3-chloropropene (HCFO-1233yc), 1-chloro-3,3-difluoropropyne, trichloroethylene, and cis-1,2-dichloroethylene.

[0058] The content of other components is preferably 7% by mass or less, more preferably 5% by mass or less, based on the total amount of the composition.

[0059] The composition of the present invention is subjected to a pressure of 1.0×10 5 The boiling point under Pa is 44-48°C.

[0060] The composition of the present invention, containing a combined total of 90% by mass or greater of 1233yd(Z) and tDCE, has a minimal impact on the global environment, is non-flammable, and exhibits minimal compositional changes upon repeated evaporation and condensation, making it virtually equivalent to the aforementioned azeotropic or azeotrope-like compositions. Consequently, when used in various applications, such as cleaning agents, solvents, and heat transfer media, it offers the advantage of achieving stable performance comparable to that of the aforementioned azeotropic or azeotrope-like compositions.

[0061] 1233yd(Z) is an olefin having a carbon-carbon double bond, and therefore has a short atmospheric lifetime and low ozone depletion potential and greenhouse effect potential.

[0062] 1233yd(Z) has a boiling point of 54°C, making it suitable for use on parts susceptible to heat. Furthermore, 1233yd(Z) has excellent performance as a cleaning agent or solvent, as it has no flash point, dries easily, and has excellent penetrating properties due to its low surface tension and viscosity.

[0063] Furthermore, 1233yd(Z) has low viscosity, so it has low resistance when passing through pipes, is excellent in transportation characteristics, and has excellent performance as a heat transfer medium.

[0064] 1233yd(Z) can be produced, for example, by the method described in International Publication No. 2017 / 018412. This method typically yields an isomeric mixture of 1233yd(Z) and 1233yd(E). This isomeric mixture can be purified by known methods such as distillation to yield 1233yd(Z).

[0065] The azeotropic composition, azeotrope-like composition, and composition of the present invention each contain the aforementioned amount of 1233yd(Z). Therefore, they have a low impact on the global environment, are non-flammable, and exhibit properties suitable for various applications such as cleaning agents, solvents, and heat transfer media.

[0066] Because tDCE is an olefin with a carbon-carbon double bond, its atmospheric lifetime is short and its impact on the global environment is minimal. The presence of chlorine atoms within the molecule makes tDCE highly soluble in organic matter.

[0067] In addition, tDCE has a boiling point of approximately 49°C, making it suitable for use in components susceptible to heat.

[0068] In addition, tDCE has excellent drying properties and excellent penetrability due to its low surface tension and viscosity, and thus has excellent performance as a cleaning agent or solvent.

[0069] Furthermore, tDCE has low viscosity, so it has low resistance when passing through pipes, excellent transport properties, and excellent performance as a heat transfer medium.

[0070] On the other hand, tDCE has a problem of having a flash point.

[0071] The azeotropic composition, azeotrope-like composition, and composition of the present invention contain tDCE, which has excellent cleaning properties, solubility, transport characteristics, etc. In addition, the boiling point can be lower than when 1233yd(Z) is used alone.

[0072] The azeotropic compositions, azeotrope-like compositions, and compositions of the present invention described above have minimal impact on the global environment, are non-flammable, and are unlikely to undergo compositional changes even after repeated evaporation and condensation. They exhibit excellent properties suitable for various applications such as cleaning agents, solvents, and heat transfer media.

[0073] The azeotropic compositions, azeotrope-like compositions and compositions of the present invention are preferably used as cleaning agents, solvents, aerosol compositions, heat transfer media, fire extinguishing agents, foaming agents and the like.

[0074] Examples of materials to which the azeotropic composition, azeotrope-like composition, and composition of the present invention can be applied include metals, plastics, elastomers, glass, ceramics, fibers, and composite materials thereof. Preferred among these are metals such as iron, copper, nickel, gold, silver, and platinum, sintered metals, glass, fluororesins, polyimides, polyphenylene sulfide, liquid crystal polymers, and engineering plastics such as PEEK.

[0075] [Cleaning agent]

[0076] The azeotropic composition, azeotrope-like composition and composition of the present invention have excellent cleaning properties and can therefore be used as a cleaning agent for degreasing cleaning, flux removal, precision cleaning, dehydration cleaning, rinsing, dry cleaning and the like.

[0077] Examples of articles to which the cleaning agent of the present invention can be applied include optical components, medical instruments, electrical equipment, precision instruments, textile products, and their components. Examples of electrical equipment, precision instruments, and optical articles and their components include integrated circuits, capacitors, printed circuit boards, micromotors, relays, bearings, optical lenses, and glass substrates. Examples of medical instruments include catheters and injection needles.

[0078] The method for cleaning an article is a method for removing stains attached to the article by bringing the cleaning agent of the present invention into contact with the article.

[0079] Examples of stains that adhere to articles include grease, processing oil, silicone oil, brazing flux, wax, ink, mineral oil, silicone-containing mold release agents, asphalt, tar, and other oils and fats, as well as dust. Examples of processing oil include cutting oil, quenching oil, rolling oil, lubricating oil, engine oil, pressurized working oil, punching oil, drawing oil, assembly oil, and wire drawing oil.

[0080] The cleaning agent of the present invention has excellent cleaning properties and can therefore be particularly advantageously used for cleaning process oils, asphalt, and asphalt.

[0081] Examples of methods for cleaning articles include manual cleaning, immersion cleaning, spray cleaning, immersion shaking cleaning, immersion ultrasonic cleaning, steam cleaning, and combinations thereof.

[0082] In the above-mentioned cleaning method, the cleaning conditions such as contact time and temperature of the article can be suitably selected according to the cleaning method. In addition, the cleaning apparatus can also suitably select a known apparatus. For example, the method and cleaning apparatus described in International Publication No. 2008 / 149907 can be used to implement.

[0083] The cleaning agent of the present invention comprises an azeotropic composition, an azeotrope-like composition, or a combination thereof. The content of the azeotropic composition, azeotrope-like composition, or combination thereof in the cleaning agent of the present invention is preferably 80% by mass or greater, more preferably 90% by mass or greater, and even more preferably 95% by mass or greater, relative to the total amount of the cleaning agent. The upper limit may be 100% by mass, for example.

[0084] The cleaning agent of the present invention may further contain a stabilizer and the like as needed.

[0085] 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-isopentylpropane, benzyl salicylate, methyl salicylate, 2,6-di-tert-butylphenol, 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, isopentene, 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, isopentene, 2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-pentene, and 2-methylpentene are preferred.

[0086] The stabilizer may be used alone or in combination of two or more.

[0087] The content of the stabilizer in the cleaning agent of the present invention is preferably 5% by mass or less, more preferably 1% by mass or less, based on the total amount of the cleaning agent.

[0088] [Solvent]

[0089] The azeotropic composition, azeotrope-like composition and composition of the present invention have excellent organic solubility and can be used as a solvent for dissolving surface treatment agents such as lubricants, rust inhibitors, moisture-proof coating agents and antifouling coating agents for coating on the surface of articles.

[0090] Examples of the article include the same articles as those to which the cleaning agent can be applied.

[0091] As a method for applying the surface treatment agent to the surface of an article, there may be mentioned a method of dissolving the surface treatment agent in the solvent of the present invention and then evaporating the solvent to form a coating film on the surface of the article.

[0092] When the surface treating agent is dissolved in the solvent of the present invention, it is preferred that the surface treating agent be dissolved to a concentration of 0.01 to 50% by mass, for example.

[0093] Examples of coating methods include brush application, spray application, and dipping. In the case of tubular articles, the surface treatment agent is sometimes dissolved in a solvent, and the resulting surface treatment agent solution is drawn up to coat the inner wall. Alternatively, spray application can be performed in the form of an aerosol encapsulated with the surface treatment agent, the solvent of the present invention, or liquefied gas or compressed gas. Specific examples of liquefied gas and compressed gas are described above.

[0094] The solvent may be evaporated by air drying or drying by heating. The drying temperature is preferably 20 to 100°C.

[0095] The solvent of the present invention includes an azeotropic composition, an azeotrope-like composition, or a composition. The content of the azeotropic composition, azeotrope-like composition, or composition of the present invention in the solvent of the present invention is preferably 80% by mass or greater, more preferably 90% by mass or greater, and even more preferably 95% by mass or greater, relative to the total amount of the solvent. The upper limit may be 100% by mass.

[0096] The solvent of the present invention may further contain a stabilizer, etc. as needed. Specific examples of the stabilizer include the stabilizers described above.

[0097] The content of the stabilizer in the solvent of the present invention is preferably 5% by mass or less, more preferably 1% by mass or less, relative to the total amount of the solvent.

[0098] [Aerosol composition]

[0099] The azeotropic composition, azeotrope-like composition and composition of the present invention can be used as an aerosol by combining with a pressure-increasing agent. The pressure of the pressure-increasing agent used in the present invention at 0°C is preferably atmospheric pressure (1.013×10 5 Pa) or above.

[0100] In the present composition, examples of the pressurizing agent include dimethyl ether (DME), propane, butane, isobutane, 1,1-difluoroethane (HFC-152a), 1,1,1,2-tetrafluoroethane (HFC-134a), 2,3,3,3-tetrafluoropropylene (HFO-1234yf), 1,3,3,3-tetrafluoropropylene (HFO-1234ze), nitrogen, carbon dioxide, and nitrous oxide. These agents may be used alone or in combination. For example, air may also be advantageously used.

[0101] As the pressurizing agent, either liquefied gas or compressed gas may be used, or a combination of liquefied gas and compressed gas may be used.

[0102] The internal pressure of the pressurizing agent contained in the aerosol composition when enclosed in a nebulizer is preferably 0.3 to 1 MPa at 35°C.

[0103] [Heat transfer medium]

[0104] The azeotropic compositions, azeotrope-like compositions, and compositions of the present invention can be used as heat transfer media for heat cycle systems.

[0105] Examples of the thermal cycle system include a Rankine cycle system, a heat pump cycle system, a refrigeration cycle system, a heat transfer system, and a secondary cooling system. More specifically, examples include refrigeration and freezing equipment, air conditioning equipment, power generation systems, heat transfer devices, and secondary cooling machines.

[0106] Hereinafter, a refrigeration cycle system will be described as an example of a heat cycle system.

[0107] A refrigeration cycle system is a system in which a heat transfer medium passes through a load fluid in an evaporator, removing heat energy, thereby cooling the load fluid to a lower temperature. A refrigeration cycle system consists of the following components: a compressor that compresses the heat transfer medium vapor into high-temperature, high-pressure heat transfer medium vapor; a condenser that cools the compressed heat transfer medium vapor into low-temperature, high-pressure heat transfer medium liquid; an expansion valve that expands the heat transfer medium liquid discharged from the condenser into low-temperature, low-pressure heat transfer medium liquid; an evaporator that heats the heat transfer medium discharged from the expansion valve into high-temperature, low-pressure heat transfer medium vapor; a pump that supplies the load fluid to the evaporator; and a pump that supplies the load fluid to the condenser.

[0108] The azeotropic, azeotrope-like, and compositions of the present invention are particularly useful as secondary refrigerants for secondary cycle cooling systems.

[0109] A secondary circulation cooling system is a system that includes a primary cooling unit that cools a primary refrigerant composed of ammonia or a hydrocarbon refrigerant, a secondary circulation cooling unit that circulates a secondary refrigerant used in the secondary circulation cooling system to cool an object to be cooled, and a heat exchanger that exchanges heat between the primary refrigerant and the secondary refrigerant to cool the secondary refrigerant. This secondary circulation cooling system can cool an object to be cooled.

[0110] The heat transfer medium of the present invention comprises an azeotropic composition, an azeotrope-like composition, or a combination thereof. The content of the azeotropic composition, azeotrope-like composition, or combination thereof in the heat transfer medium of the present invention is preferably 80% by mass or greater, more preferably 90% by mass or greater, and even more preferably 95% by mass or greater, relative to the total amount of the heat transfer medium. The upper limit may be 100% by mass, for example.

[0111] The heat transfer medium of the present invention may further contain a stabilizer, etc. as needed. Specific examples of the stabilizer include the stabilizers described above.

[0112] The content of the stabilizer in the solvent of the present invention is preferably 5% by mass or less, more preferably 1% by mass or less, relative to the total amount of the solvent.

[0113] The heat transfer medium of the present invention is usually used as a heat transfer medium composition comprising a heat transfer medium and a refrigeration oil. Examples of the refrigeration oil include polyalkylene glycols, polyol esters, and polyvinyl ethers.

[0114] The content of the refrigeration oil in the heat transfer medium composition is preferably 10 to 100 parts by mass, more preferably 20 to 50 parts by mass, based on 100 parts by mass of the heat transfer medium.

[0115] Example

[0116] The present invention will be described in detail below by way of examples, but the present invention is not limited thereto. Examples 1 to 8 are examples, and Examples 9 to 11 are comparative examples.

[0117] <1233yd production example>

[0118] 1233yd was produced by the method described in Example 1 of International Publication No. 2017 / 018412. The isomer mixture of 1233yd(Z) and 1233yd(E) obtained by the above method was purified by distillation to obtain 1233yd(Z) and 1233yd(E).

[0119] <Measurement of gas-liquid equilibrium (1)>

[0120] 300 g of the mixture 1 to 12 obtained by mixing 1233yd(Z) and tDCE in the mass ratio shown in Table 1 was placed in an Othmer vapor-liquid equilibrium distillation apparatus (manufactured by Shibata Scientific Co., Ltd.) for distillation. The pressure in the apparatus was atmospheric pressure (1.0×10 5 After confirming that the gas and liquid phases were stable and that the temperature had not changed for one hour, samples were collected from the gas and liquid phases within the apparatus and the mass ratio of 1233yd(Z) to tDCE was determined by gas chromatography. The relative volatility was calculated from the mass ratio of 1233yd(Z) to tDCE in the gas and liquid phases using the formula for calculating relative volatility described above. The results are shown in Table 1.

[0121] [Table 1]

[0122]

[0123] As shown in Table 1, the relative volatility of the mixtures with a mass ratio of 1233yd(Z) to tDCE of 28 / 72 to 41 / 59 is 1.00±0.10.

[0124] <Measurement of gas-liquid equilibrium (2)>

[0125] 300 g of a mixture 13 having a mass ratio of 1233yd(Z), 1233yd(E), and tDCE (1233yd(Z) / 1233yd(E) / tDCE) of 31.2 / 1.3 / 67.5 was placed in an Othmer vapor-liquid equilibrium distillation apparatus (manufactured by Shibata Scientific Co., Ltd.) and distilled. The pressure in the apparatus was atmospheric pressure (1.0×10 5 Samples were collected from the gas and liquid phases within the device, and the composition ratios of 1233yd(Z), 1233yd(E), and tDCE were determined by gas chromatography. The liquid phase ratio was 31.2 / 1.2 / 67.6, and the gas phase ratio was 31.1 / 1.5 / 67.4, indicating that the liquid and gas phases had essentially identical compositions.

[0126] Performance Evaluation

[0127] (1) Cleaning test of metalworking oil

[0128] A SUS-304 test piece (25 mm × 30 mm × 2 mm) was immersed in a metalworking oil product named "EM-7451 (kinematic viscosity 342 mm 2 / s: 40℃)" (manufactured by Nippon Working Oil Co., Ltd.), a test piece with metalworking oil attached was prepared. The test piece with metalworking oil attached was immersed in 50 mL of the composition of Examples 1 to 11 described in Tables 2 and 3 for 1 minute, taken out, and the residual state of metalworking oil on the test piece was visually observed as an evaluation of the cleaning property. The test was carried out at a temperature of 23℃, and the case where the metalworking oil was removed was recorded as "A", and the case where the metalworking oil was found to remain was recorded as "B". The results are shown in "Test (1)" of Tables 2 and 3.

[0129] (2) Asphalt cleaning test

[0130] A product called "Spray Asphalt" (manufactured by Kokonoe Electric Co., Ltd.) was blown onto a 10 mm × 20 mm × 5 mm glass substrate and dried overnight to prepare a glass substrate test piece with asphalt attached. 100 g of the composition of Examples 1 to 11 described in Tables 2 and 3 was placed in a 100 ml glass beaker, and each of the test pieces obtained above was immersed for 1 minute. The degree of removal of the asphalt on the test piece was visually evaluated. The case where the asphalt was successfully removed from the glass substrate test piece was recorded as "A", and the case where the asphalt component remained on the glass substrate test piece was recorded as "B". The results are shown in "Test (2)" of Tables 2 and 3.

[0131] (3) Evaluation of cleaning performance of aerosol compositions

[0132] A SUS304 test piece (25 mm×30 mm×2 mm thick) was immersed in metalworking oil (DAPHNE MARGPLUS LA-5 manufactured by Idemitsu Kosan Co., Ltd.) for 1 minute, removed, and allowed to stand overnight to serve as a test piece.

[0133] The solvent compositions of Examples 1-8 and a pressure-boosting agent (CO₂ or N₂) were filled into a spray can at a solvent composition / pressure-boosting agent mass ratio of 95 / 5. Spraying the solvent composition from the spray can successfully removed the metalworking oil from the test piece. Furthermore, any solvent composition adhering to the test piece dried immediately. The type of pressure-boosting agent did not affect cleaning performance.

[0134] (4) Flammability test

[0135] 200 mL of the compositions of Examples 1 to 11 described in Tables 2 and 3 were tested using a Cleveland open cup flash point tester (Model 828, manufactured by Yoshida Seisakusho Co., Ltd.) to determine whether they had a flash point between 23°C and the boiling point. The results are shown in the "Flash Point" section of Tables 2 and 3.

[0136] Each component column described in Tables 2 and 3 ("1233yd(Z)" column, "1233yd(E)" column, and "tDCE" column) shows the content (mass %) of each component relative to the total amount of the composition.

[0137] [Table 2]

[0138] example 1 2 3 4 5 6 1233yd(Z) 28 34.5 34.2 31 28 41 1233yd(E) - - 0.3 3 7 - tDCE 72 65.5 65.5 66 65 59 Test (1) A A A A A A Experiment (2) A A A A A A Flammability none none none none none none

[0139] [Table 3]

[0140] example 7 8 9 10 11 1233yd(Z) 40.5 31 10 15 100 1233yd(E) 0.5 10 - - - tDCE 59.0 59 90 85 - Test (1) A A A A B Experiment (2) A A A A B Flammability none none have have none

[0141] <Cleaning Test>

[0142] The compositions obtained in Examples 12 and 13 of Table 4 below are suitable for use with Figure 1 The same cleaning apparatus as shown was used to conduct a cleaning test. This cleaning test serves as both an evaluation test for the compositions described below and an example of the cleaning method of the present invention. Example 12 is an example, and Example 13 is a comparative example.

[0143] right Figure 1The compositions obtained in Examples 12 and 13 below were prepared in each of the three tanks of the cleaning apparatus 10: cleaning tank 1 (capacity: 5.2 liters), rinsing tank 2 (capacity: 5.0 liters), and steam generation tank 3 (capacity: 2.8 liters). The apparatus was then operated continuously for 8 hours without cleaning to allow the compositions in the tanks within the cleaning apparatus 10 to stabilize and reach a steady state. Furthermore, a test piece identical to the test piece used in performance evaluations (1) and (2) was prepared as the article to be cleaned D.

[0144] Use the cleaning device 10 in a stable state, such as Figure 1 As shown, the test piece was sequentially moved through the cleaning tank 1, the rinsing tank 2, and the steam zone 43 directly above the steam generating tank 3 for cleaning. The temperature of composition La in cleaning tank 1 was set to 40°C, and during cleaning in cleaning tank 1, ultrasonic waves with a frequency of 40 kHz and a power of 200 W were generated for one minute. Furthermore, the temperature of composition Lb in rinsing tank 2 was set to 25°C, while composition Lc in steam generating tank 3 was heated to a constant boiling state. During cleaning, the steam in steam zone 4 was condensed to remove water, and the resulting composition Lm was returned to the rinsing tank 2. The overflow from the rinsing tank 2 flowed into the cleaning tank 1, and the remaining composition La in the cleaning tank 1 was then transferred to the steam generating tank 3.

[0145] After cleaning was completed, the composition La in the cleaning tank 1 was collected and the composition of the collected composition was analyzed using a gas chromatograph (GC7890 manufactured by Agilent Technologies). In addition, the state of the test piece after cleaning was evaluated in the same manner as in the cleaning performance evaluations (1) and (2).

[0146] [Table 4]

[0147]

[0148] Possibility of industrial application

[0149] The azeotropic composition, azeotrope-like composition and composition of the present invention can be used in a wide range of applications such as cleaning agents, solvents, and heat transfer media.

[0150] In addition, the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2019-107140 filed on June 7, 2019 are cited herein as a disclosure of the present specification.

Claims

1. An azeotropic composition comprising 34.5 mass % of (Z)-1-chloro-2,3,3-trifluoropropene and 65.5 mass % of trans-1,2-dichloroethylene.

2. A cleaning agent comprising the azeotropic composition according to claim 1.

3. A solvent comprising the azeotropic composition according to claim 1. 4 . An aerosol composition comprising the azeotropic composition according to claim 1 .

5. A heat transfer medium comprising the azeotropic composition of claim 1.

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