JP2016147941A - Azeotrope-like composition having fluorine-containing olefin as constituent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel azeotropic or azeotrope-like mixture which has low environmental load and is safely handled, and in which a change in the liquid composition is less likely to occur.SOLUTION: A liquid composition is provided that is composed of 70 to 99.9999 mol% of (Z)-1-chloro-3,3,3-trifluoro propene (1233Z), and 0.0001 to 30 mol% of (Z)-1,1,1,4,4,4-hexafluoro-2-butene (1336Z).EFFECT: The liquid composition has a small impact on the global environment, and exhibits an azeotrope-like nature. For this reason, the composition variation practically does not occur even when used in an open system or when used for a long period of time. The composition variation is less likely to occur also in the recovery by distillation. For this reason, a liquid mixture of the present invention can be suitably used as a cleaning agent (solvent).SELECTED DRAWING: None

Description

  The present invention relates to a novel composition containing a fluorine-containing olefin.

  1 to 5 carbon atoms such as chlorofluorocarbons (hereinafter sometimes referred to as CFCs), hydrochlorofluorocarbons (sometimes referred to as HCFCs), hydrofluorocarbons (hereinafter sometimes referred to as HFCs), etc. Fluorine-containing alkanes have volatility, stability, and non-flammability characteristics, and have contributed to industrial development in applications such as refrigerants, working fluids, foaming agents, sprays, cleaning agents, solvents, and solvents. Sometimes called chlorofluorocarbons). In addition, blending a plurality of fluorine-containing alkanes has been widely performed. For example, refrigerant numbers R502, R507A, R404A, R407C, and R410A from the American Society of Heating, Refrigerating and Air Conditioning Engineers (ASHRAE) are widely used as mixed refrigerants. These mixed refrigerants are improved in coefficient of performance, refrigeration cycle, incombustibility, global warming coefficient and the like by mixing two or more kinds of chlorofluorocarbons at a specific ratio. However, since the fluorine-containing alkane has volatility, when one of the components evaporates unilaterally when used as a mixture, the composition changes during use and the physical properties change. Therefore, an azeotropic or azeotropic-like composition that volatilizes at substantially the same composition as the liquid phase is preferable. For example, since the above-mentioned R502 (mixed refrigerant of R22 and R115) and R507A (mixed refrigerant of R143a and R125) have an azeotropic composition, the compositions of the gas phase portion and the liquid phase portion are exactly the same, and are azeotropic. Used as a refrigerant. As for R410A, its constituent components R32 and R125 are non-azeotropic, but since the composition of the gas phase part and the liquid phase part is substantially the same, practically like the azeotropic composition. Since it can be handled, it is used as an azeotropic refrigerant. For non-refrigerant applications, for example, blending fluorine-containing alkanes and alcohol for use as a draining agent, adding non-flammable fluorine-containing alkanes to flammable hydrocarbon solvents to make them nonflammable, or cleaning with controlled detergency There is an agent. Also in the use of a cleaning agent or a draining agent, an azeotropic or azeotrope-like composition in which the composition of the gas phase part and the liquid phase part when volatilized is substantially the same as the refrigerant is preferable.

  Fluorine-containing alkanes as described above are very stable in the atmosphere, have a long atmospheric lifetime, and are considered to cause global warming. On the other hand, in recent years, fluorine-containing olefins having 2 to 5 carbon atoms (referring to hydrofluoroolefins, hydrochlorofluoroolefins, chlorofluoroolefins, and fluoroolefins) have been proposed as substitutes for the fluorine-containing alkanes. These fluorine-containing olefins having a double bond in the molecule are significantly more reactive with OH radicals in the atmosphere than fluorine-containing alkanes having no double bond. Currently, the atmospheric lifetime of HFC-365mfc, HFC-245fa, HFC-43-10, etc., which are widely used, is in units of years, while the atmospheric lifetime of fluorine-containing olefins is generally in units of days. Even when released into the atmosphere, it decomposes quickly, so its impact on global warming and ozone depletion is low. It has been reported that since it has physical properties similar to the above-mentioned fluorinated alkanes, it can be used in various applications such as refrigerants, working fluids, foaming agents, sprays, cleaning agents, solvents and solvents.

  Similar to fluorine-containing alkanes, the performance of fluorine-containing olefins may be improved by blending with other chemical species. For example, Patent Document 1 discloses that when (Z) -1-chloro-3,3,3-trifluoropropene and 1,1,2,2-tetrafluoro-1-methoxyethane are mixed, azeotrope-like two It is reported that a binary solvent is formed and the cleaning performance of various oils possessed by the binary solvent is at an excellent level. There are few report examples of this compared with fluorine-containing alkane. Furthermore, there are even fewer literature examples of azeotropic or azeotrope-like compositions in which fluorine-containing olefins are combined.

JP 2008-133438 A

  In such a volatile solvent composition, even if a plurality of solvents are simply prepared to improve the performance, the problem that the liquid composition tends to fluctuate due to the volatility of each component is unavoidable. For example, when a binary liquid composition is put into an ultrasonic cleaner and subjected to a cleaning process, generally low boiling point components (components with high vapor pressure) are preferentially volatilized, and high boiling point components are contained in the cleaning tank. (A component with a low vapor pressure) is concentrated. For example, in the case of a composition comprising a low-boiling component having a high detergency and a high-boiling component having a low detergency, the low-boiling component in the cleaning liquid may decrease over time, resulting in poor cleaning. In addition, the used cleaning solution is usually regenerated and reused by distillation. If the composition of the liquid phase is different from the composition of the gas phase, the liquid composition of the recovered composition must be adjusted. Not efficient. Further, when the composition is volatilized during use and the composition of the liquid is changed, not only the cleaning performance is changed, but the incombustible composition may be changed to a combustible composition.

  For this reason, an azeotropic or azeotrope-like composition in which the composition of the gas phase portion and the liquid phase portion is substantially the same during volatilization is strongly desired. In the present invention, (Z) -1-chloro-3,3,3-trifluoropropene and (Z) -1,1,1,4,4, which have a short atmospheric life because both contain double bonds. It is an object of the present invention to propose a novel azeotropic or azeotrope-like composition containing 4-hexafluoro-2-butene that hardly changes in composition even when volatilized.

  The present inventors diligently studied to solve the above problems. As a result, the Z form of 1-chloro-3,3,3-trifluoropropene (hereinafter sometimes referred to as HCFO-1233zd (Z) or 1233Z) is 70 mol% to 99.9999 mol% and 1,1 , 1,4,4,4-hexafluoro-2-butene in a Z form (hereinafter sometimes referred to as HFO-1336mzz (Z) or 1336Z) is 0.0001 mol% to 30 mol%, It was found to be an azeotrope-like composition having substantially the same composition in the gas phase portion and the liquid phase portion, and an incombustible material having no flash point under the Fire Service Law. Furthermore, it was confirmed that the azeotrope-like composition of the present invention was useful as an oil and fat removing agent, and the present invention was completed.

  That is, the present invention includes the following inventions.

[Invention 1]
(Z) -1-chloro-3,3,3-trifluoropropene (1233Z) and (Z) -1,1,1,4,4,4-hexafluoro-2-butene (1336Z) Boiling (like) composition.

[Invention 2]
The azeotropic (like) composition according to invention 1, comprising 70 mol% to 99.9999 mol% 1233Z and 0.0001 mol% to 30 mol% 1336Z.

[Invention 3]
The nonflammable azeotropic (like) composition according to Invention 1 or Invention 2, comprising 80 to 99.9999 mol% of 1233Z and 0.0001 to 20 mol% of 1336Z.

[Invention 4]
A liquid composition comprising the azeotropic (like) composition according to any one of Inventions 1 to 3 and at least one additional component.

[Invention 5]
A liquid composition comprising the azeotropic (like) composition according to any one of inventions 1 to 3 and at least one additional component of 10 ppm to 30% by mass based on the azeotropic (like) composition.

[Invention 6]
A cleaning solvent comprising the azeotropic (like) composition or liquid composition according to any one of Inventions 1 to 5.

[Invention 7]
A method for cleaning an object to be cleaned, comprising the step of bringing the azeotropic (like) composition or liquid composition according to any one of Inventions 1 to 5 into contact with the object to be cleaned.

  The present invention provides a novel azeotropic (like) composition. The composition exhibits an effect that the composition hardly changes even when used under an open condition. The azeotropic (like) composition has a low environmental impact and is a non-hazardous material under the Fire Service Law.

  The azeotropic (like) composition is useful as a solvent (cleaning solvent) for cleaning contaminants such as foreign matters and fats and oils.

Vapor-liquid equilibrium of (Z) -1-chloro-3,3,3-trifluoropropene (1233Z) and (Z) -1,1,1,4,4,4-hexafluoro-2-butene (1336Z) FIG.

  Since the fluorine-containing olefin is highly compatible with various solvents, it is relatively easy to prepare a uniform composition. However, in the case of a composition having an arbitrary composition, the problem that “the liquid composition tends to fluctuate” is inherent. That is, even if a plurality of types of liquids are mixed to ensure compatibility, the problem that the liquid composition tends to fluctuate due to the difference in volatility of each component is unavoidable. For example, when a binary liquid composition is put into an ultrasonic cleaner and used as a cleaning agent, generally low boiling point components with high volatility (components with high vapor pressure) are preferentially volatilized, and the inside of the cleaning tank High-boiling components with low volatility are concentrated. For example, in the case of a composition having a low-boiling component having a high detergency and a high-boiling component having a low detergency, the concentration of the low-boiling component in the cleaning liquid may decrease over time, resulting in poor cleaning. In particular, when a noncombustible solvent is blended with a combustible solvent to prepare a noncombustible composition, the cleaning liquid may become a combustible composition when the noncombustible component volatilizes preferentially.

  In addition, it is desirable from the viewpoint of environmental protection and economy that the cleaning solvent is recovered and reused after use by operations such as distillation. However, in the case of two-component liquids, two-component liquids generally having different boiling points are used. In order to collect and recycle them separately, it is easy to place an operational burden.

  Similar problems occur when used as a working fluid in a thermodynamic cycle. That is, even when used as a working fluid in a thermodynamic cycle, the liquid composition may fluctuate over a long period of time. If the liquid composition fluctuates, the heat capacity, viscosity, or affinity with the lubricant of the liquid may change, and the operating performance of the thermodynamic cycle may deteriorate.

  For this reason, when using a binary (multi-component) liquid composition as a cleaning agent or working fluid, the liquid composition is frequently analyzed and constantly mixed at an appropriate ratio so as to be in an appropriate composition range. And must be replenished with volatile components. However, such liquid composition management can be a heavy work load.

  On the other hand, in the case of an azeotropic composition, since it volatilizes at the same composition as the liquid composition, it is a very preferable composition in which the liquid composition does not change during use. As used herein, “azeotropic” refers to azeotropic in a thermodynamically strict sense. For example, in the case of a water / ethanol mixture, the composition of ethanol (96% by mass) and water (4% by mass) is an azeotrope, and vapor that exists in vapor-liquid equilibrium with this is also “ethanol ( 96% by mass): water (4% by mass) ”, which completely matches the liquid composition. This phenomenon is called “azeotropic”. At a specific temperature and pressure, the composition of the azeotrope is only one point.

  “Azeotropic” is also called “pseudo-azeotropic” and is not thermodynamically strict azeotrope, but for a range of liquid compositions, the liquid composition and the composition of the gas in equilibrium , Refers to such a phenomenon that may be substantially equal. Even if the compositions of the gas phase part and the liquid phase part do not completely match, those skilled in the art can handle the composition in the same manner as the azeotropic composition as long as the composition of the gas phase part and the liquid phase substance substantially match. At this time, the smaller the vapor-liquid equilibrium composition difference between the gas phase portion and the liquid phase portion, the better. As described above, a phenomenon in which the vapor-liquid equilibrium portion substantially matches the vapor-liquid equilibrium composition is called azeotropic or pseudo-azeotropic, and the composition is called azeotropic-like or pseudo-azeotropic composition. .

  Academically, azeotropic and pseudo-azeotropic (or azeotropic) should be distinguished, but in practice such as cleaning, azeotropic and azeotropic (or pseudo-azeotropic) are distinguished. In this specification, the azeotropic phenomenon and the azeotrope-like phenomenon (or pseudo-azeotrope) are collectively referred to as “azeotrope (like)”. The composition at that time is referred to as an “azeotropic (like) composition”.

  In azeotropic (like), the presence or absence of an azeotropic point is not questioned. It is sufficient that the vapor-liquid equilibrium composition of the gas phase portion and the liquid phase portion substantially coincide.

  "Azeotropic behavior" is not theoretically derived, and the vapor-liquid equilibrium was experimentally investigated for various liquid types and composition ratios. By chance, the composition of the gas phase and the composition of the liquid phase substantially coincided. Sometimes it can be found for the first time. In the present invention, (Z) -1-chloro-3,3,3-trifluoropropene (1233Z) that is commercially available as a next-generation detergent and (Z) -1 that is available as a next-generation blowing agent 1,1,4,4,4-hexafluoro-2-butene (1336Z), an azeotrope-like composition having substantially the same gas-liquid composition in a specific region could be found.

  In particular, since 1233Z and 1336Z have different boiling points and polarities, it is very difficult to predict whether or not they will become azeotropic (like). It is impossible to specify without an experiment.

  The boiling point and polarity (dipole moment (B3LYP / 6-311 ++ G ** calculated value)) of each compound are as follows.

  As shown in the examples, as a result of examining the volatilization behavior of this composition in detail, 1233Z as the first component was 70 mol% to 99.9999 mol% and 1336Z as the second component was 0.0001 mol%. ~ 30 mol%, more preferably, the composition in which the first component 1233Z is 80 mol% to 99.9999 mol% and the second component 1336Z is 0.0001 mol% to 20 mol% Since it volatilizes at a composition ratio that approximates the liquid phase composition at the time of volatilization, for example, even if it partially volatilizes from the inside of the cleaning machine in the cleaning process, it is a very suitable composition that does not practically change the composition of the cleaning liquid There was found. Among them, a composition in which 1233Z as the first component is 90 mol% to 99.9999 mol% and 1336Z as the second component is 0.0001 mol% to 10 mol% is particularly preferable because the composition variation is much smaller.

  It goes without saying that the azeotropic (like) composition of the present invention is one of preferred embodiments in which a high-purity composition is substantially free of impurities. However, depending on the application, a liquid composition with such a high purity may not be required. In such a case, a small amount of raw materials and by-products for synthesizing the first component 1233Z and the second component 1336Z (usually each component has the azeotropic (like) composition). Or less than 1% by weight with respect to the product), the remaining one can also be used.

  If desired, additional components may be added to improve the performance of the azeotropic (like) composition, resulting in a “liquid composition comprising the azeotropic (like) composition of the present invention and at least one additional component”. You can also. Examples of the additional component include a detergency enhancer (surfactant), a stabilizer (acid acceptor, antioxidant), and the like.

  Specific examples of the surfactant include sorbitan aliphatic esters such as sorbitan monooleate and sorbitan trioleate; polyoxyethylene sorbite fatty acid esters such as sorbite tetraoleate of polyoxyethylene; polyoxyethylene monolaur Polyethylene glycol fatty acid esters such as rate; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene such as polyoxyethylene oleic acid amide Nonionic surfactants such as alkylamine fatty acid amides may be mentioned. These surfactants may be used alone or in combination of two or more. In addition to these nonionic surfactants, cationic surfactants and anionic surfactants are added to the detergent containing the azeotrope-like composition of the present invention in order to synergistically improve the detergency and interfacial action. May be. The amount of the surfactant used varies depending on the type of the surfactant, but it is sufficient that it does not interfere with the azeotrope-like properties of the azeotrope-like composition. It is about mass% or less and it is preferable to set it as about 0.3 mass% or more and 5 mass% or less.

  The type of the stabilizer is not particularly limited, and examples thereof include nitro compounds, epoxy compounds, phenols, imidazoles, amines, and hydrocarbons. The liquid composition to which such a stabilizer is added is particularly useful when used under severe conditions.

  As the nitro compound, known compounds can be suitably used), and aliphatic and / or aromatic nitro compounds can be mentioned. Examples of the aliphatic nitro compound include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane and the like. As aromatic nitro compounds, for example, nitrobenzene, o-, m- or p-dinitrobenzene, trinitrobenzene, o-, m- or p-nitrotoluene, o-, m- or p-ethylnitrobenzene, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylnitrobenzene, o-, m- or p-nitroacetophenone, o-, m- or p-nitrophenol, o -, M- or p-nitroanisole and the like can be mentioned.

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

  As phenols, in addition to the phenolic hydroxyl group, various substituents such as an alkyl group, an alkenyl group, an alkoxy group, a carboxyl group, a carbonyl group, and a halogen may be contained. For example, 2,6-di-t-butyl-p-cresol, o-cresol, m-cresol, p-cresol, thymol, pt-butylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol , Eugenol, isoeugenol, butylhydroxyanisole, monovalent phenols such as phenol and xylenol, or divalent tert-butylcatechol, 2,5-di-t-aminohydroquinone, 2,5-di-t-butylhydroquinone, etc. Phenol and the like.

  As the imidazoles, imidazoles having a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, or an aryl group as the N-position substituent are preferable. Examples of such imidazoles include 1-methylimidazole, 1-n-butylimidazole, 1-phenylimidazole, 1-benzylimidazole, 1- (β-oxyethyl) imidazole, 1-methyl-2-propylimidazole, Methyl-2-isobutylimidazole, 1-n-butyl-2-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethylimidazole, 1,5-dimethylimidazole, 1,2,5-trimethylimidazole, 1, Examples include 4,5-trimethylimidazole and 1-ethyl-2-methylimidazole. These compounds may be used alone, or two or more compounds may be used in combination.

  Examples of amines include pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine, diallylamine, triethylamine, N-methylaniline, pyridine, morpholine, N-methylmorpholine, triallylamine, allylamine, α-methyl. Benzylamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, dibutylamine, tributylamine, diventylamine, triventylamine, 2-ethylhexylamine, aniline N, N-dimethylaniline, N, N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethyl Npentamin, benzylamine, dibenzylamine, diphenylamine, and diethylhydroxylamine and the like. These may be used alone, or two or more compounds may be used in combination.

  Examples of the hydrocarbons include α-methylstyrene, p-isopropenyltoluene, isoprenes, propadiene, terpenes and the like. These may be used alone, or two or more compounds may be used in combination.

<Use as cleaning agent or solvent>
The azeotropic (like) composition of the present invention (or a liquid composition containing the azeotropic (like) composition) is a precision mechanical component, an electronic material (printed circuit board, liquid crystal display, magnetic recording component, semiconductor material, etc.) It is suitable for removing foreign substances, oils, greases, greases, waxes, fluxes, inks and the like from resin processed parts, optical lenses, clothing and the like. As described above, since the azeotropic (like) composition of the present invention is nonflammable and has appropriate fluidity and solubility, foreign substances (such as particles) can be washed away or dissolved to be removed. The cleaning method is not particularly limited, but the azeotropic (like) composition of the present invention (or a liquid composition containing the azeotropic (like) composition) is immersed in precision mechanical parts, electronic materials, etc. to remove dirt. Examples of the method include washing away, wiping with a waste cloth, and spray washing. These may be used in combination. It is one of the particularly preferred embodiments that the azeotropic (like) composition is placed in an ultrasonic cleaner, the article to be cleaned is immersed in the liquid, and ultrasonic cleaning is performed.

  The azeotrope (like) composition of the present invention exhibits a stable detergency even if it is used in an open system, so that the composition does not fluctuate even if it is not frequently managed. This is a great advantage. Regardless of whether the system is open or closed, in the cleaning process, the cleaning liquid adheres to the object to be cleaned (work) and is taken out of the system. For example, in a 500-liter cleaning facility, if 20 kg of liquid decreases every week due to taking out due to adhesion to parts (workpieces) to be cleaned, charge the same amount of new liquid every week. The liquid level is kept constant. When 1233Z is 70 mol% to 99.9999 mol% and the second component 1336Z is 0.0001 mol% to 30 mol%, even if a part of the washing machine volatilizes in the cleaning practice, The composition ratio in the washing machine does not change and can be said to be a preferable region.

  If the cleaning liquid used for cleaning is recovered and then subjected to a distillation operation, oils and fats and foreign matters (particles) can be separated and removed, and the azeotropic (like) composition of the present invention can be recovered. Since a general distillation regenerator for a detergent is a single distillation system, the azeotrope-like composition of the present invention can be regenerated with a commercially available distillation regenerator with substantially no change in composition.

  When performing the distillation operation, the two liquid components 1233Z and 1336Z maintain the properties as an azeotropic (like) composition, so that the recovered liquid is then washed again without undergoing extensive composition adjustment. Can be used as In addition, when the above “additional components” are used, these “additional components” may be removed by distillation, and in this case, it is desirable to supplement them separately.

  The invention is illustrated by examples.

<Example 1>
A 50 mL three-necked flask equipped with a septum, a stirrer, and a Dimroth capable of flowing a −10 ° C. refrigerant was charged with 25 mL of 1233Z and 1336Z so that the molar concentrations shown in Table 1 were obtained. A synthetic zeolite tube was attached to the top of the Dimroth. The flask was immersed in an oil bath and heated to reflux with stirring. After 1 hour or more had passed after the refluxing started, the composition was stabilized, and then the gas phase portion was sampled from the septum with a gas tight syringe and analyzed by gas chromatography. The liquid phase portion was similarly sampled using a polypropylene syringe equipped with an injection needle, and about 1 mL was sampled and transferred to a 2 mL vial previously cooled with ice water, followed by gas chromatography analysis. In Table 1, it was set as the mol% notation using the calibration curve prepared beforehand. In FIG. 1, the horizontal axis represents the liquid phase part composition (mol%) of 1233Z and the vertical axis represents the gas phase part composition (mol%) of 1233Z, and the results of Table 1 are plotted. An azeotrope in which the composition of the gas phase portion and the liquid phase portion does not substantially change in the range where the first component 1233Z is 70 mol% to 99.9999 mol% and the second component 1336Z is 0.0001 to 30 mol%. It became clear that it was a composition.

<Example 2>
The flash points of the mixed liquids of 1233Z and 1336Z were measured in accordance with Japanese Industrial Standard JIS K2265-1 “How to Obtain Flash Point—Part 1: Tag Sealing Method”. For the flash point measurement, an automatic flash point measuring device atg-8l (Tanaka Scientific Instruments Manufacturing Co., Ltd.) was used. Table 2 shows the measurement results for each composition. In the range of azeotropic or azeotrope-like compositions of 1233Z and 1336Z, no flash point was observed under atmospheric pressure conditions.

<Example 3>
<Cleaning test>
A commercially available 25 mL graduated cylinder was cut with an 11 mL graduation line, and conditions were set for the liquid to easily volatilize. After measuring the mass of a clean glass rod having a diameter of about 7.2 mm and a length of about 40 mm, it was immersed in the oil listed in the table for 2 minutes and then drained for 10 minutes (excess oil was removed). The mass (glass rod + initially attached oil) was measured and placed in the graduated cylinder. The composition described in Table 2 below is a 1233Z 89.5742 mol% 1336Z 0.4258 mol% azeotrope-like composition charged to a liquid level of 10 mL and filled with 20 ° C water, a small ultrasonic washer (SW5800 manufactured by Citizen) ) In the center. When ultrasonic waves were irradiated, the azeotrope-like composition volatilized with time, and when it reached the 8 mL scale line, the liquid in the graduated cylinder was analyzed with a gas chromatograph. As a result, in all of Examples 3-1 to 3-5, although 2 mL was volatilized, the liquid composition before and after washing was substantially the same. That is, in actual machine cleaning, the azeotrope-like composition used in Examples 3-1 to 3-5 may have an azeotrope-like composition in which the composition of the residual liquid does not substantially change even if it partially volatilizes. Indicated. Next, the glass rod is dried, and the mass (total mass of the glass rod and the residual oil) is measured to obtain the oil removal rate (the mass of the residual oil ÷ the mass of the initial adhered oil × 100 [%]) and enlarged. The surface of the glass was observed with a mirror. As a result, in all Examples, the oil removal rate was 100%, and in the magnifying glass observation results, no oil was left, so it was judged good. The results of each example are shown in Table 3 below.

Claims (7)

(Z) -1-chloro-3,3,3-trifluoropropene (1233Z) and (Z) -1,1,1,4,4,4-hexafluoro-2-butene (1336Z) Boiling (like) composition. The azeotrope-like composition of claim 1 consisting of 70 mol% to 99.9999 mol% 1233Z and 0.0001 mol% to 30 mol% 1336Z. The nonflammable azeotrope-like composition according to claim 1 or claim 2, comprising 80 mol% to 99.9999 mol% 1233Z and 0.0001 mol% to 20 mol% 1336Z. A liquid composition comprising an azeotropic (like) composition according to any of claims 1 to 3 and at least one additional component. A liquid composition comprising the azeotropic (like) composition according to any one of claims 1 to 3 and at least one additional component of 10 ppm to 30% by mass based on the azeotropic (like) composition. object. A cleaning solvent comprising the azeotropic (like) composition or liquid composition according to any one of claims 1 to 5. A method for cleaning an object to be cleaned, comprising the step of bringing the azeotropic (like) composition or liquid composition according to any one of claims 1 to 5 into contact with the object to be cleaned.

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