JP5381272B2 - Azeotropic-like composition comprising 1,1,1,3,3-pentafluorobutane - Google Patents

Description

  The present invention relates to an azeotrope-like composition comprising 1,1,1,3,3-pentafluorobutane.

  Conventionally, chlorinated fluorinated saturated hydrocarbons, specifically, trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), 1,1-dichloro-1-fluoroethane (HCFC-141b), 1,1,1-trichloroethane and the like have been used for refrigerants, blowing agents, etc., but these substances are chlorine There is a concern that the ozone layer will be destroyed.

  Accordingly, substances that replace chlorinated fluorinated saturated hydrocarbons have been developed, such as difluoromethane (HFC-32), 1,1,2-trifluoroethane (HFC-134a), 1,1,1. , 3,3-pentafluoropropane (HFC-245fa) or 1,1,1,3,3-pentafluorobutane (HFC-365mfc) or the like is used.

  1,1,1,3,3-pentafluorobutane (HFC-365mfc), one of the fluorine-containing saturated hydrocarbon compounds, does not contain chlorine in its molecular structure and has an ozone depletion potential (ODP) of 0. It has excellent characteristics of low toxicity, low global warming potential (GWP), and clean environment, but 1,1,1,3,3-pentafluorobutane (HFC-365mfc) ) Has low solubility in oils and fats, and as a cleaning agent, there is a problem that sufficient cleaning performance cannot be obtained.

  Therefore, as a conventional technique using 1,1,1,3,3-pentafluorobutane (HFC-365mfc), in Patent Documents 1 to 3, 1,1,1,3,3-pentafluorobutane (HFC- 365 mfc), a method for improving the solubility in oil by adding a hydrocarbon compound such as normal paraffin or an alcohol compound such as methanol. In Patent Documents 4 to 6, methylene chloride, 1, A method for improving the solubility in oil by adding a halogen-based compound such as 2-dichloroethylene or normal propyl bromide is disclosed.

  On the other hand, fluorine-containing unsaturated hydrocarbons having a double bond in the molecule generally have a high reactivity with OH radicals in the atmosphere because they have a double bond, and therefore have an ozone depletion potential (ODP) and global warming. The conversion factor (GWP) is significantly reduced. Since (Z) -1-chloro-3,3,3-trifluoropropene has a double bond in the molecule, it has a relatively low global warming potential (GWP), nonflammability and low GWP. It is being considered as a composition.

  So far, Patent Documents 7 and 8 disclose that (Z) -1-chloro-3,3,3-trifluoropropene is used as a cleaning composition, but specific cleaning performance and cleaning results are disclosed. Has not been reported.

  Further, in Patent Document 9, the applicants described 1,1,2,2, -tetrafluoro-methoxyethane (HFE-254pc) and (Z) -1-chloro-3,3,3-trifluoropropene. The composition for washing | cleaning which combined these, and the washing | cleaning method are disclosed.

JP-A-6-322394 JP 2002-348692 A JP 2006-516296 A JP-A-11-152236 JP 7-188700 A JP 2002-241796 A US Patent Application No. 096246 US Patent Application Publication No. 142173 JP 2008-133438 A

  In the methods of Patent Documents 1 to 3, HFC-365mfc, hydrocarbon compounds, and alcohol compounds have a flash point and are flammable substances. Therefore, they are very useful at work sites that dislike flammability. In the methods of Patent Documents 4 to 6, since chlorinated compounds such as methylene chloride and brominated saturated hydrocarbon compounds such as normal propyl bromide are used, sufficient care is required for handling. there were.

  In addition, (Z) -1-chloro-3,3,3-trifluoropropene disclosed in Patent Documents 7 to 9 has a high cleaning ability and is useful as a cleaning agent. However, there is a problem that the plastic member is easily damaged.

  The present invention provides a novel composition that has nonflammable and low toxicity properties, is easy to handle, has a low global warming potential, and has a low greenhouse effect. It is an object of the present invention to provide a cleaning composition that is effective and particularly has little damage to a plastic member to be cleaned.

  As a result of intensive studies to solve the above problems, the present inventors have found 1,1,1,3,3-pentafluorobutane (HFC-365mfc) and (Z) -1-chloro-3,3. By combining 3-trifluoropropene, a composition that is non-flammable and has low toxicity and is very easy to handle is obtained. Furthermore, the composition of the present invention damages a plastic member or the like to be cleaned. Therefore, the inventors have obtained knowledge that they are useful cleaning compositions for metals and plastic members, and have solved the above problems.

  As shown in Example 2 described later, the composition of the present invention was remarkably superior to the case where 1,1,1,3,3-pentafluorobutane (HFC-365mfc) was used alone. It has cleaning performance.

  In addition, the combination of 1,1,1,3,3-pentafluorobutane (HFC-365mfc) and (Z) -1-chloro-3,3,3-trifluoropropene provides a stable cleaning ability at all times. The composition of the present invention has a wide range of mixing ratios, and it has been found that even if the composition is repeatedly evaporated and condensed, there is no change in the composition of the composition and an extremely stable performance can be maintained.

  In addition, no azeotrope-like composition of 1,1,1,3,3-pentafluorobutane and (Z) -1-chloro-3,3,3-trifluoropropene has been reported.

That is, the present invention provides the inventions described in [Invention 1] to [Invention 4] below.
[Invention 1]
An azeotrope-like composition comprising 1,1,1,3,3-pentafluorobutane and (Z) -1-chloro-3,3,3-trifluoropropene.
[Invention 2]
2. The invention according to invention 1, comprising 10 to 90 mol% of 1,1,1,3,3-pentafluorobutane and 90 to 10 mol% of (Z) -1-chloro-3,3,3-trifluoropropene. Azeotropic composition.
[Invention 3]
A cleaning agent comprising the azeotrope-like composition described in Invention 1 or Invention 2.
[Invention 4]
A cleaning method for cleaning an element by bringing the azeotrope-like composition according to the first or second aspect of the invention into contact with a soiled element.

    According to the present invention, a novel composition having nonflammable and low toxicity properties, easy handling, a low global warming potential, and a low greenhouse effect is provided. It is possible to provide a cleaning composition that is effective for cleaning and in particular has very little damage to a plastic member to be cleaned.

  Furthermore, since the composition of the present invention forms an azeotrope-like composition in a wide range of mixing ratios, the composition change of the composition is extremely small, stable performance can be maintained, and the flash point is relatively high. Therefore, it is possible to provide a cleaning composition that is very easy to handle.

  Hereinafter, the azeotrope-like composition according to the present invention will be described in detail.

  1-Chloro-3,3,3-trifluoropropene used in the present invention is a known compound described in the literature, for example, addition reaction of 3,3,3-trifluoropropyne with hydrogen chloride, or 3-chloro It can be produced by dehydroiodination reaction of -1,1,1, -trifluoro-3-iodopropane with potassium hydroxide.

  The (Z) -1-chloro-3,3,3-trifluoropropene used in the present invention is a liquid obtained by subjecting 1,1,1,3,3-pentachloropropane to vapor phase fluorination reaction with a chromium catalyst or without catalyst. By performing the phase fluorination reaction, it can be obtained together with (E) -1-chloro-3,3,3-trifluoropropene.

  1-Chloro-3,3,3-trifluoropropene has cis isomer (Z isomer) and trans isomer (E isomer) as stereoisomers depending on the type of substituents. Can be separated and purified.

  In the present invention, as the starting material 1-chloro-3,3,3-trifluoropropene, these stereoisomers are not particularly limited and can be used as a single isomer or a mixture of isomers. Of these two isomers, the cis form (Z form), that is, (Z) -1-chloro-3,3,3-trifluoropropene, exhibits better azeotrope-like compositional properties. Are preferably used.

  An azeotrope-like composition behaves as if it were one substance, and consists of two or more substances whose composition changes, that is, the liquid composition and the vapor composition are almost the same, and repeats evaporation and condensation. The composition is such that the composition change of the composition after this is negligible. “Azeotropic” means a composition in which a mixture of two or more components does not separate under a constant pressure and the component ratio between the liquid phase and the gas phase is substantially close.

  Next, a preferable composition of the azeotrope-like composition of the present invention will be specifically described.

  The azeotrope-like composition of the present invention comprises a compound consisting of 1,1,1,3,3-pentafluorobutane and (Z) -1-chloro-3,3,3-trifluoropropene.

  Next, with regard to these, each preferable composition ratio with respect to a specific azeotrope-like composition will be described below.

  By mixing (Z) -1-chloro-3,3,3-trifluoropropene with 1,1,1,3,3-pentafluorobutane, each normal pressure (0.0101 MPa, absolute pressure, below) The same boiling point (1,1,1,3,3-pentafluorobutane: 40.0 ° C., (Z) -1-chloro-3,3,3-trifluoropropene: 38.9 ° C.) An azeotrope-like composition having a boiling point of (38.9-40.0 ° C.) can be obtained.

  For example, in this composition, the mixing ratio of 1,1,1,3,3-pentafluorobutane and (Z) -1-chloro-3,3,3-trifluoropropene is usually 1,1, 1,3,3-pentafluorobutane 1-99 mol% and (Z) -1-chloro-3,3,3-trifluoropropene 99-1 mol%, preferably 1,1,1, 3,3-pentafluorobutane 20-99 mol% and (Z) -1-chloro-3,3,3-trifluoropropene 80-1 mol%, more preferably 1,1,1,3,3- Good azeotrope-like compositions can be formed with 40-97 mol% pentafluorobutane and 60-3 mol% (Z) -1-chloro-3,3,3-trifluoropropene.

  The azeotrope-like composition of the present invention has the same or almost the same composition of the liquid phase and the gas phase in the evaporation process, and exhibits a high dissolving power. In addition, the azeotrope-like composition of the present invention itself forms an azeotrope-like composition, and can be handled as a nonflammable or flame-retardant substance.

  Next, use of the azeotrope-like composition of the present invention as a cleaning agent will be described.

  The composition of the present invention has excellent solubility, and can be widely used for known cleaning and drying applications. In particular, the composition of the present invention can be used as a degreasing cleaning agent, a flux cleaning agent, a cleaning solvent, and a draining drying agent. As an oil, grease, wax, flux, ink remover, electronic parts (printed circuit boards, liquid crystal displays, magnetic recording parts, semiconductor materials, etc.), electrical parts, precision machine parts, resin processed parts, optical lenses, Examples thereof include detergents for clothes and the like, and draining and drying agents. As the cleaning method, a conventionally used method such as immersion, spraying, boiling cleaning, ultrasonic cleaning, steam cleaning, or a combination thereof can be employed.

  The composition of the present invention is not only effective for metal members as a cleaning agent, but also effective for plastic members such as acrylic. For example, it can be used for dry cleaning of clothes including acrylic resin buttons, plastic mold release agents, and particle cleaning of plastic parts.

  As shown in Example 3 described later, it can be seen that (Z) -1-chloro-3,3,3-trifluoropropene alone is damaging the acrylic resin. In the mixed composition of (Z) -1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3-pentafluorobutane, (Z) -1-chloro-3,3 As the mixing ratio of 1,3-trifluoropropene is decreased, the influence on the acrylic resin is reduced.

  Therefore, in using the composition of the present invention as a cleaning agent, when used as a cleaning agent for a plastic member such as an acrylic resin, the mixing ratio of (Z) -1-chloro-3,3,3-trifluoropropene is changed. It is preferable to use less than 1,1,1,3,3-pentafluorobutane, and when used as a degreasing cleaner for metal members, (Z) -1-chloro-3,3,3- The mixing ratio of trifluoropropene is preferably larger than that of 1,1,1,3,3-pentafluorobutane, and the mixing ratio can be adjusted according to the member to be cleaned.

  Furthermore, the composition ratio in the azeotropic state is the same between the liquid phase composition ratio in vapor-liquid equilibrium and the gas phase composition ratio, so even if volatilization occurs over time, the composition change is very small and always stable. It becomes possible to obtain the cleaning ability. Moreover, the composition change in the storage container during storage can be avoided.

  The composition of the present invention has a surface tension value of 16.8 mNm at a mixing ratio (HFC-365mfc / OHCFC-1233c = 50/50) and a temperature of 20 ° C., and (Z) -1-chloro- Composition of 3,3,3-trifluoropropene (OHCFC-1233c) alone (temperature 20 ° C., surface tension 18.1 mNm), 1,1,2,2, -tetrafluoro-methoxyethane (HFE-254pc) And (Z) -1-chloro-3,3,3-trifluoropropene mixed composition (temperature 20 ° C., mixing ratio: HFE-254pc / OHCFC-1233c = 50/50, surface tension 17.8 mNm) Thus, the value of the surface tension is low. For this reason, even an object to be cleaned with extremely fine gaps can penetrate smoothly to the back, and the details of the object to be cleaned can be sufficiently cleaned, which is suitable for cleaning precision parts and the like.

  Therefore, when the azeotrope-like composition of the present invention is used as a cleaning agent, it can be used as a cleaning agent in the aforementioned weight ratio.

  Usually, as a detergent in the range of 1,1,1,3,3-pentafluorobutane 99-1 mol% and (Z) -1-chloro-3,3,3-trifluoropropene 1-99 mol% Can be used, but preferably 1,1,1,3,3-pentafluorobutane 70-1 mol% and (Z) -1-chloro-3,3,3-trifluoropropene 30-99 mol% More preferably 1,1,1,3,3-pentafluorobutane 50 to 1 mol% and (Z) -1-chloro-3,3,3-trifluoropropene 50 to 99 mol%, A cleaning agent having a high cleaning ability can be formed.

  Here, the inventors have mixed ratios as nonflammable and flame retardant substances, that is, 70 to 1 mol% of 1,1,1,3,3-pentafluorobutane and (Z) -1-chloro-3. , 3,3-trifluoropropene By setting it in the range of 30 to 99 mol%, it is possible to form a cleaning agent having nonflammability or flame retardancy and high cleaning ability.

  As for the cleaning method using the cleaning agent comprising the azeotrope-like composition of the present invention, there are conventionally known methods such as immersion, spraying, boiling cleaning, ultrasonic cleaning, steam cleaning, etc. As shown in the example, a method of removing dirt by dipping is particularly suitable. The term “immersion” as used herein refers to bringing an element to which dirt such as oil is attached (corresponding to “wire mesh” in the examples described later) with the azeotrope-like composition of the present invention. By dissolving the soil in the composition, the soil can be removed from the element. Here, the “element” refers to an object (object to be cleaned) to which dirt is attached. In addition, the said immersion operation can also be combined with other cleaning operations (boiling cleaning, ultrasonic cleaning, etc.).

  Moreover, in order to further improve the detergency, interfacial action and the like, various surfactants can be added as necessary. Surfactants include sorbitan aliphatic esters such as sorbitan monooleate and sorbitan trioleate; polyoxyethylene sorbite fatty acid esters such as sorbit tetraoleate of polyoxyethylene; polyethylene glycol such as polyoxyethylene monolaurate Fatty acid esters; Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether; Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ether; Polyoxyethylene alkylamine fatty acid amides such as polyoxyethylene oleic acid amide Nonionic surfactants such as these may be mentioned, and they may be used alone or in combination of two or more. For the purpose of synergistically improving detergency and interfacial action, a cationic surfactant or an anionic surfactant may be used in combination with these nonionic surfactants. The amount of the surfactant used varies depending on the type of the surfactant, but is about 0.1 to 20% by weight in the composition as long as the azeotropic properties of the composition are not hindered. More preferably, it is about wt%.

  Generally, in the use of a refrigerant, a cleaning agent, an aerosol, or a draining drying solvent, when the mixed composition after use is recovered by evaporation or distillation and reused, the recovered composition is different from the mixed composition before use. In comparison, it is desirable that the composition does not vary as much as possible. However, the mixture according to the present invention has no or very little composition variation.

  The composition according to the present invention may further contain various stabilizers when used under severe conditions. Stabilizers are preferably those that are entrained by distillation or that form an azeotrope-like mixture. Specific examples of such stabilizers include aliphatic nitro compounds such as nitromethane, nitroethane, and nitropropane; aromatic nitro compounds such as nitrobenzene, nitrotoluene, nitrostyrene, and nitroaniline; dimethoxymethane, 1,2-dimethoxyethane, Ethers such as 1,4-dioxane, 1,3,5-trioxane and tetrahydrofuran; Epoxides such as glycidol, methyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, phenyl glycidyl ether, cyclohexene oxide and epichlorohydrin; Unsaturated hydrocarbons such as hexene, heptene, pentadiene, cyclopentene and cyclohexene; Olefinic alcohols such as allyl alcohol and 1-buten-3-ol; 3-methyl-1-buty 3-ol, 3-methyl-1-pentyn-3-acetylenic alcohols such as ol; methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid esters such as vinyl methacrylate. Further, in order to obtain a synergistic stabilizing effect, phenols, amines and benzotriazoles may be used in combination. These stabilizers may be used alone or in combination of two or more. The amount of the stabilizer used varies depending on the type of the stabilizer, but is set to such an extent that does not hinder the azeotropic properties of the composition. The amount used is usually about 0.01 to 10% by weight in the composition, more preferably about 0.1 to 5% by weight.

  Further, the azeotrope-like composition of the present invention can be used for various uses such as a foaming agent, a coating solvent, an extractant, a heat medium such as a refrigerant, an aerosol, or a draining drying solvent in addition to a cleaning agent.

  Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[Example 1]
1,1,1,3,3-pentafluorobutane (HFC-365mfc) and (Z) -1-chloro-3,3,3-trifluoro using a pressurized equilibrium distillation apparatus (manufactured by Kyowa Science Co., Ltd.) Propene (OHCFC-1233c, where OHCFC is an abbreviation for Olefine HydroChloroFluoroCarbon, which represents an unsaturated HCFC having an intramolecular double bond, and these unsaturated compounds are generally highly reactive with OH radicals in the atmosphere. Therefore, since the ozone depletion coefficient and GWP are significantly reduced, the vapor-liquid equilibrium composition (x1 and y1) and the boiling point (t) with OHCFC were measured to distinguish them from HCFC. A mixed sample having a constant composition of 1,1,1,3,3-pentafluorobutane and (Z) -1-chloro-3,3,3-trifluoropropene was placed in a sample container and heated. Then, the heating was adjusted so that the dropping speed of the vapor phase condensate was appropriate, and stable boiling was maintained for 30 minutes or more. After confirming that the pressure and boiling point were stable, they were measured.

  The boiling point in heating, and the composition ratio of the gas phase component and the liquid phase component in gas-liquid equilibrium in the sample container were determined. The results are shown in Table 1.

  As shown in Table 1, 21.5-73.8 mol% of 1,1,1,3,3-pentafluorobutane and (Z) -1-chloro-3,3,3-trifluoropropene 78.5 In the range of the liquid phase composition ratio of ˜26.2 mol%, the boiling point is 39 to 40 ° C., the boiling point of the 1,1,1,3,3-pentafluorobutane single component (40.0 ° C.), and ( Z) The boiling point between the boiling points (38.9 ° C.) of the single component of 1-chloro-3,3,3-trifluoropropene was shown, and it was confirmed that it was in an azeotropic state.

  Next, based on Table 1, the horizontal axis (X-axis) shows the molar fraction of (Z) -1-chloro-3,3,3-trifluoropropene in the liquid phase on the vertical axis (Y-axis). ) Is taken the molar fraction of (Z) -1-chloro-3,3,3-trifluoropropene in the gas phase and the temperature in the reaction system, and (Z) -1-chloro-3,3,3 A vapor-liquid equilibrium diagram (XY diagram) in a mixed system of -trifluoropropene and 1,1,1,3,3-pentafluorobutane was prepared. The result is shown in FIG.

  In the azeotrope-like state, since the composition ratio of the liquid phase and the composition ratio of the gas phase are the same, the intersection of the XY diagram and the function Y = X becomes the azeotropic composition. In the azeotrope-like state, since the composition ratio of the liquid phase and the composition ratio of the gas phase are almost the same, from the XY diagram, (Z) -1-chloro-3,3,3-trifluoropropene This phenomenon was observed in 1 to 99 mol% and 1,1,1,3,3-pentafluorobutane 99 to 1 mol%, and it was confirmed that the azeotropy was observed in a wide range.

[Example 2 and Comparative Example, Reference Example]
(Cleaning performance test)
As cleaning agents, HFC-365mfc / OHCFC-1233c = 30/70 (weight ratio), HFC-365mfc / OHCFC-1233c = 50/50 (weight ratio), HFC-365mfc / OHCFC-1233c = 65/35 (weight) Ratio) was selected and a cleaning test was performed for each. The results are shown in Table 2.

  As a comparative example, the results of washing with HFC-365mfc alone are shown in Table 3.

  As a reference example, Table 4 shows the results of cleaning tests using compositions of HFE-254pc / OHCFC-1233c = 35/65 (weight ratio) and HFE-254pc / OHCFC-1233c = 50/50 (weight ratio). It was shown to.

  The cleaning method is as follows. A 60 mesh SUS wire mesh (weight: Ag) of the size shown in FIG. 2 is immersed in various sample oils for 30 seconds and further left at room temperature for 1 hour to drain excess and then oil. After measuring the weight of the attached wire mesh (weight; Bg), it was immersed in 100 ml of cleaning agent (in a beaker in an ultrasonic water bath) kept at a predetermined temperature for 5 seconds and 30 seconds, and after removing oil, at 90 ° C. It was dried for 2 hours, and further allowed to cool at room temperature for 1 hour. The wire net weight (weight; Cg) after oil removal was measured, and the oil removal rate was determined from the following formula.

    Oil removal rate (wt%): (Bg-Cg / Bg-Ag) × 100

From the results of Tables 2 and 3 , it can be seen that the azeotrope-like composition of the present invention is superior in cleaning effect (oil removal rate) to any oil as compared to HFC-365mfc alone of the comparative example. .

  Further, from [Reference Example] in Table 4, the composition of the present invention has a cleaning ability comparable to that of the cleaning composition of HFE-254pc / OHCFC-1233c for any oil. I understand.

[Example 3 and Comparative Example, Reference Example]
(Effect test on plastic)
A test was conducted to examine the influence of the composition of the present invention on the plastic. As cleaning agents, OHCFC-1233c alone, HFC-365mfc / OHCFC-1233c = 30/70 (weight ratio), 50/50 (weight ratio), 65/35 (weight ratio), HFE-254pc / OHCFC-1233c = The composition of 30/70 (weight ratio), 50/50 (weight ratio), and 65/35 (weight ratio) was selected, and an influence test on plastics was performed. The results are shown in Table 5.

  In the test for examining the influence on plastic, acrylic resin was used as plastic, and an acrylic resin test piece (50 mm × 20 mm × 2 mm, manufactured by Nippon Test Panel) was immersed in 50 ml of each prepared composition solvent, and 40 times in a thermostatic bath. Kept at ℃. The test piece was taken out after 1 hour of immersion and the change in weight before and after the measurement was measured.

  From the results of Table 5, it can be seen that the composition of the present invention is less affected and less affected by the weight of the acrylic resin than the composition of OHCFC-1233c alone. Moreover, it turns out that the composition of this invention has little influence with respect to an acrylic resin compared with the composition of HFE-254pc / OHCFC-1233c.

Furthermore, from the results of Table 2, Table 4, and Table 5, the composition of the present invention has the same level of cleaning ability as compared with the composition of HFE-254pc / OHCFC-1233c, and is also used for acrylic resin. It turns out that there is little influence. Therefore, it can be seen that the composition of the present invention is effective as a cleaning agent for a wide range of members such as metal and plastic members as compared with the composition of HFE-254pc / OHCFC-1233c.
[Example 4 and Comparative Example, Reference Example]
(Flammability test)
As cleaning agents, HFC-365mfc / OHCFC-1233c = 95/5 (weight ratio), 90/10 (weight ratio), HFE-254pc / OHCFC-1233c = 85/15 (weight ratio), 80/20 (weight), respectively. Ratio), 75/25 (weight ratio), and 70/30 (weight ratio) were selected, and the flash point of each composition was measured (a tag-sealed flash point measuring device). The results are shown in Table 6.

  As a result, no flash point was observed at HFC-365mfc / OHCFC-1233c = 95/5 (weight ratio) and HFC-365mfc / OHCFC-1233c = 90/10 (weight ratio).

  On the other hand, with HFE-254pc / OHCFC-1233c = 85/15 (weight ratio), 80/20 (weight ratio), 75/25 (weight ratio), and 70/30 (weight ratio), the flash point is 21 ° C., respectively. 30 ° C. and 35 ° C.

From the result of Table 6, there is no flash point in the ratio of HFC-365mfc / OHCFC-1233c = 95/5 (weight ratio), 90/10 (weight ratio), and HFE-254pc / OHCFC-1233c = 85/15 ( The flash point was seen at the ratio of 80/20 (weight ratio), 75/25 (weight ratio). Therefore, the composition of HFC-365mfc / OHCFC-1233c does not have a flash point compared to the composition of HFE-254pc / OHCFC-1233c, so that it can be easily handled when used as a cleaning agent. .

The vapor-liquid equilibrium diagram in a mixed system with HFC-365mfc and OHCFC-1233c at 0.101 MPa is shown. In addition, a molar fraction represents the molar ratio of each component of HFC-365mfc and OHCFC-1233c, and temperature represents the temperature of the summit part when it heat-distills in a distillation apparatus. . The schematic in the washing test of Example 2 is shown.

Claims (4)

An azeotrope-like composition comprising 1,1,1,3,3-pentafluorobutane and (Z) -1-chloro-3,3,3-trifluoropropene. It consists of 10-90 mol% of 1,1,1,3,3-pentafluorobutane, and 90-10 mol% of (Z) -1-chloro-3,3,3-trifluoropropene. An azeotrope-like composition. A cleaning agent comprising the azeotrope-like composition according to claim 1 or 2. A cleaning method for cleaning an element by bringing the azeotrope-like composition according to claim 1 or 2 into contact with the soiled element.