JP6896991B2 - Compositions, liquid compositions, cleaning solvents, methods for producing and recovering them, and cleaning methods using cleaning solvents. - Google Patents

Description

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

Chlorofluorocarbons (hereinafter sometimes referred to as CFCs), hydrochlorofluorocarbons (sometimes referred to as HCFCs), hydrofluorocarbons (hereinafter sometimes referred to as HFCs), etc. have 1 to 5 carbon atoms. Since fluorocarbons have volatile, stable, and nonflammable characteristics, they have contributed to the development of the industry in applications such as refrigerants, working fluids, foaming agents, spray agents, cleaning agents, solvents, and solvents (these are). Freons). It has also been widely used by blending a plurality of fluorine-containing alkanes. For example, refrigerant numbers R502, R507A, R404A, R407C, R410A and the like of the American Society for Heating, Refrigerating and Air-Conditioning Engineers (ASHRAE) are widely used as mixed refrigerants. The coefficient of performance, refrigeration cycle, nonflammability, global warming potential, etc. of these mixed refrigerants are improved by mixing two or more types of fluorocarbons in a specific ratio. However, since fluorine-containing alkanes are volatile, when used as a mixture, if any of the fluorocarbons evaporates unilaterally, the composition changes during use and the physical properties change. Therefore, an azeotropic or azeotropic composition that volatilizes with 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 composition of the gas phase portion and the liquid phase portion is exactly the same and the azeotropic portion is formed. It is used as a refrigerant. Regarding R410A, its constituents R32 and R125 are non-azeotropic, but since the composition of the gas phase portion and the liquid phase portion is substantially the same, it is practically the same as the azeotropic composition. Since it can be handled, it is used as an azeotropic refrigerant. In addition to refrigerant applications, for example, a blend of fluorine-containing alkane and alcohol can be used as a drainage agent, or a nonflammable fluorine-containing alkane is added to a flammable hydrocarbon solvent to make it nonflammable, or cleaning with controlled detergency. There is an agent. Also in the use of detergents and drainers, azeotropic or azeotropic compositions having substantially the same composition of the vapor phase portion and the liquid phase portion when volatilized are preferable as in the case of the refrigerant.

Fluorine-containing alkanes as described above are extremely stable even in the atmosphere, have a long atmospheric life, and are considered to be a causative substance of 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 alternatives to the above-mentioned fluorine-containing alkanes. These fluorine-containing olefins having a double bond in the molecule have significantly higher reactivity with OH radicals in the atmosphere as compared with a fluorine-containing alkane without a double bond. Currently, the atmospheric lifespan of HFC-365mfc, HFC-245fa, HFC-43-10, etc., which are widely used, is on a yearly basis, whereas the atmospheric lifetime of fluorine-containing olefins is generally on a daily basis. Even if it is released into the atmosphere, it decomposes quickly, so its impact on global warming and ozone layer depletion is low. Since it has similar physical properties to the above-mentioned fluorine-containing alkane, it has been reported that it can be used in various applications such as a refrigerant, a working fluid, a foaming agent, a spray agent, a detergent, a solvent, and a solvent.

Like fluorine-containing alkanes, fluorine-containing olefins may improve their performance by blending with other chemical species. For example, Patent Document 1 states that when (Z) -1-chloro-3,3,3-trifluoropropene and 1,1,2,2-tetrafluoro-1-methoxyethane are mixed, they are azeotropic. It has been reported that the original solvent is formed and the cleaning performance of various oils of the binary solvent is at an excellent level. In this way, azeotrope or azeotrope specifically containing a fluorine-containing olefin is reported. There are few reported examples of fluorine-containing alkanes. Further, there are few literature examples of azeotropic or azeotropic compositions in which fluorine-containing olefins are combined.

Patent Document 2 proposes a composition of a fluorine-containing olefin having 3 carbon atoms and a general-purpose solvent. Although Example 4 of the document discloses a single degreasing test example of 1,2-dichloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene is disclosed. There is no description about the geometric isomers (E-form, Z-form) of. Patent Documents 3 to 7 describe 1,2-dichloro-3,3,3-trifluoropropene as a resist stripping agent, a buff abrasive, a solvent for removing adhering water, and a cleaning agent for dry cleaning. Similar to Document 2, there is no description about geometric isomers.

Japanese Unexamined Patent Publication No. 2008-133438 Japanese Unexamined Patent Publication No. 2-221388 Japanese Unexamined Patent Publication No. 2-221962 Japanese Unexamined Patent Publication No. 2-221389 Japanese Unexamined Patent Publication No. 2-222469 Japanese Unexamined Patent Publication No. 2-22249 Japanese Unexamined Patent Publication No. 2-222702

However, in such a volatile solvent composition, even if a plurality of solvents are simply mixed to improve the performance, the problem that the liquid composition is liable to fluctuate due to the volatility of each component can be avoided. Absent. For example, when a binary liquid composition is placed in an ultrasonic cleaner and subjected to a cleaning step, generally a low boiling point component (a component having a large vapor pressure) volatilizes preferentially, and a high boiling point component is contained in the washing tank. (Components with low vapor pressure) are concentrated. For example, in the case of a composition composed of a low boiling point component having a high detergency and a high boiling point component having a low detergency, the low boiling point component in the cleaning liquid may decrease with time, causing cleaning failure. In addition, the used washing solution is usually regenerated and reused by distillation, but if the composition of the liquid phase and the composition of the gas phase are different, the liquid composition of the recovered composition must be adjusted. Not efficient. Further, if the composition volatilizes during use and the composition of the liquid changes, not only the cleaning performance may change, but also the nonflammable composition may change to a flammable composition.

For this reason, an azeotropic or azeotropic composition in which the composition of the gas phase portion and the liquid phase portion are substantially the same at the time of volatilization is strongly desired. The present invention comprises the environmentally friendly (Z) -1,2-dichloro-3,3,3-trifluoropropene and (E) -1,2-dichloro-3,3,3-trifluoropropene and is volatile. It is an object of the present invention to propose a new azeotropic or azeotropic composition whose composition does not change easily.

The present inventors have diligently studied to solve the above problems. As a result, the Z form of 1,2-dichloro-3,3,3-trifluoropropene (hereinafter, may be referred to as HCFO-1223xd (Z) or 1223Z) is 80 mol% to 99.9999 mol%, which is 1 , 2-Dichloro-3,3,3-Trifluoropropene E-form (hereinafter sometimes referred to as HCFO-1223xd (E) or 1223E) in a composition of 0.0001 mol% to 20 mol% is substantial. It was found that it is an azeotropic composition having the same composition of the gas phase part and the liquid phase part, and is a non-combustible material (non-dangerous material) having no flash point under the Fire Service Law. Furthermore, it was confirmed that the azeotropic composition of the present invention is useful as a remover (cleaning agent) for fats and oils, and the present invention has been completed.

That is, the present invention includes the following inventions.

[Invention 1]
Azeotrope consisting of (Z) -1,2-dichloro-3,3,3-trifluoropropene (1223Z) and (E) -1,2-dichloro-3,3,3-trifluoropropene (1223E). (Like) composition.

[Invention 2]
The azeotropic composition according to Invention 1, which comprises 80 mol% to 99.9999 mol% of 1223Z and 0.0001 mol% to 20 mol% of 1223E.

[Invention 3]
The azeotropic composition according to Invention 1 or Invention 2, which comprises 90 mol% to 99.9999 mol% of 1223Z and 0.0001 mol% to 10 mol% of 1223E.

[Invention 4]
A liquid composition containing the azeotropic 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 with respect to the azeotropic (like) composition.

[Invention 6]
A cleaning solvent containing 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, which comprises a 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 composition. The composition has the effect that the composition does not easily change even when used under open conditions. The azeotropic composition has a small impact on the environment and is a non-combustible material (non-dangerous material) under the Fire Service Act. The azeotropic composition is useful as a solvent (cleaning solvent) for cleaning pollutants such as foreign substances and oils and fats.

Vapor-liquid equilibrium diagram of (Z) -1,2-dichloro-3,3,3-trifluoropropene (1223Z) and (E) -1,2-dichloro-3,3,3-trifluoropropene (1223E) Is.

Since the fluorine-containing olefin has high compatibility with various solvents, it is relatively easy to formulate a uniform composition. However, in the case of a composition having an arbitrary composition, there is an inherent problem that the liquid composition is liable to fluctuate. That is, even if a plurality of types of liquids can be mixed and compatibility can be ensured, the problem that the liquid composition tends to fluctuate due to the difference in the volatility of each component cannot be avoided. For example, when a dual liquid composition is placed in an ultrasonic cleaner and used as a detergent, the low boiling point component (component with high vapor pressure), which generally has high volatility, volatilizes preferentially in the cleaning tank. High boiling point components with low volatility are concentrated. For example, in the case of a composition of a low boiling point component having a high detergency and a high boiling point component having a low detergency, the concentration of the low boiling point component in the cleaning liquid may decrease with time, causing cleaning failure. In particular, when a nonflammable solvent is blended with a flammable solvent to prepare a nonflammable composition, the cleaning liquid may become a flammable composition if the nonflammable component volatilizes preferentially.

Further, it is desirable to recover and reuse the cleaning solvent by an operation such as distillation after use from the viewpoint of environmental protection and economy, but in the case of a two-component liquid, a two-component liquid having a different boiling point is generally used. Must be collected separately, and it is easy to impose an operational load to collect and reuse them.

There are similar problems when used as a working fluid for thermodynamic cycles. 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 of the liquid with the lubricant may change, and the operating performance of the thermodynamic cycle may deteriorate.

For this reason, when a binary (multidimensional) liquid composition is used as a cleaning agent or working fluid, the liquid composition is frequently analyzed and constantly formulated in the appropriate ratio to the proper composition range. And the volatile components must be replenished. However, such liquid composition control can be a heavy work load.

On the other hand, in the case of the azeotropic composition, since it volatilizes with 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, "azeotrope" refers to azeotrope in the strict thermodynamic 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 azeotropic mixture, and the 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 particular temperature and pressure, the composition of the azeotropic mixture is only one point.

"Azeotrope" is also called "pseudo-azeotrope" and is not thermodynamically strict azeotrope, but for a liquid with a certain range of composition, the liquid composition and the composition of the gas in equilibrium are , May be substantially equal and refer to such a phenomenon. Even if the compositions of the gas phase portion and the liquid phase portion do not completely match, those skilled in the art can handle the same as the azeotropic composition as long as the compositions of the gas phase portion and the liquid phase product substantially match. At this time, the smaller the difference in vapor-liquid equilibrium composition between the gas phase portion and the liquid phase portion, the better. Such a phenomenon in which the vapor-liquid equilibrium composition of the gas phase portion and the liquid phase portion substantially match is called an azeotropic or pseudo-azeotropic composition, and the composition is called an azeotropic composition or a pseudo azeotropic composition. ..

Academically, azeotrope and quasi-azeotrope (or azeotrope) should be distinguished, but in practice such as cleaning, azeotrope and azeotrope (or azeotrope) should be distinguished. In this specification, the azeotrope phenomenon and the azeotrope-like phenomenon (or pseudo-azeotrope) are collectively referred to as "azeotrope" because they are not necessary and can be treated in exactly the same way. The composition at that time is called "azeotropic composition".

In azeotropic (like), the presence or absence of azeotropic point does not matter. It suffices that the vapor-liquid equilibrium composition of the gas phase portion and the liquid phase portion substantially match.

"Azeotrope" is not theoretically derived, and the vapor-liquid equilibrium was investigated experimentally for various liquid types and composition ratios, and by chance, the composition of the gas phase and the composition of the liquid phase were substantially the same. Sometimes it can be found for the first time. In the present invention, the Z-form (1223Z) and E-form (1223E) of 1,2-dichloro-3,3,3-trifluoropropene have the same gas-liquid composition in a specific region. We were able to find a boiling-like composition. In particular, since 1223Z and 123E have significantly different boiling points and polarities, it is extremely difficult to infer that they are azeotropic. The boiling point and polarity (dipole moment (B3LYP / 6-311 + G ** calculated value)) of each compound are as follows.

Methods for producing 1223Z and 1223E are described in Patent Documents (Japanese Unexamined Patent Publication No. 2014-210765, WO2014 / 046250, WO2014 / 046251). That is, by reacting 1-chloro-3,3,3-trifluoropropene with chlorine in the gas phase, 1223Z and 1223E can usually be obtained as a mixture in which both are present in equilibrium or close to equilibrium. it can.

When both 1223Z and 1223E are produced as 1,2-dichloro-3,3,3-trifluoropropene, the mixture containing each component can be subjected to a purification treatment to be highly purified. For example, precision distillation can be performed in a distillation column having 30 to 300 theoretical plates. A distillation column with a large number of stages can achieve high purity with good yield in a single operation. However, for example, by redistilling a fraction having a high pure content using a distillation column with 50 stages, it is substantially realized. Distillations that do not contain mutual isomers can be obtained. It is also effective to pre-distill in advance before precision distillation.

It is also possible to adsorb and further purify the high-purity 1223Z fraction obtained by precision distillation using activated carbon, zeolite or the like. Specifically, it is preferable to concentrate 1223Z to 99.9% or more by a distillation step, and then perform the adsorption treatment. It is also possible to use an existing separation and purification method using the difference in reactivity and the difference in polarity between 1223Z and 1233E. For example, impurities may be decomposed by bringing 1223Z containing impurities into contact with a basic aqueous solution or sulfuric acid and stirring the mixture. In particular, when stirring with a basic aqueous solution, it is particularly efficient to coexist with a phase transfer catalyst. A combination of these purification methods is also effective.

After isolating 1223Z and 1223E which do not substantially contain other components, if each is mixed at a predetermined ratio, the "azeotropic (like) composition consisting of 1223Z and 1223E" of the present invention can be obtained. According to this method, for example, an azeotropic composition in which 1223Z is 99.9999 mol% and 1223E is 0.0001 mol% can be prepared.

Further, as another method from the above, a mixture in which 1223Z and 1223E coexist in a substantially equilibrium state (composition in which 1223E is the main component and 1223Z is a small amount component) is subjected to precision distillation of, for example, about 50 to 100 steps. , A fraction having a 1223Z concentration of 80 mol% or more (1223E is 20 mol% or less) can also be obtained. In this case, the distillation conditions (particularly the number of distillation stages) may be appropriately adjusted so that a distillate having a desired composition can be obtained, and unlike the above method, the process of remixing pure 1223Z and 1223E is performed. I don't need it.

However, as a result of performing precision distillation of about 100 steps, after obtaining "a composition in which 1223Z significantly exceeds 80 mol% (1223E is significantly lower than 20 mol%)", "1223Z significantly exceeds 80 mol%". It is also possible to mix with a composition having a concentration of less than 20 mol% (1223E significantly more than 20 mol%) and re-prepare as a whole to a composition having a concentration of 1223Z of 80 mol% or more (1223E is 20 mol% or less). Absent.

When performing advanced precision distillation as described above, 1223Z and 1223E can be separated from each other, but under normal conditions (that is, distillation conditions of about one stage), the concentration (content) of 1223Z increases. As it becomes difficult to separate from each other, when the composition reaches "composition of 80 mol% of 1223Z (20 mol% of 1223E)", no further change in concentration occurs substantially. That is, as is clear from the vapor-liquid equilibrium composition diagram shown in the examples, the first component 1223Z is 80 mol% to 99.9999 mol% and the second component 1223E is 0.0001 mol% to 20 mol. The composition consisting of% is an azeotropic (like) composition in which the composition of the gas phase portion and the liquid phase portion is substantially the same. Here, the value of mol% represents% of the number of moles of each component (that is, relative mol% between the two components) when the total value of the number of moles of 1223Z and the number of moles of 1223E is 100. .. With a composition within this range, in practice, even if the liquid composition is handled in an open system or even if a recovery operation is performed by simple distillation, the composition is unlikely to fluctuate.

Among them, the composition range in which the first component 1223Z is 90 mol% to 99.9999 mol% and the second component 1223E is 0.0001 mol% to 10 mol% is the gas phase part and the liquid phase part. It can be said that the composition is particularly preferable because the compositions of the above are closer to each other.

Further, the composition range in which the first component 1223Z is 95 mol% to 99.9999 mol% and the second component 1223E is 0.0001 mol% to 5 mol% is the gas phase part and the liquid phase part. Since the compositions of the above are even closer to each other, the concentration fluctuation is less likely to occur, and it can be said that the composition is particularly preferable.

Although the above is an example of a preferable composition range, it does not prevent the use of an azeotropic composition other than the above composition range. If the composition changes tolerable by those skilled in the art depending on the type of the object to be cleaned, the required cleaning accuracy, the cleaning method, the cleaning conditions, and the shape of the cleaning machine, the composition of the gas phase component and the composition of the liquid phase portion are substantially close to each other. It can be regarded as an azeotropic composition.

It goes without saying that the azeotropic (like) composition of the present invention is preferably one having a high purity and is substantially free of impurities. However, depending on the application, a liquid composition having such a high purity may not be required. In such a case, a small amount of a raw material for synthesizing 1223Z, which is the first component, and 1223E, which is the second component, and a small amount of by-products (usually, each component has the azeotropic composition). It is also possible to use the remaining one (usually less than 1% by weight).

If desired, additional ingredients may be added to improve the performance of the azeotropic composition to give "the azeotropic composition of the invention and a liquid composition containing at least one additional ingredient". You can also. Examples of additional components include detergency enhancers (surfactants), stabilizers (acid acceptants, antioxidants), and the like.

Specific examples of the surfactant include sorbitan aliphatic esters such as sorbitan monooleate and sorbitan trioleate; polyoxyethylene sorbit fatty acid esters such as sorbit tetraoleate of polyoxyethylene; polyoxyethylene monolaure. Polyethylene glycol fatty acid esters such as rates; Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether; Polyoxyethylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether; Polyoxyethylene such as polyoxyethylene oleic acid amide Examples thereof include nonionic surfactants such as alkylamine fatty acid amides. 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 detergents containing the co-boiling-like composition of the present invention for the purpose of synergistically improving the detergency and the interfacial action. You may. The amount of the surfactant used varies depending on the type, but it is sufficient as long as it does not interfere with the azeotropic properties of the azeotropic composition, and is usually 0.1% by mass or more in the azeotropic composition 30. It is about mass% or less, and is preferably about 0.3% by mass or more and 5% by mass or less.

The type of 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 harsh conditions.

As the nitro compound, known compounds can be preferably used), and examples thereof include aliphatic and / or aromatic nitro compounds. Examples of the aliphatic nitro compound include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane and the like. Aromatic nitro compounds include, 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, phenylglycidyl ether, allyl glycidyl ether, methyl glycidyl ether, and butyl glycidyl ether. Monoepoxy compounds such as 2-ethylhexyl glycidyl ether, polyepoxy compounds such as diepoxybutane, vinylcyclohexendioxide, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin polyglycidyl ether, and trimethylolpropanthrglycidyl ether. Examples include compounds.

The phenols may contain various substituents such as an alkyl group, an alkenyl group, an alkoxy group, a carboxyl group, a carbonyl group and a halogen in addition to the phenolic hydroxyl group. For example, 2,6-di-t-butyl-p-cresol, o-cresol, m-cresol, p-cresol, timol, pt-butylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol. , Eugenol, Isoeugenol, Butylhydroxyanisole, Phenol, Xylenol and other monovalent phenols or t-butylcatechol, 2,5-di-t-aminohydroquinone, 2,5-di-t-butylhydroquinone and the like. Phenol and the like can be mentioned.

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

Examples of amines include pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine, diallylamine, triethylamine, N-methylaniline, pyridine, morpholine, N-methylmorpholin, 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, tetraethylenepentamine, benzylamine, dibenzylamine, diphenylamine, diethylhydroxylamine and the like. These may be used alone or in combination of two or more compounds.

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

<Use as a cleaning agent or solvent>
The azeotropic composition (or liquid composition containing the azeotropic composition) of the present invention includes precision mechanical parts, electronic materials (printed circuit boards, liquid crystal displays, magnetic recording parts, semiconductor materials, etc.). ), Resin processed parts, optical lenses, clothing, etc., suitable for removing foreign substances, oils and fats, grease, wax, flux, ink and the like. As described above, since the azeotropic composition of the present invention is nonflammable and has appropriate fluidity and solubility, foreign substances (particles and the like) 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 the liquid composition containing the azeotropic (like) composition) of the present invention is immersed in precision machine parts, electronic materials, etc. to remove stains. Methods such as rinsing, wiping with a waste cloth, and spray washing may be mentioned, and these may be used in combination. It is one of the particularly preferable embodiments that the azeotropic (like) composition is placed in an ultrasonic cleaner, the article to be cleaned is immersed in the liquid, and the ultrasonic cleaning treatment is performed.

As described above, the azeotropic composition of the present invention exhibits stable detergency even when used in an open system, because the composition hardly fluctuates, and the composition is not controlled very frequently. However, this is a great practical advantage.

If the cleaning liquid used for cleaning is recovered and then subjected to a distillation operation, fats and oils and foreign substances (particles) can be separated and removed, and the azeotropic (like) composition of the present invention can be recovered. Since the distillation regeneration device for a general cleaning agent is a simple distillation method, the first component 1223Z is 80 mol% to 99.9999 mol% and the second component 1223E is 0.0001 mol% to 20 mol. In the case of an azeotropic composition consisting of%, it can be regenerated with a commercially available distillation regeneration device without substantially changing the composition.

During the distillation operation, the two liquid components, 1223Z and 1223E, maintain their properties as an azeotropic composition, so that the recovered liquid is then re-cleaned without major composition adjustments. Can be used as. If the above "additional components" are used, these "additional components" may be removed by distillation. In that case, it is desirable to supplement them separately.

The present invention will be described by way of examples.

<Example 1>
25 mL of 1223Z and 1223E were charged in a 50 mL three-necked flask equipped with a septum, a stir bar, and a Dimroth condenser capable of flowing a refrigerant at −10 ° C. so as to have the molar concentrations shown in Table 1. A synthetic zeolite tube was attached to the upper part of the Dimroth. The flask was immersed in an oil bath and heated to reflux with stirring. After one hour or more had passed since the start of reflux and the composition was stabilized, the gas phase part was sampled from Septam with a gas tight syringe and analyzed by gas chromatography. For the liquid phase part, about 1 mL was sampled using a polypropylene syringe similarly equipped with an injection needle, transferred to a 2 mL vial previously cooled with ice water, and then gas chromatography analysis was performed. In Table 1, the calibration curve prepared in advance was used and expressed in mol%. In FIG. 1, the horizontal axis represents the liquid phase composition of 1223Z and the vertical axis represents the gas phase composition of 1223Z, and the results in Table 1 are plotted. In particular, the composition of the gas phase portion and the liquid phase portion does not substantially change in the range of 80 mol% to 99.9999 mol% of the first component 1223Z and 0.0001 to 20 mol% of the second component 1223E. It became clear that it was an azeotropic composition.

<Example 2>
The flash point of the mixed liquid of 1223Z and 1223E was measured in accordance with Japanese Industrial Standard JIS K2265-1 "How to determine the flash point-Part 1: Tag sealing method". An automatic flash point measuring device atg-8l (Tanaka Scientific Instruments Manufacturing Co., Ltd.) was used for the flash point measurement. The measurement results for each composition are shown in Table 2. In the range of azeotropic or azeotropic compositions of 1223Z and 1223E, it was observed that there was no flash point under atmospheric pressure conditions.

<Example 3>
<Washing test>
A commercially available 25 mL graduated cylinder was cut with an 11 mL scale line to set conditions under which liquid vaporization was likely to occur. After measuring the mass of a clean glass rod of diameter: about 7.2 mm x length: about 40 mm, soak it in the oil shown in the table for 2 minutes, stand for 10 minutes and drain it (remove excess oil). After measuring the mass (glass rod + initial adhering oil), it was placed in the above-mentioned measuring cylinder.

Subsequently, as shown in Table 3 below, "1233Z 95.4545 mol%, 1223E 4.5455 mol% azeotropic composition" was charged to a liquid level of 10 mL, and was filled with water at 20 ° C. It was erected in the center of a ultrasonic cleaner (SW5800 manufactured by Citizen). When the azeotropic composition volatilized with time when irradiated with ultrasonic waves and reached a scale line of 8 mL, the liquid in the graduated cylinder was analyzed by gas chromatography. As a result, in all the experimental examples of Examples 3-1 to 3-5, the liquid composition before and after washing was substantially the same even though 2 mL was volatilized. That is, it was shown that the azeotropic composition used in Example 3 in the actual washing had an azeotropic composition in which the composition of the residual liquid did not substantially change even if it was partially volatilized. Next, the glass rod is dried and the mass (total mass of the glass rod and residual oil) is measured to obtain the oil removal rate (mass of residual oil ÷ mass of initially adhered oil × 100 [%]) and expanded. The surface of the glass was observed with a mirror. As a result, the oil removal rate was 100% in all the examples, and no residual oil was observed in the magnifying glass observation result, so that the result was judged to be "good". The results are shown in Table 3 below.

Claims (10)

81.4374 mol% or more and 99.9996 mol% or less (Z) -1,2-dichloro-3,3,3-trifluoropropene and 0.0004 mol% or more and 18.5626 mol% or less (E)- With 1,2-dichloro-3,3,3-trifluoropropene, or with (Z) -1,2-dichloro-3,3,3-trifluoropropene of 0.0001 mol% or more and 8.0892 mol% or less. Consists of (E) -1,2-dichloro-3,3,3-trifluoropropene of 91.9108 mol% or more and 99.9999 mol% or less (however, 90.5 mol% of (Z) -1,2- Azeotropic composition (excluding compositions consisting of dichloro-3,3,3-trifluoropropene and 9.5 mol% (E) -1,2-dichloro-3,3,3-trifluoropropene) Stuff. The liquid composition containing the azeotropic (like) composition according to claim 1 and a stabilizer. The liquid composition according to claim 2, wherein the concentration of the stabilizer is 0.1% by mass or more and 30% by mass with respect to the azeotropic (like) composition. The azeotropic (like) composition according to claim 1, and a liquid composition containing a surfactant. The liquid composition according to claim 4, wherein the concentration of the surfactant is 0.1% by mass or more and 30% by mass or less with respect to the azeotropic (like) composition. A cleaning solvent containing the azeotropic composition according to claim 1 or the liquid composition according to any one of claims 2 to 5. A method for producing a cleaning solvent, which comprises preparing the azeotropic composition according to claim 1 and adding a stabilizer or a surfactant to the azeotropic composition. A method for cleaning an article to be cleaned, which comprises cleaning the article to be cleaned with the azeotropic composition according to claim 1 or the liquid composition according to any one of claims 2 to 5. .. The cleaning method according to claim 8, wherein the cleaning is performed in an open system. Using the azeotropic composition according to claim 1 or the liquid composition according to any one of claims 2 to 5, the article to be washed is washed, and the washing liquid used for washing is used. A method of recovering a cleaning solvent, including distillation.

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