JP7189448B2 - Azeotrope-like composition containing Z-1,2-dichloro-3,3,3-trifluoropropene as a component - Google Patents

Description

The present invention relates to an azeotrope-like composition containing Z-1,2-dichloro-3,3,3-trifluoropropene (hereinafter also referred to as "1223xd(Z)").

Fluorine-containing saturated compounds such as chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) have been used in applications such as foaming agents, heat transfer media, solvents, and cleaning agents. In these applications, the use of single component or azeotrope-like compositions, ie, those which do not substantially fractionate upon boiling or evaporation, is particularly desirable.

These fluorine-containing saturated compounds have a large global warming potential (GWP), and their use is restricted due to concerns about their impact on the global environment. Therefore, hydrochlorofluoroolefins (HCFOs) have been developed as compounds to replace CFCs and HCFCs. HCFOs have excellent environmental performance, such as a short lifetime in the atmosphere and a small global warming potential.

However, the development of new, environmentally safe, non-fractionating compositions, including HCFOs, is difficult because the formation of azeotrope-like compositions is not readily predictable. As such, the industry is constantly seeking new HCFOs compositions that are performance acceptable and environmentally safer alternatives to CFCs and HCFCs.

By the way, Patent Document 1 proposes a composition of a fluorine-containing olefin having 3 carbon atoms and a general-purpose solvent. In particular, Example 4 of Patent Document 1 discloses a degreasing test example of 1,2-dichloro-3,3,3-trifluoropropene (hereinafter also referred to as "1223xd") alone. Similarly, Patent Documents 2 to 7 disclose buffing and cleaning test examples, resist development test examples, resist stripping test examples, dry cleaning test examples, flux cleaning test examples, and adhering water removal test examples for 1223xd alone.

JP-A-2-221388 JP-A-2-221389 JP-A-2-221962 JP-A-2-222469 JP-A-2-222496 JP-A-2-222497 JP-A-2-222702

However, in such a volatile solvent composition, even if the performance is improved by simply blending a plurality of solvents, the problem that the liquid composition tends to fluctuate due to the volatility of each component cannot be avoided. . For example, when a binary liquid composition is placed in an ultrasonic cleaner and subjected to a cleaning process, generally low boiling point components (components with high vapor pressure) volatilize preferentially, and high boiling point components (components with low vapor pressure) are concentrated. For example, in the case of a composition consisting of a low boiling point component with high detergency and a high boiling point component with low detergency, the low boiling point component in the cleaning liquid may decrease over time, resulting in poor cleaning. In addition, the used cleaning solution is usually recycled 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.

The present invention comprises a novel azeotropic (Z)-1,2-dichloro-3,3,3-trifluoropropene (1223xd(Z)) that is environmentally friendly and does not change its composition upon volatilization. An object of the present invention is to propose a composition.

The present inventors have made intensive studies to solve the above problems. As a result, it was found that the composition of 1223xd(Z) and the specific compound was an azeotrope-like composition in which the composition of the gas phase portion and the liquid phase portion were substantially the same. Further, it was confirmed in Examples that the azeotrope-like composition of the present invention is suitable as a cleaning agent for articles to be cleaned, leading to the completion of the present invention.

That is, the present invention includes each of the following inventions.

[Invention 1]
Z-1,2-dichloro-3,3,3-trifluoropropene;
Azeotropic (like) compositions with dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-hexane, cyclohexane, acetone or cyclopentane.

[Invention 2]
An azeotropic (like) composition according to invention 1, comprising 1 to 40 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 99 to 60 mol % dichloromethane.

[Invention 3]
An azeotropic (like) composition according to invention 1, comprising 67-77 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 33-23 mol % methanol.

[Invention 4]
An azeotropic (like) composition according to invention 1, comprising 80-99 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 20-1 mol % ethanol.

[Invention 5]
An azeotropic (like) composition according to invention 1, comprising 90-99 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 10-1 mol % n-propanol.

[Invention 6]
An azeotropic (like) composition according to invention 1 comprising 85-99 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 15-1 mol % isopropanol.

[Invention 7]
An azeotropic (like) composition according to invention 1, comprising 75-99 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 25-1 mol % n-hexane.

[Invention 8]
An azeotropic (like) composition according to invention 1, comprising 85-99 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 15-1 mol % cyclohexane.

[Invention 9]
An azeotropic (like) composition according to invention 1, comprising 1 to 99 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 99 to 1 mol % acetone.

[Invention 10]
An azeotropic (like) composition according to invention 1, comprising 1-60 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 99-40 mol % cyclopentane.

[Invention 11]
A liquid composition comprising at least the azeotropic (like) composition according to any one of Inventions 1 to 10.

[Invention 12]
12. The liquid composition according to invention 11, further comprising at least one additional ingredient.

[Invention 13]
13. The liquid composition according to invention 12, wherein the total amount of said additional components is 0.001 to 30% by mass relative to said azeotropic (like) composition.

[Invention 14]
An aerosol composition comprising the azeotropic (for) composition according to any one of Inventions 1 to 10 or the liquid composition according to any one of Inventions 11 to 13, and a propellant gas.

[Invention 15]
A cleaning agent comprising the azeotropic (like) composition according to any one of Inventions 1 to 10, the liquid composition according to any one of Inventions 11 to 13, or the aerosol composition according to Invention 14.

[Invention 16]
A cleaning agent according to invention 15, which is for cleaning vehicles, vehicles or transportation.

[Invention 17]
17. A cleaning agent according to invention 15 or 16 for use as a vehicle, vehicle or transport brake cleaner.

[Invention 18]
A solvent comprising the azeotropic (like) composition according to any one of Inventions 1 to 10, the liquid composition according to any one of Inventions 11 to 13, or the aerosol composition according to Invention 14.

[Invention 19]
A draining agent comprising the azeotropic (like) composition according to any one of Inventions 1 to 10, the liquid composition according to any one of Inventions 11 to 13, or the aerosol composition according to Invention 14.

[Invention 20]
A blowing agent comprising the azeotropic (like) composition according to any one of Inventions 1 to 10, the liquid composition according to any one of Inventions 11 to 13, or the aerosol composition according to Invention 14.

[Invention 21]
A heat transfer medium comprising the azeotropic (like) composition according to any one of Inventions 1 to 10, the liquid composition according to any one of Inventions 11 to 13, or the aerosol composition according to Invention 14.

[Invention 22]
A lubricant solvent comprising the azeotropic (like) composition according to any one of Inventions 1 to 10, the liquid composition according to any one of Inventions 11 to 13 or the aerosol composition according to Invention 14.

[Invention 23]
a step of contacting an article to be cleaned with the azeotropic (like) composition according to any one of Inventions 1 to 10, the liquid composition according to any one of Inventions 11 to 13, or the aerosol composition according to Invention 14; A method of cleaning said items to be cleaned, comprising:

In Patent Documents 1 to 7, there is no description regarding detailed behavior when 1,2-dichloro-3,3,3-trifluoropropene (1223xd) and the above specific compound are blended. Furthermore, 1223xd has E- and Z-geometric isomers, and these geometric isomers have their own boiling points and polarities, and therefore differ in drying properties, cleaning properties, and the like. However, the above patent documents do not disclose geometric isomers.

The present invention provides novel azeotropic (like) compositions. This azeotropic (like) composition is less burdensome to the environment, and has the effect of easily maintaining performance as a liquid whose composition does not readily change even when used under open conditions. In addition, this azeotropic (like) composition is useful as a cleaning agent for articles (articles to be cleaned) to which contaminants such as foreign substances and oils adhere.

It is a vapor-liquid equilibrium diagram of 1223xd(Z) and dichloromethane. It is a vapor-liquid equilibrium diagram of 1223xd(Z) and methanol. It is a vapor-liquid equilibrium diagram of 1223xd(Z) and ethanol. It is a vapor-liquid equilibrium diagram of 1223xd(Z) and n-propanol. It is a vapor-liquid equilibrium diagram of 1223xd(Z) and isopropanol. It is a vapor-liquid equilibrium diagram of 1223xd(Z) and n-hexane. It is a vapor-liquid equilibrium diagram of 1223xd(Z) and cyclohexane. It is a vapor-liquid equilibrium diagram of 1223xd(Z) and acetone. It is a vapor-liquid equilibrium diagram of 1223xd(Z) and cyclopentane.

[Azeotropic (like) composition]
Since fluorine-containing olefins are highly compatible with various solvents, it is possible to easily prepare a uniform composition. However, in the case of such a simple composition, there is an inherent problem that "the liquid composition tends to fluctuate". That is, even if a plurality of kinds of liquids are mixed and compatibility can be ensured, the problem that the liquid composition tends to fluctuate due to the difference in volatility of each component cannot be avoided. For example, when a binary liquid composition is placed in an ultrasonic cleaning machine and used as a cleaning agent, generally highly volatile low boiling point components (components with high vapor pressure) volatilize preferentially, high-boiling-point components with low volatility are concentrated in the For example, in the case of a composition containing a low boiling point component with high detergency and a high boiling point component with low detergency, the concentration of the low boiling point component in the cleaning liquid may decrease over time, resulting in poor cleaning. In particular, when a non-flammable solvent is blended with a non-flammable solvent to prepare a non-flammable composition, preferential volatilization of the non-flammable component may result in the cleaning liquid becoming a flammable composition.

In addition, it is desirable to recover and reuse the washing solvent by an operation such as distillation after use from the standpoint of environmental protection and economy. must be collected separately, and collection and reuse tends to impose an operational load.

A similar problem exists 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 change over a long period of time. If the liquid composition fluctuates, the liquid's heat capacity, viscosity, or affinity with the lubricant 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, it is necessary to analyze the liquid composition frequently, and to constantly adjust the proportions so that the composition range is within the proper range. to replenish the volatilized components. However, such liquid composition management can be a heavy work load.

On the other hand, the azeotropic composition volatilizes at the same composition as the liquid composition, which is a very preferable composition in which the liquid composition does not change during use. As used herein, "azeotrope" refers to azeotrope in a 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 azeotrope, and the vapor present in vapor-liquid equilibrium with this is also called "ethanol ( 96% by mass): water (4% by mass)”, which completely matches the liquid composition. This phenomenon is called "azeotrope". At a specific temperature and pressure, the composition of the azeotrope is only one point.

"Azeotrope-like" is also called "pseudo-azeotrope" and is not strictly azeotropic thermodynamically, but for a range of liquid compositions, the liquid composition and the equilibrium gas composition are , may be substantially equal and refer to such phenomena. Even if the compositions of the gas phase portion and the liquid phase portion do not completely match, if the compositions of the gas phase portion and the liquid phase portion substantially match, those skilled in the art can treat it as an azeotropic composition. At this time, the smaller the gas-liquid equilibrium composition difference between the gas phase portion and the liquid phase portion, the better. In this way, the phenomenon in which the vapor-liquid equilibrium compositions of the gas phase portion and the liquid phase portion substantially match is called azeotropic or pseudo-azeotropic, and the composition is called azeotropic-like or pseudo-azeotropic. .

Academically, azeotropic phenomenon and pseudo-azeotropic phenomenon (or azeotropic-like) should be distinguished, but in practice such as cleaning, azeotropic phenomenon and azeotropic-like phenomenon (or pseudo-azeotropic) should be distinguished. Azeotropic phenomena and azeotrope-like phenomena (or pseudo-azeotrope-like phenomena) are collectively referred to herein as "azeotrope-like" because they are not required and can be treated in exactly the same way. Moreover, the composition at that time is called an "azeotropic (like) composition". In azeotropic (like), the presence or absence of an azeotropic point does not matter. The gas-liquid equilibrium composition of the gas phase portion and the liquid phase portion should substantially match.

"Azeotropic (like)" is not derived theoretically, but by investigating the vapor-liquid equilibrium for various types of liquids and composition ratios by experiment, it happened that the composition of the gas phase and the composition of the liquid phase were substantially It is something that can be found only when it matches. In the present invention, gas-liquid equilibrium experiments were conducted between 1223xd(Z) and a specific compound, and it was found that the azeotropic point at which the gas-liquid composition completely matched and/or the gas-liquid composition was substantially the same. A boiling (like) composition could be found.

1,2-dichloro-3,3,3-trifluoropropene (1223xd) has E and Z isomers, and a method for selectively producing the Z isomer is described in patent documents (WO2014/046250, WO2014/046251 No. 1, 2003), and the highly pure Z form (1223xd(Z)) is available by precision distillation.

As is clear from the gas-liquid equilibrium measurements shown in the examples below, the composition of the present invention comprising 1223xd(Z) as the first component and a specific compound as the second component has a specific composition. , is an azeotropic (like) composition in which the compositions of the gas phase and the liquid phase are substantially the same.

In the composition containing 1223xd(Z) as the first component and dichloromethane as the second component, 1223xd(Z) is 1 to 40 mol% and dichloromethane is 99 to 60 mol%. It is an azeotropic (like) composition in which the composition of the phase portion and the liquid phase portion are substantially the same. In addition, this composition has a low risk of ignition and fire risk in the environment in which the composition is used. Furthermore, when 1223xd(Z) is 1 to 30 mol % and dichloromethane is 99 to 70 mol %, the compositions of the gas phase and the liquid phase are more closely related, and compositional fluctuations are less likely to occur, which is particularly preferred.

In the composition containing 1223xd(Z) as the first component and methanol as the second component, 67 to 77 mol% of 1223xd(Z) and 33 to 23 mol% of methanol It is an azeotropic (like) composition in which the composition of the phase portion and the liquid phase portion are substantially the same. Further, when 1223xd(Z) is 70 to 74 mol % and methanol is 30 to 26 mol %, the compositions of the gas phase and the liquid phase are more closely related, and compositional fluctuations are less likely to occur, which is particularly preferred.

In the composition containing 1223xd(Z) as the first component and ethanol as the second component, 1223xd(Z) is 80 to 99 mol% and ethanol is 20 to 1 mol%. It is an azeotropic (like) composition in which the composition of the phase portion and the liquid phase portion are substantially the same. In addition, this composition has a low risk of ignition and fire risk in the environment in which the composition is used. Furthermore, when 1223xd(Z) is 85 to 99 mol % and ethanol is 15 to 1 mol %, the compositions of the gas phase and the liquid phase are more closely related, and compositional fluctuations are less likely to occur, which is particularly preferred.

In the composition containing 1223xd(Z) as the first component and n-propanol as the second component, 90 to 99 mol% of 1223xd(Z) and 10 to 1 mol of n-propanol %, it is an azeotropic (like) composition in which the compositions of the gas phase and the liquid phase are substantially the same. In addition, this composition has a low risk of ignition and fire risk in the environment in which the composition is used. Furthermore, when 1223xd(Z) is 95 to 99 mol% and n-propanol is 5 to 1 mol%, the compositions of the gas phase portion and the liquid phase portion are closer to each other, and composition fluctuation is more difficult to occur. preferable.

In the composition containing 1223xd(Z) as the first component and isopropanol as the second component, 85 to 99 mol% of 1223xd(Z) and 15 to 1 mol% of isopropanol It is an azeotropic (like) composition in which the composition of the phase portion and the liquid phase portion are substantially the same. In addition, this composition has a low risk of ignition and fire risk in the environment in which the composition is used. Further, when 1223xd(Z) is 90 to 99 mol % and isopropanol is 10 to 1 mol %, the compositions of the gas phase and the liquid phase are more closely related, and the composition variation is less likely to occur, which is particularly preferred.

In the composition containing 1223xd(Z) as the first component and n-hexane as the second component, 75 to 99 mol% of 1223xd(Z) and 25 to 1 mol of n-hexane %, it is an azeotropic (like) composition in which the compositions of the gas phase and the liquid phase are substantially the same. In addition, this composition has a low risk of ignition and fire risk in the environment in which the composition is used. Furthermore, when 1223xd(Z) is 80 to 99 mol% and n-hexane is 20 to 1 mol%, the compositions of the gas phase portion and the liquid phase portion are closer to each other, and compositional fluctuations are more difficult to occur. preferable.

In the composition containing 1223xd(Z) as the first component and cyclohexane as the second component, 85 to 99 mol% of 1223xd(Z) and 15 to 1 mol% of cyclohexane It is an azeotropic (like) composition in which the composition of the phase portion and the liquid phase portion are substantially the same. In addition, this composition has a low risk of ignition and fire risk in the environment in which the composition is used. Further, when 1223xd(Z) is 90 to 99 mol % and cyclohexane is 10 to 1 mol %, the compositions of the gas phase and the liquid phase are more closely related to each other, and composition fluctuations are less likely to occur, which is particularly preferred.

In the composition containing 1223xd(Z) as the first component and acetone as the second component, 1223xd(Z) is 1 to 99 mol% and acetone is 99 to 1 mol%. It is an azeotropic (like) composition in which the composition of the phase portion and the liquid phase portion are substantially the same. Furthermore, when 1223xd(Z) is 45 to 99 mol% and acetone is 55 to 1 mol%, the compositions of the gas phase portion and the liquid phase portion are closer to each other, and the composition fluctuation is less likely to occur. It is particularly preferred because of its low flammability and fire risk in the environment of use.

In the composition containing 1223xd(Z) as the first component and cyclopentane as the second component, 1223xd(Z) is 1 to 60 mol% and cyclopentane is 99 to 40 mol%. , is an azeotropic (like) composition in which the compositions of the gas phase and the liquid phase are substantially the same. Furthermore, when 1223xd(Z) is 20 to 55 mol% and cyclopentane is 80 to 45 mol%, the compositions of the gas phase portion and the liquid phase portion are even closer, and the composition fluctuation is more difficult to occur, which is particularly preferable. .

Here, the value of mol % is the mole of each component when the total number of moles of 1223xd(Z) as the first component and the specific compound as the second component is 100 % of numbers (ie relative mole % between two components). If the composition is within this range, practically, even if the liquid composition is handled in an open system, and even if recovery operation by distillation is performed, compositional fluctuation is unlikely to occur.

The azeotropic (like) composition of the present invention can be produced, for example, by mixing specific amounts of 1223xd(Z) as the first component and the above specific compound as the second component. The azeotropic (like) composition of the present invention is substantially free of impurities (substantially composed of the first component and the second component) and is of high purity in one preferred embodiment. be.

In addition, the azeotropic (like) composition of the present invention includes, in addition to 1223xd(Z) as the first component and the specific compound as the second component, raw materials for synthesizing them, A small amount of by-products, etc. (for each component, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, particularly preferably 1% by mass, relative to the azeotropic (like) composition below), it may be left over. For example, the azeotropic (like) composition of the present invention may comprise, in addition to the first component and the second component, the following compounds:
1-chloro-3,3,3-trifluoropropene (1233zd), 2-chloro-3,3,3-trifluoropropene (1233xf), 2,3-dichloro-3,3-difluoropropene (1232xf), 1,2,3-trichloro-3,3-difluoropropene (1222xd), 2,3,3-trichloro-3-fluoropropene (1231xf), E-1,2-dichloro-3,3,3-tri HCFOs such as fluoropropene (1223xd(E)), 1,1-dichloro-3,3,3-trifluoropropene (1223za);
1,3,3,3-tetrachloropropene (1230zd), 1,1,2,3-tetrachloropropene (1230xa), 1,1,3,3-tetrachloropropene (1230za), 2,3,3 , 3-tetrachloropropene (1230xf) and other hydrochloroolefins (HCOs);
1,1,2-trichloro-3,3,3-trifluoropropane (233da), 1,2,2-trichloro-3,3,3-trifluoropropane (233ab), 1,1,2,2- Tetrachloro-3,3,3-trifluoropropane (223aa), 1,1,1,2,2-pentachloro-3,3,3-trifluoropropane (213ab), 1,1,2,2-tetra Hydrochlorofluorocarbons (HCFCs) such as chloro-3,3,3-trifluoropropane (223ab) and 1,1,1,2-tetrachloro-3,3,3-trifluoropropane (223db).

If desired, additional ingredients can be added to improve the performance of the azeotrope-like composition. Examples of additional components include detergency enhancers (surfactants), stabilizers (acid acceptors, antioxidants) and the like, but are not limited to these.

Specific examples of detergency enhancers include sorbitan aliphatic esters such as sorbitan monooleate and sorbitan trioleate; polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitol tetraoleate; Polyethylene glycol fatty acid esters such as laurate; Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether; Polyoxyethylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether; Nonionic surfactants such as ethylene alkylamine fatty acid amides can be mentioned. These detergency enhancers may be used alone or in combination of two or more. For the purpose of synergistically improving detergency and interfacial action, in addition to these nonionic surfactants, cationic surfactants and anionic surfactants are added to the azeotropic (like) composition of the present invention. good too.

The stabilizer is not particularly limited, but is more preferably one that is entrained by distillation or one that forms an azeotrope-like mixture. Specific examples of such stabilizers include nitro compounds, epoxy compounds, phenols, imidazoles, amines, hydrocarbons and the like.

As the nitro compound, known compounds may be used, including aliphatic and/or aromatic derivatives. Examples of aliphatic nitro compounds include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane and the like. Aromatic nitro compounds such as 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.

Examples of epoxy compounds 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 triglycidyl ether compounds and the like.

Phenols include phenols containing various substituents such as alkyl groups, alkenyl groups, alkoxy groups, carboxyl groups, carbonyl groups, and halogen groups in addition to hydroxyl groups. 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, phenol, xylenol and other monovalent phenols or t-butylcatechol, 2,5-di-t-aminohydroquinone, 2,5-di-t-butylhydroquinone and other divalent phenol and the like.

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

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, dibenzylamine, tribenzylamine, 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 two or more compounds may be used in combination.

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

The azeotropic (like) compositions of the present invention may contain additional ingredients such as lubricants, flame retardants, metal passivators, corrosion inhibitors, and the like.

The amount of the additional component to be added to the azeotropic (like) composition of the present invention varies depending on the component, but may be such that it does not interfere with the azeotropic (like) properties of the azeotropic (like) composition. For example, it is 30% by mass or less, preferably 10% by mass or less, particularly preferably 5% by mass or less, further preferably 3% by mass or less, relative to the azeotropic (like) composition. Moreover, it may be 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more relative to the azeotropic (like) composition. That is, the additional component may be added in the following amounts to the azeotropic (like) composition: 0.001 to 30% by weight; 0.001 to 10% by weight; 0.001 to 5% by weight. 0.001 to 3% by mass; 0.001 to 1% by mass; 0.001 to 0.01% by mass; 0.001 to 0.1% by mass; 0.01 to 30% by mass; % by mass; 0.01 to 5% by mass; 0.01 to 3% by mass; 0.01 to 1% by mass; 0.01 to 0.1% by mass; % by mass; 0.1 to 5% by mass; 0.1 to 3% by mass; 0.1 to 1% by mass; 1 to 30% by mass; 1 to 10% by mass; 3-30% by mass; 3-10% by mass; 3-5% by mass; 5-30% by mass; 5-10% by mass;

The azeotropic (like) composition of the present invention (or a liquid composition containing the azeotropic (like) composition) may be mixed with propellant gas to form an aerosol composition.

A liquefied gas or a compressed gas can be used as the injection gas. For example, the above gases such as LPG (liquefied petroleum gas), DME (dimethyl ether), carbon dioxide, fluorocarbon gas, nitrogen gas, compressed air, mixtures of LPG and DME, mixtures of LPG and carbon dioxide, etc. A combination of more than one species is included, but not limited to this.

The aerosol composition of the present invention can be produced by mixing the azeotropic (like) composition of the present invention (or a liquid composition containing the azeotropic (like) composition) with the propellant gas, Moreover, it can be provided by being filled in a pressure-resistant can.

[Use as cleaning agent or solvent]
The azeotropic (like) composition of the present invention (or a liquid composition containing the azeotropic (like) composition) can be used for precision machine parts, electronic materials (printed circuit boards, liquid crystal displays, magnetic recording parts, semiconductor materials, etc.). ), resin-processed parts, optical lenses, clothing, etc., to remove foreign substances, oils, greases, waxes, fluxes, inks, and the like. Since the azeotropic (like) composition of the present invention has appropriate fluidity and solubility, foreign matter (particles, etc.) can be removed by washing away or dissolving. In addition, in the cleaning of various vehicles, vehicles, and transportation facilities such as automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railroad vehicles, and ships (especially these brake cleaners), a process of wetting and washing away dirt is required. By the way, the azeotropic (like) composition of the present invention (or a liquid composition containing the azeotropic (like) composition) has an appropriate boiling point, and can wet dirt and wash it off. , is suitable for such cleaning. Although the method of cleaning is not particularly limited, the article to be cleaned is immersed in the azeotropic (like) composition of the present invention (or a liquid composition containing the azeotropic (like) composition) to wash away dirt with a waste cloth. Methods such as wiping off and spray cleaning may be mentioned, and these methods may be used in combination. It is one of the particularly preferred embodiments to put the azeotropic (like) composition in an ultrasonic cleaner, immerse the article to be cleaned in the liquid, and perform ultrasonic cleaning treatment. In addition, spray cleaning, for example, the azeotropic (like) composition of the present invention (or a liquid composition containing the azeotropic (like) composition) is mixed with a propellant gas to form an aerosol, thereby cleaning various articles to be cleaned. A method of spraying is also one of preferred embodiments.

As described above, the azeotropic (like) composition of the present invention exhibits stable detergency even if it is used in an open system because the composition hardly fluctuates without frequent composition control. . This is a great practical advantage.

The cleaning liquid used for cleaning can be recovered and subjected to a distillation operation to separate and remove oils and fats and foreign matter (particles), thereby recovering the azeotropic (like) composition of the present invention. Since a general distillation regeneration apparatus for cleaning agents is a simple distillation system, in the case of an azeotropic (like) composition consisting of 1223xd(Z) as the first component and a specific compound as the second component, commercially available can be regenerated with virtually no change in composition. In particular, in the case of an azeotropic composition, even if a distillation column with a high number of stages is used, there is no change in composition, which is preferable.

During the distillation operation, the two liquid components of 1223xd(Z) and said specific compound maintain their properties as an azeotropic (like) composition, so that the recovered liquid then undergoes extensive compositional adjustments. It can be used again as a cleaning solvent without In addition, when the above-mentioned "additional component" is used, the "additional component" may be removed by distillation, so in that case, it is desirable to supplement separately.

The azeotropic (like) composition of the present invention is also suitable as a draining agent, blowing agent, heat transfer medium, and lubricant solvent.

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples described below.

<Vapor-liquid equilibrium measurement>
[Example 1-1]
Z-1,2-dichloro-3,3,3-trifluoropropene was added to a 50 mL three-necked flask equipped with a septum, a stirrer, and a Dimroth capable of flowing -10° C. refrigerant so that the molar concentration shown in Table 1 was obtained. (1223xd(Z)) and dichloromethane (CH ₂ Cl ₂ ) were combined to prepare 25 mL. 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 one hour or more from the start of reflux and the composition was stabilized, the gas phase portion was sampled from the septum with a gas-tight syringe and analyzed by gas chromatography. About 1 mL of the liquid phase was similarly sampled using a polypropylene syringe equipped with an injection needle, transferred to a 2 mL vial previously cooled with ice water, and subjected to gas chromatography analysis. In Table 1, mol % was expressed using a calibration curve prepared in advance. In FIG. 1, the horizontal axis represents the liquid phase composition of 1223xd(Z) and the vertical axis represents the gaseous phase composition of 1223xd(Z), and the results in Table 1 are plotted. According to Example 1-1, the composition of the gas phase portion and the liquid phase portion is substantially in the range of 1 to 40 mol% of 1223xd(Z) as the first component and 99 to 60 mol% of dichloromethane as the second component. It was found to be an unchanged azeotrope or azeotrope-like composition.

[Example 1-2]
The same operation as in Example 1-1 was performed except that methanol (MeOH) was used instead of dichloromethane. In Table 2, mol % was expressed using a calibration curve prepared in advance. In FIG. 2, the horizontal axis represents the liquid phase composition of 1223xd(Z) and the vertical axis represents the gaseous phase composition of 1223xd(Z), and the results in Table 2 are plotted. According to Example 1-2, the composition of the gas phase portion and the liquid phase portion is substantially An unchanged azeotropic or azeotrope-like composition was found.

[Example 1-3]
The same operation as in Example 1-1 was performed except that ethanol (EtOH) was used instead of dichloromethane. In Table 3, the calibration curve prepared in advance was used to express mol %. In FIG. 3, the horizontal axis represents the liquid phase composition of 1223xd(Z) and the vertical axis represents the gaseous phase composition of 1223xd(Z), and the results in Table 3 are plotted. According to Example 1-3, in the range of 80 to 99 mol% of 1223xd(Z) as the first component and 20 to 1 mol% of ethanol as the second component, the composition of the gas phase portion and the liquid phase portion is substantially An unchanged azeotropic or azeotrope-like composition was found.

[Example 1-4]
The same operation as in Example 1-1 was performed except that n-propanol (n-PrOH) was used instead of dichloromethane. In Table 4, mol % was expressed using a calibration curve prepared in advance. In FIG. 4, the horizontal axis represents the liquid phase composition of 1223xd(Z) and the vertical axis represents the gaseous phase composition of 1223xd(Z), and the results of Table 4 are plotted. According to Example 1-4, in the range of 90 to 99 mol% of 1223xd(Z) as the first component and 10 to 1 mol% of n-propanol as the second component, the composition of the gas phase portion and the liquid phase portion is substantially azeotropic or azeotrope-like compositions that do not change over time.

[Example 1-5]
The same operation as in Example 1-1 was performed except that isopropanol (IPA) was used instead of dichloromethane. In Table 5, mol % was expressed using a calibration curve prepared in advance. In FIG. 5, the horizontal axis represents the liquid phase composition of 1223xd(Z) and the vertical axis represents the gaseous phase composition of 1223xd(Z), and the results of Table 5 are plotted. According to Example 1-5, the composition of the gas phase portion and the liquid phase portion was substantially in the range of 85 to 99 mol% of 1223xd(Z) as the first component and 15 to 1 mol% of isopropanol as the second component. An unchanged azeotropic or azeotrope-like composition was found.

[Example 1-6]
The same operation as in Example 1-1 was performed except that n-hexane was used instead of dichloromethane. In Table 6, mol % was expressed using a calibration curve prepared in advance. In FIG. 6, the horizontal axis represents the liquid phase composition of 1223xd(Z) and the vertical axis represents the gaseous phase composition of 1223xd(Z), and the results of Table 6 are plotted. According to Example 1-6, in the range of 75 to 99 mol% of 1223xd(Z) as the first component and 25 to 1 mol% of n-hexane as the second component, the composition of the gas phase portion and the liquid phase portion is substantially azeotropic or azeotrope-like compositions that do not change over time.

[Example 1-7]
The same operation as in Example 1-1 was performed except that cyclohexane was used instead of dichloromethane. In Table 7, mol % was expressed using a calibration curve prepared in advance. In FIG. 7, the horizontal axis represents the liquid phase composition of 1223xd(Z) and the vertical axis represents the gaseous phase composition of 1223xd(Z), and the results in Table 7 are plotted. According to Example 1-7, the composition of the gas phase part and the liquid phase part is substantially An unchanged azeotropic or azeotrope-like composition was found.

[Example 1-8]
The same operation as in Example 1-1 was performed except that acetone was used instead of dichloromethane. In Table 8, mol % was expressed using a calibration curve prepared in advance. In FIG. 8, the horizontal axis represents the liquid phase composition of 1223xd(Z) and the vertical axis represents the gaseous phase composition of 1223xd(Z), and the results of Table 8 are plotted. According to Example 1-8, the composition of the gas phase part and the liquid phase part is substantially An unchanged azeotropic or azeotrope-like composition was found.

[Example 1-9]
The same operation as in Example 1-1 was performed except that cyclopentane was used instead of dichloromethane. In Table 9, mol % was expressed using a calibration curve prepared in advance. In FIG. 9, the horizontal axis represents the liquid phase composition of 1223xd(Z) and the vertical axis represents the gaseous phase composition of 1223xd(Z), and the results in Table 9 are plotted. According to Example 1-9, the composition of the gas phase portion and the liquid phase portion is substantially in the range of 1 to 60 mol% of 1223xd(Z) as the first component and 99 to 40 mol% of cyclopentane as the second component. It was found to be an azeotropic composition or an azeotrope-like composition that does not change to

<Flash point measurement>
[Example 2-1]
The flash point of a mixed liquid of 1223xd (Z) and dichloromethane (CH ₂ Cl ₂ ) was measured in accordance with Japanese Industrial Standards JIS K 2265-1 "Determination of flash point - Part 1: Tag sealing method". . For the flash point measurement, an automatic flash point meter atg-8l (Tanaka Scientific Instruments Manufacturing Co., Ltd.) was used. As a result, no flash point was observed under atmospheric pressure conditions in the range of azeotropic or azeotrope-like compositions of 1223xd(Z) and dichloromethane described in Example 1-1.

[Example 2-2] to [Example 2-7]
The same operations as in Example 2-1 were performed except that methanol (MeOH), ethanol (EtOH), n-propanol (n-PrOH), isopropanol (IPA), n-hexane or cyclohexane was used instead of dichloromethane. rice field. As a result, each composition was observed to have no flash point under atmospheric pressure conditions in the range of azeotropic or azeotrope-like compositions described in Examples 1-2 to 1-7.

[Example 2-8]
The same operation as in Example 2-1 was performed except that acetone was used instead of dichloromethane. Table 10 shows the measurement results for each composition.

<Washing test>
[Example 3-1]
A commercially available 25 mL graduated cylinder was cut at the 11 mL graduation line. After measuring the mass of a clean glass rod with a diameter of about 7.2 mm and a length of about 40 mm, it was immersed in the oil shown in Table 11 for 2 minutes and allowed to stand for 10 minutes to drain (excessive oil was removed). Then, after measuring the mass (glass rod + initial adhered oil), it was placed in the graduated cylinder. A mixture of 1223xd(Z) and dichloromethane (CH ₂ Cl ₂ ) (pre-test composition shown in Table 11) was charged to a liquid level of 10 mL, and a small ultrasonic cleaner (SW5800 manufactured by Citizen) was filled with water at 20°C. in the center of the This mixed solution volatilized with time when ultrasonic waves were applied, and when the graduation line reached 8 mL, the solution in the graduated cylinder was analyzed with a gas chromatograph. As a result, in all Examples, although 2 mL of the liquid volatilized, the liquid composition before and after washing was substantially the same. In other words, it was shown that the mixed liquid of 1223xd(Z) and dichloromethane had an azeotropic (like) composition in which the composition of the residual liquid did not substantially change even if it partially volatilized in the cleaning of the actual machine.

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 [%]), The surface of the glass was visually observed with a magnifying glass. As a result, the oil removal rate was 100% in all the examples, and no residual oil was observed as a result of observation with a magnifying glass, so it was judged to be good. The results for each example are shown in Table 11 below.

[Example 3-2] to [Example 3-9]
Except using methanol (MeOH), ethanol (EtOH), n-propanol (nPrOH), isopropanol (IPA), n-hexane (nHex), cyclohexane (cHex), acetone or cyclopentane (cPen) instead of dichloromethane. performed the same operation as in Example 3-1. As a result, in all Examples, the liquid composition before and after washing was substantially the same, although 2 mL was volatilized. In other words, it was shown that each liquid mixture has an azeotropic (like) composition in which the composition of the residual liquid does not substantially change even if it is partially volatilized in actual machine cleaning. Tables 12 to 19 below show the results of each example with respect to the oil removal rate and observation results with a magnifying glass.

Claims (22)

Z-1,2-dichloro-3,3,3-trifluoropropene;
An azeotropic (like) composition comprising dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-hexane, cyclohexane, acetone or cyclopentane,
An azeotropic (like) composition comprising 1-40 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 99-60 mol % dichloromethane. Z-1,2-dichloro-3,3,3-trifluoropropene;
An azeotropic (like) composition comprising dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-hexane, cyclohexane, acetone or cyclopentane,
An azeotropic (like) composition comprising 67-77 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 33-23 mol % methanol. Z-1,2-dichloro-3,3,3-trifluoropropene;
An azeotropic (like) composition comprising dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-hexane, cyclohexane, acetone or cyclopentane,
An azeotropic (like) composition comprising 80-99 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 20-1 mol % ethanol. Z-1,2-dichloro-3,3,3-trifluoropropene;
An azeotropic (like) composition comprising dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-hexane, cyclohexane, acetone or cyclopentane,
An azeotropic (like) composition comprising 90-99 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 10-1 mol % n-propanol. Z-1,2-dichloro-3,3,3-trifluoropropene;
An azeotropic (like) composition comprising dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-hexane, cyclohexane, acetone or cyclopentane,
An azeotropic (like) composition comprising 85-99 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 15-1 mol % isopropanol. Z-1,2-dichloro-3,3,3-trifluoropropene;
An azeotropic (like) composition comprising dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-hexane, cyclohexane, acetone or cyclopentane,
An azeotropic (like) composition comprising 75-99 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 25-1 mol % n-hexane. Z-1,2-dichloro-3,3,3-trifluoropropene;
An azeotropic (like) composition comprising dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-hexane, cyclohexane, acetone or cyclopentane,
An azeotropic (like) composition comprising 85-99 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 15-1 mol % cyclohexane. Z-1,2-dichloro-3,3,3-trifluoropropene;
An azeotropic (like) composition comprising dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-hexane, cyclohexane, acetone or cyclopentane,
An azeotropic (like) composition comprising 1-99 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 99-1 mol % acetone. Z-1,2-dichloro-3,3,3-trifluoropropene;
An azeotropic (like) composition comprising dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-hexane, cyclohexane, acetone or cyclopentane,
An azeotropic (like) composition comprising 1-60 mol % Z-1,2-dichloro-3,3,3-trifluoropropene and 99-40 mol % cyclopentane. A liquid composition comprising at least an azeotropic (like) composition according to any one of claims 1-9 . 11. The liquid composition of Claim 10 , further comprising at least one additional ingredient. 12. The liquid composition according to claim 11 , wherein the total amount of said additional components is 0.001 to 30% by weight relative to said azeotropic (like) composition. An aerosol composition containing the azeotropic (use) composition according to any one of claims 1 to 9 or the liquid composition according to any one of claims 10 to 12 and a propellant gas. A cleaning agent comprising an azeotropic (like) composition according to any one of claims 1 to 9 , a liquid composition according to any one of claims 10 to 12 or an aerosol composition according to claim 13 . 15. The cleaning agent according to claim 14 , for cleaning vehicles, vehicles or transport. 16. A cleaning agent according to claim 14 or 15 for brake cleaners in vehicles, vehicles or transport. A solvent comprising an azeotropic (like) composition according to any one of claims 1 to 9 , a liquid composition according to any one of claims 10 to 12 or an aerosol composition according to claim 13 . A draining agent comprising the azeotropic (like) composition according to any one of claims 1 to 9 , the liquid composition according to any one of claims 10 to 12 or the aerosol composition according to claim 13 . A blowing agent comprising an azeotropic (like) composition according to any one of claims 1 to 9 , a liquid composition according to any one of claims 10 to 12 or an aerosol composition according to claim 13 . A heat transfer medium comprising an azeotropic (like) composition according to any one of claims 1 to 9 , a liquid composition according to any one of claims 10 to 12 or an aerosol composition according to claim 13 . A lubricant solvent comprising an azeotropic (like) composition according to any one of claims 1 to 9 , a liquid composition according to any one of claims 10 to 12 or an aerosol composition according to claim 13 . The azeotropic (like) composition according to any one of claims 1 to 9 , the liquid composition according to any one of claims 10 to 12 , or the aerosol composition according to claim 13 is brought into contact with an article to be cleaned. A method of cleaning the article to be cleaned, comprising the step of allowing the article to be cleaned.

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