WO2019117100A1 - Azeotrope-like composition containing z-1,2-dichloro-3,3,3-trifluoropropene - Google Patents

Abstract

The present invention addresses the problem of providing an environmentally friendly novel azeotropic (azeotrope-like) composition. This composition contains Z-1,2-dichloro-3,3,3-trifluoropropene (1223xd(Z)) as a first component, and dichloromethane, methanol, ethanol, n-propanol, isopropanol, n-hexane, cyclohexane, acetone, or cyclopentane as a second component. The composition has a small impact on the global environment and exhibits azeotropic or azeotrope-like properties.

Description

An azeotrope-like composition containing Z-1,2-dichloro-3,3,3-trifluoropropene as a component

The present invention relates to an azeotrope-like composition comprising Z-1,2-dichloro-3,3,3-trifluoropropene (hereinafter also referred to as "1223 x d (Z)") as a component.

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

These fluorine-containing saturated compounds have a large global warming potential (GWP), are concerned about the influence on the global environment, and their use is limited. Therefore, hydrochlorofluoroolefins (HCFO) 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 low global warming potential.

However, the development of new environmentally safe, non-fractional compositions, including HCFOs, is difficult because the formation of azeotropic (like) compositions is not readily predictable. Therefore, the industry is constantly seeking new performance-acceptable, environmentally safer alternative HCFO-like compositions that replace CFCs and HCFCs.

By the way, in patent document 1, the composition of a C3-C3 fluorine-containing olefin and a general purpose solvent is proposed. In particular, in Example 4 of Patent Document 1, a degreasing test example of 1,2-dichloro-3,3,3-trifluoropropene (hereinafter also referred to as "1223xd") alone is disclosed. Similarly, Patent Documents 2 to 7 disclose buffing cleaning test examples of 1223xd alone, resist development test examples, resist peeling test examples, dry cleaning test examples, flux cleaning test examples, and adhesion water removal test examples.

Unexamined-Japanese-Patent No. 2-221388 JP-A-2-221389 Unexamined-Japanese-Patent No. 2-221962 Unexamined-Japanese-Patent No. 2-222469 JP-A-2-222496 Japanese Patent Application Laid-Open No. 2-222497 Unexamined-Japanese-Patent No. 2-222702

However, in such a volatile solvent composition, even if the performance is improved simply by preparing a plurality of solvents, the problem that the liquid composition tends to fluctuate due to the volatility of each component can not be avoided . For example, when a binary liquid composition is put into an ultrasonic cleaner and subjected to a cleaning step, generally, low boiling point components (components with large vapor pressure) are volatilized preferentially, and high boiling point components in the cleaning tank (Components with small vapor pressure) are concentrated. For example, in the case of a composition comprising a low-boiling-point component having a high detergency and a high-boiling-point component having a low detergency, the low-boiling component in the washing solution may decrease over time to cause poor washing. In addition, the used washing solution is usually regenerated and reused by distillation, but in the case of a composition having different composition of liquid phase and composition of gas phase, it is necessary to adjust the liquid composition of the recovered composition. It is not efficient.

The present invention is a novel azeotrope (like) containing environmentally friendly (Z) -1,2-dichloro-3,3,3-trifluoropropene (1223xd (Z)) and whose composition does not change upon volatilization The task is to propose a composition.

The present inventors diligently studied to solve the above problems. As a result, it was found that the composition of 1223 × d (Z) and the specific compound was an azeotrope-like composition having substantially the same composition of the gas phase part and the liquid phase part. Furthermore, it was also confirmed in the examples that the azeotrope-like composition of the present invention is suitable as a cleaner for articles to be cleaned, and the present invention has been completed.

That is, the present invention includes the following inventions.

[Invention 1]
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.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Invention 16]
The cleaning agent according to invention 15, which is for cleaning a vehicle, a vehicle or a transportation vehicle.

[Invention 17]
The cleaning agent according to invention 15 or 16, which is for a vehicle, vehicle or vehicle brake cleaner.

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

[Invention 19]
An azeotropic (like) composition according to any of Inventions 1 to 10, a liquid composition according to any of Inventions 11 to 13 or an aerosol composition according to Invention 14.

[Invention 20]
An effervescent agent comprising the azeotropic (like) composition according to any of the inventions 1 to 10, the liquid composition according to any of the inventions 11 to 13 or the aerosol composition according to the invention 14.

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

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

[Invention 23]
Contacting the azeotrope (like) composition according to any of Inventions 1 to 10, the liquid composition according to any of Inventions 11 to 13 or the aerosol composition according to Invention 14 with an article to be cleaned; A method of cleaning the article to be cleaned, including:

In Patent Documents 1 to 7, there is no description of detailed behavior when blending 1,2-dichloro-3,3,3-trifluoropropene (1223xd) with the specific compound described above. Furthermore, geometric isomers of E-form and Z-form exist in 1223xd, and since these geometric isomers each have an inherent boiling point and polarity, drying properties, washing properties, and the like differ. However, the above-mentioned patent documents do not disclose geometric isomers.

The present invention provides novel azeotropic (like) compositions. This azeotropic (like) composition exerts an effect that the load on the environment is small, and the performance as a liquid whose composition does not easily change even when used under open conditions is easily maintained. Moreover, this azeotropic (like) composition is useful as a cleaning agent for an article (a to-be-cleaned article) to which a contaminant such as a foreign matter or a fat or oil adheres.

It is a vapor-liquid equilibrium diagram of 1223xd (Z) and a 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 the fluorine-containing olefin is highly compatible with various solvents, it is possible to easily prepare a homogeneous 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 types of liquids are mixed to ensure compatibility, the problem that the liquid composition tends to fluctuate due to the difference in the volatility of each component can not be avoided. For example, when a binary liquid composition is placed in an ultrasonic cleaner and used as a cleaning agent, generally, low-boiling components with high volatility (components with a large vapor pressure) are volatilized preferentially, and the inside of the cleaning tank The high volatility components with low volatility are concentrated. For example, in the case of a composition of low boiling point components having high detergency and low boiling point components, the concentration of low boiling point components in the cleaning solution may decrease with time, which may cause cleaning failure. In particular, when a nonflammable solvent is blended with a flammable solvent to prepare a nonflammable composition, if the nonflammable component preferentially volatilizes, the cleaning solution may become a flammable composition.

In addition, it is desirable from the viewpoint of both environmental protection and economics to recover and reuse the washing solvent after use by distillation and other operations, but in the case of a two-component liquid, it is generally a two-component liquid having different boiling points It is necessary to separately collect them, and it is easy to put an operational burden to collect and reuse them.

The same problem arises when used for working fluid of thermodynamic cycle. That is, even when used as a working fluid of the thermodynamic cycle, there is a possibility that the liquid composition may change in a long time. If the liquid composition changes, the heat capacity of the liquid, the viscosity, or the affinity with the lubricant may change, and the operation performance of the thermodynamic cycle may be reduced.

For this reason, when using a binary (multi-component) liquid composition as a cleaning agent or working fluid, the liquid composition is frequently analyzed, and it is constantly formulated in an appropriate ratio so that the appropriate composition range is obtained. And have to replenish the volatilized components. However, such liquid composition control can be a heavy task 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 which does not change the liquid composition during use. As used herein, "azeotropic" refers to the thermodynamically strict meaning of azeotrope. For example, in the case of a mixture of water / ethanol, the composition of ethanol (96% by mass) and water (4% by mass) is an azeotropic mixture (azeotrope), and the vapor present in vapor-liquid equilibrium is also 96% by mass): water (4% by mass) ", which completely matches the liquid composition. This phenomenon is called "azeotropic". At a certain temperature and pressure, the composition of the azeotropic mixture is only one point.

“Azeotropic-like” is also called “pseudo-azeotropic”, and is not thermodynamically strictly azeotropic, but for a liquid of a range of composition, its liquid composition and the composition of the gas in equilibrium are , Which may be substantially equal, refers to such a phenomenon. Even if the compositions of the gas phase part and the liquid phase part do not match completely, if the compositions of the gas phase part and the liquid phase substantially match, one skilled in the art can handle the same as the azeotropic composition. At this time, the smaller the gas-liquid equilibrium composition difference between the gas phase part and the liquid phase part, the better. Thus, the phenomenon in which the vapor-liquid equilibrium composition of the vapor phase part and the liquid phase part substantially match is called azeotropic or quasi azeotropic, and the composition is called azeotropic or pseudo azeotropic composition .

Scientifically, azeotropic phenomena and pseudo-azeotropic phenomena (or azeotrope-like) should be distinguished, but in practice such as washing, they distinguish between azeotropic phenomena and azeotrope-like phenomena (or quasi-azeotropic reactions) The azeotropic phenomenon and the azeotrope-like phenomenon (or pseudo-azeotrope) are collectively referred to as "azeotrope" in the present specification because they are not necessary and can be handled in exactly the same way. Also, the composition at that time is called "azeotropic (like) composition". In the azeotropic (like) manner, the presence or absence of the azeotropic point does not matter. It is sufficient if the vapor-liquid equilibrium composition of the gas phase part and the liquid phase part substantially match.

“Azeotropic (like)” is not theoretically derived, and the vapor-liquid equilibrium is experimentally investigated for various liquid types and composition ratios, and accidentally, the composition of the gas phase and the composition of the liquid phase are substantially It can only be found when it matches. In the present invention, vapor-liquid equilibrium experiments of 1223xd (Z) and a specific compound were conducted, and it was found that the azeotropic point at which the vapor-liquid composition completely matched and / or that the vapor-liquid composition was substantially identical. The boiling (like) composition could be found.

E- and Z-forms exist in 1,2-dichloro-3,3,3-trifluoropropene (1223xd), and a method for selectively producing Z-form is disclosed in the patent document (WO2014 / 046250, WO2014 / 046251). High purity Z form (1223 x d (Z)) is available by precision distillation.

As apparent from the vapor-liquid equilibrium measurement shown in the following examples, the composition of the present invention comprising the first component 1223xd (Z) and the second component specific compound has a specific composition An azeotropic (like) composition in which the compositions of the gas phase part and the liquid phase part are substantially the same.

In the composition containing the first component 1223xd (Z) and the second component dichloromethane, 1 to 40% by mole of 1223xd (Z) and 99 to 60% by mole of dichloromethane It is an azeotropic (like) composition in which the composition of the phase part and the liquid phase part is substantially the same. Also, with this composition, the risk of ignition and the risk of fire in the composition usage environment is low. Furthermore, when the composition of 1223 × d (Z) is 1 to 30 mol% and dichloromethane is 99 to 70 mol%, the compositions of the gas phase part and the liquid phase part are further closer, and composition fluctuation is further less likely to occur.

In the composition containing 1223 x d (Z) which is the first component and methanol which is the second component, in the case of 67 to 77 mol% of 1223 x d (Z) and 33 to 23 mol% of methanol, It is an azeotropic (like) composition in which the composition of the phase part and the liquid phase part is substantially the same. Further, 70 to 74 mol% of 1223 × d (Z) and 30 to 26 mol% of methanol are particularly preferable because the compositions of the gas phase part and the liquid phase part are closer to each other and composition fluctuation is less likely to occur.

In the composition containing 1223 x d (Z) as the first component and ethanol as the second component, 80 to 99 mol% of 1223 x d (Z) and 20 to 1 mol% of ethanol It is an azeotropic (like) composition in which the composition of the phase part and the liquid phase part is substantially the same. Also, with this composition, the risk of ignition and the risk of fire in the composition usage environment is low. Furthermore, in the case of 85 to 99 mol% of 1223 × d (Z) and 15 to 1 mol% of ethanol, the compositions of the gas phase part and the liquid phase part are closer to each other.

In the composition containing 1223 x d (Z) as the first component and n-propanol as the second component, 90 to 99 mol% of 1223 x d (Z) and 10 to 1 mol of n-propanol %, It is an azeotropic (like) composition in which the composition of the gas phase part and the liquid phase part is substantially the same. Also, with this composition, the risk of ignition and the risk of fire in the composition usage environment is low. Furthermore, in the case of 95 to 99 mol% of 1223 x d (Z) and 5 to 1 mol% of n-propanol, the compositions of the gas phase part and the liquid phase part are closer to each other, and composition fluctuation hardly occurs. preferable.

In the composition containing 1223 x d (Z) which is the first component and isopropanol which is the second component, in the case of 85 to 99 mol% of 1223 x d (Z) and 15 to 1 mol% of isopropanol, It is an azeotropic (like) composition in which the composition of the phase part and the liquid phase part is substantially the same. Also, with this composition, the risk of ignition and the risk of fire in the composition usage environment is low. Furthermore, in the case of 90 to 99 mol% of 1223 × d (Z) and 10 to 1 mol% of isopropanol, the compositions of the gas phase part and the liquid phase part are closer to each other, and composition fluctuation is further less likely to occur.

In the composition containing 1223 x d (Z) as the first component and n-hexane as the second component, 75 to 99 mol% of 1223 x d (Z) and 25 to 1 mol of n-hexane %, It is an azeotropic (like) composition in which the composition of the gas phase part and the liquid phase part is substantially the same. Also, with this composition, the risk of ignition and the risk of fire in the composition usage environment is low. Further, when 80 to 99 mol% of 1223 x d (Z) and 20 to 1 mol% of n-hexane, the compositions of the gas phase part and the liquid phase part are closer to each other, and composition fluctuation is further less likely to occur. preferable.

In the composition containing 1223 x d (Z) which is the first component and cyclohexane which is the second component, when 85 to 99 mol% of 1223 x d (Z) and 15 to 1 mol% of cyclohexane, It is an azeotropic (like) composition in which the composition of the phase part and the liquid phase part is substantially the same. Also, with this composition, the risk of ignition and the risk of fire in the composition usage environment is low. Further, 90 to 99 mol% of 1223 x d (Z) and 10 to 1 mol% of cyclohexane are particularly preferable because the compositions of the gas phase part and the liquid phase part are closer to each other and composition fluctuation hardly occurs.

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

In the composition containing 1223 x d (Z) which is the first component and cyclopentane which is the second component, 1 to 60 mol% of 1223 x d (Z) and 99 to 40 mol% of cyclopentane An azeotropic (like) composition in which the compositions of the gas phase part and the liquid phase part are substantially the same. Furthermore, when the composition of 1223 x d (Z) is 20 to 55 mol% and the content of cyclopentane is 80 to 45 mol%, the compositions of the gas phase part and the liquid phase part are closer to each other, and composition fluctuation is less likely to occur. .

Here, the value of the mole% is the mole of each component when the total value of the number of moles of the first component 1223 x d (Z) and the number of moles of the specific compound as the second component is 100. Represents the% of number (ie, the relative mole% between the two components). If it is a composition of this range, even if it handles a liquid composition by an open system in practice, even if it performs collection operation by distillation, composition change hardly occurs.

The azeotropic (like) composition of the present invention can be produced, for example, by mixing 1223 x d (Z) as the first component and the specific compound as the second component in a specific amount. The azeotropic (like) composition of the present invention is one that is substantially free of impurities (consisting essentially of the first component and the second component) and is of high purity in a preferred embodiment. is there.

In addition to the first component 1223xd (Z) and the specific compound as the second component, the azeotropic (like) composition of the present invention may be used as a starting material for synthesizing them, Small amounts of by-products etc. (Each component is, 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, with respect to the azeotropic (like) composition Or less) may remain. For example, the azeotropic (like) composition of the present invention may contain, 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-trile 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 Hydrochloroolefins (HCO) such as 3-tetrachloropropene (1230xf);
1,1,2-trichloro-3,3,3-trifluoropropane (233 da), 1,2,2-trichloro-3,3,3-trifluoropropane (233 ab), 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 components can also be added to improve the performance of the azeotropic (like) composition. Examples of additional components include, but are not limited to, detergency enhancers (surfactants), stabilizers (acid acceptors, antioxidants) and the like.

Specific examples of detergency enhancers include sorbitan aliphatic esters such as sorbitan monooleate and sorbitan trioleate; polyoxyethylene sorbit fatty acid esters such as polyoxyethylene sorbit 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; polyoxy acids such as polyoxyethylene oleic acid amide Nonionic surfactants, such as ethylene alkyl amine fatty acid amides, are mentioned. These detergency enhancers 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 azeotropic (like) composition of the present invention for the purpose of synergistically improving the detergency and the surface action. It is also good.

The stabilizer is not particularly limited, but it is more desirable to carry out co-distillation by distillation operation or to form 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, and aliphatic and / or aromatic derivatives and the like can be mentioned. Examples of aliphatic nitro compounds include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane and the like. As an aromatic nitro compound, 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 And m- or p-nitroanisole and the like.

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

The phenols also include phenols containing 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 a hydroxyl group. For example, 2,6-di-t-butyl-p-cresol, o-cresol, m-cresol, p-cresol, thymol, p-t-butylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol Monohydric phenols such as eugenol, isoeugenol, butylhydroxyanisole, phenol, xylenol or t-butylcatechol, bivalents such as 2,5-di-t-aminohydroquinone, 2,5-di-t-butylhydroquinone Phenol and the like.

As the imidazoles, 1-methylimidazole, 1-n-butylimidazole, 1-phenylimidazole, 1 having 1 to 18 carbon atoms and having an alkyl group, cycloalkyl group or aryl group 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 2,4-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 compounds may be used in combination.

As amines, 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, dibutylamine, tributylamine, dibenzylamine, triphenthylamine, 2-ethylhexylamine, aniline N, N-dimethylaniline, N, N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetra Renpentamin, benzylamine, dibenzylamine, diphenylamine, and diethylhydroxylamine and the like. These may be used alone, or two or more compounds may be used in combination.

Examples of 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) composition of the present invention may contain, as additional components, lubricants, flame retardants, metal passivators, corrosion inhibitors and the like.

The addition amount of the additional component in the azeotropic (like) composition of the present invention may vary depending on the component, but may be an extent that does not affect 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, and more preferably 3% by mass or less, based on the azeotropic (like) composition. Further, 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 with respect to the azeotropic (like) composition. That is, the additional components may be added in the following amounts based on the azeotropic (like) composition: 0.001 to 30% by mass; 0.001 to 10% by mass; 0.001 to 5% by mass 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; 0.01 to 10 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; 0.1 to 30% by mass; 0.1 to 10% 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; 1 to 5% by mass; 1 to 3% by mass 3 to 30% by mass; 3 to 10% by mass; 3 to 5% by mass; 5 to 30% by mass; 5 to 10% by mass; 10 to 30% by mass.

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

As the injection gas, liquefied gas or compressed gas can be used. For example, the above gases such as LPG (liquefied petroleum gas), DME (dimethyl ether), carbon dioxide gas, fluorocarbon gas, nitrogen gas, compressed air and the like, mixtures of LPG and DME, mixtures of LPG and carbon dioxide, etc. Although there may be mentioned species or combinations, it is 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) and the above-mentioned propellant gas, Moreover, it can be filled and provided in a pressure-resistant can.

[Use as detergent or solvent]
The azeotropic (like) composition (or liquid composition containing the azeotropic (like) composition) of the present invention is a precision machine part, an electronic material (printed substrate, liquid crystal display, magnetic recording part, semiconductor material, etc.) ), Resin-processed parts, optical lenses, clothing articles, etc. are suitable for removing foreign substances, fats and oils, greases, waxes, fluxes, inks and the like. Since the azeotropic (like) composition of the present invention has appropriate fluidity and solubility, foreign substances (such as particles) can be washed away or dissolved and removed. In addition, cleaning of various vehicles, vehicles and vehicles such as automobiles, bicycles, construction machines, agricultural machines, aircraft, railway vehicles and ships (especially these brake cleaners) requires a process to wet and wash away dirt. By the way, the azeotropic (like) composition (or liquid composition containing the azeotropic (like) composition) of the present invention has a suitable boiling point and can wet and wash away dirt. It is suitable for such cleaning. The cleaning method is not particularly limited, but the azeotropic (like) composition of the present invention (or a liquid composition containing the azeotropic (like) composition) is dipped in the article to be cleaned to wash away dirt, with a waste Methods such as wiping off and spray washing may be mentioned, and these may be used in combination. Placing the azeotropic (like) composition in an ultrasonic cleaner, immersing the article to be cleaned in the liquid and subjecting it to ultrasonic cleaning is one of the particularly preferred embodiments. 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 and aerosolized to produce various articles to be cleaned The method of spraying on is also one of the preferred embodiments.

As described above, the azeotropic (like) composition of the present invention exerts a stable detergency even if the composition is not frequently controlled, because the composition hardly changes even when used in an open system. . This is a great merit in practice.

If the washing | cleaning liquid used for washing | cleaning is collect | recovered and distillation operation is given, fats and oils and a foreign material (particle) can be separated and removed, and the azeotropic (like) composition of this invention can be collect | recovered. A general distillation regenerator for detergents is a simple distillation system, and in the case of an azeotropic (like) composition comprising a first component 1223xd (Z) and a second component specific compound, it is commercially available. Can be regenerated substantially without composition change. In particular, in the case of an azeotropic composition, use of a high-stage distillation column is preferable because there is no change in the composition.

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

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

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to the examples described below.

<Gas-liquid equilibrium measurement>
Example 1-1
In a 50 mL three-necked flask equipped with a septum, a stirrer, and a Dimroth capable of flowing a −10 ° C. refrigerant, Z-1, 2-Dichloro-3,3,3-trifluoropropene was brought to the molar concentration shown in Table 1. It was charged 25mL combined (1223xd (Z)) and dichloromethane (CH ₂ Cl _2). A synthetic zeolite tube was attached to the upper part of Jimroth. The flask was immersed in an oil bath and heated to reflux with stirring. After one hour or more since refluxing started and the composition became stable, the gas phase part was sampled from the septum with a gas tight syringe and analyzed by gas chromatography. The liquid phase was similarly sampled with about 1 mL using a polypropylene syringe equipped with an injection needle, transferred to a 2 mL vial previously cooled with ice water, and then subjected to gas chromatography analysis. In Table 1, using the calibration curve prepared in advance, it is indicated by mol%. In FIG. 1, the abscissa represents the liquid phase composition of 1223 × d (Z), and the ordinate represents the vapor phase composition of 1223 × d (Z), and the results of Table 1 were plotted. According to Example 1-1, the composition of the gas phase part and the liquid phase part is substantially in the range of 1 to 40 mol% of the first component 1223 × d (Z) and 99 to 60 mol% of the second component dichloromethane. It turned out to be an unchanged azeotropic or azeotrope-like composition.

Embodiment 1-2
The same operation as in Example 1-1 was performed except that methanol (MeOH) was used instead of dichloromethane. In Table 2, using the calibration curve prepared in advance, it is indicated by mol%. In FIG. 2, the abscissa represents the liquid phase composition of 1223 × d (Z), and the ordinate represents the vapor phase composition of 1223 × d (Z), and the results of Table 2 were plotted. According to Example 1-2, the composition of the gas phase part and the liquid phase part is substantially in the range of 67 to 77 mol% of the first component 1223 × d (Z) and 33 to 23 mol% of the second component methanol. It turned out to be an unchanged azeotropic or azeotrope-like composition.

Embodiment 1-3
The same operation as in Example 1-1 was performed except that ethanol (EtOH) was used instead of dichloromethane. In Table 3, using the calibration curve prepared in advance, it is indicated by mol%. In FIG. 3, the abscissa represents the liquid phase composition of 1223 × d (Z), and the ordinate represents the vapor phase composition of 1223 × d (Z), and the results of Table 3 were plotted. According to Example 1-3, the composition of the gas phase part and the liquid phase part is substantially in the range of 80 to 99 mol% of the first component 1223 × d (Z) and 20 to 1 mol% of the second component ethanol. It turned out to be an unchanged azeotropic or azeotrope-like composition.

Embodiment 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, using the calibration curve prepared in advance, it is indicated by mol%. In FIG. 4, the abscissa represents the liquid phase composition of 1223 × d (Z), and the ordinate represents the gas phase composition of 1223 × d (Z), and the results of Table 4 were plotted. According to Example 1-4, the composition of the gas phase part and the liquid phase part is substantially in the range of 90 to 99 mol% of the first component 1223 × d (Z) and 10 to 1 mol% of the second component n-propanol. It became clear that it was an azeotropic composition or an azeotrope-like composition which does not change as it is.

[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, the calibration curve prepared in advance was used to indicate mol%. In FIG. 5, the abscissa represents the liquid phase composition of 1223 × d (Z), and the ordinate represents the gas phase composition of 1223 × d (Z), and the results of Table 5 were plotted. According to Example 1-5, the composition of the gas phase portion and the liquid phase portion is substantially in the range of 85 to 99 mol% of the first component 1223 × d (Z) and 15 to 1 mol% of the second component isopropanol. It turned out to be an unchanged azeotropic or azeotrope-like composition.

[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, using the calibration curve prepared in advance, it is indicated by mol%. In FIG. 6, the abscissa represents the liquid phase composition of 1223 × d (Z), and the ordinate represents the gas phase composition of 1223 × d (Z), and the results of Table 6 were plotted. According to Example 1-6, the composition of the gas phase part and the liquid phase part is substantially in the range of 75 to 99 mol% of the first component 1223 × d (Z) and 25 to 1 mol% of the second component n-hexane. It became clear that it was an azeotropic composition or an azeotrope-like composition which does not change as it is.

[Example 1-7]
The same operation as in Example 1-1 was performed except that cyclohexane was used instead of dichloromethane. In Table 7, the calibration curve prepared in advance was used to indicate mol%. In FIG. 7, the abscissa represents the liquid phase composition of 1223 × d (Z), and the ordinate represents the vapor phase composition of 1223 × d (Z), and the results of Table 7 were plotted. According to Example 1-7, the composition of the gas phase part and the liquid phase part is substantially in the range of 85 to 99 mol% of the first component 1223 × d (Z) and 15 to 1 mol% of the second component cyclohexane. It turned out to be an unchanged azeotropic or azeotrope-like composition.

[Example 1-8]
The same operation as in Example 1-1 was performed except that acetone was used instead of dichloromethane. In Table 8, the calibration curve prepared in advance was used to indicate mol%. In FIG. 8, the abscissa represents the liquid phase composition of 1223 × d (Z), and the ordinate represents the gas phase composition of 1223 × d (Z), and the results in Table 8 were plotted. According to Example 1-8, the composition of the gas phase portion and the liquid phase portion is substantially in the range of 1 to 99 mol% of the first component 1223 × d (Z) and 99 to 1 mol% of the second component acetone. It turned out to be an unchanged azeotropic or azeotrope-like composition.

[Example 1-9]
The same operation as in Example 1-1 was performed except that cyclopentane was used instead of dichloromethane. In Table 9, using the calibration curve prepared in advance, it is indicated by mol%. In FIG. 9, the abscissa represents the liquid phase composition of 1223 × d (Z), and the ordinate represents the vapor phase composition of 1223 × d (Z), and the results of Table 9 were plotted. According to Example 1-9, the composition of the gas phase part and the liquid phase part is substantially in the range of 1 to 60 mol% of the first component 1223 × d (Z) and 99 to 40 mol% of the second component cyclopentane. It turned out that it is an azeotropic composition or an azeotrope-like composition which does not change.

<Flash point measurement>
Example 2-1
The flash point of the mixed liquid of 1223xd (Z) and dichloromethane (CH ₂ Cl ₂ ) was measured in accordance with Japanese Industrial Standard JIS K 2265-1 "How to determine the flash point-Part 1: Tag sealing method". . For flash point measurement, an automatic flash point measuring device atg-8l (Tanaka Scientific Instruments Co., Ltd.) was used. As a result, it was observed that there was no flash point under atmospheric pressure conditions in the range of the azeotropic or azeotrope-like composition of 1223 × d (Z) and dichloromethane described in Example 1-1.

[Example 2-2] to [Example 2-7]
The same operation as in Example 2-1 was carried out except using methanol (MeOH), ethanol (EtOH), n-propanol (n-PrOH), isopropanol (IPA), n-hexane or cyclohexane instead of dichloromethane. The As a result, each composition was observed to have no flash point under atmospheric pressure conditions in the range of the azeotropic or azeotrope-like composition 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. The measurement results for each composition are shown in Table 10.

<Washing test>
Example 3-1
A commercially available 25 mL graduated cylinder was cut at an 11 mL scale. Diameter: about 7.2 mm × length: After measuring the weight of a clean glass rod of about 40 mm, it was immersed in the oil described in Table 11 for 2 minutes, and it was allowed to stand for 10 minutes to drain (remove excess oil) Then, after measuring the mass (glass rod + initial adhesion oil), it was put into the above-mentioned measuring cylinder. A mixture of 1223 x d (Z) and dichloromethane (CH ₂ Cl ₂ ) (pre-test composition shown in Table 11) was charged to 10 mL and filled with water at 20 ° C. Stood in the middle of the The mixture was volatilized with time when irradiated with ultrasonic waves, and when it reached a scale of 8 mL, the liquid in the measuring cylinder was analyzed by gas chromatograph. As a result, in all the examples, the liquid composition before and after washing was substantially the same despite the fact that the liquid volatilized by 2 mL. That is, it was shown that the mixture of 1223 × d (Z) and dichloromethane had an azeotropic (like) composition that did not substantially change the composition of the residue even when partially volatilized in actual machine washing.

Next, the glass rod is dried and the mass (total mass of the glass rod and the remaining oil) is measured to determine the oil removal rate (the mass of the remaining oil / the mass of the initial adhering 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 in the observation result of the magnifying glass, it was judged to be good since no oil component remained. The results of each example are shown in Table 11 below.

[Example 3-2] to [Example 3-9]
Instead of using dichloromethane (methanol), ethanol (EtOH), n-propanol (nPrOH), isopropanol (IPA), n-hexane (nHex), cyclohexane (cHex), acetone or cyclopentane (cPen) instead of dichloromethane The same operation as in Example 3-1 was performed. As a result, in all the examples, the liquid composition before and after the washing was substantially the same despite the volatilization of 2 mL. That is, in the actual machine cleaning, it was shown that each mixed liquid was an azeotropic (like) composition which does not substantially change the composition of the residual liquid even if it partially evaporates. In addition, the results of the respective examples are shown in the following Tables 12 to 19 with respect to the oil removal rate and the observation result of the magnifying glass.

Claims (23)

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. The azeotropic (like) composition according to claim 1, comprising 1 to 40 mol% of Z-1,2-dichloro-3,3,3-trifluoropropene and 99 to 60 mol% of dichloromethane. The azeotropic (like) composition according to claim 1, comprising 67-77 mol% Z-1,2-dichloro-3,3,3-trifluoropropene and 33-23 mol% methanol. The azeotropic (like) composition according to claim 1, comprising 80 to 99 mol% of Z-1,2-dichloro-3,3,3-trifluoropropene and 20 to 1 mol% of ethanol. The azeotropic (like) composition according to claim 1, comprising 90 to 99 mol% of Z-1,2-dichloro-3,3,3-trifluoropropene and 10 to 1 mol% of n-propanol. . The azeotropic (like) composition according to claim 1, comprising 85 to 99 mol% of Z-1,2-dichloro-3,3,3-trifluoropropene and 15 to 1 mol% of isopropanol. The azeotropic (like) composition according to claim 1, comprising 75 to 99 mol% of Z-1,2-dichloro-3,3,3-trifluoropropene and 25 to 1 mol% of n-hexane. . The azeotropic (like) composition according to claim 1, comprising 85 to 99 mol% of Z-1,2-dichloro-3,3,3-trifluoropropene and 15 to 1 mol% of cyclohexane. The azeotropic (like) composition according to claim 1, comprising 1 to 99 mol% of Z-1,2-dichloro-3,3,3-trifluoropropene and 99 to 1 mol% of acetone. The azeotropic (like) composition according to claim 1, comprising 1 to 60 mol% of Z-1,2-dichloro-3,3,3-trifluoropropene and 99 to 40 mol% of cyclopentane. A liquid composition comprising at least the azeotropic (like) composition according to any one of claims 1 to 10. The liquid composition of claim 11, further comprising at least one additional component. The liquid composition according to claim 12, wherein the total amount of the additional component is 0.001 to 30% by mass with respect to the azeotropic (like) composition. An aerosol composition comprising the azeotropic (for) composition according to any one of claims 1 to 10 or the liquid composition according to any of claims 11 to 13 and a propellant gas. A detergent comprising the azeotropic (like) composition according to any of claims 1 to 10, the liquid composition according to any of claims 11 to 13 or the aerosol composition according to claim 14. The cleaner according to claim 15, which is for cleaning vehicles, vehicles or vehicles. 17. A cleaning agent according to claim 15 or 16 for a vehicle, vehicle or vehicle brake cleaner. A solvent comprising the azeotropic (like) composition according to any of claims 1 to 10, the liquid composition according to any of claims 11 to 13 or the aerosol composition according to claim 14. A drainage agent comprising the azeotropic (like) composition according to any of claims 1 to 10, the liquid composition according to any of claims 11 to 13 or the aerosol composition according to claim 14. A foaming agent comprising the azeotropic (like) composition according to any of claims 1 to 10, the liquid composition according to any of claims 11 to 13 or the aerosol composition according to claim 14. A heat transfer medium comprising an azeotropic (like) composition according to any of claims 1 to 10, a liquid composition according to any of claims 11 to 13 or an aerosol composition according to claim 14. A lubricant solvent comprising the azeotropic (like) composition according to any of claims 1 to 10, the liquid composition according to any of claims 11 to 13 or the aerosol composition according to claim 14. An azeotropic (like) composition according to any of claims 1 to 10, a liquid composition according to any of claims 11 to 13 or an aerosol composition according to claim 14 in contact with the article to be cleaned A method of cleaning the article to be cleaned, comprising the step of

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