JP2023107823A - Detergent composition and aerosol composition thereof - Google Patents

Abstract

To provide a novel detergent composition and an aerosol composition thereof that exhibit a low fire hazard and low risk in a fire and are classified as non-hazardous materials under the Fire Service Act due to being non-flammable, do not need to be stored in a hazardous materials warehouse, are not legally restricted in terms of a stored quantity of a detergent composition used in large quantities, have low toxicity and exert little environmental burden such as destruction of the ozone layer, and exhibit extremely low attacking properties against rubbers and resins while having detergency and drying performance that are equivalent to those of conventional brake cleaner detergent compositions.SOLUTION: There are provided a cleaner composition and an aerosol composition of the same that contains: an HFO-type non-flammable fluorine-based solvent such as (Z)-1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene and HCFO-1233yd; and alkoxy fluoroalkene such as methoxyperfluoroheptene or its isomeric mixture thereof.SELECTED DRAWING: None

Description

This invention provides a new cleaning method for cleaning various vehicles, vehicles, and transportation such as automobiles, two-wheeled vehicles, bicycles, construction machinery, agricultural machinery, aircraft, railroad vehicles, and ships, as well as for cleaning tools, workshops, pits, and factories. Regarding the agent composition and its aerosol composition, in particular, various vehicle parts and control devices such as bodies, brake parts, suspensions, and wheels made of metals or combinations of metals and resins in various vehicles, vehicles, and transportation Used for degreasing and cleaning, it is non-combustible, has low risk of ignition and fire, and is classified as a non-dangerous item under the Fire Service Act. There are no legal restrictions on the storage amount of the composition, and it has excellent properties such as low toxicity and low environmental load such as ozone layer depletion, and is equal to or greater than conventional detergent compositions. Although it has excellent detergency and anti-redeposition properties, it has extremely low attack on rubber and resin compared to conventional detergent compositions. The present invention relates to a detergent composition and its aerosol composition having the excellent property that the ratio can be adjusted.

Automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railroad vehicles, ships, and other types of vehicles, vehicles, and transportation have various parts and devices such as bodies, brakes, suspensions, and wheels that contain metals and various resins. etc. is used. Moreover, in recent years, with the intention of reducing weight and enhancing decorativeness, members using composite materials such as a combination of metal and resin have also been used.

Parts and devices using these metals adhere to their surfaces with oil and dirt during use, resulting in deterioration of the desired performance and decorativeness. In addition, depending on the adhered components, the metal surface corrodes, and the intended performance is irreversibly impaired. Furthermore, in vehicles, vehicles, and transportation, oil such as grease is applied to the necessary parts to make the movement of each device smooth, but these oils are sprayed by air flow and rainwater while driving. As a result, the oil gradually flows out to unintended parts, and the oil that flows out from other vehicles, vehicles, and transportation equipment is swept up from the road surface together with dirt, and adheres to each part of the vehicle, vehicle, and transportation equipment. , can be a factor in degrading the desired performance of various parts and devices. In particular, in friction brake devices in which brake shoes with brake linings, which are often used in vehicles, vehicles, and transportation, act as brakes on rotating bodies such as brake discs and brake drums, the coefficient of friction decreases when oil adheres. In addition, the dust generated by wear of the brake linings tends to adhere to the brakes, which can reduce the braking performance of the brakes. Needs to be washed.

In addition, during the assembly and manufacturing of various vehicles, vehicles, and transportation facilities, when applying resin or paint to metal and processing it, if a small amount of oil or the like remains on the metal surface, the resin or paint may be damaged. Without stable adhesion, the product peels off or degrades, resulting in a significant drop in product quality. In addition, for parts and devices that are particularly important for ensuring safety during operation, such as brakes, suspensions, and wheels, the coefficient of friction will decrease if a small amount of oil or the like adheres to them, and if they are assembled as they are, the braking performance will decrease. As a result, it becomes impossible to stably exhibit the desired performance. Therefore, when assembling and manufacturing vehicles, vehicles, and transportation facilities, it is required to sufficiently wash and remove the slight amount of oil adhering to the metal surface of each part in advance.

Therefore, as a detergent composition mainly for cleaning the bodies, brake parts, suspensions, wheels, etc. of various vehicles, vehicles, and transportation facilities, conventionally, detergent compositions containing trichloroethane as a main component, which has detergency, have been developed and used. It had been. However, trichloroethane is known to be toxic. In addition, trichloroethane is to be phased out in 1996 by gradually reducing its production and consumption in the parties to the Montreal Protocol on Substances that Deplete the Ozone Layer, which came into force under the Vienna Convention for the Protection of the Ozone Layer. bans or restrictions on imports and exports to and from non-Parties. Therefore, the use of cleaning compositions using trichloroethane has been avoided.

Therefore, a detergent composition is produced by adding alcohols such as ethanol and isopropyl alcohol to a C6 petroleum hydrocarbon such as isohexane and cyclohexane as a base to adjust the detergency, drying property and boiling point. An aerosol composition using gas and an aerosol composition using compressed air using a mobile simple aerosol filling machine have been proposed and are widely used.

However, petroleum-based hydrocarbons and alcohols used in the cleaning composition are highly flammable and are regulated as dangerous substances under the Fire Service Law. Therefore, it is necessary to install a dangerous goods warehouse for storage, and the installation cost is high. Moreover, even if a facility using a cleaning composition has a warehouse for hazardous materials, there is a limit to the amount that can be stored. In particular, many of the above cleaning compositions are classified as Category 4, 1st petroleum, but the designated quantity of Category 4, 1st petroleum that can be stored in one warehouse is set low by law. , there is a problem that only a small amount can be stored in spite of the fact that the amount of detergent composition used is large, and an improvement has been desired.

Furthermore, although the hydrocarbons used in the above detergent compositions are not as toxic as trichloroethane, there is a risk of hydrocarbon poisoning if inhaled in excess. The product must be used in a well-ventilated environment, and the product has a notice to that effect. However, since aerosol products are used, vaporized hydrocarbons flow not only in the workplace but also downwind, and there is still a risk of inhalation by people there, and improvement was required.

In addition, if the cleaning composition is sprayed or an aerosol product is vigorously sprayed during work, a large amount of the highly flammable cleaning composition may soak into the gloves and clothes of the worker. In addition, a large amount of the detergent composition may be impregnated in order to remove oil stains adhered to workers' gloves and work clothes. However, since the cleaning composition is highly flammable, if the subsequent drying is insufficient, there is a risk of ignition due to static electricity or cigarette fire. Therefore, in order to ensure reliable safety in the working environment, there has been a demand for improvement so as to avoid the use of these highly flammable components.

Halogen-based solvents are generally well-known as solvents that do not have a flash point. is difficult. Therefore, as a solution to the problem of storage volume and ensuring safety, products with a high flash point using petroleum hydrocarbons with a high carbon number and water-based products containing carbitol and alcohol as cleaning ingredients are proposed. (See Patent Document 1).

However, the water-based composition described above has very poor and slow drying properties, such as requiring 30 to 40 minutes for drying (see Patent Document 1). Therefore, when such a water-based composition is used as a detergent composition, the liquid of the water-based composition tends to remain around the brake after use, and if the brake is used with the liquid remaining, the braking force decreases. lead to significant impact. Therefore, the work process using the water-based composition described above requires sufficient drying after washing, which is cumbersome and needs to be improved. Furthermore, since it is water-based, it is inferior to conventional detergent compositions for brake cleaners in detergency, and depending on the type of dirt, it does not necessarily have sufficient detergency, so there are restrictions on the scenes of use. , improvements were sought to increase versatility.

By the way, as a solvent that can be used for cleaning metal materials, an HFO-based nonflammable fluorine-based solvent that is a hydrofluoroolefin-based solvent such as (Z)-1-chloro-3,3,3-trifluoropropene It has been known. However, although this HFO-based nonflammable fluorine-based solvent has cleaning properties for metallic materials, it is known to have strong corrosiveness against resins and elastomers that are materials other than metallic materials. (Non-Patent Document 1). Therefore, it is necessary to thoroughly examine the circumstances in which such HFO-based nonflammable fluorine-based solvents are to be used.

In particular, it is important to maintain a high degree of safety for various braking devices, lights, windows, etc. in vehicles, vehicles, and transportation such as automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railroad vehicles, and ships. Metal materials are commonly used for parts, but in addition to these metal materials, various types of materials such as polycarbonate, acrylic, ABS, polystyrene, silicone rubber, natural rubber, HNBR, NBR, fluororubber and urethane rubber are usually used. Materials made of resins and elastomers are also used at the same time. For example, brakes are controlled by the hydraulic pressure of brake fluid, which is generally filled in rubber hoses connecting devices.

However, if the HFO-based nonflammable fluorine-based solvent comes into contact with resins and elastomers, the strong corrosiveness of the above-mentioned HFO-based non-flammable fluorine-based solvent will cause important parts that require a high level of safety. Serious problems such as deterioration of resins and elastomers in In particular, polycarbonate, which is widely used in important parts of vehicles, vehicles, and transportation facilities, devitrifies, acrylic, ABS, and polystyrene dissolve, and silicone rubber, natural rubber, HNBR, NBR, fluororubber, and urethane rubber swell. (Non-Patent Document 1), there is a concern that safety will be lowered.

When used as a cleaning composition, it is necessary to sufficiently wet the area to be cleaned with the cleaning composition before rinsing it off. It dries very quickly and is not suitable for moistening and rinsing processes. When wetted, an excessive amount of HFO-based nonflammable fluorine-based solvent touches resins and elastomers in important parts, which may reduce safety.

As fluorine-based solvents, alkoxyfluoroalkene methoxyperfluoroheptene and its isomer mixture Opteon ^™ SF10 (former name: Vertrel (registered trademark) Suplion) (Mitsui-DuPont Fluorochemical Co., Ltd.) There is This Opteon ^™ SF10 is suitably used as a solvent for lubricants that use fluorine grease (Patent Document 2), but it is also used as a brake in various vehicles such as automobiles, motorcycles, construction machinery, agricultural machinery, aircraft, railroad vehicles, and railroad vehicles. By creating a situation in which these lubricating components are applied or coated on related parts, it is not possible to reduce the coefficient of friction and greatly reduce the braking force.

Japanese Patent Application Laid-Open No. 2001-207199 JP 2017-115099 A 1233Z Excellent environmental performance, high detergency Next-generation fluorine-based solvent Central Glass Co., Ltd. Catalog publication date October 2015

The problem to be solved by the present invention is that it is nonflammable, so it has a low risk of ignition, a low risk in the event of a fire, is a non-dangerous material under the Fire Service Act, does not require a warehouse for hazardous materials, and can be used in large quantities. There are no legal restrictions on the storage amount of the cleaning composition used, and it has the characteristics of low toxicity and low environmental impact such as ozone depletion, and the same cleaning performance as conventional cleaning compositions Another object of the present invention is to provide a novel detergent composition and an aerosol composition thereof, which have drying properties and are significantly less aggressive to rubber and resin than conventional detergent compositions.

Since the detergent composition is used for the task of moistening and washing away the dirt components, the amount of use and storage thereof increases. Therefore, it is required to greatly reduce the risk of fire due to ignition by selecting a solvent that does not have a flash point and does not have a flammable range under the temperature conditions of the normal use environment and storage environment.

Also, in cleaning, it is required to wet the dirt component with the detergent composition and wash it off. Therefore, the cleaning composition can be provided not only as a solution to be applied or immersed, but also as an aerosol composition containing the cleaning composition and propellant gas, so that it can be easily handled during cleaning. and to facilitate physical removal of contaminants using gas pressure. In addition, when provided as an aerosol composition, the risk of inhalation by workers increases, so it is required to select a less toxic solvent for the cleaning composition.

In addition, there is a demand for a cleansing property equal to or better than that of conventional products, which has not been achieved by high-flash-point products or water-based products, and to realize an appropriate drying property.

In order to provide a new detergent composition and its aerosol composition that solve the above problems, the inventors of the present application have confirmed the physical properties of various compounds and compositions, and are proceeding with work to investigate their detergency. rice field. Among them, important parts such as automobiles, motorcycles, bicycles, construction machines, agricultural machines, aircraft, railroad cars, ships, etc., which require high safety due to strong erosion, , HFO-based nonflammable fluorine-based solvents that are known to cause serious problems such as deterioration, devitrification, and dissolution of resins and elastomers used in tools used by workers, workshops, pits, factories, etc. A composition containing an isomer mixture of methoxyperfluoroheptene, which is an example of an alkoxyfluoroalkene that has been found not to have high compatibility with oils and fats used in various vehicles, vehicles, and transportation facilities. Surprisingly, however, resins and elastomers do not change in quality, devitrify, or dissolve, and at the same time, it is possible to obtain a composition that can maintain an appropriate level of dryness. , Automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railroad vehicles, ships, and other vehicles, vehicles, transportation, tools, workshops, pits, and factories. I found it to work. Further detailed studies were conducted on the combination of the above-described HFO-based nonflammable fluorine-based solvent and alkoxyfluoroalkene, thereby completing the invention of a new cleaning composition and its aerosol composition of the present application.

The first means of the present invention for solving the above-mentioned problems is that the above-mentioned detergent composition is used in various vehicles, vehicles and transportation such as automobiles, two-wheeled vehicles, bicycles, construction machines, agricultural machines, aircraft, railroad cars and ships. A detergent composition characterized in that it is for use in cleaning engines, tools, workshops, pits and factories.

The second means of the present invention for solving the above-mentioned problems is that the above-mentioned detergent composition can be A detergent composition according to the first aspect of the present invention, characterized in that it is used for an engine brake cleaner.

The third means of the present invention for solving the above problems is the range of the mass ratio of the HFO-based nonflammable fluorine-based solvent and the alkoxyfluoroalkene (HFO-based nonflammable fluorine-based solvent/alkoxyfluoroalkene) is 99/1 to 1/99, the detergent composition according to the first or second means of the present invention.

A fourth means of the present invention for solving the above problems is that the HFO-based nonflammable fluorine-based solvent is (Z)-1-chloro-3,3,3-trifluoropropene, 1,1- Dichloro-3,3,3-trifluoropropene and 1,2-dichloro-3,3,3-trifluoropropene, 2,3,3-trichloro-3-fluoropropene, AMOLEA® AS-300 The detergent composition according to any one of the first to third means of the present invention, characterized in that it is one or more selected from:

A fifth means of the present invention for solving the above problems is any one of the first to third means of the present invention, wherein the alkoxyfluoroalkene is an alkoxyperfluoroalkene. A cleaning composition as described.

A sixth means of the present invention for solving the above problems is that the alkoxy group of the alkoxyfluoroalkene contains an alkoxyfluoroalkene or alkoxyperfluoroalkene that is a methoxy group or an ethoxy group, A detergent composition according to any one of the first to third means of the present invention.

A seventh means of the present invention for solving the above problems is any one of the first to third aspects of the present invention, wherein the alkoxyfluoroalkene is an alkoxyfluoroalkene having 5 or more and 8 or less carbon atoms. 1. The cleaning composition according to 1.

The eighth means of the present invention for solving the above problems is that the alkoxyfluoroalkene is methoxyperfluoropentene, methoxyperfluorohexene, methoxyperfluoroheptene, or methoxyperfluorooctene, or ethoxyper The first to third aspects of the present invention, characterized in that it contains any one or more of fluoropentene, ethoxyperfluorohexene, ethoxyperfluoroheptene, or ethoxyperfluorooctene, or isomer mixtures thereof. 1. The cleaning composition according to any one of .

A ninth means of the present invention for solving the above problems is the first to third aspects of the present invention, wherein the alkoxyfluoroalkene is methoxyperfluoroheptene or an isomer mixture thereof. A cleaning composition according to any one of means.

A tenth means of the present invention for solving the above problems is an aerosol composition containing the cleaning composition according to any one of the first to ninth means of the present invention and a propellant gas. is.

The eleventh means of the present invention for solving the above problems is that the propellant gas is N ₂ , CO ₂ , (E)-1,3,3,3-tetrafluoroprop-1-ene, argon, An aerosol composition according to the tenth means of the present invention, characterized in that it is LPG, DME or compressed air.

The twelfth means of the present invention for solving the above problems is the aerosol composition according to the eleventh means of the present invention, wherein the propellant gas is _N2 .

Another means of the present invention for solving the above problems is a cleaning composition characterized by containing an HFO-based nonflammable fluorine-based solvent and an alkoxyfluoroalkene.

In the detergent composition and its aerosol composition of the means of the present invention, the HFO-based nonflammable fluorine-based solvent and the alkoxyfluoroalkene blended as main components thereof both have no flash point and are nonflammable. Therefore, the danger of ignition and the risk of fire in the environment in which these cleaning compositions and their aerosol compositions are used are low. Since the HFO-based non-flammable fluorine-based solvent and alkoxyfluoroalkene, which are the main components, are both non-dangerous materials under the Fire Service Act, they do not require a warehouse for hazardous materials and can be used in large amounts. There is no legal limit on the storage amount of In addition, since each of the above components has low toxicity and a small environmental load such as ozone depletion, the product is friendly to the human body and the environment. In addition, the cleaning agent composition and the aerosol composition of the means of the present invention are said to have detergency comparable to that of conventional brake cleaners, while being significantly less aggressive to rubber and resin than conventional brake cleaners. , which exhibits excellent characteristics.

BEST MODE FOR CARRYING OUT THE INVENTION The cleaning composition of the means of the invention and its aerosol composition are described below with reference to the following tables.

<About main ingredients>
The main components of the cleansing composition of the means of the present invention and its aerosol composition will now be described. The detergent composition and the aerosol composition of the means of the present invention contain two components, an HFO-based nonflammable fluorine-based solvent and an alkoxyfluoroalkene.

The above HFO-based nonflammable fluorine-based solvent causes alteration, devitrification, or dissolution of resins and elastomers (Non-Patent Document 1), so it is not possible to use them as they are as components of detergents that use resins and elastomers. I don't like it. In addition, the alkoxyfluoroalkene is suitably used as a solvent for lubricants using fluorine grease (Patent Document 2), and is used for brakes in various vehicles such as automobiles, motorcycles, construction machinery, agricultural machinery, aircraft, railroad vehicles, and railroad vehicles. In related parts, etc., it is avoided to create a situation in which those lubricating components are applied or coated.

However, if an HFO-based nonflammable fluorine-based solvent, which is unsuitable as a component to be blended in such a detergent composition, is contained together with an alkoxyfluoroalkene, which is preferably used as a solvent for a lubricant, it is expected that In addition, it does not cause effects such as deterioration, devitrification, and dissolution on resins and elastomers, and has a wider range of excellent cleaning properties than conventional cleaning compositions, and moderate drying properties. It became a composition that can be exhibited. Therefore, by containing both the HFO-based nonflammable fluorine-based solvent and the alkoxyfluoroalkene as main components, it is excellent in that it can be used for a wider variety of materials while maintaining various safety. It has become possible to provide a new detergent composition and its aerosol composition with such properties.

<Regarding HFO-based nonflammable fluorine-based solvent>
The cleaning composition and the aerosol composition of the means of the present invention described above contain, as one of the two essential components, an HFO-based nonflammable fluorine-based solvent, which is a hydrofluoroolefin-based solvent. It shall be. Examples of HFO-based inflammable fluorine-based solvents include (Z)-1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1,2-dichloro Non-flammable solvents such as -3,3,3-trifluoropropene, 2,3,3-trichloro-3-fluoropropene, and AMOLEA® AS-300 can be used. These HFO-based nonflammable fluorine-based solvents can be used by obtaining commercially available ones ((Z)-1-chloro-3,3,3-trifluoropropene (1233Z) (Central Glass Co., Ltd., Japan), 1,1-dichloro-3,3,3-trifluoropropene (Matrix Scientific, USA), AMOLEA® AS-300 (AGC Co., Ltd., Japan), etc.).

The above HFO-based non-flammable fluorine-based solvents are non-flammable solvents that have no flash point and no flammable range according to the explosion limit test method ASTM E681. In addition, it has environmentally friendly chemical properties such as a low ozone depletion potential ODP or substantially zero and a global warming potential GWP of <1. Therefore, it does not correspond to the components specified in the Ozone Layer Protection Law, Law Concerning the Promotion of Global Warming Countermeasures, Fluorocarbon Emission Control Law, Fire Service Law, High Pressure Gas Safety Law, etc., and its use is not subject to any special restrictions. No dangerous goods warehouse is required for storage, and there are no legal restrictions on storage volume.

On the other hand, the above-described HFO-based nonflammable fluorine-based solvents are aggressive to resins. Therefore, the above HFO-based nonflammable fluorine-based solvents such as (Z)-1-chloro-3,3,3-trifluoropropene and 1,1-dichloro-3,3,3-trifluoropropene are soft When it acts on polyvinyl chloride (PVC) resin or phenolic resin, the resin is degraded, causing changes in the weight and dimensions of the resin product. Moreover, when it acts on the polycarbonate resin, it whitens and devitrifies the resin. Furthermore, when it acts on acrylic (PMMA) resin, ABS resin, which is a copolymer synthetic resin of acrylonitrile, butadiene and styrene, and polystyrene resin, these resins are softened or dissolved. As described above, the HFO-based nonflammable fluorine-based solvent has poor compatibility with the resin material.

In addition, the above-described HFO-based nonflammable fluorine-based solvent is also aggressive to various elastomers. Therefore, HFO-based nonflammable fluorine-based solvents such as (Z)-1-chloro-3,3,3-trifluoropropene and 1,1-dichloro-3,3,3-trifluoropropene are SBR and chloroprene Acting on rubber, butyl rubber, EPDM and CSM, it denatures these elastomers resulting in weight and dimensional changes. Moreover, when it acts on silicone rubber, natural rubber, HNBR, NBR, fluororubber and urethane rubber, these elastomers swell. As described above, the HFO-based nonflammable fluorine-based solvent has poor compatibility with the elastomer as it is.

However, various vehicles and vehicles such as automobiles, motorcycles, bicycles, construction machines, agricultural machines, aircraft, railroad cars, ships, etc., such as poor resin compatibility and high drying properties of the above-mentioned HFO-based nonflammable fluorine-based solvents Unexpectedly unsuitable properties for detergent compositions for transportation and the like are overcome by including together with alkoxyfluoroalkenes that have other unsuitable properties for detergent compositions, A superior cleaning composition is provided.

<About alkoxyfluoroalkene>
The cleaning composition and the aerosol composition of the means of the invention described above shall contain an alkoxyfluoroalkene as the other of the two essential components.

As used herein, "alkoxyfluoroalkene" means a fluorinated olefin having an alkoxy group and a double bond. Alkoxyfluoroalkenes include alkoxyperfluoroalkenes. Here, "alkoxyperfluoroalkene" means perfluoroalkene having an alkoxyl group. Alkoxyl groups of alkoxyfluoroalkenes include those having 1 to 5 carbon atoms, preferably methoxy or ethoxy groups having 1 or 2 carbon atoms. In addition, perfluoroalkene means a compound in which all hydrogen atoms in a hydrocarbon having one double bond are substituted with fluorine, and includes those having 2 to 10 carbon atoms, preferably those having 2 to 10 carbon atoms. 5 or more and 8 or less are included. These alkoxyperfluoroalkenes include methoxyperfluoropentene, methoxyperfluorohexene, methoxyperfluoroheptene, or methoxyperfluorooctene, or ethoxyperfluoropentene, ethoxyperfluorohexene, ethoxyperfluoroheptene. , or ethoxy perfluorooctene. Examples of the structure of methoxyperfluoroheptene include the following, but any structure or a mixture thereof may be used.
_CF3 ( _CF2 ) _2CF =CFCF( _OCH3 ) _CF3
CF3 ( _CF2 )CF=CF( _CF2 ) ₂ ( _OCH3 ) _{CF3
CF3 ( CF2} )CF=CFCF( _OCH3 ) _CF2CF3
CF3CF = _CFCF ( _OCH3 )( _CF2 ) _2CF3
CF3CF = _CFCF2CF ( _{OCH3 ) CF2CF3
CF3} ( _CF2 )CF=C( _OCH3 ) _{( CF2} ) _2CF3

The alkoxyfluoroalkenes include methoxyperfluoroheptene or isomer mixtures thereof. This methoxyperfluoroheptene or its isomer mixture is non-flammable with no flash point and no detectable flammability point (lower limit) and flammability point (upper limit). It falls under the non-dangerous goods under the Fire Service Act, does not require a warehouse for dangerous goods, and there is no legal limit on the storage amount.

On the other hand, methoxyperfluoroheptene or an isomer mixture thereof, as described in the test examples disclosed below, is used in oils and fats such as grease, engine oil, and brake oil that are commonly used around the brakes of automobiles and the like. Not compatible.

However, this methoxyperfluoroheptene or its isomer mixture has the characteristic of constituting a lubricant as an excellent solvent, and it is not suitable for detergent compositions because it does not have high compatibility with oils and fats and solvents. The properties are unexpectedly overcome by the co-inclusion of an HFO-based non-flammable fluorinated solvent that has other properties that make it unsuitable for use in cleaning compositions for various vehicles, vehicles, transportation systems, and the like. , a better cleaning composition is provided.

Methoxyperfluoroheptene or an isomeric mixture thereof is preferably used as the alkoxyfluoroalkene in the detergent composition and its aerosol composition of the means of the present invention. For example, as an isomer mixture of methoxyperfluoroheptene which is an alkoxyfluoroalkene, Opteon ^™ SF10 (former name: Vertrel (registered trademark) Suplion) (Mitsui-DuPont Fluorochemical Co., Ltd.) can be used. .

Opteon ^™ SF10 is commercially available from Mitsui-DuPont Fluorochemicals Co., Ltd. and can be used as a nonflammable fluorine-based solvent. This solvent is a non-flammable solvent with no flash point (TCC, COC) and no flammability range. It falls under the non-dangerous goods under the Fire Service Act, does not require a warehouse for dangerous goods, and there is no legal limit on the storage amount. It has an ozone depletion potential (ODP) of zero and a global warming potential (GWP) of less than ten.

<Regarding mass ratio between HFO-based nonflammable fluorine-based solvent and alkoxyfluoroalkene>
The cleaning agent composition and the aerosol composition thereof of the means of the present invention can be used for cleaning various vehicles, vehicles, transportation facilities such as automobiles, two-wheeled vehicles, bicycles, construction machinery, agricultural machinery, aircraft, railroad vehicles, and ships, and for cleaning workers. Considering that it is used for cleaning the tools, workshops, pits, and factories used, in addition to the fact that the solvent is originally nonflammable, it has a lower invasiveness to resins and elastomers, and is compatible with oils and fats. The two-component HFO-based noncombustible material is included so as to increase the solubility and provide excellent cleaning properties for members made of various materials such as metals, resins, and elastomers, and a moderate drying rate. It is preferable to adjust the range of the mass ratio of the fluorochemical solvent and the alkoxyfluoroalkene.

In addition, it has excellent properties such as lower invasiveness to resins and elastomers, higher compatibility with oils and fats, excellent detergency and moderate drying speed for members made of various materials such as metals, resins and elastomers. In order to have a plurality of is from 99/1 to 1/99. HFO-based nonflammable fluorine-based solvents and alkoxyfluoroalkenes are used in accordance with the types of oils and fats to be cleaned and the types of resins and elastomers used in combination with the areas to be cleaned and their surrounding areas to prevent invasion. It is possible to provide a cleaning composition and its aerosol composition in which the range of the mass ratio between and is adjusted respectively.

For example, the two components contained in the detergent composition and the aerosol composition of the means of the present invention are the HFO-based nonflammable fluorine-based solvent and (Z)-1-chloro-3,3,3-trifluoropropene. , When the alkoxyfluoroalkene is methoxyperfluoroheptene or an isomer mixture thereof, the mass ratio (HFO-based nonflammable fluorine-based solvent/alkoxyfluoroalkene) ranges from 99/1 to 1/99. , preferably 99/1 to 10/90, more preferably 90/10 to 20/80, but the oil and fat to be dissolved so as to match the usage conditions of the target customer A suitable one may be selected and used from the above range of the mass ratio according to the type of resin or elastomer to be protected from invasion, and considering the cost balance. As a result, it has excellent properties such as lower invasiveness to resins and elastomers, higher compatibility with oils and fats, excellent detergency and moderate drying speed for members made of various materials such as metals, resins and elastomers. It becomes possible to have a plurality of characteristics, and it can be suitably used as a detergent composition and its aerosol composition.

<About other ingredients>
The cleaning composition and its aerosol composition of the means of the present invention, in addition to the two main components of the cleaning composition described above, further optionally do not increase the risk of ignition or the risk of fire. It is good also as what was mix|blended in the degree. In the case where the above additional components are blended, the HFO-based cleaning composition can be achieved by the main two components while maintaining the nonflammability of the detergent composition or the characteristics of a non-dangerous substance under the Fire Service Law. The nonflammable fluorinated solvent itself should be blended within a range that can maintain the characteristics of reducing invasiveness to resins and elastomers held by itself, and maintaining detergency against oil and fat components and an appropriate drying rate. The components to be blended include alcohols, saturated hydrocarbons, unsaturated hydrocarbons, aromatic hydrocarbons, stabilizers, chelating agents, etc. Examples include ^3M NOVEC ^™ 7200 and ^{3M NOVEC ™} 7300. Alcohols such as methanol, ethanol, isopropyl alcohol, butanol, hydrocarbon solvents such as normal hexane, cyclohexane, isohexane, ketone solvents such as acetone, MEK, cyclohexanone, ethyl acetate, methyl acetate, acetic acid Ester and glycol ester solvents such as butyl, ethylene glycol monomethyl ether acetate, ether and glycol ether solvents such as methyl cellosolve, butyl cellosolve, methoxymethylbutanol, hexyl diglycol, glyme solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, HCFC -141b, HCFC-225, 1-bromopropane, chlorinated solvents such as chloroform, special solvents such as N-methyl-2-pyrrolidone, tetrahydrofuran, dimethylformamide, γ-butyrolactone, 1,3-dioxolane, dimethyl sulfoxide, etc. Other solvents may be blended.

<About the aerosol composition>
A liquefied gas or a compressed gas can be used as the propellant gas in the aerosol composition. For example, LPG (liquefied petroleum gas), DME (dimethyl ether), carbon dioxide, freon-based gas, (E)-1,3,3,3-tetrafluoroprop-1-ene, nitrogen gas, noble gases such as argon, A combination of two or more of the above gases, such as a gas such as compressed air, a mixture of LPG and DME, and a mixture of LPG and carbon dioxide, can be used. Then, the detergent composition of the means of the present invention and the above propellant gas can be mixed to form an aerosol composition, which can be provided by filling it in a pressure can.

<How to use>
The solution of the detergent composition of the means of the present invention can be used to clean metals, resins, and elastomers of various vehicles, vehicles, vehicles, such as automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railroad vehicles, and ships. It can be used by applying it to members made of various materials such as, tools used by workers, workplaces, pits, and factories, or by immersing those objects to be cleaned in a solution of the cleaning composition. Alternatively, pressure-resistant cans may be filled with an aerosol composition obtained by mixing the cleaning composition of the present invention with a liquefied gas as a propellant gas to form an aerosol, or the cleaning composition of the present invention may be placed in a pail can. A mobile small filling machine is installed at the work site where it is used, and compressed air is used to convert the cleaning agent composition in the pail into an aerosol, which is then applied to parts made of various materials such as metals, resins, and elastomers to be cleaned. , can be used as an aerosol.

Examples in which the detergent composition of the present invention and its aerosol composition were produced and used are shown below as Examples and Test Examples.

<About test samples>
To prepare samples for testing, the ingredients used in the cleaning compositions of the present invention and conventional cleaning agents are purchased.
The HFO-based nonflammable fluorine-based solvent used in the cleaning composition of the present invention includes (Z)-1-chloro-3,3,3-trifluoropropene 1233Z (Central Glass Co., Ltd., Japan). ) and 1,1-dichloro-3,3,3-trifluoropropene (Matrix Scientific, USA) were purchased. In addition, AMOLEA® AS-300 was supplied by AGC Corporation (Japan). Methoxyperfluoroheptene or an isomer mixture thereof is used as ^an example of alkoxyfluoroalkene. company) was purchased.

In addition, as a conventional cleaning agent, a brake & parts cleaner (quick-drying type) (Kobe Gosei Co., Ltd., Japan) using isohexane is used as a quick-drying stock solution, and cyclohexane is used as a degreasing cleaning agent. , a degreasing detergent (Honda Access Co., Ltd., Japan), an isoparaffin-based solvent brake cleaner N04 (Suzuki Co., Ltd., Japan), and trichloroethane as an air-dry undiluted solution.

Then, the HFO-based nonflammable fluorine-based solvent of the present invention and the alkoxyfluoroalkene are contained so that the mass ratio between the HFO-based nonflammable fluorine-based solvent and the alkoxyfluoroalkene is as follows. The detergent compositions of Examples 1 to 9, which are different detergent compositions, were produced respectively.

<HFO nonflammable fluorine-based solvent/alkoxyfluoroalkene>
・Mass ratio (1233Z/Opteon ^™ SF10)
Example 1: 90/10
Example 2: 80/20
Example 3: 70/30
Example 4: 60/40
Example 5: 50/50
Example 6: 40/60
Example 7: 30/70
Example 8: 20/80
Example 9: 10/90
・Mass ratio (AS-300/Opteon ^™ SF10)
Example 10: 90/10
Example 11: 70/30
Example 12: 50/50
Example 13: 30/70
Example 14: 10/90

Also, the following Comparative Examples 1 to 4 were prepared. The quick-drying stock solution, the degreasing detergent, and the air-drying stock solution are all highly flammable, and trichloroethane is highly toxic, all of which have problematic properties as cleaning compositions. .
<Conventional product (combustible)>
Comparative Example 1: Quick-drying stock solution Comparative Example 2: Degreasing detergent Comparative Example 3: Air-drying stock solution Comparative Example 4: Trichloroethane

Furthermore, in order to compare with those of each example in which two components of an HFO-based nonflammable fluorine-based solvent and a nonflammable fluorine-based solvent methoxyperfluoroheptene or its isomer mixture are blended together, the following Comparative Examples 5 to 8 was prepared.
<HFO nonflammable fluorinated solvent>
Comparative Example 5: 1233Z only Comparative Example 6: 1,1-dichloro-3,3,3-trifluoropropene only Comparative Example 7: AS-300 only <Alkoxyfluoroalkene>
Comparative Example 8: Opteon ^™ SF10 only

Next, Test Examples 1 to 4 shown below were carried out, and it was confirmed that the detergent composition of the means of the present invention and its aerosol composition have superior properties to conventional detergents. was specifically confirmed.

<Test Example 1: Evaluation of invasiveness (long-term contact)>
· Materials and Methods Solutions of Examples 1 to 14 and Comparative Examples 1 to 8 are prepared as test solutions.
In order to evaluate invasiveness, prepare the following test pieces.
Rubber: NR (natural rubber)
: CR (chloroprene rubber)
: SBR (styrene-butadiene rubber)
: EPDM (ethylene propylene rubber)
(Both were obtained from Standard Test Piece Co., Ltd., Japan.)
Resin: ABS (acrylonitrile butadiene styrene)
: LDPE (low density polyethylene)
: PC (polycarbonate)
(Both are from Nippon Test Panel Co., Ltd.)

Measure the weight of each of the above rubber or resin test pieces (size 10 mm×10 mm×2 mm).
Next, 20 mL of the solution of Example or Comparative Example was placed in a vial, and the above rubber or resin test pieces (size: 10 mm x 10 mm x 2 mm) were immersed therein, and the vial was set to 45°C. It is placed in a constant temperature and humidity machine (HPAV-120-40, Isuzu Manufacturing Co., Ltd., Japan) and allowed to stand.
After removing each test piece from the vial bottle and observing the surface condition, the weight and thickness of the test piece were measured, the degree of swelling was calculated, and it was confirmed whether it fell within the range of ± 5.0%. Also check that the transparency of the image is not lost.
When a small amount of solution is used, the test is performed with the size of the test piece and the amount of liquid proportional to the amount used.

・Test results The results of the above tests are shown in Tables 1-1 to 1-3.

In Test Example 1, it was found that a composition containing an HFO nonflammable fluorinated solvent and an alkoxyfluoroalkene improved the invasiveness of the HFO nonflammable fluorinated solvent to rubber or resin. confirmed. Then, a comparative verification with conventional cleaning agents was conducted regarding non-invasiveness to rubber or resin.

HFO-based nonflammable fluorine-based solvents are aggressive to rubber and resin when used for a long period of time, and are especially important for ensuring the safety of various vehicles, vehicles, and transportation. Swells NR (natural rubber), SBR (styrene-butadiene rubber), EPDM (ethylene propylene rubber), dissolves and softens ABS (acrylonitrile butadiene styrene), and swells PC (polycarbonate), which are widely used in equipment and parts. , whitening, devitrification, and cracking, showing strong invasiveness, and the degree of deterioration of the rubber and resin made it impossible to guarantee the quality of the product (Table 1-1).

In addition, conventional detergents are flammable in the first place, and are strongly invasive when applied to rubbers such as NR, CR, SBR, and EPDM, and resins such as ABS, LDPE (low-density polyethylene), and PC. In the same way, the product quality could not be guaranteed (Table 1-1).

However, by blending an alkoxyfluoroalkene with an HFO-based non-flammable fluorine-based solvent, surprisingly, various rubbers and resins observed when using the above-mentioned HFO-based non-flammable fluorine-based solvent It has become clear that the phenomena of swelling, dissolution, whitening, devitrification and cracking can be eliminated (Tables 1-2 and 1-3).

It is possible to create a detergent composition that has a new characteristic of not showing invasiveness to various rubbers and resins that are widely used in important devices and parts to ensure the safety of various vehicles, vehicles, and transportation facilities. It will be appreciated that the present invention provides a highly effective means of replacing conventional aggressive cleaning agents. Moreover, it is understood that the detergent composition of the means of the present invention has a very low risk of invasiveness to rubbers and resins even when used continuously for a long period of time.

In addition, since the HFO-based non-flammable fluorine-based solvent is limited in the amount that can be produced, the cleaning composition of the means of the present invention is produced by mixing the HFO-based non-flammable fluorine-based solvent and an alkoxyfluoroalkene. Therefore, it is understood that it also has the effect of increasing the amount that can be supplied as a cleaning composition and preventing stagnation of product supply.

Among the above rubbers, SBR (styrene-butadiene rubber) is used for seals in automobile brake fluid systems and tires. is desired to be low. PC (polycarbonate) is also used in control system mechanisms such as brake devices. However, as in the present invention, by blending an alkoxyfluoroalkene with an HFO-based nonflammable fluorine-based solvent, surprisingly, the problem of corrosiveness to SBR and PC is sufficiently reduced, and their swelling is reduced. We were able to suppress the rate to 5% or less, at which the quality of the product can be maintained to a certain extent.

<Test Example 2: Evaluation of invasiveness (short-term contact)>
- Materials and methods As in Test Example 1, solutions of Examples 1 to 14 and Comparative Examples 1 to 8 are prepared. In addition, prepare the following test pieces to evaluate short-term invasiveness.
Resin: ABS (acrylonitrile butadiene styrene)
: PC (polycarbonate)
(Both are from Nippon Test Panel Co., Ltd.)

For each test piece of the above resin (size 10 mm x 10 mm x 2 mm, the surface is wiped with a microfiber cloth containing the solutions of Examples 1 to 18 or Comparative Examples 1 to 8. After that, the appearance change of each test piece surface is visually observed. If there was no change in appearance, it was rated as ◯, and if there was any change, it was rated as x, and the state of the resin surface was recorded.

・Test results The results of the above tests are shown in Tables 2-1 to 2-3.

The HFO-based nonflammable fluorine-based solvent, which is one of the main components used in the detergent composition of the means of the present invention, can be used even for a short time by wiping the surface with a microfiber cloth soaked with the solution. , ABS and PC resins are degraded (Table 2-1).

However, by blending an alkoxyfluoroalkene with an HFO-based nonflammable fluorine-based solvent to form a detergent composition according to the means of the present invention, such short-term contact causes deterioration of the resin. (Tables 2-2 to 2-3).

<Test Example 3: Evaluation of compatibility with grease and oil>
·Materials and method In the same manner as in Test Example 1, solutions of Examples 1 to 14 and Comparative Examples 1 to 8 are prepared as test solutions.

Various types of grease and oil that are commonly used in automobiles and the like are prepared as the oils and fats to be cleaned and removed.
Grease: GREASE (Orange) (Kobe Gosei Co., Ltd., Japan)
: Brake grease for rubber (Kobe Gosei Co., Ltd., Japan)
: Disk brake grease (Kobe Gosei Co., Ltd., Japan)
: Brake grease (Kobe Gosei Co., Ltd., Japan)
: Silicon grease (Kobe Gosei Co., Ltd., Japan)
: Caliper Pin Grease (Honda Access Co., Ltd., Japan)
: Pad & Shoe Grease (Honda Access Co., Ltd., Japan)
: Rubber grease (Honda Access Co., Ltd., Japan)
: Brake grease (Honda Access Co., Ltd., Japan)
Oil: Engine oil Mobil 1 0W-20 (ExxonMobil, USA)
: Brake fluid (DOT3) (Honda Access Co., Ltd., Japan)
: Brake fluid (DOT4) (Suzuki Motor Corporation, Japan)

A 10 mL vial bottle is prepared for each solution, and 1 g each of the above grease or engine oil is added. 5 mL of the solution of Example or Comparative Example is further added to the vial, and the lid of the vial is closed. Each vial is sonicated for 1 hour in an ultrasonic cleaner (AU16C, Aiwa Medical Industry Co., Ltd., Japan).
After one hour of sonication, remove each vial from the ultrasonic cleaner. Check the inside of the vial bottle, and if the grease or engine oil and the solution of the example or comparative example are completely mixed, it will be ○, if it is partially separated, it will be △, and if it is completely separated, it will be ×. Evaluate solubility. If a small amount of solution is used, the test should be conducted with a liquid volume proportional to the amount used.

・Test results The results of the above tests are shown in Tables 3-1 and 3-3.

It was found that the alkoxyfluoroalkene used in the above test had little compatibility with grease or brake oil (Comparative Example 8 in Table 3-1). In view of this, it is understood that alkoxyfluoroalkenes are unsuitable for use as cleaning agents for removing stains due to fat components such as grease or brake oil. In addition, although the HFO-based nonflammable fluorine-based solvent has moderate compatibility, it has invasiveness to resins and elastomers, as is clear from the test results of Test Examples 1 and 2. It is unsuitable for cleaning compositions used for transportation and the like. As described above, various HFO-based nonflammable fluorine-based solvents and alkoxyfluoroalkenes lack motivation to be added to cleaning compositions used for various vehicles, vehicles, transportation facilities, and the like.

However, if both the HFO-based nonflammable fluorine-based solvent and the alkoxyfluoroalkene, which cannot be used for cleaning vehicles, vehicles, and transportation facilities, as described above, are mixed, surprisingly, oils such as grease or brake oil are used. This time, it became clear that it exhibits a wide range of compatibility with components, that is, it exhibits high detergency against these oil components (Table 3-2). In addition, the range of the mass ratio between the HFO-based nonflammable fluorine-based solvent and the alkoxyfluoroalkene, which exhibit compatibility, was also wide (Tables 3-2 and 3-3). Therefore, as in the means of the present invention, the cleaning agent composition and its aerosol composition contain an HFO-based nonflammable fluorine-based solvent and an alkoxyfluoroalkene, so that oils and fats to be cleaned can be The range of the mass ratio of the HFO-based nonflammable fluorine-based solvent and the alkoxyfluoroalkene is adjusted according to the type of the cleaning agent and the type of resin and elastomer used in the area to be cleaned and the surrounding area to prevent invasion. It is understood that adjustments can be made to provide the cleaning composition and its aerosol composition with properties suitable for the scene in which the cleaning composition is used.

In addition, conventional detergents sometimes lacked compatibility with GREASE (orange) and rubber grease (Table 3-1). However, as shown in Table 3-2, by including alkoxyfluoroalkene, which has little compatibility with GREASE (orange) and rubber grease, the HFO-based nonflammable fluorine-based solvent is diluted. Also, it became clear that a compound exhibiting compatibility with GREASE (orange) and rubber grease was newly obtained.

As described above, by including an HFO-based nonflammable fluorine-based solvent and an alkoxyfluoroalkene in a cleaning composition as in the present invention, compatibility with a wide range of greases and brake oils can be exhibited. It will be appreciated that it will be possible to provide a new detergent composition that is non-flammable and of low toxicity, yet has excellent cleaning properties equal to or superior to those of conventional brake cleaners.
<Test Example 4: Evaluation of dryness in detergent composition>
- Materials and methods Similar to Test Example 1, solutions of Examples 1, 3, 5, 7, 9 to 14 and Comparative Examples 1 to 5 are prepared.

A constant temperature and humidity machine (HPAV-120-40, Isuzu Manufacturing Co., Ltd., Japan) was set to 45° C., 25° C. or 10° C. and a humidity of 70%. When the temperature of the flat plate becomes constant, 100 μL of the solutions of Examples 1, 3, 5, 7 and 9 and Comparative Examples 1 to 5 are placed in the flat plate, and the droplets of each solution are completely volatilized from the flat plate and dried. Visually measure the time it takes.

・Test results The results of the above tests are shown in Tables 4-1 to 4-3.

For detergent compositions that require good workability and safety, the optimum drying time is typically 1 to 2 minutes in a high temperature environment of 40°C and 25°C. 2 to 3 minutes in a normal temperature environment, and 3 to 4 minutes in a low temperature environment of 10°C. Among the conventional detergents, only the quick-drying undiluted type was able to achieve such conditions, and the other detergents required an excessive amount of time to dry (Table 4 -1). However, although this type of quick-drying stock solution requires a short drying time, it is highly flammable and poses a problem in terms of ensuring the high level of safety required for detergent compositions.

As was clarified in Test Example 3, the detergent composition of the means of the present invention, which contains an HFO-based nonflammable fluorine-based solvent and an alkoxyfluoroalkene, is a nonflammable cleaning agent having excellent properties against oil and fat components. agent composition. Therefore, the drying time of a detergent composition containing an HFO-based nonflammable fluorine-based solvent and an alkoxyfluoroalkene was investigated.

As a result, HFO-based nonflammable fluorine-based solvents have a short ^drying time (Table 4-1). was used, the drying time became longer, and it became clear that a standard working time could be obtained (Tables 4-2 and 4-3). It was also confirmed that a cleaning composition having a longer drying time can be obtained by increasing the blending ratio of the alkoxyfluoroalkene (Tables 4-2 and 4-3). Adjust the type of HFO-based non-flammable fluorine-based solvent and alkoxyfluoroalkene, and the mass ratio between the HFO-based non-flammable fluorine-based solvent and alkoxyfluoroalkene so that the desired drying speed can be obtained according to the usage situation. It became clear that it was possible.

Since the detergent composition contains an HFO-based nonflammable fluorine solvent and an alkoxyfluoroalkene, it is nonflammable, so the danger of ignition and the risk of fire are low, and it is a non-dangerous substance under the Fire Service Law. It does not require a warehouse for hazardous materials, has no legal restrictions on the storage amount of detergent compositions that are used in large quantities, and has low toxicity and low environmental impact such as ozone depletion. While having detergency equal to or greater than that of a detergent composition for brake cleaners, it imparts excellent properties such as extremely low attack to rubber and resin, and has a desired drying speed according to the usage scene. In addition, it is possible to provide a new detergent composition and its aerosol composition in which the mass ratio of the HFO-based nonflammable fluorine-based solvent and the alkoxyfluoroalkene is adjusted.

Claims (9)

(Z)-1-Chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-as cleaning components One or more selected from trifluoropropene, 2,3,3-trichloro-3-fluoropropene, and HCFO-1233yd, containing an HFO-based nonflammable fluorine-based solvent and an alkoxyfluoroalkene , the mass ratio of the HFO-based non-flammable fluorine-based solvent to the alkoxyfluoroalkene (HFO-based non-flammable fluorine-based solvent/alkoxyfluoroalkene) ranges from 99/1 to 1/99, provided that the HFO-based non-flammable When the fluorinated solvent is (Z)-1-chloro-3,3,3-trifluoropropene, the mass ratio is 80/20 to 40/60, and the HFO nonflammable fluorinated solvent is HCFO-1233yd. In the case of, a step of applying or spraying a cleaning composition for various vehicles, vehicles, and transportation, wherein the range is from 30/70 to 1/99, onto various vehicles, vehicles, and transportation, or a step of spraying various vehicles, vehicles, and transportation. A method for cleaning various vehicles/vehicles/transportation facilities comprising a step of immersing the vehicles/transportation facilities in the cleaning composition. 2. The cleaning method according to claim 1, wherein the alkoxyfluoroalkene is an alkoxyperfluoroalkene. 2. The cleaning method according to claim 1, wherein the alkoxy group of the alkoxyfluoroalkene includes an alkoxyfluoroalkene or alkoxyperfluoroalkene which is a methoxy group or an ethoxy group. 2. The cleaning method according to claim 1, wherein the alkoxyfluoroalkene is an alkoxyfluoroalkene having 5 or more and 8 or less carbon atoms. Alkoxyfluoroalkene is methoxyperfluoropentene, methoxyperfluorohexene, methoxyperfluoroheptene, or methoxyperfluorooctene, or ethoxyperfluoropentene, ethoxyperfluorohexene, ethoxyperfluoroheptene, or ethoxyper 2. A cleaning method according to claim 1, characterized in that it contains any one or more of fluorooctene or isomer mixtures thereof. A cleaning method according to claim 1, characterized in that the alkoxyfluoroalkene is methoxyperfluoroheptene or its isomer mixture. (Z)-1-Chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-as cleaning components One or more selected from trifluoropropene, 2,3,3-trichloro-3-fluoropropene, and HCFO-1233yd, containing an HFO-based nonflammable fluorine-based solvent and an alkoxyfluoroalkene , the mass ratio of the HFO-based non-flammable fluorine-based solvent to the alkoxyfluoroalkene (HFO-based non-flammable fluorine-based solvent/alkoxyfluoroalkene) ranges from 99/1 to 1/99, provided that the HFO-based non-flammable When the fluorinated solvent is (Z)-1-chloro-3,3,3-trifluoropropene, the mass ratio is 80/20 to 40/60, and the HFO nonflammable fluorinated solvent is HCFO-1233yd. In the case where the range is 30/70 to 1/99, an aerosol composition containing a cleaning agent composition and an injection gas for various vehicles, vehicles, and transportation is used. A method for cleaning various vehicles, vehicles, and transportation facilities, which includes a process of spraying and cleaning the engine. Claim 7, characterized in that the propellant gas is N ₂ , CO ₂ , (E)-1,3,3,3-tetrafluoroprop-1-ene, noble gases, LPG, DME or compressed air. The cleaning method described in . The cleaning method according to claim 7, characterized in that the propellant gas is _N2 .