JP7493851B2 - Detergent composition and aerosol composition thereof - Google Patents

Description

This invention relates to a new cleaning agent composition and aerosol composition thereof for use in cleaning various vehicles, conveyances and transport such as automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railroad vehicles and ships, as well as for cleaning tools, workshops, pits and factories, and in particular for degreasing and cleaning various vehicle parts and control devices, such as bodies, brake parts, suspensions and wheels, made of metal or a combination of metal and resin, in various vehicles, conveyances and transport, and is non-flammable, has a low risk of ignition and fire, and is classified as a non-hazardous material under the Fire Service Act, so no hazardous material warehouse is required. Therefore, there are no legal restrictions on the storage amount of the cleaning composition when used in large quantities, and furthermore, the cleaning composition has excellent properties such as low toxicity and low environmental impact such as ozone layer depletion, and while it has cleaning properties and dirt redeposition prevention properties equivalent to or better than conventional cleaning compositions, it is extremely less aggressive to rubber and resins than conventional cleaning compositions, and furthermore, it relates to a cleaning composition and an aerosol composition thereof that have the excellent properties of being able to adjust the drying speed by changing the blending ratio of the components that make up the composition so as to exhibit the desired drying properties according to the situation of use.

Various parts and devices such as bodies, brakes, suspensions, and wheels of various vehicles, conveyances, and transport vehicles, including automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railroad cars, and ships, are manufactured using metals and various resins. In recent years, composite materials that combine metals with resins have also been used for parts with the aim of reducing weight and increasing decorativeness.

When parts and devices made of these metals are used, oil and dirt will adhere to their surfaces, reducing their intended performance and decorativeness. Depending on the components that adhere to them, the metal surface may corrode, irreversibly impairing their intended performance. Furthermore, vehicles, conveyances, and transportation systems apply oils such as grease to necessary areas to ensure the smooth operation of each device, but this oil gradually flows into unintended areas due to air flow and rainwater being sprayed onto the vehicle while it is running. In addition, oil that has flowed out from other vehicles, conveyances, and transportation systems may be picked up from the road surface along with dirt, adhering to various parts of the vehicle, conveyance, and transportation system, reducing the intended performance of various parts and devices. In particular, in friction brake devices that use brake shoes with brake linings, which are widely used in vehicles, conveyances, and transportation, as brake elements for rotating bodies such as brake discs and brake drums, the adhesion of oil reduces the coefficient of friction, and the brake linings become more susceptible to wear and dust, which can cause a decrease in the braking performance of the brakes. This makes it necessary to carry out regular maintenance work and clean the metal parts that have become covered in oil and dirt.

In addition, when assembling and manufacturing various vehicles, conveyances, and transport systems, if even a small amount of oil or other substances remain on the metal surface when resins, paints, etc. are applied to the metal and processed, the resins or paints will not adhere stably and will peel off or change in quality, resulting in a significant decrease in product quality. Furthermore, 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 even a small amount of oil or other substances remain on the metal surface, and if the parts are assembled in this state, braking performance will be impaired, making it impossible to stably perform the desired performance. Therefore, when assembling and manufacturing vehicles, conveyances, and transport systems, it is necessary to thoroughly clean and remove any small amount of oil that may be on the metal surface of each part beforehand.

Therefore, conventionally, cleaning compositions containing trichloroethane as the main ingredient, which has cleaning properties, have been developed and used mainly for cleaning the bodies, brake parts, suspensions, wheels, etc. of various vehicles, conveyances, and transport vehicles. However, trichloroethane is known to be toxic. In addition, under 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, the production and consumption of trichloroethane in contracting countries was gradually reduced and completely phased out in 1996, and exports and imports to non-contracting countries of the protocol were prohibited or restricted. For this reason, the use of cleaning compositions using trichloroethane has come to be avoided.

Therefore, cleaning agent compositions have been produced that use C6 petroleum hydrocarbons such as isohexane and cyclohexane as a base, and alcohols such as ethanol and isopropyl alcohol have been added to adjust the cleaning properties, drying properties, and boiling point. These have been proposed as aerosol compositions using LPG gas or compressed air using a portable simple aerosol filling machine, and are widely used.

However, the petroleum-based hydrocarbons and alcohols used in the above-mentioned cleaning compositions are highly flammable and are regulated as hazardous materials under the Fire Service Act. Therefore, a hazardous materials warehouse is required for storage, which is costly. Furthermore, even if a facility using the cleaning composition has a hazardous materials warehouse, there is a limit to the amount that can be stored. In particular, many of the above-mentioned cleaning compositions are classified as Class 4, Type 1 petroleum products, but the legally designated amount of Class 4, Type 1 petroleum products that can be stored in one warehouse is set low, so there is a problem that only a small amount of the cleaning composition can be stored despite the large amount of use, and an improvement in this area has been required.

Furthermore, although the hydrocarbons used in the above-mentioned cleaning composition are not as toxic as trichloroethane, there is a risk of hydrocarbon poisoning if inhaled in excessive amounts, so they must be used in a well-ventilated environment, such as outdoors or indoors with a ventilation system, and a warning to that effect is also included on the product. However, because an aerosol product is used, vaporized hydrocarbons flow not only in the workplace but also downwind, leaving the risk of people inhaling them, and improvements were needed.

In addition, when the cleaning composition is poured over the worker or an aerosol product is forcefully sprayed during work, a large amount of the highly flammable cleaning composition may soak into the worker's gloves or clothing. In addition, a large amount of the cleaning composition may be soaked into the worker's gloves or work clothing to remove oil stains. However, since the cleaning composition is highly flammable, if the gloves or work clothing are not dried sufficiently afterwards, there is a risk of a fire caused by static electricity or a cigarette. Therefore, in order to ensure safety in the work environment, improvements have been required to avoid the use of these highly flammable ingredients.

Halogen-based solvents are well known as solvents that have no flash point, but chlorine- and bromine-based solvents are subject to restrictions on production and use due to their harmfulness, making them difficult to use in cleaning compositions. As a solution to the problems of storage volume and ensuring safety, high flash point products using petroleum hydrocarbons with long carbon numbers and water-based products containing carbitol, alcohol, etc. as cleaning ingredients have been proposed (see Patent Document 1).

However, the above-mentioned aqueous compositions have very poor drying time, requiring 30 to 40 minutes to dry (see Patent Document 1). Therefore, when these aqueous compositions are used as cleaning compositions, the aqueous composition liquid is likely to remain around the brakes after use, and if the brakes are used with the liquid remaining, this leads to serious effects such as a decrease in braking force. Therefore, the work process using the above-mentioned aqueous compositions requires sufficient drying after cleaning, which is cumbersome and requires improvement. Furthermore, because they are aqueous, they have inferior cleaning properties compared to conventional brake cleaner cleaning compositions, and depending on the type of dirt, they do not necessarily have sufficient cleaning performance, so there are limitations to the situations in which they can be used, and improvements have been required to make them more versatile.

Incidentally, HFO-based non-flammable fluorine-based solvents, which are hydrofluoroolefin-based solvents such as (Z)-1-chloro-3,3,3-trifluoropropene, are known as solvents that can be used to clean metal materials. However, although these HFO-based non-flammable fluorine-based solvents have cleaning properties for metal materials, they are known to have strong corrosive properties for resins and elastomers, which are materials other than metal materials (Non-Patent Document 1). For this reason, it is necessary to thoroughly examine the situations in which such HFO-based non-flammable fluorine-based solvents are used.

Metal materials are widely used for important parts that require high safety, such as various braking devices, lights, and windows in various vehicles, conveyances, and transport means, including automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railroad cars, and ships. In addition to these metal materials, materials made of various resins and elastomers, such as polycarbonate, acrylic, ABS, polystyrene, silicone rubber, natural rubber, HNBR, NBR, fluororubber, and urethane rubber, are also usually used at the same time. For example, brakes are controlled by the hydraulic pressure of brake fluid, and this brake fluid is generally filled in rubber hoses that connect the devices.

However, when the above-mentioned HFO-based non-flammable fluorine-based solvents come into contact with resins or elastomers, the strong corrosive properties of the above-mentioned HFO-based non-flammable fluorine-based solvents can cause serious problems, such as deterioration of resins and elastomers in important parts that require high safety. In particular, polycarbonate, which is widely used in important parts of the above-mentioned vehicles, conveyances, and transport systems, becomes devitrified, acrylic, ABS, and polystyrene dissolve, and silicone rubber, natural rubber, HNBR, NBR, fluororubber, and urethane rubber swell (Non-Patent Document 1), raising concerns about reduced safety.

When used as a cleaning composition, it is necessary to thoroughly wet the area to be cleaned with the cleaning composition and then rinse it off. However, the above-mentioned HFO-based non-flammable fluorine-based solvents have a low boiling point and therefore dry very quickly, making them unsuitable for a process of wetting and rinsing. If they are wetted, there is a concern that an excessive amount of HFO-based non-flammable fluorine-based solvent may come into contact with resins and elastomers in important parts, reducing safety.

HFE (hydrofluoroether)-based fluorine-based solvents include 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane (AE3000/HFE-347pc-f). However, it is known that it does not have high compatibility with oils and fats because it does not contain chlorine molecules in its molecule, which are highly effective in expressing solubility in substances (Non-Patent Document 2). In addition, a mixture of 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane and (Z)-1-chloro-3,3,3-trifluoropropene is known as a solvent for dissolving silicone compounds used to reduce the friction coefficient of equipment and coating the silicone compounds on the surfaces of various objects such as metals and resins (Patent Document 2). However, silicone compounds that reduce the friction coefficient and greatly reduce the braking force are not intentionally coated on brake-related parts of various vehicles such as automobiles, motorcycles, construction machines, agricultural machines, aircraft, railway vehicles, and railway cars.

HFC (hydrofluorocarbon) fluorine-based solvents include 1,1,1,3,3-pentafluorobutane (Solkane 365) and 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane (AC-2000), but they have low KB values and low oil saturation power (Non-Patent Document 3), and are not applicable to degreasing and cleaning of automobile parts (Non-Patent Document 4). They are also used as solvents for lubricants such as fluorine oil, fluorine grease, silicone oil, and silicone grease to reduce friction in equipment (Patent Document 3), but they are not used to reduce the friction coefficient and significantly reduce the braking force in brake-related parts of various vehicles such as automobiles, motorcycles, construction machines, agricultural machines, aircraft, railway cars, and railway vehicles by creating a situation in which the lubricating components are applied or coated.

Examples of PFC (perfluorocarbon) non-flammable fluorine-based solvents include Fluorinert ^™ FC-40 and Fluorinert ^™ FC-3283, but these solvents have little compatibility with water or oil (Non-Patent Document 5). Furthermore, these PFC non-flammable fluorine-based solvents are used as fluorine-based coating agents and dilution solvents for lubricants to reduce friction in equipment and the like (Non-Patent Document 6), but the friction-reducing components are not applied or coated on brake-related parts of various vehicles such as automobiles, motorcycles, construction machinery, agricultural machinery, aircraft, and railway cars, thereby lowering the friction coefficient and greatly reducing the braking force.

Other known fluorine-based solvents include alkoxyfluoroalkenes, such as methoxyperfluoroheptene and its isomer mixture Opteon ^™ SF10 (formerly known as Vertrel (registered trademark) Suprior) (Mitsui-DuPont Fluorochemicals Co., Ltd.). This Opteon ^™ SF10 is suitably used as a solvent for lubricants that use fluorine grease (Patent Document 4), but it does not create a situation in which the lubricating components are applied or coated on brake-related parts of various vehicles such as automobiles, motorcycles, construction machinery, agricultural machinery, aircraft, railway vehicles, and railroad cars, thereby lowering the friction coefficient and greatly reducing the braking force.

JP 2001-207199 A Patent No. 5648345 International Publication No. 2013/161723 JP 2017-115099 A 1233Z Excellent environmental performance, high cleaning power Next-generation fluorine-based solvent Central Glass Co., Ltd. Catalog publication date October 2015 Various properties and application development of Asahiklin AE-3000, Michiomi Nagase et al., Internet <URL: http://www.agc.com/rd/library/2004/54-10.pdf> List of main physical properties of dry cleaning solvents, Internet <URL: http://www.saneidenki.jp/cleaner/pdf/dry6_youzai.pdf> Asahiklin AC-2000 (general name) Fluorine-based solvent Product overview, Internet (URL: http://www.agc-chemicals.com/jp/ja/products/pdf/ASAHIKLIN_AK-225_03.pdf) 6-380-01 Fluorinert FC-40 1.5 kg, Internet <URL: https://axel.as-1.co.jp/asone/d/6-380-01/?print=true&pdf=true> Solvent and dispersion medium applications, Internet: <URL: http://www.mmm.co.jp/emsd/fluorine/solution/solvent.html#dtl-01>

The problem that the present invention aims to solve is to provide a new cleaning composition and an aerosol composition thereof, which are non-flammable, have a low risk of ignition, pose a low risk of fire, are classified as non-hazardous materials under the Fire Service Act, do not require a hazardous materials warehouse, and are free of legal restrictions on the storage amount of cleaning compositions used in large quantities, have low toxicity, and are environmentally friendly, such as by causing ozone layer destruction, and have cleaning properties equivalent to those of conventional cleaning compositions, but are much less aggressive to rubber and resin than conventional cleaning compositions, and furthermore, can adjust the drying speed by changing the blending ratio of the components constituting the composition so as to exhibit the desired drying properties according to the situation of use.

Since cleaning compositions are used to wet and wash away dirt components, they are used and stored in large quantities. Therefore, there is a demand to significantly reduce the risk of fire caused by ignition by selecting a solvent that has no flash point and no flammable range under the temperature conditions of normal usage and storage environments.

In addition, in cleaning, it is required to wet the dirt components with the cleaning composition and wash them off. Therefore, it is necessary to provide the cleaning composition not only as a solution to be applied or immersed in, but also as an aerosol composition containing the cleaning composition and a propellant gas, which simplifies handling during cleaning and makes it easier to physically remove dirt by utilizing gas pressure. When providing the composition as an aerosol composition, there is an increased risk of workers inhaling the composition, so it is required to select a less toxic solvent for the cleaning composition.

There is a demand for a product that has cleaning properties equal to or better than those of conventional products, which has not been achieved by high flash point products or water-based products, and that can easily achieve the appropriate level of drying properties required for the situation of use.

The inventors of the present application have been working to confirm the physical properties of various compounds and compositions and to investigate their cleaning properties in order to provide a new cleaning agent composition and aerosol composition thereof that solve the above problems. In the process, they have found that HFO-based non-flammable fluorine-based solvents, which are known to cause serious problems such as deterioration, devitrification, and dissolution of important parts of various vehicles, conveyances, and transport means, such as automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railroad vehicles, and ships, which require high safety, as well as resins and elastomers used in tools, workshops, pits, factories, etc. used by workers, reduce the coefficient of friction and reduce braking force in important parts such as brake-related parts in various vehicles, such as automobiles, motorcycles, construction machinery, agricultural machinery, aircraft, railroad vehicles, and other vehicles. It was discovered that by adding HFE (hydrofluoroether)-based fluorine-based solvents, HFC (hydrofluorocarbon)-based fluorine-based solvents, or PFC (perfluorocarbon)-based nonflammable fluorine-based solvents, which are known to be capable of causing damage to the resins and elastomers, the composition exhibits superior cleaning composition properties compared to conventional compositions, such as preventing deterioration, devitrification, and dissolution of resins and elastomers, and exhibits properties that make it a new cleaning composition that can be used to clean various vehicles, conveyances, and transportation facilities, such as automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railway vehicles, and ships, as well as tools, workshops, pits, and factories.

Furthermore, when a cleaning composition containing an HFO-based non-flammable fluorine-based solvent, an HFE-based non-flammable fluorine-based solvent, an HFC-based non-flammable fluorine-based solvent, or a PFC-based non-flammable fluorine-based solvent was further prepared by adding an alkoxyfluoroalkene, which is known to be capable of acting as a lubricant that reduces the coefficient of friction and reduces the braking force in important parts such as brake-related parts in various vehicles such as automobiles, motorcycles, construction machinery, agricultural machinery, aircraft, railway cars, and railroad cars, and which has now been confirmed to have no high compatibility with the oils and fats used in various vehicles, vehicles, and transport facilities, the composition surprisingly showed that , and the composition exhibits significantly better properties as a cleaning composition than before, by changing the blending ratio of the components constituting the composition to achieve the desired drying properties according to the scene of use while maintaining the properties of preventing resins and elastomers from being altered, devitrified, or dissolved, and by adjusting the drying speed, and the composition is found to be extremely useful as a new cleaning composition that exhibits suitable properties for use in cleaning various vehicles, vehicles, and transport means such as automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railway vehicles, and ships, as well as tools, workshops, pits, and factories. And, by further examining the combinations of the above-mentioned HFO-based non-flammable fluorine-based solvent and alkoxyfluoroalkene, and the HFO-based non-flammable fluorine-based solvent and the HFE-based non-flammable fluorine-based solvent, the HFC-based non-flammable fluorine-based solvent, or the PFC-based non-flammable fluorine-based solvent, and the alkoxyfluoroalkene, the invention of the new cleaning composition and the aerosol composition of the present application was completed.

The first means of the present invention for solving the above problems is a cleaning agent composition for cleaning various vehicles, conveyances, and transportation means such as automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railway vehicles, and ships, tools, workshops, pits, and factories, characterized by containing (A) an HFO-based non-flammable fluorine-based solvent, (B) one or more non-flammable fluorine-based solvents selected from the group consisting of HFE-based non-flammable fluorine-based solvents, HFC-based non-flammable fluorine-based solvents, and PFC-based non-flammable fluorine-based solvents, and (C) an alkoxyfluoroalkene.

The second aspect of the present invention to solve the above problems is the cleaning composition described in the first aspect of the present invention, characterized in that the cleaning composition is for use as a brake cleaner for various vehicles, conveyances, and transport means, such as automobiles, motorcycles, bicycles, construction machines, agricultural machines, aircraft, railway vehicles, and ships.

A third aspect of the present invention for solving the above problems is a composition comprising: a composition for producing a composition comprising: a composition for producing a composition having a mass ratio of component (A) to component (B) (component (A)/component (B)) of 99/1 to 1/99; and
The cleaning composition according to the first or second aspect of the present invention is characterized in that the mass ratio of the sum of the component (A) and the component (B) to the component (C), i.e., ((component (A)+component (B))/component (C)), is in the range of 99/1 to 1/99.

The fourth aspect of the present invention for solving the above problems is the cleaning composition according to any one of the first to third aspects of the present invention, characterized in that the HFO-based nonflammable fluorine-based solvent, component (A), is one or more selected from (Z)-1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene, 2,3,3-trichloro-3-fluoropropene, and AMOLEA (registered trademark) AS-300.

A fifth means of the present invention for solving the above problems is the cleaning agent composition according to any one of the first to third means of the present invention, characterized in that the HFE nonflammable fluorine-based solvent as component (B) is one or more selected from C ₄ F ₉ OCH ₃ , C ₃ F ₇ OCH ₃ , and 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane, the HFC nonflammable fluorine-based solvent as component (B) is one or more selected from 1,1,1,3,3-pentafluorobutane, and 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, and the PFC nonflammable fluorine-based solvent as component (B) is one or more selected from Fluorinert ^™ FC-40 and Fluorinert ^™ FC-3283.

The sixth aspect of the present invention for solving the above problems is the cleaning composition according to any one of the first to third aspects of the present invention, characterized in that the alkoxyfluoroalkene, component (C), is an alkoxyperfluoroalkene.

The seventh aspect of the present invention for solving the above problems is the cleaning composition according to any one of the first to third aspects of the present invention, characterized in that the alkoxy group of the alkoxyfluoroalkene, component (C), is an alkoxyfluoroalkene or alkoxyperfluoroalkene, which is a methoxy group or an ethoxy group.

The eighth aspect of the present invention for solving the above problems is the cleaning composition according to any one of the first to third aspects of the present invention, characterized in that the alkoxyfluoroalkene, component (C), is an alkoxyfluoroalkene having 5 to 8 carbon atoms.

The ninth aspect of the present invention for solving the above problems is the cleaning composition according to any one of the first to third aspects of the present invention, characterized in that the alkoxyfluoroalkene, component (C), contains one or more of methoxyperfluoropentene, methoxyperfluorohexene, methoxyperfluoroheptene, or methoxyperfluorooctene, or ethoxyperfluoropentene, ethoxyperfluorohexene, ethoxyperfluoroheptene, or ethoxyperfluorooctene, or an isomeric mixture thereof.

The tenth aspect of the present invention for solving the above problems is the cleaning composition according to any one of the first to third aspects of the present invention, characterized in that the alkoxyfluoroalkene, component (C), is methoxyperfluoroheptene or a mixture of its isomers.

The eleventh aspect of the present invention to solve the above problem is an aerosol composition containing the cleaning composition described in any one of the first to tenth aspects of the present invention and a propellant gas.

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

The thirteenth means of the present invention for solving the above problems is the aerosol composition according to the twelfth means of the present invention, characterized in that the propellant gas is _N2 .

Another aspect of the present invention to solve the above problems is a cleaning composition that contains a non-flammable HFO-based fluorine-based solvent and an alkoxyfluoroalkene.

The cleaning composition and aerosol composition of the present invention contain as their main components (A) a non-flammable HFO fluorine-based solvent and (B) one or more non-flammable fluorine-based solvents selected from the group consisting of non-flammable HFE fluorine-based solvents, non-flammable HFC fluorine-based solvents, and non-flammable PFC fluorine-based solvents. Both have no flash point and are non-flammable. Therefore, the risk of ignition and the risk of fire are low in the environment in which the cleaning composition and aerosol composition are used.

The main components, component (A) being a non-flammable HFO-based fluorine-based solvent, and component (B) being one or more non-flammable fluorine-based solvents selected from the group consisting of non-flammable HFE-based fluorine-based solvents, non-flammable HFC-based fluorine-based solvents, and non-flammable PFC-based fluorine-based solvents, are all non-hazardous materials under the Fire Service Act, so no hazardous materials warehouse is required and there are no legal restrictions on the storage volume of the cleaning composition when used in large quantities.

In addition, each of the above ingredients is low in toxicity and has a small environmental impact, such as ozone layer destruction, making it a product that is considerate of the human body and the environment. Furthermore, the cleaning agent composition and aerosol composition of the present invention have extremely excellent properties, such as being much less aggressive to rubber and resin than conventional brake cleaners while having cleaning properties that are comparable to those of conventional brake cleaners.

Furthermore, by blending the HFO-based non-flammable fluorine-based solvent as component (A) and one or more non-flammable fluorine-based solvents selected from the group consisting of HFE-based non-flammable fluorine-based solvents, HFC-based non-flammable fluorine-based solvents, or PFC-based non-flammable fluorine-based solvents as component (B), and further blending an alkoxyfluoroalkene as component (C) which is a non-flammable fluorine-based solvent that has no flash point, is non-flammable, has low toxicity, and has a small environmental impact such as ozone layer destruction, the resin or elastomer obtained by blending the components (A) and (B) retains the property of not being altered, devitrified, or dissolved, while exhibiting the desired drying property according to the usage scene, by changing the blending ratio of the components (A) + (B) and (C) constituting the composition, it is possible to adjust the drying speed, and the composition exhibits significantly superior properties as a cleaning composition compared to conventional ones.

The best mode for carrying out the present invention will be described below with reference to the table, along with the cleaning composition and aerosol composition of the present invention.

<About the main ingredients>
The main components of the cleaning composition and its aerosol composition of the present invention will be described. The cleaning composition and its aerosol composition of the present invention contain three components: (A) a non-flammable fluorine-based solvent of HFO, (B) one or more non-flammable fluorine-based solvents selected from the group consisting of non-flammable fluorine-based solvents of HFE, HFC and PFC, and (C) an alkoxyfluoroalkene.

The HFO-based non-flammable fluorine-based solvent, which is component (A), causes deterioration, devitrification, or dissolution of resins and elastomers (Non-Patent Document 1), so it is not recommended to use it as is as a component of a cleaning agent for products that use resins and elastomers.

The HFE-based non-flammable fluorine-based solvent, which is the above-mentioned component (B), does not have high compatibility with oils and fats because it does not contain chlorine molecules in its molecule, which are highly effective in expressing solubility in substances (Non-Patent Document 2). It is used as a solvent to dissolve silicone compounds used to reduce the friction coefficient of equipment and coat the silicone compounds on the surfaces of various objects such as metals and resins (Patent Document 2), so it is not applicable (Non-Patent Document 4) and is used as a solvent for lubricants (Patent Document 3). Therefore, it is not usually done to actively create a situation in which the lubricating component is applied or coated by the above-mentioned component (B) in brake-related parts of various vehicles, thereby reducing the friction coefficient and greatly reducing the braking force.

In addition, the HFC-based non-flammable fluorine-based solvent, which is the above-mentioned component (B), has a low KB value and low grease saturation power (Non-Patent Document 3), and is not applicable to degreasing and cleaning of automobile parts (Non-Patent Document 4). It is used as a solvent for lubricants (Patent Document 3). Therefore, it is not common to actively create a situation in which the lubricating component is applied or coated on brake-related parts of various vehicles, thereby lowering the friction coefficient and greatly reducing the braking force.

Furthermore, the PFC-based non-flammable fluorine-based solvent, which is component (B), has almost no compatibility with water or oil (Non-Patent Document 5), and is used as a fluorine-based coating agent to reduce friction in equipment, etc., and as a dilution solvent for lubricants (Non-Patent Document 6). Therefore, it is not common to actively create a situation in which the lubricating component is applied or coated on brake-related parts of various vehicles, thereby lowering the friction coefficient and greatly reducing the braking force.

However, when the HFO-based non-flammable fluorine-based solvent, which is component (A) and is unsuitable as a component for incorporation in such a cleaning composition, is mixed with one or more non-flammable fluorine-based solvents selected from the group consisting of HFE-based non-flammable fluorine-based solvents, HFC-based non-flammable fluorine-based solvents, and PFC-based non-flammable fluorine-based solvents, which are component (B) and have almost no oil saturation power or compatibility with water or oil and are suitably used as a solvent for lubricants, it has been revealed that, unexpectedly, the composition does not cause any effects such as deterioration, devitrification, or dissolution of resins and elastomers, and has a wider range of excellent cleaning properties than conventional cleaning compositions.

Alkoxyfluoroalkene, component (C), is preferably used as a solvent for lubricants that use fluorine grease (Patent Document 2), and should be actively avoided in creating a situation in which the lubricant component is applied or coated on brake-related parts in various vehicles, lowering the friction coefficient and creating a situation in which braking force is significantly reduced. Furthermore, as will be made clear in the test examples described below, it is not compatible with the oils and greases used in various vehicles and to be cleaned, and does not exhibit cleaning power. It can be said that it is unsuitable for a cleaning agent composition.

However, by further incorporating an alkoxyfluoroalkene, which is component (C) unsuitable for use in a cleaning composition, into a composition containing an HFO-based non-flammable fluorine-based solvent, which is component (A), and one or more non-flammable fluorine-based solvents selected from the group consisting of an HFE-based non-flammable fluorine-based solvent, an HFC-based non-flammable fluorine-based solvent, which is component (B), and which has a wider range of cleaning properties than conventional cleaning compositions, it has been revealed that, while retaining the characteristics of a cleaning composition containing both components (A) and (B) that does not cause deterioration, devitrification, or dissolution of resins and elastomers and provides a wider range of cleaning properties than conventional cleaning compositions, the composition ratio of the components that make up the composition has been changed, making it possible to adjust the drying speed so that the desired drying properties are achieved according to the situation of use, resulting in an extremely excellent cleaning composition.

Therefore, by incorporating as main components the HFO-based non-flammable fluorine-based solvent as component (A), one or more non-flammable fluorine-based solvents selected from the group consisting of HFE-based non-flammable fluorine-based solvents, HFC-based non-flammable fluorine-based solvents, and PFC-based non-flammable fluorine-based solvents as component (B), and an alkoxyfluoroalkene as component (C), it has become possible to provide a new cleaning composition and an aerosol composition thereof that have excellent properties that allow them to be used on a wider variety of materials while maintaining various safety features, and that have optimized drying properties to suit the situation of use.

<Regarding the HFO-based non-flammable fluorinated solvent, component (A)>
The cleaning composition and aerosol composition thereof according to the above-mentioned means of the present invention contain, as one of the three essential components, a non-flammable HFO-based fluorine-based solvent, which is a hydrofluoroolefin-based solvent. As the non-flammable HFO-based fluorine-based solvent, non-flammable solvents such as (Z)-1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene, 2,3,3-trichloro-3-fluoropropene, and AMOLEA (registered trademark) AS-300 can be used. These HFO-based nonflammable fluorine-based solvents can be used by, for example, obtaining commercially available products ((Z)-1-chloro-3,3,3-trifluoropropene (1233Z) (Central Glass Co., Ltd., Japan), 1,1-dichloro-3,3,3-trifluoropropene (Matrix Scientific, USA), AMOLEA (registered trademark) AS-300 (AGC Inc., Japan), etc.).

The HFO-based non-flammable fluorine-based solvent, which is component (A) above, is a non-flammable solvent that has 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 or essentially zero ozone depletion potential (ODP) and a global warming potential (GWP) of less than 1. Therefore, it does not fall under the category of ingredients specified in the Ozone Layer Protection Act, the Global Warming Countermeasures Promotion Act, the Fluorocarbons Emissions Control Act, the Fire Service Act, the High Pressure Gas Safety Act, etc., and there are no special restrictions on its use. No hazardous materials warehouse is required for storage, and there are no legal restrictions on the amount stored.

On the other hand, the HFO-based non-flammable fluorine-based solvent, which is the component (A), is aggressive to resins. Therefore, when the HFO-based non-flammable fluorine-based solvent, which is the component (A), such as (Z)-1-chloro-3,3,3-trifluoropropene or 1,1-dichloro-3,3,3-trifluoropropene, acts on soft polyvinyl chloride (PVC) resin or phenolic resin, the resin is altered, causing changes in the weight and dimensions of the resin product. Furthermore, when it acts on polycarbonate resin, it causes the resin to whiten and devitrify. Furthermore, when it acts on acrylic (PMMA) resin, ABS resin, which is a copolymer synthetic resin of acrylonitrile, butadiene, and styrene, or polystyrene resin, it softens or dissolves the resin. Thus, the HFO-based non-flammable fluorine-based solvent, which is the component (A), has poor compatibility with resin materials.

The HFO-based non-flammable fluorine-based solvent, component (A), is also aggressive to various elastomers. Therefore, when HFO-based non-flammable fluorine-based solvents, such as (Z)-1-chloro-3,3,3-trifluoropropene and 1,1-dichloro-3,3,3-trifluoropropene, act on SBR, chloroprene rubber, butyl rubber, EPDM and CSM, the elastomers are altered, causing changes in weight and dimensions. Furthermore, when they act on silicone rubber, natural rubber, HNBR, NBR, fluororubber and urethane rubber, the elastomers swell. Thus, the HFO-based non-flammable fluorine-based solvent, component (A), is poorly compatible with elastomers as is.

However, the above-mentioned properties of the HFO-based non-flammable fluorine-based solvent (A), such as poor resin compatibility and high drying speed, which are inappropriate for a cleaning composition used in various vehicles, vehicles, and transport means such as automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railway vehicles, and ships, are unexpectedly eliminated by adding one or more non-flammable fluorine-based solvents selected from the group consisting of HFE-based non-flammable fluorine-based solvents, HFC-based non-flammable fluorine-based solvents, and PFC-based non-flammable fluorine-based solvents, which are component (B) and have other properties that are inappropriate for a cleaning composition. Furthermore, even if component (A) and component (B) are further added with alkoxyfluoroalkene (C), which has other properties that are inappropriate for a cleaning composition, these properties are maintained, and by increasing the blending ratio of component (C), it is possible to slow down the drying speed, and an extremely excellent cleaning composition is provided in which the drying speed can be adjusted to achieve the desired drying property depending on the usage situation.

<Regarding the HFE-based non-flammable fluorine-based solvent, component (B)>
The cleaning composition and aerosol composition thereof according to the above-mentioned aspect of the present invention contain one or more HFE-based non-flammable fluorine-based solvents as one of the three essential components. The HFE-based fluorine-based solvents are non-flammable with no flash point and undetectable combustion points (lower limit) and undetectable combustion points (upper limit). They are classified as non-hazardous materials under the Fire Service Act, so no hazardous materials warehouse is required and there are no legal restrictions on the amount of storage.

On the other hand, non-flammable HFE fluorine-based solvents such as 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane do not contain chlorine atoms in their molecules, which are highly effective in expressing solubility in substances, and therefore do not have high compatibility with oils, fats, and solvents.

However, the inappropriate property of the HFE-based non-flammable fluorine-based solvent (B), which does not have high compatibility with oils and solvents, is unexpectedly eliminated by including an HFO-based non-flammable fluorine-based solvent (A), which has other properties that make it inappropriate for a cleaning composition to be used in various vehicles, conveyances, and transport means, and a superior cleaning composition is provided. Furthermore, even if an alkoxyfluoroalkene (C), which has other properties that make it inappropriate for a cleaning composition, is further included in components (A) and (B), this point is maintained, and by increasing the blending ratio of component (C), it is possible to slow down the drying speed, and an extremely superior cleaning composition is provided in which the drying speed can be adjusted to achieve the desired drying properties depending on the situation of use.

The nonflammable HFE fluorine-based solvent, which is component (B) in the cleaning composition and aerosol composition of the present invention, is one or more selected from C ₄ F ₉ OCH ₃ , C ₃ F ₇ OCH ₃ , and 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane. Preferably, one selected from C ₄ F ₉ OCH ₃ , C ₃ F ₇ OCH ₃ , and 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane, more preferably one selected from C ₄ F ₉ OCH ₃ or C ₃ F ₇ OCH _3, is used.

1,1,2,2-Tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane is a non-flammable fluorine-based HFE solvent, which is component (B), and can be obtained and used as a commercially available product under the name HFE-347pc-f or Asahiklin AE-3000 (AGC Inc., Japan). This solvent is a non-flammable solvent with no flash point (TCC, COC) or flammable range. It is classified as a non-hazardous material under the Fire Service Act, so no hazardous material warehouse is required and there are no legal restrictions on the amount stored.

In addition, the HFE-based non-flammable fluorine-based solvent C ₄ F ₉ OCH ₃ , which is the component (B), can be obtained and used as a commercially available product under the name of 3M ^™ NOVEC ^™ 7100 Highly Functional Liquid (3M Japan Ltd., Japan). This solvent is a non-flammable solvent with no flash point, and both the lower limit and the upper limit of the combustion point are undetectable. It is classified as a non-hazardous material under the Fire Service Act, does not require a hazardous material warehouse, and has no legal restrictions on the amount of storage. It also has an ozone depletion potential (ODP) of zero and has chemical properties that are environmentally friendly. Therefore, it does not fall under the Ozone Layer Protection Act or the Global Warming Countermeasures Promotion Act.

The HFE-based non-flammable fluorine-based solvent C ₃ F ₇ OCH ₃ , which is the component (B), can be obtained and used as a commercially available product under the name of 3M ^™ NOVEC ^™ 7000 Highly Functional Liquid (3M Japan Ltd., Japan). This solvent is a non-flammable solvent with no flash point, and both the lower limit and the upper limit of the combustion point are undetectable. It is classified as a non-hazardous material under the Fire Service Act, so no hazardous material warehouse is required, and there is no legal limit on the amount of storage. In addition, it has an ozone depletion potential (ODP) of zero, and has chemical properties that are environmentally friendly. Therefore, it does not fall under the Ozone Layer Protection Act or the Global Warming Countermeasures Promotion Act.

<Regarding the HFC-based non-flammable fluorinated solvent, component (B)>
The above-mentioned cleaning composition and aerosol composition thereof according to the present invention contain one or more HFC-based non-flammable fluorine-based solvents as one of the three essential components. The HFC-based fluorine-based solvents are non-flammable, with no flash point and undetectable combustion points (lower limit) and undetectable combustion points (upper limit). They are classified as non-hazardous materials under the Fire Service Act, so no hazardous materials warehouse is required and there are no legal restrictions on the amount of storage.

On the other hand, component (B), the HFC-based non-flammable fluorinated solvent, has a low KB value and low oil saturation power.

However, the HFC-based non-flammable fluorine-based solvent (B), which has a low KB value, low oil saturation power, and does not have high compatibility with oils and solvents, is unexpectedly eliminated by adding an HFO-based non-flammable fluorine-based solvent (A), which has other properties that are inappropriate for a cleaning composition used in various vehicles, conveyances, and transport means, to provide a superior cleaning composition. Furthermore, this point is maintained even if an alkoxyfluoroalkene (C), which has other properties that are inappropriate for a cleaning composition, is further added to components (A) and (B), and the drying speed can be slowed down by increasing the blending ratio of component (C), and an extremely superior cleaning composition is provided in which the drying speed can be adjusted to achieve the desired drying properties depending on the situation of use.

The non-flammable HFC fluorine-based solvent, which is component (B) in the cleaning composition and aerosol composition of the present invention, may be, for example, 1,1,1,3,3-pentafluorobutane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, or one or more selected from them.

1,1,1,3,3-pentafluorobutane is a non-flammable fluorine-based HFC solvent, which is component (B), and is available commercially under names such as Solkane 365 (Solvay Japan Co., Ltd., Japan). This solvent is non-flammable with no flash point (TCC, COC) and no flammable range. It is classified as a non-hazardous material under the Fire Service Act, so no hazardous material warehouse is required and there are no legal restrictions on the amount that can be stored.

1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane is a non-flammable fluorine-based HFC solvent, which is component (B), and can be purchased and used as Asahiklin AC-2000 (AGC, Japan) or other commercially available product. This solvent has no flash point (TCC, COC) and no flammable range, making it a non-flammable solvent. It is classified as a non-hazardous material under the Fire Service Act, so no hazardous material warehouse is required and there are no legal restrictions on the amount that can be stored.

<Regarding the PFC-based non-flammable fluorinated solvent, component (B)>
The cleaning agent composition and aerosol composition thereof according to the above-mentioned aspect of the present invention contain one or more PFC-based non-flammable fluorine-based solvents as one of the three essential components. The PFC-based fluorine-based solvents are non-flammable, having no flash point and undetectable combustion points (lower limit) and upper limit. They are classified as non-hazardous materials under the Fire Service Act, so no hazardous materials warehouse is required and there are no legal restrictions on the amount of storage.

On the other hand, the non-flammable fluorine-based solvent PFC, which is component (B), has almost no compatibility with water or oil.

However, the property of the PFC-based non-flammable fluorine-based solvent (B), which is almost incompatible with water and oil, making it unsuitable for a cleaning composition, is unexpectedly eliminated by including an HFO-based non-flammable fluorine-based solvent (A), which has other properties that make it unsuitable for a cleaning composition used in various vehicles, conveyances, and transport means, and a superior cleaning composition is provided. Furthermore, even if an alkoxyfluoroalkene (C), which has other properties that make it unsuitable for a cleaning composition, is further included in components (A) and (B), this point is maintained, and by increasing the blending ratio of component (C), it is possible to slow down the drying speed, and an extremely superior cleaning composition is provided in which the drying speed can be adjusted to achieve the desired drying properties depending on the situation of use.

As the PFC-based nonflammable fluorine-based solvent which is component (B) in the cleaning composition and aerosol composition thereof according to the present invention, for example, Fluorinert ^™ FC-40, Fluorinert ^™ FC-3283, or one or more selected from them may be used.

Fluorinert ^™ FC-40 and Fluorinert ^™ FC-3283, which are non-flammable PFC fluorine-based solvents, are available from 3M Japan Co., Ltd. (Japan) and can be used as such. This solvent is a non-flammable solvent with no flash point (TCC, COC) and no flammable range. It is classified as a non-hazardous material under the Fire Service Act, so no hazardous material warehouse is required and there are no legal restrictions on the amount of storage.

<Regarding the alkoxyfluoroalkene as component (C)>
The cleaning composition and the aerosol composition thereof according to the above-mentioned means of the present invention contain an alkoxyfluoroalkene as one of the three essential components.

Here, "alkoxy fluoroalkene" means a fluorinated olefin having an alkoxy group and a double bond. The alkoxy fluoroalkene includes alkoxy perfluoroalkene. Here, "alkoxy perfluoroalkene" means a perfluoroalkene having an alkoxy group. The alkoxy group of the alkoxy fluoroalkene includes those having 1 to 5 carbon atoms, and preferably those having 1 or 2 carbon atoms, such as methoxy or ethoxy groups. In addition, perfluoroalkene means a compound in which all hydrogen atoms in a hydrocarbon having one double bond are replaced with fluorine, and includes those having 2 to 10 carbon atoms, and preferably those having 5 to 8 carbon atoms. These alkoxy perfluoroalkenes include methoxy perfluoropentene, methoxy perfluorohexene, methoxy perfluoroheptene, or methoxy perfluorooctene, or ethoxy perfluoropentene, ethoxy perfluorohexene, ethoxy perfluoroheptene, or ethoxy perfluorooctene. For example, examples of the structure of methoxyperfluoroheptene include those shown below, but any of these structures may be used, and a mixture of these may also 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 above alkoxyfluoroalkene includes methoxyperfluoroheptene or its isomer mixture. This methoxyperfluoroheptene or its isomer mixture is non-flammable, with no flash point and undetectable lower and upper combustion points. It is classified as a non-hazardous material under the Fire Service Act, so no hazardous material warehouse is required and there are no legal restrictions on the amount that can be stored.

On the other hand, methoxyperfluoroheptene or a mixture of its isomers is not compatible with oils and fats such as grease, engine oil, and brake oil that are commonly used around the brakes of automobiles, etc., as described in the test examples disclosed below.

However, the characteristic of methoxyperfluoroheptene or its isomer mixture as an excellent solvent to form a lubricant and the characteristic of not having high compatibility with oils and solvents, which are inappropriate for a cleaning composition, are unexpectedly eliminated by containing both an HFO-based non-flammable fluorine-based solvent (A) and one or more non-flammable fluorine-based solvents selected from the group consisting of HFE-based non-flammable fluorine-based solvents, HFC-based non-flammable fluorine-based solvents, and PFC-based non-flammable fluorine-based solvents (B), which have other characteristics that are inappropriate for a cleaning composition to be used in various vehicles, vehicles, and transport systems, thereby providing a more excellent cleaning composition. Furthermore, even if an alkoxyfluoroalkene (C), which has other characteristics that are inappropriate for a cleaning composition, is further contained in the components (A) and (B), this point is maintained, and by increasing the blending ratio of the component (C), it is possible to slow down the drying speed, and an extremely excellent cleaning composition is provided in which the drying speed can be adjusted to exhibit the desired drying properties according to the use scene.

As the alkoxyfluoroalkene, which is the component (C) in the cleaning composition and the aerosol composition of the present invention, preferably, methoxyperfluoroheptene or an isomer mixture thereof is used. For example, as the isomer mixture of methoxyperfluoroheptene, which is an alkoxyfluoroalkene, Opteon ^™ SF10 (formerly called Vertrel (registered trademark) Supriorion) (Mitsui-DuPont Fluorochemicals Co., Ltd.) can be used.

Opteon ^™ SF10 is a non-flammable fluorine-based solvent that is commercially available from Mitsui DuPont Fluorochemicals Co., Ltd. and can be used. This solvent is non-flammable with no flash point (TCC, COC) and no flammable range. It is classified as a non-hazardous material under the Fire Service Act, so no hazardous material warehouse is required and there are no legal restrictions on the amount of storage. It has an ozone depletion potential (ODP) of 0 and a global warming potential (GWP) of less than 10.

<Regarding the mass ratio of the HFO-based nonflammable fluorine-based solvent as component (A), one or more nonflammable fluorine-based solvents selected from the group consisting of HFE-based nonflammable fluorine-based solvents, HFC-based nonflammable fluorine-based solvents, and PFC-based nonflammable fluorine-based solvents as component (B), and the alkoxyfluoroalkene as component (C)>
In the cleaning agent composition and aerosol composition thereof according to the present invention, taking into consideration the use for cleaning various vehicles, vehicles, and transport means, such as automobiles, motorcycles, bicycles, construction machines, agricultural machines, aircraft, railway vehicles, and ships, and for cleaning tools, work sites, pits, and factories used by workers, in addition to the property that the solvent is inherently nonflammable, it is preferable to adjust the range of the mass ratio of the three components contained therein, that is, the component (A) which is an HFO-based nonflammable fluorine-based solvent, the component (B) which is one or more nonflammable fluorine-based solvents selected from the group consisting of the component (A) which is an HFE-based nonflammable fluorine-based solvent, the component (B) which is an HFC-based nonflammable fluorine-based solvent, and the component (B) which is an PFC-based nonflammable fluorine-based solvent, to the component (C) which is an alkoxyfluoroalkene, so that the solvent has lower invasiveness to resins and elastomers, higher compatibility with oils and fats, and superior cleaning properties for members made of various materials, such as metals, resins, and elastomers, and an appropriate drying speed.

In order to have a combination of excellent properties, such as less invasiveness to resins and elastomers, higher compatibility with oils and fats, excellent cleaning ability for members made of various materials such as metals, resins, and elastomers, and an appropriate drying speed, the mass ratio of the HFO-based nonflammable fluorinated solvent as component (A) to one or more nonflammable fluorinated solvents selected from the group consisting of HFE-based nonflammable fluorinated solvents, HFC-based nonflammable fluorinated solvents, and PFC-based nonflammable fluorinated solvents as component (B) contained in the cleaning composition and aerosol composition of the present invention is in the range of 99/1 to 1/99, and further, the mass ratio of the component (A) + the component (B) to the alkoxyfluoroalkene as component (C) is in the range of 99/1 to 1/99. It is possible to provide a cleaning composition and an aerosol composition thereof in which the range of the mass ratio of the above component (A) to the above component (B) is adjusted in accordance with the type of oils and greases to be cleaned and the type of resin and elastomer used in combination in the site to be cleaned and the surrounding area to be prevented from invading, and further, the range of the mass ratio of the above component (A) + the above component (B) to the above component (C) is adjusted in accordance with the type of oils and greases to be cleaned and the surrounding area to be prevented from invading, and

For example, when the HFO-based nonflammable fluorine-based solvent as component (A) and the HFE-based nonflammable fluorine-based solvent as component (B) contained in the cleaning composition and aerosol composition of the present invention are 1,1-dichloro-3,3,3-trifluoropropene and C ₄ F ₉ OCH ₃ , the mass ratio of component (A) to component (B) (1,1-dichloro-3,3,3-trifluoropropene/C ₄ F ₉ OCH ₃ ) is in the range of 99/1 to 1/99, and preferably 99/1 to 10/90. In the case of (Z)-1-chloro-3,3,3-trifluoropropene and C ₄ F ₉ OCH ₃ , the mass ratio ((Z)-1-chloro-3,3,3-trifluoropropene/C ₄ F ₉ OCH ₃ ) is in the range of 50/50 to 99/1, and preferably 70/30 to 99/1. In the case of (Z)-1-chloro-3,3,3-trifluoropropene and C ₃ F ₇ OCH ₃ , the mass ratio ((Z)-1-chloro-3,3,3-trifluoropropene/C ₃ F ₇ OCH The range of _the ratio of (Z)-1-chloro-3,3,3-trifluoropropene to 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane is 50/50 to 99/1, preferably 80/20 to 99/1. In the case of (Z)-1-chloro-3,3,3-trifluoropropene and 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane, the mass ratio ((Z)-1-chloro-3,3,3-trifluoropropene/1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane) is 50/50 to 99/1, preferably 70/30 to 99/1. This makes it possible to have multiple excellent properties, such as less invasiveness to resins and elastomers, higher compatibility with oils and fats, excellent cleaning properties for members made of various materials such as metals, resins, and elastomers, and a moderate drying speed, and the like, and the composition can be suitably used as a cleaning agent composition and an aerosol composition thereof.

For example, in the case where the HFO-based non-flammable fluorine-based solvent, which is component (A) contained in the cleaning composition and aerosol composition thereof according to the present invention, is (Z)-1-chloro-3,3,3-trifluoropropene, and the HFC-based non-flammable fluorine-based solvent, which is component (B), is 1,1,1,3,3-pentafluorobutane or 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, the mass ratio (HFO-based non-flammable fluorine-based solvent/HFC-based non-flammable fluorine-based solvent) can be in the range of 99/1 to 1/99, preferably 99/1 to 10/90, and more preferably 90/10 to 30/70. However, in order to suit the usage conditions of the target customer, a suitable mass ratio can be selected from the above mass ratio range in accordance with the type of oil or fat to be dissolved and the type of resin or elastomer to be protected from attack, while also taking into account the cost balance. This makes it possible to combine multiple excellent properties, such as less invasiveness to resins and elastomers, higher compatibility with oils and fats, excellent cleaning properties for members made of various materials such as metals, resins, and elastomers, and an appropriate drying speed, making it suitable for use as a cleaning composition and an aerosol composition thereof.

For example, when the HFO nonflammable fluorinated solvent as component (A) contained in the cleaning composition and an aerosol composition thereof according to the present invention is (Z)-1-chloro-3,3,3-trifluoropropene and the PFC nonflammable fluorinated solvent as component (B) is Fluorinert ^™ FC-40 or Fluorinert ^™ FC-3283, the mass ratio (HFO nonflammable fluorinated solvent/PFC nonflammable fluorinated solvent) can be in the range of 99/1 to 1/99, preferably 99/1 to 10/90, and more preferably 90/10 to 30/70. However, a suitable mass ratio may be selected from the above ranges in accordance with the types of oils and fats to be dissolved and the types of resins and elastomers to be protected from attack, and in consideration of cost balance, so as to be suited to the usage conditions of the target customers. This makes it possible to provide a combination of excellent properties, such as less invasiveness to resins and elastomers, higher compatibility with oils and fats, excellent cleaning ability for members made of various materials such as metals, resins, and elastomers, and an appropriate drying speed, and the like, making the composition suitable for use as a cleaning agent composition and an aerosol composition thereof.

For example, when the three components contained in the cleaning composition and aerosol composition of the present invention are the above-mentioned component (A) which is a non-flammable fluorine-based solvent, and the above-mentioned component (B) which is one or more non-flammable fluorine-based solvents selected from the group consisting of HFE-based non-flammable fluorine-based solvents, HFC-based non-flammable fluorine-based solvents, or PFC-based non-flammable fluorine-based solvents, and the above-mentioned component (C) which is an alkoxyfluoroalkene is methoxyperfluoroheptene or a mixture of its isomers, the mass ratio ((component (A) + component (B))/alkoxyfluoroalkene) can be in the range of 99/1 to 1/99, preferably 99/1 to 10/90, and more preferably 90/10 to 20/80. However, in order to be suitable for the usage conditions of the target customer, a suitable ratio may be selected from the above-mentioned mass ratio range in accordance with the type of oil or fat to be dissolved and the type of resin or elastomer to be protected from invasion, while taking into consideration the cost balance. This allows the compound to have multiple properties including less aggressiveness to resins and elastomers, higher compatibility with oils and fats, and excellent cleaning properties for components made of various materials such as metals, resins, and elastomers. By adjusting the blending ratio of the alkoxyfluoroalkene, it is possible to achieve the desired drying speed, making the compound suitable for use as a cleaning composition and an aerosol composition thereof.

<Other ingredients>
The cleaning composition and aerosol composition thereof according to the present invention may further contain, as necessary, the above-mentioned three main components of the cleaning composition, to the extent that does not increase the risk of ignition or the risk of fire. When the above-mentioned additional components are contained, the cleaning composition and the aerosol composition thereof may further contain the above-mentioned additional components within a range that can maintain the characteristics of the cleaning composition, such as the non-flammable property of the HFO-based non-flammable fluorine-based solvent itself, the ability to clean oil and fat components, and the appropriate drying speed, while maintaining the non-flammable property of the cleaning composition or the non-hazardous property under the Fire Service Act. Examples of the components to be blended include alcohols, saturated hydrocarbons, unsaturated hydrocarbons, aromatic hydrocarbons, stabilizers, chelating agents, and the like. For example, HFE solvents such as 3M ^™ NOVEC ^™ 7200 and 3M ^™ NOVEC ^™ 7300; alcohols such as methanol, ethanol, isopropyl alcohol, and butanol; hydrocarbon solvents such as normal hexane, cyclohexane, and isohexane; ketone solvents such as acetone, MEK, and cyclohexanone; ethyl acetate, methyl acetate, butyl acetate, and ethylene glycol monomethyl ester. Ester and glycol ester solvents such as ether acetate, ether and glycol ether solvents such as methyl cellosolve, butyl cellosolve, methoxymethylbutanol, and hexyl diglycol, glyme solvents such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, chlorine solvents such as HCFC-141b, HCFC-225, 1-bromopropane, and chloroform, special solvents such as N-methyl-2-pyrrolidone, tetrahydrofuran, and dimethylformamide, and other solvents such as γ-butyrolactone, 1,3-dioxolane, and dimethylsulfoxide may be blended.

<Aerosol Composition>
The propellant gas in the aerosol composition may be a liquefied gas or a compressed gas. Examples of the propellant gas include LPG (liquefied petroleum gas), DME (dimethyl ether), carbon dioxide, fluorocarbon gas, (E)-1,3,3,3-tetrafluoroprop-1-ene, nitrogen gas, rare gases such as argon, compressed air, and combinations of two or more of the above gases, such as a mixture of LPG and DME, or a mixture of LPG and carbon dioxide. The cleaning agent composition of the present invention and the propellant gas described above are mixed to prepare an aerosol composition, which can be filled in a pressure-resistant can and provided.

<How to use>
The solution of the cleaning composition of the present invention can be applied to members of various materials such as metals, resins and elastomers of various vehicles, vehicles and transports such as automobiles, motorcycles, bicycles, construction machines, agricultural machines, aircraft, railway vehicles and ships, or tools, work sites, pits and factories used by workers, or can be used by immersing such objects in the solution of the cleaning composition. The cleaning composition of the present invention can be mixed with a liquefied gas as a propellant gas to prepare an aerosol composition, which is filled into a pressure can and aerosolized, or the cleaning composition of the present invention can be placed in a pail can, a mobile small filling machine is installed at the work site where it is used, and the cleaning composition in the pail can is aerosolized by compressed air, and the aerosol can be sprayed onto members of various materials such as metals, resins and elastomers, which are objects to be cleaned.

The following examples and test examples show the production and use of the cleaning composition of the present invention and its aerosol composition.

<About the test sample>
To prepare test samples, the ingredients used in the cleaning compositions of the present invention and conventional cleaning agents are purchased.
As the HFO-based nonflammable fluorine-based solvent, which is component (A) used in the cleaning composition of the present invention, (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 (registered trademark) AS-300 (HCFO-1233yd) was supplied by AGC Inc. (Japan). As the HFE-based nonflammable fluorine-based solvent 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane, which is component (B), Asahiklin AE-3000 (AGC Inc., Japan) was purchased, as the HFE-based nonflammable fluorine-based solvent C ₃ F ₇ OCH ₃ , which is component (B), 3M ^™ NOVEC ^™ 7000 High Performance Liquid (3M Japan Ltd., Japan) was purchased, and as the HFE-based nonflammable fluorine-based solvent C ₄ F ₉ OCH ₃ , which is component (B), 3M ^™ NOVEC ^™ 7100 High Performance Liquid (3M Japan Ltd., Japan) was purchased. As the HFC-based non-flammable fluorine-based solvent 1,1,1,3,3-pentafluorobutane, which is component (B), Solkane 365 (Solvay Japan Co., Ltd., Japan) was purchased, and as the HFC-based non-flammable fluorine-based solvent 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, which is component (B), Asahiklin AC-2000 (AGC Inc., Japan) was purchased. As the PFC-based non-flammable fluorine-based solvent, which is component (B), Fluorinert ^™ FC-40 (3M Japan Co., Ltd., Japan) or Fluorinert ^™ FC-3283 (3M Japan Co., Ltd., Japan) was purchased. As an example of the alkoxyfluoroalkene, which is the component (C), methoxyperfluoroheptene or a mixture of its isomers was used, and as an example thereof, Opteon ^™ SF10 (formerly known as Vertrel (registered trademark) Supriorion) (Mitsui-DuPont Fluorochemicals Co., Ltd.) was purchased.

As conventional cleaning agents, the quick-drying stock solution used was Brake & Parts Cleaner (quick-drying type) (Kobe Synthetic Co., Ltd., Japan), which uses isohexane, and the degreasing cleaning agent used was Degreasing Cleaner (Honda Access Co., Ltd., Japan), which uses cyclohexane. As normal-drying stock solutions, Brake Cleaner N04 (Suzuki Motor Co., Ltd., Japan), which is an isoparaffin-based solvent, and trichloroethane were purchased.

The cleaning compositions of the following examples were produced with the mass ratios of the above components (A) to (C) as follows:

<HFO-based non-flammable fluorine-based solvents/HFE-based non-flammable fluorine-based solvents>
Mass ratio (1233Z/NOVEC7100)
Example 1: 90/10
Example 2: 85/15
Example 3: 80/20
Example 4: 70/30
Example 5: 50/50
Example 6: 30/70
Example 7: 20/80
Example 8: 10/90

<HFO-based non-flammable fluorine-based solvents/HFE-based non-flammable fluorine-based solvents>
Mass ratio (1,1-dichloro-3,3,3-trifluoropropene/NOVEC7100)
Example 9: 90/10
Example 10: 80/20
Example 11: 70/30
Example 12: 50/50
Example 13: 30/70
Example 14: 20/80
Example 15: 10/90

<HFO-based non-flammable fluorine-based solvents/HFE-based non-flammable fluorine-based solvents>
Mass ratio (AS-300/NOVEC7100)
Example 16: 90/10
Example 17: 70/30
Example 18: 50/50
Example 19: 30/70
Example 20: 10/90

<HFO-based non-flammable fluorine-based solvents/HFE-based non-flammable fluorine-based solvents>
Mass ratio (1233Z/NOVEC7000)
Example 21: 95/5
Example 22: 90/10
Example 23: 80/20
Example 24: 70/30
Example 25: 50/50
Example 26: 30/70

<HFO-based non-flammable fluorine-based solvents/HFE-based non-flammable fluorine-based solvents>
Mass ratio (1233Z/AE-3000)
Example 27: 90/10
Example 28: 85/15
Example 29: 80/20
Example 30: 70/30
Example 31: 50/50
Example 32: 30/70

<HFO-based non-flammable fluorinated solvents/HFC-based non-flammable fluorinated solvents>
Mass ratio (1233Z/Solkane 365)
Example 33: 90/10
Example 34: 80/20
Example 35: 70/30
Example 36: 50/50
Example 37: 30/70
Example 38: 10/90

<HFO-based non-flammable fluorinated solvents/HFC-based non-flammable fluorinated solvents>
Mass ratio (1233Z/AC-2000)
Example 39: 90/10
Example 40: 80/20
Example 41: 70/30
Example 42: 50/50
Example 43: 30/70
Example 44: 10/90

<HFO-based non-flammable fluorine-based solvents/PFC-based non-flammable fluorine-based solvents>
Mass ratio (1233Z/Fluorinert ^™ FC-40)
Example 45: 90/10
Example 46: 80/20
Example 47: 70/30
Example 48: 60/40
Example 49: 50/50
Example 50: 30/70
Example 51: 10/90

Mass ratio (1233Z/Fluorinert ^™ FC-3283)
Example 52: 90/10
Example 53: 80/20
Example 54: 70/30
Example 55: 60/40
Example 56: 50/50
Example 57: 30/70
Example 58: 10/90

<HFO-based non-flammable fluorine-based solvents/alkoxyfluoroalkenes>
Mass ratio (1233Z/Opteon ^™ SF10)
Example 59: 90/10
Example 60: 80/20
Example 61: 70/30
Example 62: 60/40
Example 63: 50/50
Example 64: 40/60
Example 65: 30/70
Example 66: 20/80
Example 67: 10/90

<HFO-based non-flammable fluorine-based solvents/alkoxyfluoroalkenes>
Mass ratio (AS-300/Opteon ^™ SF10)
Example 68: 90/10
Example 69: 70/30
Example 70: 50/50
Example 71: 30/70
Example 72: 10/90

<HFO-based non-flammable fluorine-based solvents/HFE-based non-flammable fluorine-based solvents/alkoxyfluoroalkene>
Mass ratio (1233Z/NOVEC7100/Opteon ^™ SF10)
Example 73: 5/5/90
Example 74: 80/10/10
Example 75: 75/15/15
Example 76: 85/20/20
Example 77: 50/25/25
Example 78: 40/30/30
Example 79: 30/35/35
Example 80: 20/40/40
Example 81: 80/15/5
Example 82: 80/10/10
Example 83: 5/15/80
Example 84: 40/30/30
Example 85: 40/10/50
Example 86: 20/40/40
Example 87: 20/10/70

<HFO-based non-flammable fluorine-based solvents/HFE-based non-flammable fluorine-based solvents/alkoxyfluoroalkene>
Mass ratio (AS-300/NOVEC7100/ ^OpteonTM SF10)
Example 88: 30/30/40

In addition, the following Comparative Examples 1 to 4 were prepared. The quick-drying stock solution, the degreasing cleaner, and the normal-drying stock solution are all highly flammable, and trichloroethane is highly harmful, and all of these have problematic properties as cleaning compositions.
<Conventional product (flammable)>
Comparative Example 1: Quick-drying stock solution Comparative Example 2: Degreasing cleaner Comparative Example 3: Ambient-drying stock solution Comparative Example 4: Trichloroethane

Furthermore, the following comparative examples were prepared for comparison with the examples in which the components (A) to (C) were blended.
<HFO-based non-flammable fluorine-based solvents>
Comparative Example 5: 1233Z only Comparative Example 6: 1,1-dichloro-3,3,3-trifluoropropene only Comparative Example 7: AS-300 only <HFE-based non-flammable fluorine-based solvent>
Comparative Example 8: NOVEC 7100 only Comparative Example 9: NOVEC 7000 only Comparative Example 10: AE-3000 only <HFC-based non-flammable fluorine-based solvent>
Comparative Example 11: Solkane 365 only Comparative Example 12: AC-2000 only <PFC-based non-flammable fluorine-based solvent>
Comparative Example 13: Fluorinert ^™ FC-40 only Comparative Example 14: Fluorinert ^™ FC-3283 only <Alkoxyfluoroalkene>
Comparative Example 15: Opteon ^™ SF10 only

Next, the following test examples were carried out to specifically confirm that the cleaning agent composition and its aerosol composition of the present invention have superior properties compared to conventional cleaning agents.

Test Example 1: Evaluation of Invasiveness (Long-Term Contact)
Materials and Methods As test solutions, the solutions of the above-mentioned Examples and Comparative Examples are prepared.
In addition, in order to evaluate the invasiveness, the following test pieces are prepared.
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)
(All from Nippon Testpanel Co., Ltd.)

The weight of each test piece of the above rubber or resin (size 10 mm x 10 mm x 2 mm) is measured.
Next, 20 mL of the solution of the Example or Comparative Example was placed in a vial, and each of the above rubber or resin test pieces (size 10 mm x 10 mm x 2 mm) was immersed therein. The vial was then placed in a thermo-hygrostat (HPAV-120-40, Isuzu Corporation, Japan) set to 45°C and allowed to stand.
Each test piece is removed from the vial, and the surface condition is observed. The weight and thickness of the test piece are then measured, and the degree of swelling is calculated and confirmed to be within a range of ±5.0%, and also to confirm whether the transparency of the PC is lost.
When a small amount of solution is used, the test is performed using a test piece of a size and amount of liquid proportional to the amount used.

Test Results The results of the above tests are shown in the table below.

In Test Example 1, it was confirmed that a composition containing an HFO-based non-flammable fluorine-based solvent and an alkoxyfluoroalkene improves the aggressiveness of the HFO-based non-flammable fluorine-based solvent to rubber or resin. A comparative verification was then conducted with conventional cleaning agents in terms of their non-aggressiveness to rubber or resin.

HFO-based non-flammable fluorine-based solvents are aggressive to rubber and resins when used for long periods of time, and are particularly aggressive in swelling NR (natural rubber), SBR (styrene butadiene rubber), and EPDM (ethylene propylene rubber), which are widely used in important devices and parts to ensure the safety of various vehicles, conveyances, and transport facilities; dissolving and softening ABS (acrylonitrile butadiene styrene); and swelling, whitening, devitrification, and cracking of PC (polycarbonate). The extent of the deterioration of these rubbers and resins was such that the quality of the products could no longer be guaranteed (Table 1-1, etc.).

Furthermore, conventional cleaning agents are flammable to begin with, and when used on rubbers such as NR, CR, SBR, and EPDM, or resins such as ABS, LDPE (low density polyethylene), and PC, they are highly aggressive, making it impossible to guarantee the quality of the product (see Table 1-1, etc.).

However, by blending HFE-based non-flammable fluorine-based solvents, HFC-based non-flammable fluorine-based solvents, or PFC-based non-flammable fluorine-based solvents with HFO-based non-flammable fluorine-based solvents, it has surprisingly become possible to eliminate the swelling, dissolution, whitening, devitrification, and cracking of various rubbers and resins that were observed when using the above HFO-based non-flammable fluorine-based solvents (Tables 1-2 to 1-6, 1-8, 1-9, and 1-11).

In addition, it was surprisingly found that when an alkoxyfluoroalkene is added to an HFO-based non-flammable fluorine-based solvent, it is possible to eliminate the swelling, dissolution, whitening, devitrification, and cracking of various rubbers and resins that were observed when the above-mentioned HFO-based non-flammable fluorine-based solvent was used (Table 1-14 to Table 1-15).

Furthermore, it was revealed that, surprisingly, it is possible to eliminate the dissolution phenomenon observed with ABS by combining a non-flammable fluorinated solvent of HFO, a non-flammable fluorinated solvent of HFE, a non-flammable fluorinated solvent of HFC, or a non-flammable fluorinated solvent of PFC with an alkoxyfluoroalkene (see also Table 1-16).

The present invention, which can produce a cleaning composition with the new property of not being aggressive to various rubbers and resins commonly used in important devices and parts for ensuring the safety of various vehicles, conveyances, and transport systems, is understood to provide a very effective means for replacing conventional cleaning agents that have aggressive properties. It is also understood that the cleaning composition of the present invention has very little risk of aggressiveness to rubbers and resins even when used continuously for a long period of time.

In addition, while there is a limit to the amount of HFO-based non-flammable fluorine-based solvents that can be produced, the cleaning composition of the present invention is produced by mixing an HFO-based non-flammable fluorine-based solvent, an HFE-based non-flammable fluorine-based solvent, an HFC-based non-flammable fluorine-based solvent, or a PFC-based non-flammable fluorine-based solvent, with an alkoxyfluoroalkene, and therefore it is understood that this increases the amount of the cleaning composition that can be supplied and also has the effect of preventing delays in product supply.

Test Example 2: Evaluation of Invasiveness (Short-Term Contact)
Materials and Methods The solutions of the above-mentioned Examples and Comparative Examples are prepared in the same manner as in Test Example 1. In addition, the following test pieces are prepared in order to evaluate short-term invasiveness.
Resin: ABS (acrylonitrile butadiene styrene)
: PC (polycarbonate)
(All from Nippon Testpanel Co., Ltd.)

The surface of each of the above resin test pieces (size 10 mm x 10 mm x 2 mm) was wiped with a microfiber cloth soaked in the solution of Examples 1 to 18 or Comparative Examples 1 to 8. After that, the appearance of the surface of each test piece was checked visually and by touch. If there was no change in appearance, it was marked with an O, if there was a change, it was marked with an X, and the condition of the resin surface was recorded.

Test Results The results of the above tests are shown in the table below.

HFO-based non-flammable fluorine-based solvents, which are one of the main components used in the cleaning composition of the present invention, can alter resins such as ABS and PC even when they come into contact with the surface for only a short period of time, such as when wiping the surface with a microfiber cloth soaked in the solution (Table 2-1, etc.).

However, it has been revealed that by using a cleaning composition that combines a non-flammable fluorinated solvent such as an HFE, HFC, or PFC with a non-flammable fluorinated solvent such as an HFO, the resin does not deteriorate even after such short contact (Tables 2-2 to 2-6, 2-8, 2-9, 2-11, and 2-12).

It was also revealed that even when an alkoxyfluoroalkene is blended with an HFO-based non-flammable fluorine-based solvent, the resin does not deteriorate due to such short-term contact (Table 2-14, Table 2-15). Furthermore, it was also revealed that even when an HFO-based non-flammable fluorine-based solvent is blended with an HFE-based non-flammable fluorine-based solvent, an HFC-based non-flammable fluorine-based solvent, or a PFC-based non-flammable fluorine-based solvent, and then an alkoxyfluoroalkene is blended, the resin does not deteriorate due to such short-term contact. (Table 2-15).

<Test Example 3: Evaluation of compatibility with grease and oil>
Materials and Methods In the same manner as in Test Example 1, solutions of the Examples and Comparative Examples were prepared as test solutions.

As the oils and greases to be cleaned and removed, the following various types of greases and oils commonly used in automobiles, etc. are prepared.
Grease: GREASE (orange) (Kobe Synthetic Co., Ltd., Japan)
：Rubber and brake grease (Kobe Gosei Co., Ltd., Japan)
：Disc brake grease (Kobe Synthetic Co., Ltd., Japan)
：Brake grease (Kobe Gosei Co., Ltd., Japan)
：Silicone grease (Kobe Synthetic Co., Ltd., Japan)
：Caliper Pingris (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 Mobil1 0W-20 (ExxonMobil, USA)
: Brake fluid (DOT3) (Honda Access Co., Ltd., Japan)
: Brake fluid (DOT4) (Suzuki Motor Corporation, Japan)

Prepare a 10 mL vial for each solution and add 1 g of the grease or engine oil. Add 5 mL of the solution of the example or comparative example to the vial and close the lid of the vial. Ultrasonic treatment of each vial for 1 hour in an ultrasonic cleaner (AU16C, Aiwa Medical Industry Co., Ltd., Japan).
After one hour of ultrasonic treatment, each vial is removed from the ultrasonic cleaner. The inside of the vial is checked, and the compatibility is evaluated as follows: if the grease or engine oil and the solution of the Example or Comparative Example are completely mixed, it is marked as O; if they are partially separated, it is marked as △; if they are completely separated, it is marked as X. When a small amount of solution is used, the test is performed with an amount of liquid proportional to the amount used.

Test Results The results of the above tests are shown in the table below.

Various HFE-based non-flammable fluorine-based solvents have almost no compatibility with grease or brake oil (Comparative Examples 8 to 10 in Table 3-1), and are therefore unsuitable as cleaning agents for removing stains caused by oil and fat components such as grease or brake oil. In addition, although HFO-based non-flammable fluorine-based solvents have moderate compatibility, as is clear from the test results of Test Examples 1 and 2, they are aggressive to resins and elastomers and are therefore unsuitable for cleaning agent compositions used in various vehicles, conveyances, and transportation means. Thus, there is little motivation to add various HFE-based non-flammable fluorine-based solvents and HFO-based non-flammable fluorine-based solvents to cleaning agent compositions used in various vehicles, conveyances, and transportation means.

Various HFC-based non-flammable fluorine-based solvents have almost no compatibility with grease or brake oil (Comparative Examples 11 and 12 in Table 3-7), and are therefore unsuitable as cleaning agents for removing stains caused by oil and fat components such as grease or brake oil. In addition, although HFO-based non-flammable fluorine-based solvents have moderate compatibility, as is clear from the test results of Test Examples 1 and 2, they are aggressive to resins and elastomers and are therefore unsuitable for cleaning agent compositions used in various vehicles, conveyances, and transportation means. Thus, there is little motivation to add various HFO-based non-flammable fluorine-based solvents and HFC-based non-flammable fluorine-based solvents to cleaning agent compositions used in various vehicles, conveyances, and transportation means.

Various PFC-based non-flammable fluorine-based solvents have almost no compatibility with grease or brake oil (Comparative Examples 13 and 14 in Table 3-10), and are therefore unsuitable as cleaning agents for removing stains caused by oil and fat components such as grease or brake oil. In addition, HFO-based non-flammable fluorine-based solvents have moderate compatibility, but as is clear from the test results of Test Example 1, they are aggressive to resins and elastomers, and are therefore unsuitable for cleaning compositions used in various vehicles, conveyances, and transportation means. Thus, there is little motivation to add various HFO-based non-flammable fluorine-based solvents and PFC-based non-flammable fluorine-based solvents to cleaning compositions used in various vehicles, conveyances, and transportation means.

It was revealed that the alkoxyfluoroalkene used in the above test has almost no compatibility with grease or brake oil (Comparative Example 15 in Table 3-13). From this, it is understood that alkoxyfluoroalkenes are unsuitable as cleaning agents for removing stains caused by oil and fat components such as grease or brake oil. In addition, although HFO-based non-flammable fluorine-based solvents have moderate compatibility, as is clear from the test results of Test Examples 1 and 2, they are aggressive to resins and elastomers and are therefore unsuitable for cleaning agent compositions used in various vehicles, conveyances, and transportation means. Thus, there is no motivation to add various HFO-based non-flammable fluorine-based solvents and alkoxyfluoroalkenes to cleaning agent compositions used in various vehicles, conveyances, and transportation means.

However, it has now been revealed that when an HFO-based non-flammable fluorine-based solvent that cannot be used to clean vehicles, conveyances, or transport systems is mixed with an HFE-based non-flammable fluorine-based solvent, an HFC-based non-flammable fluorine-based solvent, or a PFC-based non-flammable fluorine-based solvent, it surprisingly exhibits a wide range of compatibility with oily and grease components such as grease or brake oil, that is, it exhibits high cleaning properties for these oily and grease components. Furthermore, even when an HFO-based non-flammable fluorine-based solvent is mixed with an HFE-based non-flammable fluorine-based solvent, an HFC-based non-flammable fluorine-based solvent, or a PFC-based non-flammable fluorine-based solvent, and further an alkoxyfluoroalkene is added, it surprisingly retains the characteristics of exhibiting a wide range of compatibility with oily and grease components such as grease or brake oil, and exhibiting high cleaning properties for these oily and grease components. In addition, the range of mass ratios of HFO-based non-flammable fluorine-based solvents and alkoxyfluoroalkenes that showed compatibility was also wide (Tables 3-2 to 3-6, Table 3-8, Table 3-9, Table 3-11, Table 3-12, Tables 3-14 to 3-17).

From this, it is understood that by making the cleaning composition and its aerosol composition contain an HFO-based non-flammable fluorine-based solvent, an HFE-based non-flammable fluorine-based solvent, an HFC-based non-flammable fluorine-based solvent, or a PFC-based non-flammable fluorine-based solvent, and further an alkoxyfluoroalkene, as in the means of the present invention, it is possible to provide a cleaning composition and its aerosol composition with characteristics suitable for the scene in which the cleaning composition is used, by adjusting the range of the mass ratio of each component according to the type of oil and fat to be cleaned and the type of resin and elastomer used in combination in the area to be cleaned and the surrounding area to be prevented from invasion.

In addition, conventional cleaning agents sometimes lacked compatibility with GREASE (orange) and rubber grease, but by combining an HFO-based non-flammable fluorinated solvent, which has almost no compatibility with GREASE (orange) or rubber grease, with an HFE-based non-flammable fluorinated solvent, an HFC-based non-flammable fluorinated solvent, or a PFC-based non-flammable fluorinated solvent, and further containing an alkoxyfluoroalkene, it has become clear that a new cleaning agent has been obtained that shows compatibility with GREASE (orange) and rubber grease even when the HFO-based non-flammable fluorinated solvent is diluted.

In this way, it is understood that by containing an HFO-based nonflammable fluorine-based solvent, an HFE-based nonflammable fluorine-based solvent, an HFC-based nonflammable fluorine-based solvent or a PFC-based nonflammable fluorine-based solvent, and further an alkoxyfluoroalkene in a cleaning composition as in the present invention, the cleaning composition exhibits a wide range of compatibility with grease or brake oil, and can provide a new cleaning agent composition that is nonflammable and low-toxic, yet has excellent cleaning properties equal to or greater than those of conventional brake cleaners.
Test Example 4: Evaluation of drying properties of cleaning composition
Materials and Methods As in Test Example 1, the solutions of the above-mentioned Examples and Comparative Examples were prepared.

A thermohygrostat (HPA V-120-40, Isuzu Manufacturing Co., Ltd., Japan) was set to temperature conditions of 45°C, 25°C, or 10°C and humidity of 70%, and a 2 cm flat plate was placed in it and left to stand. When the temperature of the flat plate became constant, 100 μL of the solutions of Examples 1, 3, 5, 7, and 9 and Comparative Examples 1 to 5 were placed in the flat plate, and the time until the droplets of each solution completely evaporated and dried from the flat plate was measured visually.

Test Results The results of the above tests are shown in the table below.

In a cleaning composition that is required to ensure good workability and safety, the optimal drying time is typically 1 to 2 minutes in a high temperature environment of 40°C, 2 to 3 minutes in a normal temperature environment of 25°C, and 3 to 4 minutes in a low temperature environment of 10°C. With conventional cleaning agents, only those with quick-drying concentrates have been able to achieve these conditions, and the others require excessive time to dry. However, although this type of quick-drying concentrate requires a short drying time, it is highly flammable and poses a problem in terms of ensuring the high safety required of a cleaning composition.

As was made clear in Test Example 3, the cleaning composition of the present invention, which contains the HFO-based non-flammable fluorine-based solvent as component (A), the HFE-based non-flammable fluorine-based solvent as component (B), and further contains the alkoxyfluoroalkene as component (C), is a non-flammable cleaning composition with excellent properties against oil and fat components. Therefore, we investigated what kind of drying time a cleaning composition containing the HFO-based non-flammable fluorine-based solvent as component (A), the HFE-based non-flammable fluorine-based solvent as component (B), and further contains the alkoxyfluoroalkene as component (C) could have.

As a result, it was found that HFO-based nonflammable fluorine-based solvents have a short drying time (Table 4-1), and the drying time of the HFO-based nonflammable fluorine-based solvent (Z)-1-chloro-3,3,3-trifluoropropene is slightly short, but when C ₄ F ₉ OCH ₃ (NOVEC ^™ 7100) or 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane (AE-3000) is used as the HFE-based nonflammable fluorine-based solvent, a cleaning composition that dries quickly can be obtained (Table 4-2, Table 4-3, Table 4-5). It was also found that when C ₃ F ₇ OCH ₃ (NOVEC ^™ 7000) is used, a cleaning composition that dries quickly can be obtained (Table 4-4). It was found that when Opteon ^™ SF10 is used as an isomer mixture of methoxyperfluoroheptene as an example of alkoxyfluoroalkene (C) to be contained together with HFO-based non-flammable fluorine-based solvent (A), the drying time is extended and a standard working time can be ensured. It was also confirmed that a cleaning composition having a longer drying time can be obtained by increasing the blending ratio of alkoxyfluoroalkene (C). The fact that a cleaning composition having a longer drying time can be obtained by increasing the blending ratio of alkoxyfluoroalkene (C) was also obtained when HFO-based non-flammable fluorine-based solvent (A) was blended with HFE-based non-flammable fluorine-based solvent (B) and further with alkoxyfluoroalkene (C) (Tables 4-7 to 4-10). It has become clear that the types of HFO-based nonflammable fluorine-based solvent as component (A), HFE-based nonflammable fluorine-based solvent as component (B), and alkoxyfluoroalkene as component (C), as well as the mass ratio of each of these components, can be adjusted to achieve the desired drying speed depending on the situation of use while maintaining excellent cleaning properties and the effect of reducing aggressiveness to rubber and resin.

By incorporating the HFO-based non-flammable fluorine-based solvent as component (A), one or more non-flammable fluorine-based solvents selected from the group consisting of HFE-based non-flammable fluorine-based solvents, HFC-based non-flammable fluorine-based solvents, and PFC-based non-flammable fluorine-based solvents as component (B), and an alkoxyfluoroalkene as component (C) in the cleaning composition, it is possible to provide a new cleaning composition and an aerosol composition thereof, which are non-flammable and therefore have low ignition risk and fire risk, are non-hazardous materials under the Fire Service Act, do not require a hazardous materials warehouse, and are not subject to legal restrictions on the storage amount of cleaning composition used in large quantities, are low in toxicity, and have low environmental impact such as ozone layer destruction, and have excellent properties such as extremely low attack on rubber and resin while having cleaning properties equal to or greater than conventional brake cleaner cleaning compositions, and have the mass ratio of components (A), (B), and (C) adjusted so as to have a desired drying speed according to the situation of use.

Claims (8)

a cleaning component (A) which is one or more HFO-based nonflammable fluorine-based solvents selected from (Z)-1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene, 2,3,3-trichloro-3-fluoropropene, and HCFO-1233yd;
a cleaning component (B) which is one or more non-flammable fluorine-based solvents selected from the group consisting of HFE-based non-flammable fluorine-based solvents, HFC-based non-flammable fluorine-based solvents, and PFC-based non-flammable fluorine-based solvents;
An alkoxyfluoroalkene as component (C) serving as a cleaning component;
The mass ratio of the component (A) to the component (B) (component (A)/component (B)) is in the range of 80/20 to 1/99; and
A method for cleaning various vehicles, conveyances, and transportation means, comprising a step of applying or spraying a detergent composition for cleaning various vehicles, conveyances, and transportation means , the detergent composition being characterized in that the mass ratio of component (A) + component (B) to component (C) ((component (A) + component (B))/component (C)) is in the range of 80/20 to 70/30, to the various vehicles, conveyances, and transportation means, or a step of immersing the various vehicles, conveyances, and transportation means in the detergent composition . a cleaning component (A) which is one or more HFO-based nonflammable fluorine-based solvents selected from (Z)-1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene, 2,3,3-trichloro-3-fluoropropene, and HCFO-1233yd;
a cleaning component (B) which is one or more non-flammable fluorine-based solvents selected from the group consisting of HFE-based non-flammable fluorine-based solvents, HFC-based non-flammable fluorine-based solvents, and PFC-based non-flammable fluorine-based solvents;
An alkoxyfluoroalkene as component (C) serving as a cleaning component;
The mass ratio of the component (A) to the component (B) (component (A)/component (B)) is in the range of 80/20 to 1/99; and
The mass ratio of the component (A) + the component (B) to the component (C) ((component (A) + component (B))/component (C)) is in the range of 80/20 to 70/30.
A method for cleaning various vehicles, conveyances, and transportation means, comprising a step of spraying an aerosol composition containing a cleaning agent composition for cleaning various vehicles, conveyances, and transportation means and a propellant gas onto the various vehicles, conveyances, and transportation means to clean them . The cleaning method according to claim 1 or 2, characterized in that the HFE-based nonflammable fluorine-based solvent as component (B) is one or more selected from C ₄ F ₉ OCH ₃ , C ₃ F ₇ OCH ₃ , and 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane, the HFC-based nonflammable fluorine-based solvent as component (B) is one or more selected from 1,1,1,3,3-pentafluorobutane and 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, and the PFC-based nonflammable fluorine-based solvent as component (B) is one or more selected from Fluorinert FC-40 and Fluorinert ^TM FC- 3283 . 3. The cleaning method according to claim 1, wherein the alkoxyfluoroalkene which is the component (C) is an alkoxyperfluoroalkene. 3. The cleaning method according to claim 1, wherein the alkoxy group of the alkoxyfluoroalkene which is the component (C) is an alkoxyfluoroalkene or an alkoxyperfluoroalkene in which the alkoxy group is a methoxy group or an ethoxy group. 3. The cleaning method according to claim 1, wherein the alkoxyfluoroalkene as component (C) is an alkoxyfluoroalkene having from 5 to 8 carbon atoms. 3. The cleaning method according to claim 1 or 2, characterized in that the alkoxyfluoroalkene of component (C) contains at least one of methoxyperfluoropentene, methoxyperfluorohexene, methoxyperfluoroheptene, methoxyperfluorooctene, ethoxyperfluoropentene, ethoxyperfluorohexene, ethoxyperfluoroheptene, ethoxyperfluorooctene, or an isomer mixture thereof. 3. The cleaning method according to claim 2 , characterized in that the propellant gas is N ₂ , CO ₂ , (E)-1,3,3,3-tetrafluoroprop-1-ene, argon, LPG, DME or compressed air.