WO2019093396A1

WO2019093396A1 - Detergent composition and aerosol composition thereof

Info

Publication number: WO2019093396A1
Application number: PCT/JP2018/041413
Authority: WO
Inventors: 督修宮岡; 祐士宮岡
Original assignee: 神戸合成株式会社
Priority date: 2017-11-07
Filing date: 2018-11-07
Publication date: 2019-05-16
Also published as: JP2023110009A; JP7388701B2; JP2022081551A; JPWO2019093396A1

Abstract

The purpose of the present invention is to provide a novel detergent composition with very low attacking properties to rubbers and resins and a desirable drying rate, while still having characteristics of being non-flammable and therefore exhibiting a low risk of ignition and a low risk during a fire; corresponding to a nonhazardous substance under the Fire Service Act; not requiring a hazardous materials warehouse for storage; not being under legal restrictions on the amount of storage of the detergent composition intended to be used in large quantities, and having low toxicity and little environmental load, e.g., ozone layer destruction, as well as exhibiting equivalent cleaning performance to conventional detergent compositions for brake cleaners. Provided is a detergent composition and an aerosol composition thereof. The detergent composition comprises (A) an HFO-type inflammable fluorinated solvent; (B) at least one inflammable fluorinated solvent selected from the group consisting of HFE-type inflammable fluorinated solvents, HFC-type inflammable fluorinated solvents, or PFC-type inflammable fluorinated solvents; and (C) an alkoxyfluoroalkene.

Description

Cleaner composition and aerosol composition thereof

This invention is a new cleaning method for cleaning of various vehicles, vehicles and vehicles such as automobiles, bicycles, construction machines, agricultural machines, aircraft, railway vehicles and ships, tools for cleaning, work places, pits and factories. Agent composition and its aerosol composition, in particular, various vehicle parts such as a body, a brake part, a suspension, a wheel, etc., and a control device, etc. consisting of a combination of metal, metal and resin in various vehicles, vehicles and vehicles A cleaning agent that is used for degreasing and cleaning, and is used as a non-combustible, low risk of fire and fire hazard, and non-hazardous material under the Fire Service Law because it is not necessary to store in a dangerous goods warehouse. There is no legal limitation on the storage amount of the composition, moreover, it has excellent properties such as low toxicity and low environmental impact such as ozone layer depletion, and is equal to or more than the conventional cleaning agent composition While having the cleaning property and the anti-redeposition property of dirt, the attack property to rubber and resin is extremely lower than that of the conventional cleaning agent composition, and further, the desired drying property is exhibited according to the use scene In addition, the present invention relates to a cleaning agent composition and its aerosol composition, which also have the excellent property that the drying rate can be adjusted by changing the blending ratio of the components constituting the composition.

Automobiles, two-wheeled vehicles, bicycles, construction machines, agricultural machines, aircrafts, railway vehicles, various vehicles such as ships, vehicles, vehicles, transportation, various parts and devices such as body, brakes, suspensions, wheels, etc., metal and various resins And so on. Further, in recent years, a member using a composite material or the like in which a resin is combined with a metal is also used in order to improve weight reduction and decorativeness.

Parts and devices using these metals will have oil and dirt adhering to their surfaces during use, and their desired performance and decorativeness will deteriorate. Also, depending on the deposited components, the metal surface may be corroded, and the desired performance may be irreversibly impaired. Furthermore, oil components such as grease are applied to necessary parts of vehicles, vehicles and vehicles to smooth the movement of each device, but such oil components are sprayed with air flow and rain water when traveling, etc. As a result, oil gradually drains off to unintended areas, and oil from other vehicles, vehicles and vehicles is also rolled up from the road surface with dirt, etc., and adheres to parts of vehicles, vehicles and vehicles. This is a factor that lowers the expected performance of various parts and devices. In particular, in the case of a friction brake device in which a brake shoe having a brake lining, which is often used in vehicles, vehicles, and transport engines, acts as a brake on a rotating body such as a brake disc or brake drum, the friction coefficient decreases when oil adheres. Furthermore, the brake lining is worn out and dust generated is apt to be attached, which causes the braking performance of the brake to deteriorate. Therefore, maintenance work is carried out regularly, and metal components to which oil and dirt are attached Need to wash.

In addition, when assembling and manufacturing resin, paint, etc. on metal at the time of assembly manufacture of various vehicles, vehicles, and transportations, if oil and the like remain slightly attached to the metal surface, resin, paint, etc. The quality of the product is greatly reduced by peeling or degenerating without stable adhesion. In addition, in parts and devices that are particularly important for ensuring safety during operation such as brakes, suspensions, and wheels, the coefficient of friction decreases if oil etc. is slightly attached, and if assembled as it is, the braking performance is It will be lost and it will not be possible to exhibit desired performance stably. Therefore, at the time of assembly and manufacture of vehicles, vehicles and vehicles, it is required to sufficiently clean and remove in advance the oil that slightly adheres to the metal surface of each part.

Therefore, as a cleaning agent composition for mainly cleaning the bodies, brake parts, suspensions, wheels and the like of various vehicles, vehicles and vehicles, those mainly composed of trichloroethane having a cleaning property have conventionally been developed and used. It had been. However, trichloroethane is known to be toxic. In addition, in the Montreal Protocol on Substances that Deplete the Ozone Layer, which came into effect under the Vienna Convention for the Protection of the Ozone Layer, trichloroethane will gradually reduce its production and consumption in the contracting countries and eliminate it completely in 1996. Import or export with other non- contracting parties has been banned or restricted. Therefore, the use of detergent compositions using trichloroethane has been avoided.

Therefore, based on C6 petroleum hydrocarbons such as isohexane and cyclohexane, alcohols such as ethanol and isopropyl alcohol are added to produce a detergent composition having adjusted washability, dryness and boiling point, which is then added to LPG There has been proposed and widely used an aerosol composition using a gas and an aerosol composition using compressed air using a mobile simple aerosol filling machine.

However, petroleum hydrocarbons and alcohols used in the above-mentioned detergent composition are highly flammable and are regulated as dangerous materials under the Fire Service Law. Therefore, the storage of the dangerous goods needed to be stored, and the cost for the installation was high. Moreover, even if it has a hazardous material warehouse in a cleaning composition using facility, the amount that can be stored is limited. In particular, although the above-mentioned detergent composition is mostly classified into Class 4 First Petroleum, the designated quantity of Class 4 Petroleum 1 that can be stored in a single warehouse is set low. However, there is a problem that only a small amount can be stored despite the use of a large amount of the detergent composition, and an improvement thereof has been required.

Furthermore, although the hydrocarbon used in the above-mentioned detergent composition is not toxic like trichloroethane, there is a risk of becoming a hydrocarbon poison by inhaling an excessive amount, so outdoor, indoor with ventilation system etc. It is necessary to use in the environment where there is ventilation, and the product also has a note on that effect. However, because aerosol products are used, vaporized hydrocarbons flow not only in the work place but also in the downwind, and there is still a risk of inhalation by the people there, and improvements have been sought.

In addition, when the cleaning composition is poured over the work or the aerosol product is vigorously jetted, a large amount of the cleaning composition having high flammable properties may be infiltrated into gloves and clothes of the worker. In addition, in order to remove oil stains attached to gloves and work clothes of workers, the above-mentioned detergent composition may be heavily impregnated. However, since the above-mentioned detergent composition is highly flammable, if the subsequent drying is insufficient, there is a risk that an ignition accident due to static electricity or cigarette fire may occur. Therefore, improvements have been sought to avoid the use of these highly flammable ingredients, even in order to ensure reliable safety in the working environment.

Halogenated solvents are generally well known as solvents having no flash point, but chlorine solvents and bromine solvents are limited in production and use because of their harmful effects, and their use in detergent compositions Is accompanied by difficulties. Therefore, as a solution to the problem of storage volume and securing safety, products with high flash point using petroleum hydrocarbon with long carbon number and water-based products containing carbitol, alcohol etc. as cleaning components are proposed (See Patent Document 1).

However, the water-based composition described above takes very long time to dry, for example, it takes 30 to 40 minutes to dry (see Patent Document 1). Therefore, when such aqueous compositions are used as detergent compositions, the liquid of the aqueous composition tends to remain around the brake after use, and if the brake is used while the liquid remains, the braking force decreases. It leads to having a serious influence. Therefore, in the working process using the above-mentioned aqueous composition, it is essential to perform sufficient drying after washing, which is complicated and an improvement is required. Furthermore, because they are water-based, they are inferior to the conventional cleaner compositions for cleaning with a brake cleaner, and depending on the type of dirt, they do not necessarily have sufficient cleaning performance, and their use is limited. Improvements were sought to be more versatile.

By the way, as a solvent that can be used to wash metal materials, HFO-based nonflammable fluorine-based solvents that are hydrofluoroolefin-based solvents such as (Z) -1-chloro-3,3,3-trifluoropropene It has been known. However, it is known that this HFO-based nonflammable fluorine-based solvent has a cleaning property to metal materials, but has a strong erosion property to resins and elastomers which are materials other than metal materials. (Non-Patent Document 1). Therefore, such HFO-based nonflammable fluorine-based solvents need to be thoroughly scrutinized for their use.

In particular, it is important to keep safety high in various braking devices, lights, windows, etc. in various vehicles, vehicles, vehicles such as cars, bicycles, construction machines, agricultural machines, aircrafts, railway vehicles, ships, etc. In parts, metal materials are generally used, but in addition to the metal materials, various materials such as polycarbonate, acrylic, ABS, polystyrene, silicone rubber, natural rubber, HNBR, NBR, fluorine rubber and urethane rubber are generally used. Materials made of resin and elastomer are also used at the same time. For example, the brakes are controlled by the hydraulic pressure of the brake fluid, which is generally filled in a rubber hose connecting the devices.

However, if the above HFO-based nonflammable fluorine-based solvent comes in contact with a resin or elastomer, it is an important part that is required to maintain high safety due to the strong erosion property of the above HFO-based nonflammable fluorine-based solvent. Serious problems such as deterioration of resin and elastomer in the In particular, polycarbonate commonly used in important parts of vehicles, vehicles and vehicles devitrifies, acrylic, ABS and polystyrene dissolve, and silicone rubber, natural rubber, HNBR, NBR, fluororubber and urethane rubber swell (Non-Patent Document 1), there is a concern that safety may be reduced.

And when using as a composition for washing | cleaning, it is required to fully wet and wash away the location which it is going to wash | clean with the composition for washing | cleaning, However, since said HFO-based nonflammable fluorine-type solvent is low boiling point It is very dry and not suitable for wet and rinse steps. When it is made to be wet, the excessive loss of HFO-based nonflammable fluorine-based solvent may cause a decrease in safety by touching the resin or elastomer in important parts.

HFE (hydrofluoroether) -based fluorinated solvents include 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane (AE3000 / HFE-347pc-f) . However, it is known that the compound does not have high compatibility with oils and fats because it does not contain a chlorine molecule having a high effect of expressing solubility in a substance in the molecule (Non-patent Document 2). . In addition, 1,1,2,2-tetrafluoro- as a solvent for dissolving the silicone compound used to reduce the coefficient of friction of the device and coating the silicone compound on the surface of various articles such as metals and resins. It is known that 1- (2,2,2-trifluoroethoxy) ethane is mixed with (Z) -1-chloro-3,3,3-trifluoropropene (Patent Document 2). It is possible to daringly coat a silicone compound that will lower the coefficient of friction and greatly reduce the braking force of various parts of the vehicle such as motorcycles, construction machines, agricultural machines, aircraft, railway vehicles and railway vehicles. It does not happen.

As a HFC (hydrofluorocarbon) -based fluorine-based solvent, 1,1,1,3,3-pentafluorobutane (Solkane 365) or 1,1,1,2,2,3,3,4,4,5,5 There are 5,6,6-tridecafluorohexane (AC-2000) etc., but low KB value has low oil saturation power (Non-patent document 3), and degreasing and cleaning of automobile parts is not applicable Patent Document 4). In addition, it is used as a solvent for lubricants such as fluorine oil, fluorine grease, silicone oil and silicone grease to reduce friction in equipment etc. (Patent Document 3), but it is an automobile, two-wheeled vehicle, construction machine, agricultural machine, aircraft In the brake-related parts of various vehicles such as railway cars and railway cars, the friction coefficient is lowered and the braking force is greatly reduced by creating a situation where those lubricating components are applied and coated. Absent.

PFC The nonflammable fluorine-based solvent (perfluorocarbon) system, Fluorinert ^TM FC-40 and Fluorinert ^TM FC-3283 there are such, compatibility is little to water and oil (Non-Patent Document 5). In addition, these PFC nonflammable fluorine-based solvents are used as a fluorine-based coating agent for reducing friction in equipment and the like, and as a dilution solvent for lubricants (Non-Patent Document 6), but they are automobiles, two-wheeled vehicles, In the brake-related parts of various types of vehicles such as aircraft, agricultural machines, aircraft, railway vehicles, and railway vehicles, the coefficient of friction is reduced by creating a situation where the components that reduce the friction are applied and coated, and the braking force is greatly increased. Nothing is done to reduce it.

Other fluorine-based solvent, alkoxy fluoroalkene are known, or methoxy perfluoro-heptene as an example, Oputeon ^TM SF10 its isomer mixture (formerly Vertrel (R) soup Rion) (Dupont-Mitsui Fluorochemical Co., Ltd.). The Oputeon ^TM SF10 is is preferably used in a solvent of the lubricant using fluorine grease (Patent Document 4), an automobile, motorcycle, construction machinery, agricultural machinery, aircraft, railroad vehicles, brakes in various vehicles such as rail vehicles In the related parts and the like, there is no such thing as lowering the coefficient of friction and greatly reducing the braking force by creating a situation where these lubricating components are applied and coated.

JP, 2001-207199, A Patent No. 5648345 gazette International Publication No. 2013/161723 JP, 2017-115099, A

The problems to be solved by the present invention are non-combustible, so there is low risk of ignition and low risk at the time of fire, falls under non-hazardous material under the Fire Service Act, does not require dangerous material storage, and is used in large quantities There is no legal restriction on the storage amount of the cleaning composition, and furthermore, it has the characteristics of low toxicity, low environmental impact such as ozone layer depletion, and the like, and the same cleaning performance as the conventional cleaning composition. The components that make up the composition to have a very low attack on rubber and resin than conventional detergent compositions, and still exhibit the desired dryness according to the usage It is an object of the present invention to provide a new cleaning composition and its aerosol composition, which can adjust the drying rate by changing the composition ratio of

Since the detergent composition is used for the operation of wetting and washing away dirt components, the amount of use and storage amount increase. Therefore, it is required to greatly reduce the risk of fire due to ignition by selecting a solvent having no flash point and no combustion range under temperature conditions of normal use environment and storage environment.

Also, in washing, it is required to wet and wash away the dirt component with the detergent composition. Therefore, the cleaning composition can be provided not only as a solution to be used by application or immersion but also as an aerosol composition containing a cleaning agent composition and a propellant gas, and the handling at the time of cleaning is simplified. In addition, it is necessary to use gas pressure to make it easier to physically remove dirt. In the case of providing as an aerosol composition, it is required to select a less toxic solvent for the cleaning composition, because the risk of the operator to inhale is increased.

And, it has the same or higher washability as conventional products not achieved with high flash point products and water-based products, and furthermore, it should be appropriate to exert the desired dryness according to the use situation. There is a need to provide something that is easily realized.

The inventor of the present application has been working to confirm the physical properties possessed by various compounds and compositions, and to investigate their cleaning properties, in order to provide a new detergent composition and an aerosol composition thereof that solve the above-mentioned problems. The Among them, important parts such as automobiles, motorcycles, bicycles, construction machines, agricultural machines, aircraft, railway vehicles, various vehicles such as ships, transportation vehicles, etc. which are required to keep safety high due to strong erosion. , HFO-based nonflammable fluorine-based solvents known to cause serious defects such as deterioration, devitrification and dissolution of resins and elastomers used in tools, work places, pits and factories used by workers. HFE is known to be able to reduce the braking force by reducing the coefficient of friction in important parts such as brake related parts in various vehicles such as automobiles, two-wheeled vehicles, construction machines, agricultural machines, aircrafts, railway vehicles and railway vehicles. Hydrofluoroether-based fluorinated solvents, HFC (hydrofluorocarbons) -based fluorinated solvents or PFC (perfluorocarbons) When used as a composition added with a non-combustible fluorine-based solvent, it exhibits the characteristics as a cleaning composition superior to the conventional ones, such as resin, elastomer, etc. not being degraded, devitrified or dissolved. Demonstrate the characteristics as a new cleaning composition used to clean various vehicles, vehicles, vehicles, vehicles such as motorcycles, bicycles, construction machines, agricultural machines, aircraft, railway vehicles and ships, vehicles and vehicles, work places, pits and factories Found out.

Furthermore, to a cleaning composition further comprising a HFO-based nonflammable fluorine-based solvent, and an HFE-based nonflammable fluorine-based solvent, an HFC-based nonflammable fluorine-based solvent, or a PFC-based nonflammable fluorine-based solvent It is known that it can be a lubricant that lowers the coefficient of friction in important parts such as brake-related parts in various vehicles such as automobiles, two-wheeled vehicles, construction machines, agricultural machines, aircraft, railway vehicles, and railway vehicles and reduces braking force. And, when it was made into the composition which added the alkoxy fluoro alkene which was confirmed that it does not have high compatibility with fats and oils used in various vehicles, vehicles, and transportation vehicles this time, the resin and elastomer are surprisingly deteriorated. And a composition for forming a composition so as to exhibit a desired dryness according to the usage while maintaining the characteristics that cause no devitrification and dissolution. The composition of the present invention can exhibit the characteristics as a cleaning composition significantly superior to the prior art, which makes it possible to adjust the drying rate by changing the compounding ratio of As a new cleaning composition that exhibits properties suitable for use in cleaning vehicles, vehicles, vehicles, vehicles, vehicles, vehicles, vehicles, vehicles, vehicles, vehicles, vehicles, vehicles, vehicles, vehicles, vehicles, vehicles, etc. It was found to be extremely useful. And the above HFO nonflammable fluorine-based solvent and alkoxy fluoroalkene, HFO nonflammable fluorine solvent, HFE nonflammable fluorine solvent, HFC nonflammable fluorine solvent or PFC nonflammable The invention of the new cleaning composition of the present application and its aerosol composition has been completed by examining in detail the combination of the fluorinated fluorine-based solvent and the alkoxy fluoroalkene.

The first means of the present invention for solving the above problems is a HFO-based nonflammable fluorine-based solvent as the component (A), an HFE-based nonflammable fluorine-based solvent as the component (B), and an HFC-based solvent. Characterized by containing at least one nonflammable fluorine-based solvent selected from the group consisting of nonflammable fluorine-based solvents of the above or non-combustible fluorinated solvents of the PFC type, and alkoxyfluoroalkene which is the component (C). It is a cleaning composition for cleaning vehicles, vehicles, bicycles, construction machines, agricultural machines, aircrafts, railway vehicles, various vehicles such as ships, vehicles, vehicles, work places, pits, and factories.

The second means of the present invention for solving the above-mentioned problems is that the cleaning agent composition comprises various vehicles, vehicles, transportation vehicles such as automobiles, two-wheeled vehicles, bicycles, construction machines, agricultural machines, aircrafts, railway vehicles, ships, etc. The cleaning composition according to the first means of the present invention, which is for a brake cleaner of

The third means of the present invention for solving the above problems is characterized in that the mass ratio of the component (A) to the component (B) (component (A) / component (B)) is 99/1 to 1/1. 99, and
The range of the mass ratio of (A) component + (B) component to (C) component (((A) component + (B) component) / (C) component) is 99/1 to 1/99 It is a detergent composition according to the first means or the second means of the present invention, which is characterized.

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

The fifth means of the present invention for solving the above-mentioned problems is characterized in that the HFE-based nonflammable fluorine-based solvent which is the component (B) is C ₄ F ₉ OCH ₃ , C ₃ F ₇ OCH ₃ , and 1 , 1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane, one or more non-combustible fluorocarbon solvents of the HFC type which is the component (B) Is 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 one or more that, the (B) PFC-based nonflammable fluorine-based solvent is a component, is one or more selected from Fluorinert ^TM FC-40, and Fluorinert ^TM FC-3283 What is characterized by the first to third aspects of the present invention A detergent composition according to one of the means.

The sixth means of the present invention for solving the above-mentioned problems is characterized in that the alkoxyfluoroalkene which is the component (C) is an alkoxyperfluoroalkene. It is a detergent composition as described in any one means.

A seventh means of the present invention for solving the above problems is that the alkoxy group of the alkoxy fluoroalkene which is the component (C) contains an alkoxy fluoro alken or alkoxy perfluoro alken which is a methoxy group or an ethoxy group. It is a detergent composition according to any one of the first to third means of the present invention, characterized in that

The eighth means of the present invention for solving the above-mentioned problems is characterized in that the alkoxyfluoroalkene which is the component (C) is an alkoxyfluoroalkene having 5 to 8 carbon atoms. It is a detergent composition according to any one of the first to third means of the invention.

A ninth means of the present invention for solving the above-mentioned problems is that the alkoxyfluoroalkene which is the component (C) is methoxyperfluoropentene, methoxyperfluorohexacene, methoxyperfluoroheptene or methoxyperfluorofluorene. The present invention is characterized by containing octene or any one or more of ethoxyperfluoropentene, ethoxyperfluorohexene, ethoxyperfluoroheptene or ethoxyperfluorooctene, or a mixture of isomers thereof. The cleaning composition according to any one of the first to third means of the present invention.

The tenth means of the present invention for solving the above-mentioned problems is characterized in that the alkoxyfluoroalkene which is the component (C) is methoxyperfluoroheptene or a mixture of isomers thereof. It is the cleaning composition according to any one of the first to third means.

An eleventh means of the present invention for solving the above-mentioned problems is an aerosol composition comprising the cleaning composition according to any one of the first to tenth means of the present invention and a propellant gas. It is.

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

A thirteenth means of the present invention for solving the above-mentioned problems is the aerosol composition according to the twelfth means of the present invention, characterized in that the propellant gas is N ₂ .

Another means of the present invention for solving the above problems is a detergent composition characterized by comprising an HFO-based nonflammable fluorine-based solvent and an alkoxy fluoroalkene.

The detergent composition of the means of the present invention and the aerosol composition thereof are HFO-based noncombustible fluorine-based solvents which are the component (A) blended as their main components, and HFE-based the non-combustible components which are the component (B). One or more nonflammable fluorine solvents selected from the group consisting of fluorine solvents, HFC nonflammable fluorine solvents or PFC nonflammable fluorine solvents all have no flash point and are nonflammable is there. Therefore, the danger of ignition and the risk at the time of fire in the use environment of those cleaning compositions and their aerosol compositions are low.

And, HFO-based nonflammable fluorine-based solvent which is the main component (A), HFE-based nonflammable fluorine-based solvent which is the (B) component, HFC-based nonflammable fluorine-based solvent or PFC-based Since one or more nonflammable fluorine solvents selected from the group consisting of nonflammable fluorine solvents are all non-hazardous objects under the Fire Service Law, they are cleaning agents used in large quantities without the need for dangerous goods warehouses. There is no legal limit to the amount of storage of the composition.

Moreover, since each of the above components has low toxicity and low environmental load such as ozone layer destruction, it becomes a product that is considered human body and environment. Moreover, the cleaning agent composition of the means of the present invention and the aerosol composition thereof have a cleaning property comparable to that of the conventional brake cleaner, but have an extremely lower attack on rubber and resin than the conventional brake cleaner. , Has exhibited extremely excellent characteristics.

And furthermore, the HFO-based nonflammable fluorine-based solvent as the component (A), the HFE-based nonflammable fluorine-based solvent as the component (B), the HFC-based nonflammable fluorine-based solvent or the PFC-based nonflammable Furthermore, there is no flash point, non-combustibility, low toxicity, and non-combustible non-combustible environmental load such as ozone layer destruction is small with one or more non-combustible fluorinated solvents selected from the group consisting of fluorinated solvents. The resin and elastomer obtained by blending the component (A) and the component (B) are degraded, devitrified, and dissolved by blending the alkoxy fluoroalkene which is the component (C) that becomes the reactive fluorine-based solvent (A) component + the above (B) component, and (C) component, which constitute the composition, in order to achieve the desired dryness according to the use situation while maintaining the characteristic that will not Mix ratio Adjusting the drying speed is made possible by it is assumed that the, has become one that exhibits characteristics of a remarkably better washing compositions than conventional.

The best mode for carrying out the present invention will be described with reference to the following table, the detergent composition of the means of the present invention and its aerosol composition.

<About major components>
The main components of the detergent composition of the means of the present invention and its aerosol composition will be described. The detergent composition according to the means of the present invention and the aerosol composition thereof include an HFO-based nonflammable fluorine-based solvent as the component (A), an HFE-based nonflammable fluorine-based solvent as the component (B), and an HFC-based solvent. Component (C) to which an alkoxyfluoroalkene as component (C) is further added to at least one nonflammable fluorine-based solvent selected from the group consisting of nonflammable fluorine-based solvents of It shall be contained.

The HFO-based nonflammable fluorine-based solvent, which is the component (A), causes deterioration, devitrification or dissolution of the resin and the elastomer (Non-Patent Document 1), and therefore the component of the cleaning agent of the resin and elastomer. It is not preferable to use it as it is.

The HFE-based nonflammable fluorine-based solvent which is the component (B) described above does not have high compatibility with fats and oils because it does not contain chlorine molecules having high effects of developing solubility in substances. (Non-Patent Document 2), because it is used as a solvent for dissolving the silicone compound used to reduce the coefficient of friction of the device and coating the silicone compound on the surface of various articles such as metals and resins (Patent Document 2) 2) Not applicable (Non-Patent Document 4) and used as a solvent for lubricants (Patent Document 3) It is not common practice to make the situation to be coated aggressively and to lower the coefficient of friction to make the braking force much lower.

The HFC nonflammable fluorine-based solvent which is the component (B) has a low KB value and low oil saturation (Non-Patent Document 3), and degreasing and cleaning of automobile parts is not applicable (Non-patented) Reference 4), because it is used as a solvent for lubricants (Patent Document 3), in brake-related parts in various vehicles, etc., the situation where the lubricating component is applied and coated is actively created, and the coefficient of friction is lowered to It is not usually done to create a situation that would reduce power significantly.

And, the non-flammable PFC solvent of the PFC type, which is the component (B), has little compatibility with water and oil (Non-patent document 5), a fluorine-based coating agent for reducing friction in equipment and the like Because it is used as a dilution solvent for lubricants (Non-Patent Document 6), in brake-related parts in various vehicles, etc., the situation where the lubricating component is applied and coated is made positively, and the friction coefficient is reduced to reduce the braking force. It is not usually done to create a situation that greatly reduces

However, HFO-based nonflammable fluorine-based solvents, which are not suitable as components to be blended into such detergent compositions, have no oil-saturating ability or compatibility with water or oil, and lubricants. (1) at least one member selected from the group consisting of HFE-based nonflammable fluorine-based solvents, HFC-based nonflammable fluorine-based solvents or PFC-based nonflammable fluorine-based solvents, which are components (B) suitably used for solvents In addition, the resin and the elastomer are not affected by the deterioration, devitrification, dissolution or the like unexpectedly, and it is possible to prevent the resin and the elastomer from being affected by the conventional detergent composition. It has become apparent that the composition has a wider range of superior cleaning properties.

And, the alkoxy fluoroalkene which is the above-mentioned component (C) is suitably used as a solvent of a lubricant using a fluorine grease (Patent Document 2), and a lubricant component is applied and coated in brake related parts etc. in various vehicles. It should be avoided to create a situation where the friction coefficient is reduced and the braking force is greatly reduced. Furthermore, as will be apparent from the test examples described later, the resin does not have compatibility with oils and fats to be cleaned which are used in various vehicles, and the detergency is not exhibited. It can be said that it is unsuitable for the detergent composition.

However, the above-mentioned component (A) HFO based on the component (A) is an alkoxyfluoroalkene, which is a component (C) unsuitable for a detergent composition, and has a wider range of superior cleaning properties than conventional detergent compositions. At least one selected from the group consisting of the following non-flammable fluorine solvents and the above-mentioned component (B): HFE non-flammable fluorine solvents, HFC non-flammable fluorine solvents or PFC non-flammable fluorine solvents A cleaning agent composition in which the above component (A) and the above component (B) are both unexpectedly compounded by unexpectedly incorporating the nonflammable fluorine-based solvent of While maintaining the characteristics that the resulting resin and elastomer are not affected by deterioration, devitrification or dissolution, and the cleaning properties are wider and superior to those of conventional cleaning compositions, the composition is structured. It is clear that by changing the blending ratio of the components to be used, it becomes an extremely excellent cleaning agent composition capable of adjusting the drying speed so that the desired drying property is exhibited according to the use scene. It became.

Therefore, HFO-based nonflammable fluorine-based solvents as component (A), HFE-based nonflammable fluorine-based solvents as component (B), HFC-based nonflammable fluorine-based solvents or PFC-based nonflammable fluorine-based solvents By containing at least one nonflammable fluorine-based solvent selected from the group consisting of: and an alkoxyfluoroalkene as the component (C) together as main components, various types of safety can be maintained. It has become possible to provide a new cleaning composition and its aerosol composition, which have excellent properties that can be used for a wider variety of materials, and whose drying properties have been optimized according to the use situation. .

<About the HFO-based nonflammable fluorine-based solvent which is the (A) component>
The cleaning agent composition of the means of the present invention and the aerosol composition thereof contain, as one of the three essential components, an HFO-based nonflammable fluorine-based solvent which is a hydrofluoroolefin-based solvent. It shall be. As non-flammable fluorine solvents of the HFO type, (Z) -1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1,2-dichloro Noncombustible solvents such as -3,3,3-trifluoropropene, 2,3,3-trichloro-3-fluoropropene, AMOLEA AS-300 can be used. These HFO-based nonflammable fluorine-based solvents can be used by obtaining commercially available ones ((Z) -1-chloro-3,3,3-trifluoropropene (1233Z) (central Glass Co., Ltd., Japan), 1,1-dichloro-3,3,3-trifluoropropene (Matrix Scientific, USA), AMOLEA (registered trademark) AS-300 (AGC Inc., Japan) and the like.

The HFO-based nonflammable fluorine-based solvent which is the component (A) is a nonflammable solvent which has no flash point and no burning range according to the explosion limit test method ASTM E681. In addition, it has environmentally friendly chemical properties such as a low ozone depletion potential ODP or substantially zero global warming potential GWP <1. Therefore, it does not correspond to the component specified by the ozone layer protection law, the global warming measure promotion law, the Freon emission control law, the Fire Service Law, the High Pressure Gas Safety Law, etc., and its use is not particularly restricted. There is no need to store hazardous materials in storage, and there is no legal limit on storage volume.

On the other hand, the HFO-based nonflammable fluorine-based solvent which is the component (A) has invasiveness to the resin. Therefore, the HFO-based nonflammable fluorine-based solvent which is the component (A), for example, (Z) -1-chloro-3,3,3-trifluoropropene or 1,1-dichloro-3,3,3- When trifluoropropene acts on a soft polyvinyl chloride (PVC) resin or a phenol resin, the resin is denatured and the weight and size of the resin product change. In addition, when it acts on a polycarbonate resin, the resin becomes whitened and devitrified. Further, when acting on an acrylic (PMMA) resin, an ABS resin or a polystyrene resin which is a copolymerization synthetic resin of acrylonitrile, butadiene and styrene, these resins are softened or dissolved. As described above, the HFO-based nonflammable fluorine-based solvent, which is the component (A), has poor compatibility with the resin material.

The HFO-based nonflammable fluorine-based solvent, which is the component (A), is also invasive to various elastomers. Therefore, HFO-based nonflammable fluorine-based solvents such as (Z) -1-chloro-3,3,3-trifluoropropene and 1,1-dichloro-3,3,3-trifluoropropene are SBR and chloroprene. When acting on rubber, butyl rubber, EPDM and CSM, these elastomers are degraded to cause changes in weight and size. In addition, when acting on silicone rubber, natural rubber, HNBR, NBR, fluororubber and urethane rubber, these elastomers swell. Thus, the HFO-based nonflammable fluorine-based solvent which is the component (A) has poor compatibility with the elastomer as it is.

However, cars, motorcycles, bicycles, construction machines, agricultural machines, aircrafts, railway vehicles, ships, such as the poor resin compatibility and the high degree of dryness possessed by the non-combustible HFO-based fluorine solvents that are the component (A) described above. Properties that are unsuitable for cleaning compositions used in various vehicles, vehicles, transportation vehicles, etc., are, unexpectedly, (B) components having other properties that are unsuitable for cleaning compositions. Elimination by containing together with one or more nonflammable fluorine solvents selected from the group consisting of HFE nonflammable fluorine solvents, HFC nonflammable fluorine solvents or PFC nonflammable fluorine solvents Be done. Furthermore, even if the component (A) and component (B) further contain an alkoxyfluoroalkene which is a component (C) having other properties unsuitable for forming a detergent composition, the point is Is maintained, and the drying rate can be reduced by increasing the blending ratio of the component (C), and the drying rate can be adjusted so that the desired drying property is exhibited according to the use scene. An excellent detergent composition is provided.

<About the non-flammable fluorine-based solvent of HFE system which is <(B) component>
The cleaning agent composition of the means of the present invention and the aerosol composition thereof contain one or more HFE-based nonflammable fluorine-based solvents as one of the three essential components. The HFE-based fluorine-based solvent is nonflammable, having no flash point and neither the combustion point (lower limit) nor the combustion point (upper limit) being detected. It corresponds to a non-hazardous material under the Fire Service Act, does not require a hazardous material warehouse, and has no legal limit on the storage volume.

On the other hand, HFE-based nonflammable fluorine-based solvents such as 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane have an effect of exhibiting solubility in substances Because it does not contain high chlorine atoms in its molecule, it does not have high compatibility with oils and fats and solvents.

However, the property unsuitable for the cleaning agent composition that it does not have high compatibility with the fats and oils and solvent which the non-flammable HFE-based fluorinated solvent which is the component (B) has and the solvent is unexpectedly different from various vehicles · Improved by containing together a non-flammable HFO-based fluorine solvent which is a component (A) having other properties unsuitable for use as a cleaning composition for vehicles, transportation, etc. A detergent composition is provided. Furthermore, even if the component (A) and component (B) further contain an alkoxyfluoroalkene which is a component (C) having other properties unsuitable for forming a detergent composition, the point is Is maintained, and the drying rate can be reduced by increasing the blending ratio of the component (C), and the drying rate can be adjusted so that the desired drying property is exhibited according to the use scene. An excellent detergent composition is provided.

As the non-flammable fluorine-based solvent of the HFE type which is the component (B) in the cleaning composition of the means of the present invention and the aerosol composition thereof, C ₄ F ₉ OCH ₃ , C ₃ F ₇ OCH ₃ or 1, 1 One or more selected from 2,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane is used. And preferably, 1 is selected from C ₄ F ₉ OCH ₃ , C ₃ F ₇ OCH ₃ , or 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane One, 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 HFE-based non-flammable fluorine-based solvent which is the component (B), HFE-347 pc-f or Asahi Those commercially available under the name of Klin AE-3000 (AGC Co., Ltd., Japan) can be obtained and used. This solvent is a nonflammable solvent which has no flash point (TCC, COC) and no combustion range. It corresponds to a non-hazardous material under the Fire Service Act, does not require a hazardous material warehouse, and has no legal limit on the storage volume.

Moreover, _C 4 _F 9 OCH ₃ nonflammable fluorine-based solvent HFE-based is the (B) component, 3M ^TM NOVEC ^TM 7100 high performance liquid (3M Japan Co., Ltd., Japan) is commercially available under names such You can obtain and use what you This solvent is a nonflammable solvent which does not have a flash point, and both the combustion point (lower limit) and the combustion point (upper limit) are not detected. It is a non-hazardous material under the Fire Service Act, there is no need to store dangerous goods, there is no legal limit on the storage amount, and it has an ozone layer destruction coefficient ODP of zero, and is environmentally friendly. Have. Therefore, it does not fall under the ozone layer protection law and the global warming measure promotion law.

Then, _C ₃ _F 7 OCH 3 nonflammable fluorine-based solvent HFE-based is the (B) component, 3M ^TM NOVEC ^TM 7000 high performance liquid (3M Japan Co., Ltd., Japan) is commercially available under names such You can obtain and use what you This solvent is a nonflammable solvent which does not have a flash point, and both the combustion point (lower limit) and the combustion point (upper limit) are not detected. It corresponds to a non-hazardous material under the Fire Service Act, does not require a hazardous material warehouse, and has no legal limit on the storage volume. In addition, the ozone layer destruction coefficient ODP is zero, and it has chemical properties in consideration of the environment. Therefore, it does not fall under the ozone layer protection law and the global warming measure promotion law.

<About the nonflammable fluorine-based solvent of HFC type which is <(B) component>
The detergent composition of the means of the present invention and the aerosol composition thereof contain one or more HFC nonflammable fluorine-based solvents as one of the three essential components. This HFC-based fluorinated solvent is nonflammable, having no flash point and neither the combustion point (lower limit) nor the combustion point (upper limit) being detected. It corresponds to a non-hazardous material under the Fire Service Act, does not require a hazardous material warehouse, and has no legal limit on the storage volume.

On the other hand, the HFC-based nonflammable fluorine-based solvent which is the component (B) has a low KB value and a low oil saturation power.

However, the low KB value of the HFC nonflammable fluorine-based solvent which is the component (B) has low oil and fat saturation, and is not suitable for a detergent composition having high compatibility with oils and fats and solvents Unexpectedly, the HFO-based nonflammable fluorine-based solvent, which is the component (A) having other properties unsuitable for use as a cleaning composition for various vehicles, vehicles, transportation, etc. It is eliminated by containing, and a better detergent composition is provided. Furthermore, even if the component (A) and component (B) further contain an alkoxyfluoroalkene which is a component (C) having other properties unsuitable for forming a detergent composition, the point is Is maintained, and the drying rate can be reduced by increasing the blending ratio of the component (C), and the drying rate can be adjusted so that the desired drying property is exhibited according to the use scene. An excellent detergent composition is provided.

Examples of the non-flammable HFC-based fluorinated solvent which is the component (B) in the cleaning composition of the means of the present invention and the aerosol composition thereof include: 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 therefrom.

1,1,1,3,3-Pentafluorobutane is commercially available under the name of Solkane 365 (Solbay Japan Co., Ltd., Japan) etc. as the HFC-based nonflammable fluorine-based solvent which is the component (B). It can be obtained and used. This solvent is a nonflammable solvent which has no flash point (TCC, COC) and no combustion range. It corresponds to a non-hazardous material under the Fire Service Act, does not require a hazardous material warehouse, and has no legal limit on the storage volume.

In addition, 1,1,1,2,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane is a component (B) of the HFC-based nonflammable fluorine-based solvent, Commercially available products such as Asahi Clean AC-2000 (AGC Co., Ltd., Japan) can be obtained and used. This solvent is a nonflammable solvent which has no flash point (TCC, COC) and no combustion range. It corresponds to a non-hazardous material under the Fire Service Act, does not require a hazardous material warehouse, and has no legal limit on the storage volume.

<Non-combustible fluorine-based solvent of PFC type that is (B) component>
The cleaning agent composition of the means of the present invention and the aerosol composition thereof contain one or more PFC nonflammable fluorine-based solvents as one of the three essential components. This PFC type fluorine-based solvent is nonflammable, having no flash point and neither the combustion point (lower limit) nor the combustion point (upper limit) being detected. It corresponds to a non-hazardous material under the Fire Service Act, does not require a hazardous material warehouse, and has no legal limit on the storage volume.

On the other hand, the nonflammable fluorine-based solvent of the PFC type, which is the component (B), has little compatibility with water or oil.

However, the property unsuitable for the cleaning agent composition that the non-combustible fluorine-based solvent of the PFC type, which is the component (B), has almost no compatibility with water and oil is unexpectedly unexpectedly various vehicles, vehicles, A cleaner composition which is eliminated by containing together an HFO-based nonflammable fluorine-based solvent which is a component (A) having other properties unsuitable for use as a cleaning composition for transportation etc. The goods are provided. Furthermore, even if the component (A) and component (B) further contain an alkoxyfluoroalkene which is a component (C) having other properties unsuitable for forming a detergent composition, the point is Is maintained, and the drying rate can be reduced by increasing the blending ratio of the component (C), and the drying rate can be adjusted so that the desired drying property is exhibited according to the use scene. An excellent detergent composition is provided.

The nonflammable fluorine-based solvent PFC system component (B) in the detergent composition and aerosol compositions of the means of the present invention, for example, Fluorinert ^TM FC-40, and or Fluorinert ^TM FC-3283, from which It shall use one or more selected.

Fluorinert ^TM FC-40 and Fluorinert ^TM FC-3283 of the PFC nonflammable fluorine-based solvent as the component (B) can obtain those commercially available from 3M Corporation (Japan) use. This solvent is a nonflammable solvent which has no flash point (TCC, COC) and no combustion range. It corresponds to a non-hazardous material under the Fire Service Act, does not require a hazardous material warehouse, and has no legal limit on the storage volume.

<About (C) component alkoxy fluoro alkene>
The detergent composition of the means of the present invention described above and the aerosol composition thereof contain an alkoxyfluoroalkene as one of the three essential components.

Here, "alkoxy fluoroalkene" means an alkoxy group and a fluorinated olefin having a double bond. Alkoxyfluoroalkenes include alkoxyperfluoroalkenes. Here, "alkoxyperfluoroalkene" means a perfluoroalkene having an alkoxyl group. The alkoxyl group of the alkoxyfluoroalkene includes one having 1 to 5 carbon atoms, preferably one having 1 or 2 carbon atoms, that is, a methoxy or ethoxy group. In addition, perfluoroalkene means a compound having one double bond, in which all hydrogen atoms are substituted with fluorine, and includes those having 2 to 10 carbon atoms, preferably carbon atoms 5 or more and 8 or less are included. As these alkoxy perfluoroalkenes, methoxyperfluoropentene, methoxyperfluorohexene, methoxyperfluoroheptene or methoxyperfluorooctene, or ethoxyperfluoropentene, ethoxyperfluorohexene, ethoxyperfluoroheptene Or ethoxyperfluoro octene is included. And, for example, as the structure of methoxyperfluoroheptene, the following may be mentioned, but any structure may be used, and a mixture thereof may be used.
_{_{_{CF 3 (CF 2) 2 CF}}} = CFCF (OCH 3) CF 3
_{_{CF 3 (CF 2) CF =}} CF (CF 2) 2 (OCH 3) CF 3
_{_{CF 3 (CF 2) CF =}} CFCF (OCH 3) CF 2 CF 3
CF ₃ CF = CFCF (OCH ₃ ) (CF ₂ ) ₂ CF ₃
CF ₃ CF = CFCF ₂ CF (OCH ₃ ) CF ₂ CF ₃
_{_{CF 3 (CF 2) CF =}} C (OCH 3) (CF 2) 2 CF 3

The above alkoxy fluoroalkenes include methoxyperfluoroheptene or a mixture of isomers thereof. The methoxyperfluoroheptene or its isomer mixture is nonflammable, having no flash point and neither a combustion point (lower limit) nor a combustion point (upper limit) being detected. It corresponds to a non-hazardous material under the Fire Service Act, does not require a hazardous material warehouse, and has no legal limit on the storage volume.

On the other hand, methoxyperfluoroheptene or an isomer mixture thereof is used as a grease, an engine oil, a brake oil, etc., commonly used around a brake of an automobile or the like, as described in the test examples disclosed below. It has no compatibility.

However, this methoxyperfluoroheptene or its isomer mixture is not suitable for a detergent composition having the property of constituting a lubricant as an excellent solvent and not having high compatibility with oils and fats and solvents Unexpectedly, the HFO-based nonflammable fluorine-based solvent, which is the component (A), has other properties unsuitable for use as cleaning compositions used in various vehicles, vehicles, transportation vehicles, etc. B) Component (B): One or more non-combustible materials selected from the group consisting of HFE-based nonflammable fluorine-based solvents, HFC non-flammable fluorocarbon solvents or PFC-based nonflammable fluorine-based solvents. The elimination of the fluorine-based solvent together provides a better cleaning composition. Furthermore, even if the component (A) and component (B) further contain an alkoxyfluoroalkene which is a component (C) having other properties unsuitable for forming a detergent composition, the point is Is maintained, and the drying rate can be reduced by increasing the blending ratio of the component (C), and the drying rate can be adjusted so that the desired drying property is exhibited according to the use scene. An excellent detergent composition is provided.

As the alkoxy fluoroalkene which is the component (C) in the detergent composition of the means of the present invention and the aerosol composition thereof, preferably, methoxy perfluoro heptene or a mixture of isomers thereof is used. Then, for example, as the isomeric mixture of methoxy perfluoro heptene an alkoxy fluoroalkenes, Oputeon ^TM SF10: can be used (formerly Vertrel (R) soup Rion) (Mitsui-Dupont Fluorochemicals Co., Ltd.) .

Oputeon ^TM SF10 as nonflammable fluorinated solvent can be utilized to obtain those commercially available from DuPont-Mitsui Fluorochemicals Co., Ltd.. This solvent is a nonflammable solvent which has no flash point (TCC, COC) and no combustion range. It corresponds to a non-hazardous material under the Fire Service Act, does not require a hazardous material warehouse, and has no legal limit on the storage volume. The ozone depletion potential (ODP) is zero and the global warming potential (GWP) is less than ten.

Consisting of an HFO-based nonflammable fluorine-based solvent (A) and an HFE nonflammable fluorine-based solvent (B), an HFC nonflammable fluorine-based solvent, or a PFC nonflammable fluorine-based solvent Regarding mass ratio of at least one nonflammable fluorine-based solvent selected from the group and alkoxyfluoroalkene which is the component (C)>
In the cleaning agent composition of the means of the present invention and the aerosol composition thereof, cleaning of various vehicles, vehicles and vehicles such as automobiles, two-wheeled vehicles, bicycles, construction machines, agricultural machines, aircrafts, railway vehicles, ships and vehicles, workers In addition to the property that the solvent is noncombustible in the first place considering that it is used for cleaning the used tool, work place, pit, and factory, it further lowers the invasiveness to resin and elastomer, and the phase to fats and oils etc. The component (A) is a component contained so as to enhance the solubility and to provide better cleaning performance to members made of various materials such as metals, resins and elastomers, and appropriate drying speed. HFO-based nonflammable fluorine-based solvents and (B) component HFE-based nonflammable fluorine-based solvents, HFC-based nonflammable fluorine-based solvents, or PFC-based nonflammable fluorine-based solvents. And one or more non-flammable fluorinated solvent selected from the group consisting of system solvent, it is preferable to adjust the range of the mass ratio of alkoxysilane fluoroalkene as the component (C).

In addition, it has excellent properties such as having low invasiveness to resins and elastomers, higher compatibility with higher fats and oils, etc., and excellent cleaning properties and moderate drying rates for members made of various materials such as metals, resins and elastomers. In the detergent composition of the means of the present invention and the aerosol composition thereof, the HFO-based nonflammable fluorine-based solvent which is the component (A) and the HFE-based material which is the component (B) The range of the mass ratio to one or more nonflammable fluorine-based solvents selected from the group consisting of nonflammable fluorine-based solvents of HF, non-combustible fluorocarbon solvents of HFC type or non-flammable fluorocarbon solvents of PFC type is 99 / The range of the mass ratio of the component (A) + the component (B) to the component (C) alkoxyfluoroalkene is 99/1 to 1/9. To. The mass of the component (A) and the component (B) according to the type of fats and oils to be cleaned, and the types of resin and elastomer used in combination in the site to be cleaned and the peripheral area to be treated The range of the ratio is adjusted, and the range of the mass ratio of the above component (A) + the above component (B) to the above component (C) is adjusted so as to obtain the desired drying speed. The present invention can provide a detergent composition and an aerosol composition thereof.

For example, the detergent composition according to the means of the present invention and the HFO-based nonflammable fluorine-based solvent which is the component (A) contained in the aerosol composition thereof and the HFE-based nonflammable fluorine-based solvent which is the component (B) When the solvent is 1,1-dichloro-3,3,3-trifluoropropene and C ₄ F ₉ OCH ₃ , the mass ratio of the component (A) to the component (B) (1,1) The range of -dichloro-3,3,3-trifluoropropene / C ₄ F ₉ OCH ₃ ) is 99/1 to 1/99, 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-triol is used. The range of fluoropropene / C ₄ F ₉ OCH ₃ ) is 50/50 to 99/1, 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-triol is used. The range of fluoropropene / C ₃ F ₇ OCH ₃ is 50/50 to 99/1, preferably 80/20 to 99 / 1. (Z) -1-chloro-3,3,3-trifluoro When propene and 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane are used, their mass ratio ((Z) -1-chloro-3,3 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, which makes it less invasive to resins and elastomers To have a plurality of excellent properties such as good compatibility with higher fats and oils and superior cleanability and appropriate drying speed for members made of various materials such as metals, resins and elastomers. It becomes possible and can be suitably used as a detergent composition and its aerosol composition.

For example, the detergent composition according to the means of the present invention and the HFO-based nonflammable fluorine-based solvent which is the above-mentioned component (A) contained in the aerosol composition thereof can be (Z) -1-chloro-3,3,3- Trifluoropropene, the non-combustible fluorine-based solvent of the HFC type, which is the component (B), is 1,1,1,3,3-pentafluorobutane or 1,1,1,2,2,3,3,4,4, In the case of 4,5,5,6,6-tridecafluorohexane, the range of the mass ratio (HFO non-flammable fluorine solvent / HFC non-flammable fluorine solvent) is 99/1 The ratio may be 1/99, preferably 99/1 to 10/90, and more preferably 90/10 to 30/70, but it should be dissolved so as to be compatible with the usage situation of the target customer. Protection against the types of fats and oils According to the type of the feeder resin or elastomer, also taking into account the balance of the cost, it may be used to select a suitable among the above range weight. As a result, the resin, elastomer, etc. have lower invasiveness, higher compatibility with oils and fats, etc., and excellent cleaning ability and moderate drying speed for members made of various materials such as metal, resin and elastomer. It becomes possible to have a plurality of properties in combination, and it can be suitably used as a detergent composition and its aerosol composition.

For example, the detergent composition according to the means of the present invention and the HFO-based nonflammable fluorine-based solvent which is the above-mentioned component (A) contained in the aerosol composition thereof can be (Z) -1-chloro-3,3,3- trifluoropropene, (B) above when nonflammable fluorinated solvent of the PFC system is a component is Fluorinert ^TM FC-40 or Fluorinert ^TM FC-3283 Doo is nonflammable fluorinated solvent of the mass ratio (HFO system The range of (non-flammable fluorine-based solvent) of (PFC series) can be 99/1 to 1/99, preferably 99/1 to 10/90, more preferably 90/10 to 30/70. Consider the balance of costs according to the types of fats and oils to be dissolved, and the types of resins and elastomers to be protected from invasion, so as to be compatible with the usage situation of the target customer While, it may be used to select a suitable among the above range weight. As a result, the resin, elastomer, etc. have lower invasiveness, higher compatibility with oils and fats, etc., and excellent cleaning ability and moderate drying speed for members made of various materials such as metal, resin and elastomer. It becomes possible to have a plurality of properties in combination, and it can be suitably used as a detergent composition and its aerosol composition.

And, for example, the detergent composition of the means of the present invention and the three components contained in the aerosol composition thereof are the HFO-based nonflammable fluorine-based solvent which is the component (A) and the HFE which is the component (B) At least one nonflammable fluorine-based solvent selected from the group consisting of non-combustible fluorine-based solvents of the system, non-flammable fluorine-based solvents of the HFC system, or non-flammable fluorine-based solvents of the PFC system; In the case where an alkoxyfluoroalkene is a methoxyperfluoroheptene or a mixture of isomers thereof, the range of the mass ratio (((A) component + (B) component) / alkoxyfluoroalkene) is 99/1 to The ratio may be 1/99, preferably 99/1 to 10/90, more preferably 90/10 to 20/80, but adapted to the usage situation of the target customer Select the appropriate one from the above mass ratio range, taking into consideration the cost balance and according to the type of fat to be dissolved, the type of resin and elastomer to be protected from invasion, and You may use it. As a result, it has lower invasiveness to resins and elastomers, higher compatibility with oils and fats, and excellent cleaning properties for members made of various materials such as metals, resins and elastomers, as well as alkoxyfluoro By adjusting the compounding ratio of the alkene, it becomes possible to have a desired drying rate, and can be suitably used as a cleaning composition and its aerosol composition.

<About other ingredients>
The detergent composition of the means of the present invention and the aerosol composition thereof, in addition to the three main components as the above-mentioned detergent composition, do not further increase the risk of fire or risk of fire, if necessary. It may be compounded in degree. When the above-mentioned additional components are incorporated, the HFO system is achieved by the main three components while maintaining the non-combustibility as a detergent composition or the non-hazardous property in the Fire Service Law. The non-combustible fluorine-based solvent itself is incorporated in a range capable of reducing the invasiveness to the resin or elastomer held by the non-combustible fluorine-based solvent itself and maintaining the cleaning property for the oil component and the appropriate drying rate. Examples of components this is compounded, alcohols, saturated hydrocarbons, unsaturated hydrocarbons, aromatic hydrocarbons, stabilizers, and the like can be illustrated chelating agent, for ^{^{^{example, 3M TM NOVEC TM 7200,3M TM NOVEC}}} TM 7300 HFE solvents such as methanol, 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, acetic acid Esters and glycol ester solvents such as butyl and ethylene glycol monomethyl ether acetate, and ether and glycol ether solvents such as methyl cellosolve, butyl cellosolve, methoxymethyl butanol and hexyl diglycol Glyme solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, chlorinated solvents such as HCFC-141b, HCFC-225, 1-bromopropane, chloroform, special solvents such as N-methyl-2-pyrrolidone, tetrahydrofuran, dimethylformamide, Other solvents such as γ-butyrolactone, 1,3-dioxolane and dimethylsulfoxide can be blended.

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

<How to use>
The solution of the cleaning agent composition according to the means of the present invention is a metal, resin and elastomer of various vehicles, vehicles and vehicles such as automobiles, two-wheeled vehicles, bicycles, construction machines, agricultural machines, aircraft, railway vehicles and ships to be cleaned. The material may be applied to members made of various materials such as tools, tools used by workers, work places, pits, and factories, or objects to be cleaned may be used by being immersed in a solution of the cleaning composition. In addition, an aerosol composition in which the cleaning agent composition of the means of the present invention is mixed with a liquefied gas serving as a propellant gas is filled in a pressure can and aerosolized, or the cleaning agent composition of the means of the present invention is used as a pale can A portable small-sized filling machine is installed at the work place to be used, and the cleaning composition put in a pail can be aerosolized by compressed air, and it is a member made of various materials such as metal, resin and elastomer to be cleaned. It can be used by spraying as an aerosol.

Below, the example which manufactured and used the cleaning composition of this invention and its aerosol composition is shown as an Example and a test example.

<About the test sample>
The components used in the detergent composition of the present invention and conventional detergents are purchased to prepare test samples.
As the HFO-based nonflammable fluorine-based solvent used as the (A) component in the cleaning composition of the present invention, (Z) -1-chloro-3,3,3-trifluoropropene 1233Z (central glass shares) Company, Japan) and 1,1-dichloro-3,3,3-trifluoropropene (Matrix Scientific, USA) were purchased. Furthermore, AMOLEA (registered trademark) AS-300 was supplied from AGC Corporation (Japan). As the 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane of the HFE-based nonflammable fluorine-based solvent which is the component (B), there is Ltd., Japan), as _C ₃ _F 7 OCH 3 of HFE-based nonflammable fluorine-based solvent is, 3M ^TM NOVEC ^TM 7000 high performance liquid (3M Japan Co., Ltd., Japan), is a component (B) the _C 4 _F 9 OCH ₃ in HFE-based nonflammable fluorine-based solvent, were purchased 3M ^TM NOVEC ^TM 7100 high performance liquid (3M Japan Co., Ltd., Japan), respectively. As 1,1,1,3,3-pentafluorobutane which is a nonflammable fluorine-based solvent of the HFC system which is the (B) component, it is HFC system which is Solkane365 (Sorbay Japan KK, Japan) and which is the (B) component ASAHIKLIN AC-2000 (AGC Co., Ltd., Japan) as 1,1,1,2,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, a nonflammable fluorine-based solvent ) Were purchased respectively. The PFC-based nonflammable fluorine-based solvent as the component (B), were purchased Fluorinert ^TM FC-40 (3M Japan Co., Ltd., Japan) or Fluorinert ^TM FC-3283 (3M Japan Co., Ltd., Japan), respectively. As an example of alkoxy fluoroalkene as the component (C), and the use of methoxy perfluoro-heptene or isomer mixtures thereof, as an example, Oputeon ^TM SF10 (formerly Vertrel (R) soup Rion) (Mitsui Purchased Dupont Fluoro Chemical Co., Ltd.).

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

Then, the cleaning agent compositions of the following examples were produced so that the mass ratio of each component of the above (A) to (C) would be as follows.

<HFO-based nonflammable fluorine-based solvent / HFE-based nonflammable fluorine-based solvent>
・ 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 nonflammable fluorine-based solvent / HFE-based nonflammable fluorine-based solvent>
Mass ratio (1,1-dichloro-3,3,3-trifluoropropene / NOVEC 7100)
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 nonflammable fluorine-based solvent / HFE-based nonflammable fluorine-based solvent>
・ 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 nonflammable fluorine-based solvent / HFE-based nonflammable fluorine-based solvent>
・ 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 nonflammable fluorine-based solvent / HFE-based nonflammable fluorine-based solvent>
・ 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 nonflammable fluorine-based solvent / HFC non-flammable fluorine-based solvent>
・ 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 nonflammable fluorine-based solvent / HFC non-flammable fluorine-based solvent>
・ 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 nonflammable fluorine-based solvent / PFC-based nonflammable fluorine-based solvent>
Mass ratio (1233Z / Fluorinert ^TM 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 ^TM 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

<Non-combustible fluorinated solvents of HFO series / Alkoxyfluoroalkenes>
Mass ratio (1233Z / Oputeon ^TM 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

<Non-combustible fluorinated solvents of HFO series / Alkoxyfluoroalkenes>
Mass ratio (AS-300 / Oputeon ^TM SF10)
Example 68: 90/10
Example 69: 70/30
Example 70: 50/50
Example 71: 30/70
Example 72: 10/90

<HFO-based nonflammable fluorine-based solvent / HFE-based nonflammable fluorine-based solvent / alkoxyfluoroalkene>
Mass ratio (1233Z / NOVEC7100 / Oputeon ^TM SF10)
Example 73: 90/5/5
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: 80/5/15
Example 84: 40/30/30
Example 85: 40/10/50
Example 86: 20/40/40
Example 87: 20/10/70

<HFO-based nonflammable fluorine-based solvent / HFE-based nonflammable fluorine-based solvent / alkoxyfluoroalkene>
Mass ratio (AS-300 / NOVEC7100 / Oputeon ^TM SF10)
Example 88: 30/30/40

Further, the following Comparative Examples 1 to 4 were prepared. The quick-drying stock solution, the degreasing detergent, and the ordinary-drying stock solution are all highly combustible, and trichloroethane is highly harmful, and all of them have problematic properties as a cleaning composition. .
<Conventional product (flammable)>
Comparative Example 1: Quick-drying stock solution Comparative example 2: Degreasing detergent Comparative example 3: After-drying stock solution Comparative example 4: Trichloroethane

Furthermore, the following comparative examples were prepared in order to compare them with the examples of each of the examples (A) to (C).
<Non-flammable fluorine-based solvent of HFO series>
Comparative Example 5: Only 1233Z Comparative Example 6: Only 1,1-Dichloro-3,3,3-trifluoropropene Comparative Example 7: Only AS-300 <Non-combustible fluorine-based solvent of HFE system>
Comparative Example 8: Only NOVEC 7100 Comparative Example 9: Only NOVEC 7000 Comparative Example 10: Only AE-3000 <HFC non-combustible fluorine-based solvent>
Comparative Example 11: Solkane 365 only Comparative Example 12: AC-2000 only <PFC-based nonflammable fluorine-based solvent>
Comparative Example 13: Fluorinert ^TM FC-40 only Comparative Example 14: Fluorinert ^TM FC-3283 only <alkoxyalkyl fluoroalkene>
Comparative Example 15: Oputeon ^TM SF10 only

Next, the test examples shown below are carried out to specifically show that the cleaning agent composition of the means of the present invention and the aerosol composition thereof have excellent properties as compared with conventional cleaning agents. confirmed.

<Test Example 1: Evaluation of invasiveness (long-term contact)>
-Materials and Methods As a test solution, the solutions of the above Examples and Comparative Examples are prepared.
In addition, to evaluate invasiveness, prepare the following test pieces.
Rubber: NR (Natural rubber)
: CR (chloroprene rubber)
: SBR (styrene-butadiene rubber)
: EPDM (ethylene propylene rubber)
(All are obtained from Standard Test Piece, Inc., Japan.)
Resin: ABS (acrylonitrile butadiene styrene)
: LDPE (low density polyethylene)
: PC (polycarbonate)
(All are Nippon Test Panel Co., Ltd.)

The weight of each of the above rubber or resin test pieces (size 10 mm × 10 mm × 2 mm) is measured.
Next, 20 mL of the solution of Example or Comparative Example was placed in a vial, into which each test piece of rubber or resin (size 10 mm × 10 mm × 2 mm) was immersed, and the vial was set to 45 ° C. Place in a constant temperature and humidity chamber (HPAV-120-40, Isuzu Seisakusho Co., Ltd., Japan) and leave to stand.
After taking out each test piece from the vial and observing the surface condition, the weight and thickness of the test piece are measured, the degree of swelling is calculated, and it is confirmed whether it falls within ± 5.0% and PC Also check if the transparency of is lost.
If the solution used is small, the test is performed with the size and volume of the test piece proportional to the volume used.

-Test result The result of having carried out the above-mentioned test is shown in the following tables.

Test Example 1 shows that the composition comprising the HFO-based nonflammable fluorine-based solvent and the alkoxyfluoroalkene improves the invasiveness to the rubber or resin possessed by the HFO-based nonflammable fluorine-based solvent. confirmed. Then, comparisons with non-abrasive properties to rubber or resin were compared with conventional detergents.

HFO-based nonflammable fluorine-based solvents are invasive to rubber and resin when acting for a long period of time, and are particularly important for securing safety in various vehicles, vehicles, transportation, etc. Swells NR (natural rubber), SBR (styrene butadiene rubber), EPDM (ethylene propylene rubber) widely used in equipment and parts, dissolves and softens ABS (acrylonitrile butadiene styrene), swells PC (polycarbonate) It shows strong invasiveness such as whitening, devitrification and cracking, and the degree of deterioration of these rubbers and resins is such that the quality as a product can not be secured (Table 1-1 etc.).

In addition, conventional cleaning agents are originally flammable, and when applied to rubbers such as NR, CR, SBR, EPDM, or resins such as ABS, LDPE (low density polyethylene), PC, etc., they are highly invasive. Similarly, the product quality could not be secured (Table 1-1, etc.).

However, it is surprising that the HFO nonflammable fluorine solvent is mixed with the HFE nonflammable fluorine solvent, the HFC nonflammable fluorine solvent or the PFC nonflammable fluorine solvent. It has become clear that it is possible to eliminate the phenomena of swelling, dissolution, whitening, devitrification and cracking of various rubbers and resins observed when using the above HFO-based nonflammable fluorine-based solvents (Table 1-2 to Table 1-6, Table 1-8, Table 1-9, Table 1-11).

In addition, various rubbers and resins that were observed when using the above HFO-based nonflammable fluorine-based solvent, surprisingly, even when the alkoxyfluoroalkene is blended with the HFO-based nonflammable fluorine-based solvent It became clear that it was possible to eliminate the phenomena of swelling, dissolution, whitening, devitrification and cracking (Tables 1-14 to 1-15).

Furthermore, an HFO nonflammable fluorine solvent, an HFE nonflammable fluorine solvent, an HFC nonflammable fluorine solvent or a PFC nonflammable fluorine solvent, and an alkoxyfluoroalkene are further added thereto. Also, surprisingly, it became clear that it was possible to eliminate the dissolution phenomena that had been observed in ABS (see also Table 1-16).

To create a cleaning composition having a new characteristic of not showing the invasiveness to various rubbers and resins generally used for devices and parts important for securing the safety of various vehicles, vehicles and vehicles. It is understood that the present invention which is capable provides a very effective means to replace conventional cleaning agents which are invasive. In addition, it is understood that the detergent composition of the means of the present invention is very less likely to be invasive to rubber and resin, even if it is used for a long time.

In addition, although the HFO-based nonflammable fluorine-based solvent is limited in the amount that can be produced, the cleaning agent composition of the means of the present invention comprises HFO-based nonflammable fluorine-based solvent and HFE-based nonflammable fluorine-based solvent And HFC-based nonflammable fluorine-based solvents or PFC-based nonflammable fluorine-based solvents and alkoxyfluoroalkenes in combination, thereby increasing the amount that can be supplied as a cleaning agent composition, and the product supply It is understood that it also has the effect of preventing delay.

<Test Example 2: Evaluation of invasiveness (short-term contact)>
Materials and Methods In the same manner as in Test Example 1, the solutions of the above-described Examples and Comparative Examples are prepared. In addition, to evaluate short-term invasiveness, prepare the following test pieces.
Resin: ABS (acrylonitrile butadiene styrene)
: PC (polycarbonate)
(All are Nippon Test Panel Co., Ltd.)

The surface of each of the test pieces of the above resin (size 10 mm x 10 mm x 2 mm is wiped with a microfiber cloth containing the solution of Examples 1 to 18 or Comparative Examples 1 to 8. Thereafter, the appearance change of each test piece surface is visually observed. When no change in appearance was observed, the state of the resin surface was recorded.

-Test result The result of having carried out the above-mentioned test is shown in the following table.

The HFO-based nonflammable fluorine-based solvent, which is one of the main components used in the detergent composition of the means of the present invention, is obtained by wiping the surface with a microfiber cloth containing the solution only for a short time of contact. , ABS and PC will be altered (such as Table 2-1).

However, a cleaning agent composition comprising an HFE nonflammable fluorine solvent and an HFE nonflammable fluorine solvent, an HFC nonflammable fluorine solvent or a PFC nonflammable fluorine solvent mixed with the HFO nonflammable fluorine solvent It was revealed that the resin does not deteriorate due to such a short time contact (Table 2-2 to Table 2-6, Table 2-8, Table 2-9, Table 2-11). , Table 2-12.

In addition, it has become clear that even if an alkoxyfluoroalkene is mixed with an HFO-based nonflammable fluorine-based solvent, the resin does not deteriorate due to such short contact (Table 2-14, Table 2) 2-15). Furthermore, an HFO nonflammable fluorine solvent, an HFE nonflammable fluorine solvent, an HFC nonflammable fluorine solvent or a PFC nonflammable fluorine solvent, and an alkoxyfluoroalkene are further added thereto. It has also been found that the resin does not deteriorate due to such a short time contact. (Table 2-15).

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

As greases to be cleaned and removed, various greases and oils generally used in automobiles and the like shown below are prepared.
Grease: GREASE (Orange) (Kobe Kogyo Co., Ltd., Japan)
: Rubber combined brake grease (Kobe Kogyo Co., Ltd., Japan)
: Grease for disc brakes (Kobe Kogyo Co., Ltd., Japan)
: Brake grease (Kobe Kogyo Co., Ltd., Japan)
: Silicone grease (Kobe Kogyo Co., Ltd., Japan)
: Caliper Pingris (Honda Access, Japan)
: Pad & Shoe (HONDA ACCESS CO., LTD., Japan)
: Rubber grease (HONDA ACCESS CO., LTD., Japan)
: Brake grease (HONDA ACCESS CO., LTD., Japan)
Oil: Engine oil Mobil 1 0 W-20 (Exxon Mobil, USA)
: Brake fluid (DOT3) (HONDA ACCESS CO., LTD., Japan)
: Brake fluid (DOT 4) (Suzuki Corporation, Japan)

Prepare 10 mL vials for each solution and add 1 g of the above grease or engine oil. Further 5 mL of the solution of Example or Comparative Example is added to the vial, and the lid of the vial is closed. Each vial is sonicated for 1 hour in an ultrasonic cleaner (AU 16 C, AIWA Medical Industries Ltd., Japan).
After one hour of sonication, remove each vial from the sonicator. The inside of the vial is checked, and if the grease or engine oil and the solution of Example or Comparative Example are completely mixed, ○, if it is partially separated, Δ if it is completely separated, × if it is completely separated Evaluate solubility. In addition, when the solution to be used becomes small, it tests by the liquid quantity proportional to usage-amount.

Since various HFE-based nonflammable fluorine-based solvents have little compatibility with grease or brake oil (Comparative Example 8 to Comparative Example 10 in Table 3-1), dirt due to grease components such as grease or brake oil can be eliminated. Not suitable for use as a cleaning agent to remove. In addition, although the HFO-based nonflammable fluorine-based solvent has appropriate compatibility, various types of vehicles, vehicles, vehicles, vehicles, vehicles, vehicles, etc., because they have invasiveness to resins and elastomers as apparent from the test results of Test Example 1 and Test Example 2. It is unsuitable for the detergent composition used for a transportation etc. Thus, various HFE-based nonflammable fluorine-based solvents and HFO-based nonflammable fluorine-based solvents both lack motivation to be added to cleaning compositions used in various vehicles, vehicles, transportation vehicles, and the like.

Since various HFC-based nonflammable fluorine-based solvents have almost no compatibility with grease or brake oil (Comparative Example 11 and Comparative Example 12 in Table 3-7), dirt due to grease components such as grease or brake oil can be eliminated. Not suitable for use as a cleaning agent to remove. In addition, although the HFO-based nonflammable fluorine-based solvent has appropriate compatibility, various types of vehicles, vehicles, vehicles, vehicles, vehicles, vehicles, etc., because they have invasiveness to resins and elastomers as apparent from the test results of Test Example 1 and Test Example 2. It is unsuitable for the detergent composition used for a transportation etc. As described above, various HFO-based nonflammable fluorine-based solvents and HFC-based nonflammable fluorine-based solvents both lack motivation to be added to cleaning compositions used for various vehicles, vehicles, transportation vehicles, and the like.

Since various PFC nonflammable fluorine-based solvents have almost no compatibility with grease or brake oil (Comparative Example 13 and Comparative Example 14 in Table 3-10), dirt due to grease components such as grease or brake oil can be eliminated. Not suitable for use as a cleaning agent to remove. In addition, although HFO-based nonflammable fluorine-based solvents have appropriate compatibility, they have invasiveness to resins and elastomers as evidenced by the test results of Test Example 1, and therefore they can be used in various vehicles, vehicles, and transport vehicles. It is unsuitable for the detergent composition to be used. As described above, various HFO-based nonflammable fluorine-based solvents and PFC non-flammable fluorine-based solvents both lack motivation to be added to cleaning compositions used for various vehicles, vehicles, transportation vehicles, and the like.

It became clear that the alkoxy fluoro alkene used in the said test has hardly compatibility with grease or brake oil (comparative example 15 of Table 3-13). In view of this, it is understood that alkoxyfluoroalkenes are not suitable for use as detergents for removing dirt from grease components such as grease or brake oil. In addition, although the HFO-based nonflammable fluorine-based solvent has appropriate compatibility, various types of vehicles, vehicles, vehicles, vehicles, vehicles, vehicles, etc., because they have invasiveness to resins and elastomers as apparent from the test results of Test Example 1 and Test Example 2. It is unsuitable for the detergent composition used for a transportation etc. As described above, various HFO-based nonflammable fluorine-based solvents and alkoxyfluoroalkenes both lack motivation to be added to cleaning compositions used in various vehicles, vehicles, transportation vehicles, and the like.

However, HFO-based nonflammable fluorine-based solvents and HFE-based nonflammable fluorine-based solvents, HFC-based nonflammable fluorine-based solvents or PFC-based nonflammables that can not be used for cleaning vehicles, vehicles and vehicles as described above It is surprising to show a wide compatibility with fat and oil components such as grease or brake oil, that is, to exhibit high washability to these fat and oil components, if they are contained together with a fluorinated solvent. But this time it became clear. Furthermore, an HFO nonflammable fluorine solvent, an HFE nonflammable fluorine solvent, an HFC nonflammable fluorine solvent or a PFC nonflammable fluorine solvent, and an alkoxyfluoroalkene are further added thereto. Also, surprisingly, the property of maintaining wide compatibility with fat and oil components such as grease or brake oil and maintaining high detergency for the fat and oil components was maintained. In addition, the range of mass ratio of the HFO-based nonflammable fluorine-based solvent and the alkoxy fluoroalkene showing compatibility was wide (Table 3-2 to Table 3-6, Table 3-8, Table 3-9, Tables 3-11, 3-12, 3-14 to 3-17).

From this, as in the means of the present invention, the cleaning agent composition and the aerosol composition thereof can be prepared by combining an HFO-based nonflammable fluorine-based solvent and an HFE-based nonflammable fluorine-based solvent, an HFC-based nonflammable fluorine-based solvent or PFC By containing a non-flammable fluorine-based solvent of the type and an alkoxy fluoroalkene further, it is used in combination with the kind of oils and fats to be cleaned and the area to be cleaned and its peripheral area to be protected against invasion. Adjust the range of the mass ratio of each component according to the type of resin and elastomer used to provide the detergent composition of the characteristics suitable for the scene using the detergent composition and its aerosol composition It is understood that

In addition, conventional cleaning agents may lack compatibility with GREASE (orange) and rubber grease, but HFO-based nonflammable fluorine-based solvents and HFE that are hardly compatible with GREASE (orange) and rubber grease. The HFO-based nonflammable fluorine-based solvent is diluted by further containing an alkoxyfluoroalkene together with a non-flammable fluorine-based solvent of HFC, a nonflammable fluorine-based solvent of HFC, or a nonflammable fluorine-based solvent of PFC. Even in the state, it became clear that those showing compatibility with GREASE (orange) and rubber grease were newly obtained.

Thus, in the cleaning composition, as in the present invention, HFO non-flammable fluorine solvents and HFE non-flammable fluorine solvents, HFC non-flammable fluorine solvents or PFC non-flammable fluorine solvents And by further containing an alkoxy fluoroalkene, it becomes widely compatible with grease or brake oil, and is at the same level as or better than conventional brake cleaners while being incombustible and less toxic. It is understood that new detergent compositions having cleaning properties can be provided.
<Test Example 4 Evaluation of Drying Property of Cleaning Composition>
Materials and Methods In the same manner as in Test Example 1, the solutions of the above-described Examples and Comparative Examples are prepared.

A constant temperature and humidity chamber (HPAV-120-40, Isuzu Seisakusho Co., Ltd., Japan) was set to a temperature condition of 45 ° C., 25 ° C. or 10 ° C. and a humidity of 70%, a 2 cm flat plate was placed and allowed to stand. When the temperature of the pan became constant, 100 μL of the solutions of Examples 1, 3, 5, 7 and 9 and Comparative Examples 1 to 5 were put in the pan, and the droplets of each solution were completely evaporated from the pan and dried. The time until it is done is measured visually.

In detergent compositions that are required to ensure good workability and safety, the optimum time required for drying is typically 1 minute to 2 minutes in a high temperature environment of 40 ° C., 25 ° C. It is preferable that the temperature is 2 minutes to 3 minutes in the normal temperature environment and 3 minutes to 4 minutes in the low temperature environment of 10 ° C. With conventional detergents, only those of the fast-drying stock type that have been able to achieve such conditions, others have required excessive time to dry. However, although this type of quick-drying stock solution requires a short time for drying, it is highly flammable and has problems in terms of securing the high safety required for the detergent composition.

As clarified in Test Example 3, the HFO-based nonflammable fluorine-based solvent as the component (A), the HFE-based nonflammable fluorine-based solvent as the component (B), and the component (C) are further included. The detergent composition of the means of the present invention containing an alkoxy fluoroalkene is a non-combustible detergent composition having the properties for superior fat and oil components. Therefore, the HFO-based nonflammable fluorine-based solvent as the component (A), the HFE-based nonflammable fluorine-based solvent as the component (B), and the alkoxyfluoroalkene as the component (C) are further contained. It was examined what drying time the detergent composition could have.

As a result, HFO-based nonflammable fluorine-based solvents have a short drying time (Table 4-1), HFO-based nonflammable fluorine-based solvents (Z) -1-chloro-3,3,3- trifluoropropene is the drying time is short slightly both _C 4 _F 9 _OCH 3 as HFE-based nonflammable fluorine-based solvent to be contained (NOVEC ^TM 7100) and 1,1,2,2-tetrafluoro-1- ( It was found that using 2,2,2-trifluoroethoxy) ethane (AE-3000) provides a product that can ensure standard working time (Table 4-2, Table 4-3, Table) 4-5). _Moreover, the use of _{_{C 3 F 7 OCH 3 (NOVEC}} TM 7000), revealed that it is possible to obtain a detergent composition dry rapidly (Table 4-4). When opteon ^TM SF10 is used as an isomer mixture of methoxyperfluoroheptene as an example of the alkoxyfluoroalkene which is a component (C) to be contained together with the HFO-based nonflammable fluorine-based solvent which is a component (A), It has become clear that the time is increased, and that the standard working time can be secured. In addition, it was confirmed that when the blending ratio of the alkoxy fluoroalkene which is the component (C) is increased, a detergent composition having a longer drying time can be obtained. When the compounding ratio of the alkoxy fluoro alkene which is the component (C) is increased, a detergent composition having a longer drying time can be obtained because the non-flammable fluorine-based solvent of the HFO type which is the component (A) The same was true when the HFE-based nonflammable fluorine-based solvent which is the component (B) and the alkoxyfluoroalkene which is the component (C) were further blended (Tables 4-7 to 4-10). HFO-based non-flammable fluorine-based solvent which is the component (A) so as to obtain the desired drying speed according to the usage while maintaining the excellent cleaning properties and the reducing effect on the invasiveness to rubber and resin. It became clear that the HFE-based nonflammable fluorine-based solution which is the (B) component, the kind of the alkoxyfluoroalkene which is the (C) component, and the mass ratio of each of the components can be adjusted.

A group consisting of an HFO-based nonflammable fluorine-based solvent as component (A) and an HFE-based nonflammable fluorine-based solvent as component (B), an HFC nonflammable fluorine-based solvent or a PFC nonflammable fluorine-based solvent At the time of fire hazard or fire because it is non-combustible by containing in the cleaning agent composition at least one nonflammable fluorine-based solvent selected from the above and alkoxyfluoroalkene which is the component (C). Low risk, corresponding to non-hazardous substances under the Fire Service Act, no need for dangerous goods storage, no legal restrictions on the storage amount of cleaning composition used in large quantities, and low toxicity, ozone layer destruction And the like, as well as having a cleaning property equal to or greater than that of a conventional cleaning composition for a brake cleaner, yet imparting an excellent property that the attack against rubber or resin is extremely low, According to the use scene It is possible to provide a new detergent composition and its aerosol composition in which the mass ratio of (A) component, (B) component and (C) component is adjusted so as to have the desired drying rate. .

Claims

HFO-based nonflammable fluorine-based solvent which is component (A),
(B) at least one nonflammable fluorine-based solvent selected from the group consisting of HFE-based nonflammable fluorine-based solvents, HFC-based nonflammable fluorine-based solvents or PFC nonflammable fluorine-based solvents;
(C) component alkoxyfluoroalkene,
Cleaning compositions for cleaning vehicles, vehicles, vehicles, vehicles, vehicles, construction machines, agricultural machines, aircraft, railway vehicles, ships, etc., tools, workplaces, pits, and factories, characterized in that .
The detergent composition is for brake cleaners of various vehicles, vehicles, vehicles such as cars, two-wheeled vehicles, bicycles, construction machines, agricultural machines, aircraft, railway vehicles, ships, etc. Detergent composition.
The range of the mass ratio of the (A) component to the (B) component ((A) component / (B) component) is 99/1 to 1/99, and
The range of the mass ratio of (A) component + (B) component to (C) component (((A) component + (B) component) / (C) component) is 99/1 to 1/99 The detergent composition according to claim 1, which is characterized.
The HFO-based nonflammable fluorine-based solvent which is the component (A) is (Z) -1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, At least one selected from 1,2-dichloro-3,3,3-trifluoropropene, 2,3,3-trichloro-3-fluoropropene and AMOLEA® AS-300 The detergent composition according to any one of claims 1 to 3, characterized in that
The HFE-based nonflammable fluorine-based solvent which is the component (B) is C 4 F 9 OCH 3 , C 3 F 7 OCH 3 , and 1,1,2,2-tetrafluoro-1- (2,2,2 -Non-flammable fluorine-based solvent of the HFC type which is one or more selected from -trifluoroethoxy) ethane and which is the component (B) is 1,1,1,3,3-pentafluorobutane, and PFC, which is one or more selected from 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, and is a component (B) nonflammable fluorine-based solvent, and wherein the at one or more selected from Fluorinert TM FC-40, and Fluorinert TM FC-3283, according to any one of claims 1 to 3 Detergent composition.
The detergent composition according to any one of claims 1 to 3, wherein the alkoxyfluoroalkene which is the component (C) is an alkoxyperfluoroalkene.
4. The method according to claim 1, wherein the alkoxy group of the alkoxyfluoroalkene which is the component (C) is an alkoxyfluoroalkene or alkoxyperfluoroalkene which is a methoxy group or an ethoxy group. The detergent composition as described in.
The detergent composition according to any one of claims 1 to 3, wherein the alkoxyfluoroalkene which is the component (C) is an alkoxyfluoroalkene having 5 to 8 carbon atoms.
The alkoxyfluoroalkene which is the component (C) is methoxyperfluoropentene, methoxyperfluorohexene, methoxyperfluoroheptene or methoxyperfluorooctene, or ethoxyperfluoropentene, ethoxyperfluorohexene, or ethoxyperfluoro. The detergent composition according to any one of claims 1 to 3, characterized in that it contains any one or more of heptene, or ethoxyperfluorooctene, or a mixture of isomers thereof.
The detergent composition according to any one of claims 1 to 3, wherein the alkoxyfluoroalkene which is the component (C) is methoxyperfluoroheptene or a mixture of isomers thereof.
An aerosol composition comprising the cleaning composition according to any one of claims 1 to 10 and a propellant gas.
A method according to claim 11, 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. Aerosol composition as described.
Propellant gas, characterized in that it is N 2, the aerosol composition according to claim 12.