WO2019082998A1

WO2019082998A1 - Detergent composition and aerosol composition thereof

Info

Publication number: WO2019082998A1
Application number: PCT/JP2018/039788
Authority: WO
Inventors: 督修宮岡; 祐士宮岡
Original assignee: 神戸合成株式会社
Priority date: 2017-10-25
Filing date: 2018-10-25
Publication date: 2019-05-02
Also published as: JP7084046B2; JP7328722B2; JPWO2019082998A1; JP2022122931A

Abstract

In order to provide a novel detergent composition and an aerosol composition thereof that have a very low ability to attack rubbers and resins even while having cleaning and drying properties equivalent to those of conventional detergent compositions for brake cleaners, the compositions having such properties as: low danger of ignition and low risk of fire because the compositions are nonflammable; correspondence to a nonhazardous material under the Fire Service Act, obviating need for a dangerous goods warehouse; no legal restriction on the storage quantity of detergent composition, which is to be used in large amounts; and low toxicity and little environmental impact such as damage to the ozone layer, the detergent composition and the aerosol composition thereof contain: (Z)-1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, AMOLEA (registered trademark) AS-300, or another such HFO nonflammable fluorine solvent; and 1,1,1,3,3-pentafluorobutane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, or another such HFC nonflammable fluorine solvent.

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 load such as ozone layer depletion, and further, a conventional detergent composition A detergent composition and an excellent property that it has the same or higher detergency, drying property, anti-redeposition property as dirt, but has extremely low attack on rubber and resin than conventional detergent compositions. It relates to the aerosol 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.

When using as a cleaning composition, it is necessary to sufficiently wet and wash away the portion to be cleaned with the cleaning composition, but since the above HFO-based nonflammable fluorine-based solvent has a 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.

In addition, as a fluorocarbon solvent of HFC (hydrofluorocarbon) type, 1,1,1,3,3-pentafluorobutane (Solkane 365) or 1,1,1,2,2,3,3,4,4, There are 5,5,6,6-tridecafluorohexane (AC-2000) etc., but low KB value has low oil saturation power (Non-patent document 2), and degreasing of automobile parts is not applicable (Non-Patent Document 3). 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.

JP, 2001-207199, A Patent No. 5619836 International Publication No. 2013/161723

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. It is an object of the present invention to provide a new detergent composition and its aerosol composition, which have drying properties, but have extremely low attack on rubber and resin than conventional detergent compositions.

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 is required to have a washing property equal to or higher than that of a conventional product which has not been achieved with a product having a high flash point or a water-based product, and to realize appropriate drying property.

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. When a composition containing HFC-based nonflammable fluorine-based solvent not having high compatibility with fats and oils is added, surprisingly, the resin and elastomer do not deteriorate, devitrify and dissolve, and furthermore, they are conventionally used. It exhibits superior properties as a cleaning composition, and various vehicles, vehicles, vehicles, vehicles, vehicles, tools, workplaces, such as automobiles, two-wheeled vehicles, bicycles, construction machines, agricultural machines, aircraft, railway vehicles, and ships. Tsu bets, was found to exhibit the properties of a new cleaning composition used for cleaning factory. And the invention of the new cleaning composition of this application and its aerosol composition is completed by examining the combination of the above-mentioned HFO nonflammable fluorine-based solvent and the HFC nonflammable fluorine-based solvent in more detail. I did.

The first means of the present invention for solving the above-mentioned problems is a detergent composition characterized by comprising an HFO nonflammable fluorine solvent and an HFC nonflammable fluorine solvent. is there.

A second means of the present invention for solving the above-mentioned problems is that the above-mentioned detergent composition comprises various vehicles, vehicles, transports such as cars, two-wheeled vehicles, bicycles, construction machines, agricultural machines, aircrafts, railway vehicles and ships. The cleaning composition according to the first means of the present invention, which is for use in engine, tool, work place, pit, and factory cleaning.

The third means of the present invention for solving the above-mentioned problems is that the above-mentioned detergent composition comprises various vehicles, vehicles, transports such as cars, two-wheeled vehicles, bicycles, construction machines, agricultural machines, aircrafts, railway cars and ships. It is the cleaning agent composition according to the second means of the present invention, which is for engine brake cleaners.

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

According to a fifth means of the present invention for solving the above-mentioned problems, the above-mentioned HFC nonflammable fluorine-based solvent is 1,1,1,3,3-pentafluorobutane, and 1,1,1,2 Any one of 1 to 3 of the present invention, characterized in that it is one or more selected from 2, 3, 3, 4, 3, 4, 5, 5, 6, 6-tridecafluorohexane; It is a detergent composition as described in the means of 1.

According to a sixth means of the present invention for solving the above-mentioned problems, the range of the mass ratio (HFO nonflammable fluorine solvent / HFC nonflammable fluorine solvent) is 99/1 to 1/99. It is a detergent composition according to any one of the first to fifth means of the present invention, characterized in that

A seventh 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 sixth means of the present invention and a propellant gas. It is.

The eighth means of the present invention for solving the above 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 seventh means of the invention, characterized in that it is LPG, DME or compressed air.

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

In the detergent composition of the means of the present invention and the aerosol composition thereof, both the HFO-based nonflammable fluorine-based solvent and the HFC-based nonflammable fluorine-based solvent blended as main components have no flash point, It is nonflammable. 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 since both HFO-based nonflammable fluorine-based solvents and HFC-based nonflammable fluorine-based solvents, which are the main components, correspond to non-hazardous substances under the Fire Service Law, dangerous goods warehouses are not required, and they are used in large quantities There is no legal restriction on the storage amount of the cleaning 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 excellent characteristics.

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 of the means of the present invention and the aerosol composition thereof contain two components, a HFO-based nonflammable fluorine-based solvent and an HFC-based nonflammable fluorine-based solvent.

The above-mentioned HFO-based nonflammable fluorine-based solvents cause deterioration, devitrification or dissolution of resins and elastomers (Non-Patent Document 1), and therefore, they can be used as they are as cleaning agent components of resins and elastomers. Not desirable. Further, the above-mentioned HFC-based fluorinated solvents have a low KB value and low oil and fat saturation (Non-patent Document 2), and degreasing and cleaning of automobile parts is not applicable (Non-patent document 3).

However, HFO-based nonflammable fluorine-based solvents, which are not suitable as components to be incorporated into such detergent compositions, have low oil saturation power and are not subject to degreasing and cleaning. HFC-based nonflammable fluorine-based solvents Unexpectedly, the resin and the elastomer are not affected by deterioration, devitrification, dissolution and the like, and have wider and superior cleaning properties than conventional cleaning compositions. It became a composition. Therefore, by including both HFO nonflammable fluorine-based solvents and HFC nonflammable fluorine solvents as main components, various types of materials can be maintained while maintaining various types of safety. It has become possible to provide a new detergent composition and its aerosol composition with excellent properties that can be used against it.

<About HFO-based nonflammable fluorine-based solvents>
The detergent composition of the means of the present invention and the aerosol composition thereof contain an HFO-based nonflammable fluorine-based solvent, which is a hydrofluoroolefin-based solvent, as one of the two essential components. 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 above-mentioned HFO-based nonflammable fluorine-based solvents are nonflammable solvents which have 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 above-mentioned HFO-based nonflammable fluorine-based solvent is invasive to resin. Therefore, the above-mentioned HFO-based nonflammable fluorine-based solvents such as (Z) -1-chloro-3,3,3-trifluoropropene and 1,1-dichloro-3,3,3-trifluoropropene are soft. When the resin acts on polyvinyl chloride (PVC) resin or 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 has poor compatibility with resin materials.

Further, the above-mentioned HFO-based nonflammable fluorine-based solvent 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 has poor compatibility with the elastomer as it is.

However, various vehicles and vehicles such as automobiles, two-wheeled vehicles, bicycles, construction machines, agricultural machines, aircrafts, railway vehicles, ships, etc., such as the resin compatibility of the non-combustible fluorine-based solvents of HFO series mentioned above and the high drying property.・ The property unsuitable for the detergent composition used for transportation etc. unexpectedly includes an HFC noncombustible fluorine-based solvent having other properties unsuitable for making the detergent composition together Thus, a better detergent composition is provided.

<About HFC-based nonflammable fluorine solvents>
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 the other of the two 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, HFC-based nonflammable fluorine-based solvents have a low KB value and low oil and fat saturation (Non-patent Document 2).

However, the low KB value of this HFC nonflammable fluorine-based solvent has low oil and fat saturation and is not compatible with oils and fats and solvents. Also, a cleaning agent which is eliminated by containing together an HFO-based nonflammable fluorine-based solvent having other properties that are unsuitable for use as cleaning compositions for various vehicles, vehicles, transportation, etc. A composition is provided.

Examples of HFC-based nonflammable fluorine-based solvents in the cleaning composition of the means of the present invention and the aerosol composition thereof include 1,1,1,3,3-pentafluorobutane, and 1,1,1,2 Or 2,3,3,4,3,4,5,5,6,6-tridecafluorohexane or one or more selected therefrom.

1,1,1,3,3-Pentafluorobutane can be obtained and used as a non-flammable HFC-based fluorocarbon solvent commercially available under the name of Solkane 365 (Solbay Japan Co., Ltd., Japan) it can. 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. And, it has a boiling point of 40.2 ° C. and has appropriate drying properties.

In addition, 1,1,1,2,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane is a non-flammable fluorocarbon solvent of the HFC type, Asahi Clean AC-2000 ( Commercially available products such as 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. And, it has a boiling point of 70.8 ° C. and has appropriate drying properties.

<About the mass ratio of the HFO-based nonflammable fluorine-based solvent to the HFC-based nonflammable fluorine-based solvent>
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. Non-combustible to the HFO system, which is contained in two components so as to improve the solubility and to provide better cleaning performance to members made of various materials such as metals, resins and elastomers, and appropriate drying speed. It is preferable to adjust the range of the mass ratio of the fluorocarbon solvent to the HFC nonflammable fluorine solvent.

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. The cleaning agent composition according to the means of the present invention and the aerosol composition of the means of the present invention are a HFO-based nonflammable fluorine-based solvent and an HFC-based nonflammable fluorine-based solvent, which are contained in the aerosol composition. The range of mass ratio is 99/1 to 1/99. HFO-based nonflammable fluorine-based solvents and HFC-based noncombustibles according to the types of oils and fats to be cleaned, and the types of resins and elastomers used in combination at the site to be cleaned and the surrounding area to be treated. It is possible to provide a cleaning composition and an aerosol composition thereof, in which the range of the mass ratio to the fluorocarbon solvent is adjusted respectively.

For example, the detergent composition according to the means of the present invention and the two components contained in the aerosol composition thereof are HFO-based nonflammable fluorine-based solvents (Z) -1-chloro-3,3,3-trifluoropropene And HFC nonflammable fluorine-based solvents are 1,1,1,3,3-pentafluorobutane or 1,1,1,2,2,3,3,4,4,5,5,6,6- In the case of tridecafluorohexane, the range of the mass ratio (HFO nonflammable fluorine solvent / HFC nonflammable fluorine solvent) is set to 99/1 to 1/99, preferably 99/1. It may be 1 to 10/90, more preferably 90/10 to 30/70, but the type of fat to be dissolved, the invasion, etc., so as to be compatible with the usage situation of the target customer Depending on the type of resin or elastomer to be protected Align, also taking into account the balance of the cost, it may be used to select a suitable among the above range weight. For example, AMOLEA (registered trademark) AS-300 is a HFO-based nonflammable fluorine-based solvent, and the proportion of the HFC-based nonflammable fluorine-based solvent is increased in order to enhance the protection against invasion to rubber or resin. The mass ratio may be 20/80 to 10/90 or the like. By adjusting the compounding ratio in this way, the resin and elastomer are less invasive, higher compatibility with oils and fats, etc., excellent cleaning property and moderate drying for members made of various materials such as metal, resin and elastomer. It becomes possible to combine a plurality of excellent properties such as having a speed, and the composition 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 main two components as the above-mentioned detergent composition, do not, if necessary, increase the risk of fire or fire. It may be compounded in degree. When the above-mentioned additional components are incorporated, the HFO system is achieved by the two main 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 which is a component used for the cleaning composition of the present invention, (Z) -1-chloro-3,3,3-trifluoropropene 1233Z (Central Glass Co., Ltd., Japan And 1,1-dichloro-3,3,3-trifluoropropene (Matrix Scientific, USA) were purchased. Furthermore, AMOLEA (registered trademark) AS-300 was supplied from AGC Corporation (Japan). In addition, as 1,1,1,3,3-pentafluorobutane which is a nonflammable fluorine-based solvent of HFC type, Solkane 365 (Sorbay Japan Japan, Japan) can be used as 1,1 as a nonflammable fluorine-based solvent of HFC type. As 1,2,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, Asahiklin AC-2000 (AGC Corporation, Japan) was purchased respectively.

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 mass ratio of the HFO-based nonflammable fluorine-based solvent to the HFC-based nonflammable fluorine-based solvent is as follows, and the HFO-based nonflammable fluorine-based solvent and the HFC-based solvent of the present invention The detergent compositions of Examples 1 to 12, which are detergent compositions comprising the nonflammable fluorine-based solvent of

<HFO-based nonflammable fluorine-based solvent / HFC non-flammable fluorine-based solvent>
・ Mass ratio (1233Z / Solkane 365)
Example 1: 90/10
Example 2: 80/20
Example 3: 70/30
Example 4: 50/50
Example 5: 30/70
Example 6: 10/90
・ Mass ratio (1233Z / AC-2000)
Example 7: 90/10
Example 8: 80/20
Example 9: 70/30
Example 10: 50/50
Example 11: 30/70
Example 12: 10/90
Mass ratio (AS-300 / Solkane 365)
Example 14: 10/90
Example 15: 20/80

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 5 to 8 were prepared for comparison with those of Examples in which two components of HFO-based nonflammable fluorine-based solvent and HFC-based nonflammable fluorine-based solvent were blended together.
<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 13: Only AS-300 <Non-combustible fluorine-based solvent of HFC system>
Comparative Example 7: Only Solkane 365 Comparative Example 8: Only AC-2000

Next, Test Examples 1 to 3 shown below are carried out, and the cleaning agent composition of the means of the present invention and the aerosol composition thereof have superior characteristics to conventional cleaning agents. Was specifically confirmed.

<Test Example 1: Evaluation of invasiveness (long-term contact)>
Materials and Methods The solutions of Examples 1 to 12 and 14 to 15 and Comparative Examples 1 to 8 and 13 are prepared as test solutions.
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 Results The results of the above tests are shown in Tables 1-1 to 1-4.

In Test Example 1, the composition containing the HFO-based nonflammable fluorine-based solvent and the HFC-based nonflammable fluorine-based solvent improves the attack on the rubber or resin possessed by the HFO-based nonflammable fluorine-based solvent. I confirmed that I did. 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 product quality can not be secured (Table 1-1).

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).

However, it is surprisingly observed when the above-mentioned HFO-based nonflammable fluorine-based solvent is used, by blending the HFC-based non-flammable fluorine-based solvent 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 of various rubbers and resins (Tables 1-2 to 1-4).

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.

Further, the HFO 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 the HFO nonflammable fluorine based solvent and the HFC nonflammable fluorine based solvent. It is understood that it has an effect of increasing the supply amount as a detergent composition and preventing the stagnation of the product supply, since it is manufactured by mixing B.

Among the above-mentioned rubbers, SBR (styrene-butadiene rubber) is also used for sealing a brake fluid system of an automobile or for a tire etc. Therefore, the cleaning agent used for cleaning a brake device and its periphery is erosive to SBR. Is desired to be low. Further, PC (polycarbonate) is also used in control system mechanisms such as a brake device. However, as in the present invention, by blending the HFC non-combustible fluorine solvent with the HFO non-combustible fluorine solvent astonishingly, the problem of the erosibility to SBR and PC is also sufficiently enough. It was possible to reduce and limit their swelling rate to 5% or less at which the product quality can be maintained to a certain extent.

<Test Example 2: Evaluation of invasiveness (short-term contact)>
Materials and Methods In the same manner as in Test Example 1, the solutions of Examples 1 to 12 and 14 and Comparative Examples 1 to 8 and 13 described above 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 Results The results of the above tests are shown in Tables 2-1 to 2-4.

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 (Table 2-1).

However, the HFC non-flammable fluorine-based solvent is blended with the HFC non-flammable fluorine-based solvent to form the cleaning agent composition of the means of the present invention, such short-term contact It became clear that the resin did not deteriorate (Table 2-2 to Table 2-4).

<Test Example 3: Evaluation of compatibility with grease and oil>
Materials and Methods In the same manner as in Test Example 1, the solutions of Examples 1 to 12, 14 and 15 and Comparative Examples 1 to 8 and 13 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.

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

Since various HFC-based nonflammable fluorine-based solvents have almost no compatibility with grease or brake oil (Comparative Example 7 to Comparative Example 8 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. 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.

However, it is surprising that grease or HFO-based nonflammable fluorine-based solvent and HFC-based nonflammable fluorine-based solvent can not be used for cleaning vehicles, vehicles and vehicles as described above. It has become clear this time to show a wide compatibility with fat and oil components such as brake oil, that is, to exhibit high washability to these fat and oil components (Table 3-2 to Table 3-3). . Further, the range of the mass ratio of the HFO-based nonflammable fluorine-based solvent and the HFC-based nonflammable fluorine-based solvent showing compatibility was wide (Tables 3-2 to 3-3). Furthermore, HFO-based nonflammable fluorine-based solvents such as AMOLEA (registered trademark) AS-300 contain a large amount of HFC-based nonflammable fluorine-based solvents to improve the invasiveness to rubber and resin, and the HFO-based noncombustible Even when the volatile fluorine-based solvent was diluted, no decrease in the cleaning properties to various greases was confirmed. From this, as in the means of the present invention, the cleaning agent composition and the aerosol composition thereof contain the HFO-based nonflammable fluorine-based solvent and the HFC-based nonflammable fluorine-based solvent, thereby achieving the cleaning. HFO-based nonflammable fluorine-based solvents and HFC-based nonflammables according to the types of target oils and fats, and the types of resins and elastomers used in combination at the site to be cleaned and the peripheral site to be treated for suppression of invasion. It is understood that it is possible to adjust the range of the mass ratio with the fluorinated solvent to variously provide the cleaning agent composition and its aerosol composition having characteristics suitable for the scene using the cleaning agent composition. .

Moreover, in the conventional cleaning agent, there was a case where compatibility with GREASE (orange) and rubber grease was lacking (Table 2-1). However, as shown in Tables 2-2 to 2-3, HFC-based nonflammable fluorine-based solvents having little compatibility with GREASE (orange) or rubber grease and HFO-based nonflammable fluorine-based solvents It was revealed that, even when diluted with HFO-based nonflammable fluorine-based solvents, those showing compatibility with these GREASE (orange) and rubber grease were newly obtained. .

Thus, by including the HFO-based nonflammable fluorine-based solvent and the HFC-based nonflammable fluorine-based solvent in the cleaning composition as in the present invention, the composition is widely compatible with grease or brake oil. It will be appreciated that new detergent compositions can be provided which are rendered non-combustible and less toxic and yet have the same or better cleaning properties as conventional brake cleaners.

The fire-fighting law and fire-fighting law are low because the HFO-based nonflammable fluorine-based solvent and the HFC-based nonflammable fluorine-based solvent are nonflammable because they are contained in the cleaning agent composition. It corresponds to the above non-hazardous substances, there is no need to store dangerous goods, there are no legal restrictions on the storage amount of cleaning compositions used in large quantities, and furthermore it has low toxicity and low environmental impact such as ozone layer destruction. New cleaning agent composition and aerosol thereof having excellent properties such as extremely low attack property to rubber and resin while having the property and the cleaning property equal to or more than the conventional cleaning agent composition for brake cleaner It becomes possible to provide a composition.

Claims

Various vehicles such as automobiles, two-wheeled vehicles, bicycles, construction machines, agricultural machines, aircrafts, railway vehicles, ships, etc., characterized in that they contain HFO-based nonflammable fluorine-based solvents and HFC-based nonflammable fluorine-based solvents. Cleaning compositions for vehicles and vehicles, tools, workplaces, pits and factories.
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 mass ratio of the HFO-based nonflammable fluorine-based solvent to the HFC-based nonflammable fluorine-based solvent (HFO-based nonflammable fluorine-based solvent / HFC-based nonflammable fluorine-based solvent) is 99/1 to 1/99 The detergent composition according to claim 1 or 2, characterized in that
HFO-based nonflammable fluorine-based solvents are (Z) -1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene, 1,2-dichloro- The compound according to claim 1, characterized in that it is one or more selected from 3,3,3-trifluoropropene, 2,3,3-trichloro-3-fluoropropene, AMOLEA® AS-300. The cleaning composition according to any one of claims 1 to 3.
The nonflammable fluorine-based solvents of HFC series are 1,1,1,3,3-pentafluorobutane and 1,1,1,2,2,3,3,4,4,5,5,6,6 The detergent composition according to any one of claims 1 to 3, characterized in that it is one or more selected from-tridecafluorohexane.
An aerosol composition comprising the cleaning composition according to any one of claims 1 to 5 and a propellant gas.
7. The method according to claim 6, wherein 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 7.