AEROSOL DETERGENT COMPOSITION

Abstract

A method for washing of car/vehicle/transportation means and braking device using an aerosol composition containing (Z)-1-chloro-3,3,3-trifluoropropene and gas propellant which is N.sub.2, compressed air, CO.sub.2, argon, or a mixture of two or more thereof.

Claims

1. A method for washing car/vehicle/transportation means, the method comprising spraying onto car/vehicle/transportation means an aerosol composition, thereby washing the car/vehicle/transportation means, wherein the aerosol composition consists of (Z)-1-chloro-3,3,3-trifluoropropene and gas propellant which is at least one of the group consisting of N.sub.2, compressed air, CO.sub.2 and argon.

2. A method for washing a braking device of car/vehicle/transportation means, the method comprising spraying onto a braking device of car/vehicle/transportation means an aerosol composition, thereby washing the braking device of the car/vehicle/transportation means, wherein the aerosol composition consists of (Z)-1-chloro-3,3,3-trifluoropropene and gas propellant which is at least one of the group consisting of N.sub.2, compressed air, CO.sub.2 and argon.

Description

WORKING EXAMPLES

[0029] Indicated below in the form of working examples and exemplary tests are examples of manufacture and use of detergent compositions and aerosol compositions of same in accordance with the present invention.

Test Samples

[0030] Test samples were prepared. As (Z)-1-chloro-3,3,3-trifluoropropene, which is a component used in the detergent composition in accordance with the present invention, 1233Z (Central Glass Co., Ltd.; Japan) was purchased. Furthermore, as conventional detergents, Brake and Parts Cleaner (Quick-Drying Type) (Kobegosei Co., Ltd.; Japan) employing isohexane was used as quick-drying stock solution; moreover, the following were respectively purchased: Degreasing Cleaner (Honda Access Corporation; Japan) employing cyclohexane which was used as degreasing cleaner; the isoparaffinic solvent Brake Cleaner N04 (Suzuki Motor Corporation; Japan) serving as air-dry stock solution; and also trichloroethane.

[0031] In addition, aerosol compositions in accordance with the present invention were manufactured by causing pressure-resistant cans to respectively be filled with the aerosol compositions indicated below at Working Example 1 through Working Example 3. [0032] Working Example 1: Aerosol composition containing (Z)-1-chloro-3,3,3-trifluoropropene and containing gas propellant in the form of N.sub.2 [0033] Working Example 2: Aerosol composition containing (Z)-1-chloro-3,3,3-trifluoropropene and containing gas propellant in the form of compressed air [0034] Working Example 3: Aerosol composition containing (Z)-1-chloro-3,3,3-trifluoropropene and containing gas propellant in the form of CO.sub.2

[0035] Furthermore, an aerosol composition serving as comparative example was manufactured by causing a pressure-resistant can to be filled with the aerosol composition indicated below at Comparative Example 4. Moreover, conventional detergent compositions were prepared by respectively using quick-drying stock solution, degreasing cleaner, and air-dry stock solution as Comparative Examples 5 through 7. Note that the quick-drying stock solution, the degreasing cleaner, and the air-dry stock solution were all highly combustible; that the trichloroethane was highly harmful; and that these all had properties that would be problematic in the context of a composition for washing. [0036] Comparative Example 4: Aerosol composition containing (Z)-1-chloro-3,3,3-trifluoropropene and containing gas propellant in the form of LPG (liquefied petroleum gas) [0037] Comparative Example 5: Quick-drying stock solution [0038] Comparative Example 6: Degreasing cleaner [0039] Comparative Example 7: Air-dry stock solution [0040] Comparative Example 8: Trichloroethane

[0041] Next, the respective Exemplary Tests indicated below were carried out, and it was confirmed in specific terms that aerosol compositions in accordance with the means of the present invention had superior properties.

Exemplary Test 1: Evaluation of Miscibility with Grease and Oil

Materials and Methods

[0042] As test samples, Working Examples 1 through 3 and Comparative Examples 4 through 8 were prepared.

[0043] As the lipids to be washed and removed, the various types of greases and oils indicated below which are in general use in automobiles and so forth were prepared.

Grease: GREASE (Orange) (Kobegosei Co., Ltd.; Japan)

[0044] : Rubber and Brake Dual-Purpose Grease (Kobegosei Co., Ltd.; Japan) [0045] : Disc Brake Grease (Kobegosei Co., Ltd.; Japan) [0046] : Brake Grease (Kobegosei Co., Ltd.; Japan) [0047] : Silicon Grease (Kobegosei Co., Ltd.; Japan) [0048] : Caliper Pin Grease (Honda Access Corporation; Japan) [0049] : Pad & Shoe Grease (Honda Access Corporation; Japan) [0050] : Rubber Grease (Honda Access Corporation; Japan) [0051] : Brake Grease (Honda Access Corporation; Japan)

Oil: Engine Oil Mobil 1 OW-20 (Exxon Mobil; USA)

[0052] : Brake Fluid (DOT3) (Honda Access Corporation; Japan) [0053] : Brake Fluid (DOT4) (Suzuki Motor Corporation; Japan)

[0054] 10-mL vials were prepared, 1 g of the foregoing grease or engine oil being placed into each one thereof. The aerosol compositions and solutions according to Working Examples 1 through 3 and Comparative Examples 4 through 8 were further added to the vials. After the caps of the vials were closed, each of the vials was subjected to ultrasonic processing using an ultrasonic washer (AU16C; Aiwa Medical Industry Co., Ltd.; Japan).

[0055] Following ultrasonic processing for 1 hour, the respective vials were removed from the ultrasonic washer. The interiors of the vials were examined, miscibility being evaluated as GOOD if the grease or engine oil and the solutions according to each of Working Examples 1 through 3 and Comparative Examples 4 through 8 were completely mixed, FAIR if these were partly separated, and BAD if these were completely separated.

Test Results

[0056] Results of tests carried out as described above are shown at TABLE 1.

TABLE-US-00001 TABLE 1 Working Comparative Comparative Working Example Working Comparative Example Comparative Example Comparative Example 2 Example Example 5 Example 7 Example 1 3 4 Quick drying stock 6 Air dry 8 Component  N.sub.2 compressed air 12  CO.sub.2 12  LPG  cleaner stock solution GOOD GOOD GOOD GOOD BAD BAD BAD GOOD Rubber and Brake GOOD GOOD GOOD GOOD GOOD GOOD GOOD GOOD Dual Purpose FAIR FAIR FAIR FAIR FAIR FAIR FAIR GOOD Brake GOOD GOOD GOOD GOOD GOOD GOOD GOOD GOOD Silicone GOOD GOOD GOOD GOOD GOOD GOOD GOOD GOOD Caliper GOOD GOOD GOOD GOOD GOOD GOOD GOOD GOOD GOOD GOOD GOOD GOOD GOOD GOOD GOOD GOOD Rubber GOOD GOOD GOOD GOOD FAIR FAIR FAIR GOOD Brake FAIR FAIR FAIR FAIR GOOD GOOD GOOD GOOD GOOD GOOD GOOD GOOD GOOD GOOD GOOD GOOD Brake Fluid (DOT3) GOOD GOOD GOOD GOOD BAD GOOD GOOD GOOD Brake Fluid (DOT4) GOOD GOOD GOOD GOOD BAD GOOD GOOD GOOD indicates data missing or illegible when filed

[0057] It was found that Working Examples 1 through 3 and Comparative Example 4, which employed (Z)-1-chloro-3,3,3-trifluoropropene, had generally satisfactory miscibility with respect to various types of greases and oils which are in general use in automobiles, it being clear that these were miscible with a larger number of types of greases and oils than was the case for conventional quick-drying stock solution, degreasing cleaner, or air-dry stock solution (TABLE 1). It is clear from this that employment of (Z)-1-chloro-3,3,3-trifluoropropene makes it possible to achieve a miscibility with respect to greases and oils that is as good as or better than that of conventional detergent compositions, there being adequate potential for it to make it possible for grease, oil, and/or other such dirt adhering to automobiles, two-wheeled vehicles, bicycles, construction equipment, farm equipment, aircraft, railroad cars, ships, and/or various other types of car/vehicle/transportation means to be effectively washed therefrom.

[0058] Exemplary Test 2: Evaluation of Drying Characteristics

Materials and Methods

[0059] In similar fashion as at Exemplary Test 1, aerosol compositions and solutions according to the foregoing Working Examples 1 through 3 and Comparative Examples 4 through 8 were respectively prepared.

[0060] Temperature conditions at a Temperature & Humidity Chamber (HPAV 40; Isuzu Seisakusho Co., Ltd.; Japan) were adjusted to be 70% humidity and 40° C., 25° C., or 10° C., 2-cm flat dishes were placed therein, and these were allowed to stand. When the temperatures of the flat dishes had stabilized, amounts corresponding to 100 μl of the compositions and solutions according to Working Examples 1 through 3 and Comparative Examples 4 through 8 were placed in flat dishes, and visual inspection was employed to measure the times until the respective droplets of solution in the flat dishes had completely evaporated and dried.

Test Results

[0061] Upon carrying out the aforementioned test, it was found that drying times at 40° C., 25° C., and 10° C. were respectively 1 minute 36 seconds, 2 minutes 11 seconds, and 3 minutes 54 seconds for conventional quick-drying stock solution (Comparative Example 5); were respectively 3 minutes 48 seconds, 5 minutes 58 seconds, and 6 minutes 38 seconds for conventional degreasing cleaner (Comparative Example 6); and were respectively 15 minutes or more, 15 minutes or more, and 10 minutes or more for conventional air-dry stock solution.

[0062] On the one hand, at Comparative Example 4 (the aerosol composition containing (Z)-1-chloro-3,3,3-trifluoropropene and containing gas propellant in the form of LPG), which employed LPG, LPG being frequently used in conventional aerosol compositions, the LPG evaporated immediately following spraying, and the (Z)-1-chloro-3,3,3-trifluoropropene was made into fine droplets which also immediately evaporated.

[0063] On the other hand, at Working Example 1 (the aerosol composition containing (Z)-1-chloro-3,3,3-trifluoropropene and containing gas propellant in the form of N.sub.2), Working Example 2 (the aerosol composition containing (Z)-1-chloro-3,3,3-trifluoropropene and containing gas propellant in the form of compressed air), and Working Example 3 (the aerosol composition containing (Z)-1-chloro-3,3,3-trifluoropropene and containing gas propellant in the form of CO.sub.2), the aerosol did not undergo evaporation or the like immediately following spraying but remained in the form of a solution and was rod-like in shape as it was sprayed, being made into a solution comprising (Z)-1-chloro-3,3,3-trifluoropropene, the drying times of which were respectively 0 minutes 57 seconds, 1 minute 37 seconds, and 2 minutes 14 seconds for Working Example 1; were respectively 0 minutes 52 seconds, 1 minute 32 seconds, and 2 minutes 9 seconds for Working Example 2; and were respectively 0 minutes 50 seconds, 1 minute 30 seconds, and 2 minutes 5 seconds for Working Example 3.

[0064] From these results, it is clear that the aerosol compositions which employed gas propellant in the form of N.sub.2, compressed air, or CO.sub.2 in accordance with Working Example 1 through Working Example 3 were such that the (Z)-1-chloro-3,3,3-trifluoropropene was not made into fine droplets that evaporated immediately but remained in the form of a solution and was rod-like in shape as it was sprayed, arriving in the form of a solution at the item being sprayed, where it continued to exist in the form of a solution for a given time. Based on the foregoing, it was all the more clear that use of an aerosol composition employing gas propellant in the form of N.sub.2, compressed air, or CO.sub.2 permitted attainment of a substance that had adequate potential to cause target dirt to be moistened with and removed by (Z)-1-chloro-3,3,3-trifluoropropene solution.

[0065] On the other hand, whereas LPG gas propellant is frequently used in conventional aerosol compositions, it is clear that the aerosol composition of Comparative Example 4 was such that immediately following spraying the LPG, contrary to what might be expected, evaporated, and the (Z)-1-chloro-3,3,3-trifluoropropene was made into fine droplets that also evaporated immediately, it not being the case that this was able to arrive in the form of a solution at the item being sprayed where it might continue to exist in the form of a solution for a given time. It was all the more clear that when gas propellant in the form of LPG, which is frequently used in conventional aerosol compositions, was used in combination with (Z)-1-chloro-3,3,3-trifluoropropene solution, it was difficult to cause target dirt to be moistened with and adequately removed by the (Z)-1-chloro-3,3,3-trifluoropropene solution.

Exemplary Test 3: Evaluation of Gas Propellant Used in Aerosol Composition

Materials and Methods

[0066] In similar fashion as at Exemplary Test 1, aerosol compositions according to the foregoing Working Examples 1 through 3 and Comparative Example 4 were respectively prepared.

[0067] Investigation was carried out to determine whether any differences in sprayed state, drying time, sprayable distance, or washability were respectively observed as a function of the type of gas employed in the aerosol composition. Using metal plates, aerosol compositions in accordance with the foregoing Working Examples 1 through 3 and Comparative Example 4 were sprayed for 10 seconds from locations separated 5 cm, 10 cm, 50 cm, 1 m, 2 m, and 10 m from the metal plates, visual inspection being employed to observe the sprayed state of the aerosols, the state of the liquid after it was sprayed onto the metal plates, and to measure the time until the liquid had dried.

Test Results

[0068] For those which employed gas propellant in the form of N.sub.2, compressed air, or CO.sub.2 in accordance with Working Example 1 through Working Example 3 which were aerosol compositions that were means in accordance with the present invention, the aerosol did not undergo evaporation or the like immediately following spraying for 10 seconds, but rather the aerosol composition remained in the form of a solution, being rod-like in shape as it was sprayed, and it was confirmed that a small region 5 cm in diameter on the metal plates that were separated 5 cm, 10 cm, 50 cm, and 1 m therefrom could be wetted in focused fashion by the (Z)-1-chloro-3,3,3-trifluoropropene solution. Where CO.sub.2 was used, it was found that it was possible to cause this to be sprayed in such fashion that it remained in the form of a solution and was rod-like in shape for internal pressures of the gas within the pressure-resistant can that were up to 0.2 MPa, but that for internal pressures which exceeded this the aerosol became mist-like. It can be understood that by keeping the internal pressure at or below a roughly constant value, it is possible to cause the aerosol to be rod-like in shape such that the aerosol composition can be sprayed in pinpoint fashion on only those desired locations at metal members that are contaminated by lipids and the like and to avoid causing the (Z)-1-chloro-3,3,3-trifluoropropene solution to come in contact with resins and elastomers at important components such as brakes and other such braking devices of car/vehicle/transportation means. Furthermore, with N.sub.2 or compressed air, even where internal pressure was greater than 0.2 MPa, the aerosol composition did not become mist-like, it being confirmed that it was possible to cause the aerosol composition to remain in the form of a solution and be rod-like in shape as it arrived at metal plates that were separated by even longer distances as far away as 2 m and 10 m, such that a small region 5 cm in diameter on the metal plates could be wetted in focused fashion by the (Z)-1-chloro-3,3,3-trifluoropropene solution. Where N.sub.2 or compressed air is used, it can be understood that it is possible to cause the aerosol composition to remain in the form of a solution and be rod-like in shape as it arrives at metal plates separated by even longer distances, increasing the degrees of freedom with which washing can be carried out while avoiding causing the (Z)-1-chloro-3,3,3-trifluoropropene solution to come in contact with resins and elastomers at important components such as brakes and other such braking devices of car/vehicle/transportation means.

[0069] On the other hand, while LPG gas propellant is frequently used in conventional aerosol compositions, because the aerosol composition of Comparative Example 4 was such that immediately following spraying the LPG evaporated, in accompaniment to which the (Z)-1-chloro-3,3,3-trifluoropropene solution also quickly evaporated, and it was not possible for the metal plates to be moistened by the (Z)-1-chloro-3,3,3-trifluoropropene solution, confirming that it was not suitable for washing car/vehicle/transportation means where resins and elastomers are used in combination with other materials at important components.

Exemplary Test 4: Evaluation of Washability of Aerosol Composition

Materials and Methods

[0070] In similar fashion as at Exemplary Test 1, aerosol compositions according to the foregoing Working Examples 1 through 3 and Comparative Example 4 were respectively prepared.

[0071] Washability of the aerosol compositions was ascertained. A plurality of metal plates that each had a plurality of grooves 1 mm in width and 1 mm in depth on the surface thereof were prepared, and the greases and oils used at Exemplary Test 1 were respectively applied thereto. Aerosol compositions in accordance with Working Examples 1 through 3 and Comparative Example 4 were sprayed for 10 seconds or 30 seconds, with spray distance being varied, and the diameter of the region wetted by solution at the time that the aerosol arrived at the metal plate was measured, and evaluation was carried out such that it was deemed to be EXCELLENT if the solution of the aerosol did not dry but flowed downward and dissolved the grease or oil and caused it to be adequately washed away therefrom so that there was no residue remaining therefrom; GOOD if the solution of the aerosol did not dry but dripped downward therefrom and generally washed away the grease or oil; FAIR if the solution of the aerosol stayed where it was and while causing the grease or oil to be dissolved by the solution of the aerosol was such that the solution of the aerosol dried before it could complete its task so that residue from the grease or oil remained on the metal plate; and BAD if evaporation of the solution of the aerosol from the metal plate caused the grease or oil to remain as it was without being adequately dissolved thereby.

Test Results

[0072] For those which employed gas propellant in the form of N.sub.2, compressed air, or CO.sub.2 in accordance with Working Example 1 through Working Example 3 which were aerosol compositions that were means in accordance with the present invention, upon spraying for 10 seconds it was found that a small region which was 5 cm in diameter on the metal plate could be wetted in focused fashion by the (Z)-1-chloro-3,3,3-trifluoropropene solution, and that this was able to receive an evaluation of GOOD, as the solution of the aerosol did not dry but dripped downward therefrom and generally washed away the grease or oil. Furthermore, upon spraying for 30 seconds it was found that a small region which was 5 cm in diameter on the metal plate could be wetted in focused fashion by the (Z)-1-chloro-3,3,3-trifluoropropene solution, and that this was able to receive an evaluation of EXCELLENT, as the solution of the aerosol did not dry but flowed downward and dissolved the grease or oil and caused it to be adequately washed away therefrom so that there was no residue remaining therefrom. For those which employed N.sub.2 or compressed air, washability of grease and oil on metal plates separated by an even longer distance of 10 m was also ascertained when internal pressure was increased to greater than 0.2 MPa, it being found in each case upon spraying for 90 seconds that a small region 5 cm in diameter on the metal plate could be wetted in focused fashion by the (Z)-1-chloro-3,3,3-trifluoropropene solution, and that this was able to receive an evaluation of GOOD, as the solution of the aerosol did not dry but dripped downward therefrom and generally washed away the grease or oil; and moreover, upon spraying for 180 seconds that a small region 5 cm in diameter on the metal plate could be wetted in focused fashion by the (Z)-1-chloro-3,3,3-trifluoropropene solution, and that this was able to receive an evaluation of EXCELLENT, as the solution of the aerosol did not dry but flowed downward and dissolved the grease or oil and caused it to be adequately washed away therefrom so that there was no residue remaining therefrom. It can be understood that, the sprayed state of the aerosol being rod-like in shape, because it is possible to carry out washing in such fashion that contaminated locations are targeted in pinpoint fashion, and because it is possible to carry out washing in such fashion that the sprayed state of the aerosol is rod-like in shape and contaminated locations are targeted in pinpoint fashion even from longer distances, this makes it possible to carry out washing from a distance, without the need to disassemble the device so that washing may be carried out in close proximity thereto, permitting increase in universality during washing operations in terms of ability to accommodate mechanization and so forth.

[0073] On the other hand, because the aerosol composition of Comparative Example 4 was such that immediately following spraying the LPG evaporated, in accompaniment to which the (Z)-1-chloro-3,3,3-trifluoropropene solution also quickly evaporated and spread out over a wide area, it was not possible for the metal plates to be moistened by the (Z)-1-chloro-3,3,3-trifluoropropene solution, and this received an evaluation of BAD, as evaporation of the solution of the aerosol from the metal plate caused the grease or oil to remain as it was without being adequately dissolved thereby. Furthermore, when the metal plates were brought into close proximity with the aerosol spray nozzle, it was found that immediately following spraying the LPG evaporated, and the (Z)-1-chloro-3,3,3-trifluoropropene was made into fine droplets that adhered thereto over a wide area. It can be understood that this will cause there to be an extremely high risk that the (Z)-1-chloro-3,3,3-trifluoropropene solution could come in contact with resins and elastomers used in combination with other materials at important components such as brakes and other such braking devices of car/vehicle/transportation means, and that the resins and elastomers would be eroded thereby, making it unsuitable as an aerosol composition for washing automobiles, two-wheeled vehicles, bicycles, construction equipment, farm equipment, aircraft, railroad cars, ships, and/or various other types of car/vehicle/transportation means.

Exemplary Test 5: Evaluation of Gas Propellant (Gas Mixture) Used in Aerosol

Composition

Materials and Methods

[0074] Aerosol compositions employing gas propellants and (Z)-1-chloro-3,3,3-trifluoropropene in accordance with the present invention were also evaluated by mixing the gas propellants used.

[0075] In similar fashion as at Exemplary Test 1, pressure-resistant cans were filled with (Z)-1-chloro-3,3,3-trifluoropropene and gas propellant in the form of N.sub.2, CO.sub.2 and N.sub.2, or CO.sub.2 to manufacture the substances in accordance with Working Examples 9 through 16. Moreover, the conditions under which these were filled with the gas propellants were established as follows. [0076] Working Example 9: Filling by N.sub.2 was carried out until internal pressure reached 0.6 MPa. [0077] Working Example 10: Filling by CO.sub.2 was carried out so as to cause internal pressure to be 0.1 MPa, and then filling by N.sub.2 was carried out until internal pressure reached 0.6 MPa. [0078] Working Example 11: Filling by CO.sub.2 was carried out so as to cause internal pressure to be 0.2 MPa, and then filling by N.sub.2 was carried out until internal pressure reached 0.6 MPa. [0079] Working Example 12: Filling by CO.sub.2 was carried out so as to cause internal pressure to be 0.3 MPa, and then filling by N.sub.2 was carried out until internal pressure reached 0.6 MPa. [0080] Working Example 13: Filling by CO.sub.2 was carried out so as to cause internal pressure to be 0.4 MPa, and then filling by N.sub.2 was carried out until internal pressure reached 0.6 MPa. [0081] Working Example 14: Filling by CO.sub.2 was carried out so as to cause internal pressure to be 0.5 MPa, and then filling by N.sub.2 was carried out until internal pressure reached [0082] Working Example 15: Filling by CO.sub.2 was carried out until internal pressure reached 0.6 MPa.

[0083] Furthermore, as comparative examples, Comparative Example 16 which used gas propellant in the form of LPG, the internal pressure of which was chosen to be 0.25 MPa; Comparative Example 17 at which a manually operated spray bottle was filled with (Z)-1-chloro-3,3,3-trifluoropropene; and Comparative Example 18 at which a wash bottle was filled with (Z)-1-chloro-3,3,3-trifluoropropene, were also prepared.

[0084] The foregoing Working Examples 9 through 15 and Comparative Examples 16 through 18 were used to respectively investigate sprayed state, degree of dripping, washing zone size, and washability. For Working Examples 9 through 15 and Comparative Example 16, the amount (g) of aerosol composition that was sprayed when spraying was carried out for 2 seconds was first measured. The amount sprayed in 2 seconds was approximately 20 g for each of Working Examples 9 through 12, while the amount sprayed in 2 seconds was less than this for each of Working Examples 13 through 15 and Comparative Example 16. During testing to ascertain washing effect, for Working Examples 9 through 12, spraying time was therefore set to 2 seconds so as to cause the amount sprayed to be approximately 20 g; but for Working Examples 13 through 15 and Comparative Example 16, for which the amount sprayed was smaller, spraying time was set longer than this so as to cause the amount sprayed to be approximately 20 g.

[0085] The metal plates used at Exemplary Test 4 were employed, 0.2 g of brake grease being applied in the shape of a circle 36 mm in diameter to the surface of each thereof. Next, Working Examples 9 through 15 and Comparative Examples 16 through 18 were used to spray 20 g of (Z)-1-chloro-3,3,3-trifluoropropene solution on each of the metal plates to which brake grease had been applied, and the sprayed state of the aerosol, as well as the degree of dripping, washing zone size, and washability of the (Z)-1-chloro-3,3,3-trifluoropropene solution, were measured.

Test Results

[0086] Results of tests carried out as described above are shown at TABLE 2.

TABLE-US-00002 TABLE 2 Working Working Working Working Working Working Criterion Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Pressure at time Not filled 0.1 0.20 0.70 0.41 0.90 filled with CO.sub.2 (MPa) with CO.sub.2 Pressure after 0.61 0.60 0.60 0.61 0.60 0.61 filling with 10.35 30.16 20.0#z,899 19.25 16.19 14.98 Pressure after 0.56 0.56 0.56 0.56 0.56 0.56 spraying (MPa) Sprayed Rod-like Rod-like Misty Misty Misty Mist-like Mist-like Washing  one or more 8.25 8.00 9.00 9.75 Washing  one or more 5.25 7.25 7.90 8.00 8.25 8.00 Working Comparative Comparative Comparative Example 15 Example 16 Example 17 Example 18 CO.sub.2 LPG (Manually operated (Wash bottle) spray bottle) Pressure at time filled with CO.sub.2 (MPa) Pressure after filling with Not filled with N.sub.2 13.61 7.57 Pressure after 0.56 0.25 spraying (MPa) Sprayed Mist-like Evaporated Mist-like Rod-like Washing 9.00 Washing 8.00 indicates data missing or illegible when filed

[0087] It was found that the aerosol compositions for washing in accordance with the present invention were such that use of gas propellant in the form of N.sub.2 made it possible for the (Z)-1-chloro-3,3,3-trifluoropropene solution to not immediately evaporate but to be rod-like in shape as it was sprayed, such that the solution was able to accurately arrive at the surface of the metal plate being washed even when the distance therefrom was kept to 20 cm or 50 cm, causing the portions at which it arrived to be wetted thereby, and for the solution to adequately drip from such portions, which is to say that following washing the solution did not stay at the contaminated region but flowed downward, causing the washed location to become clean. It was also found that the size of the washing zone was relatively small, being 5.25 cm to 6.25 cm (TABLE 2). It can be understood that where a contaminated region is focused at a single spot, use of an aerosol composition employing gas propellant in the form of N.sub.2 will make it possible to carry out washing operations with good efficiency. Moreover, similar to that which was confirmed at the foregoing Exemplary Test, where gas propellant in the form of CO.sub.2 is used, because when a pressure-resistant can is filled with CO.sub.2 at an internal pressure not greater than 0.2 MPa the (Z)-1-chloro-3,3,3-trifluoropropene solution does not immediately evaporate but is rod-like in shape as it is sprayed, it can be understood that where a contaminated region is focused at a single spot, CO.sub.2 may also similarly be employed as gas propellant in combination with an aerosol composition for washing that employs (Z)-1-chloro-3,3,3-trifluoropropene solution.

[0088] Moreover, when a pressure-resistant can was filled with gas propellant in the form of CO.sub.2 such that the internal pressure thereof reached 0.6 MPa, it was confirmed that the sprayed state stayed mist-like such that the (Z)-1-chloro-3,3,3-trifluoropropene solution was able to arrive at the surface of the metal plate, and that the brake grease which had been applied thereto could be adequately washed therefrom. Furthermore, upon investigating the washing zone size, it was found that the size of the washing zone was 8.00 cm to 9.00 cm, which was larger than that of the nitrogen gas which was rod-like in shape (TABLE 2). In addition, when a pressure-resistant can was filled with gas propellant in the form of a mixture of N.sub.2 and CO.sub.2 such that the internal pressure thereof reached 0.6 MPa, when filling was carried out beforehand such that CO.sub.2 reached 0.2 MPa, it was confirmed that the sprayed state was misty-rod-like, the size of the washing zone being larger than that of the N.sub.2 which was rod-like but the size of the washing zone following spraying being smaller than that which existed with CO.sub.2 alone, such that the (Z)-1-chloro-3,3,3-trifluoropropene solution was able to arrive at the surface of the metal plate, and that the brake grease which had been applied thereto could be adequately washed therefrom. Furthermore, when filling was carried out beforehand with 0.3 MPa or more of CO.sub.2, it was confirmed that the sprayed state stayed mist-like such that the (Z)-1-chloro-3,3,3-trifluoropropene solution was able to arrive at the surface of the metal plate, and that the brake grease which had been applied thereto could be adequately washed therefrom (TABLE 2).

[0089] It was found in all cases that the aerosol compositions in accordance with the present invention were able to adequately cause the washed locations to become clean. Furthermore, it was also clear that when a plurality of gas propellants employed in accordance with the present invention were mixed, it was still possible to provide a substance that had adequate washability. It can moreover be understood that substances such as compressed air, the major components of which are N.sub.2 and CO.sub.2, were also similarly capable of exhibiting washability. Furthermore, it can be understood that aerosol compositions in accordance with the present invention are such that the type(s) of gas propellant(s) employed and the internal pressure(s) thereof at time(s) when pressure-resistant can(s) are filled therewith are such as to permit adjustment over wide ranges depending on the degree to which contamination is concentrated within a small region (or the degree to which it is spread out over a large region) at the location being washed.

[0090] On the other hand, with LPG, which is in general use as a gas propellant in conventional aerosol compositions, it was found following spraying that the (Z) chloro-3,3,3-trifluoropropene solution was made into a fine mist and evaporated immediately, such that it was unable to reach the surface of the metal plate being washed to an extent sufficient to cause it to be adequately wetted thereby (TABLE 2). Moreover, presumably due to occurrence of a sudden decrease in temperature as a result of evaporation of the LPG and the (Z)-1-chloro-3,3,3-trifluoropropene solution, it was found that the surface of the metal plate that was sprayed had frozen. Because circumstances that would cause washed locations to freeze, i.e., to be wetted by moisture, are to be avoided in the context of washing of automobiles, two-wheeled vehicles, bicycles, construction equipment, farm equipment, aircraft, railroad cars, ships, and various other types of car/vehicle/transportation means that include brake portions and/or various types of important components, it can be understood that the combination of (Z)-1-chloro-3,3,3-trifluoropropene and LPG is undesirable. Furthermore, at Comparative Example 17, in which a manually operated spray bottle was filled with (Z)-1-chloro-3,3,3-trifluoropropene, the solution became mist-like, such that it did not reach the surface of the metal plate that was meant to be washed thereby (TABLE 2). At Comparative Example 18, in which a wash bottle was filled with (Z)-1-chloro-3,3,3-trifluoropropene, while it was possible for the washing procedure to be carried out such that the solution was ejected in rod-like fashion from the wash bottle to reach the surface of the metal plate (TABLE 2), as this was a completely manual procedure it would not be suited to incorporation in work operations. Note that upon investigating the internal pressure following spraying, it was found that there had been no change in the internal pressure of the LPG that evaporated immediately and did not reach the surface of the metal plate that was meant to be washed thereby. Based on the foregoing, it is thought that the LPG was highly miscible with the (Z)-1-chloro-3,3,3-trifluoropropene solution, and that following spraying the LPG which was highly miscible with the (Z)-1-chloro-3,3,3-trifluoropropene solution evaporated immediately. On the other hand, for those that employed gas propellants in the form of N.sub.2, CO.sub.2, and mixtures thereof, for which it was possible to cause the (Z)-1-chloro-3,3,3-trifluoropropene solution to reach the item being washed as a result of its having been rod-like in shape, misty-rod-like, or mist-like as it was sprayed, it was found that the internal pressure within the pressure-resistant can had decreased following spraying. Based on the foregoing, it can be understood that it was probably the case that those which employed gas propellant in the form of N.sub.2, CO.sub.2, or a mixture thereof were such that as, unlike LPG, these would be immiscible with the (Z)-1-chloro-3,3,3-trifluoropropene solution and thus able to contribute to causing the (Z)-1-chloro-3,3,3-trifluoropropene solution to be sprayed from the pressure-resistant can, this would make it possible for these to reach the surface being washed as a result of their being made rod-like in shape, misty-rod-like, or mist-like as they were sprayed, and it can be understood that the same would be true for compressed air which contains similar components, and for noble gases such as argon that have almost no reactivity with respect to other substances.

Industrial Utility

[0091] By causing an aerosol composition to be characterized in that it contains (Z)-1-chloro-3,3,3-trifluoropropene and gas propellant which is N.sub.2, compressed air, CO.sub.2, argon, or a mixture of two or more thereof, it is possible to provide a novel aerosol composition which is for washing automobiles, two-wheeled vehicles, bicycles, construction equipment, farm equipment, aircraft, railroad cars, ships, and/or various other types of car/vehicle/transportation means, and which, because it is nonflammable, possesses little hazard of ignition or risk during fire, and which falls within the definition of a nonhazardous material under the Fire Prevention Law and does not require a hazardous material storage warehouse, and which is not subject to legal restrictions with respect to amounts that may be stored when the detergent composition is to be used in large quantities, and which moreover is of low toxicity, and which while having properties such that the environmental impact thereof in terms of depletion of the ozone layer and so forth is small, as well as washability and drying characteristics as good as or better than those of conventional detergent compositions which are used as brake cleaner, is such that the sprayed state of the aerosol is rod-like in shape, misty-rod-like, or mist-like, making it possible to cause (Z)-1-chloro-3,3,3-trifluoropropene to be sprayed within a given region, as a result of which it is possible to carry out washing effectively and in such fashion that contaminated locations at automobiles, two-wheeled vehicles, bicycles, construction equipment, farm equipment, aircraft, railroad cars, ships, and various other types of car/vehicle/transportation means are targeted in pinpoint fashion, making it possible to carry out washing from a distance, without the need to disassemble the device that is to be washed at the car/vehicle/transportation means so that washing may be carried out in close proximity to contaminated locations, permitting increase in universality during washing operations in terms of ability to accommodate mechanization and so forth, and is also imparted with superior properties in that it makes it possible to avoid causing resins and elastomers used in combination with other materials in car/vehicle/transportation means to be eroded by (Z)-1-chloro-3,3,3-trifluoropropene.