JP3277978B2 - Nonflammable gas pressurized degreasing detergent and spray can using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-combustible gas pressurized degreasing system for spraying a non-combustible gas as a spray material onto a surface of an object to be cleaned in a liquid mass and wiping off the contaminated oil adhering thereto to remove the contaminated oil. The present invention relates to an agent and a spray can using the same.

[0002]

2. Description of the Related Art Conventionally, a non-flammable chlorine-based cleaning agent (hereinafter simply referred to as a chlorine-based cleaning agent) has been sprayed from a cylinder orifice by a pressurized material made of pressurized fluorocarbons. 2. Description of the Related Art A spray-type degreasing cleaning device for cleaning oil stains by using a cleaning method is generally known. For example, JP-A-59-17328
No. 0 discloses an invention of a degreasing cleaning apparatus in which non-combustible 1-1-1 trichloroethane is used as a cleaning agent and is injected by Freon 112, which is also a non-combustible injection material.

On the other hand, Japanese Unexamined Patent Publication No. 6-100060 discloses a flammable, low-flash point, low-carbon number hydrocarbon having from 1 to 3 carbon dioxide or nitrogen gas as a basic solvent containing a cleaning effective component. The invention of a jet-type degreasing and cleaning composition in which the flame length can be suppressed to 50 cm or less even if the propellant gas ignites by adjusting the temperature and injecting into a liquid mass is disclosed. In addition, detergents in which a surfactant is mixed with water, which is a nonflammable solvent (hereinafter referred to as
A number of spray-type degreasing and cleaning compositions using LP gas as a propellant other than Freon, which is an environmentally destructible product, have also been proposed in which a water-based cleaning agent is simply referred to as a hand-washing type degreasing and cleaning device. .

[0004]

As is well known, fluorocarbon used as a propellant causes environmental destruction, so that not only its use but also its manufacture is regulated, and even a substitute for it is not sufficient. Since the safety is not guaranteed, the use as an injection material remains uneasy. A chlorine-based detergent used as a detergent has a strong solubility in most resins, and thus has a drawback that it cannot be used for degreasing and cleaning of the resin surface. In addition, when performing degreasing cleaning work, after spraying and applying the cleaning agent to the object to be cleaned by spraying, the cleaning agent must be wiped off within a short time,
Due to the high volatility of the solvent, oil stains dissolved in the cleaning agent cannot be prevented from re-adhering to the surface to be cleaned due to evaporation of the solvent. Furthermore, since chlorine-based cleaning agents have a strong irritating odor and are toxic, they are not suitable for spray-type degreasing and cleaning work in an enclosed space, and there are restrictions on use such as sufficient consideration of ventilation.

On the other hand, in a degreasing cleaning apparatus in which a cleaning agent containing a lower hydrocarbon as a main component is injected in a liquid mass using carbon dioxide or nitrogen gas as an injection material, the flash point is low. It will catch fire if exposed to
Even if the flame length can be suppressed by adjusting the injection pressure, it is not sufficient in terms of fire safety in an environment in which sparks or arc discharge due to static electricity or electric contacts occur, and there is a problem in practical use.
It has also been proposed to use a water-based cleaning agent for industrial degreasing and cleaning operations.However, water has a higher surface tension than organic solvents, and it is difficult for the cleaning agent to penetrate into narrow details. In addition, a special cleaning method such as ultrasonic cleaning has to be used, and furthermore, since it has a rust-generating property, there is a restriction in working steps such as a sufficient drying treatment after the degreasing cleaning work. In addition, since surfactants dissolved in water are toxic, workers must wear protective equipment such as masks during degreasing and cleaning work, for example, in open spaces such as escalator installation sites. In degreasing and cleaning work, it was necessary to consider safety for general customers.

In a cleaning agent using LP gas as an injection material, the main composition is 80% by weight of propane,
Since most of the residue is n-butane, the propellant dissolves into the cleaning agent, the spraying state tends to be in the form of a spray, which promotes flammability, and LP gas, which is easily volatilized from the cleaning agent, volatilizes into the working space. Due to the possibility of charging and inflammation explosion, sufficient attention must be paid to fire. further,
While chlorofluorocarbon itself has oil absorption capacity,
Since LP gas itself does not have oil absorption capacity,
The cleaning agent using LP gas as the injection material also has a disadvantage that the oil cleaning ability is relatively reduced as compared with the cleaning agent using CFC as the injection material. The present invention has been made to solve such problems in the prior art, and has excellent degreasing and cleaning performance and workability, and has high safety against fire, and has non-flammability with no solubility, toxicity and odor to resin. An object of the present invention is to provide a gas pressurized degreasing cleaning agent and a nonflammable gas pressurized degreasing cleaning spray can.

[0007]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention uses a non-combustible gas pressurized degreasing agent as a non-combustible gas pressurized degreasing detergent using a paraffinic hydrocarbon having 11 or 12 carbon atoms as a main component. As a spray can using a cleaning agent, the diameter of the suction port of the injection cylinder is 0.4 mm or more and the diameter of the nozzle of the injection cylinder or less, and the diameter of the nozzle of the injection cylinder is 0.8 to 1.2 mm.
It is what it was.

[0008]

Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 shows various physical properties and results of various property tests of a cleaning agent composed of paraffinic hydrocarbon, naphthenic hydrocarbon and trichloroethane hydrocarbon, an aqueous cleaning agent and a chlorine-based cleaning agent according to Examples and Comparative Examples of the present invention. FIG. Iso-P in the field of compositions in the table diagram isoparaffinic hydrocarbon _{(C n H 2n + 2)} , n-Pa is normal paraffinic hydrocarbons _{(C n H 2n + 2)} , Na naphthenic hydrocarbon , Et represent a trichloroethane-based hydrocarbon, respectively. In the present embodiment, a cleaning agent made of paraffinic hydrocarbons belonging to the third petroleum class in the Fire Service Law, which is less toxic than the products to which the organic solvent regulation is applied, is used.

Hereinafter, test methods and evaluation methods of various characteristic tests shown in FIG. 1 will be described. (1) Deoiling detergency test and its evaluation method In this test, the effect of removing contaminated oil adhering to the surface of the object to be cleaned was examined, and the degreasing and cleaning ability of the detergent was evaluated. A specific test method is to apply a certain amount of test oil to the surface of a sample piece (stainless steel rod; 40 mm x 40 mm x 1.5 mm) that has been sufficiently washed in advance, and apply it to a certain amount of cleaning agent kept at room temperature for a predetermined time. After immersion, take out and air dry, measure the weight before and after the test, calculate the residual amount of the sample oil by taking the difference between them, and calculate the ratio with the applied sample oil. Calculate the residual ratio of the test oil. The sample oils used in this example were Galbu EP140 (gear oils for automobiles; SAE140) manufactured by Nippon Oil Co., Ltd. and Hydro N32 (2 types of industrial lubricating oils; IS manufactured by Japan Energy).
OVG32). The immersion time was 3 minutes, and the evaluation of the deoiling and cleaning properties was such that the removal rate (= 100-residual rate) of the test oil was 80.
% Or more, good degreasing power (良好), 80%
When it was less than 3, the degreasing power was judged to be insufficient (x).

(2) Drying test and its evaluation method This test measures the time from the removal of the object to be cleaned immersed in the cleaning agent until the cleaning agent attached to the surface is completely volatilized and dried. Was measured, and the quality of the drying property was determined based on the length of the time. The specific test method is an annular sample piece (outer diameter 40φ; inner diameter 20φ; thickness
1.5 mm) for 10 seconds in a cleaning agent kept at room temperature, then taken out, wiped off the cleaning agent adhering to the sample piece, and spraying air at 25 ° C on the sample piece to completely clean the surface of the sample piece. The time until drying was measured. The drying property is evaluated as follows: if the time from wiping off the detergent attached to the sample to complete drying is 1 minute or more and less than 10 minutes, the drying property is good (良好), and this time is 1 minute. When the drying time was less than 10 minutes, the drying property was too strong. When the drying time was more than 10 minutes, the drying property was too weak. If the drying property is too strong, it is inappropriate because the contaminated oil dissolved in the cleaning material will re-adhere to the surface of the object to be cleaned during the wiping operation of the cleaning material. The cleaning agent remained on the surface of the object to be cleaned for a long time even after the completion of the wiping operation of the agent, so that the appearance was poor and the workability was poor, so it was determined to be inappropriate.

(3) Rust prevention test and its evaluation method In this test, when the object to be cleaned immersed in the cleaning agent is a metal, the quality of the rust prevention is determined by the presence or absence of rust generated on the metal. did. Specifically, a metal test piece (stainless steel rod; 40 mm × 40 mm × 1.5 mm) was sufficiently washed in advance with diethyl ether, and then the test piece was washed in a detergent maintained at a liquid temperature of about 30 ° C.
The sample was immersed for 4 hours, then taken out, and the presence or absence of rusting was determined by weight change and gloss reduction of the sample before and after the test or by visual observation. The metal sample pieces used in this example were JIS-G-3141 iron pieces, JIS-H-3103 copper pieces, JIS-H-3201 brass pieces and JIS-H-5.
202 is an aluminum alloy piece. The evaluation of rust prevention is based on whether or not the metal sample has changed in weight or gloss, and whether or not rusting can be visually recognized. Judged.

(4) Resin stability test and its evaluation method This test evaluates the solubility of the resin in the detergent when the object to be cleaned immersed in the detergent is the resin. . The specific test method is to thoroughly dry the resin sample in advance with a hot air drier, immerse it in a cleaning agent kept at 30 ° C. for only 24 hours, and then take out the sample before and after the test. The resin stability of the detergent was determined by observing changes in dimensions and changes in appearance. Samples with no change in weight or dimensions and no change in appearance are good (〇), those with no change in appearance and less than 3% in weight or size are slightly good (、), and changes in appearance are good. Those having a change in weight or dimensions of 3% or more were judged to be defective (x). The resin sample used in this example was manufactured by Mitsubishi Plastics, Inc.
Hard vinyl chloride manufactured by Takato Kasei Co., Ltd.
1179 soft vinyl chloride, GS manufactured by Ube Sycon Co., Ltd.
ABS resin of E, acrylic resin of Acrylic Light 001 manufactured by Mitsubishi Rayon Co., Ltd., KEL-G manufactured by Shin Kobe Electric Co., Ltd.
E epoxy glass, NL-MG-1 manufactured by Nikko Kasei Co., Ltd.
No. 3 melamine glass, IS-825 manufactured by Irumagawa Rubber Co., Ltd.
Silicon rubber and IF-900 fluorine rubber were used as materials.

(5) Toxicity test and its evaluation method In this test, the toxicity of the detergent was evaluated based on the presence or absence of toxicity in rats. The specific test method was evaluated based on the Ministry of Health and Welfare / Ministry of International Trade and Industry Public Notice No. 1 “Guidelines for Information Provision of Chemical Substances” by the co-test amount at which the survival rate of rats was less than 50%. Those with an LD ₅₀ value of 15 g / kg or more corresponding to the degree of toxicity “practically harmless” were judged as good (〇), and those with less than this value were judged as poor (×).

(6) Odor sensory test and its evaluation method This test was conducted to evaluate the possibility that not only the worker who uses the detergent, but also a third party would give discomfort due to the odor of the detergent. is there. The specific test method is a sensory test conducted by 12 testers, which quantifies the unpleasantness of the odor in six stages, and removes the maximum and minimum evaluation points from the evaluation results, and removes the remaining 10 evaluation points. The average value of the points was calculated and rounded to obtain an unpleasant odor value. The odor sniffing method is caliber 2
After 30 ml of the detergent sample was sealed in a 7-mm screw-cap bottle having a capacity of 50 mm, the screw-cap bottle was shaken vigorously, and then the bottle lid was opened, and the tester smelled the odor at the opening to evaluate the odor. The specific evaluation method of the 6-point evaluation score is "Slightly pleasant smell" is +1
0 points for "Smell that is neither pleasant nor unpleasant", -1 point for "Slightly unpleasant odor", -2 points for "Unpleasant odor",
"Very unpleasant smell" was -3 points, "Extremely unpleasant smell"
Scored -4 points. Those having an unpleasant odor value of -1 or more were judged to be odors that would be acceptable for practical use, that is, those having an unpleasant odor of good (度) and those having an unpleasant odor of -2 or less were judged as poor (x).

The comprehensive evaluation of the properties of each cleaning agent is described in the above (1) to
In the evaluation of each property test of (6), if all items were good (〇) or slightly good (△), good (良)
If one item was evaluated as defective (x), it was judged as defective (x)
It was determined. As shown in the table of FIG. 1, the samples judged to be good (〇) in the comprehensive evaluation were paraffin-based paraffins having carbon numbers of 11 and 12 (flash points of about 60 to 80 ° C.) in Examples 101 to 103. It was a hydrocarbon. Although the cleaning agent of Comparative Example 104 having 13 carbon atoms even with the cleaning agent composed of paraffinic hydrocarbon, satisfactory evaluation was obtained in each test result of rust prevention, resin stability, toxicity and odor, Because of its poor degreasing and cleaning ability and low volatility against contaminated oil, it was unsuitable as a cleaning agent.

Next, a cleaning agent having the composition of Example 102 (NS
Clean 200; Nippon Mineralization) and non-flammable carbon dioxide gas as the propellant are enclosed in a spray cylinder and spray cans with different diameters at different filling pressures, and a cleaning agent is sprayed from each spray can. Then, the injection state was observed, and the filling pressure (injection pressure) and the size of the cylinder diameter of the injection material that brought the appropriate injection state were evaluated. FIG. 2 is a table showing test results of the injection state test. The specific test method used was a spray can of a spray can and a spray cylinder with a suction port diameter of 0.3 to 1.0 mm and a cylinder mouth of 0.6 to 1.4 mm, which are general-purpose products of the cylinder mouth. And the filling pressure of the propellant is 0.049MPa (megapascal) close to the minimum use pressure, 0.735MPa close to the maximum use pressure and 0.588MPa which is an intermediate pressure between them, and the cleaning agent is sprayed from the cylinder port. The injection state was observed. The test results using the injection cylinder having a suction port with a diameter of 0.5 mm or more were the same as those using the injection cylinder with a diameter of 0.5 mm, so that the illustration in the table of FIG. 2 was omitted. Although not shown, the cleaning agents having the compositions of Examples 101 and 103 (C-1200H, C-12
[0000] The test results of the injection state test using the (Kyowa fermentation) were the same as those shown in FIG.

Evaluation of the spraying state of the cleaning agent is in the form of a liquid mass (rod shape).
What was ejected as good (〇), what was ejected as a liquid droplet in a state close to a liquid mass was slightly good (△),
Those sprayed and sprayed were judged to be defective (x). In the comprehensive evaluation of the spray state test, the filling pressure of the spray material in the spray can changes within the range of 0.049 to 0.735 MPa, so that the spray state of the detergent becomes a liquid mass under any filling pressure. It is necessary that the evaluation of the spray state of the cleaning agent be good (〇) at all the filling pressures of the spray materials tested. Cleaning agents with a flash point close to 60 ° C have high flammability, so sprays with a sprayed cleaning agent are highly dangerous in terms of fire safety, and may be flammable even in droplet form. Therefore, not only those in which the evaluation of the jetting state of the cleaning agent was determined to be poor (x), but also those in which the evaluation was somewhat good (△) were determined to be poor (x) in the comprehensive evaluation. As is clear from FIG.
2 to 14 were determined to be good (〇) in the overall evaluation. That is, the diameter of the suction port of the injection cylinder evaluated as appropriate in the comprehensive evaluation of the injection state test is 0.4 mm or more and the diameter of the injection port or less, and the diameter of the injection port is 0.8 to 1.2 mm. It turns out there is.

Next, the cleaning agent was sprayed from a spray can by changing the combination of the cleaning agent and the propellant, and a test was conducted on the flammability of the cleaning agent when a flame was approached. FIG. 3 is a table showing test results of the flammability test of the detergent. The specific test method is that the diameter of the suction port of the spray cylinder and the diameter of the cylinder port of the spray cylinder are 0.5 mm and 1.1 mm, respectively, and the non-combustible carbon dioxide (nitrogen) gas, LP gas and 2
The same volume mixture gas and cleaning agent of the two gases
No. 03 paraffinic hydrocarbon and Comparative Example 106 naphthenic hydrocarbon were used. The cleaning agent is sprayed from the spray cylinder of the spray can at a room temperature of 20 to 25 ° C., and the flame of the burner provided at a position 15 cm away from the tip of the cylinder opening of the spray cylinder penetrates below the spray trajectory axis of the cleaning agent. The test was then performed to determine if the detergent ignited. In consideration of fire safety when there is a source of electric spark or a flame generator such as a burner near the work site, the comprehensive evaluation of the flammability test of the cleaning agent does not depend on the length of the flame. Only those that did not exist were judged as good (〇).

As is apparent from FIG.
Eighteen samples were judged as good (〇) in the overall evaluation, and the others were judged as bad (×). That is, a cleaning agent composed of a naphthenic hydrocarbon having a carbon number of 8 and a low flash point of 10 ° C. uses a nonflammable carbon dioxide (nitrogen) gas as an injection material, and the injection state of the cleaning agent is a liquid mass. Even if it ignites, also when the LP gas is used as the propellant, even if the cleaning agent composed of paraffinic hydrocarbons of Examples 101 to 103, the spraying state of the cleaning agent is all in a spray state,
When the same volume mixture of LP gas and non-combustible gas is used as the propellant, the cleaning agent is sprayed or liquefied, but both of them will catch fire.

As a result of the characteristic test of the above-mentioned cleaning agent or the combination of the cleaning agent and the propellant, the cleaning agent comprising a paraffinic hydrocarbon having 11 or 12 carbon atoms was formed into a liquid mass using a nonflammable gas as the propellant. When sprayed, a spray can for degreasing and cleaning can be obtained which has excellent deoiling and cleaning properties, drying properties, rust prevention properties, resin stability, toxicity and odor, and high fire safety. When normal paraffinic hydrocarbons are used as paraffinic hydrocarbons, they are excellent in biodegradability when scattered in soil, and therefore are suitable for cleaning from the viewpoint of environmental pollution resistance.

[0021]

As described above, according to the first aspect of the present invention, a non-combustible gas pressurized degreasing detergent has 1 carbon atom.
As the main component was 1,12 paraffinic hydrocarbons,
It is excellent in degreasing and cleaning performance and workability, has high safety against fire, and can be reduced in solubility, toxicity and odor to resin to such an extent that it is practically acceptable. According to the second aspect of the present invention, since the non-combustible gas is carbon dioxide or nitrogen gas, an inexpensive material can be used as the injection material. According to the third aspect of the present invention, the diameter of the suction port of the injection cylinder is 0.4 mm or more and not more than the diameter of the cylinder port of the injection cylinder, and the diameter of the cylinder port of the injection cylinder is 0.8 to 1.2.
Since it is mm, the spray form of the degreasing cleaning agent can be surely made into a liquid mass at a practical level of spray pressure.

[Brief description of the drawings]

FIG. 1 is a table showing various physical properties and various characteristic test results of a hydrocarbon-based cleaning agent, a water-based cleaning agent, and a chlorine-based cleaning agent according to Examples and Comparative Examples of the present invention.

FIG. 2 is a table showing test results of a spray state test of a cleaning agent according to an example of the present invention and a comparative example enclosed in a spray can together with a spray material.

FIG. 3 is a table showing test results of a flammability test of cleaning agents according to Examples and Comparative Examples of the present invention when the combination of the cleaning agent and the propellant is changed.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI B65D 83/58 C11D 7/50 C23G 5/024 (56) References JP-A-2-302500 (JP, A) JP-A-62-39699 ( JP, A) JP-A-4-122479 (JP, A) JP-A-3-37300 (JP, A) JP-A-6-100060 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , (DB name) C11D 7/24 B05B 7/24 B65D 83/16 B65D 83/28 B65D 83/42 B65D 83/58 C11D 7/50

Claims (3)

(57) [Claims] An incombustible gas pressurized degreasing cleaning agent for injecting a non-combustible gas as a propellant into a liquid mass on the surface of an object to be cleaned and removing contaminated oil adhering thereto.
A noncombustible gas pressurized degreasing detergent characterized by containing 1,12 paraffinic hydrocarbons as main components. 2. The noncombustible gas pressurized degreasing cleaner according to claim 1, wherein the noncombustible gas is carbon dioxide or nitrogen gas. 3. A spray can using a non-combustible gas pressurized degreasing cleaning agent for injecting a non-combustible gas as a propellant into the surface of an object to be cleaned in a liquid mass and removing contaminated oil adhering thereto. The diameter of the suction port of the cylinder is 0.4 mm or more and less than the diameter of the cylinder port of the injection cylinder, and the diameter of the cylinder port of the injection cylinder is 0.8 to 1.2.
A spray can using the noncombustible gas pressurized degreasing cleaning agent according to claim 1, characterized in that it is mm.