Detergent composition

Abstract

To provide a detergent composition that prevents plastic from having a crack due to a spattered detergent in a non-flammable detergent which is charged into an aerosol can and, is ejected, and is used.SOLUTION: A detergent composition includes (A) to (C) components, where a mass ratio of (A) component and (B) component is 100:0-100:500. (A) component is hydrochlorofluoroolefin whose vapor pressure in 20-25°C atmosphere is 30-40 kPa; (B) component is fluorine-containing solvent whose vapor pressure in 20-25°C atmosphere is lower than that of (A) component; and (C) component is a propellant.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a non-flammable cleaning composition suitable for cleaning oil and grease contaminants on metal or resin surfaces. [Background technology]

[0002] Patent Document 1 describes an invention related to a fluorine-based non-flammable cleaning agent, and it is known that it contains cis-1-chloro-3,3,3-trifluoropropene. It is evaluated for its invasiveness (erosion) of rubber and resin and its reduced transparency as problems with the cleaning agent. This is because cis-1-chloro-3,3,3-trifluoropropene has a strong cleaning power, and tends to erode plastics or dissolve the surface of plastics. In Patent Document 1, evaluations are performed by immersing plate-shaped rubber or resin in the cleaning agent, but since it is used as part of a specific structure, stress is applied to specific areas, which are likely to be eroded by the cleaning agent and crack first. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2017-200989 A Summary of the Invention [Problem to be solved by the invention]

[0004] The non-flammable cleaning agent was filled into an aerosol can and sprayed, but even when sprayed only on a specific area, splattering could be unavoidable, and in the worst case scenario, the splattered cleaning agent could cause cracks in the plastic. [Means for solving the problem]

[0005] As a result of intensive research aimed at achieving the above object, the present inventors discovered a method for a cleaning composition and completed the present invention. In the present specification, a numerical range expressed with "~" indicates a range including the upper and lower limits.

[0006] The gist of the present invention will now be described. A first embodiment of the present invention is a cleaning composition comprising the following components (A) to (C), in which the mass ratio of component (A) to component (B) is 100:0 to 100:500: Component (A): A hydrochlorofluoroolefin having a vapor pressure of 30 to 40 kPa in an atmosphere at 20 to 25°C. Component (B): A fluorine-containing solvent that has a lower vapor pressure than component (A) in an atmosphere of 20 to 25°C. (C) Component: Propellant

[0007] A second embodiment of the present invention is the cleaning composition according to the first embodiment, wherein the component (B) is a fluorine-containing solvent that does not contain chlorine in the molecule.

[0008] A third embodiment of the present invention is the cleaning composition according to the first embodiment, in which the component (A) is a mixture of cis-isomer and trans-isomer.

[0009] A fourth embodiment of the present invention is the cleaning composition according to the first embodiment, wherein the mixture of the component (A) and the component (B) has a boiling point of 54° C. or higher.

[0010] A fifth embodiment of the present invention is the cleaning agent composition according to the first embodiment, wherein the component (C) includes at least one selected from the group consisting of LPG, DME, carbon dioxide, nitrogen and helium.

[0011] A sixth embodiment of the present invention is the cleaning agent composition according to the first embodiment, comprising 5 to 500 parts by mass of the component (B) and 0.01 to 10 parts by mass of at least one selected from the group consisting of carbon dioxide, nitrogen and helium as the component (C), relative to 100 parts by mass of the component (A).

[0012] A seventh embodiment of the present invention is the cleaning composition according to claim 1, further comprising at least one selected from the group consisting of a stabilizer, an antioxidant, and a rust inhibitor.

[0013] An eighth embodiment of the present invention is a cleaning agent in which the cleaning agent composition according to any one of the first to seventh embodiments is filled in a pressure-resistant aerosol can. Effect of the Invention

[0014] The non-flammable cleaning agent is packed into an aerosol can and sprayed onto plastics, such as car headlights, without cracking them, allowing it to dissolve and repair the cloudy areas. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The present invention will be described in detail below. The component (A) that can be used in the present invention is a hydrochlorofluoroolefin (HCFO) having a vapor pressure of 30 to 40 kPa in an atmosphere of 20 to 25°C. More preferably, it is 31 to 39 kPa. The hydrochlorofluoroolefin is used as a solvent. Here, if the vapor pressure is 30 to 40 kPa, there is a time lag for wrapping oily dirt before volatilization. In consideration of repairability, 1-chloro-2,3,3-trifluoropropene is preferable as the component (A), and in consideration of reducing the separation process of the component (A), it is preferable to use a mixture of cis-type and trans-type. The component (A) is a main component that exerts a cleaning action on contaminants. The boiling point of the component (A) is preferably 50 to 60°C, more preferably 52 to 58°C. If the boiling point is 50 to 60°C, it has good cleaning power. Here, the notation "to" includes the upper and lower limits.

[0016] The component (B) that can be used in the present invention is a fluorine-containing solvent that has a lower vapor pressure than the component (A) under an atmosphere of 20 to 25°C. The component (B) does not include the component (A). In consideration of low volatility, the component (B) is preferably a fluorine-containing solvent that does not contain chlorine. The vapor pressure of the component (B) is preferably 0.1 to 30 kPa. Examples of the component (B) include hydrofluoroether (HFE), perfluoropolyether (PFPE), hydrofluoroolefin (HFO), perfluoroamine (PFA), etc., but are not limited to these. By combining the components (A) and (B), it is possible to remove dirt without erosion.

[0017] Hydrofluoroethers (HFEs) are saturated ether compounds containing fluorine and hydrogen. Examples of the Novec series manufactured by 3M include 7100 (boiling point: 61°C, vapor pressure (25°C): 28 kPa) and 7200 (boiling point: 76°C, vapor pressure (25°C): 16 kPa), but are not limited to these.

[0018] Perfluoropolyethers (PFPEs) are saturated ether compounds that contain fluorine and no hydrogen. Examples of GALDEN manufactured by Solvay Japan include SV55 (boiling point: 55°C, vapor pressure (20°C): 30 kPa) and SV135 (boiling point: 135°C, vapor pressure (20°C): 1.1 kPa), but are not limited to these.

[0019] Hydrofluoroolefins (HFOs) are unsaturated hydrocarbon compounds that contain fluorine. Hydrofluoroolefins are fluorine compounds that have an unsaturated bond in the molecule and an ether group. Specifically, n F 2n-1 -OC m H 2m+1In this case, n is an integer of 5 to 10, and m is an integer of 1 to 5. In consideration of the corrosiveness to resins such as plastics, the boiling point is preferably 80° C. or higher, more preferably 90° C. or higher, and most preferably 100° C. or higher. Specific examples include Opteon (registered trademark) SF10 (boiling point: 110° C., vapor pressure (25° C.): 2.9 kPa) manufactured by Mitsui-Chemours Fluoroproducts Inc., but are not limited thereto.

[0020] Perfluoroamines (PFA) are saturated amine compounds containing fluorine. A specific example is N,N-bis(heptafluoropropyl)amine (boiling point: 130°C, vapor pressure (20°C): 0.5 kPa).

[0021] The component (B) may be used alone or in combination of two or more types.

[0022] The mass ratio of the (A) component to the (B) component is 100:0 to 100:500, which allows both the detergency against oils and the like and the suppression of erosion against plastics. Here, the mass ratio of the (A) component to the (B) component is 100:0 to 100:500 means that the (A) component is contained but the (B) component is not contained, or that the (B) component is contained but the (B) component is contained in an amount of 500 parts by mass or less per 100 parts by mass of the (A) component. When the (A) component and the (B) component are mixed, the mass ratio is more preferably 100:5 to 100:500. The boiling point of the mixture of the (A) component and the (B) component is preferably 50°C or higher, and most preferably 54°C or higher. In order to maintain high detergency and low erosion, the cleaning composition preferably contains only the (A) component and the (B) component as a solvent.

[0023] The component (C) that can be used in the present invention is a propellant. However, the components (A) and (B) are excluded. The propellant may be a known substance, and may be selected from dimethyl ether (DME), liquefied petroleum gas (LPG), carbon dioxide, nitrogen, nitrous oxide, rare gases such as argon and helium, isobutane, haloalkyl, hydrofluorofine, compressed air, etc., but is not limited thereto. From the viewpoints of availability, safety, environmental load, etc., carbon dioxide and nitrogen are particularly suitable, and carbon dioxide is most preferable. In the case of liquefied gas such as liquefied petroleum gas (LPG) or dimethyl ether (DME), it is preferable to add 20 to 60 parts by mass per 100 parts by mass of the total of the components (A) and (B). In the case of compressed gas such as carbon dioxide, nitrogen, helium, etc., it is preferable to add 0.01 to 10 parts by mass per 100 parts by mass of the total of the components (A) and (B).

[0024] The cleaning composition of the present invention may contain any component other than components (A) and (B) as long as the characteristics of the present invention are not impaired. Examples of such components include, but are not limited to, solvents other than components (A) and (B) (excluding component (C)), surfactants, UV absorbers, stabilizers, antioxidants, chelating agents, rust inhibitors, fragrances, etc.

[0025] In the present invention, the solvent other than the components (A) and (B) may include normal paraffin-based solvents, isoparaffin-based solvents, naphthenic solvents, aromatic solvents, glycol-based solvents, glycol ether-based solvents, aliphatic solvents, alcohol-based solvents, etc. However, it is preferable that the solvent other than the components (A) and (B) does not include cis-1-chloro-3,3,3-trifluoropropene. When cis-1-chloro-3,3,3-trifluoropropene is accidentally applied to the headlights of an automobile, it will cause cracks in the stress concentration area that cannot be repaired. It is most preferable that the solvent does not include any other solvent than the components (A) and (B).

[0026] The cleaning composition according to the present invention can be filled into a pressure-resistant cleaning aerosol can together with a propellant, which is component (C), or the present invention can be filled into a double-structure container having an inner bag inside the can, and the cleaning composition containing components (A) and (B) can be filled into a cleaning sprayer that pushes the inner bag with compressed air in the gap between the inner bag and the can to spray it. A specific embodiment of the cleaning aerosol in which the cleaning agent and the propellant are filled into a pressure-resistant container is a cleaning composition containing 5 to 500 parts by mass of component (B) and 0.01 to 10 parts by mass of at least one selected from the group consisting of carbon dioxide, nitrogen, and helium, per 100 parts by mass of (A).

[0027] The fields and applications of the present invention include, but are not limited to, the cleaning of industrial machinery, transport vehicles, electrical and electronic equipment, and industrial parts. In particular, the present invention can be suitably used for transport vehicles such as automobiles and trains. Contaminated parts include brake devices of transport vehicles, but are also suitable for cleaning other machines. In particular, the present invention may be used for cleaning contaminated parts containing non-metallic materials such as resins such as polycarbonate and ABS, and fibers. In addition, the present invention can also be used for applications other than cleaning, such as applications that require dissolving oils and fats, such as gear oil and brake fluid, and solids that are contaminants, such as removing adhesives and adhesives. The present invention can be used to clean contaminated areas caused by oils and fats on surfaces made of metal or resin.

[0028] Even if the cleaning agent splashes on resin such as polycarbonate during cleaning with the cleaning composition of the present invention and the surface dissolves, it can be repaired. The part where the surface dissolution has occurred is polished with waterproof paper, and gradually polished with finer paper. Furthermore, the surface is further smoothed by coating with a headlight coating agent, and transparency and gloss are restored. EXAMPLES

[0029] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. The detergent composition is also simply called a composition.

[0030] [Examples 1 to 17 and Comparative Examples 1 to 22] Component (A): A hydrochlorofluoroolefin having a vapor pressure of 30 to 40 kPa in an atmosphere at 20 to 25°C. 1-Chloro-2,3,3-trifluoropropene (a mixture of cis and trans isomers) (AMOLEA® AS-300 manufactured by AGC Inc.) Component (A'): Hydrochlorofluoroolefin other than component (A) Cis-1-chloro-3,3,3-trifluoropropene (SOLVIA, manufactured by Solvex Corporation) Component (B): A fluorine-containing solvent that has a lower vapor pressure than component (A) in an atmosphere of 20 to 25°C. C4F9OCH3(HFE) (Novec(registered trademark) 7100 manufactured by 3M) C4F9OC2H5(HFE) (Novec(registered trademark) 7200 manufactured by 3M) Perfluoropolyether (PFPE) (GALDEN SV55 SOLVAY) Perfluoropolyether (PFPE) (GALDEN SV135 SOLVAY) Hydrofluoroolefin (HFO) (Opteon SF10 manufactured by Mitsui-Chemours Fluoroproducts Co., Ltd.) ·N,N-Bis(heptafluoropropyl)amine (hereinafter abbreviated as BHHA) (PFA) (XP-3288 Time Chemical Co., Ltd.) (C) Component: Propellant Liquefied petroleum gas (hereinafter referred to as LPG) (manufactured by San-ai Gas Supply Kanto Co., Ltd.) Dimethyl ether (hereinafter abbreviated as DME) (manufactured by San-ai Gas Supply Kanto Co., Ltd.) Carbon dioxide gas (produced by Liquefied Carbonate Co., Ltd.) Nitrogen gas (manufactured by Iwatani Corporation) Helium gas (manufactured by Tokyo High Pressure Yamazaki Co., Ltd.)

[0031] Mix component (A) (or component (A')) and component (B) and fill a 180 ml pressure-resistant aerosol can with component (C). Detailed amounts of the mixture are shown in Tables 1 and 2, and all values ​​are expressed in parts by mass.

[0032] [Table 1]

[0033] [Table 2]

[0034] An erosion confirmation test and a repairability confirmation test were carried out for Examples 1 to 17 and Comparative Examples 1 to 22. The results are summarized in Table 3.

[0035] [Erosion confirmation test] The cleaning solution filled in an aerosol can is sprayed onto the polycarbonate surface of a headlight (used STANLEY W1169 for Honda Accord Hybrid) from a distance of 10 cm for 5 seconds. The spray area is 10 cm wide, and the area not to be sprayed is masked to prevent it from coming into contact with the cleaning solution. After spraying the cleaning agent, the cleaning solution is left to stand until it dries naturally. After drying, the polycarbonate part is visually inspected. The "erosion" is determined by visual inspection according to the following evaluation criteria. Here, surface dissolution refers to the surface of the test piece becoming cloudy. It is preferable for the erosion to be rated as "◎" or "〇". Evaluation criteria ◎: No cracks or surface dissolution occurs ◯: No cracks occurred and surface dissolution occurred ×: Cracks occurred and surface dissolution also occurred

[0036] [Repairability verification test] If the above erosion is "good", repair is attempted. The area where surface dissolution has occurred is polished using waterproof sandpaper (manufactured by Sankyo Rikagaku Co., Ltd.). The grit size used is gradually increased to finer sizes in the order of #1000 → #1500 → #2000 → #6000. After the dissolved area has been sufficiently smoothed, the surface is coated using headlight coating agent ThreeBond 6604H. After 24 hours in an environment of 25°C and 55% RH, visual inspection is performed according to the following evaluation criteria. If the "erosion" is "bad", cracks have occurred, so a repairability confirmation test is not performed and it is recorded as "-". It is preferable that the repairability is "good". Evaluation criteria 〇:Repaired and now transparent ×: Not transparent and could not be repaired

[0037] [Table 3]

[0038] Comparing Examples 1 to 17 with Comparative Examples 1 to 22, it can be seen that the Comparative Examples containing the component (A') have a high vapor pressure and volatilize quickly, but the erosion is marked as "x", resulting in cracks. On the other hand, the erosion of Examples 1 to 17 containing the component (A) is marked as "good", and although no cracks are formed, surface dissolution is observed, and when repairability was confirmed, it was found to be repaired. This confirmed that even if the composition splashes onto plastic during cleaning, it can be repaired. [Industrial Applicability]

[0039] The cleaning composition of the present invention can clean oils and solids adhering to contaminated parts of industrial machinery parts, transportation equipment parts, electrical and electronic parts, civil engineering, architectural and construction materials, etc., made of metal or plastic, and can also restore plastics even if they are eroded. Since it is non-flammable, it can be used in a variety of fields and applications.

Claims

1. A cleaning composition comprising the following components (A) to (C), in which the mass ratio of component (A) to component (B) is 100:0 to 100:500: Component (A): a hydrochlorofluoroolefin having a vapor pressure of 30 to 40 kPa in an atmosphere of 20 to 25°C. Component (B): a fluorine-containing solvent having a lower vapor pressure than component (A) in an atmosphere of 20 to 25°C. Component (C): Propellant

2. 2. The cleaning composition according to claim 1, wherein the component (B) is a fluorine-containing solvent that does not contain chlorine in the molecule.

3. 2. The cleaning composition according to claim 1, wherein the component (A) is a mixture of cis- and trans-isomers.

4. 2. The cleaning composition according to claim 1, wherein the mixture of the component (A) and the component (B) has a boiling point of 54° C. or higher.

5. 2. The cleaning composition according to claim 1, wherein the component (C) comprises at least one selected from the group consisting of LPG, DME, carbon dioxide, nitrogen and helium.

6. 2. The cleaning agent composition according to claim 1, comprising, relative to 100 parts by mass of the component (A), 5 to 500 parts by mass of the component (B) and 0.01 to 10 parts by mass of the component (C) of at least one selected from the group consisting of carbon dioxide, nitrogen and helium.

7. 2. The cleaning composition according to claim 1, further comprising at least one selected from the group consisting of a stabilizer, an antioxidant and a rust inhibitor.

8. A cleaning agent comprising the cleaning composition according to any one of claims 1 to 7 filled in a pressure-resistant aerosol can.

9. A cleaning agent filled in a dual-structure sprayer, comprising the following components (A) and (B), wherein the mass ratio of component (A) to component (B) is 100:0 to 100:500: Component (A): a hydrochlorofluoroolefin having a vapor pressure of 30 to 40 kPa in an atmosphere of 20 to 25°C. Component (B): a fluorine-containing solvent having a lower vapor pressure than component (A) in an atmosphere of 20 to 25°C.

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