Cleaning agent composition, cleaning aerosol, and method for cleaning a soiled portion

Abstract

The present invention relates to a cleaning agent composition which is excellent in cleaning property and does not corrode plastic substrates such as polycarbonate and polystyrene which are not resistant to solvents. The cleaning agent composition of the present invention comprises the following (A) to (C) components, the mass ratio of the (A) component and the (B) component being 11:89 to 99:1, (A) cis-1-chloro-3,3,3-trifluoropropene, (B) one or more compounds selected from the group consisting of hydrofluoroolefins, hydrofluorocarbons and hydrofluoroethers which do not contain a chlorine atom, and (C) a hydrocarbon solvent.

Description

Technical Field

[0001] This invention relates to a cleaning agent composition that reduces the corrosiveness to plastic substrates such as polycarbonate and polystyrene, and improves the cleaning ability against grease and oil. Furthermore, this invention relates to a cleaning aerosol using this cleaning agent composition and a cleaning method for removing contaminated parts using the cleaning aerosol. Background Technology

[0002] Traditionally, cleaning agents for industrial parts were used to remove grease adhering to the surfaces of industrial machinery, conveyors, electrical and electronic equipment, and building materials. In particular, for conveyors such as vehicles, trams, tractors, ships, airplanes, and forklifts, grease used for lubrication and cooling adheres to various parts of the drive and sliding components. This grease may be dispersed during operation or adhere to contaminants present in the surrounding environment, causing surface contamination. Until now, cleaning agents containing petroleum hydrocarbons and alcohols have been used to remove such contamination. These solvents are highly flammable and classified as hazardous materials under fire safety laws. If they are classified as hazardous materials, the establishment and management of hazardous materials warehouses are necessary, incurring costs in terms of introduction and maintenance. Therefore, a non-hazardous cleaning agent is needed. Cleaning agent compositions containing fluorinated solvents, which are non-hazardous, have also been used to clean such stains. Furthermore, while the parts targeted for cleaning have traditionally been metal, with the diversification of parts, there is also a demand for cleaning agents for composites of plastic and metal parts. However, cleaning agents using fluorinated solvents, which have been used in the past, have the problem of corroding plastic substrates. In particular, polycarbonate and polystyrene have low solvent resistance, so they will be corroded if conventional cleaning agent compositions are used. Against this backdrop, there has been a demand in recent years for the development of cleaning agent compositions that do not corrode plastic substrates. (Patent Document 1)

[0003] Existing technical documents

[0004] Patent documents

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2020-41090 Summary of the Invention

[0006] Technical problem solved by the present invention

[0007] However, cleaning agent compositions that do not corrode plastic substrates have the problem of reduced cleaning effectiveness against stains such as grease and oil compared to conventional cleaning agents.

[0008] Technical means to solve technical problems

[0009] As a result of in-depth research in order to achieve the aforementioned objective, the inventors discovered a method involving a cleaning agent composition that does not corrode even when used on parts containing plastic substrates with low solvent resistance, such as polycarbonate and polystyrene, and also has excellent cleaning properties against grease, oil, etc., thus completing the present invention.

[0010] The main points of this invention will now be explained. [1]

[0012] A cleaning agent composition comprising components (A) to (C) thereof, wherein the mass ratio of component (A) to component (B) is 11:89 to 99:1.

[0013] (A) cis-1-chloro-3,3,3-trifluoropropene

[0014] (B) A compound selected from one or more of the following: compounds that do not contain chlorine atoms and have hydrogen or fluorine bonded to a carbon chain with a double bond, hydrofluorocarbons, and hydrofluoroethers.

[0015] (C) Hydrocarbon solvents. [2]

[0017] According to the cleaning agent composition described in item [1], wherein,

[0018] The amount of component (C) is 0.1 to 100 parts by mass relative to the total amount of components (A) and (B). [3]

[0020] According to the cleaning agent composition described in item [1] or [2], wherein,

[0021] The (B) component is a compound that does not contain chlorine atoms and has hydrogen or fluorine bonded to a carbon chain with double bonds. [4]

[0023] The cleaning agent composition according to any one of items [1] to [3], wherein,

[0024] The number of carbon atoms in component (C) is 5 to 20. [5]

[0026] The cleaning agent composition according to any one of items [1] to [4], wherein,

[0027] The boiling point of component (C) is 50℃~200℃. [6]

[0029] The cleaning composition according to any one of items [1] to [5] contains only the components (A) to (C). [7]

[0031] A cleaning aerosol is made of a cleaning agent composition and a spray agent as described in any one of the items [1] to [6]. [8]

[0033] A method for cleaning a contaminated part, wherein contaminants are removed by spraying the cleaning aerosol described in item [7] onto the contaminated part. [9]

[0035] According to the cleaning method for the contaminated part described in item [8], wherein,

[0036] The contaminated part contains a plastic substrate.

[10]

[0038] According to the cleaning method for the contaminated part described in item [8], wherein,

[0039] The contaminant is oil or grease.

[11]

[0041] According to the cleaning method for the contaminated part described in item [9], wherein,

[0042] The plastic substrate comprises polycarbonate and / or polystyrene.

[0043] The effects of the invention

[0044] The cleaning agent composition of the present invention has excellent cleaning properties for oils, greases and other greases, and poses no risk of corroding plastics. Therefore, it can be used for a wider range of parts and applications, and is very useful.

[0045] Specific embodiments of the present invention

[0046] The present invention will now be described in detail. It should be noted that in this specification, "X to Y" means that the values ​​(X and Y) recorded before and after it are included as the lower limit and upper limit, respectively, and means "above X and below Y".

[0047] The component (A) used in this invention is cis-1-chloro-3,3,3-trifluoropropene, which is the main component responsible for cleaning grease. Component (A), when mixed with components (B) and (C), can clean grease without corroding the plastic substrate. Regarding component (A), from the viewpoint of grease-cleaning properties, a kauri butanol (KB) value of 10 or higher is preferred. A kauri butanol value of component (A) is more preferably 20 or higher, and most preferably 30 or higher. The kauri butanol value is an indicator of the grease saturation power of a sample. A higher value indicates that the sample can dissolve more grease. As a measurement method, a kauri resin butanol solution is placed in a flask containing a certain volume, placed on movable type paper, and the sample is added dropwise. The volume (ml) of the sample that produces turbidity and renders the movable type unreadable is taken as the kauri butanol value. In this invention, a KB value of component (A) of 10 or higher is preferred because it exhibits excellent grease-cleaning performance. (A) There is no particular limit to the upper limit of the kauri butyl alcohol value of the ingredient, for example, it can be below 150.

[0048] The component (B) used in this invention is one or more compounds selected from hydrofluoroolefins, hydrofluorocarbons, and hydrofluoroethers that do not contain chlorine atoms. By mixing component (B) with component (A), the corrosiveness to the plastic substrate can be reduced and the drying properties can be adjusted, thereby improving workability. Component (B) can be used alone or in combination of two or more.

[0049] The hydrofluoroolefins that do not contain chlorine atoms refer to compounds with hydrogen or fluorine bonds bonded to their carbon chains containing double bonds. Examples include Z-1,1,1,4,4,4-hexafluoro-2-butene, 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene, methoxydecafluoroheptene, and methoxyperfluoroheptene.

[0050] Hydrofluorocarbons refer to compounds whose carbon chains without double bonds are bonded with hydrogen or fluorine. Specifically, examples include 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,2,2,3,3,4,4-octafluorobutane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecylfluorooctane, and 1,1,1,3,3-pentafluorobutane. These hydrofluorocarbons may contain chlorine atoms.

[0051] The hydrofluoroether refers to a compound in which hydrogen or fluorine is bonded to a carbon chain without double bonds, and the carbon chain contains ether bonds. Specifically, examples include perfluoropropyl methyl ether, nonafluorobutyl methyl ether, decafluorobutyl ethyl ether, 1,1,1,2,2,3,4,4,5,5,6,6,6-tridecylfluoro-3-methoxyhexane, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4(trifluoromethyl)pentane, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, and nonafluoro-n-butyl ethyl ether. The hydrofluoroether may contain chlorine atoms.

[0052] In component (B), from the viewpoint of excellent cleaning properties against greases and low corrosivity to plastic substrates, hydrofluoroolefins without chlorine atoms are preferred, and from the viewpoint of cleaning properties, compounds without ether bonds in their molecules are preferred.

[0053] The boiling point of component (B) is preferably 30–200°C, more preferably 40–150°C, and most preferably 50–130°C. If the boiling point is above 30°C, the drying properties will not be too high, and the workability will be good; if the boiling point is below 200°C, the drying properties will not be too low. The boiling point in this invention is the value determined according to JIS K 0066 (1992).

[0054] The content of component (B) is expressed as a mass ratio of component (A) to component (B) of 11:89 to 99:1. From the viewpoint of cleanliness and low corrosivity, the mass ratio of component (A) to component (B) is preferably 11:89 to 90:10, more preferably 20:80 to 80:20, and most preferably 25:75 to 75:25. Within this range, both cleanliness against grease and low corrosivity to plastic substrates can be maintained.

[0055] Commercially available products that are components of (B) mentioned above include: Opteon SF01, Opteon SF05, Opteon SF10, Opteon SF33, Opteon SF79, DR CFX70, Vertrel XF, Vertrel XF-UP, Vertrel XF-Select, Vertrel XE, Vertrel X-E10 manufactured by Chemours-Mitsui Fluoroproducts Co., Ltd.; Novec7000, Novec7100, Novec7200, Novec7300 manufactured by 3M Japan Co., Ltd.; and ASAHIKLIN AE-3000 and ASAHIKLIN AC-6000 manufactured by 3M Japan Co., Ltd.

[0056] The component (C) used in this invention is a hydrocarbon solvent. By mixing component (C) with components (A) and (B), the cleaning power of component (C) on greases and oils can be improved. From the viewpoint of low corrosivity to plastics, component (C) is preferably a saturated hydrocarbon solvent. From the viewpoint of cleaning properties and drying properties as a cleaning agent composition, the number of carbon atoms in component (C) is preferably 5 to 20, more preferably 5 to 15, and most preferably 5 to 10. Specific examples of component (C) include n-hexane, isohexane, cyclohexane, ethylcyclohexane, methylcyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, and isodecanane. From the viewpoints of compatibility with components (A) and (B), low corrosivity to plastic substrates, and cleaning properties as a cleaning agent composition, component (C) is preferably cyclohexane, ethylcyclohexane, methylcyclohexane, or isooctane, more preferably ethylcyclohexane, methylcyclohexane, or isooctane, and most preferably methylcyclohexane or isooctane. Component (C) can be used alone or in combination of two or more.

[0057] The boiling point of component (C) is preferably 50 to 200°C, more preferably 55 to 150°C, and most preferably 60 to 120°C, from the viewpoint of the drying properties of the cleaning agent composition.

[0058] The mixing amount of component (C) relative to a total of 100 parts by mass of components (A) and (B) is preferably 0.1 to 100 parts by mass, more preferably 1 to 70 parts by mass, and most preferably 5 to 50 parts by mass. If the mixing amount of component (C) relative to a total of 100 parts by mass of components (A) and (B) is 0.1 parts by mass or more, the cleaning properties of the cleaning agent composition will not be reduced; if it is 100 parts by mass or less, there is no risk of corroding the plastic substrate.

[0059] The mixing amount of component (C) relative to 100 parts by weight of component (A) is preferably 0.1 to 200 parts by weight, more preferably 1 to 150 parts by weight, and most preferably 10 to 100 parts by weight. If the mixing amount of component (C) is 0.1 parts by weight or more relative to 100 parts by weight of component (A), the cleaning properties of the cleaning agent composition will not be reduced; if it is 200 parts by weight or less, there is no risk of corroding the plastic substrate.

[0060] The mixing amount of component (C) relative to 100 parts by weight of component (B) is preferably 0.1 to 200 parts by weight, more preferably 1 to 150 parts by weight, and most preferably 5 to 100 parts by weight. If the mixing amount of component (C) is 0.1 parts by weight or more relative to 100 parts by weight of component (B), the cleaning properties of the cleaning agent composition will not be reduced; if it is 200 parts by weight or less, there is no risk of corroding the plastic substrate.

[0061] <Optional Ingredients>

[0062] In the cleaning agent composition of the present invention, optional components may be added without impairing the characteristics of the present invention. Examples of such components include surfactants, ultraviolet absorbers, antioxidants, chelating agents, rust inhibitors, fragrances, etc., as long as the substance can be uniformly dissolved and dispersed in components (A) to (C), it is suitable to select such components. The cleaning agent composition of the present invention preferably contains only components (A) to (C) and does not contain any optional components. If the cleaning agent composition does not contain any optional components, the cleaning performance will not be degraded.

[0063] <Cleaning Method>

[0064] Examples of cleaning methods using the cleaning agent composition of the present invention include wiping with cloths, soaking, ultrasonic cleaning, and spraying with aerosols or air guns, but are not limited to these. Examples of aerosols according to the present invention include products packaged as aerosols by filling a pressure-resistant container together with the propellant, or dual-structure spray containers that separate the cleaning agent composition and the propellant by placing small bags in a pressure-resistant container. The can is reusable, and from the viewpoint of reducing waste after use, dual-structure spray containers are preferred. Known substances can be used as the propellant. The propellant can be selected from dimethyl ether (DME), carbon dioxide, liquefied petroleum gas (LPG), nitrogen, nitrous oxide, isobutane, haloalkanes, hydrofluoroolefins, compressed air, etc. From the viewpoints of ease of acquisition, safety, and environmental impact, hydrofluoroolefins, carbon dioxide, and nitrogen are particularly preferred as the propellant, with nitrogen being the most preferred.

[0065] <Drying Method>

[0066] The cleaning agent composition of the present invention has excellent drying properties, and therefore can be used in low-temperature environments. The preferred drying temperature range is -10°C to 50°C, and more preferably -5°C to 40°C.

[0067] <Substrate>

[0068] Because the cleaning agent composition of the present invention has low corrosiveness to plastic substrates, it is suitable for cleaning plastic substrates or composite parts comprising plastic and metal substrates. Examples of plastics include polystyrene, polyethylene, polycarbonate, polyacetal, polypropylene, 6-nylon, 6,6-nylon, PBT (polybutylene terephthalate), ABS (acrylonitrile butadiene styrene copolymer), FRP (fiber-reinforced plastic), PMMA (acrylic resin), PPS (polyphenylene sulfide), and PEN (polyethylene naphthalate). Examples of metals include iron, stainless steel, copper, nickel, zinc, aluminum, magnesium, gold, and silver.

[0069] <Applications>

[0070] The cleaning agent composition of the present invention exhibits excellent cleaning properties against stains such as oils and greases. Examples of oils include engine oil, gear oil, turbine oil, silicone oil, fluorinated oil, and brake fluid, but there are no particular limitations. The cleaning agent composition of the present invention is particularly suitable for use on parts used in transportation machinery such as vehicles, trams, and airplanes, but is also applicable to the cleaning of other types of machinery. Furthermore, due to its low corrosiveness to plastic substrates, it is also suitable for cleaning composite parts containing both plastic and metal substrates. Moreover, it can be used for applications other than cleaning, such as in applications requiring the removal of greases and solids as contaminants, for example, the removal of adhesives and bonding agents. [Example]

[0071] The invention will now be described in more detail with reference to specific embodiments, but the invention is not limited to these embodiments. Unless otherwise specified, the tests were conducted at 25°C and 55% RH.

[0072] [Examples 1-9, Comparative Examples 1-6]

[0073] The following ingredients were prepared for the purpose of preparing the composition.

[0074] (A) cis-1-chloro-3,3,3-trifluoropropene, boiling point 39℃, KB value 34. Trade name: 1233zd(Z). Manufactured by Honeywell Japan Co., Ltd.

[0075] (A') 1-Chloro-2,3,3-trifluoro-1-propene, boiling point 54℃, KB value 44. Trade name: 1233yd, manufactured by AGC Co., Ltd.

[0076] (B-1) Compounds containing no chlorine atoms or ether bonds and with hydrogen or fluorine bonded to a carbon chain having double bonds; boiling point 71°C; trade name: CFX70; manufactured by Chemours-Mitsui Fluoroproducts Co., Ltd. (B-2) Methoxyperfluoroheptene; boiling point 110°C; trade name: Opteon SF10; manufactured by Chemours-Mitsui Fluoroproducts Co., Ltd.

[0077] (B-3) Hydrofluoroether C4F9OC2H5 Boiling point 76°C Trade name: Novec7200 Manufactured by 3M Japan Co., Ltd.

[0078] (B-4) Hydrofluoroether C2F5CF(OCH3)C3F7 Boiling point 98℃ KB value: 5 Trade name: Novec 7300 Manufactured by 3M Corporation

[0079] (B-5) Hydrofluorocarbon CF3(CFH)2CF2CF3 boiling point 55°C Trade name: Vertrel XF Chemour s-Mitsui Fluoroproducts Co., Ltd.

[0080] (B'-1) Perfluoropolyether, boiling point 80℃, trade name: Galden SV80, manufactured by Solvay.

[0081] (B'-2) Perfluoropolyether, boiling point 135℃. Trade name: Galden SV135, manufactured by Solvay.

[0082] (C-1) Methylcyclohexane boiling point 100.9°C Trade name: Swaclean MCH manufactured by Maruzen Petrochemical Co., Ltd.

[0083] (C-2) Isooctane boiling point 62°C Trade name: Kyowasol C800 KH Neochem Co., Ltd.

[0084] Weigh components (A) and (B) into a mixing container, add component (C), and stir for 30 minutes. Detailed preparation amounts are shown in Tables 1 and 2, all values ​​are expressed in parts by mass.

[0085] [Cleanability]

[0086] Apply 2g each of contaminant 1 (turbo oil / Daphne Super turbine oil) and contaminant 2 (ALVANIA GREASE EP2) to an A4-sized iron plate, forming a circle with a diameter of 40mm. Hold the iron plate vertically and, using a double-layered spray container, spray the cleaning agent from a distance of 15cm at 0.5MPa for 5 seconds, visually confirming whether the contaminants have been removed. Nitrogen was used in the spray. If the contaminants are not removed after 5 seconds of spraying, apply an additional 5 seconds of spray and visually confirm again.

[0087] <Qualification Standards>

[0088] ◎: A 5-second spray can wash away oil or grease from a metal plate.

[0089] ○: A 10-second spray can wash away oil or grease from a metal plate.

[0090] ×: After 10 seconds of spraying, oil or grease remains on the iron plate.

[0091] [Corrosive]

[0092] A 6mm diameter hole was drilled in the center of a polycarbonate sheet (Teijin Corporation L-1225Y) or polystyrene sheet (DIC Corporation HIPS) measuring 25mm wide x 100mm long x 2mm thick using an electric drill bit. An M6 bolt was then passed through the hole, and a nut was tightened to a torque of 6N to secure the sheet. This was used as a test piece. 90ml of each cleaning agent composition was added to a 100ml glass bottle, and the test piece was immersed for 15 seconds at 25°C and 55% RH. The removed test piece was then allowed to stand at 25°C and 55% RH for 10 minutes to dry, and the condition of the resin sheet was visually inspected.

[0093] <Qualification Standards>

[0094] ○: No melting or cracking occurred on the plastic board.

[0095] ×: The plastic sheet has melted or cracked.

[0096] [Table 1]

[0097]

[0098] [Table 2]

[0099]

[0100] As shown in Table 1, the compositions of Examples 1-9, which contain components (A) to (C) and components (A) and (B) in specific proportions, exhibit excellent cleaning properties for turbine oils and greases without corroding plastic substrates such as polycarbonate and polystyrene. On the other hand, it can be seen that if component (A) is insufficient, as in Comparative Example 1 of Table 2, or if component (C) is not present, as in Comparative Example 4, the cleaning properties of the turbine oils and greases deteriorate. Comparative Example 2, which uses component (A') instead of component (A), or Comparative Example 3, which does not contain component (B), corrodes polycarbonate and polystyrene. Furthermore, when component (B') is used instead of component (B), the cleaning properties of the turbine oils and greases also deteriorate. Based on these results, by mixing components (A) to (C) in specific proportions, both low corrosivity and cleaning properties for plastic substrates can be achieved simultaneously.

[0101] The present invention has been described in detail above with reference to specific embodiments. However, various changes or modifications can be made without departing from the spirit and scope of the invention, which is obvious to those skilled in the art. This application is based on Japanese Patent Application 2020-211352, filed on December 21, 2020, the contents of which are incorporated herein by reference.

[0102] Industrial applicability

[0103] The cleaning agent composition of the present invention has excellent cleaning properties and does not corrode plastic substrates such as polycarbonate and polystyrene that are not solvent-resistant. Therefore, it can be used for a wide range of cleaning applications and is very useful.

Claims

1. A cleaning agent composition comprising components (A) to (C) below, wherein the mass ratio of component (A) to component (B) is 11:89 or more and less than 50:

50. The amount of component (C) is 5 to 50 parts by mass relative to 100 parts by mass of the combined amount of components (A) and (B). (A) cis-1-chloro-3,3,3-trifluoropropene (B) One or more compounds selected from those whose molecules do not contain chlorine atoms and ether bonds, and whose carbon chains with double bonds are bonded with hydrogen or fluorine. (C) Methylcyclohexane or isooctane.

2. The cleaning agent composition according to claim 1, wherein, The number of carbon atoms in component (C) is 5 to 20.

3. The cleaning agent composition according to claim 1 or 2, wherein, The boiling point of component (C) is 50℃~200℃.

4. The cleaning agent composition according to claim 1 or 2, wherein it contains only components (A) to (C).

5. A cleaning aerosol, which is made by filling the cleaning agent composition and spray agent according to any one of claims 1 to 4.

6. A method for cleaning a contaminated part, wherein contaminants are removed by spraying the cleaning aerosol of claim 5 onto the contaminated part.

7. The cleaning method for the contaminated part according to claim 6, wherein, The contaminated part contains a plastic substrate.

8. The cleaning method for the contaminated part according to claim 6, wherein, The contaminant is oil or grease.

9. The cleaning method for the contaminated part according to claim 7, wherein, The plastic substrate comprises polycarbonate and / or polystyrene.

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