Low-corrosive cleaning composition

Abstract

To provide a detergent composition having excellent detergency and not attacking a plastic base material which is not resistant to solvents such as polycarbonate and polystyrene.SOLUTION: A detergent composition comprises the following (A) to (C), where the mass ratio of (A) to (B) is 11:89 to 99:1, (A) cis-1-chloro-3,3,3-trifluoropropene, (B) one or more compounds selected from the group consisting of hydrofluoro-olefins, hydrofluorocarbons, and hydrofluoroethers that do not contain chlorine atoms and (C) hydrocarbon solvents.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a cleaning composition which has reduced corrosiveness to plastic substrates such as polycarbonate and polystyrene and has improved cleaning properties for grease and oil. [Background technology]

[0002] Conventionally, cleaning agents for industrial parts have been used to clean greases attached to the surfaces of industrial machines, transport vehicles, electrical and electronic equipment, building materials, etc. In particular, in transport vehicles such as automobiles, trains, tractors, ships, aircraft, and forklifts, greases for lubrication, cooling, etc. are attached to various parts of the drive and sliding parts, and the surfaces are contaminated when these greases are scattered by driving, or when contaminants present in the surrounding environment are attached during driving. Cleaning agents containing petroleum-based hydrocarbons and alcohols have been used to remove such contamination, but these solvents are highly flammable and therefore fall under the category of hazardous materials under the Fire Service Act. If they fall under the category of hazardous materials, the installation and management of a hazardous materials warehouse is required, and the introduction and maintenance of these materials are costly, so there has been a demand for non-hazardous cleaning agents. In order to clean such dirt, cleaning agent compositions containing non-hazardous fluorine-based solvents are used. Furthermore, conventionally, the components to be cleaned were metal, but due to the diversification of components, cleaning agents are also required for composites of plastic parts and metal parts. However, there is a problem that cleaning agents using fluorine-based solvents used in conventional cleaning agents corrode plastic substrates. In particular, polycarbonate and polystyrene have low solvent resistance and are corroded by conventional cleaning compositions. In light of this, there has been a demand in recent years for the development of cleaning compositions that do not corrode plastic substrates. (Patent Document 1) [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2020-41090 Summary of the Invention [Problem to be solved by the invention]

[0004] However, there is a problem that cleaning compositions that do not attack plastic substrates have poorer cleaning properties against stains such as grease and oil than conventional cleaning agents. [Means for solving the problem]

[0005] As a result of intensive research to achieve the above object, the inventors discovered a method for a cleaning composition that does not cause corrosion even when used on members including plastic substrates with low solvent resistance, such as polycarbonate or polystyrene, and has excellent cleaning properties against grease, oil, etc., and have completed the present invention.

[0006] [1] A cleaning composition comprising the following (A) to (C), in which the mass ratio of (A) to (B) is 11:89 to 99:1: (A) cis-1-chloro-3,3,3-trifluoropropene (B) Chlorine atom Compounds in which hydrogen or fluorine is bonded to a carbon chain that does not have a double bond , one or more compounds selected from the group consisting of hydrofluorocarbons and hydrofluoroethers (C) Hydrocarbon solvents

[0007] [2] The cleaning composition according to claim 1, wherein the blending amount of (C) is 0.1 to 70 parts by mass per 100 parts by mass of the total amount of (A) and (B).

[0008] [3] The above (B) contains a chlorine atom Compounds in which hydrogen or fluorine is bonded to a carbon chain that does not have a double bond The cleaning composition according to [1] or [2],

[0009] [4] The cleaning composition according to any one of [1] to [3], wherein the (C) has 5 to 20 carbon atoms.

[0010] [5] The cleaning composition according to any one of [1] to [4], wherein the boiling point of (C) is 50°C to 200°C.

[0011] [6] The cleaning composition according to any one of [1] to [5], which consists essentially of the components (A) to (C).

[0012] [7] A cleaning aerosol comprising the cleaning composition according to any one of [1] to [6] and a propellant.

[0013] [8] A cleaning method for removing contaminants by spraying the cleaning aerosol according to [7] to a contaminated area.

[0014] [9] A method for cleaning a contaminated area, wherein the contaminated area contains a plastic component, as described in [8].

[0015]

[10] A method for cleaning a contaminated part, wherein the contaminant according to [8] is oil or grease.

[0016]

[11] [9] A method for cleaning dyed parts, wherein the plastic part contains polycarbonate and / or polystyrene. Effect of the Invention

[0017] INDUSTRIAL APPLICABILITY The detergent composition of the present invention has excellent detergency against oils and fats such as oil and grease, and further has no risk of attacking plastics, and therefore can be used for a wider range of materials and applications, making it extremely useful. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The present invention will be described in detail below. In this specification, "X to Y" is used to mean that the numerical values ​​before and after it (X and Y) are included as the lower and upper limits, and means "X or more and Y or less."

[0019] The (A) used in the present invention is cis-1-chloro-3,3,3-trifluoropropene, which is a main component that exerts a cleaning effect on grease. By mixing (A) with (B) and (C), grease can be cleanly cleaned without corroding plastic substrates. From the viewpoint of cleaning performance against grease, it is preferable that the (A) component has a Kauri-butanol (KB) value of 10 or more. It is more preferably 20 or more, and most preferably 30 or more. The Kauri-butanol value is an index showing the grease saturation power of a sample. The larger the value, the more grease the sample can dissolve. The measurement method is to put a certain amount of Kauri resin butanol solution into a flask, place it on a piece of type paper, and drip the sample. The number of ml of sample at the time when the paper becomes turbid and the type becomes unreadable is represented. In the present invention, a KB value of 10 or more can exhibit excellent cleaning performance against grease.

[0020] (B) that can be used in the present invention is one or more compounds selected from the group consisting of hydrofluoroolefins, hydrofluorocarbons, and hydrofluoroethers that do not have chlorine atoms. (B) can be mixed with (A) to reduce the corrosiveness of plastic substrates and adjust the drying property, thereby improving workability. (B) may be used alone or in combination of two or more.

[0021] The hydrofluoroolefin having no chlorine atoms is a compound having a carbon chain having a double bond to which hydrogen or fluorine is bonded. Specific examples include Z-1,1,1,4,4,4-hexafluoro-2-butene, 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene, methoxytridecafluoroheptene, and methoxyperfluoroheptene.

[0022] The hydrofluorocarbon is a compound in which hydrogen or fluorine is bonded to a carbon chain having no double bonds. Specific 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-tridecafluorooctane, and 1,1,1,3,3-pentafluorobutane.

[0023] The hydrofluoroether is a compound in which hydrogen or fluorine is bonded to a carbon chain that does not have a double bond, and an ether bond is present in the carbon chain.Specific examples include methyl perfluoropropyl ether, nonafluorobutyl methyl ether, decafluorobutyl ethyl ether, 1,1,1,2,3,4,4,5,5,6,6,6-tridecafluoro-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.

[0024] Among the above (B), it is preferable to use a hydrofluoroolefin that does not have a chlorine atom in view of excellent cleaning properties against oils and fats and low corrosion to plastic substrates, and it is preferable to use one that does not have an ether bond in the molecule in view of cleaning properties.

[0025] The boiling point of (B) is preferably 30 to 200° C., more preferably 40 to 150° C., and most preferably 50 to 130° C. If it is 30° C. or higher, the drying speed is not too fast and the workability is good, and if it is 200° C. or lower, the drying speed is not too slow. The boiling point in the present invention is a value measured in accordance with JIS K 0066.

[0026] The content of (B) is 11:89 to 99:1 in terms of the mass ratio of (A) to (B). From the viewpoints of cleanability and low erosion, it is preferably 11:89 to 90:10, more preferably 20:80 to 80:20, and most preferably 75:25 to 25:75. Within the above range, cleanability against oils and fats can be maintained, and low erosion of plastic substrates can be maintained.

[0027] Examples of commercially available products of (B) include Opteon SF01, Opteon SF05, Opteon SF10, Opteon SF33, Opteon SF79, CFX70, Vertrel XF, Vertrel XF-UP, Vertrel XF-Select, Vertrel XE, and Vertrel X-E10, all of which are manufactured by Mitsui-Chemours Fluoroproducts Co., Ltd.; and Novec 7000, Novec 7100, Novec 7200, Novec 7300, Asahiclin AE-3000, and Asahiclin AC-6000, all of which are manufactured by 3M Japan Ltd.

[0028] The component (C) that can be used in the present invention is a hydrocarbon solvent. By mixing (C) with (A) and (B), the cleaning property for greases and oils can be improved. Among them, from the viewpoint of low erosion to plastics, saturated hydrocarbon solvents are preferred. From the viewpoint of cleaning properties and drying properties as a cleaning composition, those having 5 to 20 carbon atoms are preferred, more preferably 5 to 15, and most preferably 5 to 10. Specific examples include n-hexane, isohexane, cyclohexane, ethylcyclohexane, methylcyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, and isodecane. From the viewpoint of compatibility with (A) and (B), low erosion to plastic substrates, and cleaning properties as a cleaning composition, cyclohexane, ethylcyclohexane, methylcyclohexane, and isooctane are preferred, ethylcyclohexane, methylcyclohexane, and isooctane are more preferred, and most preferably methylcyclohexane and isooctane are preferred. (C) may be used alone or in a mixture of two or more.

[0029] The boiling point of (C) is preferably from 50 to 200°C, more preferably from 55 to 150°C, and most preferably from 60 to 120°C, from the viewpoint of drying properties of the cleaning composition.

[0030] The blending amount of (C) is preferably 0.1 to 70 parts by mass, more preferably 1 to 100 parts by mass, and most preferably 5 to 50 parts by mass, per 100 parts by mass of the total of (A) and (B). When it is 0.1 part by mass or more, the cleaning properties of the detergent composition are not reduced, and when it is 70 parts by mass or less, there is no risk of corroding plastic substrates.

[0031] The blending amount of (C) is preferably 0.1 to 200 parts by mass, more preferably 1 to 150 parts by mass, and most preferably 10 to 100 parts by mass, relative to 100 parts by mass of (A). When it is 0.1 part by mass or more, the cleaning properties of the cleaning composition are not reduced, and when it is 100 parts by mass or less, there is no risk of corroding plastic substrates.

[0032] The blending amount of (C) is preferably 0.1 to 200 parts by mass, more preferably 1 to 150 parts by mass, and most preferably 5 to 100 parts by mass, relative to 100 parts by mass of (B). When it is 0.1 part by mass or more, the cleaning properties of the cleaning composition are not reduced, and when it is 100 parts by mass or less, there is no risk of corroding plastic substrates.

[0033] <Optional ingredients> The cleaning composition of the present invention may contain optional components within the range that does not impair the characteristics of the present invention. Examples of such components include surfactants, ultraviolet absorbers, antioxidants, chelating agents, rust inhibitors, fragrances, etc., and any component that can be uniformly dissolved and dispersed in (A) to (C) may be appropriately selected.

[0034] <Cleaning method> The cleaning method of the cleaning composition of the present invention includes, but is not limited to, wiping or immersion using a cloth rag, ultrasonic cleaning, spraying using an aerosol or an air gun, etc. The aerosol in the present invention includes a pressure-resistant container filled with a propellant and packaged as an aerosol, and a double-structured spray container in which a pouch is provided in a pressure-resistant container to separate the cleaning composition from the propellant. It is preferable to use a double-structured spray container because the can can be used repeatedly and waste after use can be reduced. A known substance 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, haloalkyl, hydrofluoroolefin, compressed air, etc., but from the viewpoints of availability, safety, environmental load, etc., hydrofluoroolefin, carbon dioxide, and nitrogen are particularly suitable, and nitrogen is most preferred.

[0035] <Drying method> The cleaning composition of the present invention has excellent drying properties and can be used even in low temperature environments. The drying temperature range is preferably from -10°C to 50°C, and more preferably from -5°C to 40°C.

[0036] <Base material> The cleaning composition of the present invention has low corrosion resistance to plastic substrates, and is therefore suitable for cleaning plastic substrates or composite members consisting of plastic substrates 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), PEN (polyethylene naphthalate), etc., and examples of metals include iron, stainless steel, copper, nickel, zinc, aluminum, magnesium, gold, silver, etc.

[0037] <Application> The cleaning composition of the present invention has excellent cleaning properties against oily and grease-based stains. Examples of oils include, but are not limited to, engine oil, gear oil, turbine oil, silicone oil, fluorine oil, and brake oil. The cleaning composition of the present invention is particularly suitable for parts used in transportation equipment such as automobiles, trains, and aircraft, but is also suitable for cleaning other machines. In addition, since it has low erosion properties against plastic substrates, it can be suitably used for cleaning composite members made of plastic substrates and metal substrates. Furthermore, it can also be used in applications other than cleaning, such as applications requiring the removal of oils and fats or solids that are contaminants, such as the removal of adhesives and adhesives. EXAMPLES

[0038] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, tests were carried out in an environment of 25°C and 55% RH.

[0039] [Examples 1 to 9, Comparative Examples 1 to 6] The following ingredients were prepared to prepare the composition:

[0040] (A) cis-1-chloro-3,3,3-trifluoropropene Boiling point 39℃ KB value 34 Product name: 1233zd(Z) manufactured by Honeywell Japan Co., Ltd. (A') 1-chloro-2,3,3-trifluoro-1-propene Boiling point: 54°C KB value: 4 4 Product name: 1233yd Manufactured by AGC Inc. (B-1) Chlorine atom and ether bond Compounds in which hydrogen or fluorine is bonded to a carbon chain that does not have a double bond Boiling point: 71℃ Product name: CFX70 Manufactured by Mitsui Chemours Fluoroproducts Co., Ltd. (B-2) Methoxyperfluoroheptene Boiling point 110℃ Product name: Opteon SF10 Manufactured by Mitsui Chemours Fluoroproducts Co., Ltd. (B-3) Hydrofluoroether C4F9OC2H5 Boiling point 76℃ Product name: Nov ec7200 Manufactured by 3M Japan Ltd. (B-4) Hydrofluoroether C2F5CF(OCH3)C3F7 Boiling point 98℃ KB value: 5 Product name: Novec7300 Manufactured by 3M Ltd. (B-5) Hydrofluorocarbon CF3(CFH)2CF2CF3 Boiling point 55℃ Product name: Vertrel XF, manufactured by Mitsui Chemours Fluoroproducts Co., Ltd. (B'-1) Perfluoropolyether Boiling point 80℃ Product name: Galden SV80 Sol Made by Bay (B'-2) Perfluoropolyether Boiling point 135℃ Product name: Galden SV135 Solvay (C-1) Methylcyclohexane Boiling point 100.9℃ Product name: Swaclean MCH Round Manufactured by Zen Petrochemical Co., Ltd. (C-2) Isooctane Boiling point 62℃ Product name: Kyowasol C800 KH Neochem Co., Ltd.

[0041] The above (A) and (B) were weighed into a mixing vessel, (C) was added, and the mixture was stirred for 30 minutes with a mixer. The detailed amounts of the mixture were as shown in Tables 1 and 2, and all the values ​​were expressed in parts by mass.

[0042] [Washability] Drop 2g of either Contaminant 1 (turbine oil / product name Daphne Super Turbine Oil) or Contaminant 2 (grease / product name Albania Grease EP2) onto an A4-sized iron plate, spreading it over a circle with a diameter of 40mm. Stand the iron plate vertically, and spray the cleaning agent at 0.5MPa for 5 seconds from a distance of 15cm using a double-walled spray container, and visually check whether the contaminant can be washed away. Nitrogen was used as the propellant. If the contaminant cannot be washed away after 5 seconds of spraying, spray for an additional 5 seconds and visually check again. <Pass criteria> ◎: A 5-second spray can wash away oil or grease from an iron plate. ○: Oil or grease on a metal plate can be washed away with a 10-second spray. ×: Oil or grease remains on the iron plate even after 10 seconds of spraying. [Erosive] A 6 mm diameter hole is drilled in the center of a 25 mm wide x 100 mm long x 2 mm thick polycarbonate plate (L-1225Y manufactured by Teijin Limited) or polystyrene plate (HIPS manufactured by DIC Corporation) using an electric drill, and then an M6 bolt is passed through the hole and fastened with a nut at a tightening torque of 6 N to prepare a test piece. 90 ml of each detergent composition is placed in a 100 ml glass bottle, and the test piece is immersed in an environment of 25°C x 55% RH for 15 seconds. The detergent composition is removed and left to dry for 10 minutes in an environment of 25°C x 55% RH, and the state of the resin plate is visually confirmed. <Pass criteria> ◯: No melting or cracking occurred in the plastic plate. ×: Dissolution or cracking was observed in the plastic plate.

[0043] [Table 1]

[0044] [Table 2]

[0045] As shown in Table 1, the compositions of Examples 1 to 9, which contain (A) to (C) and contain (A) and (B) in a specific ratio, do not corrode plastic substrates such as polycarbonate and polystyrene, and have excellent cleaning properties against turbine oil and grease. On the other hand, when there is a small amount of (A) as in Comparative Example 1 in Table 2, or when there is no (C) as in Comparative Example 4, the cleaning properties against turbine oil and grease are poor, and Comparative Example 2, which has a different (A), and Comparative Example 3, which does not contain (B), corrode polycarbonate and polystyrene. Furthermore, it can be seen that the cleaning properties against turbine oil and grease are also poor when (B') is used. From the above, it can be seen that by blending (A) to (C) in a specific ratio, both corrosion resistance and cleaning properties for plastic substrates can be achieved. [Industrial Applicability]

[0046] INDUSTRIAL APPLICABILITY The detergent composition of the present invention has excellent detergency and does not attack plastic substrates that lack solvent resistance, such as polycarbonate and polystyrene, and therefore can be deployed in a wide range of cleaning applications and is extremely useful.

Claims

1. A cleaning composition comprising the following (A) to (C), wherein the mass ratio of (A) to (B) is 11:89 to 99:1: (A) cis-1-chloro-3,3,3-trifluoropropene (B) A fluorine-based solvent having a boiling point of 50 to 130°C, which is a compound in which hydrogen or fluorine is bonded to a carbon chain having a double bond and no chlorine atom. (C) Hydrocarbon Solvent

2. 2. The cleaning composition according to claim 1, wherein the blending amount of (C) is 0.1 to 70 parts by mass per 100 parts by mass of the total amount of (A) and (B).

3. The cleaning composition according to claim 1 or 2, further characterized in that (B) does not have an ether bond.

4. The cleaning composition according to any one of claims 1 to 3, wherein the (C) has 5 to 20 carbon atoms.

5. The cleaning composition according to any one of claims 1 to 4, wherein the boiling point of (C) is 50°C to 200°C.

6. The cleaning composition according to any one of claims 1 to 5, consisting essentially of the components (A) to (C).

7. A cleaning aerosol comprising the cleaning composition according to any one of claims 1 to 6 and a propellant.

8. A cleaning method for removing contaminants by spraying the cleaning aerosol according to claim 7 onto a contaminated area.

9. The method for cleaning a contaminated portion according to claim 8, wherein the contaminated portion includes a plastic member.

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

11. The method for cleaning a contaminated portion, wherein the plastic member according to claim 9 contains polycarbonate and / or polystyrene.

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