JP7653012B2 - Low-corrosive cleaning composition - Google Patents

Description

The present invention relates to a cleaning agent composition that reduces corrosion to plastic substrates such as polycarbonate and polystyrene and improves cleaning properties for grease and oil.

Conventionally, cleaning agents for industrial parts have been used to clean greases attached to the surfaces of industrial machinery, transport equipment, electrical and electronic equipment, building materials, etc. In particular, transport equipment such as automobiles, trains, tractors, ships, aircraft, and forklifts have greases attached to various parts of the drive and sliding parts for lubrication and cooling, and these greases are scattered when driven, or contaminants present in the surrounding environment adhere to the surface when driven, causing contamination. 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 fluorine-based solvents, which are non-hazardous materials, have been used. Furthermore, although the components to be cleaned in the past were metals, the diversification of components has led to a demand for cleaning agents 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, so they are corroded by conventional cleaning compositions. In recent years, there has been a demand for the development of cleaning compositions that do not corrode plastic substrates. (Patent Document 1)

Patent Publication No. 2020-41090

However, there was a problem in that cleaning compositions that do not attack plastic substrates had poorer cleaning properties against stains such as grease and oil than conventional cleaning agents.

As a result of intensive research into achieving the above object, the inventors discovered a method for a cleaning composition that does not corrode components containing plastic substrates with low solvent resistance, such as polycarbonate and polystyrene, and has excellent cleaning properties against grease and oil, and thus completed the present invention.

[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) one or more compounds selected from the group consisting of a compound having a carbon chain having a double bond without a chlorine atom to which hydrogen or fluorine is bonded , a hydrofluorocarbon, and a hydrofluoroether; and (C) a hydrocarbon solvent.

[2] The cleaning composition according to claim 1, in which the 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 [1] or [2], wherein (B) is a compound in which hydrogen or fluorine is bonded to a carbon chain having a double bond and no chlorine atom.

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

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

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

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

[8] A cleaning method for removing contaminants by spraying the cleaning aerosol described in [7] on a contaminated area.

[9] A method for cleaning a contaminated area according to [8], the contaminated area including a plastic member.

[10] A method for cleaning a contaminated part, in which the contaminant described in [8] is oil or grease.

[11] A method for cleaning dyed parts in which the plastic member described in [9] contains polycarbonate and/or polystyrene.

The cleaning composition of the present invention has excellent cleaning properties against oils, greases, and other greases, and furthermore, has no risk of attacking plastics, making it highly useful and applicable to a wider range of materials and applications.

The details of the present invention are described below. In this specification, "X to Y" is used to mean that the numerical values (X and Y) written before and after it are included as the lower and upper limits, and means "X or more and Y or less."

The (A) used in the present invention is cis-1-chloro-3,3,3-trifluoropropene, and is the 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. More preferably, it is 20 or more, and most preferably, it is 30 or more. The Kauri-butanol value is an index that indicates 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 exert excellent cleaning performance against grease.

(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. By mixing (B) with (A), it is possible to reduce the corrosiveness of plastic substrates and adjust the drying properties, thereby improving workability. (B) may be used alone or in a mixture of two or more.

The hydrofluoroolefins that do not have chlorine atoms are compounds in which hydrogen or fluorine is bonded to a carbon chain that has a double bond. 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.

The hydrofluorocarbon is a compound in which hydrogen or fluorine is bonded to a carbon chain that does not have a double bond. 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.

The hydrofluoroether is a compound in which hydrogen or fluorine is bonded to a carbon chain that does not have a double bond, and the carbon chain has an ether bond. 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.

Among the above (B), it is preferable to use hydrofluoroolefins that have no chlorine atoms, because they have excellent cleaning properties against oils and fats, and are less corrosive to plastic substrates, and it is preferable to use those that do not have ether bonds in the molecule, because they have excellent cleaning properties against oils and fats, and they are less corrosive to plastic substrates.

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 workability is good, and if it is 200°C or lower, the drying speed is not too slow. The boiling point in this invention is a value measured in accordance with JIS K 0066.

The content of (B) is 11:89 to 99:1 in terms of the mass ratio of (A) to (B). From the viewpoint 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 and low erosion of plastic substrates can be maintained.

Commercially available products of (B) include Opteon SF01, Opteon SF05, Opteon SF10, Opteon SF33, Opteon SF79, CFX70, Bartrel XF, Bartrel XF-UP, Bartrel XF-Select, Bartrel XE, and Bartrel X-E10 manufactured by Mitsui-Chemours Fluoroproducts Co., Ltd., and Novec 7000, Novec 7100, Novec 7200, Novec 7300, Asahiclin AE-3000, and Asahiclin AC-6000 manufactured by 3M Japan Ltd.

The component (C) that can be used in the present invention is a hydrocarbon solvent. By mixing (C) with (A) and (B), the cleaning properties for oils and fats can be improved. Among them, saturated hydrocarbon solvents are preferred from the viewpoint of low erosion to plastics. From the viewpoint of cleaning properties and drying properties as a cleaning agent composition, those with 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 agent composition, cyclohexane, ethylcyclohexane, methylcyclohexane, and isooctane are preferred, ethylcyclohexane, methylcyclohexane, and isooctane are more preferred, and most preferably methylcyclohexane and isooctane. (C) may be used alone or in combination of two or more.

From the viewpoint of drying properties as a cleaning composition, the boiling point of (C) is preferably 50 to 200°C, more preferably 55 to 150°C, and most preferably 60 to 120°C.

The 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). If it is 0.1 part by mass or more, the cleaning properties of the cleaning composition will not decrease, and if it is 70 parts by mass or less, there is no risk of eroding plastic substrates.

The 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, per 100 parts by mass of (A). If it is 0.1 part by mass or more, the cleaning properties of the cleaning composition will not decrease, and if it is 100 parts by mass or less, there is no risk of eroding plastic substrates.

The 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, per 100 parts by mass of (B). If it is 0.1 part by mass or more, the cleaning properties of the cleaning composition will not decrease, and if it is 100 parts by mass or less, there is no risk of eroding plastic substrates.

<Optional ingredients>
The cleaning composition of the present invention may contain optional components within the scope of not impairing 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.

<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. Since the can can be used repeatedly and waste after use can be reduced, it is preferable to use a double-structured spray container. As the propellant, a known substance can be used. As the propellant, dimethyl ether (DME), carbon dioxide, liquefied petroleum gas (LPG), nitrogen, nitrous oxide, isobutane, haloalkyl, hydrofluoroolefin, compressed air, etc. are selected, but from the viewpoints of availability, safety, environmental load, etc., hydrofluoroolefin, carbon dioxide, and nitrogen are particularly suitable, and nitrogen is most preferred.

<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.

<Substrate>
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.

<Applications>
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.

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 performed in an environment of 25°C and 55% RH.

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

(A) cis-1-chloro-3,3,3-trifluoropropene Boiling point: 39°C 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) A compound in which hydrogen or fluorine is bonded to a carbon chain having a double bond that does not have a chlorine atom or an ether bond Boiling point: 71°C Product name: CFX70 Manufactured by Mitsui-Chemours Fluoroproducts Co., Ltd. (B-2) Methoxyperfluoroheptene Boiling point: 110°C Product name: Opteon SF10
(B-3) Hydrofluoroether C ₄ F ₉ OC ₂ H ₅ Boiling point 76°C, manufactured by Mitsui Chemours Fluoroproducts Co., Ltd. Trade name: Nov
ec7200 3M Japan Ltd. (B-4) _{Hydrofluoroether C2F5CF} ( _OCH3 ) _C3F7 Boiling _point 98°C
KB value: 5 Product name: Novec 7300, manufactured by 3M Limited (B-5) Hydrofluorocarbon CF ₃ (CFH) ₂ CF ₂ CF ₃ Boiling point: 55° C. Product name: Vertrel XF, manufactured by Mitsui-Chemours Fluoroproducts Co., Ltd. (B'-1) Perfluoropolyether Boiling point: 80° C. Product name: Galden SV80, manufactured by Solvay (B'-2) Perfluoropolyether Boiling point: 135° C. Product name: Galden SV135
(C-1) Methylcyclohexane manufactured by Solvay, boiling point 100.9°C, product name: Swaclean MCH; (C-2) Isooctane manufactured by Maruzen Petrochemical Co., Ltd., boiling point 62°C, product name: Kyowasol C800; (C-3) Isooctane manufactured by KH Neochem Co., Ltd.

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

[Cleaning ability]
Drop 2 g of contaminant 1 (turbine oil/trade name Daphne Super Turbine Oil) or contaminant 2 (grease/trade name Albania Grease EP2) onto an A4-sized iron plate, and apply it in a circle with a diameter of 40 mm. Stand the iron plate vertically, spray the cleaning agent at 0.5 MPa for 5 seconds from a distance of 15 cm using a double-structure 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.
<Passing criteria>
⊚: Oil or grease on the iron plate can be washed away with a 5-second spray.
◯: Oil or grease on the iron plate can be washed away by spraying for 10 seconds.
×: Oil or grease remains on the iron plate even after 10 seconds of spraying.
[Erosive]
A 6 mm diameter hole was drilled in the center of a polycarbonate plate (L-1225Y manufactured by Teijin Limited) or a polystyrene plate (HIPS manufactured by DIC Corporation) measuring 25 mm in width, 100 mm in length, and 2 mm in thickness using an electric drill, and then an M6 bolt was passed through the hole and a nut was used to fasten the plate with a tightening torque of 6 N to prepare a test piece. 90 ml of each detergent composition was placed in a 100 ml glass bottle, and the test piece was immersed in an environment of 25° C. and 55% RH for 15 seconds. The detergent composition was then removed and allowed to stand for 10 minutes in an environment of 25° C. and 55% RH to dry, and the condition of the resin plate was visually confirmed.
<Passing criteria>
◯: No dissolution or cracking occurred in the plastic plate.
×: Dissolution or cracks were observed in the plastic plate.

As shown in Table 1, the compositions of Examples 1 to 9, which contain (A) to (C) and (A) and (B) in specific ratios, do not corrode plastic substrates such as polycarbonate and polystyrene, and have excellent cleaning properties for 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 for 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 for turbine oil and grease are poor when (B') is used. From the above, it can be seen that by blending (A) to (C) in specific ratios, both corrosion resistance and cleaning properties for plastic substrates can be achieved.

The cleaning composition of the present invention has excellent cleaning properties and does not attack plastic substrates that are not solvent-resistant, such as polycarbonate and polystyrene, making it extremely useful and applicable to a wide range of cleaning applications.

Claims (11)

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 without a chlorine atom.
(C) Hydrocarbon Solvent The cleaning composition according to claim 1, wherein the 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 , wherein the (B) further has no ether bond . The cleaning composition according to any one of claims 1 to 3, wherein the number of carbon atoms in (C) is 5 to 20. The cleaning composition according to any one of claims 1 to 4, wherein the boiling point of (C) is 50°C to 200°C. The cleaning composition according to any one of claims 1 to 5, which consists only of (A) to (C). A cleaning aerosol containing the cleaning composition according to any one of claims 1 to 6 and a propellant. A cleaning method for removing contaminants by spraying the cleaning aerosol according to claim 7 onto a contaminated area. A method for cleaning a contaminated part, the contaminated part according to claim 8 including a plastic member. A method for cleaning a contaminated part, wherein the contaminant according to claim 8 is oil or grease. A method for cleaning contaminated areas, in which the plastic member according to claim 9 contains polycarbonate and/or polystyrene.