WO2018110679A1 - 洗浄剤組成物及びそのエアゾール組成物 - Google Patents
洗浄剤組成物及びそのエアゾール組成物 Download PDFInfo
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- WO2018110679A1 WO2018110679A1 PCT/JP2017/044997 JP2017044997W WO2018110679A1 WO 2018110679 A1 WO2018110679 A1 WO 2018110679A1 JP 2017044997 W JP2017044997 W JP 2017044997W WO 2018110679 A1 WO2018110679 A1 WO 2018110679A1
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- Prior art keywords
- chloro
- trifluoropropene
- cleaning composition
- aerosol
- composition
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
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- C11D7/5018—Halogenated solvents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/30—Materials not provided for elsewhere for aerosols
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/28—Organic compounds containing halogen
- C11D7/30—Halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds
Definitions
- This invention is used for cleaning various vehicles, vehicles, transportation vehicles such as automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, airplanes, railway vehicles, ships, and gloves, work clothes, tools, and workplaces used by workers.
- a new detergent composition and its aerosol composition for use in various vehicles such as bodies, brake parts, suspensions, wheels, etc. made of metal or a combination of metal and resin in various vehicles, vehicles and transportation It is intended to degrease and clean parts, control devices, workers' gloves, and work clothes. It is nonflammable and has a low risk of ignition and fire, and is a non-hazardous material under the Fire Service Act.
- the present invention relates to a cleaning composition and an aerosol composition having excellent characteristics.
- a friction brake device in which a brake shoe with brake lining, which is often used in vehicles, vehicles, and transportation facilities, acts as a brake on a rotating body such as a brake disc and a brake drum, the friction coefficient decreases when oil adheres.
- the dust generated by the wear of the brake lining is likely to adhere, and the braking performance of the brake will be reduced, regular maintenance work is performed, and metal members with oil or dirt are attached. Need to wash.
- a cleaning composition mainly for cleaning bodies, brake parts, suspensions, wheels, etc. of various vehicles / vehicles / transportation systems conventionally, a composition mainly composed of trichloroethane having a cleaning property has been developed and used. It had been.
- trichloroethane is known to be toxic. Trichloroethane was also phased out in 1996 by the Montreal Protocol on Substances that Deplete the Ozone Layer under the Vienna Treaty for the Protection of the Ozone Layer, which will be phased out in 1996 and will be abolished in 1996. Exports and imports from and to non-parties are prohibited or restricted. Therefore, the use of a cleaning composition using trichloroethane has been avoided.
- the hydrocarbon used in the cleaning composition is not as toxic as trichloroethane, there is a risk of intoxication of hydrocarbons by inhaling an excessive amount. It must be used in a well ventilated environment, and the product has a notice to that effect.
- aerosol products because aerosol products are used, the vaporized hydrocarbons flow not only in the workplace but also in the lee, and there is still a risk of inhalation by those who remain there, and improvements were required.
- the cleaning composition is sprinkled or the aerosol product is sprayed vigorously during the work, the above-mentioned cleaning composition having high flammability may permeate a large amount into the operator's gloves and clothes. Moreover, in order to remove the oil dirt adhering to a worker's gloves and work clothes, the said cleaning composition may be infiltrated in large quantities.
- the cleaning composition is highly flammable, if the subsequent drying is insufficient, there is a risk of causing an ignition accident due to static electricity or tobacco fire. Therefore, in order to ensure reliable safety in the working environment, improvement has been demanded so as to avoid the use of those highly flammable components.
- Halogen-based solvents are well-known as solvents that do not have a flash point, but chlorine and bromine are limited in production and use due to their harmfulness, and are used in cleaning compositions. Is difficult. Therefore, as a solution to the problem of securing storage volume and safety, water-based products containing carbitol, alcohol, etc. are proposed as products with high flash points using petroleum-based hydrocarbons with a long carbon number and cleaning ingredients. (See Patent Document 1).
- the above-described aqueous composition is very poor in drying properties and slow, such as requiring 30 to 40 minutes to dry (see Patent Document 1). Therefore, when these aqueous compositions are used as cleaning compositions, the aqueous composition liquid tends to remain around the brake after use, and the brake braking force decreases if the brake is used with the liquid remaining. It leads to a serious influence. For this reason, the above-described working process using the aqueous composition is essential to perform sufficient drying after washing, is complicated, and has been required to be improved. Furthermore, because it is water-based, it is inferior in cleaning properties compared to conventional brake cleaner cleaning compositions, and depending on the type of dirt, it does not necessarily have sufficient cleaning performance, so there are restrictions on the usage scenes. Therefore, improvement has been demanded so as to enhance versatility.
- (Z) -1-chloro-3,3,3-trifluoropropene is known as a solvent that can be used for cleaning metal materials.
- (Z) -1-chloro-3,3,3-trifluoropropene has detergency for metal materials, it has strong erosion properties for resins and elastomers that are materials other than metal materials. (Non-Patent Document 1). Therefore, (Z) -1-chloro-3,3,3-trifluoropropene needs to be thoroughly scrutinized when used.
- metal materials are widely used for parts, but in addition to these metal materials, various kinds of materials such as polycarbonate, acrylic, ABS, polystyrene, silicone rubber, natural rubber, HNBR, NBR, fluorine rubber and urethane rubber are usually used. Materials made of resin or elastomer are also used at the same time.
- the brake is controlled by the hydraulic pressure of the brake fluid, and the brake fluid is generally filled in a rubber hose connecting the devices.
- 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane (AE3000 / HFE-347pc-f) as a fluorine-based solvent of HFE (Hydrofluoroether).
- HFE Hydrofluoroether
- Patent Document 2 2-,2,2-trifluoroethoxy) ethane blended with (Z) -1-chloro-3,3,3-trifluoropropene is known (Patent Document 2). It is possible to deliberately coat a silicone compound that will reduce the friction coefficient and greatly reduce the braking force of brake related parts in various vehicles such as motorcycles, construction machinery, agricultural machinery, aircraft, railway vehicles, railway vehicles, etc. Not done.
- JP 2001-207199 A Japanese Patent No. 5648345 1233Z Excellent environmental performance and high detergency Next-generation fluorinated solvent Central Glass Co., Ltd. Catalog publication date October 2015 Properties of Asahi Clin AE-3000 and application development, Michiomi Nagase et al., Internet ⁇ URL: http://www.agc.com/rd/library/2004/54-10.pdf>
- the problem to be solved by the present invention is non-flammable, so the risk of ignition is low, the risk at the time of fire is low, it falls under non-dangerous goods under the Fire Service Act, no dangerous goods warehouse is required, and mass use There are no legal restrictions on the amount of cleaning composition to be stored, and it has the characteristics of low toxicity, low environmental impact such as ozone layer destruction, and cleaning performance equivalent to that of conventional cleaning compositions.
- Another object of the present invention is to provide a new cleaning composition and an aerosol composition thereof, which have a drying property and have an extremely low attack property against rubber and resin as compared with conventional cleaning compositions.
- the cleaning composition is used for the work of moistening and washing away the soil components, the amount used and the amount of storage increase. Therefore, there is a demand for greatly reducing the risk of fire due to ignition by selecting a solvent that does not have a flash point and does not have a combustion range under the temperature conditions of normal use environment and storage environment.
- the cleaning composition can be provided not only as a solution to be used by being applied or immersed, but also as an aerosol composition containing a cleaning composition and a propellant gas.
- the cleaning composition it is necessary to make it easier to physically remove dirt by using gas pressure.
- when providing as an aerosol composition since the risk that an operator attracts
- the product has a cleaning property equal to or higher than that of a conventional product that has not been achieved with a high flash point product or a water-based product, and an appropriate drying property is realized.
- the resin composition was made by adding 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane, a non-combustible fluorine-based solvent of HFE type. Or elastomer Deterioration, devitrification, and dissolution are eliminated, and moreover, it exhibits properties as a cleaning composition superior to conventional ones, such as automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircrafts, rail vehicles, ships, etc. It has been discovered that it can be used as a new cleaning composition for cleaning gloves, work clothes, tools, and workplaces used by various vehicles, vehicles, transportation facilities, and workers.
- (Z) -1-chloro-3,3,3-trifluoropropene which is known to cause serious problems such as deterioration, devitrification, and dissolution of resins and elastomers, has improved solubility in substances.
- a combination of C 4 F 9 OCH 3 or C 3 F 7 OCH 3 is used as the composition.
- the resin and the elastomer are not altered, devitrified or dissolved, and further exhibit superior properties as a cleaning composition.
- the invention of the new cleaning composition of this application and its aerosol composition was completed by examining the combination of said 2 components in detail.
- the first means of the present invention for solving the above problems comprises (Z) -1-chloro-3,3,3-trifluoropropene and an HFE-based nonflammable fluorine-based solvent.
- the second means of the present invention for solving the above problem is that the HFE-based nonflammable fluorine-based solvent is C 4 F 9 OCH 3 , C 3 F 7 OCH 3 , and 1,1,2,2 -A cleaning composition according to the first means of the invention, characterized in that it is one or more selected from tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane.
- the third means of the present invention for solving the above problems is that the range of the mass ratio ((Z) -1-chloro-3,3,3-trifluoropropene / HFE-based nonflammable fluorine-based solvent) is The cleaning composition according to the first or second means of the present invention, wherein the cleaning composition is 50/50 to 99/1.
- the fourth means of the present invention for solving the above problems comprises (Z) -1-chloro-3,3,3-trifluoropropene and C 4 F 9 OCH 3, and its mass
- the ratio ((Z) -1-chloro-3,3,3-trifluoropropene / C 4 F 9 OCH 3 ) is 50/50 to 99/1, preferably 70/30 to 99/1
- the cleaning composition according to the third means of the present invention is 50/50 to 99/1, preferably 70/30 to 99/1.
- the fifth means of the present invention for solving the above problems comprises (Z) -1-chloro-3,3,3-trifluoropropene and C 3 F 7 OCH 3, and its mass
- the third means of the present invention is characterized in that the ratio ((Z) -1-chloro-3,3,3-trifluoropropene / C 3 F 7 OCH 3 is 80/20 to 99/1 It is a cleaning composition of description.
- the sixth means of the present invention for solving the above-mentioned problems is that (Z) -1-chloro-3,3,3-trifluoropropene and 1,1,2,2-tetrafluoro-1- (2 , 2,2-trifluoroethoxy) ethane, and its mass ratio ((Z) -1-chloro-3,3,3-trifluoropropene / 1,1,2,2-tetrafluoro- 1- (2,2,2-trifluoroethoxy) ethane) is from 50/50 to 99/1, preferably from 70/30 to 99/1, according to the third means of the invention
- the cleaning composition is from 50/50 to 99/1, preferably from 70/30 to 99/1, according to the third means of the invention.
- the seventh means of the present invention for solving the above-mentioned problems is that the cleaning composition is a vehicle, a vehicle, a vehicle, a vehicle such as an automobile, a motorcycle, a bicycle, a construction machine, an agricultural machine, an aircraft, a railway vehicle, and a ship.
- the cleaning composition according to any one of the first to sixth means of the present invention characterized in that it is used for cleaning an engine, a glove used by an operator, work clothes, a tool, or a workplace. It is a thing.
- the eighth means of the present invention for solving the above-mentioned problems is that the cleaning composition is a vehicle, a vehicle, a vehicle, a vehicle such as an automobile, a motorcycle, a bicycle, a construction machine, an agricultural machine, an aircraft, a railway vehicle, and a ship.
- a ninth means of the present invention for solving the above-mentioned problem is an aerosol composition containing the cleaning composition according to any one of the first to eighth means of the present invention and a propellant gas. It is.
- the cleaning composition of the means of the present invention and the aerosol composition thereof comprise (Z) -1-chloro-3,3,3-trifluoropropene and an HFE-based nonflammable fluorine-based solvent, which are blended as main components.
- all have no flash point and are nonflammable. Therefore, the danger of ignition and the risk at the time of a fire in those cleaning composition and its aerosol composition use environment are low.
- these main components (Z) -1-chloro-3,3,3-trifluoropropene and HFE nonflammable fluorinated solvents are both non-hazardous substances under the Fire Service Law, There is no need for dangerous goods warehouses and there are no legal restrictions on the amount of storage of cleaning compositions used in large quantities.
- each of the above components is low in toxicity and has a low environmental load such as ozone depletion, so that it is a product that takes into consideration the human body and the environment.
- the cleaning composition of the means of the present invention and the aerosol composition thereof have a cleaning performance and drying performance comparable to those of conventional brake cleaners, but have an attacking property against rubber and resin more than conventional brake cleaners. It has an excellent characteristic of being extremely low.
- the main components of the cleaning composition and the aerosol composition of the means of the present invention will be described.
- the cleaning composition of the means of the present invention and its aerosol composition contain two components of (Z) -1-chloro-3,3,3-trifluoropropene and an HFE-based nonflammable fluorine-based solvent. Shall be allowed to.
- Non-Patent Document 1 The above (Z) -1-chloro-3,3,3-trifluoropropene causes alteration, devitrification, or dissolution of the resin and elastomer (Non-Patent Document 1). It is not preferable to use it as a component of the agent.
- HFE-based fluorinated solvents such as 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane are highly effective in expressing solubility in substances. Since the molecule is not contained in the molecule, it does not have high compatibility with fats and oils (Non-patent Document 2) and does not become a component for exerting detergency.
- (Z) -1-chloro-3,3,3-trifluoropropene which is unsuitable as a component to be incorporated into such a detergent composition, is an HFE-based noncombustible material that does not become a component that exhibits detergency. Unexpectedly, it will not cause effects such as alteration, devitrification, and dissolution on resins and elastomers, and it has a wider range of excellent cleaning properties than conventional ones. It becomes a thing. Therefore, (Z) -1-chloro-3,3,3-trifluoropropene and HFE-based non-flammable fluorine solvent are included together as main components to maintain various safety. However, a new cleaning composition and its aerosol composition having excellent characteristics that can be used for a wider variety of materials can be provided.
- the above-described cleaning composition of the means of the present invention and its aerosol composition contain (Z) -1-chloro-3,3,3-trifluoropropene as one of the two essential components. It shall contain.
- (Z) -1-Chloro-3,3,3-trifluoropropene is a hydrofluoroolefin solvent that is commercially available under the name 1233Z (Central Glass Co., Ltd., Japan). be able to.
- (Z) -1-Chloro-3,3,3-trifluoropropene is a nonflammable solvent that does not have a flash point and does not have a combustion range according to the explosion limit test method ASTM E681.
- it has chemical properties that are environmentally friendly, such as the ozone depletion coefficient ODP is substantially zero and the global warming coefficient GWP is ⁇ 1. Therefore, it does not fall under the components specified in the Ozone Layer Protection Law, the Global Warming Countermeasures Promotion Law, the Freon Emission Control Law, the Fire Service Law, the High Pressure Gas Safety Law, etc., and there are no special restrictions on its use.
- (Z) -1-chloro-3,3,3-trifluoropropene has invasiveness to the resin. Therefore, for example, when (Z) -1-chloro-3,3,3-trifluoropropene acts on a soft polyvinyl chloride (PVC) resin or a phenol resin, the resin is altered and the weight and dimensions of the resin product are changed. Changes. In addition, when it acts on a polycarbonate resin, the resin is devitrified. Furthermore, when it acts on an acrylic (PMMA) resin, an ABS resin or a polystyrene resin which is a copolymerized synthetic resin of acrylonitrile, butadiene and styrene, those resins are dissolved. As described above, (Z) -1-chloro-3,3,3-trifluoropropene is not compatible with the resin material as it is.
- PVC polyvinyl chloride
- phenol resin phenol resin
- PVC polyvinyl chloride
- the resin is altered
- (Z) -1-chloro-3,3,3-trifluoropropene is invasive to various elastomers. Therefore, for example, when (Z) -1-chloro-3,3,3-trifluoropropene acts on SBR, chloroprene rubber, butyl rubber, EPDM and CSM, these elastomers are altered to change the weight and dimensions. Moreover, when it acts on silicone rubber, natural rubber, HNBR, NBR, fluorine rubber and urethane rubber, these elastomers swell. Thus, (Z) -1-chloro-3,3,3-trifluoropropene as such is poorly compatible with elastomers.
- (Z) -1-chloro-3,3,3-trifluoropropene has a boiling point as low as 39 ° C. and is too dry, as it is, it requires a process of moistening and washing away dirt. It is not suitable for cleaning compositions used in various vehicles such as automobiles, bicycles, construction machinery, agricultural machinery, airplanes, railway vehicles, and ships, vehicles, and transportation.
- the above-mentioned (Z) -1-chloro-3,3,3-trifluoropropene has poor resin compatibility and high dryness, such as automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railways.
- the unsuitable properties of the cleaning composition used in various vehicles such as vehicles and ships, vehicles, transportation, etc. are unexpectedly HFE non-flammable fluorine having other characteristics that are inappropriate for the cleaning composition. It is eliminated by containing the system solvent together, and a more excellent cleaning composition is provided.
- the above-described cleaning composition of the means of the present invention and its aerosol composition contain one or more HFE-based non-flammable fluorine solvents as the other of the two essential components.
- This HFE-based fluorinated solvent does not have a flash point and is non-flammable with both a combustion point (lower limit) and a combustion point (upper limit) not detected. It falls under non-dangerous goods under the Fire Service Act, no dangerous goods warehouse is required, and there is no legal limit on the amount of storage.
- HFE-based nonflammable fluorine-based solvents such as 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane have the effect of exhibiting solubility in substances. Since the high chlorine atom is not included in the molecule, it does not have high compatibility with fats and oils and solvents (Non-patent Document 2).
- HFE-based nonflammable fluorine-based solvent in the cleaning composition and the aerosol composition according to the present invention examples include C 4 F 9 OCH 3 , C 3 F 7 OCH 3 , and 1,1,2,2-tetra One or more selected from fluoro-1- (2,2,2-trifluoroethoxy) ethane is used. And preferably 1 selected from C 4 F 9 OCH 3 , C 3 F 7 OCH 3 , or 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane More preferably, one selected from C 4 F 9 OCH 3 or C 3 F 7 OCH 3 is used.
- 1,1,2,2-Tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane is HFE-347pc-f or Asahiklin AE-3000 (Asahi Glass) as an HFE non-flammable fluorine-based solvent. It is possible to obtain and use products that are commercially available under the names such as Co., Ltd.
- This solvent is a nonflammable solvent having no flash point (TCC, COC) and no burning range. It falls under non-dangerous goods under the Fire Service Act, no dangerous goods warehouse is required, and there is no legal limit on the amount of storage. And the boiling point is 56 degreeC and it has moderate drying property.
- the HFE nonflammable fluorine-based solvent C 4 F 9 OCH 3 is obtained by using a commercially available product such as 3M TM NOVEC TM 7100 highly functional liquid (3M Japan, Japan). can do.
- This solvent has no flash point, and is a non-flammable solvent whose combustion point (lower limit) and combustion point (upper limit) are not detected.
- no dangerous goods warehouse is required, there is no legal limit on the amount of storage, and the ozone layer depletion coefficient ODP is zero, and it has chemical properties that are environmentally friendly. Have. Therefore, it is not applicable to the Ozone Layer Protection Law or the Global Warming Prevention Promotion Law. And the boiling point is 61 degreeC, and it has moderate drying property.
- the above-mentioned HFE-based non-flammable fluorine-based solvent C 3 F 7 OCH 3 is obtained and used under the name of 3M TM NOVEC TM 7000 highly functional liquid (3M Japan, Japan). can do.
- This solvent has no flash point, and is a non-flammable solvent whose combustion point (lower limit) and combustion point (upper limit) are not detected. It falls under non-dangerous goods under the Fire Service Act, no dangerous goods warehouse is required, and there is no legal limit on the amount of storage.
- the ozone layer depletion coefficient ODP is zero, and it has chemical properties that are environmentally friendly. Therefore, it is not applicable to the Ozone Layer Protection Law or the Global Warming Prevention Promotion Law.
- the mass ratio with the non-combustible fluorine-based solvent is preferably 50/50 to 99/1.
- the two components contained in the cleaning composition and the aerosol composition of the means of the present invention are (Z) -1-chloro-3,3,3-trifluoropropene and C 4 F 9 OCH 3 .
- the mass ratio ((Z) -1-chloro-3,3,3-trifluoropropene / C 4 F 9 OCH 3 ) ranges from 50/50 to 99/1, preferably 70 / 30 to 99/1.
- it has lower invasiveness to resins and elastomers, higher compatibility with fats and oils, etc., excellent cleaning properties for members made of various materials such as metals, resins and elastomers, and an appropriate drying speed. It becomes possible to have a plurality of characteristics, and it can be suitably used as a cleaning composition and an aerosol composition thereof.
- the two components contained in the cleaning composition and the aerosol composition of the means of the present invention are (Z) -1-chloro-3,3,3-trifluoropropene and C 3 F 7 OCH 3 .
- the mass ratio ((Z) -1-chloro-3,3,3-trifluoropropene / C 3 F 7 OCH 3 ranges from 50/50 to 99/1, preferably 80 / 20 to 99/1, thereby lower invasiveness to resins and elastomers, higher compatibility with oils and fats, and excellent cleanability and moderateness for members made of various materials such as metals, resins and elastomers. It is possible to have a plurality of excellent properties such as having a good drying speed, and it can be suitably used as a cleaning composition and its aerosol composition.
- the two components contained in the cleaning composition and the aerosol composition of the means of the present invention are (Z) -1-chloro-3,3,3-trifluoropropene and 1,1,2,2-
- the mass ratio ((Z) -1-chloro-3,3,3-trifluoropropene / 1,1 , 2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane) is 50/50 to 99/1, preferably 70/30 to 99/1.
- the cleaning composition of the means of the present invention and the aerosol composition thereof in addition to the two main components as the above-described cleaning composition, may further contain additional components as a risk of ignition or a fire risk. It is good also as what was mix
- (Z) -1-chloro which is achieved by the two main components, while maintaining the nonflammability as a cleaning composition or the non-hazardous property in the Fire Service Act.
- -3,3,3-Trifluoropropene is blended within a range that can reduce the invasiveness to the resin and elastomer held by the resin itself, and maintain the characteristics of cleaning the oil and fat component and maintaining an appropriate drying speed.
- alcohols saturated hydrocarbons, unsaturated hydrocarbons, aromatic hydrocarbons, stabilizers, chelating agents, and the like can be used.
- 3M TM NOVEC TM 7200 3M TM NOVEC TM 7300, etc.
- HFE solvents alcohols such as methanol, ethanol, isopropyl alcohol, butanol, hydrocarbon solvents such as normal hexane, cyclohexane, isohexane, ketone solvents such as acetone, MEK, cyclohexanone, ethyl acetate, methyl acetate, butyl acetate, Esters such as ethylene glycol monomethyl ether acetate and glycol ester solvents, ethers such as methyl cellosolve, butyl cellosolve, methoxymethylbutanol, hexyl diglycol, and glycol ether solvents, Glyme solvents such as lenglycol dimethyl ether and diethylene glycol dimethyl ether, chlorine solvents such as HCFC-141b, HCFC-225, 1-bromopropane and chloroform, special solvents such as N-methyl-2-pyrrolidone, tetrahydrofuran and dimethylformamide,
- liquefied gas or compressed gas can be used as the propellant gas in the aerosol composition.
- two gases such as LPG (liquefied petroleum gas), DME (dimethyl ether), carbon dioxide gas, chlorofluorocarbon gas, nitrogen gas, compressed air, a mixture of LPG and DME, and a mixture of LPG and carbon dioxide gas are used.
- LPG liquefied petroleum gas
- DME dimethyl ether
- carbon dioxide gas chlorofluorocarbon gas
- nitrogen gas compressed air
- compressed air compressed air
- compressed air compressed air
- a mixture of LPG and DME a mixture of LPG and carbon dioxide gas
- the detergent composition of the means of this invention and said injection gas can be mixed, and it can be provided by filling a pressure-resistant can into an aerosol composition.
- the solution of the cleaning composition of the means of the present invention includes metals, resins, and elastomers of various vehicles, vehicles, and transportation engines such as automobiles, motorcycles, bicycles, construction machines, agricultural machines, aircrafts, railway vehicles, and ships to be cleaned. It can be used by being applied to members made of various materials such as gloves, work clothes, tools, and workplaces used by workers, or by immersing those objects to be cleaned in a solution of a cleaning composition.
- the pressure-resistant can is filled with an aerosol composition obtained by mixing the cleaning composition of the means of the present invention with a liquefied gas serving as a jet gas, or the cleaning composition of the means of the present invention is applied to a pail can.
- a mobile small filling machine in the working place and aerosolize the cleaning composition put in the pail can with compressed air to make it a member made of various materials such as metals, resins and elastomers to be cleaned It can be used by spraying as an aerosol.
- HFE nonflammable fluorine 3M TM NOVEC TM 7000 highly functional liquid 3M Japan, Japan
- 3M is used as C 4 F 9 OCH 3 as a non-flammable fluorine-based solvent as an HFE type
- TM NOVEC TM 7100 highly functional liquid 3M Japan, Japan
- (Z) -1-chloro-3,3,3-trifluoropropene and the above-mentioned HFE-based nonflammable fluorine-based solvent have a mass ratio of
- the cleaning compositions of Examples 1 to 20 which are cleaning compositions containing 1-chloro-3,3,3-trifluoropropene and an HFE-based non-flammable fluorine-based solvent Manufactured.
- Example 1 30/70
- Example 2 50/50
- Example 3 70/30
- Example 4 80/20
- Example 5 85/15
- Example 6 90/10
- Example 20 99/1 ⁇ Mass ratio (1233Z / NOVEC7000)
- Example 7 30/70
- Example 8 50/50
- Example 9 70/30
- Example 10 80/20
- Example 11 90/10
- Example 12 95/5 ⁇ Mass ratio (1233Z / NOVEC7100)
- Example 14 50/50
- Example 15 70/30
- Example 16 80/20
- Example 17 85/15
- Example 18 90/10
- Example 19 99/1
- Comparative Examples 1 to 4 were prepared.
- the quick-drying stock solution, the degreasing detergent, and the normal-drying stock solution are all highly flammable, and trichloroethane is highly harmful, and all of these have problematic properties as cleaning compositions.
- Comparative Example 1 Fast-drying stock solution
- Comparative Example 2 Degreasing detergent
- Comparative example 3 Normal-drying stock solution
- Comparative Example 4 Trichloroethane
- Comparative Example 5 1233Z only Comparative Example 6: AE-3000 only Comparative Example 7: NOVEC7000 only Comparative Example 8: NOVEC7100 only
- Test Examples 1 to 6 shown below are carried out, and the cleaning composition and the aerosol composition of the means of the present invention have excellent characteristics as compared with conventional cleaning agents. Was confirmed specifically.
- Grease GREASE (Orange) (Kobe synthesis Co., Japan) : Rubber grease combined with rubber (Kobe synthesis Co., Japan) : Grease for disc brake (Kobe synthesis Co., Japan) : Brake grease (Kobe synthesis company, Japan) : Silicone grease (Kobe synthesis Co., Japan) : Caliper Pingris (Honda Access, Japan) : Pad & shoe grease (Honda Access, Japan) : Rubber Squirrel (Honda Access, Japan) : Brake grease (Honda Access, Japan) Oil: Engine oil Mobile1 0W-20 (ExxonMobil, USA) : Brake fluid (DOT3) (Honda Access, Japan) : Brake fluid (DOT4) (Suzuki, Japan)
- Test results The results of the above tests are shown in Table 1-1 to Table 1-4.
- HFE-based non-flammable fluorine-based solvents have little compatibility with grease or brake oil (Comparative Examples 6 to 9 in Table 1-4). It is unsuitable for use as a cleaning agent for removal. Further, although (Z) -1-chloro-3,3,3-trifluoropropene has moderate compatibility, as is apparent from the test results of Test Example 3 and Test Example 4 to be described later, Since it has invasiveness, it is unsuitable for a detergent composition used for various vehicles, vehicles, transportation facilities and the like. As described above, various HFE-based non-flammable fluorine-based solvents and (Z) -1-chloro-3,3,3-trifluoropropene are both used as cleaning compositions for various vehicles, vehicles and transportation facilities. It lacks the motivation to add.
- thermo-hygrostat HPAV-120-40, Isuzu Manufacturing Co., Ltd., Japan
- a temperature condition of 45%, 25 ° C. or 10 ° C. and a humidity of 70% was placed and allowed to stand.
- 100 ⁇ L of the solutions of Examples 1 to 18 and Comparative Examples 1 to 8 are placed in the flat plate, and the time until the droplets of each solution completely evaporate from the flat plate and dry is visually observed.
- Test results The results of the above tests are shown in Tables 2-1 to 2-4.
- the optimum time required for drying is typically 1 to 2 minutes under a high temperature environment of 40 ° C, and 25 ° C. It is preferable that it is 2 minutes to 3 minutes in a normal temperature environment and 3 minutes to 4 minutes in a low temperature environment of 10 ° C.
- those that can achieve such conditions are only those of the quick-drying stock solution type, and others require excessive time to dry (Table 2). -4).
- this type of quick-drying stock solution has a short time required for drying, but has a high flammability and has a problem in terms of ensuring high safety required for the detergent composition.
- the cleaning composition of the means of the present invention containing (Z) -1-chloro-3,3,3-trifluoropropene and an HFE-based nonflammable fluorine-based solvent Is a non-flammable detergent composition having excellent properties for oil and fat components. Therefore, the cleaning composition containing (Z) -1-chloro-3,3,3-trifluoropropene and an HFE-based nonflammable fluorine-based solvent can have any drying time. I examined.
- ⁇ Test Example 3 Evaluation of invasiveness (long term)> Materials and Methods
- Rubber NR (natural rubber) : CR (chloroprene rubber) : SBR (styrene-butadiene rubber) : EPDM (ethylene propylene rubber) (All are from Standard Test Piece Co., Ltd., Japan.)
- Resin ABS (Acrylonitrile Butadiene Styrene) : LDPE (low density polyethylene) : PC (polycarbonate) (All are Japan Test Panel Co., Ltd.)
- Each rubber or resin test piece (size 10 mm ⁇ 10 mm ⁇ 2 mm) is weighed.
- 20 mL of the solutions of Examples 1 to 18 and Comparative Examples 1 to 8 are placed in a vial, and the rubber or resin test pieces (size 10 mm ⁇ 10 mm ⁇ 2 mm) are immersed therein, and the vial is Put in a constant temperature and humidity machine (HPAV-120-40, Isuzu Seisakusho Co., Ltd., Japan) set at 45 ° C and let stand for 1 month.
- a constant temperature and humidity machine HPAV-120-40, Isuzu Seisakusho Co., Ltd., Japan
- Test Example 1 and Test Example 2 a composition comprising (Z) -1-chloro-3,3,3-trifluoropropene and an HFE-based nonflammable fluorine-based solvent can be used as an excellent fat and oil. It was confirmed that compatibility and good and moderate drying properties can be maintained.
- Test Example 3 a composition comprising (Z) -1-chloro-3,3,3-trifluoropropene and an HFE-based nonflammable fluorine-based solvent was obtained as (Z) -1-chloro-3 , 3,3-trifluoropropene has improved the invasiveness to rubber or resin, and compared with the conventional cleaning agent for non-invasiveness to rubber or resin under accelerated processing conditions at 45 ° C for 1 month went.
- (Z) -1-Chloro-3,3,3-trifluoropropene is invasive to rubbers and resins when applied for a long period of time, especially in various vehicles, vehicles and transportation SBR (styrene butadiene rubber), commonly used in equipment and parts important to ensure safety, is swollen, ABS (acrylonitrile butadiene styrene) is dissolved, PC (polycarbonate) is swollen, whitened, and It showed strong invasiveness such as cracking, and the degree of alteration of these rubbers and resins could not guarantee the quality of the product (Table 3-4).
- SBR styrene butadiene rubber
- ABS acrylonitrile butadiene styrene
- PC polycarbonate
- SBR styrene-butadiene rubber
- SBR styrene-butadiene rubber
- the cleaning agent used for cleaning the brake device and its surroundings is erosive to SBR. Is desirable to be low.
- increasing the HFE-based non-flammable fluorine-based solvent compounded to solve the problem of erosion of (Z) -1-chloro-3,3,3-trifluoropropene against SBR Product cost increases. Then, it examined whether there was room to further reduce the quantity of the HFE type nonflammable fluorine-type solvent to mix
- Example 19 mass ratio (1233Z / NOVEC7100) is 99/1
- Example 20 mass ratio (1233Z / AE-3000), in which the amount of HFE-based non-flammable fluorine-based solvent is further reduced. 99/1) were prepared, and 5 g each was put in a vial. The SBR test piece whose thickness was measured was dipped in it, and left for 24 hours under accelerated processing conditions at 40 ° C. After that, the SBR test piece was taken out and the liquid on the surface was wiped off. The thickness was measured and the rate of change was determined. The results are shown in Table 3-5.
- the surface is wiped with a microfiber cloth containing the solutions of Examples 1 to 18 or Comparative Examples 1 to 8. After that, the appearance change of each test piece surface is visually observed. When there was no change in appearance, it was marked as ⁇ , and when there was a change, it was marked as x and the state of the resin surface was recorded.
- ⁇ Test Example 5 Evaluation of invasiveness (examination with actual vehicle brake hose)> -Materials and methods Obtain a rear brake hose set for a car sold by Suzuki Motor Corporation (model MH23S) or a car sold by Hyundai Motor Co., Ltd. (model GE6), and use the brake hose as a test sample. Measure the thickness of the brake hose before testing.
- the brake hose is put in a bottle, and the solution of Example 3, Comparative Example 1, Comparative Example 2, or Comparative Example 3 is put so that the brake hose is immersed. Thereafter, the bottle is placed in a thermo-hygrostat (HPAV-120-40, Isuzu Manufacturing Co., Ltd., Japan) set at 40 ° C. and left to stand for 72 hours. After 72 hours, each brake hose is taken out from the bottle, the solution is wiped with a cloth, the surface state is observed, the weight and thickness of the brake hose are measured, and the swelling rate (%) is calculated.
- the cleaning composition of the means of the present invention has excellent drying properties as confirmed in Test Example 2, and even if the cleaning composition adheres, it does not remain as it is for a long time and volatilizes. Even when the brake hose is washed, even if the detergent composition is left immersed for a long time as in Test Example 5 above, the swelling rate due to the detergent composition is small, cracking due to rubber deterioration and Abnormal appearance such as tearing does not occur. Furthermore, in addition to rubber, various resins are used in brake devices such as front wheel brakes, rear wheel brakes, calipers, and cylinders. As confirmed in Test Example 3, the cleaning composition of the means of the present invention is used.
- the cleaning composition of the means of the present invention has characteristics more suitable for cleaning the brake device and its surroundings than the conventional cleaning agent.
- Example 6 Evaluation of drying property (aerosol composition)> -Materials and methods
- the solutions of Example 3 and Example 15 described above are prepared.
- LPG liquefied petroleum gas
- the solution of Example 3 or Example 15 and LPG are mixed to form an aerosol composition, which is filled in a pressure can.
- a constant temperature and humidity machine (HPAV-120-40, Isuzu Manufacturing Co., Ltd., Japan) was set at a temperature of 45 ° C., 25 ° C. or 10 ° C. and a humidity of 70%, and the standard test plate SPCC-SB (1- ( ⁇ 5 ⁇ 0.8 ⁇ 70 ⁇ 150 mm) (Nippon Test Panel Co., Ltd., Japan) is placed on a saucer in a constant temperature and temperature chamber so as to stand vertically and is allowed to stand.
- the aerosol composition was sprayed on the standard test plate from a pressure can filled with the solution of Example 3 or Example 15 for about 10 seconds from a position about 20 cm away, and dripped. The time until the liquid dries was measured visually.
- an aerosol composition was further prepared using the cleaning composition of Example 15, the quick-drying stock solution of Comparative Example 1, the degreasing detergent of Comparative Example 2 or the normal-drying stock solution of Comparative Example 3, and LPG or compressed air. , Spraying it as an aerosol on standard test plates under various temperature conditions of 40 ° C, 30 ° C, 20 ° C, 5 ° C, coating temperature, post-drying temperature, temperature difference between them, and drying The time required was measured, and the characteristics were compared. The test results are shown in Table 5-2 and Table 5-3.
- Example 15 As a result of the above test, it is clear that when the detergent composition of Example 15 is an aerosol composition together with LPG and sprayed on a standard test plate, it has the property of drying as quickly as when using a conventional quick-drying stock solution. (Table 5-2). Also, it is usually assumed that the drying rate of the sprayed aerosol composition simply increases as the temperature of the test plate increases to 30 ° C. and 40 ° C. In the case of a composition, the temperature after drying after spraying on the test plate is greatly reduced and the temperature difference before and after spraying is increased, so that the time until drying becomes extremely short at high temperatures and workability deteriorates. This was avoided (Table 5-2). It is understood that the means of the present invention has an appropriate drying time even at high temperatures and has good workability in various temperature ranges.
- ⁇ Test Example 7 Evaluation of aerosol detergency> Materials and Methods As in Test Example 6, aerosol compositions prepared using the cleaning compositions of Example 3, Example 15, Comparative Example 1, Comparative Example 3, and Comparative Example 4 are prepared. Stand the test plate and spread 1 g of silicone grease to a width of 35 mm x 50 mm. The aerosol composition is sprayed onto a part of the area that has been smeared with grease and washed with only the aerosol pressure. Measure the contact angle at the blank part where the silicone grease is not attached, the part where the silicone grease is attached, the part where the silicone grease is washed only with the aerosol pressure, and the part where the silicone grease is washed off with the aerosol composition. . If grease remains, the contact angle increases due to the hydrophobic nature of the grease.
- Example 3 or Example 15 When the aerosol composition prepared using the cleaning composition of Example 3 or Example 15 was sprayed, the oil and fat that the cleaning composition of Example 3 or Example 15 had silicone grease It was almost completely removed only by the compatibility with the liquid and the spraying pressure of aerosol. The sprayed part and the part where the liquid dripped became dry within tens of seconds.
- a nonflammable cleaning composition comprising (Z) -1-chloro-3,3,3-trifluoropropene and HFE-based nonflammable fluorine-based solvent according to the means of the present invention.
- Example 8 Evaluation of gas used in aerosol composition> Material and Method As in Test Example 1, the solution of Example 15 described above is prepared. In addition to LPG (liquefied petroleum gas), 1234ZE ((E) -1,3,3,3-tetrafluoroprop-1-ene / trans-1,3,3,3-tetra as an injection gas in the aerosol composition Fluoropropene, HFO-1234Zze- (E))), and CO 2 at 0.2 MPa or more are mixed with the above solution to form an aerosol composition, each of which is filled in a pressure can.
- LPG liquid petroleum gas
- 1234ZE ((E) -1,3,3,3-tetrafluoroprop-1-ene / trans-1,3,3,3-tetra as an injection gas in the aerosol composition Fluoropropene, HFO-1234Zze- (E))
- CO 2 at 0.2 MPa or more
- 1234ZE is classified as a “non-combustible gas” in the UN Recommendations and in the flammability category of the United States, Europe, and other Asian countries other than Japan. It is classified as a flammable gas under the Japanese High Pressure Gas Safety Law due to the difference in measurement method.
- the aerosol composition was sprayed for 10 seconds from a pressure can filled with the solution of Example 15 on the test plate from a position about 5 cm away, and the sprayed state of the aerosol, the state of the liquid after spraying on the test plate, and the liquid The time until it dries was measured visually.
- silicone grease is applied to the test plate, sprayed by changing the spray distance of each aerosol, and when the aerosol reaches the test plate, the diameter of the range wetted with the solution is measured.
- the aerosol solution flowed down without drying, the silicone grease was dissolved and thoroughly washed away, and the silicone grease remained, ⁇ . ⁇ , the aerosol solution stays in place, and the silicone solution is dissolved by the aerosol solution, but the aerosol solution dries halfway and the silicone grease remains on the test plate, ⁇ , the aerosol solution
- the case where the silicone grease did not dissolve sufficiently to evaporate on the test plate and remained remained was marked with x. , It was evaluated.
- LPG is a flammable gas
- consideration is required for large-scale use even if the main agent is non-flammable.
- LPG is used as the injection gas
- the injection distance is short, it can be washed away by the amount of liquid and pressure after it gets wet so that dust does not scatter, and an aerosol solution is applied to the cloth. It is understood that it can be wiped off and the loss can be reduced without dripping.
- the time until drying is faster than in the case of LPG, and up to a spray distance of 5 cm, the aerosol solution can be wetted to a diameter of 8 cm. Although it was almost washed away, when the spraying distance was increased to 10 cm, the aerosol solution could be wetted to a range of 8 cm in diameter, but the aerosol solution was dried in the middle and silicone grease remained on the test plate.
- the spraying distance was 20 cm or more, the solution of Example 15 of the main agent and the solution of 1234ZE were vaporized together on the test plate, so that they were not wet and washed away, and the silicone grease remained.
- Example 15 the solution of Example 15 described above is prepared.
- CO 2 was 0.2MPa or more
- CO 2 was 0.2MPa or less
- N 2 which was 0.2MPa or more
- silicone grease is applied to the test plate, sprayed by changing the spray distance of each aerosol, and when the aerosol reaches the test plate, the diameter of the range wetted with the solution is measured.
- the aerosol solution flowed down without drying, the silicone grease was dissolved and thoroughly washed away, and the silicone grease remained, ⁇ . ⁇ , the aerosol solution stays in place, and the silicone solution is dissolved by the aerosol solution, but the aerosol solution dries halfway and the silicone grease remains on the test plate, ⁇ , the aerosol solution
- the case where the silicone grease did not dissolve sufficiently to evaporate on the test plate and remained remained was marked with x. , It was evaluated.
- the one using 0.2 MPa or more of CO 2 as the injection gas was in a mist-like injection state with an injection distance of up to 2 m, and the oil applied on the test plate was injected for 10 seconds. It remained in a state that was almost washed away.
- the spray gas is not gasified in an instant, and the spray state of the aerosol is rod-shaped.
- the spray distance can be greatly extended to 10 m.
- the oil component could be completely removed by 10 second injection.
- the aerosol injection state is rod-like and since there is no gas compatibility, it can be injected from a distance as long as 10 m by adjusting the pressure.
- N 2 has no concern for global warming unlike CO 2, and further superiority can be confirmed in that it can achieve incombustibility as a product.
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Abstract
Description
本発明の手段の洗浄剤組成物およびそのエアゾール組成物の主要成分について説明する。本発明の手段の洗浄剤組成物およびそのエアゾール組成物には、(Z)-1-クロロ-3,3,3-トリフルオロプロペンと、HFE系の不燃性フッ素系溶剤との2成分を含有させるものとする。
上述した本発明の手段の洗浄剤組成物およびそのエアゾール組成物には、必須となる2成分のうちの一方の成分として、(Z)-1-クロロ-3,3,3-トリフルオロプロペンを含有するものとする。(Z)-1-クロロ-3,3,3-トリフルオロプロペンは、ハイドロフルオロオレフィン系の溶剤として、1233Z(セントラル硝子株式会社,日本)などの名称で市販されているものを入手し利用することができる。
上述した本発明の手段の洗浄剤組成物およびそのエアゾール組成物は、必須となる2成分のうちの他方の成分として、HFE系の不燃性フッ素系溶剤を1つ以上含有するものとする。このHFE系のフッ素系溶剤は、引火点がなく、燃焼点(下限)並びに燃焼点(上限)が共に非検出の、不燃性である。消防法上の非危険物に該当し、危険物倉庫が不要で、保管量に法的な制限がない。
本発明の手段の洗浄剤組成物およびそのエアゾール組成物においては、自動車、二輪自動車、自転車、建機、農機、航空機、鉄道車両、船舶などの各種車両・乗物・輸送機関の洗浄や、作業者の使用した手袋、作業着、工具、作業場の洗浄に用いることを考慮すると、溶剤がそもそも不燃性であるという特性に加え、さらに、樹脂やエラストマーに対する侵襲性をより低くし、油脂類などへの相溶性をより高め、かつ、金属、樹脂及びエラストマーなどの様々な素材からなる部材に対するより優れた洗浄性と、適度な乾燥速度をもたらすものとなるよう、含有される二成分である(Z)-1-クロロ-3,3,3-トリフルオロプロペンとHFE系の不燃性フッ素系溶剤との質量比の範囲を調節することが好ましい。そして、樹脂やエラストマーに対するより低い侵襲性、より高い油脂類などへの相溶性、金属、樹脂及びエラストマーなどの様々な素材からなる部材に対する優れた洗浄性と適度な乾燥速度を有するといった優れた特性を複数あわせ持つようにするため、本発明の手段の洗浄剤組成物およびそのエアゾール組成物において含有される二成分である(Z)-1-クロロ-3,3,3-トリフルオロプロペンとHFE系の不燃性フッ素系溶剤との質量比の範囲は、50/50~99/1とすることが好ましい。
本発明の手段の洗浄剤組成物及びそのエアゾール組成物は、上述した洗浄剤組成物としての主要な2成分に加えて、さらに必要に応じて、追加成分を引火の危険性や火災時のリスクを高めない程度において配合したものとしてもよい。上記追加成分を配合する場合には、洗浄剤組成物としての不燃性または消防法における非危険物としての特性を保持しながらも、主要な2成分により達成される、(Z)-1-クロロ-3,3,3-トリフルオロプロペンそのものが保持する樹脂やエラストマーに対する侵襲性を低減し、かつ、油脂成分に対する洗浄性と適度な乾燥速度を保持するという特性を保持できる範囲内において配合する。この追加成分としては、アルコール類、飽和炭化水素、不飽和炭化水素、芳香族炭化水素、安定剤、キレート剤などを用いることができ、例えば、3MTM NOVECTM7200、3MTM NOVECTM7300などのHFE系溶剤、メタノール、エタノール、イソプロピルアルコール、ブタノールなどのアルコール類、ノルマルヘキサン、シクロヘキサン、イソヘキサンなどの炭化水素系溶剤、アセトン、MEK、シクロヘキサノンなどのケトン系溶剤、酢酸エチル、酢酸メチル、酢酸ブチル、エチレングリコールモノメチル エーテルアセテートなどのエステルおよびグリコールエステル系溶剤、メチルセロソルブ、ブチルセロソルブ、メトキシメチルブタノール、ヘキシルジグリコールなどのエーテル及びグリコールエーテル系溶剤、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテルなどのグライム系溶剤、HCFC-141b、HCFC-225、1-ブロモプロパン、クロロホルムなどの塩素系溶剤、N-メチル-2-ピロリドン、テトラヒドロフラン、ジメチルホルムアミドなどの特殊溶剤、γ-ブチロラクトン、1,3-ジオキソラン、ジメチルスルホキシドなどのその他の溶剤を配合したものを用いることができる。
エアゾール組成物における噴射ガスとしては、液化ガスや圧縮ガスを使用することができる。例えば、LPG(液化石油ガス)、DME(ジメチルエーテル)、炭酸ガス、フロン系ガス、窒素ガス、圧縮空気などのガスやLPGとDMEの混合物、LPGと炭酸ガスとの混合物などといった上記のガスを二種以上組み合わせたものをあげることが出来る。そして、本発明の手段の洗浄剤組成物と上記の噴射ガスを混合してエアゾール組成物とし、耐圧缶に充填して提供することが出来る。
本発明の手段の洗浄剤組成物の溶液は、洗浄対象となる自動車、二輪自動車、自転車、建機、農機、航空機、鉄道車両、船舶などの各種車両・乗物・輸送機関の金属、樹脂及びエラストマーなどの様々な素材からなる部材や、作業者の使用した手袋、作業着、工具、作業場に塗布して用いたり、それらの洗浄対象を洗浄剤組成物の溶液に浸漬させて用いることができる。また、本発明の手段の洗浄剤組成物を噴射ガスとなる液化ガスと混合したエアゾール組成物を耐圧缶に充填してエアゾール化させ、または、本発明の手段の洗浄剤組成物をペール缶に入れ、使用する作業場に移動式小型充填機を設置し、圧縮空気によりペール缶に入れた洗浄剤組成物をエアゾール化させ、洗浄対象となる金属や樹脂及びエラストマーなどの様々な素材からなる部材に、エアゾールとして吹き付けて用いることができる。
試験用サンプルを調製するため、本発明の洗浄剤組成物に用いる成分と、従来の洗浄剤とを、購入する。
本発明の洗浄剤組成物に用いる成分である(Z)-1-クロロ-3,3,3-トリフルオロプロペンとしては、1233Z(セントラル硝子株式会社,日本)を、HFE系の不燃性フッ素系溶剤の1,1,2,2-テトラフルオロ-1-(2,2,2-トリフルオロエトキシ)エタンとしては、アサヒクリン AE-3000(旭硝子株式会社,日本)を、HFE系の不燃性フッ素系溶剤のC3F7OCH3としては、3MTM NOVECTM7000 高機能性液体(スリーエム ジャパン株式会社,日本)を、HFE系の不燃性フッ素系溶剤のC4F9OCH3としては、3MTM NOVECTM7100 高機能性液体(スリーエム ジャパン株式会社,日本)をそれぞれ購入した。
また、従来の洗浄剤として、速乾原液としては、イソヘキサンを用いる、ブレーキ&パーツクリーナー(速乾タイプ)(神戸合成株式会社,日本)を使用し、さらに、脱脂洗浄剤としては、シクロヘキサンを用いる、脱脂洗浄剤(株式会社ホンダアクセス,日本)を、常乾原液としては、イソパラフィン系溶剤の、ブレーキクリーナーN04(スズキ株式会社,日本)を、また、トリクロロエタンを、それぞれ購入した。
・質量比(1233Z/AE-3000)
実施例1: 30/70
実施例2: 50/50
実施例3: 70/30
実施例4: 80/20
実施例5: 85/15
実施例6: 90/10
実施例20: 99/1
・質量比(1233Z/NOVEC7000)
実施例7: 30/70
実施例8: 50/50
実施例9: 70/30
実施例10: 80/20
実施例11: 90/10
実施例12: 95/5
・質量比(1233Z/NOVEC7100)
実施例13: 30/70
実施例14: 50/50
実施例15: 70/30
実施例16: 80/20
実施例17: 85/15
実施例18: 90/10
実施例19: 99/1
比較例1: 速乾原液
比較例2: 脱脂洗浄剤
比較例3: 常乾原液
比較例4: トリクロロエタン
比較例5: 1233Zのみ
比較例6: AE-3000のみ
比較例7: NOVEC7000のみ
比較例8: NOVEC7100のみ
・材料および方法
試験溶液として、実施例1~18ならびに比較例1~8の溶液を用意する。
グリス:GREASE(オレンジ)(神戸合成株式会社,日本)
:ラバー兼用ブレーキグリス(神戸合成株式会社,日本)
:ディスクブレーキ用グリス(神戸合成株式会社,日本)
:ブレーキグリス(神戸合成株式会社,日本)
:シリコングリス(神戸合成株式会社,日本)
:キャリパーピングリス(株式会社ホンダアクセス,日本)
:パッド&シューグリス(株式会社ホンダアクセス,日本)
:ラバーグリス(株式会社ホンダアクセス,日本)
:ブレーキグリス(株式会社ホンダアクセス,日本)
オイル:エンジンオイル Mobil1 0W-20(エクソンモービル,米国)
:ブレーキフルード(DOT3)(株式会社ホンダアクセス,日本)
:ブレーキフルード(DOT4)(スズキ株式会社,日本)
1時間の超音波処理後に、超音波洗浄機から各バイアル瓶を取り出す。バイアル瓶の内部を確認し、グリスまたはエンジンオイルと、実施例1~18または比較例1~8の溶液とが、完全に混ざっていれば○、一部分離していれば△、完全に分離していれば×として、相溶性を評価する。
上記試験を実施した結果を表1-1~表1-4に示す。
・材料および方法
試験例1と同様に、上述した実施例1~18ならびに比較例1~8の溶液をそれぞれ用意する。
上記試験を実施した結果を表2-1~表2-4に示す。
・材料および方法
試験例1と同様に、上述した実施例1~18ならびに比較例1~8の溶液をそれぞれ用意する。また、侵襲性を評価するため、次に示すテストピースを用意する。
ゴム:NR(天然ゴム)
:CR(クロロプレンゴム)
:SBR(スチレン・ブタジエンゴム)
:EPDM(エチレンプロピレンゴム)
(いずれも、株式会社スタンダードテストピース,日本より入手。)
樹脂:ABS(アクリロニトリルブタジエンスチレン)
:LDPE(低密度ポリエチレン)
:PC(ポリカーボネート)
(いずれも、日本テストパネル株式会社)
次に、バイアル瓶に、実施例1~18ならびに比較例1~8の溶液を20mLを入れ、その中に、上記のゴムまたは樹脂の各テストピース(サイズ10mmx10mmx2mm)を浸漬させ、そのバイアル瓶を、45℃に設定した恒温恒湿機(HPAV-120-40,株式会社いすゞ製作所,日本)に入れ、1ヶ月間静置する。
1ヶ月後、バイアル瓶から各テストピースを取り出し、表面状態を観察した後、テストピースの重量および厚みを測定し、膨潤度を算出し、±5.0%の範囲内に収まるか否か確認するとともに、PCの透明度が失われないかについても確認する。
上記試験を実施した結果を表3-1~表3-4に示す。
・材料および方法
試験例1と同様に、上述した実施例1~18ならびに比較例1~8の溶液をそれぞれ用意する。また、短期間の侵襲性を評価するため、次に示すテストピースを用意する。
樹脂:ABS(アクリロニトリルブタジエンスチレン)
:PC(ポリカーボネート)
(いずれも、日本テストパネル株式会社)
上記試験を実施した結果を表4-1~表4-4に示す。
・材料および方法
スズキ株式会社で販売される自動車(型式MH23S)または本田技研工業株式会社で販売される自動車(型式GE6)のリアブレーキホースセットを入手し、ブレーキホースを試験サンプルとする。試験前にブレーキホースの厚みを測定する。
瓶に上記ブレーキホースを入れ、さらに実施例3、比較例1、比較例2または比較例3の溶液をブレーキホースが浸かるように入れる。その後、瓶を、40℃に設定した恒温恒湿機(HPAV-120-40,株式会社いすゞ製作所,日本)に入れ、72時間静置する。
72時間後、瓶から各ブレーキホースを取り出し、溶液を布で拭き取り表面状態を観察した後、ブレーキホースの重量および厚みを測定し、膨潤率(%)を算出する。
自動車(型式MH23S)のブレーキホースにおけるの72時間後の膨潤率は、実施例3,比較例1,比較例2,比較例3でそれぞれ、-4.8%,-4.0%、-3.7%、-3.5%であった。また、自動車(型式GE6)のブレーキホースにおけるの72時間後の膨潤率は、実施例3,比較例1,比較例2,比較例3でそれぞれ、-3.1%,-2.3%,-4.0%,-1.8%であった。ゴムの劣化によるひび割れや裂けなどの外観の異常は観察されなかった。
さらに、フロントホイールブレーキ、リアホイールブレーキ、キャリパー、シリンダーなどのブレーキ装置には、ゴムの他、各種の樹脂が使用されるが、試験例3で確認したように、本願発明の手段の洗浄剤組成物はそれら樹脂に低侵襲性であることから、洗浄による異常を生じさせる危険性が従来の洗浄剤より低い。
このように、本願発明の手段の洗浄剤組成物は、従来の洗浄剤に比して、ブレーキ装置やその周辺の洗浄により適した特性を有するものであることが理解される。
・材料および方法
試験例1と同様に、上述した実施例3および実施例15の溶液を用意する。エアゾール組成物における噴射ガスとしてLPG(液化石油ガス)を用い、実施例3または実施例15の溶液とLPGとを混合してエアゾール組成物とし、それぞれ耐圧缶に充填する。
上記試験を実施した結果を表5-1に示す。
・材料および方法
試験例6と同様にして、実施例3、実施例15、比較例1、比較例3ならびに比較例4の洗浄剤組成物を用いて調製されたエアゾール組成物をそれぞれ用意する。試験板を立て掛け、シリコーングリス1gを35mmx50mm幅に塗り広げる。グリスを塗り広げて汚染した部位の一部に、エアゾール組成物を噴霧し、エアゾールの圧力だけで洗浄する。
シリコーングリスの付着していないブランクとなる部位と、シリコーングリスが付着した部位、シリコーングリスがエアゾールの圧力だけで洗浄された部位、シリコーングリスがエアゾール組成物とともに流れ落ちた部位における接触角をそれぞれ測定する。グリスが残存していると、グリスが有する疎水性の性質により、接触角が上がる。
実施例3または実施例15の洗浄剤組成物を用いて調製されたエアゾール組成物を吹き付けた場合には、シリコーングリスを、実施例3または実施例15の洗浄剤組成物が有する油脂類への相溶性とエアゾールの吹きつけ圧力だけで、ほぼ完全に除去していた。吹き付けた箇所ならび液が垂れた箇所は、数十秒以内で乾燥した状態となった。本発明の手段の(Z)-1-クロロ-3,3,3-トリフルオロプロペンとHFE系の不燃性フッ素系溶剤とを含有させてなる不燃性の洗浄剤組成物をエアゾール組成物として提供することで、安全に、かつ、極めて速やかに付着した油脂類を洗浄できることが理解できる。
・材料および方法
試験例1と同様に、上述した実施例15の溶液を用意する。エアゾール組成物における噴射ガスとして、LPG(液化石油ガス)のほか、1234ZE((E)-1,3,3,3-テトラフルオロプロパ-1-エン/トランス-1,3,3,3-テトラフルオロプロペン、HFO-1234Zze-(E)))、0.2MPa以上としたCO2を用い、上記溶液と混合してエアゾール組成物とし、それぞれ耐圧缶に充填する。1234ZEは、国連勧告、また日本以外の米国、欧州、その他アジア諸国の燃焼性区分では「不燃性ガス」に分類されている。なお、測定方法の違いにより日本の高圧ガス保安法下では可燃性ガスに分類される。
そこで、洗浄性を高めるべく、CO2の内圧をより高めた場合を検討した。さらに、噴射ガスとして地球温暖化に影響を及ぼさないN2を用いた場合についても検討した。
試験例1と同様にして、上述した実施例15の溶液を用意する。エアゾール組成物における噴射ガスとして、0.2MPa以上としたCO2、0.2MPa以下としたCO2、0.2MPa以上としたN2、を用い、上記溶液と混合してエアゾール組成物とし、それぞれ耐圧缶に充填する。
Claims (9)
- (Z)-1-クロロ-3,3,3-トリフルオロプロペンとHFE系の不燃性フッ素系溶剤とを含有してなり、質量比((Z)-1-クロロ-3,3,3-トリフルオロプロペン/HFE系の不燃性フッ素系溶剤)の範囲が30/70~99/1であることを特徴とする、自動車、二輪自動車、自転車、建機、農機、航空機、鉄道車両、船舶などの各種車両・乗物・輸送機関の洗浄用洗浄剤組成物。
- 上記HFE系の不燃性フッ素系溶剤が、C4F9OCH3、C3F7OCH3、または1,1,2,2-テトラフルオロ-1-(2,2,2-トリフルオロエトキシ)エタンから選択される1つまたはそれ以上であることを特徴とする、請求項1に記載の洗浄剤組成物。
- (Z)-1-クロロ-3,3,3-トリフルオロプロペンとC4F9OCH3とを含有してなり、その質量比((Z)-1-クロロ-3,3,3-トリフルオロプロペン/C4F9OCH3)が50/50~99/1であることを特徴とする、請求項1に記載の洗浄剤組成物。
- (Z)-1-クロロ-3,3,3-トリフルオロプロペンとC3F7OCH3とを含有してなり、その質量比((Z)-1-クロロ-3,3,3-トリフルオロプロペン/C3F7OCH3)が80/20~99/1であることを特徴とする、請求項1に記載の洗浄剤組成物。
- (Z)-1-クロロ-3,3,3-トリフルオロプロペンと1,1,2,2-テトラフルオロ-1-(2,2,2-トリフルオロエトキシ)エタンとを含有してなり、その質量比((Z)-1-クロロ-3,3,3-トリフルオロプロペン/1,1,2,2-テトラフルオロ-1-(2,2,2-トリフルオロエトキシ)エタン)が50/50~99/1であることを特徴とする、請求項1に記載の洗浄剤組成物。
- 上記洗浄剤組成物が、自動車、二輪自動車、自転車、建機、農機、航空機、鉄道車両、船舶などの各種車両・乗物・輸送機関のブレーキクリーナー用であることを特徴とする、請求項1~請求項5のいずれか1項に記載の洗浄剤組成物。
- 請求項1~請求項5のいずれか1項に記載の洗浄剤組成物と噴射ガスとを含有する自動車、二輪自動車、自転車、建機、農機、航空機、鉄道車両、船舶などの各種車両・乗物・輸送機関の洗浄用エアゾール組成物。
- 上記噴射ガスが、N2、CO2、(E)-1,3,3,3-テトラフルオロプロパ-1-エン、LPGまたは圧縮空気であることを特徴とする、請求項7に記載のエアゾール組成物。
- 上記噴射ガスが、N2であることを特徴とする、請求項8に記載のエアゾール組成物。
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