# Patent

## Title
Azeotropic and azeotrope-like compositions of methyl perfluoroheptene ethers and trans-1,2-dichloroethylene and uses thereof

## Abstract

The present disclosure provides azeotropic and azeotrope-like compositions comprised of methylperfluoroheptene ethers and trans-1,2-dichloroethylene. The present disclosure also provides for methods of use for the azeotropic and azeotrope-like compositions.

## Background
BACKGROUND INFORMATION
1. Field of the Disclosure
The present disclosure is in the field of methyl perfluoroheptene ether compositions. These compositions are azeotropic or azeotrope-like and are useful in cleaning applications as a defluxing agent and for removing oils or residues from a surface.
2. Description of the Related Art
Flux residues are always present on microelectronics components assembled using rosin flux. As modern electronic circuit boards evolve toward increased circuit and component densities, thorough board cleaning after soldering becomes a critical processing step. After soldering, the flux-residues are often removed with an organic solvent. De-fluxing solvents should be non-flammable, have low toxicity and have high solvency power, so that the flux and flux-residues can be removed without damaging the substrate being cleaned. For proper operation in use, microelectronic components must be cleaned of flux residues, oils and greases, and particulates that may contaminate the surfaces after completion of manufacture.
In cleaning apparatuses, including vapor degreasing and vapor defluxing equipment, compositions may be lost during operation through leaks in shaft seals, hose connections, soldered joints and broken lines. In addition, the working composition may be released to the atmosphere during maintenance procedures on equipment. If the composition is not a pure component, the composition may change when leaked or discharged to the atmosphere from the equipment, which may cause the composition remaining in the equipment to exhibit unacceptable performance. Accordingly, it is desirable to use a composition comprising a single unsaturated fluorinated ether as a cleaning composition.
Alternative, non-ozone depleting solvents have become available since the elimination of nearly all previous chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) as a result of the Montreal Protocol. While boiling point, flammability and solvent power characteristics can often be adjusted by preparing solvent mixtures, these mixtures are often unsatisfactory because they fractionate to an undesirable degree during use. Such solvent mixtures also fractionate during solvent distillation, which makes it virtually impossible to recover a solvent mixture of the original composition.
Many industries use aqueous compositions for the surface treatment of metals, ceramics, glasses, and plastics. Cleaning, plating, and deposition of coatings are often carried out in aqueous media and are usually followed by a step in which residual water is removed. Hot air drying, centrifugal drying, and solvent-based water displacement are methods used to remove such residual water.
While hydrofluorocarbons (HFCs) have been proposed as replacements for the previously used CFC solvents in drying or dewatering applications, many HFCs have limited solvency for water. The use of surfactant, which assists in removal of water from substrates, is therefore necessary in many drying or dewatering methods. Hydrophobic surfactants have been added to dewatering or drying solvents to displace water from substrates.
The primary function of the dewatering or drying solvent (unsaturated fluorinated ether solvent) in a dewatering or drying composition is to reduce the amount of water on the surface of a substrate being dried. The primary function of the surfactant is to displace any remaining water from the surface of the substrate. When the unsaturated fluorinated ether solvent and surfactant are combined, a highly effective displacement drying composition is attained.
Azeotropic solvent mixtures may possess the properties needed for de-fluxing, de-greasing applications and other cleaning agent needs. Azeotropic mixtures exhibit either a maximum or a minimum boiling point and do not fractionate on boiling. The inherent invariance of composition under boiling conditions insures that the ratios of the individual components of the mixture will not change during use and that solvency properties will remain constant as well.
The present disclosure provides azeotropic and azeotrope-like compositions useful in semiconductor chip and circuit board cleaning, defluxing, and degreasing processes. The present compositions are non-flammable, and as they do not fractionate, will not produce flammable compositions during use. Additionally, the used azeotropic solvent mixtures may be re-distilled and re-used without composition change.
SUMMARY
The present disclosure provides an azeotrope-like composition comprising methylperfluoroheptene ethers (“MPHE”) and trans-1,2-dichloroethylene. The present disclosure further provides a method for removing residue from a surface of an article comprising: (a) contacting the article with a composition comprising an azeotrope-like composition of MPHE and trans-1,2-dichloroethylene; and (b) recovering the surface from the composition.


DETAILED DESCRIPTION
As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
Also, use of “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present disclosure, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a particular passage is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
Many aspects and embodiments have been described above and are merely exemplary and not limiting. After reading this specification, skilled artisans appreciate that other aspects and embodiments are possible without departing from the scope of the invention.
Described herein are azeotropic and azeotrope-like compositions of MPHE and trans-1,2-dichloroethylene. MPHE is described in pending U.S. patent application Ser. No. 12/701,802, the disclosure of which is herein incorporated by reference. Also described herein are novel methods of using an azeotropic or azeotrope-like composition comprising MPHE and trans-1,2-dichloroethylene.
As used herein, an azeotropic composition is a constant boiling liquid admixture of two or more substances wherein the admixture distills without substantial composition change and behaves as a constant boiling composition. Constant boiling compositions, which are characterized as azeotropic, exhibit either a maximum or a minimum boiling point, as compared with that of the non-azeotropic mixtures of the same substances. Azeotropic compositions include homogeneous azeotropes which are liquid admixtures of two or more substances that behave as a single substance, in that the vapor, produced by partial evaporation or distillation of the liquid, has the same composition as the liquid. Azeotropic compositions, as used herein, also include heterogeneous azeotropes where the liquid phase splits into two or more liquid phases. In these embodiments, at the azeotropic point, the vapor phase is in equilibrium with two liquid phases and all three phases have different compositions. If the two equilibrium liquid phases of a heterogeneous azeotrope are combined and the composition of the overall liquid phase calculated, this would be identical to the composition of the vapor phase.
As used herein, the term “azeotrope-like composition” also sometimes referred to as “near azeotropic composition,” means a constant boiling, or substantially constant boiling liquid admixture of two or more substances that behaves as a single substance. One way to characterize an azeotrope-like composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the liquid from which it was evaporated or distilled. That is, the admixture distills or refluxes without substantial composition change. Alternatively, an azeotrope-like composition may be characterized as a composition having a boiling point temperature of less than the boiling point of each pure component.
Further, yet another way to characterize an azeotrope-like composition is that the bubble point pressure of the composition and the dew point vapor pressure of the composition at a particular temperature are substantially the same. Near-azeotropic compositions exhibit dew point pressure and bubble point pressure with virtually no pressure differential. Hence, the difference in the dew point pressure and bubble point pressure at a given temperature will be a small value. It may be stated that compositions with a difference in dew point pressure and bubble point pressure of less than or equal to 3 percent (based upon the bubble point pressure) may be considered to be a near-azeotropic.
A composition of one embodiment of the invention comprises MPHE and an effective amount of trans-1,2-dichloroethylene to form an azeotropic composition. An “effective amount” is defined as an amount which, when combined with MPHE, results in the formation of an azeotropic or near-azeotropic mixture. MPHE comprises isomeric mixtures of unsaturated fluoroethers which are the products of the reaction of perfluoroheptenes such as perfluoro-3-heptene with methanol in the presence of a strong base. In one embodiment, the mixture comprises a mixture of one or more of the following compounds:

    CF3CF2CF═CFCF(OR)CF2CF3, CF3CF2C(OR)═CFCF2CF2CF3, CF3CF═CFCF(OR)CF2CF2CF3, and CF3CF2CF═C(OR)CF2CF2CF3;

wherein R═CH3.



Compositions may be formed that comprise azeotrope-like compositions comprise from about 0.1 mole percent to about 9.7 mole percent MPHE, and trans-1,2-dichloroethylene. In another embodiment of the invention, the azeotrope-like compositions comprise from about 0.1 mole percent to about 9.7 mole percent MPHE, and trans-1,2-dichloroethylene, with the vapor pressure ranging from about 2.11 psia to about 207.8 psia, and the temperature ranging from about 0° C. to about 160° C. In yet another embodiment of the invention, azeotrope-like compositions comprise from about 0.1 mole percent to about 9.7 mole percent MPHE, and trans-1,2-dichloroethylene. The trans-1,2-dichloroethylene may comprise from about 90.3 mole percent to about 99.9 mole percent. The vapor pressure ranges from about 2.11 psia to about 207.8 psia. The temperature ranges from about 0° C. to about 160° C.
In one embodiment of the invention, the azeotrope like compositions consist essentially of from about 0.1 mole percent to about 9.7 mole percent MPHE, and trans-1,2-dichloroethylene. In another embodiment of the invention, the azeotrope-like compositions consist essentially of from about 0.1 mole percent to about 9.7 mole percent MPHE, and trans-1,2-dichloroethylene, with the vapor pressure ranging from about 2.11 psia to about 207.8 psia, and the temperature ranging from about 0° C. to about 160° C. In yet another embodiment of the invention, the azeotrope-like compositions comprise from about 0.1 mole percent to about 4.7 mole percent MPHE, and trans-1,2-dichloroethylene, with a vapor pressure of 1 atm, and a temperature of from 47.6 to 47.9° C.
In yet another embodiment, the azeotropic compositions comprise about 1.0 mole percent methyl perfluoroheptene ethers and trans-1,2-dichloroethylene having a vapor pressure of about 1 atm, at a temperature of about 46° C. In yet another embodiment, the azeotropic compositions consist essentially of about 1.0 mole percent methyl perfluoroheptene ethers and trans-1,2-dichloroethylene having a vapor pressure of about 1 atm, at a temperature of about 46° C.
In yet another embodiment, the azeotrope like compositions comprise from about 0.6 mole percent to about 8.7 mole percent methyl perfluoroheptene ether and trans-1,2-dichloroethylene, having a vapor pressure of about 1 atm, at a temperature of from about 48.3° C. to 48.5° C. In yet another embodiment, the azeotrope like compositions consist essentially of from about 0.6 mole percent to about 8.7 mole percent methyl perfluoroheptene ether and trans-1,2-dichloroethylene, having a vapor pressure of about 1 atm, at a temperature of from about 48.3° C. to about 48.5° C.
In one embodiment, the present compositions may further comprise a propellant. Aerosol propellant may assist in delivering the present composition from a storage container to a surface in the form of an aerosol. Aerosol propellant is optionally included in the present composition in up to about 25 weight percent of the total composition. Representative aerosol propellants comprise air, nitrogen, carbon dioxide, 2,3,3,3-tetrafluoropropene (HFO-1234yf), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,2,3,3,3-pentafluoropropene (HFO-1225ye), difluoromethane (CF2H2, HFC-32), trifluoromethane (CF3H, HFC-23), difluoroethane (CHF2CH3, HFC-152a), trifluoroethane (CH3CF3, HFC-143a; or CHF2CH2F, HFC-143), tetrafluoroethane (CF3CH2F, HFC-134a; or CF2HCF2H, HFC-134), pentafluoroethane (CF3CF2H, HFC-125), and hydrocarbons, such as propane, butanes, or pentanes, dimethyl ether, or combinations thereof.
In another embodiment, the present compositions may further comprise at least one surfactant. The surfactants of the present disclosure include all surfactants known in the art for dewatering or drying of substrates. Representative surfactants include alkyl phosphate amine salts (such as a 1:1 salt of 2-ethylhexyl amine and isooctyl phosphate); ethoxylated alcohols, mercaptans or alkylphenols; quaternary ammonium salts of alkyl phosphates (with fluoroalkyl groups on either the ammonium or phosphate groups); and mono- or di-alkyl phosphates of fluorinated amines. Additional fluorinated surfactant compounds are described in U.S. Pat. No. 5,908,822, incorporated herein by reference.
The amount of surfactant included in the dewatering compositions of the present invention can vary widely depending on the particular drying application in which the composition will be used, but is readily apparent to those skilled in the art. In one embodiment, the amount of surfactant dissolved in the unsaturated fluorinated ether solvent is not greater than about 1 weight percent, based on the total weight of the surfactant/solvent composition. In another embodiment, larger amounts of surfactant can be used, if after treatment with the composition, the substrate being dried is thereafter treated with solvent containing either no or minimal surfactant. In one embodiment, the amount of surfactant is at least about 50 parts per million (ppm, on a weight basis). In another embodiment, the amount of surfactant is from about 100 to about 5000 ppm. In yet another embodiment, the amount of surfactant used is from about 200 to about 2000 ppm based on the total weight of the dewatering composition.
Optionally, other additives may be included in the present compositions comprising solvents and surfactants for use in dewatering. Such additives include compounds having antistatic properties; the ability to dissipate static charge from non-conductive substrates such as glass and silica. Use of an antistatic additive in the dewatering compositions of the present invention may be necessary to prevent spots and stains when drying water or aqueous solutions from electrically non-conductive parts such as glass lenses and mirrors. Most unsaturated fluoroether solvents of the present invention also have utility as dielectric fluids, i.e., they are poor conductors of electric current and do not easily dissipate static charge.
Boiling and general circulation of dewatering compositions in conventional drying and cleaning equipment can create static charge, particularly in the latter stages of the drying process where most of the water has been removed from a substrate. Such static charge collects on non-conductive surfaces of the substrate and prevents the release of water from the surface. The residual water dries in place resulting in undesirable spots and stains on the substrate. Static charge remaining on substrates can bring out impurities from the cleaning process or can attract impurities such as lint from the air, which results in unacceptable cleaning performance.
In one embodiment, desirable antistatic additives are polar compounds, which are soluble in the present unsaturated fluorinated ether solvent and result in an increase in the conductivity of the unsaturated fluorinated ether solvent resulting in dissipation of static charge from a substrate. In another embodiment, the antistatic additives have a normal boiling point near that of the unsaturated fluorinated ether solvent and have minimal to no solubility in water. In yet another embodiment, the antistatic additives have a solubility in water of less than about 0.5 weight percent. In one embodiment, the solubility of antistatic agent is at least 0.5 weight percent in unsaturated fluorinated ether solvent. In one embodiment, the antistatic additive is nitromethane (CH3NO2).
In one embodiment, the dewatering composition containing an antistatic additive is effective in both the dewatering and drying and rinse steps of a method to dewater or dry a substrate as described below.
Another embodiment relates to a method for dewatering or drying a substrate comprising:

    
    
        a) contacting the substrate with a composition comprising a solvent, wherein the solvent comprises an azeotropic or azeotrope-like composition of MPHE and trans-1,2-dichloroethylene, containing surfactant, thereby dewatering the substrate; and
        b) recovering the dewatered substrate from the composition.
    
    


In one embodiment, the surfactant for dewatering and drying is soluble to at least 1 weight percent based on the total solvent/surfactant composition weight. In another embodiment, the dewatering or drying method of the present disclosure is very effective in displacing water from a broad range of substrates including metals, such as tungsten, copper, gold, beryllium, stainless steel, aluminum alloys, brass and the like; from glasses and ceramic surfaces, such as glass, sapphire, borosilicate glass, alumina, silica such as silicon wafers used in electronic circuits, fired alumina and the like; and from plastics such as polyolefin (“Alathon”, Rynite®, “Tenite”), polyvinylchloride, polystyrene (Styron), polytetrafluoroethylene (Teflon®), tetrafluoroethylene-ethylene copolymers (Tefzel®), polyvinylidenefluoride (“Kynar”), ionomers (Surlyn®), acrylonitrile-butadiene-styrene polymers (Kralac®), phenol-formaldehyde copolymers, cellulosic (“Ethocel”), epoxy resins, polyacetal (Delrin®), poly(p-phenylene oxide) (Noryl®), polyetherketone (“Ultrapek”), polyetheretherketone (“Victrex”), poly(butylene terephthalate) (“Valox”), polyarylate (Arylon®), liquid crystal polymer, polyimide (Vespel®), polyetherimides (“Ultem”), polyamideimides (“Torlon”), poly(p-phenylene sulfide) (“Rython”), polysulfone (“Udel”), and polyaryl sulfone (“Rydel”). In another embodiment, the compositions for use in the present dewatering or drying method are compatible with elastomers.
In one embodiment, the disclosure is directed to a process for removing at least a portion of water from the surface of a wetted substrate (dewatering), which comprises contacting the substrate with the aforementioned dewatering composition, and then removing the substrate from contact with the dewatering composition. In another embodiment, water originally bound to the surface of the substrate is displaced by solvent and/or surfactant and leaves with the dewatering composition. As used herein, the term “at least a portion of water” means at least about 75 weight percent of water at the surface of a substrate is removed per immersion cycle. As used herein, the term “immersion cycle” means one cycle involving at least a step wherein substrate is immersed in the present dewatering composition.
Optionally, minimal amounts of surfactant remaining adhered to the substrate can be further removed by contacting the substrate with surfactant-free halocarbon solvent. Holding the article in the solvent vapor or refluxing solvent will further decrease the presence of surfactant remaining on the substrate. Removal of solvent adhering to the surface of the substrate is effected by evaporation. Evaporation of solvent at atmospheric or subatmospheric pressures can be employed and temperatures above and below the boiling point of the halocarbon solvent can be used.
Methods of contacting the substrate with dewatering composition are not critical and can vary widely. For example, the substrate can be immersed in the composition, or the substrate can be sprayed with the composition using conventional equipment. Complete immersion of the substrate is preferred as it generally insures contact between the composition and all exposed surfaces of the substrate. However, any other method, which can easily provide such complete contact may be used.
The time period over which substrate and dewatering composition are contacted can vary widely. Usually, the contacting time is up to about 5 minutes, however, longer times may be used if desired. In one embodiment of the dewatering process, the contacting time is from about 1 second to about 5 minutes. In another embodiment, the contacting time of the dewatering process is from about 15 seconds to about 4 minutes.
Contacting temperatures can also vary widely depending on the boiling point of the composition. In general, the contacting temperature is equal to or less than the composition's normal boiling point.
In one embodiment, the compositions of the present disclosure may further contain a co-solvent. Such co-solvents are desirable where the present compositions are employed in cleaning conventional process residue from substrates, e.g., removing soldering fluxes and degreasing mechanical components comprising substrates of the present invention. Such co-solvents include alcohols (such as methanol, ethanol, isopropanol), ethers (such as diethyl ether, methyl tertiary-butyl ether), ketones (such as acetone), esters (such as ethyl acetate, methyl dodecanoate, isopropyl myristate and the dimethyl or diisobutyl esters of succinic, glutaric or adipic acids or mixtures thereof), ether alcohols (such as propylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and tripropylene glycol monomethyl ether), and hydrocarbons (such as pentane, cyclopentane, hexane, cyclohexane, heptane, octane), and hydrochlorocarbons (such as trans-1,2-dichloroethylene). When such a co-solvent is employed with the present composition for substrate dewatering or cleaning, it may be present in an amount of from about 1 weight percent to about 50 weight percent based on the weight of the overall composition.
Another embodiment of the disclosure relates to a method of cleaning a surface comprising:

    
    
        a. contacting the surface with a composition comprising a solvent, wherein the solvent comprises an azeotropic or azeotrope-like composition of MPHE and trans-1,2-dichloroethylene, and
        b. recovering the surface from the composition.
    
    


In one embodiment, the compositions of the invention are useful as cleaning compositions, cleaning agents, deposition solvents and as dewatering or drying solvents. In another embodiment, the invention relates to a process for removing residue from a surface or substrate comprising contacting the surface or substrate with a cleaning composition or cleaning agent of the present disclosure and, optionally, recovering the surface or substrate substantially free of residue from the cleaning composition or cleaning agent.
In yet another embodiment, the present disclosure relates to a method for cleaning surfaces by removing contaminants from the surface. The method for removing contaminants from a surface comprises contacting the surface having contaminants with a cleaning composition of the present invention to solubilize the contaminants and, optionally, recovering the surface from the cleaning composition. The surface is then substantially free of contaminants. As stated previously, the contaminants or residues that may be removed by the present method include, but are not limited to oils and greases, flux residues, and particulate contaminants.
In one embodiment of the present disclosure, the method of contacting may be accomplished by spraying, flushing, wiping with a substrate e.g., wiping cloth or paper, that has the cleaning composition incorporated in or on it. In another embodiment of the present disclosure, the method of contacting may be accomplished by dipping or immersing the article in a bath of the cleaning composition.
In one embodiment of the present disclosure, the process of recovering is accomplished by removing the surface that has been contacted from the cleaning composition bath. In another embodiment of the invention, the process of recovering is accomplished by allowing the cleaning composition that has been sprayed, flushed, or wiped on the disk to drain away. Additionally, any residual cleaning composition that may be left behind after the completion of the previous steps may be evaporated in a manner similar to that for the deposition method.
The method for cleaning a surface may be applied to the same types of surfaces as the method for deposition as described below. Semiconductor surfaces or magnetic media disks of silica, glass, metal or metal oxide, or carbon may have contaminants removed by the process of the invention. In the method described above, contaminant may be removed from a disk by contacting the disk with the cleaning composition and recovering the disk from the cleaning composition.
In yet another embodiment, the present method also provides methods of removing contaminants from a product, part, component, substrate, or any other article or portion thereof by contacting the article with a cleaning composition of the present disclosure. As referred to herein, the term “article” refers to all such products, parts, components, substrates, and the like and is further intended to refer to any surface or portion thereof.
As used herein, the term “contaminant” is intended to refer to any unwanted material or substance present on the article, even if such substance is placed on the article intentionally. For example, in the manufacture of semiconductor devices it is common to deposit a photoresist material onto a substrate to form a mask for the etching operation and to subsequently remove the photoresist material from the substrate. The term “contaminant,” as used herein, is intended to cover and encompass such a photo resist material. Hydrocarbon based oils and greases and dioctylphthalate are examples of the contaminants that may be found on the carbon coated disks.
In one embodiment, the method of the invention comprises contacting the article with a cleaning composition of the invention, in a vapor degreasing and solvent cleaning method. In one such embodiment, vapor degreasing and solvent cleaning methods consist of exposing an article, preferably at room temperature, to the vapors of a boiling cleaning composition. Vapors condensing on the object have the advantage of providing a relatively clean, distilled cleaning composition to wash away grease or other contamination. Such processes thus have an additional advantage in that final evaporation of the present cleaning composition from the object leaves behind relatively little residue as compared to the case where the object is simply washed in liquid cleaning composition.
In another embodiment, for applications in which the article includes contaminants that are difficult to remove, the method of the invention involves raising the temperature of the cleaning composition above ambient temperature or to any other temperature that is effective in such application to substantially improve the cleaning action of the cleaning composition. In one such embodiment, such processes are also generally used for large volume assembly line operations where the cleaning of the article, particularly metal parts and assemblies, must be done efficiently and quickly.
In one embodiment, the cleaning methods of the present disclosure comprise immersing the article to be cleaned in liquid cleaning composition at an elevated temperature. In another embodiment, the cleaning methods of the present disclosure comprise immersing the article to be cleaned in liquid cleaning composition at about the boiling point of the cleaning composition. In one such embodiment, this step removes a substantial amount of the target contaminant from the article. In yet another embodiment, this step removes a major portion of the target contaminant from the article. In one embodiment, this step is then followed by immersing the article in freshly distilled cleaning composition, which is at a temperature below the temperature of the liquid cleaning composition in the preceding immersion step. In one such embodiment, the freshly distilled cleaning composition is at about ambient or room temperature. In yet another embodiment, the method also includes the step of then contacting the article with relatively hot vapor of the cleaning composition by exposing the article to vapors rising from the hot/boiling cleaning composition associated with the first mentioned immersion step. In one such embodiment, this results in condensation of the cleaning composition vapor on the article. In certain preferred embodiments, the article may be sprayed with distilled cleaning composition before final rinsing.
It is contemplated that numerous varieties and types of vapor degreasing equipment are adaptable for use in connection with the present methods. One example of such equipment and its operation is disclosed by U.S. Pat. No. 3,085,918, which is incorporated herein by reference. The equipment disclosed therein includes a boiling sump for containing a cleaning composition, a clean sump for containing distilled cleaning composition, a water separator, and other ancillary equipment.
The present cleaning methods may also comprise cold cleaning in which the contaminated article is either immersed in the fluid cleaning composition of the present disclosure under ambient or room temperature conditions or wiped under such conditions with rags or similar objects soaked in the cleaning composition.
EXAMPLES
The concepts described herein will be further described in the following examples, which do not limit the scope of the invention described in the claims. Note that not all of the activities described above in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more further activities may be performed in addition to those described. Still further, the order in which activities are listed are not necessarily the order in which they are performed.
In the foregoing specification, the concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the invention as set forth in the claims below. Accordingly, the specification is to be regarded in an illustrative, rather than a restrictive sense, and all such modifications are intended to be included within the scope of invention.
Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.
It is to be appreciated that certain features are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. Further, reference to values stated in ranges include each and every value within that range.
Example 1
Dew Point and Bubble Point Pressures for Mixtures of MPHE and t-DCE
The dew point and bubble point pressures for compositions disclosed herein were calculated from measured and calculated thermodynamic properties. The near azeotrope range is indicated by the minimum and maximum concentration of MPHE (mole percent, mol %) for which the difference in dew point and bubble point pressures is less than or equal to 3%, based on the bubble point pressure. The results are summarized in Table 1.









TABLE 1








Near azeotrope




compositions,


Temperature,
mol % MPHE









° C.
Minimum
Maximum





 0
0.1
2.3


 20
0.1
3.2


47.6-47.9*
0.1
4.7


 60
0.1
5.2


100
0.1
6.9


140
0.1
8.6


160
0.1
9.7





*at 1 atm. Pressure.






Example 2
MPHE and Trans-1,2-dichloroethylene Azeotrope-Like Mixtures
An ebulliometer apparatus was used to determine the azeotrope-like range of the MPHE and trans-1,2-dichloroethylene mixtures. The apparatus consisted of a flask with thermocouple, heating mantle and condenser. A side neck on the flask was fitted with a rubber septum to allow the addition of one component into the flask. Initially the flask contained 100% trans-1,2-dichloroethylene, and the liquid was heated gradually until reflux and the boiling temperature was recorded to the nearest 0.1° C. Additions of MPHE were made into the flask through the side neck, at approximately 1 or 2 wt % increments. Each time an addition of MPHE was made, the flask boiling temperature was allowed to stabilize and then recorded. The MPHE was added to the trans-1,2-dichloroethylene mixture in the flask until a composition of approximately 50 wt % MPHE and 50 wt % trans-1,2-dichloroethylene was present. A similar experiment began with 100% MPHE in the flask and trans-1,2-dichloroethylene was then incrementally added to the flask, to again 50% MPHE and 50% trans-1,2-dichloroethylene. In this way, the boiling temperatures of MPHE and trans-1,2-dichloroethylene mixtures from 0 to 100% were obtained. The results are presented in Table 2.









TABLE 2





Mole % trans-1,2-
Mole %



dichloroethylene
MPHE
Temperature (° C.)

















100
0
48.9


99.4
0.6
48.5


98.7
1.3
48.3


98.1
1.9
48.3


97.5
2.5
48.3


96.9
3.1
48.4


96.3
3.7
48.6


95.7
4.3
48.4


95.2
4.8
48.4


94.6
5.4
48.4


94.0
6.0
48.5


93.5
6.5
48.7


92.9
7.1
48.6


92.4
7.6
48.8


91.8
8.2
48.9


91.3
8.7
48.8


90.8
9.2
48.9


90.3
9.7
48.9


89.7
10.3
49.0


89.2
10.8
49.0


88.7
11.3
49.1


88.2
11.8
49.0


87.7
12.3
49.1


87.3
12.7
49.2


86.8
13.2
49.4


86.3
13.7
49.2


85.8
14.2
49.4


85.4
14.6
49.4


84.9
15.1
49.4


84.4
15.6
49.4


84.0
16.0
49.6


83.6
16.4
49.6


83.1
16.9
49.5


82.7
17.3
49.6


82.2
17.8
49.5


81.8
18.2
49.7


81.4
18.6
49.8


81.0
19.0
49.8


80.6
19.4
49.8


80.1
19.9
49.8


79.7
20.3
49.8


79.3
20.7
50.0


79.3
20.7
49.7


79.0
21.0
49.9


78.9
21.1
50.0


78.7
21.3
49.8


78.6
21.4
50.1


78.4
21.6
49.9


78.2
21.8
50.1


78.0
22.0
49.9


77.7
22.3
50.0


77.3
22.7
50.0


77.0
23.0
50.0


76.6
23.4
50.1


76.2
23.8
50.1


75.8
24.2
50.3


75.4
24.6
50.3


74.9
25.1
50.3


74.5
25.5
50.3


74.0
26.0
50.5


73.5
26.5
50.4


73.0
27.0
50.5


72.5
27.5
50.5


71.9
28.1
50.7


71.3
28.7
50.8


70.7
29.3
50.8


70.1
29.9
50.8


69.5
30.5
51.1


68.8
31.2
51.1


68.1
31.9
51.3


67.3
32.7
51.3


66.6
33.4
51.7


65.7
34.3
51.6


64.9
35.1
51.8


64.0
36.0
52.1


63.0
37.0
52.3


62.1
37.9
52.5


61.0
39.0
52.8


59.9
40.1
53.1


58.7
41.3
53.7


57.5
42.5
54.0


56.1
43.9
54.3


54.7
45.3
54.8


53.2
46.8
55.3


51.6
48.4
55.6


49.9
50.1
56.7


48.0
52.0
57.6


46.0
54.0
58.5


43.9
56.1
59.2


41.6
58.4
61.2


39.0
61.0
62.9


36.3
63.7
64.9


33.2
66.8
67.2


29.9
70.1
71.0


26.2
73.8
76.2


22.1
77.9
81.6


17.6
82.4
88.2


12.4
87.6
92.5


6.6
93.4
105.7


0.0
100
111.1









Compositions which have a boiling temperature of less than the boiling point of each pure component were considered evidence of azeotrope-like behavior. For the MPHE and trans-1,2-dichloroethylene mixtures, this azeotrope-like range was found to be about 0.6 mole % MPHE to about 8.7 mole % MPHE.
Example 3
MPHE & 1,2-trans-dichloroethylene azeotrope
A mixture which contained 2.4 mole % MPHE and 97.6 mole % 1,2-trans-dichloroethylene (t-DCE) was prepared. The mixture was distilled in a 5-plate Oldershaw distillation column at 1 atmosphere pressure using a 10:1 reflux to take-off ratio. Head and flask temperatures were read directly to 1° C. Distillate samples were taken at 30 minute intervals throughout the distillation for determination of composition by gas chromatography. The results are shown in Table 3.












TABLE 3









Temperature

Distillate Composition












Distillation Cut
(° C.)

MPHE
t-DCE











(vol %)
Head
Flask
(mole %)
(mole %)





 0
46
47
2.4%
97.6%


10
46
47
1.0%
99.0%


20
46
47
0.8%
99.2%


30
46
47
0.9%
99.1%


40
46
47
1.0%
99.0%


50
46
47
1.0%
99.0%


60
46
48
1.1%
98.9%


80
46
48
1.7%
98.3%


Heel


7.7%
92.3%









Throughout the distillation, especially between the cuts at 10% and 60%, the distillation temperatures and compositions remained remarkably constant, which indicates the presence of an azeotrope. On average the composition of 1.0±0.1 mole % MPHE and 99.0±0.1 mole % 1,2-trans-dichloroethylene was observed.
Example 4
Use as a Cleaning Agent
Azeotropic compositions of fluorinated fluids and hydrochlorocarbons, such as 1,2-trans-dichloroethylene are often useful as cleaning agents. The hydrochlorocarbon has the ability to dissolve oils but may be flammable and therefore not desirable in some situations. 1,2-trans-dichloroethylene is flammable. The fluorinated fluid is often non-flammable but will not dissolve hydrocarbon oils. If mixtures of the two are determined to be non-flammable, they are especially useful.
An azeotropic composition of about 96.5 wt % 1,2-trans-dichloroethylene and 3.5% MPHE was prepared, and the closed cup flash point test was performed. The mixture was found to be not flammable.
The azeotropic mixture was used to remove oil from parts as described in the example below. The mixture was heated to boiling in a beaker. Pre-weighed aluminum coupons (size approximately 2′′×3′′) were coated with mineral oil using a swab. The coupons were reweighed, and submerged into the boiling solvent for 5 minutes. The coupons were removed from the solvent, allowed to air dry for 1 minute, and weighed a final time. The experiment was repeated using Dow Corning 200 silicone fluid (10,000 cSt) as the soil. The % of soil removed was calculated to demonstrate cleaning effectiveness. Table 4 shows that results of the experiment.







TABLE 4







% Soil Removed with MPHE and t-DCE azeotropic mixture












Clean
Contaminated
Coupon Wt.




Coupon
Coupon
after cleaning
% Soil


Coupon
wt.(g)
wt.(g)
(g)
removed














1-Mineral Oil
29.7392
29.7695
29.7392
100


2-Mineral Oil
30.9008
30.9408
30.9010
99.5


3-Mineral Oil
33.3787
33.4021
33.3788
99.6





Mean
99.7


1-Silicone
33.3794
33.4960
33.3795
100


Fluid


2-Silicone
30.9052
31.0526
30.9045
100


Fluid


3-Silicone
29.7416
29.8525
29.7416
100


Fluid





Mean
100









As shown above, the azeotropic mixture is very effective in removing the mineral oil and silicone fluid.

## Claims

1. An azeotropic or azeotrope-like composition comprising methylperfluoroheptene ethers and an effective amount of trans-1,2-dichloroethylene.

2. The azeotrope-like composition of claim 1, comprising from about 0.1 mole percent to about 9.7 mole percent methylperfluoroheptene ethers, and trans-1,2-dichloroethylene.

3. The azeotrope-like composition of claim 1, comprising from about 0.1 mole percent to about 9.7 mole percent methylperfluoroheptene ethers, and trans-1,2-dichloroethylene, having a vapor pressure of from about 2.11 psia to about 207.8 psia, at a temperature of from about 0° C. to about 160° C.

4. The azeotrope-like composition of claim 1 wherein said composition consists essentially of from about 0.1 mole percent to about 9.7 mole percent methylperfluoroheptene ethers, and trans-1,2-dichloroethylene, having a vapor pressure of from about 2.11 psia to about 207.8 psia, at a temperature of from about 0° C. to about 160° C.

5. The azeotrope-like composition of claim 1, comprising from about 0.1 mole percent to about 4.7 mole percent methylperfluoroheptene ethers, and trans-1,2-dichloroethylene, having a vapor pressure of from about 1 atm., at a temperature of from about 47.6° C. to about 47.9° C.

6. The azeotropic composition of claim 1, comprising about 1.0 mole percent methylperfluoroheptene ethers and trans-1,2-dichloroethylene, having a vapor pressure of about 1 atm, at a temperature of 46° C.

7. The azeotropic composition of claim 1, consisting essentially of about 1.0 mole percent methylperfluoroheptene ethers and trans-1,2-dichloroethylene, having a vapor pressure of about 1 atm, at a temperature of 46° C.

8. The azeotrope-like composition of claim 1, comprising from about 0.6 mole percent to about 8.7 mole percent methylperfluoroheptene ethers and trans-1,2-dichloroethylene, having a vapor pressure of about 1 atm., at a temperature of from about 48.3° C. to about 48.5° C.

9. The compositions of claim 1, consisting essentially of from about 0.6 mole percent to about 8.7 mole percent methylperfluoroheptene ethers and trans-1,2-dichloroethylene, having a vapor pressure of about 1 atm., at a temperature of from about 48.3° C. to about 48.5° C.

10. The composition of claim 1, having a dew point pressure and a bubble point pressure difference that is less than or equal to 3%, based upon the bubble point pressure.

11. A method for removing residue from a surface of an article comprising:
a. contacting said surface with a composition comprising an azeotropic or azeotrope-like composition of methylperfluoroheptene ethers and trans-1,2-dichloroethylene; and
b. recovering said surface from the composition.

12. The method of claim 11, wherein said composition further comprises a propellant.

13. The method of claim 12, wherein said propellant is comprised of air, nitrogen, carbon dioxide, 2,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, difluoromethane, trifluoromethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, hydrocarbons, or dimethyl ether, or combinations thereof.

14. The method of claim 11, wherein said composition further comprises at least one surfactant.

15. The method of claim 11, wherein said contacting is accomplished by vapor degreasing.

16. The method of claim 11, wherein said vapor degreasing is performed by:
a. boiling the composition; and
b. exposing the article to vapors of said composition.

17. The method of claim 11, wherein said contacting is accomplished by a first step of immersing the article in said composition, wherein the composition is at a temperature greater than ambient temperature or room temperature.

18. The method of claim 17, wherein the composition is at a temperature of about the boiling point of the composition.

19. The method of claim 17, further comprising a second step of immersing the article in said composition, wherein said composition is at a temperature lower than the temperature of the first immersing step.

20. The method of claim 19, wherein the composition in the second immersing step is at ambient temperature or room temperature.

21. The method of claim 19, further comprising the steps of boiling the composition and exposing the article to vapors of the boiling composition.

22. The method of claim 11, wherein the composition is at ambient temperature or room temperature.

23. The method of claim 11, wherein said contacting is accomplished by wiping the surface with an object saturated with the composition.