Azeotrope-like solvent blends exhibiting low global warming potential and methods of use

Abstract

Cleaning solvent blends containing HCFOs, such as 1-chloro-2,3,3-trifluoropropene and trans-dichloroethylene, and high-boiling HFEs, such as HFE-7300, have utility as non-flammable, low global warming potential, azeotrope-like cleaning solvent compositions. Additional solvent components may include surfactants and co-solvents. A method for cleaning soiling substances from an article includes contacting the article with the solvent composition by suitable means, such as a spray delivered by a propellant gas, as in a conventional vapor degreaser apparatus, or by contact with a liquid and / or vapor solvent composition, and removing the composition from the article.

Description

[Technical Field]

[0001] This application claims priority to U.S. Provisional Application No. 63 / 487,906, filed March 2, 2023, in the name of Trenessa Rioux and entitled "AZEOTROPE-LIKE SOLVENT BLENDS EXHIBITING LOW GLOBAL WARMING POTENTIAL AND METHODS OF USE."

[0002] The present invention relates to solvent-based cleaning compositions (sometimes referred to herein as "blends") of the type used in industrial processes for cleaning a variety of articles, including metals and plastics, in metalworking, electronics, and other industrial fields. These solvent-based cleaning compositions are non-flammable, azeotrope-like, composed of non-ozone-depleting, low global warming potential ingredients, and have high cleaning efficiency. The solvent blends of the present invention are also used as carrier fluids for lubricants and the like. [Background technology]

[0003] Solvent blends are used in industrial processes to clean a variety of soiling substances and residues (hereinafter sometimes referred to as "soils" or "soiling materials"). The electronics industry typically cleans fluxes, solder pastes, adhesives, and coatings from various devices before and after component assembly. The devices may contain a wide range of materials, including one or more metals, including metal, ceramic, and synthetic polymer (plastic) substrates and components. In metalworking processes, lubricants and foams, grinding media, and grease must be removed from metal surfaces. Many of these soils are very difficult to remove from metal surfaces, especially with non-aqueous cleaners.

[0004] Of particular interest are non-flammable blends of solvents that provide cleaning solvents that can be safely used in aerosol packages, or as wipes or in bulk cleaning tanks, e.g., vapor degreasing ("VDG") units. These cleaning solvents typically contain halogenated compounds that are non-flammable themselves or that can be rendered non-flammable in mixtures with other halogenated compounds. For example, it is known to use chlorinated hydrocarbons, such as flammable trans-dichloroethylene (TDCE), as a highly soluble component along with a fluorinated component to help render the cleaning solvent blend non-flammable. Furthermore, particularly for VDG applications, cleaning solvent blends should exhibit azeotropic or azeotrope-like behavior and be non-flammable, so that the vapors are also non-flammable. Therefore, it is highly desirable that the azeotrope not significantly fractionate after distillation, condensation, and recombination, as occurs in vapor degreasers. That is, in the boil sump, as well as in the rinse sump in VDG, or in the boil flask and receiver in the complete distillation process, the component ratios should be approximately the same, or at least not change dramatically.

[0005] The industry strives to maximize the cleaning power of its products, which is typically defined as the Kauri-Butanol Index ("KB value"). A high KB value indicates high cleaning power of a solvent component or solvent blend. To achieve a high KB value, the concentration of TDCE or other high KB value components in the blend is increased as much as possible. However, as the amount of high KB value components in a composition increases, it becomes more difficult to impart non-flammability to the solvent blend. A significant advance in this field was made by DuPont with the introduction of an azeotrope-like blend of 4% by weight methylperfluoroheptene (MPHE) ether, 0.8% by weight Vertrel XF, and 95.2% by weight TDCE, offered by Chemours as Opteon SF79. This is currently the highest concentration of TDCE in a commercially available product. This product has a KB value of 100. However, high concentrations of TDCE adversely affect flammability, making the Opteon SF79 solvent more flammable than desired.

[0006] In paragraph

[0010] of patent application publication US 2016 / 0326468 A1 published on November 10, 2016, Robin et al. disclose a composition comprising 0.1 to 0.8% by weight of methyl perfluoroheptene ether, 90 to 99% by weight of trans-1,2-dichloroethylene, and 0.6 to 2% by weight of a hydrofluorocarbon (HFC) selected from a very large group including heptafluorocyclopentane.

[0007] U.S. Patent 10,669,502, issued June 2, 2020, to D. Ikeda et al., describes a cleaning and carrier liquid composition containing 65 to 80% TDCE, 5 to 25% low-boiling point (40 to 60%) dimethyl ether (DMBE), and dimethyl ether (DMBE). o C) HFE and 5 to 25% by mass of a high boiling point (70 to 120 o C) Disclose the HFE.

[0008] U.S. Patent 10,828,579 to R. Singh et al., issued November 10, 2020, discloses aerosol compositions of trans- and cis-1-chloro-2,3,3-trifluoro-1-propene (HCFO 1233yd E&Z) along with a number of cosolvents.

[0009] U.S. Patent Publication 2022 / 0073804 to H. Mitsuoka, published March 10, 2022, discloses an azeotropic mixture of TDCE (34.5%) and HCFO1233ydZ (65.5%).

[0010] U.S. Provisional Patent Application Serial No. 63 / 351,969 (Attorney Specification MCC0125US) discloses an azeotropic solvent blend of 70 to 95.7% TDCE, 3.8 to 15% heptafluorocyclopentane, and 0.5 to 15% 1-chloro-2,3,3-trifluoro-1-propene.

[0011] In addition to maximizing cleaning power and reducing flammability, the industry strives for cleaning products that have minimal environmental impact. Ideally, cleaning products should have zero ozone depletion potential and negligible global warming potential.

[0012] High ozone-depleting hydrochlorofluorocarbons have been replaced in the marketplace by non-ozone-depleting hydrofluorocarbons. Today, many hydrofluorocarbons are also being replaced due to their high global warming potential. For example, HFC-43-10mee, commonly known as Vertrel XF, has a global warming potential ("GWP") of 1640.

[0013] Global warming potential (GWP) was developed to allow comparison of the global warming impact of various gases. Specifically, it is a measure of the energy absorbed by one ton of a gas emitted over a given period of time compared to one ton of carbon dioxide (CO2) emitted. The higher the GWP, the more the gas will warm the earth over that period compared to CO2. A typical time period used for GWP is 100 years. GWP provides a common unit of measurement that allows analysts to add up emission estimates for different gases. Hydrofluoroethers (HFEs), hydrofluoroolefins (HFOs), and hydrochlorofluoroolefins (HCFOs) have low global warming potentials and are therefore preferred ingredients in cleaning products. [Prior art documents] [Patent documents]

[0014] [Patent Document 1] Patent Application Publication US 2016 / 0326468 A1 [Patent Document 2] U.S. Patent 10,669,502 [Patent Document 3] U.S. Patent 10,828,579 [Patent Document 4] U.S. Patent Publication 2022 / 0073804 [Patent Document 5] U.S. Provisional Patent Application Serial No. 63 / 351,969 Summary of the Invention [Problem to be solved by the invention]

[0015] The present invention relates to low-flammability, low-global-warming-potential cleaning solvent compositions that exhibit azeotrope-like behavior. The azeotrope-like behavior allows for the efficient use of these solvent compositions (sometimes referred to herein as solvent blends or blends) in vapor degreasing processes. The cleaning solvent compositions of the present invention undergo substantially no or only limited fractionation upon distillation, which is important for the efficient and safe performance of cleaning processes and the safety of various solvent packages, such as bulk solvents, solvent aerosols, wipes, and pump sprays. The solvent compositions of the present invention are also useful in other applications, such as acting as carrier fluids for lubricants or other materials, e.g., lubricant applications in manufacturing processes. [Means for solving the problem]

[0016] The present invention provides a solvent blend comprising about 40 to about 90% by weight of trans-dichloroethylene, monochlorotrifluoropropene, a hydrofluoroether, and, optionally, a C1 to C3 alcohol. Either or both of a suitable surfactant and a suitable co-solvent may be added in amounts that do not significantly adversely affect the non-flammable, azeotrope-like, and effective cleaning capabilities of the solvent blend.

[0017] For example, one embodiment of the solvent blend of the present invention comprises 59 to 80% trans-dichloroethylene, 11 to 23% monochlorotrifluoropropene, such as one or more of those described in column 5, lines 1 to 17 of U.S. Patent 10,828,579, 5 to 20% high-boiling hydrofluoroether (HFE) described in claim 2 of U.S. Patent 10,669,502, and 0 to 5% C1 to C3 alcohol. In certain embodiments, the solvent blend of the present invention may contain other components, such as surfactants and cosolvents described below, as well as other components of a nature and amount that maintain the azeotrope-like properties, low global warming potential, and cleaning efficacy properties of the solvent blend. Alternatively, the solvent blend of the present invention may be limited to only the claimed components ("consisting of"), or to components in addition to the claimed components that do not affect the basic characteristics of the invention ("consisting essentially of")

[0018] Monochlorotrifluoropropenes include, for example, transCF3CH=CClH (1233zdE); cisCF3CH=CClH (1233zdZ); transCHF2CF=CClH (1233ydE); cisCHF2CF=CClH (1233ydZ); transCHF2CH=CClF (1233zbE); cisCHF2CH=CClF (1233zbZ); transCHF2CCl=CHF (1233xeE); cisCHF2CCl=CHF (1233xeZ); CH2FCCl=CF2 (1233x0); transCHFClCF=CFH (1233yeE); cisCHFClCF=CFH (1233yeZ); CH2ClCF=CF2 (1233yc); CF2ClCF=CH2 (1233xf), and two or more thereof.

[0019] For example, the hydrofluoroether may be selected from the group consisting of one or more of ethoxynonafluorobutane, 1,1,2,3,3,3-hexafluoropropyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3,3-pentafluoropropyl ether, 1,1-difluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl-2,2,3,3,3-pentafluoropropyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl-2,2,3,3-tetrafluoropropyl ether, and 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane, and two or more thereof.

[0020] Yet another aspect of the present application is a process for preparing a zeolite-based azeotrope-like polymer, the process comprising: about 71 to about 75% by weight trans-dichloroethylene (TDCE), about 15 to about 19% by weight 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 7 to about 10% by weight 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300); about 85 to about 95% by weight trans-dichloroethylene (TDCE), about 1 to about 5% by weight 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 1 to about 5% by weight 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300); about 90% by weight trans-dichloroethylene (TDCE), about 5% by weight 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 5% by weight 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300); about 59 to about 70% by weight trans-dichloroethylene (TDCE), about 10 to about 25% by weight 1-chloro-2,3,3-trifluoro-1-propene (AS300), about 11 to about 18% by weight 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300), and about 1 to about 5% by weight ethanol; about 63% by weight of trans-dichloroethylene (TDCE), about 20% by weight of 1-chloro-2,3,3-trifluoro-1-propene (AS300), about 15% by weight of 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300), and about 2% by weight of ethanol; about 40 to about 60% by weight trans-dichloroethylene (TDCE), about 15 to about 40% by weight 1,1,2,2-tetrafluoroethyl-2,2,2-triethyl ether (AE3000), and about 10 to about 25% by weight 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356); about 40 to about 60% by weight of trans-dichloroethylene (TDCE), about 11 to about 21% by weight of 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 20 to about 40% by weight of 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356); and about 53% by weight of trans-dichloroethylene (TDCE), about 11% by weight of 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 36% by weight of 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356); A solvent composition comprising:

[0021] A method aspect of the present invention provides a method for cleaning soiling materials from metal, ceramic, and synthetic polymer articles, comprising contacting one or more of the articles with a solvent composition that exhibits azeotrope-like properties as described herein, and removing the solvent composition from the articles.

[0022] The present invention overcomes or at least ameliorates the problems of prior art, such as U.S. Patent 10,669,502. This is achieved by substituting monochlorotrifluoropropene (HCFO) for the low-boiling hydrofluoroethers specified in U.S. Patent 10,669,502, thereby substantially increasing the KB value due to the inherently high KB value of HCFO while maintaining the concentration of TDCE. Furthermore, the excellent flame retardant properties of HCFO allow the optional incorporation of C1-C3 alcohols into the solvent blends of the present invention, thereby further improving the KB value of the blend without imparting flammability to the blend, while still allowing for a low mass percentage of TDCE. This is crucial for applications such as the removal of highly polar / ionic contaminants in so-called "no-clean" fluxes used in the electronics industry. Where compatibility with plastic substrates is required, a low TDCE content may be necessary, as high TDCE levels can affect compatibility with plastic substrates.

[0023] One embodiment of the cleaning solvent composition of the present invention comprises about 59 to about 70 wt. % trans-dichloroethylene (TDCE), about 10 to about 25 wt. % 1-chloro-2,3,3-trifluoro-1-propene (AS300), about 11 to about 18 wt. % 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300), and about 1 to about 5 wt. % ethanol. This blend has a KB value of 99.

[0024] A second embodiment of the cleaning solvent composition of the present invention comprises about 70 to about 80 weight percent trans-dichloroethylene (TDCE), about 11 to about 21 weight percent 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 5 to about 15 weight percent 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300). This blend has a KB value of 99.

[0025] A third embodiment of the cleaning solvent composition of the present invention comprises about 40 to about 60 weight percent trans-dichloroethylene (TDCE), about 11 to about 21 weight percent 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 20 to about 40 weight percent 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356). This blend has a KB value of 57.

[0026] A fourth embodiment of the cleaning solvent composition of the present invention comprises about 40 to about 60 weight percent trans-dichloroethylene (TDCE), about 15 to about 40 weight percent 1,1,2,2-tetrafluoroethyl-2,2,2-triethyl ether (AE3000), and about 10 to about 25 weight percent 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356). This blend has a KB value of 58.

[0027] A fifth embodiment of the cleaning solvent composition of the present invention comprises about 85 to about 95 weight percent trans-dichloroethylene (TDCE), about 1 to about 5 weight percent 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 1 to about 5 weight percent 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300). This blend has a KB value of 115.

[0028] In yet another embodiment of the cleaning solvent composition of the present invention, any one of the above embodiments is further supplemented with a surfactant at a concentration of about 0.1 to about 3 weight percent. Suitable surfactants include, but are not limited to, Rhodafac RS-710 (80-90% polyoxyethylene tridecyl ether phosphate [CAS#9046-01-9], 15-20% alcohol ethoxylate [CAS#78330-21-9], 1-5% phosphoric acid [CAS#7664-38-2], <1% water [CAS#7732-18-5]), Tergitol 15-S-3 (C12-14 secondary alcohol ethoxylate), and Steposol (N,N-dimethyl-9-decenamide [MET10U]).

[0029] Yet another embodiment of the cleaning solvent composition of the present invention is any one of the above cleaning solvent compositions of the present invention, further comprising the addition of a co-solvent in an amount of from about 1 to about 50% by weight of the other components of the solvent. This embodiment of the present invention is hereinafter referred to as the "high cosolvent blend." In this embodiment, the boil tank of the vapor degreasing unit is supplied with the high cosolvent blend, and no co-solvent is distilled into the rinse tank. Suitable co-solvents include, but are not limited to, Steposol (N,N-dimethyl-9-decenamide, [MET10U]), Rhodafac RS-710 (80-90% polyoxyethylene tridecyl ether phosphate [CAS#9046-01-9], 15-20% alcohol ethoxylate [CAS#78330-21-9], 1-5% phosphoric acid [CAS#7664-38-2], <1% water [CAS#7732-18-5]), benzyl alcohol, and hexylene glycol.

[0030] Unless specifically stated otherwise or apparent from the context, all percentages of a particular component, whether designated "wt %, " "mass %", "weight percent", or otherwise, are the weight percent of that component in the solvent blend, based on the total weight of the solvent blend.

[0031] As used herein, "azeotrope-like" behavior or properties, or terms of similar meaning, when used with respect to the cleaning solvent blends of the present invention, means that while the solvent blend may not exhibit perfect azeotropic properties (although some of the blends of the present invention may), the compositional change after repeated distillation steps is small or limited, i.e., less than 20% by weight of the amount of each component initially present in the blend, over a sustained distillation (evaporation and condensation) period of at least 5 hours. Generally, an "azeotrope-like composition" refers to a constant-boiling or substantially constant-boiling liquid mixture of two or more substances that behaves like or nearly behaves like a single substance under distillation. That is, the vapor produced by distillation of the liquid has at least approximately the same composition (within the aforementioned 20% by weight change) as the liquid from which it was distilled. In other words, no substantial compositional change occurs during the distillation of the mixture. Furthermore, an azeotrope-like composition is characterized as a composition having a boiling point temperature lower than the boiling points of each of the pure components of the composition.

[0032] As an example, see Example 5 below for the azeotrope-like behavior of one embodiment of the solvent blend of the present invention. The TDCE component was initially present in an amount of 75 wt.% of the blend, and even after the ninth stage of fractionation, when the remaining blend was only 24 wt.% of the starting amount, TDCE was present in an amount of 75.44 wt.%. The weight percent of TDCE removed by fractionation is calculated as follows: (75.44-75) / 75 x 100 = 0.58 weight percent, demonstrating the azeotrope-like behavior of this solvent blend.

[0033] The solvent compositions of the present invention may contain other ingredients, such as surfactants and the cosolvents described above, provided that the type and amount of these other ingredients do not significantly adversely affect the low global warming potential, azeotrope-like properties, or cleaning efficacy of the composition. That is, the solvent blends of the present invention may comprise, consist of, or consist essentially of the specified components. In some cases, the solvent blends may consist only of the specified components, excluding trace impurities found in the commercially available components used to prepare the solvent blends of the present invention. Propellant agents may also be used to deliver the solvent compositions of the present invention. These propellants evaporate and therefore do not affect the low global warming potential, azeotrope-like properties, or cleaning efficacy of the solvent compositions. [Brief explanation of the drawings]

[0034] [Figure 1] FIG. 1 is a schematic diagram of a benchtop simulation evaluation of a standard two-sump steam degreaser, including a dual-valve apparatus of the type used to develop the dual-bulb distillation data described below. [Figure 2] 1 is a graph showing the change in component concentrations of a particular solvent blend during double bulb or fractional distillation. [Figure 3] 1 is a graph showing the change in component concentrations of a particular solvent blend during double bulb or fractional distillation. [Figure 4] 1 is a graph showing the change in component concentrations of a particular solvent blend during double bulb or fractional distillation. [Figure 5] 1 is a graph showing the change in component concentrations of a particular solvent blend during double bulb or fractional distillation. [Figure 6] 1 is a graph showing the change in component concentrations of a particular solvent blend during double bulb or fractional distillation. [Figure 7] 1 is a graph showing the change in component concentrations of a particular solvent blend during double bulb or fractional distillation. [Figure 8]1 is a graph showing the change in component concentrations of a particular solvent blend during double bulb or fractional distillation. [Figure 9] 1 is a graph showing the change in component concentrations of a particular solvent blend during double bulb or fractional distillation. [Figure 10] 1 is a graph showing the change in component concentrations of a particular solvent blend during double bulb or fractional distillation. [Figure 11] 1 is a graph showing the change in component concentrations of a particular solvent blend during double bulb or fractional distillation. DETAILED DESCRIPTION OF THE INVENTION

[0035] The following abbreviations, trademarks, and trade names, whether used in singular or plural, have the following meanings:

[0036] "TDCE" or "Trans". Trans-Dichloroethylene. Chemical Substance Registry Number ("CAS#") 156-60-5.

[0037] "XF". Hydrofluorocarbon, 2,3-dihydrodecafluoropentane (HFC 43-10me) [trade name Vertrel XF]. CAS# 1384-95-42.

[0038] "AS300": A specific blend of cis and trans geometric isomers of 1-chloro-2,3,3-trifluoropropene, consisting of >89% (Z)-1-chloro-2,3,3-trifluoropropene and less than 10% (E)-1-chloro-2,3,3-trifluoropropene, supplied by AGC Chemicals Company under the trade name "Amolea AS300."

[0039] "SF33". Hydrofluoroolefin, (Z)-1,1,1,4,4,4-hexafluoro-2-butene; trade name Opteon SF33 from Chemours Corporation. CAS# 692-49-9.

[0040] "HFX-110". Methyl perfluoroheptene ether; trade name HFX-110. CAS# not disclosed (Proprietary).

[0041] "HFCs", such as 2,3-dihydrodecafluoropentane (HFC 43-10mee) and heptafluorocyclopentane.

[0042] "HFCP". 1,1,2,2,3,3,4-Heptafluorocyclopentane. Trade name: Zerora. CAS#15290-77-4.

[0043] "HFEs." Hydrofluoroethers such as 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane. CAS#132182-92-4 (HFE-7300).

[0044] "Vertrel® SFR" - A blend of 67% trans-dichloroethylene, 18% 2,3-dihydrodecafluoropentane (HFC 43-10mee), 12% heptafluorocyclopentane, and 3% methanol. This material has a boiling point of 106°F (41.1°C) and is available from Chemours, Wilmington, Delaware.

[0045] "Opteon SF79" - Nominally a blend of 95.2% trans-dichloroethylene, 4.0% methyl perfluoroheptene ether (HFX-110), and 0.8% 2,3-dihydrodecafluoropentane (HFC 43-10mee). This material has a boiling point of 121°F (49.4°C) and is available from Chemours Corporation, Wilmington, Delaware.

[0046] "Opteon SF80" - Nominally a blend of 95.2% trans-dichloroethylene, 4.0% methyl perfluoroheptene ether (HFX-110), and 0.8% (Z)-1,1,1,4,4,4-hexafluoro-2-butene (Opteon SF33). This material has a boiling point of 121°F (49.4°C) and is available from Chemours, Wilmington, Delaware.

[0047] "EtOH" - Ethyl alcohol.

[0048] "MeOH". Methyl alcohol.

[0049] 1 shows laboratory glassware 10 including a boil bulb 12 having a neck 12a that projects into a rinse valve 14. Neck 12a defines an opening 12b that is disposed within rinse valve 14. Condenser 16 is mounted to outlet end 14a of rinse valve 14 and includes a cooling coil 18 mounted within condenser 16. Cold water inlet 18a is connected to a cold water source (not shown), and cold water outlet 18b is connected to a drain (not shown). Boil valve 12 is mounted on a heating mantle 20.

[0050] In use, the solvent composition to be tested is introduced into boil valve 12 and heated to boil the solvent composition, generating vapor, as shown by arrow V1, which rises into rinse valve 14 and flows into condenser 16. The vapor condenses upon contact with cooling coil 18 and flows into rinse valve 14, as shown by arrow C1. When the condensate collected in rinse valve 14 reaches the level of opening 12b, the overflowing solvent flows back into boil valve 12, as shown by arrow C2. [Example]

[0051] Standard Test ProceduresTesting was performed in a standard two-tank vapor degreaser or benchtop simulation using a "double valve" apparatus of the type shown in Figure 1, with standard solvent up to the head, along with sampling ports (not shown in Figure 1) in the recovery flask and boiling flask. Samples from various locations and time points were analyzed by gas chromatography using an Agilent Corporation DB-200 capillary column (trifluoropropylmethyldimethylsiloxane stationary phase) and an FID detector. The following examples report the results of tests performed according to this standard test procedure.

[0052] [Table 1]

[0053] Although this solvent blend remains essentially azeotrope-like, it can be seen that the vapor composition changes rapidly and dramatically: the TDCE ratio between the boiling and rinsing tanks changed by more than 10% from its original value (67.7% to 78.2% by mass).

[0054] [Table 2]

[0055] This product blend also shows that there continues to be a significant change in the mass percentage of Vertrel XF in the blend between the "boiling" and "rinse" flasks. Most notably, Vertrel XF, which is present to improve the non-flammable properties of the blend, is substantially depleted from the boiling flask early in the distillation process.

[0056] [Table 3]

[0057] This product blend also shows a change in the ratio between the "boil" and "rinse" flasks. Most notably, the SF33 present in the boil vessel was substantially reduced to improve the non-flammable properties of the blend.

[0058] Example 4 Blend 25-68-2 One embodiment of the present invention was fractionated and the results are summarized in Table 1 below.

[0059] [Table 4]

[0060] Figure 2 presents the data in Table 1 graphically.

[0061] Example 4 shows that embodiments of the present invention maintain azeotrope-like properties for approximately 70% of the fraction before the concentration of the ethanol component changes by 20%, which is within the safe operating parameters of a vapor degreasing operation.

[0062] The composition of fraction 5 distillate 25-68-2 was rounded to the nearest integer value. 13% HFE-7300 67% TDCE 2% EtOH 20% AS300

[0063] ASTM D56 flash point testing of fractions 1 through 5 showed no detectable ignition. Similarly, double bulb distillation of solvent blend 25-68-2 also demonstrated azetrope-type behavior of this blend, as shown in Table 2 below. The blend composition changed only slightly up to turnover 6 ("turnover" refers to the number of rinse bath volumes distilled per rotation). Double bulb distillation closely replicated an efficient vapor degreasing operation.

[0064] [Table 5] [Table 6]

[0065] Figure 3 shows the data from Table 2 graphically.

[0066] Example 4 has a Kb value of 99, which indicates good solvation and therefore efficient cleaning action.

[0067] Example 5 Blend 25-74-1, an embodiment of the present invention, was fractionated as shown in Table 3. Fractions up to 76% of the distillation showed azeotrope-like properties of this solvent blend.

[0068] [Table 7]

[0069] Figure 4 presents the data in Table 3 graphically.

[0070] The results of the double valve fractional distillation of solvent blend 25-74-1 are shown in Table 4.

[0071] [Table 8]

[0072] Figure 5 graphically depicts the data from Table 4. Even after eight turnovers, the double valve data remained virtually unchanged (Kb of 99), supporting efficient vapor degreasing performance.

[0073] Examples 6 and 7 below are based on moderate TDCE content levels (less than 60% by weight TDCE). Moderate TDCE levels may be necessary when plastic substrate compatibility is required, i.e., when not degrading the plastic surface of the substrate.

[0074] Example 6 Solvent Blend 25-64-3 has the following initial amounts of components: HFE 356:36.0% by mass TDCE 52.8% by mass AS300 11.2% by mass

[0075] Fractional distillation of this blend gave the following results:

[0076] [Table 9]

[0077] At 80% of the fractionation, the variation in component ratios is less than 20%, clearly indicating an azeotrope-like blend.

[0078] Figure 6 presents the data from Table 5 graphically.

[0079] Double bulb distillation of solvent blend 25-64-3 showed only slight variations in component ratios over eight turnovers, demonstrating that this blend is an azeotrope-like solvent.

[0080] [Table 10]

[0081] Figure 7 shows the data from Table 6 in a graphical representation.

[0082] The solvent blend of Example 6 had a KB value of 57 and was tested for non-flammability.

[0083] Example 7 Fractional distillation of formula 25-61-1 There are two low boiling HFE solvent components in this formulation: HFE 356 and AE3000 (1,1,2,2-tetrafluoroethyl-2,2,2-triethyl ether), each with a boiling point of approximately 54°C.

[0084] [Table 11]

[0085] Figure 8 illustrates the data in Table 7.

[0086] Table 8 shows the results of double bulb distillation of blend 25-65-1.

[0087] [Table 12] [Table 13]

[0088] Blend 25-65-1 had a KB value of 58 and was tested for non-flammability.

[0089] Figure 9 shows the data from Table 8 in a graphical representation.

[0090] Example 8 Fractional distillation of 18-119-5

[0091] Table 9. Fractional Distillation of the Present Embodiments Consisting of Trans-Dichloroethylene (TDCE) and High-Boiling HFE and HFCO Blends

[0092] [Table 14]

[0093] Table 10 shows the double bulb distillation of blend 18-119-5.

[0094] [Table 15]

[0095] Figure 10 shows the data in Table 10 graphically.

[0096] Blend 18-119-5 is non-flammable and has a KB value of 115.

[0097] Table 11 shows the results of a series of tests of blend 25-68-2 in a steam degreaser over a four day period.

[0098] [Table 16]

[0099] Figure 11 shows the data from Table 11 graphically.

[0100] Although the present invention has been described in detail with reference to specific embodiments, these embodiments are illustrative and not limiting.

Claims

1. A solvent composition comprising about 40 to about 90% by weight of trans-dichloroethylene, monochlorotrifluoropropene, a hydrofluoroether, and, optionally, a C1 to C3 alcohol.

2. The monochlorotrifluoropropenes are selected from the group consisting of transCF3CH=CClH (1233zdE); cisCF3CH=CClH (1233zdZ); transCHF2CF=CClH (1233ydE); cisCHF2CF=CClH (1233ydZ); transCHF2CH=CClF (1233zbE); cisCHF2CH=CClF (1233zbZ); transCHF2CCl=CHF (1233xeE); cisCHF2CCl=CHF (1233xeZ); CH2FCCl=CF2 (1233xO); transCHFClCF=CFH (1233yeE); cisCHFClCF=CFH (1233yeZ); CH2ClCF=CF2 (1233yc); CF2ClCF=CH2 1233xf).

3. 2. The solvent composition of claim 1, wherein the hydrofluoroether is selected from the group consisting of one or more of ethoxynonafluorobutane, 1,1,2,3,3,3-hexafluoropropyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3,3-pentafluoropropyl ether, 1,1-difluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl-2,2,3,3,3-pentafluoropropyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl-2,2,3,3-tetrafluoropropyl ether, and 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane.

4. 3. The solvent composition of claim 2, wherein the hydrofluoroether is selected from the group consisting of one or more of ethoxynonafluorobutane, 1,1,2,3,3,3-hexafluoropropyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3,3-pentafluoropropyl ether, 1,1-difluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl-2,2,3,3,3-pentafluoropropyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl-2,2,3,3-tetrafluoropropyl ether, and 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane.

5. 2. The solvent composition of claim 1, comprising about 59 to about 70% by weight of trans-dichloroethylene (TDCE), about 10 to about 25% by weight of 1-chloro-2,3,3-trifluoro-1-propene (AS300), about 11 to about 18% by weight of 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300), and about 1 to about 5% by weight of ethanol.

6. 2. The solvent composition of claim 1, comprising about 70 to about 80% by weight of trans-dichloroethylene (TDCE), about 11 to about 21% by weight of 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 5 to about 15% by weight of 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300).

7. 2. The solvent composition of claim 1, comprising about 40 to about 60% by weight of trans-dichloroethylene (TDCE), about 11 to about 21% by weight of 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 20 to about 40% by weight of 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356).

8. 2. The solvent composition of claim 1, comprising about 40 to about 60% by weight of trans-dichloroethylene (TDCE), about 15 to about 40% by weight of 1,1,2,2-tetrafluoroethyl-2,2,2-triethyl ether (AE3000), and about 10 to about 25% by weight of 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356).

9. 4. The solvent composition of claim 3, further comprising a surfactant at a concentration of about 0.1 to about 3% by weight.

10. 4. The solvent composition of claim 3, further comprising any cosolvent for the other components of the solvent composition in an amount of from about 1 to about 50% by weight.

11. A solvent composition comprising about 71 to about 75 wt. % trans-dichloroethylene (TDCE), about 15 to about 19 wt. % 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 7 to about 10 wt. % 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300), wherein the solvent composition exhibits azeotrope-like properties.

12. 12. The composition of claim 11, comprising about 85 to about 95% by weight of trans-dichloroethylene (TDCE), about 1 to about 5% by weight of 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 1 to about 5% by weight of 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300).

13. 12. The composition of claim 11, comprising about 90% by weight of trans-dichloroethylene (TDCE), about 5% by weight of 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 5% by weight of 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300).

14. 12. The composition of claim 11, comprising about 59 to about 70% by weight of trans-dichloroethylene (TDCE), about 10 to about 25% by weight of 1-chloro-2,3,3-trifluoro-1-propene (AS300), about 11 to about 18% by weight of 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300), and about 1 to about 5% by weight of ethanol.

15. 12. The composition of claim 11, comprising about 63% by weight of trans-dichloroethylene (TDCE), about 20% by weight of 1-chloro-2,3,3-trifluoro-1-propene (AS300), about 15% by weight of 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFE-7300), and about 2% by weight of ethanol.

16. A solvent composition comprising about 40 to about 60 wt. % trans-dichloroethylene (TDCE), about 15 to about 40 wt. % 1,1,2,2-tetrafluoroethyl-2,2,2-triethyl ether (AE3000), and about 10 to about 25 wt. % 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356), and exhibiting azeotrope-like properties.

17. 17. The composition of claim 16, comprising about 40 to about 60% by weight of trans-dichloroethylene (TDCE), about 11 to about 21% by weight of 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 20 to about 40% by weight of 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356).

18. 17. The composition of claim 16, comprising about 53% by weight of trans-dichloroethylene (TDCE), about 11% by weight of 1-chloro-2,3,3-trifluoro-1-propene (AS300), and about 36% by weight of 1,1,1,2,3,3-hexafluoro-3-methoxypropane (HFE-356).

19. 19. A method for cleaning soiling substances from metal, ceramic, and synthetic polymer articles, comprising contacting one or more of the articles with the solvent composition of any one of claims 3, 10, 11, 12, 13, 14, 15, 16, 17, and 18, and removing the composition from the one or more articles.

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