HK1132293B - Azeotropic compositions comprising fluorinated compounds for cleaning applications - Google Patents

Description

Azeotrope compositions comprising fluoride for cleaning applications

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. provisional application 60/777,350 filed on 28.2.2006.

Background

Technical Field

The present invention relates to compositions comprising a fluorinated olefin or fluorinated ketone and at least one alcohol, halogenated hydrocarbon, fluoroalkyl ether or hydrofluorocarbon, and combinations thereof. These compositions are azeotropic or azeotrope-like and are useful as defluxing agents for cleaning applications and for removing oil or residues from surfaces.

Background

Solder residue is always present on microelectronic components assembled using rosin solder. As modern electronic circuit boards move toward increasing circuit and component densities, cleaning of the entire board after soldering becomes an important process step. After soldering, flux residues are typically removed with an organic flux. The flux remover solvent should be non-flammable, have low toxicity and have high solvency power so that flux and flux residues can be removed without damaging the cleaned substrate. Moreover, other types of residue, such as oils and greases, must be effectively removed from these devices for optimum performance in use.

Alternatively, non-ozone depleting solvents have become available due to the elimination of almost all previous CFCs and HCFCs as a result of the Montreal Protocol (Montreal Protocol). While boiling point, flammability and solvency characteristics can often be adjusted by preparing solvent mixtures, these mixtures are often unsatisfactory because they fractionate to an undesirable extent during use. This solvent mixture is also fractionated during the solvent distillation, making it practically impossible to recover the solvent mixture of the original composition.

The azeotropic solvent mixture may have properties required for these defluxing, degreasing applications, and other cleaning agents. Azeotropic mixtures exhibit either a maximum or minimum boiling point and do not fractionate upon boiling. The inherent constancy of the composition under boiling conditions ensures that the ratio of the individual components of the mixture does not change during use and that the solubility properties also remain constant.

The present invention provides azeotropic and azeotrope-like compositions useful in semiconductor chip and circuit board cleaning, defluxing and degreasing processes. The compositions of the present invention are non-flammable and do not produce flammable compositions during use because they do not fractionate. In addition, the azeotropic solvent mixture used can be redistilled and reused without changing the composition.

Brief description of the invention

The present invention relates to compositions comprising a fluorinated olefin and at least one compound selected from the group consisting of alcohols, halogenated hydrocarbons, fluoroalkyl ethers and hydrofluorocarbons, and combinations thereof. In one embodiment, the at least one compound is selected from:

n-propyl bromide;

trichloroethylene;

tetrachloroethylene;

trans-1, 2-dichloroethylene;

methanol;

ethanol;

n-propanol;

isopropyl alcohol;

C₄F₉OCH₃；

C₄F₉OC₂H₅；

HFC-43-10mee；

HFC-365mfc and combinations thereof.

In one embodiment, the composition is azeotropic or azeotrope-like. In addition, the present invention relates to methods of cleaning surfaces or removing residue from surfaces such as integrated circuit devices.

Detailed Description

The inventors specifically incorporate the entire contents of all documents cited in this disclosure by reference. Further, when an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. When a range of values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. The scope of the invention is not intended to be limited to the specific values listed when defining a range.

In one embodiment, the invention relates to compositions comprising compounds having the formula E-or Z-R¹CH＝CHR²(formula I) wherein R¹And R²Independently a C1-C5 perfluoroalkyl group and at least one alcohol, halocarbon, fluoroalkyl ether or hydrofluorocarbon, and combinations thereof. R¹And R²Examples of groups include, but are not limited to, CF₃、C₂F₅、n-C₃F₇、i-C₃F₇、n-C₄F₉、n-C₅F₁₁And i-C₄F₉. Typical, non-limiting compounds of formula I are listed in Table 1.

TABLE 1

Code	Structure of the product	IUPAC name
			F11E	CF3CH＝CHCF3	1, 1, 1, 4, 4, 4-hexafluoro-2-butene
F12E	CF3CH＝CHC2F5	1, 1, 1, 4, 4, 5, 5, 5-octafluoro-2-pentene
			F13E	CF3CH＝CH(n-C3F7)	1, 1, 1, 4, 4, 5, 5, 6, 6, 6-decafluoro-2-hexene
F13iE	CF3CH＝CH(i-C3F7)	1, 1, 1, 4, 4, 5, 5, 5-heptafluoro-4- (trifluoromethyl) -2-pentene
			F22E	C2F5CH＝CHC2F5	1, 1, 1, 2, 2, 5, 5, 6, 6, 6-decafluoro-3-hexene
F14E	CF3CH＝CH(n-C4F9)	1, 1, 1, 4, 4, 5, 5, 6, 6, 7, 7, 7-dodecafluorohept-2-ene
			F23E	C2F5CH＝CH(n-C3F7)	1, 1, 1, 2, 2, 5, 5, 6, 6, 7, 7, 7-dodecafluorohept-3-ene
F23iE	C2F5CH＝CH(i-C3F7)	1, 1, 1, 2, 2, 5, 6, 6, 6-nonafluoro-5- (trifluoromethyl) hex-3-ene
			F15E	CF3CH＝CH(n-C5F11)	1, 1, 1, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-decatetrafluorooct-2-ene
F24E	C2F5CH＝CH(n-C4F9)	1, 1, 1, 2, 2, 5, 5, 6, 6, 7, 7, 8, 8, 8-decatetrafluorooct-3-ene
			F3i3iE	i-C3F7CH＝CH(i-C3F7)	1, 1, 1, 2, 5, 6, 6, 6-octafluoro-2, 5-bis (trimethylfluoro) hex-3-ene
F33iE	n-C3F7CH＝CH(i-C3F7)	1, 1, 1, 2, 5, 5, 6, 6, 7, 7, 7-undecafluoro-2 (trifluoromethyl) hept-3-ene
			F34E	n-C3F7CH＝CH(n-C4F9)	1, 1, 1, 2, 2, 3, 3, 6, 6, 7, 7, 8, 8, 9, 9, 9-decahexafluoronon-4-ene
F3i4E	i-C3F7CH＝CH(n-C4F9)	1, 1, 1, 2, 5, 5, 6, 6, 7, 7, 8, 8, 8-tridecafluoro-2 (trifluoromethyl) oct-3-ene
			F44E	n-C4F9CH＝CH(n-C4F9)	1, 1, 1, 2, 2, 3, 3, 4, 4, 7, 7, 8, 8, 9, 9, 10, 10, 10-octadecafluorodec-5-ene

Can be prepared by reacting a compound of formula R¹Perfluoroalkyl iodides of formula I and R²CH＝CH₂To form a perfluoroalkyl trihydroalkene of the formula R¹CH₂CHIR²To the trihydroiodoperfluoroalkane of formula (I). The trihydroiodoperfluoroalkanes can then be dehydroiodinated to produce R¹CH＝CHR². Alternatively, by the formula R¹CHICH₂R²Preparation of said olefin R by dehydroiodination of trihydroiodoperfluoroalkanes₁CH＝CHR²And said trihydroiodoperfluoroalkane is in turn prepared by reacting a compound of formula R²Perfluoroalkyl iodides of formula I and R¹CH＝CH₂Is formed by reacting a perfluoroalkyl trihydroalkene of (a).

Perfluoroalkyl iodides andsaid contacting of the perfluoroalkyltrihydroalkene can take place in a batch mode by mixing the reactants in a suitable reaction vessel capable of operation at the reaction temperature under autogenous pressures of the reactants and products. Suitable reaction vessels include those made of stainless steel, especially of the austenitic type, and well-known high nickel alloys such asNickel-copper alloy,A nickel-based alloy anda nickel-chromium alloy. Alternatively, the reaction may be carried out in a semi-batch mode in which the perfluoroalkyl trihydroalkene reactant is added to the perfluoroalkyl iodide reactant by a suitable addition device, such as a pump, at the reaction temperature.

The ratio of perfluoroalkyl iodide to perfluoroalkyl trihydroalkene should be from about 1:1 to about 4:1, preferably from about 1.5:1 to 2.5: 1. As reported by Jeanneaux et al in Journal of Fluorine Chemistry, Vol.4, pp.261-270 (1974), ratios less than 1.5:1 tend to result in large amounts of the 2:1 adduct.

The temperature of the contacting of the perfluoroalkyl iodide with the perfluoroalkyl trihydroalkene is preferably in the range of about 150 ℃ to 300 ℃, more preferably about 170 ℃ to about 250 ℃, and most preferably about 180 ℃ to about 230 ℃. The pressure at which the perfluoroalkyl iodide is contacted with the perfluoroalkyl trihydroolefin is preferably the autogenous pressure of the reactants at the reaction temperature.

Suitable contact times for perfluoroalkyl iodides with perfluoroalkyl trihydroolefins are from about 0.5 hours to about 18 hours, preferably from about 4 hours to about 12 hours.

The trihydroiodoperfluoroalkanes produced by the reaction of perfluoroalkyl iodides with perfluoroalkyl trihydroolefins may be used directly in the dehydroiodination step or may preferably be recovered and purified by distillation prior to the dehydroiodination step.

In yet another embodiment, allThe contacting of the fluoroalkyl iodide with the perfluoroalkyl trihydroalkene occurs in the presence of a catalyst. In one embodiment, a suitable catalyst is a group VIII transition metal complex. Representative group VIII transition metal complexes include, but are not limited to, zero-valent NiL₄The complex, wherein the ligand L may be a phosphine ligand, a phosphite ligand, a carbonyl ligand, an isonitrile ligand, an alkene ligand, or a combination thereof. In one such embodiment, Ni (0) L₄The complex being NiL₂(CO)₂A complex compound. In one embodiment, the group VIII transition metal complex is bis (triphenylphosphine) nickel (0) dicarbonyl. In one embodiment, the ratio of perfluoroalkyl iodide to perfluoroalkyl trihydroalkene is between about 3:1 and about 8: 1. In one embodiment, the temperature of contacting the perfluoroalkyl iodide with the perfluoroalkyl trihydroalkene in the presence of a catalyst is in the range of about 80 ℃ to about 130 ℃. In another embodiment, the temperature is from about 90 ℃ to about 120 ℃.

In one embodiment, the contact time for the reaction of the perfluoroalkyl iodide and perfluoroalkyl trihydroalkene in the presence of the catalyst is from about 0.5 hours to about 18 hours. In another embodiment, the contact time is from about 4 to about 12 hours.

The dehydroiodination step is carried out by contacting the trihydroiodoperfluoroalkane with a basic material. Suitable basic materials include alkali metal hydroxides (e.g., sodium hydroxide or potassium hydroxide), alkali metal oxides (e.g., sodium oxide), alkaline earth metal hydroxides (e.g., calcium hydroxide), alkaline earth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g., sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, or mixtures of basic materials such as soda lime. Preferred alkaline substances are sodium hydroxide and potassium hydroxide.

Said contacting of the trihydroiodoperfluoroalkane with the basic material may take place in the liquid phase, preferably in the presence of a solvent capable of dissolving a portion of at least two reactants. Solvents suitable for the dehydroiodination step include one or more polar organic solvents such as alcohols (e.g., methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol, and t-butanol), nitriles (e.g., acetonitrile, propionitrile, butyronitrile, benzonitrile, or adiponitrile), dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, or sulfolane. The choice of solvent depends on the solubility of the basic substance, the solubility of the perfluoroalkyl iodide, and the solubility of the perfluoroalkyl trihydroalkene, as well as the boiling point of the product and the ease of separating traces of solvent from the product during purification. Typically, ethanol or isopropanol is a good solvent for the reaction. Separation of the solvent from the product can be achieved by distillation, extraction, phase separation, or a combination of the three.

Typically, the dehydroiodination reaction can be carried out by adding one reactant (either the basic material or the trihydroiodoperfluoroalkane) to the other reactant in a suitable reaction vessel. The reaction vessel may be made of glass, ceramic or metal and is preferably stirred with a stirrer or other stirring mechanism.

Suitable temperatures for the dehydroiodination reaction are from about 10 ℃ to about 100 ℃, preferably from about 20 ℃ to about 70 ℃. The dehydroiodination reaction can be carried out at ambient pressure or at reduced or elevated pressure. It is noteworthy that the compound of formula I in the dehydroiodination reaction distills out of the reaction vessel with formation.

Alternatively, the dehydroiodination reaction may be carried out by contacting the aqueous base with a solution of iodoform perfluoroalkane in the presence of a phase transfer catalyst in one or more less polar solvents such as an alkane (e.g. hexane, heptane or octane), an aromatic hydrocarbon (e.g. toluene), a halogenated hydrocarbon (e.g. dichloromethane, dichloroethane, chloroform, carbon tetrachloride or perchloroethylene) or an ether (e.g. diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, dimethoxyethane, diglyme or tetraglyme). Suitable phase transfer catalysts include quaternary ammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, triethylbenzylammonium chloride, dodecyltrimethylammonium chloride, and trioctyl (tricaprylyl) methylammonium chloride), quaternary phosphonium halides (e.g., triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride), cyclic ether compounds known in the art such as crown ethers (e.g., 18-crown-6 and 15-crown-5).

Alternatively, the dehydroiodination reaction can be carried out in the absence of a solvent by adding a trihydroiodoperfluoroalkane to one or more solid or liquid basic materials.

Suitable reaction times for the dehydroiodination reaction range from about 15 minutes to about 6 hours or more depending on the solubility of the reactants. Typically, the dehydroiodination reaction is rapid and takes about 30 minutes to about 3 hours to complete.

The compound of formula I may be recovered from the dehydroiodinated reaction mixture by phase separation, optionally after addition of water, by distillation, or a combination thereof.

In another embodiment, the present invention relates to a composition comprising perfluoroethylisopropyl ketone (1, 1, 1, 2, 2, 4, 5, 5, 5-nonafluoro-4- (trifluoromethyl) -3-Pentanone) (PEIK) and at least two compounds selected from the group consisting of alcohols, halogenated hydrocarbons, fluoroalkyl ethers, and hydrofluorocarbons. PEIK has CAS registry No.756-13-8 and is available from 3M^TM(St.Paul，MN)。

In yet another embodiment, the invention relates to a composition comprising nonafluoro-1-hexene (3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluoro-1-hexene) (PFBE) and at least one compound selected from the group consisting of alcohols, halogenated hydrocarbons, fluoroalkyl ethers and hydrofluorocarbons and combinations thereof. 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluoro-1-hexene, also known as HFC-1549fz, having CAS registry No.19430-93-4 and available from e.i. dupont DE nemours & Co (Wilmington, DE).

In yet another embodiment, the invention relates to a method of cleaning a surface using an azeotropic or azeotrope-like composition comprising a fluorinated olefin or a fluorinated ketone and at least one compound selected from the group consisting of alcohols, halogenated hydrocarbons, fluoroalkyl ethers, and hydrofluorocarbons.

The fluorinated olefins, PEIK and PFBE of table 1 may be mixed with the compounds listed in table 2 to form the compositions of the present invention. The at least one to be mixed with PFBE is selected from the group consisting of alcohol, halogenated hydrocarbon, fluoroalkyl etherOr the hydrofluorocarbon compound should not be an alcohol, trans-1, 2-dichloroethylene alone, C alone₄F₉OCH₃HFC-43-10mee alone, HFC-365mfc alone, or trans-1, 2-dichloroethylene with C₄F₉OC₂H₅A mixture of (a).

TABLE 2

The compounds listed in table 2 are available from chemical supply companies. C₄F₉OCH₃And C₄F₉OC₂H₅Commercially available from 3M^TM(st. paul, MN). HFC-43-10mee is available from E.I. DuPont de Nemours&Co (Wilmington, DE). HFC-365mfc is available from Solvay-Solexis.

The compositions of the present invention may be prepared in any convenient manner by mixing the required amounts of the individual components. A preferred method is to weigh the required amounts of the components and then mix the components in a suitable container. Stirring may be used if desired.

The compositions of the present invention comprise a composition comprising one of the fluorinated olefins listed in Table 1, PEIK or PFBE and at least one member selected from the group consisting of trichloroethylene, tetrachloroethylene, trans-1, 2-dichloroethylene, n-propyl bromide, methanol, ethanol, n-propanol, isopropanol, C₄F₉OCH₃、C₄F₉OC₂H₅HFC-43-10mee, HFC-365mfc and combinations thereof. In one embodiment, the composition is azeotropic or azeotrope-like. The compositions according to the invention are distinguished by the fact that PFBE is not reacted with alcohol, trans-1, 2-dichloroethylene, C alone₄F₉OCH₃HFC-43-10mee alone, HFC-365mfc alone, or trans-1, 2-dichloroethylene with C₄F₉OC₂H₅Mixing the above mixtures.

As used herein, an azeotropic composition is a constant boiling liquid admixture of two or more substances, wherein the admixture distills substantially without compositional change and behaves as a constant boiling composition. Constant boiling compositions characterized as azeotropes exhibit either a maximum or minimum boiling point as compared to the boiling point of a non-azeotropic mixture of the same substances. An azeotropic composition as used herein includes a homogeneous azeotrope, which is a liquid mixture of two or more substances that behaves as a single substance, i.e., 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 in which the liquid phase is separated 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 mixed and the composition of all the liquid phases is calculated, it will be the same as the composition of the gas phase.

As used herein, the term "azeotrope-like composition," also sometimes referred to as a "near azeotrope composition," refers to a constant boiling or substantially constant boiling liquid mixture of two or more substances that behaves as a single substance. One way to characterize azeotrope-like compositions is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the liquid being evaporated or distilled. That is, the mixture distills/refluxes with essentially no change in composition. Another way to characterize azeotrope-like compositions is that, at a particular temperature, the bubble vapor pressure of the composition and the dew point vapor pressure of the composition are substantially the same. Here, a composition is azeotrope-like if after 50 wt% of the composition is removed, e.g., by evaporation or distillation, the difference in vapor pressure between the original composition and the composition remaining after 50 wt% of the original composition is removed by evaporation or distillation is less than 10%.

In cleaning devices, such as steam degreasers or desolders, the cleaning composition may be partially lost during operation through leakage at shaft seals, hose connections, welds and fold lines. In addition, during equipment maintenance procedures, the working composition may be released into the environment. If the composition is not a pure compound or an azeotropic or azeotrope-like composition, the composition may change when leaked or discharged from the equipment to the environment, which may cause the composition remaining in the device to become flammable or to exhibit unacceptable performance. Thus, it is desirable that individual fluorinated hydrocarbons or azeotropic or azeotrope-like compositions fractionally to negligible extent upon leakage or evaporation be used as cleaning compositions.

The azeotropic composition of one embodiment of the present invention is set forth in table 3.

TABLE 3

Component A Component B wt％A wt％B T(C)

F14E methanol 85.114.959.1

F14E Isopropanol 87.112.966.9

F14E ethanol 87.912.165.2

F14E t-DCE 44.3 55.7 44.0

F14E nPBr 54.4 45.6 66.6

F24E methanol 72.127.963.4

F24E Isopropanol 78.121.974.1

F24E ethanol 79.220.871.8

F24E t-DCE 24.5 75.5 45

F24E nPBr 25.7 74.3 70.2

F24E PCE 85.2 14.8 89.9

F24E TCE 65.0 35.0 75.9

PEIK methanol 97.03.043.5

PEIK isopropanol 96.73.345.5

PEIK ethanol 96.83.244.7

PEIK t-DCE 72.9 27.1 34.7

PEIK 43-10mee 73.2 26.8 47.7

PEIK 365mfc 38.8 61.2 38.1

PFBE methanol 92.27.850.6

PFBE isopropanol 95.24.856.3

PFBE ethanol 94.85.255.2

PFBE t-DCE 52.8 472 41.3

PFBE nPBr 82.3 17.7 57.1

F22E methanol 95.84.243.7

F22E Isopropanol 98.02.047.2

F22E ethanol 97.62.446.6

F22E t-DCE 71.0 29.0 33.9

F22E nPBr 87.0 13.0 43.3

F22E 43-10mee 89.8 10.2 47.9

F22E 365mfc 29.3 70.7 39.2

F13iE methanol 95.54.544.4

F13iE Isopropanol 97.82.248.0

F13iE ethanol 97.42.647.5

F13iE t-DCE 702 29.8 34.4

F13iE nPBr 86.4 13.6 44.0

F13iE 43-10mee 95.3 4.7 48.8

F13iE 365mfc 24.6 75.4 39.5

F3i3iE methanol 85.015.059.8

F3i3iE Isopropanol 89.210.870.0

F3i3iE ethanol 89.011.067.8

F3i3iE t-DCE 44.1 55.9 44.5

F3i3iE C₄F₉OC₂H₅ 22.8 77.2 75.7

F3i3iE nPBr 67.4 32.6 61.3

F13E methanol 94.45.647.3

F13E Isopropanol 96.93.151.9

F13E ethanol 9653.551.1

F13E t-DCE 663 33.7 36.3

F13E nPBr 83.7 16.3 47.1

F13E 43-10mee 59.5 40.5 52.3

F3i4E t-DCE 7.6 92.4 47.6

F3i4E methanol 42.857.265.4

F3i4E Isopropanol 57.842.281.0

F3i4E ethanol 58.741.377.3

F3i4E nPBr 31.9 68.1 69.6

F44E nPBr 8.1 91.9 70.9

Furthermore, in another embodiment, the azeotropic compositions of the present invention also include ternary and quaternary azeotropic compositions comprising the compounds in table 2. Non-limiting examples of these higher copolymerization compositions are listed in Table 4, along with the boiling points of the compositions at atmospheric pressure.

TABLE 4

Component A Component B Component C wt％A wt％B wt％C T(C)

F14E t-DCE methanol 34.459.06.639.9

F14E t-DCE ethanol 41.955.13.043.2

F24E t-DCE methanol 10.380.39.441.0

F24E t-DCE ethanol 24.870.94.343.0

PEIK t-DCE methanol 71.526.42.133.0

PEIK t-DCE ethanol 73.025.71.334.2

PEIK t-DCE 43-10mee 57.0 26.9 16.1 34.3

PEIK t-DCE 365mfc 43.7 24.1 32.2 32.6

PFBE t-DCE C₄F₉OCH₃ 40.1 47.5 12.4 41.3

F22E t-DCE methanol 67929.72.432.6

F22E t-DCE 365mfc 454 27.2 27.4 33.0

F13iE t-DCE methanol 66.930.62.533.0

F13iE t-DCE 43-10mee 69.8 29.8 0.4 34.4

F13iE t-DCE 365mfc 41.9 27.8 30.3 333

F3i3iE t-DCE methanol 32.960.26.940.1

F3i3iE t-DCE ethanol 41.156.32.643.8

F13E t-DCE methanol 62.23473.134.5

F13E t-DCE 43-10mee 48.0 33.2 18.8 36.1

F13E t-DCE 365mfc 23.1 30.3 46.6 34.4

Binary azeotrope-like compositions of the present invention are listed in Table 5.

TABLE 5

Component A Component B wt％A wt％B T(C)

F14E methanol 60-991-4059.1

F14E Isopropanol 70-991-3066.9

F14E ethanol 72-991-2865.2

F14E t-DCE 1-75 25-99 44.0

F14E nPBr 1-99 1-99 66.6

F14E C₄F₉OCH₃ 1-99 1-99 50

F14E C₄F₉OC₂H₅ 1-99 1-99 50

F14E 43-10mee 1-99 1-99 50

F24E methanol 1-919-9963.4

F24E Isopropanol 57-919-4374.1

F24E ethanol 57-928-4371.8

F24E t-DCE 1-63 37-99 46.1

F24E nPBr 1-70 30-99 70.2

F24E PCE 61-99 1-39 89.9

F24E TCE 40-84 16-60 75.9

F24E C₄F₉OC₂H₅ 1-99 1-99 50

PEIK methanol 91-991-943.5

PEIK Isopropanol 57-991-1645.5

PEIK ethanol 85-991-1544.7

PEIK t-DCE 50-88 12-50 34.7

PEIK 4310mcee 1-99 1-99 47.7

PEIK 365mfc 1-99 1-99 38.1

PEIK C₄F₉OCH₃ 1-99 1-99 50

PFBE methanol 80-991-2050.6

PFBE isopropanol 83-991-17563

PFBE ethanol 83-991-1755.2

PFBE t-DCE 21-79 21-79 41.3

PFBE nPBr 44-99 1-55 57.1

PFBE C₄F₉OCH₃ 1-99 1-99 50

PFBE C₄F₉OC₂H₅ 1-99 1-99 50

PFBE 43-10mee 1-99 1-99 50

PFBE 365mfc 1-99 1-99 50

F22E methanol 86-991-1443.7

F22E Isopropanol 88-991-1247.2

F22E ethanol 88-991-1246.6

F22E t-DCE 48-87 13-52 33.9

F22E nPBr 64-99 1-36 43.3

F22E 43-10mee 1-99 1-99 47.9

F22E 365mfc 1-99 1-99 39.2

F22E C₄F₉OCH₃ 1-99 1-99 50

F13iE methanol 86-991-1444.4

F13iE Isopropanol 87-991-1348.0

F13iE ethanol 88-991-1247.5

F13iE t-DCE 46-86 14-54 34.4

F13iE nPBr 64-99 1-36 44.0

F13iE 43-10mee 1-99 1-99 48.8

F13iE 365mfc 1-99 1-99 39.5

F13iE C₄F₉OCH₃ 1-99 1-99 50

F3i3iE methanol 57-991-4359.8

F3i3iE Isopropanol 73-991-2770.0

F3i3iE ethanol 73-991-2767.8

F3i3iE t-DCE 1-76 24-99 44.5

F3i3iE C₄F₉OC₂H₅ 1-99 1-99 75.7

F3i3iE nPBr 43-86 14-57 61.3

F3i3iE C₄F₉OCH₃ 1-99 1-99 50

F13E methanol 84-991-1647.3

F13E Isopropanol 86-991-1451.9

F13E ethanol 86-991-1451.1

F13E t-DCE 42-84 16-58 36.3

F13E nPBr 61-99 1-39 47.1

F13E 43-10mee 1-99 1-99 52.3

F13E C₄F₉OCH₃ 1-99 1-99 50

F13E C₄F₉OC₂H₅ 1-99 1-99 50

F13E 365mfc 1-99 1-99 50

F3i4E t-DCE 1-69 31-99 47.6

F3i4E methanol 1-8911-9965.4

F3i4E Isopropanol 1-8812-9981

F3i4E ethanol 1-8911-9977.3

F3i4E nPBr 1-72 28-99 69.6

F44E nPBr 1-70 30-99 70.9

In addition to the binary azeotrope-like compositions of the preceding tables, the present invention includes higher (ternary or quaternary) azeotrope-like compositions. Non-limiting examples of ternary or higher azeotrope-like compositions are given in table 6.

TABLE 6

Component A Component B Component C wt％A wt％B wt％C T(C)

F14E t-DCE C₄F₉OCH₃ 1-70 20-70 1-70 50

F14E t-DCE C₄F₉OC₂H₅ 1-70 29-90 1-60 50

F14E t-DCE 43-10mee 1-80 15-60 1-80 50

F14E t-DCE 365mfc 1-70 10-60 1-80 50

F14E t-DCE methanol 1-7029-981-3039.9

F14E t-DCE ethanol 1-7029-981-2043.2

F24E t-DCE C₄F₉OCH₃ 1-70 20-70 1-70 50

F24E t-DCE C₄F₉OC₂H₅ 1-60 30-80 1-60 50

F24E t-DCE methanol 1-5040-981-2541.0-

F24E t-DCE ethanol 1-6039-981-2045.0

PEIK t-DCE C₄F₉OCH₃ 1-70 20-50 1-70 50

PEIK t-DCE methanol 50-8514-491-933.0

PEIK t-DCE ethanol 50-8514-491-934.2

PEIK t-DCE 43-10mee 1-85 10-65 1-80 34.3

PEIK t-DCE 365mfc 1-85 1-55 1-85 32.6

PFBE t-DCE 43-10mee 1-70 20-60 1-79 50

PFBE t-DCE 365mfc 1-70 15-60 1-80 50

PFBE t-DCE C₄F₉OCH₃ 1-75 24-75 1-70 41.3

F22E t-DCE C₄F₉OCH₃ 1-70 29-70 1-70 50

F22E t-DCE 43-10mee 1-80 19-60 1-80 50

F22E t-DCE methanol 45-8514-541-1032.6

F22E t-DCE 365mfc 1-89 10-60 1-85 33.0

F13iE t-DCE C₄F₉OCH₃ 1-75 24-70 1-70 50

F13iE t-DCE methanol 45-8514-541-1033.0

F13iE t-DCE 43-10mee 1-89 10-60 1-80 34.4

F13iE t-DCE 365mfc 1-89 10-60 1-84 33.3

F3i3iE t-DCE methanol 1-7029-951-2540.1

F3i3iE t-DCE ethanol 1-6534-

F3i3iE t-DCE C₄F₉OCH₃ 1-69 30-70 1-69 50

F3i3iE t-DCE C₄F₉OC₂H₅ 1-69 30-80 1-69 50

F13E t-DCE methanol 45-8019-541-34.5

F13E t-DCE 43-10mee 1-85 14-60 1-3 6.1

F13E t-DCE 365mfc 1-85 14-60 1-3 4.4

F13E t-DCE C₄F₉OCH₃ 1-80 19-70 1-70 50

F3i4E t-DCE C₄F₉OCH₃ 1-30 25-69 30-69 50

F3i4E t-DCE C₄F₉OC₂H₅ 1-50 30-98 1-60 50

F44E t-DCE C₄F₉OC₂H₅ 1-70 1-60 29-98 50

In yet another embodiment of the present invention, the composition of the present invention may further comprise an aerosol propellant. An aerosol propellant may assist in the delivery of the composition of the invention from a storage container to a surface in aerosol form. Aerosol propellants may optionally be included in the compositions of the present invention in amounts up to 25% by weight of the total composition. Representative aerosol propellants include air, nitrogen, carbon dioxide, difluoromethane (HFC-32, CH)₂F₂Trifluoromethane (HFC-23, CHF)₃) Difluoroethane (HFC-152a, CHF)₂CH₃) Trifluoroethane (HFC-143a, CH)₃CF₃(ii) a Or HFC-143, CHF₂CH₂F) Tetrafluoroethane (HFC-134a, CF)₃CH₂F；HFC-134，CHF₂CHF₂) Pentafluoroethane (HFC-125, CF)₃CHF₂) Heptafluoropropane (HFC-227ea, CF)₃CHFCF₃) Pentafluoropropane (HFC-245fa, CF)₃CH₂CHF₂) Dimethyl ether (CH)₃OCH₃) Or mixtures thereof.

In one embodiment of the invention, the azeotropic compositions of the present invention are effective cleaning agents, defluxing agents, and degreasing agents. In particular, the azeotropic compositions of the present invention are useful in removing solder from circuit boards having components such as flip chips, μ BGA (ball grid array) and Chip scale (Chip scale) or other advanced high density packaging components. Flip-chip, μ BGA and chip scale are terms that describe high density packaging components used in the semiconductor industry and are well known to those skilled in the art.

In another embodiment the invention relates to a method for removing residue from a surface or substrate comprising: contacting a surface or substrate with a composition of the invention and recovering said surface or substrate from the composition.

In a method embodiment of the invention, the surface or substrate may be an integrated circuit device, in which case the residue comprises rosin flux or oil. The integrated circuit device may be a circuit board with various types of components such as flip-chip, μ BGA, or chip scale package components. Further, the surface or substrate may be a metal surface such as stainless steel. The rosin flux can be of any type commonly used for integrated circuit device soldering, including but not limited to RMA (mild activated rosin), RA (activated rosin), WS (water soluble), OA (organic acid). Oil residues include, but are not limited to, mineral oil, motor oil, and silicone oil.

In the method of the invention, the method used to contact the surface or substrate is not critical and can be achieved by: immersing the device in a bath containing the composition, spraying the device with the composition or wiping the device with a substrate that has been wetted with the composition. Alternatively, the composition may also be used in a vapor degreasing or flux-stripping apparatus designed to remove such residues. Such vapor degreasing or flux-stripping devices are commercially available from various suppliers, such as Forward Technology (a subsidiary of the Crest Group, Trenton, NJ), Trek Industries (Azusa, CA), and ultraronix, Inc.

An effective composition for removing residue from a surface has a kauri-butanol value (Kb) of at least about 10, preferably about 40, more preferably about 100. The kauri-butanol value (Kb) for a given composition reflects the ability of the composition to dissolve various organic residues, such as machine and conventional refrigeration lubricants. The Kb value can be determined by ASTM D-1133-94.

The following specific examples are intended to be merely illustrative of the invention and are not intended to be limiting in any way.

Examples

Example 1

Synthesis of 1, 1, 1, 4, 4, 5, 5, 6, 6, 7, 7, 7-dodecafluorohept-2-ene (F14E)₄F₉CH₂CHICF₃Synthesis of (2)

Hastelloy at 400ml^TMThe tube was shaken with perfluoro-n-butyl iodide (180.1gm, 0.52mol) and 3, 3, 3-trifluoropropene (25.0gm, 0.26mol) and heated to 200 ℃ for 8 hours under autogenous pressure, which was increased to a maximum of 428 PSI. After cooling the reaction vessel to room temperature, the product was collected. The product of this reaction and two other products from reactions carried out in essentially the same manner except that one of the reactions had twice the amount of reactant were mixed and distilled to provide 322.4gm of C₄F₉CH₂CHICF₃(52.2 ℃ C./35 mm, 70% yield).

C₄F₉CH₂CHICF₃Conversion to F14E

Isopropanol (95ml), KOH (303.7gm, 0.54mol), and water (303ml) were charged to a 2 liter round bottom flask equipped with a stir bar and a packed distillation column and distillation head. Dropwise addition of C at room temperature via addition funnel₄F₉CH₂CHICF₃(322.4gm, 0.73mol) to an aqueous KOH/IPA mixture. The reaction was then heated to 65-70 ℃ to recover the product by distillation. The distillate was collected, washed with sodium metabisulfite and water, over MgSO₄Dried and then distilled through a 6-inch (15.2cm) column packed with a glass spiral tube. Product F14E (173.4gm, 76% yield) boiled at 78.2 ℃. Characterization of the product by NMR Spectroscopy (¹⁹F：δ-66.7(CF₃，m，3F)，-81.7(CF₃，m，3F)，-124.8(CF₂，m，2F)，-126.4(CF₂，m，2F)，-114.9ppm(CF₂，m，2F)；¹H：6.58d)。

Example 2

Synthesis C of 1, 1, 1, 2, 2, 5, 5, 6, 6, 7, 7, 8, 8, 8-decatetrafluorooct-3-ene (F24E)₄F₉CHICH₂C₂F₅Synthesis of (2)

Hastelloy at 400ml^TMPerfluoroethyl iodide (220gm, 0.895mol) and 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohex-1-ene (123gm, 0.50mol) were added to the shaker tube and heated to 200 ℃ for 10 hours under autogenous pressure. The product of this reaction and two other products obtained by carrying out the reaction under substantially similar conditions were mixed and washed with two 200mL portions of a 10 wt% aqueous solution of sodium bisulfite. The organic phase was dried over calcium chloride, followed by distillation to provide 277.4gm of C in 37% yield₄F₉CH₂CHICF₃(79-81℃/67-68mm Hg)。

C₄F₉CHICH₂C₂F₅Conversion to F24E

C is to be₄F₉CHICH₂C₂F₅(277.4gm, 0.56mol) and isopropanol (217.8g) were charged to a 1 liter round bottom flask equipped with a mechanical stirrer, addition funnel, condenser and thermocouple. The addition funnel was charged with a potassium hydroxide solution (74.5g, 1.13mol) dissolved in 83.8g of water. During the course of about 1 hour with a slow increase in temperature from 21 ℃ to 42 ℃, the KOH solution was added dropwise to the flask with rapid stirring. The reaction mass was diluted with water and the product recovered by phase separation. The product was washed with 50mL portions of a 10 wt% aqueous solution of sodium bisulfite and water, dried over calcium chloride, and then distilled at atmospheric pressure. Product F24E (128.7gm, 63%) boiled at 95.5 ℃ and was characterized by NMR (r: (m) ())¹⁹F：δ-81.6(CF₃，m，3F)，-85.4(CF₃，m，3F)，-114.7(CF₂，m，2F)，-118.1(CF₂，m，2F)，-124.8ppm(CF₂，m，2F)，-126.3ppm(CF₂，m，2F)；¹H: δ 6.48; chloroform-d solution).

Example 3

Synthesis of 1, 1, 1, 4, 5, 5, 5-heptafluoro-4- (trifluoromethyl) -pent-2-ene (F13iE)₃CHICH₂CF(CF₃)₂Synthesis of (2)

Hastelloy at 400ml^TMIn an oscillating tubeAdding (CF)₃)₂CFI (265gm, 0.9mol) and 3, 3, 3-trifluoropropene (44.0gm, 0.45mol) and heated to 200 ℃ for 8 hours under autogenous pressure increased to a maximum of 585 psi. The product was collected at room temperature to give 110gm (CF) in 62% yield₃)₂CFCH₂CHICF₃(76-77℃/200mm)。

(CF₃)₂CFCH₂CHICF₃Conversion to F13iE

Isopropanol (50ml), KOH (109gm, 1.96mol) and water (109ml) were charged to a 500ml round bottom flask equipped with a stir bar and connected to a short path distillation column and a dry ice trap. The mixture was heated to 42 ℃ and added dropwise through an addition funnel (CF)₃)₂CFCH₂CHICF₃(109gm, 0.28 mol). During the addition, the temperature rose from 42 ℃ to 55 ℃. After refluxing for 30 minutes, the temperature of the flask was raised to 62 ℃, and the product was collected by distillation. The product was collected, washed with water and MgSO₄Dried and distilled. Product F13iE (41gm, 55% yield) boiled at 48-50 ℃ and characterized by NMR (¹⁹F: δ -187.6(CF, m, 1F), -77.1(CF3, m, 6F), -66.3(CF3, m, 3F); chloroform-d solution).

Example 4

Synthesis of C4F9CHICH2C2F5

Hastelloy at 210ml^TM3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohex-1-ene (20.5gm, 0.0833mol), bis (triphenylphosphine) nickel (0) dicarbonyl (0.53g, 0.0008mol) and perfluoroethyl iodide (153.6gm, 0.625mol) were added to a shaker tube and heated at 100 ℃ for 8 hours under autogenous pressure. Product analysis by GC-MS indicated the presence of C4F9CHICH2C2F5(64.3GC area%) and the binary adduct (3.3GC area%); the conversion of 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohex-1-ene was 80.1%.

Example 5

Defluxing agent

The compositions of the present invention are effective for cleaning ionic contaminants (flux) from surfaces. The test for determining surface cleanliness comprises the steps of:

1. rosin flux was applied in large quantities to FR-4 test boards (epoxy printed circuit boards with traces made of tin-plated copper).

2. The thus treated board is then heated in an oven at about 175 c for about 1-2 minutes to activate the rosin flux.

3. The board was then dipped into flux (Sn63, 63/37 Sn/lead flux) at about 200 ℃ for about 10 seconds.

4. The plate was then cleaned by immersion in a boiling cleaning composition for about 3 minutes and moving the plate slightly. Next, the panels were immersed in a freshly prepared bath of room temperature cleaning composition for about 2 minutes.

5. The plates were then tested for residual ions using an Omega Meter600SMD ion analyzer.

Cleaning performance was determined by weighing the panels before depositing the flux, after depositing the flux, and then after the cleaning step. The results are given in table 7.

TABLE 7

Example 6

Metal cleaning

A 2 "x 3" sample of stainless steel (type 316) that was grit blasted to provide a rough surface was pre-cleaned and oven dried to remove any residual soil. The tare weight of each sample was determined to be 0.1 mg. A small amount of mineral oil was applied with a cotton swab and the sample was then weighed again to obtain a "loaded" weight. The sample was then cleaned by immersion in a boiling cleaning composition for 1 minute, left in steam for 30 seconds, and then air dried for 1 minute. Next, the sample was weighed again and the percent soil removal was calculated using the three recorded weights. The results are shown in Table 8.

TABLE 8

The results show that mineral oil residues are effectively removed from stainless steel surfaces by the composition of the invention.

Example 7

Metal cleaning

A 2 "x 3" sample of stainless steel (type 316) that was grit blasted to provide a rough surface was pre-cleaned and oven dried to remove any residual soil. The tare weight of each sample was determined to be 0.1 mg. A small amount of DC200 siloxane was applied with a cotton swab and the sample was then weighed again to obtain a "loaded" weight. The sample was then cleaned by immersion in a boiling cleaning composition for 1 minute, left in steam for 30 seconds, and then air dried for 1 minute. Next, the sample was weighed again and the percent soil removal was calculated using the three recorded weights. The results are shown in Table 9.

TABLE 9

The results show that siloxane residues are effectively removed from stainless steel surfaces by the composition of the invention.

Example 8

Metal cleaning efficacy

A 2 "x 3" sample of stainless steel (type 316) that was grit blasted to provide a rough surface was pre-cleaned and oven dried to remove any residual soil. Each specimen was weighed 4 positions to obtain a tare weight. A small amount of mineral oil was applied with a cotton swab and the sample was then weighed again to obtain a "loaded" weight. The sample was then cleaned by immersion in a boiling cleaning composition for 1 minute, left in steam for 30 seconds, and then air dried for 1 minute. Next, the sample was weighed again and the percent soil removal was calculated using the three recorded weights. The results are shown in Table 10.

Watch 10

The results show that mineral oil residues are effectively removed from stainless steel surfaces by the composition of the invention.

Example 9

Metal cleaning efficacy

A 2 "x 3" sample of stainless steel (type 316) that was grit blasted to provide a rough surface was pre-cleaned and oven dried to remove any residual soil. Each specimen was weighed 4 positions to obtain a tare weight. A small amount of DC200 siloxane was applied with a cotton swab and the sample was then weighed again to obtain a "loaded" weight. The sample was then cleaned by immersion in a boiling cleaning composition for 1 minute, left in steam for 30 seconds, and then air dried for 1 minute. Next, the sample was weighed again and the percent soil removal was calculated using the three recorded weights. The results are shown in Table 11.

TABLE 11

Example 10

Metal cleaning efficacy

A 2 "x 3" sample of stainless steel (type 316) that was grit blasted to provide a rough surface was pre-cleaned and oven dried to remove any residual soil. Each specimen was weighed 4 positions to obtain a tare weight. A small amount of mineral oil was applied with a cotton swab and the sample was then weighed again to obtain a "loaded" weight. The sample was then cleaned by immersion in a boiling cleaning composition for 1 minute, left in steam for 30 seconds, and then air dried for 1 minute. Next, the sample was weighed again and the percent soil removal was calculated using the three recorded weights. The results are shown in Table 12.

TABLE 12

Example 11

Metal cleaning efficacy

A 2 "x 3" sample of stainless steel (type 316) that was grit blasted to provide a rough surface was pre-cleaned and oven dried to remove any residual soil. Each specimen was weighed 4 positions to obtain a tare weight. A small amount of DC200 silicone oil was applied with a cotton swab and the sample was then weighed again to obtain a "loaded" weight. The sample was then cleaned by immersion in a boiling cleaning composition for 1 minute, left in steam for 30 seconds, and then air dried for 1 minute. Next, the sample was weighed again and the percent soil removal was calculated using the three recorded weights. The results are shown in Table 13.

Watch 13

The results show that siloxane residues are effectively removed from stainless steel surfaces by the composition of the invention.

Example 12

A mixture of 21.8 wt% F24E and 78.2 wt% 1, 2-trans-dichloroethylene (t-DCE) was prepared and placed in a 5-plate distillation apparatus having a 10:1 reflux ratio. The temperature at the distillation head was recorded and several fractions of the distillation mass were removed over time. The distilled material was analyzed by gas chromatography. The data are shown in Table 14 below. The composition and temperature remained stable throughout the experiment, indicating the azeotropic behavior of this mixture.

TABLE 14

Distillation cut	Distillation head temperature (C)	Wt% distillate	％F24E	％t-DCE
					1	45	8	24.5	75.6
2	45	15	24.3	757
					3	45	22	24.2	75.8
4	45	28	24.2	758

Example 13

A mixture of 20.0 wt% F24E, 75.8 wt% 1, 2-trans-dichloroethylene (t-DCE), and 4.2 wt% ethanol was prepared and placed in a 5-plate distillation apparatus having a 10:1 reflux ratio. The temperature at the distillation head was recorded and several fractions of the distillation mass were removed over time. The distilled material was analyzed by gas chromatography. The data are shown in Table 15 below. The composition and temperature remained stable throughout the experiment, indicating the azeotropic behavior of this mixture.

Watch 15

Distillation cut	Distillation head temperature (C)	Wt% distillate	％F24E	％t-DCE	％EtOH
						1	43	13	24.8	71.0	4.3
2	43	19	25.3	70.4	4.3
						3	43	25	24.8	70.8	4.3
4	43	32	24.8	70.9	4.3
						5	43	40	24.9	70.8	4.3
6	43	47	24.8	70.9	4.3

Claims (8)

1. An azeotropic or azeotrope-like composition, wherein said azeotrope-like composition is such that after 50 weight percent of said composition has been removed by evaporation or distillation, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed by evaporation or distillation is less than 10%, said composition comprising a compound having the formula E-or Z-R¹CH＝CHR²And at least one compound selected from the group consisting of alcohols, halogenated hydrocarbons, fluoroalkyl ethers, hydrofluorocarbons, and combinations thereof, wherein R is a hydrogen atom¹And R²Independently selected from C1-C5 perfluoroalkyl groupsSaid composition comprising an azeotropic or azeotrope-like composition selected from the group consisting of:

60-99 wt% of F14E and 1-40 wt% of methanol;

70-99 wt% of F14E and 1-30 wt% of isopropanol;

72-99 wt% of F14E and 1-28 wt% of ethanol;

1-75 wt% of F14E and 25-99 wt% of trans-1, 2-dichloroethylene;

1-99 wt% of F14E and 99-1 wt% of n-propyl bromide;

1-99 wt% of F14E and 99-1 wt% of C₄F₉OCH₃；

1-99 wt% of F14E and 99-1 wt% of C₄F₉OC₂H₅；

1-99 wt% of F14E and 99-1 wt% of HFC-43-10 mee;

1-91 wt% of F24E and 99-9 wt% of methanol;

57-91 wt% of F24E and 43-9 wt% of isopropanol;

57-92 wt% of F24E and 43-8 wt% of ethanol;

1-63 wt% of F24E and 99-37 wt% of trans-1, 2-dichloroethylene;

1-70 wt% of F24E and 99-30 wt% of n-propyl bromide;

61-99 wt% of F24E and 39-1 wt% of perchloroethylene;

40-84 wt% of F24E and 60-16 wt% of trichloroethylene;

1-99 wt% of F24E and 99-1 wt% of C₄F₉OC₂H₅；

86-99 wt% of F22E and 14-1 wt% of methanol;

88 to 99 wt% of F22E and 12 to 1 wt% of isopropanol;

88-99 wt% of F22E and 12-1 wt% of ethanol;

48 to 87 weight percent of F22E and 52 to 13 weight percent of trans-1, 2-dichloroethylene;

64 to 99 wt% of F22E and 36 to 1 wt% of n-propyl bromide;

1-99 wt% of F22E and 99-1 wt% of HFC-43-10 mee;

1-99 wt% of F22E and 99-1 wt% of HFC-365 mfc;

1-99 wt% of F22E and 99-1wt% of C₄F₉OCH₃；

86-99 wt% of F13iE and 14-1 wt% of methanol;

87-99 wt% of F13iE and 13-1 wt% of isopropanol;

88-99 wt% of F13iE and 12-1 wt% of ethanol;

46-86% by weight of F13iE and 54-14% by weight of trans-1, 2-dichloroethylene;

64 to 99 wt% of F13iE and 36 to 1 wt% of n-propyl bromide;

1-99 wt% of F13iE and 99-1 wt% of HFC-43-10 mee;

1-99 wt% of F13iE and 99-1 wt% of HFC-365 mfc;

1-99 wt% of F13iE and 99-1 wt% of C₄F₉OCH₃；

57-99 wt% of F3i3iE and 43-1 wt% of methanol;

73-99 wt% of F3i3iE and 27-1 wt% of isopropanol;

73-99 wt% of F3i3iE and 27-1 wt% of ethanol;

1-76 wt% of F3i3iE and 99-24 wt% of trans-1, 2-dichloroethylene;

1-99 wt% of F3i3iE and 99-1 wt% of C₄F₉OC₂H₅；

43-86 wt% of F3i3iE and 57-14 wt% of n-propyl bromide;

1-99 wt% of F3i3iE and 99-1 wt% of C₄F₉OCH₃；

84-99 wt% of F13E and 16-1 wt% of methanol;

86-99 wt% of F13E and 14-1 wt% of isopropanol;

86-99 wt% of F13E and 14-1 wt% of ethanol;

42 to 84 wt% of F13E and 58 to 16 wt% of trans-1, 2-dichloroethylene;

61-99 wt% F13E and 39-1 wt% n-propyl bromide;

1-99 wt% of F13E and 99-1 wt% of HFC-43-10 mee;

1-99 wt% of F13E and 99-1 wt% of C₄F₉OCH₃；

1-99 wt% of F13E and 99-1 wt% of C₄F₉OC₂H₅；

1-99 wt% of F13E and 99-1 wt% of HFC-365 mfc;

1-69 wt% of F3i4E and 99-31 wt% of trans-1, 2-dichloroethylene;

1-89 wt% of F3i4E and 99-11 wt% of methanol;

1-88 wt% of F3i4E and 99-12 wt% of isopropanol;

1-89 wt% of F3i4E and 99-11 wt% of ethanol;

1-72 wt% of F3i4E and 99-28 wt% of n-propyl bromide;

1-70 wt% of F44E and 99-30 wt% of n-propyl bromide;

1-70 wt% of F14E, 29-98 wt% of trans-1, 2-dichloroethylene and 1-30 wt% of methanol;

1-70 wt% of F14E, 29-98 wt% of trans-1, 2-dichloroethylene and 1-20 wt% of ethanol;

1-70 wt% of F14E, 20-70 wt% of trans-1, 2-dichloroethylene and 1-70 wt% of C₄F₉OCH₃；

1-70 wt% of F14E, 29-90 wt% of trans-1, 2-dichloroethylene and 1-60 wt% of C₄F₉OC₂H₅；

1-80 wt% of F14E, 15-60 wt% of trans-1, 2-dichloroethylene and 1-80 wt% of HFC-43-10 mee;

1-70 wt% of F14E, 10-60 wt% of trans-1, 2-dichloroethylene and 1-80 wt% of HFC-365 mfc;

1-50 wt% of F24E, 40-98 wt% of trans-1, 2-dichloroethylene and 1-25 wt% of methanol;

1-60 wt% of F24E, 39-98 wt% of trans-1, 2-dichloroethylene and 1-20 wt% of ethanol;

1-70 wt% of F24E, 20-70 wt% of trans-1, 2-dichloroethylene and 1-70 wt% of C₄F₉OCH₃；

1-60 wt% of F24E, 30-80 wt% of trans-1, 2-dichloroethylene and 1-60 wt% of C₄F₉OC₂H₅；

45-85 wt% of F22E, 14-54 wt% of trans-1, 2-dichloroethylene and 1-10 wt% of methanol;

1-89 wt% of F22E, 10-60 wt% of trans-1, 2-dichloroethylene and 1-85 wt% of HFC-365 mfc;

1-70 wt% of F22E, 29-70 wt% of trans-1, 2-dichloroethylene and 1-70 wt% of C₄F₉OCH₃；

1-80 wt% of F22E, 19-60 wt% of trans-1, 2-dichloroethylene and 1-80 wt% of HFC-43-10 mee;

45-85 wt% of F13iE, 14-54 wt% of trans-1, 2-dichloroethylene and 1-10 wt% of methanol;

1-89 wt% of F13iE, 10-60 wt% of trans-1, 2-dichloroethylene and 1-80 wt% of HFC-43-10 mee;

1-89 wt% of F13iE, 10-60 wt% of trans-1, 2-dichloroethylene and 1-84 wt% of HFC-365 mfc;

1-75 wt% of F13iE, 24-70 wt% of trans-1, 2-dichloroethylene and 1-70 wt% of C₄F₉OCH₃；

1-70 wt% of F3i3iE, 29-95 wt% of trans-1, 2-dichloroethylene and 1-25 wt% of methanol;

1-65 wt% of F3i3iE, 34-98 wt% of trans-1, 2-dichloroethylene and 1-15 wt% of ethanol;

1-69 wt% of F3i3iE, 30-70 wt% of trans-1, 2-dichloroethylene and 1-69 wt% of C₄F₉OCH₃；

1-69 wt% of F3i3iE, 30-80 wt% of trans-1, 2-dichloroethylene and 1-69 wt% of C₄F₉OC₂H₅；

45-80 wt% of F13E, 19-54 wt% of trans-1, 2-dichloroethylene and 1-10 wt% of methanol;

1-85 wt% of F13E, 14-60 wt% of trans-1, 2-dichloroethylene and 1-80 wt% of HFC-43-10 mee;

1-85 wt% of F13E, 14-60 wt% of trans-1, 2-dichloroethylene and 1-80 wt% of HFC-365 mfc;

1-80 wt% of F13E, 19-70 wt% of trans-1, 2-dichloroethylene and 1-70 wt% of C₄F₉OCH₃；

1-30 wt% of F3i4E, 25-69 wt% of trans-1, 2-dichloroethylene and 30-69 wt% of C₄F₉OCH₃；

1-50 wt% of F3i4E, 3098% by weight of trans-1, 2-dichloroethylene and 1 to 60% by weight of C₄F₉OC₂H₅(ii) a And

1-70 wt% of F44E, 1-60 wt% of trans-1, 2-dichloroethylene and 29-98 wt% of C₄F₉OC₂H₅。

2. An azeotropic or azeotrope-like composition, wherein said azeotrope-like composition is such that after 50 weight percent of said composition has been removed by evaporation or distillation, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed by evaporation or distillation is less than 10%, said composition comprising a compound having the formula E-or Z-R¹CH＝CHR²And at least one compound selected from the group consisting of alcohols, halogenated hydrocarbons, fluoroalkyl ethers, hydrofluorocarbons, and combinations thereof, wherein R is a hydrogen atom¹And R²Independently selected from C1-C5 perfluoroalkyl groups, wherein the composition comprises an azeotropic or azeotrope-like composition selected from:

85.1 wt% F14E and 14.9 wt% methanol having a vapor pressure of 101kPa at a temperature of 59.1 ℃;

87.1% by weight of F14E and 12.9% by weight of isopropanol having a vapour pressure of 101kPa at a temperature of 66.9 ℃;

87.9 wt% F14E and 12.1 wt% ethanol having a vapor pressure of 101kPa at a temperature of 65.2 ℃;

44.3% by weight of F14E and 55.7% by weight of trans-1, 2-dichloroethylene having a vapor pressure of 101kPa at a temperature of 44.0 ℃;

54.4 wt% F14E and 45.6 wt% n-propyl bromide having a vapor pressure of 101kPa at a temperature of 66.6 ℃;

72.1 wt% F24E and 27.9 wt% methanol having a vapor pressure of 101kPa at a temperature of 63.4 ℃;

78.1 wt% F24E and 21.9 wt% isopropanol having a vapor pressure of 101kPa at a temperature of 74.1 ℃;

79.2% by weight of F24E and 20.8% by weight of ethanol having a vapor pressure of 101kPa at a temperature of 71.8 ℃;

24.5% by weight of F24E and 75.5% by weight of trans-1, 2-dichloroethylene having a vapor pressure of 101kPa at a temperature of 45 ℃;

25.7 weight percent F24E and 74.3 weight percent n-propyl bromide having a vapor pressure of 14.7psia (101kPa) at a temperature of 70.2 ℃;

85.2% by weight of F24E and 14.8% by weight of perchloroethylene having a vapor pressure of 101kPa at a temperature of 89.9 ℃;

65.0% by weight of F24E and 35.0% by weight of trichloroethylene having a vapour pressure of 101kPa at a temperature of 75.9 ℃;

95.8 wt% F22E and 4.2 wt% methanol having a vapor pressure of 101kPa at a temperature of 43.7 ℃;

98 wt% F22E and 2.0 wt% isopropanol having a vapor pressure of 101kPa at a temperature of 47.2 ℃;

97.6 wt% F22E and 2.4 wt% ethanol having a vapor pressure of 101kPa at a temperature of 46.6 ℃;

71.0% by weight of F22E and 29.0% by weight of trans-1, 2-dichloroethylene having a vapor pressure of 101kPa at a temperature of 33.9 ℃;

87.0 wt% F22E and 13.0 wt% n-propyl bromide having a vapor pressure of 101kPa at a temperature of 43.3 ℃;

89.8 weight percent F22E and 10.2 weight percent HFC-43-10mee having a vapor pressure of 101kPa at a temperature of 47.9 ℃;

29.3% by weight of F22E and 70.7% by weight of HFC-365mfc having a vapour pressure of 101kPa at a temperature of 39.2 ℃;

95.5 wt% F13iE and 4.5 wt% methanol having a vapor pressure of 101kPa at a temperature of 44.4 ℃;

97.8 wt% F13iE and 2.2 wt% isopropanol having a vapor pressure of 101kPa at a temperature of 48.0 ℃;

97.4 wt% F13iE and 2.6 wt% ethanol having a vapor pressure of 101kPa at a temperature of 47.5 ℃;

70.2% by weight of F13iE and 29.8% by weight of trans-1, 2-dichloroethylene having a vapor pressure of 101kPa at a temperature of 34.4 ℃;

86.4 wt% F13iE and 13.6 wt% n-propyl bromide having a vapor pressure of 101kPa at a temperature of 44.0 ℃;

95.3% by weight of F13iE and 4.7% by weight of HFC-43-10mee having a vapour pressure of 101kPa at a temperature of 48.8 ℃;

24.6% by weight of F13iE and 75.4% by weight of HFC-365mfc having a vapour pressure of 101kPa at a temperature of 39.5 ℃;

85.0 wt% F3i3iE and 15.0 wt% methanol having a vapor pressure of 101kPa at a temperature of 59.8 ℃;

89.2 wt% F3i3iE and 10.8 wt% isopropanol having a vapor pressure of 101kPa at a temperature of 70.0 ℃;

89.0 wt% F3i3iE and 11.0 wt% ethanol having a vapor pressure of 101kPa at a temperature of 67.8 ℃;

44.1% by weight of F3i3iE and 55.9% by weight of trans-1, 2-dichloroethylene having a vapor pressure of 101kPa at a temperature of 44.5 ℃;

22.8 wt% F3i3iE and 77.2 wt% C having a vapor pressure of 101kPa at a temperature of 75.7 DEG C₄F₉OC₂H₅；

67.4 wt% F3i3iE and 32.6 wt% n-propyl bromide having a vapor pressure of 101kPa at a temperature of 61.3 ℃;

94.4 wt% F13E and 5.6 wt% methanol having a vapor pressure of 101kPa at a temperature of 47.3 ℃;

96.9 wt% F13E and 3.1 wt% isopropanol having a vapor pressure of 101kPa at a temperature of 51.9 ℃;

96.5 wt% F13E and 3.5 wt% ethanol having a vapor pressure of 101kPa at a temperature of 51.1 ℃;

66.3% by weight of F13E and 33.7% by weight of trans-1, 2-dichloroethylene having a vapor pressure of 101kPa at a temperature of 36.3 ℃;

83.7 wt% F13E and 16.3 wt% n-propyl bromide having a vapor pressure of 101kPa at a temperature of 47.1 ℃;

59.5% by weight of F13E and 40.5% by weight of HFC-43-10mee having a vapour pressure of 101kPa at a temperature of 52.3 ℃;

7.6% by weight of F3i4E and 92.4% by weight of trans-1, 2-dichloroethylene having a vapor pressure of 101kPa at a temperature of 47.6 ℃;

42.8 wt% F3i4E and 57.2 wt% methanol having a vapor pressure of 101kPa at a temperature of 65.4 ℃;

57.8 wt% F3i4E and 42.2 wt% isopropanol having a vapor pressure of 101kPa at a temperature of 81.0 ℃;

58.7 wt% F3i4E and 41.3 wt% ethanol having a vapor pressure of 101kPa at a temperature of 77.3 ℃;

31.9 wt% F3i4E and 68.1 wt% n-propyl bromide having a vapor pressure of 101kPa at a temperature of 69.6 ℃;

8.1% by weight of F44E and 91.9% by weight of n-propyl bromide having a vapor pressure of 101kPa at a temperature of 70.9 ℃;

34.4% by weight of F14E, 59.0% by weight of trans-1, 2-dichloroethylene and 6.6% by weight of methanol having a vapor pressure of 101kPa at a temperature of 39.9 ℃;

41.9% by weight of F14E, 55.1% by weight of trans-1, 2-dichloroethylene and 3.0% by weight of ethanol having a vapor pressure of 101kPa at a temperature of 43.2 ℃;

10.3% by weight of F24E, 80.3% by weight of trans-1, 2-dichloroethylene and 9.4% by weight of methanol having a vapor pressure of 101kPa at a temperature of 41.0 ℃;

24.8% by weight of F24E, 70.9% by weight of trans-1, 2-dichloroethylene and 4.3% by weight of ethanol having a vapor pressure of 101kPa at a temperature of 43.0 ℃;

67.9% by weight of F22E, 29.7% by weight of trans-1, 2-dichloroethylene and 2.4% by weight of methanol having a vapor pressure of 101kPa at a temperature of 32.6 ℃;

45.4% by weight of F22E, 27.2% by weight of trans-1, 2-dichloroethylene and 27.4% by weight of HFC-365mfc having a vapor pressure of 101kPa at a temperature of 33.0 ℃;

66.9% by weight of F13iE, 30.6% by weight of trans-1, 2-dichloroethylene and 2.5% by weight of methanol having a vapor pressure of 101kPa at a temperature of 33.0 ℃;

69.8% by weight of F13iE, 29.8% by weight of trans-1, 2-dichloroethylene and 0.4% by weight of HFC-43-10mee having a vapor pressure of 101kPa at a temperature of 34.4 ℃;

41.9% by weight of F13iE, 27.8% by weight of trans-1, 2-dichloroethylene and 30.3% by weight of HFC-365mfc having a vapor pressure of 101kPa at a temperature of 33.3 ℃;

32.9% by weight of F3i3iE, 60.2% by weight of trans-1, 2-dichloroethylene and 6.9% by weight of methanol having a vapor pressure of 101kPa at a temperature of 40.1 ℃;

41.1% by weight of F3i3iE, 56.3% by weight of trans-1, 2-dichloroethylene and 2.6% by weight of ethanol having a vapor pressure of 101kPa at a temperature of 43.8 ℃;

62.2% by weight of F13E, 34.7% by weight of trans-1, 2-dichloroethylene and 3.1% by weight of methanol having a vapor pressure of 101kPa at a temperature of 34.5 ℃;

48.0% by weight of F13E, 33.2% by weight of trans-1, 2-dichloroethylene and 18.8% by weight of HFC-43-10mee having a vapor pressure of 101kPa at a temperature of 36.1 ℃;

23.1% by weight of F13E, 30.3% by weight of trans-1, 2-dichloroethylene and 46.6% by weight of HFC-365mfc having a vapor pressure of 101kPa at a temperature of 34.4 ℃.

3. The composition of claim 1 or 2, further comprising an aerosol propellant.

4. The composition of claim 3 wherein said aerosol propellant is selected from the group consisting of air, nitrogen, carbon dioxide, difluoromethane, trifluoromethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, heptafluoropropane, and pentafluoropropane.

5. A method for cleaning, comprising:

a) contacting a surface comprising a residue with a composition according to claim 1 or 2, and

b) recovering the surface from the composition.

6. The process of claim 5, wherein the residue comprises oil.

7. The method of claim 5, wherein the residue comprises rosin flux.

8. The method of claim 5, wherein the surface is an integrated circuit device.