EP3129165A1 - Compositions, procédés, dispositifs et systèmes de dégraissage et de défluxage en phase vapeur de solvant - Google Patents

Compositions, procédés, dispositifs et systèmes de dégraissage et de défluxage en phase vapeur de solvant

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Publication number
EP3129165A1
EP3129165A1 EP15777203.9A EP15777203A EP3129165A1 EP 3129165 A1 EP3129165 A1 EP 3129165A1 EP 15777203 A EP15777203 A EP 15777203A EP 3129165 A1 EP3129165 A1 EP 3129165A1
Authority
EP
European Patent Office
Prior art keywords
component
weight percent
composition
azeotrope
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15777203.9A
Other languages
German (de)
English (en)
Other versions
EP3129165A4 (fr
Inventor
Rajat S. Basu
Ryan Hulse
Jeffrey BEARD
Carlos Roberto CEDENO
Hannelore RITTINGER
Eric Borgstedt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell International Inc
Original Assignee
Honeywell International Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US14/678,322 external-priority patent/US20150290686A1/en
Application filed by Honeywell International Inc filed Critical Honeywell International Inc
Publication of EP3129165A1 publication Critical patent/EP3129165A1/fr
Publication of EP3129165A4 publication Critical patent/EP3129165A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5018—Halogenated solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5022—Organic solvents containing oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5027—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5036—Azeotropic mixtures containing halogenated solvents
    • C11D7/5068—Mixtures of halogenated and non-halogenated solvents
    • C11D7/5077—Mixtures of only oxygen-containing solvents
    • C11D7/5081—Mixtures of only oxygen-containing solvents the oxygen-containing solvents being alcohols only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
    • C23G5/02809—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons containing chlorine and fluorine
    • C23G5/02812—Perhalogenated hydrocarbons
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/26—Cleaning or polishing of the conductive pattern
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/46—Specific cleaning or washing processes applying energy, e.g. irradiation
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/24—Hydrocarbons
    • C11D7/248—Terpenes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/263—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/28—Organic compounds containing halogen
    • C11D7/30—Halogenated hydrocarbons
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3489—Composition of fluxes; Methods of application thereof; Other methods of activating the contact surfaces

Definitions

  • the present invention relates, generally, to compositions, particularly solvent or cleaning compositions, for vapor phase degreasing and defluxing of substrate materials, and to solvent cleaning methods, devices and systems .
  • Solvent vapor phase degreasing and defluxing is a process of immersing a soiled substrate (e.g., a printed circuit board or a fabricated metal, glass, ceramic, plastic, or elastomer part or composite) into a boiling liquid such as certain chlorocarbon or chlorofluorocarbon fluids or admixtures, followed by rinsing the part in a second tank or cleaning zone by immersion or distillate spray with a clean solvent which is the same chlorocarbon or chlorofluorocarbon as used in the first cleaning zone.
  • the parts are then dried by maintaining the cooled part in the condensing vapors until temperature has reached equilibrium.
  • Solvent cleaning of various types of parts generally occurs in batch, hoist-assisted batch, conveyor batch, or in-line type conveyor degreaser and defluxer equipment.
  • Such in-line conveyor degreaser and defluxer equipment are disclosed in U.S. Pat, No. 5,007, 179 (entitled “Cold Air Lock Vapor Seal"), commonly assigned to the assignee of the present invention.
  • Parts may also be cleaned in open top clefluxing or degreasing equipment, such as that disclosed in U.S. patent application Ser. No. 07/587,893, filed Sep. 25, 1990, now U.S. Fat. No. 5,075,982, also commonly assigned.
  • the entrance and/or exit ends of the equipment are generally in open communication with both the ambient environment and the solvent within the equipment.
  • a common practice in the art is to use water-cooled or refrigerant-cooled coils which create a vapor blanket over a hot or ambient zone region in the degreaser/def!uxer tank, such as disclosed in U.S. Pat. No. 4,261 ,111 to Rand, which is incorporated herein by reference.
  • hydrochlorofiuorocarbon (HCFC) based solvents have been developed to provide more environmentally acceptable alternatives to CFC based vapor phase degreasing and deftuxing processes. While these materials have been shown to be excellent substitutes for previously used CFC materials in a variety of cleaning
  • perfluorinated, saturated hydrocarbons and hydrofluorocarbons are known to possess many desirable solvent properties, such as : zero ozone depletion potential; stable, non-reactive, high compatibility with plastics; good water displacement potential; generally non-toxic and inert, and ideally suited to vapor phase solvent cleaning equipment.
  • solvent properties such as : zero ozone depletion potential; stable, non-reactive, high compatibility with plastics; good water displacement potential; generally non-toxic and inert, and ideally suited to vapor phase solvent cleaning equipment.
  • peril uorocarbons have been found to be very poor solvents for many common organic and inorganic soils, e.g., fluxes. While certain
  • hydrofluorocarbons may offer improved but still limited cleaning ability over perfiuorocarbons, it has been a concern that such materials will to exhibit undesirable tlammability properties comparable to their hydrocarbon analogs,
  • European Patent Publication 0 431 458 published Jun. 12, 1991 teaches aliphatic hydrofluorocarbons of the formula CnF m H2n+2-m wherein 4 ⁇ n ⁇ 6 and 6 ⁇ m ⁇ 12 which are useful as cleaning compositions.
  • the reference teaches that the aliphatic hydrofluorocarbon is the a ctive component in the removal of the fluxes, fats and oils, and dust from soiled parts.
  • an organic solvent selected from hydrocarbons, alcohols, esters, and ketones may be added in various amounts to the aliphatic hydrofluorocarbon.
  • Aqueous cleaning generally involves the cleaning of a substrate or a part in an aqueous solution of detergents or surfactants, followed by multiple rinsing steps with purified water. The part is then dried by lengthy evaporation in air or by energy intensive thermal drying machines. This process is not always desirable due to the high energy cost for drying and the additional capital investment and operating cost burden to provide aqueous waste water cleanup required by state and local authorities before sewering to ground water.
  • Another cleaning process semi-aqueous cleaning, consists of cleaning a substrate in a hydrocarbon solvent based on, for example, terpenes, esters, or petroleum distillates having a high affinity for oils, waxes, and greases being cleaned from the parts, with or without the aid of a surfactant.
  • the cleaned substrate is rinsed in the high boiling hydrocarbon solvent with multiple rinsing steps using purified water.
  • the hydrocarbon solvent is phase separated back to the wash sump while the aqueous effluent must be processed before sewering to ground water. Consequently, high costs associated with drying energy and with processing waste effluent are evident, similar to the before-mentioned aqueous cleaning process.
  • a further drawback is that the hydrocarbon solvent usually possesses a flash point and this must be carefully handled or blanketed with a nonflammable compressed gas such as nitrogen to avoid explosion. Nitrogen gas is much more fugiti ve than the dense vapors of a fluorocarbon contained in a condensing zone. Furthermore, in a number of applications, while the substrate to be cleaned may be compatible with the hydrocarbon solvent, some plastics or metals may be incompatible with the aqueous rinse solvent, resulting in water absorption or rusting of the substrate.
  • solvent cl eaning compositions include (a.) a first component comprising an alcohol selected from the group consisting of methanol, ethanoi and isopropanol, (b) a second component selected from the group consisting of a glycol ether, a terpene, a halogenated hydrocarbon, and combinations thereof, and (c) a third component selected from the group consisting of a hydro fluorocarbon (other than the halogenated hydrocarbon second component), a hydrohaloether, a decahalopentane, and combinations thereof, wherein the second and third components are not the same.
  • the third component is provided in an amount effective to form an azeotrope or azeotrope-like composition with at least one alcohol of the first component.
  • the second component (b) includes a halogenated hydrocarbon, which preferably is provided in the relative amounts described herein.
  • the halogenated hydrocarbon preferably includes compounds comprised of from, one (1) to ten (10) carbon atoms, preferably comprising or in some embodiments consisting of Ci to Cg alkyl groups, Ci to Cg alkenyl groups, Ci to Cg alcohol groups, Ci to Cio ethers, and C5 to C7 cyclic alkenyl groups, which compounds are substituted with at, least one halogen selected from F, C!, Br, or I.
  • the halogenated hydrocarbon preferably includes compounds comprised of from, one (1) to ten (10) carbon atoms, preferably comprising or in some embodiments consisting of Ci to Cg alkyl groups, Ci to Cg alkenyl groups, Ci to Cg alcohol groups, Ci to Cio ethers, and C5 to C7 cyclic alkenyl groups, which compounds are substituted with at, least one halogen selected from F, C
  • the halogenated hydrocarbon comprises, consists essentially of or consists of trans- 1 ,2- dichloroethylene, perchloroethylene, trichloroethylene, and combinations thereof.
  • the second component (b) includes a glycol ether, which preferably is provided in the amounts described herein.
  • the glycol ether in preferred embodimenst includes the structure R'O-R-OR', where R is selected from a C] to Cg alkyl group, a C-. to Cg alkenyl group, a Cj to Cg alcohol group, a C ⁇ to C 10 ether group, a C5 to C 7 cyclic alkyl group, a C5 to C 7 cyclic alkenyl group, a C5 to C? heterocyclic alkyl group, and a. C 5 to C 7 heterocyclic alkenyl group, and each R' is selected from a C] to Cg alkyl group, a C-. to Cg alkenyl group, a Cj to Cg alcohol group, a C ⁇ to C 10 ether group, a C5 to C 7 cyclic alkyl group, a C5 to C 7 cyclic alkenyl group
  • R is a C 1 -C4 alkyl group.
  • the glycol ether is a compound according to the structure R'-0-(CH 2 ) 2 -0-R', where at least one R' is H and the other R' is selected from the group consisting of a C j to Cg alkyl group, a C3 ⁇ 4 to Cg alkenyl group, a Ci to Cg alcohol group, a C3 ⁇ 4 to C 10 ether, and a C 5 to C- cyclic alkenyl group.
  • the glycol ether is selected from the group consisting of ethylene glycol monobutyl ether, 2-etboxyethanol, 2-methoxyethanol, 2-propxyethanol, 2-phenoxyethanol, 2- benzoxy ethanol, methyl carbitol, carbitol cellosolve, diethoxyethane, dimethoxyethane, dibutoxybutane, dipropylene glycol methyl ether, dipropylene glycol mono n-butyl ether, dipropylene glycol monomethyl ether acetate, propylene glycol mononiethyl ether, propylene glycol mononiethyl ether acetate, and/or propylene glycol phenyl ether.
  • the second component includes a terpene, which is preferably provided in the amounts disclosed herein. While the terpene may be any of or combination of terpenes provided herein, in certain aspects the terpene comprises, consists essentially of or consisits of s d-Limonene and/or pinene.
  • the third component preferably comprises a hydrohaioether.
  • the hydrohaioether has the structure R-O-R', wherein R and R' are each independently selected from the group consisting of a Cj to C20 alkyl group, C] to C?o alkenyl group, Ci to C?o alcohol group, Cj to C?o ether group, C5 to C 7 cyclic alkyl group, C>, to C 7 cyclic alkenyl group, C5 to C 7 heterocyclic alkyl group, and C5 to C- heterocyclic alkenyl group, where at least one of R and/or R' is substituted at one or more positions with a halogen atom.
  • the hydrohaioether is a. hydrofluoroether, wherein in certain embodiments it has or includes the structure CH 2 OCF 2 CF 2 CF 2 CF 3 .
  • the third component, including and preferably the hydrohaloether component is present in the composition in an amount from about 25 weight percent to about 99 weight percent, in certain embodiments, in an amount from about 50 weight percent to about 99 weight percent, in certain embodiments in an amount from about 75 weight percent to about 99 weight percent, in certain embodiments in an amount from about 90 weight percent to about 99 weight percent, and in certain embodiments in an amount from about 92 weight percent to about 96 weight percent, based on the total of components (a), (b) and (c) of the composition.
  • the third component preferably includes a decahalopentane, which in certain preferred embodiments is a decafluoropentane.
  • the decafiuoropentane in preferred embodiments comprises, consists essentially of or is selected from the group consisting of 1 ,1 ,1 , 2,3,4,4,5,5 ,5-decafj.uoropentane, 1 ,1,1 ,2,2,3,4,5,5,5-decafluoropentane, and/or 1 ,1,1 ,2,3,3,4,5, 5,5-decafluoropentane.
  • the decahalopentane is preferably provided in an amount from about 30 weight percent to about 99 weight percent, in certain embodiments, in an amount from about 50 weight percent to about 99 weight percent, in certain embodiments in an amount from about 70 weight percent to about 99 weight percent, in certain embodiments in an amount from about 90 weight percent to about 99 weight percent, and in certain embodiments in an amount from about 92 weight percent to about 96 weight percent, based on the total of components (a), (b) and (c) of the composition.
  • solvent cleaning compositions include (i) l-chloro-3,3,3-trifluorpropene and (ii) at least one second component that is the same as the second component of the first aspect and is present in the same concentration as described in connection with the irst aspect, in certain embodiments of this second aspect, component (i) comprises an azeotrope or azeotrope-like composition consisting essentially of l-chloro-3,3,3-trifluorpropene and an alcohol selected from the group consisting of methanol, ethanol and isopropanol, and in such embodiments it is preferred that the components (i) and (ii) do not form a separate azeotrope.
  • compositions of the present invention may be used in sprayable compositions, solvents, or aerosols.
  • such compositions may be used in methods for removing residual soils or surface contamination from a part.
  • Such a method may include immersing the part in a solvent, composition of the present invention. .
  • the part is then preferably dried within the flammability-suppression blanket.
  • flammability-suppression blanket means a vapor space that contains gases which have no flame limit as measured according to ASTM E-681 -09, which is incorporated herein by reference.
  • the second component may have a boiling point that is at least 10 °C higher, in certain aspects at least 25 °C higher, and in further aspects at least 50 °C higher than: ( 1) in the case of the first aspect, the first and third components (a) and (c) and/or any azeotrope or azeotrope-like compositions formed therebetween; and (2) in the case of the second aspect component (i), namely the 1 -chloro- 3,3,3-trifluoropropene and/or any azeotrope or azeotrope-like compositions formed between 1- chloro-3,3,3-trifluoropropene and an alcohol if present (particularly methanol, ethanol, and isopropanol).
  • Figure 1 illustrates a partial schematic view of degreasing or defluxiiig equipment that may be used in one embodiment of the present invention.
  • the preferred compositions include (a) a first component consisting essentially of or consisting of or more alcohols, (b) a second component selected from the group consisting a glycol ether, a terpene, and/or a halgenated hydrocarbon5 (other than a decahalopentane), and (c) a third component selected from the group consisting a hydroiiuorocarbon, a halogenated ether and/or a decahalopentane, wherein the second (b) and third components (b) are not the same.
  • the second component(s) (b) is a solvent that has a boiling point that is greater than that of either the first (a) or third (c) components.
  • the second component (b) does not form an azeotrope or0 azeotrope-like composition (or is provided in amounts to not form an azeotrope or azeotrope- like composition) with either or both of the first (a) and third (c) components.
  • the compositions particularly solvent or cleaning compositions, preferably include a first component of l-chloro-3,3,3-trifluoropropene (HCFO-1233zd) alone or as an azeotrope or azeotrope-like composition with an alcohol, and a second component (b) as described herein in connection with the first aspect.
  • HCFO-1233zd l-chloro-3,3,3-trifluoropropene
  • the second component (b) is a solvent that has a boiling point that is greater than that of the HCFO-1233zd included in the composition, whether cis or trans isomers or combinations thereof, or any azeotropic or azeotrope-like composition that forms between HCFO-1233zd and the alcohol(s) as described herein.
  • the second component (b) does not form an azeotrope or azeotrope-like composition (or is provided in amounts to not form an azeotrope or azeotrope-like composition) with HCFO ⁇ 1233zd and/or the alcohol.
  • compositions of the invention are advantageous, inter alia, as solvents for the removal of unwanted debris from a substrate, such as the removal of solder flux or other residue from printed circuit boards or petroleum, synthetic or semi-snythetic based oil or grease from a metallic or nonmetallic part.
  • such compositions are advantageous for use in vapor degreasing machines (particularly multi-sump machines), as a cold cleaner or as a spray, e.g. an aerosol spray.
  • HCFO-1233zd refers to the compound l-chloro-3,3,3-trifluoropropene, independent of whether it is the cis- or trans-form.
  • cis-HCFO-1233zd and trans- HCFO-1233zd are used to describe the cis- and trans-forms of l-chloro-3,3,3-trifluoropropene, respectively.
  • HCFO-1233zd therefore includes within its scope cis-HFCO- 1233zd, trans-HCFO-1233zd, and all combinations and mixtures of these.
  • cis-HCFO-1233zd means that the amount cis-HCFO- 1233zd relative to all isomers of HCFO-1233zd is at least about 95 %, more preferably at least about 98 %, even more preferably at least about 99 %, even more preferably at least about 99.9 %.
  • the cis-HCFO- 1233zd component is essentially pure eis-HCFO- 1233zd.
  • trans-HCFO- 1233zd means that the amount of trans-HCFO- 1233zd relative to all isomers of HCFO-1233zd is at least about 95 %, more preferably at least about 98%, even more preferably at, least about 99 %, even more preferably at least about 99.9 %.
  • the trans-HCFO- 1233zd component is essentially pure trans- HCFO- 1233zd.
  • the alcohol may refer to any component having an alcohol group attached thereto.
  • the alcohols include a C .-C) alcohol, and in certain preferred embodiments the alcohol comprises at least one of methanol, ethanol, or isopropanol.
  • glycol ether refers to compounds a class of solvents based on alky] ethers of an alkylene glycol. In certain non-limiting aspects, it may be represented by Formula I having the structure R'O-R-OR', where R is selected from a C
  • heterocyclic aikyl group or C5 to C 7 heterocyclic alkenyl group, where any of the foregoing (if applicable) may be straight or branch chained and may be optionally substituted at one or more positions.
  • Each R' is independently selected from an H, a C ⁇ to Cg aikyl group, a Cj to Cg alkenyl group, a C-.
  • At least one R' is not an H.
  • R is a C]-Ce straight or branch chained alkyl moiety and forms an aikylene glycol of an alkyl ether.
  • R is a ( * . ⁇ -( ' ; straight or branch chained alkyl moiety.
  • R is an ethyl moiety and forms an aikylene glycol of an ethylene ether and having the structure R'-O- (CH 2 ) 2 -0-R ⁇ Each R' may be defined as indicated above.
  • it includes at least one Ci to Cg alkyl group, Cj to Cg alkenyl group, d to Cg alcohol group, C ⁇ to C 10 ether, or C5 to C 7 cyclic alkenyl group, any of which may be straight or branched chained (if applicable) and/or optionally substituted at one or more positions.
  • At least one R' is H and the second R' includes at least one Cj to Cg alkyl group, Ci to Cg alkenyl group, Q to Cg alcohol group, C-. to C 10 ether, or C 5 to C 7 cyclic alkenyl group, any of which may be straight or branched chained or optionally substituted at one or more positions.
  • the glycol ether is selected from one or a combination of the following: ethylene glycol mono butyl ether (also called “butyl celiosolve”), 2-ethoxy ethanol (also known as “ethyl celiosolve”), 2-methoxyethanol, 2-propoxyethanol, 2- phenoxyethanol, 2-benzoxy ethanol, methyl carbitol, 2-(2-ethoxyethoxy)ethanol (also known as “carbitol celiosolve”), diethoxyethane, dimethoxyethane, dibutoxybutane, dipropylene glycol methyl ether, dipropylene glycol mono n- butyl ether, dipropylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and/or propylene glycol phenyl ether.
  • ethylene glycol mono butyl ether also called “butyl celiosolve”
  • 2-ethoxy ethanol also
  • the term "terpene” means a compound, which is comprised of at least ten carbon atoms and contains at least one, and preferably at least two isoprene moieties.
  • isoprene moiety refers to any portion of a molecule, which includes a radical, which can be formed from substituted or unsubstituted isoprene. In certain preferred embodiments, unsubstituted terpenes are preferred.
  • the terpene compound of the present invention comprises at least one head- to-tail condensation product of modified or unmodified isoprene molecules. It, is contemplated that any one or more terpene compounds are adaptable for use in accordance with the present invention and that those skilled in the art will be able, in view of the teachings contained herein, to sel ect the number and type of terpene compound(s) for any particular application without undue experimentation.
  • the preferred terpenes of the present invention are hydrocarbons having molecular formula (CsHs) G in a cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted structure, with n preferably being from 2 to about 6, and even more preferably 2 to 4.
  • CsHs molecular formula
  • Terpenes according to the present invention having the formula C 10 H 16 (including substituted forms) are sometimes referred to herein as monoterpenes, while terpenes having the formula C]sH 24 (including substituted forms) are sometimes referred to herein as sesquiterpenes.
  • Terpenes according to the present invention having the formula C 20 H 32 are sometimes referred to herein as diterpenes, while terpenes having the formula ( . ' :.;! S ⁇ : (including substituted forms) are sometimes referred to as triterpenes, and so on.
  • Terpenes containing 30 or more carbons are usually formed by the fusion of two terpene precursors in a regular pattern. While it is contemplated that all such terpenes are adaptable for use in accordance with the present invention, the use of
  • the terpene compound(s) of present compositions comprise, preferably in major proportion, and even more preferably consist essentially of, one or more acyclic terpene compounds.
  • acyclic terpene compounds it is contemplated that such compounds may be within the class of compounds identified as head-to-tail linked isoprenoids or within the class of compounds that are not joined in that manner.
  • Acyclic terpenes which are preferred for use in accordance with certain aspects of the present invention include myrcene (2-methyl-6-methyleneocta- 1 ,7-diene), allo-cimene, beta-ocimene.
  • the terpene compounds of the present invention may comprise cyclic terpene compounds.
  • cyclic terpenes mono-, bi ⁇ , tri-, or tetracyclic compounds having varying degrees of unsaturation are contemplated for use in accordance with the present invention.
  • the terpene is a cyclic terpene compound having the formula l-methyl-4-isopropenyl-l-cyclohexene also called "d- Limonene," which has the following structure.
  • the terpene is a cyclic terpene compound comprising pinene, which may have the following chemical structure:
  • terpene derivatives in accordance with the present invention include oxygen-containing derivatives of terpenes such as alcohols, aldehydes or ketones containing hydroxy! groups or carbonyl groups, as well as hydrogenated derivates. Oxygen-containing derivatives of terpenes are sometimes referred to herein as terpenoids.
  • the diene -based compounds of the present invention comprise the terpenoid Carnosic acid.
  • Carnosic acid is a phenolic diterpene that corresponds to the empirical formula C20H28O4. it occurs naturally in plants of the Libiatae family.
  • carnosic acid is a constituent of the species Salvia officinalis (sage) and Rosmarinus officinalis (rosemary) where it is mainly found in the leaves. Carnosic acid is also found in thyme and marjoram (see Linde in Salvia officinalis [Helv. Chim Acta 47, 1234 (1962)] and Wenkert et al. in Rosmarinus officinalis [J. Org. Chem. 30, 2931 (1965)], and in various other species of sage, (see Salvia canadensis [Savona and Bruno, J. Nat. Prod. 46, 594 (1983)] and Salvia willeana [de la Torre et al, Photochemistry 29, 668 (1990)]). It is also present in Salvia triloba and Salvia sclarea. Other potential terpenoids are illustrated below:
  • halogenated hydrocarbons refers to a hydrocarbon chain or ring where at least one position is substituted with a halogen atom.
  • the hydrocarbon chain may include a Q to C 20 alkyl group, a C. to C 20 alkenyl group, a Ci to C 20 alcohol group, a Ci to C 20 ether, a C 5 to C7 cyclic alkenyl group, a C5 to C 7 heterocyclic alkyl group, or C 5 to C 7 heterocyclic alkenyl group, any of which may be straight or branched chained (if applicable) and'or optionally substituted at one or more positions.
  • it includes a Cj to C 8 alkyl group, a C-.
  • the hydrocarbon is preferably substituted with at least one halogen selected from F, CI, Br, or I.
  • the halogenated hydrocarbon is a Cj to C5 alkyl group or a C>. to C5 alkenyl group. In further embodiments, it is a C 2 alkenyl group that contains at least one chlorine atom.
  • Non- limiting examples of such solvents include, trans- 1,2-dichIoroethylene, perehloroethylene, trichloroethylene, and combinations thereof.
  • the halogenated hydrocarbon used as the second component does not include a decahalopentane, particularly a decafluoropentane.
  • halogentated hydrocarbon are applicable equally to the hydrofiuorooiefin of component (c), provided that at least on F substituent is present in the compound.
  • a hydrohaloether refers to a class of solvents having the structure R-O- R ⁇ R and R' may be independently is selected from, a CI to C20 alkyl group, CI to C20 alkenyl group, Ci to C20 alcohol group, CI to C20 ether group, C5 to C7 cyclic alkyl group, C5 to C7 cyclic alkenyl group, C5 to C7 heterocyclic alkyl group, or C5 to C7 heterocyclic alkenyl group, where any of the foregoing (if applicable) may be straight or branch chained and at least one group is substituted at one or more positions with a halogen atom.
  • the hydrohaloether is a hydrofluoroefher, which may include monomic or polymerized structures in accordance with the foregoing, where one or more of the R or R' substituent groups is substituted with a fluorine atom.
  • the hydrofluoroether includes at least one nonafluoro alky! ether, wherein the alkyl may include 1 -10 carbon atoms.
  • the nonafluoro alkyl ether includes a nonafluor butyl ether and/or a nonafluoro isobutyl ether, including, but not limited to, those commercially available under the tradename OVEC®, particularly though not exclusively NOVEC® 7200(available from 3M).
  • the hydrohaloether has or otherwise includes the following structure CH30CF2CF2CF2CF3 ⁇ - ⁇ - (CF3)2CFCF20CH3, CH30CF2CF2CF3 or any combination of these with trans- 1,2-dichloroethylene.
  • a "decahalopentane” means a five carbon alkyi chain substituted with 10 halogen atoms, which may be selected from F, CI, Br, or I. In certain preferred
  • the decahalopentane is a decafluoropentane.
  • Non-limiting examples of such a. compound include 1 ,1,1 ,2,3,4,4,5,5, 5-decafluoropentane, 1 ,1,1 ,2,2, 3,4,5, 5,5-deeafluoropentane, and/or 1, 1,1,2,3,3,4,5,5, 5-decafluoropentane.
  • the decahalopentane or decafluoropentane includes at least one such compound commercially available under the tradename VERTREL® (available from DuPoiit), including, but not limited to, VERTREL SFR and/or VERTREL XV. COMPONENT AMOUNTS
  • the alcohol(s) provided in the first component (a) or as part of component (i) are preferably collectively provided in an amount from greater than about 0 weight percent to about 15 weight percent, based on the total weight of the composition. In certain aspects, the alcohol(s) is provided in an amount from about 0.01 weight percent to about 10 weight percent, based on the total weight of the composition. In certain preferred embodiments, the
  • the second component (h), including particularly glycol ether, when used in the second component (b), is preferably provided in an amount from greater than about 0 weight percent to about 30 weight percent, ba sed on the total weight of the composition.
  • the second component, including particularly glycol ether is provided in an amount from about 0.01 weight percent to about 25 weight percent, based on the total weight of the composition.
  • the second component, including particularly glycol ether is provided in an amount from about 1 weight percent to about 20 weight percent, based on the total weight of the
  • glycol ether when present glycol ether is preferably provided in an amount from about 0.01 weight percent to about 30 weight percent, more preferably from about 0.05 weight percent to about 10 weight percent, and even more preferably from about 1 weight percent to about 5 weight percent based on the total weight of the composition.
  • component (i) is preferably provided in amounts from about 70 weight percent to about 99.99 weight percent, more preferably from about 90 weight percent to about 99.95 weight percent, and even more preferably from about 95 weight percent to about 99 weight percent, based on the total weight of the composition
  • the second component (b) comprises a terpene
  • it is preferably provided in an amount from greater than about 0 weight percent to about 30 weight percent, based on the total weight of the composition.
  • the terpene is provided in an amount from about 0.01 weight percent to about 25 weight percent, based on the total weight of the composition.
  • the terpene is provided in an amount from about 1 weight percent to about 20 weight percent, based on the total weight of the composition.
  • component (i) when present terpene(s) is preferably provided in an amount from about 0.01 weight percent to about 30 weight percent, more preferably from about 0.05 weight percent to about 10 weight percent, and even more preferably from about 1 weight percent to about 5 weight percent based on the total weight of the composition.
  • component (i) is preferably provided in amounts from about 70 weight percent to about, 99.99 weight percent, more preferably from about, 90 weight percent, to about 99.95 weight percent, and even more preferably from about 95 weight percent to about 99 weight percent, based on the total weight of the composition
  • the second component (b) comprises a halogenated hydrocarbon
  • it may be provided in an amount from greater than about 0 weight percent to about 50 weight percent, from about 0.05 weight percent to about 40 weight percent, or from about 1 weight percent to about 30 weight percent, based on the total weight of the composition.
  • volving component (i) when present halogenated hydrocarbon is preferably provided in an amount from about 0.01 weight percent to about 95 weight percent, more preferably from about 0.01 weight percent to about 80 weight percent, and even more preferably from about 1 weight percent to about 50 weight percent, and in certain embodiments from about 1 weight percent to about 30 weight percent based on the total weight of the composition.
  • component (i) is preferably provided in amounts from about 5 weight percent to about 99.99 weight percent, more preferably from about 20 weight percent to about 99.99 weight percent, and even more preferably from about 50 weight percent to about 99 weight percent, based on the total weight of the composition.
  • the second component (h) is trans- 1,2-didiloroethylene
  • it is preferably provided in an any amount from about 1 to about 99%, from greater than about 5 weight percent to about 50 weight percent, from about 6 weight percent to about 30 weight percent, and in certain embodiments from about 6 weight percent to about 20 weight percent, based on the total weight of the composition.
  • the trans- 1 ,2- dichloroethylene is provided in an amount from about 6 weight percent to about 35 weight percent, based on the total weight of the composition.
  • trans- 1 ,2,- dichloroethylene when present trans- 1 ,2,- dichloroethylene is preferably provided in an amount from about 5 weight percent to about, 95 weight percent, more preferably from about 6 weight, percent to about 95 weight percent, and even more preferably from about 6 weight, percent to about 80 weight percent, even more preferably in certain embodiments from about 6 weight percent, to about 50 weight percent, and in certain embodiments from about 6 weight percent to about 25 weight percent, based on the total weight of the composition.
  • component (i) is preferably provided in amounts from about 5 weight percent to about 95 weight percent, more preferably from about 5 weight percent to about 94 weight percent, even more preferably from about 20 weight percent to about 94 weight percent, and in certain embodiments from about 50 weight percent to about 94 weight percent, based on the total weight of the composition.
  • such third components (c) are provided in an amount from greater than 0.01 weight percent to about 99 weight percent, based on the total weight of the composition.
  • the third component is provided in an amount from about 25 weight percent to about 99 w r eight percent, or in certain embodiments from about 20 w r eight percent to about 99 weight percent, based on the total weight of the composition.
  • the third component (c) is provided in an amount from about 50 weight percent to about 99 weight percent, based on the total weight of the composition.
  • the third component is provided in an amount from about 70 weight percent to about 99 weight percent, or the third component is provided in an amount from about 75 weight percent to about 99 weight percent, based on the total weight of the composition.
  • the third component is provided in an amount from about 90 weight percent to about 99 weight percent, and in certain embodiments the third component is provided in an amount, from about 92 weight percent to about 96 weight percent, based on the total weight of the composition.
  • the first component (a) and third components (c) form azeotrope-like compositions, or the first component (i) comprises an azeotrope or azeotrope- like composition.
  • azeotrope-like relates io compositions that are strictly azeolropic or that generally behave like azeoiropic mixtures.
  • An azeotropie mixture is a system of two or more components in which the liquid composition and vapor composition are equal at die stated pressure and temperature. In practice, this means that, the components of an azeotropie mixture are constant-boiling or essentially constant-boiling and generally cannot be thermodynamically separated during a phase change.
  • the vapor composition formed by boiling or evaporation of an azeotropie mixture is identical, or substantially identical, to the original liquid composition.
  • concentration of components in the liquid and vapor phases of azeotrope-like compositions change only minimally, if at ail, as the composition boils or otherwise evaporates.
  • boiling or evaporating non-azeotropic mixtures changes the component concentrations in the liquid phase to a significant degree.
  • the term "consisting essentially of,” with respect to the components of an azeotrope-like composition means the composition contains the indicated components in an azeotrope-like ratio, and may contain additional components provided that the additional components do not form new azeotrope-like systems.
  • azeotrope-like mixtures consisting essentially of two compounds are those that form binary azeotropes, which optionally may include one or more additional components, provided that the additional components do not render the mixture non-azeotropic and do not form an azeotrope with either or both of the compounds.
  • azeotropic compositions means the amount of each component which, upon combination with the other components, results in the formation of an azeotrope or azeotrope-like composition of the present invention.
  • ambient pressure with respect to boiling point data means the atmospheric pressure surrounding the relevant medium, in genera], ambient pressure is 14.7 psia, but could vary +/- 0.5 psi.
  • the azeotrope-like compositions of the present invention can be produced by combining effective amounts of HFO-.1233zd with one or more alcohols, preferably in fluid form. Any of a wide variety of methods known in the art for combining two or more components to form a composition can be adapted for use in the present methods. For example, HFO-1233zd and the alcohol can be mixed, blended, or otherwise combined by hand and/or by machine, as part of a batch or continuous reaction and/or process, or via combinations of two or more such steps. n light of the disclosure herein, those of skill in the art will be readily able to prepare azeotrope-like compositions according to the present invention without undue experimentation.
  • the azeotrope-like composition comprises effective amounts of HFO-1233zd and a CI - C3 alcohol.
  • the CI - C3 alcohol is selected from the group consisting of methanol, ethanol, and isopropanol.
  • Non-limiting examples of such azeotropes are provided in U.S. Patent No. 8,163,19(5, the contents of which are incorporated herein by reference in its entirety.
  • HFQ- 1233zd is the trans isomer.
  • the azeotrope-like composition comprises effective amounts of trans-HFO- 1233zd and methanol.
  • These binary azeotrope-like compositions may consist essentially of about 70 to about 99.95 wt. % trans-HFO- 1233zd and from about 0.05 to about 30 wt. % methanol, more preferably from about 90 to about 99.95 wt. % trans-HFO- 1233zd and about, 0.05 to about 10 wt. % methanol, and even more preferably from about 95 to about 99.95 wt. % trans-HFO- 1233zd and from about 0.05 to about, 5 wt. % methanol.
  • such trans-HFO- 1233zd/methanol compositions have a boiling point of from about 17 oC to about 19 °C, more preferably about 17 °C to about 18 oC, even more preferably about 17 °C to about 17.5 °C, and most preferably about 17.15 °C ⁇ 1 °C, all measured at ambient pressure.
  • the azeotrope-like composition comprises effective amounts of cis-HFO-1233zd and methanol.
  • These binary azeotrope-like compositions consist essentially of about 78 to about 99.9 wt. % cis-HFO-1233zd and from about 0.1 to about 22 wt. % methanol, more preferably from about 85 to about 99.9 wt. % cis-HFO-1233zd and about 0.1 to about 15 wt. % methanol, and even more preferably from about 88 to about 99.5 wt. % cis- HFO-1233zd and from about 0.5 to about 12 wt. % methanol.
  • such cis- HFO-1233zd/methanol compositions have a boiling point of about 35.2 ⁇ 1 °C at ambient pressure.
  • the azeotrope-iike composition comprises effective amounts of trans-HFO-1233zd and ethanol.
  • These binary azeotrope-like compositions may consist essentially of about 85 to about 99.9 wt. % trans-HFO-1233zd and from about 0,1 to about 15 wt. % ethanol, more preferably from about 92 to about 99.9 wt, % trans-HFO-1233zd and about 0.1 to about 8 wt. % ethanol, and even more preferably from about 96 to about 99,9 wt. % trans-HFO- 1233zd and from about 0.1 to about 4 wt. % ethanol.
  • trans-HFO- 1233zd/ethanol compositions have a normal boiling point of about 18.1 °C ⁇ 1 °C at ambient pressure.
  • the azeotrope-like composition comprises effective amounts of cis-HFO- 1233zd and ethanol.
  • These binary azeotrope-like compositions may consist essentially of about 65 to about 99.9 wt. % cis-HFO- 1233zd and from about 0, 1 to about 35 wt. % ethanol, more preferably from about 79 to about 99.9 wt, % cis-HFO- 1233zd and about 0.1 to about 21 wt. % ethanol, and even more preferably from about 88 to about 99,5 wt. % cis- HFO- 1233zd and from about 0.5 to about 12 wt. % ethanol.
  • such cis-HFO- 1233zd'ethanoi compositions have a normal boiling point of about 37.4 °C ⁇ 1 °C at ambient pressure.
  • the azeotrope-like composition comprises effective amounts of trans-HFO- 1233zd and isopropanol.
  • These binary azeotrope-like compositions may consist essentially of about 90 to about 99.9 wt. % trans-HFO- 1233zd and from about 0.1 to about 10 wt. % isopropanol, more preferably from about 94 to about 99.9 wt. % trans-HFO- 1233zd and about 0.1 to about 6 wt. % isopropanol, and even more preferably from about 95 to about 99.9 wt. % trans-HFO-1233zd and from about 0.1 to about 5 wt. % isopropanol.
  • trans-HFO-1233zd'isopropanol compositions have a normal boiling point of about 17.9 °C ⁇ 1 °C at ambient pressure.
  • the azeotrope-iike composition comprises effective amounts of cis-HFO-1233zd and isopropanol.
  • These binary azeotrope-iike compositions consist essentially of about 85 to about 99.9 wt. % cis-HFQ-1233zd and from about 0.1 to about 15 wt. % isopropanol, and even more preferably from about 90 to about 99.9 wt. % cis- HFO-1233zd and about 0.1 to about 10 wt. % isopropanol.
  • such cis-HFO- 1233zd/isopropanol compositions have a boiling point of about 38.4 ⁇ 1 °C, and even more preferably 38.4 ⁇ 0.1 at ambient pressure.
  • the second component (b) is preferably to form the compositions of the present invention.
  • the second component is a solvent, particularly a solvent capable to functioning in accordance with the methods and advantages discussed herein.
  • the solvent is capable of, at least partially, solubilizing solder flux and other residues associated with print circuit board manufacture or removal of residues (such as oils and greases) from metallic or non-metallic substrates.
  • the second component is a high boiling point solvent compound.
  • high boiling point solvent refers to solvent compounds having a boiling point that is greater than the boiling points of at least the first and third components and/or any azeotrope or azeotrope-like composition formed with such components discussed above in connection with the first aspect or, in connection with the second aspect, HCFO-1233zd (cis or trans) which is present, and/or any azeotrope or azeotrope-like composition formed with HCFO-1233zd and an alcohol (particularly methanol, ethanol, and/or isopropaiiol), , that is present.
  • the "high boiling point" compounds have a boiling point that is at least 10 "C greater than, in certain preferred embodiments at least 25 °C greater than, and in certain preferred embodiments at least 50°C or more than at least the boiling points of the first and third components and/or any azeotrope or azeotrope-like composition formed therewith, in connection with the first aspect or, in connection with the second aspect, the boiling points of HCFO-1233zd (cis or trans isomers) and/or any azeotrope or azeotrope-like composition formed with HCFO-1233zd and an alcohol (particularly methanol, ethanol, and/or isopropanol).
  • the second components (b), when present, are non-azeotropic with any of the first (a) or third (c ) components present in the composition or are provided in amounts to be non-azeotropic with respect to such components.
  • compositions of the invention exhibit characteristics that make them particularly desirable for a number of applications, including as solvents in a number of cleaning and other applications, especially for cleaning solder fluxes and also as aerosols and other sprayahle compositions.
  • GWPs global warming potentials
  • the present invention includes a. sprayable composition
  • a. sprayable composition comprising the composition described herein, an active ingredient, and, optionally, inert ingredients and/or solvents and/or aerosol propellants.
  • the compositions of this invention may be used as solvents in sprayable compositions, either alone or in combination with other known propellants.
  • the solvent composition comprises, more preferably consists essentially of, and, even more preferably, consists of the compositions of the invention.
  • the sprayable composition is an aerosol.
  • Suitable active materials to be sprayed include, without, limitation, cosmetic materials such as deodorants, perfumes, hair sprays, cleaning solvents, lubricants, insecticides as well as medicinal materials, such as anti-asthma medications.
  • cosmetic materials such as deodorants, perfumes, hair sprays, cleaning solvents, lubricants, insecticides as well as medicinal materials, such as anti-asthma medications.
  • medicinal materials is used herein in its broadest sense to include any and all materials which are, or at least are believed to be, effective in connection with therapeutic, diagnostic, pain relief, and similar treatments, and as such would include for example drugs and biologically active substances.
  • compositions described herein can be used as a solvent in cleaning various soils such as mineral oil, rosin based fluxes, silicon oils, lubricants, etc., from various substrates by wiping, vapor degreasing, or other means, in other embodiments, the compositions of the present invention are used in a vapor degreaser machine, particularly to remove solder flux and other residues from printed circuit board and/or oil- or grease-based residues from metallic or non-metallic surfaces.
  • Figure 1 provides a partial schematic illustration of one type of apparatus which can be used in such a process.
  • a vessel 5 is divided into three sumps, 10, 20, and 30 where, at least initially, the compositions described herein are provided in all of the sumps.
  • Each sump is separated by sump walls 35A and 35B, which are of differing sizes.
  • walls 35A and 35B form three sumps of differing sizes which are oriented such that fluid overflowing from sump 30 flows into sump 20 and fluid overflowing from sump 20 flows into sump 10.
  • At least sump 10 further includes a heater element 40.
  • each of sumps 10, 20, and 30 all contain the same ratio of each component to the compositions described herein.
  • the heater 40 in sump 10 heats the composition to a temperature above the boiling point of the first and third components in the case of the first aspect, or above component (i) in the case of the second aspect, but below the boiling point of the second component. This causes the first and third components
  • the coils may include groups of upper coils 50 A. and lower coils 50B.
  • Sump 30 continues to cascade over to sump 20 and finally to sump 10. In doing so, the concentration in the sumps will change such that sumps 20 and 30 contain more of the first and third components in the case of the first aspect or component (i) in the case of the second aspect, and the sump 10 contains more of the second component.
  • sump 10 provides an area where the bulk of the soil and organic cleaning agent can be washed from the substrate (e.g. printed circuit board coated with a rosin-based flux or other residue or a metallic or nonmetallic part coated with a petroleum, synthetic, or semi-synthetic based oil or grease) by either immersing into a fluid composition of the present invention and/or by placement in a spray stream 18 of the composition of the present invention, whereby the contaminated liquid drops into the sump 10 below.
  • the substrates are then rinsed in sumps 20 and 30 to clean the parts and remove the unwanted debris.
  • the parts may be dried by holding above one of the sumps, particularly sumps 20 or 30 and/or using evaporation in a known manner.
  • the parts or substrates to be cleaned may be convey ored to sump 10 and between sumps 10, 20, and 30 utilizing known conveyor or hoist means.
  • the tanks may be part of conventional or known in-line convevorized degreasing/defluxing equipment, separate open top defSuxing tanks, or open top defluxing tanks modified to contain the cleaning and rinsing tanks or sumps.
  • the parts are dried under vapor blanket or within a vapor zone 45 that is formed (at least in part) from the portion of the first and third components (alone or as an azeotrope-like composition) in the first aspect or component (i) in the case of the second aspect boiled off from sump 50.
  • this vapor zone is free of or substantially free of the second component.
  • substantially free when referred to the content of the second component in the vapor zone means that the amount of the second component present is sufficiently low so as to make the vapor composition nonflammable or to otherwise result in no substantial, or even more preferably no readily measurable, increase in the fiammability of the vapor zone compared to fiammability in the vapor zone in a case where no second component were present.
  • This vapor blanket is advantageous because it lessens or mitigates the fiammability of the third component and/or minimizes the possibility of explosion.
  • it may also include one or more additional inert materials.
  • additional inert materials may include, but are not limited to, one or more of nitrogen, carbon dioxide, perfluorocarbon, hydrofiuorocarbon, or hydrochlorocarbon.
  • the vapor zo e 45 is formed above the respective sumps 10, 20, and 30.
  • Optional cooling coils 50 of a type known in the art (such as disclosed in U.S. Pat. No.
  • 4,261,1 11 defines the uppermost extent of the vapor zone 45 to condense vapor for return of condensate to sumps 10, 20, or 30, preferably sumps 10 or 30 and most preferably sump 30.
  • concentration of the first and third components (alone or as an azeotropic composition), or component (i) in the case of the second aspect, within the vapor zone 45 may be maintained at a relatively constant concentration in the vessel 5 by either returning the vapor condensate back into the sump(s) and/or pumping fluid from sump 10 to sumps 20 and/or 30 through control with a volume or level sensing transducer (not shown).
  • the present invention is not limited to a three sump arrangement, as discussed above and illustrated in Figure 1. Rather, a two sump arrangement, a four sump arrangement is also contemplated. To this end, any number of sumps may be used in accordance with the teachings, objectives, and advantages herein.
  • the vessel 5 of Figure 1 is depicted as an open top type of defluxer or degreaser.
  • the vessel 5 in its schematic form, may also characterize an in-line type of degreaser or defluxer wherein conveyor means (not shown) may be used to successively convey the parts from sumps 10 to sumps 20 and 30.
  • Mixtures are prepared including 3 wt% of one of methanol, 92 -96 wt%
  • decafluoropentane (commercially available as Vertrel®), and 1-5 wt% of a glycol ether selected from 2-ethoxyethanol, 2-methoxyethanol, 2-propxyethanoI, 2-phenoxyethanol, 2- benzoxy ethanol, methyl carbitol, carbitol cellosolve, diethoxyethane, dimethoxyethane, and dibutoxybutane.
  • Printed circuit boards are sol dered with a number of commercial solder core wires, such as, Kester 44, Alpha reliacore 15, Alpha Energized Plus and then cleaned in the boiling solvent for 10 min and are removed and dried. These cleaned boards are found to be clean.
  • Mixtures are prepared including 3 wt% of one of methanol, 92 -96 wt%
  • hydro fluoroether (HFE) (commercially available as Novec® 7200), and 1 -5 wt% of a glycol ether selected from 2-ethoxyethanol, 2-methoxyethanol, 2-propxyethanoi, 2-phenoxyethanoi, 2-benzoxy ethanol, methyl carbitol, carbitol cellosolve, diethoxyethane, dimethoxyethane, and dibutoxybutane.
  • Printed circuit boards are soldered with a number of commercial solder core wires, such as, Kester 44, Alpha reliacore 15, Alpha Energized Plus and then cleaned in the boiling solvent for 10 min and are removed and dried. These cleaned boards are found to be clean.
  • Mixtures were prepared including 3 wt% methanol, 6-25 wt% tr-l,2-dichloroethyiene, and 72- 92 wt% tr-1233zd.
  • Printed circuit boards were soldered with a number of commercial solder core wires, such as, Kester 44, Alpha reliacore 15, Alpha Energized Plus and then cleaned in the boiling solvent for 10 min and was removed and dried. These cleaned boards were the visually observed for cleanliness. The boards were found to be clean.
  • Example 2 Mixtures were prepared including 3 wt% methanol, 1-5 wt% butyl cellosolve, and 92 -96 wt% tr-1233zd.
  • Printed circuit boards were soldered with a number of commercial solder core wires, such as, Kester 44, Alpha reliacore 15, Alpha Energized Plus and then cleaned in the boiling solvent for 10 min and was removed and dried. These cleaned boards were the visually observed for cleanliness. The boards were found to be clean.
  • a mixture was prepared including 3 wt% methanol, 1-5 wt% d-limoiiene, and 92 -96 wt% tr- 1233zd.
  • Printed circuit boards were soldered with a number of commercial solder core wires, such as, Kester 44, Alpha reliacore 15, Alpha Energized Plus and then cleaned in the boiling solvent for 10 min and was removed and dried. These cleaned boards were the visually observed for cleanliness. The boards were found to be clean.
  • Mixtures is prepared including 3 wt% methanol, 70-90 wt% tr-1 ,2-dichloroethylene, and 10-30 wt% tr-1233zd.
  • Printed circuit boards are soldered with a number of commercial solder fluxes, such as, Kester 1544, Kester 197, Kester 186 and Hygrade 209 and then cleaned in the boiling solvent for 10 min and is removed and dried. ' These cleaned boards are then visually observed for cleanliness. The boards were found to be clean.
  • Mixtures were prepared including 3 wt% methanol, 1-5 wt% butyl cellosolve, and 92-96 wt% tr-1233zd.
  • Printed circuit boards were soldered with a number of commercial solder fluxes, such as, Kester 1544, Kester 197, Kester 186 and Hygrade 209 and then cleaned in the boiling solvent for 10 min and was removed and dried. These cleaned boards were the visually observed for cleanliness. The boards were found to be clean.
  • Mixtures were prepared including 3 wt% methanol, 1-5 wt% d-limonene, and 92-96 wt% tr- 1233zd.
  • Printed circuit boards were soldered with a number of commercial solder fluxes, such as, Kester 1544, Kester 197, Kester 186 and Hygrade 209 and then cleaned in the boiling solvent for 10 min and was removed and dried. These cleaned boards were the visually observed for cleanliness. The boards were found to be clean.
  • solder pastes such as, Indium SMQ55 AC, Alpha 390, Indium NC-SMQ92J.
  • solder pastes were applied using squeegee through a stencil on the board and then heated to 45 OF in a hot air knife. They were then cleaned in the boiling solvent for 10 min and was removed and dried. These cleaned boards were the visually observed for cleanliness. The boards were found to be clean.
  • an aerosol valve is crimped into pla ce and HFC- 134a is added through the valve to achieve a pressure in the can of about 20 PSIG.
  • Printed circuit boards are soldered with Kester 1544 flux, Kester 44, Alpha Reliacore 15 and Alpha Energized Plus solder core wires. The mixture is then sprayed onto surface to demonstrate whether the mixture is useful as an aerosol.
  • the aerosols have a different co-aerosol agent or no co-aerosol agent, and optionally have at least one active ingredient selected from the group consisting of deodorants, perfumes, hair sprays, cleaning solvents, lubricants, insecticides, and medicinal materials.
  • Mixtures are prepared including 3 wt% of one of methanol, ethanol, or isopropanol, 92 -96 wt% tr-1233zd, and 1-5 wt% of a glycol ether selected from 2-ethoxyethanol, 2- methoxyethanol, 2-propxyefhanol, 2-phenoxyethanol, 2-benzoxy ethanol, methyl carbitol, carbitol cellosolve, diethoxy ethane, dimethoxyethane, and dibutoxybutane.
  • Printed circuit boards are soldered with a number of commercial solder core wires, such as, Kester 44, Alpha reliacore 15, Alpha Energized Plus and then cleaned in the boiling solvent for 10 min and are removed and dried. These cleaned boards are found to be clean.
  • Mixtures are prepared including 6-25 wt% tr-l ,2-dichloroethylene and 75-94 wt% tr-1233zd.
  • Printed circuit boards are soldered with a number of commercial solder core wires, such as, Kester 44, Alpha reliacore 15, Alpha Energized Plus and then cleaned in the boiling solvent for 10 min and are removed and dried. These cleaned boards are found to be clean.
  • Mixtures are prepared including 1-5 wt% butyl ceilosolve and 95 -99 wt% tr-1233zd.
  • Printed circuit boards are soldered with a number of commercial solder core wires, such as, Kester 44, Alpha reliacore 15, Alpha Energized Plus and then cleaned in the boiling solvent for 10 min and are removed and dried. These cleaned boards are found to be clean.
  • a mixture is prepared including 1 -5 wt% d-limonene and 95 -99 w r t% tr-1233zd.
  • Printed circuit boards are sol dered with a number of commercial solder core wires, such as, Kester 44, Alpha reliacore 15, Alpha Energized Plus and then cleaned in the boiling solvent for 10 min and are removed and dried. These cleaned boards are found to be clean.
  • a mixture is prepared including 3 wt% methanol, 1 -5 wt% pinene, and 92 -96 wt% tr-1233zd.
  • Printed circuit boards are soldered with a number of commercial solder core wires, such as,
  • a mixture is prepared including 1 -5 wt% pinene and 95 -99 wt% tr-1233zd.
  • Printed circuit boards are soldered with a number of commercial solder core wires, such as, Kester 44, Alpha reliacore 15, Alpha Energized Pius and then cleaned in the boiling solvent for 10 min and are removed and dried. These cleaned boards are found to be clean.
  • Example 16
  • Mixtures are prepared including 95 -99 wt% tr-1233zd, and 1 -5 wt% of a glycol ether selected from 2-ethoxyefhano , 2-metlioxyethanol, 2-propxyethanol, 2-phenoxyethanol, 2-benzoxy ethanol, methyl carbitol, carbitol cellosolve, diethoxyethane, dimethoxyethane, and dibutoxybutane.
  • Printed circuit boards are soldered with a number of commercial solder core wires, such as, Kester 44, Alpha reliacore 15, Alpha. Energized Plus and then cleaned in the boiling solvent for 10 min and are removed and dried. These cleaned boards are found to be clean.
  • an aerosol valve was crimped into place and HFO-1234ze was added through the valve to achieve a pressure in the can of about 20 PSIG.
  • Printed circuit boards were soldered with Kester 1544 flux, Kester 44, Alpha Reliacore 15 and Alpha Energized Plus solder core wires. The mixture was then sprayed onto surface to demonstrate whether the mixture was useful as an aerosol.
  • the aerosols had a different co- aerosol agent or no co-aerosol agent, and optionally had at least one active ingredient selected from the group consisting of deodorants, perfumes, hair sprays, cleaning solvents, lubricants, insecticides, and medicinal materials.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Detergent Compositions (AREA)
  • Cleaning By Liquid Or Steam (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Toxicology (AREA)

Abstract

La présente invention concerne, en partie, des compositions qui comprennent (1) un premier composant comprenant un alcool, (b) un second composant choisi dans le groupe constitué d'un éther de glycol, d'un terpène, d'un hydrocarbure halogéné, et des combinaisons de ceux-ci, (c) un troisième composant choisi dans le groupe constitué d'un hydrohalogénoéther, d'un décahalopentane et de combinaisons de ceux-ci.
EP15777203.9A 2014-04-11 2015-04-07 Compositions, procédés, dispositifs et systèmes de dégraissage et de défluxage en phase vapeur de solvant Withdrawn EP3129165A4 (fr)

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US201461978271P 2014-04-11 2014-04-11
US14/678,322 US20150290686A1 (en) 2014-04-11 2015-04-03 Solvent vapor phase degreasing and defluxing compositions, methods, devices and systems
PCT/US2015/024652 WO2015157240A1 (fr) 2014-04-11 2015-04-07 Compositions, procédés, dispositifs et systèmes de dégraissage et de défluxage en phase vapeur de solvant

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WO2017057669A1 (fr) * 2015-09-30 2017-04-06 旭硝子株式会社 Procédé de nettoyage, procédé d'utilisation de dispositif de nettoyage, et dispositif de nettoyage
WO2018101324A1 (fr) * 2016-11-30 2018-06-07 旭硝子株式会社 Composition de solvants et procédé d'élimination d'une résine de polyuréthane
CN111954709B (zh) * 2018-04-27 2021-12-31 三键有限公司 洗涤剂组合物、洗涤用气溶胶和污染部位的洗涤方法
JP7215841B2 (ja) * 2018-07-27 2023-01-31 株式会社ダイゾー 噴霧用組成物および噴霧製品
US20200069553A1 (en) * 2018-08-31 2020-03-05 Honeywell International Inc. Personal care spray compositions and methods comprising trans-1-chloro-3,3,3-trifluoropropene
WO2021041956A1 (fr) * 2019-08-28 2021-03-04 Honeywell International Inc. Produit de soins personnels sec non inflammable contenant trans-1233 zd et de l'éthanol

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US6355113B1 (en) * 1991-12-02 2002-03-12 3M Innovative Properties Company Multiple solvent cleaning system
JP3209450B2 (ja) * 1992-05-29 2001-09-17 旭硝子株式会社 洗浄用溶剤組成物
CN1127017A (zh) * 1993-06-01 1996-07-17 联合讯号公司 多溶剂清洗体系
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TWI259202B (en) * 2000-06-01 2006-08-01 Asahi Kasei Corp Cleaning method and cleaning apparatus
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TW200517488A (en) * 2003-10-03 2005-06-01 Asahi Kasei Chemicals Corp Partially azeotropic composition
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KR101951618B1 (ko) * 2011-05-19 2019-02-25 알케마 인코포레이티드 클로로-트리플루오로프로펜의 불연성 조성물
US20130090280A1 (en) * 2011-10-06 2013-04-11 Honeywell International Inc. Cleaning compositions and methods

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JP2017513711A (ja) 2017-06-01
EP3129165A4 (fr) 2018-03-28
CN106457320A (zh) 2017-02-22
TW201604325A (zh) 2016-02-01
MX2016013283A (es) 2017-01-18
KR20160145620A (ko) 2016-12-20
WO2015157240A1 (fr) 2015-10-15

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