EP4455191A2 - Composition for use in cleaning metal components - Google Patents
Composition for use in cleaning metal components Download PDFInfo
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- EP4455191A2 EP4455191A2 EP24199985.3A EP24199985A EP4455191A2 EP 4455191 A2 EP4455191 A2 EP 4455191A2 EP 24199985 A EP24199985 A EP 24199985A EP 4455191 A2 EP4455191 A2 EP 4455191A2
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5036—Azeotropic mixtures containing halogenated solvents
- C11D7/5068—Mixtures of halogenated and non-halogenated solvents
- C11D7/5077—Mixtures of only oxygen-containing solvents
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/028—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
- C23G5/02854—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 characterised by the stabilising or corrosion inhibiting additives
- C23G5/02861—Oxygen-containing compounds
- C23G5/02874—Aldehydes or ketones
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
- C23G5/02854—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 characterised by the stabilising or corrosion inhibiting additives
- C23G5/02861—Oxygen-containing compounds
- C23G5/02877—Ethers
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D2111/16—Metals
Definitions
- composition for use in cleaning metal components. More specifically, the composition includes a blend of organic solvents that, while being exempted from, or not classified as, a volatile organic compound, a hazardous air pollutant, or a potential carcinogen.
- Metal parts cleaners generally fall in to one of two categories: chlorinated solvents and hydrocarbon solvents. Although chlorinated solvents are non-flammable and are not classified as a volatile organic compound (VOC), they are generally considered to be a potential carcinogen and pose an less than acceptable health risk to users. Hydrocarbon solvents, on the other hand, possess favorable cleaning action and fast evaporation without residue, however, they have varying serious health risks, including potential carcinogenic effects. These solvents, such as toluene, benzene, xylene, and hexane, are classified as a VOC or a hazardous air pollutant (HAP), which limits their use in commercial settings. It would be beneficial to create a metal parts cleaner that has the solubility and cleaning action properties of these traditional solvents, but without the associated health risks to the user.
- VOC volatile organic compound
- HAP hazardous air pollutant
- the Hansen Solubility Parameters for the composition are ⁇ D ⁇ 15, ⁇ P ⁇ 6, and ⁇ H from about 5.5 to about 6.9.
- the composition includes a blend of organic solvents.
- none of the organic solvents are classified as a volatile organic compound, a hazardous air pollutant, or a potential carcinogen, or wherein the solvent exhibits a vapor pressure of less than 0.1 mmHg at 20°C.
- the blend of organic solvents may include a halogenated aromatic solvent having one or more halide groups and from 6 to 8 carbon atoms, wherein the Hansen Solubility Parameters for the halogenated aromatic solvent are in the range of about ⁇ D : 17 - 19, ⁇ P: 5-7, and ⁇ H: 3-5; an organic solvent having one or more ester functional group and from 3 to 9 carbon atoms, wherein the Hansen Solubility Parameters for the organic solvent are in the range of about ⁇ D : 14 - 16, ⁇ P: 3.5-7.5, and ⁇ H: 5-10; and one or more of the following: a linear or branched hydrocarbon solvent with 6-12 carbon atoms with a single polar moiety head group, wherein the Hansen Solubility Parameters for the hydrocarbon solvent are in the range of about ⁇ D : 6-9, ⁇ P: 1-3, and ⁇ H: 5-7; and a solvent containing one or more ketone functional groups and from 2 to 5 carbon
- the halogenated aromatic solvent is parachlorobenzotriflouride which is present in an amount from about 0.25% to about 20% of the composition.
- the organic solvent with one or more ester functional groups is selected from the group consisting of tert-butyl acetate, methyl acetate, dimethyl carbonate, diethylene glycol monoethyl acetate, and diethylene glycol monobutyl ether acetate.
- the organic solvent with one or more ester functional groups is tert-butyl acetate which is present in an amount from about 25% to about 65% of the composition.
- the hydrocarbon solvent having a single polar moiety head group is 1-butoxyhexanol or 2-ethyl-hexanol which is present in an amount from about 0.1% to about 1% of the composition.
- the solvent containing one or more ketone functional groups is acetone which is present in an amount from about 5% to about 50% of the composition.
- Figure 1 is the graphical representation of evaporation curves for various example formulations.
- a composition for use in cleaning metal parts includes a blend of organic solvents.
- the blend includes one or more organic solvent, each of which are either 1) not classified as, or are exempt from being classified as, a VOC, a HAP, or a potential carcinogen or 2) have a vapor pressure of less than 0.1 mmHg at 20°C.
- this blend of organic solvents exhibits a cleaning action, solubility parameters, and evaporation rates (leading to decreased residue on the component) that are comparable to solvents considered to pose potential health risks.
- the resulting composition exhibits Hansen Solubility Parameters that are similar to those substances. Specifically, the Hansen Solubility Parameters for the blended composition have been found to be ⁇ D ⁇ 14-16, ⁇ P ⁇ 3.5 - 7, and ⁇ H from about 5.5 to about 6.9.
- the composition is created by combining a halogenated aromatic solvent having one or more halide groups and from 6 to 8 carbon atoms, an organic solvent having one or more ester functional groups and from 3 to 9 carbon atoms, and one or more of a linear or branched hydrocarbon solvent with 6-12 carbon atoms with a single polar moiety head group and a solvent containing one or more ketone functional groups and from 2 to 5 carbon atoms.
- the halogenated aromatic solvent having one or more halide groups and from 6 to 8 carbon atoms has Hansen Solubility Parameters that are in the range of about ⁇ D : 17 - 19, ⁇ P: 5-7, and ⁇ H: 3-5 and is present in the composition in an amount of from 0.25% to 20%, and preferably from about 1% to about 9%, of the total composition.
- these halogenated aromatic solvents are not considered a HAP or potential carcinogen and are exempted from VOC, or they exhibit a vapor pressure of less than about 0.1 mmHg at 20°C.
- the halogenated aromatic solvent is parachlorobenzotriflouride (PCBTF).
- the organic solvent having one or more ester functional group and from 3 to 9 carbon atoms has Hansen Solubility Parameters that are in the range of about ⁇ D : 14 - 16, ⁇ P: 3.5-7.5, and ⁇ H: 5-10 and is present in the composition in an amount from about 25% to about 65% of the total composition.
- these ester-containing organic solvents are not considered a HAP or potential carcinogen and are exempted from VOC, or they exhibit a vapor pressure of less than about 0.1 mmHg at 20°C.
- ester-containing organic solvent may be methyl acetate, dimethyl carbonate, diethylene glycol monoethyl ether/diethylene glycol monobutyl ether acetate (commercially available from Eastman Chemical Company), t-butyl acetate.
- the solvent is t-butyl acetate.
- the linear or branched hydrocarbon solvent with 6-12 carbon atoms and a single polar moiety head group has Hansen Solubility Parameters that are in the range of about ⁇ D : 6-9, ⁇ P: 1-3, and ⁇ H: 5-7 and when present in the composition, is present in the amount of about 0.1 to about 1.2%, and in another embodiment from about 0.1 to about 1.0%.
- these linear or branched hydrocarbon solvents are not considered a HAP or potential carcinogen and are exempted from VOC, or they exhibit a vapor pressure of less than about 0.1 mmHg at 20°C.
- the hydrocarbon solvent is 2-butoxyhexanol or 2-ethylhexanol. In another embodiment, the hydrocarbon solvent is 2-ethylhexanol.
- medium chain length organic solvents may function as a surfactant, lowering the surface tension between the product and the soiled surfaces. Moreover, the organic solvents have been found to enhance the composition's wetting action, and thus, its cleaning ability without leaving a residue or adversely affecting the drying rate.
- the solvent containing one or more ketone functional groups and from 2 to 5 carbon atoms has Hansen Solubility Parameters that are in the range of about ⁇ D : 14-16, ⁇ P: 8.5 - 11, and ⁇ H: 5-8 and when present in the composition, is present in an amount of about 5% to about 50%. Further, it should be understood that these solvents are not considered a HAP or potential carcinogen and are exempted from VOC, or they exhibit a vapor pressure of less than about 0.1 mmHg at 20°C.
- the solvent containing one or more ketone functional group is acetone. It has been found that the addition of a solvent, such as acetone, enhances the evaporation rate of the blended composition.
- solvents were evaluated by visual inspection of solvation action when applied to various soils encountered in automotive cleaning procedures.
- the soils used for testing included 10W-30 motor oil, DOT 3 brake fluid, #2 Lithium Grease, and Power Steering Fluid. Solvation was evaluated on a relative scale: Poor, Fair, Good and Excellent. The rating is based on the solvent's ability to blend with the soil of interest, the rate of the blending, the amount of solvent required to remove the soil from the substrate and the amount of residue left behind by the solvent.
- the individual solvents were evaluated.
- Aluminum test dishes were prepared by applying approximately 5 drops of each soil to the dishes. Neat solvent was added dropwise beside each soil so that the edges of the two materials came in contact with one another. The solvation action of the solvent was observed. The extent to which the soil and the solvent mixed and the rate of mixing was observed. Additional solvent was then applied to each section and the dish was lifted to observe the removal of the soil. Another addition of solvent was applied by pipette (approx. 1-2 mL) to observe the spray-off characteristics of each soil/solvent combination.
- Solvation in this context can be readily characterized by example.
- No solvation can be described by two materials that will not blend in any proportions, i.e. oil and water. For example, if a drop of oil and a drop of water are placed beside each other with edges touching, they will not blend and thus have no solvation.
- excellent solvation would be two materials that are miscible and will blend in any proportion.
- One example would be water and ethanol. If a drop of each were placed beside one another, with edges touching, the two would rapidly blend together and form a homogenous phase. Most materials have some degree of solubility with each other.
- the relative scale used above describes this, but also includes an observation of the rate at which it occurs. Excellent is near instantaneous. Good occurs over 1-3 seconds. Fair is over 5-20 seconds and poor requires significant time to solvate 30 seconds to several minutes. Similar quantification methods were used for the solvent blend tests, described below.
- the solvent blends were evaluated by visual inspection of their solvation action when applied to various soils encountered in automotive cleaning procedures.
- the soils used for testing were 10W-30 motor oil, DOT 3 brake fluid, #2 Lithium Grease, and Power Steering Fluid.
- Solvation was evaluated on a relative scale: Poor, Fair, Good and Excellent. The rating is based on the solvent blends ability to remove various soils from test panels. The effect is bracketed by the performance of the 10% VOC Parts cleaner on the low end and by the 45% VOC Parts Cleaner on the upper end and characterizes the solvent blend's ability to blend with the soil of interest, the rate of the blending, the amount of solvent blend required to remove the soil from the substrate, and the amount of residue left behind by the solvent.
- Steel test panels were prepared by the following method. A thin film of NLGI #2 lithium complex grease, polyurea grease, and calcium sulfonate grease were applied to the steel test panels in sections with a rag. Approximately 3-5 mL of 10w-30 conventional motor oil, DOT 3 brake fluid, and power steering fluid were then applied in small puddles and smeared with a rag or paper towel. The panels were then baked at 60 °C for approximately 16 hours to simulate service conditions.
- the individual solvent blends were prepared by mixing together the individual components in a glass beaker and then stirring the blends for 1-2 minutes. About 200 g of the blends were then charged into standard 12 oz aerosol cans. The cans were then pressurized to approximately 100 PSI with CO 2 , shaken well, and allowed to sit at least two hours to ensure CO 2 dissolution.
- the individual solvent blends were then tested by the following method. Performance of test blends were compared to the Valvoline Professional Series (VPS) 10% VOC Parts Cleaner (commercially available from Valvoline LLC), for a low performance mark, and the VPS 45% VOC Parts Cleaner (commercially available from Valvoline LLC), for a high-performance mark. In a well-ventilated area or fume hood, the prepared panels were positioned above a catch pan. The test blends were then sprayed onto the soils in 2-3 second bursts, targeting each soil type individually. Each test blend was allowed to penetrate the soils for approximately 5-10 seconds. The test blends were then sprayed onto the soils again, targeting each soil type individually for an additional 2-3 second burst.
- VPS Valvoline Professional Series
- VPS VOC Parts Cleaner
- the cleaning performance was inspected visually between the first and second burst and after the panel was allowed to dry. They were evaluated by the same relative rating standards as above.
- compositions of the sample solvent blends are set forth in Table 4 below: Table 4 Sample # Acetone t-butyl acetate PCBTF 2-ethylhexanol Eastman EEH 1 50 25 25 0 0 2 75 12.5 12.5 0 0 3 90 5 5 0 0 4 50 50 0 0 0 5 75 25 0 0 0 6 90 10 0 0 0 7 50 0 50 0 0 8 75 0 25 0 0 9 90 0 10 0 0 10 80 10 10 0 0 11 80 15 5 0 0 12 80 5 15 0 0 13 75 15 10 0 0 14 75 20 5 0 0 15 75 10 15 0 0 16 65 35 0 0 0 17 65 25 10 0 0 18 65 30 5 0 0 19 50 40 10 0 0 20 50 45 5 0 0 21 25 65 10 0 0 22 0 85 15 0 0 23 65 32.5 2.5 0 0 24 50 0 0 50 0 25
- blended compositions that include about 25 to 30% acetone, about 97 to 65% t-butyl acetate, about 2.5 to about 5% PCBTF, and about 1% 2-ethylhexanol produce high quality cleaning composition, without the expected health risks generally associated with known metal parts cleaners.
- the blended composition will preferably include about 29% acetone, about 67.5% t-butyl acetate, about 2.5% PCBTF, and about 1% 2-ethylhexanol, as in Sample #48..
- the data shows that the ability to control the evaporation rate has a large impact on the blended composition's overall performance.
- a "stepwise" evaporation curve with components in increasingly small amounts, with increasingly slower evaporation rates allows for soil penetration, but prevents a significant amount of residual cleaner from remaining on the soiled component part. This will ultimately improve the performance of the blended composition and reduce the amount needed.
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Abstract
Description
- This disclosure is directed to a solvent composition for use in cleaning metal components. More specifically, the composition includes a blend of organic solvents that, while being exempted from, or not classified as, a volatile organic compound, a hazardous air pollutant, or a potential carcinogen.
- Metal parts cleaners generally fall in to one of two categories: chlorinated solvents and hydrocarbon solvents. Although chlorinated solvents are non-flammable and are not classified as a volatile organic compound (VOC), they are generally considered to be a potential carcinogen and pose an less than acceptable health risk to users. Hydrocarbon solvents, on the other hand, possess favorable cleaning action and fast evaporation without residue, however, they have varying serious health risks, including potential carcinogenic effects. These solvents, such as toluene, benzene, xylene, and hexane, are classified as a VOC or a hazardous air pollutant (HAP), which limits their use in commercial settings. It would be beneficial to create a metal parts cleaner that has the solubility and cleaning action properties of these traditional solvents, but without the associated health risks to the user.
- A composition for use in cleaning metal components is disclosed. In one embodiment, the Hansen Solubility Parameters for the composition are δD ≥ 15, δP < 6, and δH from about 5.5 to about 6.9. Moreover, the composition includes a blend of organic solvents. In one embodiment, none of the organic solvents are classified as a volatile organic compound, a hazardous air pollutant, or a potential carcinogen, or wherein the solvent exhibits a vapor pressure of less than 0.1 mmHg at 20°C.
- Specifically, the blend of organic solvents may include a halogenated aromatic solvent having one or more halide groups and from 6 to 8 carbon atoms, wherein the Hansen Solubility Parameters for the halogenated aromatic solvent are in the range of about δD : 17 - 19, δP: 5-7, and δH: 3-5; an organic solvent having one or more ester functional group and from 3 to 9 carbon atoms, wherein the Hansen Solubility Parameters for the organic solvent are in the range of about δD : 14 - 16, δP: 3.5-7.5, and δH: 5-10; and one or more of the following: a linear or branched hydrocarbon solvent with 6-12 carbon atoms with a single polar moiety head group, wherein the Hansen Solubility Parameters for the hydrocarbon solvent are in the range of about δD : 6-9, δP: 1-3, and δH: 5-7; and a solvent containing one or more ketone functional groups and from 2 to 5 carbon atoms, wherein the Hansen Solubility Parameters for the solvent containing one or more ketone functional groups are in the range of about δD : 14-16, δP: 8.5 - 11, and δH: 5-8.
- In one embodiment, the halogenated aromatic solvent is parachlorobenzotriflouride which is present in an amount from about 0.25% to about 20% of the composition.
- In another embodiment, the organic solvent with one or more ester functional groups is selected from the group consisting of tert-butyl acetate, methyl acetate, dimethyl carbonate, diethylene glycol monoethyl acetate, and diethylene glycol monobutyl ether acetate. In yet another embodiment, the organic solvent with one or more ester functional groups is tert-butyl acetate which is present in an amount from about 25% to about 65% of the composition.
- In another embodiment, the hydrocarbon solvent having a single polar moiety head group is 1-butoxyhexanol or 2-ethyl-hexanol which is present in an amount from about 0.1% to about 1% of the composition.
- In another embodiment, the solvent containing one or more ketone functional groups is acetone which is present in an amount from about 5% to about 50% of the composition.
- The accompanying figures, which are incorporated in and constitute a part of the specification, illustrate various example configurations and data, and are used merely to illustrate various example embodiments. In the figures, like elements bear like reference numerals.
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Figure 1 is the graphical representation of evaporation curves for various example formulations. - A composition for use in cleaning metal parts is provided. Specifically the composition includes a blend of organic solvents. In one embodiment, the blend includes one or more organic solvent, each of which are either 1) not classified as, or are exempt from being classified as, a VOC, a HAP, or a potential carcinogen or 2) have a vapor pressure of less than 0.1 mmHg at 20°C. Surprisingly, it has been found that this blend of organic solvents exhibits a cleaning action, solubility parameters, and evaporation rates (leading to decreased residue on the component) that are comparable to solvents considered to pose potential health risks.
- Although none of the components of the blended composition are classified (or are exempt from being classified) as a VOC, HAP, or potential carcinogen, the resulting composition exhibits Hansen Solubility Parameters that are similar to those substances. Specifically, the Hansen Solubility Parameters for the blended composition have been found to be δD ≥ 14-16, δP < 3.5 - 7, and δH from about 5.5 to about 6.9.
- In one embodiment, the composition is created by combining a halogenated aromatic solvent having one or more halide groups and from 6 to 8 carbon atoms, an organic solvent having one or more ester functional groups and from 3 to 9 carbon atoms, and one or more of a linear or branched hydrocarbon solvent with 6-12 carbon atoms with a single polar moiety head group and a solvent containing one or more ketone functional groups and from 2 to 5 carbon atoms.
- In one embodiment, the halogenated aromatic solvent having one or more halide groups and from 6 to 8 carbon atoms has Hansen Solubility Parameters that are in the range of about δD : 17 - 19, δP: 5-7, and δH: 3-5 and is present in the composition in an amount of from 0.25% to 20%, and preferably from about 1% to about 9%, of the total composition. Further, it should be understood that these halogenated aromatic solvents are not considered a HAP or potential carcinogen and are exempted from VOC, or they exhibit a vapor pressure of less than about 0.1 mmHg at 20°C. In one embodiment, the halogenated aromatic solvent is parachlorobenzotriflouride (PCBTF).
- In another embodiment, the organic solvent having one or more ester functional group and from 3 to 9 carbon atoms has Hansen Solubility Parameters that are in the range of about δD : 14 - 16, δP: 3.5-7.5, and δH: 5-10 and is present in the composition in an amount from about 25% to about 65% of the total composition. Further, it should be understood that these ester-containing organic solvents are not considered a HAP or potential carcinogen and are exempted from VOC, or they exhibit a vapor pressure of less than about 0.1 mmHg at 20°C. In one embodiment the ester-containing organic solvent may be methyl acetate, dimethyl carbonate, diethylene glycol monoethyl ether/diethylene glycol monobutyl ether acetate (commercially available from Eastman Chemical Company), t-butyl acetate. In another embodiment, the solvent is t-butyl acetate.
- In another embodiment the linear or branched hydrocarbon solvent with 6-12 carbon atoms and a single polar moiety head group has Hansen Solubility Parameters that are in the range of about δD : 6-9, δP: 1-3, and δH: 5-7 and when present in the composition, is present in the amount of about 0.1 to about 1.2%, and in another embodiment from about 0.1 to about 1.0%. Further, it should be understood that these linear or branched hydrocarbon solvents are not considered a HAP or potential carcinogen and are exempted from VOC, or they exhibit a vapor pressure of less than about 0.1 mmHg at 20°C. In one embodiment, the hydrocarbon solvent is 2-butoxyhexanol or 2-ethylhexanol. In another embodiment, the hydrocarbon solvent is 2-ethylhexanol.
- These medium chain length organic solvents may function as a surfactant, lowering the surface tension between the product and the soiled surfaces. Moreover, the organic solvents have been found to enhance the composition's wetting action, and thus, its cleaning ability without leaving a residue or adversely affecting the drying rate.
- In another embodiment, the solvent containing one or more ketone functional groups and from 2 to 5 carbon atoms has Hansen Solubility Parameters that are in the range of about δD : 14-16, δP: 8.5 - 11, and δH: 5-8 and when present in the composition, is present in an amount of about 5% to about 50%. Further, it should be understood that these solvents are not considered a HAP or potential carcinogen and are exempted from VOC, or they exhibit a vapor pressure of less than about 0.1 mmHg at 20°C. In one embodiment, the solvent containing one or more ketone functional group is acetone. It has been found that the addition of a solvent, such as acetone, enhances the evaporation rate of the blended composition.
- Individual solvents were evaluated by visual inspection of solvation action when applied to various soils encountered in automotive cleaning procedures. The soils used for testing included 10W-30 motor oil, DOT 3 brake fluid, #2 Lithium Grease, and Power Steering Fluid. Solvation was evaluated on a relative scale: Poor, Fair, Good and Excellent. The rating is based on the solvent's ability to blend with the soil of interest, the rate of the blending, the amount of solvent required to remove the soil from the substrate and the amount of residue left behind by the solvent.
- In one example, the individual solvents were evaluated. Aluminum test dishes were prepared by applying approximately 5 drops of each soil to the dishes. Neat solvent was added dropwise beside each soil so that the edges of the two materials came in contact with one another. The solvation action of the solvent was observed. The extent to which the soil and the solvent mixed and the rate of mixing was observed. Additional solvent was then applied to each section and the dish was lifted to observe the removal of the soil. Another addition of solvent was applied by pipette (approx. 1-2 mL) to observe the spray-off characteristics of each soil/solvent combination.
Relative Solvation Rating Standards - Table 1 Rating Explanation Poor Little or no solvation. Very slow rate of solvation. Large amount of soil residue after spray. Fair Some, slow solvation effect. Slow to Moderate solvation rate. Moderate amount of soil residue after spray. Good Significant solvation effect. Moderate to rapid solvation rate. Small amount of residue after spray. Excellent Significant solvation effect. Rapid/extensive solvation rate. No soil residue after spray. - The results of the Hansen Solubility calculations and evaporation rate data are shown below in Table 2:
Table 2 Hansen Data Solvents VOC dD dP dH MVol Evaporation Rate (BuAc = 1) Toluene Yes 18 1.4 2 106.6 1.9 Xylene Yes 17.6 1 3.1 123.9 0.6 Heptane Yes 15.3 0 0 147 4.3 Eastman EEH No 7.8 2 2.5 195.9 0.003 2-ethyl hexanol No 7.8 1.6 5.8 123.9 < 0.01 dibasic ester LVP No 8.3 2.2 0 151.21 0.009 Dowanol Eph No 17.8 5.7 14.3 124.5 0.001 Eastman Omnia No 7.87 3.13 5.62 164.99 0.01 Eastman DE Acetate No 7.9 2.5 4.5 174.12 0.008 Eastman DB Acetate No 7.8 3.4 5.2 208.44 0.003 Eastman DP Solvent No 7.8 3.5 5.5 152.78 0.01 Eastman Texanol No 7.8 3.5 5.5 152.78 0.002 Acetone No 15.5 10.4 7 73.8 14.4 PCBTF No 18 5.9 3.9 134.75 0.9 t-butyl acetate No 15 3.7 6 132.6 2.8 dimethyl carbonate No 8.5 4.7 1.9 84.2 3.22 Carbitol Solvent No 16.1 9.2 12.2 135.56 0.01 Methyl Acetate No 15.5 7.2 7.6 79.8 6 Propylene Carbonate No 20 18 4.1 85.2 0.005 - The results of the Solvent Effect data for various soils are shown below in Table 3:
Table 3 Solvent Effect - Varied Soils Solvents VOC Motor Oil Brake Fluid Power Steering Fluid Greases Toluene Yes Excellent Good Good Good Xylene Yes Excellent Good Good Good Heptane Yes Excellent Good Good Good Eastman EEH No Good Good Fair Fair 2-ethyl hexanol No Good Fair Poor Excellent dibasic ester LVP No Poor/Fair Poor Poor/Fair Good Dowanol Eph No Good Excellent Good Fair Eastman Omnia No Good Good Good Poor/Fair Eastman DE Acetate No Fair/Good Good Fair/Good Poor Eastman DB Acetate No Fair/Good Good Fair/Good Poor Eastman DP Solvent No Fair/Good Good Fair/Good Poor Eastman Texanol No Good Fair/Good Good Poor Acetone No Poor Good Excellent Poor PCBTF No Excellent Excellent Fair Fair t-butyl acetate No Excellent Excellent Fair Fair dimethyl carbonate No Poor Good Good Poor Carbitol Solvent No Fair/Good Good Good Poor Methyl Acetate No Fair/Good Excellent Good Poor Propylene Carbonate No Fair Fair/Good Good Poor - Solvation in this context can be readily characterized by example. "No solvation" can be described by two materials that will not blend in any proportions, i.e. oil and water. For example, if a drop of oil and a drop of water are placed beside each other with edges touching, they will not blend and thus have no solvation. The opposite, and thus "excellent solvation," would be two materials that are miscible and will blend in any proportion. One example would be water and ethanol. If a drop of each were placed beside one another, with edges touching, the two would rapidly blend together and form a homogenous phase. Most materials have some degree of solubility with each other. The relative scale used above describes this, but also includes an observation of the rate at which it occurs. Excellent is near instantaneous. Good occurs over 1-3 seconds. Fair is over 5-20 seconds and poor requires significant time to solvate 30 seconds to several minutes. Similar quantification methods were used for the solvent blend tests, described below.
- In one example, the solvent blends were evaluated by visual inspection of their solvation action when applied to various soils encountered in automotive cleaning procedures. The soils used for testing were 10W-30 motor oil, DOT 3 brake fluid, #2 Lithium Grease, and Power Steering Fluid. Solvation was evaluated on a relative scale: Poor, Fair, Good and Excellent. The rating is based on the solvent blends ability to remove various soils from test panels. The effect is bracketed by the performance of the 10% VOC Parts cleaner on the low end and by the 45% VOC Parts Cleaner on the upper end and characterizes the solvent blend's ability to blend with the soil of interest, the rate of the blending, the amount of solvent blend required to remove the soil from the substrate, and the amount of residue left behind by the solvent.
- Steel test panels were prepared by the following method. A thin film of NLGI #2 lithium complex grease, polyurea grease, and calcium sulfonate grease were applied to the steel test panels in sections with a rag. Approximately 3-5 mL of 10w-30 conventional motor oil, DOT 3 brake fluid, and power steering fluid were then applied in small puddles and smeared with a rag or paper towel. The panels were then baked at 60 °C for approximately 16 hours to simulate service conditions.
- Once the panels were prepared, the individual solvent blends were prepared by mixing together the individual components in a glass beaker and then stirring the blends for 1-2 minutes. About 200 g of the blends were then charged into standard 12 oz aerosol cans. The cans were then pressurized to approximately 100 PSI with CO2, shaken well, and allowed to sit at least two hours to ensure CO2 dissolution.
- The individual solvent blends were then tested by the following method. Performance of test blends were compared to the Valvoline Professional Series (VPS) 10% VOC Parts Cleaner (commercially available from Valvoline LLC), for a low performance mark, and the VPS 45% VOC Parts Cleaner (commercially available from Valvoline LLC), for a high-performance mark. In a well-ventilated area or fume hood, the prepared panels were positioned above a catch pan. The test blends were then sprayed onto the soils in 2-3 second bursts, targeting each soil type individually. Each test blend was allowed to penetrate the soils for approximately 5-10 seconds. The test blends were then sprayed onto the soils again, targeting each soil type individually for an additional 2-3 second burst.
- The cleaning performance was inspected visually between the first and second burst and after the panel was allowed to dry. They were evaluated by the same relative rating standards as above.
- The compositions of the sample solvent blends are set forth in Table 4 below:
Table 4 Sample # Acetone t-butyl acetate PCBTF 2-ethylhexanol Eastman EEH 1 50 25 25 0 0 2 75 12.5 12.5 0 0 3 90 5 5 0 0 4 50 50 0 0 0 5 75 25 0 0 0 6 90 10 0 0 0 7 50 0 50 0 0 8 75 0 25 0 0 9 90 0 10 0 0 10 80 10 10 0 0 11 80 15 5 0 0 12 80 5 15 0 0 13 75 15 10 0 0 14 75 20 5 0 0 15 75 10 15 0 0 16 65 35 0 0 0 17 65 25 10 0 0 18 65 30 5 0 0 19 50 40 10 0 0 20 50 45 5 0 0 21 25 65 10 0 0 22 0 85 15 0 0 23 65 32.5 2.5 0 0 24 50 0 0 50 0 25 75 0 0 25 0 26 65 0 0 35 0 27 90 0 0 10 0 28 0 50 0 50 0 29 0 65 0 35 0 30 0 75 0 25 0 31 0 90 0 10 0 32 65 0 0 0 35 33 75 0 0 0 25 34 90 0 0 0 10 35 0 65 0 0 35 36 0 75 0 0 25 37 0 90 0 0 10 38 50 45 2.5 2.5 0 39 50 45 4 1 0 40 50 40 9 1 0 41 50 40 0 10 0 42 50 45 0 5 0 43 50 40 5 5 0 44 0 90 5 5 0 45 0 90 9 1 0 46 29 65 5 1 0 47 0 95 4 1 0 48 29 67.5 2.5 1 0 49 0 96.5 2.5 1 0 - The Hansen Solubility Parameters were calculated for each sample. The data from those calculations are provided below in Table 5.
Table 5 Sample # Hansen Solubility Parameters dD dP dH 1 13.8 6.9 5.5 2 15.8 9.0 6.5 3 15.6 9.84 6.795 4 15.25 7.05 6.5 5 15.375 8.725 6.75 6 15.45 9.73 6.9 7 16.75 8.15 5.45 8 16.125 9.275 6.225 9 15.75 9.95 6.69 10 15.7 9.28 6.59 11 15.55 9.17 6.695 12 15.85 9.39 6.485 13 15.675 8.945 6.54 14 15.525 8.835 6.645 15 15.825 9.055 6.435 16 15.325 8.055 6.65 17 15.625 8.275 6.44 18 15.475 8.165 6.545 19 15.55 7.27 6.29 20 15.4 7.16 6.395 21 15.425 5.595 6.04 22 15.45 4.03 5.685 23 15.4 8.11 6.5975 24 11.65 6 6.4 25 13.575 8.2 6.7 26 12.805 7.32 6.58 27 14.73 9.52 6.88 28 11.4 2.65 5.9 29 12.48 2.965 5.93 30 13.2 3.175 5.95 31 14.28 3.49 5.98 32 12.805 7.46 5.425 33 13.575 8.3 5.875 34 14.73 9.56 6.55 35 12.48 3.105 4.775 36 13.2 3.275 5.125 37 14.28 3.53 5.65 38 15.145 7.0525 6.4425 39 15.298 7.117 6.414 40 15.448 7.227 6.309 41 14.53 6.84 6.48 42 14.89 6.945 6.49 43 15.04 7.055 6.385 44 14.79 3.705 5.885 45 15.198 3.877 5.809 46 15.223 5.732 6.183 47 15.048 3.767 5.914 48 15.148 5.677 6.2355 49 15.003 3.734 5.9455 - The results of the solvent removal data are set forth in Table 6, below.
Table 6 Sample # Observations (based on a summary of all soils used) Solvency Soil Removal Evaporation Rate Residue 1 Fair Fair Fair (slow) Significant 2 Fair Poor Fair Extensive 3 Poor Poor Too fast Extensive 4 Fair Good Fair Significant 5 Fair Fair - Significant 6 Poor Poor Too fast Extensive 7 Good Good Too slow Significant 8 Fair Good Too slow Significant 9 Poor Fair Fair Extensive 10 Fair Fair Fair Extensive 11 Fair Fair Fair Extensive 12 Fair Fair Too slow Extensive 13 Fair Good Fair Significant 14 Good Good Fair Significant 15 Fair Good Too slow Significant 16 Good Fair Fair Minimal 17 Good Good Good Minimal 18 Good Good Good Minimal 19 Excellent Good Good Minimal 20 Excellent Good Good Minimal 21 Excellent Good Fair None 22 Excellent Good Fair None 23 Good Fair Good Significant 24 Poor Fair Too slow Extensive 25 Fair Fair Too slow Extensive 26 Fair Good Too slow Significant 27 Poor Fair Too slow Extensive 28 Fair Good Too slow None 29 Good Good Too slow None 30 Good Good Too slow None 31 Excellent Excellent Too slow None 32 Fair Good Too slow Significant 33 Fair Good Too slow Significant 34 Poor Poor Fair Significant 35 Good Good Too slow None 36 Good Good Too slow None 37 Excellent Excellent Fair None 38 Good Good Fair Minimal 39 Good Good Good Minimal 40 Good Good Good Minimal 41 Good Excellent Too slow Significant 42 Good Excellent Too slow Significant 43 Good Excellent Too slow Significant 44 Excellent Excellent Poor None 45 Excellent Excellent Good None 46 Excellent Excellent Good None 47 Excellent Excellent Fair None 48 Excellent Excellent Excellent None 49 Excellent Excellent Good None - It will be understood that if a composition has an evaporation rate that is deemed to be "too slow," the solvent composition can be observed to linger on the cleaning surface or area around it for a significant amount of time (approximately 5 to about 10 minutes). If an evaporation rate is too slow, one would have to clean the soiled surface by another means (rag/paper towel, etc.) before continuing work.
- Conversely, if a composition has an evaporation rate that is considered to be "too fast," the solvent composition does not dwell long enough on the soiled surface to either solvate the soil completely or facilitate its transport from the surface being cleaned. This results in having to use more product to transport the soil from the surface of the component being cleaned and can result in significant residue as well.
- As can be seen from the data above, blended compositions that include about 25 to 30% acetone, about 97 to 65% t-butyl acetate, about 2.5 to about 5% PCBTF, and about 1% 2-ethylhexanol produce high quality cleaning composition, without the expected health risks generally associated with known metal parts cleaners. In one embodiment, the blended composition will preferably include about 29% acetone, about 67.5% t-butyl acetate, about 2.5% PCBTF, and about 1% 2-ethylhexanol, as in
Sample # 48.. - There seems to be a strong relation between soil removal efficiency and the evaporation rate of the composition, with slow evaporation rates favoring improved soil removal. Moreover, while large amounts of 2-ethylhexanol appeared to negatively impact the evaporation rate of the overall composition, small amounts, that is less than about 2.5% of the total weight percent of the blend, appear to improve the wetting action of the other solvents and helped to improve the soil removal action of the blended composition. While not being bound to theory, it is believed that the presence of a small amount of 2-ethylhexanol reduces the evaporation rate of the composition enough to allow for thorough penetration of persistent soils, thus reducing the amount of blended composition required to achieve acceptable soil removal.
- To that end, the evaporation rates of examples formulations were compared. Approximately 3 grams of each sample were weighed onto a 3 inch watch glass and left exposed in a fume hood at a face velocity of 109 feet per minute (FPM). The weight change of each sample was recorded as a function of time over approximately 15 - 17. As shown in
Figure 1 , this data was then plotted by weight change per minute. With continuing reference toFigure 1 , it was found that the methyl acetate and PCBTF formula, lost nearly 85% of its weight in only 16 minutes.Sample # 48, however, performed much better, losing only about 67.7%, while the toluene composition lost only 41.5% weight. The optimized evaporation rate ofSample # 48 allow the formulations to remain on the soil for longer periods of time, increasing the soil removal capability, while minimizing the residue left behind. - In addition, the data shows that small amounts of PCBTF, from about 2.0% to about 20%, appears to have a synergistic solvation effect with acetone and t-butyl acetate. It is likely that the presence of an aromatic moiety and a chlorinated/fluorinated functionality contributes to this effect.
- Finally, the data shows that the ability to control the evaporation rate has a large impact on the blended composition's overall performance. Preferably, a "stepwise" evaporation curve, with components in increasingly small amounts, with increasingly slower evaporation rates allows for soil penetration, but prevents a significant amount of residual cleaner from remaining on the soiled component part. This will ultimately improve the performance of the blended composition and reduce the amount needed.
- While the invention has been described with respect to specific examples including presently preferred modes of carrying out the invention, those skilled in the art will appreciate that there are numerous variations and permutations of the above described systems and techniques that fall within the spirit and scope of the invention as set forth in the appended claims.
- The invention is further drawn to the following embodiments ("embs"):
- Emb 1. A composition for use in cleaning metal components, wherein the Hansen Solubility Parameters for the composition are δD from about 12.0 to about 16.0, δP from about 3.0 to about 10.0, and δH from about 4.0 to about 6.9, and wherein the composition comprises a blend of organic solvents, wherein either none of the solvents are classified as a volatile organic compound, a hazardous air pollutant, or a potential carcinogen, or wherein the solvent exhibits a vapor pressure of less than 0.1 mmHg at 20°C, wherein the blend of organic solvents comprises:
- a halogenated aromatic solvent having one or more halide groups and from 6 to 8 carbon atoms, wherein the Hansen Solubility Parameters for the halogenated aromatic solvent are in the range of about δD : 17 - 19, δP: 5-7, and δH: 3-5;
- an organic solvent having one or more ester functional group and from 3 to 9 carbon atoms, wherein the Hansen Solubility Parameters for the organic solvent are in the range of about δD : 14 - 16, δP: 3.5-7.5, and δH: 5-10; and one or more of the following:
- a linear or branched hydrocarbon solvent with 6-12 carbon atoms with a single polar moiety head group, wherein the Hansen Solubility Parameters for the hydrocarbon solvent are in the range of about δD : 6-9, δP: 1-3, and δH: 5-7; and
- a solvent containing one or more ketone functional groups and from 2 to 5 carbon atoms, wherein the Hansen Solubility Parameters for the solvent containing one or more ketone functional groups are in the range of about δD : 14-16, δP: 8.5 - 11, and δH: 5-8.
- Emb 2. The composition of Emb 1, wherein the halogenated aromatic solvent is parachlorobenzotriflouride, and wherein the parachlorobenzotriblouride is present in an amount from about 0.25% to about 20% of the composition.
- Emb 3. The composition of Emb 1, wherein the organic solvent with one or more ester functional groups is selected from the group consisting of tert-butyl acetate, methyl acetate, dimethyl carbonate, diethylene glycol monoethyl acetate, and diethylene glycol monobutyl ether acetate.
- Emb 4. The composition of Emb 3, wherein the organic solvent with one or more ester functional groups is tert-butyl acetate, and wherein the tert-butyl acetate is present in an amount from about 15% to about 95% of the composition.
- Emb 5. The composition of Emb 1, wherein the hydrocarbon solvent having a single polar moiety head group is 1-butoxyhexanol or 2-ethyl-hexanol, and wherein the hydrocarbon solvent is present in an amount from about 0.1% to about 2.5% of the composition.
- Emb 6. The composition of Emb 1, wherein the solvent containing one or more ketone functional groups is acetone, and where in the acetone is present in an amount from about 5% to about 75% of the composition.
- Emb 7. The composition of Emb 6, wherein the organic solvent with one or more ester functional groups is selected from the group consisting of tert-butyl acetate, methyl acetate, dimethyl carbonate, diethylene glycol monoethyl acetate, and diethylene glycol monobutyl ether acetate.
- Emb 8. The composition of Emb 7, wherein the organic solvent with one or more ester functional groups is tert-butyl acetate.
- Emb 9. The composition of Emb 6, wherein the composition further comprises a hydrocarbon solvent having a single polar moiety head group, and wherein the hydrocarbon solvent is 1-butoxyhexanol or 2-ethyl-hexanol.
- Emb 10. A composition for use in cleaning metal components, wherein the Hansen Solubility Parameters for the composition are δD ≥ 15, δP < 6, and δH from about 5.5 to about 6.9, and wherein the composition comprises a blend of organic solvents, and wherein either none of the solvents are classified as a volatile organic compound, a hazardous air pollutant, or Potential Carcinogen, or wherein the organic solvent exhibits a vapor pressure of less than 0.1 mmHg at 20°C, the blend of organic solvents comprising:
from about 1% to about 9% parachlorobenzotriflouride; and from about 25% to about 70% tert-butyl acetate; and one or more of the following:- from about 0.1 to about 1% 2-ethylhexanol, and
- from about 5% to about 75% acetone.
-
Emb 11. The composition of Emb 10, wherein the composition comprises both 2-ethylexanol and acetone. - Emb 12. The composition of
Emb 11, wherein the composition comprises about 25% to about 29% acetone, about 65% to about 67.5% t-butyl acetate, about 1% to about 2.5% PCBTF, and about 1% 2-ethylhexanol.
Claims (8)
- A composition for use in cleaning metal components, wherein the Hansen Solubility Parameters for the composition are δD from about 12.0 to about 16.0, δP from about 3.0 to about 10.0, and δH from about 4.0 to about 6.9, and wherein the composition comprises a blend of organic solvents, wherein either none of the solvents are classified as a volatile organic compound, a hazardous air pollutant, or a potential carcinogen, or wherein the solvent exhibits a vapor pressure of less than 0.1 mmHg at 20°C, wherein the blend of organic solvents comprises:a halogenated aromatic solvent having one or more halide groups and from 6 to 8 carbon atoms, wherein the Hansen Solubility Parameters for the halogenated aromatic solvent are in the range of about δD : 17 - 19, δP: 5-7, and δH: 3-5 and wherein the halogenated aromatic solvent is not parachlorobenzotriflouride (PCBTF);an organic solvent having one or more ester functional group and from 3 to 9 carbon atoms, wherein the Hansen Solubility Parameters for the organic solvent are in the range of about δD : 14 - 16, δP: 3.5-7.5, and δH: 5-10; and one or more of the following:a linear or branched hydrocarbon solvent with 6-12 carbon atoms with a single polar moiety head group, wherein the Hansen Solubility Parameters for the hydrocarbon solvent are in the range of about δD : 6-9, δP: 1-3, and δH: 5-7; anda solvent containing one or more ketone functional groups and from 2 to 5 carbon atoms, wherein the Hansen Solubility Parameters for the solvent containing one or more ketone functional groups are in the range of about δD : 14-16, δP: 8.5 - 11, and δH: 5-8.
- The composition of claim 1, wherein the organic solvent with one or more ester functional groups is selected from the group consisting of tert-butyl acetate, methyl acetate, dimethyl carbonate, diethylene glycol monoethyl acetate, and diethylene glycol monobutyl ether acetate.
- The composition of claim 2, wherein the organic solvent with one or more ester functional groups is tert-butyl acetate, and wherein the tert-butyl acetate is present in an amount from about 15% to about 95% of the composition.
- The composition of claim 1, wherein the hydrocarbon solvent having a single polar moiety head group is 1-butoxyhexanol or 2-ethyl-hexanol, and wherein the hydrocarbon solvent is present in an amount from about 0.1% to about 2.5% of the composition.
- The composition of claim 1, wherein the solvent containing one or more ketone functional groups is acetone, and where in the acetone is present in an amount from about 5% to about 75% of the composition.
- The composition of claim 5, wherein the organic solvent with one or more ester functional groups is selected from the group consisting of tert-butyl acetate, methyl acetate, dimethyl carbonate, diethylene glycol monoethyl acetate, and diethylene glycol monobutyl ether acetate.
- The composition of claim 6, wherein the organic solvent with one or more ester functional groups is tert-butyl acetate.
- The composition of claim 5, wherein the composition further comprises a hydrocarbon solvent having a single polar moiety head group, and wherein the hydrocarbon solvent is 1-butoxyhexanol or 2-ethyl-hexanol.
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| EP24199985.3A EP4455191A3 (en) | 2019-08-27 | 2019-08-27 | Composition for use in cleaning metal components |
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| PCT/US2019/048255 WO2021040695A1 (en) | 2019-08-27 | 2019-08-27 | Composition for use in cleaning metal components |
| EP19943565.2A EP4022022B1 (en) | 2019-08-27 | 2019-08-27 | Composition for use in cleaning metal components |
| EP24199985.3A EP4455191A3 (en) | 2019-08-27 | 2019-08-27 | Composition for use in cleaning metal components |
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| US5207838A (en) * | 1991-08-29 | 1993-05-04 | Martin Marietta Energy Systems, Inc. | Nonhazardous solvent composition and method for cleaning metal surfaces |
| US5612303B1 (en) | 1993-06-15 | 2000-07-18 | Nitto Chemical Industry Co Ltd | Solvent composition |
| US6048471A (en) * | 1997-07-18 | 2000-04-11 | Richard G. Henry | Zero volatile organic compound compositions based upon organic solvents which are negligibly reactive with hydroxyl radical and do not contribute appreciably to the formation of ground based ozone |
| WO1998050517A1 (en) * | 1997-05-02 | 1998-11-12 | Advanced Chemical Design | Environmentally-safe solvent compositions utilizing 1-bromopropane that are stabilized, non-flammable, and have desired solvency characteristics |
| US6541435B2 (en) * | 2000-12-07 | 2003-04-01 | 3M Innovative Properties Company | Engine cleaner composition |
| US20080287331A1 (en) * | 2007-05-18 | 2008-11-20 | Hai-Hui Lin | Low voc cleaning composition for cleaning printing blankets and ink rollers |
| WO2012006404A2 (en) * | 2010-07-07 | 2012-01-12 | Greensolve, Llc | Solvent systems and methods of producing high flash point solvent systems including terpenes |
| US9422434B2 (en) * | 2013-03-15 | 2016-08-23 | Packaging Service Co, Inc. | Low VOC coating reducers |
| US10934506B2 (en) * | 2016-06-07 | 2021-03-02 | 3M Innovative Properties Company | Siloxane/hydrocarbon compositions and cleaning method using the same |
| US20180155557A1 (en) * | 2016-11-26 | 2018-06-07 | Packaging Service Co., Inc. | Abrasive paint remover compositions and methods for making and using same |
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