Patent Application
20100293723
The present invention relates to cleaning compositions, to methods of preparing such compositions, and to methods of using the cleaning compositions for cleaning of various substrates.
A variety of methods and systems are known for cleaning substrates that are sensitive to soluble and insoluble contaminants. These methods and systems typically use water, perchloroethylene, petroleum, and other solvents that are liquid at or substantially near atmospheric pressure and room temperature for cleaning the substrate.
Such conventional methods and systems generally had been considered satisfactory for their intended purpose. Recently, however, the desirability of employing these conventional methods and systems has been questioned due to environmental, hygienic, occupational hazard, and waste disposal concerns, among other things. For example, perchloroethylene frequently is used as a solvent to clean delicate substrates, such as textiles, in a process referred to as “dry cleaning” Some locales require that the use and disposal of this solvent be regulated by environmental agencies, even when only trace amounts of this solvent are to be introduced into waste streams.
Furthermore, there are significant regulatory burdens placed on solvents such as perchloroethylene by agencies such as the Environmental Protection Agency (EPA), Occupational Safety and Health Administration (OSHA) and the Department of Transportation (DOT). Such regulation results in increased costs to the user which in turn are passed to the ultimate consumer. For example, filters that have been used in conventional perchloroethylene dry cleaning systems must be disposed of in accordance with hazardous waste or other environmental regulations. Certain other solvents used in dry cleaning, such as hydrocarbon solvents, are extremely flammable, resulting in greater occupational hazards to the user and increased costs to control their use.
The present invention provides cleaning compositions and methods for using the same to clean various substrates such as, inter alia, textiles, flexible substrates (e.g. plastics, polymers, rubbers, etc.), precision substrates (e.g. circuits, electronic components), delicate substrates and porous substrates.
In one embodiment, the present invention provides a cleaning composition comprising an organic solvent and one or more cleaning additives. The interchangeable terms “cleaning composition” and “cleaning fluid” are used herein to describe a cleaning material that is liquid under ambient conditions and that comprises organic solvent and at least one cleaning additive other than an organic solvent. In one embodiment, such cleaning compositions contain no pressurized or densified fluid solvent, for example liquid carbon dioxide. In another embodiment, the organic solvent is a glycol ether.
In another embodiment, the present invention provides a cleaning composition comprising an organic solvent, water, and one or more of a surfactant, an antistatic agent, a neutralizing agent and an optical whitener. In one embodiment, the cleaning composition comprises a cationic surfactant and an anionic surfactant. In another embodiment, the surfactant is a phosphate ester.
In another embodiment, the present invention provides a cleaning composition comprising a glycol ether and a phosphate ester. In still another embodiment, a cleaning composition comprising a glycol ether, a phosphate ester and water is provided. In yet another embodiment, a cleaning composition comprising a glycol ether, a phosphate ester, a neutralizing agent and water is provided.
In still other embodiments, the present invention provides methods for preparing such cleaning compositions and for using the cleaning compositions to clean various substrates. In one embodiment, cleaning compositions of the invention are useful at removing both water soluble and water insoluble contaminants from a substrate.
These and other embodiments of the present invention are described in further detail hereinbelow.
While the present invention is capable of being embodied in various forms, the description below of several embodiments is made with the understanding that the present disclosure is to be considered as an exemplification of the invention, and is not intended to limit the invention to the specific embodiments illustrated. Headings are provided for convenience only and are not to be construed to limit the invention in any way. Embodiments illustrated under any heading may be combined with embodiments illustrated under any other heading.
The use of numerical values in the various ranges specified in this application, unless expressly indicated otherwise, are stated as approximations as though the minimum and maximum values within the stated ranges were both preceded by the word “about.” In this manner, slight variations above and below the stated ranges can be used to achieve substantially the same results as values within the ranges. As used herein, the terms “about” and “approximately” when referring to a numerical value shall have their plain and ordinary meanings to one skilled in the pertinent art at issue. Also, the disclosure of ranges is intended as a continuous range including every value between the minimum and maximum values recited as well as any ranges that can be formed thereby. This includes ranges that can be formed that do or do not include a finite upper and/or lower boundary as well as ratios that are derivable by dividing a given recited numeric value into any other recited numeric value. Accordingly, the skilled person will appreciate that many such ratios, ranges, and ranges of ratios can be unambiguously derived from the data and numbers presented herein and all such ratios, ranges, and ranges of ratios represent various embodiments of the present invention.
In one embodiment, cleaning compositions of the present invention comprise one or more organic solvents. The term “organic solvent” herein refers to carbon-containing compounds with capability of dissolving solids, gases and/or liquids and that are liquid under ambient conditions.
In one embodiment, the organic solvent (a) has a flash point of greater than about 100° F. to allow for increased safety and less governmental regulation, (b) has a low evaporation rate (e.g.<30 where n-butyl acetate=100) to minimize fugitive emissions, (c) is able to remove soils consisting of insoluble particulate soils and water or solvent soluble contaminants such as oils and greases, and/or (d) prevents or reduces redeposition of contaminant onto the textiles being cleaned.
In another embodiment, any organic solvent or mixture of organic solvents exhibiting any one or more of the following physical properties is suitable for use in accordance with the present invention: (1) soluble in carbon dioxide at a pressure of between about 600 and about 1050 pounds per square inch and at a temperature of between about 5 and about 30° C.; (2) specific gravity of greater than about 0.7 (generally, the higher the density, the better the organic solvent); (3) Hansen solubility parameters of about 7.2-8.1 (cal/cm3)1/2 for dispersion, about 2.0-4.8 (cal/cm3)1/2 for polar, and about 4.0-7.3 (cal/cm3)1/2 for hydrogen bonding (based on values cited in Publication No. M-167P from Eastman Chemical Products); (4) flash point greater than about 200° F.; and/or (5) evaporation rate of lower than about 30 (where n-butyl acetate=100).
The Hansen solubility parameters were developed to characterize solvents for the purpose of comparison. Each of the three parameters (i.e., dispersion, polar and hydrogen bonding) represents a different characteristic of solvency. In combination, the three parameters are a measure of the overall strength and selectivity of a solvent. The above Hansen solubility parameter ranges identify solvents that are suitable for a wide range of substances and also exhibit a degree of solubility in liquid carbon dioxide. The Total Hansen solubility parameter, which is the square root of the sum of the squares of the three parameters mentioned previously, provides a more general description of the solvency of the organic solvents.
Illustratively, propylene glycol n-butyl ether, tripropylene glycol n-butyl ether and tripropylene glycol methyl ether fall within all of the above parameters; however, any organic solvent or mixture of organic solvents that meet one or more of the above properties is suitable for use in the present invention. In one embodiment, the solvent meets 2 or more, 3 or more, or 4 or more of the above parameters. In another embodiment, the organic solvent exhibits each of the foregoing characteristics (i.e., those identified as (1) through (5)).
In another embodiment, the organic solvent has commercially acceptable environmental impact and toxicity (i.e. meeting or exceeding relevant EPA, FDA or other government regulations). Table 1 below shows the physical properties of a number of organic solvents suitable for use in compositions of the invention.
Solvents shown in Table 1 are soluble in carbon dioxide between 570 psig/5° C. and 830 psig/20° C. The flash point was measured using Tag Closed Cup for ethylene glycol ethyl ether and ethylene glycol ethyl ether acetate; using SETA Flash for diethylene glycol butyl ether, propylene glycol t-butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol n-butyl ether, and dipropylene glycol n-propyl ether; and using Pensky Martens Closed Cup for tripropylene glycol n-butyl ether. The values for the evaporation rate are based on n-butyl acetate=100. Finally, the specific gravity, flash point, evaporation rate and Hansen solubility parameters were obtained from Publication No. M-167P from Eastman Chemical Products for ethylene glycol ethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol butyl ether, and propylene glycol t-butyl ether; from “Products for Cleaners and the Personal Care Industry,” Arco Chemicals (1997), for dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol n-butyl ether, and dipropylene glycol n-propyl ether; and from Lyondell Chemical Company for tripropylene glycol n-butyl ether.
In still another embodiment, organic solvents suitable for use in the present invention include any of the following alone or in combination: cyclic terpenes, alkyl lactates (e.g. methyl, ethyl, propyl or butyl lactate) halocarbons, glycol ethers, polyols, ethers, esters of glycol ethers, esters of monobasic carboxylic acids, fatty alcohols, short chain alcohols, siloxanes, hydrofluoroethers, aliphatic hydrocarbons, esters of dibasic carboxylic acids, ketones and aprotic solvents.
Cyclic terpenes, specifically, α-terpene isomers, pine oil, α-pinene isomers, and d-limonene. Additionally, any cyclic terpene exhibiting the following physical characteristics is suitable for use in the present invention; (1) soluble in carbon dioxide at a pressure of between 600 and about 1050 pounds per square inch and at a temperature of between 5 and about 30 degrees Celsius; (2) specific gravity of greater than about 0.800 (the higher the specific gravity the better the organic solvent); (3) Hansen solubility parameters of about 13.0-17.5 (MPa)1/2 for dispersion, about 0.5-9.0 (MPa)1/2 for polar, and about 0.0-10.5 (MPa)1/2 for hydrogen bonding.
Halocarbons, specifically, chlorinated, fluorinated and brominated hydrocarbons exhibiting the following physical characteristics; (1) soluble in carbon dioxide at a pressure of between 600 and about 1050 pounds per square inch and at a temperature of between 5 and about 30 degrees Celsius; (2) specific gravity of greater than about 1.100 (the higher the specific gravity the better the organic solvent); (3) Hansen solubility parameters of about 10.0-17.0 (MPa)1/2 for dispersion, about 0.0-7.0 (MPa)1/2 for polar, and about 0.0-5.0 (MPa)1/2 for hydrogen bonding.
Glycol ethers, specifically, mono-, di-, triethylene and mono-, di- and tripropylene glycol ethers exhibiting the following physical characteristics; (1) soluble in carbon dioxide at a pressure of between 600 and about 1050 pounds per square inch and at a temperature of between 5 and about 30 degrees Celsius; (2) specific gravity of greater than about 0.800 (the higher the specific gravity the better the organic solvent); (3) Hansen solubility parameters of about 13.0-19.5 (MPa)1/2 for dispersion, about 3.0-7.5 (MPa)1/2 for polar, and about 8.0-17.0 (MPa)1/2 for hydrogen bonding.
Polyols, specifically, glycols and other organic compounds containing two or more hydroxyl radicals and exhibiting the following physical characteristics; (1) soluble in carbon dioxide at a pressure of between 600 and about 1050 pounds per square inch and at a temperature of between 5 and about 30 degrees Celsius; (2) specific gravity of greater than about 0.920 (the higher the specific gravity the better the organic solvent); (3) Hansen solubility parameters of about 14.0-18.2 (MPa)1/2 for dispersion, about 4.5-20.5 (MPa)1/2 for polar, and about 15.0-30.0 (MPa)1/2 for hydrogen bonding.
Ethers, specifically, ethers containing no free hydroxyl radicals and exhibiting the following physical characteristics; (1) soluble in carbon dioxide at a pressure of between 600 and about 1050 pounds per square inch and at a temperature of between 5 and about 30 degrees Celsius; (2) specific gravity of greater than about 0.800 (the higher the specific gravity the better the organic solvent); (3) Hansen solubility parameters of about 14.5-20.0 (MPa)1/2 for dispersion, about 1.5-6.5 (MPa)1/2 for polar, and about 5.0-10.0 (MPa)1/2 for hydrogen bonding.
Esters of glycol ethers, specifically, esters of glycol ethers exhibiting the following physical characteristics; (1) soluble in carbon dioxide at a pressure of between 600 and about 1050 pounds per square inch and at a temperature of between 5 and about 30 degrees Celsius; (2) specific gravity of greater than about 0.800 (the higher the specific gravity the better the organic solvent); (3) Hansen solubility parameters of about 15.0-20.0 (MPa)1/2 for dispersion, about 3.0-10.0 (MPa)1/2 for polar, and about 8.0-16.0 (MPa)1/2 for hydrogen bonding.
Esters of monobasic carboxylic acids exhibiting the following physical characteristics; (1) soluble in carbon dioxide at a pressure of between 600 and about 1050 pounds per square inch and at a temperature of between 5 and about 30 degrees Celsius; (2) specific gravity of greater than about 0.800 (the higher the specific gravity the better the organic solvent); (3) Hansen solubility parameters of about 13.0-17.0 (MPa)1/2 for dispersion, about 2.0-7.5 (MPa)1/2 for polar, and about 1.5-6.5 (MPa)1/2 for hydrogen bonding.
Fatty alcohols, specifically alcohols in which the carbon chain adjacent to the hydroxyl group contains five carbon atoms or more and exhibiting the following physical characteristics; (1) soluble in carbon dioxide at a pressure of between 600 and about 1050 pounds per square inch and at a temperature of between 5 and about 30 degrees Celsius; (2) specific gravity of greater than about 0.800 (the higher the specific gravity the better the organic solvent); (3) Hansen solubility parameters of about 13.3-18.4 (MPa)1/2 for dispersion, about 3.1-18.8 (MPa)1/2 for polar, and about 8.4-22.3 (MPa)1/2 for hydrogen bonding.
Short chain alcohols in which the carbon chain adjacent to the hydroxyl group contains four or fewer carbon atoms and exhibiting the following physical characteristics; (1) soluble in carbon dioxide at a pressure of between 600 and about 1050 pounds per square inch and at a temperature of between 5 and about 30 degrees Celsius; (2) specific gravity of greater than about 0.800 (the higher the specific gravity the better the organic solvent); (3) Hansen solubility parameters of about 13.5-18.0 (MPa)1/2 for dispersion, about 3.0-9.0 (MPa)1/2 for polar, and about 9.0-16.5 (MPa)1/2 for hydrogen bonding.
Siloxanes exhibiting the following physical characteristics; (1) soluble in carbon dioxide at a pressure of between 600 and about 1050 pounds per square inch and at a temperature of between 5 and about 30 degrees Celsius; (2) specific gravity of greater than about 0.900 (the higher the specific gravity the better the organic solvent); (3) Hansen solubility parameters of about 14.0-18.0 (MPa)1/2 for dispersion, about 0.0-4.5 (MPa)1/2 for polar, and about 0.0-4.5 (MPa)1/2 for hydrogen bonding.
Hydrofluoroethers exhibiting the following physical characteristics; (1) soluble in carbon dioxide at a pressure of between 600 and about 1050 pounds per square inch and at a temperature of between 5 and 30 degrees Celsius; (2) specific gravity of greater than about 1.50; (3) total Hansen solubility parameters of about 12.0 to 18.0 (MPa)1/2 for dispersion, about 4.0-10.0 (MPa)1/2 for polar, and about 1.5-9.0 (MPa)1/2 for hydrogen bonding.
Aliphatic hydrocarbons exhibiting the following physical characteristics; (1) soluble in carbon dioxide at a pressure of between 600 and about 1050 pounds per square inch and at a temperature of between 5 and about 30 degrees Celsius; (2) specific gravity of greater than about 0.700 (the higher the specific gravity the better the organic solvent); (3) Hansen solubility parameters of about 14.0-17.0 (MPa)1/2 for dispersion, about 0.0-2.0 (MPa)1/2 for polar, and about 0.0-2.0 (MPa)1/2 for hydrogen bonding.
Esters of dibasic carboxylic acids exhibiting the following physical characteristics; (1) soluble in carbon dioxide at a pressure of between 600 and about 1050 pounds per square inch and at a temperature of between 5 and about 30 degrees Celsius; (2) specific gravity of greater than about 0.900 (the higher the specific gravity the better the organic solvent); (3) Hansen solubility parameters of about 13.5-18.0 (MPa)1/2 for dispersion, about 4.0-6.5 (MPa)1/2 for polar, and about 4.0-11.0 (MPa)1/2 for hydrogen bonding.
Ketones exhibiting the following physical characteristics; (1) soluble in carbon dioxide at a pressure of between 600 and about 1050 pounds per square inch and at a temperature of between 5 and about 30 degrees Celsius; (2) specific gravity of greater than about 0.800 (the higher the specific gravity the better the organic solvent); (3) Hansen solubility parameters of about 13.0-19.0 (MPa)1/2 for dispersion, about 3.0-8.0 (MPa)1/2 for polar, and about 3.0-11.0 (MPa)1/2 for hydrogen bonding.
Aprotic solvents. These include solvents that do not belong to any of the aforementioned solvent groups, contain no dissociable hydrogens, and exhibit the following physical characteristics; (1) soluble in carbon dioxide at a pressure of between 600 and about 1050 pounds per square inch and at a temperature of between 5 and about 30 degrees Celsius; (2) specific gravity of greater than about 0.900 (the higher the specific gravity the better the organic solvent); (3) Hansen solubility parameters of about 15.0-21.0 (MPa)1/2 for dispersion, about 6.0-17.0 (MPa)1/2 for polar, and about 4.0-13.0 (MPa)1/2 for hydrogen bonding.
In yet another embodiment, in addition to the three physical properties described with respect to each of the above groups of organic solvents, the organic solvent further exhibits one or more of the following physical properties: (4) flash point greater than about 100° F.; and (5) evaporation rate of lower than about 50 (where n-butyl acetate=100). In another embodiment, the organic solvent is selected from one or more of the above groups and exhibits 2 or more, 3 or more, 4 or more or all 5 of the characteristics identified as (1) through (5).
Table 2 below shows the physical properties of a number of organic solvents that may be suitable for use in the present invention. In Table 2, the solvents are soluble in carbon dioxide between 570 psig/5° C. and 830 psig/20° C.
aBarton A. F. M.; Handbook of Solubility Parameters and Other Cohesion Parameters, 2nd Edition; CRC Press, 1991 (ISBN 0-8493-0176-9)
bWypych, George; Handbook of Solvents, 2001; ChemTec (ISBN 1-895198-24-0)
cAG Environmental Products, website.
dEstimated.
eClean Tech Proceedings 1998, pg 92
fFluorochem USA
gGE Silicones Fluids Handbook, Bulletin No. 59 (9/91).
hFedors Method: R.F. Fedoers, Polymer Engineering and Science, 1974.
In one embodiment, the organic solvent is composed at least in part of a chemical having the following general chemical formula:
CaXjHkOz General Chemical Formula A
wherein:
a=5n and 1≦n≦3;
0≦z≦4;
0≦j, k≦(10n+2); and
8≦(j+k)≦(10n+2);
each X is independently F, Cl, Br, or I.
Non-limiting examples of organic solvents described by General Chemical Formula A include pine oil, d-limonene, dipentene, myrcene, pinene, and alpha-terpineol.
In another embodiment, the organic solvent is composed at least in part of a chemical having the following general chemical formula:
CnXjHk General Chemical Formula B
wherein:
1≦n≦22;
0≦j, k≦(2n+2); and
(2n−4)≦(j+k)≦(2n+2);
each X is independently F, Cl, Br, or I.
Some examples of organic solvents described by General Chemical Formula B include n-propyl bromide, 1,1,2-trichlorotrifluoroethane, perfluorohexane, isoparaffins such as isodecane, isoundecane, isododecane, isotridecane, isotetradecane, isopentadecane, isohexadecane and isooctadecane, and n-paraffins such as n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane and n-octadecane.
In another embodiment, the organic solvent is composed at least in part of a chemical having the following general chemical structure:
wherein:
Ri═O, S, C,
Rii═CkHsXt or benzyl, phenyl, partially or fully fluorinated benzyl or phenyl;
Riv═CjHqXr or benzyl, phenyl, partially or fully fluorinated benzyl or phenyl;
0≦j, k≦18;and
0≦(j+k)≦18;
0≦q, r≦(2j+1); and
1≦(q+r)≦(2j+1);
0≦s, t≦(2j+1); and
1≦(s+t)≦(2k+1);
If j=0, then r=0;
If k=0, then t=0;
R1-4 and R9-12 are independently CmHnXp,
R5-8 and R13-16 are independently CaHbXd,
Some examples of organic solvents described by General Chemical Structure 1 include alpha-phenyl-ω-hydroxy-tetra (oxy-1,2-ethanediyl) and tetraethylene glycol dimethyl ether.
In another embodiment, the organic solvent is composed at least in part of a chemical having the following general chemical structure:
wherein:
0≦x, y, z≦1;and
1≦(x+y+z)≦3;
Ri═O, S, C,
Rii═CkHsXt or benzyl, phenyl, partially or fully fluorinated benzyl or phenyl;
Riv═CjHqXr or benzyl, phenyl, partially or fully fluorinated benzyl or phenyl;
j or k may equal 0;
If j=0, then [14−3(x+y+z)]≦k≦[37−3(x+y+z)];
If k=0, then [14−3(x+y+z)]≦j≦[37−3(x+y+z)];
If neither j nor k=0, then [14−3(x+y+z)]≦(j+k)≦[37−3(x+y+z)];
1≦(q+r)≦(2j+1);
1≦(s+t)≦(2k+1);
R1-3 and R7-9 are independently CmHnXp,
R4-6 and R10-12 are independently CaHbXd,
Some examples of organic solvents described by General Chemical Structure 2 include triethylene glycol mono-oleyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, methoxy triglycol, ethoxy triglycol, butoxy triglycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol n-butyl ether, propylene glycol t-butyl ether, dipropylene glycol n-propyl ether, and ethylene glycol phenyl ether.
In another embodiment, the organic solvent is composed at least in part of a chemical having the following general chemical formula:
CnHjXk(OH)r General Chemical Formula C
wherein:
each X is independently F, Cl, Br, or I;
1≦n≦22
0≦r≦4;
0≦j, k≦(2n+2−r) and
4≦(j+k)≦(2n+2−r)
Some examples of organic solvents described by General Chemical Formula C include hexylene glycol, 1,4-butanediol, glycerine, lauryl alcohol, n-hexanol and 2-ethyl hexanol.
In another embodiment, the organic solvent is composed at least in part of a chemical having the following general chemical formula:
CnHjXkOb General Chemical Formula D
wherein:
each X is independently F, Cl, Br, or I;
2≦n≦32
0≦j, k≦(2n+2);
6≦(j+k)≦2n+2; and
1≦b≦6.
Some examples of organic solvents described by General Chemical Formula D include di-n-butyl ether, di-n-amyl ether, 1-methoxy nonafluorobutane, 1-ethoxy nonafluorobutane, 3-ethoxy-2-trifluoromethyl perfluorohexane, and anisole.
In another embodiment, the organic solvent is composed at least in part of a chemical having the following general chemical structure:
wherein:
0≦w, x, y, z≦1;
1≦(w+x+y+z)≦4;
Ri═O, S, C,
Rii═CkHaXb or benzyl, phenyl, partially or fully fluorinated benzyl or phenyl;
Riii═CjHuXv or benzyl, phenyl, partially or fully fluorinated benzyl or phenyl;
0≦(j+k)≦[34−3(w+x+y+z)]; and
0≦u, v≦(2j+1); and
(2j−7)≦(u+v)≦(2j+1); and
0≦a, b≦(2k+1); and
(2k−7)≦(a+b)≦(2k+1);
R1-4 and R9-12 are independently CmHnXp,
R5-8 and R13-16 are independently CqHaXt,
each X is independently F, Cl, Br, or I.
Some examples of organic solvents described by General Chemical Structure 3 include tripropylene glycol methyl ether, dipropylene glycol methyl ether, dipropylene glycol methyl ether acetate, propylene glycol n-butyl ether, propylene glycol t-butyl ether, tripropylene glycol n-butyl ether, dipropylene glycol dimethyl ether, and propylene glycol phenyl ether.
In another embodiment, the organic solvent is composed at least in part of a chemical having the following general chemical structure:
wherein:
0≦w, x, y, z≦1; and
1≦(w+x+y+z)≦4;
Ri═O, S, C,
Rii═CkHaXb or benzyl, phenyl, partially or fully fluorinated benzyl or phenyl;
Riv=ester, or carbonyl;
Rv═CjHaXv or benzyl, phenyl, partially or fully fluorinated benzyl or phenyl;
0≦(j+k)≦[34−3(w+x+y+z)];
0≦u, v≦(2j+1);
(2j−7)≦(u+v)≦(2j+1);
0≦a,b≦(2k+1);
(2k−7)≦(a+b)≦(2k+1); and
R1-4 and R9-12 are independently CmHnXp,
R5-8 and R13-16 are independently CqHsXt,
each X is independently F, Cl, Br, or I.
Some examples of organic solvents described by General Chemical Structure 4 include ethylene glycol diacetate, and propylene glycol diacetate.
In another embodiment, the organic solvent is composed at least in part of a chemical having the following general chemical structure:
Cn(CO2)mHaXb General Chemical Formula D
wherein:
each X is independently F, Cl, Br, or I;
2≦n≦38;
1≦m≦3;
0≦a, b≦(2n+2); and
(2n−2)≦(a+b)≦(2n+2).
Examples of organic solvents described by General Chemical Formula D include dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl succinate, 2-ethylhexyl acetate, n-hexyl acetate, n-amyl acetate, isobutyl isobutyrate, n-butyl propionate, n-amyl propionate, glycerol triacetate, and soy methyl esters.
In another embodiment, a cleaning composition of the invention comprises on organic solvent of the following general chemical formula:
Cn(CO3)mHaXb General Chemical Formula E
wherein:
each X is independently F, Cl, Br, or I;
2≦n≦18;
0≦a, b≦(2n+2); and
(2n−4)≦(a+b)≦(2n+2).
Some examples of organic solvents described by General Chemical Formula E include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and diphenyl carbonate.
In another embodiment, the organic solvent is composed at least in part of a chemical having the following general chemical structure:
wherein:
R1═CJHaXb
R2═CkHdXe
R3═CmHfXg
each X is independently F, Cl, Br, or I.
Some examples of organic solvents that are described by General Chemical Structure 5 include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, and tributyl phosphate.
In another embodiment, the organic solvent is composed at least in part of a chemical having the following general chemical formula:
SOeCnHjXk General Chemical Formula F
wherein:
each X is independently F, Cl, Br, or I;
1≦e≦2;
2≦n≦8;
0≦j, k≦(2n+2); and
2n≦(j+k)≦(2n+2).
Examples of organic solvents described by General Chemical Formula F are dimethylsulfoxide and sulfolane.
In another embodiment, the organic solvent is composed at least in part of a chemical having the following general chemical formula:
CnHyNaObXz General Chemical Formula G
wherein:
1≦n≦10;
1≦a, b≦2; and
a=b;
0≦y, z≦(2n+1); and
(2n−1)≦(y+z)≦(2n+1);
Each X is independently F, Cl, Br, or I.
Some examples of organic solvents that are described by General Chemical Formula G include dimethylformamide and dimethylacetamide.
In another embodiment, the organic solvent is composed at least in part of a chemical having the following general chemical structure:
wherein:
0≦n≦500
each R equals CaXyHz independently;
1≦a≦6; and
0≦y, z≦(2a+1);
and (y+z)=(2a+1);
each X is independently F, Cl, Br, or I.
Examples of solvents described by General Chemical Structure 6 are dimethicones.
In another embodiment, the organic solvent is composed at least in part of a chemical having the following general chemical structure:
wherein:
2≦n≦4;
each R equals CaHyXz independently;
each X is independently F, Cl, Br, or I;
1≦a≦6
0≦y, z≦(2a+1); and
(y+z)=(2a+1).
Examples of solvents described by General Chemical Structure 7 are octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.
In another embodiment of the invention, the organic solvent comprises a glycol ether described by General Chemical Structure 8:
A complete description of the glycol ether compounds that fall within the generic structure above and that fulfill the functional parameters of the invention takes into account some variability in the number of subunits identified by subscripts “x”, “y” and “z”. Subscripts “x”, “y” and “z” can each be either zero or one and each of their values is independent of the value of the other two subscripts. That is, the subscripts can have values different from each other. However, at least one of “x”, “y” or “z” is one. Group R′ has the structure of a straight-chain or branched alkyl group; that is a structure of CjH2j+1. Subscript value “j” is an integer ranging from one and the value of the difference calculated by 13−3(x+y+z). Because at least one of “x”, “y” and “z” must always have the value of 1, “j” has a value ranging from 4 to 10. Groups R1, R2 and R3 are each independently either H or CH3. The identities of R1, R2 and R3 are selected independent of each other; therefore, R1 and R2 can be H while R3 is CH3. The types of glycol ether compounds that are encompassed by this chemical structure include, but are not limited to, mono and polyethylene and propylene glycol aliphatic ethers.
Another group of organic solvent compositions that can be used in the cleaning processes of the invention include solvents that can be described as having the chemical structure of:
The subscripts “x”, “y” and “z” can each be either zero or one and each of their values is independent of the value of the other two subscripts. That is, the subscripts can have values different from each other. However, at least one of “x”, “y” or “z” is one.
Group R″ has the structure of benzyl, phenyl, their fluorinated and partially fluorinated analogues, CjH2j+1, or CjHaFb. Subscript value “j” is an integer ranging from one and the value of the difference calculated by 13−3(x+y+z). Subscript values “a” and “b” range from zero to 2j+1; and a+b=2j+1. Because at least one of “x”, “y” and “z” must always have the value of 1, “j” has a value ranging from 4 to 10. Group R′ can be any one of an O, S, carbonyl or ester groups. Lastly, R1-12 have a general formula of CmHnFp or CdHeFg. The subscripts “m”, “n” and “p” have the values described as follows: “m” is an integer ranging from zero to two; “n” and “p” are integers ranging from zero to five; and n+p=2m+1. The subscripts “d,” “e” and “g” have the values described as follows: “d” is an integer ranging from zero to two; “e” and “g” are integers ranging from zero to five; and e+g=2d+1. The types of glycol ether compounds that are encompassed by this chemical structure include, but are not limited to, aromatic, aliphatic, and fluorinated and partially fluorinated, aliphatic and aromatic mono and poly glycol ethers and thioethers, and carbonyl and ester derivatives thereof.
The General Chemical Structure 9 described above can also be broken down further into various subgroups, as is shown in Table 3 below.
In each of the groups described in Table 3 above, R1-12 are grouped together as R1-3, R4-6, R7-9, and R10-12 for ease of description. Where the individual components of a group can be different elements, the elements are described in the chart in the alternative. For example, R1-3 may be described as “H or F.” In a given solvent compound with this description, each of R1, R2 and R3 may be H or each of R1, R2 and R3 may be F. Alternatively, R1 and R2 may be H while R3 is F, and so forth with the various combinations of “H” and “F”. This is the same throughout all Tables in this specification.
Another group of suitable organic solvent include solvents that can be described as having the chemical structure of:
In General Chemical Structure 10, subscripts “x”, “y” and “z” each have a value of either zero or one, but at least one of “x”, “y” and “z” has a value of one. Group R″ has a structure of CjH2j+1 or CjHuFv and group RW has a structure of CkH2k+1 or CkHrFs. The values of subscripts “j” and “k” are integers ranging from one and the value of 13−3(x+y+z). Therefore, subscripts “j” and “k” can have integer values ranging from one and a maximum value of 10 (if two of “x”, “y” and “z” are zero). Further, the sum, j+k is an integer ranging from two and the value of 13−3(x+y+z). The subscripts “u” and “v” are integers ranging from zero to 2j+1; and u+v=2j+1. The subscripts “r” and “s” are integers ranging from zero to 2k+1; and r+s=2k+1.
In further defining General Chemical Structure 10, groups R1-3 and R10-12 can be hydrogen (“H”), fluorine (“F”), methyl (“CH3”), ethyl (“CH2CH3”), or partially or fully fluorinated methyl or ethyl groups. Each one of R1-3 and R10-12 are selected independently of each other so as to achieve various combinations of the above as contemplated by the invention. Generally, R1-3 have the formula of CmHnFp. The subscripts “m”, “n” and “p” have the values described as follows: “m” is an integer ranging from zero to two; “n” and “p” are integers ranging from zero to five; and n+p=2m+1. Additionally, groups R4-9 can each be hydrogen, fluorine or methyl groups. As with the other groups, the identity of each of R4-9 is selected independent of the identity of the other groups. Finally, the identity of group R′ in General Chemical Structure R is either O, S, a carbonyl group or an ester group. Each of the solvent compounds characterized by General Chemical Structure R is suitable for use as an organic solvent in compositions of the invention. The types of glycol ether compounds that are encompassed by this chemical structure include, but are not limited to, aliphatic and fluorinated and partially fluorinated aliphatic mono and poly glycol diethers and ether thioethers and carbonyl and ester derivatives thereof.
The General Chemical Structure 10 described above can also be broken down further into various subgroups, as is shown in Table 4 below.
In each of the groups described in Table 4 above, one or more of R1-12 are described together. For example, R1-3 may be described as “H or CH3 independently.” In a given solvent compound with this description, each of R1, R2 and R3 may be H or each of R1, R2 and R3 may be CH3. Alternatively, R1 and R2 may be H while R3 is CH3, and so forth with the various combinations of “H” and “CH3”.
In another embodiment, the organic solvent is of the following structural formula:
In General Chemical Structure 11, subscripts “x”, “y” and “z” each have a value of either zero or one, but at least one of “x”, “y” and “z” has a value of one. Group R″ is either H or has one of the following structures:
where R′″ is H, F or combinations of H and F and group RIV is either H or one of the following structures:
where RV is H, F or combinations of H and F. Where R″ is H or F, RIV is not H or F.
Groups R′″ and RV are either H or F groups or combinations of H and F. Therefore, within a given R″ or RIV group, the R″′ groups and RV groups can be both hydrogens and fluorines; they are not limited to being only hydrogen or fluorine. In further defining General Chemical Structure 11, groups R1-3 can be H, F, CH3, CH2F, CHF2 or CF3. Each one of R4-12 is independently either H or F.
In another embodiment the organic solvent has the following structural formula:
In General Chemical Structure 12, R′ is:
and R″ is:
Each R′″ is O or N independently. Where R″′ is O, j is 1. Where R″′ is N, j is 2. Each RIV is independently H, CH3 or CH2CH3 and k, n, r and s are integers between zero and two inclusive. R is CyH2y+1 and y is an integer between one and (23−(3k+3n+x)) inclusive or an integer between one and (23−(4r+4s+x) inclusive, and x is an integer between one and (23−(3k+3n+y)) inclusive or an integer between one and 23−(4r+4s+y) inclusive.
In another embodiment, the organic solvent is of the following structural formula:
In General Chemical Structure 13, R′ and R″ are as follows:
where n is an integer between two and 15 inclusive and z is an integer between zero and n inclusive. Each RIV is independently H, CH3 or CH2CH3. R is CyH2y+1 and y is an integer between one and (36−(3n+x)) inclusive, and x is an integer between one and (36−(3n+y)), inclusive, and 3n+x+y is less than or equal to 36, and m is zero or one.
In one embodiment, cleaning composition of the invention comprise one or more cleaning additives, also referred to herein as “additives”. A “cleaning additive” herein is any compound or ingredient that enhances the cleaning capability of the cleaning composition or imparts a desirable characteristic on the substrate being cleaned.
Non-limiting examples of cleaning additives useful in various embodiments of the present invention include water, detergents, cleaning aids (e.g. solvents, bleaches, enzymes, dispersants and suspending agents), sizing agents, fabric conditioners, water repellents, soil repellents, fragrances, deodorizers, optical whiteners, biocides, antistatics, defoamers, corrosion inhibitors, viscosity modifiers, hydrotropes, etc. Any such cleaning additives can optionally be present in cleaning compositions of the present invention, for example, in amounts of 0% to 99%, by weight, for example, about 0.001, about 0.01%, about 0.1%, about 1%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 100% or within any range of percentages formable thereby.
Detergents are substances that can (a) carry moisture to aid in the removal of water soluble soils, (b) aid in the removal of insoluble soils from the substrate, (c) suspend soil after it has been removed from the fabric and prevent/reduce redeposition; and/or (d) act as a stain removal aid. Based on their charge and how they carry water, there are three classifications of detergents: anionic detergents are negatively charged and carry water by means of solubilization/emulsification; non-anionic detergents carry no charge and carry water by solubilization/emulsification; cationic detergents are positively charged and carry water by means of solubilization/emulsification.
Non-limiting examples of detergents include surfactants (also called surface-active agents) from the following general classes: alcohols, alkanolamides, alkanolamines, alkylaryl sulfonates, alkylaryl sulfonic acids, salts of alkylaryl sulfonic acids, sulfonates & sulfates of alkylbenzenes, alpha olefins, amine acetates, amine oxides, amines, sulfonated amine and amides, betaines, betaine derivatives, block polymers and block copolymers, carboxylated alcohol or alkyphenol ethoxylates, carboxylic acids and fatty acids, salts of carboxylic acids and fatty acids, diphenyl sulfonate derivatives, ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated amines and or amides, ethoxylated aryl phenols, ethoxylated fatty acids, ethoxylated fatty esters and oils, fatty esters, fluorocarbon-based glycerol esters, imidazolines and imidazoline derivatives, isethionates, lanolin-based derivatives, lecitin and lecithin derivatives, lignin and lignin derivatives, maleic or succinic anhydrides, methyl esters, monoglycerides and derivatives of glycerol esters, olefin sulfonates, phosphate esters, phosphorous organic derivatives, polyethylene glycols, polymeric (polyaccharides, polyacrylic acid, polyacrylamide), propoxylated and ethoxylated fatty acid alcohols or alkyl phenols, protein-based surfactants, quaternary surfactants, sarcosine derivatives, silicone-based materials, soap, sodium isethionate, sorbitan derivatives, sucrose and glucose esters and derivatives, sulfates and sulfonates of oils and fatty acids, sulfates and sulfonated ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols, sulfates of fatty esters, sulfonates of benzene cumene toluene and xylene, sulfonates of condensed naphthalenes, sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthalene and alkyl naphthalene, sulfonates of petroleum, sulfosuccinamates, sulfosuccinates and derivatives, taurates, thio and mercapto derivatives, tolulene sulfonic acids, tridecyl and dodecyl benzene sulfonic acids.
Suitable surfactant can be a cationic or anionic or non-anionic. Non-limiting examples of specific surfactants include: (1) akanolamides such as Mackamide® ISA, available from McIntyre Group; Monamide® S available from Uniqema, Chemical; Ninol L-9 available from Stepan Company; (2) alkylaryl sulfonates such as Witconate 1240 available from Akzo-Nobel; (3) amine oxides such as Ammonyx® MO available from Stepan Company; (4) amines such as Armeen® C available from Akzo Nobel; (5) betaines such as Mackam® BC-39 available from McIntyre Group; (6) block copolymers such as T-Det® BP-1 available from Harcros Chemicals; (7) alkyphenol ethoxylates such as Incrodet® TD7-C available from Croda, Inc., (8) ethoxylated fatty acids such as Lumulse®40-L available from Lambent Technologies; (9) ethoxylated alcohols such as Neodol®45-7 available from Shell Chemical, (10) phosphate ester-containing compounds such as Colafax®3376 available from Colonial Chemical, octylphenol phosphate ester, for example ethoxylated (e.g. 3-15, 4-10 or 7-10 moles) octylphenol phosphate ester, ethoxylated (e.g. 3-15, 4-10 or 7-10 moles) nonylphenol phosphate ester, ethoxylated (e.g. 3-15, 4-10 or 7-10 moles) isodecyl alcohol phosphate ester, ethoxylated linear or branched alcohol C8-C10 phosphate ester, for example ethoxylated linear alcohol C8-C10 phosphate ester, or ethoxylated (e.g. 3-15, 4-10 or 7-10 moles) octylphenol phosphate ester; (11) quaternary surfactants such as Arquad® 2HT-75 available from Akzo-Nobel; (12) sulfates of alcohols such as Calfoam® SLS-30 available from Pilot Chemical and (13) dodecyl benzene sulfonic acid or salts thereof such as Biosoft® S-100 available from Stepan Company.
The term “phosphate ester-containing compound” herein refers to a compound containing the following phosphate ester functional group:
where any of the R groups can be a hydrogen or any organic radical.
If desired, one or more detergents are optionally present in a composition of the invention in an amount of about 0.001% to about 90%, about 0.1% to about 40% or about 1% to about 20%, by weight or volume, or within any range formable by numbers within the foregoing ranges. In another embodiment, one or more detergents are optionally present in a composition of the invention in an amount of about 0.01, 0.5%, 0.75%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% or 25%, by weight or volume.
Compositions of the invention optionally comprise one or more neutralizing agents. Neutralizing agents are agents that neutralize acidic or basic compounds in a cleaning composition. Neutralizing agents useful in the present invention include agents possessing activity as a weak or strong base or acid.
In one embodiment, neutralizing agents useful in accordance with the present invention comprise an amine compound. Amine compounds can include but are not limited to primary, secondary and tertiary amines with a carbon chain length from 2 to 22 (C2-22). The carbon chain attached to the nitrogen can be straight chain or branched and can optionally contain an alcohol, amide, ester or ketone group. Compounds containing more than one nitrogen are possible as are compounds containing more than one carbon chain. The amine can also be ethoxylated or propoxylated. Specific examples of amine compounds include but are not limited to: ammonia, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, Armeen® C, Armeen® 2C, Armeen® 316, Duomeen® T, Ethomeen® O/12, Propomeen® T/12 (all available from Akzo-Nobel Chemical).
In another embodiment, the neutralizing agent comprises a salt of a Group Ia, IIa, and/or transition metal as defined in the periodic table of elements. Non-limiting examples of salts of Group Ia metals include: sodium bicarbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, potassium hydroxide, sodium citrate, sodium hydroxide, sodium phosphate, sodium polyphosphate, sodium pyrophosphate, sodium sesquicarbonate, sodium acetate, sodium tripolyphosphate, tetrapotassium pyrophosphate, tetrasodium pyrophosphate, tripotassium phosphate, and trisodium phosphate.
Non-limiting examples of salts of Group IIa metals include magnesium hydroxide, calcium carbonate, calcium phosphate, calcium hydroxide, calcium bicarbonate, calcium citrate, calcium borate, magnesium hydroxide, magnesium, metasilicate aluminate, and magnesium oxide. Non-limiting examples of a suitable salt of a transition metal includes zinc hydroxide.
If desired, one or more neutralizing agents are optionally present in a composition of the invention in an amount of about 0.001% to about 20%, about 0.005% to about 10%, about 0.01% to about 5%, about 0.1% to about 2.5%, or in any amount within any of the foregoing ranges. In other embodiments, the neutralizing agent is present in an amount of about 0.001%, 0.01%, 0.1%, about 0.25%, about 0.5%, about 0.75%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11% or within any range formable thereby.
In one embodiment, a neutralizing agent can be admixed directly with other components of the cleaning composition. In another embodiment, one or more neutralizing agents can be prepared as a solution (e.g. an aqueous solution), for example a potassium hydroxide solution (e.g. about 1% to about 90% in water). Such a neutralizing agent solution can then be admixed with other components of the cleaning composition so as to comprise about 0.0001% to about 99%, about 0.001% to about 40%, or about 0.01% to about 30%, by weight or volume, of the final cleaning composition. It will be understood that the total volume of neutralizing agent solution added will depend on the concentration of the neutralizing agent in solution. Such neutralizing agent or neutralizing agent solution typically will be added in an amount sufficient to neutralize other acidic or basic compounds in a cleaning composition to form cationic and anionic surface active substances (surfactants), respectively.
Compositions of the invention can optionally comprise one or more cleaning aids. Cleaning aids include solvents that increase the ability of the organic solvent to remove oily types of soil from a substrate. Non-limiting examples of general classes of cleaning aids include hydrocarbons (e.g. olefins, cycloparaffins, aromatics and terpenes), halogenated hydrocarbons (e.g. chlorinated, fluorinated, brominated, iodinated and combinations thereof), nitroparaffins, organic sulfur compounds, monohydric alcohols and their derivatives (e.g. methanol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, etc.), polyhydric alcohols and their derivatives (e.g. ethylene glycol, propylene glycol, glycerol), phenols, aldehydes (e.g. furfural), ethers (e.g. dimethyl ether and isopropyl ether), glycol ethers, ketones (e.g. methyl isobutyl ketone and acetone), amines, heterocyclic compounds (e.g. 2-pyrrolidone and morpholine), and esters (e.g. formates, acetates, propionates, butyrates, adipates, oxalates, lactates and carbonates).
Non-limiting examples of specific cleaning aids include: Per Sec® available from R.R. Street & Co. Inc., DF-2000® available from R.R. Street & Co. Inc., isopropyl alcohol available from Brenntag Chemical, Armeen®12 available from Akzo-Nobel Chemical, and ethylene glycol monobutyl ether available from Dow Chemical.
If desired, one or more optional cleaning aids are present in a composition of the invention in an amount of about 0.01% to about 60%, about 0.1% to about 40%, or about 1% to about 30%, by weight or volume, or in any specific amount within such ranges.
Compositions of the invention optionally comprise one or more bleaches. Bleaches can be classified as either oxidizing or reducing. Non-limiting examples of oxidizing bleaches include sodium percarbonate, sodium perborate and sodium hypochlorite and hydrogen peroxide. Non-limiting examples of reducing bleaches include sodium bisulfite, sodium hydrosulfite, titanium sulfate and oxalic acid. If desired, one or more optional bleaches can be present in a composition of the invention in an amount of about 0.01% to about 60%, about 0.1% to about 40%, or about 1% to about 30%, by weight or in any specific amount within the foregoing ranges.
Compositions of the invention optionally comprise one or more enzymes. Enzymes are substances that assist in removal of selected soils from a substrate. Non-limiting examples of enzymes include protease, lipase, amylase, cellulase, and pectinase. Non-limiting examples of suitable enzymes include: Alcalase® 3.0T, Celluzym® 0.7T and Termamyl® 120L, all available for Novo Nordisk. If desired, one or more optional enzymes are typically present in a composition of the invention in an amount of about 0.001% to about 25%, about 0.01% to about 20%, or 1% to about 15%, by weight or by volume, or any specific amount within the foregoing ranges.
Compositions of the invention optionally comprise one or more dispersants. Dispersants are materials that increase the stability of removed soil particles (e.g. removed from the substrate being cleaned) in a cleaning fluid and helps keep them dispersed. Non-limiting examples of classes of dispersants include polyacrylate copolymers, dioctyl esters of sodium sulfosuccinic acid, organically modified clay, and phosphate esters. Non-limiting examples of dispersants include Good-rite® K-723 available from Noven Inc., Alcosperse® 157 available from Alco Chemical, and Maphos® 60A available from BASF Specialty Chemicals.
Compositions of the invention optionally comprise one or more suspending agents. Suspending agents are compounds that assist in suspending soils within a cleaning media. Non-limiting examples of suitable classes of suspending agents include acrylic polymers, sodium carboxymethylcellulose, hydroxyethylcellulose, organically modified clay, xanthan gum, etc. Non-limiting examples of suitable suspending agents include Acusol® 803 available from Rohm & Haas Company, Carbopol® 941NF available from Novon Inc., Kelfo® available from CP Kelco Chemical, and Natrosol® HHR available from Hercules Chemical. If desired, one or more optional suspending agents are present in a composition of the invention in an amount of about 0.01% to about 60%, about 2% to about 40%, or about 5% to about 30%, by weight, or within any range formable thereby.
Compositions of the invention optionally comprise one or more sizing agents. Sizing agents are materials that function to impart stiffness on a substrate such as a textile. Illustratively, sizing agents can include acrylamides, acrylates, alchols, aliphatics, aliphatic esters, aromatics, aromatic esters, cellulosic materials, ethers, polyesters, etc. Non-limiting examples of sizing agents include butylmethacrylate/methacrylate, methymethacrylate, acrylate/hydroxylesteracrylate, vinylacetate, vinylacetate/butyl maleate/isobornyl acrylate, vinylacetate/crotonate copolymer, terpene, C5, vinylacetate/ethylene, methylstryrene/vinyltoluene, methylstyrene, isophthalic acid/trimellitic anhydride, stryrene/maleic anhydride, hydroxypropyl cellulose, cationic cellulose, ethoxylated cellulose, hydroxypropyl guar, ethylene oxide, isobutylenethylmaleimide/hydroxymaleimide, methacrylic acid/sodium acrylamidomethyl, propane sulfonate, polyvinylpyrrolidone, polyvinyl caprolactam, quaternized vinylpyrrolidone, straight and branched hydrocarbon materials and pentaerythritol ester of rosin.
Non-limiting examples of specific sizing agents include Amphomer® LV-71 National Starch & Chemical Co., Aquaflex® FX-64 from International Specialty Products, Luviskol® VA-W from BASF Corporation, Kristalex 3100 hydrocarbon resin from Eastman, and Unicare Polymer® LK from Amerchol Corporation. In one embodiment, the sizing agent comprises a styrene-based polymer resin. In another embodiment, the styrene-based polymer resin is soluble in glycol ether. One or more sizing agents, if desired, are typically present in a composition of the invention in an amount of about 0.01% to about 20%, about 0.1% to about 10%, or about 3% to about 8%, by weight or by volume, for example about 0.1%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 15%, by weight or by volume, or within any range formable thereby.
Compositions of the invention optionally comprise one or more fabric conditioning agents. Fabric conditioning agents are materials that impart a soft feel on a substrate. Non-limiting examples of types of fabric conditioning agents include quaternary ammonium salts, ethoxylated quaternary ammonium salts, amine oxides, amides, tertiary amines, tertiary amine salts, clay, silicone, and silicone polymers. Non-limiting examples of specific conditioning agents include Adogen® 432 available from Degussa Chemical, Arquad® 2HT-75 available from Akzo-Nobel Chemical, Rewoquat® SQ24 available from Degussa Chemical, Magnisoft (amino silicone polymer available from GE Silicones), and Varisoft® 222 available from Degussa Chemical and mixtures thereof.
One or more fabric conditioning agents, if desired, can be present in a composition of the invention in an amount of about 0.001% to about 20%, about 0.01% to about 10%, or about 0.1% to about 8%, by weight or by volume, or any specific amount within the foregoing ranges.
Compositions of the invention optionally comprise one or more water repellants. Water repellents are substances that assist in repelling water from a substrate. Non-limiting examples of suitable classes of water repellents include fluorocarbon polymers, silicone polymers, quaternary ammonium salts, waxes, stearates, etc. In various embodiments, the water repellent is selected from aluminum stearate, calcium stearate, paraffin wax, polyethylene wax, Arquad® 2HT-75 from Akzo-Nobel Chemical, Ganex® V-220 from International Specialty Products, Mirasil® Wax-B from Rhodia Home Personal Care & Industrial Ingredients, Witco® Calcium Stearate F from Crompton Corp., Zony® 8740 from Du Pont Corporation, and mixtures thereof.
One or more water repellents, if desired, are present in a composition of the invention in an amount of about 0.001% to about 20%, about 0.01% to about 10%, or about 0.1% to about 8%, by weight or by volume, or any specific amount within the foregoing ranges, for example about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 15%, by weight or by volume.
Compositions of the invention optionally comprise one or more soil repellants. Soil repellents are materials that assist in repelling soil from a substrate. Non-limiting examples of suitable soil repellents include fluorocarbon polymers, silicone polymers, quaternary ammonium salts, polyethylene wax, aluminum stearate and calcium stearate. One or more soil repellents, if desired, can be present in a composition of the invention in an amount of about 0.001% to about 20%, about 0.01% to about 10%, or about 0.1% to about 8%, by weight or by volume, or any specific amount within such ranges, for example about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 15%, by weight or by volume, or within any range formable thereby.
Compositions of the invention optionally comprise one or more fragrances. Fragrances are substances that impart a desirable odor to a substrate. Fragrances can comprise esters or ketones, among other chemical structures. Illustrative fragrances are available from the following companies: Bell Flavors & Fragrances, Northbrook, Ill., Givavdan S. A., Geneva, Switzerland, and International Flavors and Fragrances, New York, N.Y. One or more fragrances, if desired, are typically present in a composition of the invention in an amount of about 0.001% to about 20%, about 0.01% to about 10%, or about 0.1% to about 8%, by weight or by volume, or any specific amount within such ranges, for example about 1% about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 15%, by weight or by volume.
Compositions of the invention optionally comprise one or more deodorizers. Deodorizers are substances that assist in neutralizing or masking malodors. Non-limiting examples of deodorizers include zinc ricinoleate, cyclodextrins, as well as fragrances, or odor masks. One illustrative deodorizer includes TEGO® Sorb Ready 24 available from Degussa/Goldschmidt Chemcial.
One or more deodorizers, if desired, are typically present in a composition of the invention in an amount of about 0.001% to about 20%, about 0.01% to about 10%, or about 0.1% to about 8%, by weight or by volume, or any specific amount within such ranges, for example about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 15%, by weight or by volume, or within any range formable thereby.
Compositions of the invention optionally comprise one or more optical whitening agents (also referred to as fluorescent whitening agents, optical bleaches or optical dyes). Optical whitening agents are substances that improve the whiteness of a substrate. Non-limiting examples of whitening agents include substances such as 4,4′-distyrylbiphenyl sodium sulfonate (Tinopal® CBSX from Ciba Specialty Chemicals) or coumarin derivatives such as Burcofluor® OBS 100 from Burlington Chemical. One or more fluorescent whitening agents, if desired, are typically present in a composition of the invention in an amount of about 0.001% to about 20%, about 0.01% to about 10%, or about 0.1% to about 8%, by weight or by volume, or any specific amount within such ranges, for example about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 15%, by weight or by volume or within any range formable thereby.
Compositions of the invention optionally comprise one or more biocides. Biocides are agents that reduce or eliminate biological activity in the solvent in which a substrate is being cleaned. Biocides can also eliminate biological activity on the substrate itself Non-limiting examples of biocides include quaternary ammonium salts, hydantoins, carbonates, alcohols and sodium hypochlorite. One illustrative commercial biocide includes Dantogard® Plus, which is manufactured by Lonza of Fairlawn, N. J. Dantogard® Plus is a mixture of hydantoin derivative compounds in the form of a white crystalline powder. One or more biocides, if desired, are typically present in a composition of the invention in an amount of about 0.001% to about 20%, about 0.01% to about 10%, or about 0.1% to about 8%, by weight, or any specific amount within such ranges, for example about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 15%, by weight, or within any range formable thereby.
Compositions of the invention optionally comprise one or more antistatic agents. Antistatic agents are substances that reduce or eliminate static electricity on the substrate being cleaned. Illustratively, antistatic agents can include quaternary ammonium salts, ethoxylated quaternary ammonium salts, amine oxides, amides, tertiary amines, tertiary amine salts and clay or clay derivatives. Non-limiting examples of suitable antistatic agents include Armostat® 550 available from Akzo-Nobel Chemical, Atmer® 163 available from Uniqema Chemical, Incroquat® CTC-30 available from Croda Chemical, and Laponite® RDS available from Southern Clay Products.
One or more antistatic agents, if desired, are typically present in a composition of the invention in an amount of about 0.01% to about 20%, about 0.1% to about 10%, or about 1% to about 8%, by weight or by volume, or any specific amount within such ranges, for example about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 15%, by weight, or within any range formable thereby.
Compositions of the invention optionally comprise one or more defoamers. Defoamers are agents that reduce or eliminate foam in a solvent. Illustratively, defoamers can comprise alcohols, silicone, fluorosilicones and their derivatives. Non-limiting examples of suitable defoamers include AF-70 available from GE Silicones, Dow Corning 1510, and Fluowet® PL-80 available from Clariant Corporation. One or more defoamers, if desired, are typically present in a composition of the invention in an amount of about 0.01% to about 20%, about 2% to about 10%, or about 3% to about 8%, by weight, for example about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 15%, by weight, or any combination thereof.
Compositions of the invention optionally comprise one or more corrosion inhibitors. Corrosion inhibitors prevent corrosion on metal surfaces. Non-limiting examples of corrosion inhibitors include sodium hypophosphite monohydrate, borate compounds, alkanolamides, bisulfite, phosphate ester, and amines. Specific examples of marketed corrosion inhibitors include Alkaterge® E available from Angus Chemical, Aqualox® 232H available from Lubrizol Company, Colalube® 3419EPL available from Colonial Chemical, and DePhos® 8028FA available from DeForest Enterprises. One or more corrosion inhibitors, if desired, are typically present in a composition of the invention in an amount of about 0.01% to about 20%, about 0.1% to about 10%, or about 1% to about 8%, by weight or volume, or any specific amount within such ranges, for example about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 15%, by weight, or within any range formable thereby.
Compositions of the invention optionally comprise one or more viscosity modifiers. Viscosity modifiers are agents that can increase the viscosity of the cleaning media. Non-limiting examples of viscosity modifiers include alkanolamides, polyacrylic polymers, organically modified clay, ethoxylated cellulose, xanthan gum, and hydroxypropylcellulose. Non-limiting examples of suitable viscosity modifiers include Acusol® 830, Alkamide® DC, Bentone® 34, Carbopol® 676, and Keltrol® HP. One or more viscosity modifiers, if desired, are typically present in a composition of the invention in an amount of about 0.001% to about 20%, about 0.01% to about 10%, or about 0.1% to about 8%, by weight, or any specific amount within such ranges, for example about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, or about 15%, by weight or volume, or within any range formable thereby.
The foregoing organic solvents and additives can have multiple roles as is known in the art. For example, organic solvents can also serve as additives (e.g. cleaning aids). The classification of organic solvents and additives above is not to be construed as limiting in any manner. Additives and organic solvents categorized in a particular manner may also operate under various different categories of additives or organic solvents as will be readily appreciated by one of ordinary skill in the art.
In another embodiment, a cleaning composition of the invention comprises at least one organic solvent, at least one surfactant, and at least one further additive selected from an antistatic agent, a neutralizing agent, a sizing agent, an optical whitener and/or water. In a related embodiment, the at least one organic solvent is present in an amount of about 20% to about 99.9%, by weight or volume, and the at least one surfactant is present in an amount of about 0.01% to about 20%, by weight or volume. Optionally, water is present in an amount of about 0.1% to about 20%, by weight or volume.
In another embodiment, a cleaning composition of the invention comprises at least one organic solvent in an amount of about 15% to about 99.9% by weight or volume, at least one surfactant in an amount of about 0.01% to about 60% by weight or volume, at least one antistatic agent in an amount of about 0.01% to about 10% by weight or volume, at least one neutralizing agent, (for example a solution of about 5% to about 50% neutralizing agent in water) in an amount of about 0.01% to about 20%, by weight or volume, at least one sizing agent in an amount of about 0.01% to about 10%, by weight or volume, at least one optical whitener in an amount of about 0.01% to about 5%, by weight or volume, and water in an amount of about 0.01% to about 20%, by weight or volume.
Cleaning compositions of the invention can be prepared in any suitable manner. In one embodiment, a cleaning composition is prepared by (1) providing, in an organic solvent vessel, one or more organic solvents; and (2) providing, in a second vessel, an additive composition (also referred to herein as a Base Detergent Formulation). At a desired time, the Base Detergent Formulation can be combined with the organic solvent to form a cleaning composition of the invention. This can be accomplished in any suitable manner, for example, by: (1) transferring Base Detergent Formulation to the organic solvent vessel to form the cleaning fluid, (2) combining the organic solvent and Base Detergent Formulation in a third vessel (for example in a cleaning fluid tank, cleaning vessel or cleaning drum) to form the cleaning fluid, or (3) transferring organic solvent to the Base Detergent Formulation vessel to form the cleaning fluid. Alternatively, all components of the cleaning fluid can be prepared via step-wise or substantially simultaneous admixture of organic solvent and additive(s) in a single or multiple vessels.
In another embodiment, a process for making a cleaning composition is provide, the process comprising the steps of: admixing, in any order, a first organic solvent such as a glycol ether, a surfactant such as a phosphate ester-containing compound and a neutralzing agent to form a base detergent formulation; and combining, in any order, the base detergent formulation with a second organic solvent (e.g. a glycol ether) that is the same or different from the first organic solvent, and optionally with one or more additives as described herein such as an antistatic agent, a sizing agent, a bleach or an optical whitener. Water can be added at any point during the admixing and/or combining steps.
Where the cleaning composition is prepared by adding the base detergent formulation to a vessel (e.g. organic solvent tank) already containing the organic solvent, the base detergent formulation will typically be added in an amount of about 0.005% to about 10%, about 0.05% to about 5%, or about 0.1% to about 3%, by final volume of the cleaning composition.
In another embodiment, base detergent formulation is added directly to a cleaning vessel, wheel or drum where it is combined with organic solvent (that is already present therein or that is subsequently added thereto).
Cleaning compositions of the invention are useful for cleaning a wide variety of substrates. Non-limiting examples of suitable substrates that can be cleaned with compositions of the invention include textiles such as garments (made of cotton, polyester, silk or blends thereof), fabric, draperies, etc), flexible substrates (e.g. plastics, polymers, rubber etc), precision substrates (e.g. circuitry, microprocessors, electronics, etc.), metal substrates, delicate substrates, as well as other porous and nonporous and substrates.
Cleaning compositions of the invention can be used to clean a variety of substrates in any suitable cleaning system. In one embodiment, cleaning compositions of the invention are used in conventional textile cleaning systems such as washing machines. In another embodiment, compositions of the invention are used in a cleaning system as shown in
Referring now to
A cleaning fluid tank130 holds any suitable cleaning fluid (or organic solvent without additives present), as previously described, to be introduced to the cleaning vessel 110 through the inlet 114. A pressurized fluid solvent tank 132 holds pressurized fluid solvent to be added to the pressurizable drying vessel 120 through the inlet 124. Filtration assembly 140 contains one or more filters that can continuously remove contaminants from the cleaning fluid 110 as cleaning occurs.
The components of the cleaning system 100 are connected with lines 150-156, which transfer organic solvents/cleaning fluids and vaporized and pressurized fluid solvents between components of the system. The term “line” as used herein is understood to refer to a piping network or similar conduit capable of conveying fluid and, for certain purposes, is capable of being pressurized. The transfer of the cleaning fluid/organic solvents and vaporized and pressurized fluid solvents through the lines 150-156 is directed by valves 170-176 and pumps 190-193. While pumps 190-193 are shown in the described embodiment, any method of transferring liquid and/or vapor between components can be used, such as adding pressure to the component using a compressor to force the liquid and/or vapor from the component.
The substrates are cleaned with cleaning fluid such as those previously described, or mixtures thereof. In one embodiment, the cleaning fluid contains no amount of pressurized fluid solvent. In another embodiment, the substrates may also be cleaned with a combination of organic solvent and pressurized fluid solvent, and this combination may be in varying proportions from about 50% by weight to 100% by weight of organic solvent and 0% by weight to 50% by weight of pressurized fluid solvent. In the cleaning process, the substrates can be sorted as necessary to place the substrates into groups suitable to be cleaned together. The substrates may then optionally be spot treated as necessary to remove any stains that may not be removed during the cleaning process. The substrates are then placed into the cleaning drum 112 of the cleaning system 100. Cleaning drum 112 can be perforated or otherwise adapted (pierced, punctured, etc.) to allow for free interchange of cleaning fluid between the cleaning drum 112 and the cleaning vessel 110 as well as to transport soil from the substrates to the filtration assembly 140. In one embodiment, the drum 112 is a horizontally mounted perforated basket also referred to as a wheel.
Before or after the substrates are placed in the cleaning drum 112, cleaning fluid (or organic solvent if no additives are present) contained in the cleaning fluid tank130 is added to the cleaning vessel 110 via line 152 by opening valve 171, closing valves 170, 172, 173 and 174, and activating pump 190 to pump cleaning fluid through the inlet 114 of the cleaning vessel 110. In one embodiment, organic solvent is contained in tank 130 and is added to the cleaning vessel 110 where it is combined with additive composition that is added directly to the cleaning vessel 110 or drum 112. In one embodiment, pressurized fluid solvent may also be added to the cleaning vessel 110 along with the organic solvent or cleaning fluid to enhance cleaning Pressurized fluid solvent can be added to the cleaning vessel 110 via line 154 by opening valve 174, closing valves 170, 171, 172, 173, and 175, and activating pump 192 to pump pressurized fluid solvent through the inlet 114 of the cleaning vessel 110. Of course, if pressurized fluid solvent is included in the cleaning cycle, the cleaning vessel 110 will need to be pressurized in the same manner as the drying vessel 120, as discussed below.
Typically, the cleaning fluid or organic solvent will be added to the drum 112 in an amount of about 1% to 90% by volume. When a sufficient amount of the cleaning fluid, organic solvent, or combination of cleaning fluid and pressurized fluid solvent, is added to the cleaning vessel 110, the motor (not shown) is activated and the perforated cleaning drum 112 is agitated and/or rotated within cleaning vessel 110. Typically, rotation or agitation will take place for a period of about 1 to about 100 minutes, about 1 to about 60, about 1 to about 45, about 1 to about 30 minutes, about 1 to about 20 minutes or about 1 to about 10 minutes. During this phase, the cleaning fluid can be continuously cycled through the filtration assembly 140 by opening valves 170 and 172, closing valves 171, 173 and 174, and activating pump 191. Filtration assembly 140 may include one or more fine mesh filters to remove particulate contaminants from the organic solvent passing there through and may alternatively or additionally include one or more absorptive or adsorptive filters to remove water, dyes and other dissolved contaminants from the organic solvent. Exemplary configurations for filter assemblies that can be used to remove contaminants from either the cleaning fluid or the pressurized fluid solvent are described more fully in U.S. application Ser. No. 08/994,583 incorporated herein by reference. As a result, the cleaning fluid is pumped through outlet 116, valve 172, line 151, filter assembly 140, line 150, valve 170 and re-enters the cleaning vessel 110 via inlet 114. This cycling advantageously removes contaminants, including particulate contaminants and/or soluble contaminants, from the cleaning fluid and reintroduces filtered cleaning fluid to the cleaning vessel 110. Through this process, contaminants are removed from the textiles. Of course, in the event the cleaning vessel 110 is pressurized, this recirculation system will be maintained at the same pressure/temperature levels as those in cleaning vessel 110.
In one embodiment, a predetermined portion of cleaning fluid (e.g. about 1 to about 100 about 2 to about 50, or about 5 to about 30 gallons per pound of substrates being cleaned) can be pumped from cleaning fluid tank 130 to a still (not shown) for distillation, and then reintroduced into the cleaning fluid tank 130, for example via one or more lines and pumps (not shown). Optionally, the removed cleaning fluid can be replaced during the cleaning process by new cleaning fluid, by organic solvent without additives (the additives then optionally being added to the cleaning drum), or by the same cleaning fluid/organic solvent that was distilled. In one embodiment, the cleaning fluid that was removed is replaced by substantially the same amount, by volume, of cleaning fluid or organic solvent. In another embodiment, the removed portion of cleaning fluid is replaced by a larger or smaller volume of cleaning fluid or organic solvent, e.g. 25%, 50%, 75%, 100%, 125%, by volume, of the removed portion).
After sufficient time has passed (e.g. about 1 to about 60 min., about 5 to about 40 min., or about 10 to about 30 min.) so that the desired level of contaminants (for example some amount of contaminant, a substantial portion of the contaminant, at least about 25%, at least about 50%, or at least about 75% of the contaminant, etc.) is removed from the substrates by the cleaning fluid, at least a portion of the cleaning fluid is removed from the cleaning drum 112 and cleaning vessel 110 by opening valve 173, closing valves 170, 171, 172 and 174, and activating pump 191 to pump the cleaning fluid through outlet 116 via line 153. The cleaning drum 112 can then be rotated at a high speed, such as about 75 to about 1000, about 150 to about 900, or about 400 to about 800 rpm, to further remove cleaning fluid from the substrates. The cleaning drum 112 is preferably perforated or pierced so that, when the substrates are rotated in the cleaning drum 112, the cleaning fluid can drain from the cleaning drum 112. Any cleaning fluid removed from the substrates by rotating the cleaning drum 112 is also removed from the cleaning drum 112 in the manner described above. After the cleaning fluid is removed from the cleaning drum 112, it can either be discarded or recovered and decontaminated for reuse using solvent recovery systems known in the art. Furthermore, multiple cleaning cycles can be used if desired, with each cleaning cycle using the same cleaning fluid or different cleaning fluid. If multiple cleaning cycles are used, each cleaning cycle can occur in the same cleaning vessel, or a separate cleaning vessel can be used for each cleaning cycle.
After a desired amount of the cleaning fluid is removed from the substrates, for example by rotating the cleaning drum 112 at high speed, the substrates are moved from the cleaning drum 112 to the drying drum 122 within the drying vessel 120 in the same manner substrates are moved between machines in conventional cleaning systems. In an alternate embodiment, a single drum can be used in both the cleaning cycle and the drying cycle, so that, rather than transferring the substrates between the cleaning drum 112 and the drying drum 122, a single drum containing the substrates is transferred between the cleaning vessel 110 and the drying vessel 120. If the cleaning vessel 110 is pressurized during the cleaning cycle, it must be depressurized before the substrates are removed. Once the substrates have been placed in the drying drum 122, pressurized fluid solvent, such as that contained in the pressurized fluid solvent tank 132, is added to the drying vessel 120 via lines 154 and 155 by opening valve 175, closing valves 174 and 176, and activating pump 192 to +pump pressurized fluid solvent through the inlet 124 of the drying vessel 120 via lines 154 and 155. When pressurized fluid solvent is added to the drying vessel 120, at least a portion (e.g. substantially all, at least 50%, at least 75%, etc.) of the cleaning fluid remaining on the substrates is dissolved in the pressurized fluid solvent.
After a sufficient amount of pressurized fluid solvent is added so that substantially all or a desired level of cleaning fluid has been dissolved, the pressurized fluid solvent and cleaning fluid combination is removed from the drying vessel 120, and therefore also from the drying drum 122, by opening valve 176, closing valve 175 and activating pump 193 to pump the pressurized fluid solvent and cleaning fluid combination through outlet 126 via line 156. If desired, this process may be repeated to remove additional cleaning fluid. The drying drum 122 is then rotated at a high speed, such as about 75 to about 1000, about 150 to about 900, or about 400 to about 800 rpm, to further remove the pressurized fluid solvent and cleaning fluid combination from the substrates. The drying drum 122 is preferably perforated or pierced so that, when the textiles are rotated in the drying drum 122 at a high speed, the pressurized fluid solvent and cleaning fluid combination can drain from the drying drum 122. Any pressurized fluid solvent and cleaning fluid combination removed from the substrates by spinning the drying drum 122 at high speed is also pumped from the drying vessel 120 in the manner described above. After the pressurized fluid solvent and cleaning fluid combination is removed from the drying vessel 120, it can either be discarded or separated and recovered for reuse with solvent recovery systems known in the art. Note that it is not necessary to include a high speed spin cycle to remove pressurized fluid solvent from the substrates.
After a desired amount of the pressurized fluid solvent is removed from the substrates by rotating the drying drum 122, the drying vessel 120 is depressurized over a period of about 1 to about 30 minutes or about 5 to about 15 minutes. The depressurization of the drying vessel 120 vaporizes any remaining pressurized fluid solvent, leaving dry, substantially solvent-free textiles in the drying drum 122. The pressurized fluid solvent that has been vaporized is then removed from the drying vessel 120 by opening valve 176, closing valve 175, and activating pump 193. As a result, the vaporized pressurized fluid solvent is pumped through the outlet 126, line 156 and valve 176, where it can then either be vented to the atmosphere or recovered and recompressed for reuse.
While the cleaning system 100 has been described as a complete system, an existing conventional dry cleaning system may be converted for use in accordance with the present invention. To convert a conventional dry cleaning system, the cleaning fluid described above is used to clean substrates in the conventional system. A separate pressurized vessel is added to the conventional system for drying the substrates with pressurized fluid solvent. Thus, the conventional system is converted for use with a pressurized fluid solvent. For example, the system in
While the system shown in
Referring now to
A cleaning fluid tank 220 holds any suitable cleaning fluid (or organic solvent without additives added), such as those described above, to be introduced to the vessel 210 through the inlet 214. A pressurized fluid solvent tank 222 holds pressurized fluid solvent to be added to the vessel 210 through the inlet 214. Filtration assembly 224 contains one or more filters that continuously remove contaminants from the cleaning fluid from the vessel 210 and drum 212 as cleaning occurs.
The components of the cleaning system 200 are connected with lines 230-234 that transfer cleaning fluid, organic solvents and vaporized and pressurized fluid solvent between components of the system. The term “line” as used herein is understood to refer to a piping network or similar conduit capable of conveying fluid and, for certain purposes, is capable of being pressurized. The transfer of the cleaning fluid, organic solvents and vaporized and pressurized fluid solvent through the lines 230-234 is directed by valves 250-254 and pumps 240-242. While pumps 240-242 are shown in the described embodiment, any method of transferring liquid and/or vapor between components can be used, such as adding pressure to the component using a compressor to force the liquid and/or vapor from the component.
The substrates are cleaned with a cleaning fluid such as those previously described. In one embodiment, the cleaning fluid contains no amount of pressurized fluid solvent. In another embodiment, the substrates may be cleaned with a combination of organic solvent and pressurized fluid solvent, and this combination may be in varying proportions from about 50% by weight to 100% by weight of organic solvent and 0% by weight to 50% by weight of pressurized fluid solvent.
In the cleaning process, the substrates can be sorted as necessary to place the substrates into groups suitable to be cleaned together. The substrates may then optionally be spot treated as necessary to remove any stains that may not be removed during the cleaning process. The substrates are then placed into the drum 212 within the vessel 210 of the cleaning system 200. Cleaning drum 212 can be perforated or otherwise adapted (pierced, punctured, etc.) to allow for free interchange of cleaning fluid between the drum 212 and the vessel 210 as well as to transport soil from the substrates to the filtration assembly 224.
Before or after the substrates are placed in the drum 212, cleaning fluid (or organic solvent if no additives are present) contained in the cleaning fluid tank 220 is added to the vessel 210 via line 231 by opening valve 251, closing valves 250, 252, 253 and 254, and activating pump 242 to pump cleaning fluid through the inlet 214 of the vessel 210 or drum 212. In one embodiment, organic solvent is contained in tank 220 and is added to the vessel 210 where it is then combined with additive composition that is added directly to the vessel 210. Pressurized fluid solvent may also be added to the vessel 210 along with the organic solvent or cleaning fluid to enhance cleaning The pressurized fluid solvent is added to the vessel 210 via line 230 by opening valve 250, closing valves 251, 252, 253 and 254, and activating pump 240 to pump the pressurized fluid solvent through the inlet 214 of the vessel 210. Typically, the cleaning fluid or organic solvent will be added to the drum 212 in an amount of about 1 to 90% by volume.
When a sufficient amount of the cleaning fluid, organic solvent, or combination of cleaning fluid, organic solvent, and/or pressurized fluid solvent as described above, is added to the vessel 210, the motor (not shown) is activated and the drum 212 is agitated and/or rotated. Typically, rotation or agitation will take place for a period of about 1 to about 60, about 1 to about 45, or about 1 to about 30 minutes. During this phase, the cleaning fluid, as well as pressurized fluid solvent if used in combination, can be continuously cycled through the filtration assembly 224 by opening valves 252 and 253, closing valves 250, 251 and 254, and activating pump 241. Filtration assembly 224 may include one or more fine mesh filters to remove particulate contaminants from the cleaning fluid and pressurized fluid solvent passing there through and may alternatively or additionally include one or more absorptive or adsorptive filters to remove water, dyes, and other dissolved contaminants from the organic solvent. Exemplary configurations for filter assemblies that can be used to remove contaminants from either the organic solvent or the pressurized fluid solvent are described more fully in U.S. application Ser. No. 08/994,583 incorporated herein by reference. As a result, the cleaning fluid is pumped through outlet 216, valve 253, line 233, filter assembly 224, line 232, valve 252 and reenters the vessel 210 via inlet 214. This cycling advantageously removes contaminants, including particulate contaminants and/or soluble contaminants, from the cleaning fluid and pressurized fluid solvent and reintroduces filtered cleaning fluid to the vessel 210. Through this process, contaminants are removed from the substrates.
In one embodiment, a predetermined portion of cleaning fluid (e.g. about 1 to about 100, about 2 to about 50 or a bout 5 to about 30 gallons per pound of substrates being cleaned) can be pumped from cleaning fluid tank 220 to a still (not shown) for distillation, and then reintroduced into the cleaning fluid tank 220, for example via one or more lines and pumps (not shown). Optionally, the removed cleaning fluid can be replaced during the cleaning process by new cleaning fluid, by organic solvent without additives (the additives then optionally being added to the cleaning drum), or by the same cleaning fluid/organic solvent that was distilled. In one embodiment, the cleaning fluid that was removed is replaced by substantially the same amount, by volume, of cleaning fluid or organic solvent. In another embodiment, the removed portion of cleaning fluid is replaced by a larger or smaller volume of cleaning fluid or organic solvent, e.g. 25%, 50%, 75%, 100%, 125%, by volume, of the removed portion).
After sufficient time has passed (e.g. about 1 to about 60 min., about 5 to about 40 min., or about 10 to about 30 min.) so that the desired level of contaminants (for example some amount of contaminant, a substantial portion of the contaminant, at least about 25%, at least about 50%, or at least about 75% of the contaminant, etc.) is removed from the substrates by the cleaning fluid, at least a portion of the cleaning fluid is removed from the vessel 210 and drum 212 by opening valve 254, closing valves 250, 251, 252 and 253, and activating pump 241 to pump the cleaning fluid through outlet 216 and line 234. If pressurized fluid solvent is used in combination with cleaning fluid, it may be necessary to first separate the pressurized fluid solvent from the cleaning fluid. The cleaning fluid can then either be discarded or, preferably, contaminants may be removed from the cleaning fluid and the cleaning fluid recovered for further use. Contaminants may be removed from the organic solvent with solvent recovery systems known in the art. The drum 212 can then be rotated, for example at a high speeds such as about 75 to about 1000, about 150 to about 900, or about 400 to about 800 rpm, to further remove cleaning fluid from the substrates. The drum 212 is preferably perforated or pierced so that, when the substrates are rotated in the drum 212, cleaning fluid can drain from the cleaning drum 212. Any cleaning fluid removed from the substrates by rotating the drum 212 can also either be discarded or recovered for further use.
After a desired amount of cleaning fluid is removed from the substrates, for example by rotating the drum 212, pressurized fluid solvent contained in the pressurized fluid tank 222 is added to the vessel 210 by opening valve 250, closing valves 251, 252, 253 and 254, and activating pump 240 to pump pressurized fluid solvent through the inlet 214 of the pressurizable vessel 210 via line 230. When pressurized fluid solvent is added to the vessel 210, at least a portion (e.g. substantially all, at least about 50%, at least about 75%, etc.) of the cleaning fluid remaining on the substrates is dissolved in the pressurized fluid solvent.
After a sufficient amount of pressurized fluid solvent is added so that substantially all or a desired level of cleaning fluid has been dissolved, the pressurized fluid solvent and cleaning fluid combination is removed from the vessel 210 by opening valve 254, closing valves 250, 251, 252 and 253, and activating pump 241 to pump the pressurized fluid solvent and organic solvent combination through outlet 216 and line 234. Note that pump 241 may actually require two pumps, one for pumping the low pressure cleaning fluid in the cleaning cycle and one for pumping the pressurized fluid solvent in the drying cycle.
The pressurized fluid solvent and cleaning fluid combination can then either be discarded or the combination may be separated and the organic solvent and pressurized fluid solvent separately recovered for further use. The drum 212 is then rotated at a high speed, such as about 75 to about 1000, about 150 to about 900, or about 400 to about 800 rpm, to further remove pressurized fluid solvent and cleaning fluid combination from the substrates. Any pressurized fluid solvent and cleaning fluid combination removed from the substrates by spinning the drum 212 at high speed can also either be discarded or retained for further use. Note that it is not necessary to include a high speed spin cycle to remove pressurized fluid solvent from the substrates.
After a desired amount of the pressurized fluid solvent is removed from the substrates by rotating the drum 212, the vessel 210 is depressurized over a period of about 1 to about 30 or about 5 to about 15 minutes. The depressurization of the vessel 210 vaporizes remaining pressurized fluid solvent, leaving dry, substantially solvent-free substrates in the drum 212. The pressurized fluid solvent that has been vaporized is then removed from the vessel 210 by opening valve 254, closing valves 250, 251, 252 and 253, and activating pump 241 to pump the vaporized pressurized fluid solvent through outlet 216 and line 234. Note that while a single pump is shown as pump 241, separate pumps may be necessary to pump cleaning fluid, pressurized fluid solvent and pressurized fluid solvent vapors, at pump 241. The remaining vaporized pressurized fluid solvent can then either be vented into the atmosphere or compressed back into pressurized fluid solvent for further use.
The following examples illustrate cleaning compositions of various embodiments of the present invention and are for illustrative purposes only. They are not to be construed as limiting the scope of the invention in any manner whatsoever.
Thirteen base detergent formulations, BDF1-BDF13, were prepared having compositions shown in Table 1.
Soil removal capability of cleaning compositions comprising one of BDF1-BDF13 of Example 1 was quantified using the Delta Whiteness Index. This method entails measuring the Whiteness Index of each swatch before and after processing. Each Base Detergent Formulation was tested using WFK10C soil swatches from Testfabrics, Inc. The Delta Whiteness Index is calculated by subtracting the Whiteness Index of the swatch before processing from the Whiteness Index of the swatch after processing. The Whiteness Index is a function of the light reflectance of the swatch and in this application is an indication of the amount of soil on the swatch. More soil results in a lower light reflectance and a lower Whiteness Index for the swatch. The Whiteness indices were measured using a reflectometer manufactured by Hunter Laboratories. After obtaining a baseline whiteness index value, the swatches were individually placed in Launder-O-Meter cups with 25 stainless steel balls and optionally 150 ml of DPNB as set forth below. An amount of one of Base Detergent Formulation BDF1-BDF13 was then added to create a final Cleaning Formulation. Final compositions of each Cleaning Formulation (CF1-CF13) used in the test are shown in Table 2. The swatches were cleaned for 12 minutes and each swatch was then removed from the cup and processed through an Atlas wringer to remove excess cleaning formulation. The swatch was then rinsed and dried in a Parr Bomb with liquid carbon dioxide and read on the Reflectometer to obtain a final whiteness index value.
Cleaning results are shown in Table 3. As can be seen, Cleaning Formulations CF2-CF7 (each containing a phosphate ester) produced a greater change in whiteness index than did cleaning formulations not containing a phosphate ester (CF8-CF12) or the control DPNB or DPNB plus water formulations (CF1 and CF13, respectively). Further, CF7 containing a phosphate ester, glycol ether and water (3.5%) exhibited the most soil removal in this test.
Two additional Base Detergent Formulations, BDF14 and BDF15, were prepared as shown in Table 4.
Cleaning ability of each of Base Detergent Formulations BDF1, BDF2, BDF11, BDF12, BDF14 and BDF15 of the previous Examples were tested using swatches stained with a water soluble food dye obtained from the Dryclean & Laundry Institute. After obtaining a baseline whiteness index value, the swatches were individually placed in Launder-O-Meter cups with 25 stainless steel balls and optionally 150 ml of DPNB. Water was also added to each cup at 3.5%, by weight or volume, of the cleaning formulations. Final composition of each of the cleaning formulations tested (prior to addition of water) is shown in Table 5.
The swatches were cleaned for 6 minutes and each swatch was then removed from the cup and blotted to remove excess cleaning formulation. The swatch was then rinsed and dried in a Parr Bomb with liquid carbon dioxide and read on the Reflectometer to obtain a final whiteness index value. Change in whiteness after cleaning (delta whiteness index) for each swatch is shown in Table 6.
Overall, Cleaning Formulation CF2 resulted in the greatest soil removal in this test. The % Food Dye Removal is calculated by measuring the Y values of the swatches before and after cleaning and placing these values in the Kubelka Monk equation.
Cleaning Formulations CF16-CF21 were prepared containing various glycol ethers and BDF2 as shown in Table 7.
Cleaning performance of each formulation CF16-CF21 as evaluated using WFK 10C swatches available from Testfabric, Inc. After obtaining a baseline whiteness index value, the swatches were individually placed in Launder-O-Meter cups containing 150 ml of one of the glycol ethers listed in Table 7. One percent by volume of BDF2 was also added to each cleaning cup. The swatches were cleaned for 12 minutes and each swatch was then removed from the cup and placed in an Atlas ringer to remove excess cleaning fluid. Each swatch was then rinsed and dried in a Parr Bomb with liquid carbon dioxide and read on the Reflectmeter to obtain a final whiteness index value. The above process was repeated using 150 ml of each individual glycol ether without any Base Detergent Formulation added (controls) to compare cleaning in each glycol ether with and without added phosphate ester. Change in whiteness index after cleaning (delta whiteness index) for each swatch is shown in Table 8.
As can be observed from Table 8, addition of BDF enhanced soil removal for each glycol ether tested.
Cleaning of cotton (Style 400 from Testfabrics, Inc.) and polyester 1)Dacron 64 from Testfabrics, Inc.) swatches stained with used motor oil was evaluated using Base Detergent Formulations BDF1, BDF2, BDF7, BDF12, BDF13, BDF14 and BDF15 (of the previous Examples) added to DPNB.
After baseline whiteness values were obtained, swatches were individually placed in Launder-O-Meter cups containing 150 ml of DPNB and 25 stainless steel balls. BDF1, BDF2, BDF7, BDF12, BDF13, BDF14 or BDF15 were individually added to one of each of the cups in the same amounts (v/v) used to prepare CF1, CF2,CF7, CF12, CF13, CF14 and CF15 in the above Examples. The swatches were cleaned for 10 minutes and each swatch was then removed and placed in an Atlas ringer to remove excess cleaning fluid. Each swatch was then rinsed and dried in a Parr Bomb with liquid carbon dioxide and was read on the Reflectometer to obtain a final whiteness value. Change in whiteness after cleaning (delta whiteness index) for each swatch is shown in Table 9.
Base Detergent Formulation BDF22 was prepared as shown in Table 10.
A static control test was performed using 3×9 inch thin polyester swatches. Swatches were individually placed into 3 Launder-O-Meter cups containing 150 ml of DPNB along with 25 stainless steel balls. Cup 1 (Swatch 1) was not charged with any further material. Cup 2 (Swatch 2) was charged with 1.5% v/v of BDF2 from Example 1. Cup 3 (Swatch 3) was charged with 1.5% v/v of BDF22 of Example 7.
The Launder-O-Meter was run for 12 minutes. The swatches were then placed in an Atlas Ringer to remove excess solvent and were then rinsed and dried in a Parr Bomb with liquid carbon dioxide. Swatches were then heated to 60° C. in an oven for 45 minutes, placed in a dessicator overnight, and then pressed with a hand iron. The swatches were then tested for clinging using AATCC test method 115-2005. Specifically, the swatches were tested to determine the amount of time before clinging to metal ceases. Results are shown in Table 11.
As can be seen from Table 11, Swatch 3 exhibited the shortest time to absence of metal clinging.
Base Detergent Formulation BDF23 was prepared as shown in Table 12.
A fabric sizing test was performed to assess fabric stiffness and body using 1×6 inch WFK 10C white cotton swatches available from Testfabrics, Inc. Swatches were individually placed into each of 3 Launder-O-Meter cups containing 150 ml of DPNB along with 25 stainless steel balls. Cup 1 (Swatch 1) was not charged with any further material. Cup 2 (Swatch 2) was charged with 3% v/v of BDF2 as shown in Example 1. Cup 3 (Swatch 3) was charged with 3% v/v of BDF23 of Example 9. The swatches were cleaned in the Launder-O-Meter for 12 minutes. The swatches were then placed in an Atlas Ringer to remove excess solvent and then were rinsed and dried in a Parr Bomb with liquid carbon dioxide. The swatches were pressed, measured for length and tested for stiffness according to ASTM Test Method D1388. To perform the test, each swatch was slid across a 41.5° (from horizontal) incline. The length of fabric overhang just prior to touching the horizontal plane was then measured. Tests were run in duplicate and sizing measurements were run before and after treatment. Results are shown in Table 13.
As shown in Table 13, length of fabric overhang increases upon treatment with the cleaning formulation containing BDF23 and DPNB.
Stiffness of each swatch was also evaluated by a 10 person blinded panel. Panel members were asked to rank swatches from each of the three treatment groups from stiffest (1) to least stiff (3). Results are shown in Table 14.
As shown in Table 14, in each case swatches treated with the cleaning composition comprising BDF23 and DPNB were ranked the stiffest.
Base Detergent Formulation BDF24 was prepared having a composition as shown in Table 15.
A test was performed to assess fabric softness after processing with various compositions. Cotton terrycloth fabric was cut into 5×5 inch squares. Swatches were individually placed into each of 4 Launder-O-Meter cups containing 150 ml of DPNB along with 25 stainless steel balls. Cup 1 (Swatch 1) was not charged with any further material. Cup 2 (Swatch 2) was charged with 2% v/v of BDF2 as shown in Example 1. Cup 3 (Swatch 3) was charged with 2% v/v of BDF23 of Example 9. Cup 4 (Swatch 4) was charged with 2% v/v of BDF24 as set forth in Example 11.
The swatches were cleaned in the Launder-O-Meter for 12 minutes. The swatches were then placed in an Atlas Ringer to remove excess solvent and then rinsed and dried in a Parr Bomb with liquid carbon dioxide. The swatches then given to a panel that was asked to rank them as to their softness: (1) softest—(4) least soft. Results are shown in Table 16.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/US08/66140 | 6/6/2008 | WO | 00 | 8/2/2010 |
| Number | Date | Country | |
|---|---|---|---|
| 60942969 | Jun 2007 | US |
