CA2330328A1 - Dry cleaning system using densified carbon dioxide and a surfactant adjunct - Google Patents
Dry cleaning system using densified carbon dioxide and a surfactant adjunct Download PDFInfo
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- CA2330328A1 CA2330328A1 CA002330328A CA2330328A CA2330328A1 CA 2330328 A1 CA2330328 A1 CA 2330328A1 CA 002330328 A CA002330328 A CA 002330328A CA 2330328 A CA2330328 A CA 2330328A CA 2330328 A1 CA2330328 A1 CA 2330328A1
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- alkylene
- carbon dioxide
- substituted
- alkenylene
- acid
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
- D06L1/02—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents
- D06L1/04—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents combined with specific additives
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
Abstract
A system for dry cleaning soils from fabrics is described which contains densified carbon dioxide combined with a selected surfactant. The densified carbon dioxide is used in a temperature range of about -78.5 ~C to about 100 ~C and a pressure range of about 14.7 psi to about 10,000 psi. The surfactant is selected from one of two groups of compounds having formula (I) as described in the text or a second group of siloxane compounds having a formula ¢AB!y as described. A process for using the dry cleaning system is also described.
Description
DRY CLEANING SYSTEM USING DENSIFIED CARBON DIOXIDE
AND A SURFACTANT ADJUNCT
Field of the Inyention This invention pertains to a dry cleaning system utilizing densified carbon dioxide and a particular surfactant adjunct.
Background of the Invention Densified carbon dioxide provides a nontoxic, inexpensive, recyclable and environmentally acceptable solvent to remove soils in the dry cleaning process. Effective dry cleaning systems using densified carbon dioxide in combination with selected surfactants are described in US-A-5,683,977, US-A-5,667,705 and US-A-5,683,473. Preferred surfactants described in these patents are combinations of densified carbon dioxide -philic and -phobic functional groups such as hydrocarbon/halocarbon and polymeric siloxane containing surfactants.
Applicants have further discovered additional selected surfactants which are both soluble in the densified solvent and effective for removing a variety of stains from a myriad of fabrics.
Summary of the Invention It is therefore an object of the present invention to provide additional selected surfactants which are combined with a nonpolar solvent, such as densified carbon dioxide, to provide a dry cleaning system which effectively removes a variety of soils on fabrics.
AND A SURFACTANT ADJUNCT
Field of the Inyention This invention pertains to a dry cleaning system utilizing densified carbon dioxide and a particular surfactant adjunct.
Background of the Invention Densified carbon dioxide provides a nontoxic, inexpensive, recyclable and environmentally acceptable solvent to remove soils in the dry cleaning process. Effective dry cleaning systems using densified carbon dioxide in combination with selected surfactants are described in US-A-5,683,977, US-A-5,667,705 and US-A-5,683,473. Preferred surfactants described in these patents are combinations of densified carbon dioxide -philic and -phobic functional groups such as hydrocarbon/halocarbon and polymeric siloxane containing surfactants.
Applicants have further discovered additional selected surfactants which are both soluble in the densified solvent and effective for removing a variety of stains from a myriad of fabrics.
Summary of the Invention It is therefore an object of the present invention to provide additional selected surfactants which are combined with a nonpolar solvent, such as densified carbon dioxide, to provide a dry cleaning system which effectively removes a variety of soils on fabrics.
2 Another object of the invention is to provide a dry cleaning system of solvent, surfactant and optionally including a bleach or an enzyme for the total cleaning of fabrics using densified carbon dioxide that gives results equivalent to the cleaning demonstrated by conventional dry cleaning solvents.
In one aspect of the present invention, the dry cleaning systems used for cleaning a variety of soiled fabrics comprises densified carbon dioxide and about 0.001$ to about 5$ of a surfactant selected from one of two groups of compounds having the formula:
~H3 ~H3 ~H3 ~H3 ~H3 R"~i O'-'~Si O'~i O~i O-"'~i~R"
CH3 CH3 ~ R ~ R' CH3 x y y' as described or [AB],,as described.
The surfactant has a densified COZ-philic functional moiety connected to a densified COZ-phobic functional moiety.
Preferred C02-philic moieties of the surfactant include halocarbons such as fluorocarbons, chlorocarbons and mixed fluoro-chlorocarbons, polysiloxanes, and branched polyalkylene oxides. The COz-phobic groups for the surfactant contain preferably polyalkylene oxides, carboxylates, C1-3o alkylene sulfonates, carbohydrates, glycerates, phosphates, sulphates and C1_3o hydrocarbons.
The dry cleaning system may also be designed to include a modifier, such as water, or an organic solvent up to about
In one aspect of the present invention, the dry cleaning systems used for cleaning a variety of soiled fabrics comprises densified carbon dioxide and about 0.001$ to about 5$ of a surfactant selected from one of two groups of compounds having the formula:
~H3 ~H3 ~H3 ~H3 ~H3 R"~i O'-'~Si O'~i O~i O-"'~i~R"
CH3 CH3 ~ R ~ R' CH3 x y y' as described or [AB],,as described.
The surfactant has a densified COZ-philic functional moiety connected to a densified COZ-phobic functional moiety.
Preferred C02-philic moieties of the surfactant include halocarbons such as fluorocarbons, chlorocarbons and mixed fluoro-chlorocarbons, polysiloxanes, and branched polyalkylene oxides. The COz-phobic groups for the surfactant contain preferably polyalkylene oxides, carboxylates, C1-3o alkylene sulfonates, carbohydrates, glycerates, phosphates, sulphates and C1_3o hydrocarbons.
The dry cleaning system may also be designed to include a modifier, such as water, or an organic solvent up to about
3 10~ by volume, a bleaching agent such as a peracid, or an enzyme such as an amylase, protease, lipase or oxidase.
In a second aspect of the invention, a method for dry cleaning a variety of soiled fabrics is provided wherein a selected surfactant and optionally a modifier, bleaching agent, an enzyme or mixtures thereof are combined and the cloth is contacted with the mixture. Densified carbon dioxide is introduced into a cleaning vessel which is then pressurized from about 14.7 psi to about 10,000 psi and the temperature is adjusted to a range of about -78.5°C to about 100°C. Fresh densified carbon dioxide may be used to flush the cleaning vessel.
Brief Description of the Drawing Figure 1 is a diagrammatic flow chart of the densified carbon dioxide dry cleaning process according to the invention.
Detailed Description of Preferred Embodiments The invention provides a dry cleaning system which replaces conventional solvents with densified carbon dioxide in combination with selected cleaning surfactants.
Optionally, modifiers, bleaching agents, enzymes and mixtures thereof are combined with the solvent and surfactant to provide a total cleaning system.
For purposes of the invention, the following definitions are used:
"Densified carbon dioxide" means carbon dioxide that has a density (g/ml) greater than that of carbon dioxide gas at 1 atm and 20°C.
In a second aspect of the invention, a method for dry cleaning a variety of soiled fabrics is provided wherein a selected surfactant and optionally a modifier, bleaching agent, an enzyme or mixtures thereof are combined and the cloth is contacted with the mixture. Densified carbon dioxide is introduced into a cleaning vessel which is then pressurized from about 14.7 psi to about 10,000 psi and the temperature is adjusted to a range of about -78.5°C to about 100°C. Fresh densified carbon dioxide may be used to flush the cleaning vessel.
Brief Description of the Drawing Figure 1 is a diagrammatic flow chart of the densified carbon dioxide dry cleaning process according to the invention.
Detailed Description of Preferred Embodiments The invention provides a dry cleaning system which replaces conventional solvents with densified carbon dioxide in combination with selected cleaning surfactants.
Optionally, modifiers, bleaching agents, enzymes and mixtures thereof are combined with the solvent and surfactant to provide a total cleaning system.
For purposes of the invention, the following definitions are used:
"Densified carbon dioxide" means carbon dioxide that has a density (g/ml) greater than that of carbon dioxide gas at 1 atm and 20°C.
4 "Supercritical fluid carbon dioxide" means carbon dioxide which is at or above the critical temperature of 31°C and the critical pressure of 71 atmospheres and which cannot be condensed into a liquid phase despite the addition of further pressure.
The.term "nonpolar stains" refers to those which are at least partially made by nonpolar organic compounds such as oily soils, sebum and the like.
The term "polar stains" is interchangeable with the term "hydrophilic stains" and refers to stains such as grape juice, coffee and tea.
The term "compound hydrophobic stains" refers to stains such as lipstick and red candle wax.
The term "particulate soils" means soils containing insoluble solid components such as silicates, carbon black, etc.
Densified carbon dioxide, preferably liquid or supercritical fluid carbon dioxide, is used in the inventive dry cleaning system. It is noted that other molecules having densified properties may also be employed alone or in mixture. These molecules include methane, ethane, propane, ammonia, butane, n-pentane, n-hexane, cyclohexane, n-heptane, ethylene, propylene, methanol, ethanol, isopropanol, benzene, toluene, p-xylene, sulfur dioxide, chlorotrifluoromethane, trichlorofluoromethane, perfluoropropane, chlorodifluoromethane, sulfur hexafluoride and nitrous oxide.
During the dry cleaning process, the temperature range is
The.term "nonpolar stains" refers to those which are at least partially made by nonpolar organic compounds such as oily soils, sebum and the like.
The term "polar stains" is interchangeable with the term "hydrophilic stains" and refers to stains such as grape juice, coffee and tea.
The term "compound hydrophobic stains" refers to stains such as lipstick and red candle wax.
The term "particulate soils" means soils containing insoluble solid components such as silicates, carbon black, etc.
Densified carbon dioxide, preferably liquid or supercritical fluid carbon dioxide, is used in the inventive dry cleaning system. It is noted that other molecules having densified properties may also be employed alone or in mixture. These molecules include methane, ethane, propane, ammonia, butane, n-pentane, n-hexane, cyclohexane, n-heptane, ethylene, propylene, methanol, ethanol, isopropanol, benzene, toluene, p-xylene, sulfur dioxide, chlorotrifluoromethane, trichlorofluoromethane, perfluoropropane, chlorodifluoromethane, sulfur hexafluoride and nitrous oxide.
During the dry cleaning process, the temperature range is
5 between about -78.5°C and about 100°C, preferably about 5°C
to about 60°C and most preferably about 5°C to about 25°C.
The pressure during cleaning is about 14.7 psi to about 10,000 psi, preferably about 75.1 psi to about 7,000 psi and most preferably about 300 psi to about 6,000 psi.
A "substituted methylsiloxyl group" is a methylsiloxyl group substituted with a C02-phobic group RZ or R3. RZ or R3 are each represented in the following formula:
-~CHZ)a(CsHq)b~A)d-- ~~L)e~A')f)n-- ~L')qZ2~G)h wherein a is 1-30, b is 0-1, CsH4 is substituted or unsubstituted with a C1_lo alkylene or alkenylene and A, d, L, e, A', F, n L', g, Z2, G and h are defined below.
A "substituted arylene" is an arylene substituted with a Cl-so alkylene, alkenylene or hydroxyl, preferably a C1_zo alkylene or alkenylene.
A "substituted carbohydrate" is a carbohydrate substituted with a C1_lo alkylene or alkenylene, preferably a C1_s alkylene.
The terms "polyalkylene oxide", "alkylene" and "alkenylene"
each contain a carbon chain which may be either straight or branched unless otherwise stated.
WO 99/57358 PC'T/EP99/02770
to about 60°C and most preferably about 5°C to about 25°C.
The pressure during cleaning is about 14.7 psi to about 10,000 psi, preferably about 75.1 psi to about 7,000 psi and most preferably about 300 psi to about 6,000 psi.
A "substituted methylsiloxyl group" is a methylsiloxyl group substituted with a C02-phobic group RZ or R3. RZ or R3 are each represented in the following formula:
-~CHZ)a(CsHq)b~A)d-- ~~L)e~A')f)n-- ~L')qZ2~G)h wherein a is 1-30, b is 0-1, CsH4 is substituted or unsubstituted with a C1_lo alkylene or alkenylene and A, d, L, e, A', F, n L', g, Z2, G and h are defined below.
A "substituted arylene" is an arylene substituted with a Cl-so alkylene, alkenylene or hydroxyl, preferably a C1_zo alkylene or alkenylene.
A "substituted carbohydrate" is a carbohydrate substituted with a C1_lo alkylene or alkenylene, preferably a C1_s alkylene.
The terms "polyalkylene oxide", "alkylene" and "alkenylene"
each contain a carbon chain which may be either straight or branched unless otherwise stated.
WO 99/57358 PC'T/EP99/02770
6 Surfactant Adjuncts A surfactant which is effective for use in a densified carbon dioxide dry cleaning system requires the combination of densified carbon dioxide-philic functional groups with densified carbon dioxide-phobic functional groups (see definitions above). The resulting compound may form reversed micelles with the COZ-philic functional groups extending into a continuous phase and the COZ-phobic functional groups directed toward the center of the micelle.
The surfactant is present in an amount of from 0.001 to 10 wt. ~, preferably 0.01 to 5 wt.$.
The COZ-philic moieties of the surfactants are groups exhibiting low Hildebrand solubility parameters, as described in Grant, D.J. W, et al., "Solubility Behavior of Organic Compounds", Techniques of Chemistry Series, J.
Wiley & Sons, N.Y. (1990) pp. 6-55 which describes the Hildebrand solubility equation, herein incorporated by reference. These COZ-philic moieties also exhibit low polarizability and some electron donating capability allowing them to be solubilized easily in densified fluid carbon dioxide.
As defined above, the COZ-philic functional groups are soluble in densified carbon dioxide to greater than 10 wt. ~, preferably greater than 15 wt. ~, at pressures of 500-10,000 psi and temperatures of 0°-100°C.
Preferred densified COz-philic functional groups include halocarbons (such as fluoro-, chloro- and fluoro-chlorocarbons), polysiloxanes and branched polyalkylene oxides.
The surfactant is present in an amount of from 0.001 to 10 wt. ~, preferably 0.01 to 5 wt.$.
The COZ-philic moieties of the surfactants are groups exhibiting low Hildebrand solubility parameters, as described in Grant, D.J. W, et al., "Solubility Behavior of Organic Compounds", Techniques of Chemistry Series, J.
Wiley & Sons, N.Y. (1990) pp. 6-55 which describes the Hildebrand solubility equation, herein incorporated by reference. These COZ-philic moieties also exhibit low polarizability and some electron donating capability allowing them to be solubilized easily in densified fluid carbon dioxide.
As defined above, the COZ-philic functional groups are soluble in densified carbon dioxide to greater than 10 wt. ~, preferably greater than 15 wt. ~, at pressures of 500-10,000 psi and temperatures of 0°-100°C.
Preferred densified COz-philic functional groups include halocarbons (such as fluoro-, chloro- and fluoro-chlorocarbons), polysiloxanes and branched polyalkylene oxides.
7 The COZ-phobic portion of the surfactant molecule is obtained either by a hydrophilic or a hydrophobic functional group which is less than 10 wt. ~ soluble in densified COz, preferably less than 5 wt. $, at a pressure of about 14.7 to about 10,000 psi and temperatures about -78.5°C to about 100°C. Examples of moieties contained in the COZ-phobic groups include polyalkylene oxides, carboxylates, branched acrylate esters, C1_3o hydrocarbons, aryls which are unsubstituted or substituted, sulfonates, glycerates" phosphates, sulfates and carbohydrates.
Especially preferred C02-phobic groups include CZ-2o staight chain or branched alkyls, polyalkylene oxides, glycerates, carboxylates, phosphates, sulfates and carbohydrates.
The C02-philic and COZ-phobic groups may be directly connected or linked together via a linkage group. Such groups include ester, keto, ether, amide, amine, thio, alkyl, alkenylene, fluoroalkyl, fluoroalkenylene or fluoroalkenylene.
Surfactants which are useful in the invention may be selected from two groups of compounds.
I. First Group The first group of compounds has the following formula I:
R-Si- -Si O- i i O-Si -Si-R
CH3 CH3 ~ R ~ R cH3 x y y
Especially preferred C02-phobic groups include CZ-2o staight chain or branched alkyls, polyalkylene oxides, glycerates, carboxylates, phosphates, sulfates and carbohydrates.
The C02-philic and COZ-phobic groups may be directly connected or linked together via a linkage group. Such groups include ester, keto, ether, amide, amine, thio, alkyl, alkenylene, fluoroalkyl, fluoroalkenylene or fluoroalkenylene.
Surfactants which are useful in the invention may be selected from two groups of compounds.
I. First Group The first group of compounds has the following formula I:
R-Si- -Si O- i i O-Si -Si-R
CH3 CH3 ~ R ~ R cH3 x y y
8 PCT/EP99/02770 wherein the ratio of x:y and y' is greater than 0.5:1, preferably greater than 0.7:1 and most preferably greater than 1:1, wherein, R, R', R" , and R " ' are each independently CH3 (with the proviso that they are not all CH3 ) or have the following formula:
-~C~aU6H4)b~A)d--{~)e~A~)f}n -~L~)~~G)h wherein, a is 1-30, preferably 1-25, most preferably 1-20.
b is 0 or 1, C6H4 is unsubstituted or substituted with a C,_lo alkyl or alkenylene branched or straight chain, and A and A' are each independently a linking moiety representing an ester, a keto, an ether, a thin, an amido, an amino, a C1_4 fluoroalkylene, a Cl_9 fluoroalkenylene, a branched or straight chain polyalkylene oxide, a phosphato, a sulfonyl, a sulfate, an ammonium, a lactam, and mixtures thereof;
d is 0 or 1;
L and L~ are each independently a C1_3o straight chain or~
branched alkyl or alkenylene or an aryl which is unsubstituted or substituted and mixtures thereof;
a is 0-3;
f is 0 or 1;
n is 0-10, preferably 0-5, most preferably 0-3;
g is 0-3;
o is 0-5, preferably 0-3;
-~C~aU6H4)b~A)d--{~)e~A~)f}n -~L~)~~G)h wherein, a is 1-30, preferably 1-25, most preferably 1-20.
b is 0 or 1, C6H4 is unsubstituted or substituted with a C,_lo alkyl or alkenylene branched or straight chain, and A and A' are each independently a linking moiety representing an ester, a keto, an ether, a thin, an amido, an amino, a C1_4 fluoroalkylene, a Cl_9 fluoroalkenylene, a branched or straight chain polyalkylene oxide, a phosphato, a sulfonyl, a sulfate, an ammonium, a lactam, and mixtures thereof;
d is 0 or 1;
L and L~ are each independently a C1_3o straight chain or~
branched alkyl or alkenylene or an aryl which is unsubstituted or substituted and mixtures thereof;
a is 0-3;
f is 0 or 1;
n is 0-10, preferably 0-5, most preferably 0-3;
g is 0-3;
o is 0-5, preferably 0-3;
9 Z is a hydrogen, a carboxylic acid, a hydroxy, a phosphato, a phosphato ester, a sulfonyl, a sulfonate, a sulfate, a branched or straight-chained polyalkylene oxide, a nitryl, a glyceryl, an aryl unsutstituted or substituted with a C1_3o alkylene or alkenylene, (preferably C,_z5alkylene), a carbohydrate unsubstituted or substituted with a C,_lo alkylene or alkenylene (preferably a C1_5 alkylene) or an ammonium G is an anion or cation such as H+, Na', Li+, K+, NH9+, Ca+2, Mg+2, C1-, Br-, 1-, mesylate, or tosylate; and h is 0-3, preferably 0-2.
Non-limiting examples of this group of surfactants are:
Si- -Si O- i i O- i O-Si-R"
R
CH3 ~H3 ~ R ~ R' CH3 x y y x = 1-300, y = 1-100, y' - 1-100 and R, R' , R' ' , o r R' ' ' -CHZ-CH2-CH2-N ~OH
U
II. Second Group The second group of compounds, for which Silsoft A-843 and Magnasoft SRS from Witco are commercially available examples, have the following structure II:
[AB]y (II) wherein, A is a repeating dimethyl siloxane unit:
-~i-O-f -~i-O ~i CH CH ~~H
x = 0-30, B is a COZ-phobic group represented by R or R' where R or R' are independently represented by the formula:
Non-limiting examples of this group of surfactants are:
Si- -Si O- i i O- i O-Si-R"
R
CH3 ~H3 ~ R ~ R' CH3 x y y x = 1-300, y = 1-100, y' - 1-100 and R, R' , R' ' , o r R' ' ' -CHZ-CH2-CH2-N ~OH
U
II. Second Group The second group of compounds, for which Silsoft A-843 and Magnasoft SRS from Witco are commercially available examples, have the following structure II:
[AB]y (II) wherein, A is a repeating dimethyl siloxane unit:
-~i-O-f -~i-O ~i CH CH ~~H
x = 0-30, B is a COZ-phobic group represented by R or R' where R or R' are independently represented by the formula:
10 -(CHZ)a~CgHq)b~A~)a-- ~~L)e~Am)f~n-- ~L~)9ZZ~G)n~CsH9)b"(CHZ)a wherein, a is 1-30, preferably 1-25; most preferably 1-20, b is 0 or 1, C6Hq is unsubstituted or substituted with a C1_lo alkyl or alkenylene branched or straight, and A' and A" are each independently a linking moiety representing an ester, a keto, an ether, a thio, an amido, an amino, a C1_4 fluoroalkyl, a C~_4 fluoroalkenylene, a branched or straight chain polyalkylene oxide, a phosphato, a sulfonyl, a sulfate, an ammonium, a lactam, and mixtures thereof d is 0 or 1;
L and L' are each independently a C1_3o straight chained or branched alkyl or alkenylene or an aryl which is unsubstituted or substituted and mixtures thereof;
a is 0-3;
f is 0 or l;
n is 0-10, preferably 0-5, most preferably 0-3;
L and L' are each independently a C1_3o straight chained or branched alkyl or alkenylene or an aryl which is unsubstituted or substituted and mixtures thereof;
a is 0-3;
f is 0 or l;
n is 0-10, preferably 0-5, most preferably 0-3;
11 g is 0-3;
o is 0-5, preferably 0-3;
Z is a hydrogen, a carboxylic acid, a hydroxy, a phosphato, a phosphato ester, a sulfonyl, a sulfonate, a sulfate, a branched or straight-chained polyalkylene oxide, a nitryl, a glyceryl, an aryl unsubstituted or substituted with a C1-so alkyl or alkenyl, (preferably ~~-zs alkyl), a carbohydrate unsubstituted or substituted with a C1-,o alkyl or alkenylene (preferably a C1_5 alkyl ) or an ammonium;
G is an anion or cation such as H+, Na+, Li+, K+, NHQ+, Ca+z, Mg+z, C1-, Br~, 1-, mesylate, or tosylate; and h is 0-3; preferably 0-2, y is 2-100.
Nonlimiting examples of this [AB],, type surfactant are:
-ski-o~--~;-o~~~
Y
wherein y is 2-100, x is 0-30, and R and R' (i.e. B) -(CHz)a(CzHaO)b(C3Hs0)c(CHz)a (CHz) aNH (CHz) a~ (CzH4~) a (CsH60) ~ (CHz) a~NH (CHz) a COOG
(CH2)a (CHZ)a'
o is 0-5, preferably 0-3;
Z is a hydrogen, a carboxylic acid, a hydroxy, a phosphato, a phosphato ester, a sulfonyl, a sulfonate, a sulfate, a branched or straight-chained polyalkylene oxide, a nitryl, a glyceryl, an aryl unsubstituted or substituted with a C1-so alkyl or alkenyl, (preferably ~~-zs alkyl), a carbohydrate unsubstituted or substituted with a C1-,o alkyl or alkenylene (preferably a C1_5 alkyl ) or an ammonium;
G is an anion or cation such as H+, Na+, Li+, K+, NHQ+, Ca+z, Mg+z, C1-, Br~, 1-, mesylate, or tosylate; and h is 0-3; preferably 0-2, y is 2-100.
Nonlimiting examples of this [AB],, type surfactant are:
-ski-o~--~;-o~~~
Y
wherein y is 2-100, x is 0-30, and R and R' (i.e. B) -(CHz)a(CzHaO)b(C3Hs0)c(CHz)a (CHz) aNH (CHz) a~ (CzH4~) a (CsH60) ~ (CHz) a~NH (CHz) a COOG
(CH2)a (CHZ)a'
12 (CH2)a (CH2)a' ~ CH2 ) aN ~ CH3 ) 2 t CH2 ) a~ G
a = 1-30; a' - 1-30 b = 0-50; c = 0-50 G = H+, Na+, K+, NH4+, Mg+2, Ca+2, Cl-, Br-, I-, mesylate or tosylate.
Compounds of this type are prepared as described in U5-A-4,150,048, incorporated herein by reference.
Modifiers In a preferred embodiment, a modifier such as water, or a useful organic solvent may be added to the cleaning drum in a small volume. Water is specifically added into the drum.
Water absorbed onto the fabrics to be drycleaned or present in residual amounts in the surfactant compound from the process of preparing the compounds is not calculated when determining the amount of the modifier which should be added. Preferred amounts of modifier should be 0.1~ to about 10$ by volume, more preferably 0.1$ to about 5~ by volume, most preferably 0.1~ to about 3~. Preferred solvents include water, acetone, glycols, acetonitrile, C1-,o alcohols and C5_15 hydrocarbons. Especially preferred solvents include water, ethanol, methanol and hexane.
a = 1-30; a' - 1-30 b = 0-50; c = 0-50 G = H+, Na+, K+, NH4+, Mg+2, Ca+2, Cl-, Br-, I-, mesylate or tosylate.
Compounds of this type are prepared as described in U5-A-4,150,048, incorporated herein by reference.
Modifiers In a preferred embodiment, a modifier such as water, or a useful organic solvent may be added to the cleaning drum in a small volume. Water is specifically added into the drum.
Water absorbed onto the fabrics to be drycleaned or present in residual amounts in the surfactant compound from the process of preparing the compounds is not calculated when determining the amount of the modifier which should be added. Preferred amounts of modifier should be 0.1~ to about 10$ by volume, more preferably 0.1$ to about 5~ by volume, most preferably 0.1~ to about 3~. Preferred solvents include water, acetone, glycols, acetonitrile, C1-,o alcohols and C5_15 hydrocarbons. Especially preferred solvents include water, ethanol, methanol and hexane.
13 Peracid Precursors Organic peracids which are stable in storage and which solubilize in densified carbon dioxide are effective at bleaching stains in the dry cleaning system. The selected organic peracid should be soluble in carbon dioxide to greater than 0.001 wt. $ at pressures of about 500 to about 10,000 psi and temperatures of about 0°C to about 100°C. The peracid compound should be present in an amount of about 0.01$ to about 5~, preferably 0.1~ to about 3~.
The organic peroxyacids usable in the present invention can contain either one or two peroxy groups and can be either aliphatic or aromatic. When the organic peroxy acid is aliphatic, the unsubstituted acid has the general formula:
O
HO-O-~-(CH2)n-Y
where Y can be, for example, H, CH3, CHZCI, COOH, or COOOH;
and n is an integer from 1 to 20.
When the organic peroxy acid is aromatic, the unsubstituted acid has the general formula:
O
HO-O-~-C6H4-Y
wherein Y is hydrogen, alkylene, alkylenehalogen, halogen, or COOH or COOOH.
Typical monoperoxyacids useful herein include alkylene peroxyacids and arylene peroxyacids such as:
The organic peroxyacids usable in the present invention can contain either one or two peroxy groups and can be either aliphatic or aromatic. When the organic peroxy acid is aliphatic, the unsubstituted acid has the general formula:
O
HO-O-~-(CH2)n-Y
where Y can be, for example, H, CH3, CHZCI, COOH, or COOOH;
and n is an integer from 1 to 20.
When the organic peroxy acid is aromatic, the unsubstituted acid has the general formula:
O
HO-O-~-C6H4-Y
wherein Y is hydrogen, alkylene, alkylenehalogen, halogen, or COOH or COOOH.
Typical monoperoxyacids useful herein include alkylene peroxyacids and arylene peroxyacids such as:
14 (i) peroxybenzoic acid and ring-substituted peroxybenzoic acid, e.g. peroxy-"-naphthoic acid;
(ii) aliphatic, substituted aliphatic and arylenealkylene monoperoxy acids, e.g. peroxylauric acid, peroxystearic acid, and N,N-phthaloylaminoperoxycaproic acid (PAP); and (iii) amidoperoxy acids, e.g. monononylamide of either peroxysuccinic acid (NAPSA) or of peroxyadipic acid (NAPAA).
Typical diperoxy acids useful herein include alkylene diperoxy acids and arylenediperoxy acids, such as:
(iv) 1,12-diperoxydodecanedioic acid;
(v) 1,9-diperoxyazelaic acid;
(vi) diperoxybrassylic acids diperoxysebacic acid and diperoxyisophthalic acid;
{vii) 2-decyldiperoxybutane-1,4-dioic acid (viii) 4,4'-sulfonylbisperoxybenzoic acids and (ix) N,N'-terephthaloyl-di(6-aminoperoxycaproic acid) {TPCAP) .
Particularly preferred peroxy acids include PAP, TPCAP, haloperbenzoic acid and peracetic acid.
Enzymes Enzymes may additionally be added to the dry cleaning system of the invention to improve stain removal. Such enzymes include proteases (e.g., Alcalase~, Savinase~ and Esperase~ from Novo Industries A/S; amylases (e. g., Termamyl~ and Duramyl~ bleach resistant amylases from Novo Industries A/S); lipases (e. g., Lipolase~ from Novo Industries A/S)~ and oxidases. The enzyme should be added to the cleaning drum in an amount from 0.001$ to 10$, preferably 0.01$ to 5$. The type of soil dictates the WO 99/57358 PCT/EP99/02?70 choice of enzyme used in the system. The enzymes should be delivered in a conventional manner, such as by preparing an enzyme solution, typically of l~ by volume (i.e., 3 mls enzyme in buffered water or solvent).
Dry Cleaning Process A process of dry cleaning using densified carbon dioxide as the cleaning fluid is schematically represented in Figure 1. A cleaning vessel 5, preferably a rotatable drum, 10 receives soiled fabrics as well as the selected surfactant, and any modifier, peracid and mixtures thereof. The cleaning vessel may also be referred to as an autoclave, particularly as described in the examples below.
(ii) aliphatic, substituted aliphatic and arylenealkylene monoperoxy acids, e.g. peroxylauric acid, peroxystearic acid, and N,N-phthaloylaminoperoxycaproic acid (PAP); and (iii) amidoperoxy acids, e.g. monononylamide of either peroxysuccinic acid (NAPSA) or of peroxyadipic acid (NAPAA).
Typical diperoxy acids useful herein include alkylene diperoxy acids and arylenediperoxy acids, such as:
(iv) 1,12-diperoxydodecanedioic acid;
(v) 1,9-diperoxyazelaic acid;
(vi) diperoxybrassylic acids diperoxysebacic acid and diperoxyisophthalic acid;
{vii) 2-decyldiperoxybutane-1,4-dioic acid (viii) 4,4'-sulfonylbisperoxybenzoic acids and (ix) N,N'-terephthaloyl-di(6-aminoperoxycaproic acid) {TPCAP) .
Particularly preferred peroxy acids include PAP, TPCAP, haloperbenzoic acid and peracetic acid.
Enzymes Enzymes may additionally be added to the dry cleaning system of the invention to improve stain removal. Such enzymes include proteases (e.g., Alcalase~, Savinase~ and Esperase~ from Novo Industries A/S; amylases (e. g., Termamyl~ and Duramyl~ bleach resistant amylases from Novo Industries A/S); lipases (e. g., Lipolase~ from Novo Industries A/S)~ and oxidases. The enzyme should be added to the cleaning drum in an amount from 0.001$ to 10$, preferably 0.01$ to 5$. The type of soil dictates the WO 99/57358 PCT/EP99/02?70 choice of enzyme used in the system. The enzymes should be delivered in a conventional manner, such as by preparing an enzyme solution, typically of l~ by volume (i.e., 3 mls enzyme in buffered water or solvent).
Dry Cleaning Process A process of dry cleaning using densified carbon dioxide as the cleaning fluid is schematically represented in Figure 1. A cleaning vessel 5, preferably a rotatable drum, 10 receives soiled fabrics as well as the selected surfactant, and any modifier, peracid and mixtures thereof. The cleaning vessel may also be referred to as an autoclave, particularly as described in the examples below.
15 Densified carbon dioxide is introduced into the cleaning vessel from a storage vessel 1. Since much of the C02 cleaning fluid is recycled within the system, any losses during the dry cleaning process are made up through a COZ
supply vessel 2. The COZ fluid is pumped into the cleaning vessel by a pump 3 at pressures ranging between about 14.7 and about 10,000 psi, preferably about 300 to about 7000 psi, most preferably about 800 psi to about 6000 psi. The C02 fluid is maintained at temperatures of about -78.5°C to about 100°C, preferably about 50°C to about 60°C, most preferably about 5°C to about 60°C by a heat exchanger 4, or by pumping a cooling solution through an internal condenser.
As an example of the operation of the system, the densified COZ is transferred from the supply vessel 2 to the cleaning vessel 5 through line 7 for a dry cleaning cycle of between about 15 to about 30 minutes. Before or during the
supply vessel 2. The COZ fluid is pumped into the cleaning vessel by a pump 3 at pressures ranging between about 14.7 and about 10,000 psi, preferably about 300 to about 7000 psi, most preferably about 800 psi to about 6000 psi. The C02 fluid is maintained at temperatures of about -78.5°C to about 100°C, preferably about 50°C to about 60°C, most preferably about 5°C to about 60°C by a heat exchanger 4, or by pumping a cooling solution through an internal condenser.
As an example of the operation of the system, the densified COZ is transferred from the supply vessel 2 to the cleaning vessel 5 through line 7 for a dry cleaning cycle of between about 15 to about 30 minutes. Before or during the
16 cleaning cycle, surfactants, modifiers, enzymes, peracid and mixtures thereof as discussed above are introduced into the cleaning vessel, preferably through a line and pump system connected to the cleaning vessel.
At the end of the dry cleaning cycle, dirty CO2, soil and spent cleaning agents are transferred through an expansion valve 6, a heat exchanger 8 by way of a line 9 into a flash drum 10. In the flash drum, pressures are reduced to 1.0 between about 260 and about 1,000 psi and to a temperature of about 23°C to about 60°C. Gaseous COZ is separated from the soil and spent agents and transferred via line 11 through a filter 12 and condenser 13 to be recycled back to the supply vessel 2. Any pressure losses are recovered by using pump 16. The spent agents and residue C02 are transferred via line 14 to an atmospheric tank 15, where the remaining COZ is vented to the atmosphere.
Other processes known in the art may be used in the claimed dry cleaning system such as those described in US-A-5,267,455 and JP 08052297 , herein incorporated by reference.
The following examples will more fully illustrate the embodiments of the invention. All parts, percentages arid proportions referred to herein and in appended claims are by weight unless otherwise indicated. The definitions and examples are intended to illustrate and not limit the scope of the invention.
At the end of the dry cleaning cycle, dirty CO2, soil and spent cleaning agents are transferred through an expansion valve 6, a heat exchanger 8 by way of a line 9 into a flash drum 10. In the flash drum, pressures are reduced to 1.0 between about 260 and about 1,000 psi and to a temperature of about 23°C to about 60°C. Gaseous COZ is separated from the soil and spent agents and transferred via line 11 through a filter 12 and condenser 13 to be recycled back to the supply vessel 2. Any pressure losses are recovered by using pump 16. The spent agents and residue C02 are transferred via line 14 to an atmospheric tank 15, where the remaining COZ is vented to the atmosphere.
Other processes known in the art may be used in the claimed dry cleaning system such as those described in US-A-5,267,455 and JP 08052297 , herein incorporated by reference.
The following examples will more fully illustrate the embodiments of the invention. All parts, percentages arid proportions referred to herein and in appended claims are by weight unless otherwise indicated. The definitions and examples are intended to illustrate and not limit the scope of the invention.
17 Example 1 The hydrophilic stain, grape juice, was dry cleaned using liquid carbon dioxide, a polydimethylsiloxane surfactant, water as a modifier and mixtures thereof according to the invention.
Two inch by three inch polyester cloths were cut and soaked in concentrated grape juice which was diluted 1:4 with water.
The cloths were then removed and dried overnight on plastic sheets. The stained fabrics were then placed in a 300 ml autoclave having a gas compressor and an extraction system as shown in Figure 1. The stained cloth was hung from the bottom of the autoclave's overhead stirrer using a copper wire to promote good agitation during washing and extraction. After placing the cloth in the autoclave and sealing it, liquid COZ
at a tank pressure of 850 psi was allowed into the system and was cooled to reach a temperature of about 11°C at which point the liquid COZ was at a pressure of about 800 psi. The stirrer was then turned on for 15 minutes to mimic a wash cycle. At the completion of the wash cycle, 20 cubic feet of fresh COZ were passed through the system to mimic a rinse cycle. The pressure of the autoclave was then released to atmospheric pressure and the cleaned cloths were removed from the autoclave. To measure the extent of cleaning, spetrophotometric readings were taken using a Hunter Ultrasacn XE' spectrophotometer. The R scale, which measures darkness from black to white, was used to determine stain removal. Cleaning results were reported as the percent stain removal according to the following calculation:
stain removed cleaned cloth reading - stained cloth reading °~ stain removal = - - x 100%
stain applied unstained cloth reading - stained cloth reading W~ 99/57358 f'(~T"I~)'99/c)2??~
'I~Wt.7 Clf f E2:E'Tlt ~!;i ~.'ylt~.l:;lE.t~ltJ.l.':il, t:~::ilT ' ;iL L i ~l<:t~eill!~~> WE'RE' ais~';~
:a ~ U11E: ur 1 1~ t'S~:L'L~ : Altl'~ ':.CiCl W1 ~ t-1 {) ~: :1 C i in't~t~E:.I- <1IM~ I %:(1i i C:.j '~arbcra dic:x:l.c.t~'_~. Ttla ~~~nt_ra_~1 cv~R~ ~i_q~ i i ._::~x-btom c..ii.~txi.ci'~
~; ,i!.t~Tlc: .
'I'hF_~ hit=er virt.r_t_ ~ ~IS,~ t u_.tm;t c~':.
wa.~: aci<~e!9 y '_e: tie ~:~tat ~~c~L~ve 1Ti!1 1-'C>t t.ti~s' _1.~ ;>(:u t 't a' , _1,: Wl~.',t.'dllt.
c: r! ~;tv,~y~_z(slat: ~rv'~i'> cl~.?. ~ l.f~'.;
diractiy tc:~tilE=~ u cr: true'c:~! 1i, "it:ttor- ~_he~
w~t.ai c:~ ~rfa:;r~ t rlG
1(~ rir~~sc.v:~, ~_::cvani~~ : cart uf~: ce t ,~~:~:u,-1:eti r-.yc~i~ l l :r arid trig-~e:~uir;> zw~3;;r~te~-itl; 'I~at~l~.. .~!_<- .
arf=
1 ~~ 'r~a'~>7.e ) Clry ~~.e~ning Results or,, ,,doe) a ~uzce ~ta_in~~ Using Supercritical. C~arbor~a Dic~xirae ;~r-~C~ !'c~l~:~:a.methy.Ls~lc>xnne Surf~.Ctant.
~TaF.~ i~zi t=a ~'u;lyE~ -,~t'r hd ,r:c, a J >.':t~ ~.
. gra) e~ ~juic:el':;)ye=.,=c~lv ~I~~:c_ ~.}. :road' i is a ~. c_> r c~r.a~~E, _~ula:.S~1';il yEa..! :~ :.i:L;sW!i.. '_:~ 11. ; ~.
E'L. (~ . E. .~ . w ,' . V~ c' ~. F > r-~_~.-_-.-.__ ......_ _._...._.-j.~ _ ~~._. w_.___._ __.._._~._.__...
. ~ ._-. _ .._.._.._...
~ra~'~ ~L:.:~~~ !:'_,lyr'. t_e~~~t ?~..na " ~ nr4 s~..~~
; !~.., l ;! t~S. Wdt t?r I
h'~. -~,l---.._~. .~,~v,-,-~_._._.~~:::~_._~--.-_.:.___ __._.e__.__.
__=- ......_~_.~:
:_~_ ' ~LZp.ps i ec:,~V ~ !.a:Va,; ~ _~t~ :; ynler .
b~ ( AHD j Y ,~~ ;c: ~
( L.-:
;l,p,~l .i.ecby M~rraa ~:miLl::t.r.1 , t aL ~~ >t-ifwi ~: i_ i ~: , occ , J ~vc>>;~~
c~~pt~ ~. ymEy r .
2_'I t ~a~,s c~b,ervetl that t:ila_~ c«ml~ i ~l~w i cal to t wa c.E>z ~> z rnt.: cii i i ~~r.
~r71.':rl ~tlE' ;~E'.~.Pc:~'t:.'i~ s 1 1. ~:::)11E-.' S 1i i:rt':'.-~lrl ;~
l.lLt~~L'C7\iE'~ t:~r'~:r t- ~.f_'~lTILC:t( results in liquid carbon dioxide. Liquid carbon dioxide alone or with water added did not appreciably clean the stain.
Example 2 The hydrophilic stain, grape juice, was dry cleaned using liquid carbon dioxide, and mixtures of liquid carbon dioxide, polydimethylsiloxane surfactant, and water according to the invention.
8.75" X 4.75" cloths had a 2" diameter circle inscribed in pencil in the middle and concentrated grape juice which was diluted 1:4 with water was applied using a micropipet to the inside of the circles and spread to the edges of the circle. The following amounts were used: on polyester and wool, 475 microliters; on cotton 350 microliters; and on silk, 2 applications of 200 microliters with 15 minutes in between applications. The cloths were then dried overnight.
Four replicates of each cloth type (for a total of 12 cloths) were placed in the cleaning chamber of a COZ dry cleaning unit constructed as taught in US patent 5,467,492 and employing hydrodynamic agitation of garments by use of appropriately angled nozzles. To simulate a full load of clothes, 1.5 pounds of cotton ballast sheets (11" X 11") were also placed in the cleaning chamber. The dry cleaning unit employed had a cleaning chamber which holds about~76 liters of liquid CO2. The piping in the cleaning loop held an additional 37 liters for a total volume in the cleaning loop of 113 liters. There was also a storage tank on the unit from which the fresh liquid COZ was added once the chamber door was closed and sealed. The cleaning cycle lasted for 15 minutes at about 850 psi and 11 degrees Celsius. After the cleaning cycle, the liquid COZ in the cleaning loop was pumped back into the storage tank, and the chamber door opened. To measure the extent of cleaning, spectrophotometric readings were taken on the washed grape juice cloths using a Hunter Ultrascan XE' spectrophotometer.
5 The L,a,b scale was used to measure cleaning. Cleaning results were reported as stain removal index values (SRI'S) using the following calculation:
SRI = 100 -1I (L~,ashed - Lclean)2 + ~awashed - aclean)2 + (bwashed - bclean)2 where, L measures black to white differences, a measures green to red differences and, b measures blue to yellow differences.
Two experiments were run - concentrations are in weight/volume of C02:
1. no additive (liquid C02 alone) 2. 0.05 Monasil PCA + 0.075 water Surfactant and water were premixed and added directly to the bottom of the cleaning chamber below the ballast and not on the stains themselves. After the wash cycle removal of COZ from the cleaning chamber, cleaning results were evaluated, and are reported in Table 2 below.
Table 2 Stain Fabric Experiment Stain Removal Number Index grape juice wool (LSD* = 2 72.90 4.90) 1 65.06 polyester (LSD 2 71,63 - 3.51) 1 61.41 cotton (LSD = 2 63.45 1.03) 1 61.35 *LSD stands for the "least significant difference" and the numbers shown are at the 95~ confidence level.
It was observed that for all three cloth types studied, addition of Monasil PCA plus water improved the dry cleaning results in liquid carbon dioxide.
Two inch by three inch polyester cloths were cut and soaked in concentrated grape juice which was diluted 1:4 with water.
The cloths were then removed and dried overnight on plastic sheets. The stained fabrics were then placed in a 300 ml autoclave having a gas compressor and an extraction system as shown in Figure 1. The stained cloth was hung from the bottom of the autoclave's overhead stirrer using a copper wire to promote good agitation during washing and extraction. After placing the cloth in the autoclave and sealing it, liquid COZ
at a tank pressure of 850 psi was allowed into the system and was cooled to reach a temperature of about 11°C at which point the liquid COZ was at a pressure of about 800 psi. The stirrer was then turned on for 15 minutes to mimic a wash cycle. At the completion of the wash cycle, 20 cubic feet of fresh COZ were passed through the system to mimic a rinse cycle. The pressure of the autoclave was then released to atmospheric pressure and the cleaned cloths were removed from the autoclave. To measure the extent of cleaning, spetrophotometric readings were taken using a Hunter Ultrasacn XE' spectrophotometer. The R scale, which measures darkness from black to white, was used to determine stain removal. Cleaning results were reported as the percent stain removal according to the following calculation:
stain removed cleaned cloth reading - stained cloth reading °~ stain removal = - - x 100%
stain applied unstained cloth reading - stained cloth reading W~ 99/57358 f'(~T"I~)'99/c)2??~
'I~Wt.7 Clf f E2:E'Tlt ~!;i ~.'ylt~.l:;lE.t~ltJ.l.':il, t:~::ilT ' ;iL L i ~l<:t~eill!~~> WE'RE' ais~';~
:a ~ U11E: ur 1 1~ t'S~:L'L~ : Altl'~ ':.CiCl W1 ~ t-1 {) ~: :1 C i in't~t~E:.I- <1IM~ I %:(1i i C:.j '~arbcra dic:x:l.c.t~'_~. Ttla ~~~nt_ra_~1 cv~R~ ~i_q~ i i ._::~x-btom c..ii.~txi.ci'~
~; ,i!.t~Tlc: .
'I'hF_~ hit=er virt.r_t_ ~ ~IS,~ t u_.tm;t c~':.
wa.~: aci<~e!9 y '_e: tie ~:~tat ~~c~L~ve 1Ti!1 1-'C>t t.ti~s' _1.~ ;>(:u t 't a' , _1,: Wl~.',t.'dllt.
c: r! ~;tv,~y~_z(slat: ~rv'~i'> cl~.?. ~ l.f~'.;
diractiy tc:~tilE=~ u cr: true'c:~! 1i, "it:ttor- ~_he~
w~t.ai c:~ ~rfa:;r~ t rlG
1(~ rir~~sc.v:~, ~_::cvani~~ : cart uf~: ce t ,~~:~:u,-1:eti r-.yc~i~ l l :r arid trig-~e:~uir;> zw~3;;r~te~-itl; 'I~at~l~.. .~!_<- .
arf=
1 ~~ 'r~a'~>7.e ) Clry ~~.e~ning Results or,, ,,doe) a ~uzce ~ta_in~~ Using Supercritical. C~arbor~a Dic~xirae ;~r-~C~ !'c~l~:~:a.methy.Ls~lc>xnne Surf~.Ctant.
~TaF.~ i~zi t=a ~'u;lyE~ -,~t'r hd ,r:c, a J >.':t~ ~.
. gra) e~ ~juic:el':;)ye=.,=c~lv ~I~~:c_ ~.}. :road' i is a ~. c_> r c~r.a~~E, _~ula:.S~1';il yEa..! :~ :.i:L;sW!i.. '_:~ 11. ; ~.
E'L. (~ . E. .~ . w ,' . V~ c' ~. F > r-~_~.-_-.-.__ ......_ _._...._.-j.~ _ ~~._. w_.___._ __.._._~._.__...
. ~ ._-. _ .._.._.._...
~ra~'~ ~L:.:~~~ !:'_,lyr'. t_e~~~t ?~..na " ~ nr4 s~..~~
; !~.., l ;! t~S. Wdt t?r I
h'~. -~,l---.._~. .~,~v,-,-~_._._.~~:::~_._~--.-_.:.___ __._.e__.__.
__=- ......_~_.~:
:_~_ ' ~LZp.ps i ec:,~V ~ !.a:Va,; ~ _~t~ :; ynler .
b~ ( AHD j Y ,~~ ;c: ~
( L.-:
;l,p,~l .i.ecby M~rraa ~:miLl::t.r.1 , t aL ~~ >t-ifwi ~: i_ i ~: , occ , J ~vc>>;~~
c~~pt~ ~. ymEy r .
2_'I t ~a~,s c~b,ervetl that t:ila_~ c«ml~ i ~l~w i cal to t wa c.E>z ~> z rnt.: cii i i ~~r.
~r71.':rl ~tlE' ;~E'.~.Pc:~'t:.'i~ s 1 1. ~:::)11E-.' S 1i i:rt':'.-~lrl ;~
l.lLt~~L'C7\iE'~ t:~r'~:r t- ~.f_'~lTILC:t( results in liquid carbon dioxide. Liquid carbon dioxide alone or with water added did not appreciably clean the stain.
Example 2 The hydrophilic stain, grape juice, was dry cleaned using liquid carbon dioxide, and mixtures of liquid carbon dioxide, polydimethylsiloxane surfactant, and water according to the invention.
8.75" X 4.75" cloths had a 2" diameter circle inscribed in pencil in the middle and concentrated grape juice which was diluted 1:4 with water was applied using a micropipet to the inside of the circles and spread to the edges of the circle. The following amounts were used: on polyester and wool, 475 microliters; on cotton 350 microliters; and on silk, 2 applications of 200 microliters with 15 minutes in between applications. The cloths were then dried overnight.
Four replicates of each cloth type (for a total of 12 cloths) were placed in the cleaning chamber of a COZ dry cleaning unit constructed as taught in US patent 5,467,492 and employing hydrodynamic agitation of garments by use of appropriately angled nozzles. To simulate a full load of clothes, 1.5 pounds of cotton ballast sheets (11" X 11") were also placed in the cleaning chamber. The dry cleaning unit employed had a cleaning chamber which holds about~76 liters of liquid CO2. The piping in the cleaning loop held an additional 37 liters for a total volume in the cleaning loop of 113 liters. There was also a storage tank on the unit from which the fresh liquid COZ was added once the chamber door was closed and sealed. The cleaning cycle lasted for 15 minutes at about 850 psi and 11 degrees Celsius. After the cleaning cycle, the liquid COZ in the cleaning loop was pumped back into the storage tank, and the chamber door opened. To measure the extent of cleaning, spectrophotometric readings were taken on the washed grape juice cloths using a Hunter Ultrascan XE' spectrophotometer.
5 The L,a,b scale was used to measure cleaning. Cleaning results were reported as stain removal index values (SRI'S) using the following calculation:
SRI = 100 -1I (L~,ashed - Lclean)2 + ~awashed - aclean)2 + (bwashed - bclean)2 where, L measures black to white differences, a measures green to red differences and, b measures blue to yellow differences.
Two experiments were run - concentrations are in weight/volume of C02:
1. no additive (liquid C02 alone) 2. 0.05 Monasil PCA + 0.075 water Surfactant and water were premixed and added directly to the bottom of the cleaning chamber below the ballast and not on the stains themselves. After the wash cycle removal of COZ from the cleaning chamber, cleaning results were evaluated, and are reported in Table 2 below.
Table 2 Stain Fabric Experiment Stain Removal Number Index grape juice wool (LSD* = 2 72.90 4.90) 1 65.06 polyester (LSD 2 71,63 - 3.51) 1 61.41 cotton (LSD = 2 63.45 1.03) 1 61.35 *LSD stands for the "least significant difference" and the numbers shown are at the 95~ confidence level.
It was observed that for all three cloth types studied, addition of Monasil PCA plus water improved the dry cleaning results in liquid carbon dioxide.
Claims (12)
1. A dry cleaning composition for removing stains from fabrics comprising:
(a) an effective amount of densified carbon dioxide;
(b) 0.001% to 10% by weight of a surfactant compound characterized in that the surfactant compound is a compound of formula I
[AB]y (I) wherein A is a repeating dimethyl siloxane unit:
x = 0-30, B is a CO2-phobic group represented by the formula:
-(CH2)a(C6H4)b (A')d~ ((L)~ (A'')f)n~ (L') gZ (G) h (C6H4)b ~ (CH2)a~
wherein, a is 1-30, b is 0 or 1, C6H4 is unsubstituted or substituted with a C1-10 alkylene or alkenylene branched or straight, and A' and A" are each independently a linking moiety representing an ester, a keto, an ether, a thio, an amido, an amino, a C1-4 fluoroalkylene, a C1-4, fluoroalkenylene, a branched or straight chain polyalkylene oxide, a phosphato, a sulfonyl, a sulfate, an ammonium, a lactam, and mixtures thereof, d is 0 or 1, L and L' are each independently a C1-30 straight chained or branched alkylene or alkenylene or an aryl which is unsubstituted or substituted and mixtuxes thereof, e is 0-3, f is 0 or 1, n is 0-10, g is 0-3, Z is a hydrogen, a carboxylic acid, a hydroxy, a phosphato, a phosphato ester, a sulfonyl, a sulfonate, a sulfate, a branched or straight-chained polyalkylene oxide, a nitryl, a glyceryl, an aryl unsubstituted or substituted with a C1-10 alkylene or alkenylene, (preferably C1-23 alkylene), a carbohydrate unsubstituted or substituted with a C1-10 alkylene or alkenylene (preferably a C1-5 alkylene) or an ammonium:
G is an anion or cation selected from H', Na', Li', K', NH4+, Ca+2, Mg+2, Cl~, Br-, l-, mesylate, or tosylate, h is 0-3, and y is 2-100, 3. The composition according to claim 1 Wherein the compounds of formula I are those wherein y is 2 to 100, x is 0 to 30 and .beta.
(a) an effective amount of densified carbon dioxide;
(b) 0.001% to 10% by weight of a surfactant compound characterized in that the surfactant compound is a compound of formula I
[AB]y (I) wherein A is a repeating dimethyl siloxane unit:
x = 0-30, B is a CO2-phobic group represented by the formula:
-(CH2)a(C6H4)b (A')d~ ((L)~ (A'')f)n~ (L') gZ (G) h (C6H4)b ~ (CH2)a~
wherein, a is 1-30, b is 0 or 1, C6H4 is unsubstituted or substituted with a C1-10 alkylene or alkenylene branched or straight, and A' and A" are each independently a linking moiety representing an ester, a keto, an ether, a thio, an amido, an amino, a C1-4 fluoroalkylene, a C1-4, fluoroalkenylene, a branched or straight chain polyalkylene oxide, a phosphato, a sulfonyl, a sulfate, an ammonium, a lactam, and mixtures thereof, d is 0 or 1, L and L' are each independently a C1-30 straight chained or branched alkylene or alkenylene or an aryl which is unsubstituted or substituted and mixtuxes thereof, e is 0-3, f is 0 or 1, n is 0-10, g is 0-3, Z is a hydrogen, a carboxylic acid, a hydroxy, a phosphato, a phosphato ester, a sulfonyl, a sulfonate, a sulfate, a branched or straight-chained polyalkylene oxide, a nitryl, a glyceryl, an aryl unsubstituted or substituted with a C1-10 alkylene or alkenylene, (preferably C1-23 alkylene), a carbohydrate unsubstituted or substituted with a C1-10 alkylene or alkenylene (preferably a C1-5 alkylene) or an ammonium:
G is an anion or cation selected from H', Na', Li', K', NH4+, Ca+2, Mg+2, Cl~, Br-, l-, mesylate, or tosylate, h is 0-3, and y is 2-100, 3. The composition according to claim 1 Wherein the compounds of formula I are those wherein y is 2 to 100, x is 0 to 30 and .beta.
is selected from the group consisting of:~
(CH2)a(C2H4O)b(C3H6O)=(CH2)a (CH2) a NH (CH2) a' (C2H4O) b (C3H6O) c (CH2) a NH (CH2) a or (CH2)a N(CH3)2(CH2)a'G
a = 1-30; a' - 1-30 b = 0-50. C = 0-50 G = H+, Na+, K+, NH4+, Mg+2, Ca+2, Cl-, Br-, I-, mesylate or tosylate.
(CH2)a(C2H4O)b(C3H6O)=(CH2)a (CH2) a NH (CH2) a' (C2H4O) b (C3H6O) c (CH2) a NH (CH2) a or (CH2)a N(CH3)2(CH2)a'G
a = 1-30; a' - 1-30 b = 0-50. C = 0-50 G = H+, Na+, K+, NH4+, Mg+2, Ca+2, Cl-, Br-, I-, mesylate or tosylate.
3. The composition according to claim 1, further comprising 0.1%
to about 10% by volume of a modifier selected from the group consisting of water, acetone, a glycol, acetonitrile, C1-10 alcohol and C5-15 hydrocarbon.
to about 10% by volume of a modifier selected from the group consisting of water, acetone, a glycol, acetonitrile, C1-10 alcohol and C5-15 hydrocarbon.
4. The composition according to claim 1, wherein the densified carbon dioxide is in a liquid phase having a pressure of about 14.7 psi to about 10,000 psi and a temperature of about -78.5°C to about 100°C.
5. The composition according to claim 1, wherein the composition further comprises an organic peracid selected from the group consisting of N,N-phthaloylaminoperoxycaproic acid (PAP) and N,N'-terephthaloyl-di(6-aminoperoxycaproic acid (TPCAP), a haloperbenzoic acid and peracetic acid.
6. A method of drycleaning fabrics comprising:
1) selecting a drycleaning/composition comprising (a) an effective amount of densified carbon dioxide;
(b) 0.001% to 10% by weight of a surfactant compound, and 2) cleaning soils from fabrics in a dry cleaning cycle, characterized in that the surfactant compound is a compound of formula I
[AB] y (I) wherein A is a repeating dimethyl siloxane unit:
x = 0-30, B is a CO2-phobic group represented by the formula:
-(CH2)a(C5H4)b(A') ~ ((L)e (A'')f)n ~ (L')gZ (G) h (C6H4)b-(CH2)a ~ .
wherein, a is 1-30, b is 0 or 1, C6H4 is unsubstituted or substituted with a C1-10 alkylene or alkenylene branched or straight, and A' and A" are each independently a linking moiety representing an ester, a keto, an ether, a thio, an amido, an amino, a C1-4 fluoroalkylene, a C1-4 fluoroalkenylene, a branched or straight chain polyalkylene oxide, a phosphato, a sulfonyl, a sulfate, an ammonium, a lactam, and mixtures thereof, d is 0 or 1, L and L' are each independently a C1-30 straight chained or branched alkylene or alkenylene or are aryl which is unsubstituted or substituted and mixtures thereof, a is 0-3, f is 0 or 1, n is 0-10, g is 0-3, Z is a hydrogen, a carboxylic acid, a hydroxy, a phosphate, a phosphate ester, a sulfonyl, a sulfonate, a sulfate, a branched or straight-chained polyalkylene oxide, a nitxyl, a glyceryl, an aryl unsubstituted or substituted with a C1-30 alkylene or alkenylene, (preferably C1-25 alkylene), a carbohydrate unsubstituted or substituted with a C1-10 alkylene or alkenylene (preferably a C1-5 alkylene) or an ammonium:
G is an anion or cation selected from H+, Na+, Li+, K+, NH4+, Ca+2, Mg+2, Cl-, Br-, 1-, mesylate, or tosylate, h is 0-3, and y is 2-100,
1) selecting a drycleaning/composition comprising (a) an effective amount of densified carbon dioxide;
(b) 0.001% to 10% by weight of a surfactant compound, and 2) cleaning soils from fabrics in a dry cleaning cycle, characterized in that the surfactant compound is a compound of formula I
[AB] y (I) wherein A is a repeating dimethyl siloxane unit:
x = 0-30, B is a CO2-phobic group represented by the formula:
-(CH2)a(C5H4)b(A') ~ ((L)e (A'')f)n ~ (L')gZ (G) h (C6H4)b-(CH2)a ~ .
wherein, a is 1-30, b is 0 or 1, C6H4 is unsubstituted or substituted with a C1-10 alkylene or alkenylene branched or straight, and A' and A" are each independently a linking moiety representing an ester, a keto, an ether, a thio, an amido, an amino, a C1-4 fluoroalkylene, a C1-4 fluoroalkenylene, a branched or straight chain polyalkylene oxide, a phosphato, a sulfonyl, a sulfate, an ammonium, a lactam, and mixtures thereof, d is 0 or 1, L and L' are each independently a C1-30 straight chained or branched alkylene or alkenylene or are aryl which is unsubstituted or substituted and mixtures thereof, a is 0-3, f is 0 or 1, n is 0-10, g is 0-3, Z is a hydrogen, a carboxylic acid, a hydroxy, a phosphate, a phosphate ester, a sulfonyl, a sulfonate, a sulfate, a branched or straight-chained polyalkylene oxide, a nitxyl, a glyceryl, an aryl unsubstituted or substituted with a C1-30 alkylene or alkenylene, (preferably C1-25 alkylene), a carbohydrate unsubstituted or substituted with a C1-10 alkylene or alkenylene (preferably a C1-5 alkylene) or an ammonium:
G is an anion or cation selected from H+, Na+, Li+, K+, NH4+, Ca+2, Mg+2, Cl-, Br-, 1-, mesylate, or tosylate, h is 0-3, and y is 2-100,
7. The method according to claim 6 wherein the densified carbon dioxide of the system is introduced into a cleaning vessel at a pressure haying from between about 14.7 to about 10,000 psi.
8. The method according to claim 7 wherein the densified carbon dioxide is maintained at a temperature of about - 78.5°C to about 100°C during the cleaning step (2).
~
~
9. The method according to claim 6 wherein a modifier is further introduced during the cleaning step (2) in an amount of 0.1% to 10% by volume.
10. The method according to claim 9 wherein the modifier is selected from the group consisting of water, acetone, a glycol, acetonitrile, C1-C10 alcohol and C6-C15 hydrocarbon.
11. The method according to claim 6 wherein the compounds of formula I are those wherein y is 2 to 100, x is 0 to 30 and selected from the group consisting of:
(CH2)a(C2H4O)b(C3H6O)c(CH2)a (CH2)a NH(CH2)a'(C2H4O)b(C3H6O)c(CH2)a'NH(CH2)a or ~~(CH2)a N(CH3)2(CH2)a' G
a = 1-30; a' = 1-30 b = 0-50; c = 0-50 G = H+, Na+, K+, NH4+, Mg+2, Ca+2, Cl-, Br-, I-, mesylate or tosylate.
(CH2)a(C2H4O)b(C3H6O)c(CH2)a (CH2)a NH(CH2)a'(C2H4O)b(C3H6O)c(CH2)a'NH(CH2)a or ~~(CH2)a N(CH3)2(CH2)a' G
a = 1-30; a' = 1-30 b = 0-50; c = 0-50 G = H+, Na+, K+, NH4+, Mg+2, Ca+2, Cl-, Br-, I-, mesylate or tosylate.
12. The method according to claim 6 wherein the system further comprises an organic peracid selected from the group consisting of N,N-phthaloylaminoperoxycaproic acid (PAP) and N,N'-terephthaloyl-di(6-aminoperoxycaproic acid (TPCAP), a haloperbenzoic acid and peracetic acid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/072,773 | 1998-05-06 | ||
| US09/072,773 US5977045A (en) | 1998-05-06 | 1998-05-06 | Dry cleaning system using densified carbon dioxide and a surfactant adjunct |
| PCT/EP1999/002770 WO1999057358A1 (en) | 1998-05-06 | 1999-04-21 | Dry cleaning system using densified carbon dioxide and a surfactant adjunct |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2330328A1 true CA2330328A1 (en) | 1999-11-11 |
Family
ID=22109664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002330328A Abandoned CA2330328A1 (en) | 1998-05-06 | 1999-04-21 | Dry cleaning system using densified carbon dioxide and a surfactant adjunct |
Country Status (10)
| Country | Link |
|---|---|
| US (2) | US5977045A (en) |
| EP (1) | EP1075559B1 (en) |
| AU (1) | AU3822499A (en) |
| BR (1) | BR9910209A (en) |
| CA (1) | CA2330328A1 (en) |
| DE (1) | DE69918292T2 (en) |
| ES (1) | ES2219013T3 (en) |
| TR (1) | TR200003208T2 (en) |
| WO (1) | WO1999057358A1 (en) |
| ZA (1) | ZA200005626B (en) |
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-
1998
- 1998-05-06 US US09/072,773 patent/US5977045A/en not_active Expired - Fee Related
-
1999
- 1999-04-21 CA CA002330328A patent/CA2330328A1/en not_active Abandoned
- 1999-04-21 AU AU38224/99A patent/AU3822499A/en not_active Abandoned
- 1999-04-21 EP EP99920770A patent/EP1075559B1/en not_active Expired - Lifetime
- 1999-04-21 ES ES99920770T patent/ES2219013T3/en not_active Expired - Lifetime
- 1999-04-21 TR TR2000/03208T patent/TR200003208T2/en unknown
- 1999-04-21 WO PCT/EP1999/002770 patent/WO1999057358A1/en active IP Right Grant
- 1999-04-21 DE DE69918292T patent/DE69918292T2/en not_active Expired - Lifetime
- 1999-04-21 BR BR9910209-9A patent/BR9910209A/en not_active IP Right Cessation
- 1999-09-02 US US09/388,887 patent/US6114295A/en not_active Expired - Fee Related
-
2000
- 2000-10-12 ZA ZA200005626A patent/ZA200005626B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE69918292T2 (en) | 2004-10-14 |
| DE69918292D1 (en) | 2004-07-29 |
| US5977045A (en) | 1999-11-02 |
| WO1999057358A1 (en) | 1999-11-11 |
| ES2219013T3 (en) | 2004-11-16 |
| AU3822499A (en) | 1999-11-23 |
| ZA200005626B (en) | 2001-10-12 |
| US6114295A (en) | 2000-09-05 |
| TR200003208T2 (en) | 2001-03-21 |
| EP1075559B1 (en) | 2004-06-23 |
| BR9910209A (en) | 2001-01-09 |
| EP1075559A1 (en) | 2001-02-14 |
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