U.S. patent application number 12/663657 was filed with the patent office on 2010-11-25 for cleaning compositions and methods for using same.
This patent application is currently assigned to EMINENT TECHNOLOGIES, LLC. Invention is credited to Gene R. Damaso, Dylan M. Klopfenstein, Timothy L. Racette, James E. Schulte.
Application Number | 20100293723 12/663657 |
Document ID | / |
Family ID | 40130152 |
Filed Date | 2010-11-25 |
United States Patent
Application |
20100293723 |
Kind Code |
A1 |
Racette; Timothy L. ; et
al. |
November 25, 2010 |
CLEANING COMPOSITIONS AND METHODS FOR USING SAME
Abstract
The present invention relates to cleaning compositions and to
methods of using the cleaning compositions for cleaning of various
substrates and to processes for making such cleaning
compositions.
Inventors: |
Racette; Timothy L.;
(Naperville, IL) ; Schulte; James E.; (Naperville,
IL) ; Klopfenstein; Dylan M.; (Naperville, IL)
; Damaso; Gene R.; (Naperville, IL) |
Correspondence
Address: |
K&L Gates LLP
P.O. Box 1135
CHICAGO
IL
60690
US
|
Assignee: |
EMINENT TECHNOLOGIES, LLC
Naperville
IL
|
Family ID: |
40130152 |
Appl. No.: |
12/663657 |
Filed: |
June 6, 2008 |
PCT Filed: |
June 6, 2008 |
PCT NO: |
PCT/US08/66140 |
371 Date: |
August 2, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60942969 |
Jun 8, 2007 |
|
|
|
Current U.S.
Class: |
8/142 ;
510/288 |
Current CPC
Class: |
C11D 1/345 20130101;
C11D 3/2068 20130101; C11D 3/43 20130101; C11D 11/0011 20130101;
D06L 1/02 20130101; D06L 1/04 20130101 |
Class at
Publication: |
8/142 ;
510/288 |
International
Class: |
D06L 1/04 20060101
D06L001/04 |
Claims
1. A cleaning composition comprising: (a) a glycol ether in an
amount of at least about 95%, by weight and (b) a phosphate
ester-containing compound in an amount of about 0.01% to about 4%,
by weight.
2. The composition of claim 1 wherein the glycol ether (a) has a
flash point of greater than about 100.degree. F., (b) is 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.degree. C. and about 30.degree. C.; and (c) has a specific
gravity greater than about 0.7;
3. The composition of claim 1 wherein the glycol ether has Hansen
solubility parameters of about 7.2-8.1 (cal/cm.sup.3).sup.1/2 for
dispersion, about 2.0-4.8 (cal/cm.sup.3).sup.1/2 for polar, and
about 4.0-7.3 (cal/cm.sup.3).sup.1/2 for hydrogen bonding.
4. The composition of claim 2 wherein the glycol ether is of
formula: ##STR00025## wherein x, y and z each is zero or one and at
least one of x, y and z is one; R'' is a C.sub.1-10 linear or
branched alkyl; R.sub.1-12, if present, are independently
C.sub.mH.sub.nF.sub.p where m is an integer between zero and two,
inclusive, and n and p are integers between zero and five,
inclusive; and R' is O, S, carbonyl or ester.
5. The composition of claim 1 wherein the glycol ether comprises
one or more of dipropylene glycol n-butyl ether, ethylene glycol
ethyl ether, diethylene glycol butyl ether, propylene glycol
t-butyl ether, dipropylene glycol methyl ether, tripopylene glycol
methyl ether, dipropylene glycol n-propyl ether or tripropylene
glycol n-butyl ether.
6. The composition of claim 1 wherein the phosphate
ester-containing compound comprises: octylphenol phosphate ester,
nonylphenol phosphate ester, isodecyl alcohol phosphate ester,
linear or branched alcohol C.sub.8-C.sub.10 phosphate ester.
7. The composition of claim 6 wherein the phosphate
ester-containing compound is ethoxylated.
8. The composition of claim 7 wherein the phosphate
ester-containing compound comprises on average about 4 to about 10
moles of ethoxyl groups.
9. The composition of claim 1 further comprising a neutralizing
agent.
10. The composition of claim 9 wherein the neutralizing agent
comprises an amine compound or a salt of a Group Ia, IIa or
transition metal.
11. The composition of claim 7 wherein the neutralizing agent
comprises a salt of a Group Ia, IIa or transition metal is selected
from 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,
magnesium hydroxide, calcium carbonate, calcium phosphate, calcium
hydroxide, calcium bicarbonate, calcium citrate, calcium borate,
magnesium hydroxide, magnesium, metasilicate aluminate, magnesium
oxide and zinc hydroxide.
12. The composition of claim 1 further comprising water.
13. The composition of claim 8 further comprising one or more
additives selected from an antistatic agent, a sizing agent, a
bleach and an optical whitener.
14. A cleaning composition comprising: (a) a glycol ether in an
amount of at least about 95%, by weight, (b) a phosphate
ester-containing compound in an amount of about 0.01% to about 2%,
by weight, and (c) a neutralizing agent.
15. A cleaning composition comprising: (a) dipropylene glycol
n-butyl ether in an amount of at least about 95%, by weight, (b) a
phosphate ester-containing compound selected from octylphenol
phosphate ester, nonylphenol phosphate ester, isodecyl alcohol
phosphate ester, linear or branched alcohol C.sub.8-C.sub.10
phosphate ester in an amount of about 0.01% to about 2%, by weight,
a neutralizing agent and water.
16. The cleaning composition of claim 15 wherein the phosphate
ester-containing compound comprises about 4 to about 10 moles of
ethoxyl groups.
17. A process for making a cleaning composition, the process
comprising the steps of: admixing, in any order, a glycol ether, 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 glycol ether and optionally with an
antistatic agent, a sizing agent, a bleach or an optical whitener
to foim the cleaning composition.
18. The process of claim 17 further comprising adding water during
the admixing and/or combining steps.
19. A process for cleaning a substrate comprising: placing the
substrate to be cleaned in a non-pressurizable cleaning vessel;
adding the cleaning composition of claim 1 to the cleaning vessel;
cleaning the substrate in presence of the cleaning composition and
in absence of pressurized fluid solvent; removing a portion of the
cleaning composition from the cleaning vessel; placing the
substrates in a pressurizable drying vessel and pressurizing the
drying vessel; adding pressurized fluid solvent to the drying
vessel; removing at least a portion of the pressurized fluid
solvent from the drying vessel; and removing the substrates from
the drying vessel, wherein the process removes water soluble and
water insoluble contaminants from the substrates..
20. A process for cleaning substrates comprising: placing the
substrates to be cleaned in a pressurizable vessel wherein the
vessel is not pressurized; adding the cleaning composition of claim
1 to the vessel; cleaning the substrates in presence of the
cleaning composition; removing a portion of the cleaning
composition from the vessel; pressurizing the vessel and adding
pressurized fluid solvent to the vessel; removing at least a
portion of the pressurized fluid solvent from the vessel; and
removing the substrates from the vessel, wherein the process
removes water soluble and water insoluble contaminants from the
substrates.
Description
FIELD OF THE INVENTION
[0001] 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.
BACKGROUND OF THE INVENTION
[0002] 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.
[0003] 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.
[0004] 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.
SUMMARY OF THE INVENTION
[0005] 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.
[0006] 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.
[0007] 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.
[0008] 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.
[0009] 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.
[0010] These and other embodiments of the present invention are
described in further detail hereinbelow.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a block diagram of a dual vessel cleaning system
according to one embodiment of the invention.
[0012] FIG. 2 is a block diagram of a single vessel cleaning system
according to one embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0013] 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.
[0014] 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.
Organic Solvent
[0015] 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.
[0016] In one embodiment, the organic solvent (a) has a flash point
of greater than about 100.degree. 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.
[0017] 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.degree. 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/cm.sup.3).sup.1/2 for dispersion,
about 2.0-4.8 (cal/cm.sup.3).sup.1/2 for polar, and about 4.0-7.3
(cal/cm.sup.3).sup.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.degree. F.; and/or (5)
evaporation rate of lower than about 30 (where n-butyl
acetate=100).
[0018] 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.
[0019] 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)).
[0020] 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.
TABLE-US-00001 TABLE 1 Evaporation Hansen Solubility Parameters
Soluble in Specific Flash Rate Hydrogen carbon Gravity Point
(n-butyl Dispersion Polar Bonding Total Solvent dioxide (20.degree.
C./20.degree. C.) (.degree. F.) acetate = 100)
(cal/cm.sup.3).sup.1/2 (cal/cm.sup.3).sup.1/2
(cal/cm.sup.3).sup.1/2 (cal/cm.sup.3).sup.1/2 Ethylene Glycol Yes
0.931 110 30 7.9 4.5 7.0 11.5 Ethyl Ether Ethylene Glycol Yes 0.973
130 20 7.8 2.3 5.2 9.7 Ethyl Ether Acetate Diethylene Yes 0.956 222
0.3 7.8 3.4 5.2 10.0 Glycol Butyl Ether Propylene Yes 0.872 113 25
7.5 3.0 5.3 9.6 Glycol t-butyl (25.degree. C./25.degree. C.) Ether
Dipropylene Yes 0.951 167 2 7.6 2.8 5.5 9.8 Glycol Methyl Ether
Tripropylene Yes 0.962 232 0.2 7.4 3.0 5.7 9.8 Glycol Methyl Ether
Dipropylene Yes 0.912 214 0.4 7.4 2.2 5.5 9.5 Glycol n-Butyl Ether
Dipropylene Yes 0.922 190 1.3 7.4 2.4 5.7 9.6 Glycol n-Propyl Ether
Tripropylene Yes 0.934 255 0.029 7.4 2.4 5.1 9.3 Glycol n-Butyl
Ether
[0021] Solvents shown in Table 1 are soluble in carbon dioxide
between 570 psig/5.degree. C. and 830 psig/20.degree. 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.
[0022] 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.
[0023] Cyclic terpenes, specifically, .alpha.-terpene isomers, pine
oil, .alpha.-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).sup.1/2 for
dispersion, about 0.5-9.0 (MPa).sup.1/2 for polar, and about
0.0-10.5 (MPa).sup.1/2 for hydrogen bonding.
[0024] 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).sup.1/2 for dispersion, about
0.0-7.0 (MPa).sup.1/2 for polar, and about 0.0-5.0 (MPa).sup.1/2
for hydrogen bonding.
[0025] 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).sup.1/2 for
dispersion, about 3.0-7.5 (MPa).sup.1/2 for polar, and about
8.0-17.0 (MPa).sup.1/2 for hydrogen bonding.
[0026] 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).sup.1/2 for
dispersion, about 4.5-20.5 (MPa).sup.1/2 for polar, and about
15.0-30.0 (MPa).sup.1/2 for hydrogen bonding.
[0027] 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).sup.1/2 for dispersion, about 1.5-6.5 (MPa).sup.1/2 for
polar, and about 5.0-10.0 (MPa).sup.1/2 for hydrogen bonding.
[0028] 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).sup.1/2 for dispersion, about 3.0-10.0 (MPa).sup.1/2 for
polar, and about 8.0-16.0 (MPa).sup.1/2 for hydrogen bonding.
[0029] 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).sup.1/2 for
dispersion, about 2.0-7.5 (MPa).sup.1/2 for polar, and about
1.5-6.5 (MPa).sup.1/2 for hydrogen bonding.
[0030] 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).sup.1/2 for dispersion, about 3.1-18.8 (MPa).sup.1/2 for
polar, and about 8.4-22.3 (MPa).sup.1/2 for hydrogen bonding.
[0031] 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).sup.1/2
for dispersion, about 3.0-9.0 (MPa).sup.1/2 for polar, and about
9.0-16.5 (MPa).sup.1/2 for hydrogen bonding.
[0032] 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).sup.1/2 for dispersion, about 0.0-4.5 (MPa).sup.1/2 for
polar, and about 0.0-4.5 (MPa).sup.1/2 for hydrogen bonding.
[0033] 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).sup.1/2 for dispersion,
about 4.0-10.0 (MPa).sup.1/2 for polar, and about 1.5-9.0
(MPa).sup.1/2 for hydrogen bonding.
[0034] 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).sup.1/2 for dispersion, about
0.0-2.0 (MPa).sup.1/2 for polar, and about 0.0-2.0 (MPa).sup.1/2
for hydrogen bonding.
[0035] 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).sup.1/2 for
dispersion, about 4.0-6.5 (MPa).sup.1/2 for polar, and about
4.0-11.0 (MPa).sup.1/2 for hydrogen bonding.
[0036] 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).sup.1/2 for dispersion, about 3.0-8.0 (MPa).sup.1/2 for
polar, and about 3.0-11.0 (MPa).sup.1/2 for hydrogen bonding.
[0037] 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).sup.1/2 for dispersion, about 6.0-17.0 (MPa).sup.1/2 for
polar, and about 4.0-13.0 (MPa).sup.1/2 for hydrogen bonding.
[0038] 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.degree. 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).
[0039] 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.degree. C. and 830 psig/20.degree. C.
TABLE-US-00002 TABLE 2 Evaporation Hansen Solubility Parameters
Soluble in Specific Flash Rate Hydrogen carbon Gravity Point
(n-butyl Dispersion Polar Bonding Total Solvent dioxide (20.degree.
C./20.degree. C.) (.degree. F.) acetate = 100) (MPa).sup.1/2
(MPa).sup.1/2 (MPa).sup.1/2 (MPa).sup.1/2 Terpenes Pine Oil y
.929.sup.a 193.sup.a 0.5.sup.a 13.9.sup.a 8.0.sup.a 10.2.sup.a
19.0.sup.a d-limonene y .843.sup.c 121.sup.c 0.5.sup.c 16.6.sup.c
0.6.sup.c 0.0.sup.c 16.6.sup.c (25.degree. C./25.degree. C.)
Halocarbons 1,1,2- y 1.57.sup.b none.sup.b 2100.sup.b 14.7.sup.b
1.6.sup.b 0.0.sup.b 14.7.sup.b trifluoro- trichloroethane n-propyl
y 1.35 none 5.8 16.0.sup.h 6.5.sup.h 4.7.sup.h 17.9 bromide
(25.degree. C./25.degree. C.) Perfluorohexane y 1.67.sup.f
none.sup.f 1000.sup.d 12.1.sup.d 0.0.sup.d 0.0.sup.d 12.1 Glycol
Ethers Triethylene y 0.92 @ >200.sup.d <1.sup.d 13.3.sup.a
3.1.sup.a 8.4.sup.a 16.0.sup.a glycol 15.5.degree. C. mono-oleyl
ether Ethylan y 1.12 >200.sup.d <0.5.sup.d 17.4.sup.d
9.2.sup.d 13.0.sup.d 23.6.sup.d HB4* Polyols Hexylene y .921.sup.b
201.sup.b 1.0.sup.b 15.8.sup.b 8.4.sup.b 17.8.sup.b 25.2 glycol
Ethers Tetraethylene y 1.005.sup.b 285.sup.b ~<0.5.sup.d
15.7.sup.b 2.0.sup.b 8.2.sup.b 17.8.sup.b glycol dimethyl ether
Esters of Glycol Ethers Ethylene y 1.124.sup.b 181.sup.b 2.0.sup.b
16.4.sup.b 10.4.sup.b 12.9.sup.b 23.3.sup.b glycol diacetate Esters
of Carboxylic Acids Decyl y 0.869.sup.b 212.sup.b 0.6.sup.b
14.9.sup.b 5.7.sup.b 3.1.sup.b 16.4.sup.b acetates** Tridecyl y
0.875.sup.b 261.sup.b 0.1.sup.b 15.1.sup.b 5.1.sup.b 1.6.sup.b
16.1.sup.b acetates*** Soy methyl y 0.87.sup.c @ 425.sup.c
<0.5.sup.c 16.1.sup.c 4.9.sup.c 5.9.sup.c 17.8 esters*
25.degree. C./25.degree. C. Fatty Alcohols 2-ethyl- y 0.829.sup.b
171.sup.b 2.0.sup.b 15.9.sup.b 3.3.sup.b 11.9.sup.b 20.2.sup.b
hexanol Aprotic Solvents Dimethylsulfoxide y 1.097.sup.b 203.sup.b
2.6.sup.b 18.4.sup.b 16.4.sup.b 10.2.sup.b 26.6.sup.b Dimethyl y
.94.sup.b 136.sup.b 20.sup.b 17.4.sup.b 13.7.sup.b 11.2.sup.b
24.7.sup.b formamide Propylene y 1.185.sup.b 270.sup.b 0.5.sup.b
20.0.sup.b 18.0.sup.b 4.1.sup.b 27.3.sup.b carbonate Siloxanes
Octamethyl y 0.96.sup.g @ 144.sup.g <1.sup.d 15.1.sup.d
0.8.sup.d 0.0.sup.d 15.1.sup.h cyclotetra 25.degree. C./25.degree.
C. siloxane/decamethyl cyclopenta- siloxane++ Hydrofluoroethers
1-methoxy- y 1.52 none 900.sup.d 13.7.sup.d 6.1.sup.d 8.2.sup.d
17.1.sup.d nonafluoro- butane Aliphatic Hydrocarbons Isoparaffins y
0.77 140 <10 15.7.sup.d 0.0.sup.d 0.0.sup.d 17.1.sup.d (DF 2000)
Dibasic Esters Dimethyl y 1.084.sup.b 225.sup.b <0.9.sup.b
17.0.sup.b 4.7.sup.b 9.8.sup.b 20.2.sup.b glutarate
*Phenyl-.omega.-hydroxy-poly (oxy 1,2 ethanediyl): Akzo Nobel
**Exxate 1000; Exxon ***Exxate 1300; Exxon +Soy Gold 1100; AG
Environmental Products ++SF 1204; General Electric Silicones
.sup.aBarton A. F. M.; Handbook of Solubility Parameters and Other
Cohesion Parameters, 2.sup.nd Edition; CRC Press, 1991 (ISBN
0-8493-0176-9) .sup.bWypych, George; Handbook of Solvents, 2001;
ChemTec (ISBN 1-895198-24-0) .sup.cAG Environmental Products,
website. .sup.dEstimated. .sup.eClean Tech Proceedings 1998, pg 92
.sup.fFluorochem USA .sup.gGE Silicones Fluids Handbook, Bulletin
No. 59 (9/91). .sup.hFedors Method: R.F. Fedoers, Polymer
Engineering and Science, 1974.
[0040] In one embodiment, the organic solvent is composed at least
in part of a chemical having the following general chemical
formula:
C.sub.aX.sub.jH.sub.kO.sub.z General Chemical Formula A
[0041] wherein:
[0042] a=5n and 1.ltoreq.n.ltoreq.3;
[0043] 0.ltoreq.z.ltoreq.4;
[0044] 0.ltoreq.j, k.ltoreq.(10n+2); and
[0045] 8.ltoreq.(j+k).ltoreq.(10n+2);
[0046] each X is independently F, Cl, Br, or I.
[0047] Non-limiting examples of organic solvents described by
General Chemical Formula A include pine oil, d-limonene, dipentene,
myrcene, pinene, and alpha-terpineol.
[0048] In another embodiment, the organic solvent is composed at
least in part of a chemical having the following general chemical
formula:
C.sub.nX.sub.jH.sub.k General Chemical Formula B
[0049] wherein:
[0050] 1.ltoreq.n.ltoreq.22;
[0051] 0.ltoreq.j, k.ltoreq.(2n+2); and
[0052] (2n-4).ltoreq.(j+k).ltoreq.(2n+2);
[0053] each X is independently F, Cl, Br, or I.
[0054] 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.
[0055] In another embodiment, the organic solvent is composed at
least in part of a chemical having the following general chemical
structure:
##STR00001##
[0056] wherein:
[0057] R.sup.i.dbd.O, S, C,
##STR00002##
[0058] R.sup.ii.dbd.C.sub.kH.sub.sX.sub.t or benzyl, phenyl,
partially or fully fluorinated benzyl or phenyl;
[0059] R.sup.iv.dbd.C.sub.jH.sub.qX.sub.r or benzyl, phenyl,
partially or fully fluorinated benzyl or phenyl;
[0060] 0.ltoreq.j, k.ltoreq.18;and
[0061] 0.ltoreq.(j+k).ltoreq.18;
[0062] 0.ltoreq.q, r.ltoreq.(2j+1); and
[0063] 1.ltoreq.(q+r).ltoreq.(2j+1);
[0064] 0.ltoreq.s, t.ltoreq.(2j+1); and
[0065] 1.ltoreq.(s+t).ltoreq.(2k+1);
[0066] If j=0, then r=0;
[0067] If k=0, then t=0;
[0068] R.sub.1-4 and R.sub.9-12 are independently
C.sub.mH.sub.nX.sub.p, [0069] where 0.ltoreq.m.ltoreq.2; [0070]
1.ltoreq.(n+p).ltoreq.5; and [0071] (n+p)=(2m+1);
[0072] R.sub.5-8 and R.sub.13-16 are independently
C.sub.aH.sub.bX.sub.d, [0073] wherein a is 0 or1; [0074]
1.ltoreq.(b+d).ltoreq.3; and [0075] (b+d)=(2a+1); and each X is
independently F, Cl, Br, or I.
[0076] Some examples of organic solvents described by General
Chemical Structure 1 include alpha-phenyl-.omega.-hydroxy-tetra
(oxy-1,2-ethanediyl) and tetraethylene glycol dimethyl ether.
[0077] In another embodiment, the organic solvent is composed at
least in part of a chemical having the following general chemical
structure:
##STR00003##
[0078] wherein:
[0079] 0.ltoreq.x, y, z.ltoreq.1;and
[0080] 1.ltoreq.(x+y+z).ltoreq.3;
[0081] R.sup.i.dbd.O, S, C,
##STR00004##
[0082] R.sup.ii.dbd.C.sub.kH.sub.sX.sub.t or benzyl, phenyl,
partially or fully fluorinated benzyl or phenyl;
[0083] R.sup.iv.dbd.C.sub.jH.sub.qX.sub.r or benzyl, phenyl,
partially or fully fluorinated benzyl or phenyl;
[0084] j or k may equal 0;
[0085] If j=0, then
[14-3(x+y+z)].ltoreq.k.ltoreq.[37-3(x+y+z)];
[0086] If k=0, then
[14-3(x+y+z)].ltoreq.j.ltoreq.[37-3(x+y+z)];
[0087] If neither j nor k=0, then
[14-3(x+y+z)].ltoreq.(j+k).ltoreq.[37-3(x+y+z)];
[0088] 1.ltoreq.(q+r).ltoreq.(2j+1);
[0089] 1.ltoreq.(s+t).ltoreq.(2k+1);
[0090] R.sub.1-3 and R.sub.7-9 are independently
C.sub.mH.sub.nX.sub.p, [0091] wherein 0.ltoreq.m.ltoreq.2; [0092]
1.ltoreq.(n+p).ltoreq.5; and [0093] (n+p)=(2m+1);
[0094] R.sub.4-6 and R.sub.10-12 are independently
C.sub.aH.sub.bX.sub.d, [0095] wherein a is 0 or 1; [0096]
1.ltoreq.(b+d).ltoreq.3; and [0097] (b+d)=(2a+1); and each X is
independently F, Cl, Br, or I.
[0098] 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.
[0099] In another embodiment, the organic solvent is composed at
least in part of a chemical having the following general chemical
formula:
C.sub.nH.sub.jX.sub.k(OH).sub.r General Chemical Formula C
[0100] wherein:
[0101] each X is independently F, Cl, Br, or I;
[0102] 1.ltoreq.n.ltoreq.22
[0103] 0.ltoreq.r.ltoreq.4;
[0104] 0.ltoreq.j, k.ltoreq.(2n+2-r) and
[0105] 4.ltoreq.(j+k).ltoreq.(2n+2-r)
[0106] 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.
[0107] In another embodiment, the organic solvent is composed at
least in part of a chemical having the following general chemical
formula:
C.sub.nH.sub.jX.sub.kO.sub.b General Chemical Formula D
[0108] wherein:
[0109] each X is independently F, Cl, Br, or I;
[0110] 2.ltoreq.n.ltoreq.32
[0111] 0.ltoreq.j, k.ltoreq.(2n+2);
[0112] 6.ltoreq.(j+k).ltoreq.2n+2; and
[0113] 1.ltoreq.b.ltoreq.6.
[0114] 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.
[0115] In another embodiment, the organic solvent is composed at
least in part of a chemical having the following general chemical
structure:
##STR00005##
[0116] wherein:
[0117] 0.ltoreq.w, x, y, z.ltoreq.1;
[0118] 1.ltoreq.(w+x+y+z).ltoreq.4;
[0119] R.sup.i.dbd.O, S, C,
##STR00006##
[0120] R.sup.ii.dbd.C.sub.kH.sub.aX.sub.b or benzyl, phenyl,
partially or fully fluorinated benzyl or phenyl;
[0121] R.sup.iii.dbd.C.sub.jH.sub.uX.sub.v or benzyl, phenyl,
partially or fully fluorinated benzyl or phenyl;
[0122] 0.ltoreq.(j+k).ltoreq.[34-3(w+x+y+z)]; and
[0123] 0.ltoreq.u, v.ltoreq.(2j+1); and
[0124] (2j-7).ltoreq.(u+v).ltoreq.(2j+1); and
[0125] 0.ltoreq.a, b.ltoreq.(2k+1); and
[0126] (2k-7).ltoreq.(a+b).ltoreq.(2k+1);
[0127] R.sub.1-4 and R.sub.9-12 are independently
C.sub.mH.sub.nX.sub.p, [0128] wherein 0.ltoreq.m.ltoreq.2; [0129]
1.ltoreq.(n+p).ltoreq.5; and [0130] n+p=2m+1;
[0131] R.sub.5-8 and R.sub.13-16 are independently
C.sub.qH.sub.aX.sub.t, [0132] wherein q is 0 or 1; [0133]
1.ltoreq.(s+t).ltoreq.3;and [0134] (s+t)=(2q+1); and
[0135] each X is independently F, Cl, Br, or I.
[0136] 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.
[0137] In another embodiment, the organic solvent is composed at
least in part of a chemical having the following general chemical
structure:
##STR00007##
[0138] wherein:
[0139] 0.ltoreq.w, x, y, z.ltoreq.1; and
[0140] 1.ltoreq.(w+x+y+z).ltoreq.4;
[0141] R.sup.i.dbd.O, S, C,
##STR00008##
[0142] R.sup.ii.dbd.C.sub.kH.sub.aX.sub.b or benzyl, phenyl,
partially or fully fluorinated benzyl or phenyl;
[0143] R.sup.iv=ester, or carbonyl;
[0144] R.sup.v.dbd.C.sub.jH.sub.aX.sub.v or benzyl, phenyl,
partially or fully fluorinated benzyl or phenyl;
[0145] 0.ltoreq.(j+k).ltoreq.[34-3(w+x+y+z)];
[0146] 0.ltoreq.u, v.ltoreq.(2j+1);
[0147] (2j-7).ltoreq.(u+v).ltoreq.(2j+1);
[0148] 0.ltoreq.a,b.ltoreq.(2k+1);
[0149] (2k-7).ltoreq.(a+b).ltoreq.(2k+1); and
[0150] R.sub.1-4 and R.sub.9-12 are independently
C.sub.mH.sub.nX.sub.p, [0151] wherein 0.ltoreq.m.ltoreq.2; [0152]
1.ltoreq.(n+p).ltoreq.5; and [0153] n+p=2m+1;
[0154] R.sub.5-8 and R.sub.13-16 are independently
C.sub.qH.sub.sX.sub.t, [0155] wherein q is 0 or 1; [0156]
1.ltoreq.(s+t).ltoreq.3; and [0157] (s+t)=(2q+1); and
[0158] each X is independently F, Cl, Br, or I.
[0159] Some examples of organic solvents described by General
Chemical Structure 4 include ethylene glycol diacetate, and
propylene glycol diacetate.
[0160] In another embodiment, the organic solvent is composed at
least in part of a chemical having the following general chemical
structure:
C.sub.n(CO.sub.2).sub.mH.sub.aX.sub.b General Chemical Formula
D
[0161] wherein:
[0162] each X is independently F, Cl, Br, or I;
[0163] 2.ltoreq.n.ltoreq.38;
[0164] 1.ltoreq.m.ltoreq.3;
[0165] 0.ltoreq.a, b.ltoreq.(2n+2); and
[0166] (2n-2).ltoreq.(a+b).ltoreq.(2n+2).
[0167] 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.
[0168] In another embodiment, a cleaning composition of the
invention comprises on organic solvent of the following general
chemical formula:
C.sub.n(CO.sub.3).sub.mH.sub.aX.sub.b General Chemical Formula
E
[0169] wherein:
[0170] each X is independently F, Cl, Br, or I;
[0171] 2.ltoreq.n.ltoreq.18;
[0172] 0.ltoreq.a, b.ltoreq.(2n+2); and
[0173] (2n-4).ltoreq.(a+b).ltoreq.(2n+2).
[0174] 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.
[0175] In another embodiment, the organic solvent is composed at
least in part of a chemical having the following general chemical
structure:
##STR00009##
[0176] wherein:
[0177] R.sub.1.dbd.C.sub.JH.sub.aX.sub.b [0178] 1.ltoreq.j.ltoreq.6
[0179] 0.ltoreq.a, b.ltoreq.(2j+1); and [0180]
(2j-7).ltoreq.(a+b).ltoreq.(2j+1);
[0181] R.sub.2.dbd.C.sub.kH.sub.dX.sub.e [0182]
1.ltoreq.k.ltoreq.6; [0183] 0.ltoreq.d, e.ltoreq.(2k+1); and [0184]
(d+e)=(2k+1);
[0185] R.sub.3.dbd.C.sub.mH.sub.fX.sub.g [0186]
1.ltoreq.m.ltoreq.6; [0187] 0.ltoreq.f, g.ltoreq.(2m+1); and [0188]
(f+g)=(2m+1); and
[0189] each X is independently F, Cl, Br, or I.
[0190] Some examples of organic solvents that are described by
General Chemical Structure 5 include trimethyl phosphate, triethyl
phosphate, tripropyl phosphate, and tributyl phosphate.
[0191] In another embodiment, the organic solvent is composed at
least in part of a chemical having the following general chemical
formula:
SO.sub.eC.sub.nH.sub.jX.sub.k General Chemical Formula F
[0192] wherein:
[0193] each X is independently F, Cl, Br, or I;
[0194] 1.ltoreq.e.ltoreq.2;
[0195] 2.ltoreq.n.ltoreq.8;
[0196] 0.ltoreq.j, k.ltoreq.(2n+2); and
[0197] 2n.ltoreq.(j+k).ltoreq.(2n+2).
[0198] Examples of organic solvents described by General Chemical
Formula F are dimethylsulfoxide and sulfolane.
[0199] In another embodiment, the organic solvent is composed at
least in part of a chemical having the following general chemical
formula:
C.sub.nH.sub.yN.sub.aO.sub.bX.sub.z General Chemical Formula G
[0200] wherein:
[0201] 1.ltoreq.n.ltoreq.10;
[0202] 1.ltoreq.a, b.ltoreq.2; and
[0203] a=b;
[0204] 0.ltoreq.y, z.ltoreq.(2n+1); and
[0205] (2n-1).ltoreq.(y+z).ltoreq.(2n+1);
[0206] Each X is independently F, Cl, Br, or I.
[0207] Some examples of organic solvents that are described by
General Chemical Formula G include dimethylformamide and
dimethylacetamide.
[0208] In another embodiment, the organic solvent is composed at
least in part of a chemical having the following general chemical
structure:
##STR00010##
[0209] wherein:
[0210] 0.ltoreq.n.ltoreq.500
[0211] each R equals C.sub.aX.sub.yH.sub.z independently;
[0212] 1.ltoreq.a.ltoreq.6; and
[0213] 0.ltoreq.y, z.ltoreq.(2a+1);
[0214] and (y+z)=(2a+1);
[0215] each X is independently F, Cl, Br, or I.
[0216] Examples of solvents described by General Chemical Structure
6 are dimethicones.
[0217] In another embodiment, the organic solvent is composed at
least in part of a chemical having the following general chemical
structure:
##STR00011##
[0218] wherein:
[0219] 2.ltoreq.n.ltoreq.4;
[0220] each R equals C.sub.aH.sub.yX.sub.z independently;
[0221] each X is independently F, Cl, Br, or I;
[0222] 1.ltoreq.a.ltoreq.6
[0223] 0.ltoreq.y, z.ltoreq.(2a+1); and
[0224] (y+z)=(2a+1).
[0225] Examples of solvents described by General Chemical Structure
7 are octamethylcyclotetrasiloxane and
decamethylcyclopentasiloxane.
[0226] In another embodiment of the invention, the organic solvent
comprises a glycol ether described by General Chemical Structure
8:
##STR00012##
[0227] 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 C.sub.jH.sub.2j+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 R.sub.1, R.sub.2 and R.sub.3 are each
independently either H or CH.sub.3. The identities of R.sub.1,
R.sub.2 and R.sub.3 are selected independent of each other;
therefore, R.sub.1 and R.sub.2 can be H while R.sub.3 is CH.sub.3.
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.
[0228] 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:
##STR00013##
[0229] 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.
[0230] Group R'' has the structure of benzyl, phenyl, their
fluorinated and partially fluorinated analogues, C.sub.jH.sub.2j+1,
or C.sub.jH.sub.aF.sub.b. 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, R.sub.1-12 have a
general formula of C.sub.mH.sub.nF.sub.p or C.sub.dH.sub.eF.sub.g.
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.
[0231] The General Chemical Structure 9 described above can also be
broken down further into various subgroups, as is shown in Table 3
below.
TABLE-US-00003 TABLE 3 Sub- group R.sub.1-3 R.sub.4-6 R.sub.7-9
R.sub.10-12 R; R;; B1 H or CH.sub.3 H H H O C.sub.jH.sub.2j+1 B2 H
or CH.sub.3 H H H S, carbonyl or C.sub.jH.sub.2j+1 ester B3 H,
CH.sub.3, or H H H O C.sub.jH.sub.2j+1 C.sub.2H.sub.5, and at least
one is CH.sub.2CH.sub.3 B4 H, CH.sub.3, or H H H S, carbonyl or
C.sub.jH.sub.2j+1 C.sub.2H.sub.5, and at ester least one is
CH.sub.2CH.sub.3 B5 H H H H or CH.sub.3 and at O C.sub.jH.sub.2j+1
least one is CH.sub.3 B6 H H H H or CH.sub.3 and at S, carbonyl or
C.sub.jH.sub.2j+1 least one is CH.sub.3 ester B7 H H H H, CH.sub.3,
or O C.sub.jH.sub.2j+1 C.sub.2H.sub.5, and at least one is
CH.sub.2CH.sub.3 B8 H H H H, CH.sub.3, or S, carbonyl or
C.sub.jH.sub.2j+1 C.sub.2H.sub.5, and at ester least one is
CH.sub.2CH.sub.3 B9 H, F, CH.sub.3, H or F H or F H or F O
C.sub.jH.sub.aF.sub.b CH.sub.2F, CHF.sub.2, or CF.sub.3 and at
least one is CH.sub.3, CH.sub.2F, CHF.sub.2, or CF.sub.3 B10 H, F,
CH.sub.3, H or F H or F H or F S, carbonyl, or
C.sub.jH.sub.aF.sub.b CH.sub.2F, CHF.sub.2, or ester CF.sub.3 and
at least one is CH.sub.3, CH.sub.2F, CHF.sub.2, or CF.sub.3 B11
C.sub.mH.sub.nF.sub.p and at H or F H or F H or F O
C.sub.jH.sub.aF.sub.b least one is C.sub.2H.sub.nF.sub.p B12
C.sub.mH.sub.nF.sub.p and at H or F H or F H or F S, carbonyl, or
C.sub.jH.sub.aF.sub.b least one is ester C.sub.2H.sub.nF.sub.p B13
H or F H or F H or F H, F, CH.sub.3, O C.sub.jH.sub.aF.sub.b
CH.sub.2F, CHF.sub.2 or CF.sub.3 and at least one is CH.sub.3,
CH.sub.2F, CHF.sub.2 or CF.sub.3 B14 H or F H or F H or F H, F,
CH.sub.3, S, carbonyl or C.sub.jH.sub.aF.sub.b CH.sub.2F, CHF.sub.2
or ester CF.sub.3 and at least one is CH.sub.3, CH.sub.2F,
CHF.sub.2 or CF.sub.3 B15 C.sub.mH.sub.nF.sub.p H or F H or F
C.sub.dH.sub.eF.sub.g O C.sub.jH.sub.aF.sub.b B16
C.sub.mH.sub.nF.sub.p H or F H or F C.sub.dH.sub.eF.sub.g S,
carbonyl, or C.sub.jH.sub.aF.sub.b ester B17 H, CH.sub.3, or H H H
O benzyl or phenyl C.sub.2H.sub.5, and at least one is
CH.sub.2CH.sub.3 B18 H, CH.sub.3, or H H H S, carbonyl or benzyl or
phenyl C.sub.2H.sub.5, and at ester least one is CH.sub.2CH.sub.3
B19 H H H H or CH.sub.3 and at O benzyl or phenyl least one is
CH.sub.3 B20 H H H H or CH.sub.3 and at S, carbonyl or benzyl or
phenyl least one is CH.sub.3 ester B21 H H H H, CH.sub.3, or O
benzyl or phenyl C.sub.2H.sub.5, and at least one is
CH.sub.2CH.sub.3 B22 H H H H, CH.sub.3, or S, carbonyl or benzyl or
phenyl C.sub.2H.sub.5, and at ester least one is CH.sub.2CH.sub.3
B23 C.sub.mH.sub.nF.sub.p and at H or F H or F H or F O benzyl,
phenyl, or least one is fluorinated or C.sub.2H.sub.nF.sub.p
partially fluorinated benzyl or phenyl B24 C.sub.mH.sub.nF.sub.p
and at H or F H or F H or F S, carbonyl or benzyl, phenyl, or least
one is ester fluorinated or C.sub.2H.sub.nF.sub.p partially
fluorinated benzyl or phenyl B25 H or F H or F H or F H, F,
CH.sub.3, O benzyl, phenyl or CH.sub.2F, CHF.sub.2 or fluorinated
or CF.sub.3 and at least partially one is CH.sub.3, fluorinated
benzyl CH.sub.2F, CHF.sub.2 or or phenyl CF.sub.3 B26 H or F H or F
H or F H, F, CH.sub.3, S, carbonyl or benzyl, phenyl, or CH.sub.2F,
CHF.sub.2 or ester fluorinated or CF.sub.3 and at least partially
one is CH.sub.3, fluorinated benzyl CH.sub.2F, CHF.sub.2 or or
phenyl CF.sub.3 B27 H or F H or F H or F C.sub.mH.sub.nF.sub.p and
at O benzyl, phenyl, or least one is fluorinated or
C.sub.2H.sub.nF.sub.p partially fluorinated benzyl or phenyl B28 H
or F H or F H or F C.sub.mH.sub.nF.sub.p and at S, carbonyl or
benzyl, phenyl, or least one is ester fluorinated or
C.sub.2H.sub.nF.sub.p partially fluorinated benzyl or phenyl B29
C.sub.mH.sub.nF.sub.p H or F H or F C.sub.dH.sub.eF.sub.g O benzyl,
phenyl, or fluorinated or partially fluorinated benzyl or phenyl
B30 C.sub.mH.sub.nF.sub.p H or F H or F C.sub.dH.sub.eF.sub.g S,
carbonyl or benzyl, phenyl, or ester fluorinated or partially
fluorinated benzyl or phenyl
[0232] In each of the groups described in Table 3 above, R.sub.1-12
are grouped together as R.sub.1-3, R.sub.4-6, R.sub.7-9, and
R.sub.10-12 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, R.sub.1-3
may be described as "H or F." In a given solvent compound with this
description, each of R.sub.1, R.sub.2 and R.sub.3 may be H or each
of R.sub.1, R.sub.2 and R.sub.3 may be F. Alternatively, R.sub.1
and R.sub.2 may be H while R.sub.3 is F, and so forth with the
various combinations of "H" and "F". This is the same throughout
all Tables in this specification.
[0233] Another group of suitable organic solvent include solvents
that can be described as having the chemical structure of:
##STR00014##
[0234] 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
C.sub.jH.sub.2j+1 or C.sub.jH.sub.uF.sub.v and group R.sup.W has a
structure of C.sub.kH.sub.2k+1 or C.sub.kH.sub.rF.sub.s. 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.
[0235] In further defining General Chemical Structure 10, groups
R.sub.1-3 and R.sub.10-12 can be hydrogen ("H"), fluorine ("F"),
methyl ("CH.sub.3"), ethyl ("CH.sub.2CH.sub.3"), or partially or
fully fluorinated methyl or ethyl groups. Each one of R.sub.1-3 and
R.sub.10-12 are selected independently of each other so as to
achieve various combinations of the above as contemplated by the
invention. Generally, R.sub.1-3 have the formula of
C.sub.mH.sub.nF.sub.p. 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 R.sub.4-9 can each be hydrogen,
fluorine or methyl groups. As with the other groups, the identity
of each of R.sub.4-9 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.
[0236] The General Chemical Structure 10 described above can also
be broken down further into various subgroups, as is shown in Table
4 below.
TABLE-US-00004 TABLE 4 Sub- group R.sub.1-3 R.sub.4-6 R.sub.7-9
R.sub.10-12 R; R;; R.sup.IV C1 H or CH.sub.3 H H H O
C.sub.jH.sub.2j+1 C.sub.kH.sub.2k+1 C2 H or CH.sub.3 H H H S,
carbonyl C.sub.jH.sub.2j+1 C.sub.kH.sub.2k+1 or ester C3 H,
CH.sub.3, or H H H O C.sub.jH.sub.2j+1 C.sub.kH.sub.2k+1
C.sub.2H.sub.5 and at least one is CH.sub.2CH.sub.3 C4 H, CH.sub.3,
or H H H S, carbonyl C.sub.jH.sub.2j+1 C.sub.kH.sub.2k+1
C.sub.2H.sub.5 and at or ester least one is CH.sub.2CH.sub.3 C5 H H
H H or CH.sub.3 and O C.sub.jH.sub.2j+1 C.sub.kH.sub.2k+1 at least
one is CH.sub.3 C6 H H H H or CH.sub.3 and S, carbonyl
C.sub.jH.sub.2j+1 C.sub.kH.sub.2k+1 at least one is or ester
CH.sub.3 C7 H H H H, CH.sub.3 or O C.sub.jH.sub.2j+1
C.sub.kH.sub.2k+1 C.sub.2H.sub.5 and at least one is
CH.sub.2CH.sub.3 C8 H H H H, CH.sub.3 or S, carbonyl
C.sub.jH.sub.2j+1 C.sub.kH.sub.2k+1 C.sub.2H.sub.5 and at or ester
least one is CH.sub.2CH.sub.3 C9 H, F, CH.sub.3, H or F H or F H or
F O C.sub.jH.sub.uF.sub.v C.sub.kH.sub.rF.sub.s CH.sub.2F,
CHF.sub.2, or CF.sub.3 C10 H, F, CH.sub.3, H or F H or F H or F S,
carbonyl C.sub.jH.sub.uF.sub.v C.sub.kH.sub.rF.sub.s CH.sub.2F,
CHF.sub.2, or ester or CF.sub.3 C11 C.sub.mH.sub.nF.sub.p and at H
or F H or F H or F O C.sub.jH.sub.uF.sub.v C.sub.kH.sub.rF.sub.s
least one is C.sub.2H.sub.nF.sub.p C12 C.sub.mH.sub.nF.sub.p and at
H or F H or F H or F S, carbonyl C.sub.jH.sub.uF.sub.v
C.sub.kH.sub.rF.sub.s least one is or ester C.sub.2H.sub.nF.sub.p
C13 H or F H or F H or F H, F, CH.sub.3, O C.sub.jH.sub.uF.sub.v
C.sub.kH.sub.rF.sub.s CH.sub.2F, CHF.sub.2 or CF.sub.3 and at least
one is CH.sub.3, CH.sub.2F, CHF.sub.2 or CF.sub.3 C14 H or F H or F
H or F H, F, CH.sub.3, S, carbonyl C.sub.jH.sub.uF.sub.v
C.sub.kH.sub.rF.sub.s CH.sub.2F, CHF.sub.2 or ester or CF.sub.3 and
at least one is CH.sub.3, CH.sub.2F, CHF.sub.2 or CF.sub.3 C15 H,
F, CH.sub.3, H, F, CH.sub.3, H, F, CH.sub.3, C.sub.mH.sub.nF.sub.p
and at O C.sub.jH.sub.uF.sub.v C.sub.kH.sub.rF.sub.s CH.sub.2F,
CHF.sub.2, CH.sub.2F, CH.sub.2F, least one is or CF.sub.3
CHF.sub.2, or CHF.sub.2, or C.sub.2H.sub.nF.sub.p CF.sub.3 CF.sub.3
C16 H, F, CH.sub.3, H, F, CH.sub.3, H, F, CH.sub.3,
C.sub.mH.sub.nF.sub.p and at S, carbonyl C.sub.jH.sub.uF.sub.v
C.sub.kH.sub.rF.sub.s CH.sub.2F, CHF.sub.2, CH.sub.2F, CH.sub.2F,
least one is or ester or CF.sub.3 CHF.sub.2, or CHF.sub.2, or
C.sub.2H.sub.nF.sub.p CF.sub.3 CF.sub.3
[0237] In each of the groups described in Table 4 above, one or
more of R.sub.1-12 are described together. For example, R.sub.1-3
may be described as "H or CH.sub.3 independently." In a given
solvent compound with this description, each of R.sub.1, R.sub.2
and R.sub.3 may be H or each of R.sub.1, R.sub.2 and R.sub.3 may be
CH.sub.3. Alternatively, R.sub.1 and R.sub.2 may be H while R.sub.3
is CH.sub.3, and so forth with the various combinations of "H" and
"CH.sub.3".
[0238] In another embodiment, the organic solvent is of the
following structural formula:
##STR00015##
[0239] 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:
##STR00016##
[0240] where R''' is H, F or combinations of H and F and group
R.sup.IV is either H or one of the following structures:
##STR00017##
[0241] where R.sup.V is H, F or combinations of H and F. Where R''
is H or F, R.sup.IV is not H or F.
[0242] Groups R''' and R.sup.V are either H or F groups or
combinations of H and F. Therefore, within a given R'' or R.sup.IV
group, the R''' groups and R.sup.V 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 R.sub.1-3
can be H, F, CH.sub.3, CH.sub.2F, CHF.sub.2 or CF.sub.3. Each one
of R.sub.4-12 is independently either H or F.
[0243] In another embodiment the organic solvent has the following
structural formula:
##STR00018##
[0244] In General Chemical Structure 12, R' is:
##STR00019##
[0245] and R'' is:
##STR00020##
[0246] Each R''' is O or N independently. Where R''' is O, j is 1.
Where R''' is N, j is 2. Each R.sup.IV is independently H, CH.sub.3
or CH.sub.2CH.sub.3 and k, n, r and s are integers between zero and
two inclusive. R is C.sub.yH.sub.2y+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.
[0247] In another embodiment, the organic solvent is of the
following structural formula:
##STR00021##
[0248] In General Chemical Structure 13, R' and R'' are as
follows:
R' is
##STR00022##
[0249] and R'' is
##STR00023##
[0250] where n is an integer between two and 15 inclusive and z is
an integer between zero and n inclusive. Each R.sup.IV is
independently H, CH.sub.3 or CH.sub.2CH.sub.3. R is
C.sub.yH.sub.2y+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.
Cleaning Additives
[0251] 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.
[0252] 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.
[0253] 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.
[0254] 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.
[0255] Suitable surfactant can be a cationic or anionic or
non-anionic. Non-limiting examples of specific surfactants include:
(1) akanolamides such as Mackamide.RTM. ISA, available from
McIntyre Group; Monamide.RTM. 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.RTM. MO available from Stepan Company; (4) amines
such as Armeen.RTM. C available from Akzo Nobel; (5) betaines such
as Mackam.RTM. BC-39 available from McIntyre Group; (6) block
copolymers such as T-Det.RTM. BP-1 available from Harcros
Chemicals; (7) alkyphenol ethoxylates such as Incrodet.RTM. TD7-C
available from Croda, Inc., (8) ethoxylated fatty acids such as
Lumulse.RTM.40-L available from Lambent Technologies; (9)
ethoxylated alcohols such as Neodol.RTM.45-7 available from Shell
Chemical, (10) phosphate ester-containing compounds such as
Colafax.RTM.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 C.sub.8-C.sub.10 phosphate ester, for
example ethoxylated linear alcohol C.sub.8-C.sub.10 phosphate
ester, or ethoxylated (e.g. 3-15, 4-10 or 7-10 moles) octylphenol
phosphate ester; (11) quaternary surfactants such as Arquad.RTM.
2HT-75 available from Akzo-Nobel; (12) sulfates of alcohols such as
Calfoam.RTM. SLS-30 available from Pilot Chemical and (13) dodecyl
benzene sulfonic acid or salts thereof such as Biosoft.RTM. S-100
available from Stepan Company.
[0256] The term "phosphate ester-containing compound" herein refers
to a compound containing the following phosphate ester functional
group:
##STR00024##
where any of the R groups can be a hydrogen or any organic
radical.
[0257] 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.
[0258] 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.
[0259] 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
(C.sub.2-22). 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.RTM. C, Armeen.RTM. 2C, Armeen.RTM. 316,
Duomeen.RTM. T, Ethomeen.RTM. O/12, Propomeen.RTM. T/12 (all
available from Akzo-Nobel Chemical).
[0260] 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.
[0261] 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.
[0262] 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.
[0263] 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.
[0264] 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).
[0265] Non-limiting examples of specific cleaning aids include: Per
Sec.RTM. available from R.R. Street & Co. Inc., DF-2000.RTM.
available from R.R. Street & Co. Inc., isopropyl alcohol
available from Brenntag Chemical, Armeen.RTM.12 available from
Akzo-Nobel Chemical, and ethylene glycol monobutyl ether available
from Dow Chemical.
[0266] 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.
[0267] 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.
[0268] 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.RTM.
3.0T, Celluzym.RTM. 0.7T and Termamyl.RTM. 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.
[0269] 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.RTM. K-723 available from
Noven Inc., Alcosperse.RTM. 157 available from Alco Chemical, and
Maphos.RTM. 60A available from BASF Specialty Chemicals.
[0270] 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.RTM. 803 available from Rohm &
Haas Company, Carbopol.RTM. 941NF available from Novon Inc.,
Kelfo.RTM. available from CP Kelco Chemical, and Natrosol.RTM. 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.
[0271] 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.
[0272] Non-limiting examples of specific sizing agents include
Amphomer.RTM. LV-71 National Starch & Chemical Co.,
Aquaflex.RTM. FX-64 from International Specialty Products,
Luviskol.RTM. VA-W from BASF Corporation, Kristalex 3100
hydrocarbon resin from Eastman, and Unicare Polymer.RTM. 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.
[0273] 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.RTM. 432 available from Degussa
Chemical, Arquad.RTM. 2HT-75 available from Akzo-Nobel Chemical,
Rewoquat.RTM. SQ24 available from Degussa Chemical, Magnisoft
(amino silicone polymer available from GE Silicones), and
Varisoft.RTM. 222 available from Degussa Chemical and mixtures
thereof.
[0274] 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.
[0275] 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.RTM. 2HT-75 from Akzo-Nobel Chemical, Ganex.RTM. V-220
from International Specialty Products, Mirasil.RTM. Wax-B from
Rhodia Home Personal Care & Industrial Ingredients, Witco.RTM.
Calcium Stearate F from Crompton Corp., Zony.RTM. 8740 from Du Pont
Corporation, and mixtures thereof.
[0276] 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.
[0277] 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.
[0278] 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.
[0279] 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.RTM. Sorb Ready 24 available from Degussa/Goldschmidt
Chemcial.
[0280] 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.
[0281] 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.RTM. CBSX from Ciba Specialty Chemicals) or coumarin
derivatives such as Burcofluor.RTM. 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.
[0282] 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.RTM. Plus, which is manufactured by Lonza of Fairlawn, N.
J. Dantogard.RTM. 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.
[0283] 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.RTM. 550 available from Akzo-Nobel
Chemical, Atmer.RTM. 163 available from Uniqema Chemical,
Incroquat.RTM. CTC-30 available from Croda Chemical, and
Laponite.RTM. RDS available from Southern Clay Products.
[0284] 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.
[0285] 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.RTM. 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.
[0286] 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.RTM. E
available from Angus Chemical, Aqualox.RTM. 232H available from
Lubrizol Company, Colalube.RTM. 3419EPL available from Colonial
Chemical, and DePhos.RTM. 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.
[0287] 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.RTM. 830, Alkamide.RTM. DC, Bentone.RTM.
34, Carbopol.RTM. 676, and Keltrol.RTM. 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.
[0288] 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.
[0289] 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.
[0290] 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.
Preparation of Cleaning Composition
[0291] 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.
[0292] 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.
[0293] 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.
[0294] 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).
Substrates
[0295] 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 Process and System
[0296] 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 FIG. 1 and FIG. 2 and as described in
further detail below.
[0297] Referring now to FIG. 1, a block diagram of a cleaning
system having separate vessels for cleaning and drying textiles is
shown. The cleaning system 100 generally comprises a cleaning
machine 102 having a cleaning vessel 110 operatively connected to,
for example via one or more motor activated shafts (not shown), a
rotatable cleaning drum or wheel (that can be perforated or
otherwise composed to allow for exchange of cleaning fluid in and
out of the drum or wheel) 112 within the cleaning vessel 110 with
an inlet 114 to the cleaning vessel 110 and an outlet 116 from the
cleaning vessel 110 through which cleaning fluids can pass. A
drying machine 104 has a drying vessel 120 capable of being
pressurized. The pressurizable drying vessel 120 is operatively
connected to, for example via one or more motor activated shafts
(not shown), a perforated rotatable drying drum or wheel 122 within
the drying vessel 120 with an inlet 124 to the drying vessel 120
and an outlet 126 from the drying vessel 120 through which
pressurized fluid solvent can pass. The cleaning vessel 110 and the
drying vessel 120 can either be parts of the same machine, or they
can comprise separate machines. Furthermore, both the cleaning and
drying steps of this invention can be performed in the same vessel,
as is described with respect to FIG. 2 below.
[0298] 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.
[0299] 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.
[0300] 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.
[0301] 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.
[0302] 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.
[0303] 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).
[0304] 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.
[0305] 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.
[0306] 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.
[0307] 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.
[0308] 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 FIG. 1 could
represent such a converted system, wherein the components of the
cleaning machine 102 are conventional, and the pressurized fluid
solvent tank 132 is not in communication with the cleaning vessel
100. In such a situation, the drying machine 104 is the add-on part
of the conventional cleaning machine.
[0309] While the system shown in FIG. 1 comprises a single cleaning
vessel, multiple cleaning vessels can be used, so that the
substrates are subjected to multiple cleaning steps, with each
cleaning step carried out in a different cleaning vessel using the
same or different cleaning fluid in each step. The description of
the single cleaning vessel is merely for purposes of description
and should not be construed as limiting the scope of the
invention.
[0310] Referring now to FIG. 2, a block diagram of an alternate
embodiment of the present invention, a cleaning system having a
single chamber for cleaning and drying the substrates, is shown.
The cleaning system 200 generally comprises a cleaning machine
having a pressurizable vessel 210. The vessel 210 is operatively
connected to, for example via one or more motor activated shafts
(not shown), a perforated or pierced rotatable drum or wheel 212
within the vessel 210 with an inlet 214 to the vessel 210 and an
outlet 216 from the vessel 210 through which cleaning fluids can
pass.
[0311] 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.
[0312] 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.
[0313] 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.
[0314] 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.
[0315] 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.
[0316] 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.
[0317] 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).
[0318] 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.
[0319] 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.
[0320] 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.
[0321] 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.
[0322] 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.
Examples
[0323] 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.
Example 1
[0324] Thirteen base detergent formulations, BDF1-BDF13, were
prepared having compositions shown in Table 1.
TABLE-US-00005 TABLE 1 Base Detergent Formulations BDF1-BDF13.
Amount BDF Composition (% weight) BDF 1 Dipropylene glycol n-butyl
ether (hereinafter 100 DPNB) BDF 2 DPNB 45 Ethoxylated (7-10 moles)
octylphenol phosphate 45 ester* KOH (45% in water) 10 BDF 3 DPNB 45
Ethoxylated (7-9 moles) C.sub.12-C.sub.16 linear alcohol 45
phosphate ester* KOH (45% in water) 10 BDF 4 DPNB 45 Ethoxylated
(9-13 moles)nonylphenol phosphate 45 ester* KOH (45% in water) 10
BDF 5 DPNB 45 Ethoxylated (4-8 moles) isodecyl alcohol 45 phosphate
ester* KOH (45% in water) 10 BDF6 DPNB 45 Ethoxylated (5-7 moles)
C.sub.8-C.sub.10 linear alcohol 45 phosphate ester* KOH (45% in
water) 10 BDF 7 DPNB 95.95 Ethoxylated (7-10 moles) octylphenol
phosphate 0.45 ester* KOH (45% in water) 0.1 Water 3.5 BDF8 Water
70 Cocamine oxide** 30 BDF9 Water 30 Disodium
cocoamphodipropionate** 70 BDF10 Water 70 Sodium
lauriminodipropionate** 30 BDF11 Water 60 Sodium alpha olefin
sulfonate*** 40 BDF12 Water 70 Sodium lauryl sulfate*** 30 BDF13
DPNB 96.5 Water 3.5 *Available from Harcross Chemicals, Inc.
**Available from McIntyre Group ***Available from Pilot
Chemical
Example 2
[0325] 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.
TABLE-US-00006 TABLE 2 Composition of Cleaning Formulations
CF1-CF13. Cleaning Formulation Component Amount CF1 BDF1 100% CF2
BDF2 1% v/v DPNB 99% v/v CF3 BDF3 1% v/v DPNB 99% v/v CF4 BDF4 1%
v/v DPNB 99% v/v CF5 BDF5 1% v/v DPNB 99% v/v CF6 BDF6 1% v/v DPNB
99% v/v CF7 BDF7 100% CF8 BDF8 1.67% v/v DPNB 98.33% v/v CF9 BDF9
0.67% v/v DPNB 99.33% v/v CF10 BDF10 1.67% v/v DPNB 98.33% v/v CF11
BDF11 1.24% v/v DPNB 98.76% v/v CF12 BDF12 1.67% v/v DPNB 98.33%
v/v CF13 BDF13 100% v/v
[0326] 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.
TABLE-US-00007 TABLE 3 Cleaning Results. Cleaning Delta Whiteness
Formulation Index CF1 13.49 CF2 18.01 CF3 20.91 CF4 20.45 CF5 17.22
CF6 18.83 CF7 20.71 CF8 11.58 CF9 11.8 CF10 11.8 CF11 10.93 CF12
12.67 CF13 14.4
Example 3
[0327] Two additional Base Detergent Formulations, BDF14 and BDF15,
were prepared as shown in Table 4.
TABLE-US-00008 TABLE 4 Base Detergent Formulations 14 and 15.
Amount BDF Composition (% weight) BDF 14 Sodium 35 dodecylbenzene
sulfonate Water 65 BDF 15 Sodium dioctyl 75 sulfosuccinate
Propylene glycol 25
Example 4
[0328] 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.
TABLE-US-00009 TABLE 5 Cleaning Formulations CF1, CF2, CF11, CF12,
CF14 and CF15. Cleaning Formulation Component Amount CF1 BDF1 100%
CF2 BDF2 1% v/v DPNB 99% v/v CF11 BDF11 1.24% v/v DPNB 98.76% v/v
CF12 BDF12 1.67% v/v DPNB 98.33% v/v CF14 BDF14 1.41% v/v DPNB
98.59% v/v CF15 BDF15 0.67% v/v DPNB 99.33% v/v
[0329] 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.
TABLE-US-00010 TABLE 6 Cleaning Results for CF1, CF2, CF11-12 and
CF14-15. Cleaning % Food Dye Formulation Removal CF1 41.4 CF2 44.7
CF11 6.8 CF12 0 CF14 0.7 CF15 25.5
[0330] 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.
Example 5
[0331] Cleaning Formulations CF16-CF21 were prepared containing
various glycol ethers and BDF2 as shown in Table 7.
TABLE-US-00011 TABLE 7 Composition of CF16-CF21. CF16 CF17 CF18
CF19 CF20 CF21 Component (% Vol) Diethylene glycol 99 -- -- -- --
-- butyl ether Propylene glycol -- 99 -- -- -- -- t-butyl ether
Dipropylene glycol -- -- 99 -- -- -- methyl ether Tripropylene
clycol -- -- -- 99 -- -- methyl ether Tripropylene glycol -- -- --
-- 99 -- n-butyl ether Dipropylene glycol -- -- -- -- -- 99 n-butyl
ether BDF2 1 1 1 1 1 1 Total 100 100 100 100 100 100
[0332] 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.
TABLE-US-00012 TABLE 8 Delta Whiteness Index for CF16-CF 21 and
Matching Controls. Delta Whiteness Index Delta Cleaning Control
Whiteness Formula (No BDF) With BDF2 Index CF16 17.75 18.48 0.73
CF17 18.23 23.1 4.87 CF18 15.28 18.75 3.47 CF19 15.32 17.52 2.2
CF20 16.03 21.57 5.54 CF21 13.49 18.00 4.51
[0333] As can be observed from Table 8, addition of BDF enhanced
soil removal for each glycol ether tested.
Example 6
[0334] 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.
[0335] 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.
TABLE-US-00013 TABLE 9 Change in Whiteness for Oil Stained
Swatches. Delta Whiteness Cleaning Index Formulation Cotton
Polyester CF1 98.18 74.76 CF2 125.75 98.45 CF7 123.66 99.78 CF11
123.28 84.68 CF12 131.94 84.68 CF13 101.39 72.04 CF14 128.8 86.51
CF15 107.66 88.41
Example 7
[0336] Base Detergent Formulation BDF22 was prepared as shown in
Table 10.
TABLE-US-00014 TABLE 10 Composition of Base Detergent Formulation
BDF22. Material Percent Weight DPNB 35 Ethoxylated (7-10 moles) 45
octylphenol phosphate ester KOH (45% in water) 10 Polypropoxyl
(30-45 moles) 10 methyl diethyl ammonium chloride Total 100
Example 8
[0337] A static control test was performed using 3.times.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.
[0338] 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.degree. 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.
TABLE-US-00015 TABLE 11 Time To No Metal Clinging. Time to no
Cleaning metal clinging Swatch Formulation (Seconds) 1 Control
(DPNB alone) 406.5 2 DPNB + BDF2 262.5 3 DPNB + BDF22 179.5
[0339] As can be seen from Table 11, Swatch 3 exhibited the
shortest time to absence of metal clinging.
Example 9
[0340] Base Detergent Formulation BDF23 was prepared as shown in
Table 12.
TABLE-US-00016 TABLE 12 Composition of Base Detergent Formulation
BDF23. Material Percent Weight DPNB 35 Kristalex 3100 hydrocarbon
resin* 10 Ethoxylated 7-10 moles 45 octylphenol phosphate ester
with KOH (45% in water) 10 Total 100 *Available from Eastman.
Example 10
[0341] A fabric sizing test was performed to assess fabric
stiffness and body using 1.times.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.degree. (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.
TABLE-US-00017 TABLE 13 Sizing Test Results. BDF2 + BDF23 + DPNB
DPNB DPNB Run 1 Run 2 Run 1 Run 2 Run 1 Run 2 Before Treatment
Length (cm) 4.5 4.6 4.5 4.5 4.4 4.2 After Treatment Length (cm) 4.5
4.6 4.5 4.5 4.9 4.5
[0342] As shown in Table 13, length of fabric overhang increases
upon treatment with the cleaning formulation containing BDF23 and
DPNB.
[0343] 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.
TABLE-US-00018 TABLE 14 Panel Test Results. Panelist Stiffest (1)
(2) Least Stiff (3) 1 BDF23 + DPNB DPNB BDF2 + DPNB 2 BDF23 + DPNB
BDF2 + DPNB DPNB 3 BDF23 + DPNB BDF2 + DPNB DPNB 4 BDF23 + DPNB
DPNB BDF2 + DPNB 5 BDF23 + DPNB DPNB BDF2 + DPNB 6 BDF23 + DPNB
BDF2 + DPNB DPNB 7 BDF23 + DPNB DPNB BDF2 + DPNB 8 BDF23 + DPNB
DPNB BDF2 + DPNB 9 BDF23 + DPNB BDF2 + DPNB DPNB 10 BDF23 + DPNB
BDF2 + DPNB DPNB
[0344] As shown in Table 14, in each case swatches treated with the
cleaning composition comprising BDF23 and DPNB were ranked the
stiffest.
Example 11
[0345] Base Detergent Formulation BDF24 was prepared having a
composition as shown in Table 15.
TABLE-US-00019 TABLE 15 Composition of Base Detergent Formulation
BDF24. Material Percent Weight DPNB 35 Ethoxylated (7-10 moles) 45
octylphenol phosphate ester KOH (45% in water) 10 Water 0.5
Dipropylene glycol 6.5 Magnasoft SRS* 3 Total 100 *Available from
Momentive Performance Materials
Example 12
[0346] A test was performed to assess fabric softness after
processing with various compositions. Cotton terrycloth fabric was
cut into 5.times.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.
[0347] 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.
TABLE-US-00020 TABLE 16 Softness Panel Results Panelist Softest (1)
(2) (3) Least Soft (4) 1 BDF24 + DPNB BDF2 + DPNB BDF23 + DPNB DPNB
2 BDF24 + DPNB DPNB BDF2 + DPNB BDF23 + DPNB 3 BDF24 + DPNB BDF23 +
DPNB BDF2 + DPNB DPNB 4 BDF24 + DPNB BDF2 + DPNB DPNB BDF23 + DPNB
5 BDF24 + DPNB BDF2 + DPNB DPNB BDF23 + DPNB 6 BDF2 + DPNB BDF24 +
DPNB DPNB BDF23 + DPNB 7 BDF2 + DPNB BDF24 + DPNB DPNB BDF23 + DPNB
8 BDF2 + DPNB BDF24 + DPNB BDF23 + DPNB DPNB 9 BDF24 + DPNB BDF2 +
DPNB DPNB BDF23 + DPNB 10 BDF24 + DPNB BDF2 + DPNB DPNB BDF23 +
DPNB
* * * * *