Note: Descriptions are shown in the official language in which they were submitted.
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
1
Description
METHOD FOR CHEMICALLY CLEANING TEXTILE MATERIAL
Washing with water and laundry detergents, within the home or in industrial
and
institutional laundries, is not the only important cleaning process applied to
textiles. Dry
cleaning is employed on water-sensitive textiles, but also in the case of
stubborn soiling,
especially oily and greasy stains.
Halogenated hydrocarbons are still being used as dry-cleaning medium. They
include
the hydrochlorocarbons trichloroethene, 1,1,1-trichloroethane and
dichloromethane
which are no longer permissible in Germany for example. Similarly, the
chlorofluorocarbons (CFCs), which used to be widely used in dry cleaning, are
no
longer permitted for this application in many countries.
The solvent which is still being widely used is tetrachloroethene
(perchloroethylene,
perchlorethylene, perc, PER). Tetrachloroethene is a volatile chlorinated
hydrocarbon
which, by virtue of its fat-dissolving ability, has come to be widely used in
industry,
including dry cleaning, as a solvent/cleaner.
The disadvantages of PER are in particular its potential carcinogenic effect
on humans;
its high volatility; its ready solubility in fat-containing foods; and its
strongly water-
endangering properties.
PER is classified as dangerous in the EU's Black List and Germany's Haz Chem
regulations.
Dry cleaning solvents, in particular perchloroethylene, pose dangers if
allowed to pass
into the environment. Potential sources of emissions are the cleaning machine,
the
drying air, the contact water, the distillation sludge, the textile material
if inadequately
dried and/or due to solvent retention, as well as accidents.
The control of the emission paths for organic solvents in the dry cleaning
sector varies
between different countries according to their environmental legislation and
the degree
to which their laws are observed and policed.
In Germany, dry cleaning operators and machine manufacturers have to meet a
multiplicity of requirements to limit perchloroethylene emissions, such as
maximum
permissible values for PER emissions in the exit gas, in the drum region and
in adjacent
rooms, which entails a substantial engineering commitment.
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
2
However, irrespectively of the extent to which PER emissions are policed in
dry
cleaning establishments, appreciable amounts of PER may be retained in the
most
important textile substrates (wool, polyester) so that the emission of
solvents by the
textiles is important as well. In the case of PER, this can lead to indoor air
exposures
suffered by the consumer far away from the dry cleaning establishment.
The chlorofluorocarbons (CFCs) mentioned at the beginning, which are now no
longer
permitted in dry cleaning in most countries, made extremely low drying
temperatures
and, because of the high volatility, also short drying times and hence low
mechanical
stress on the textiles possible.
Irreversible damage to textiles bearing the care symbol "F" could thus
reliably be
avoided.
Halogen-free hydrocarbon solvents (HCS) have now been used for some time as
technical alternatives to the banned CFCs as well as to the widely used PER.
Originally,
HCS solvents were only considered as a replacement for CFCs with regard to the
cleaning of particularly sensitive textiles.
The HCS solvents are straight-chain aliphatics or mixtures of straight-chain,
branched
and cyclic aliphatics having 10 to 14 carbon atoms. Their higher boiling range
from
about 180 to 210 C makes them distinctive from the petroleum fractions
formerly
likewise used in dry cleaning, or from perchloroethylene which has a boiling
point of
only 121 C. HCS solvents are widely used in dry cleaning in the US and Japan.
However, one disadvantage with the use of HCS is that, as a consequence of the
low
vapor pressures, the drying temperatures have to be raised and/or the drying
times
distinctly extended. This imposes a distinctly greater thermal and mechanical
stress on
sensitive textiles, which shortens their useful consumer lives.
In addition, the energy requirements to distill and recycle HCS are distinctly
higher
compared with PER.
There is accordingly still a need for organic solvents which not only possess
good
cleaning power, but also can be deemed superior to the prior art in the eyes
of
toxicologists and ecologists and because of their physical-chemical
properties.
Moreover, they should be substantially usable in the cleaning processes which
the prior
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
3
art employs for perchloroethylene (PER) and the hydrocarbon solvents (HCS).
The PER cleaning process consists of three stages:
1) The actual cleaning operation in a solvent bath which further includes some
water and cleaning boosters (comprising surfactants, cosolvents and other
components).
2) The drying with hot air and the recovery of the solvent by condensation and
adsorption.
3) The solvent regeneration through filtration and distillation, or
desorption.
The cleaning with HCS in principle involves the same stages as the PER
cleaning
process. The cleaning techniques on offer from various producers differ by
separation of
cleaning and drying (reloading technique), cleaning and drying being
integrated in one
machine (closed circuit) and also by inertization during cleaning and drying
(nitrogen,
combination of fresh air and circulating air or vacuum).
The following requirements should be at least substantially met by organic
solvents
contemplated as an alternative to perchloroethylene and/or to the hydrocarbon
solvents:
Good cleaning power in general and good ability to detach water-soluble or
water-
swellable soil and pigmentary soil, if appropriate through water-surfactant
combinations
(cleaning boosters); very good dissolving capacity for fats and oils; good
dispersing
capacity and sufficient dispersion stability for pigmentary soil to avoid
graying; very little
if any influencing of fibers, dyeings and finishes, i.e., only limited
swelling of fibers, no
adverse influence on the felting shrinkage of wool, negligible changes to the
thermo-
mechanical properties of fibers, no detachment of dyes, finishes, hotmelt
adhesives,
etc. (nor in the course of drying); very low retention in the fibrous
substrate; no solvent
odor in the cleaned textiles; a high volatility to facilitate drying and
recovery; a
sufficiently high flashpoint; little if any corrosivity toward metals and
other materials of
the cleaning and drying machines, not even in the presence of water; only
minimal if
any decomposition under cleaning and distillation conditions, i.e., in the
presence of soil
and at higher temperatures; low viscosity to facilitate soil detachment and
for better
mechanical removal of the solvent by centrifugation; low solubility in water
but a certain
amount of solvent power for water (if appropriate through the addition of
surfactants and
other solubilizers); dissolving power for so-called cleaning boosters
(comprising for
example nonionic, anionic, cationic, amphoteric surfactants, other solvents,
for example
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
4
(2-methoxymethylethoxy)propanol, specific salts, bleaching agents,
disinfectants,
antistats and other additives); formation of stable water-surfactant emulsions
in the
solvent; compliance with the maximum processing values mandated by the care-
labeling scheme; and also low toxicity to humans and the environment.
The present invention has for its object to provide organic solvents which
achieve the
aforementioned dry cleaning requirements better than prior art solvents and
which
possess a better toxicological and ecological profile.
It has now been found that, surprisingly, compounds of the formula (1) possess
superior
cleaning or dissolving capacity for fats and oils and superior soil-suspending
capacity
and hence produce less graying and are judged as toxicologically and
ecologically
substantially more favorable than perchloroethylene and hydrocarbon solvents
and in
addition also fulfill the other aforementioned requirements and thus are very
useful as
dry cleaning medium.
The present invention accordingly provides for the use of compounds of the
formula (1)
as an organic cleaning agent and solvent in the dry cleaning of textiles
R'-O O-R2
HA-C
R4 -0 O-R3
(1)
where
where
A is (CH2)a or phenylene,
R1 , R2, R3 and R4 identically or independently denote Cl to C22-n- and/or iso-
alkyl,
C5- or C6-cycloalkyl, phenyl-Cl-C4-alkyl, Cl-Cg-alkylphenyl or phenyl,
and a is an integer from 0 to 6.
Preferably R1 , R2, R3 and R4 identically or independently are Cl to C13-n-
and/or iso-
alkyl, C5- or C6-cycloalkyl, phenyl-Cl-C2-alkyl, Cl-Cg-alkylphenyl or phenyl
and a is an
integer from 0 to 2.
CA 02601177 2007-09-14
WO 2006/097213 PCTIEP2006/002014
More preferably, R1 , R2, R3 and R4 identically or independently are Cl to Cg-
n- and/or
iso-alkyl, cyclohexyl, benzyl or phenyl and a is 0 or 1.
Most preferably, R1, R2, R3 and R4 identically or independently are Cl to C3-n-
and/or
iso-alkyl and a is 0.
Examples of the R1 to R4 radicals are for example: methyl, ethyl, n-propyl,
isopropyl,
n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, isoamyl, tert-amyl,
neopentyl, cyclopentyl,
n-hexyl, isohexyl, cyclohexyl, octyl, decyl, isotridecyl, phenyl, benzyl,
phenylethyl,
nonylphenyl.
The compounds of the general formula (1) are acetals. Acetals are generally
obtained
by reaction of aidehydes with 2 mol of an alcohol per carbonyl group in the
presence of
catalysts, such as dry hydrogen chloride for example.
Dialdehydes have to be used to synthesize compounds of the formula (1).
Preferred
dialdehydes for synthesizing compounds of the formula (1) are glyoxal,
malonaldehyde
(1,3-propanedial, 1,3-propanedialdehyde), 1,4-butanedial and
terephthalaldehyde.
A greatly preferred dialdehyde is glyoxal, which leads to compounds of formula
(1)
where a = 0.
A particularly preferred compound for the purpose described is
tetramethoxyethane (2)
from Clariant
H3C-O O-CH3
H
H3C-O O-CH3
(2)
and the analogous compound tetraethoxyethane
Compounds of the formula (1) can be utilized at various stages of the dry
cleaning
process, both in the industrial and institutional sector and in domestic dry
cleaning.
These include in particular the use as a dissolving and cleaning agent in the
basic
cleaning operation. Here, the compounds of the formula (1) can wholly replace
the
cleaning agents perchloroethylene, hydrocarbons and also other solvents.
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
6
The use of the solvents of the formula (1) can be effected in accordance with
existing
processes in so-called PER machines or in HCS machines (for example from
Satec).
Representative processing conditions for using the compounds of the formula
(1) are
indicated by the hereinbelow described processing conditions for PER and HCS
machines.
Process parameter PER machine HCS machine
Speeds
Cleaning 35 rpm 30 - 40 rpm
Whizzing 380 rpm 700 - 800 rpm
g-factor (whizzing) 77 330
Load 18 kg 18 kg
Liquor ratio
Low level 1: 1.7 kg/I 1: 3.9 kg/I
High level 1: 3.9 kg/i 1: 6.7 kg/i
Whirlbath --- 1 : 6.7 kg/I
Filter Centrifugal filters Cartridges
Drying temperature 60 C 70 C
Drying process Completion of drying process at in- Nitrogen inertization
drum PER content of < 2 g/m3 at Heating unlocked at
fabric temperature of at least 35 C oxygen content < 9%
Solvent distillation Under atmospheric pressure max. -70 cm Hg
Process modifications or modifications to the cleaning machines may be
necessary,
depending on the physical-chemical properties of specific compounds of the
formula (1).
For instance, different boiling points, due to different R1 to R4 radicals
and/or different a
values, may necessitate different drying temperatures and, for example,
variations in
the distillation conditions to recover the solvent (pressure, temperature).
Flashpoints other than those of the HCS solvents used may also necessitate
safety-
engineering modifications, for example through the type of inertization
(residual oxygen
contents).
More particularly, the organic R radicals in the solvents of the formula 1 can
be varied to
CA 02601177 2007-09-14
WO 2006/097213 PCTIEP2006/002014
7
control the dissolving power for apolar substances (other solvents, fats,
oils) and also
for polar substances and solvents (including water).
Different retentions and viscosities may also for example necessitate
different g factors
for whizzing off the solvent. In commercial practice, HCS machines utilize
higher g
factors than PER machines.
Further factors which may be altered/optimized through the use of solvents of
the
formula (1) include, for example, cleaning time, liquor ratio, reversing
rhythm, load level,
identity and amount of cleaning booster used, application of a whirlbath
through
injection of an air-solvent mixture for gentle cleaning of sensitive textiles.
All such modifications to the conventional process of dry cleaning which are
the result of
using the novel solvents of the formula (1) are easily determined by one of
ordinary skill
in the art through preliminary tests.
Dry cleaning processes are further distinguished between the one bath process
and the
two bath process. Standard work is generallv cleaned in the two bath process
by
employing a short liquor ratio in the first bath and a longer liquor ratio in
the second
bath. The first bath serves to detach the main soil. Solvents of the formula
(1) can be
used in the one bath process and in the two bath process.
But in principle it is also possible to combine cleaning agents of the formula
(1) with
perchloroethylene, hydrocarbons or other solvents and thus partially replace
the
traditional solvents.
As well as being used as "main cleaning agent" (for the basic cleaning
operation),
compounds of the formula (1) can also be utilized in spotting agents, in
cleaning
activators or in cleaning boosters. Spotting agents are used for spot removal
from
textiles in industrial textile cleaning. The following groups of spotting
agents are
distinguished:
1) Brushing agents are used for the prespotting of large soiled areas of
textiles.
They are applied neat, with a soft brush or by spraying, to the badly soiled
areas
prior to the basic cleaning operation.
2) Dedicated spotting agents are used to treat intensive specific stains on
textiles.
They are applied directly to the stain, and allowed to act thereon, prior to
the
basic cleaning operation.
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
8
3) Postspotting agents are used after the basic cleaning operation, to remove
any
stains remaining.
Cleaning activators are used to remove spots and may also comprise odor
absorbents
for example. They are applied in the pretreatment bath and, being soil
dissolvers,
obviate any brushing.
Cleaning boosters, being added to the organic solvent used as cleaning medium,
are
intended to enhance the cleaning performance and, more particularly, also to
effect the
detachment of water-soluble or water-swellable soils which are only sparingly
soluble, if
at all, in the organic solvent. Examples of such water-soluble compounds
include gritting
salt (NaCl in high purity or else in mixture with CaC12 or MgCI2 sols) as used
in winter to
deice sidewalks and streets. They shall further remove insoluble, pigmentary
soil and
exhibit a pigment-dispersing capacity and so inhibit the redeposition of
detached
particulate soil. They further serve to avoid pilling and to improve fabric
hand.
Cieaning boosters typically comprise surfactants (in particular anionic,
nonionic,
amphoteric surfactants or else cationic surfactants), solvents, antistats,
softeners or
hand-improving additives and, if appropriate, specialty adds such as
disinfectants and
bleaching agents. Furthermore, the cleaning booster can be used to introduce
small
amounts of water into the cleaning bath that is emulsified into the organic
solvents with
the surfactants.
The cleaning agent bath, i.e., the solvent of the formula (1) used for the
basic cleaning
operation, the spotting agents, the cleaning activators and the cleaning
boosters
comprising solvent of the formula (1) may comprise the following further soil
release
enhancers.
Surfactants
Surfactants which may be used in addition to or in the cleaning agents of the
formula
(1), for example in tetramethoxyethane (2), are:
Anionic surfactants
Useful anionic surfactants include sulfates, sulfonates, carboxylates,
phosphates and
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
9
mixtures thereof. Suitable cations are alkali metals, for example sodium or
potassium,
or alkaline earth metals, for example calcium or magnesium, and also ammonium,
substituted ammonium compounds, including mono-, di- or triethanolammonium
cations, and mixtures thereof.
The following types of anionic surfactants are particularly preferred:
alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates,
alkylbenzenesulfonates,
alkanesulfonates and soaps as described in what follows.
Alkyl ester sulfonates include linear esters of C8-C22-carboxylic acids (i.e.,
fatty acids)
which are sulfonated with gaseous SO3. Suitable starting materials are natural
fats,
such as tallow, coco oil and palm oil for example. But the carboxylic acids
may also be
synthetic in nature. Preferred alkyl ester sulfonates are compounds of the
formula
R' CH COOR
1
SO3M
where R1 is a C8-C20-hydrocarbyl radical, preferably alkyl, and R is a Cl-C6-
hydro-
carbyl radical, preferably alkyl. M represents a cation which forms a water-
soluble salt
with the alkyl ester sulfonate. Suitable cations are sodium, potassium,
lithium or
ammonium cations, such as monoethanolamine, diethanolamine and
triethanolamine.
Preferably, R1 is C1o-C16-alkyl and R is methyl, ethyl or isopropyl.
Particular preference
is given to methyl ester sulfonates wherein R1 is C10-C16-alkyl.
Alkyl sulfates are salts or acids of the formula ROSO3M, where R is a C10-C24-
hydrocarbyl radical, preferably an alkyl or hydroxyalkyl radical having a C10-
C20-alkyl
component, more preferably a C12-C18 alkyl or hydroxyalkyl radical.
M is hydrogen or a cation, for example an alkali metal cation (examples being
sodium,
potassium, lithium) or ammonium or substituted ammonium, for example methyl-,
dimethyl- and trimethylammonium cations and quaternary ammonium cations such
as
tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium
cations derived from alkylamines, such as ethylamine, diethylamine,
triethylamine and
mixtures thereof.
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
Alkyl ether sulfates are salts or acids of the formula RO(A)m SO3M, where R is
an
unsubstituted C10-C24-alkyl or hydroxyalkyl radical, preferably a C12-C20
alkyl or
hydroxyalkyl radical, more preferably a C12-C18-alkyl or hydroxyalkyl radical.
A is an
ethoxy or propoxy unit, m is a number greater than 0, preferably between about
0.5 and
about 6, and more preferably between about 0.5 and about 3, and M is a
hydrogen
atom or a cation, for example sodium, potassium, lithium, calcium, magnesium,
ammonium or a substituted ammonium cation.
Specific examples of substituted ammonium cations are methyl-, dimethyl- and
trimethylammonium and quaternary ammonium cations such as tetramethylammonium
and dimethylpiperidinium cations and also those derived from alkylamines, such
as
ethylamine, diethylamine, triethylamine or mixtures thereof. Examples which
may be
mentioned are C12- to C18-fatty alcohol ether sulfates wherein the EO content
is 1, 2,
2.5, 3 or 4 mol per mole of the fatty alcohol ether sulfate and wherein M is
sodium or
potassium.
The alkyl group in secondary alkanesulfonates may be either saturated or
unsaturated,
branched or linear and optionally hydroxy substituted. The sulfo group may be
situated
on any position of the carbon chain, although the primary methyl groups at
either end of
the chain do not possess any sulfonate groups.
The preferred secondary alkanesulfonates comprise linear alkyl chains having
about 9
to 25 carbon atoms, preferably about 10 to about 20 carbon atoms and more
preferably
about 13 to 17 carbon atoms. The cation is for example sodium, potassium,
ammonium,
mono-, di- or triethanolammonium, calcium or magnesium, or mixtures thereof.
Sodium
is the preferred cation.
Secondary alkanesulfonate is obtainable under the trade name of Hostapur SAS
(from
Clariant).
As well as secondary alkanesulfonates primary alkanesulfonates can likewise be
used
in the washing compositions of the present invention. The preferred alkyl
chains and
cations are as for the secondary alkanesulfonates.
Useful anionic surfactants further include alkenyl- or alkylbenzenesulfonates.
The
alkenyl or alkyl group may be branched or linear and optionally hydroxyl
substituted.
The preferred alkylbenzenesulfonates comprise linear alkyl chains having about
9 to 25
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
11
carbon atoms and preferably from about 10 to about 13 carbon atoms; the cation
is
sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or
magnesium and mixtures thereof.
Magnesium is the preferred cation for mild surfactant systems, whereas sodium
is the
preferred cation for standard applications. The same applies to alkenylbenzene-
sulfonates.
The term "anionic surfactants" also comprehends olefinsulfonates, which are
obtained
by sulfonation of C8-C24-olefins and preferably C14-C16-a-olefins with sulfur
trioxide
and subsequent neutralization. Their method of production is such that these
olefinsulfonates may comprise minor amounts of hydroxyalkanesulfonates and
alkanedisulfonates.
Preferred anionic surfactants further include carboxylates, examples being
fatty acid
soaps and comparable surfactants. The soaps may be saturated or unsaturated
and
may comprise various substituents, such as hydroxyl groups or a-suifonate
groups.
Preference is given to linear saturated or unsaturated hydrocarbyl radicals as
a
hydrophobic moiety having about 6 about 30 and preferably about 10 to about 18
carbon atoms.
Useful anionic surfactants further include salts of acylamino carboxylic
acids, acyl
sarcosinates formed by reaction of fatty acid chlorides with sodium
sarcosinate in an
alkaline medium; fatty acid-protein condensation products obtained by reaction
of fatty
acid chlorides with oligopeptides; salts of alkylsulfamido carboxylic acids;
salts of alkyl
and alkylaryl ether carboxylic acids; sulfonated polycarboxylic acids; alkyl
and alkenyl
glycerol sulfates such as oleyl glycerol sulfates, alkylphenol ether sulfates,
alkyl
phosphates, alkyl ether phosphates, isethionates, such as acyl isethionates, N-
acyltaurides, alkyl succinates, sulfosuccinates, monoesters of sulfosuccinates
(particularly saturated and unsaturated C12-C18 monoesters) and diesters of
sulfosuccinates (particularly saturated and unsaturated C12-C18 diesters),
acyl
sarcosinates, sulfates of alkylpolysaccharides such as sulfates of
alkylpolyglycosides,
branched primary alkyl sulfates and alkyl polyethoxy carboxylates such as
those of the
formula RO(CH2CH2)kCH2COO M+, where R is C8 to C22 alkyl, k is from 0 to 10
and M
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
12
is a cation.
Nonionic surfactants
Condensation products of aliphatic alcohols with about 1 to about 25 mol of
ethylene
oxide.
The alkyl chain of the aliphatic alcohols may be linear or branched, primary
or
secondary, and comprises in general from about 8 to about 22 carbon atoms.
Particular
preference is given to the condensation products of Clp- to C20-alcohols with
about 2 to
about 18 mol of ethylene oxide per mole of alcohol. The alkyl chain may be
saturated or
else unsaturated. The alcohol ethoxylates may comprise the ethylene oxide in a
narrow
homolog distribution ("narrow range ethoxylates") or in a broad homolog
distribution
("broad range ethoxylates"). This class of product includes for example the
Genapol
brands (from Clariant).
Condensation products of ethyiene oxide with a hydrophobic base, formed by
condensation of propylene oxide with propylene glycol.
The hydrophobic part of these compounds preferably has a molecular weight
between
about 1500 and about 1800. The addition of ethylene oxide onto this
hydrophobic part
leads to improved solubility in water. The product is liquid up to a
polyoxyethylene
content of about 50% of the overall weight of the condensation product, which
corresponds to a condensation with up to about 40 mol of ethylene oxide.
Commercially
available examples of this class of products are the Genapol PF brands (from
Clariant).
Condensation products of ethylene oxide with a reaction product of propylene
oxide and
ethylenediamine.
The hydrophobic unit of these compounds consists of the reaction product of
ethylenediamine with excess propylene oxide and generally has a molecular
weight in
the range of about 2500 to 3000. Ethylene oxide is added onto this hydrophobic
unit up
to a level of about 40% to about 80% by weight of polyoxyethylene and a
molecular
weight of about 5000 to 11 000. Commercially available examples of this class
of
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
13
compounds are the Tetronic brands from BASF and the Genapol PN brands from
Clariant GmbH.
Semipolar nonionic surfactants
This category of nonionic compounds comprises water-soluble amine oxides,
water-
soluble phosphine oxides and water-soluble sulfoxides, each having an alkyl
radical of
about 10 to about 18 carbon atoms. Semipolar nonionic surfactants further
include
amine oxides of the formula
0
~
R (OR2)xN (R ) 2
where R is an alkyl, hydroxyalkyl or alkylphenol group having a chain length
of about 8
to about 22 carbon atoms, R2 is an alkylene or hydroxyalkylene group having
about 2 to
3 carbon atoms or mixtures thereof, every R1 radical is an alkyl or
hydroxyalkyl group
having about 1 to about 3 carbon atoms or a polyethylene oxide group having
about 1 to
about 3 ethylene oxide units and x is from 0 to about 10. The R1 groups may be
joined
together via an oxygen or nitrogen atom and thus form a ring. Amine oxides of
this kind
are particularly C10-C18-alkyldimethylamine oxides and C8-C12-
alkoxyethyldihydroxy-
ethylamine oxides.
Fatty acid amides
Fatty acid amides have the formula
0
11
R C N(R')2
where R is an alkyl group having about 7 to about 21 and preferably about 9 to
about 17
carbon atoms and every R1 radical is hydrogen, Cl-C4-alkyl, Cl-C4-hydroxyalkyl
or
CA 02601177 2007-09-14
WO 2006/097213 PCTlEP2006/002014
14
(C2H40)xH, where x varies from about 1 to about 3. C8-C20 amides,
monoethanolamides, diethanolamides and isopropanolamides are preferred.
Useful nonionic surfactants further include alkyl and alkenyl oligoglycosides
and also
fatty acid polyglycol esters or fatty amine polyglycol esters each having 8 to
20 and
preferably 12 to 18 carbon atoms in the fatty alkyl moiety, alkoxylated
triglycamides,
mixed ethers or mixed formyls, alkyl oligoglycosides, alkenyl oligoglycosides,
fatty acid
N-alkyl glucamides, phosphine oxides, dialkyl sulfoxides and protein
hydrolyzates.
Polyethylene, polypropylene and polybutylene oxide condensates of
alkylphenols.
These compounds comprise the condensation products of alkylphenols having a C6-
to
C20-alkyl group, which may be either linear or branched, with alkene oxides.
Preference
is given to compounds having about 5 to about 25 mol of alkene oxide per mole
of
alkvlphenol. Commercially available surfactants of this type are for example
the
Arkopal N brands (from Clariant). These surfactants are referred to as
alkylphenol
alkoxylates, an example being alkylphenol ethoxylates.
Zwitterionic surfactants
Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines,
alkylamide
betaines, aminopropionates, aminoglycinates, or amphoteric imidazolinium
compounds
of the formula
R3
I
R'CON(CH2)nN+-CH2Z
I
R4 R2
where R1 denotes C8-C22-alkyl or -alkenyl, R2 denotes hydrogen or CH2CO2M, R3
denotes CH2CH2OH or CH2CH2OCH2CH2CO2M, R4 denotes hydrogen, CH2CH2OH
or CH2CH2COOM, Z denotes CO2M or CH2CO2M, n denotes 2 or 3, preferably 2, M
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
denotes hydrogen or a cation such as alkali metal, alkaline earth metal,
ammonium or
alkanolammonium.
Preferred amphoteric surfactants of this formula are monocarboxylates and
dicarboxylates. Examples thereof are cocoamphocarboxypropionate, cocoamido
carboxy propionic acid, cocoamphocarboxyglycinate (or else referred to as
cocoamphodiacetate) and cocoamphoacetate.
Preferred amphoteric surfactants further include alkyl dimethyl betaines (
Genagen
LAB/ Clariant GmbH) and alkyl dipolyethoxy betaines having an alkyl radical of
about 8
to about 22 carbon atoms, which may be linear or branched, preferably 8 to 18
carbon
atoms and more preferably having about 12 to about 18 carbon atoms.
Useful cationic surfactants include substituted or unsubstituted straight-
chain or
branched quatemary ammonium salts of the type R1 N(CH3)3+ X, R1 R2N(CH3)2+ X,
1 2 3 +- 1 2 3 4+- 1 2 3 4
R R R N(CH3) X or R R R R N X. The R, R, R and R radicals may preferably
independently be unsubstituted alkyl having a chain length of between 8 and 24
carbon
atoms and especially between 10 and 18 carbon atoms, hydroxyalkyl having about
1 to
about 4 carbon atoms, phenyl, C2- to C18-alkenyl such as, for example, tallow
alkyl or
oleyl, C7- to C24-aralkyl, (C2H40)xH, where x is from about 1 to about 3, or
else alkyl
radicals comprising one or more ester groups, or cyclic quaternary ammonium
salts. X
is a suitable anion.
As well as surfactants, further materials may be present:
odor absorbents, deodorants, scents, antistats, microbicides such as
bactericides and
fungicides, preservatives, solubilizers, fiber regenerants, finishes,
emulsifiers, enzymes,
impregnants and also water in small amounts.
Examples
The hereinbelow described investigations were carried out using
tetramethoxyethane
(TME) of the formula (2) as an example of a solvent of the formula (1).
The following were utilized as references:
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
16
tetrachlorethene (= perchloroethylene, = PER)
C10-13 isoalkanes (= hydrocarbon solvent = HCS)
Example 1
The power to remove a liquid paraffin stain from various
Waschereiforschunganstalt
Krefeld laundry research institute standard test fabrics was investigated.
The test fabrics used were:
cotton wfk 10A, cotton-polyester wfk 20A, polyester wfk 30A, polyamide wfk
40A, acrylic
wfk 50A, wool wfk 60A and silk wfk 70A.
These test fabrics were each soiled with paraffin oil colored with the fat-
soluble dye
Sudan Red. The reflectance (whiteness) of the soiled fabrics was measured.
The test fabrics were then washed with tetramethoxyethane and the reference
solvents
at room temperature in a Linitest laboratory washing machine. For each type of
fabric
the wash included an unstained white fabric of the same type in order that the
soil
transfer/redeposition may be investigated. After trie wash, the test fabrics
were dried
and assessed as follows.
To quantify soil release, the reflectance (whiteness) of the cleaned fabrics
was
determined and the difference to the values measured for the soiled fabrics
was
calculated.
The higher the dR reflectance values, the better the removal of the test soil.
To
determine soil redeposition, the L,a,b values of the adjacent white fabrics
before and
after the wash were compared to calculate the color difference dE.
The lower the color difference dE, the less the swatches were stained by soil
transfer
(redeposition).
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
17
Table 1: Removal of paraffin oil by tetramethoxyethane compared with PER and
HSC
Test fabric dR whiteness (%) after cleaning with....
tetramethoxyethane PER HCS
wfk 10A 47.1 45.8 38.6
wfk 20A 41.9 41.4 37.1
wfk 30A 38.2 36.8 36.4
wfk 40A 21.7 21.5 20.1
wfk 50A 40.9 39.5 39.6
wfk 60A 35.0 34.0 34.2
wfk 70A 28.0 26.3 27.6
Total (all fabrics) 252.8 245.3 233.6
Table 2: Staining dE of white fabrics by soil redeposition
TEst fabrii, Staining dE Of white fabrics by soil redeposition in....
tetramethoxyethane PER HCS
wfk 10A 1.7 2.0 4.6
wfk 20A 1.7 2.1 2.6
wfk 30A 0.7 0.9 1.0
wfk 40A 2.2 2.2 3.2
wfk 50A 0.8 2.5 1.2
wfk 60A 3.0 3.5 1.0
wfk 70A 0.7 2.6 0.5
Total (all fabrics) 10.8 15.8 14.1
Example 2
The power to remove a vegetable oil stain from various
Waschereiforschungsanstalt
Krefeld laundry research institute standard test fabrics was investigated. The
vegetable
oil used was sunflower oil, likewise colored with Sudan Red.
Procedure and analysis were similar to Example 1.
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
18
Table 3: Removal of sunflower oil by tetramethoxyethane compared with PER and
HCS
Test fabric dR whiteness (%) after cleaning with....
tetramethoxyethane PER HCS
wfk 10A 46.0 42.9 36.2
wfk 20A 43.3 41.3 38.3
wfk 30A 36.5 34.7 35.3
wfk 40A 21.1 19.8 19.9
wfk 50A 24.8 23.3 22.1
wfk 60A 17.0 17.1 17.6
wfk 70A 15.9 15.2 15.8
Total (all fabrics) 204.6 194.3 185.2
Table 4: Staining dE of white fabrics by soil redeposition
Test fabric Staining dE of white fabrics by soil redeposition in....
tetramethoxyethane PER HCS
wfk 10A 1.8 2.4 4.0
wfk 20A 1.8 2.0 2.8
wfk 30A 0.8 1.2 1.0
wfk 40A 2.2 2.3 3.2
wfk 50A 0.7 1.8 1.4
wfk 60A 3.5 3.6 1.0
wfk 70A 0.6 1.6 0.8
Total (all fabrics) 11.4 14.9 14.2
Example 3
The cleaning power of tetramethoxyethane compared with PER and HCS was
investigated on various standardized soiled fabrics from the Wascherei-
forschungsanstalt Krefeld laundry research institute. The following test
fabrics were
used: cotton-polyester wfk 20C (blend fabric with fat-pigment soiling) and
cotton-
polyester wfk 20D (blend fabric with synthetic sebum soiling). The test
fabrics were
washed in a Linitest laboratory washing machine at room temperature. The wash
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
19
included unsoiled cotton-polyester white fabric wfk 20A in order that the soil
transfer
from soiled to white test fabrics may be investigated.
The cleaning of the fabrics and the measurement-based quantification of the
cleaning
performance and of the soil transfer/graying were carried out as described in
Example
1.
Table 5: Cleaning of standard test soil fabrics by tetramethoxyethane compared
with PER and HCS
Test fabric dR (%) whiteness increase after cleaning with...
tetramethoxyethane PER HCS
wfk 20C 17.9 13.7 17.2
wfk 20D 17.6 9.5 11.5
Total (all fabrics) 35.5 23.2 28.7
Table 6: Staining dE of white fabrics by soil redeposition
White fabrics washed in
Staining dE of white fabrics by soil deposition in....
presence of ...
tetramethoxyethane PER HCS
wfk 20C 4.3 9.2 5.9
wfk 20D 6.5 7.2 5.1
Total (all fabrics) 10.8 16.4 11.0
Example 4: Stability of textile dyeings
The stability of textile dyeings was tested on various commercially available
colored
fabrics. The colored fabrics were:
1. 100% polyamide, turquoise
2. 100% polyester, royal blue
3. 100% polyester, yellow
4. 100% silk, bordeaux
5. 100% silk, dark green
6. 100% viscose, bordeaux
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
7. 100% viscose, black
8. 100% wool, ochre
Two swatches at a time of a colored fabric were washed together with 4 white
swatches
of the wfk 20A test fabric with tetramethoxyethane and the reference solvents
in the
Linitest washing machine at room temperature.
One of the colored swatches and two of the white swatches were removed after
10 min.
The second colored swatch and the remaining two white swatches were each
washed
for another 50 minutes.
After drying, the colored fabrics and the white fabrics were assessed as
follows.
The color difference dE to the unwashed colored fabrics was determined to
quantify the
preservation of the color of the colored fabrics. The lower the dE color
differences, the
less the dyeings are attacked by the cleaning agent.
A possible color transfer due to detached dye was quantified by measuring the
color
different dE of the washed white swatches to the unwashed white fabric. The
lower the
dE value, the less the white fabrics were stained by the colored fabrics.
Ideally, the dE values are zero both for the preservation of color and for the
transfer of
color.
Table 7: Color preservation of various colored textiles after washing with
tetramethoxyethane for 10 min compared with PER and HCS
Colored fabric Color differences dE after a 10 min wash in ...
TME PER HCS
100% polyamide, turquoise 0.6 2.1 2.1
100% polyester, royal blue 0.2 0.4 0.2
100% polyester, yellow 0.9 1.4 1.0
100% silk, bordeaux 1.0 0.1 0.6
100% silk, dark green 0.4 0.2 0.3
100% viscose, bordeaux 1.0 0.9 1.1
100% viscose, black 0.6 1.1 0.8
100% wool, ochre 0.4 0.6 1.0
Total (all fabrics) 5.1 5.8 7.1
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
21
Table 8: Color preservation of various colored textiles after washing with
tetramethoxyethane for 60 min compared with PER and HCS
Colored fabric Color differences dE after a 60 min wash in ...
TME PER HCS
100% polyamide, turquoise 1.0 2.7 2.4
100% polyester, royal blue 0.4 0.4 0.3
100% polyester, yellow 1.2 1.5 1.5
100% silk, bordeaux 1.8 0.8 1.4
100% silk, dark green 0.6 1.3 0.4
100% viscose, bordeaux 2.6 0.9 2.3
100% viscose, black 0.7 1.1 1.2
100% wool, ochre 0.9 1.2 1.2
Total (all fabrics) 9.2 9.9 10.7
Table 9: Dye transfer to white fabric by washing with colored textiles in
tetramethoxyethane for 10 min compared with PER and HCS
White fabric washed in
Staining dE after 10 min wash in ...
presence of colored fabric ...
TME PER HCS
100% polyamide, turquoise 4.4 4.5 3.5
100% polyester, royal blue 2.6 3.0 3.2
100% polyester, yellow 2.1 2.1 2.0
100% silk, bordeaux 2.8 3.0 2.9
100% silk, dark green 2.8 3.4 2.6
100% viscose, bordeaux 2.4 2.8 2.6
100% viscose, black 2.3 2.5 2.4
100% wool, ochre 2.5 2.9 2.8
Total (all fabrics) 21.9 24.2 22.0
CA 02601177 2007-09-14
WO 2006/097213 PCT/EP2006/002014
22
Table 10: Dye transfer to white fabric by washing with colored textiles in
tetramethoxyethane for 60 min compared with PER and HCS
White fabric washed in
Staining dE after 60 min wash in ...
presence of colored fabric ...
TME PER HCS
100% polyamide, turquoise 4.9 4.7 4.6
100% polyester, royal blue 2.6 3.0 3.2
100% polyester, yellow 2.1 2.1 2.2
100% silk, bordeaux 3.2 3.2 2.9
100% silk, dark green 2.9 3.6 2.8
100% viscose, bordeaux 3.0 3.4 2.7
100% viscose, black 2.4 2.7 2.7
100% wool, ochre 2.7 3.0 2.9
Total (all fabrics) 23.8 25.7 24.0
