Note: Descriptions are shown in the official language in which they were submitted.
CA 02822855 2013-06-25
PF 0000071519
1
Use of optionally oxidized thioethers of alcohol alkoxylates in detergents and
cleaning
agents
Description
The present invention relates to the use of (oxidized) thioethers of alcohol
alkoxylates
in washing and cleaning compositions, especially in dishwashing compositions,
and to
washing and cleaning compositions, especially dishwashing compositions, which
comprise (oxidized) thioethers of alcohol alkoxylates. These (oxidized)
thioethers are
especially suitable as surfactants with rinse aid function (rinse aid
surfactants).
"Oxidized" relates to the sulfur atom in the thioether, which may be present
in oxidized
form as sulfoxide (SO) or sulfonyl (SO2).
Surfactants are substances which can lower interfacial tension. Typically,
surfactants
possess a characteristic structure and have at least one hydrophilic and at
least one
hydrophobic functional group. When the two parts of the molecule are in
equilibrium
with respect to one another, the substance will accumulate and become aligned
at an
interface, i.e. hydrophilic groups point, for example, into an aqueous phase
and the
hydrophobic groups in the direction of other solid, liquid or gaseous phases.
A further
special feature of surfactants is the formation of higher aggregates, known as
micelles.
In these, the surfactant molecules become ordered in such a way that the polar
groups,
for example, form a spherical surface. This has the effect that substances
such as soil
particles are solubilized in an aqueous solution with formation of micelles.
Surfactants
are therefore suitable especially for cleaning surfaces and as an additive in
washing
compositions.
Surfactants which have a hydrophobic block and a hydrophilic block are
widespread.
However, their tendency to form foam makes them unsuitable or suitable only to
a
limited degree for many applications. For applications in which strong foam
formation is
unwanted, therefore, nonionic surfactants which have a second hydrophobic
block
have been developed, which limits the foam volume.
The second hydrophobic block can derive, for example, from a fatty alcohol.
However,
the use of dishwashing compositions which comprise such a surfactant,
especially of
dishwashing compositions for machine dishwashers, frequently leads to residues
remaining on the dishware cleaned therewith (deposit formation; called
"spotting" in the
case of formation of spot deposits or "filming" in the case of film-like
deposits).
The second hydrophobic block can alternatively derive from a fatty acid. In
the case of
dishwashing compositions which comprise such surfactants, the problem of
deposit
CA 02822855 2013-06-25
PF 0000071519
2
formation is no longer as great; however, these surfactants are hydrolysis-
sensitive due
to the ester group, which greatly restricts the usability thereof in alkaline
formulations
and at relatively high temperatures, especially in prolonged washing
operations.
Thioethers of alcohol alkoxylates and the oxidized form thereof (i.e. the
sulfoxides and
sulfones) are known in principle; for example from US 3,627,845. This document
describes the use of such compounds as biologically active compositions, for
example
as fungicides, acaricides and anthelmintics, and as surface-active substances
in
agrochemical formulations and coating compositions. Use as a washing or
cleaning
composition is not mentioned.
It was an object of the present invention to provide compounds which do not
have the
disadvantages of the prior art surfactants. More particularly, the compounds
should
have no strong tendency, if any, to foam formation; they should leave behind a
lower
level of residues, especially spotting residues, on the dishware washed
therewith, and
they should at least be less hydrolysis-labile, if at all, than the
surfactants based on
fatty acid esters. More particularly, the compounds should, however, have a
maximum
melting point such that they can also be formulated in solid washing and
cleaning
compositions.
The object is achieved by the use of compounds of the formula I
R-04CH2CH(R1)-011-fCH2CH2-0}m-fCH2CH(R2)-01,,-CH2CH2-S(0).-R. (I)
in which
is C8-C24-alkyl;
R' is C6-C18-alkyl;
IR, and R2 are each independently at each instance C1-05-alkyl;
m is from 10 to 100;
I and n are each independently from 0 to 15; and
is 0, 1 or 2;
in washing or cleaning compositions, especially in dishwashing compositions.
The invention also relates to washing or cleaning compositions, especially
dishwashing
compositions, comprising at least one compound of the formula I as defined
above.
CA 02822855 2013-06-25
PF 0000071519
3
In the context of the present invention, C1-05-alkyl is a linear or branched
alkyl radical
having 1 to 5 carbon atoms. Examples thereof are methyl, ethyl, propyl,
isopropyl, n-
butyl, sec-butyl, isobutyl, tert-butyl, pentyl and positional isomers thereof.
C6-C18-Alkyl is a linear or branched alkyl radical having 6 to 18 carbon
atoms.
Examples thereof are hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 2-
propylheptyl,
undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,
octadecyl and
positional isomers thereof.
C8-C24-Alkyl is a linear or branched alkyl radical having 8 to 24 carbon
atoms.
Examples thereof are octyl, 2-ethylhexyl, nonyl, decyl, 2-propylheptyl,
undecyl,
dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,
nonadecyl,
eicosyl, henicosyl, docosyl, tricosyl, tetracosyl and positional isomers
thereof.
Branched C8-C24-alkyl is the positional isomers of octyl, such as 2-
ethylhexyl, the
positional isomers of n-nonyl, the positional isomers of n-decyl, such as 2-
propylheptyl,
the positional isomers of n-undecyl, the positional isomers of n-dodecyl, the
positional
isomers of n-tridecyl, the positional isomers of n-tetradecyl, the positional
isomers of n-
pentadecyl, the positional isomers of n-hexadecyl, the positional isomers of n-
heptadecyl, the positional isomers of n-octadecyl, the positional isomers of n-
nonadecyl, the positional isomers of n-eicosyl, the positional isomers of n-
henicosyl,
the positional isomers of n-docosyl, the positional isomers of n-tricosyl and
the
positional isomers of n-tetracosyl.
Clo-C14-Alkyl is a linear or branched alkyl radical having 10 to 14 carbon
atoms.
Examples thereof are decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl,
tetradecyl and
the positional isomers thereof.
Branched C10-C14-alkyl is the positional isomers of n-decyl, such as 2-
propylheptyl, the
positional isomers of n-undecyl, the positional isomers of n-dodecyl, the
positional
isomers of n-tridecyl and the positional isomers of n-tetradecyl.
C10-C15-Alkyl is a linear or branched alkyl radical having 10 to 15 carbon
atoms.
Examples thereof are decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl,
tetradecyl,
pentadecyl and positional isomers thereof.
Branched C10-C15-alkyl is the positional isomers of n-decyl, such as 2-
propylheptyl, the
positional isomers of n-undecyl, the positional isomers of n-dodecyl, the
positional
CA 02822855 2013-06-25
PF 0000071519
4
isomers of n-tridecyl, the positional isomers of n-tetradecyl and the
positional isomers
of n-pentadecyl.
C8-C15-Alkyl is a linear or branched alkyl radical having 8 to 15 carbon
atoms.
Examples thereof are the radicals mentioned above for Clo-C15-alkyl, and also
octyl, 2-
ethylhexyl, nonyl and positional isomers thereof.
Branched C8-C15-alkyl is the positional isomers of octyl, such as 2-
ethylhexyl, the
positional isomers of n-nonyl, the positional isomers of n-decyl, such as 2-
propylheptyl,
the positional isomers of n-undecyl, the positional isomers of n-dodecyl, the
positional
isomers of n-tridecyl, the positional isomers of n-tetradecyl and the
positional isomers
of n-pentadecyl.
C12-Alkyl is dodecyl and the positional isomers thereof.
The remarks which follow regarding preferred embodiments, especially regarding
preferred embodiments of the compounds I, the use thereof and the compositions
comprising them, apply either taken alone or in any conceivable combination
with one
another. Unless anything is mentioned to the contrary, the remarks apply both
to the
inventive use and to the inventive washing and cleaning compositions.
The compounds I being used in accordance with the invention may be chemically
pure
substances or mixtures of different compounds I. In general, due to the
production
process therefor and the reactants used therein, which may be technical-grade
products or product mixtures, mixtures of different compounds I will be
involved, which
differ, for example, in the definition of the variables R, R', I, m, n and/or
x.
In the compounds I, R is preferably C8-C15-alkyl, more preferably Clo-C15-
alkyl and
especially C10-C14-alkyl. In a specific embodiment, the alkyl radical R is
branched.
Specific examples of R are 2-propylheptyl, tridecyl and the positional isomers
thereof,
such as isotridecyl (i.e. branched tridecyl radicals and mixtures thereof), n-
dodecyl
(lauryl), n-tetradecyl (myristyl) and mixtures thereof.
R' is preferably Clo-C14-alkyl and especially C12-alkyl (dodecyl); especially
n-dodecyl.
R1 and R2 are preferably each independently methyl.
m is preferably from 20 to 50, more preferably from 25 to 50, even more
preferably
from 25 to 45 and especially from 25 to 40.
CA 02822855 2013-06-25
PF 0000071519
I and n are preferably each independently from 0 to 5 and more preferably 0,
1, 2 or 3.
More particularly, I and n are each 0.
When at least one of the indices I or n is not 0, the ethyleneoxy repeat units
(-CH2-CH2-
5 0-) and the different repeat units (-CH2-CH(R1)-0-) and/or (-CH2-CH(R2)-0-
) may be
arranged randomly or in blocks. They are preferably arranged in blocks; in
other words,
all I repeat units -CH2-CH(R1)-0- which may be present form a block which is
followed
by ethyleneoxy block (-CH2-CH2-0-)m which is followed by all n repeat units -
CH2-
CH(R2)-0- which may be present as a block.
xis preferably 0 or 1.
The compounds I are notable for a relatively high melting point. The melting
point is
preferably at least 35 C, for example 35 to 50 C, preferably 35 to 47 C and
especially
35 to 45 C; more preferably at least 38 C, for example 38 to 50 C, preferably
38 to
47 C and especially 38 to 45 C; and especially at least 40 C, for example 40
to 50 C,
preferably 40 to 47 C and especially 40 to 45 C.
Processes for preparing compounds I are known in principle; for example from
US
3,627,845. For instance, in the case that I is not 0, an alcohol R-OH can be
reacted
with an epoxide
0
R1
and then with ethylene oxide.
In the case that n is not 0, the product obtained is then reacted with an
epoxide
0
R2.
This is followed by the reaction with a mercaptoethanol R'-S-CH2CH2-0H to give
the
compound I. If x should be 1 or 2, the thioether obtained is subsequently
oxidized.
The reaction with the epoxides is effected preferably in an anhydrous medium
under
base catalysis. The reaction is preferably effected under inert gas
atmosphere, such as
nitrogen or argon. The reaction is preferably performed in bulk, i.e. without
further
solvents. Suitable bases are, for example, inorganic bases, such as alkali
metal
hydroxides, e.g. lithium, sodium or potassium hydroxide, alkaline earth metal
hydroxides, e.g. magnesium or calcium hydroxide, alkali metal carbonates, e.g.
lithium,
sodium or potassium carbonate, or alkaline earth metal carbonates, e.g.
magnesium or
CA 02822855 2013-06-25
PF 0000071519
6
calcium carbonate. Preference is given to sodium hydroxide and potassium
hydroxide.
The reaction temperature is preferably 50 to 200 C, more preferably 100 to 150
C. The
reaction is effected preferably under elevated pressure, for example at 1.1 to
10 bar or
1.2 to 5 bar, which is built up by the inert gas and/or the epoxide
(especially ethylene
oxide). In a preferred embodiment, introduction of the epoxide is preceded by
buildup
of an initial pressure with inert gas, generally nitrogen. This initial
pressure is preferably
in the range from 1.1 to 5 bar, more preferably from 1.2 to 3 bar and
especially from 1.2
to 2 bar. The addition of the epoxide (especially ethylene oxide) generally
then leads to
a further pressure increase. The pressure during the actual reaction is in the
range
from preferably 1.2 to 10 bar, more preferably from 2 to 8 bar. On completion
of
conversion, the product mixture obtained can be neutralized if desired.
The condensation with the mercaptoethanol is effected preferably under acidic
catalysis. Suitable acids are, for example, p-toluenesulfonic acid,
methanesulfonic acid,
phosphoric acid and acidic ion exchangers. During the reaction, the water of
reaction
formed is preferably removed, for example by azeotropic distillation or
stripping with an
inert gas. If the water of reaction is to be removed by azeotropic
distillation, the
condensation is advantageously performed in a solvent which forms a minimum
azeotrope with water, such as toluene or the xylenes. On completion of
conversion, the
product mixture obtained can be neutralized if desired.
The sulfur atom in the thioether obtained can be oxidized to the sulfoxide (x
= 1) or
sulfone (x = 2) by means of customary oxidizing agents, such as hydrogen
peroxide,
manganese dioxide, a permanganate, m-chloroperbenzoic acid or a perchlorate.
Whether the oxidation proceeds up to the sulfoxide or up to the sulfone can be
determined by factors including the selection of the oxidizing agent, the
concentration
thereof and the reaction temperature.
The compounds I can be used in accordance with the invention in the form of
the
solution obtained in the preparation thereof. However, they are preferably
isolated by
means of customary processes and purified if desired.
The compounds of the formula I are usable in principle in all common washing
and
cleaning compositions.
In the context of the present invention, washing compositions are understood
to mean
those compositions which are used for cleaning of flexible materials with high
absorptivity, for example of materials with textile character, whereas
cleaning
compositions in the context of the present invention are understood to mean
those
CA 02822855 2013-06-25
PF 0000071519
7
compositions which are used for cleaning of materials with a continuous
surface, i.e.
with a surface which has only few and small pores, if any, and as a result has
only low
absorptivity, if any.
Examples of flexible materials with high absorptivity are those which comprise
or
consist of natural, synthetic or semisynthetic fiber materials, and which
accordingly
generally at least partially have textile character. The fibrous materials, or
those
consisting of fibers, may in principle be present in any form which occurs in
use or in
production and processing. For example, fibers may be present in unordered
form in
the form of staple or aggregate, in ordered to form in the form of fibers,
yarns, threads,
or in the form of fabrics such as nonwovens, lodens or felt, wovens, knits, in
all
conceivable binding types. The fibers may be raw fibers or fibers in any
processing
state. Examples are natural protein or cellulose fibers, such as wool, silk,
cotton, sisal,
hemp or coconut fibers, or synthetic fibers, for example polyester, polyamide
or
polyacrylonitrile fibers.
Examples of materials which have only few and small pores, if any, and have
only low
absorptivity, if any, are metal, glass, enamel or ceramic. Typical objects
made of these
materials are, for example, metal sinks, cutlery, glass and porcelain
dishware,
bathtubs, washbasins, tiles, flags, hardened synthetic resins, for example
decorative
melamine resin surfaces on kitchen furniture, or finished metal surfaces, for
example
refrigerators and automobile bodies, printed circuit boards, microchips,
sealed or
varnished wood, for example parquet or wall paneling, window frames, doors,
plastic
coverings such as floor coverings made of PVC or hard rubber, or hard or soft
foams
with substantially continuous surfaces.
Examples of cleaning compositions which comprise the compounds I comprise
dishwashing compositions, such as manual dishwashing compositions or machine
dishwashing compositions (= dishwashing compositions for the machine
dishwasher),
metal degreasers, glass cleaners, floor cleaners, all-purpose cleaners, high-
pressure
cleaners, neutral cleaners, alkaline cleaners, acidic cleaners, spray
degreasers, dairy
cleaners, industrial kitchen cleaners, equipment cleaners in industry,
especially in the
chemical industry, cleaners in car washes, and also domestic all-purpose
cleaners.
The compounds I are preferably used in dishwashing compositions. They are more
preferably used in machine dishwashing compositions. Among these, preference
is
given to dishwashing compositions, especially machine dishwashing
compositions, with
rinse aid function.
CA 02822855 2013-06-25
PF 0000071519
8
The washing and cleaning compositions which comprise the compounds I are
preferably solid at room temperature (20 C).
The solid washing and cleaning compositions may be pulverulent or tableted
products
("tabs"). They are preferably tableted products ("tabs"). More preferably,
they are
tableted dishwashing compositions, especially tableted machine dishwashing
compositions.
Tableted dishwashing compositions may be simple tabs or else what are called
"2 in
1", "3 in 1", "5 in 1", "7 in 1" products and the like (multifunctional
products; generally
speaking "x in 1" products where x = integer). Further details of these
formulations can
be found in Hermann G. Hauthal, G. Wagner (eds.), Reinigungs- und Pflegemittel
im
Haushalt [Domestic Cleaning and Care Compositions], Verlag fur chemische
Industrie,
H. Ziolkowsky GmbH, Augsburg 2003, chapter 4.2, pages 161-184. "2 in 1"
products
comprise, as well as the customary constituents of machine dishwashing
compositions,
additionally a rinse aid. "3 in 1" products also comprise a water softener. "5
in 1"
products generally also comprise a glass protector and a rinsing power
enhancer. "7 in
1" products also comprise a precious metal brightener and an encrustation
remover.
The compounds I are preferably used in tableted multifunctional machine
dishwashing
compositions, where they completely or partially replace the customary rinse
aids.
The compounds I have an effect both as a surfactant and as a rinse aid. The
invention
therefore also relates to the use of the compounds I as a surfactant and/or as
a rinse
aid. More particularly, the invention relates to the use of the compounds I as
a
surfactant with rinse aid effect or as a rinse aid surfactant.
The compounds I used in accordance with the invention are notable especially
for
excellent deposition-inhibiting action in the case of use in the rinse cycle
of the
machine dishwasher. They have inhibiting action both with respect to inorganic
deposits and with respect to organic deposits. The inorganic deposits are
especially
calcium and magnesium phosphate, calcium and magnesium carbonate, calcium and
magnesium silicate and/or calcium and magnesium phosphonate, which form from
the
calcium and magnesium salts present in the water and the builders present in
customary dishwashing compositions. The organic deposits are especially soil
constituents from the rinse liquor, for example protein, starch and grease
deposits. The
compounds I used in accordance with the invention are also effective against
what are
called carry-over deposits, which originate from the residual amount of water
in the
bottom of the dishwasher and comprise, inter alia, dishwashing composition
residues
CA 02822855 2013-06-25
PF 0000071519
9
and possibly also soil residues from the previous wash cycle of the machine
dishwasher.
The invention further provides washing or cleaning compositions which comprise
at
least one compound of the formula I. With regard to suitable washing or
cleaning
compositions, reference is made to the above remarks.
The washing and cleaning compositions are preferably dishwashing compositions,
among which machine dishwashing compositions are preferred. These are
especially
dishwashing compositions, especially machine dishwashing compositions, with
rinse
aid function.
The inventive washing and cleaning composition is preferably solid at room
temperature (20 C). With regard to suitable and preferred solid washing and
cleaning
compositions, reference is made to the above remarks. More particularly, the
inventive
washing and cleaning compositions are tableted multifunctional machine
dishwashing
compositions. The compounds I may be present therein in the rinse core;
preferably,
however, they are present as a solid in the tableted dishwashing composition.
The inventive dishwashing composition preferably comprises the following
constituents:
a) at least one compound of the formula I;
b) at least one builder (also referred to as a sequestrant, framework
substance,
complexing agent, chelator, chelating agent or softener);
c) optionally at least one enzyme; and
d) optionally at least one bleach; and
e) optionally at least one further additive preferably selected from
surfactants other
than a), bases, corrosion inhibitors, defoamers, dyes, fragrances, fillers,
tableting
aids, disintegrants, thickeners, solubilizers, organic solvents and water.
These constituents are preferably present in the inventive dishwashing
composition in
the following ratios:
a) at least one compound of the formula I: from 0.1 to 20% by weight;
b) at least one builder: from 5 to 80% by weight;
c) at least one enzyme: from 0 to 8% by weight;
d) at least one bleach: from 0 to 30% by weight; and
e) at least one further additive: from 0 to 50% by weight.
The percentages by weight are based on the total weight of the dishwashing
composition. The weights from a) to e) add up to 100% by weight.
CA 02822855 2013-06-25
PF 0000071519
The inventive dishwashing composition more preferably comprises at least one
enzyme.
5 More preferably, the abovementioned constituents are present in the
inventive
dishwashing composition in the folllowing ratios:
a) at least one compound of the formula I: from 0.1 to 10% by weight;
b) at least one builder: from 20 to 80% by weight;
10 c) at least one enzyme: from 0.1 to 6% by weight;
d) at least one bleach: from 0 to 30% by weight; and
e) at least one further additive: from 0 to 50% by weight.
The percentages by weight are based on the total weight of the dishwashing
composition. The weights from a) to e) add up to 100% by weight.
Even more preferably, the inventive dishwashing composition also comprises at
least
one bleach.
Even more preferably, the abovementioned constituents are present in the
inventive
dishwashing composition in the following ratios:
a) at least one compound of the formula I: from 0.1 to 10% by weight;
b) at least one builder: from 20 to 80% by weight;
c) at least one enzyme: from 0.1 to 6% by weight;
d) at least one bleach: from 5 to 25% by weight; and
e) at least one further additive: from 0 to 50% by weight.
The percentages by weight are based on the total weight of the dishwashing
composition. The weights from a) to e) add up to 100% by weight.
With regard to suitable and preferred compounds I, reference is made to the
above
remarks.
Builders, which are sometimes also referred to as sequestrants, structural
substances,
complexing agents, chelators, chelating agents or softeners, bind alkaline
earth metals
and other water-soluble metal salts without precipitating. They help to break
up soil,
disperse soil components, help to detach soil and in some cases themselves
have a
CA 02822855 2013-06-25
PF 0000071519
11
washing effect. In addition, when they are solid and are used in pulveruient
formulations, they keep the powder free-flowing.
Suitable builders may be either organic or inorganic in nature. Examples are
aluminosilicates, carbonates, phosphates and polyphosphates, polycarboxylic
acids,
polycarboxylates, hydroxycarboxylic acids, phosphonic acids, e.g.
hydroxyalkylphosphonic acids, phosphonates, aminopolycarboxylic acids and
salts
thereof, and polymeric compounds containing carboxylic acid groups and salts
thereof.
Suitable inorganic builders are, for example, crystalline or amorphous
aluminosilicates
with ion-exchanging properties, such as zeolites. Various types of zeolites
are suitable,
especially zeolites A, X, B, P, MAP and HS in the sodium form thereof, or in
forms in '
which Na has been partially exchanged for other cations such as Li, K, Ca, Mg
or
ammonium. Suitable zeolites are described, for example, US-A-4604224.
Crystalline
silicates suitable as builders are, for example, disilicates or sheet
silicates, e.g. 5-
Na251205 or B-Na2S1205 (SKS 6 or SKS 7). The silicates can be used in the form
of
their alkali metal, alkalkine earth metal or ammonium salts, preferably as
sodium,
lithium and magnesium silicates. Amorphous silicates, for example sodium
metasilicate
which has a polymeric structure, or amorphous disilicate (Britesil H 20,
manufacturer:
Akzo), are likewise usable. Among these, preference is given to sodium
disilicate.
Suitable inorganic builder substances based on carbonate are carbonates and
hydrogencarbonates. These can be used in the form of their alkali metal,
alkaline earth
metal or ammonium salts. Preference is given to using sodium, lithium and
magnesium
carbonates or sodium, lithium and magnesium hydrogencarbonates, especially
sodium
carbonate and/or sodium hydrogencarbonate.
Customary phosphates used as inorganic builders are alkali metal
orthophosphates
and/or polyphosphates, for example pentasodium triphosphate.
Suitable organic builders are, for example, C4-C30-di-, -tri- and -
tetracarboxylic acids,
for example succinic acid, propanetricarboxylic acid, butanetetracarboxylic
acid,
cyclopentanetetracarboxylic acid, and alkyl- and alkenylsuccinic acids with C2-
C20-alkyl
or -alkenyl radicals.
Suitable organic builders are also hydroxycarboxylic acids and
polyhydroxycarboxylic
acids (sugar acids). These include C4-C20-hydroxycarboxylic acids, for example
malic
acid, tartaric acid, glutonic acid, mucic acid, lactic acid, glutaric acid,
citric acid,
PF 0000071519 CA 02822855 2013-06-25
12
tartronic acid, glucoheptonic acid, lactobionic acid, and sucrosemono-, -di-
and
-tricarboxylic acid. Among these, preference is given to citric acid and salts
thereof.
Suitable organic builders are also phosphonic acids, for example
hydroxyalkylphosphonic acids, aminophosphonic acids and the salts thereof.
These
include, for example, phosphonobutanetricarboxylic acid, aminotris-
methylenephosphonic acid, ethylenediaminetetraethylenephosphonic acid,
hexamethylenediaminetetramethylenephosphonic acid, diethylenetriamine-
pentamethylenephosphonic acid, morpholinomethanediphosphonic acid, 1-hydroxy-
C1-
to Co-alkyl-1,1-diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic
acid.
Among these, preference is given to 1-hydroxyethane-1,1-diphosphonic acid and
salts
thereof.
Suitable organic builders are additionally aminopolycarboxylic acids, such as
nitrilotriacetic acid (NTA), nitrilomonoacetic dipropionic acid,
nitrilotripropionic acid, p-
alaninediacetic acid (13-ADA), ethylenediaminetetraacetic acid (EDTA),
diethylenetriaminepentaacetic acid, 1,3-propylenediaminetetraacetic acid, 1,2-
propylenediaminetetraacetic acid, N-(alkyl)ethylenediaminetriacetic acid,
N-(hydroxyalkyl)ethylenediaminetriacetic acid, ethylenediaminetriacetic acid,
cyclohexylene-1,2-diaminetetraacetic acid, iminodisuccinic acid,
ethylenediaminedisuccinic acid, serinediacetic acid, isoserinediacetic acid, L-
asparaginediacetic acid, L-glutaminediacetic acid, methylglycinediacetic acid
(MGDA),
and the salts of the aforementioned aminopolycarboxylic acids. Among these,
preference is given to L-glutaminediacetic acid, methylglycinediacetic acids
and salts
thereof.
Suitable organic builders are additionally polymeric compounds containing
carboxylic
acid groups, such as acrylic acid homopolymers. These preferably have a number-
average molecular weight in the range from 800 to 70 000 g/mol, more
preferably from
900 to 50 000 g/mol, particularly from 1000 to 20 000 g/mol, especially 1000
to 10
000 g/mol. The term "acrylic acid homopolymer" also comprises polymers in
which
some or all of the carboxylic acid groups are present in neutralized form.
These include
acrylic acid homopolymers in which some or all of the carboxylic acid groups
are
present in the form of alkali metal salts or ammonium salts. Preference is
given to
acrylic acid homopolymers in which the carboxylic acid groups are protonated
or in
which some or all of the carboxylic acid groups are in the form of sodium
salts.
Suitable polymeric compounds containing carboxylic acid groups are also
oligomaleic
acids, as described, for example, in EP-A 451 508 and EP-A 396 303.
CA 02822855 2013-06-25
PF 0000071519
13
Suitable polymeric compounds containing carboxylic acid groups are also
terpolymers
of unsaturated Ca-Cs-dicarboxylic acids, where the polymerized comonomers may
include monoethylenically unsaturated monomers from group (i) specified below
in
amounts of up to 95% by weight, from group (ii) in amounts of up to 60% by
weight and
from group (iii) in amounts of up to 20% by weight. Suitable unsaturated 04-08-
dicarboxylic acids in this context are, for example, maleic acid, fumaric
acid, itaconic
acid and citraconic acid. Preference is given to maleic acid. Group (i)
comprises
monoethylenically unsaturated C3-C8-monocarboxylic acids, for example acrylic
acid,
methacrylic acid, crotonic acid and vinylacetic acid. Group (i), preference is
given to
using acrylic acid and methacrylic acid. Group (ii) comprises
monoethyienically
unsaturated C2-C22-olefins, vinyl alkyl ethers with C1-08-alkyl groups,
styrene, vinyl
esters of Cl-Ca-carboxylic acids, (meth)acrylamide and vinylpyrrolidone. From
group
(ii), preference is given to using C2-C6-olefins, vinyl alkyl ethers with Cl-
C4-alkyl groups,
vinyl acetate and vinyl propionate. If the polymers of group (ii) comprise
vinyl esters in
polymerized form, they may also be present partly or fully hydrolyzed to vinyl
alcohol
structural units. Suitable co- and terpolymers are known, for example, from US-
A
3887806 and DE-A 4313909. Group (iii) comprises (meth)acrylic esters of C1-C8-
alcohols, (meth)acrylonitrile, (meth)acrylamides of C1-C8-amines, N-
vinylformannide
and N-vinylimidazole.
Suitable polymeric compounds containing carboxylic acid groups are also
homopolymers of the monoethylenically unsaturated C3-Ca-monocarboxylic acids,
for
example acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid,
especially of
acrylic acid and methacrylic acid, copolymers of dicarboxylic acids, for
example
copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95:5,
more
preferably those in a weight ratio of from 30:70 to 90:10 with molar masses of
from
1000 to 150 000; terpolymers of maleic acid, acrylic acid and a vinyl ester of
a Cl-C3-
carboxylic acid in a weight ratio of from 10 (maleic acid):90 (acrylic acid +
vinyl ester) to
95 (maleic acid):10 (acrylic acid + vinyl ester), where the weight ratio of
acrylic acid to
the vinyl ester may vary within the range from 30:70 to 70:30; copolymers of
maleic
acid with C2-C8-olefins in a molar ratio of from 40:60 to 80:20, particular
preference
being given to copolymers of maleic acid with ethylene, propylene or isobutene
in a
molar ratio of 50:50.
Suitable polymeric compounds containing carboxylic acid groups are also
copolymers
of 50 to 98% by weight of ethylenically unsaturated weak carboxylic acids with
2 to
50% by weight of ethylenically unsaturated sulfonic acids, as described, for
example, in
EP-A-0877002. Suitable weak ethylenically unsaturated carboxylic acids are
especially
C3-Cs-monocarboxylic acids, such as acrylic acid and methacrylic acid.
Suitable
PF 0000071519 CA 02822855 2013-06-25
14
ethylenically unsaturated sulfonic acids are 2-acetylamidomethy1-1-
propanesulfonic
acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-
hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid,
allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-
propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid,
styrenesulfonic
acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate,
sulfomethylacrylamide, sulfomethylmethacrylamide and salts of these acids. The
copolymers may also comprise, in copolymerized form, 0 to 30% by weight of
ethylenically unsaturated C4-C8-dicarboxylic acids, such as maleic acid, and 0
to 30%
by weight of at least one monomer which is copolymerizable with the
aforementioned
monomers. The latter are, for example, Cl-C4-alkyl esters of (meth)acrylic
acid, C1-C4-
hydroxyalkyl esters of (meth)acrylic acid, acrylamide, alkyl-substituted
acrylamide, N,N-
dialkyl-substituted acrylamide, vinylphosphonic acid, vinyl acetate, allyl
alcohols,
sulfonated allyl alcohols, styrene and other vinylaromatics, acrylonitrile, N-
vinylpyrrolidone, N-vinylformamide, N-vinylimidazole or N-vinylpyridine. The
weight-
average molecular weight of these copolymers is within the range from 3000 to
50 000.
Particularly suitable copolymers are those with about 77% by weight of at
least one
ethylenically unsaturated C3-C6-monocarboxylic acid and about 23% by weight of
at
least one ethylenically unsaturated sulfonic acid.
Graft polymers of unsaturated carboxylic acids onto low molecular weight
carbohydrates or hydrogenated carbohydrates, cf. US-A 5227446, DE-A 4415623
and
DE-A 4313909, are likewise suitable. Suitable unsaturated carboxylic acids in
this
context are, for example, maleic acid, fumaric acid, itaconic acid, citraconic
acid, acrylic
acid, methacrylic acid, crotonic acid and vinylacetic acid and also mixtures
of acrylic
acid and maleic acid, which are grafted on in amounts of 40 to 95% by weight,
based
on the component to be grafted. For modification, it is additionally possible
for up to
30% by weight, based on the component to be grafted, of further
monoethylenically
unsaturated monomers to be present in polymerized form. Suitable modifying
monomers are the abovementioned monomers of groups (ii) and (iii). Suitable
graft
bases are degraded polysaccharides, for example acidically or enzymatically
degraded
starches, inulins or cellulose, protein hydrolyzates and reduced (hydrogenated
or
hydrogenatingly aminated) degraded polysaccharides, for example mannitol,
sorbitol,
aminosorbitol and N-alkylglucamine, as are polyalkylene glycols with molar
masses of
up to NA,, = 5000, for example polyethylene glycols, ethylene oxide/propylene
oxide or
ethylene oxide/butylene oxide or ethylene oxide/propylene oxide/butylene oxide
block
copolymers and alkoxylated mono- or polyhydric C1-C22-alcohols (cf. US-A-
5756456).
CA 02822855 2013-06-25
PF 0000071519
Likewise suitable are polyglyoxylic acids, as described, for example, in EP-B-
001004,
US-A-5399286, DE-A-4106355 and EP-A-656914. The end groups of the
polyglyoxylic
acids may have different structures.
5 Additionally suitable are polyamidocarboxylic acids and modified
polyamidocarboxylic
acids; these are, for example, known from EP-A-454126, EP-B-511037, WO-A-
94/01486 and EP-A-581452.
Polyaspartic acids or cocondensates of aspartic acid with further amino acids,
C4-C25-
10 mono- or -dicarboxylic acids and/or C4-C25-mono- or -diamines can also
be used as
polymeric compounds containing carboxylic acid groups. Particular preference
is given
to using polyaspartic acids which have been prepared in phosphorus acids and
have
been modified with C6-C22-mono- or -dicarboxylic acids or with C6-C22-mono- or
-
diamines.
Among the polymeric compounds containing carboxylic acid groups, polyacrylic
acids
are preferred, including in partly or fully neutralized form.
Suitable organic builders are also iminodisuccinic acid, oxydisuccinic acid,
aminopolycarboxylates, alkyl polyaminocarboxylates,
aminopolyalkylenephosphonates,
polyglutamates, hydrophobically modified citric acid for example agaric acid,
poly-a -
hydroxyacrylic acid, N-acylethylenediamine triacetates such as
lauroylethylenediamine
triacetate and alkylamides of ethylenediaminetetraacetic acid, such as EDTA
tallow
amide.
In addition, it is also possible to use oxidized starches as organic builders.
Preference is given to using, as component b), a mixture of different
builders.
The mixture of different builders preferably comprises at least two of the
following
constituents: at least one carbonate (e.g. sodium carbonate), at least one
silicate (e.g.
sodium disilicate), at least one polymeric compound containing carboxylic acid
groups
or at least one polymeric compound which contains carboxylic acid groups of
which all
or some are present in neutralized form (e.g. polyacrylic acid), at least one
(poly)hydroxycarboxylic acid or a salt thereof (e.g. citric acid or a
citrate), at least one
aminopolycarboxylic acid or a salt thereof (e.g. methylglycinediacetic acid or
a salt
thereof, e.g. a sodium salt thereof), at least one phosphonic acid (e.g. 1-
hydroxyethane-1-(1,1-diphosphonic acid); HEDP), at least one phosphate. More
preferably, the mixture comprises at least one carbonate, at least one
silicate and at
CA 02822855 2013-06-25
PF 0000071519
16
least one polymeric, optionally (partially) neutralized compound containing
carboxylic
acid groups, and optionally at least one of the following constituents: at
least one
(poly)hydroxycarboxylic acid or a salt thereof, at least one phosphonic acid,
at least
one phosphate. The mixture especially comprises at least one carbonate, at
least one
silicate, at least one polymeric, optionally (partially) neutralized compound
containing
carboxylic acid groups, at least one (poly)hydroxycarboxylic acid or a salt
thereof, and
at least one phosphonic acid, and optionally at least one phosphate.
In such a mixture, the constituents are present preferably in the following
amounts:
b1) at least one carbonate: 10 to 50% by weight;
b2) at least one silicate, 1 to 10% by weight;
b3) at least one polymeric, optionally (partially) neutralized compound
containing
carboxylic acid groups: 5 to 20% by weight;
b4) at least one (poly)hydroxycarboxylic acid or a salt thereof: 0 to 50%
by weight;
b5) at least one aminopolycarboxylic acid or a salt thereof: 0 to 60% by
weight;
b6) at least one phosphonic acid: 0.2 to 1% by weight;
b7) at least one phosphate: 0 to 60% by weight.
The percentages by weight are based on the total weight of the builder. The
weights
from b1) to b7) add up to 100% by weight.
The enzymes are preferably selected from hydrolases, such as proteases,
esterases,
glucosidases, lipases, amylases, cellulases, mannanases, other
glycosylhydrolases,
and mixtures of the aforementioned enzymes. All these hydrolases contribute to
dissolution and removal of soil from protein-, grease- or starch-containing
stains. For
bleaching, it is also possible to use oxidoreductases. Particularly suitable
are active
enzymatic ingredients obtained from bacterial strains or fungi, such as
Bacillus subtilis,
Bacillus licheniformis, Streptomyceus griseus and Humicola insolens.
Suitable hydrolases are, for example, a-glucosidases (EC number 3.2.1.20),
proteases
(Ovozyme (from Novozymes); EC number 3.2.1.20), amylases [Purastar0 (from
Genencor), Termamy10 (from Novozymes), Stainzyme (from Novozymes), Duramy10
(from Novozymes)], mannanases [Purabrite (from Genencor), Mannastar0 (from
Genencor), Mannaway0 (from Novozymes)] and cellulases [CarezymeC:) (from
Novozymes), Celluzyme (from Novozymes), endolase, Puradax (from Genencor)].
The suitable amylases include especially a-amylases (EC number 3.2.1.1), iso-
amylases, pullulanases and pectinases. The cellulases used are preferably
cellobiohydrolases, endoglucanases and 113-glucosidases, which are also
referred to as
cellobiases, or mixtures thereof. Since different cellulase types differ by
their CMCase
CA 02822855 2013-06-25
=
PF 0000071519
17
and Avicelase activities, it is possible to establish the desired activities
by means of
controlled mixtures of the cellulases.
Suitable lipases are esterases, such as Lipex and Lipolase. Examples of
lipolytically
active enzymes are the known cutinases.
Peroxidases or oxidases have also been found to be suitable in some cases.
The inventive dishwashing composition preferably comprises at least one
protease
and/or amylase.
The inventive dishwashing composition preferably comprises an enzyme mixture.
Preference is given, for example, to enzyme mixtures which comprise or consist
of the
following enzymes:
protease and amylase,
protease and lipase (or lipolytically active enzymes),
protease and cellulase,
amylase, cellulase and lipase (or lipolytically active enzymes),
- protease, amylase and lipase (or lipolytically active enzymes),
protease, lipase (or lipolytically active enzymes) and cellulase.
Particular preference is given to protease and/or amylase-containing mixtures.
Preferred proteases in the aforementioned mixtures are proteases of the
subtilisin type
(Savinase, etc.; EC number 3.4.21.62).
The enzymes may be adsorbed onto carriers in order to protect them from
premature
decomposition.
Optionally, the inventive washing and cleaning composition may also comprise
enzyme
stabilizers, for example calcium propionate, sodium formate or boric acids or
salts
thereof, and/or antioxidants.
The bleaches d) are preferably bleach systems which, in addition to bleaches,
optionally also comprise bleach activators, bleach catalysts and/or bleach
stabilizers.
Suitable bleaches are, for example, percarboxylic acids, for example
diperoxododecanedicarboxylic acid, phthalimidopercaproic acid or
monoperoxophthalic
acid or -terephthalic acid, salts of percarboxylic acids, for example sodium
CA 02822855 2013-06-25
PF 0000071519
18
percarbonate, adducts of hydrogen peroxide onto inorganic salts, for example
sodium
perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate
perhydrate
or sodium phosphate perhydrate, adducts of hydrogen peroxide onto organic
compounds, for example urea perhydrate, or of inorganic peroxo salts, for
example
alkali metal persulfates or peroxodisulfates.
Suitable bleach activators are, for example, polyacylated sugars, e.g.
pentaacetylglucose; acyloxybenzenesulfonic acids and their alkali metal and
alkaline
earth metal salts, e.g. sodium p-nonanoyloxybenzenesulfonate or sodium
p-benzoyloxybenzenesulfonate: N,N-diacylated and N,N,N',N'-tetraacylated
amines,
e.g. N,N,N',N'-tetraacetylmethylenediamine and -ethylenediamine (TAED), N,N-
diacetylaniline, N,N-diacetyl-p-toluidine or 1,3-diacylated hydantoins such as
1,3-
diacety1-5,5-dimethylhydantoin; N-alkyl-N-sulfonylcarbonamides, e.g. N-methyl-
N-
mesylacetamide or N-methyl-N-mesylbenzamide; N-acylated cyclic hydrazides,
acylated triazoles or urazoles, e.g. monoacetylmaleic hydrazide; 0,N,N-
trisubstituted
hydroxylamines, e.g. 0-benzoyl-N,N-succinylhydroxylamine, 0-acetyl-N,N-
succinylhydroxylamine or 0,N,N-triacetylhydroxylamine; N,N'-
diacylsulfurylamides, z.B.
N,N'-dimethyl-N,N'-diacetylsulfurylamide or N,N'-diethyl-N,N'-
dipropionylsulfurylamide;
acylated lactams, for example acetylcaprolactam, octanoylcaprolactam,
benzoylcaprolactam or carbonylbiscaprolactam; anthranil derivatives, for
example 2-
methylanthranil or 2-phenylanthranil; triacyl cyanurates, e.g. triacetyl
cyanurate or
tribenzoyl cyanurate; oxime esters and bisoxime esters, for example 0-
acetylacetone
oxime or bisisopropyl iminocarbonate; carboxylic anhydrides, e.g. acetic
anhydride,
benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride; enol
esters, for
example isopropenyl acetate; 1,3-diacy1-4,5-diacyloxyimidazolines, e.g. 1,3-
diacety1-
4,5-diacetoxyimidazoline; tetraacetylglycoluril and tetrapropionylglycoluril;
diacylated
2,5-diketopiperazines, e.g. 1,4-diacety1-2,5-diketopiperazine; ammonium-
substituted
nitrites, for example N-methylmorpholinioacetonitrile methylsulfate; acylation
products
of propylenediurea and 2,2-dimethylpropylenediurea, e.g.
tetraacetylpropylenediurea;
a -acyloxypolyacylmalonamides, e.g. a -acetoxy-N,N'-diacetylmalonamide;
diacyldioxohexahydro-1,3,5-triazines, e.g. 1,5-diacety1-2,4-dioxohexahydro-
1,3,5-
triazine; benz-(4H)-1,3-oxazin-4-ones with alkyl radicals, e.g. methyl, or
aromatic
radicals, e.g. phenyl, in the 2 position.
A bleach system composed of bleaches and bleach activators may optionally also
comprise bleach catalysts. Suitable bleach catalysts are, for example,
quaternized
imines and sulfonimines, which are described, for example, in US-A 5 360 569
and EP-
A 453 003. Particularly effective bleach catalysts are manganese complexes,
which are
described, for example, in WO-A 94/21777. In the case of use thereof in the
washing
CA 02822855 2013-06-25
PF 0000071519
19
and cleaning compositions, such compounds are incorporated at most in amounts
up
to 1.5% by weight, especially up to 0.5% by weight, and in the case of very
active
manganese complexes in amounts up to 0.1% by weight. In addition to the
described
bleach system composed of bleaches, bleach activators and optionally bleach
catalysts, it is also possible to use systems with enzymatic peroxide release
or
photoactivated bleach systems for the inventive washing and cleaning
compositions.
Surfactants from group e) other than component a) may be cationic, anionic,
zwitterionic or nonionic.
Suitable nonionic surfactants are, for example, alkoxylated, advantageously
ethoxylated, especially primary alcohols having preferably 8 to 18 carbon
atoms and an
average of 1 to 20, preferably 1 to 12, mol of ethylene oxide (E0) per mole of
alcohol,
in which the alcohol radical may be linear or preferably 2-methyl-branched, or
may
comprise linear and methyl-branched radicals in a mixture, as are typically
present in
oxo alcohol radicals. Especially preferred, however, are alcohol ethoxylates
with linear
radicals formed from alcohols of native origin having 12 to 18 carbon atoms,
for
example from coconut alcohol, palm alcohol, tallow fat alcohol or oleyl
alcohol, and an
average of 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols
include,
for example, C12-C14-alcohols with 3 E0, 4 EO or 7 E0, Cs-C11-alcohol with 7
E0, 013-
C15-alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C12-C18-alcohols with 3 EO, 5 EO
or 7 EO
and mixtures thererof, such as mixtures of C12-C14-alcohol with 3 EO and C12-
C16-
alcohol with 7 EQ. The degrees of ethoxylation stated are statistical averages
which,
for a specific product, may be an integer or a fraction. Also suitable are
alcohol
ethoxylates which have a narrowed homolog distribution (narrow range
ethoxylates,
NRE). In addition to these nonionic surfactants, it is also possible to use
fatty alcohols
with more than 12 E0. Examples thereof are tallow fat alcohol with 14 EO, 25
EO or 30
EQ. It is also possible to use nonionic surfactants which comprise EO and PO
groups
together in the molecule. In this case, it is possible to use block copolymers
with E0-
PO block units or P0-E0 block units, but also E0-P0-E0 copolymers or P0-E0-P0
copolymers. It will be appreciated that it is also possible to use mixed-
alkoxylation
nonionic surfactants in which EO and PO units are not in blockwise but in
random
distribution. Such products are obtainable by the simultaneous action of
ethylene oxide
and propylene oxide on fatty alcohols.
In addition, further nonionic surfactants used may also be alkyl glycosides of
the
general formula (1)
RaO(G)y (1)
CA 02822855 2013-06-25
PF 0000071519
in which Ra is a primary straight-chain or methyl-branched, especially 2-
methyl-
branched, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms
and G is a
glycoside unit having 5 or 6 carbon atoms, preferably glucose. The degree of
5 oligomerization y, which reports the distribution of monoglycosides and
oligoglycosides,
is any number between 1 and 10; y is preferably 1.2 to 1.4.
A further class of suitable nonionic surfactants, which can be used either as
the sole
nonionic surfactant or in combination with other nonionic surfactants, is that
of
10 alkoxylated, preferably ethoxylated or ethoxylated and propoxylated,
fatty acid alkyl
esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially
fatty acid
methyl esters as described, for example, in Japanese patent application JP
58/217598,
or which are preferably prepared by the process described in international
patent
application WO-A-90/13533.
Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-
dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and of
the fatty
acid alkanolamide type, may also be suitable. The amount of these nonionic
surfactants is preferably not more than that of the ethoxylated fatty
alcohols, especially
not more than half thereof.
Further suitable surfactants are polyhydroxy fatty acid amides of the formula
(2)
0
Rb N [Z] (2)
I,
in which RbC(=0) is an aliphatic acyl radical having 6 to 22 carbon atoms, Ftc
is
hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms, and [Z]
is a
linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3
to 10
hydroxyl groups. The polyhydroxy fatty acid amides are known substances which
can
be obtained typically by reductive amination of a reducing sugar with ammonia,
an
alkylamine or an alkanolamine, and subsequent acylation with a fatty acid, a
fatty acid
alkyl ester or a fatty acid chloride.
The group of the polyhydroxy fatty acid amides also includes compounds of the
formula
(3)
moi ot tatty acid, or in tne transestentication ot trigiycendes with O.:3 to 2
mol ot
glycerol. Preferred sulfonated fatty acid glyceryl esters are the sulfonation
products of
saturated fatty acids having 6 to 22 carbon atoms, for example of caproic
acid, caprylic
CA 02822855 2013-06-25
PF 0000071519
21
Rf¨O¨Rg
[Z]i (3)
0
in which Re is a linear or branched alkyl or alkenyl radical having 7 to 12
carbon atoms,
Rf is a linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms
or an
arylene radical having 6 to 8 carbon atoms, and Rg is a linear, branched or
cyclic alkyl
radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms,
preference
being given to C1-C4-alkyl or phenyl radicals, and [Z]l is a linear
polyhydroxyalkyl
radical, the alkyl chain of which has been substituted by at least two
hydroxyl groups,
or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this
radical. [Z]l is
preferably obtained by reductive amination of a sugar, for example glucose,
fructose,
maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-
substituted
compounds can then be converted, for example according to WO-A-95/07331, to
the
desired polyhydroxy fatty acid amides by reaction with fatty acid methyl
esters in the
presence of an alkoxide as a catalyst.
Suitable anionic surfactants are, for example, those of the sulfonate and
sulfate type.
Useful surfactants of the sulfonate type preferably include C9-C13-
alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of alkene- and
hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C12-
C18-
monoolefins with terminal or internal double bonds by sulfonation with gaseous
sulfur
trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation
products. Also
suitable are alkanesulfonates, which are obtained from C12-C15-alkanes, for
example,
by sulfochlorination or sulfoxidation with subsequent hydrolysis or
neutralization.
Equally suitable are also the esters of a-sulfo fatty acids (ester
sulfonates), for example
the a-sulfonated methyl esters of hydrogenated coconut fatty acids, palm
kernel fatty
acids or tallow fatty acids.
Further suitable anionic surfactants are sulfonated fatty acid glyceryl
esters. Fatty acid
glyceryl esters are understood to mean the mono-, di- and triesters and
mixtures
thereof, as obtained in the preparation by esterification of a monoglycerol
with 1 to 3
mol of fatty acid, or in the transesterification of triglycerides with 0.3 to
2 mol of
glycerol. Preferred sulfonated fatty acid glyceryl esters are the sulfonation
products of
saturated fatty acids having 6 to 22 carbon atoms, for example of caproic
acid, caprylic
acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or
behenic acid.
= CA 02822855 2013-06-25
PF 0000071519
22
Preferred alk(en)yl sulfates are the alkali metal salts and especially the
sodium salts of
the sulfuric monoesters of the C12-C18 fatty alcohols, for example of coconut
fatty
alcohol, tallow fatty alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol
or stearyl
alcohol, or of the C10-C20 oxo alcohols, and those monoesters of secondary
alcohols of
these chain lengths. Additionally preferred are alk(en)yl sulfates of the
chain length
mentioned, which comprise a synthetic straight-chain alkyl radical which has
been
produced on a petrochemical basis and which has analogous degradation behavior
to
the equivalent compounds based on fatty chemical raw materials. From the point
of
view of washing, the C12-C15-alkyl sulfates and Cu-Cm-alkyl sulfates, and also
C14-C15-
alkyl sulfates, are preferred. 2,3-Alkyl sulfates, which are prepared, for
example,
according to US patents 3,234,258 or 5,075,041 and can be obtained as
commercial
products from Shell Oil Company under the DAN name, are also suitable anionic
surfactants.
The sulfuric monoesters of the straight-chain or branched C7-C21-alcohols
which have
been ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched
C9-C11-
alcohols with an average of 3.5 mol of ethylene oxide (EO), or C12-C18 fatty
alcohols
with 1 to 4 EO, are also suitable. Owing to their high foaming level, they are
used in
cleaning compositions only in relatively small amounts, for example in amounts
of 1 to
5% by weight.
Further suitable anionic surfactants are also the salts of alkylsulfosuccinic
acid, which
are also referred to as sulfosuccinates or as sulfosuccinic esters, and which
are
monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably
fatty alcohols
and especially ethoxylated fatty alcohols. Preferred sulfosuccinates comprise
C8-C18
fatty alcohol radicals or mixtures thereof. Especially preferred
sulfosuccinates comprise
a fatty alcohol radical which derives from ethoxylated fatty alcohols.
Particular
preference is given in turn to sulfosuccinates whose fatty alcohol radicals
derive from
ethoxylated fatty alcohols with a narrow homolog distribution. It is likewise
also possible
to use alk(en)ylsuccinic acid having preferably 8 to 18 carbon atoms in the
alk(en)yl
chain, or salts thereof.
Suitable anionic surfactants are also soaps. Saturated and unsaturated fatty
acid soaps
are suitable, such as the salts of lauric acid, myristic acid, palmitic acid,
stearic acid,
(hydrogenated) erucic acid and behenic acid, and especially soap mixtures
derived
from natural fatty acids, for example coconut fatty acids, palm kernel fatty
acids, olive
oil fatty acids or tallow fatty acids.
CA 02822855 2013-06-25
PF 0000071519
23
The anionic surfactants including the soaps may be present in the forrn of
their sodium,
potassium or ammonium salts, or as soluble salts of organic bases, such as
mono-, di-
or triethanolamine. The anionic surfactants are preferably in the form of
their sodium or
potassium salts, especially in the form of the sodium salts.
Cationic surfactants are, for example, ammonium salts such as C8-C16-
dialkyldimethylammonium halides, dialkoxydimethylammonium halides or
imidazolinium salts with a long-chain alkyl radical.
Amphoteric surfactants are, for example, derivatives of secondary or tertiary
amines,
for example C6-C18-alkyl betaines or C6-C15-alkyl sulfobetaines, or amine
oxides such
as alkyldimethylamine oxides.
Solvents present in component e) originate, for example, from the group of
mono- or
polyhydric alcohols, alkanolamines or glycol ethers. They are preferably
selected from
ethanol, n- or isopropanol, butanols, glycol, propane- or butanediol,
glycerol, diglycol,
propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether,
ethylene glycol
ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether,
diethylene
glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl,
ethyl or
propyl ether, dipropylene glycol monomethyl or monoethyl ether, diisopropylene
glycol
monomethyl or monoethyl ether, methoxy-, ethoxy- or butoxytriglycol,
isobutoxyethoxy-
2-propanol, 3-methyl-3-methoxybutanol, propylene glycol tertbutyl ether and
mixtures
of these solvents.
Useful foam inhibitors or defoamers of component e) may, for example, be
soaps,
paraffins or silicone oils, which may optionally be applied to carrier
materials.
Suitable bases of component e) are especially the carbonates mentioned above
for the
builders.
In an alternatively preferred embodiment of the invention, the inventive
washing and
cleaning compositions are in gel form. The washing and cleaning composition
gels are
preferably dishwashing composition gels, among which particular preference is
given to
machine dishwashing composition gels. More particularly, these are dishwashing
composition gels, preferably machine dishwashing composition gels, with rinse
aid
function.
Washing and cleaning composition gels are understood to mean fluid
compositions
which, at room temperature (20 C), have a viscosity higher than that of water,
but are
CA 02822855 2013-06-25
PF 0000071519
24
still sufficiently free-flowing that they can be dosed without any problem
with
conventional dosage aids. The inventive washing and cleaning composition gels
preferably have a viscosity of 0.5 to 100, more preferably of 0.5 to 50 and
especially of
1 to 30 Pas at 20 C.
The inventive dishwashing composition gel preferably comprises the following
constituents:
a) at least one compound of the formula I;
b) at least one builder (also known as a sequestrant, structural substance,
complexing agent, chelator, chelating agent or softener);
c) optionally at least one enzyme;
d) optionally at least one bleach;
el) water;
e2) at least one thickener; and
e3) optionally at least one further additive preferably selected from
surfactants other
than a), bases, corrosion inhibitors, defoamers, dyes, fragrances, fillers,
solubilizers and organic solvents.
These constituents are preferably present in the inventive dishwashing
composition gel
in the following ratios:
a) at least one compound of the formula I: from 0.1 to 20% by weight;
b) at least one builder: from 5 to 80% by weight;
c) at least one enzyme: from 0 to 8% by weight;
d) at least one bleach: from 0 to 30% by weight;
el) water: from 10 to 90% by weight;
e2) at least one thickener: from 0.1 to 8% by weight; and
e3) at least one further additive: from 0 to 25% by weight.
The percentages by weight are based on the total weight of the dishwashing
composition. The weights of a) to e3) add up to 100% by weight.
The inventive dishwashing composition more preferably comprises at least one
enzyme.
The abovementioned constituents are more preferably present in the inventive
dishwashing composition gel in the following ratios:
a) at least one compound of the formula I: from 0.1 to 10% by weight;
b) at least one builder: from 5 to 60% by weight;
= CA 02822855 2013-06-25
PF 0000071519
c) at least one enzyme: from 0.1 to 6% by weight;
d) at least one bleach: from 0 to 30% by weight; and
el) water: from 10 to 90% by weight;
e2) at least one thickener: from 0.1 to. 6% by weight; and
5 e3) at least one further additive: from 0 to 25% by weight.
The percentages by weight are based on the total weight of the dishwashing
composition. The weights of a) to e3) add up to 100% by weight.
10 The abovementioned constituents are even more preferably present in the
inventive
dishwashing composition gel in the following ratios:
a) at least one compound of the formula I: from 0.1 to 10% by weight;
b) at least one builder: from 5 to 40% by weight;
15 c) at least one enzyme: from 0.1 to 6% by weight;
d) at least one bleach: from 0 to 25% by weight; and
el) water: from 20 to 80% by weight;
e2) at least one thickener: from 0.3 to 50% by weight; and
e3) at least one further additive: from 0 to 25% by weight.
The percentages by weight are based on the total weight of the dishwashing
composition. The weights of a) to e3) add up to 100% by weight.
The thickeners serve to impart the desired viscosity to the inventive
dishwashing
composition.
Any known thickener (rheology modifier) is suitable in principle, provided
that it does
not exert any adverse effect on the efficacy of the dishwashing composition.
Suitable
thickeners may either be of natural origin or of synthetic nature.
Examples of thickeners of natural origin are xanthan, carob flour, guar flour,
carrageenan, agar, tragacanth, gum arabic, alginates, modified starches such
as
hydroxyethyl starch, starch phosphate esters or starch acetates, dextrins,
pectins and
cellulose derivatives, such as carboxymethylcellulose, hydroxyethylcellulose,
hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose and the
like.
Thickeners of natural origin are also inorganic thickeners, such as
polysilicic acids and
clay minerals, for example sheet silicates, and also the silicates mentioned
for the
builders.
= CA 02822855 2013-06-25
PF 0000071519
26
Examples of synthetic thickeners are polyacrylic and polymethacrylic
compounds, such
as (partly) crosslinked homopolymers of acrylic acid, for example homopolymers
of
acrylic acid which have been crosslinked with an allyl ether of sucrose or
pentaery-
thritol, or with propylene (carbomers), for example the Carbopol brands from
BF
Goodrich (e.g. Carbopol 676, 940, 941, 934 and the like) or the Polygel0
brands from
3V Sigma (e.g. Polygel DA), copolymers of ethylenically unsaturated mono- or
dicarboxylic acids, for example terpolymers of acrylic acid, methacrylic acid
or maleic
acid with methyl acrylate or ethyl acrylate and a (meth)acrylate which derives
from
long-chain ethoxylated alcohols, for example the Acusol brands from Rohm &
Haas
(e.g. Acusol 820 or 1206A), copolymers of two or more monomers which are
selected
from acrylic acid, methacrylic acid and the C1-C4-alkyl esters thereof, for
example
copolymers of methacrylic acid, butyl acrylate and methyl methacrylate or of
butyl
acrylate and methyl methacrylate, for example the Aculyn and Acusol brands
from
Rohm & Haas (e.g. Aculyn0 22, 28 or 33 and Acusol 810, 823 and 830), or
crosslinked high molecular weight acrylic acid copolymers, for example
copolymers of
C10-C30-alkyl acrylates with one or more comonomers selected from acrylic
acid,
methacrylic acid and the C1-C4-alkyl esters thereof, said copolymers having
been
crosslinked with an ally' ether of sucrose or pentaerythritol (e.g. Carbopol
ETD 2623,
Carbopol 1382 or Carbopol AQUA 30 from Rohm & Haas).
Examples of synthetic thickeners are also reaction products of maleic acid
polymers
with ethoxylated long-chain alcohols, for example the Surfonic L series from
Texaco
Chemical Co. or Gantrez AN-119 from ISP; polyethylene glycols, polyamides,
polyimines and polycarboxylic acids.
Also suitable are mixtures of the abovementioned thickeners.
Preferred thickeners are xanthans and the abovementioned polyacrylic and
polymethacrylic compounds.
With regard to suitable and preferred components a) to d) and e3), reference
is made
to the above remarks.
The compounds I used in accordance with the invention are notable for a high
melting
point compared to customary prior art surfactants, which allows the use
thererof in solid
washing and cleaning compositions. They have no strong tendency, if any, to
form
foam, they have a good deposit-inhibiting action on dishware washed therewith,
especially in relation to spotting, and they are not hydrolysis-labile.
CA 02822855 2013-06-25
PF 0000071519
27
The application is now illustrated further by the nonlimiting examples which
follow.
Examples
1. Synthesis examples
General method
1.1 Preparation of alkyloxy ethylene glycol dodecylmercaptoethanols
1.1.1 Preparation of the alcohol ethoxylate:
In a 2 I autoclave from Mettler, the alcohol to be alkoxylated (isotridecanol,
2-
propylheptanol or C12/C14-alcohol; 1.0 eq) is admixed with an aqueous KOH
solution
which comprises 50% by weight of KOH. The amount of KOH is 0.2% by weight of
the
product to be prepared. While stirring, the mixture is dewatered at 100 C and
20 mbar
for 2 h. This is followed by purging three times with N2, establishing an
initial pressure
of approx. 1.3 bar of N2 and increasing the temperature to 120 C. The ethylene
oxide
(n mol eq.) is metered in such that the temperature remains between 125 and
135 C.
This is followed by stirring at 125 C for a further 5 h, purging with N2,
cooling to 70 C
and emptying the reactor. The crude product is degassed on the rotary
evaporator at
100 C (<20 mbar) for 2 h. This basic crude product can be deionized with
commercial
magnesium silicates, which are subsequently filtered off. Alternatively, the
neutralization can also be performed with the aid of acetic acid. The light-
colored
product is characterized with the aid of 1H NMR spectrum in CDCI3 and gel
permeation
chromatography, and also an OH number determination, and the yield is
determined
(>98%).
1.1.2 Reaction with dodecylmercaptoethanol
A 500 ml apparatus with a water trap is initially charged with the alkoxylate
from
example 1.1.1 (1 mol eq.), para-toluenesulfonic acid (0.005 mol eq.) and
toluene. The
reaction mixture is heated to reflux. Dodecylmercaptoethanol (x mol eq.) is
added
dropwise. The water which forms is removed by means of a water trap overnight.
The
reaction mixture is cooled, neutralized with sodium carbonate (0.005 mol eq.),
filtered
and freed completely of the solvent at 100 C and 6 mbar. This gave a white
solid
product. The structure was determined by TAI NMR (`)/0 OH groups converted).
The
CA 02822855 2013-06-25
=
PF 0000071519
28
residual amount of toluene (always <0.5%) and dodecylmercaptoethanol was
determined by means of GC.
Name Structure n x Conversion Residue of
[%]*
dodecylmercaptoethanol
IN**
= i-C13 - 35 EO - 35 1.0 93 0.1
dodecylmercaptoethanol
2PH - 35 E0 - 35 1.2 94 0.1
dodecylmercaptoethanol
= C12/C14 alcohol -27 EO - 27 1.2 94 0.1
dodecylmercaptoethanol
= i-C13- 40 E0 - 40 1.0 84 0.1
dodecylmercaptoethanol
* according to TAI NMR
** according to quant. GC
i-C13 = "isotridecanol"; mixture of different tridecanol isomers
EO = ethylene oxide
PO = propylene oxide
2PH = 2-propylheptanol
1.2. Oxidation of the product C to the corresponding sulfoxide D
71.6 g of the above-described product C (40 mmol, 1 mol eq.) were melted in a
250 ml
flask, introduced into water and heated to 70 C. Hydrogen peroxide (50%) (4.1
g,
60 mmol, 1.5 mol eq.) was added dropwise. The reaction mixture was stirred at
70 C
for 2 hours, then cooled and concentrated at 100 C and 6 mbar. This gave 69.2
g (96%
yield) of a solid yellow product. The absence of hydrogen peroxide was checked
by
means of IR, and the conversion (100%) was determined by means of 1H NMR.
Method description for TAI NMR:
In order to be able to (quantitatively) determine signals of primary and/or
secondary
alcohols superimposed in the 1H NMR spectrum, a sample in CDCI3 is admixed
with an
excess of TAI (trichloroacetyl isocyanate). The isocyanate reacts immediately
with the
alcohol groups to give the carbamate. The compounds CI3CC(0)NHC(0)-00-12R or
CI3CC(0)NHC(0)-OCH-RR' present therein have different, typical shifts for OCH2
and
OCHRR' in the 1H NMR spectrum.
The typical shift range for "primary carbamates" is 4.0 to 4.5 ppm, while that
for
"secondary carbamates" is 5.0 to 5.3 ppm.
CA 02822855 2013-06-25
PF 0000071519
29
2 Use examples
Various surfactants were tested in this application. A is a comparative
polymer.
Name Surfactant
A C6-C10 alcohol - 1 PO - 20 EO - 1 De0 (according to WO
94/22800)
i-C13- 35 EO - dodecylmercaptoethanol
2PH - 35 EO - dodecylmercaptoethanol
2PH - 35 EO - dodecylmercaptoethanol oxidized to sulfoxide
C12/C1.4 alcohol - 27 EO - dodecylmercaptoethanol
i-C13- 40 EO - dodecylmercaptoethanol
PO = propylene oxide
EO = ethylene oxide
De0 = 1,2-decene oxide
i-C13 = "isotridecanol"; mixture of differant tridecanol isomers
2PH = 2-propylheptanol
2.1 Melting point determinations
The melting points were measured by DSC (differential scanning calorimetry).
Surfactant A
Melting point [ C] 33.1 40.1 41.8 41.1 44.1 44.9
2.2 Foam volume in a machine dishwasher
The foam volume was determined indirectly by the measurement of foam formation
via
the speed of the spray arm of the machine dishwasher. For this purpose, 10 ml
of
beaten chicken egg, 19 g of a base dishwashing composition (48 parts sodium
metasilicate x 5H20, 45 parts sodium triphosphate, 5 parts sodium carbonate)
and 1 g
of the surfactant (A-F) were introduced into the dishwasher (Miele Desinfektor
G 7735
CD MCU; programmable control unit MCU version SO4.01). At different
temperatures,
the number of rotations of the spray arm was then measured. The spray arm is
slowed
down at a high foam level; it can work with the highest possible speed
(approx. (125
rpm) at a low foam level. The peak speed of the dishwasher is usually approx.
125 rpm
when no foam is present. The maximum speed in the machine dishwasher was set
artificially in the present test (by means of bores on the spray arm, position
of the
CA 02822855 2013-06-25
=
PF 0000071519
nozzles), in order to obtain a broader range which allows better distinction
of the
products.
The rotation rate was measured at 40, 50 and 60 C. The table which follows
lists the
5 rotor speeds in rpm at different temperatures.
Temperature A
[ C] 119 99 128 122 84 89
50[0C] 121 111 131 122 106 90
60 [ C] 122 117 122 122 117 101
2.3 Rinse aid test
10 All examples were carried out with a base formulation of the following
composition:
1 part by weight of protease (Ovozyme0 64 T)
0.2 part by weight of amylase (Stainzyme0 12 T)
3 parts by weight of surfactant
15 10 parts by weight of polyacrylic acid with molar mass 4000 g/mol
(Sokalan PA 25
Cl)
10.5 parts by weight of sodium percarbonate
4 parts by weight of tetraacetylethylenediamine
2 parts by weight of sodium disilicate (Britesil0 H 265 LC)
20 18.8 parts by weight of sodium carbonate
33 parts by weight of sodium citrate dihydrate
15 parts by weight of methylglycinediacetic acid trisodium salt (Trilon0 M)
0.5 part by weight of 1-hydroxyethane-(1,1-diphosphonic acid) (HEDP; Cublen K
8514 GR)
Ovozyme and Stainzyme are brand names of Novozymes, Sokalan0 and Trilon
are brand names of BASF SE, Britesil0 is a brand name of PQ Corp., Cublen0 is
a
brand name of Zschimmer&Schwarz Mohsdorf GmbH & Co KG.
All rinse aid tests were carried out in a Miele machine dishwasher (G1222
SCL). The
program at 50 C (R time 2) was selected for the wash cycle, and 65 C for the
rinse
cycle. The tests were conducted with hardened water with water hardness 21 dH
(Ca/Mg):HCO3 (3:1):1.35. No separate rinse aid was added, and the incorporated
water
softener (ion exchanger) was not regenerated with regenerating salt. The
abovementioned formulation was used in a dosage of 21 g in each case. For each
CA 02822855 2013-06-25
PF 0000071519
31
rinse cycle, 100 g of ballast soil consisting of grease, protein and starch
was added.
The test dishware in each cleaning cycle was Cronnargan knives, blue melamine
plates, glasses and porcelain plates. Between the rinse cycles, there was a
wait period
of one hour in each case, 10 min with the door closed, 50 min with the door
open.
After the sixth rinse cycle had ended, the dishware was inspected visually in
a
darkened chamber under light behind an aperture plate, and assessed according
to a
scale of marks from 1 (= severe residues) to 10 (= no residues) with regard to
deposits
in the form of spots, streaks and films.
Spotting marks A
Knives 1 5 2 2 5 2
Glasses 1 2 1 2 1 1
Melamine plates 1 3 2 2 2 3
Total 3 10 5 6 8 6
Filming marks A
Knives 6 6 5 6 5 6
Glasses 6 5 5 7 5 5
Melamine plates 6 7 7 9 7 7
Total 18 18 17 22 17 18
2.4 Stability tests over the use range
Test analogous to 2.2. The rotation speed was measured at maximum temperature
(57 C - 70 C) over a period of 2 h. In the table below, the rotation speeds
are listed in
rpm. Below the rotation speed, the exact temperatures are listed in square
brackets.
Time 10 20 30 40 50 60 70 80 90 100 110 120
[min]
A 129 127 128 125 127 127 127 127 126 126 124 122
[60] [61] [62] [64] [64] [65] [67] [68] [68] [68] [68] [69]
B 119 121 122 118 117 117 116 114 111 108 104 97
[57] [58] [59] [60] [61] [62] [63] [64] [65] [66] [67] [68]
C 114 115 118 117 122 126 125 125 126 123 124 125
[58] [60] [61] [62] [63] [64] [65] [66] [67] [68] [69] [70]
D 117 119 118 120 120 122 122 120 120 121 119 120
[58] [60] [61] [62] [64] [65] [66] [67] [68] [68] [69] [70]
E 123 124 122 122 121 119 119 115 113 113 109 111
CA 02822855 2013-06-25
PF 0000071519
32
Time 10 20 30 40 50 60 70 80 90 100 110 120 I
[min]
[59] [60] [61] [63] [64] [65] [66] [67] [68] [69] [70] [70]
F 103 97 97 99 104 102 105 104 104 105 104 102
[58] [58] [59] [60] [61] [62] [63] [64] [65] [63] [66] [67]
