Note: Descriptions are shown in the official language in which they were submitted.
. PF 72944 CA 02850127 2014-03-26
,
Preparations, their production and use
Description
The present invention relates to the use of preparations comprising
(al) at least one copolymer obtainable by copolymerization of
(a1.1) at least one N-vinylamide,
(a1.2) vinyl acetate,
(a1.3) at least one polyether,
(a1.4) optionally at least one further comonomer,
(a2) at least one alkoxylate of the general formula (I)
R1-(OCH2CHR2)m0R3 (I)
where the variables are defined as follows:
R1 is Ca-C24-alkyl, linear or branched,
R2 is Cl-Cio-alkyl, in each case identical or different, linear or
branched, or hydrogen,
R3 is hydrogen or Cl-C4-alkyl, linear or branched,
m is a number in the range from 1 to 100,
in formulations for automatic dishwashing.
The present invention further relates to the use of specific copolymers.
Demanding requirements are placed on formulations for machine dishwashing.
Besides the
actual residue-free cleaning, it is desirable to obtain dishes, metal objects
and glasses which
shine faultlessly. Up until about 2001, in many cases, a detergent, a rinse
aid and a so-called
regenerating salt were therefore metered separately into the dishwasher, the
regenerating salt
having the task of binding calcium ions and magnesium ions, and the rinse aid
having the task
of ensuring water runs off the whole area of the ware and preventing the
formation of lime
marks and water marks.
"3 in 1" dishwashing detergents introduced since then combine the function of
detergent, rinse
aid and regenerating salt in one product. As a result, there is no need for
the consumer to
replenish rinse aid and salt in the dishwasher. The incorporation of further
functions (e.g.
protection against glass corrosion and protection against the tarnishing of
silver) led to the
development of x in 1 (where e.g. x = 6 or 9) or "all in one" products.
WO 2008/132131 discloses the use of a combination of at least one alcohol
alkoxylate, at least
one short-chain alcohol ethoxylate, at least one sulfonate-group-containing
polymer and/or at
PF 72944 CA 02850127 2014-03-26
A 2
least one hydrophilically modified polycarboxylate and optionally a
polycarboxylate, together
with generally customary further constituents, for improving the clear-rinse
performance in
phosphate-containing and in phosphate-free machine dishwashing detergents.
DE 102 33 834 A discloses, as nonionic surfactants in compositions for machine
dishwashing,
alkoxylated, preferably ethoxylated, primary alcohols having 8 to 18 carbon
atoms and on
average Ito 12 mol of ethylene oxide (EO) per mole of alcohol. Preference is
given to alcohol
ethoxylates of alcohols of native origin having 12 to 18 carbon atoms, such as
coconut, palm,
tallow fatty or oleyl alcohol, having on average 2 to 8 mol of EO per mole of
alcohol.
Many "X in 1" or "all-in-one" dishwashing detergents still do not achieve the
good clear-rinse
result which can be achieved with the use of separate rinse aid, namely streak-
free and droplet-
free run-off of the water from the dishes such that they are obtained in a
shiny form and without
dried-on water drops (spotting). It has also been found that when washing
especially in
somewhat harder water, i.e. at 10 German hardness and above, the filming can
also be
improved. In this connection, filming is understood as meaning the formation
of an undesired
deposit over an area. Accordingly, the values for filming are better the more
uniform and smaller
the deposits arising on the surfaces of the objects to be washed.
It was therefore the object to provide formulations which can be used in "X in
1" or "all in one"
dishwashing detergents such that the rinse aid or rinse aids can be dosed for
example via a
tablet in the main wash cycle, but a good effect is only observed in the clear-
rinse cycle.
Accordingly, the use of preparations defined at the start in formulations for
machine
dishwashing have been found, also called preparations used according to the
invention for
short.
Preparations used according to the invention comprise
(al) at least one copolymer, also called copolymer (al) for short. Copolymer
(al) is obtainable
by copolymerization of
(a1.1) at least one N-vinylamide, for example N-vinylformamide or
N-vinylacetamide,
preferably at least one N-vinyllactam, for example N-vinylpyrrolidone and N-
vinylcaprolactam,
(a1.2) vinyl acetate,
(a1.3) at least one polyether,
(a1.4) optionally at least one further comonomer, for example (meth)acrylic
acid,
(meth)acrylonitrile and C1-C4-alkyl (meth)acrylates.
PF 72944 CA 02850127 2014-03-26
3
Examples of suitable polyethers (a1.3) are polybutylene glycols, obtainable by
the
polymerization of 2,3-dimethyloxirane or 2-ethyloxirane. Preferred polyethers
(a1.3) are
selected from polyethylene glycol, polypropylene glycol and
polytetrahydrofuran, and from
mixed polymers of ethylene oxide and propylene oxide and/or 2,3-
dimethyloxirane or
2-ethyloxirane. The aforementioned mixed polymers of ethylene oxide and
propylene oxide
and/or 2,3-dimethyloxirane or 2-ethyloxirane can be random copolymers or block
copolymers,
for example those of ethylene oxide and propylene oxide may be of the AB type
or of the ABA
type.
Polyether (a1.3) can be unilaterally or bilaterally etherified with C1-C20-
alkanol or an alkylating
agent, in each case identical or different, preferably with C1-C18-alkanol,
for example with
methanol, ethanol, n-butanol, isopropanol, n-propanol, isobutanol, n-pentanol,
n-hexanol,
n-octanol, n-nonanol, n-decanol, n-dodecyl alcohol, n-tridecanol, n-
hexadecanol or
n-octadecanol.
In another embodiment of the present invention, polyether (a1.3) is a diol.
In one embodiment of the present invention, polyether (a1.3) has an average
molecular weight
Mw in the range from 1000 to 100 000 g/mol, preferably 1500 to 35 000 g/mol,
particularly
preferably 10 000 g/mol. The average molecular weights Mw are determined
starting from the
OH number measured in accordance with DIN 53240, or by gel permeation
chromatography
(GPC).
In a preferred embodiment of the present invention, copolymer (al) is a graft
copolymer in
which at least one polyether (a1.3) serves as graft base onto which N-
vinylamide (a1.1), vinyl
acetate (a1.2) and optionally at least one further comonomer (a1.4) are
grafted, for example by
free-radical copolymerization.
In one embodiment of the present invention, in those copolymers (al) which are
graft
Examples of suitable further comonomers (a1.4) are (meth)acrylic acid,
(meth)acrylonitrile and
Cl-C4-alkyl (meth)acrylates, preferably acrylic acid, methyl acrylate, ethyl
acrylate and n-butyl
acrylate.
M, in the range from 90 000 to 140 000 g/mol, determined by GPC.
PF 72944 CA 02850127 2014-03-26
4
In one embodiment of the present invention, copolymer (al) has a K value in
accordance with
Fikentscher in the range from 10 to 60, preferably 15 to 40, measured in a 1%
by weight
ethanolic solution at room temperature.
In one embodiment of the present invention, copolymer (al) comprises, in
polymerized-in form:
in total in the range from 30 to 80% by weight, preferably 40 to 70% by
weight, particularly
preferably 50 to 60% by weight, of N-vinylamide (a1.1),
in total in the range from 10 to 50% by weight, preferably 15 to 35% by
weight, particularly
preferably 25 to 35% by weight, of vinyl acetate (a1.2),
in total in the range from 10 to 50% by weight, preferably up to 30% by
weight, particularly
preferably up to 25% by weight and very particularly preferably up to 20% by
weight, of
polyether (a1.3),
in total in the range from zero to 10% by weight of comonomer(s) (a1.4),
in each case based on the mass of the total copolymer (al).
Preparations used according to the invention furthermore comprise
(a2) at least one alkoxylate of the general formula (I),
R1-(OCH2CHR2)m0R3 (I)
also called alkoxylate (a2) for short, in which the variables are:
R1 is C5-C24-alkyl, branched or preferably linear, for example n-octyl,
n-decyl, n-dodecyl,
n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl,
R2 is Cl-Clo-alkyl, in each case identical or different, linear or
branched, methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,
isoamyl, isopentyl;
n-hexyl, isohexyl, sec.-hexyl, n-octyl, n-decyl, isodecyl, particularly
preferably methyl
or preferably hydrogen,
R3 is hydrogen or C1-C4-alkyl, branched or preferably linear, for
example methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, particularly
preferably methyl or
n-butyl,
m is a number in the range from 1 to 100. The number m refers to an
average value and can
be an integer, but does not have to be an integer.
Alkoxylates of the formula (I) can, if m is chosen to be greater than 1 and at
least two R2 are
different from one another, be random copolymers or block copolymers; they are
preferably
block copolymers. In embodiments in which the groups R2 are different and m is
chosen to be
, PF 72944 CA 02850127 2014-03-26
- 5
greater than 3, preferably greater than 5, the different alkoxide units can be
arranged in
alkoxylate (a2) in random distribution or blockwise, preferably blockwise.
Preferred alkoxylates (a2) are alkoxylated, preferably ethoxylated, primary
alkanols having 8 to
18 carbon atoms and on average 1 to 12 mol of ethylene oxide (BO) per mole of
alkanol.
Particular preference is given to alkoxylates of alcohols of native origin
having 12 to 18 carbon
atoms, such as coconut, palm, tallow fatty or oleyl alcohol, ethoxylated with
on average 2 to 8
mol of EO per mole of C5-C15-alkanol. By way of example, mention may be made
specifically of
C12-C14-alkanols, ethoxylated with on average 3 or 4 mol of EO per mole of
alkanol, C9-C11-
alkanols, ethoxylated with on average 7 mol of BO per mole of alkanol, C13-C15-
alkohols,
ethoxylated with on average 3, 5, 7 or 8 mol of BO per mole of alkanol, and
also C12-C15-
alcohols, ethoxylated with on average 5 mol of BO per mole of alkanol.
Furthermore, mention may specifically be made of
- mixtures of C13- to C15-0X0 alcohols, alkoxylated with 9 mol of ethylene
oxide and 2 mol of
butylene oxide per mole,
- iso-C10-alkohols, alkoxylated with 10 mol of ethylene oxide and
on average 1.5 mol of
1 ,2-pentene oxide,
- Clo- to C12-fatty alcohols, alkoxylated with 9 mol of ethylene
oxide and 5 mol of propylene
oxide,
- C13- to C15-oxo alcohols, alkoxylated with on average 4.46 mol of
ethylene oxide +
0.86 mol of butylene oxide, terminally capped in a single position with a
methyl group,
- 2-propylheptanol, alkoxylated with 4.5 mol of ethylene oxide and
on average 0.9 mol of
propylene oxide
and mixtures of at least two of the aforementioned alkoxides (a2).
Of alkoxylates of the formula (I), preference is given to ethoxylates of the
formula (II)
R1-(OCH2CH2)¨OR3 (II)
where
R1 is a linear C16-C15-alkyl radical,
R3 is a linear or branched Cl-C6-alkyl or preferably hydrogen,
x is in the range from 8 to 10, preferably 8, 9 or 10.
Particularly preferred ethoxylates of the formula (II) are those based on
tallow fatty alcohols
(C16-C15-alcohols) having on average 9 mol of ethylene oxide per mole of
tallow fatty alcohol.
Preferred linear C16-C15-alkanols are n-hexadecanol and n-octadecanol. These
can be obtained
by hydrogenation of natural tallow fat. Also of suitability, however, is the
linear C17-alkanol.
PF 72944 CA 02850127 2014-03-26
6
Mixtures of linear C16- and C16-alkanols of natural origin are also known as
tallow fatty alcohol.
Tallow fatty alcohols have a small proportion of unsaturated fractions, in
particular fractions of
mono- or polyunsaturated 016- and 018-alcohols. However, based on the amount
of alcohol,
these are generally at most 5% by weight, preferably 0.1 to 2% by weight.
Within the context of
the present invention, tallow fatty alcohols should preferably be included
under C16-018-alkanols
on account of the only slight contamination with unsaturated alkanols.
In one embodiment of the present invention, preparations used according to the
invention
comprise in the range from 1 to 60% by weight of copolymer (al) and 40 to 99%
by weight of
alkoxylate (a2), preferably 1 to 50% by weight of copolymer (al) and 50 to 99%
by weight of
alkoxylate (a2).
In one embodiment of the present invention, copolymer (al) and alkoxylate (a2)
are present in
preparations used according to the invention as a solid solution. In this
connection, the term
"solid solution" is intended to refer to a state in which copolymer (al) is in
microdisperse
distribution, or ideally in molecularly disperse distribution, in a solid
matrix of alkoxylate (a2), as
can be shown, for example, by microscopy.
In one embodiment of the present invention, preparations used according to the
invention (a)
are in the form of pourable and flowable water-soluble powders.
In one embodiment of the present invention, preparations used according to the
invention (a)
are in the form of powders with an average particle diameter in the range from
100 to 1500 pm.
In another embodiment of the present invention, preparations used according to
the invention
(a) are in the form of granules.
In another embodiment of the present invention, preparations used according to
the invention
(a) are in the form of compact mixtures or of a layer, for example as spheres
or hemispheres for
dishwasher tablets or in the form of coatings of whole dishwasher tablets or
as coatings of parts
of dishwasher tablets, for example individual surfaces or segments of surfaces
of dishwasher
tablets.
Using preparations used according to the invention as or for producing
formulations for
dishwashing gives dishes which are superbly cleaned and in particular have few
lime marks.
Furthermore, when using formulations described above, washed dishes exhibit
very good
filming properties.
The present invention further provides the use of preparations used according
to the invention
in formulations for machine dishwashing, also called use according to the
invention for short.
The present invention further provides a machine dishwashing method using at
least one
formulation used according to the invention. The present invention further
provides formulations
for machine dishwashing comprising at least one preparation used according to
the invention,
PF 72944 CA 02850127 2014-03-26
7
for example in the range from 0.1 to 20% by weight, based on the formulation
used according to
the invention.
In one embodiment of the present invention, formulations used according to the
invention
comprise:
(a) in total in the range from 0.1 to 20% by weight of at least one
preparation used
according to the invention, preferably 0.5 to 15% by weight, particularly
preferably 1
to 10% by weight,
(b) in total in the range from 0 to 10% by weight of nonionic surfactant which
is different
from copolymer (al) and from alkoxylate (a2), also called surfactant (b) for
short,
(C) in total in the range from 0 to 20% by weight of one or more
polycarboxylates, also
called polycarboxylate (c) for short,
(d) in total in the range from 0 to 50% by weight of complex formers which are
different
from inorganic phosphates, also called complex formers (d) for short,
(e) in total in the range from 0 to 70% by weight of one or more inorganic
phosphates,
also called phosphate (e) for short,
(f) in total in the range from 0 to 60% by weight of further builders and
cobuilders which
are in each case different from complex formers (d), also called builders (f)
or
cobuilders (f) for short,
(g) in total in the range from 0 to 30% by weight of bleaches, also called
bleaches (g) for
short, and optionally bleach activators or bleach catalysts,
(h) in total in the range from 0 to 8% by weight of enzyme(s),
(i) in total in the range from 0 to 50% by weight of one or more further
additives,
and optionally water.
Here, data in `)/0 by weight are based on total solids content of formulation
used according to the
invention.
In one embodiment of the present invention, formulations used according to the
invention have
a pH in the range from 5 to 14, preferably 8 to 13.
In one embodiment of the present invention, formulations used according to the
invention can
have a water content in the range from 0.1 to 10% by weight, based on the
total solids content
of formulation used according to the invention.
Surfactant (b) can also be referred to below as component (b). Polycarboxylate
(c) can also be
referred to below as component (c). Complex former (d) can also be referred to
below as
component (d), etc. Preferably, formulations used according to the invention
comprise at least
one substance selected from component (b) to component (i), where component
(i) is different
from water.
PF 72944 CA 02850127 2014-03-26
8
In one embodiment of the present invention, additives (i) are selected from
anionic or
zwitterionic surfactants, alkali carriers, corrosion inhibitors, antifoams,
dyes, fragrances, fillers,
organic solvents, tableting auxiliaries, disintegrants, thickeners and
solubility promoters.
Components (b) to (i) are described in more detail below by way of example.
Besides the nonionic surfactants of component (a) present in preparations (a)
used according to
the invention, formulations used according to the invention can comprise up to
10% by weight of
surfactant(s) (b), for example weakly or low-foaming nonionic surfactants.
Preferably, formulations used according to the invention comprise in total in
the range from 0.1
to 10% by weight, preferably from 0.25 to 5% by weight, of surfactant (b).
In one embodiment of the present invention, surfactant (b) is selected from di-
and multiblock
In another embodiment of the present invention, surfactant (b) is selected
from reaction
products of sorbitan esters with ethylene oxide and/or propylene oxide.
Further suitable
surfactants (b) are selected from ethoxylated or propoxylated sorbitan esters.
Amine oxides or
In one embodiment of the present invention, formulations used according to the
invention
comprise a mixture of two or more different surfactants (b).
In one embodiment of the present invention, preparation used according to the
invention
comprises at least one polycarboxylate (c), for example alkali metal salts of
(meth)acrylic acid
homopolymers or (meth)acrylic acid copolymers. Preferably, formulations used
according to the
invention comprise in total in the range from 0.1 to 20% by weight of
polycaboxylate(s) (c).
Suitable comonomers for (meth)acrylic acid copolymers are monoethylenically
unsaturated
dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride,
itaconic acid and
citraconic acid. A suitable acrylic acid polymer is in particular polyacrylic
acid, which preferably
has an average molecular weight M, in the range from 2000 to 40 000 g/mol,
preferably 2000 to
It is also possible to use copolymers of at least one monomer from the group
consisting of
PF 72944 CA 02850127 2014-03-26
9
Suitable hydrophobic monomers are, for example, isobutene, diisobutene,
butene, pentene,
hexene and styrene, olefins having 10 or more carbon atoms or mixtures
thereof, such as, for
example, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-
eicosene,
1-docosene, 1-tetracosene and 1-hexacosene, C22-a-olefin, a mixture of C20-C24-
a-olefines and
polyisobutene having on average 12 to 100 carbon atoms.
Suitable hydrophilic monomers are monomers with sulfonate or phosphonate
groups, and also
nonionic monomers with hydroxy function or alkylene oxide groups. By way of
example,
mention may be made of: allyl alcohol, isoprenol, methoxypolyethylene glycol
(meth)acrylate,
methoxypolypropylene glycol (meth)acrylate, methoxypolybutylene glycol
(meth)acrylate,
methoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate,
ethoxypolyethylene glycol
(meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene
glycol
(meth)acrylate and ethoxypoly(propylene oxide-co-ethylene oxide)
(meth)acrylate. The
polyalkylene glycols here comprise 3 to 50, in particular 5 to 40 and
especially 10 to 30 alkylene
oxide units.
Particularly preferred sulfonic-acid-group-containing monomers here are 1-
acrylamido-1-
propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-
methylpropane-
sulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-
2-
hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid,
allyloxybenzenesulfonic
acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-
propenyloxy)propanesulfonic acid, 2-
methy1-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-
sulfopropyl acrylate,
2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide,
sulfomethyl-
methacrylamide, and salts of said acids, such as sodium, potassium or ammonium
salts thereof.
Particularly preferred phosphonate-group-containing monomers are
vinylphosphonic acid and
its salts.
In one embodiment of the present invention, formulations used according to the
invention
comprise in the region of up to 50% by weight of complex former (d), for
example at least 0.1%
by weight, preferably 1 to 45% by weight and particularly preferably 1 to 40%
by weight.
Preferred complex formers (d) are selected from aminocarboxylates and
polyaminocarboxylates
and salts thereof, in particular alkali metal salts, and derivatives thereof,
such as, for example,
methyl esters.
Within the context of the present invention, aminocarboxylates are understood
as meaning
nitrilotriacetic acid and those organic compounds which have a tertiary group
which has one or
two CH2-000H groups which - as mentioned above - can be partially or
completely
neutralized. Within the context of the present invention,
polyaminocarboxylates are understood
as meaning those organic compounds which have at least two tertiary amino
groups which,
PF 72944 CA 02850127 2014-03-26
independently of one another, each have one or two CH2-COOH groups which - as
mentioned
above - can be partially or completely neutralized.
In another embodiment of the present invention, aminocarboxylates are selected
from those
5 organic compounds which have a secondary amino group which has one or two
CH(COOH)CH2-COOH group(s) which - as mentioned above - can be partially or
completely
neutralized. In another embodiment of the present invention,
polyaminocarboxylates are
selected from those organic compounds which have at least two secondary amino
groups which
each have a CH(COOH)CH2-COOH group which - as mentioned above - can be
partially or
10 completely neutralized.
Particularly preferred aminocarboxylates and polyaminocarboxylates are
selected from nitrilo-
triacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA),
diethylenetriaminepentaacetic
acid, hydroxyethylethylenediaminetriacetic acid and methylglycinediacetic acid
(MGDA),
glutamic acid-diacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic
acid, ethylenediamine-
disuccinic acid, aspartic acid-diacetic acid, and salts thereof, for example
alkali metal salts
thereof, in particular potassium and sodium salts thereof. Particularly
preferred complex formers
(d) are methylglycinediacetic acid and salts thereof.
As component (e), formulation used according to the invention can comprise in
the region of up
to 70% by weight of phosphate (e), for example in the range from 5 to 60% by
weight,
particularly preferably in the range from 20 to 55% by weight.
Examples of phosphates (e) are in particular alkali metal phosphates and
polymeric alkali metal
phosphates, which can be selected in the form of their alkaline, neutral or
acidic sodium or
potassium salts. Examples of such phosphates (e) are trisodium phosphate,
tetrasodium
diphosphate, disodium dihydrogendiphosphate, pentasodium tripolyphosphate, so-
called
sodium hexametaphosphate, oligomeric trisodium phosphate with a degree of
oligomerization of
5 to 1000, preferably 5 to 50, and the corresponding potassium salts, or
mixtures of sodium
hexametaphosphate and the corresponding potassium salts, or mixtures of the
sodium and
potassium salts. Preferred phosphates (e) are alkali metal phosphates, in
particular
pentasodium or pentapotassium triphosphate (sodium or potassium
tripolyphosphate), also
sodium metaphosphate.
In a preferred embodiment of the present invention, formulation used according
to the invention
comprises no phosphate (e); formulations having less than 100 ppm by weight of
phosphate (e),
based on the solids content of the particular formulation used according to
the invention, are
deemed to be phosphate-free within the context of the present invention.
As component (f), formulation used according to the invention can comprise in
the region of up
to 60% by weight of builder (f) or cobuilder (f), for example in the range
from 0.1 to 60% by
weight. Within the context of the present invention, builder (f) and cobuilder
(f) are to be
understood as meaning water-soluble or water-insoluble substances which are
different from
PF 72944 CA 02850127 2014-03-26
= 11
inorganic phosphate and from complex former (d) and whose main aim consists in
the binding
of calcium ions and magnesium ions.
Builders (f) can be selected from low molecular weight carboxylic acids and
salts thereof, such
as citric acid and its alkali metal salts, in particular anhydrous trisodium
citrate or trisodium
citrate dihydrate. Further suitable builders (f) are also succinic acid and
its alkali metal salts,
fatty acid sulfonates, a-hydroxypropionic acid, alkali metal malonates, fatty
acid sulfonates,
C1-C20-alkyl or C2-C20-alkenyl disuccinates, tartaric acid diacetate, tartaric
acid monoacetate,
oxidized starch, oxydisuccinate, gluconic acids, oxadiacetates,
carboxymethyloxysuccinates,
tartrate monosuccinate, tartrate disuccinate, tartrate monoacetate, tartrate
diacetate and
a-hydroxypropionic acid.
Further examples of suitable builders (f) are silicates, in particular
sodiumdisilicate and sodium
metasilicate, zeolites, sheet silicates, in particular those of the formula a-
Na2Si205, 3-Na2Si205,
and 6-Na2S1205.
Examples of cobuilders (f) are phosphonates, for example
hydroxyalkanephosphonates and
aminoalkanephosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-
1,1-
diphosphonate (HEDP) is preferred as cobuilder (f). It is preferably used as
the sodium salt, the
disodium salt giving a neutral reaction and the tetrasodium salt giving an
alkaline reaction
(pH 9). Suitable aminoalkanephosphonates are preferably
ethylenediaminetetramethylene-
phosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and
higher
homologs thereof. They are preferably used in the form of the neutrally
reacting sodium salts,
e.g. as hexasodium salt of EDTMP or as hepta- and octasodium salt of DTPMP.
Furthermore, carbonates and hydrogencarbonates are used, of which preference
is given to the
alkali metal salts, in particular sodium salts, for example sodium carbonate
and sodium
hydrogencarbonate.
In one embodiment of the present invention, formulations used according to the
invention
comprise in the region of up to 30% by weight of bleach (g) and optionally one
or more bleach
activators or bleach catalysts.
In one embodiment of the present invention, formulations used according to the
invention
comprise one or more oxygen bleaches or one or more chlorine-containing
bleaches. Examples
of suitable oxygen bleaches are sodium perborate, anhydrous or for example as
monohydrate
or as tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or
for example as
monohydrate, hydrogen peroxide, persulfates, organic peracids such as
peroxylauric acid,
peroxystearic acid, peroxy-a-naphthoic acid, 1,12-diperoxydodecanedioic acid,
perbenzoic acid,
1,9-diperoxyazelaic acid, diperoxyisophthalic acid, in each case as free acid
or as alkali metal
salt, in particular as sodium salt, also sulfonylperoxy acids and cationic
peroxy acids.
= PF 72944 CA 02850127 2014-03-26
12
Formulations used according to the invention can comprise, for example, in the
range from 0.5
to 15% by weight of oxygen bleaches.
Suitable chlorine-containing bleaches are, for example, 1,3-dichloro-5,5-
dimethylhydantoin,
N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium
hypochlorite,
magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate
and sodium
dichloroisocyanurate.
Formulations used according to the invention can comprise, for example, in the
range from 3 to
10% by weight of chlorine-containing bleach.
Formulations used according to the invention can comprise one or more bleach
catalysts.
Bleach catalysts can be selected from bleach-boosting transition metal salts
or transition metal
complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or
molybdenum-salen
complexes or manganese-, iron-, cobalt-, ruthenium- or molybdenum-carbonyl
complexes.
Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper
complexes
with nitrogen-containing tripod ligands, and also cobalt-, iron-, copper- and
ruthenium-amine
complexes can also be used as bleach catalysts.
Formulations used according to the invention can comprise one or more bleach
activators, for
example N-methylmorpholinium-acetonitrile salts ("MMA salts"),
trimethylammonium acetonitrile
salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1,5-diacety1-
2,2-dioxohexa-
hydro-1,3,5-triazine ("DADHT") or nitrile quats, i.e. trimethylammonium
acetonitrile salt(s).
In one embodiment of the present invention, formulation used according to the
invention
comprises in the range from 0.1 to 10% by weight of bleach activator,
preferably from 1 to 9%
by weight, particularly preferably from 1.5 to 8% by weight, based on the
total formulation used
according to the invention.
Formulations used according to the invention can comprise, for example, in
total up to 8% by
weight of enzyme (h), preferably 0.1 to 3% by weight, in each case based on
the total solids
content of the formulation used according to the invention. Examples of
enzymes (h) are
lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases,
lactases and
peroxidases.
In one embodiment of the present invention, formulations used according to the
invention can
comprise in total in the range from 0.1 to 50% by weight of one or more
additives (i). Examples
of additives (i) are anionic or zwitterionic surfactants, alkali carriers,
corrosion inhibiters,
antifoams, dyes, fragrances, fillers, organic solvents, tableting auxiliaries,
disintegrants,
thickeners and solubility promoters.
Disintegrants are also called tablet disintegrants. Examples are crosslinked
polyvinyl-
pyrrolidones.
PF 72944 CA 02850127 2014-03-26
13
An example of a tableting auxiliary is polyethylene glycol, for example with a
molecular weight
IA, of at least 1500 g/mol. An example of a tableting auxiliary is
polyethylene glycol, for example
with a molecular weight M, of more than 1500 g/mol up to at most 8000 g/mol.
Examples of anionic surfactants are C8-C20-alkyl sulfates, C5-C20-
alkylsulfonates and C8-C20-
alkyl ether sulfates having one to 6 ethylene oxide units per molecule.
Examples of zwitterionic surfactants are derivatives of quaternary aliphatic
ammonium salts or
phosphonium salts or of tertiary sulfonium salts in which the aliphatic groups
may be
unbranched or branched and in which one of the aliphatic substituents has a C6-
C20-alkylene
radical, preferably a C8-C18-alkylene radical, which carries an anionic group,
for example a
carboxyl group, a sulfate group, a phosphate group or a phosphonic acid group.
Specific examples of zwitterionic surfactants are betaines, for example
cocamidopropylbetaine.
Formulations used according to the invention can comprise one or more alkali
carriers. Alkali
carriers ensure, for example, a pH of at least 9 if an alkaline pH is desired.
Of suitability are, for
example, alkali metal carbonates, alkali metal hydrogencarbonates, alkali
metal hydroxides and
alkali metal metasilicates. A preferred alkali metal in each case is
potassium, particularly
preferably sodium.
Formulations used according to the invention can comprise one or more
corrosion inhibitors. In
the present case, these are to be understood as meaning those compounds which
inhibit the
corrosion of metal. Examples of suitable corrosion inhibitors are triazoles,
in particular benzo-
triazoles, bisbenzotriazoles, aminotriazoles, alkYlaminotriazoles, also phenol
derivatives such
as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid,
pholoroglucine
or pyrogallol.
In one embodiment of the present invention, formulations used according to the
invention
comprise in total in the range from 0.1 to 1.5% by weight of corrosion
inhibitor.
In one embodiment of the present invention, formulations used according to the
invention
comprise glass corrosion inhibitors. Glass corrosion can be evident from
clouding, iridescence,
streaking and lines on glass surfaces. Preferred glass corrosion inhibitors
are selected from the
group of magnesium, zinc and bismuth salts and complex compounds of zinc,
magnesium or
bismuth.
Formulations used according to the invention can comprise one or more
antifoams, selected for
example from silicone oils and paraffin oils.
In one embodiment of the present invention, formulations used according to the
invention
comprise in total in the range from 0.05 to 0.5% by weight of antifoam.
' PF 72944 CA 02850127 2014-03-26
* 14
In one embodiment of the present invention, formulations used according to the
invention can
comprise one or more acids, for example methanesulfonic acid or its salts.
In one embodiment of the present invention, formulations used according to the
invention can
have one or more dyes. An example of a suitable dye is patent blue.
In one embodiment of the present invention, formulations used according to the
invention can
comprise one or more fragrances, for example a perfume.
In one embodiment of the present invention, formulations used according to the
invention can
comprise one or more preservatives, for example 2-methyl-2Hisothiazol-3-one
(Kathon (CG).
A suitable filler is, for example, sodium sulfate.
Examples of suitable organic solvents are ethanol, isopropanol and propylene
glycol.
Cleaning formulations used according to the invention can be liquid, a gel or
in solid form,
single-phase or multiphase, in the form of tablets or in the form of other
dosage units.
If formulations used according to the invention are used for washing dishes,
then dishes are
obtained which are cleaned superbly and in particular have very few lime
marks. Furthermore,
dishes washed using formulations used according to the invention exhibit very
good filming
properties.
The present invention further provides the use of formulations used according
to the invention
for machine dishwashing. The present invention further provides a method for
machine
dishwashing using at least one formulation described above
In this connection, the expression "dishes" in connection with dishwashing
should be
understood as meaning not only porcelain crockery and plastic dishes, but also
cutlery, for
example silver cutlery or plastic cutlery, and also pots, pans, kitchen
utensils such as, for
example, lemon presses or garlic presses or measuring jugs, and also glasses
and glass
vessels for cooking.
Preferably, the machine dishwashing is washing using a dishwasher (automatic
dishwashing).
In one embodiment of the present invention, water with a hardness in the range
from 1 to 30
German hardness, preferably 2 to 25 German hardness, is used, German hardness
being
understood in particular as meaning the calcium hardness.
, PF 72944 CA 02850127 2014-03-26
i 15
As a result of the washing method according to the invention, dishes are
obtained which are
cleaned superbly and in particular have very few lime marks. Furthermore,
dishes washed using
formulations used according to the invention exhibit very good filming
properties.
The present invention further provides the use of copolymer (al) obtainable by
copolymerization
of
(a1.1) at least one N-vinylamide,
(a1.2) vinyl acetate,
(a1.3) at least one polyether,
(a1.4) optionally at least one further comonomer,
in formulations for machine dishwashing.
In one preferred variant, wherein copolymer (al) is obtainable by
copolymerization of
in total in the range from 30 to 80% by weight of N-vinylamide (a1.1),
in total in the range from 10 to 50% by weight of vinyl acetate (a1.2),
in total in the range from 10 to 50% by weight of a polyether (a1.3),
in total in the range from zero to 10% by weight of comonomer(s) (a1.4),
in each case based on the mass of the total copolymer (al).
Further properties of copolymer (al) are described above.
The present invention further provides a process for producing preparations
used according to
the invention wherein at least one copolymer (al) and at least one alkoxylate
(a2) are mixed
together.
In a preferred variant, the procedure involves melting at least one copolymer
(al) or at least one
alkoxylate (a2), mixing it with copolymer (al) or alkoxylate (a2) and then
leaving it to cool.
In another preferred variant, the procedure involves mixing together at least
one copolymer (al)
and at least one alkoxylate (a2), each in the molten state, and then leaving
them to cool.
In one embodiment, copolymer (al) and alkoxylate (a2) are mixed together, for
example without
dilution or in the presence of water, and then the water is optionally
removed. Water can be
removed for example by evaporation.
In a preferred embodiment of the present invention, copolymer (al) is melted,
for example in a
stirred vessel, in a heatable tube or an extruder, and is then mixed with
alkoxylate (a2) in solid
or molten form. It can then be left to cool. In another embodiment of the
present invention,
alkoxylate (a2) is melted, for example in a stirred vessel, in a heatable tube
or an extruder, and
is then mixed with copolymer (al) in solid or molten form. It can then be left
to cool.
, PF 72944 CA 02850127 2014-03-26
f
16
In a preferred embodiment of the present invention, copolymer (al) and
alkoxylate (a2), each in
solid form, are mixed, then the resulting mixture is melted, for example in a
stirred vessel, in a
heatable tube or an extruder, and is then left to cool.
In another preferred embodiment of the present invention, copolymer (al) can
be admixed, in
molten form, with solid alkoxylate (a2), whereupon alkoxylate (a2) melts.
During this or
subsequently, mixing is carried out, and the mixture is then left to cool.
In another preferred embodiment of the present invention, copolymer (al) and
alkoxylate (a2)
are melted separately, the two melts are mixed and then left to cool.
Thus, it is for example possible to further process melt-liquid copolymer
(al), as is produced
after the purification operations following its preparation, in a further
step. For example, melt-
liquid copolymer (al) can be incorporated into a suitable mixing element and
mixed with at least
one alkoxylate (a2). Suitable mixing elements are, for example, a second
extruder, kneader,
dynamic and static mixers, and combinations thereof.
A suitable embodiment is the melting of copolymers (al) and mixing with
alkoxylate (a2). Here,
the procedure may involve metering in the copolymer (al) and alkoxylate (a2)
individually or as
a mixture into one or more inlet openings of an extruder and melting these
with mixing and then
cooling again and granulating. Or, only the copolymer (al) is melted and
alkoxylate (a2) is
metered in at one or more points via a side dosage (side conveyor belt) into
the liquid melt of
copolymer (al). In this embodiment, the extruder screw should be provided with
suitable mixing
elements. Suitable mixing elements can be, for example, conveying and
nonconveying
kneading blocks, toothed mixing elements, elements with perforated bars,
turbomixing
elements, knurled mixing elements, toothed blocks etc.
According to one embodiment, the dry copolymer (al) is obtained in the
presence of alkoxylate
(a2). For this, the alkoxylate (a2) can be added to a solution or dispersion
of the copolymer (al)
or to the molten copolymer (al) and the resulting mixture can be passed to an
extruder, or
alkoxylate (a2) is introduced into the extruder separately. For example, the
nonionic surfactant
(a2) can be introduced as initial charge into the extruder cold in the form of
a solid or liquid, and
the polymer solution can be pumped in, and both degassed together, or the
polymer solution
can be introduced as initial charge, i.e. is pumped into the heated extruder
and firstly a certain
fraction of the solvent (for example 50-95%) is evaporated, and then, in a
later stage, the
nonionic surfactant (a2) is added as a solid or as a suspension (slurry) and
solvents are
evaporated together.
After cooling the mixture of copolymer (al) and alkoxylate (a2), it can be
left to cool and
optionally comminuted. Of suitability for the comminution are in principle all
customary
techniques known for this purpose, such as hot or cold beating. Being left to
cool and
comminution can be carried out in any desired order. Thus, for example, it is
possible to beat an
= PF 72944 CA 02850127 2014-03-26
17
extrudate of copolymer (al) and alkoxylate (a2) with rotating knives or with a
jet of air and then
to cool it with air or under protective gas. In another variant, it is
possible to lay an extrudate of
copolymer (al) and alkoxylate (a2) as melt strand on a chilled belt (stainless
steel, Teflon, chain
belt) and, following solidification, to granulate it or to grind it.
Other comminution methods such as e.g. spray-solidification are also possible.
Compounds of the general formula (I) can be obtained by alkoxylation of the
corresponding
C5-C24-alkohols with alkylene oxides. Here, the alkoxylation can be followed
by an etherification,
e.g. with a suitable alcohol or with another alkylating agent, in particular
with dimethyl sulfate, or
an esterification with a carboxylic acid.
Preferably, R2 is hydrogen.
The alkoxylation can be carried out for example using alkaline catalysts, such
as alkali metal
hydroxides or alkali metal alcoholates, or with acidic catalysts, for example
BF3 = H3PO4, BF3 =
2 (C2H5)20, BF3, SbCI5, SnCl4 = 2 H20 or hydrotalcite, or with double metal
cyanide catalysts.
Processes for the preparation of copolymer (al) are known per se, see, for
example,
WO 2007/051743. The preparation takes place preferably by means of radically
initiated
polymerization, preferably in solution, in nonaqueous organic solvents or in
mixtures of water
and nonaqueous organic solvents. Suitable nonaqueous organic solvents are, for
example,
alcohols, such as methanol, ethanol, n-propanol and isopropanol, and also
glycols, such as
ethylene glycol and glycerol. Also of suitability as solvents are esters, such
as, for example,
ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate or butyl
acetate, with ethyl
acetate being preferred. To carry out the free-radical copolymerization,
preference is given to
introducing polyether (a1.3) as initial charge and adding N-vinylamide (a1.1),
vinyl acetate
(a1.2) and optionally further comonomer (a1.4), together or separately,
simultaneously or
successively.
The free-radical copolymerization is preferably carried out at temperatures of
60 to 100 C. A
suitable pressure is, for example, atmospheric pressure, but it is also
possible to select a higher
or lower pressure.
The invention is illustrated in more detail by the working examples below.
Working examples
I. Substances used
1.1 Preparation of copolymers (al)
1.1.1 Preparation of copolymer (a1-1)
_ . PF 72944 CA 02850127 2014-03-26
18
Feed 1: 240 g of vinyl acetate (a1.2)
Feed 2: 456 g of vinylcaprolactam (a1,1-1), dissolved in 240 g of ethyl
acetate
Feed 3: 10.44 g of tert-butyl perpivalate (75% by weight in aliphatics
mixture), diluted with
67.90 g of ethyl acetate
104.0 g of polyethylene glycol (Mw: 6000 g/mol) (a1.3-1), dissolved in 25 g of
ethyl acetate, are
introduced as initial charge in a stirred apparatus and heated to 77 C under
an N2 atmosphere.
As soon as the internal temperature of 77 C had been reached, 1 g of feed 3
was added and
the mixture was polymerized for 15 min. The metered addition of feed 1, feed 2
and feed 3 was
then started simultaneously. Feed 1 and feed 2 were metered in over the course
of 5 hours, and
feed 3 was metered in over the course of 2 hours. After all of the feeds had
been metered in,
the reaction mixture was stirred for a further 3 hours at 77 C. The reaction
mixture was then
diluted with 500 ml of water. Volatile constituents were then removed by steam
distillation. The
aqueous solution of copolymer (a1-1) obtainable in this way was freeze-dried.
Copolymer (a1-1)
were obtained after grinding as a very readily flowable powder. Mw: 44 000
g/mol
1.1.2 Preparation of copolymer (a1-2)
Feed 1: 500 g of vinylcaprolactam (a1.1-1) and 180 g vinyl acetate (a1.2),
dissolved in 100 g of
ethyl acetate
Feed 2: 10.50 g of tert-butyl perethylhexanoate (98% by weight), diluted with
94.50 g of ethyl
acetate
100.0 g of polyethylene glycol (Mw: 6000 g/mol) (a1.3-1) and 20 g of vinyl
acetate (a1.2),
dissolved in 165 g of ethyl acetate, were introduced as initial charge in a
stirred apparatus and
heated to 77 C under an N2 atmosphere. As soon as the internal temperature of
77 C had been
reached, 10.5 g of feed 2 were added and the mixture was partially polymerized
for 15 min. The
metered addition of feed 1 and feed 23 was then started simultaneously. Feed 1
was metered in
over the course of 5 hours, and feed 2 was metered in over the course of 2
hours. After all of
the feeds had been metered in, the reaction mixture was stirred for a further
3 hours at 77 C.
The reaction mixture was then diluted with 500 ml of water. Volatile
constituents were then
removed by steam distillation. The aqueous solution of copolymer (a1-1)
obtainable in this way
was freeze-dried. Copolymer (a1-2) were obtained after grinding as a very
readily flowable
powder.
1.1.3 Preparation of further copolymers (a1-3) to (a1-5)
The procedure was as described in example 1.1.2, but choosing different
compositions of feed 1
and feed 2 in each case.
This gave the following copolymers according to Table 1.
Ati= PF 72944 CA 02850127 2014-03-26
4
19
Table 1: Composition of copolymers (a1-1) to (a1-5)
Composition in % by weight K value
Copolymer (1% by weight in
(a1.3-1) (a1.1-1) (a1.2)
ethanol)
(a1-1) 13 57 30 19.8
(a1-2) 12.5 62.5 25 18.5
(a1-3) 12.5 60 27.5 40.4
(a1-4) 14 51 35 25.2
(a1-5) 14 53.5 32.5 22.4
The alkoxylate (a2-1) used was: n-C18H37-(OCH2CH2)9-0H
II. Preparation of formulations used according to the invention and
also of comparison
formulations
11.1 Preparation of basis mixtures
The polycarboxylate (c-1) used was: random copolymer of acrylic acid/AMPS (2-
acrylamido-2-
methylpropanesulfonic acid), weight ratio 7:3, partially neutralized with
NaOH, Mw:
20 000 g/mol, K value: 40, pH 5 (1% in distilled water).
To produce basis mixtures, in each case the substances in question as in Table
2 were mixed
together dry in a kitchen appliance and divided with the help of a sample
divider.
Table 2: Composition of basis mixtures
BF-P-free BF-P-containing
Protease 1 1
Amylase 0.2 0.2
Polycarboxylate (c-1) 10 6.5
Sodium percarbonate 10.5 14
Tetraacetylethylenediamine 4 4
Sodium tripolyphosphate 50
Na2Si205 2 2
Na2CO3 18.8 18.8
Sodium citrate dihydrate 33
Methylglycinediacetic acid, trisodium salt 15
HEDP 0.5 0.5
HEDP: Disodium salt of hydroxyethane-(1,1-diphosphonic acid)
All quantitative data in g.
' PF 72944 CA 02850127 2014-03-26
11.2 Preparation of preparations used according to the invention and of
comparison
preparations
Preparation of preparation according to the invention EZ-1
5 10 g of alkoxylate (a2-1) were melted and mixed with 5 g of solid
copolymer (a1-1). This
produced firstly an inhomogeneous mixture in the form of a cloudy solution.
After cooling to
room temperature and re-melting, a homogeneous mixture was obtained in the
form of a clear
solution. This was left to cool to room temperature, giving preparation EZ-1.
EZ-1 was solid at
room temperature.
11.3 Preparation of phosphate-free formulation used according to the invention
EF-1
19.95 g of basis mixture BP-P-free was introduced as initial charge. EZ-1 was
then melted and
1.6 g of EZ-1, comprising 1.05 g of (a2-1) and 0.55 g of (a1-1) were added to
BP-P-free. The
formulation EF-1 obtainable in this way was left to solidify.
11.4 Preparation of phosphate-containing formulations used according to the
invention and
comparison formulations
11.4.1 Preparation of formulation EF-1P used according to the invention
20.4 g of basis mixture BP-P-containing were introduced as initial charge. 0.9
g of EZ-1 was
then melted and added dropwise to BP-P-containing. The formulation EF-1P
obtainable in this
way was left to solidify.
11.4.2 Preparation of comparison formulation V-F-2P
20.4 g of basis mixture BP-P-containing were introduced as initial charge. 0.6
g of alkoxylate
(a2-1) were then melted and added dropwise to BP-P-containing. The comparison
formulation
V-F-2P obtainable in this way was left to solidify.
III. Testing of formulations used according to the invention and
comparison formulations
For the tests for the machine dishwashing, the following experimental
conditions were chosen:
Dishwasher: Miele G 1222 SCL
Program: 50 C with R-time 2 (8 min) (without prerinse)
Ware: 3 knives (WMF Tafelmesser Berlin, Monoblock)
3 Amsterdam 0.21 drinking glasses
3 "OCEAN BLUE" BREAKFAST PLATES (made of melamine resin)
3 porcelain plates RIMMED PLATES FLAT 19 CM
Arrangement: Knives in the cutlery tray, glasses in the top basket,
plates in the lower basket
Dishwashing detergent: 21 g
a PF 72944 CA 02850127 2014-03-26
21
Addition of soiling: 100 g of clear-rinse soiling (comprises egg, starch
and grease) were
dosed in a frozen state
Clear-rinse temperature: 65 C
Water hardness: 21 German hardness (Ca/Mg):HCO3 (3:1):1.35
Wash cycles: 6; in each case 1 h break in between (10 min with opened
dishwasher door,
50 min with closed dishwasher door)
Evaluation: Visually after 6 wash cycles in a darkened chamber under
light behind a
perforated plate
The ware was assessed after 6 wash cycles using a grading scale from 10 (very
good) to 1
(very poor). Grades from 1 ¨ 10 were awarded for spotting (very many,
intensive spots = 1
ranging to no spots = 10) and for filming the grades 1 ¨ 10 were awarded (1 =
very significant
deposit, 10 = no deposit).
IV.1 Results with phosphate-free formulations
The test results are summarized in Table 3 (see following page).
IV.2 Results with phosphate-containing formulations
The test results are summarized in Table 4 (see following page).
-T3
-n
Table 3: Dishwasher tests with phosphate-free formulation EF-1
-4
A3
Spotting
Filming W
Formulation Knives Glasses Melamine Porcelain plates
Knives Glasses Melamine Porcelain plates
_ plates
plates
EF-1 10 10 8 7 5
6 6 6
Table 4: Dishwasher tests with phosphate-containing formulations
Spotting
Filming
_
Formulation Knives Glasses Melamine Porcelain plates
Knives Glasses Melamine Porcelain plates P
plates
plates
.
0
._
m
EF-1P 7 7 9 8 5
7 8 7 0
u,
0
na ,-
V-F-2P 7 2 2 3 6
7 8 8 n..)
,7
IV
0
I--,
tA
I
0
CO
I
M
131
