Note: Descriptions are shown in the official language in which they were submitted.
PF 73447 CA 02870785 2014-10-17
1
Formulations, their use as or for producing dishwashing compositions and their
preparation
The present invention relates to formulations comprising
(A) at least one aminocarboxylate, selected from methylglycine diacetate
(MGDA),
iminodisuccinic acid (IDA) and glutaminic acid diacetate (GLDA), and salts
thereof, and
(B) at least one alkyleneimine polymer which is covalently modified with at
least one
carboxylic acid or at least one derivative of a carboxylic acid or at least
one derivative of
carbonic acid, where up to at most 75 mol% of the nitrogen atoms of the
primary and
secondary amino groups of the alkyleneimine polymer have been reacted with
carboxylic
acid or derivative of carboxylic acid or carbonic acid.
Furthermore, the present invention relates to a process for the preparation of
formulations
according to the invention and their use as or for producing dishwashing
compositions, in
particular dishwashing compositions for machine dishwashing.
Dishwashing compositions have to satisfy many requirements. Thus, they have to
fundamentally clean the dishes, they should have no harmful or potentially
harmful substances
in the waste water, they should permit the run-off and drying of the water
from the dishes, and
they should not lead to problems during operation of the dishwasher. Finally,
they should not
lead to esthetically undesired consequences on the ware to be cleaned. In this
connection,
mention is to be made particularly of glass corrosion.
Glass corrosion arises not only as the result of mechanical effects, for
example by glasses
rubbing together or mechanical contact of the glasses with parts of the
dishwasher, but is
primarily caused by chemical effects. For example, certain ions can be
dissolved out of the
glass through repeated machine washing, which changes the optical and thus the
esthetic
properties in an adverse manner.
In the event of glass corrosion, several effects are observed. Firstly, the
formation of
microscopically fine cracks can be observed, which become noticeable in the
form of lines.
Secondly, in many cases, a general hazing can be observed, for example a
roughening, which
makes the glass in question appear unattractive. Effects of this type are
overall also subdivided
into iridescent discoloration, formation of ridges, and also sheet-like and
ring-like hazing.
It is known from WO 2002/64719 that certain copolymers of ethylenically
unsaturated carboxylic
acids with, for example, esters of ethylenically unsaturated carboxylic acids
can be used in
dishwashing compositions.
WO 2006/108857 discloses alkoxylated polyethyleneimines as additives to
detergents. By way
of example, detergents are disclosed which comprise zeolites or
polyaminocarboxylates such
as EDTA or triethylenediamine pentaacetate as complexing agents.
. PF 73447 CA 02870785 2014-10-17
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2
WO 01/96516 proposes formulations which comprise alkoxylated polyethyleneimine
for cleaning
hard surfaces. Purified water is used for rinsing.
WO 2010/020765 discloses dishwashing compositions which comprise
polyethyleneimine.
Dishwashing compositions of this type can comprise phosphate or be phosphate-
free. They are
attributed good inhibition of glass corrosion. Zinc- and bismuth-containing
dishwashing
compositions are advised against. However, in many cases, the glass corrosion,
in particular
the line corrosion and the hazing, is not adequately delayed or prevented.
It was thus the object to provide formulations which are suitable as or for
producing dishwashing
compositions and which avoid the disadvantages known from the prior art and
inhibit glass
corrosion or at least reduce it particularly well. It was also the object to
provide a process for the
preparation of formulations which are suitable as or for producing dishwashing
compositions
and which avoid the disadvantages known from the prior art. It was also the
object to provide
uses of formulations.
Accordingly, the formulations defined at the start have been found, also
abbreviated to
formulations according to the invention.
Formulations according to the invention comprise
(A) at least one aminocarboxylate selected from methylglycine diacetate
(MGDA),
iminodisuccinic acid (IDA) and glutamic acid diacetate (GLDA), and salts
thereof, within the
context of the present invention also abbreviated to aminocarboxylate (A) or
else compound (A).
Compound (A) is preferably selected as free acid, particularly preferably in
partially or
completely neutralized form, i.e. as salt. Suitable counterions are, for
example, inorganic
cations, for example ammonium, alkali metal or alkaline earth metal,
preferably Mg2+, Ca2t, Nat,
Kt, or organic cations, preferably ammonium substituted with one or more
organic radicals, in
particular triethanolammonium, N,N-diethanolammonium, N-mono-Ci-C4-
alkyldiethanolammonium, for example N-methyldiethanolammonium or N-n-
butyldiethanolammonium, and N,N-di-C1-C4-alkylethanolammonium.
Very particularly preferred compounds (A) are the alkalki metal salts, in
particular the sodium
salts of methylglycine diacetate (MGDA), iminosuccinic acid (IDA) and
glutaminic acid diacetate
(GLDA).
Very particularly preferably, methylglycine diacetate (MGDA), iminosuccinic
acid (IDA) or
glutaminic acid diacetate (GLDA) is completely neutralized.
Furthermore, formulations according to the invention comprise
(B) at least one alkyleneimine polymer which is covalently modified with at
least one
carboxylic acid or at least one derivative of a carboxylic acid or at least
one derivative of
carbonic acid, also called modified polyalkyleneimine (B) for short, where up
to at most
PF 73447 CA 02870785 2014-10-17
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75 mol% of the nitrogen atoms of the primary and secondary amino groups of the
alkyleneimine polymer have been reacted with carboxylic acid or derivative of
carboxylic
acid or carbonic acid.
Within the context of the present invention, alkyleneimine polymers are to be
understood as
meaning those polymeric materials which are obtained by homo- or
copolymerization of one or
more cyclic imines, or by grafting a (co)polymer with at least one cyclic
imine. Examples are
polyalkylenepolyamines and polyimidoamines grafted with ethyleneimine.
Within the context of the present invention, polyalkylenepolyamines are
preferably understood
as meaning those polymers which comprise at least 6 nitrogen atoms and at
least five C2-C10-
alkylene units, preferably C2-C3-alkylene units, per molecule, for example
pentaethylenehexamine, and in particular polyethyleneimines.
Polyalkylenepolyamine and in particular polyethyleneimine can, for example,
have an average
molecular weight (Mw) of at least 300 g/mol; preferably, the average molecular
weight of
alkyleneimine polymer is in the range from 500 to 1 000 000 g/mol,
particularly preferably 800 to
000 g/mol, ascertained by gel permeation chromatography (GPC).
20 Polyalkylenepolyamines can be covalently modified in partially
quaternized (alkylated) form as
alkyleneimine polymer. Suitable quaternizing agents (alkylating agents) are,
for example, alkyl
halides, in particular Cl-Clo-alkyl chloride, such as methyl chloride, methyl
bromide, methyl
iodide, ethyl chloride, ethyl bromide, n-butyl chloride, tert-butyl chloride,
n-hexyl chloride, also
epichlorohydrin, dimethyl sulfate, diethyl sulfate and benzyl chloride. If
quaternized (alkylated)
25 polyalkylenepolyamines as alkyleneimine polymer are covalently modified,
the degree of
quaternization (alkylation) is preferably 1 to 25, particularly preferably up
to 20 mol%, based on
quaternizable (alkylatable) N atoms in alkyleneimine polymer.
Furthermore, polyalkylenepolyamines and in particular polyethyleneimines can
be covalently
modified in partially C2-C22-epoxide-alkoxylated form as alkyleneimine
polymer. Examples of
suitable C2-C22-epoxides are ethylene oxide, propylene oxide, n-hexylene
oxide, styrene oxide.
If polyalkylenepolyamines partially alkoxylated with C2-C22-epoxides as
alkyleneimine polymer
are covalently modified, the degree of alkoxylation is preferably 1 to 25,
particularly preferably
up to 20 mol%, based on alkoxylatable N atoms in the alkyleneimine polymer in
question.
Furthermore, polyamidoamines grafted with ethyleneimine are suitable as
alkyleneimine
polymers. Suitable polyamidoamines are obtainable for example by reacting C4-
C10-dicarboxylic
acids with polyalkylenepolyamines which preferably comprise 3 to 10 basic
nitrogen atoms in
the molecule. Suitable dicarboxylic acids are, for example, succinic acid,
maleic acid, adipic
acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. It is
also possible to use
mixtures of the aforementioned dicarboxylic acids, for example mixtures of
adipic acid and
glutaric acid or mixtures of maleic acid and adipic acid. Preference is given
to using adipic acid
for producing polyamidoamines. Suitable polyalkylenepolyamines which have been
condensed
= PF 73447 CA 02870785 2014-10-17
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with the aforementioned dicarboxylic acids are, for example,
diethylenetriamine,
triethylenetetramine, dipropylenetriamine, tripropylenetetramine,
dihexamethylenetriamine,
aminopropylethylenediamine and bis-aminopropylethylenediamine. Aforementioned
polyalkylenepolyamines can also be used in the form of mixtures in the
preparation of
polyamidoamine. The preparation of polyamidoamine preferably takes place
without dilution, but
can optionally also be carried out in inert solvents. The condensation of
dicarboxylic acid with
polyalkylenepolyamine takes place at elevated temperatures, for example in the
range from 120
to 220 C. The water formed during the reaction is distilled off from the
reaction mixture. The
condensation can optionally be carried out in the presence of lactones or
lactams of carboxylic
acids having 4 to 8 carbon atoms. In general, 0.8 to 1.4 mol of
polyalkylenepolyamine are used
per mole of dicarboxylic acid. Polyamidoamines obtainable in this way have
primary and
secondary NH groups and are soluble in water.
Polyamidoamines grafted with ethyleneimine can be prepared by allowing
ethyleneimine to act
on the polyamidoamine described above in the presence of Bronstedt acids or
Lewis acids, for
example sulfuric acid, phosphoric acid or boron trifluoride etherate. As a
result, ethyleneimine is
grafted onto the polyamidoamine in question. For example, 1 to 10
ethyleneimine units can be
grafted on per basic nitrogen atom in the polyamidoamine, i.e. about 10 to 500
parts by weight
of ethyleneimine are used per 100 parts by weight of polyamidoamine.
A preferred alkyleneimine polymer is polyethyleneimine.
In one embodiment of the present invention, polyethyleneimine has an average
molecular
weight Mõ, in the range from 500 to 1 000 000 g/mol, preferably in the range
from 600 to
75 000 g/mol, particularly preferably in the range from 800 to 25 000 g/mol,
determinable for
example by gel permeation chromatography (GPC).
In one embodiment of the present invention, polyethyleneimines are selected
from highly
branched polyethyleneimines. Highly branched polyethyleneimines are
characterized by their
high degree of branching (DB). The degree of branching can be determined, for
example, by
13C-NMR spectroscopy, preferably in D20, and is defined as follows:
DB = D +T/D+T+L
with D (dendritic) corresponding to the fraction of tertiary amino groups, L
(linear) corresponding
to the fraction of secondary amino groups and T (terminal) corresponding to
the fraction of
primary amino groups.
Within the context of the present invention, highly branched
polyethyleneimines are
polyethyleneimines with DB in the range from 0.1 to 0.95, preferably 0.25 to
0.90, particularly
preferably in the range from 0.30 to 0.80 and very particularly preferably at
least 0.5.
PF 73447 CA 02870785 2014-10-17
In one embodiment of the present invention, the polyethyleneimine is highly
branched
polyethyleneimines (homopolymers) with an average molecular weight M, in the
range from 600
to 75 000 g/mol, preferably in the range from 800 to 25 000 g/mol.
5 Within the context of the present invention, alkyleneimine polymer is
used in covalently modified
form, and specifically such that in total up to at most 75 mol%, preferably in
total 5 to 60 mor/o,
of the nitrogen atoms of the primary and secondary amino groups of the
alkyleneimine polymer
have been reacted with at least one carboxylic acid or at least one derivative
of a carboxylic
acid or at least one derivative of carbonic acid. Within the context of the
present application, the
reaction (modification) can thus be, for example, an alkylation or an
amidation.
In one embodiment of the present invention, modified polyalkyleneimine (B) is
selected from
alkyleneimine polymers and in particular polyethyleneimines
(B1) which have been reacted with at least one ethylenically unsaturated C3-
C10 carboxylic acid
or
(B2) which have been reacted with at least one Cs-C12-carboxylic acid which
has no ethylenic
double bond,
(B3) which have been reacted with at least one carbonic acid ester and
(B4) which have been reacted with hydrocyanic acid and formaldehyde, for
example in the
sense of a Strecker synthesis.
Examples of ethylenically unsaturated C3-C10-carboxylic acids are unsaturated
fatty acids and
preferably a,3-ethylenically unsaturated C3-C10-carboxylic acids, for example
(E)- or (Z)-crotonic
acid, methacrylic acid and in particular acrylic acid. As a result of a
reaction with C3-C10-
carboxylic acid(s), C3-C10-carboxylic acid(s) is/are added onto nitrogen atoms
from NH2 groups
or NH groups from alkyleneimine polymer preferably in the sense of a Michael
addition.
Examples of Cs-C12-carboxylic acid which have no ethylenic double bond are
valeric acid,
caproic acid, caprylic acid, n-octanoic acid, n-decanoic acid and lauric acid.
As a result of a
reaction with C5-C12-carboxylic acid(s) which have no ethylenic double bond,
an amidation of
nitrogen atoms from NH2 groups or NH groups from alkyleneimine polymer is
preferably carried
out.
Examples of derivatives of C5-C12-carboxylic acids which have no ethylenic
double bond are
esters thereof, for example the C1-C4-alkylesters, in particular the ethyl and
the methylesters.
Examples are methyl valerate, methyl caproate, methyl caprylate, methyl n-
octanoate, methyl n-
decanoate, ethyl valerate, ethyl caproate, ethyl caprylate, ethyl n-octanoate
and ethyl n-
decanoate.
Examples of carbonic acid derivatives are the di-C1-C2-alkyl esters of
carbonic acid, such as
dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate, and in
particular cyclic
carbonates such as ethylene carbonate and propylene carbonate. Preference is
given to
ethylene carbonate.
= PF 73447 CA 02870785 2014-10-17
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In this connection, in modified polyalkyleneimine (B), up to in total at most
75 mol /0 of the
nitrogen atoms of the primary and secondary amino groups of the alkyleneimine
polymer have
been reacted with carboxylic acid or derivative of carboxylic acid or carbonic
acid, preferably in
total 5 to 60 mar/0.
Tertiary nitrogen atoms in polyalkyleneimine (B) have generally not been
reacted with carboxylic
acid or derivative of carboxylic acid or carbonic acid.
In another embodiment of the present invention, modified polyalkyleneimine (B)
which is
obtainable from alkyleneimine polymers and in particular polyethyleneimines
(31) which have
been reacted with at least one ethylenically unsaturated C3-Clo-carboxylic
acid is used in
formulation according to the invention as free acid.
Modified polyalkyleneimine (B) can have, as counterions, high molecular weight
or low
molecular weight anions, organic or preferably inorganic. Within the context
of the present
invention, high molecular weight anions have an average molecular weight of
200 g/mol or
more, for example up to 2500 g/mol, low molecular weight anions have a
molecular weight of
less than 200 g/mol, for example from 17 to 150 g/mol. Examples of low
molecular weight
organic counterions are acetate, propionate and benzoate. Examples of low
molecular weight
inorganic counterions are sulfate, chloride, bromide, hydroxide, carbonate,
methanesulfonate
and hydrogencarbonate.
In one embodiment of the present invention, modified polyalkyleneimine (B) has
a cationic
charge density of at least 5 meq/g (milliequivalents/g), preferably 5 to 22
meq/g, the data in g
referring to modified polyalkyleneimine (B) without taking into consideration
the counterions.
The cationic charge density can be ascertained for example by titration, for
example by titration
with polyvinyl sulfate.
Modified polyalkyleneimines (B) can also comprise one or more anionic
comonomers in
copolymerized form, for example (meth)acrylic acid. Cationic polymers (B)
which also comprise
one or more anionic comonomers in copolymerized form, however, have more
cationic c than
anionic charges per molecule.
In one embodiment of the present invention, modified polyalkyleneimine (B) has
a molecular
weight distribution Mw/Mn in the range from 1.1 to 10, preferably 1.5 to 5.
In one embodiment of the present invention, modified polyalkyleneimine (B) has
a molecular
weight Mw in the range from 550 to 1.5.106 g/mol.
In one embodiment of the present invention, formulations according to the
invention comprise
in total in the range from 1 to 50% by weight of aminocarboxylate (A),
preferably 10 to 25% by
weight,
' PF 73447 CA 02870785 2014-10-17
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in total in the range from 0.001 to 5% by weight of modified polyalkyleneimine
(B), preferably
0.05 to 2.5% by weight,
based in each case on solids content of the formulation in question.
In one variant of the present invention, formulation according to the
invention comprises
compound (A) and modified polyalkyleneimine (B) in a weight ratio of from
1000:1 to 25:1.
In a preferred embodiment of the present invention, formulation according to
the invention is
free from phosphates and polyphosphates, with hydrogen phosphates being
subsumed
therewith, for example free from trisodium phosphate, pentasodium
tripolyphosphate and
hexasodium metaphosphate. "Free from" in connection with phosphates and
polyphosphates is
to be understood as meaning, within the context of the present invention, that
the content of
phosphate and polyphosphate in total is in the range from 10 ppm to 0.2% by
weight,
determined by gravimetry.
Formulations according to the invention can comprise further components which
are
advantageous for example for use when washing dishes and/or kitchen utensils.
In another embodiment of the present invention, formulations according to the
invention
comprise no further components which are advantageous for example for use when
washing
dishes and/or kitchen utensils, but can be readily formulated with further
components and are
therefore suitable as starting material.
In one embodiment of the present invention, formulations according to the
invention comprise
sodium citrate (C). In this connection, the term sodium citrate includes the
monosodium salt and
preferably the disodium salt. Sodium citrate can be used as anhydrous salt or
as hydrate, for
example as dihydrate.
In one embodiment of the present invention, formulations according to the
invention comprise
(D) at least one compound selected from alkali metal percarbonate, alkali
metal perborate and
alkali metal persulfate, within the context of the present invention also
called "bleach (D)".
Preferred bleaches (D) are selected from sodium perborate, anhydrous or, for
example, as
monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate,
anhydrous or, for
example, as monohydrate, and sodium persulfate, the term "persulfate" in each
case including
the salt of the peracid H2S05 and also the peroxodisulfate.
In this connection, the alkali metal salts can in each case also be alkali
metal hydrogen
carbonate, alkali metal hydrogen perborate and alkali metal hydrogen
persulfate. However,
preference is given in each case to the dialkyl metal salts.
In one embodiment of the present invention, formulation according to the
invention comprises 0
to 50% by weight of sodium citrate (C), preferably 1 to 30% by weight,
particularly preferably at
= PF 73447 CA 02870785 2014-10-17
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least 5% by weight of sodium citrate (C), determined as anhydrous sodium
citrate,
in total zero to 15% by weight of bleach (D), preferably at least 0.5% by
weight of bleach (D)
selected from alkali metal percarbonate, alkali metal perborate and alkali
metal persulfate,
based in each case on solids content of the formulation in question.
In one embodiment of the present invention, formulation according to the
invention is solid at
room temperature, for example a powder or a tablet. In another embodiment of
the present
invention, formulation according to the invention is liquid at room
temperature. In one
embodiment of the present invention, formulation according to the invention is
granules, a liquid
preparation or a gel.
In one embodiment of the present invention, formulation according to the
invention comprises
0.1 to 10% by weight of water, based on the sum of all solids of the
formulation in question.
In one embodiment of the present invention, formulation according to the
invention is free from
those heavy metal compounds which do not act as bleach catalysts, in
particular from
compounds of iron and of bismuth. In connection with heavy metal compounds,
"free from" is to
be understood as meaning, within the context of the present invention, that
the content of heavy
metal compounds which do not act as bleach catalysts is in total in the range
from 0 to
100 ppm, determined in accordance with the Leach method and based on the
solids content.
Preferably, formulation according to the invention has a heavy metal content
below 0.05 ppm,
based on the solids content of the formulation in question.
Within the context of the present invention, "heavy metals" are all metals
with a specific density
of at least 6 g/cm3. In particular, heavy metals are precious metals and also
zinc, bismuth, iron,
copper, lead, tin, nickel, cadmium and chromium.
Preferably, formulation according to the invention comprises no measurable
fractions of zinc
and bismuth compounds, i.e. for example less than 1 ppm.
In one embodiment of the present invention, formulation according to the
invention can have
further ingredients (E), for example one or more surfactants, one or more
enzymes, one or more
builders, in particular phosphorus-free builders, one or more cobuilders, one
or more alkali
metal carriers, one or more bleaches, one or more bleach catalysts, one or
more bleach
activators, one or more bleach stabilizers, one or more antifoams, one or more
corrosion
inhibitors, one or more builders, buffers, dyes, one or more fragrances, one
or more organic
solvents, one or more tableting auxiliaries, one or more disintegrants, one or
more thickeners,
or one or more solubility promoters.
Examples of surfactants are in particular nonionic surfactants and also
mixtures of anionic or
zwitterionic surfactants with nonionic surfactants. Preferred nonionic
surfactants are alkoxylated
alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of
ethylene oxide and
' PF 73447 CA 02870785 2014-10-17
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9
propylene oxide and reaction products of sorbitan with ethylene oxide or
propylene oxide, alkyl
glycosides and so-called amine oxides.
Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are,
for example,
compounds of the general formula (I)
R1
(I)
in which the variables are defined as follows:
R1 is identical or different and selected from linear C1-C10-
alkyl, preferably in each case
identical and ethyl and particularly preferably methyl,
R2 is selected from C8-C22-alkyl, for example n-C8H17, n-C10H21,
n-C12H25, n-C14H29, n-C16H33
or n-C18H37,
R3 is selected from Ci-Clo-alkyl, methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl,
sec.-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-
dimethylpropyl,
isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-
nonyl, n-decyl or
isodecyl,
m and n are in the range from zero to 300, where the sum of n and m is at
least one. Preferably,
m is in the range from 1 to 100 and n is in the range from 0 to 30.
Here, compounds of the general formula (I) may be block copolymers or random
copolymers,
preferably block copolymers.
Other preferred examples of alkoxylated alcohols and alkoxylated fatty
alcohols are, for
example, compounds of the general formula (II)
R1 Ri
(II)
in which the variables are defined as follows:
R1 is identical or different and selected from linear Craw-alkyl,
preferably in each case
identical and ethyl and particularly preferably methyl,
R4 is selected from C6-C20-alkyl, in particular n-C8H17, n-
C10H21, n-C12H25, n-C14H29, n-C16H33,
n-Ci8H37,
' PF 73447 CA 02870785 2014-10-17
a is a number in the range from 1 to 6,
b is a number in the range from 4 to 20,
5
d is a number in the range from 4 to 25.
Here, compounds of the general formula (II) can be block copolymers or random
copolymers,
preferably block copolymers.
Further suitable nonionic surfactants are selected from di- and multiblock
copolymers,
composed of ethylene oxide and propylene oxide. Further suitable nonionic
surfactants are
selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or
alkyl glycosides are
likewise suitable. An overview of suitable further nonionic surfactants can be
found in EP-A
0 851 023 and in DE-A 198 19 187.
Mixtures of two or more different nonionic surfactants may also be present.
Examples of anionic surfactants are C8-C20-alkyl sulfates, C8-C20-
alkylsulfonates and C8-C20-
alkyl ether sulfates with one to 6 ethylene oxide units per molecule.
In one embodiment of the present invention, formulation according to the
invention can
comprise in the range from 3 to 20% by weight surfactant.
Formulations according to the invention can comprise one or more enzymes.
Examples of
enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases,
pectinases,
lactases and peroxidases.
Formulations according to the invention can comprise, for example, up to 5% by
weight of
enzyme, preferably 0.1 to 3% by weight, in each case based on the total solids
content of the
formulation according to the invention.
Besides sodium citrate (C), formulations according to the invention can
comprise one or more
builders, in particular phosphate-free builders. Examples of suitable builders
are silicates, in
particular sodium disilicate and sodium metasilicate, zeolites, sheet
silicates, in particular those
of the formula a-Na2Si205, 13-Na2Si205, and 6-Na2Si205, also fatty acid
sulfonates, a-
hydroxypropionic acid, alkali metal malonates, fatty acid sulfonates, alkyl
and alkenyl
disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized
starch, and polymeric
builders, for example polycarboxylates and polyaspartic acid.
In one embodiment of the present invention, builders are selected from
polycarboxylates, for
example alkali metal salts of (meth)acrylic acid homopolymers or (meth)acrylic
acid copolymers.
= PF 73447 CA 02870785 2014-10-17
11
Suitable comonomers are monoethylenically unsaturated dicarboxylic acids such
as maleic
acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. A
suitable polymer is in
particular polyacrylic acid, which preferably has an average molecular weight
Mw in the range
from 2000 to 40 000 g/mol. preferably 2000 to 10 000 g/mol, in particular 3000
to 8000 g/mol.
Also of suitability are copolymeric polycarboxylates, in particular those of
acrylic acid with
methacrylic acid and of acrylic acid or methacrylic acid with maleic acid
and/or fumaric acid.
It is also possible to use copolymers of at least one monomer from the group
consisting of
monoethylenically unsaturated C3-C10-mono- or C4-C10-dicarboxylic acids or
anhydrides thereof,
such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric
acid, itaconic acid
and citraconic acid, with at least one hydrophilically or hydrophobically
modified monomer, as
listed below.
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-olefins and
polyisobutene having, on average, 12 to 100 carbon atoms per molecule.
Suitable hydrophilic monomers are monomers with sulfonate or phosphonate
groups, and also
nonionic monomers with hydroxyl 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. Polyalkylene
glycols here can comprise 3 to 50, in particular 5 to 40 and especially 10 to
30 alkylene oxide
units per molecule.
Particularly preferred monomers containing sulfonic acid groups here are 1-
acrylamido-1-
propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-
methyl-
propanesulfonic 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-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid,
3-sulfopropyl
acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate,
sulfomethacrylamide,
sulfomethylmethacrylamide, and salts of said acids, such as their sodium,
potassium or
ammonium salts.
Particularly preferred monomers containing phosphonate groups are
vinylphosphonic acid and
its salts.
Moreover, amphoteric polymers can also be used as builders.
' PF 73447 CA 02870785 2014-10-17
12
Formulations according to the invention can comprise, for example, in the
range from in total 10
to 50% by weight, preferably up to 20% by weight, of builders.
In one embodiment of the present invention, formulations according to the
invention can
comprise one or more cobuilders.
Examples of cobuilders are phosphonates, for example hydroxyalkanephosphonates
and
aminoalkanephosphonates. Among the hydroxyalkanephosphonates, the 1-
hydroxyethane-1,1-
diphosphonate (HEDP) is of particular importance as cobuilder. It is
preferably used as sodium
salt, the disodium salt being neutral and the tetrasodium salt being alkaline
(pH 9). Suitable
aminoalkanephosphonates are preferably
ethylenediaminetetramethylenephosphonate
(EDTMP), diethylenetriaminepentamethylenphosphonate (DTPMP), and also their
higher
homologues. They are preferably used in the form of the neutrally reacting
sodium salts, e.g. as
hexasodium salt of the EDTMP or as hepta- and octa-sodium salts of the DTPMP.
Formulations according to the invention can comprise one or more alkali
carriers. Alkali carriers
provide, for example, for the pH of at least 9 if an alkaline pH is desired.
For example, alkali
metal carbonates, alkali metal hydrogen carbonates, alkali metal hydroxides
and alkali metal
metasilicates are suitable. A preferred alkali metal is in each case
potassium, particular
preference being given to sodium.
In addition to bleaches (D), formulations according to the invention can
comprise one or more
chlorine-containing 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 according to the invention can comprise, for example, in the
range from 3 to 10%
by weight of chlorine-containing bleach.
Formulations according to the invention can comprise one or more bleach
catalysts. Bleach
catalysts can be selected from bleach-boosting transition metal salts and/or
transition metal
complexes, such as, for example, manganese-, iron-, cobalt-, ruthenium- or
molybdenum-salen
complexes or -carbonyl complexes. It is also possible to use manganese, iron,
cobalt,
ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-
containing
tripod ligands, and also cobalt-, iron-, copper- and ruthenium-amine complexes
as bleach
catalysts.
Formulations according to the invention can comprise one or more bleach
activators, for
example N-methylmorpholinium-acetonitrile salts ("MMA salts"),
trimethylammoniumacetonitrile
PF 73447 CA 02870785 2014-10-17
13
salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1,5-diacety1-
2,2-dioxo-
hexahydro-1,3,5-triazine ("DADHT") or nitrile quats (trimethylammonium
acetonitrile salts).
Further examples of suitable bleach activators are tetraacetylethylenediamine
(TAED) and
tetraacetylhexylenediamine.
Formulations according to the invention can comprise one or more corrosion
inhibitors. In the
present case, this is to be understood as meaning those compounds which
inhibit the corrosion
of metal. Examples of suitable corrosion inhibitors are triazoles, in
particular benzotriazoles,
bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, also phenol
derivatives such as, for
example, hydroquinone, pyrocatechin, hydroxyhydroquinone, gallic acid,
phloroglucine or
pyrogallol.
In one embodiment of the present invention, formulations according to the
invention comprise in
total in the range from 0.1 to 1.5% by weight of corrosion inhibitor.
Formulations according to the invention can comprise one or more builders, for
example sodium
sulfate.
Formulations 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 according to the
invention comprise in
total in the range from 0.05 to 0.5% by weight of antifoam.
Formulations according to the invention can comprise phosphonic acid or one or
more
phosphonic acid derivatives, for example hydroxyethane-1,1-diphosphonic acid.
The present invention further provides the use of formulations according to
the invention for the
machine washing of dishes and kitchen utensils. Within the context of the
present invention,
kitchen utensils to be mentioned are, for example, pots, pans, casseroles,
also metallic objects
such as, for example, skimmers, fish slices and garlic presses.
Preference is given to the use of formulations according to the invention for
the machine
cleaning of objects which have at least one surface made of glass, which may
be decorated or
undecorated. In this connection, within the context of the present invention,
a surface made of
glass is to be understood as meaning that the object in question has at least
one section made
of glass which comes into contact with the surrounding air and may be soiled
upon using the
object. Thus, the objects in question may be those which, like drinking
glasses or glass bowls,
are essentially made of glass. However, they may, for example, also be lids
which have
individual components made of another material, for example pot lids with
edges and handle
made of metal.
PF 73447 CA 02870785 2014-10-17
14
Surface made of glass may be decorated, for example colored or imprinted, or
be undecorated.
The term "glass" includes any desired glasses, for example lead glass and in
particular soda-
lime glass, crystal glass and borosilicate glasses.
Preferably, machine cleaning is washing using a dishwasher (automatic
dishwashing).
In one embodiment of the present invention, at least one formulation according
to the invention
is used for the machine cleaning of drinking glasses, vases made of glass and
glass vessels for
cooking.
In one embodiment of the present invention, water with a hardness in the range
from 1 to 300
German hardness, preferably 2 to 25 German hardness, is used for the
cleaning, where
German hardness is to be understood in particular as meaning the calcium
hardness.
For the rinsing as well, it is possible to use water with a hardness in the
range from 1 to 30
German hardness, preferably 2 to 25 German hardness.
If formulations according to the invention are used for machine cleaning,
then, even upon the
repeated machine cleaning of objects which have at least one surface made of
glass, only a
very low tendency towards glass corrosion is observed, and then only if
objects which have at
least one surface made of glass are cleaned together with heavily soiled
cutlery or crockery.
Moreover, it is significantly less harmful to use formulation according to the
invention for
cleaning glass together with objects made of metal, for example together with
pots, pans or
garlic presses.
Furthermore, it can be observed that formulations according to the invention
have a very good
bleaching effect when used for washing dishes and kitchen utensils and glass
surfaces.
The present invention further provides a process for the preparation of
formulations according to
the invention, also abbreviated to preparation process according to the
invention. To carry out
the preparation process according to the invention, the procedure may involve,
for example,
mixing, for example stirring,
(A) aminocarboxylate, selected from methylglycine diacetate (MGDA),
iminodisuccinic acid
(IDA) and glutaminic acid diacetate (GLDA), and salts thereof, and
(B) at least one alkyleneimine polymer which is covalently modified with at
least one carboxylic
acid or at least one derivative of a carboxylic acid or at least one
derivative of carbonic acid,
where up to at most 75 mol% of the nitrogen atoms of the primary and secondary
amino
groups of the alkyleneimine polymer have been reacted with carboxylic acid or
derivative of
carboxylic acid or carbonic acid,
and optionally
(C) sodium citrate or
' PF 73447 CA 02870785 2014-10-17
(D) at least one compound selected from alkali metal percarbonate, alkali
metal perborate and
alkali metal persulfate,
and optionally further components (E) in one or more steps with one another in
the presence of
water, and then removing the water, completely or at least partially.
5
Compound (A), modified polyalkyleneimine (B) and bleach (D) are defined above.
In one embodiment of the present invention, before the water is at least
partially removed, it is
possible to mix with one or more further ingredients (E) for formulation
according to the
10 invention, for example with one or more surfactants, one or more
enzymes, one or more
builders, one or more cobuilders, in particular phosphorus-free builders, one
or more alkali
carriers, one or more bleaches, one or more bleach catalysts, one or more
bleach activators,
one or more bleach stabilizers, one or more antifoams, one or more corrosion
inhibitors, one or
more builders, with buffer or dye.
In one embodiment, the procedure involves removing the water completely or
partly, for
example to a residual moisture in the range from 0.1 to 10% by weight, from
formulation
according to the invention by evaporating it, in particular by spray-drying,
spray-granulation or
compaction.
In one embodiment of the present invention, the water is removed, completely
or partially, at a
pressure in the range from 0.3 to 2 bar.
In one embodiment of the present invention, the water is removed, completely
or partially, at
temperatures in the range from 60 to 220 C.
By means of the preparation process according to the invention, formulation
according to the
invention can be readily obtained.
The cleaning formulations according to the invention can be provided in liquid
or solid form, in
single-phase or multi-phase, as tablets or in the form of other metering
units, in packaged or
unpackaged form. The water content of liquid formulations can vary from 35 to
90% water.
The invention is illustrated by working examples.
General: It was ensured that following the first cleaning of the test pieces
in the domestic
dishwasher until after weighing and visual assessment of the glasses, the test
pieces were only
handled using clean cotton gloves so that the weight and/or the visual
impression of the test
pieces was not falsified.
Data in % are % by weight unless expressly stated otherwise.
PF 73447 CA 02870785 2014-10-17
16
I. Formulations according to the invention
The charge density of modified polyethyleneimines (B) was always determined as
follows (see
also: Horn, Prog. Colloid & Polym. Sci. 1978, 65, 251):
1 g of the (co)polymer (B) in question was dissolved in 100 ml of
demineralized water. A buffer
solution and aqueous HCI were used to establish a pH of 4.0, determined
potentiometrically.
3 ml of an aqueous solution of toluidine blue (50 mg/I of water) were added
and N/400-KPVS
(potassium polyvinyl sulfate) solution (Wako) with a concentration of 0.0004
meq/ml was titrated
until the color changed from blue to pink. The charge density was calculated
as follows:
LA = 0.4 = KV
where
LA: charge density of the modified polyethyleneimine (B) in question,
meq/g (milliequivalent/g)
KV: consumption of the N/400-KPVS
solution, ml
1.1 Preparation of basis mixtures
Firstly, basis mixtures were prepared from the feed materials according to
table 1. The feed
materials were mixed dry.
Table 1: Base mixtures for experiments with formulations according to the
invention and
comparative formulations
Base-1 Base-2 Base-3
Protease 2.5 2.5 2.5
Amylase 1 1 1
n-C18H37(OCH2CH2)90H 5 5 5
Polyacrylic acid M, 4000 g/mol, as 10 10 10
sodium salt, completely neutralized
Sodium percarbonate (D.1) 10.5 10.5 10.5
TAED 4 4 4
Na2CO3 19.5 19.5 19.5
Sodium citrate dihydrate 5 22.5 19.5
Na2Si205 2 2 2
All data in g.
Abbreviations:
MGDA: methylglycinediacetic acid as trisodium salt
TAED: N,N,N',N'-tetraacetylethylenediamine
HEDP: disodium salt of hydroxyethane(1,1-diphosphonic acid)
PF 73447 CA 02870785 2014-10-17
-
17
1.2 Preparation of formulations according to the invention
1.2.1 Preparation of formulations 2 to 13 according to the invention and of
comparison
formulations Cl to C8
Modified polyethyleneimines (B) as per table 2 were used:
Table 2: Modified polyethyleneimines
Abbreviation M,, (g/mol) Modification with Functionalization
Cationic charge
(mol-`)/0)
density (meq/g)
6.1.1.1 800 Acrylic acid 5 15
6.1.1.2 800 Acrylic acid 20 11
B.1.1.3 800 Acrylic acid 40 7
B.1.2.1 2000 Acrylic acid 15 12
B.1.3.1 5000 Acrylic acid 15 13
B.1.4.1 50 000 Acrylic acid 15 11.5
B.2.1.1 800 Formic nitrile 20 12
B.2.2.2 2000 Formic nitrile 15 11
B.2.3.3 5000 Formic nitrile 25 9
B.2.4.4 50 000 Formic nitrile 10 14
6.3.1.1 800 Valeric acid 10 16
6.3.2.2 2000 Valeric acid 40 9
B.3.3.3 5000 Valeric acid 15 14
B.4.1.1 800 Lauric acid 5 18
B.4.1.2 800 Lauric acid 15 14.5
B.4.2.3 2000 Lauric acid 20 12.5
B.4.3.3 5000 Lauric acid 20 12
B.5.1.1 800 Ethylene carbonate 10 16
6.5.1.2 800 Ethylene carbonate 20 13
8.5.1.3 800 Ethylene carbonate 50 9
6.5.2.4 2000 Ethylene carbonate 15 11.5
6.5.3.2 5000 Ethylene carbonate 20 12.5
B.5.4.1 50 000 Ethylene carbonate 10 14.5
The molecular weight M, was determined on the underlying polyethyleneimines,
i.e. before the
modification in each case. The functionalization refers to the sum of the
primary and secondary
N atoms in the polyethyleneimine in question.
Procedure:
In a 100 ml beaker, 20 ml of distilled water were introduced and modified
polyethyleneimine (B)
according to Tables 2 and 3 was added with stirring.
The mixture was then stirred for 10 minutes. MGDA trisodium salt (Al),
dissolved in 30 ml of
water, was then added according to Table 3. This gave a clearly transparent
solution. Then,
PF 73447 CA 02870785 2014-10-17
18
base mixture according to Table 3 was added, the mixture was stirred again,
and the water was
evaporated.
If, during the test, the corresponding fractions of base mixture were metered
separately from
aqueous solution of (Al), (B), (C.1) or (D.1), the same results were obtained
as when the dried
formulation with identical amounts of active ingredient was tested. It is thus
not a question of the
order of the metered addition.
Additionally using 2.5% by weight of polyvinyl alcohol during the compaction
gives formulations
with improved powder morphology (grain size, bulk density) and a reduced water
absorption in
the air.
II. Use of formulations according to the invention and comparison
formulations for the
machine cleaning of glasses
General: It was ensured that following the first cleaning of the test pieces
in the domestic
dishwasher until after weighing and visual assessment of the glasses, the test
pieces were only
handled using clean cotton gloves so that the weight and/or the visual
impression of the test
pieces was not falsified.
The testing of formulations according to the invention and comparison
formulations was carried
out as follows.
11.1 Test method for dishwasher with continuous operation
Dishwasher: Miele G 1222 SCL
Program: 65 C (with prewash)
Ware: 3 "GILDE" champagne glasses, 3 "INTERMEZZO" brandy glasses
For the cleaning, the glasses were arranged in the upper crockery basket of
the dishwasher.
The dishwashing detergent used was in each case 25 g of formulation according
to the
invention or 25 g of comparison formulation as per table 2, table 2 specifying
in each case the
active components (Al), base mixture, silicate (0.1 or C.2) and compound (D)
or (E) and (B) of
formulation according to the invention. Washing was carried out at a clear-
rinse temperature of
55 C. The water hardness was in each case in the range from zero to 2 German
hardness.
Washing was carried out in each case for 100 wash cycles, i.e. the program was
left to run
100 x. The evaluation was made gravimetrically and visually after 100 wash
cycles.
The weight of the glasses was determined before the start of the first wash
cycle and after
drying after the last wash cycle. The weight loss is the difference in the two
values.
Besides the gravimetric evaluation, a visual assessment of the ware after 100
cycles in a
darkened chamber with light behind a perforated plate was carried out using a
grading scale
. PF 73447 CA 02870785 2014-10-17
4.
19
from 1 (very poor) to 5 (very good). In this connection, in each case, grades
were determined
for patchy corrosion/clouding and/or line corrosion.
Experimental procedure:
For the purposes of the pretreatment, the test pieces were firstly washed in a
domestic
dishwasher (Bosch SGS5602) with 1 g of surfactant (n-C181-137(OCH2OH2)100H)
and 20 g of citric
acid in order to remove any contaminations. The test pieces were dried, their
weight was
determined, and they were fixed to the mesh base insert.
In order to assess the gravimetric abrasion, the dry test pieces were weighed.
The visual
assessment of the test pieces was then carried out. For this, the surface of
the test pieces was
assessed with regard to line corrosion (glass ridges) and hazing corrosion
(sheet-like hazing).
The evaluations were made in accordance with the following scheme.
Line corrosion:
L5: no lines visible
L4: slight line formation in very few areas, fine line corrosion
L3: line corrosion in a few areas
L2: line corrosion in several areas
L1: severe line corrosion
Glass hazing
L5: no hazing visible
L4: slight hazing in very few areas
L3: hazing in a few areas
L2: hazing in several areas
L1: severe hazing over virtually the whole glass surface
During the assessment, intermediate grades (e.g. L3-4) were also allowed.
11.3 Results
The results are summarized in table 3.
Only slight or even no glass corrosion was established in the inventive
examples.
If, instead of water, hardness water with 2 German hardness was used for the
tests, then
formulations according to the invention were likewise always superior to the
corresponding
comparison formulations in terms of the inhibition of the glass corrosion.
,
Table 3: Results of the tests with dishwasher (continuous operation) -u
-n
il
Visual
Weight loss Weight
loss Visual
Base mixture:
assessment
Example No. (A.1) [g] (B) [mg] champagne brandy
glass assessment
[9]
champagne
glass [mg] [mg]
brandy glass
glass
C-1 Base-3: 17 3 --- 42.60 22.70
L1-2, 11-2 L2, T2
2 Base-3: 17 3 48 (B.5.1.1) 8
6 L5, T5 L4-5, T5
3 Base-3: 17 3 24 (B.5.1.1) 9
6 L4, T5 L4-5, T5
4 Base-1: 17 3 24 (B.5.1.2) 16
12 L4, T4-5 L4, T4-5
Base-3: 17 3 24 (B.5.1.3) 14 10
L3-4, T4 L4, T4 P
6 Base-2: 17 3 24 (B.1.1.2) 16
11 L4, T3-4 L3-4, T4 -
,,
.3
_,
7 Base-3: 17 3 24 (B.1.1.3) 17
13 L3, T3-4 L3, T4 0
_,
0
6 Base-3: 17 3 12 (B.1.3.1) 10
7 L4, T4-5 L4, T4-5
r.) .
8 Base-3: 17 3 24 (B.2.3.3) 16
12 L3, 13-4 L2-3, T3-4 a
,
,
.
'
9 Base-3: 17 3 24 (B.3.3.3) 13
10 L3, T4 L3, T4 ,
_,
Base-3: 17 3 24 (B.4.1.2) 19 12
L2-3, T3 L3, T3-4
