Note: Descriptions are shown in the official language in which they were submitted.
PF 72612 CA 02849358 2014-03-20
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1
Formulations, their use as or for producing dishwashing detergents and their
production
The present invention relates to formulations comprising
(A) at least one compound selected from aminocarboxylates and
polyaminocarboxylates,
(B) at least one homopolymer or copolymer of ethyleneimine,
(C) sodium citrate and
(D) at least one compound selected from alkali metal percarbonate, alkali
metal perborate
and alkali metal persulfate.
Furthermore, the present invention relates to a process for producing
formulations according to
the invention and to their use as or for producing dishwashing detergents, in
particular
dishwashing detergents for machine dishwashing.
Dishwashing detergents have to meet many requirements. For example, they have
to clean the
dishes thoroughly, they should have no harmful or potentially harmful
substances in the waste
water, they should permit the running-off and drying of the water from the
dishes, and they
should not lead to problems during the operation of the dishwasher. Finally,
they should not
lead to esthetically undesirable results on the item to be cleaned. In this
connection, glass
corrosion is to be mentioned in particular.
Glass corrosion arises not only as a result of mechanical effects, for example
as a result of
glasses rubbing together or mechanical contact between the glasses and parts
of the
dishwasher, but is primarily promoted by chemical influences. For example,
certain ions can be
dissolved out of the glass as a result of repeated machine cleaning, which
adversely alters the
optical and thus esthetic properties.
Several effects are observed with glass corrosion. Firstly, the formation of
microscopically fine
cracks can be observed which become noticeable in the form of lines. Secondly,
in many cases,
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,
scoring, as well as patchy and circular clouding.
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 detergents.
WO 2010/020765 discloses dishwashing detergents which comprise
polyethyleneimine.
Dishwashing detergents of this type can comprise phosphate or be phosphate-
free. They are
attributed good inhibition of glass corrosion. Zinc-containing and bismuth-
containing
dishwashing detergents are discouraged. Glass corrosion, in particular line
corrosion and
clouding, however, is in many cases still not adequately delayed or prevented.
, PF 72612 CA 02849358 2014-03-20
2
It was therefore the object to provide formulations which are suitable as or
for producing
dishwashing detergents and which avoid the disadvantages known from the prior
art and which
inhibit glass corrosion or at least reduce it particularly well. It was also
the object to provide a
process for producing formulations which are suitable as or for producing
dishwashing
detergents 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 outset have been found, also
called for short
formulations according to the invention.
Formulations according to the invention comprise
(A) at least one compound selected from aminocarboxylates and
polyaminocarboxylates, in the
scope of the present invention also called for short aminocarboxylate (A) or
polyaminocarboxylate (A) or else compound (A), and also derivatives and
preferably salts
thereof.
Compound (A) can be present as a free acid or preferably in partially or
completely neutralized
form, i.e. as a salt. Suitable counterions are, for example, inorganic
cations, for example
ammonium, alkali metal or alkaline earth metal, preferably Mg2+, preferably
Na, K+, or organic
cations, preferably ammonium substituted with one or more organic radicals, in
particular
triethanolammonium, N,N-diethanolammonium, N-mono-C1-C4-
alkyldiethanolammonium, for
example N-methyldiethanolammonium or N-n-butyldiethanolammonium, and N,N-di-C1-
C4-
alkylethanolammonium.
In one embodiment of the present invention, compound (A) is selected from
derivatives of
aminocarboxylates and polyaminocarboxylates, for example from methyl or ethyl
esters.
Within the context of the present invention, aminocarboxylates (A) are
understood as meaning
nitrilotriacetic acid and those organic compounds which have a tertiary amino
group which has
one or two CH2-COOH groups which ¨ as mentioned above ¨ can be partially or
completely
neutralized. Within the context of the present invention,
polyaminocarboxylates (A) are
understood as meaning those organic compounds which have at least two tertiary
amino
groups, each of which, independently of the other, has one or two CH2-COOH
groups which ¨
as mentioned above ¨ can be partially or completely neutralized.
In another embodiment of the present invention, aminocarboxylates (A) are
selected from those
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 (A) are
selected from those organic compounds which have at least two secondary amino
groups,
which each have one CH(COOH)CH2-COOH group, which ¨ as mentioned above ¨ can
be
partially or completely neutralized.
PF 72612 CA 02849358 2014-03-20
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Preferred polyaminocarboxylates (A) are selected from 1,2-
diaminoethanetetracetic acid,
tetraacetylmethylenediamine, tetraacetylhexylenediamine, iminodisuccinate
(IDS),
diethylenetriaminepentaacetate (DTPA), hydroxyethylenediaminetriacetate
(HEDTA), and their
respective salts, particularly preferably alkali metal salts, in particular
the sodium salts.
Preferred aminocarboxylates (A) and polyaminocarboxylates (A) are
nitrilotriacetic acid and
those organic compounds which have a structure based on an amino acid, the
amino group(s)
of which has or have one or two CH2-000H groups and are tertiary amino groups.
In this
connection, amino acids can be selected from L-amino acids, R-amino acids and
enantiomer
mixtures of amino acids, for example the racemates.
In one embodiment of the present invention, compound (A) is selected from
methylglycinediacetate (MGDA), nitrilotriacetic acid and glutamic acid
diacetate, and derivatives
thereof and preferably salts thereof, in particular the sodium salts thereof.
Very particular
preference is given to methylglycinediacetate and also the trisodium salt of
MGDA.
The formulation according to the invention further comprises
(B) at least one homopolymer of ethyleneimine, together for short also called
polyethyleneimine
(B).
According to a particular embodiment of the invention, polyethyleneimine (B)
has an average
molecular weight Mn of from 500 g/mol to 125 000 g/mol, preferably from 750
g/mol to
100 000 g/mol.
In one embodiment of the present invention, polyethyleneimine (B) has an
average molecular
weight Mw 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 (B) are
selected from highly
branched polyethyleneimines. Highly branched polyethyleneimines (B) are
characterized by
their high degree of branching (DB). The degree of branching can be determined
for example by
13C-NMR spectroscopy, preferably in 020, 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.
. PF 72612 CA 02849358 2014-03-20
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4
Within the context of the present invention, highly branched
polyethyleneimines (B) are
polyethyleneimines (B) 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.
Within the context of the present invention, dendrimeric polyethyleneimines
(B) are
polyethyleneimines (B) with a structurally and molecularly uniform
constitution.
In one embodiment of the present invention, polyethyleneimine (B) is highly
branched
polyethyleneimines (homopolymers) with an average molecular weight Mõ in the
range from 600
to 75 000 g/mol, preferably in the range from 800 to 25 000 g/mol.
According to a particular embodiment of the invention, polyethyleneimine (B)
is highly branched
polyethyleneimines (homopolymers) with an average molecular weight Mn of from
500 g/mol to
125 000 g/mol, preferably from 750 g/mol to 100 000 g/mol, which is selected
from dendrimers.
Formulations according to the invention further comprise sodium citrate (C).
Here, the term
sodium citrate includes the mono- and preferably the disodium salt. Sodium
citrate can be used
as the anhydrous salt or as the hydrate, for example as the dihyd rate.
Formulations according to the invention further comprise
(D) at least one compound selected from alkali metal percarbonate,
alkali metal perborate and
alkali metal persulfate, within the scope of the present invention also called
"bleach (D)'.
Preferred bleaches (D) are selected from sodium perborate, anhydrous or, for
example, as the
monohydrate or as the tetrahydrate or so-called dihydrate, sodium
percarbonate, anhydrous or,
for example, as the monohydrate, and sodium persulfate, where the term
"persulfate" in each
case includes 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, the
dialkali metal salts are preferred in each case.
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 compound (A), preferably 10
to 25% by weight,
in total 0.05 to 2% by weight of homopolymer of ethyleneimine (B), preferably
0.1 to 0.5% by
weight,
1 to 50% by weight of sodium citrate (C), preferably 5 to 30% by weight,
determined as
anhydrous sodium citrate,
in total 0.5 to 15% by weight of bleach (D), selected from alkali metal
percarbonate, alkali metal
perborate and alkali metal persulfate,
based in each case on the solids content of the formulation in question.
. PF 72612 CA 02849358 2014-03-20
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In one embodiment of the present invention, the formulation according to the
invention is solid
at room temperature, for example a powder or a tablet. In another embodiment
of the present
invention, the formulation according to the invention is liquid at room
temperature. In one
5 embodiment of the present invention, the formulation according to the
invention is granules, a
liquid preparation or a gel.
In one embodiment of the present invention, the formulation according to the
invention
comprises 0.1 to 10% by weight of water, based on the sum of all solids in the
formulation in
question.
In one embodiment of the present invention, the formulation according to the
invention is free
from phosphates and polyphosphates, with hydrogenphosphates being subsumed,
for example
free from trisodium phosphate, pentasodium tripolyphosphate and hexasodium
metaphosphate.
In connection with phosphates and polyphosphates, "free from" should be
understood within the
context of the present invention as meaning that the content of phosphate and
polyphosphate is
in total in the range from 10 ppm to 0.2% by weight, determined by gravimetry.
In one embodiment of the present invention, the formulation according to the
invention is free
from those heavy metal compounds which do not act as bleach catalysts, in
particular from
compounds of ion and of bismuth. In connection with heavy metal compounds,
within the
context of the present invention, "free from" should be understood as meaning
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.
Within the context of the present invention, "heavy metals" are all metals
having 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, the 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, the 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
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 builder substances, 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.
PF 72612 CA 02849358 2014-03-20
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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
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
R2/ R3M _ n
(I)
in which the variables are defined as follows:
R1 is selected from linear C1-C10-alkyl, preferably ethyl and
particularly preferably methyl,
R2 is selected from C8-C22-alkyl, for example n-C8H17, n-C10H21, n-
C12H25, n-C14H29, ri-C16H33
or n-C181-137,
R3 is selected from Cl-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,
preference being given to block copolymers.
Other preferred examples of alkoxylated alcohols and alkoxylated fatty
alcohols are, for
example, compounds of the general formula (II)
R1 R1
(II)
in which the variables are defined as follows:
R1 is identical or different and selected from linear Cl-C4-alkyl,
preferably identical in each
case and ethyl and particularly preferably methyl,
PF 72612 CA 02849358 2014-03-20
7
R4 is selected from C6-C20-alkyl, in particular n-C8H17, n-C10H21, n-C12F-
125, rl-C14H29, 11-C161-133,
n-Ci8H37,
a is a number in the range from 1 to 6,
b is a number in the range from 4 to 20,
c is a number in the range from 4 to 25.
Here, compounds of the general formula (II) may be block copolymers or random
copolymers,
preference being given to 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-alkyl
sulfonates and C8-C2o-
alkyl ether sulfates with one to 6 ethylene oxide units per molecule.
In one embodiment of the present invention, the formulation according to the
invention can
comprise in the range from 3 to 20% by weight of 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, preference being given to 0.1 to 3% by weight, in each case based on
the total solids
content of the formulation according to the invention.
Over and above sodium citrate, 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 15-Na2S1205, 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.
PF 72612 CA 02849358 2014-03-20
8
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.
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
NA, 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 with 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: ally' 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 sulfonic-acid-group-containing monomers here are 1-
acrylamido-1-
propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-
methylpropanesulfonic 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 sodium,
potassium or ammonium salts thereof.
. PF 72612 CA 02849358 2014-03-20
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9
Particularly preferred phosphonate-group-containing monomers are
vinylphosphonic acid and
its salts.
Moreover, amphoteric polymers can also be used as builders.
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, 1-hydroxyethane-
1,1-
diphosphonate (HEDP) is of particular importance as a cobuilder. It is
preferably used as the
sodium salt, the disodium salt giving a neutral reaction and the tetrasodium
salt an alkaline
reaction (pH 9). Suitable aminoalkanephosphonates are preferably
ethylenediaminetetra-
methylenephosphonate (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.
Formulations 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 hydrogen carbonates, alkali
metal hydroxides and
alkali metal metasilicates. A preferred alkali metal is in each case
potassium, particular
preference being given to sodium.
Besides bleach (D), formulations according to the invention comprise one or
more chlorine-
containing bleaches.
Suitable chlorine-containing bleaches are, for example, 1,3-dichloro-5,5-
dimethylhydantoin, N-
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 or
transition metal
complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or
molybdenum-salen
complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium,
molybdenum, titanium,
= PF 72612 CA 02849358 2014-03-20
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 according to the invention can comprise one or more bleach
activators, for
5 example N-methylmorpholinium-acetonitrile salts ("MMA salts"),
trimethylammonium acetonitrile
salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1,5-diacety1-
2,2-
dioxohexahydro-1,3,5-triazine ("DADHT") or nitrile quats (trimethylammonium
acetonitrile salts).
Formulations according to the invention can comprise one or more corrosion
inhibitors. In the
10 present case, this is to be understood as including 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, pyrocatechol, hydroxyhydroquinone, gallic acid,
phloroglucinol 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 builder
substances, 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 cleaning of dishes and kitchen utensils. Within the scope of the
present invention,
kitchen utensils which may be mentioned are, for example, pots, pans,
casseroles, also objects
made of metal such as, for example, slotted spoons, 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 ambient air and can become soiled
upon use of 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
. PF 72612 CA 02849358 2014-03-20
11
individual components made of a different material, for example pot lids with
rim and handle
made of metal.
Surfaces made of glass can be decorated, for example colored or imprinted, or
be undecorated.
The term "glass" includes any desired types of glass, for example lead glass
and in particular
soda-lime glass, crystal glass and borosilicate glasses.
Preferably, machine cleaning is washing with 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, glass vases and glass
vessels for cooking.
In one embodiment of the present invention, for the cleaning, water with a
hardness in the range
from 1 to 30 German hardness, preferably 2 to 25 German hardness is used,
with German
hardness being understood in particular as meaning the calcium hardness.
If formulations according to the invention are used for machine cleaning, then
even in the case
of repeated machine cleaning of objects which have at least one surface made
of glass, only a
very slight tendency towards glass corrosion is observed, and only then if
objects which have at
least one surface made of glass are cleaned together with heavily soiled
cutlery or dishes.
Furthermore, it is significantly less harmful to use the formulation according
to the invention to
clean 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 producing formulations
according to the
invention, for short also called production process according to the
invention. To carry out the
production process according to the invention, the procedure may, for example,
be such that
(A) at least one compound selected from aminocarboxylates and
polyaminocarboxylates,
and salts and derivatives thereof,
(B) at least one salt of bismuth,
(C) at least one homopolymer or copolymer of ethyleneimine
and optionally further components (E) are mixed, for example stirred, in one
or more steps with
one another in the presence of water, and then the water is removed,
completely or at least
partially.
Compound (A), salt of bismuth (B) and polyethyleneimine (C) are defined above.
' PF 72612 CA 02849358 2014-03-20
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12
In one embodiment of the present invention, before the water is at least
partially removed,
mixing with one or more further ingredients (E) for the formulation according
to the invention is
possible, 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 builder substances, with buffer or dye.
In one embodiment, the procedure involves removing the water from the
formulation according
to the invention entirely or partially, for example to a residual moisture in
the range from zero to
5% by weight, by evaporating it, in particular by means of 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 production process according to the invention, formulations
according to the
invention can be obtained easily.
The cleaning formulations according to the invention can be provided in liquid
or solid form, in a
single-phase or multiphase, as tablets or in the form of other dosage 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 after the first cleaning of the test bodies in
the domestic
dishwasher until after the weighing and visual inspection of the glasses, the
test bodies were
handled only with clean cotton gloves so that the weight and/or the visual
impression of the test
bodies was not falsified.
I. Preparation of formulations according to the invention
1.1 Preparation of basis mixtures
Firstly, basis mixtures were prepared which comprised the feed materials
according to table 1.
The feed materials were mixed dry.
* PF 72612 CA 02849358 2014-03-20
,
13
Table 1: Basis mixtures for experiments with formulations according to the
invention and
comparison formulations
Basis-1 Basis-2 Basis-3
Protease 2.5 2.5 2.5
Amylase 1 1 1
n-C18H37(OCH2CH2)90H 5 5 5
Polyacrylic acid Mw 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
Na2Si205 2 2 2
Na2CO3 19.5 19.5 19.5
Sodium citrate dihydrate (0.1) 5 22.5 30
HEDP 0.5 0.5 0.5
All quantitative 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)
1.2 Preparation of formulations according to the invention
ml of distilled water were introduced as initial charge in a 100 ml beaker,
and the following
were added in succession with stirring:
15 Polyethyleneimine (B.1), (B.2), (B.3), (B.4) or (B.5) according to
table 2 (or 3)
The mixture was stirred for 10 minutes at room temperature. MGDA-trisodium
salt (A.1),
dissolved in 30 ml of water, as per table 2 (or 3) was then added. This gave a
clearly
transparent solution. The basis mixture as per table 2 (or 3) was then added,
the mixture was
20 stirred again and the water was evaporated.
This gave formulations according to the invention which were tested according
to table 2 (or 3).
To prepare comparison formulations, the procedure was analogous but leaving
the
polyethyleneimine (B) out or using a copolymer of ethyleneimine.
If, in the test "Dishwasher with continuous operation" (or in the immersion
test), the
corresponding fractions of basis mixture are metered in separately from
aqueous solution of
(Al), (B), (C.1) or (D.1), the same results are obtained as when the dried
formulation with the
same amounts of active ingredients was tested. The order of the metered
addition is therefore
of no consequence.
PF 72612 CA 02849358 2014-03-20
14
(B.1): polyethyleneimine homopolymer, Mw 800 g/mol, DB 0.63
(B.2): polyethyleneimine homopolymer, M, 2000 g/mol, DB 0.64
(B.3): polyethyleneimine homopolymer, M 5000 g/mol, DB 0.67
(B.4): polyethyleneimine homopolymer, Mw 25 000 g/mol, DB 0.7
(B.5) polyethyleneimine homopolymer, M, 750 000 g/mol, DB 0.69
(B.6) polyethyleneimine, ethoxylated
(B.7) polyethyleneimine, carboxymethylated, sodium salt, functionalization 80
mol% of the
primary amino groups, Mw 50 000 g/mol (after carbomethoxylation)
II. Use of formulations according to the invention and comparison
formulations for the
machine cleaning of glasses
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 comparison formulation according to table 2, where table 2
specifies the active
components (Al), basis mixture (including (Cl) and (D.1) and optionally (B))
of formulation
according to the invention in each case individually. Washing was carried out
at a clear-rinse
temperature of 55 C. The water hardness was in each case in the range from 0
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.
As well as the gravimetric evaluation, a visual assessment of the ware after
100 cycles in a
darkened chamber with light behind a perforated plate was awarded using a
grading scale from
1 (very poor) to 5 (very good). In this connection, grades were determined in
each case for
patchy corrosion/clouding and/or line corrosion.
11.2 Test method for immersion test
= PF 72612 CA 02849358 2014-03-20
Equipment:
Stainless steel pot (volume ca. 6 liters) with lid with hole for contact
thermometer
Grid base insert with holder for the stainless steel pot
Magnetic stirrer with stirrer rod, contact thermometer, rubber stopper with
hole
5
Experimental conditions:
Temperature: 75 C
Time: 72 hours
5 liters of distilled water or water with defined water hardness ("hardness
water")
The test bodies used were in each case one champagne glass and one brandy
glass from
Libbey (NL), material: lime-soda glasses.
Experimental procedure:
Firstly, for the purposes of pretreatment, the test bodies were washed in a
domestic dishwasher
(Bosch SGS5602) with 1 g of surfactant (n-C181-137(OCH2CH2)100H) and 20 g of
citric acid in
order to remove any soilings. The test bodies were dried, their weight was
determined and they
were fixed to the grid base insert.
The stainless steel pot was filled with 5.5 liters of water and 25 g of
formulation according to the
invention or comparison formulation were added; table 3 specifies the active
components (Al),
optionally (B), optionally (C) and basis mixture of formulation according to
the invention or
comparison formulation in each case individually. The cleaning liquor obtained
in this way was
stirred using the magnetic stirrer at 550 revolutions per minute. The contact
thermometer was
installed and the stainless steel pot was covered with the lid so that no
water could evaporate
during the experiment. It was heated to 75 C and the grid base insert with the
two test bodies
was inserted into the stainless steel pot, it being ensured that the test
bodies were completely
immersed in the liquid.
When the experiment was complete, the test bodies were removed and rinsed
under running
distilled water. The test bodies were then washed in the domestic dishwasher
using a
formulation consisting of 1 g of surfactant (n-C181-137(OCH2CH2)100H) and 20 g
of citric acid,
again on the 55 C program, in order to remove any deposits.
To assess the gravimetric abrasion, the dry test bodies were weighed. The
visual assessment
of the test bodies was then made. For this, the surface of the test bodies was
assessed with
regard to line corrosion (cord lines) and clouding corrosion (patchy
clouding).
The assessments were carried out according to the following scheme.
Line corrosion:
= PF 72612 CA 02849358 2014-03-20
,
16
L5: no lines evident
L4: slight line formation in a very few areas, fine line corrosion
L3: line corrosion in some areas
L2: line corrosion in a number of areas
L1: pronounced line corrosion
Glass clouding
L5: no clouding evident
L4: slight clouding in a very few areas
L3: clouding in some areas
L2: clouding in a number of areas
L1: pronounced clouding over virtually the entire glass surface
In the case of the inspection, interim grades (e.g. L3-4) were also allowed.
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 as far as inhibiting the glass corrosion is concerned.
11.3 Results
The results are summarized in tables 2 and 3.
_
,
PF 72612
.
17
Table 2: Results of the tests with dishwasher (continuous operation)
Visual
Weight loss
Weight loss
assessment Visual assessment
Example No. Basis mixture: [g] (A.1) [g] (B) [mg] Champagne
Brandy glass [mg]
Champagne Brandy glass
glass [mg]
glass
C-1 Basis-3: 21.25 3/5 --- 42.60 22.70
L1-2, T1-2 L2, T2
2 Basis-3: 21.25 3.75 30 (B.2) 11 7
L3-4, T4-5 L4, T4-5
3 Basis-3: 21.25 3.75 15 (B.2) 13 8
L3, T4-5 L3-4, T4-5
4 Basis-2: 19.37 5.63 30 (B.2) 14 8
L3, T4-5 L3-4, T4-5
¨
Basis-2: 19.37 5.63 15 (B.2) 17 10 L3, T4-5
L2-3, T4-5
6 Basis-1: 15.0 10.0 30 (B.2) 21 12
L2-3, T4-5 L2-3, T4 n
0
7 Basis-1: 15.0 10.0 15 (B.2) 23 14
L2-3, T4 L2-3, T4 I.)
0
8 Basis-3: 21.25 3.75 30 (B.1) 9 6
L4, T5 L4, T5 a,
l0
-
LO
Ul
9 Basis-3: 21.25 3.75 15 (B.1) 12 9
L3-4, T5. L4, T4-5 0
I.)
0
H
FP
I
0
LO
I
IV
0
,
PF 72612
4
18
Table 3: Immersion tests
Visual
Weight loss
Weight loss
assessment Visual assessment
Example No. Basis mixture: [g] (A.1) [g] (6) [mg] Champagne
Brandy glass [mg]
Champagne Brandy glass
glass [mg]
glass
C-1 Basis-3: 21.25 3.75 --- 167 98
L2, T2 L2, T2
2 Basis-3: 21.25 , 3.75 30 (B.5) 148
92 L2-3, T2-3 L2, T2-3
3 Basis-3: 21.25 3.75 30 (13.4) 100 55
L3, T4-5 L3, T4-5
4 Basis-3: 21.25 _ 3.75 30 (B.3) 70
38 L3, T4-5 L3-4, T4-5
Basis-3: 21.25 , 3.75 30 (B.2) 62 33
L3-4, T5 L4, T4-5 0
6 Basis-3: 21.25 3.75 30 (B.1) , 58 31
L3-4, T5 L4, T5
0
0-7 Basis-3: 21.25 3.75 30 (B.6) 152 89
L2-3, T2-3 L2, T2-3 I.)
co
a,
C-8 Basis-3: 21.25 , 3.75 30 (B.7) 122
75 L2-3, T3-4 L2, T3-4 '.0
LO
Ul
9 Basis-3: 21.253.75 7.5 (B.1) 73 40
L2-3, T4-5 L2, T4-5
.
co
I.)
Basis-3: 21.25 3.75 12 (6.1) 68 39 L2-3, T4-5
L2-3, T4-5 0
H
FP
I
11 Basis-3: 21.25 3.75 16.5 (B.1) 63 35
L3, T4-5 L3, T4-5 0
u.)
1
12 Basis-3: 21.25 3.75 24 (B.1) 60 33
L3-4, T5 L4, T4-5 I.)
0
