Title:

Dishwashing detergent with biodegradable builder component I

German Patent DE4321429

Kind Code:

A1

Inventors:

BOOK MEIER WILLI DR (DE)

ANDREE HANS DR (DE)

KRINGS PETER DR (DE)

BURG BIRGIT DR (DE)

Härer JUERGEN DR (DE)

JESCHKE PETER DR (DE)

Application Number:

DE4321429A

Publication Date:

05/01/1995

Filing Date:

06/28/1993

Export Citation:

Click for automatic bibliography generation

Assignee:

HENKEL KGAA, 40589 DUESSELDORF, DE

International Classes:

C11D3 / 37 C11D17 / 00 C11D17 / 06 (IPC1-7): C11D3 / 37 C11D17 / 00

Claims:

1. Low Alkaline means for machine cleaning of dishware, whose 1 wt .-% aqueous solution is preferably
9 to 10.5 has a pH value of 8 to 11.5, comprising water-soluble builder components and oxygen-based
bleaching agents, characterized in that it as a water-soluble builder component is a copolymer which is
composed at least of the monomers of a monoethylenically unsaturated C · äC½-carboxylic acid, a 2-
alkyl allyl or 2-Arylallylsulfonsäure and a carbohydrate contains.

2. Composition according to claim 1, characterized in that the copolymer to 40 to 60 wt .-%, preferably

45 to 55 wt .-%, of (meth) acrylic acid, preferably acrylic acid, to 10 to 30 wt .-%, preferably 15 to 25 wt .-
%, from methallyl wherein methallyl can be partially replaced by a formed by the addition of 1 to 10
ethylene oxide to methacrylic Methacrylsäurepolyethylenglykolester, then the weight ratio between
Methacrylsäurepolyethylenglykolester and methallyl 1: 10 to 10: 1, and 15 to 40 wt .-%, preferably 20 to
40 wt .-%, of a carbohydrate, preferably sucrose, is made.

3rd Composition according to claim 1 and 2, characterized in that it contains 0.5 to 30 wt .-%, preferably
2 to 20 wt .-% copolymer and 0.5 to 20 wt .-%, preferably 5 to 15 wt .-% , a bleaching agent based on
oxygen, in particular alkali metal perborate and / or percarbonate, and in that it is free of anionic,
cationic or amphoteric surfactants and the content of nonionic surfactants max. 5 wt .-%, preferably
max. 2 wt .-%, each based on the total composition weight.

4th Composition according to claim 1 to 3, characterized in that it contains up to 60 wt .-%, preferably 5

to 50 wt .-%, alkali carbonate and / or bicarbonate.

5th Composition according to claim 1 to 4, characterized in that it preferably complexing agents from
the group of di- and polyfunctional organic carboxylic acids or salts thereof, more particularly citric acid
or salts thereof, in an amount of 0.5 to 60 wt .-%, 20 to 50 wt .-%, based on the total composition,
contains.

6th Composition according to claim 1 to 5, characterized in that it contains up to 30 wt .-%, preferably 5

to 20 wt .-%, based on the total agent, alkali metal silicate with a molar ratio SiO ¥ / M ¥ O (M = alkali
metal atom) from 1.5: 1 to 2.5: 1.
7th Composition according to claim 1 to 6, characterized in that it is free from active chlorine donors
means.

Eighth Composition according to claim 1 to 7, characterized in that it contains enzymes in a quantity of

0.1 to 5 wt .-%, preferably 0.5 to 2 wt .-%, based on the total agent.

9th Tablet-shaped composition according to claim 1 to 8, characterized in that it is obtainable by mixing

all its constituents in a mixer, and pressing the mixture by means of a tablet press under pressures of 2 ±
107 ± 108 Pa to 1.5 Pa.

10th Powder or granular composition according to claim 1 to 8, characterized in that it has a bulk
density of 750 g / l to 1000 g / l.

11th Use of the agent according to one of claims 1 to 10 for the machine cleaning of crockery.

description:

The invention relates to low-alkali dishwashing detergent for machine dishwashing a biodegradable
builder component. Free low of the latest generation for machine dishwashing in addition bleaching
agents based on oxygen, surfactants and enzymes, a combination of water-soluble builders, consisting
of complexing agents, eg., Citrate, from alkali carriers, z. B. soda, hydrogen carbonate or disilicate, and
consists of such dispersants. B. polycarboxylates. Other possible builder components are
organophosphonic, aminocarboxylic acids or crystalline layer silicates; the phosphates previously used,
z. B. pentasodium is now largely avoided for ecological reasons. .

The polycarboxylates used in the present dishwashing detergents, for example maleate / acrylate
copolymers, prevent the deposition of lime deposits at excessively high residual water hardness in the
cleaning and rinsing cycle; at high salt load of wash liquor they also improve the clear rinse. A
disadvantage of these polycarboxylates but must be considered that they are not readily biodegradable.
There is a need for machine dishwashing detergents containing biodegradable builder components, but
at the same time show the usual range of modern dishwashing detergents.

Many readily biodegradable builder components such. As oxidized starch or polyaspartic acid are good
dispersants for precipitated calcium but poor complexing agents for water hardness. We have found
that certain made up of at least three individual blocks, readily biodegradable copolymers are
outstandingly suitable as builder components in dishwasher detergents. The invention is a low-alkaline
composition for machine dishwashing detergent of which 1 wt .-% aqueous solution has a pH of 8 to
11.5 and preferably 9 to 10.5, comprising water-soluble builder components and bleach to oxygen-
based, characterized in that it as water-soluble builder component a copolymer which is composed at
least of the monomers of a monoethylenically unsaturated C · äC½-carboxylic acid, a 2-alkylallyl or 2-
Arylallylsulfonsäure and contains a carbohydrate.

The inventive dishwasher detergents include those in which the copolymers are partially or completely
replaced by the salts of copolymers, ie those copolymers in which the carboxyl groups have been
partially or completely converted to carboxylate groups. The copolymers used in the invention include,
in the simplest case, two carboxylic acids and / or salts thereof and a carbohydrate as monomers.

The first acidic monomer or its salt is derived from a monoethylenically unsaturated C · äC½-
monocarboxylic acid, preferably acrylic acid of a C · äC © monocarboxylic acid, in particular of the
(meth). The second acidic monomer or its salt is a derivative of an allyl sulfonic acid which is substituted
in the 2-position with an alkyl radical, preferably a C £ © äC alkyl radical, or an aromatic radical
preferably derived from benzene or benzene derivatives.

Further, the incorporation of additional monomer units in the copolymer is not excluded. Preferred
copolymers contain 40 to 60 wt .-%, in particular 45 to 55 wt .-% of (meth) acrylic acid or (meth) acrylate
with particular preference of acrylic acid or acrylate, 10 to 30 wt .-%, preferably 15 to 25 wt .-%
methallyl or methallyl, with methallyl or methallyl partly can be replaced by one formed by addition of
from 1 to 10 ethylene oxide units of methacrylic acid Methacrylsäurepolyethylenglycolester, then the
weight ratio between Methacrylsäurepolyethylenglycolester and methallyl or sulfonate 1: 10 to 10: 1,
and 15 to 40 wt .-%, preferably 20 to 40 wt .-% of a carbohydrate.

This carbohydrate may be for example a mono-, di-, oligo- or polysaccharide, mono-, di- or oligo-
saccharides are preferred. By installing this carbohydrate predetermined breaking points are
incorporated in the polymer that are responsible for the degradation of the polymer. It is particularly
preferred as the carbohydrate sucrose. The copolymers used in the invention can be prepared by any of
the known and conventional processes. The monomeric acids can be implemented in particular with the
carbohydrate, whereupon optionally a neutralizing the acids will preferably their alkali metal salts, such
as the sodium or potassium salts, or ammonium salts or alkanolamine salts, such as the
monoethanolamine salt or the triethanolamine salt performed in the terminal. In analogy with the usual
(co) polymeric polycarboxylic acids or polycarboxylates such as the homo- or copolymeric acrylic acids or
acrylates are also preferred such copolymers which are either completely or at least partially, in
particular more than 50%, based on the carboxyl groups present, are neutralized. Particularly preferred
is a fully neutralized copolymer, ie consisting of the salts of the monomeric acids, especially the sodium
or potassium salts of the monomeric acids, and a carbohydrate. The copolymers generally have a
relative molecular weight from 1000 to 200,000, preferably 2000-50000 and especially 3000-10000 on.
They are preferably used in powder, spray-dried form. Particularly preferred copolymers are produced
by a process that is described in the earlier German Patent Application P 42 21 381.9. Preferred
dishwashing detergents according to the invention contain the copolymer in quantities of 0.5 to 30 wt .-
%, preferably 2 to 20 wt .-%, further 0.5 to 20 wt .-%, preferably 5 to 15 wt .-%, of a bleaching agent
oxygen-based, in particular alkali metal perborate and / or percarbonate, and nonionic surfactants in an
amount of at most 5 wt .-%, preferably at most 2 wt .-%, wherein the agents are free of anionic, cationic
or amphoteric surfactants. In a preferred embodiment, as alkalinity sources, alkali metal carbonates
and / or bicarbonates, especially the sodium salts, in an amount of up to 60 wt .-%, preferably 5 to 50 wt
.-% contain. The inventive dishwasher detergent can other water-soluble builder components, such.

As synthetic polymers, in which the salts of polymerization of unsaturated carboxylic acids are
understood and to which, for example, polyacrylates, polymethacrylates, polymaleates or copolymers of
acrylic acid with maleic acid or maleic anhydride include, in an amount of 0.5 to 30 wt .-%, preferably 2
included to 20 wt .-%. Suitable polyacrylates are, for example Alcosperse® 102, 104, 106, 404, 406 of
Alco, Acrysole® A N1, LMW 45 N, LMW 10 N from Norsohaas, Degapas® Degussa. Suitable copolymers of
polyacrylic acid and maleic acid are, for. example, Sokalan CP 5, SP 7 BASF, Acrysol® QR 1014 of the
company Norsohaas, Alcosperse® 175 of Alco. In principle, phosphates may be present, but preferably
the dishwashing products are free of phosphate-containing builder components. The usable in the
inventive surfactants whose foam behavior is crucial. Because of the machine's mechanical foaming
compounds are preferred. These are mainly non-ionic surfactants; dishwashing detergents according to
the invention are therefore preferably free of anionic, cationic or amphoteric surfactants. The content of
nonionic surfactants is not more than 5 wt .-%, preferably at most 2 wt .-%. Suitable nonionic surfactants
are especially addition products of from 1 to 20 moles of ethylene oxide (E0) and / or 1 to 20 moles of
propylene oxide (PO) and 1 mole of an aliphatic compound having 10 to 20 carbon atoms selected from
the group of alcohols, carboxylic acids, fatty amines, carboxylic acid amides and alkanesulfonamides of
interest. Important addition to the water-soluble nonionic surfactants but no or substantially water-
insoluble polyglycol ethers containing 2 to 7 ethylene glycol ether in the molecule, preferably they are
used in combination with water-soluble nonionic surfactants. In addition, as nonionic surfactants are
alkylpolyglycosides of the formula RäOä (G) x, where R is a primary, linear or branched aliphatic radical
having from 8 to 22, preferably 12 to 18 carbon atoms, G is a glycose unit having 5 or 6 C-atoms and the
degree of oligomerization x is 1 to 10 Preferred dishwashing detergents according to the invention also
contain complexing agents from the group of di- and polyfunctional organic carboxylic acids or their
salts, eg. Nitrilotriacetic example, but in particular citric acid and salts thereof, in an amount of 0.5 to 60
wt .-%, preferably 20 to 50 wt .-%. Among the common used in low-alkali machine dishwashing
detergents alkalizing agents include alkali metal carbonates, bicarbonates and alkali metal silicates with
a SiO ¥ / M ¥ O (M = alkali metal atom) of 1.5: 1 to 2.5: 1. The preferably used in the inventive
compositions alkali metal carbonates and bicarbonates are the sodium carbonates and hydrogen
carbonates contained in the amounts already mentioned above. On the use of the highly alkaline
metasilicates as alkali carriers are preferably omitted. Instead of the metasilicates are preferably alkali
metal silicates, preferably sodium silicates with a molar ratio SiO ¥ / Na ¥ O of 1.5: 1 to 2.5: 1, in
amounts of up to 30 wt .-%, preferably 5 to 20 wt .-% , based on the total dishwashing composition
used. Among the bleaching agent serving Oxygenbased compounds sodium perborate tetrahydrate
(NaBO ¥ ± H ¥ O ¥ ± 3H ¥ O) sodium perborate monohydrate (NaBO ¥ ± H ¥ O ¥) and the peroxy
carbonate (Na ¥ CO · ± 1, 5 H O ¥ ¥) special significance. Other useful bleaching agents are, for. Example,
peracid salts of organic acids such as perbenzoates or salts of diperdodecanedioic. Preferably, 0.5 to 20
wt .-%, particularly preferably 5 to 15 wt .-%, of a bleach based on oxygen, in particular alkali metal
perborates and / or percarbonates included. Moreover, as can the addition of small quantities of known
bleach stabilizers, borates or Metabo and metasilicates and magnesium salts, eg. Magnesium sulfate be
useful. Suitable bleach activators for these oxidizing agents are, in particular N-acyl and O-acyl
compounds, preferably tetraacylated diamines such as N, N, N ', N'-tetraacetylethylenediamine (TAED).
The compositions of the invention contain such conventional bleach activators in an amount of 0.1 to 10
wt .-%, preferably 1 to 5 wt .-%. The compositions of the invention are preferably free of active chlorine
donor agents such. As trichloroisocyanuric. To improve the removal of protein- or starch-containing food
particles, enzymes such as proteases, amylases, lipases or cellulases are used, for example proteases
such BLAP.RTM 140 Henkel, Optimase® AEM 440, AEM Optimase® 330 Opticlean® AEM-375, OptiClean ®
AEM-250 from Solvay Enzymes, Maxacal® CX 450,000, Maxapem® the company Ibis, Savinase 4.0 T, 6.0
T, 8.0 T from Novo or Experase® T company Ibis; Amylases as Termamyl.RTM 60 T, 90 T from Novo,
Amylase-LT® from Solvay Enzymes or Maxamyl® P 5000, CXT 5000 or CXT 2900 the company Ibis; Lipases
as Lipolase.RTM 30 T from Novo; Cellulases such as Celluzym® 0.7 T from Novo Nordisk. Enzymes are
present in the inventive compositions in an amount of 0.1 to 5 wt .-%, preferably 0.5 to 2 wt .-% contain,
based on the total dishwashing composition. To prevent the tarnishing of silverware can optionally silver
protection agents, as described in the earlier German Patent Application P 43 15 397.6, in particular
water-soluble Mn (II) salts, in an amount of up to 2 wt .-%, preferably 0.1 to be 0.5 wt .-% contained. The
inventive dishwasher detergent are preferably in powdered, granular or tableted preparations which
can be prepared in a conventional per se, for example by mixing, granulation, roll compaction and / or
by spray drying. To produce detergents according to the invention in tablet form, the procedure is
preferably by mixing all the ingredients together in a mixer and the mixture using conventional tablet
presses, for example eccentric presses or rotary presses, under under pressures in the range of 200 ±
105 Pa to 1500 ± 105 Pa. Obtained so easily shatter resistant and nevertheless sufficiently rapidly soluble
under conditions of use tablets with flexural strengths of normally about 150 N. Preferably, a tablet
prepared in has a weight of 15 g to 40 g, especially from 20 g to 30 g, with a diameter of 35 mm to 40
mm. The production of the machine dishwashing detergent in the form of non-dusting, storable free-
flowing powders and / or granules having high bulk densities in the range of 800 to 900 g / l is
characterized in that in a first process part stage, the builder components with at least a portion of liquid
mixture components while increasing the bulk density of this premix are mixed and the like below, if
desired, combining the other components of the automatic dishwashing agent with the premix thus
obtained after an intermediate drying ä. Since the alkali metal carbonate content greatly influences the
alkalinity of the product, the intermediate drying must be performed so that the decomposition of the
sodium bicarbonate to sodium carbonate is as low as possible (or at least as constant as possible). An
additional emerging through the drying sodium carbonate content should namely be taken into
consideration in the formulation of the granular formulation. Low drying temperatures have not only
the decomposition of sodium bicarbonate contrary, but also increase the solubility of the granulated
detergent in the application. It is advantageous, therefore, when drying a supply air temperature, which
should be as low as possible to avoid bicarbonate decomposition on the one hand and the other hand
must be as high as necessary to obtain a product with good storage properties. During drying is
preferred inlet air temperature of about 80 ° C. The granules themselves should not be heated to
temperatures above about 60 ° C. In the first part stage of the mixing process is builder usually applied
in admixture with at least one other component of the dishwashing agent with the liquid components.
Consideration should be here, for example, a precursor, in which the builder component is applied in
admixture with perborate with the liquid nonionic surfactants and / or the solution of fragrances and
intimately mixed. Subsequently, the remaining components are added and worked and homogenized
the entire mixture in the Mischvorrichtunçà04672DEA104321429 DE941128 g. The use of additional
amounts of liquid, ie in particular the use of additional water here is not usually required. The accrued
mixture is then present as free-flowing non-dusting powder to the desired high bulk densities
approximately in the range of 800 to 900 g / l. The pregranules are then mixed with the missing
components of the dishwashing detergent into the finished product. The mixing time is in all cases
illustrated here, both in the preliminary stage of compacting mixing under the influence of liquid
components such as in the following final mixing with the other components in the region of a few
minutes, for example in the range of 1 to 5 minutes. In a particular embodiment, it may be expedient in
the production of fine granules, set by powdering the surface of the granules formed a further
stabilization and equalization. Suitable for this purpose are in particular small amounts of water glass
powder or powdered alkali. The automatic dishwashing agents according to the invention products are
available that are superior in addition to their better biodegradability conventional modern dishwashing
detergents especially in terms of film deposition inhibition and Klarspüleffektes on glassware or knife
blades. The following examples illustrate the subject invention in more detail, but without it in any way
to beschränken.Beispiele It granular dishwashing detergent of the following composition (composition
of the invention A and B comparison means and inventive composition C) were prepared. Medium A
contained 10 wt .-% of the copolymer, the prepared as disclosed in German Patent Application P 42 21
381.9 of 50 wt .-% acrylic acid, 33 wt .-% sucrose and 17 wt .-% 2-methallyl and then completely was
neutralized. Comparative Example B contained 10 wt .-% of products marketed by BASF under the trade
name Sokalan CP5 acrylate maleate Copolymers.Reinigungsleistung The cleaning performance of the
agent A and B was in a dishwasher Miele G 531 (program Universal 65 ° C) at doses with 16 ° dH tested
each of 30 g in 7.0 liters of water in the cleaning cycle (stains as described "Th old creator, SFW, 98
(1972), 763ä765.": tea, milk, minced meat, pudding, grease pencil, starch, oatmeal ). The agent A of the
invention had over the non-inventive agent B in particular in the removal of starch, Fettstift- and
oatmeal stains superior cleaning performance and exhibited in the remaining soils similar to the tea
stain like a comparable Reinigungsleistung.Belagsinhibierung The deposit formation the agents a and B
was in a dishwasher Miele g 590 (universal program 65 ° C) at doses of 20 g in 7.0 liters of water with 16
° dH with the addition of 50 g pumpable soils (mixture of ketchup, gravy, mustard , potato starch, egg
yolk, milk, margarine) tested in the presence of 3.0 ml of a commercially available rinse aid over 10 wash
cycles. The rinse effect ( "spotting") was (very bad = rinse effect) rated a scale of 1 to 8 (= very good rinse
effect, no water spots). The results of the agent A according to the invention with and the comparison
means B made of glasses, knife blades and porcelain plates Klarspüleffekte can found in Table 1.
werden.Tabelle 1 It appears that the inventive composition A the comparison means B, especially with
regard to the Klarspüleffektes on glassware or knife blades is superior. The agent C according to the
invention showed the agent A similar inventive cleaning and Belagsinhibierungsleistungen; due to the
presence of MnSO © it showed superior properties, especially in terms of anti-tarnishing of silver
cutlery.