WO1996012783A1

WO1996012783A1 - Crystalline layered silicates in washing agents for use in dish washers

Info

Publication number: WO1996012783A1
Application number: PCT/EP1995/004019
Authority: WO
Inventors: Willi Buchmeier; Rainer Sorg; Peter Jeschke; Christian Nitsch; Jürgen Härer
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1994-10-20
Filing date: 1995-10-12
Publication date: 1996-05-02
Also published as: DE4437486A1

Abstract

The present invention concerns washing agents for use in dish washers and containing crystalline layered silicates to improve protection of patterns and glass and improve tea-stain removal.

Description

'Crystalline layered silicates in automatic dishwashing detergents'

The present invention relates to machine dishwashing detergents with improved protection for delicate washware, in particular glasses and decorated washware, which at the same time have high tea cleaning performance. The automatic dishwashing detergents contain a citrate builder and, as a co-builder, crystalline layered silicates.

The latest generation of automatic dishwashing detergents contain, in addition to oxygen-based bleaches, surfactants and enzymes, a combination of water-soluble builders, e.g. Citrate or polycarboxylates, and alkali carriers, e.g. Soda, bicarbonate or disilicate.

Since dishwashers in households more widespread have ge found is known that a few years ago mainly be¬ used highly alkaline dishwashing detergent based phosphate / metasilicate ^• th verhal¬ of decorated ware -I unfavorable in terms of corrosion, ie color on porcelain applied overglaze and in-glaze decorations, colored glasses and gold decorations lose their color intensity and luster over time.

The above-mentioned low-alkaline machine dishwashing detergents based on citrate or phosphate have also been shown in the market in recent years. Impact, albeit to a lesser extent.

These disadvantages can largely be eliminated by adding larger amounts of water-soluble amorphous disilicates, but at the same time irreversible damage to glasses occurs after a few rinsing programs with disilicate-containing cleaners, which are noticeable through clouding and iridescence (diminishing colors). So far there has not been a satisfactory solution to the problem of achieving cleaning that is gentle on decor and glass. In addition, the latest generation of dishwashing detergents in particular have the disadvantage that tea impurities are not always completely removed.

The present invention was therefore based on the object of providing a machine dishwashing detergent which has the abovementioned. Disadvantages does not have, i.e. that even after repeated use does not cause damage to the decor or glass and at the same time has good tea cleaning performance.

The object was achieved by using crystalline layered silicates of the formula I.

NaMSi _x 0 _{2x +} i ^• y H ₂ 0 (I),

where M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably 1.9 to 4, and y is a number from 0 to 30, as a decorative and glass-protecting component and as an additive for increasing the tar agreement.

Another task is to provide special low-alkaline dishwashing detergents of the latest generation based on citrate-builder, which Do not have disadvantages.

Low-alkaline automatic dishwashing detergents are known from the prior art which contain both citric acid or citrate or else phosphate and also crystalline layered silicates; However, these agents do not correspond to the cleaners of the latest generation described above with a predominant citrate builder fraction. For example, European patent application EP 416 366 A2 discloses a machine dishwashing detergent which contains 30% by weight sodium triphosphate, 30% by weight crystalline sodium layer silicate, but only 14% by weight citric acid. The European patent application EP 504 091 A1 describes cleaners which contain crystalline phyllosilicates and 15% by weight of citric acid. The present invention therefore furthermore relates to compositions for the mechanical cleaning of dishes containing 25 to 80% by weight, preferably 35 to 55% by weight, of a builder system consisting of at least two builder substances and 5 to 20% by weight, preferably 10 to 15% by weight of an oxygen-based bleaching agent, in each case based on the total agent, characterized in that two of the builder substances contained in the builder system include citric acid (or its alkali metal or ammonium salts) and a crystalline sheet silicate of the formula I.

NaMSi _x 0 _2x + i ^• y H ₂ 0 (I),

wherein M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably 1.9 to 4, and y is a number from 0 to 30, and citric acid in an amount of 16 to 55% by weight. %, preferably 25 to 45% by weight, and crystalline layered silicates in an amount of 0.5 to 25, preferably 2 to 10% by weight, based in each case on the total composition.

Agents which contain crystalline phyllosilicates of the formula I in which x is 2 are particularly suitable.

The main builder component is citric acid or its alkali or ammonium salts. Trisodium citrate is usually used, either in anhydrous form or as a dihydrate. (The percentages by weight are always calculated for free citric acid (anhydrous)).

The layered silicates of formula I are sold by Hoechst AG (Germany) under the trade name Na-SKS, for example Na-SKS-1 (Na ₂ Si ₂₂ θ45-xH ₂ 0, Kenyait), Na-SKS-2 (Na Sii4θ ₂ g-xH ₂ 0, magadiite), Na-SKS-3 (Na ₂ Siβ0i7-xH ₂ 0) or Na-SKS-4 (Na ₂ Si4θg-xH ₂ 0, makatite).

For the purposes of the present invention, Na-SKS-5 (α-Na ₂ Si ₂ 05), Na-SKS-7 (β-Na ₂ Si ₂ 05, natrosilite), Na-SKS-9 (NaHSi ₂ 0s-H ₂ 0), Na-SKS-10 (NaHSi ₂ θ5 ^« 3H 0, Kane it), Na-SKS-11 (T-Na Si ₂ 0s) and Na-SKS-13 (NaHSi θ5), but especially Na-SKS-6 (δ'-Na Si 05). An overview of crystalline layered silicates is given, for example, in "Hoechst High Chem Magazine Articles 14/1993 "on pages 33 - 38 and in" Soap-oil-fat-waxes, 116 year, No. 20/1990 "on pages 805 - 808.

In principle, all builders commonly used in machine dishwashing detergents can be used as optional additional builder components, e.g. B. poly ere alkali phosphates, which may be in the form of their alkali neutral or acidic sodium or potassium salts. Examples of these are: tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. Their amounts are in the range of up to about 20% by weight, based on the total agent; however, the agents according to the invention are preferably free of such phosphates for ecological reasons. Other possible water-soluble builder components are e.g. B. organic polymers of native or synthetic origin, especially polycarboxylates, which in particular act as co-builders under hard water conditions. For example, polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids are suitable. Commercial products are, for example, Sokalan ( ^R ) CP 5 and PA 30 from BASF, Alcosperse ( ^R ) 175 or 177 from Alco, LMW ( ^R ) 45 N and SP02 N from Norsohaas. These synthetic polymers can also be dispensed with for ecological reasons.

The native polymers include, for example, oxidized starch (e.g. German patent application P 42 28 786.3) and polyamino acids such as polyglutic acid or polyaspartic acid, e.g. B. from Cygnus, Bayer, Rohm & Haas, Rhône-Poulenc or SRCHEM. Other possible builder components are naturally occurring hydroxycarboxylic acids such as. B. mono-, dihydroxysuccinic acid, o-hydroxypropionic acid and gluconic acid.

The alkali carriers commonly used include carbonates and hydrogen carbonates. The alkali carrier system preferably used in the agents according to the invention consists of sodium carbonate and sodium hydrogen carbonate in an amount of 10 to 50% by weight, preferably 20 to 35% by weight, based on the total agent, the weight ratio between see sodium carbonate and sodium bicarbonate 1:15 to 2: 1 be¬.

Sodium perborate mono- and tetrahydrate or sodium percarbonate are primarily considered as oxygen-based bleaches. The use of sodium percarbonate has advantages because it also has a particularly favorable effect on the corrosion behavior on glasses. The oxygen-based bleaching agent is therefore preferably a percarbonate salt, in particular stabilized sodium percarbonate. Since active oxygen only develops its full effect on its own at elevated temperatures, so-called bleach activators are often used to activate it at about 60 ° C., the approximate temperatures of the cleaning process in the dishwasher. The bleach activators are e.g. PAG (pentaacetyl glucose), DADHT (l, 5-diacetyl-2,2-dioxo-hexahydro-l, 3,5-triazine), ISA (isatoic anhydride) and NOBS (nonaoyloxybenzenesulfonic acid sodium salt), preferably however, N, N, N '.N'-tetraacetylethylene diamine (TAED) are present in amounts of 1 to 10% by weight, preferably 2 to 6% by weight. In addition, the addition of small amounts of known bleach stabilizers, such as, for example, phosphonates, borates or metaborates, and magnesium salts such as magnesium sulfate, can also be useful. Within the scope of the present invention, however, the use of the abovementioned. Bleach activators are not absolutely necessary.

Although chlorine-containing bleaching agents can in principle be contained in the agents according to the invention and the invention also includes chlorine-containing formulations, preferably only chlorine-free bleaching agents are used for ecological reasons.

To better remove protein or starch-containing food residues, enzymes such as proteases, amylases, lipases and cellulases are usually used, for example proteases such as BLAP ( ^R ) 140, 170 or 200 from Henkel; 0ptimase ( ^R ) -M-440, 0ptimase ( ^R ) -M-330, 0pticlean ( ^R ) -M-375, 0pticlean ( ^R ) -M-250 from Solvay Enzymes; Maxacal ( ^R ) CX 450,000, Maxapem () from Gist-brocades, Savinase ( ^R ) 4.0 T; 6.0 T; 8.0 T and 16 T from Novo; Esperase ( ^R ) T from Gist-brocades and amylases such as Termamyl () 60 T; 90 T from Novo; Amylase-LT ( ^R ) from Solvay Enzymes or Maxamyl ( ^R ) P 5000, CXT 5000 or CXT 2900 from Gistbrocades, lipases such as Lipolase ( ^R ) 30 T from Novo, cellulases such as Celluzym ( ^R ) 0.7 T from Novo Nordisk. Their total amounts in the agents according to the invention are up to 6% by weight, preferably up to 3% by weight.

If appropriate, surfactants, in particular low-foaming nonionic surfactants, can also be added to the agents according to the invention, which serve to better detach fatty food residues, as wetting agents and as granulating aids. Their amount is then up to 6% by weight, preferably up to 3.5% by weight. Extremely low-foam connections are usually used. These preferably include C ₂ -C 8 ** alkyl polyethylene glycol polypropylene glycol ether, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule. But you can also use other non-foaming non-foaming surfactants known, such as. B. Cι ₂ -Ci8-Alkylpolyethy- lenglykol-polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, end-capped alkyl polyalkylene glycol mixed ethers and the foaming but ecologically attractive C8-Cj4-alkyl polyglucosides with a degree of polymerization of about 1-4 (eg APG ( ^R ) 225 and APG ( ^R ) 600 from Henkel) and / or C ₂ -C 14 alkyl polyethyleneglycols with 3 - 8 ethylene oxide units in the molecule. Bleached quality should be used, otherwise brown granules will result. Also suitable are surfactants from the Gluca ide family, such as, for example, alkyl-N-methyl-glucamides (alkyl = fatty alcohol with the C chain length C6-C14). It is sometimes advantageous if the surfactants described are used as mixtures, e.g. B. the combination of alkyl polyglycoside with fatty alcohol ethoxylates or glucamides with alkyl polyglycosides etc.

If the cleaning agents foam too much during use, they can still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-suppressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, Paraffin oil / Guerbet alcohols, paraffins, hydrophobized silica, the bisstearic acid amides, and other other known commercially available defoamers can be added. Other optional additives are e.g. B. Perfume oils. In addition, the dishwashing detergents according to the invention can contain anticorrosive agents or silver preservatives in order to prevent the corrosion of silver cutlery. Such silver protection agents are, for example, benzotriazoles, iron (III) chloride or the silver protection agents disclosed in international patent applications PCT / EP94 / 01386 and PCT / EP94 / 01387, e.g. B. MnS04, or the silver protection agents disclosed in international patent application W094 / 19445, in which Mn (III) and Mn (IV) complexes are present, or, for example, cysteine.

These silver protection agents can be contained in amounts of up to 5% by weight.

The dishwashing detergents according to the invention are preferably in the form of powdery, granular or tablet-like preparations which can be prepared in a conventional manner, for example by mixing, granulating, roller compacting and / or by spray drying.

For the preparation of the inventive cleaning compositions in tablet form, the procedure is preferably such that they shear mixing all ingredients in a Mi¬ together and the mixture using conventional Tablet¬ tenpressen, for example eccentric presses or rotary presses with press pressures in the range of 200 ^• 10 * ^ Pa to 1500 ^• 10 ^ Pa pressed. In this way, unbreakable tablets are obtained which, under application conditions, dissolve sufficiently quickly and have a flexural strength of normally more than 150 N. A tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter from 35 m to 40 mm.

The production of machine dishwashing detergents in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range from 750 to 1000 g / 1 is characterized in that in a first process sub-stage, the builder components with at least a proportion liquid mixture components are mixed while increasing the bulk density of this premix and subsequently - if desired - after an intermediate drying - the further components of the dishwasher detergent are combined with the premix obtained in this way. The agents to be used can be used both in household dishwashers and in commercial dishwashers. They are added by hand or using suitable dosing devices. The application concentrations in the cleaning liquor are about 2 to 8 g / 1, preferably 2 to 5 g / 1; 1% by weight aqueous solution of the compositions have pH values in the range from 8.5 to 11.0, preferably 9.0 to 10.0.

The rinse program is generally supplemented and ended with a few intermediate rinse cycles with clear water and a rinse cycle with a common rinse aid following the cleaning cycle. After drying, completely clean dishes are freed from tar residues and are hygienically perfect. Even after a large number of rinses, there is no visible damage to the decor or glass.

B e i s p i e l e

I. Granular dishwashing detergents of the following compositions were prepared. Composition A serves for comparison, compositions B to F are according to the invention.

A B- C D E F

Trisodium citrate 43.4 38.4 33.4 38.4 38.4 38.4

Na-SKS-1 - - - 5.0 - -

Na-SKS-2 - - - - 5.0 -

Na-SKS-6 - - - - - 5.0

NA-SKS-9 - 5.0 10.0 - - -

Na ₂ C03 6.0 6.0 6.0 6.0 6.0 6.0

NaHC03 32.0 32.0 32.0 32.0 32.0 32.0

Na percarbonate 12.0 12.0 12.0 12.0 12.0 12.0

TAED 3.0 3.0 3.0 3.0 3.0 3.0

Amylase 1.0 1.0 1.0 1.0 1.0 1.0

Protease 1.0 1.0 1.0 1.0 1.0 1.0

Plurafac LF403 from BASF (C12 / I8 "1.0 1.0 1.0 1.0 1.0 1.0 fatty alcohol x E0x4P0

Perfume oil 0.6 0.6 0.6 0.6 0.6 0.6

The following crystalline sheet silicates from Hoechst AG were used: Na-SKS-1 Na Si 045 ^• xH 0 (Kenyaite) Na-SKS-2 a Sii4θ ₂ g ^• xH ₂ 0 (Magadiite) Na-SKS-6 fr - Na Si 05 Na-SKS-9 NaHSi ₂ 05 ^• H ₂ 0

The effects of agents A to F on sensitive wash ware were measured in a continuously operating dishwasher Bosch SMS 7082 (Bj. 1993) (program Universal 65 ° C) at doses of 30 g each in 5.0 l water with a hardness of 2-3 ° dH tested in the cleaning cycle.

Coca-Cola drinking glasses, "Nostalgie" decor (Ruhr-Glas AG) and "Moosrose Ramona" dessert plates (Rosenthal) were washed; Color loss (FV) and gloss loss (GV) were assessed according to the following rating scale:

0: no change

1: slight change, still acceptable

2: medium change, still acceptable

3: major change, no longer acceptable

4: very strong change, no longer acceptable.

The values were determined after 50 to 450 rinsing cycles and can be found in Tables 1 and 2. (The values obtained with pure water serve as the norm).

Table 1

Drinking glass of Coca-Cola

Cleaner 50 rinse cycles 100 rinse cycles 150 rinse cycles

Water FV 2 FV 3 GV 3 GV 3

A FV 2 FV 2 FV 3 GV 3 GV 4 GV 4

B FV 1 FV 2 FV 2 GV 2 GV 2 GV 3

CM

I.

O 96/12783 PC17-EP95 / 04019

- 13th

II. Powdered dishwashing detergents of the following compositions were prepared; H and I are compositions according to the invention, G is used for comparison.

G H I

Trisodium citrate 45.0 45.0 45.0

Na-SKS-6 - 5.0 5.0

Na ₂ C03 5.0 5.0 5.0

NaHC03 31.9 26.9 28.9

Na percarbonate 12.0 12.0 12.0

TAED 2.0 2.0 -

Amylase 1.0 1.0 1.0

Protease 1.0 1.0 1.0

Plurafac LF403 from BASF (C12 / I8 "1.5 1.5 1.5 fatty alcohol x E0x4P0

Perfume oil 0.6 0.6 0.6

The effects of agents G, H and I on the removal of tea impurities on porcelain were measured in a Miele G 575 dishwasher (Universal 55 ° C program) at a dosage of 20 g in 5.0 l of water with a hardness of 3 ° dH (soft water) tested in the cleaning cycle.

It was found that the tea cleaning performance of composition H was significantly better than composition G according to the invention. The tea cleaning performance of Composition I was in the absence a classic bleach activator (TAED) as well as that of the non-inventive composition G with TAED.

(In principle, the increased tea cleaning performance of compositions according to the invention compared to non-inventive compositions is all the more significant the softer the water used for cleaning.)

Claims

claims

1. Use of layered silicates of the formula I

NaMSi _x 0 _{2x +} ι ^• y H ₂ 0 (I),

where M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably 1.9 to 4, and y is a number from 0 to 30, in machine dishwashing detergents as a decorative and glass-protecting component.

2. Use of layered silicates of the formula I in machine dishwashing detergents as an additive for increasing the tea cleaning performance.

3. Means for machine cleaning of dishes containing 25 to 80% by weight, preferably 35 to 55% by weight, of a builder system consisting of at least two builder substances and 5 to 20% by weight, preferably 10 to 15% by weight. -%, of an oxygen-based bleaching agent, in each case based on the total agent, characterized in that two of the builder substances contained in the builder system include citric acid (or its alkali metal or ammonium salts) and a crystalline layered silicate of the formula I.

NaMSi _x 0 _{2x +} ι ^• y H ₂ 0 (I),

wherein M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably 1.9 to 4, and y is a number from 0 to 30, and citric acid in an amount of 15 to 55% by weight. %, preferably 25 to 45% by weight, and crystalline layered silicates in an amount of 0.5 to 25, preferably 2 to 10 wt .-%, each based on the total agent, are included.

4. Composition according to claim 3, characterized in that in the crystalline layered silicate of formula I x is 2.

5. Composition according to claim 3 and 4, characterized in that an alkali carrier system consisting of sodium carbonate and sodium hydrogen carbonate in an amount of 10 to 50 wt .-%, preferably 20 to 35 wt .-%, based on the total composition is, the weight ratio between sodium carbonate and sodium bicarbonate is 1:15 to 2: 1.

6. Composition according to claim 3 to 5, characterized in that the bleaching agent based on oxygen is a percarbonate salt, preferably Na per carbonate.

7. Composition according to claim 3 to 6, characterized in that it additional Lich a bleach activator, preferably N, N, N ', N'-tetraacetyl-ethylenediamine, in an amount of 1 to 10 wt .-%, preferably 2 to 6 wt., Contains.

8. Composition according to claim 3 to 7, characterized in that it additionally contains enzymes in an amount of up to 6% by weight, preferably up to 3% by weight.

9. Composition according to claim 3 to 8, characterized in that it additionally contains surfactants, preferably low-foaming nonionic surfactants, in an amount of up to 6% by weight, preferably up to 3.5% by weight.

10. Composition according to claim 3 to 9, characterized in that a 1 wt .-% solution in water has a pH of 8.5 to 11.0, preferably 9.0 to 10.0.

11. Powder or granular composition according to claim 3 to 10, characterized in that it has a bulk density of 750 g / 1 to 1000 g / 1.

12. Tablet-like composition according to claim 3 to 10, characterized gekennzeich¬ net that it is available by mixing all of its components in a mixer and pressing the mixture by means of a tablet press at pressures of 2 ^• 10 ⁷ Pa to 1.5 • 10 ⁸ Pa .