EP0876459B9 - Clear-rinsing agents with cationic polymers - Google Patents

Abstract

PCT No. PCT/EP96/03724 Sec. 371 Date May 6, 1998 Sec. 102(e) Date May 6, 1998 PCT Filed Aug. 23, 1996 PCT Pub. No. WO97/09408 PCT Pub. Date Mar. 13, 1997A process for improving the soil release properties of dishwashing machine rinse aid compositions used to rinse dishware and remove starch-containing soils therefrom by adding to the compositions a cationic polymer containing monomer units corresponding to formula I: in which R1 is hydrogen or a methyl group, R2, R3 and R4 are the same or different and represent hydrogen or a C1-8 alk(en)yl group, R8 is a linear, cyclic or branched alkylene group containing 2 to 8 carbon atoms, and X represents a monofunctional anion or the 1/m part of an m-functional anion.

Description

The invention relates to the use of cationic polymers as soil release compounds in rinse aid for dishwashers.

Commercial rinse aids for dishwashers are mixtures of low-foaming fatty alcohol polyethylene / polypropylene glycol ether, solubilizers (for example cumene sulfonate), organic acids (for example citric acid) and solvents (for example ethanol). The task of these agents is to influence the interfacial tension of the water so that it is in a thin, coherent film can run off the wash ware, so that no water drops, streaks or films remain during the subsequent drying process. An overview of the composition of rinse aid and methods for checking performance can be found by W. Schirmer et al. in tens. Surf. Det. 28 , 313 (1991).

When washing dishes by machine it can be observed in some cases that especially strongly adhering soiling, such as. B. oatmeal and starch deposits, cannot be completely removed during the cleaning process.

It is from the publications EP-A-0 167 382, EP-A-0 342 997 and DE-OS-26 16 404 known to add cleaning agents cationic polymers, so as streak-free as possible To achieve cleaning of the surfaces.

EP-A-0 167 382 describes liquid detergent compositions which can contain cationic polymers as thickeners. As particularly suitable cationic polymers become hydroxypropyltrimethylammonium guar; copolymers of aminoethyl methacrylate and acrylamide and copolymers of dimethyldiallylammonium chloride and acrylamide.

EP-A-0 342 997 describes all-purpose cleaners, the cationic polymers may contain, in particular polymers with imino groups are used.

DE-OS-26 16 404 describes cleaning agents for glass, the cationic Contain cellulose derivatives. The addition of the cationic cellulose derivatives in the agents better drainage of the water to get streak-free cleaned glass.

In EP-A-0 467 472 e.g. Cleaning agents for hard surfaces are described contain cationic homo- and / or copolymers as so-called soil-release polymers. These polymers have quaternized ammonium alkyl methacrylate groups as monomer units. These compounds are used to make the surfaces like this equip that the next time cleaning the dirt is easier let peel off.

The publications mentioned above disclose the use of cationic polymers in detergents. None of these publications give any indication of it which way it is possible with machine dishwashing, the removal of stubborn dirt, such as B. from starchy soiling to facilitate.

The object of the present invention is to provide a rinse aid by means of which Use heavily adhering soiling in subsequent cleaning processes such as oat flakes and other starch deposits can be easily removed from the dishes.

worin

R¹ für Wasserstoff oder eine Methylgruppe steht und

R², R³ und R⁴ gleich oder verschieden sein können und für Wasserstoff oder eine C_1-8-Alk(en)ylgruppe, R⁸ für eine gradkettige, cyclische oder verzweigte Alkylengruppe mit 2 bis 8 C-Atomen steht und

X für ein einwertiges Anion bzw. für den 1/m Teil eines m-wertigen Anions stehen,

enthalten, als Soil-Release-Verbindungen in Klarspülmitteln für Geschirrspülmaschinen. The present invention relates to the use of cationic homo- or copolymers, the monomer units with the formula I.

wherein

R ^{1 represents} hydrogen or a methyl group and

R ² , R ³ and R ^{4 may be the} same or different and represent hydrogen or a C _1-8 alk (en) yl group, R ^{8 represents} a straight-chain, cyclic or branched alkylene group having 2 to 8 C atoms and

X stands for a monovalent anion or for the 1 / m part of an m-valent anion,

included as soil release compounds in rinse aid for dishwashers.

Surprisingly, it was found that when machine cleaning Dishes that add rinse aid soil-release compounds to the next one Cleaning strongly adhering and often critical soiling, such as B. starchy Soiling, remove completely. These stains can be done without Remove additional manual processing of the wash ware.

Suitable anions in formula I are, for example, halide ions, such as chloride or bromide, SO ₄ ^2- or CH ₃ SO ₄ ^- .

The preferred polymers can be the monomer units with the formula I in one Contain from 40 mol% to 100 mol%. The proportion of monomer units with of the formula I should preferably not fall below 40 mol%, since otherwise the polymers do not have sufficient water solubility. In addition to the monomer units with the formula I Unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, Crotonic acid and the like, olefins such as ethylene, propylene and butene, alkyl esters of unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, methyl methacrylate, their Hydroxy derivatives such as 2-hydroxy-ethyl methacrylate, unsaturated aromatic compounds such as styrene, methyl styrene, vinyl styrene and heterocyclic compounds such as Vinyl pyrrolidone can be used. Preferred comonomers are acrylic acid, Methacrylic acid and vinyl pyrrolidone used.

The cationic polymers described above can be used in amounts from 0.1% by weight to 30% % By weight, based on the rinse aid, are used.

a) 0,1 Gew.-% bis 30 Gew.-% kationische Homo- oder Copolymere, die Monomereinheiten mit der Formel I

worin

R¹ für Wasserstoff oder eine Methylgruppe steht und

R², R³ und R⁴ gleich oder verschieden sein können und für Wasserstoff oder eine C_1-8-Alk(en)ylgruppe, R⁸ für eine gradkettige, cyclische oder verzweigte Alkylengruppe mit 2 bis 8 C-Atomen steht und

X für ein einwertiges Anion bzw. für den 1/m Teil eines m-wertigen Anions stehen,

enthalten,

b) 0,5 bis 30 Gew.-%, organische Carbonsäuren,

c) 0,5 bis 30 Gew.-%, nichtionische Tenside ausgewählt aus der Gruppe der engruppenverschlossenen und OH-Engruppen-haltigen Fettalkoholpolypropylenglykol/polyethylenglykolethern, der Alkylpolyglykoside, der C₆-C₂₂-Fettsäure-N-alkylpolyhydroxyalkylamide, C₆-C₂₂-Fettsäurealkanolamide, C₆-C₂₂-Fettsäure-N-alkylpolyhydroxyalkylamide, Fettalkylaminoxide und beliebigen Mischungen der voranstehenden und

d) 10 Gew.-% bis 98,1 Gew.-% Wasser.

Another object of the present invention are rinse aid for dishwashers containing

a) 0.1 wt .-% to 30 wt .-% cationic homo- or copolymers, the monomer units with the formula I.

wherein

R ^{1 represents} hydrogen or a methyl group and

R ² , R ³ and R ^{4 may be the} same or different and represent hydrogen or a C _1-8 alk (en) yl group, R ^{8 represents} a straight-chain, cyclic or branched alkylene group having 2 to 8 C atoms and

X stands for a monovalent anion or for the 1 / m part of an m-valent anion,

contain,

b) 0.5 to 30% by weight, organic carboxylic acids,

c) 0.5 to 30% by weight, nonionic surfactants selected from the group consisting of fatty alcohol polypropylene glycol / polyethylene glycol ethers which are capped and contain OH groups, the alkyl polyglycosides, the C ₆ -C ₂₂ fatty acid N-alkyl polyhydroxyalkylamides, C ₆ -C ₂₂ fatty acid alkanolamides, C ₆ -C ₂₂ fatty acid N-alkyl polyhydroxyalkylamides, fatty alkylamine oxides and any mixtures of the above and

d) 10% by weight to 98.1% by weight of water.

Water-soluble homopolymers or copolymers are preferably used as cationic polymers Monomer units with the above formula I used.

Examples of organic carboxylic acids are aliphatic hydroxy di and tricarboxylic acids such as malic acid (monohydroxysuccinic acid), tartaric acid (dihydroxysuccinic acid); saturated aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, Adipic acid, gluconic acid (hexane-pentahydroxy-1-carboxylic acid), but preferably anhydrous citric acid. The carboxylic acids are preferably used in amounts from about 1 to 20% by weight.

worin R¹⁰ für einen linearen oder verzweigten, aliphatischen Alkyl- und/oder Alkenylrest mit 8 bis 14 Kohlenstoffatomen, R¹¹ für einen linearen oder verzweigten Alkylrest mit 1 bis 4 Kohlenstoffatomen oder einen Benzylrest, a für 0 oder Zahlen von 1 bis 2 und b für Zahlen von 5 bis 15 steht,
der Fettalkoholpolypropylenglykol/polyethylenglykolether der Formel IV,

worin R¹² für einen linearen oder verzweigten, aliphatischen Alkyl- und/oder Alkenylrest mit 8 bis 16 Kohlenstoffatomen, c für 0 oder Zahlen von 1 bis 3 und d für Zahlen von 1 bis 5 steht, und
der Alkylpolyglykoside der Formel V, R¹³O-[G]_p worin R¹³ für einen Alkylrest mit 8 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen, vorzugsweise einen Glucoserest, und p für Zahlen von 1 bis 10 stehen.The surfactant base of the rinse aid is preferably formed by nonionic surfactants, which can preferably be contained in an amount of 2 to 20% by weight. The nonionic surfactants are preferably selected from the group of mixed ethers of the formula III,

wherein R ¹⁰ for a linear or branched, aliphatic alkyl and / or alkenyl radical with 8 to 14 carbon atoms, R ¹¹ for a linear or branched alkyl radical with 1 to 4 carbon atoms or a benzyl radical, a for 0 or numbers from 1 to 2 and b represents numbers from 5 to 15,
the fatty alcohol polypropylene glycol / polyethylene glycol ether of the formula IV,

wherein R ^{12 is} a linear or branched, aliphatic alkyl and / or alkenyl radical having 8 to 16 carbon atoms, c is 0 or numbers from 1 to 3 and d is numbers from 1 to 5, and
the alkyl polyglycosides of the formula V, R ¹³ O- [G] _p wherein R ^{13 is} an alkyl radical having 8 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms, preferably a glucose radical, and p are numbers from 1 to 10.

Mixed ethers of the formula II are to be understood as meaning known end group-capped fatty alcohol polyglycol ethers which can be obtained by the relevant methods of preparative organic chemistry. Fatty alcohol polyglycol ethers are preferably reacted in the presence of bases with alkyl halides, in particular butyl or benzyl chloride. Typical examples are mixed ethers of the formula (I) in which R ^{10 represents} an industrial, C _12/14 cocoalkyl radical, a represents 0, b represents 5 to 10 and R11 represents a butyl group (Dehypon® LS-54 or LS- 104, Henkel KGaA). The use of mixed ethers capped with butyl or benzyl groups is particularly preferred for technical reasons.

The fatty alcohol polypropylene / polyethylene glycol ether with the formula III are known nonionic surfactants which are obtained by adding initially propylene oxide and then ethylene oxide or exclusively ethylene oxide to fatty alcohols. Typical examples are polyglycol ethers of the formula IV in which R ^{12 represents} an alkyl radical having 12 to 18 carbon atoms, c represents 0 or 1 and d represents numbers from 2 to 5. (Dehydol® LS-2, LS-4, LS-5, from Henkel KGaA, Düsseldorf / FRG). However, the fatty alcohols are preferably only ethoxylated, ie c is zero.

Alkyl polyglycosides (APG) with the formula IV are known substances that according to the relevant Preparative organic chemistry processes can be obtained. Representative of the extensive literature on EP-A-0 301 298 and WO 90/3977.

The alkyl polyglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl polyglycosides are thus alkyl polyglucosides.
The index number p in the general formula III indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound, and here before can assume all the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter which usually represents a fractional number. Alkyl polyglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl polyglycosides are preferred whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6.

Solubilizers, e.g. Cumene sulfonate, as well as color and Fragrances in question, being in the agents according to the invention in a preferred embodiment solution brokers are dispensed with.

The following examples are intended to illustrate the subject matter of the invention without it to limit it.

Examples

To make soiling, white dinner plates were placed in a hot potato starch or oatmeal porridge dipped, drained and dried at 80 ° C. The The cleaning performance was assessed visually by means of the iodine-starch reaction by after the cleaning with iodine solution, the blue stains of the residues are sampled has been.

When trying to rinse, clean dishes were first rinsed in the dishwasher treated with the rinse aid formulations 1 to 4 shown in Table 1 (Dosage: 4 ml). After the rinse cycle was completed, the plates were as described above soiled. The cleaning was then carried out in a commercially available Dishwasher with standard dishwashing detergent (Somat® supra, commercial product from Henkel KGaA, Düsseldorf, FRG).

Preparation of the cationic polymer used

To 1600g of a 50% solution of methacrylamidopropyltrimethylammonium chloride in Water and 1440 g of water, demineralized, were 3.2 g of azobiscyanpentanoic acid, which with the addition of 4.3 g of 12.5% strength aqueous ammonia in 160 g of water, given.

The mixture was heated to 70 ° C. and left at this temperature for 30 minutes. Subsequently was allowed to react for a further hour at 80 ° C.

A light yellow polymer solution which was clear at room temperature and had a Brookfield viscosity of 600 mPas was obtained. 1 2 3 4 C _12/14 coconut fatty alcohol-5 EO-butyl ether 15.0 15.0 - - C _12/14 coconut fatty alcohol 10 EO butyl ether - - 9.0 9.0 C _12/14 coconut fatty alcohol-4 EO adduct - - 5.0 5.0 cationic polymer 10 - 10 - Citric acid anhydrous 3.0 3.0 3.0 3.0 Na cumene 5.0 7.0 4.0 7.0 perfume oil 0.5 0.5 0.5 0.5 demineralized water ad 100 ad 100 ad 100 ad 100

The cleaning performance was then rated on a scale from 0 to 10, 0 means no cleaning and 10 means complete cleaning.

The cleaning performance at water temperatures of 55 ° C and 65 ° C for starch and oatmeal was assessed, the results are shown in Table 2: potato starch oatmeal A B A B example 1 8.3 8.2 7.0 7.0 Example 2 (comparison) 7.8 7.2 3.8 5 Example 3 8.0 8.5 7.0 7.5 Example 4 (comparison) 7.5 7.0 4 4.5 A: 55 ° C, 20 G detergent dosage, softened water B: 65 ° C, 30 g detergent dosage, hard water (14-16 ° dH)

The examples clearly show that the use of the cationic polymers in rinse aids for machine dishwashing to improve the cleaning of strongly adhering soiling such as oat flakes and other starch deposits leads.

Claims (6)

1. The use of cationic homopolymers or copolymers containing monomer units corresponding to formula I:

   

   in which

   R¹ is hydrogen or a methyl group and

   R², R³ and R⁴ may be the same or different and represent hydrogen or a C_1-8 alk(en)yl group, R⁸ is a linear, cyclic or branched alkylene group containing 2 to 8 carbon atoms and

   X represents a monofunctional anion or the 1/m part of an m-functional anion,

   as soil release compounds in rinse aids for dishwashing machines.
2. The use claimed in claim 1, characterized in that the cationic polymers contain 40 to 100 mole-% of the monomers corresponding to formula I.
3. The use claimed in claim 1 or 2 as soil-release polymers for the removal of starch-containing soils.
4. Rinse aids containing

   a) 0.1% by weight to 30% by weight of cationic polymers according to claim 1,

   b) 0.5 to 30% by weight of organic carboxylic acids, more particularly citric acid,

   c) 0.5 to 30% by weight of nonionic surfactants selected from the group of end-capped and OH-terminated fatty alcohol polypropylene glycol/ polyethylene glycol ethers, alkyl polyglycosides, C_6-22 fatty acid-N-alkyl polyhydroxyalkylamides, C_6-22 fatty acid alkanolamides, C_6-22 fatty acid-N-alkyl polyhydroxyalkyl amides, fatty alkyl amine oxides and mixtures thereof and

   d) 10% by weight to 98.1 % by weight of water.
5. Rinse aids as claimed in claim 4, characterized in that citric acid is used as the organic carboxylic acid.
6. Rinse aids as claimed in claim 4 or 5, characterized in that the nonionic surfactants used are mixed ethers corresponding to formula III:

   

   in which R¹⁰ is a linear or branched, aliphatic alkyl and/or alkenyl group containing 8 to 14 carbon atoms, R¹¹ is a linear or branched alkyl group containing 1 to 4 carbon atoms or a benzyl group, a is 0 or a number of 1 to 2 and b is a number of 5 to 15,
   fatty alcohol polypropylene glycol/polyethylene glycol ethers corresponding to formula IV:

   

   in which R¹² is a linear or branched, aliphatic alkyl and/or alkenyl group containing 8 to 16 carbon atoms, c is 0 or a number of 1 to 3 and d is a number of 1 to 5, or
   alkyl polyglycosides corresponding to formula V: R¹³O-[G]_p in which R¹³ is an alkyl group containing 8 to 22 carbon atoms, G is a sugar unit containing 5 or 6 carbon atoms, preferably a glucose unit, and p is a number of 1 to 10.