DE4417919A1 - Rinse aid with biodegradable polymers - Google Patents

Abstract

The invention relates to dishwasher rinsing agents containing highly biodegradable polymers. The highly biodegradable polymers are terpolymers made from monomers of a monoethylenically unsaturated C3-C8 carboxylic acid, a 2-alkylallyl sulphonic acid or 2-arylallyl sulphonic acid and a carbohydrate.

Description

Field of the Invention

The invention relates to the use of terpolymers resulting from the mono mer of a monoethylenically unsaturated C₃-C₈ carboxylic acid, a 2- Alkylallylsulfonic acid or 2-arylallylsulfonic acid and a carbohydrate are built up.

State of the art

Commercial rinse aids are mixtures of low-foaming fat alcohol polyethylene / polypropylene glycol ethers, solubilizers (e.g. Cu molsulfonate) organic acids (e.g. citric acid) and solvents (eg ethanol). The task of these means is to limit to influence the surface tension of the water so that it is as possible thin, coherent film can run off the dishes, so that when closing drying process no water drops, streaks or films stay behind. 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 using modern phosphate-free and low-alkaline cleaners for machine dishwashing, it can also form limescale or silicate deposits on the wash ware and inside the machine, because the calcium binding capacity of these cleaners is lower than that of the classic products containing phosphate. Disturbing lime or silicate coverings tre particularly when the dishwashing water from the dishwasher  is not or not sufficiently softened and a water hardness of 4 ° d is exceeded.

The object of the present invention is therefore to provide rinse aid places whose use provides spotless dishes; Furthermore should the rinse aid be low-foaming, with a high phase stability dispose of and be biodegradable.

The European patent application EP-A1 561 464 describes the use of Polyamino acids described in rinse aid; the polyamino acids are there for a good drainage behavior of the rinsing water from the rinsed waiters surfaces.

The present invention relates to the use of terpolymers, from the monomers of a monoethylenically unsaturated C₃-C₈ carbon acid, a 2-alkylallylsulfonic acid or 2-arylallylsulfonic acid and one Carbohydrates are built up in rinse aid.

The terpolymers used according to the invention contain the simplest Case two carboxylic acids and / or their salts and a carbohydrate as Monomers. The first acidic monomer or its salt is derived from one monoethylenically unsaturated C₃-C₈ monocarboxylic acid and preferably of a C₃-C₄ monocarboxylic acid, in particular from the (meth) acrylic acid. The second acidic monomer or its salt is a derivative of an allyl sulfonic acid in the 2-position with an alkyl radical, preferably with a C₁-C₄-alkyl radical, or an aromatic radical, which is preferably from Derives benzene or benzene derivatives, is substituted. Furthermore is the incorporation of further monomer units into the copolymer is not excluded sen. Preferred terpolymers contain 40 to 60% by weight, in particular 45 to 55 wt .-% (meth) acrylic acid or (meth) acrylate with special Be preference for acrylic acid or acrylate, 10 to 30% by weight, preferably 15 up to 25% by weight of methallylsulfonic acid or methallylsulfonate, where meth allylsulfonic acid or methallylsulfonate also partially through Addition of 1 to 10 ethylene oxide units formed on methacrylic acid Methacrylic acid polyethylene glycol ester can be replaced, which then Weight ratio between methacrylic acid polyethylene glycol ester and meth  allylsulfonic acid or sulfonate is 1:10 to 10: 1, and 15 to 40 % By weight, preferably 20 to 40% by weight, of a carbohydrate. This coal hydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides are preferred. By installation of this carbohydrate, predetermined breaking points are built into the polymer, which are responsible for the degradability of the polymer. In particular is preferred as carbohydrate sucrose. The used according to the invention Terpolymers can be prepared by any of the known and customary methods produce.

In particular, the monomeric acids are reversed with the carbohydrate sets, whereupon a neutralization of the acids if necessary to preferably their alkali salts, such as the sodium or potassium salts, or ammonium salts or alkanolamine salts such as the monoethanolamine salt or the triethanolamine salt.

Analogous to the known (co) polymeric polycarboxylic acids or Polycarboxylates such as the homo- or copolymeric acrylic acids or acrylates terpolymers that are either complete or too are preferred at least partially, especially more than 50%, based on the existing which carboxyl groups are neutralized. It is particularly preferred a completely neutralized terpolymer, which consists of the salts of monomeric acids, especially the sodium or potassium salts of the monomers ren acids, and a carbohydrate. The terpolymers have generally a relative molecular mass between 1000 and 200000, preferably wise between 2000 and 50000 and especially between 3000 and 10000 on. They are preferably in powdered, spray-dried form used. Particularly preferred terpolymers are made by one method ren manufactured, that in the older German patent application P 42 21 381.9 is described.

The terpolymers are generally in rinse aid. in an amount of 0.1 to 10 wt .-%, preferably 1 to 5 wt .-%, based on the total clear detergent included.  

Rinse aids contained in such terpolymers show a very low level Foam development, high phase stability and ensure spotless, shiny dishes.

Rinse aids according to the invention furthermore contain organic carboxylic acid ren.

As organic carboxylic acids such. B. aliphatic hydroxy di and tri carboxylic acids such as malic acid (monohydroxysuccinic acid), tartaric acid (Di hydroxy succinic acid); saturated aliphatic dicarboxylic acids such as oxal acid, malonic acid, succinic acid, glutaric acid, adipic acid; Gluconic acid (Hexane-pentahydroxy-1-carboxylic acid), but preferably anhydrous citro Nenoic acid into consideration. They are preferred in amounts of about 0.5 to 50 as used from about 1 to 20 wt .-%.

The surfactant base of the rinse aid according to the invention is formed from a nonionic surfactant, in an amount of 0.5 to 50 wt .-%, preferably 2 to 20 wt .-%, and is selected from the Group of mixed ethers of formula I, the fatty alcohol polypropylene glycol / po polyethylene glycol ether of the formula II, the alkyl polyglycosides of the formula III and their mixtures, where in the mixed ethers of the formula I,

R¹ is a linear or branched, aliphatic alkyl and / or Al kenyl radical with 8 to 14 carbon atoms, R² for a linear or ver branched alkyl radical with 1 to 4 carbon atoms or a benzyl radical, a stands for 0 or numbers from 1 to 2 and b stands for numbers from 5 to 15,  in the fatty alcohol polypropylene glycol / polyethylene glycol ethers of the formula (II),

R³ represents a linear or branched, aliphatic alkyl and / or al kenyl radical having 8 to 16 carbon atoms, c represents 0 or numbers from 1 to 3 and d represents numbers from 1 to 5,
and in the alkyl polyglycosides of the formula (III),

R⁴O- [G] _p (III)

R⁴ for an alkyl radical with 8 to 22 carbon atoms, G for a sugar residue with 5 or 6 carbon atoms, preferably a glucose residue, and p stands for numbers from 1 to 10.

Among mixed ethers of the formula I are known end group-locked fats to understand alcohol polyglycol ethers, which one according to relevant methods of preparative organic chemistry. Preferably be Fatty alcohol polyglycol ether in the presence of bases with alkyl halides, in particular butyl or benzyl chloride implemented. Typical examples are Mixed ether of the formula (I) in which R¹ is for a technical C₁₂ / ₁₄ coconut alkyl radical, a is 0, b is 5 to 10 and R² is a butyl group (De hypon® LS-54 or LS-104, from Henkel KGaA). The use of butyl or benzyl group-capped mixed ethers is from application technology Reasons particularly preferred.

In the case of the fatty alcohol polypropylene / polyethylene glycol ethers of the formula II han it is known nonionic surfactants, which can be added by of first propylene oxide and then ethylene oxide or exclusively ethyl lenoxid to fatty alcohols. Typical examples are polyglycol ethers  of the formula (II) in which R³ is an alkyl radical having 12 to 18 carbon atoms atoms, c stands for 0 or 1 and d stands for numbers from 2 to 5 (Dehydol® LS-2, LS-4, LS-5₁ from Henkel KGaA, Düsseldorf / FRG). Preferably, however, the fatty alcohols are only ethoxylated, i.e. H. c is equals zero.

Alkyl polyglycosides (APG) are known substances, which according to the relevant methods of preparative organic chemistry can be obtained can. Representative of the extensive literature here on the References EP-A1 0 301 298 and WO 90/3977 referenced.

The alkyl polyglycosides can differ from aldoses or ketoses with 5 or 6 Carbon atoms, preferably derived from glucose. The preferred Al Alkyl polyglycosides are thus alkyl polyglucosides.

The index number p in the general formula (III) gives the oligomerisie degree (DP degree), d. H. the distribution of mono- and oligoglycosides and stands for a number between 1 and 10. While p in a given The connection must always be an integer, especially the values p = 1 can assume up to 6, the value p is for a certain alkyl oligoglycoside an analytically calculated quantity, mostly a broken one represents a number. Alkyl polyglycosides with a mean leren degree of oligomerization p used from 1.1 to 3.0. From application From an industrial point of view, those alkyl polyglycosides whose oligomes are preferred degree of risk is less than 1.7 and in particular between 1.2 and 1.6 lies.

The agents according to the invention can be nonionic as further surfactants Fabrics e.g. B. contain the type of fatty acid N-alkylglucamides. As another Additives come solubilizers, e.g. B. cumene sulfonate, and color and Fragrances in question, being in a preferred embodiment of agents according to the invention are dispensed with solubilizers.

The following examples are intended to explain the subject matter of the invention in more detail without restricting him to it.  

Examples

A terpolymer was used, which according to the disclosure of the older German patent application P 42 21 381.9 from 50% by weight acrylic acid, 33 % By weight of sucrose and 17% by weight of 2-methallylsulfonic acid and was then completely neutralized.

• Surfactants used
• A) C _12/14 coconut fatty alcohol-5 EO-butyl ether Dehypon® LS-54
• B) C _12/14 coconut fatty alcohol-10 EO-butyl ether Dehypon® LS-104
• C) C _12/14 coconut fatty alcohol-4 EO adduct Dehydol® LS-4
• D) C _8/10 alkyl oligoglucoside, DP 1.6 Plantaren® APG 225.

All surfactants are sales products from Henkel KGaA, Düsseldorf / FRG.

Rinse aid formulations of compositions 1 to 9 were obtained poses.  

Performance test of the rinse aid formulations I. Testing the foam behavior of the rinse aid formulations

The foam development of the rinse aid was with the help of a revolution pressure measuring device determined. The rinse aid (3 ml) was Hand rinse cycle at 50 ° C.

Here mean:

0 points = no foam development
1 point = weak foaming
2 points = medium foam development (still acceptable)
3 points = strong foaming

II. Drying

The door of the Ge dishwasher fully open. After 5 minutes the Drying by counting the remaining drops on those listed below Dishware determined.

Rating:
0 points = more than 5 drops
1 point = 5 drops
2 points = 4 drops
3 points = 3 drops
4 points = 2 drops
5 points = 1 drop
6 points = 0 drops (optimal drying)

III. Rinse aid effect

After assessing the drying, the dishes were placed outside the dishwasher for 30 minutes to cool and then visually checked under lighting in a black box. The dried-up residual drops, streaks, deposits, cloudy films etc. remaining on the dishes and cutlery were assessed.
Rating:
0 points = poor rinse aid effect
8 points = optimal rinse aid effect

For the performance test III. were the trials in the dishes dishwasher (Miele G 590) with softened water (1.6 ° dH) and with not softened water (13.8 ° dH). This was 65 ° C Normal program selected. 30 g of Somat® cleaner were used in the cleaning cycle (Henkel) dosed. The amount of rinse aid - each in Table 1 given rinse aid composition - was 3 ml and was done by hand dosed at 50 ° C in the rinse aid. The salt load of the water was between 600 and 700 mg / l. There were 3 rinses per rinse aid formulation carried out.

To assess the drying and rinse aid effects, fol The following dishes are used:

• - "Neckar-Becher" glasses (Schott-Zwiesel), 6 pieces
• - Stainless steel knife "Brasilia" (from WMF), 3 pieces
• - White porcelain dinner plates (from Arzberg), 3 pieces
• - red plastic plate "Valon dinner plate" (Fa. Haßmann), 3 pieces

Results of examinations of the rinse aid effect

The results of the rinse aid effect studies show that Terpoly Mer-containing rinse aid formulations depending on the type of surfactants used and the washware used consistently at least equally good to clear to have better rinse aid effects on the items used than correspond Suitable terpolymer-free formulations.

Claims (4)

1. Use of terpolymers made from the monomers of a monoethyl niche unsaturated C₃-C₈ carboxylic acid, a 2-alkylallylsulfonic acid or 2-arylallylsulfonic acid and a carbohydrate are built in Rinse aid. 2. Use according to claim 1, characterized in that the terpoly 40 to 60% by weight, preferably 45 to 55% by weight, of (meth) - acrylic acid, preferably acrylic acid, 10 to 30% by weight, preferably 15 to 25 wt .-%, from methallylsulfonic acid, with methallylsulfonic acid partly also by adding 1 to 10 ethylene oxide units of methacrylic acid polyethylene glycol formed on methacrylic acid kolester can be replaced, the weight ratio between Methacrylic acid polyethylene glycol ester and methallylsulfonic acid 1:10 is up to 10: 1, and 15 to 40% by weight, preferably 20 to 40 Wt .-%, consist of a carbohydrate, preferably sucrose. 3. containing rinse aid,

• 0.1 to 10% by weight, preferably 1 to 5% by weight, of terpolymer according to claim 1 or 2,
• - 0.5 to 50 wt .-%, preferably 1 to 20 wt .-% organic carboxylic acids, especially citric acid and
• - 0.5 to 50 wt .-%, preferably 2 to 20 wt .-% of a nonionic surfactant selected from the group of mixed ethers of the formula I, the fatty alcohol polypropylene glycol / polyethylene glycol ethers of the formula II, the alkyl polyglycosides of the formula III and mixtures thereof, wherein in the mixed ethers of the formula I,

R¹ for a linear or branched, aliphatic alkyl and / or alkenyl radical with 8 to 14 carbon atoms, R² 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 for numbers stands from 5 to 15,
in the fatty alcohol polypropylene glycol / polyethylene glycol ethers of the formula (II), R³ represents a linear or branched, aliphatic alkyl and / or alkenyl radical with 8 to 16 carbon atoms, c stands for 0 or numbers from 1 to 3 and d stands for numbers from 1 to 5,
and in the alkyl polyglycosides of the formula (III), R⁴O- [G] _p (III) R⁴ for an alkyl radical having 8 to 22 carbon atoms, G for a sugar radical with 5 or 6 carbon atoms, preferably a glucose radical, and p for numbers of 1 to 10.