EP0708816A1

EP0708816A1 - Hard surface cleaning agent

Info

Publication number: EP0708816A1
Application number: EP94901884A
Authority: EP
Inventors: Jürgen Härer; Peter Jeschke; Karl Schmid; Karin Koren
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1993-07-12
Filing date: 1993-11-26
Publication date: 1996-05-01
Anticipated expiration: 2013-11-26
Also published as: DE4323252C2; US5759987A; ES2122220T3; DE4323252A1; WO1995002668A1; EP0708816B1; DE59309068D1

Abstract

New agents for cleaning hard surfaces contain (a) mixed ethers having formula (I), in which R1 stands for a linear or branched aliphatic alkyl and/or alkenyl residue with 8 to 18 carbon atoms, R2 stands for a linear or branched alkyl residue with 1 to 4 carbon atoms or a benzyl residue, m1 is 0 or a number from 1 to 2 and n1 is a number from 5 to 15; and (b) fatty alcohol polypropylene glycol/polyethylene glycol ethers having formula (II), in which R2 stands for a linear or branched aliphatic alkyl and/or akenyl residue with 8 to 16 carbon atoms, m2 is 0 or a number from 1 to 3 and n2 is a number from 1 to 5.

Description

Means for cleaning hard surfaces

Field of the Invention

The invention relates to new agents for the mechanical cleaning of hard surfaces, in particular rinse aids, containing mixed ethers and special fatty alcohol polyglycol ethers, and to the use of these mixtures for the preparation of the agents mentioned.

State of the art

Commercial rinse aids are mixtures of low-foaming fatty alcohol polyethylene / polypropylene glycol ethers, solubilizers (for example cumene sulfonate), organic acids (for example citric acid) and solvents (for example ethanol). The purpose of these agents is to increase the interfacial tension of the water influence that it can run off in the thinnest possible coherent film from the wash ware, so that no water drops, strips or films remain in the subsequent drying process. An overview of the composition of rinse aids and methods for checking performance can be found by W. Schirmer et al. in Tenε. Surf. Det. 28, 313 (1991). When using modern phosphate-free and low-alkali cleaners for automatic dishwashing, lime or silicate deposits can also form on the dishes and in the interior of the machine, since the calcium binding capacity of these cleaners is lower than that of classic phosphate-containing products . Disturbing lime or silicate deposits occur particularly when the dishwashing water of the dishwasher is not or not sufficiently softened and a water hardness of 4 ° d is exceeded. In such cases, limescale or silicate deposits can be effectively avoided if citric acid is dosed into the rinse aid via the rinse aid. However, since the amounts of rinse aid normally added during the rinse cycle with 3 ml - 6 ml are very small, the citric acid content in rinse aid formulations which are to ensure effective deposit inhibition must be relatively high in order to achieve sufficient acid or complexing capacity . Such high citric acid contents support the effect of the phosphate substitutes and ensure spotless dishes.

From EP-Bl 0 197 434 (Henkel) rinse aids are known which contain mixed ethers as surfactants. A variety of different materials (glass, metal, silver, plastic, porcelain) are cleaned in the dishwasher. This variety of materials must be wetted as well as possible in the rinse cycle. Rinse aid formulations which contain only mixed ethers as the surfactant component do not meet these requirements, or do so only to a small extent, so that the rinse aid or drying effect is unsatisfactory, particularly in the case of plastic surfaces. For use in detergents, that is to say also in rinse aid formulations, only recipe constituents which are completely biodegradable and toxicologically harmless are still suitable today. Solvent-free products are of particular interest.

The object of the present invention was therefore to provide new formulations which are ecologically and toxicologically flawless and which, in terms of their application properties, give the same results as commercially available cleaning agents and do not have the disadvantages mentioned above.

Description of the invention

The invention relates to compositions for cleaning hard surfaces containing

a) mixed ethers of the formula (I),

CH ₃

I Rlθ- (CH ₂ CHO) _ml (CH2CH2θ) _nl -OR2 (I)

in the R * for a linear or branched, aliphatic alkyl and / or alkenyl radical with 8 to 18 carbon atoms, R ^ for a linear or branched alkyl radical with 1 to 4 carbon atoms or a benzyl radical, ml for 0 or numbers from 1 to 2 and nl stands for numbers from 5 to 15, and b) fatty alcohol polypropylene glycol / polyethylene glycol ether of the formula (II),

CH ₃

I R3θ- (CH ₂ CHO) _πl 2 (CH2CH2θ) _n 2H (II)

in which R ^ stands for a linear or branched, aliphatic alkyl and / or alkenyl radical with 8 to 16 carbon atoms, m2 for 0 or numbers from 1 to 3 and n2 for numbers from 1 to 5.

Surprisingly, it was found that detergents, in particular rinse aids containing mixed ethers and fatty alcohol polypropylene / polyethylene glycol ethers, not only have a high level of ecotoxicological compatibility, but also fully meet the requirements for a branded product with regard to the application properties.

Another advantage, which preferably relates to rinse aid, is that for the preparation of their homogeneous, low-viscosity and therefore easy to dose solutions no further, mostly inert and therefore ineffective solubilizers for drying and the rinse aid effect such. As sodium cumene sulfonate, ethanol or glucose syrup are required, unless they are required in small quantities for the incorporation of colorants and / or fragrances. Mixed ether

Mixed ethers 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. In the presence of bases, fatty alcohol polyglycol ethers are preferably reacted with alkyl halides, in particular butyl or benzyl chloride. Typical examples are mixed ethers of the formula (I) in which R ^{1 stands} for an industrial Ci2 18 ~ or Ci2 / 14 cocoalkyl radical, ml for 0, nl for 5 to 10 and R ² for a butyl group (Dehypon ( ^R ) LS-54, LS-104, LT-54, LS-104, Henkel KGaA, Düsseldorf / FRG). The use of mixed ethers capped with butyl or benzyl groups is particularly preferred for technical reasons.

Fatty alcohol polypropylene / polyethylene glycol ether

The polyglycol ethers which form component b) 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 (II) in which R3 represents an alkyl radical having 12 to 18 carbon atoms, m2 represents 0 or 1 and n2 represents numbers from 2 to 5 (dehydol ( ^R ) LS-2, LS-4 , LS-5, Fa.Henkel KGaA, Düsseldorf / FRG). The polyglycol ethers can preferably have a narrow homolog distribution; in these cases, formulations with particularly advantageous physical properties are obtained. The agents according to the invention can contain components a) and b) in a weight ratio of 10:90 to 80:20, preferably 30:70 to 70:30 and in particular 30:70 to 40:60.

Surfactants, auxiliaries and additives

The agents according to the invention can contain nonionic substances of the alkyl oligoglucoside and / or fatty acid N-alkyl glucamide type as further surfactants. The most important additives are mono- and polyvalent carboxylic acids, preferably hydroxycarboxylic acids. Typical examples are Äpp¬ rock 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. They can be used in amounts of about 1 to 50, preferably from about 1 to 30,% by weight. Dyes and fragrances are particularly suitable as additional additives.

KlarBPÜler formulations

Typical formulations of the agents according to the invention, provided they are rinse aids, can for example have the following composition (ad 100% by weight water): 0.5 to 20% by weight of mixed ether,

0.5 to 20% by weight of fatty alcohol polypropylene glycol / polyethylene glycol ether and 1 to 50% by weight of carboxylic acids.

Recipes containing are particularly advantageous

3 to 10 wt .-% mixed ether

3 to 10 wt .-% fatty alcohol polyethylene glycol ether and

1 to 30% by weight of citric acid.

Industrial applicability

The agents according to the invention contain ecotoxicologically particularly compatible ingredients, can be formulated without solvents and show an excellent network capacity compared to a wide variety of materials.

Another object of the invention therefore relates to the use of mixtures of mixed ethers and fatty alcohol polypropylene glycol / polyethylene glycol ethers for the preparation of agents for cleaning hard surfaces, in particular dishes, in which they are present in amounts of 0.5 to 20, preferably 1 to 10 % By weight, based on the composition, may be present. Typical examples are rinse aids, all-purpose cleaners, hygiene cleaners, bottle cleaners and general agents in which low-foam surfactants are usually used. The following examples are intended to explain the subject matter of the invention in more detail without restricting it.

Examples

Surfactants used

AI) Ci2 / 14 ^_κ ° kosfettalkohol-5 EO-butyl ether

Dehypon ( ^R ) LS-54 A2) Ci2 / l4 ~ coconut fatty alcohol-10 EO-butyl ether

Dehypon ( ^R ) LS-104 A3) Ci2 / ιg-coconut fatty alcohol-10 EO-butyl ether

Bl) Ci2 / 14 coconut fatty alcohol 2 EO adduct

Dehydol ( ^R ) LS-2 ^B2 ) Ci2 / 14-K ° Kosfettalkohol-4 EO adduct

Dehydol ^(R ) LS-4 ^B3 ) Ci2 / 14 ~ coconut fatty alcohol-5 EO adduct

Dehydol ( ^R) LS-5 B4) Ci2 / i4 coconut fatty alcohol-2 PO adduct B5) 2-ethylhexyl alcohol-2 EO adduct ^B6 ) Ci2 / 14- ^{coconut fat} lkθhθl-3 EO adduct NRE * ^cl ) Ci2 / 14 ~ Coconut alcohol 5EO-4PO adduct

Dehydol ( ^R ) LS-54 C2) Cχ2 / i4 coconut fatty alcohol 4EO-5PO adduct

Dehydol ( ^R) LS-45

*) NRE «narrow ranks ethoxylate (narrow homolog distribution

All surfactants are sales products from Henkel KGaA, Düsseldorf / FRG. Components A and B are according to the invention, and components C were used for comparison purposes. Application test of rinse aid

The composition of the surfactant component of the rinse aid formulations tested is shown in Tab. 1. The mixtures Ml to M6 are according to the invention, the mixtures M7 to MIO are used for comparison.

Tab. 1; Rinse aid surfactant composition Percentages as% by weight

M AI A2 A3 Bl B2 B3 B4 B5 B6

%%%%%%%%%

Ml 30 70

M2 50 20 30

M3 50 30 20

M4 30 40 40

M5 50 40 10

M6 35 65

M AI A2 Bl B2 B3 B4 B5 Cl C2

%%%%%%%%%

M7 100

M8 100

M9 100

MIO 30 70

Legend; M = mixture Foaming behavior of the surfactant mixtures

To determine the foaming behavior of the surfactant mixtures, 2 eggs (approx. 100 to 110 g) were diluted 1: 1 with water at 16 ° d in an electric mixer and stirred for 2 minutes. 100 g of the resulting emulsion were then made up in a double-walled measuring cylinder from 2000 ml to 500 ml with water at 16 ° C. and the temperature was raised to 50 ° C. After the test temperature had been reached, 20 g of the surfactant mixtures M1 to M9 were added to this mixture. With the help of a laboratory peristaltic pump, the solution was sucked from the bottom of the measuring cylinder with a glass tube. The return was carried out via a second tube, the lower end of which ended at the height of the 2000 ml mark of the measuring cylinder. The liquid was pumped around at a rate of 4 l / min. After 5, 10, 20 and 30 min the volume was read from the foam and the liquid. The results are summarized in Tab. 2:

Tab. 2: Foam behavior of the surfactant mixtures

Mix volume in ml after min

5 10 20 30

Ml 750 850 1030 1060

M2 720 825 1000 1020

M3 710 800 980 1020

M4 720 810 900 990

M5 600 750 1020 1040

M6 700 840 900 1000

M7 760 900 1100 1120

M8 600 700 1040 1060

M9 600 700 900 1000

MIO 750 920 1100 1120

Foaming behavior of the rinse aid formulations

The foam development of the rinse aid was determined with the aid of a rolling pressure measuring device. The rinse aid (3 ml) was dosed by hand in the rinse aid 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 c) drying:

The dishwasher door was fully opened 15 minutes after the end of the washing program. After 5 minutes, the drying was determined by counting the remaining drops on the dishes listed below. 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)

d) rinse aid effect:

After the drying had been assessed, the crockery parts were placed outside the dishwasher for 30 minutes to cool and then visually inspected in a black box under illumination. The dried residual drops, streaks, deposits, cloudy films etc. remaining on the dishes and cutlery were assessed. Evaluation:

0 points - poor rinse aid effect 8 points = optimal rinse aid effect For performance tests c) and d), the tests were carried out in the Bauknecht GSF 1162 dishwasher with softened water. The 65 ^C C normal program was selected for this. 40 ml of Somat ( ^R ) cleaner (Henkel) were dosed into the cleaning cycle. The amount of rinse aid was 3 ml and was dosed manually at 50 ° C in the rinse aid. The salt load in the water was between 600 and 700 mg / 1. 3 rinse cycles were carried out for each rinse aid formulation. The following dishes were used to assess the drying and the rinse aid effect:

o glasses "Neckar-Becher" (from Schott-Zwiesel), 6 pieces o stainless steel knife "Brasilia" (from WMF), 3 pieces o white Prozellan dinner plates (from Arzberg), 3 pieces o red plastic plates "Valon dinner plates "(Fa. Haßmann), 3 pieces

Examples 1 to 5, Comparative Examples VI to V4:

Tab. 3: Rinse aid test results, percentages as% by weight to 100% by weight of water

Ex. M cfTenside it. DS St. Aus. S

%%% ° C

1 ml 17.5 3.0 0.5> 70 clear 0

2 M2 17.5 3.0 0.5> 70 clear 0

3 M3 17.5 3.0 0.5> 70 clear 0

4 M4 17.5 3.0 0.5> 70 clear 0

5 M5 17.5 3.0 0.5> 70 clear 0

VI M6 17.5 3.0 0.5> 75 clear 1

V2 M7 17.5 3.0 0.5> 75 clear 1

V3 M8 17.5 3.0 0.5> 75 clear 1

V4 M9 17.5 3.0 0.5> 75 clear 1

Examples 6 to 10, Comparative Examples V5 to V9:

Tab. 4: Drying of the dishes / rinse aid effect

E.g. M. Glasses Knife Porcelain Art.

T KSE T KSE T KSE T KSE

6 ml 3.7 6.2 4.1 3.0 5.0 6.3 4.0 5.3

7 M2 3.5 6.1 4.2 2.9 5.1 6.3 3.9 5.5

8 M3 3.6 6.2 4.3 3.1 4.8 6.4 4.1 5.3

9 M4 3.4 6.1 4.4 3.2 4.9 6.4 4.1 5.1

10 M5 3.3 6.0 4.5 3.1 4.8 6.3 4.0 5.3

V5 * 4.8 6.0 4.8 6.6 5.0 8.0 5.0 6.8

V6 M6 2.7 5.7 4.1 2.0 4.9 6.0 4.0 5.3

V7 M7 2.5 5.8 4.2 1.9 4.0 6.0 4.0 5.1

V8 M8 1.3 5.3 2.3 1.7 4.0 4.3 2.7 4.5

V9 M9 2.4 5.8 4.4 2.2 4.9 6.4 4.1 5.1

Legend: T = drying

KSP = rinse aid effect

* »Marketable rinse aid

Claims

claims

1. Means for cleaning hard surfaces, containing

a) mixed ethers of the formula (I),

CH3

I.

Rlθ- (CH ₂ CHO) _1Ill (CH2CH2θ) _nl -OR ² (I)

in the R1 for a linear or branched, aliphatic alkyl and / or alkenyl radical with 8 to 18 carbon atoms, R2 for a linear or branched alkyl radical with 1 to 4 carbon atoms or a benzyl radical, ml for 0 or numbers from 1 to 2 and nl stands for numbers from 5 to 15, and

b) fatty alcohol polypropylene glycol / polyethylene glycol ether of the formula (II),

CH3

IR ³ 0- (CH ₂ CHO) _Ill 2 (CH2CH2θ) _n 2H (II)

in which R3 stands for a linear or branched, aliphatic alkyl and / or alkenyl radical with 8 to 16 carbon atoms, m2 for 0 or numbers from 1 to 3 and n2 for numbers from 1 to 5.

2. Composition according to claim 1, characterized in that they contain components a) and b) in a weight ratio of 10:90 to 80:20.

3. Composition according to claims 1 and 2, characterized gekennzeich¬ net that they contain other nonionic surfactants and conventional auxiliaries and additives.

4. rinse aid according to claims 1 to 3, characterized ge indicates that they

0.5 to 20% by weight of mixed ether,

0.5 to 20 wt .-% fatty alcohol polypropylene glycol / polyethylene glycol ether, 1 to 50 wt .-% carboxylic acids and

contain ad 100 wt .-% water.

5. Use of mixtures of mixed ethers and fatty alcohol polypropylene glycol / polyethylene glycol ether for the production of agents for cleaning hard surfaces.