WO1998023723A1

WO1998023723A1 - Detergents

Info

Publication number: WO1998023723A1
Application number: PCT/EP1997/006419
Authority: WO
Inventors: Thomas Molz; Gabriele Hecht
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1996-11-27
Filing date: 1997-11-18
Publication date: 1998-06-04
Also published as: EP0944712B1; DE59703741D1; EP0944712A1; ATE201901T1; DE19649102A1

Abstract

The invention relates to liquid, viscose detergents which remain liquid up to 0 °C and show no turbidity or flocculation, and contain water and a) 3-15 wt.% of one or more potassium salts from fatty acids, b) 1-10 wt.% of one or more solutizing agents from the group of ethoxylated alcohols and/or alkylamines, and c) 1-8 wt.% of a thickening system, consisting of low-ethoxylated fatty alcohols and/or fatty amines and fatty alcohol ether sulphates and/or fatty alcohol sulphates and/or their ethoxylation products and electrolytes.

Description

.Cleaning supplies"

The invention relates to a liquid viscous cleaning agent, for example for soiled surfaces, in particular human skin, which, in addition to being used as a hand cleaning agent, can also be used as an auxiliary in metal forming operations.

While humid leaves, damp white sand and later sawdust have been used for cleaning purposes against the pollution that was common at the beginning of human history, especially in the course of industrialization, work with paints, varnishes, glazes, oils, tars, pigments, bitumen, printing inks became more frequent or similar substances for which contamination of the surfaces and hands could not be avoided and which required special cleaning agents. The increasing motorization also made it necessary to clean dirty hands without water, for example after repairs in the event of breakdowns ("roadside repairs"). As a result, around the turn of the century, the first hand cleaning agents, which generally contained abrasives, surfactants, water, organic solvents and possibly others GB 00 04 145 (R. Stewart) from 1897, for example, discloses the production of a hand cleaning agent by boiling up glue with soda and adding alum and ash to the clear liquid that separates. Soap-containing hand cleaning agents are first described in GB 00 05 047 (TN Wilson) from 1907, according to the teaching of which lubricating soap is mixed with methanol, gelatin and aromatic oil, GB 00 18 523 (H. Wade) from 1914 discloses a hand cleaning agent comprising 6 parts of sawdust and one part of powdered soap and the like GB 01 23 597 (R. and H. Moore) from 1918 discloses the use of a mixture of sand, soda and a cooling lubricant of water, oil, ammonium salts and glycerol as a hand cleaning agent and for cleaning hard surfaces and as an auxiliary in the forming of metals .

More recent patents disclose hand cleaning agents that contain synthetic surfactants, flow improvers and other additives in addition to the soaps and abrasives. These products are flowable to pasty and ensure that - undiluted when applied to the skin - they do not flow off immediately and give a pleasant feeling when rubbed in the hands. DE 28 20 109 (Colgate Palmolive) describes, for example, cleaning agents for hard surfaces and hands, 2 to 60% by weight alkylbenzenesulfonates (ABS), 2 to 20% by weight of an inorganic salt, 2 to 20% by weight urea as well as up to 40 wt .-% soap. DD 231 800 (VEB Leuna Werk Ulbricht) discloses phosphate-containing hand cleaning agents that contain 24 to 45% by weight of surfactants (oleoylmethyl taurides, wC _12th _I8 alkyl sulfonic acids, C _{12th] 5} - fatty alcohol ether sulfates in a ratio of 1: 0.5-0, 75: 0.1-0.25), 1 to 4% by weight of sodium chloride, 3 to 8% by weight of disodium hydrogenphosphate and 8 to 20% by weight of pentasodium tripolyphosphate. A homogeneous, liquid, pasty or cream-shaped hand-cleaning agent based on water, the anionic and / or nonionic surfactants, abrasives and a combination of hydrogenated castor oil with a carboxylic acid ester of the formula R-CO- (OCH ₂ CH ₂ ) _n -OX, in which R for a C ,. ₃ - alkyl radical, X for a C ,. ₅ -alkyl radical and n is 1 to 4 is described in EP-A-0 521 899 (Henkel). This hand cleaning agent maintains a constant viscosity over a long period of time. Finally, DE 195 30 833 (Ciba Geigy) describes disinfectant hand cleaning agents which contain 0.05 to 20% by weight of surfactants and / or soap (s) and 0 to 10% by weight (uns) saturated fatty acid salts and 0.1 to 25% by weight of a hydrotope, preferably a sulfonate.

All hand cleaning agents of the prior art, despite their cleaning action and storage stability, have the disadvantage that the viscosity of the agents The decrease in temperature increases drastically in some cases and the agents solidify in a gel-like manner or even give solids at temperatures around the freezing point, in most cases irreversible phenomena such as flocculation and / or phase separation being observed before the solidification. This has disadvantages in terms of application technology, since these agents can neither be used nor stored at the low temperatures mentioned. For example, processing or cleaning hard surfaces such as metal sheets at temperatures below 5 ° C is not possible and the products must be stored in heated rooms, which is why it is not sensible to carry them in a motor vehicle in winter, for example. This also makes it difficult to transfer the cleaning agents from the camsters or drums, which have been in unheated storage rooms, into the usual hand dispenser or small container, or make them impossible due to the unusability of the product.

The invention is therefore based on the object of developing a low-temperature agent, for example for use as a hand cleaning, metalworking and shaping aid, which has a viscous consistency desired by the consumer at room temperature and remains clear and liquid up to 0 ° C., with the cleaning ability compared fresh and dried paints, varnishes, glazes, oils, tars, pigments, bitumen, printing inks or similar substances should be comparable or better with the means of the prior art.

The object on which the invention is based is achieved by a homogeneous and liquid-viscous aqueous potassium soap / surfactant combination which comprises water and a) 3 to 15% by weight of one or more potassium salts of fatty acids, b) 1 to 10% by weight. -% of one or more solubilizers from the group of ethoxylated alcohols and / or alkylamines and c) 1 to 8 wt .-% of a thickening system consisting of lower ethoxylated fatty alcohols and fatty alcohol ether sulfates and / or fatty alcohol sulfates and / or fatty amines and / or their ethoxylation products and electrolytes.

The agents according to the invention can moreover be selected from the group of anionic, nonionic and / or amphoteric surfactants, abrasives, refatting agents, further electrolytes, preservatives, further alkalis, enzymes, sequestering agents, oxidizing agents, dyes and / or perfumes contain. They are viscous liquids that remain liquid and flowable down to 0 ° C and show no flocculation or phase separation phenomena. Thanks to the dermatologically safe ingredients they contain, they show very good cleaning effects on human skin against paints, varnishes, glazes, oils, tar, pigments, bitumen, printing inks or similar substances.

Unless otherwise stated, the proportions given below relate to the entire composition according to the invention. The naturally occurring fatty acids are always mixtures of fatty acids with different chain lengths, which may contain a different number of double bonds. The same applies to natural fatty alcohols. The ethoxylation of fatty alcohols is based on a statistical distribution. To the extent that C chain lengths and degrees of ethoxylation are given in this document, the information relates in principle to the statistical mean values of the C chain distribution and the degrees of ethoxylation.

., The potassium salts of fatty acids ( "potash-based soaps") contained in the inventive compositions as component a) can be prepared from the corresponding fatty acids obtained by neutralization with potassium hydroxide advantageously be C _I2 _lg -. Used fatty acids, with a small proportion of higher fatty acids can be tolerated. the potassium salts of natural fatty acids C ₁₆ _lg. particular preference is given in the agents the alkyl chains of fatty acids can here. also contain double bonds, that is, strictly speaking, be alkenyl chains. Technical mixtures of the various saturated and unsaturated fatty acids, such as those obtained from native oils and fats, are preferred for reasons of cost. The proportion of potassium soaps in the agents according to the invention is 3 to 15% by weight, preferably 5 to 12% by weight.

In addition to the proportion of these potassium salts, the agents can also free, i.e. contain non-neutralized fatty acids of the chain lengths mentioned. This proportion of free fatty acids can be advantageous for fine adjustment of the viscosity of the agents.

Nonionic surfactants used as solubilizers or component b) in the agents according to the invention are ethoxylated fatty alcohols or fatty amines, the chain length of the alcohols advantageously being between 6 and 18 and in particular between 8 and 14 carbon atoms and the alcohols or fatty amines with 4 to 16 moles of ethylene oxide are ethoxylated per mole of alcohol or amine. Here too, the technical mixtures with varying degrees of ethoxylation and alkyl chain lengths are less expensive. Component b) is present in the agents according to the invention in an amount of 1 to 10% by weight, preferably 3 to 8% by weight. Preferred component b) are ethoxylated alcohols, for example C ₆ . ₁₀ alkyl alcohols with 4 to 6 mol EO used.

The compositions according to the invention further contain, as component c), 1 to 8% by weight, preferably 2 to 6% by weight, of a thickening system which consists of lower ethoxylated fatty alcohols and / or fatty amines and fatty alcohol sulfates and / or fatty alcohol ether sulfates and / or their ethoxylation products. As lower-ethoxylated fatty alcohols and / or fatty amines, those with a degree of ethoxylation of <4 and a chain length of 10 to 18 carbon atoms are advantageous, a C _{12 being} preferred. ₁₄ fatty alcohol with 3 moles of ethylene oxide per mole of alcohol used. In this case too, the technical mixtures with varying degrees of ethoxylation and alkyl chain lengths are advantageously used. In addition to this nonionic surfactant, component c) contains one or more anionic surfactants from the group of fatty alcohol sulfates or fatty alcohol ether sulfates, a ratio of nonionic surfactant to anionic surfactant between 1: 1 and 1: 8, in particular from 1: 2 to 1: 6, being preferred. As a third component, component c) contains electrolytes. These electrolyte additives are helpful for adjusting the viscosity of the agent according to the invention and can come from the group of chlorides, bromides, sulfates or carbonates, but can also be selected from other groups in order to bring about any additional effects. For example, the builders properties of phosphate, citrate or tartrations can be used. The electrolytes in the agent according to the invention are preferably used in the form of their potassium salts, with potassium chloride being particularly preferred.

The agents according to the invention can contain further surfactant components, both anionic surfactants and nonionic surfactants and possibly amphoteric surfactants being used, diluents, acidic or alkaline constituents, builders and cobuilders, for example polymers and further active ingredients and / or auxiliary agents selected from the group of anionic, nonionic and / or amphoteric surfactants, abrasives, refatting agents, further electrolytes, preservatives, further alkalis, enzymes, sequestering agents, oxidizing agents, dyes and / or perfumes.

Other suitable anionic surfactants in the agents according to the invention are mainly alkylbenzenesulfonates (ABS), α-sulfofatty acid esters (ester sulfonates), short- and long-chain glycerol esters, alkylsulfosuccinic acid (ASB) and soaps. Examples of anionic surfactants from the above groups are the Eltesol commercially available ^® SX30 (sodium xylene, a product of Albright & Wilson), Triton ^® H55 (Kaliumphosphatester, a product of Union Carbide), Marlinat ^® DF8 (sodium sulfosuccinate, a product of Huls ), Hamposyl ^® L 30 (Natriumlauroylsarkosinat, commercial product from Hampshire); Fenopon ^® T33 (sodium N-methyl-N-oleyl taurate, commercial product from GAS) and Fenopon ^® AC 78 (sodium coconut isothionate, commercial product from GAS). Nonionic surfactants optionally additionally used in the agents according to the invention come from the group of the amine oxides, the glucosides and alkylpolyglucosides (APG), the alkoxylated sucrose and sugar esters, and the fatty acid esters. Examples include Triton ^® CGI 10 (alkyl glucoside, commercial product from Union Carbide), Glucam ^® E10 (methyl glucoside with 10 EO, commercial product from Amerchol), Crodesta ^® SL 40 (sucrose cocoate, commercial product from Croda) and Tegosoft ^® 16 B ( Cetyl isooctanoate, a commercial product from Goldschmidt).

Amphoteric surfactants which may be used in the agents according to the invention in addition to the surfactants required according to the invention and are mostly used only in combination with anionic surfactants are selected from the group of alkyl betaines, alkylaminopropionates, alkyliminodipropionates, alkylglycinates, carboxyglycinates, alkylimidazolines, sulfobetaines, alkylpolyaminocarboxylates and

Polyamphocarboxyglycinates. Examples of these types of surfactants are Tegobetain ^® A4080 (alkyldimethylbetaine, commercial product from Goldschmidt), Ampholak ^® XCU (coconut amphoglycolate, commercial product from Bero Nobel), amphoteric surfactant CT ^® (alkylimidazoline-based amphoteric surfactant, commercial product from Zschimmer and Schwarz), Ampholak ^® XCO 30 (coconut amphocarboxyglycinate, commercial product from Bero Nobel) and Sandobet ^® SC (coconut amide sulfobetaine, commercial product from Sandoz).

The abrasive materials that can be added to the agents according to the invention include micro glass balls, quartz flours, wood flours, chalks and plastic flours. Polyurethane flours are preferably used. The abrasive substances can be contained in the agents according to the invention in amounts of up to 10% by weight, with amounts of 2 to 6% by weight being preferred.

All dermatologically harmless substances which counteract the degreasing of human skin through the use of the agents according to the invention are suitable as refatting agents for the agents according to the invention. These include in particular Fatty acid alkanolamines, fatty acid polyalkanolamines, their ethylene and / or propylene oxide addition products and fatty acid monoglycerides. Compounds whose fatty acid content contains 12 to 18 carbon atoms are particularly suitable. The refatting agents can be present in the agents according to the invention, for example in amounts of up to 20% by weight, but preferably in amounts of 1 to 10% by weight.

Known builders which can be used in the agents according to the invention are monomeric or oligomeric phosphates such as, for example, monophosphates, pyrophosphates, triphosphates and cyclic or polymeric metaphosphates. Further groups of inorganic builder substances include carbonates, hydrogen carbonates, borates and silicates, preferably those with a molar ratio of SiO ₂ : M ₂ O (M = alkali metal) in the range from 0.5 to about 4, in particular from about 1.0 to about 2.4 . Organic builder substances can preferably be selected from the polymers and copolymers of acrylic acid, hydroxyacrylic acid, maleic acid and allyl alcohol. Poly (tetramethylene-1,2-dicarboxylates) and poly (4-methoxytetramethylene-1,2-dicarboxylates) can also be used. The inorganic and organic builders mentioned are used in the form of their water-soluble salts, in particular their potassium salts.

In addition to the alkali metal hydroxides, sodium or potassium carbonate and sodium or potassium silicates, for example, may be considered as additional alkalis, with the potassium salts being preferred. Suitable chelating agents are, for example, the alkali salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polyacrylates, polymaleates and polysulfonates. Low molecular weight hydroxycarboxylic acids such as citric acid, tartaric acid, malic acid or gluconic acid are also suitable. Suitable complexing agents can also be selected from organophosphonates such as, for example, l-hydroxyethane-l, l-diphosphonic acid (HEDP),

Aminotri (methylenephosphonic acid) (ATMP), diethylenetriaminepenta (methylenephosphonic acid) and 2-phosphonobutane-l, 2,4-tricarboxylic acid (PBS-AM). Oxidizing agents can also be added to the agents according to the invention in order to be able to better remove oxidatively bleachable dirt and / or to simultaneously remove germs from the surfaces to be cleaned. However, germ killing is preferably achieved by means of more skin-friendly preservatives, for example sodium hydroxymethylglycinate.

The pH of the agents according to the invention is preferably in a range between 6 and 11, with values between 8.5 and 10 being particularly preferred.

The viscosity of the agents according to the invention, which is measured in accordance with DIN 53211 with a 4 mm Ford flow cup, is 20 ° C. over 50 seconds, values between 70 and 120 seconds being preferred. At 0 ° C the agents flow well and uniformly and have viscosities of less than 1000 seconds.

The hand cleaning and shaping aids according to the invention can be used at room temperature or at elevated or reduced temperatures and can be used up to 0 ° C. without flocculation, phase separation or solidification. They can easily be washed off with cold or warm water. In addition to cleaning hands soiled with paints, varnishes, glazes, oils, tars, pigments, bitumen, printing inks or similar substances, the agents can also be used to remove paints, varnishes, glazes, oils, tars, pigments, bitumen, printing inks or similar substances hard surfaces or textiles. It can also be used as a forming aid in metal processing. Examples of such processes are forming, deep drawing, cold extrusion, wire or tube drawing.

The agents according to the invention are advantageously metered out from wall dispensers which are replenished from larger containers according to consumption. These dispensers enable clean and economical dosing on dirty or machined surfaces or on human skin. The preparation of the agents according to the invention has no special features. The easiest way to do this is to mix the individual components, if necessary at elevated temperature, in a stirrer and then fill them, if necessary after cooling, into conventional containers such as canisters, tubes, pumping vessels, dispensers or cans. The potassium soaps can be prepared beforehand, for example, directly in the batch container by saponifying the fatty acids with potassium hydroxide solution at 85 to 95 ° C.

Examples:

An aqueous potassium soap solution was prepared from 70.32 g of water, 2.58 g of 45% KOH and 5.6 g of C _{16.18 soybean} oil _fatty acid, which as a preliminary mixture was mixed with other components. The agents E1 and E2 according to the invention and comparative examples VI and V2 were produced, in each of which one of the components b) or c) of the main claim was used in too low a concentration. The composition of the agents can be found in Table 1.

The viscosities of the agents were measured using a 4 mm Ford flow cup (DIN 53211), the samples being heated to 20 ° C. or 0 ° C. After storage for two weeks at 0 ° C., the viscosities were measured again. The viscosity values in seconds of run-down time are summarized in Table 2.

Table 1: Composition [% by weight]

El E2 VI V2

K soap solution, 7.2% * 78.5 78.5 78.5 78.5

C ₁₂ . ₁₄ - fatty alcohol + 3 EO 0.8 0.8 0.4 0.8

C ₁₂ . ₁₄ -fatty alcohol + 2EO -sulfate 3.2 3.2 1.6 3.2

Octanol + 4 EO 2.8 5.6 - -

Potassium chloride 0.7 2.4 0.9 0.4

Water ad 100 ad 100 ad 100 ad 100

Potassium salt of a C ₁₆ . _lg soybean oil fatty acid Table 2: Viscosity values [s]

El E2 VI V2

20 ° C * 107 59 51 87

0 ° C * 438 176 743 1357

Appearance * clearly clear cloudy cloudy

0 ° C ** 440 177 gel-like *** solid

*: after 24 h storage at the appropriate temperature **: after 14 days storage at 0 ° C ***: not measurable with flow cup

Claims

Claims:

1. To 0 ° C homogeneous and liquid-viscous aqueous potassium soap-surfactant combination, characterized in that it contains water and a) 3 to 15% by weight of one or more potassium salts of fatty acids, b) 1 to 10% by weight of one or several solubilizers from the group of ethoxylated alcohols and / or alkylamines and c) 1 to 8 wt .-% of a thickening system consisting of low ethoxylated fatty alcohols and / or fatty amines and fatty alcohol ether sulfates and / or fatty alcohol sulfates and / or their ethoxylation products and electrolytes.

2. Composition according to claim 1, characterized in that as component a) potassium salts of C _12th , _8- fatty acids, preferably of natural C _16th ₁₈ fatty acids are used.

3. Composition according to one of claims 1 or 2, characterized in that component a) is used in amounts of 5 to 12 wt .-%.

4. Composition according to one or more of claims 1 to 3, characterized in that as component b) a C ₆ ethoxylated with 4 to 16 moles of ethylene oxide per mole of fatty alcohol. ₁₈ fatty alcohol is used.

5. Composition according to one or more of claims 1 to 4, characterized in that component b) is used in amounts of 3 to 8 wt .-%.

6. Composition according to one or more of claims 1 to 5, characterized in that component c) contains as the lower ethoxylated fatty alcohol a C _10.18 fatty alcohol with less than 4 moles of ethylene oxide per mole of alcohol.

7. Composition according to one or more of claims 1 to 6, characterized in that the ratio of nonionic surfactant to anionic surfactant in component c) is 1: 1 to 1: 8, preferably 1: 2 to 1: 6.

8. Composition according to one or more of claims 1 to 7, characterized in that component c) contains additional electrolytes, in particular potassium salts and preferably potassium chloride.

9. Composition according to one or more of claims 1 to 8, characterized in that component c) is used in amounts of 2 to 6 wt .-%.

10. Composition according to one or more of claims 1 to 9, characterized in that it additionally contains builders and / or complexing agents.

11. A composition according to one or more of claims 1 to 10, characterized in that it contains further active ingredients and / or auxiliary substances selected from the group consisting of anionic, nonionic and / or amphoteric surfactants, abrasives, refatting agents, further electrolytes, preservatives, further alkalis , Enzymes, sequestering agents, oxidizing agents, dyes and / or perfumes.

12. Agent according to one or more of claims 1 to 11, characterized in that the viscosity of the agent at 20 ° C for 50 seconds, preferably in the range of 70 to 120 seconds, measured with a 4mm Ford flow cup (DIN 53211) , is.

13. Agent according to one or more of claims 1 to 12, characterized in that the agent is good and uniformly flowable at 0 ° C and the viscosity is less than 1000 seconds, measured with a 4mm Ford flow cup (DIN 53211).

14. Use of an agent according to one or more of claims 1 to 13 for skin cleaning, in particular for hand cleaning.

15. Use of an agent according to one or more of claims 1 to 13 for cleaning hard surfaces.

16. Use of an agent according to one or more of claims 1 to 13 as a surface processing or forming aid in metalworking.