DE2257642A1 - BIODEGRADABLE DETERGENTS AND DETERGENTS - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG

Our sign? O.Z. 29 546 Ze / L 6700 Ludwigshafen, 23.II.1972

Biodegradable washing and cleaning agents

The invention relates to new biodegradable washing and Rexnigungsmittelkorapositionen, which contain an oxyethylated alcohol mixture as a washing-active principle, the one special has good biodegradability, coupled with great washing and cleaning power.

It is known that nonionic detergent substances ^ in particular those based on oxyalkylation products Have good detergency »They also generally develop relatively little foam, which is particularly important when used in automatic washing and cleaning machines.

So far, compounds were known ₉ which are characterized by excellent washing and cleaning power, ζ «Β« oxethylated fatty alcohols and, above all, oxethylated alkylphenols. Examples of extremely low-foam compounds are, for example, oxyethylated polypropylene glycols and the oxyethylated polypropylene glycol ether derivatives of ethylene diamine _o Other cleaning agents contain oxyethylated alkylphenols, which usually contain 8 to 12 carbon atoms in the phenol nucleus and which are preferably between 4 and 30 times oxyethylated. However, as a result of the aromatic nucleus they contain, such compounds are only insufficiently biodegradable, a disadvantage that has recently become more and more apparent, since the legislation of all countries in the world strives to put environmental protection at the top of their legislative work. In the detergent sector in particular, the property of biodegradability is becoming more and more fundamental, since these substances are consumed in very large quantities and have to be broken down in wastewater.

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The previously known oxethylated linear fatty alcohols generally consist primarily of an alcohol mixture with a chain length of 12 to 20 carbon atoms and are im significantly more biodegradable than the oxyethylated aromatics. However, their degradability is not yet optimal either. For example, when achieving a hydrophilic / lipophilic balance that is sometimes desired, relatively high degrees of ethoxylation are necessary. This often means a ratio of 1 mole of fatty alcohol to 20, 25 or more moles of ethylene oxide. With oxyethylation products with over 20 moles of ethylene oxide, however, is a biological one Degradability can hardly be achieved.

In contrast to the alkylphenol oxyethylates, the oxyethylated fatty alcohols are generally pasty in the oxyethylation range necessary for an optimal washing and cleaning effect or even solid. Concentrated aqueous solutions cannot easily be prepared. In addition, conventional are oxyethylated Fatty alcohols compared to alkylphenol oxyethylates only mi ■; significantly higher costs can be produced.

In the recently known oxpropylation of such prepared oxethylated fatty alcohols, it is true that sometimes a more fluid consistency than with pure oxethylated fatty alcohols and also a further reduction, which is often desired the foaming power is achieved, however, on the other hand, both the pure surfactant properties and the biological properties are usually the same Degradability at a reduced level compared to oxethylated fatty alcohols. This trend is even stronger in the oxethylated polypropylene glycols and oxethylated polypropylene glycol ether derivatives of ethylenediamine.

With regard to the biodegradable polyether derivatives teaches the German Auslegeschrift 1 645 011 more complexly structured compositions which, as evidenced by the table examples, are satisfactory appear. The disadvantage, however, is that this is a relatively complicated mixture for the production of the biological degradable oxalkylated alcohols is required.

Another development step in the desired direction

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257642

shows the teaching of OT-OS 2 056 565. There are cleaning agents described, which are built up from a mixture of two oxethylated alcohol mixtures. The first mix component consists of a 5- to 10-fold oxethylated alcohol or alcohol mixture with 6 to 10 carbon atoms and a 5- to 10-fold oxethylated mixture of alcohols with 11 to 20 carbon atoms, the alcohols being prepared by hydroformylation of the corresponding mixed olefins.

The disadvantage that still clings to this doctrine consists in the relatively complicated production method, namely by first showing two different mixture components and these then in the - as it says in the literature section - desired Composition must be mixed. Another The disadvantage is the relatively wide range of carbon chain lengths. It is well known that fat solubility decreases with decreasing carbon chain length, and on the other hand the water solubility increases with increasing degree of oxethylation, Es So here, if one uses such mixtures, in In each case, exactly how big the mixing ratios should be tried out must be so that the desired balance between hydrophobic and hydrophilic groups is achieved. This is true in in the same way for achieving optimal biodegradability, washing power and foam absorption. That this is time-consuming Tersuche are necessary, is evident from the fact that the hydroformylation of various olefins in general results in a rather heterogeneous range of products, so that one can never specify in advance which mixture will be used has the required optimal properties. A detergent should not only have good washing power, but also one have good biodegradability. The detergent should be effective as far as possible at lower temperatures; Everyone these requirements cannot be achieved by the above teaching without time-consuming special experiments.

The aim of the invention was therefore to produce detergent and cleaning agent formulations produce containing oxyethylated alcohols that are easy and cheap to produce by their liquid consistency during transport and storage problem-free

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INSPECT *)

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are, are miscible with water, and which have both an optimal washing and sloping ability and at the same time - paired with a good foam absorption - optimal biodegradability exhibit.

The aim of the invention was achieved with detergents and cleaning agents which, in addition to inorganic and / or organic builder salts and complexing agents and optionally bleaching and lightening substances, defoamers and disinfecting agents, contain at least one surfactant based on a mixture of Ziegler or cracking agents mixed from hydrofonnylation. Olefins containing oxyethylated alcohols as a cleaning principle, which are characterized in that the detergents and cleaning agents contain 2- to 15-fold oxyethylated alcohol mixtures with 9 to 11 carbon atoms in the alcohol part, which were obtained by hydroformylation of olefin mixtures, which are derived from 15 to 85 mole percent Cg olefins,
0 to 70 mole percent Cg olefins and

85 to 15 mole percent C 1-4 olefins
put together.

With these surfactants, a cleaning component has now become found that not only has the same effect as the compositions mentioned in DT-OS 2 056 565, but even surpasses it. In addition, these surfactants are easier to produce because they are made up of simple and technical means derive more easily obtainable olefin cuts.

For the purposes of the present invention, the alcohol mixture which is oxyethylated by definition is essential. It is particularly important here that pure Cg, C ^ _Q - or C ^^ - alcohols do not meet the objectives of the invention, in that in particular the optimal detergency is not guaranteed to the desired extent. What is essential - and this is the surprising factor - is the mixture obtained from olefin mixtures, which must consist of at least two partners in the composition defined above.

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The alcohols to be oxyethylated are produced from the Olefins through hydroformylation (oxo synthesis) using cobalt carbonate hydrogen as catalysts ", there is no need for detailed data on the maturity; it is in this context on Falbe, "Syntheses with carbon monoxide '", Springer-Verlag (1967) pointed out. ·

Suitable olefin mixtures are those as defined above. They originate from the high pressure polymerization of ethylene with organoaluminum compounds (Ziegler), which produces even-numbered α-olefins. To obtain the Cg / CjQ-olefin mixtures in the sense of the invention, the polymer mixture must be fractionated, the conditions must be observed so that the definition according to the percentages of Cg and C ₁ Q-olefins result. One fractionates. in the sense of the invention 15 to 85 mol percent Cg and 85 to 15 mol percent C | _Q -, preferably 30 to 60 mole percent Cg and 60 to 30 mole percent C 1-4 olefins.

Such Ziegler-olefin cuts do not contain amounts of C _Q ~ olefin and contribute to over 80 i> terminal double bonds and are unbranched.

Another source of starting olefins according to the invention is petroleum, which can be thermally cracked in a manner known per se (cracking process). Here also mainly terminally unsaturated, branched to a maximum of 5 $> arising suitable procedure olefins worked up by fractional distillation in the above sense and thus essential to the invention cq- to C .- "- cuts result. The herausfraktionierten _Q C - C '^ - sections contain up to 70 mole percent, preferably up to 40 mole percent, to Cq-olefins in addition to the CG and C. ^ - olefins. Both types of mixtures result in their further processing by hydroformylation to alcohol mixtures which are predominantly straight-chain having 9 to 11 carbon atoms and containing not more than 40 $> branches, namely mostly a-methyl branches.

The Öxäthylierung of the described Cq to C ₁ ^ alcohol cuts

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takes place according to methods known per se and no longer needs special mention. US Pat. No. 2,870,720, DT-AS 1 300 540 and DT-AS 1 240 062, for example, explain procedural measures which also produce favorable results within the scope of the invention. A degree of oxethylation of 2 to 15, preferably 2 to 7.5 _f. Is essential in the context of the invention. Mixtures of compounds which are on average 5 to 7 times oxyethylated are of the greatest technical interest.

This results in mixtures of surfactants that are not only excellent surface-active properties, such as lowering the surface tension, high wetting effect, high cleaning and cleaning properties Detergency, also characterized by their particularly good biodegradability. Add to this the liquid consistency as well the dilutability that can be achieved with water in any ratio. In this connection it should be noted that the surfactant mixtures explained in DT-OS 2,056,565 meet the latter criterion not even close, because of the wide range of carbon chain lengths excludes this from the start.

Those generally preferred so far for fatty alcohol oxyethylates higher alcohols or alcohol mixtures with considerable spread in terms of chain length, due to the large proportion of larger hydrophobic residues, require a longer hydrophilic one Chain. These compounds were previously considered to have a satisfactory washing power. That in the context of the present invention also a narrow, easily producible carbon chain range to oxyethylation products leads, which not only result in no loss of washing power but even a considerable improvement, represents an important moment in the present composition according to the invention.

The Cq to C _1. , - Oxoalkoholoxäthylate can be added to a large number of different detergent and cleaning agent preparations. The amount of oxethylated alcohols to be added varies within wide limits and can include a ratio of oxethylated alcohol to other substances, such as 1: 9 to 9: 1. However, the ratio is expediently 1: 9 to 3: 1.

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Usual detergent and cleaning agent combinations contain, in addition to the Cq- to C ^ -alkoholoxäthylaten to be used according to the invention at least one other substance with a cleansing effect. This can consist of another surface-active substance and / or an inorganic and / or organic builder salt (builder).

Among the surface-active detergent raw materials, which may also be contained in the agents according to the invention in special cases, primarily weakly foaming compounds are additionally considered for all areas of application in which foam development is to be completely or largely excluded, including in particular directional ethylene oxide Adducts of ethyl alcohols or Cg = to Cj p-alky! Phenols, fatty acids and fatty acid amides, which contain 12 to 18 carbon atoms in the hydrocarbon radical and 3 to 15 alkoxy groups. Other suitable foam-suppressing nonionic surfactants are the water-soluble 20 to 250 Oxäthylatgruppen "un &" ¹ O to 100 Oxpropylatgruppen containing polyethylene oxide adduct © to Polypropylenglykoleny ithylendiaminpolypropylenglykolen IMD Alkylpolypropylenglykolen having 1 to 10 carbon atoms in d © r Alky! Chain. The compounds mentioned usually contain per propylene glycol -Unit 1 to 5 ethylene glycol units «,

Detergents and cleaning agents that develop foam is not serious or where they are caused by foam-absorbing Additives can be kept under control, can also contain anionic detergent raw materials of the sulfonate or sulfate type. Examples are e.g. Cg to C ^ 2 ™ alkylbenzenesulfonates or α-01efinsulfonate, as they are e.g. by sulfonation, primary or secondary aliphatic monoolefins with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis are obtained; also alkyl sulfonates, such as those from n-alkanes by sulfochlorination or sulf'oxidation and then Hydrolysis and neutralization or by bisulfite addition to olefins can be obtained »Primary also come into consideration and secondary alkyl sulfates, sulfates of oxethylated. and oxpropylated Alcohols and α-sulfo fatty acid esters.

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The carbon chain length is in the case of the aliphatic anion-active ones Suitably means between 8 and 22 carbon atoms.

Other compounds of this class, which may be used in detergents are higher molecular sulfated partial ethers and partial esters of polyhydric alcohols such as alkali salts the monoalkyl ether or the monofatty acid ester, the Glycerol monosulfuric acid ester or 1,2-dioxopropanesulfonic acid. There are also sulfates of oxyethylated and oxopropylated Fatty acid amides and alkylphenols as well as fatty acid taurides and fatty acid bis-eththionates. Apart from the mentioned washing raw materials of the sulfate and sulfonate type, the agents can also the usual alkali soaps of fatty acids, ampholytes, such as alkyl betaines and alkyl sulfobetaines and nonionic surfactants of the type of amine oxides and sulfoxides.

The anion-active detergent raw materials can be in the form of sodium, potassium and ammonium salts as well as salts of organic bases, such as mono-, di- or triethanolamine, are present. Unless the mentioned Active washing compounds have an aliphatic hydrocarbon residue, this should be for biological reasons Degradability preferably be straight-chain and have 8 to 22 carbon atoms.

In the case of the alkyl aromatics, they also contain them whenever possible unbranched alkyl chains have an average of 8 to 12 carbon atoms.

Inorganic builder salts (builders) are, for example. To mention phosphates, such as o-phosphates, pyrophosphates, tripolyphosphates and more highly condensed phosphates in the form of the neutral or acidic sodium, potassium or ammonium salts. Alkali silicates are also suitable, such as, for example, sodium silicate with a ratio of Na ₂ O to SlO ₂ such as 1:?, 5 to 1: 1.

Suitable organic builders are those with a complexing effect Alkali and ammonium salts of aminopolycarboxylic acids and / or Aminopolyphosphoric acids, especially the sodium or potassium salts of nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediamine triacetic acid, the hydroxyethane diphosphoric acid,

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methylenediphosphoric acid and analogous compounds. Further the corresponding salts of polycarboxylic acids, such as citric acid, adipic acid, glutaric acid, lactic acid, Mellith- · acid or the free acids themselves can be used.

Other organic builders that can be used are homopolymers and copolymers which, as monomers, include acrylic acid, methacrylic acid, maleic acid, Ethylene, styrene, methyl vinyl ether and other such homopolymerizable and copolymerizable carbon multiple bonds exhibit. The latter builder types include lately especially the 1: 1 copolymers of alkyl vinyl ethers and maleic anhydride have become known.

The detergents and cleaning agents can release oxygen or bleaching agents containing active chlorine, such as alkali perborates »alkali percarbonates, Alkali perphosphates, urea peroxides, alkali hypochlorites, chlorinated trisodium phosphate and chlorinated cyanuric acid or their alkali salts and stabilizers, such as Magnesium silicate and activators included. Often they also contain oxidizable substances together with other peroxides, such as for example urea or sulfamic acid. In the case of industrial cleaners, the last-mentioned compounds can also be used alone be present (as a mild complexing agent).

Furthermore, substances that act as dirt carriers, such as carboxymethyl cellulose or polyvinylpyrrolidone, as well as other auxiliaries, such as enzymes, coloring and fragrances, viscosity regulators ,. optical brighteners and water may be included. ■

The amount of alkaline substances should be measured so that the pH of a usable wash liquor for Coarse wash approx. 9 to 12, for heavy wash approx. 5 to 9 and for Detergent for solid surfaces is between 6 and 13. Cleaning agents for manual use preferably have a weakly acidic, neutral or weakly basic reaction in order to have as little skin irritation as possible.

Through a suitable combination of different surface-active

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The raw materials and builders among each other can be found in many Päl-Len Increases in effectiveness can be achieved. One obtains, for example, a Improved washing and cleaning power and a nOCK strengthener reduced foaming power.

In the context of the present invention, apart from those according to the invention oxyethylated oxo alcohols, the above surface-active additives are often only necessary in 'subordinate' amounts and therefore only have to be used for special formulations recommended.

The detergents and cleaning agents can be liquid, pasty or solid, e.g. powdery, granulated or lumpy Form. Liquid products can be used for solubility purposes Water-miscible solvents, in particular ethanol and isopropanol, and solubilizers such as alkali salts of benzene, toluene, xylene or ethylbene-zoliulfoic acid, contain. Technical cleaners and hand detergents included in addition, often water-insoluble solvents, such as trichlorethylene, Dipentene, petroleum, white spirit or paraffin.

The oxyethylated C «- to C ^ obtained according to the invention Alcohols are highly biodegradable and draw thanks to their good washing and cleaning power for textiles, Objects made of glass, metal, plastics and as hand detergents. Also their foam-absorbing properties are generally such that in many cases one can without the addition of any special ones mentioned in this description Foam suppressors can do.

Although the determination of the biodegradability of nonionic Surfactants is not yet regulated by international or national legal regulations and in particular about the Methods for their determination is still being discussed, but the application of one of these methods can also be envy of 'non-ionogenic' At least very far-reaching conclusions can be drawn if one considers the values of the compares biological degradation rates with each other.

One of the best methods of determination is considered to be that of 1, Wickbold developed, in detail, in the 'yearbook; vom / Wasser * /' volume

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(1967), page 229 ff, is published, in combination with the blowing out of the nonionic surfactants by means of a gas stream (E. Wickbold, Tenside 8 (1971), pages 61 to 63).

According to this method, ₁ ^ -OxoallcQholgemisch at a CQ to C oxyethylated with 5.2 moles of ethylene oxide, a degradation rate of 97.5 ¹ ic reached at a Cg to C ^ ₁ -Oxoalkoho! Mixture with 7 moles of ethylene oxide, a Reduction quota of $ 95. Work was carried out in a laboratory living sludge system according to Husmann and a residence time of 3 hours. With the exception of the different type of analytical detection required due to the chemical nature of the nonionic surfactants, namely the. according to R. Wickbold, were..the. in the ordinance on the degradability of detergents in detergents and cleaning agents for anion-active detergents determined determination methods (Federal Law Gazette I (1962), page 698 ff) adhered to the prescribed conditions. Comparable Nonylphenoloxäthylate show in contrast. ·. Husmann apparatus a 'degradation of approx. 60 to a maximum of 70 % "

The determination of the biochemical oxygen demand (BOD ₁ -) provides information on the biological degradation. This method is used to determine the oxygen that the microorganisms need to oxidize the substances contained in the wastewater. _{After adaptation, a BOD ^ value of 750 mg O 2} Zg substance was measured, for example, for a Cq to C ₁ .j-oxo alcohol mixture with 5.2 mol of ethylene oxide. With a Cq to C ₁ ^ oxo alcohol mixture + 7 moles of ethylene oxide, a BOD ^ value of 660 mg 0 ₂ / g substance was found after adaptation. The values for comparable nonylphenol oxyethylates are below 300 mg Op / g substance.

The criterion for assigning the oxyethylated Cq- to C ₁ .j-oxo alcohol mixtures according to the invention to the corresponding nonylphenol oxyethylates was the comparison of the cloud points, measured for example in a 1% aqueous solution.

The oxyethylated Cq to C ₁ ..- Oxoalkoholge- .. mixtures according to the invention form very stable solutions and show a slight turbidity only at very low temperatures. However, this can be completely prevented by adding 10 to 15 $ water. the

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surface-active properties of the compounds according to the invention are of such high quality that the application-technical criteria are also met by the aforementioned addition of water the corresponding! Tony lphenoloxät hy late achieved without further ado and in many cases they are exceeded »The addition of water itself is carried out without any difficulties.

As soon as the addition of a small amount of water has resulted in complete clarity of the oxyethylated C ₁ -C 1 -oxy alcohol mixture, the solution remains completely homogeneous! obtained even at the low temperatures mentioned. For example, the pour points of the 85 to 90% surfactant solutions are below> tO ° * O; while some of the corresponding Honylphenoloxäthylate already have pour points ^{between +10 and 0 ° C.}

In practice, for example, in liquid. Cleaning formulations, however, often use relatively dilute solutions *. A surprising effect of the Cg to Cj oxo alcohol mixtures according to the invention is that, at least in the upper range of the oxyethylation stages according to the invention, they give clear solutions over the entire range when diluted even up to 0.01% solutions. In contrast, the corresponding; Nonylphenoloxäthylate, when diluted, generally gives fairly stiff gels with a knowledge increase in viscosity, which are difficult to dilute with water. Other alchtionogenic surfactants with comparable cloud points as feiteriwi »such as oxyethylated C ₁₂ - to C ^ -fatty alcohols .tint ■ generally neither as a 100% substance, nor in a highly concentrated mixture with water, but either solid or highly viscous. When diluted to a greater extent, they show strong opacities * ζ., Β, to 5 ^ surfactant in 95 # water and below.

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In the tables below, various stages of oxyethylation of the C ₁ to C 1 ^ oxo alcohol mixtures are compared with Uonylph.enoloxa.thylaten. It should be noted that the Cq-bia C ₁₁ -oxoalkoholoxäthylate ^ were diluted with water in the ratio 85:15 in order to obtain completely clear solutions, while the Nonylphenoloxäthylate contained 100 % active substance.

Table 1

Starting mixture - -ι · 140 seconds Nonylphenol + 6O ⁰ C 30 to. 40 $> Octene-1 '(with 4 moles of 10 small proportions of octene-2) $ 70 to $ 60> Decen-1 (with small proportions of decene-2) 28.1. dyn / cm from the Z.iegler polymer - sation of.ethylene 28.5 dynes / cm 85 parts Cq- to C ₁₁ -OxO-
alcohol mixture +3.5 mol AO 18 ml 15 parts of water. · Cloud point 6O ⁰ C (10 # in 25 % 125 seconds Butyl diglycol solution) Surface tension 23.7 dynes / cm a solution with ΙΟ " ² mol / l 23.9 dynes / cm Surface tension
a solution with 10 ~ ³ mol / l 9 ml Wetting effect at 20 ° ( (Sinking time of tree wool lobes in sec. 0.5g of product + 2g Soda / 1 Foaming effect after Ross-Miles (DIN 53902, in drinking water water of 11 ° dH at 5O ⁰ C 2 g product / 1 after 30 seconds

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Cloud point Au: Parts C _n - to C ₁₁ -OxO- ' Share water 2257642 (10 #ig in 25 1 ° butyl 20th alcohol mixture + 5 ^ 2 mol AO Nonylphenol diglycol solution) 10 15th 70 ° C ■ Surface tension 40 + 7 moles EO a solution with 10 "^
Mon 1/1 approx. Surface tension,
a solution with 10
Mon 1/1 24.3 dynes / cm Wetting effect at 2O ⁰ C 3 cracked olefin mixture 24.5 dynes / cm (Sink time of tree up to 30 # octene, wool lobes in Se up to 40 fi nons, Customers; up to 70 i * decen, 0.5g of product + 2g 22 io not terminal Soda / 1 unsaturated parts 100 seconds 7O ⁰ C Foaming effect after 85 Ross-Miles (DIN 53902, in drinking water
ser of 11 dH 26.6 dynes / cm 5O ⁰ C) 27.8 dynes / cm 2 g product / 1 after 30 seconds 135 ml 180 seconds 30 ml

Table 3

f From cracked olefin mixture 20 to 30 # octene 10 to 40 # nonene 40 to 70 # decene approx. 22 Ji non-terminal unsaturated components 85 parts C _g - to C _1t oxo alcohol mixture + 7 Hol AO 15 parts water

Non |! Phenol + 10 mol AO

Cloud point (1 % in water)

Surface tension of a solution with 10 " Mon 1/1

Surface tension of a solution with 10 " Minor

Wetting effect at 20 ^° C

Foaming effect according to Ross-Miles

61 ⁰ C dyn / cm 25.4 dyn / cm 25.7 Seconds 125 ml 200

61 ⁰ C

29.1 dynes / cm

29.6 dynes / cm

100 seconds 195 ml

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Washing tests were carried out to determine the washing effect on textiles carried out under variation of the test conditions "

For example, »WFK fabric from laundry research in Krefeld was created in Launder-Q-meter (Atlas Electric Devices Co. * Chicago, 111., USA) washed with water at 16 ° dH for 30 minutes. The liquor ratio was 1:50, the liquor was previously at pH 10.5 been discontinued. Washing was done with a surfactant-builder mixture, which was composed as follows:

33.3 ° i surfactant
$ 66.7 Builder.

The surfactants compared with each other were a concentrated aqueous solution consisting of "85 parts of CQ to C ^ -oxo alcohol mixture, (from cracked olefin mixture - see Tables 2 and 3) with 5.2 moles of ethylene oxide and 15 parts of water (hereinafter referred to as 85 io Cq- to C ^ - 5.2) against nonylphenol with 7 mol Ätliylenoxid (hereinafter referred to as NP - 7 ") and a concentrated aqueous solution consisting of 85 parts of Cg- to C ^ - Oxo alcohol mixture (from cracked olefin mixture - see Tables 2 and 3) with 7 moles of ethylene oxide and 15 parts of water ( hereinafter referred to as 85 io Cq- to C ....- 7) against Konylphenöl with 10 moles of ethylene oxide (hereinafter referred to as MP - 10 designated).

As builders for _: other combinations pentasodium tripolyphosphate (STPP) and the trisodium salt of nitrilotriacetic acid (NTA) were used.

The washing tests were evaluated by measuring the degree of whiteness boil over on the Elrepho device from Zeiss. The evaluation of the Elrepho values found in percent happened as follows:

(Whiteness washed fabric -

Fabric soiled with whiteness

Detergency =

(Degree of whiteness of raw tissue -

Whiteness soiled fabric)

The following washing effects can be seen in the tables below:

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Wash temperature 60 C concentration

Whiteness jji] whiteness jjfj

85 $ C _q - to C ₁₁ - 5.2 (HP - 7 ■ + STPP)

+ STPP ^Ψ ) )

0.75 g / l 48.2 Ji 45.9

1.50 g / L 64.4 $ 55.2

2.25 g / l ί 70.5 Ji 54.3

3.00 g / L $ 71.8 .55.0

4.50 g / l 68.9 96 50.2

0.75 g / l 44.2 $ 43, β *

1.50 g / l 71.6 96 67.6 0

2.25 g / l 72.0? 6 58.5 56

3.00 g / l 70.0 0 "50-, 9'J *

4.50 g / L 70.1? 53.5 # pounds

85 96 CQ to C _11-7

⁹ **) "" ¹⁰

0.75 g / l $ 51.5 60 _f 4 Ji.

1.50 g / l 66.3? I 66 »9 $»

2.25 g / L 71.7 Ji 7O ₁ O Ji

3.00 g / l 70.2 Ji 67.5 f

4.50 g / l 67.1 ^. 65.0 f

85 Ji CQ to C _11-7

+ NTA *) ^{wr f +}

0.75 g / l 45.4 Jt 62.5 fi

1.50 g / l 70.4 Ji 72 * 4? I

2.25 g / L 72.5 Ji 71.3 Ji

3.00 g / l 71.2 ji 68.7>

4.50 g / L 67.7 jo 65.0 Ji.

♦) STPP = pentasodium triphosphate **) Aua Crao.k-Olefin

NTA = ^Na triumnitriloacetat (Tab. 2 and 3)

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2257642 Washing temperature 95 ° C 1.50 g / l - concentration 2.25 g / l Whiteness
(85 io C _g- to Whiteness
(NP - 7 + STPP) 3.00 g / l + STPP) - 7th 0.75 g / l 4.50 g / l 55.0 io 50.5 io 1.50 g / l 71.9 io 63.7 io 2.25 g / l 0.75 g / l ■ $ 72.6 61.9 # 3.00 g / l 1.50 g / l 72.4 io 5.2 *) 51.6 io 4.50 g / l 2.25 g / l 62.8 # $ 49.9 3.00 g / l O5 1 ° Cq ^1- C ₁ - | - - ^C 11- NP - 7 + NTA 0.75 g / l 4.50 g / l $ 48.6> 45.0? C 1.50 g / l 74.2 / ₀ 71.8 # 2.25 g / l 73.2 # 56.6 <fo 3.00 g / l 72.6 io *) 52.7? P 4.50 g / l $ 65.5 $ 54.0> 85? » ^ q "^ 11 ~"
+ STPP NP - 10 + STJP 56.7 io • 67.4 # 74.4 # 74.0 i> 73.6 % 72.5 9i 70.1 # 7 ·) 68.8 io. $ 65.6 64.3 5έ 85 i> Cq- bis NP - 10 + NTA 51.2 io • 63.4 % . 73.3? * $ 74.7> 74.5 io 69.4 9έ 70.9 # 67.7? Έ 67.4 # 65.1 %

*) From a Ziegler olefin mixture (Table 1)

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O.Z. 29

In addition to nonylphenol oxyethylates, other nonionic surfactants were compared with the oxyethylated Cq to C ₁₁ oxo alcohol mixtures according to the invention, love a concentrated aqueous solution of 85 parts of Cq to C ₁ oxo alcohol mixture *) with 7 moles of ethylene oxide and 15 parts of water (in the following again referred to as 85 $ Cq- to C ₁ ^ - 7.0) were a tallow fatty alcohol mixture with 11 moles of ethylene oxide (hereinafter referred to as TPA - 11), an oleyl-cetyl alcohol mixture with 12 moles of ethylene oxide (hereinafter with OCA - 12 referred to) and a tallow fatty acid monoethanolamide with 11 moles of ethylene oxide (referred to below as FSA - 12). The wash temperature was 95 ⁰ C, as builders STPP was used. The other conditions have not been changed from those described above. Since this series involved washing tests with a different test fabric delivery, the numerical values are somewhat different from those already given above for 85 i> Cq- to C ₁₁ - 7.0.

concentration g / l Whiteness Ί *) Whiteness 1) Whiteness 12) Whiteness g / l (85 $> C ₍ * until (TFA- 1 (OCA - (FSA - 12) g / l C ₁₁ - τ * * ■ ' 1.50 g / l 66.1 * 74.0 * 73, Z * $ 67.8 2.25 72.2 * 72.7 * 74.1 $ 70.6 3.00 71 * 4 68.6 68.7 * 70.9 t 4.50 67.8 65.4 65.2 $ 71.4

In addition to biodegradability, the toxicological and dermatological behavior are also in the foreground of interest. _{The oxyethylated Cq to C 11} oxoalko alcohol mixtures according to the invention also perform very well in these points compared with, for example, nonylphenol oxyethylates.

The approximate lethal dose for Cq to C ₁₁ alcohol mixtures **) with 7 mol ethylene oxide in the mouse is 240 mg / kg body weight intraperitoneally compared to 100 mg / kg for the corresponding nonylphenol +10 MqI ethylene oxide. With the rat

*) From a Ziegler olefin mixture (see Table 1) **) From a cracked olefin mixture (see Tables 2 and 3)

409825/0941

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- 10 - O.Z. 29

was the value after oral administration of Cq- "to O. ^ - oxo alcohol mixture + 7 moles of ethylene oxide "at 2,500 mg / kg body weight, for nonylphenol +10 moles of ethylene oxide at 1,600 mg / kg Body weight.

In the case of the Cq- to C -.-.- oxo alcohol mixture + 5.2 moles of ethylene oxide were the values in the mouse i.p. at 200 mg / kg body weight, in the rat p.o. at 3,400 mg / kg body weight. That corresponding nonylphenol + 7 moles of ethylene oxide resulted in Mouse i.p. 100 mg / kg, in the rat p.o. 2,000 mg / kg body weight. . ■

The values for a C _Q - to C ₁ ^ oxo alcohol mixture *) + 3.5 moles of ethylene oxide corresponding to a bonylphenol + 4 moles of ethylene oxide were 400 mg / kg in the mouse ip and 4,500 mg / kg in the rat po cheaper.

In the comparative dermatological test on the shaved dorsal skin of white rabbit 10 moles of ethylene oxide after 15 minutes was at Uony! Phenol + already established a weak redness, with CQ to C ₁ -i-Oxoalkoholgemisch + 7 moles of ethylene oxide redness only after 20 hours .

The fish toxicity test was carried out in the usual way on guppies (lebistes reticulatus) with an average weight of 300 mg. 1 l glasses were used as test vessels; all dilutions were made with tap water. The test temperature was 20 to 22 ^° C. The following LT-50 values were obtained?

20 ppm C _g - to Cjj-oxo alcohol mixture + 7.0 mol AO **) 120 hours nonylphenoi + 10 mol ethylene oxide 48 hours

Cg- to C ₁₁ -OxOaIkOhOl +5.2 moles of ethylene oxide -4 hours Fonylphenol + 7 moles of ethylene oxide · 1 hour

Cq- to C ₁₁ -OxOaIkOhOl +3.5 mol ethylene oxide 2 hours

Fonylphenol + 4 moles of ethylene oxide. not be

tunable.

*) From cracked olefin mixture (see Tables 2 and 3), "' **) 'From Ziegler olefin mixture (see Table 1)

- -20-

40982.5 / 0941

- 20 - O.Z. 29

In the case of nonylphenol + 4 mol of ethylene oxide, an LT-50 value of only 2 hours was observed at a concentration of 10 ppm. All three C _n - to C ^ -oxo alcohol mixture oxyethylates are significantly less toxic than the corresponding nonylphenol oxyethylates.

The examples which now follow explain the invention on the basis of individual formulations without restricting its scope. Percentages are based on weight on the formulation.

1. Machine detergent

(a) (b) (c) (d) Cg to C ₁₁ oxoalcohol mixture + 7 mol AO 5 $ 10 $> $. # 2Q f (from Ziegler olefin mixture, Table 1)

linear sodium _{dodecyl- 1n} ^ in 4.

^{benzene sulfonate 1U} "~ ■ ■ 1Ü *

C ₁ C-- to C _1Q - ^a -01efin- ' _Λ '

sulfonate ^{ιυ ψ}

C ₂₀ to C ₂₂ fatty acids

Sodium or other 4 <f ₀ 2 io 4 ^ 2 $ foam-suppressing substance

Sodium tripolyphosphate 40 3 $ 5> 35 f> 15'Si 10 f6 Na ₅ NTA - 1, 5 * - 20 Jt ' 25 Si Sodium silicate 0, 5 * 5 t '. 3 # Carboxymethyl cellulose O, 1 i 2.5 JC 2 $ i Na ₄ EDTA 2 0.5 i - - optical brighteners 28 0.5 ji -0.5 i 0.5 | έ Magnesium silicate 5, $ 2 1 ^ 1 <f> Perborate 28 io $ 28 ■ 28 S ^. hydrotropes,
Enzymes, perfumes, color
substances, inert salts,
Water etc. 11 * .; 7t5? I Pre-wash detergent

Cq to C ^ oxo alcohol mixture
(Cracked olefin mixture) + 7 mol AO 4 ί> linear sodium dodecylbenzenesulfonate 4 $

409825/0941 -21-

- 21 - - OZ 29

Alkali salt of a higher chain

gene fatty acid. . "■ _; $ 2

Sodium tripolyphosphate ■ 70. ^

Enzymes, perfumes and dyes,
Dirt carrier rest ■

3. Delicates detergent (oxo alcohol mixture from a mixture of cracked olefins -

see tab. 2 and 3)

Cq to Cj ₁ oxo alcohol mixture

+ 7 moles of ethylene oxide 10 $>

Sodium salts from C ^ - to C-j / -

Alkyl sulfate. 10 ^.

Sodium t ripo Iy pho sphat 20 fo

Neutral salts, water etc. 60 fo

Liquid soap (oxo alcohol mixture from crack olefin mixture -

see tab. 2 and 3)

C9 to Gh oxo alcohol mixture *

+ 7 moles of ethylene oxide 25 %

Olein. '. 5 f

Glycerin $ 6> ■

Trichlorethylene 2 ^:. Ji

Water 62 ^

Hand washing paste (oxo alcohol mixture from crack olefin mixture -

see tab. 2 and 3)

Cg to C -] - j-oxo alcohol mixture

+ 7 moles of ethylene oxide 10 <f>

Monoethanolamine 5 ^

Oleic acid. . 12 ^ Dipentene $ 2

Tetrasodium salt of EDTA 0.5 #

- Trichlorethylene 25 ^ ·

Manual dishwashing detergent (oxo alcohol mixture from crack olefin mixture - see Tab. 2 and -3)

• C5 to Cii oxo alcohol mixture

+ 7 moles of ethylene oxide 10 <fo

Fatty alcohol ether sulfate 35 $> Polyvinylpyrrolidone, K value 30 0.3 ^ 'Sodium chloride 3 $>: '

Opacifier, water etc. rest

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? · Detergents for use in ig dishwashers (Ziegler-Olefingemiach - Table 1)

Cq- to C ₁₁ -OxOaIkOhO! Mixture

+ 5.2 moles of ethylene oxide 1 $ 1 $ 1 £ 1 + polyethylene glycol ether,

Molecular weight 4,000 1 $> - \ 1 ° Ethylene oxide / propylene oxide-

Block polymer or alk- _Λ a ₁ ^

oxylated petroleum alcohol "'*" ¹ ^ (C ₁₂ to C ₁₄ )

Sodium Carbonate 5 # 5? 6 5? Ί 5 $>

Sodium Metasilicate 9H ₂ O 48 i> 48 $ 47 $ Mi Sodium Tripolyphosphate 45 Ji 45 5 ^ 45 ^ 45 $

Active chlorine donors, such as

dichloroisocyanuric acid - - 1 $> 1 ^

sodium

8. Rinse aid (Ziegler olefin mixture - Table 1)

Cq- to C ₁₁ -OxOaIkOhO! Mixture

+5.2 moles of ethylene oxide 5 $ 7 $ 2j $

alkoxylated fatty alcohol - $ 8> polyethylene glycol,

Molecular weight 4,000 .. ■■ - - 10? 6

Citric Acid $ 50 30 % $ 5

Isopropanol 15 ^

Water 30 f 55 1 * $ 40

9.Universal cleaners (Ziegler olefin chemicals - Table 1)

Cq to C ₁ .j oxo alcohol mixture

+ 7 moles of ethylene oxide 5 ί>

Diethanolamine salt of alkylbenzenesulfonic acid 5 #

Urea 4 i ^

Tetrasodium salt of EDTA 1 $>

Water rest

10. Cold cleaners (oxo alcohols from a cracked olefin mixture - Tab.2u.3)

Cg to Cn oxo alcohol mixture

+ 3.5 moles of ethylene oxide 7 $

Cq to C-ji oxo alcohol mixture

+ 5.2 moles of ethylene oxide - 7 f>

Petroleum or white spirit $ 93 96 93>

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. . "- 2) - O.Z. 29,546

11. High pressure cleaning agents (oxo alcohols from crack olefins

mixed - Tables 2 and 3)

Cq to C ^ oxo alcohol mixture,

+ 5.2 moles of ethylene oxide 18 $

Sodium Sulphate '10 ^.

Tetrasodium Pyrophosphate $ 47

Sodium metasilicate 5 H ₂ O 5 #

Sodium triphosphate $ 20

12. Pearling agents (oxo alcohols from cracked olefin mixture - tables

2 and 3)

Cq- to Cii

+ 5.2 moles of ethylene oxide 1 _f 5? I

Dimethyl fatty alkyl benzyl

ammonium chloride $ 12

Dipents $ 5

Water rest

13. Wiping wax for floor care (oxo alcohols from cracked olefin

mix - tables 2 and 3)

Cq to C-j-j mixed oxo alcohol

+ 7 moles of ethylene oxide $ 5

Soft soap $ 25

Tetrasodium salt of EDTA $ 2

Isopropanol $ 2

Water rest

14. Remover for floor self-shine emulsions (oxo alcohols from

Crack olefin mixture - Tab. 2 and 3)

Cg to C-j-j mixed oxo alcohol

+ 7 moles of ethylene oxide 8 <$>

Diethanolamine salt of alkyl

benzenesulfonic acid. . $ 2

Sodium metasilicate 3 ^

ethylene diglycol '10 #

White oil (paraffin) 1.5 i>

Water 72.5 ip

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15 Tile cleaner (oxo alcohols from a crack olefin mixture -

Tables 2 and 3)

Cq to C ... oxo alcohol mixture

+ 7 moles of ethylene oxide $ 20

Urea $ 6

Sulfamic acid 10 $>

Water 64 f>

16.Aluminum cleaner (oxo alcohols from a cracked olefin mixture -

Tables 2 and 3)

Cq- to C ₁ * -oxo alcohol mixture 12 ^ + 7 mol ethylene oxide

Butyl Glycol $ 9

Phosphoric acid 15 ^

Citric Acid $ 9

Water 55 ^

-25-Α09825 / 09 4Ί

Claims (1)

- $ 2 - OZ 29 2 2 b 7 6 4 2 Patent application ■ ' Detergents and cleaning agents, the apart from inorganic ^ and / or organic builder salts and complexing agents and optionally bleaching and lightening substances, defoamers and disinfecting agents, at least one surfactant based on a mixture of Ziegler or crack olefins mixed from hydroformylation containing derived oxyethylated alcohols as a cleaning principle, characterized in that the detergents and cleaning agents contain as [surfactants 2- to 15-fold oxyethylated alcohol mixtures with 9 to 11 carbon atoms in the alcohol part, which were obtained by hydroformylation of oil fin mixtures, which consist of 15 to 85 mole percent Cg olefins, 0 to, 70 mole percent Cg olefins and 85 to 15 mole percent C 1-4 olefins. Badische Anilin- & Soda-Fabrik AG 4098-25 / 09 * 1