DE2165773A1 - Detergent compositions - Google Patents

Description

Dr. F. Zumsteln sen. - Dr. E. Assmann Dr. R. Koenlgsberger - Dlpl.-Phys. R. Holzbauer - Dr. F. Zumsteln | un.

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Detergent compositions

The invention relates to the use of certain aliphatic polycarboxylic acids and their salts in detergent compositions. This gives these detergent compositions improved cleaning power.

It is known that certain materials have the ability, detergency and detergency effects of detergent compositions or detergent formulations. These materials act as detergent additives or as builders are used in the laundry detergent industry widely used, and the resulting compositions are called "builf detergents, i.e. detergents, that contain additives. This "built" detergent are beneficial as a certain amount of detergent gives better cleaning. Also are they are cheaper than the detergent compositions which do not contain additives.

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The most widely used and best known detergent additives are water soluble inorganic ones alkaline detergent additive salts such as alkali metal polyphosphates, for example sodium tripolyphosphate or sodium pyrophosphate, and others such as alkali metal carbonates, bicarbonates, borates and silicates. Often these detergent additives are used mixed together.

Recently there has been a great need for new, suitable additives, especially for organic

fe nical additives. Among the currently known organic Additive materials are alkali metal, Ammonium or substituted ammonium aminopolycarboxylates, for example sodium and potassium ethylenediaminetetraacetafc, Sodium and potassium N- (2-hydroxyethyl) ethylenediamine triacetate and sodium and potassium triethanolammonium N- (2-hydroxyethyl) nitrilodiacetate. Alkali metal salts of phytic acid, e.g. sodium phytate, are also suitable as organic detergent additives. Other suitable organic detergent additives such as polyelectrolytic ones Detergent additives that contain water-soluble salts from polymeric aliphatic polycarboxylic acids alone or in the form of copolymers of the salts with alkyl

w NEN or contain particular monocarboxylic acids, are described in U.S. Patent 3,308,067.

Some of these organic detergent additives are satisfactory from the standpoint of detergency. However, they often do not have other essential properties that the known inorganic additives have. Beispielsweiae are many organic detergent additives not biologically they abbaubar.und accumulate after repeated washing Mineralabseheidungen on the fabrics and do not have good efficiencies to _r disperse in minerals. There is therefore an Ee-

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may after additional organic additives, which have the same beneficial properties as the inorganic detergent additives and which also have a good increased cleaning power.

The invention relates to two aliphatic polycarboxylic acid detergent additives which result in a surprising increase in cleaning power and which have other desirable properties of detergent additives. These are ethane-1,1 _f 2,2-tetracarboxylic acid, n-butane-1,2,3 »4-tetracarboxylic acid and their water-soluble salts of the formula

HH
OO
OO
CC HHHH

H-C-C-H and H-C-C-C-C-H

It suffered

CC CCCC

OO 0 0 0 0

OO 0 0 0 0

HM HHHH

wherein M is H, NH, or an alkali metal. This aliphatic Polycarboxylic acids or their water-soluble salts form when combined with an organic, water-soluble one Detergent foam generators are mixed in weight ratios of 1:20 to 100: 1 and preferably 1: 3 to 10: 1, new and valuable cleaning and washing compositions, in which the aliphatic polycarboxylic acid or its water-soluble salts act as a detergent additive.

The ethane-1,1,2,2-tetracarboxylic acid can be prepared according to the following Process are produced. Dimethyl malonate is dissolved in a suitable solvent such as methyl alcohol and reacted with elemental sodium, the sodium derivative of dimethyl malonate being formed. The sodium derivative is then with. Bromine reacted in ethyl alcohol as a solvent, the tetramethyl-ethane-1,1,2,2-tetra-

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carboxylic acid and sodium bromide are formed. This procedure is well known and was used by Walker and Appleyard,
Journal of Chemical Society, 67 »page 770 (1895). The resulting tetramethyl-ethane-1,1,2,2-tetracarboxylate is then mixed with sodium hydroxide
and heated to reflux until a clear, colorless
Solution received. In general, 1-1 / 2 is sufficient
To reflux for hours. The resulting colorless solution is then passed through an ion exchange resin to remove sodium levels and replace them with hydrogen. Stripping the solution in vacuo gives || a colorless or white powder that can be identified as ethane-1,1,2,2-tetracarboxylic acid.

Another synthesis is used to produce n-butane-1,2,3,4-tetracarboxylic acid. At the first stage of this
In synthesis, butadiene and maleic anhydride are dissolved in a suitable solvent such as benzene. These two
Compounds react at room temperature to form cis-4-cyclohexene-1,2-dicarboxylic anhydride. This latter compound is also commercially available, and
the manufacturing process does not form part of the present invention. 4-Cyciohexene-1,2-dicarboxylic anhydride
is oxidized by nitric acid, and meso-n- * butane-1,2,3,4-tetracarboxylic acid is formed. The oxidation

with nitric acid is described by Aider and Schumacher in Liebigs Annalen der Chemie, 564 t page 108 (1949) ».

Another method for producing n-butane-1,2,3,4-tetracarboxylic acid is as follows. Butadiene and pumaryl chloride are reacted together at essentially room temperature in an ether reaction medium. Then the resulting acid chloride is hydrolyzed in water,
whereby trans-4-cyclohexene-1,2-dicarboxylic acid is formed. This acid intermediate product is then in an aqueous solution containing sodium carbonate, with an aqueous potassium perma-

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manganate solution oxidized. The resulting reaction product is acidified with HCl and then extracted by repeated extractions with acetone and distilling in vacuo Obtaining product, purified and reconditioned. The resulting product is a light, dark yellow Powder that is identified as dl-n-butane-1,2,3,4-tetracarboxylic acid will. The production of this tetracarboxylic acid is described by Aider and Schumacher in Liebig's annals of Chemie, 5j> 4, pages 107 and 108 (1949).

If one of the compounds, the preparation of which has been described above, is used in detergent formulations, then is it is generally customary to use them in the form of their water-soluble alkali metal salts. This can be done by they are equal to their water-soluble salts, for example ammonium or alkali metal salts such as sodium or Potassium salts, before adding them to the detergent formulation mixed, or they can be formed in situ during the manufacture of the detergents and then the formulation dry to obtain the desired product.

In making the detergent compositions of the present invention the main ingredients are: (a) an organic, water-soluble, surfactant detergent material, as defined and described in more detail below, and (b) one of the above-described aliphatic Polycarboxylic acids, namely ethane-1,1,2,2-tetracarboxylic acid or n-butane-1,2,5f4-tetracarboxylic acid and mixtures thereof. The detergent compositions contain these essential ingredients in a ratio of aliphatic polycarboxylic acid / ash additive to detergent surfactant in the range of 1:20 to approximately 100: 1 in terms of weight. Such compositions give an aqueous solution having a pH of about 9 to about 12. The preferred ratio of aliphatic polycarboxylic acid detergent additive to

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Detergent foam is about 1: 3 to 10 1/1 and the optimum pH range of the resulting detergent composition is 9.5 to about 11.5. The detergent foaming agents, detergent foaming agents or detergent surfactant compounds contained in the Compositions according to the invention can be used include anionic, nonionic, zwitterionic, ampholytic detergent compounds and mixtures thereof. Suitable compounds are detailed in Table V.

It has been found that the 3-hydroxy-4-decoxybutylmethyl sulfoxide is a particularly effective detergent foam. Contains a superior detergent composition this sulfoxide together with the detergent auxiliaries according to the invention.

The anionic, nonionic, ampholytic and zwitterionic detergent foams shown in Table V can be used in the present invention either alone or mixed together. The examples of the Table V is intended only as an example of the numerous detergents that can be used in the context of the present Invention can be used.

The organic foam detergent compounds of Table V can add to any commercially desirable ones Composition forms are processed, for example as granules, flakes, liquids and tablets.

The finished detergent composition according to the invention will often contain small amounts of compounds which make up the product make it more effective or more attractive. The following compounds are intended to be mentioned as examples will. Soluble sodium carboxymethyl cellulose can be used add in small amounts to improve the separation of the feathers

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Inhibit soil. Metal fog inhibitors can also be used in amounts up to about $ 2 add such as benzotriazole or ethylene thiourea. Fluorescence enhancers, perfumes and dyes can also be added to the invention in amounts up to about 1% Compositions are added. However, they are not essential. An alkaline compound or compounds such as sodium hydroxide or potassium hydroxide can also be added in small amounts as auxiliaries to adjust the pH. As suitable additives there can also be mentioned water, whitening agents, bleaching agents, sodium sulfate and sodium carbonate.

In general, corrosion inhibitors will also be added. Soluble silicates are very effective inhibitors and they can be added to certain compositions of the invention in amounts from about 3% to about 8%. Alkali metal, preferably potassium or sodium silicates with a weight ratio of Si0 ₂ : Mp0 of 1: 1 to 2.8: 1 can be used. M in this formula means sodium or potassium. A sodium silicate with a SiOptNapO ratio of about 1.6: 1 to 2.45: 1 is particularly preferred for economic reasons and for its effectiveness.

The above-described ethane-1,1,2,2-tetracarboxylic acid and n-butane-1,2,3,4-tetracarboxylic acid and its water-soluble ones Salts, especially the sodium and potassium salts, are particularly good detergent additives, but surprisingly they are not chelating agents. This is very important because certain ones have been found Detergent additives are not suitable because they have the ability to bind heavy metals and other metal compounds when they are released into the soil. They then carry these metals into both the earth and water currents on earth. These heavy metals

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when released, tend to increase heavy metal contamination of the water in the water stream. The property of the aliphatic carboxylic acid and its salts according to the invention not to form "chelates" is very unusual as the properties of good detergent additives are generally combined with high capabilities are to form chelates or act as sequestrants (separating or separating agents).

One method of determining the ability of a compound to chelate is by assessing the capacity Separate calcium, intended. A method for determining the calcium separation capacity (calcium sequestering capacity) of a detergent additive consists in the fact that the sample at about 25 ° C with an aqueous Titrated calcium nitrate or another solution of an aqueous calcium salt, using an electrode, which is sensitive to calcium ions (e.g. an Orion electrode with activity against divalent Cations), and the potentiometric equivalent point is determined. The equivalent point, i.e. when the sample is no longer Calcium ions deposited is due to a rapid change in the potential of the electrode, due to the Presence of free calcium ions.

It has also been found that the invention Ethane tetracarboxylic acid and butane tetracarboxylic acid detergent additives described above also have high kaolin dispersion efficiencies on the order of $ 190 to $ 245 that of sodium tripolyphosphate. The kaolin dispersibility is a measure of the ability of the detergent additives to be similar to a floor Material, e.g. kaolin, suspended in water, compared to sodium tripolyphosphate. Ever The greater the kaolin dispersion efficiency, the better the detergent additive properties the fabric has.

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The kaolin dispersion efficiency is "determined by" a mixture of 100 g of kaolin (washed with acid, American Standard) and 130 ml of water and a Forms slurry and adjusts the pH of the slurry to 10.0 with 5N NaOH. The slurry then becomes placed in a suitable beaker and its viscosity is determined with a 'Brookfield Viscometer Model LVT. An aqueous solution of the sample having a concentration of 500 mg / 100 ml is then added in parts to the slurry Has water and its pH was adjusted to 10.0 with 5N NaOH. The viscosity of the slurry will determined at 25 ° C after each part of the solution had been added. The amount of sample that is required is to bring the viscosity of the slurry to 200 cP. to decrease is determined and written down. A comparison experiment is carried out using sodium tripolyphosphate and the weight ratio of Add sodium tripolyphosphate to the amount of sample, which is required to determine the viscosity of the slurry 200 cP. to reduce, multiplied by 100 is the dispersion efficiency of the sample, expressed in percent.

It was found that the aliphatic tetracarboxylic acids and their water-soluble salts used in the present invention are completely biodegradable are. This is very important because it will return the constituent elements to their natural state if the detergent additive is released into sewage or into the soil. The biodegradability is an important requirement for detergent additives because of serious pollution problems would if they weren't biodegradable.

Another property of the aliphatic tetracarboxylic acids and their salts is the fact that the mineral precipitation these additives on fabrics or materials that

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is extremely low in the detergent compositions containing them, the mineral precipitation . · Is an increasing, difficult problem that some of the synthetic detergent additives are almost unresolved can be. For example, sodium polymaleate is used as a detergent additive in detergent formulations it has been proposed to have a mineral elimination capacity which is more than 50 times that of the detergent additives according to the invention amounts to. This is in contrast to the very low mineral precipitation capacity found in the general inorganic detergent additives such as ^ sodium tripolyphosphate.

According to the invention, excellent cleaning results are obtained if the aliphatic tetracarboxylic acid detergent additives according to the invention are used used in a wide variety of detergent active materials containing surfactant materials and mixtures thereof. the Additives according to the invention are particularly effective when used alone or mixed together. The additives according to the invention clean cotton fabrics

about as good and synthetic! fibers better than Sodium tripolyphosphate, a standard inorganic detergent additive, which is widely used in industry.

The following examples illustrate the invention without, however, restricting it. The proportions in the examples are unless otherwise stated, expressed by weight.

example 1 Production of ethane-1,1,2,2-tetracarboxylic acid

In a 1000 ml three-necked round bottom flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, 500 ml of methyl alcohol was added. _{While cooling and stirring, 23 f} 0 g of sodium are added in portions to the methyl alcohol during the addition and wait until it is

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all the sodium has dissolved. Are then added for 10 minutes at 25 ⁰ G 114.5 ml (132 g) Dirnethylmalonat. A heavy, white slurry forms. 25.6 ml (80 g) of bromine are added dropwise to the flask at 25 to 30 ^° C. over the course of 30 minutes. The reaction mixture is stirred vigorously during the addition, and a mild exothermic reaction occurs. After one hour, a heavy precipitate separates out from the alcohol when it is stripped off in vacuo. The solid residue is then slurried in 200 ml of water, filtered and the filter cake is washed several times with different amounts of water until the filtrate with silver nitrate in nitric acid gives a negative test for bromide. The sample was recrystallized from benzene, giving a colorless, crystalline powder which ^{melted at 138 °} C. and was identified as tetramethylethane tetracarboxylate.

13.1 g of this ester were mixed with 140 ml of 2.5N sodium hydroxide in a flask equipped with a reflux condenser and refluxed for 1.5 hours. A clear, colorless solution was obtained which was passed through a 200 g column of Dowex 50W-X8 ion exchange resin to remove sodium ions and replace them with hydrogen ions. The effluent from this column material and the washings this column were mm in vacuo at 1 and distilled 95 ⁰ C to yield 9.5 g of a colorless powder which melted and t67 to 168 ⁰ C, the elemental analysis as ethane-1 , 1,2,2-tetracarboxylic acid was identified.

It was determined the Calciumabscheidekapazität a sample by reacting the sample at 25 ⁰ C and a pH of 10 using 0.1 N calcium nitrate solution and an electrode, which was sensitive to calcium ions (Orion electrode sensitive to divalent cations), titrated to the potentiometric endpoint. The results obtained are given in Table I.

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The kaolin dispersion efficiency described above was " on the tetrasodium salt of ethane-1,1,2,2-tetracarboxylic acid determined using sodium tripolyphosphate as a standard. The results of the kaolin dispersion efficiency are given in Table I.

The detergent additive efficacy of the sodium salt of the above acid with respect to sodium tripolyphosphate was also tested according to the following procedure. Cloth swatches made of certain materials, namely cotton, finished 65/35 dacron / cotton and nylon fabrics, all of which were uniformly soiled using an aqueous emulsion of natural, airborne, small materials and synthetic sebum, were in a Terg-O -Tometer washing machine washed with the solutions of detergents that should be examined. Three wash cycles were performed on each material using the following conditions: 300 ppm hard water with a Ca: Mg gram ion ratio of 3i2. The tfaschmittelzusatzstoff contained 50 wt.% Of the detergent formulation with a formulation concentration of 0.15 wt. "Ss> in the wash water. The temperature was about 5O ⁰ C, the pH was 9.5. The V / aschzeit was for 10 minutes to rinsed for 2 minutes, rinsing twice with 300 ppm hard water, and soil removal measured with a Hunter reflectometer.

Weight

Linear Sodium Dodecylbenzene

sulfonate (SuIframin 85) 20.0

Sodium Metasilicate · 5-Hydrate 12.0

Carboxymethyl cellulose. 0.5 '

Sodium sulfate 17.5

Detergent additive 50.0

Experiments were carried out with a total of

Ca and Mg ⁺ ions of 300 ppm to compensate for the differences in

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the cleaner or in the required quantities Show detergent clearly. The results obtained are expressed as the ratio of percent reflection strength or The whiteness of the samples is expressed against an STPP standard and is obtained by comparing the whiteness values of the samples by the hot content values of the standard divided. The results-the cleaner are in Table II given.

The ethane-1,1,2,2-tetracarboxylic acid detergent additive was also subjected to the mineral precipitation test. In this experiment, the sodium salt of ethane-1,1,2,2-tetracarboxylic acid was used used to make a detergent formulation. One worked the same way as it did at the experiment to determine the detergent additive effectiveness is specified '. This detergent composition was dissolved in 300 ppm hard water, producing a 0.15% strength by weight solution of the composition. A 50 ml aliquots of this solution were then diluted to 1000 ml with 300 ppm hard water and the resulting Solution was successively through 8, 4.5 and 0.1 / u cellulose filters filtered with millipores. The filtered mixtures are then dried and weighed, taking the Receives amounts of insoluble matter. These insoluble substances correspond to the mineral precipitates that are on Garments that have been washed in detergent formulations with water that has a hardness of 300 ppm will. The results of these tests are given in Table III.

It was then the biodegradability of ethane-1,1,2,2-tetracarboxylic acid studied by the carbon dioxide formation of a biological culture of the compound with Certain wastewater bacteria. Apparatus similar to that used by Thompson and Duthie, J. Water Pollution Control Federation, 40, page 306 (1968),

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was written. The culture medium used was that described by Bunch and Chambers, ibid, 39. " ^s eite 181 (1967), described for their static tests. The process consists of three two week periods. In the first period, the adaptation period, the culture was developed using waste water. Subcultures were grown in the second and third periods. Comparative experiments, which were carried out in parallel with the experiments in which the test compounds were examined, show that 74 to 78 $ of the carbon in a glucose-glutamic acid mixture during the adaptation time in carbon dioxide was from 63 to 70 $ in the first subculture time and from $ 62 to $ 86 were transferred in the second subculture period. In general, the higher the conversion of carbon in percent into carbon dioxide, the higher the degree of biodegradability. The results of these experiments are given in Table IV.

Example 2 Production of meso-n-butane-1,2,3,4-tetracarboxylic acid

A round bottom flask was filled with 18.0 g of cis-4-cyclohexene-1,2-dicarboxylic anhydride and dissolved in 216 ml of 70 to 71% nitric acid. Then 23 ml of fuming nitric acid (about $ 90 ENT) was added. The reaction mixture was stirred at room temperature for 118 hours and filtered through a sintered glass filter and dried in vacuo to give a colorless powdery product. After Umrkistallisation of this product from acetone and chloroform, it showed a melting point 184-186 ⁰ C. In the literature, a melting point of 188 ⁰ C is specified for meso-n-butane-1,2,3,4-tetracarboxylic acid. The neutralization equivalent was found to be 58, the theoretical value is 59. From these and other results, the product was identified as meso-n-butane-1,2,3,4-tetracarboxylic acid. The sodium salt of this acid was then reduced to its capacity to secrete calcium

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Dispersion effectiveness, its effectiveness as a detergent additive and its mineral precipitation and biological Degradability investigated. The same tests were carried out as described in Example 1, and the results are given in Tables I, II, III and IV.

To compare the results of the detergent additives according to the invention with known detergent additives to be able to, double attempts were also made with pentasodium tripolyphosphate, Trisodium nitrilotriacetate. 1 hydrate, Sodium polymaleate carried out. The calcium separation capacity, the kaolin dispersion efficiency, the detergent additive efficiency and the mineral deposition examined. The results are given in the corresponding tables. Furthermore, the biodegradability of a known synthetic detergent, namely the sodium polymaleate according to the The method used to determine the biodegradability of the detergent additives according to the invention is determined to determine. The results of these tests are shown in Table IV along with a comparative sample of Glucose-glutamic acid indicated to ensure that the process for determining biodegradability has been carried out effectively or correctly.

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Table I.

Calcium separation capacities and effective dispersion of ethane and butane tetracarboxylic acids

1 1

Compound calcium separation capacity dispersion efficiency

State of the art Pentasodium tripolyphosphate n ^> trisodium nitrilotriacetate. 1 hydrate

to sodium polymaleate

ω According to the invention

^ Tetrasodium ethane 1,1,2,2-tetracarboxylate - * ■ tetrasodium-meo-n-butane-1,2,3,4-tetra- ° carboxylate

'The calcium separation capacities and the dispersion efficiencies were increased to Determined based on the pure anhydrous specified sodium salts.

(«Ca / 100 *) («Ions Ca / Mol) (# of STPP) 11.0 1.01 100 15.6 1.00 16 19-20 0.76-0.80 84-107 2.2 0.17 210 · » 0.0 0.00 189

Table II. Efficacies of Ethane and Butanteirraic Acids as

Compound wasefamittel ^ usa1; zstoff-efficacy

Cotton Daexon / nylon

BaiamwojLle

According to the state -äex technology

Trinatxiiimni tr ilo triacetai.i hydrate 1

Pentana ^ riiimtrlpDly-

phosphate 1, © 1.0 III 1.0 - - - Pore size Insoluble matter
(/ u) (mg) 0.4 Haijriaampolj maleate 1.1-1. , 2 1.1-1.2 1.5 Te tranatriiaaaätliaffl-1,1,2,2- 8.00 0.2 tetraearboxylate 1.0 1.0 1.1 0.45 2.1 Tetrasodium-meso-n-lsntaii- 0.10 0.5 1,2,3,4-tetraearboxylate 0.9 1.1 1.1 all in all 0.0 Tabel 8.00 0.0
0.5 Mineral precipitation of ethane and butane tetracarboxylic acids 0.45 18.5 link 0.10
all in all 15.6 According to the state of the art 8.00 0.4 Pentasodium tripolyphosphate 0.45 52.5 0.10 all in all 1.2 »
0.5 Trisodium nitrilotr 8.00 0.0
ΤΓ5 acetate.1 hydrate 0.45 0.10
all in all Sodium polymaleate According to the invention Tetrasodium ethane-1,1,2,2- tetracarboxylate

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Tetrasodium meso-n-butane

1,2,3,4-tetracarboxylate 8.00 1.2

0.45 1.1

0.10 0.1

total 2.4

Table IY Biodegradability of ethane and butane tetracarboxylic acids

Compound carbon- Developed $ S carbon as

fabric i. CO2 at the end of every two-week d. Ver period

Adaptation first second subculture subculture

Control attempt

Glucose-Glutamine- 40.4 78 70 acid 74 63

74 68

State of the art

Sodium polymaleate - 0 0

According to the invention

Ethane ^ · 1,1,2,2-t tetracarboxylic acid ;

meso-n-butane-1,2,3,4-tetracarboxylic acid ι

0 64 62 58 0 0 83 69 Tabel V

1. Anionic detergent compositions that can be used in the compositions of the invention include soap and non-soap detergent compounds. Examples of suitable soaps are the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids (C ₁₀ -C ₂ Q). Particularly useful are the sodium or potassium salts of mixtures of fatty acids derived from coconut oil and tallow, for example sodium or potassium tallow and coconut soap. Examples of anionic organic, non-soap detergent compounds are the water-soluble salts, alkali metal salts, organic sulfuric acid and sulfur reaction products, which in their molecular structure

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contain an alkyl group ranging from about 8 to about Contains 22 carbon atoms, and one sulfonic acid group and / or contain sulfuric acid ester groups. (The term "alkyl" is also intended to include the higher alkyl part Acyl groups are included.) Important examples of synthetic detergents which form part of the invention Forming compositions are the sodium or potassium alkyl sulfates, especially those obtained by adding higher alcohols (Cq to C ^ carbon atoms), the formed by reducing the glycerides of tallow or coconut oil, sulfated; Sodium or potassium alkylbenzenesulfonates, such as those described in U.S. Patents 2,220,009 and 2,477,383 wherein the alkyl group from about 9 to about 15 carbon atoms contains. Other examples of alkali metal alkyl benzene sulfonates are those in which the alkyl portion is a straight chain aliphatic group ranging from about 10 to contains about 20 carbon atoms, for example 2-phenyldodecanesulfonate and 3-phenyldodecanesulfonate, Sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols that differ from tallow and coconut oil Derive Sodium Coconut Oil Fatty Acid Monoglyeeride Sulphate and sulfonates, sodium or potassium salts of sulfuric acid esters of the reaction product of 1 mole of one higher fatty alcohol (for example tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide, sodium or Potassium salts of Alkylphenoläthylenoxydäthersulfat with about 1 to about 10 units of ethylene oxide per Molecule and wherein the alkyl groups contain from about 9 to about 12 carbon atoms, the reaction product of fatty acids, esterified with isethionic acid and neutralized with sodium hydroxide, for example the Fatty acids derived from coconut oil, sodium or potassium salts of fatty acid amide from methyl tauride, in which the fatty acids derived for example from coconut oil, and other known compounds, with a number of such

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Compounds are described in U.S. Patents 2,486,921, 2,486,922 and 2,396,278.

2. Nonionic synthetic detergents can be broadly defined as compounds that are of their nature are aliphatic or alkylaromatic, and which do not ionize in aqueous solution. For example, a well known class of nonionic synthetic detergents sold commercially under the trademark "Pluronic". These compounds are made by condensing ethylene oxide with a hydrophobic base produced by Condensation of propylene oxide with propylene glycol is obtained. The hydrophobic part of the molecule that is natural due to its insolubility in water, has a molecular weight of approximately 1500 to 1800. The addition of polyoxyethylene groups this hydrophobic part causes the water solubility to increase in the molecules as a whole and the liquid character of the product becomes to the point where the polyoxyethylene content is approximately $ 50 based on the total weight of the condensation product is maintained.

Other suitable nonionic synthetic detergent compounds include: '(a) the polyethylene oxide condensates of alkyl phenols, for example the condensation products of alkylphenols having an alkyl group containing about 6 to 12 carbon atoms either straight chain or contains branched-chain, with ethylene oxide, the ethylene oxide being present in amounts that range from 10 to 25 moles of ethylene oxide / mole Alkylphenol. The alkyl substituent can be TOn such compounds, for example from polymerized propylene, diisobutylene, octene or honing derived.

(b) The compounds obtained in the condensation of ethylene oxide with the product produced by Reaction of propylene oxide with ethylenediamine is formed.

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For example, compounds ranging from about 40% by weight to about 80% by weight polyoxyethylene are satisfactory and have a molecular weight of from about 5,000 "to about 11,000 and" in the reaction of ethylene oxide groups are formed with a hydrophobic base, the hydrophobic base being the reaction product of ethylene diamine and excess propylene oxide and has a molecular weight on the order of 2500 owns up to 3000.

(c) The condensation products of aliphatic alcohols containing 8 to 18 carbon atoms and are either straight-chain or branched-chain, with ethylene oxide, for example a coconut alcohol-ethylene oxide condensate, containing 10 to 30 moles of ethylene oxide / mole of coconut alcohol, and wherein the coconut alcohol is a Fraction that contains 10 to H carbon atoms.

(d) Long-chain tertiary amine oxides which correspond to the following general formula ILRpR ^ N- ^ 0, where R. is an alkyl group having approximately 8 to 18 carbon atoms and R ₂ and R, each are methyl or ethyl groups. The arrow in the formula is the usual representation of a semi-polar bond. Examples of amine oxides useful in the present invention include dimethyldodecylamine oxide, dimethyloctylamine oxide, dimethyldecylamine oxide, dimethyltetradecylamine oxide, dimethylhexadecylamine oxide.

(e) Long-chain tertiary phosphine oxides, which have the general formula RR'R "P -> 0, where R is an alkyl, alkenyl or monohydroxyalkyl group, which has a chain length in the range from 10 to 18 carbon atoms, and R 'and R "are each alkyl or monohydroxyalkyl groups with 1 to 3 carbon atoms. The arrow in the formula is the usual representation of a

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semi-polar bond. Examples of suitable phosphine oxides are:

Dimethyldodecylphosphine oxide

Dimethyltetradecylphosphine oxide

Ethylmethyltetradecylphosphine oxide

Cetyldimethylphosphine oxide

Whore thyls tearylphosphine oxide

Cetylethylpropylphosphine oxide

Diethyldodecylphosphine oxide

Diethyltetradecylphosphine oxide

Bis (hydroxymethyl) dodecylphosphine oxide

Bis (2-hydroxyethyl) dodecylphosphine oxide W 2-hydroxypropylmethyltetradecylphosphine oxide

Dimethyloleylphosphine oxide and

Dimethyl-2-hydroxydodecylphosphine oxide.

(f) Dialkylsulfoxides which ^{correspond to the following formula RR 1} S -> 0, in which R is an alkyl, alkenyl, β- or T'-monohydroxyalkyl group or an alkyl or β- or 3 ^ -monohydroxyalkyl group is one or two other oxygen atoms in the chain and the groups R have a chain length in the range from 10 to 18 carbon atoms, and wherein R ^{1 is} methyl or ethyl. Examples of suitable sulfoxide compounds are

P dodecyl methyl sulfoxide

Tetradecyl methyl sulfoxide

3-Hydroxytridecylmethylsulfoxide

2-hydroxydodecylmethyl sulfoxide

3-hydroxy-4-decoxybutylmethyl sulfoxide

3-hydroxy-4-dodecoxybutylmethyl sulfoxide

2-hydroxy-3-decoxypropylmethyl sulfoxide

2-hydroxy-3-d ο dec oxypropyl methyl sulfoxide

Dodecyläthylsulfoxyd and

2-hydroxydodecylethyl sulfoxide.

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3. Ampholytic synthetic detergents can generally be used as derivatives, aliphatic secondary and tertiary Amines "are described in which the aliphatic group can be straight or branched chain and in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one has an anionic, water solubility contains mediating group (i.e. a group that causes solubility in water). Examples of connections, encompassed by this definition are sodium 3-dodecylaminopropanesulfonate.and Sodium 3-dodecylamine propionate.

4. Zwitterionic synthetic detergents can generally be used as derivatives of aliphatic quaternary ammonium compounds in which the aliphatic group can be straight-chain or branched and in which one of the aliphatic substituents may contain from about 8 to 18 carbon atoms, and one of the substituents contains the anionic group which brings about the solubility in water. Examples of compounds that Included in this definition are 3- (N, N-dimethyl-N-hexadecylammonio) propane-1-sulfonate and 3- (N, N-dimethyl-N-hexadecylammonio) -2-hydroxypropane-1-sulfonate. These compounds are because of their excellent detergent properties particularly preferred in cold water.

The term "detergent foam" is intended to include all of the above Detergents and detergent compositions.

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Claims (5)

Claims (i) detergent and detergent composition, containing (a) an organic, water-soluble detergent foaming agent such as anionic, nonionic, zwitterionic and / or ampholytic detergent foams and their Mixtures, and (b) a detergent additive, thereby characterized in that ethane-1,1,2,2-tetracarboxylic acid, n-butane-1,2,3,4-tetracarboxylic acid and / or its water-soluble salts are used and that the fc ratio of detergent additive to detergent foam in the range of 1:20 to 100: 1, expressed by the weight, lisgt. 2. detergent and detergent composition according to claim 1, characterized in that the ratio from polyelectrolyte detergent additive to detergent foam in the range of 1: 3 "to 10: 1, expressed by the weight lies. 3. detergent and detergent composition according to claim 1, characterized in that as Detergent foam is an anionic, water-soluble "Used alkali salt of an organic sulfuric acid reaction product, which in its molecular structure has a Contains an alkyl group having 8 to 22 carbon atoms and a sulfonic acid group and / or sulfuric acid ester groups and wherein the ratio of detergent additive to detergent foam is from 1: 3 to 10: 1, expressed by is the weight, and wherein the composition in aqueous solution gives a pH of 9 to 12. 4. Composition according to claim 1, characterized in that the detergent additive is ethane-1,1,2,2-tetracarboxylic acid and their water-soluble salts are used. 209830/1 109 5. Composition according to claim 1, characterized in that that the detergent additive is n-butane-1 »2,3» 4-tetracarboxylic acid and their water-soluble salts used. 209830/1109