NO141563B - LIQUID DETERGENT MIXTURE. - Google Patents

Description

The present invention relates to a liquid detergent mixture,

which contain complexing agents, non-ionic compounds and water, optionally alkylene glycols and usual additives.

There are many proposals for the formulation of liquid

detergents, but nevertheless such products have not made any decisive commercial progress. This is probably due to the fact that it has not yet been possible to combine an effective surfactant with sufficient amounts of complex formers so that good washing

ability must be achievable. Furthermore, the product obtained must be clear and liquid within a large temperature range.

It has now been shown that a clear, liquid detergent mixture with good washing effect and water solubility can be obtained by using a previously unknown ampholyte of the betaine type as surface-active component. The detergent mixture according to

the invention is characterized in that it contains a combination of at least one surfactant, non-

ionic alkylene oxide adduct and at least one ampholyte with the gen-

real formula

where denotes an aliphatic or cycloaliphatic group with 6-22 carbon atoms or an aromatic group substituted with one or more alkyl groups with a total of 4-18 carbon atoms in the alkyl group

1*2 and R., independently of each other, denote alkyl groups having 1-3 carbon atoms;

n^ is 2 and/or 3 and/or 4;

p^ is an integer from 0-10; and

q is an integer 1, 2 or 3,

the weight ratio between the complexing agent, the alkylene oxide adduct, the ampholyte and water being 4-25:1-20:1-15:40-90, preferably 6-20:2-15:1-10:45-80.

Detergent mixtures with this composition form a clear, liquid solution with a good cleaning effect and relatively low foaming. For. achieving additional foam suppression, if desired, an alkylene glycol with the general formula can be added

where n2 is 2, 3 and/or 4, preferably 2 and/or 3 and p2 is a number from 1-10; preferably 1-5.

The amount of alkylene glycol can vary from no addition at all up to twice the amount by weight of added nonionic surfactant. In certain cases, e.g. when the surface-active agent is poorly soluble and is present in high concentration, the alkylene glycol also has a solubility-mediating effect.

The complex former included in the cleaning agent mixture is preferably of an inorganic nature] such as sodium or potassium pyrophosphate, sodium phosphate, sodium tripolyphosphate and sodium hexametaphosphate. Organic complexing agents have also shown good effect in mixtures according to the invention, and of this type, above all, alkene phosphonates, salts of aminocarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), hydroxyethylethylenediaminotriacetic acid (HEDTA) and diethylenetriaminepentaacetic acid (DPTA), hydroxyethyliminodiacetic acid

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acid (HEIDA), salts of oxycarboxylic acids, such as citric acid and glyconic acid, as well as salts of polycarboxylic acids, such as polymaleic acid, polyicamic acid and polyacrylic acid. The quantity of the specified complex formers is generally 10-30% of the total weight of the mixture.

As non-ionic surfactants, alkylene oxide adducts and ethylene oxide and propylene oxide adducts of monoalkyl phenols, dialkyl phenols, fatty alcohols, secondary alcohols, alkylamines and alkyl mercaptans are used, in which compounds the total number of carbon atoms in the hydrophobic part goes up to 8-20 carbon atoms and the polyalkylene glycol chain comprises 5-30 alkylene glycol groups. Particularly suitable are the non-ionic compounds, which are covered by the general formula

where R4 denotes an aliphatic or cycloaliphatic group with 8-20 carbon atoms or a mono- or dialkylphenyl with a total of 4-18 carbon atoms in the alkyl groups and

p3 is an integer from 5-30, preferably from 5-20. Specific examples of suitable non-ionic surfactants, which are included

of this formula are ethylene oxide adducts with decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol, oleyl alcohol, cyclooctanol, cyclododecanol, cyclohexadecanol, octylphenol, nonylphenol, dodecylphenol, hexadecylphenol, dibutylphenol, dioctylphenol and dinonylphenol.

Of the ampholytic compounds covered by the preceding

given formula, those where the nitrogen atoms and the carboxyl groups are bound to the same carbon atom should be emphasized. Preferably, q denotes the number 1. Furthermore, compounds are generally preferred where n^ is 2 or where p^ is 0 and R, and R^ denote methyl groups.

In the preparation of the ampholytic compounds, one preferably starts from an aliphatic or cycloaliphatic alcohol with 6-22 carbon atoms, or from an aromatic hydroxyl compound containing a total of 10-24 carbon atoms, to which optionally, in a manner known per se, ethylene oxide, propene oxide and/or or butene oxide is anchored in an amount of 0-10 alkylene oxide units. All isomers of butene oxide can be used. The aliphatic, cycloaliphatic or aromatic hydroxyl compound, which thus optionally contains alkylene oxide units, is reacted with epichlorohydrin to the corresponding chloroglyceryl ether, which is an important intermediate product. The glyceryl ether can then be aminated and quaternized either in two steps by reaction with first a dialkylamine of the formula

where R ? and R-. has the meaning set out above,

and then with a straight or branched monohalocarboxylic acid of the formula

where Hal denotes a halogen atom, such as bromine or chlorine and

q has the above meaning,

or in one step with an amino acid of the formula

where R 2 and R 1 and q have the above meaning.

Of the two reaction variants, the one with amino acid is preferred,

as it practically only gives rise to compounds according to the invention. In contrast, in the reaction between the glyceryl ether and the dialkylamine, an undesirable quaternary compound can be obtained if the amount of glyceryl ether compound is not precisely controlled. Moreover, it has surprisingly been shown that the glyceryl ether compound and the amino acid in the presence of alkali can react with each other and give the corresponding quaternary compound with such a high yield as more than 95%.

The reaction between the hydroxyl compound, possibly in the form of an alkylene oxide adduct and epichlorohydrin is carried out at a temperature of approx. 100-150°C in the presence of a catalyst. SnCl 4 , BF 4 and HC 1 O 4 in particular have proven to be excellent as catalysts, and they provide a rapid and easily controllable reaction, but other acidic catalysts, such as toluenesulfonic acid and sulfuric acid, are also applicable. In order to achieve a complete reaction of the alcohol compound, the epichlorohydrin is usually added in excess. The amination of the chloroglyceryl ether with the secondary amine is carried out in the presence of alkali, such as sodium hydroxide, at a temperature of 100-150°C. Usually the reaction is carried out in the presence of a polar solvent, e.g. water or low molecular alcohol, such as methanol, ethanol, monoethylene glycol, diethylene glycol, ethyl diglycol and ethyl glycol. To avoid quaternization during the amination step, the molar ratio in the initial step between the dialkylamine and the chloroglyceryl ether must be at least 3 and the temperature at this molar ratio must not be below 140°C. At higher molar ratios, the temperature can be lowered to 100°C. The quaternization of the tertiary amine with the halocarboxylic acid is carried out in a neutralized water solution, whereby the reaction temperature is 50-100°C and the reaction time approx. 2-6 hours.

Contains tertiary amine hydrocarbon groups with more than

14 carbon atoms have also proven advantageous to add

a glycol compound, such as ethyl diglycol, partly to increase the solubility of the amine and partly to lower the viscosity of the reaction mixture. If the chloroglyceryl ether is reacted with an amino acid, the reaction is carried out at a neutral or slightly basic pH, preferably between 7 and 10. The solvent must be polar and in principle the same solvent as in the amination with dialkylamine can be used. The reaction temperature is suitable within the interval 50-140°C and the reaction time is from approx. 15 minutes to approx. 3 hours.

The compounds can also be produced by different variations of the above-mentioned methods.

Thus, one can cause the chloroglyceryl ether to react with ammonia or a primary amine with a methyl or ethyl substituent and then introduce further alkylene substituents with, for example, methyl or ethyl chloride or dimethyl or diethyl sulfate. Likewise, a monoalkyl-substituted amino acid can be used and the quaternization is carried out with one of the reactants specified above.

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However, the methods described here are more complicated

than those previously described and include several reaction steps. In addition, they give rise to a larger number of by-products and

lower total dividend.

The aliphatic alcohols, with 6-22 carbon atoms, which are used

in the production of the ampholyte included in the mixture can be both synthetic and derived from natural products. The "naturally" derived, the so-called fatty alcohols, are usually produced by the reduction of fatty acids or fatty acid esters obtained from vegetable oils, such as coconut oil, palm oil, soybean oil, linseed oil, corn oil or castor oil: animal oils or fats, such as fish oil, h<y> aloe oil, tallow or lard. Examples of suitable alcohols include the following: octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol, oleyl alcohol or eicosenyl alcohol. Synthetic alcohols are preferably produced according to the Ziegler method or by the Oxo process. Most alcohols produced using the Oxo process have a more or less branched carbon chain, which is why in this case a large number of isomers are possible. The physical and chemical properties of these alcohols closely resemble those of the straight-chain primary alcohols.

Besides aliphatic alcohols, cycloaliphatic and aromatic hydroxyl compounds can also be used as starting product. Suitable cycloaliphatic alcohols are cyclohexanol, cycloheptanol, cyclooctanol, cyclododecanol and cyclohexadecanol. Of suitable aromatic hydroxyl compounds, synthetically produced mono- and dialkyl-substituted phenols, such as octylphenol, nonylphenol, dodecylphenol, hexadecylphenol, dibutylphenol, dioctylphenol and dinonylphenol, should be highlighted. Suitable amines are dimethylamine and diethylamine, both of which are commercially available. In order to achieve a rapid reaction with the tertiary amine, the monohalocarboxylic acid must be oc-halogenated. Examples of preferred cc-halocarboxylic acids are monochloroacetic acid, monochloropropionic acid and α-monochlorobutyric acid. Of the aminocarboxylic acids that can be used according to the invention, the oc-aminocarboxylic acids are the most suitable, although e.g. p-aminocarboxylic acids can in principle be used. Particular mention is made of the amino acids dimethylglycine, dimethylalanine and dimethylvaline.

In detail, the preparation of the ampholytic compounds can be illustrated with the following experiment.

In a glass flask fitted with a stirrer, heating device

as well as return slips, 200 g (1 mol) of a mixture of 55% lauryl alcohol and 45% myristyl alcohol was introduced, which was heated to 75°C, after which 2 g of SnCl 4 and 101 g (1.1 mol) of epichlorohydrin were added. The addition of the latter took place over the course of 1 hour. The temperature was then raised to 125°C with continued stirring and the mixture was kept at this temperature for 2 hours. Remaining epichlorohydrin was removed by vacuum treatment of the product, which consisted of a slightly yellow colored liquid. With stirring, 134 g of sodium dimethylglycine and 344 g of monoethylene glycol were heated to 125°C and were then added dropwise over 25 minutes with the glyceryl ether. After a further 10 minutes at 125°C, the reaction was interrupted, and the mixture, which essentially consisted of NaCl and an ampholyte according to the invention, was hot-filtered, whereby a clear slightly yellow liquid was obtained. The degree of conversion of the chloroglyceryl ether with dimethylglycine was 98%.

The final product obtained had the formula

Alkyl^2_i4 <b>denotes sn myristyl or lauryl group.

Another detailed example of the production of ampholytes according to the invention is the synthesis below.

To 1 mole of nonylphenol ethylene oxide adduct with the formula

1.1 mol of epichlorohydrin is added according to the same procedure as stated above, 80 g (0.2 mol) of the glyceryl ether product obtained was mixed with 67.5 g of a 40% aqueous solution of dimethylamine (0.6 mol). The reaction mixture was allowed to stand for 2 hours at 150°C. The hydrochloric acid formed was neutralized with 8.32 g of NaOH, after which the mixture was transferred to a separatory funnel and the upper phase containing the tertiary amine was separated. Dimethylamine dissolved in the amine phase was driven off by vacuum evaporation. The product was analyzed by titration with perchloric acid in glacial acetic acid and with sodium lauryl sulfate at pH 11, and was found to consist of 95% tertiary amine but no quaternary compounds. 58 g of the tertiary amine were dissolved in 61 g of water and 26 g of ethylene diglycol. The mixture was heated to 70°C and then a 40% solution of monochloroacetic acid in water neutralized with sodium hydroxide was added dropwise over the course of 1 hour. so that the total amount of added chloroacetic acid went up to 15.7 g. After a further 1 hour the temperature was raised to 90°C.' The reaction was stopped after 3 hours at this temperature [when 97% of the tertiary amine had reacted and 99% of the theoretical quantity of chloride ions had been formed. The product consisted of

had a syrup-like consistency at room temperature.

In addition to the specified ingredients, the mixture according to the invention can also contain a large number of additives usable in cleaning agent mixtures. Examples of this are bleaching agents, such as sodium perborate, sodium percarbonate, sodium perpyrophosphate and sodium persulphate; soil suspending agents, such as carboxymethyl cellulose and polyvinylpyrrolidone; fillers, such as sodium sulfate, sodium chloride and carbamide; buffer substances, such as phosphorus, carbonates, borates and silicates in the form of their alkali metal salts as well as potassium and sodium hydroxide; optical refreshers; enzymes; dyes; germicides; corrosion inhibitors, such as various types of alkyl ether phosphate; wetting agents; emollients; perfumes etc. The mixture may also contain surfactant components of an and/or cationic nature, such as soaps, alkyl sulphate, alkyl ether sulphate, alkyl aryl sulphonate, alkyl sulphonate, alkenyl sulphonate, primary alkyl amide salts and quaternary ammonium compounds with 1 or 2 long alkyl groups.

The mixtures according to the invention are primarily suitable for washing or cleaning material, such as textiles, metals, plastics, leather, wood, stone, glass, porcelain, milled surfaces etc. within the household sector as well as within industry. As the mixtures are low-foaming, they are particularly suitable for use in machine washing or machine washing or other applications where high foaming should be avoided.

The following examples are intended to further illustrate the present invention:

EXAMPLE 1

A cleaning agent mixture was formulated with the following components:

The obtained cleaning agent mixture consists of a clear, easy-flowing liquid within the temperature range -4°C to +45°C.

Its foam stability in water was determined in an apparatus after Fries, which imitates the mechanical processing of a detergent solution in a cylinder washing machine. The method is described in Seifen-6le-Fette-Wachse, No 25/65, p 913-917, "Messmethode zur Testung gesteuterter Schaume". For comparison, the same sample was carried out partly with a commercial detergent specially formulated for washing at 60 C and partly with an ampholyte mixture without the surfactant. The composition of the comparison mixtures was as follows:

The commercial pesticide mixture

Ampholyte mixture without i^e-ionic_surfactant_agent

In the foam stability studies which were carried out with 0.5% detergent solutions, the following results were obtained.

If the foam level exceeds 250 mm there is a significant risk of

that overfoaming occurs in the cylinder machine. The results show that the ampholyte mixture according to the invention has low foaming, especially at high temperatures, which makes it well suited for machine washing.

The three cleaning agent mixtures were also examined with respect

to their ability to remove fat. During the washing test, sample patches made of polyester/cotton were soaked with isotopically labeled glyceryl trioleate, which after drying were washed in a Terg-0-Tometer. The samples' content of glyceryl trioleate was determined as well

for and after washing when analyzing the radioactivity.

The following results were obtained.

The results show that the mixture according to the invention exhibits a significantly higher cleaning effect than the two comparative mixtures.

In order to compare the washing effect of the commercial products and the mixture according to the invention on pigment dirt (mainly silicates), a washing test in a Terg-O-tometer was carried out at a temperature of 4o°C, a water hardness of 2.8°dH and a detergent concentration of 5 g/l. Artificially soiled cotton fabric from Waschereiforschung, Krefeld, West Germany was used as laundry. The fabric's reflectance was measured before and after washing and the measurements are converted according to Kubelka-Munk's formula K/S=(l-R 2)/2R, where R is the reflectance. For other things, see W.G. Catler and R.C. Davis; Detergency, Theory and Test Method, part 1, New York 1972, p-387-392. The washing effect was expressed as the relative reduction of K/s, whereby the following result is obtained:

The mixture according to the invention also removed pigment dirt better than the commercial product.

In the same way as for the pigment soiled cotton fabric, a washing trial at 60°C was carried out with cotton fabric soiled with cocoa, which fabric was obtained from Eidgenossische Materialprufungsanstalt, St Gallen, Schweiz. The following results were obtained:

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The results show that the washing effect was also clearly better in this case for the mixture according to the invention than for the commercial comparison product.

EXAMPLE 2

A liquid detergent was formulated from the same ingredients

as in Example 1, except that the potassium pyrophosphate was replaced by an equivalent amount of sodium nitrilotriacetic acid. The washing effect of the obtained mixture was then tested in almost the same way as described in example 1, on cotton fabric soiled with either silicate pigment or cocoa. This achieves a washing effect of no less than 52.2% and 28.7% respectively. These values, which can be directly compared with those in example 1, show that the mixture according to the invention has a very good washing ability.

EXAMPLE 3

A liquid detergent was formulated with the following ingredients:

The washing effect of the obtained mixture was then tested on cotton fabric soiled with silicate pigment or cocoa.

The test, which was carried out in almost the same way as in example 1, resulted in a washing effect of 51.2% and 28.1% respectively, which shows that this mixture according to the invention also has an excellent washing ability.

COMPARISON EXAMPLE

US Patent No. 3,507,796 discloses an antibacterial mixture whose bactericidal effect is based on a special mixture of an organic compound that forms organic cations and a zwitterionic surface-active compound. If desired, according to the patent, other surfactants can also be added such as amine oxide, phosphine oxide, non-ionic, sulfoxide and olefin sulfonate surfactants. The mixture according to the US patent is to be used for the production of diluted aqueous solutions with an antibacterial effect. The US patent thus relates to a completely different field from the present invention and does not mention at all the special ampholytic compound, which contains the characteristic building block

which, with its functional hydroxyl group, imparts compounds with special properties. These properties are evident from the washing test set out below, which was carried out under the following conditions:

Composition of the dishwashing liquid:

When washing WEK cotton, the following results were obtained: Ampholyte A is the same as stated in example 3. Ampholyte B has the formula covered by the compounds described in US patent no. 3,507,796.

From the results shown above, it appears that the detergent mixtures according to the present invention exhibit washing effects that are better than the comparison mixtures. A significant and decisive advantage of the present washing mixtures is that they have moderate foaming, while the high foaming of the comparison mixtures is a very serious disadvantage, which makes their use impossible in large areas.

Claims (1)

Liquid detergent mixture containing complexing agents, non-ionic compounds and water, possibly alkylene glycol and common additives, characterized in that it contains a combination of at least one surface-active, non-ionic alkylene oxide adduct and at least one ampholyte with the general formula as detergent active mixture where represents an aliphatic or cycloaliphatic group with 6-22 carbon atoms or an aromatic t group substituted with one or more alkyl groups with a total of 4-18 carbon atoms in the alkyl groups; R 1 and R 3 independently of each other denote alkyl groups with 1-3 carbon atoms; n^ is 2 and/or 3 and/or 4; P1 is an integer from 0-10; and q is a number 1, 2 or 3, in which the weight ratio between the complex former, the alkylene oxide adduct, the ampholyte and the water is 4-25:1-20:1-15:40-90, preferably 6-20:2-15:1-10:4 5-80.