DE1617178B2 - Liquid detergent - Google Patents

Description

R ₆ -N ⁺ - CH ₂ - R ₈ - X-

R ₇

in which R _{5 is} an aliphatic chain with 10 to 20 carbon atoms, R ₆ and R ₇ (which can be identical or different) each have a hydrogen atom or a methyl, ethyl or hydroxyethyl group, R _{8 is} an alkylene chain with 1 to 3 carbon atoms, X either - SO ₃ or - COO and Y represent a hydrogen atom or a hydroxyl group;

(4) sulfoxides of the general formula R ₉ R ₁₀ SK), where R _{9 is} an alkyl, alkenyl, hydroxyalkyl or alkoxyalkyl group with 10 to 18 carbon atoms and R _{10 is} a methyl or ethyl group,

being the total amount of the fatty acids of the soaps and the organic synthetic detergent 16 to 60 percent by weight of the total detergent and the weight ratio of fatty acids to the organic detergent is 1.5: 1 to 4: 1; (b) a proportion of one or more water soluble organic chelating salts, corresponding to 4 to 8 percent by weight of their acid, and (c) water, where the pH of the agent is in the range between 8 and 12 and the cations of the fatty acids, Soaps and chelating agents are sodium, potassium, an ethanolamine, or mixtures thereof.

2. Means according to claim 1, characterized in that the total amount of fatty acids and the organic synthetic detergent is 20 to 30 percent by weight of the composition.

3. Composition according to claim 1 and 2, characterized in that the ratio of fatty acids to the organic synthetic detergent is 2: 1 to 3: 1.

4. Composition according to claim 1, 2 or 3, characterized in that the proportion of the organic Chelating agent is 6 to 8 percent by weight of its acid, based on the total detergent.

5. Agent according to one of the preceding claims, characterized in that the fatty acids from lauric acid or a mixture of fatty acids with a content of at least 80 percent by weight of lauric acid.

6. Agent according to one of the preceding claims, characterized in that the organic synthetic detergent is a tertiary amine oxide.

7. Composition according to claim 6, characterized in that the amine oxide is dodecyldimethylamine oxide is.

8. Agent according to one of the preceding claims, characterized in that the organic Chelating agent is an aminopolycarboxylate.

9. Composition according to claim 8, characterized in that the organic chelating agent nitrilotriacetate is.

10. Composition according to one of the preceding claims, characterized in that it is up to Contains 15 percent by weight of a hydrotropic agent.

11. Composition according to claim 10, characterized in that the hydrotropic agent has a low saturated monohydric alcohol with 1 to 4 carbon atoms or a sodium, potassium or Contains ethanolamine toluene or xylene sulfonate or a mixture thereof.

12. Agent 'according to one of the preceding claims, characterized in that it is potassium or monoethanolamine in a chemically equivalent amount to the fatty acid, and where essentially all remaining cations are sodium.

13. Agent according to one of the preceding claims, characterized in that the pH ranges from 8.7 to 9.7.

14. Means according to one of the preceding claims, characterized in that there is a contains optical brightener.

15. A method for producing an agent according to claim 14, characterized in that the optical brightener first in an aqueous solution of the organic synthetic detergent is dispersed and this solution then with the other components of the Is mixed by means.

The present invention relates to liquid detergents which are used for fine and coarse washing of fabrics as well as being suitable for dishwashing.

In recent years, liquid detergents, particularly those based on synthetic detergents, have become popular largely for washing dishes and for washing lightly soiled or easily too used in washing fabrics. They are especially useful for washing dishes and washing fabrics suitable by hand, where their advantages over conventional granulated detergents, namely light and quick dispersibility in the washing liquid and easy handling make them particularly valuable do. However, it has proven difficult to use both soap-based liquid laundry detergents a synthetic detergent with a detergent power comparable to that of the usual

built granulated detergent for washing heavily soiled fabrics, d. H. for coarse laundry, compare is.

It has now been found that liquid detergents based on selected soaps are certain nonionic and zwitterionic detergents, especially tertiary amine oxides and certain Organic chelating agents have a detergency comparable to that of conventional granulated detergents is, especially when used in water with a hardness of up to 8 °. Some of these agents are foaming also quite good and are very suitable as dishwashing detergents. Some have the further advantage that they retain their foaming power in very soft water, even if they are so constructed that they have good washing power in fairly hard water. (In general, synthetic detergents foam especially if they are designed to clean effectively in hard water, in very soft water Water, for example in water with a hardness of about 2 ° or less, weak.)

The soap-based agents Y) according to the invention have another advantage over this, however synthetic detergents insofar as that which occurs abundantly and is permanent in the washing liquid Foam is relatively easily destroyed in the rinse water.

According to the present invention, a liquid detergent is prepared which consists of (a) a mixture from one or more water-soluble soaps of fatty acids having 10 to 16 carbon atoms and one or several of the following organic synthetic detergents:

(1) tertiary amine oxides of the formula R ₁ R ₂ R ₃ N- ^ O, where R _{1 is} an alkyl, polyethoxyalkyl, monohydroxyalkyl or alkoxymonohydroxypropyl group with 10 to 18 carbon atoms in the alkyl or alkoxy group and R ₂ and R ₃ ( which may be the same or different) each represent an alkyl, hydroxyalkyl or alkoxy group having 1 to 3 carbon atoms or together form a heterocyclic group;

(2) Compounds of the formula R ₄ (C ₂ H ₄ O) _x H, in which R _{4 is} an alkoxy group having 10 to 18 carbon atoms

■ or denotes an alkylphenoxy group, the alkyl group containing 6 to 12 carbon atoms, and χ being an integer from 4 to 30;

(3) zwitterionic detergent compounds of the general formula

R ₅

R ₆ -N + _{- CH 2} - R ₈ -XR ₇ Y

in which R _{5 is} an aliphatic chain with 10 to 20 carbon atoms, R ₆ and R ₇ (which can be identical or different) each have a hydrogen atom or a methyl, ethyl or hydroxyethy group, R _{8 is} an alkylene chain with 1 to 3 carbon atoms , X is either - SO ₃ or - COO and Y is a hydrogen atom or a hydroxyl group;

(4) sulfoxides of the general formula R ₉ R ₁₀ SK), where R _{9 is} an alkyl, alkenyl, hydroxyalkyl or alkoxyalkyl group having 10 to 18 carbon atoms and R _{10 is} a methyl or ethyl group; wherein the total amount of the fatty acids of the soaps and the organic synthetic detergent is 16 to 60 percent by weight of the total detergent and the weight ratio of fatty acids to the organic synthetic detergent is 1.5: 1 to 4: 1; (b) a proportion of one or more water-soluble organic chelating agent salts corresponding to 4 to 8 percent by weight, their acid, based on the total detergent and (c) water

ίο consists, the pH of the agent being in the range is between 8 and 12 and the cations of the fatty acid soaps and chelating agents sodium, potassium, Are ethanolamine or mixtures thereof. The preferred ratio of fatty acids to the · organic synthetic detergent is 2: 1 to 3: 1.

Preferably the soaps should be a larger one

Contains a proportion of lauric acid soaps. They can therefore be made from essentially pure lauric acid or from mixed fatty acids which contain a high proportion, e.g. B. contain at least 80% lauric acid. Such fatty acid mixtures can, for example, from the fatty acids of oils, such as. B. coconut or palm kernel oil, can be prepared by appropriate fractional distillation. Soaps of fatty acids which contain larger amounts than about 10% C ₁₀ and lower fatty acids have poor detergency, those which contain larger amounts than about 10% C ₁₄ and higher fatty acids have less foaming power in the agent according to the invention.

The cations of the soaps are sodium, potassium, ethanolamine or mixtures thereof. Preferably it is potassium or an ethanolamine, in particular monoethanolamine, as explained in more detail below will.

The choice of the organic synthetic detergent to be used depends to a certain extent on the special coordination of the properties desired in the finished product. Therefore, since all agents according to the invention have excellent detergency, if a maximum of foaming power is required, preference is given to those which contain tertiary amine oxides and in particular dodecyldimethylamine oxide. The preferred zwitterionic detergent compounds are the sultaines, especially the 3- (N, N-dimethyl-N-alkylammonio) -2-hydroxypropane-1-sulfonates, in which the alkyl group has 10 to 18 carbon atoms. If a product with weaker foaming power is required, the compounds of the formula R ₄ (C ₂ H ₄ O) _n H are most suitable. Examples of the sulfoxides are dodecylmethylsulfoxide and 3-hydroxytridecylmethylsulfoxide.

Anyone who can chelate the metal ions, the which cause water hardness, such as certain water-soluble salts of aminopolycarboxylic acids, for example a nitrilotriacetate or ethylenediaminetetraacetate, or the salt of ethane-hydroxy-l, l-diphosphonic acid. Preferred chelating agents are nitrilotriacetates. The amount of chelating agent salt present in the detergent corresponds to 4 to 8 percent by weight of the corresponding acid of the chelating agent, preferably 6 to 8% of the same. The chelating agents can be added to the other ingredients of the agent in the form of their salts or but added in the form of their acid and with suitable bases in the presence of other constituents of the detergent be neutralized. The cations in these

Compounds can be sodium, potassium, ethanolamine, or mixtures thereof, as follows is described.

The agents can contain up to 15 percent by weight of a hydrotropic substance in order to increase solubility to increase the other components. The hydrotropic substance can be a lower saturated monovalent one Alcohol TQit_ 1 to 4 carbon atoms, such as. B. Methanol, ethanol, isopropanol, etc., or a hydrotropic electrolyte such as toluene or Be xylene sulfonates or a mixture thereof. The cations of the sulfonates can be sodium, potassium, Ethanolamine or mixtures thereof, as will be explained below. The preferred proportion of hydrotropic substance in a given detergent according to the invention depends on factors such as. B. the nature and amounts of the other ingredients and the storage conditions that the detergent will be used for is likely to be exposed and can be determined through experimentation.

The agents can also contain small amounts of compatible additives, which are usually detergents be added, such as anti-fogging and anti-corrosion agents, dirt carriers such as carboxymethyl cellulose, Odor substances, dyes and similar foam improvers, such as lauric acid monoethanolamide, and optical brighteners can also be added in small amounts.

If optical brighteners are added to the liquid detergent, especially liquid detergents, which are intended for washing fabrics, it is highly desirable that they be dissolved in the composition or at least evenly and finely distributed. This is often difficult to achieve because of the limited Solubility of many optical brighteners in aqueous solutions. It has been found that this difficulty can be eliminated in that the agents according to the invention are produced in that the optical brighteners first dissolved in an aqueous solution of the organic synthetic detergent or is dispersed and then the synthetic detergent solution with the other ingredients of the agent is mixed. The optical brightener can thereby be dispersed essentially uniformly in the mixture will.

Apart from small amounts of impurities that are present with the other components, Water normally makes up the rest of the remedy, and the other ingredients are in it dissolved or dispersed.

From the foregoing description it can be seen that at least three main types of sodium, Potassium or ethanolamine salts can be present in the agents according to the invention, namely soap, Chelating agents and hydrotropic salts. The solubility of the mixture depends in part on the proportions of these cations in the agent. If essentially only sodium salts are used, the tend Means of separating into two or more phases at temperatures that are undesirably high may as they are higher than the lowest temperatures that the agents are likely to experience upon storage or may be exposed to transport. Hence, at least some proportion of the cations are potassium or ethanolamine, usually at least one third on a molar basis. In aqueous solutions, as in the Agents according to the invention in which the electrolyte dissociates into ions to a considerable degree the distribution of the ions in the solution does not depend on the source of the ions. Therefore, the Soaps, chelating agents and hydrotropic salts in each case to the agent as sodium, potassium or ethanolamine salt are added, provided that these cations on the whole in appropriate proportions are present in the mixture.

The agents can optionally contain a total amount of potassium and / or ethanolamine (in particular

ίο Monoethanolamine) that are chemically the same as the Is fatty acid of the soap with essentially all of the remaining cation being sodium.

In practice, the agents can be combined in the following sequence during production if the organic synthetic detergent is an amine oxide. Amine oxide, usually in the form of an aqueous solution containing about 27 weight percent amine oxide, is first added to the mixing vessel and the optical brightener is dissolved or dispersed therein, if desired. The hydrotrope is then added, if desired, water and caustic soda, corresponding to the salt of the chelating agent, depending on the final pH of the agent. The acidic chelating agent, caustic potassium or ethanolamine in a chemically equivalent amount to the fatty acid, the fatty acid and finally ethanolamide, which serves as a foam improver, are added. The corresponding sequence can also be followed if the synthetic detergent is a zwitterionic compound, a compound of the formula R ₄ (C ₂ H ₄ O) _n H or a sulfoxide.

The pH of the agent is in the range from 8 to 12, preferably 8.7 to 9.7 and in particular around about 9.5. In the above-described, particularly preferred method, the pH depends on the Amount of caustic soda added and is controlled by the same.

The invention is illustrated by the following examples.

example 1
The following detergents were manufactured:

45 Components Weight percent B. C. A. 23.8 Potassium laurate 23.8 7.0 - Dodecyldimethylamine oxide 7.0 - 22nd Sodium dodecylbenzenesulfonate - 2.0 - Lauric monoethanolamide 2.0 Sodium salt of ethylenediamine - - tetraacetic acid (as acid) .... 6.0 Sodium salt of nitriloacetic 6.0 acid (as acid) 36 Sodium tripolyphosphate 0.5 Carboxymethyl cellulose 34 Sodium sulfate 61.2 7.5 60 water 61.2

The means A and B correspond to the present invention. Agent C contains a detergent, inorganic builder salt and a dirt carrier of the type and in proportions as they are for Granular detergents are typical, and are used as a comparative sample, showing the performance of a

shows typical granulated detergent. Agents A and B were homogeneous liquids.

The detergency of these agents was compared by converting them to 0.5% solutions in Water of 2 ° hardness at 46 ° C made and common soiled cotton test pieces in the solutions washed under standard conditions and with gentle agitation. In all cases, the test pieces were soiled four times, washed and assessed by visual inspection. It was found, that mean A 1.6 units better than mean C and mean B 1.0 units better than mean C could be rated on a scale showing a difference of 0.4 units within the experimental margin of error.

The foamability of agent A was similar to that of a liquid fully synthetic detergent which had Structure D below.

Components by weight

Sodium dodecylbenzenesulfonate 16.0

Sodium alkyl triethylene glycol ether

sulfate 16.0

Lauric acid monoethanolamide 1.0

Industrial denatured alcohol 8.5

Moisture and miscellaneous 58.5

A frame was set up in which two or more glass cylinders could rotate upside down. In a given amount of a 0.3% test solution of agents A and B in water was added to each cylinder filled with a certain hardness. Each solution was made with a first subset of a standardized fat soil addition offset. The cylinders then rotated for a standardized time in the frame, were placed upright and the foam height read. It became another subset Dirt added and the process repeated until almost no foam remained. The sum of the The foam heights read was recorded as the "foam height".

The following results were obtained in water with a hardness of 0 to 6 °.

Example 2
The following remedies were made:

Components

to

Potassium laurate

Sodium Nitrilotriacetate ...

Nqnylphenyl, which with g mol
Ethylene oxide was condensed

3- (N, N-dimethyl-N-alkylammonio) -2-hydroxy-
propane-1-sulfonate, at
which the alkyl group
of coconut alcohols
originates

Dodecylmethylsulfoxide ...

Fluorescent substance

Water and miscellaneous

Weight percent
EIFI G

21.3
6.0

7.1

0.3
rest

21.3
6.0

7.1

0.3
rest

21.3 *)

6.0
as acid

7.1
0.3
rest

*) Corresponding to 17.9% lauric acid.

The detergents were compared with a detergent C, which corresponded to the structure C of Example 1, but with the addition of 0.03% of a fluorescent substance. The procedure was that of Example 1 with the difference that in this case the test samples were assessed after soiling, washing and rinsing once. The mean values given below were determined by repeating the procedure six times for each mean.
Compared to mean C, mean E was found to be 0.07 units, mean F 0.18 units, and mean G 0.33 units better on a scale with a difference of 0.31 Units was within the experimental error limits. It was thus found that agent G had better detergency than agent C and agents E and F had at least the same detergency.

The means E to G were also with regard to their foaming power in water of 2 ° hardness with the Mean D of Example 1 compared by the method of Example 1, but in this case below Use of dishwashing water containing a lot of dirt, milk, egg, sugar, Contained potato solids and fat. Overall, the following foam heights were obtained:

Medium D 38.10 cm

Medium E 2.54 cm

Medium F 68.58 cm

Medium G 25.39 cm

Medium A gave significantly better foam heights than 55 Medium F was a high foaming product and Agent D in water of 0 and 2 ° hardness and similar agent E a relatively low-foaming Foam heights in harder water of 4 ° and 6 ° hardness. Product.

Water hardness 0 ° 2 °
Schaur 4 °
nheight 6 ° Means A 11.2
0 10.7
5.2 9.2
9.5 9.3
10.6 Medium D

Claims (1)

Patent claims: 1. Liquid detergent, consisting of (a) a mixture of one or more water-soluble Soaps of fatty acids having 10 to 16 carbon atoms and one or more of the following organic ones synthetic detergents: (1) tertiary amine oxides of the formula R ₁ R ₂ R ₃ NK), where R _{1 is} an alkyl, polyethoxyalkyl, monohydroxyalkyl or alkoxymonohydroxypropyl group with 10 to 18 carbon atoms in the alkyl or alkoxy group and R ₂ and R ₃ (the same or may be different) each represent an alkyl, hydroxyalkyl or alkoxy group having 1 to 3 carbon atoms or together form a heterocyclic group; (2) Compounds of the formula R ₄ (C ₂ H ₄ O) ₃ JH, where R ₄ denotes an alkoxy group having 10 to 18 carbon atoms or an alkylphenoxy group in which the alkyl group contains 6 to 12 carbon atoms, and χ is an integer is from 4 to 30; (3) zwitterionic detergent compounds of the general formula R ₅