DE1617172B2 - Soap compositions - Google Patents

Description

The present invention relates to improved Soap compositions particularly suitable for use in hard water.

Soap is an excellent detergent, but it has one serious drawback. This disadvantage is related to the tendency of soaps to react with the metal ions that make up the hardness of water, especially with calcium and magnesium ions. During this reaction it forms an insoluble, cheesy precipitate known as lime seifo. This insoluble lime soap forms unwanted deposits on the inner surfaces of washing machines. The lime soap beats also settle on fabrics that are washed in hard water when used as Delergen's soap will. These precipitates result in a bad smell and color of the washed Textiles. In addition, these precipitates show a tendency to reduce the water absorption capacity of tissues, Such as towels, to diminish that in hard water with the use of soap were washed.

It has already been attempted, these disadvantages _def: to reduce soap largely characterized in that complexing agent is used, which prevent the formation of lime soap by complex formation with the betref- 'fenden metal ions. Other attempts aimed at using all or part of the soap in the detergent using synthetic detergents

20: to replace those as such with the metal ions of the hard water does not form insoluble compounds. Synthetic detergents are also used to disperse the lime soap and prevent its deposition on the inner surfaces of the washing machine

25: machine and on the washed textiles. The proportion of such synthetic detergents however, that required to effectively disperse the lime soap is quite large and thus does so Product expensive.

An object of the present invention is to provide a new soap detergent composition. Furthermore, the present invention aims to provide a soap detergent composition, by which the disadvantages listed above are avoided.

The use of compositions of hardness sensitive treatment agents such as soap and water-soluble salts of certain linear, polymeric carboxylic acids, certain linear, polymeric phosphoric acids with more than 2 phosphorus atoms in the molecule, or of nitrilotriacetic acid or mixtures thereof became known from the DT-AS ^ l0 98 131. It was now surprisingly found that the per se known ability of certain synthetic detergents, Disperse the lime soap can be increased significantly when used in conjunction with such salts can be used.

The invention relates to a soap composition with improved lime soap dispersibility, consisting of a fatty acid soap and at least one water-soluble salt of linear, polymeric Phosphoric acids with more than 2 phosphorus atoms in the molecule; linear, polymeric carboxylic acids in the acid form has a molecular weight of at least 350 and an equivalent weight between 50 and 80 and are derived from a monomeric carboxylic acid with at least 2 carboxyl groups in the molecule and / or nitrilotriacetic acid, which is characterized in that it also contains at least one synthetic Detergent, which from the group of A) has a zwitterion or a semipolar in its molecular structure Detergents having binding and B) the group of amphoteric, synthetic detergents is selected, the weight ratio of A and / or B to the water-soluble Salt (s) about 1: 4 to 4: 1 and the sum of A and / or B and the water-soluble salt (s) at least 5 percent by weight, based on the

weight of the fatty acid soap. The weight ratio from component A and / or B to the water-soluble salt (s) in the mixture, which has a synergistic, lime soap-dispensing effectiveness, is preferably between I: 2 and 2: 1.

The synergistic mixture of A and or B and the aforementioned water-soluble salt (s) should represent at least about 5 percent by weight of the fatty acid soap. It can be up to about 100 percent by weight make up the soap component. Preferably it should be in amounts from about 20 up to about 80 percent by weight of the fatty acid soap is present.

The compositions according to the invention can also contain up to about 20 percent by weight of the soap, contain a low-foaming, nonionic, synthetic detergent.

The fatty acid soaps suitable for use in the compositions of the invention are the sodium, potassium and alkylolammonium salts of higher fatty acids (C ₁₀ -C ₂₀ ) - that is, the sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow the sodium or potassium tallow and coconut oil soaps are particularly suitable. Similarly, palm oil and palm kernel oil, as well as synthetic, e.g. sebum-like fats, are useful starting materials.

The amphoteric synthetic detergents suitable for use in the compositions of the invention Synthetic detergents that are both acidic in structure are suitable as well as a basic function. With the usual, amphoteric, synthetic detergents the acidic reacting group is a carboxyl, sulfuric acid, sulfonic acid or phosphoric acid group, while the basic group contains a non-quaternary nitrogen atom. The following compounds can as examples of suitable amphoteric, synthetic detergents are given:

a) water-soluble salts of alkylaminoalkanecarboxylic acids the general formula

R-NH- (CH ₂ LCOOH

N-CH, -CH, -N

HOOC — CH,

CH ₂ -COOH

d) water-soluble salts of N-alkyl-N'-sulfophenyliilhylenediamine the general formula

45

wherein χ is 1 or 2; a particular example is the sodium salt of dodecylaminomethane carboxylic acid; b) water-soluble salts of N, N'-dialkylethylenediaminediacetic acids of the general formula

55

a particular example is the sodium salt of HN'-dodecylethylenediaminediacetic acid;

c) water-soluble salts of N-alkyltaurines of general formula

R-NH-CH ₂ -CH ₂ -SO ₃ H.

a particular example is the sodium salt of N-methyltaurine;

R-NH

CH ₂ -CH ₂ -NH

SO ₃ H

a particular example is the sodium salt of N-methyl-N'-sulfophenylethylenediamine.

In the above general formulas, R represents an alkyl group having 10 to 18 carbon atoms.

The preferred amphoteric synthetic detergent is the sodium salt of N-lauryl - ^ - alanine.

Mixtures of amphoteric detergents are also suitable.

Useful zwitterionic detergents include aliphatic quaternary ammonium compounds, in which one aliphatic substituent 10 to 18 carbon atoms and another aliphatic substituent contains an anionic group which increases the water solubility. Examples of such compounds are water-soluble, alkylated betaines and sultaines of the general formula

R ₂
R ₁ -N ⁺ -R ₄ -X "

R3

wherein R _{1 is} an alkyl group with 10 to 18 carbon atoms, R _{2 is} an alkyl group with 1 to 3 carbon atoms, R _{3 is} an alkyl group with 1 to 3 carbon atoms, R _{4 is} an alkylene or hydroxyalkylene group with 1 to 4 carbon atoms and X "is a carboxylic acid or Particularly preferred compounds are salts of (N-alkyl-N, N-dimethylammonio) methane carboxylic acid, in which the alkyl group is derived from a mixture of lauric and myristic alcohols. Other suitable compounds are 3- (N-alkyl-N , N-dimethylammonio) - 2 - hydroxypropane - 1 - sulfonate and 3 - (N - alkyl - N ₁ N - dimethylammonio) - propane-1-sulfonate, in which the alkyl group contains about 10 to 18, preferably 12 to 16 carbon atoms.

Suitable detergents which contain a semipolar bond are, for example, tertiary amine oxides of the general formula R ₅ R ₆ R ₇ N - + O and tertiary phosphine oxides of the general formula

R ₅ R ₆ R ₇ P- ^ O

wherein R _{5 is} an alkyl, alkenyl or hydroxyalkyl radical having 10 to 18 carbon atoms, R ₆ and R _{7 are} each an alkyl or monohydroxyalkyl radical having 1 to 3 carbon atoms, for example dodecyldimethylamine oxide, dodecyldiethanolamine oxide, decyldimethylamine oxide, tetradecyldimethylamine oxide or dodecyl-bis- ) phosphine oxide, tetradecyldimethylphosphine oxide and sulfoxides of the general formula R ₈ R ₉ S - »- O, where R _{8 is} an alkyl, alkenyl, hydroxy or alkoxyalkyl radical having 10 to 18 carbon atoms and R _{9 is} methyl or ethyl. Examples are 3-Hydroxytridecylmethylsulfoxid or the preferred compound S-Hydroxy- ^ decoxybutylmethylsulfoxid.

Mixtures of the detergents listed above can also be used, for example a mixture of equal parts by weight of N - lauryl - // - alanine, 3- (N- dodecyl - N, N - dimelhylammonio) - 2 - hydroxypropane - 1 - sulfonate and dodecyldimethylamine oxide.

One component of the synergistic, lime soap dispersant Mixture is, as mentioned above, a water-soluble salt of a linear, polymeric carboxylic acid which, in the acid form, has a molecular weight of at least 350 and an equivalent weight from 50 to 80 and differing from a monomeric, with at least 2 carboxyl groups in the Molecule-containing carboxylic acid derives; or a water-soluble salt of a linear, polymeric phosphoric acid, which contains more than 2 phosphorus atoms in the molecule, or a water-soluble salt of nitrilotriacetic acid or a mixture thereof.

Suitable salts of polymeric carboxylic acids are water-soluble salts of

a) Polymers of asymmetrical polycarboxylic acids, ζ. B. polyitaconic acid, polyaconitic acid and copolymers of itaconic acid and aconitic acid,

b) linear polymers of dicarboxylic acids in which there are no interfering groups between the carboxyl groups Branches are present, for example polymaleic acid, copolymers of ethylene and Maleic anhydride,

c) linear polymers of dicarboxylic acids in which there are no carboxylic acid groups disturbing branches are present, e.g. B. Copolymers of vinyl methyl ether with maleic anhydride, Copolymers of styrene and maleic anhydride, as well as carboxypolystyrene.

In all cases the polymeric carboxylic acid must have a molecular weight of at least 350 and a Have equivalent weights of 50 to 80. The molecular weight can be as high as 1,500,000. Preferably the molecular weight should be between 500 and about 175,000. Is the polymeric carboxylic acid a Copolymer of a carboxylic acid monomer and a monomer without carboxyl groups, so must the quantitative proportion of the monomer without carboxyl groups must be so large that the equivalent weight of the polymeric acids is between 50 and 80.

The salt of the polymeric carboxylic acids can also be a mixture of such salts.

A more detailed description of polymeric carboxylic acid compounds, which can be used according to the invention can be found in the German Auslegeschrift 14 67 656 listed. Specific examples of suitable salts of polymeric carboxylic acids are given in the aforementioned Patent cited. '

The exact destination. the molecular weights of polymeric compounds is extremely difficult. the numbers obtained generally vary depending on that used for molecular weight determination method used. For example, it is known that molecular weights given by producers polymeric materials an average of the molecular weights in the relevant Represent molecules present in polymer. In addition, molecular weight ranges are usually given, which vary widely depending on the method used to measure molecular weight. Of the various methods that are commonly used to

30th

35 Determination of the molecular weights of polymeric compounds are osmometricc. Endgroup, cryoscopic and ebullioscopic imaging procedures as well as procedures carried out using light scattering and ultracentrifuges should be mentioned. Each of these processes is currently at a different stage of development. In addition, for each of these processes there are specific types of polymeric compounds for which it is best suited.

The minimum molecular weight of 350 cited above has been found empirically and is largely based on those obtained when working with these polyelectrolytic polycarboxylic acid polymers Knowledge and experience.

Viscosity is a property that polymer chemists use more often than molecular weights Characterization of polymeric compounds is used. The reason for this is undoubtedly in the relatively easier and less complicated methods of determining viscosity data. To make such information clear, the test conditions under which the measurements were carried out must also be specified became. Because between the viscosity of polymeric compounds and their relative molecular weights there is a known relationship and since numerical values relating to this are more unambiguous and often easier to obtain as molecular weights are the polymeric builder compounds used in the following examples characterized by their specific viscosity. In all cases, the viscosity indicator corresponds to a value substantially above 350 Molecular weight.

Suitable salts of linear polymeric phosphoric acids are the alkali salts of linear polymeric phosphoric acids with more than 2 phosphorus atoms in the molecule, e.g. triphosphoric acid, H ₅ P ₃ O ₁₀ , tetraphosphoric _{acid, H 6} P ₄ O ₁₃ , or hexametaphosphoric acid, H ₆ P ₆ O ₁₈ . Salts of pyrophosphoric acid, which is linear but only has 2 phosphorus atoms in the molecule, and salts of cyclic polymeric phosphoric acid, such as trimetaphosphoric acid, are not suitable. The preferred salts of polymeric phosphoric acids are sodium tripolyphosphate and sodium hexametaphosphate. In all cases the alkaline cation can be sodium, potassium or lithium.

A mixture of such salts is also to be understood as a salt of a linear polymeric phosphoric acid.

Unexpectedly it has now been found that water-soluble Salts of nitrilotriacetic acid also have a synergistic effect in terms of dispersing lime soap Have an effect with the organic non-soap detergents described above. Examples of such compounds are trisodium nitrilotriacetate and tripotassium nitrilotriacetate. Salts other aminopolycarboxylic acids, for example ethylenediaminetetraacetic acid, probably have a high Complexing ability for calcium ions, but show no synergism with regard to the lime soap dispersing Effect in the context of the invention. Salts of such aminopolycarboxylic acids however, the compositions of the invention can be used in small amounts for others Purposes, for example to stabilize peroxy bleaches such as sodium perborate, or to protect the soap against oxidative damage during storage.

'5

The synergistic, lime soap dispersing cndc (ic table mixed can also be mixtures of salts of carboxylic acids, Contains salts of phosphoric acid and salts of nitrilotriacetic acid. Such mixtures can be mixtures within each comprehensive s group as well as binary and ternary mixtures selected from all three classes. So you can, for example, mixtures of carboxylic acids Salts and phosphoric acid salts, mixtures of carboxylic acid salts and Nilrilotriacclatcn and also use mixtures of phosphoric acid salts and Nilrilotriacetalcn. The latter binary Mixtures are particularly valuable; in particular a mixture of Nalriumlripolyphosphat with Natriumnitrilolriacctal in a molar ratio of 4: 1 to 1: 4.

The water-soluble salts of the as one component in the synergistic, lime scifcndispersing mixture (whose other component is A and / or B) compounds used can be the sodium, Potassium, lithium. Ammonium or substituted ammonium compounds such as triethanolammonium and the like.

Albeit the ainpholeren, zwitterionic and semipolar synthetic detergents in themselves already have a certain calcium carbonate dispersibility, see above however, it becomes the same with the addition of any of the special salts of polymeric carboxylic acids in the specified proportions or by adding the special salts polymeric! "phosphoric acids or of Salts of nitrilotriacetic acid in the specified proportions still increased significantly, although the salts The polymeric acids themselves have only a very low dispersing power of lime soap. This synergism the calcium carbonate dispersibility is illustrated by the following investigations.

The sodium salt used in test series I (table 1) and in test series III (tables 5 and 6) the polyitaconic acid has an equivalent weight of 65.

A 1 percent by weight solution in dimethylformamide has a specific viscosity of 0.29 and a 0.06 weight percent solution in water is 0.07. (Both the dimethylformamide as well as the water were at room temperature.)

ΊΛ LBA Number of ml of 1%
Soap solution for production
a cloudy deposit 100 0 0 80 20th 42.5 60 40 122 40 60 100 20th 80 23 0 100 17.5

Study series I

A number of solutions were prepared by adding 1 g of a mixture of the sodium salt of N-lauryl - / <- alanine (LBA) with a sodium salt of polyitaconic acid (PIA) in hard water at about 54 ° C (130 ⁰ F) containing 0.936 g hardness builder / 3.791 water (14.4grains / gallon). The various blends used contained 100, 55, 80, 60, 40, 20 and 0% LBA and 0, 20, 40, 60 and 100% PIA, respectively. The pH of each solution was adjusted to 10.0.

A 1% solution of a sodium soap (made from a mixture of 20% coconut oil and 80% tallow) from a burette with constant stirring of the solution, until a cloudy deposit appeared in the solution. The number of milliliters of soap solution used for Generating the cloudy deposit is a measure of the lime soap dispersibility of the mixture. The results are given in Table 1 below:

The table above shows an increase in lime soap dispersibility of the combination of LBA with PIA compared to the expected value based on the individual values for the lime soap dispersibility of the two components of the mixture. Particularly noteworthy are the results that you get in terms of the lime soap dispersibility at the proportions 60/40 and 40/60.

Study series Il

A series of solutions was prepared by adding 2 g of a mixture of the sodium salt of N-lauryl-ß-alanine (LBA) with the salt of a linear polymeric phosphoric acid or the salt of nitrilotriacetic acid in 400 ml of hard water at 54.4 ⁰ C dissolved, which contained 0.936 g hardness constituents / 3.79 1 water. The polymeric phosphoric acid salts tested were sodium tripolyphosphate (STPP) and sodium hexametaphosphate (SHMP). The nitrilotriacetic acid salt investigated was trisodium nitrilotriacetate (NTA).

The various blends used contained 100, 80, 60, 40, 20 and 0% LBA and 0, 20, 40, 60, 80, respectively or 100% of the polymeric phosphate or nitrilotriacetate. The pH of each solution was increased to 10.0 set.

A 1% solution of a sodium soap (obtained from a mixture of 20% Coconut oil and 80% tallow) from a burette while the solution is stirred evenly until it had a cloudy appearance. The number of milliliters of soap solution needed to form a cloudy Precipitation is a measure of the chalk soap dispersibility of the mixture. The results are given in Tables 2, 3 and 4 below:

STPP LBA Number of ml of 1%
Soapy solution for education
a cloudy precipitation 509 530/388 100 0 1 80 20th 35 60 40 58 40 60 65 20th 80 45 0 100 30th

fabcllc 3

Table 5

LUA

Λη /; ιΙιΙ the l% igeii soap solution for the formation of a
cloudy precipitation

100 0 1 80 20th 30th 60 40 60 40 60 60 20th 80 50 0 100 30th Table 4

> 5

LBA

Number of ml of I%
Soapy solution for education
a cloudy filling '

100 0 5 80 20th 85 60 40 • 130 40 60 130 20th 80 100 0 100 30th

The tables above show an increase in the lime soap dispersibility of the combination of LBA with the salt of polymeric phosphoric acid (Tables 2 and 3) or with nitrilotriacetate (Table 4) in comparison to that from the individual values for the lime soap dispersibility of the two components expected value of the mixture. The lime soap dispersibility of NTA is at ratios of 60:40 and 40:60 are particularly noteworthy.

Series of studies III

45

There was prepared a series of solutions by adding 1 g of a mixture of an organic detergent and a sodium salt of PoIyitaconsäure (PIA) in water with 0.936 g per 3,791 hardness components of water at 54.4 ⁰ C dissolved. The various mixtures used contained 100, 80, 60, 40, 20 and 0% organic detergent and 0, 20, 40, 60, 80 and 100% PIA, respectively. The pH of each solution was adjusted to 10.0. Two surfactants have been investigated, namely (N-lauryl myristyl- ^ N-dimethylammonioVmethane carboxylate (AMC) and N-dodecyl-RN-dimethylamine oxide (DDMA).

A 1% solution of a sodium soap (obtained from a mixture of 20% Coconut oil and 80% tallow) from a burette until the solution became cloudy in appearance. The number of milliliters of 1% soap solution required to form a cloudy precipitate represents a measure of the lime soap dispersibility of the mixture. The results are in the following Tables 5 and 6 listed.

AMC " PIA Number of ml of 1%
Soap solution for education
a cloudy precipitation 100 0 20th 80 20th 25th 60 40 55 40 60 60 20th 80 30th 0 100 10 Table 6

DDMA PIA Number of ml of I%
Soapy solution for education
a cloudy precipitation 100 0 15th 80 20th 25th 60 40 60 40 60 80 20 ■ ¹ 80 60 0 100 10

The tables above show a substantial increase in the lime soap dispersibility of the combination a zwitterionic (AMC) or a semi-polar (DDMA) organic detergent with a Polyitaconate, compared with that value based on the individual values for the lime soap dispersibility of the individual components of the mixture was to be expected.

Study IV

A series of solutions were prepared by adding 2 g of a mixture of an organic Detergent with sodium tripolyphosphate (STPP) dissolved in 400 ml of water at 54.4 ° C, which contained 0.936 g of hardener per contained 3.791 water. The pH was adjusted to 10.0. The different solutions those used contained 100, 80, 60, 40, 20 and 0%, respectively, of the organic surfactant Mean with 0, 20, 40, 60, 80 or 100% STPP. The detergents tested were dodecyldimethylamine oxide (DDMA), 3- (N-dodecyl-N, N-dimethylammonio) - 2 - hydroxy -1 - propanesulfonate (DAHPS), 2 - (N - alkyl - Ν, Ν - dimethylammonio) -1 - ethane carboxylate, in which the alkyl radical is a mixture of lauryl and myristyl groups (LAEC); /? - Hydroxyundecylmethylsulfoxide (HUMS). The pH of each solution was adjusted to 10.0.

A 1% solution of a sodium soap (obtained from a mixture of 20% Coconut oil and 80% tallow) poured in from a burette while stirring evenly until the Solution became cloudy. The number of milliliters of 1% soap solution used to create a cloudy Precipitation is required is a measure of the lime soap dispersibility of the mixture Results are given in Tables 7 to 10 below:

11th

Table 7
DDMA

STPP number ml of I "/" igen

Soapy solution for the formation of a cloudy precipitate

100 0 35 80 20th 45 60 40 75 50 50 70 40 60 65 20th 80 60 0 100 0 Table 8 DAHPS STPP Ar

carried out with the sodium salts of nitrilotriacetic acid (NTA), whereby the following organic detergents were investigated: 3- (N, N-dimethyl-N-dodecyi) -ammonio-2-hydroxypropane-1-sulfonate (DAHPS) and 3- (N, N-dimethyl-N-lauryl-myristyl) -ammoniomethane carboxylate (AMC). The results are
listed in Tables 11 and 12.

Table 11

DAIIPS

NTA

Number of ml of 1%
Soapy solution for education
a cloudy precipitation

Number of ml of the 1% soap solution for the formation of a cloudy precipitate

100 0 25th 80 20th 45 60 40 60 50 50 60 40 60 55 20th 80 40 0 100 0 Table 9

100 0 25th 80 20th 120 60 40 150 '20 ⁴⁰ 60 135 20th 80 90 0 100 5 ■ 25 Table 12

AMC NTA _ Number of ml of 1%

Soapy solution for education
a cloudy precipitation

LAEC STPP Number of ml of 1%

Soapy solution for the formation of a cloudy precipitate

100 0 40 80 20th 65 60 40 80 50 50 80 40 60 75 20th 80 45 0 100 0 Table 10 HUMS STPP Number of ml of 1%
Soapy solution for education
a cloudy filling 100 0 0 80 20th 40 60 40 50 40 60 45 20th 80 20th 0 100 0

100 0 40 80 20th 120 60 40 140 40 60 140 20th 80 90 0 100 5

Similar studies have been made using mixtures of organic detergents The tables above show a large increase in the lime soap dispersibility of the combinations of the various zwitterionic or semi-polar organic surfactants with sodium tripolyphosphate or trisodium nitrilotriacetate compared to the values obtained from the Individual values for the lime soap dispersibility of the components of the mixtures are to be expected.

The surprisingly well-developed synergistic lime soap dispersibility of the in Tables 11 and 12 indicated mixtures is particularly noteworthy.

The compositions of the invention can be made in any form, e.g. B. as sticks, powder, bars, liquids or pastes. The amount of soap in the compositions can naturally as high as in the case of the usual soap compositions and is known per se. For example, a liquid soap composition can contain about 10 to about 30 weight percent soap together with about 0.5 to about 30 percent by weight of the novel, synergistic, contain lime soap dispersing mixture, the remainder to 100% being essentially a liquid carrier, z. B. water is. Another embodiment of the present invention is a toilet cleaner piece, the essentially about 80 to about 95% fatty acid soap (e.g. from 80% tallow - 20% coconut oil) and about 5 to about 20% of a synergistic, lime

Soap-dispersed mixtures according to the invention contains.

The invention is particularly useful for granulated detergent compositions, how they z. B. are used in washing processes in the house, suitable. Such compositions preferably contain from about 40 to about 80 weight percent soap, based on on the weight of the entire composition, and can also include the usual additives of Detergents, such as alkaline builder salts, ζ. Β. Sodium carbonate, sodium silicate, sodium sulfate, Carboxymethyl cellulose, bleaching agents e.g. B. peroxy compounds such as sodium perborate, optical Contain brighteners, color additives, perfuming agents and the like. Such granulated detergent compositions should have a content of about 2 to about 50 percent by weight of the composition of the invention have synergistic, lime soap dispersing mixture.

Another advantage of the compositions according to the invention lies in the possibility of using them in this way to assume that solutions of such compositions in hard water only foam strongly, until all the hardness of the water is removed and the solution contains enough free soap to make a have effective washing power. This avoids underdosing the composition. When adding high-foaming, synthetic detergents to soap for the purpose of prevention A separation of lime soap occurs even at low concentrations of the product, at which If there is not enough free soap for an effective wash, foam will form. The consumer is tempted to use too little of the product and only achieves a moderate cleaning effect. This tendency is in the inventive Compositions avoided, as they only foam strongly when already sufficient free soap is available for effective washing.

The compositions according to the invention provide an effective one during the washing process Dispersion of the lime soap. If the washed pieces are rinsed in hard water, the im Tissue remaining wash solution diluted with a large amount of the added hard water. Under these conditions a certain amount of lime soap can be formed in undispersed form. According to the present invention, this tendency can largely be prevented or completely eliminated by adding a low-foaming, alkylene oxide-containing, non-ionic to the soap composition Detergent of the type described below is added. In addition, there are little foaming, nonionic Detergents used to prevent foam from appearing in the rinse water.

Suitable alkylene oxide-containing, nonionic, synthetic detergents which can be used according to the invention Type are the following:

1. The polyethylene oxide condensates of alkylphenols and dialkylphenols, e.g. B. the condensation products of alkylphenols, their alkyl group about Contains 6 to 12 carbon atoms in a straight or branched chain arrangement, with ethylene oxide, wherein the ethylene oxide is present in amounts of about 5 to 30 moles of ethylene oxide per mole of alkylphenol is. In such compounds the alkyl substituent may e.g. B. of polymerized propylene, Be derived from diisobutylene, octene or nonene.

2. Alkylene oxide-containing, nonionic detergents, which are produced by condensation of Älhylcnoxyd with the Product obtained from the reaction of propylene oxide with ethylene diamine.

Here, too, a number of compounds are suitable, the properties of which can be adjusted so that one the desired balance between the hydrophobic and hydrophilic components is obtained. For example compounds containing about 40 to about 80 weight percent polyoxyethylene give satisfactory results and have a molecular weight between about 5,000 and about 11,000, these Compounds arise in the reaction of ethylene oxide groups with a hydrophobic base, such as in turn built up from the reaction product of ethylenediamine with excess propylene oxide and this base has a molecular weight in the range of 2500 to 3000.

3. The condensation product of aliphatic alcohols having 8 to 22 carbon atoms in a straight-chain or branched-chain arrangement with ethylene oxide, e.g. B. a coconut alcohol-ethylene oxide condensate with about 4 to 30, preferably 5 to 15 moles of ethylene oxide per mole of coconut alcohol. The preferred coconut alcohol is a distilled coconut alcohol having 10 to 16 carbon atoms and the following approximate wise distribution of the chain length: 2% - C _10, 66% - C _12, 23% - C _14, and 9% - C ₁₆ .'Eine Another preferred compound is the Condensation product of an alcohol derived from tallow with about 3 to about 15 mol ethylene oxide per mole of tallow alcohol; a specific example is the condensation product of 1 mole of tallow alcohol with

4 moles of ethylene oxide (TE ₄ ).

4. A known class of alkylene oxide, nonionic, synthetic detergents of this type is available on the market under the trade name "Pluronic". These connections will produced by condensation of ethylene oxide with a hydrophobic base, which in turn is produced by Condensation of propylene oxide with propylene glycol is obtained. The hydrophobic part of the molecule, which is of course water-insoluble, has a molecular weight of about 1500 to 1800. Die Addition of polyoxyethylene residues to this hydrophobic part of the molecule has the effect of increasing it Water solubility of the entire molecule. The liquid character of the product remains for a long time obtained until the polyoxyethylene content is about 50% of the total weight of the condensation product.

5. Specific examples of the above classes of compounds are as follows are only used to illustrate the type in question: nonylphenone, which is either with about 5 or about 30 moles of ethylene oxide per mole of phenol was condensed, and the condensation products of coconut alcohol with an average of either about 4 or about 15 moles of ethylene oxide per mole of alcohol, as well as the condensation product of about 15 mol of ethylene oxide with one mol of tridecanol. Further illustrative examples are dodecylphenol, which contains 12 moles of ethylene oxide per mole of phenol was condensed; Dinonylphenol, which has been condensed with 15 mol of ethylene oxide per mol of phenol; Dodecyl mercaptan condensed with 10 moles of ethylene oxide per mole of mercaptan; Bis (N-2-hydroxyethyl) lauramide; Nonylphenol, which with 20 moles of ethyl

lcnoxide was condensed per mole of nonylphenol; Myristyl alcohol, with 10 moles of ethylene oxide per Moles of myristyl alcohol has been condensed; Lauramid, with 15MoI ethylene oxide per mole of lauramid was condensed and Diisooclylphcnol, which was condensed with moles of ethylene oxide.

The preferred, nonionic detergent is the condensation product of 1 mole of hydrogenated talc alcohol with 4 moles of ethylene oxide. The proportion of the low-foaming, nonionic detergent in the Composition can constitute up to about 20 percent by weight of the soap content and is preferably at at least about 2 to about 15 weight percent of the soap content of the composition.

The invention is illustrated using the following examples:

example 1

A spray-dried, granulated soap composition is produced, with the proportions in the finished product are the following:

Weight percent sodium soap (20% coconut: 80%

Sebum): 54

Sodium salt of N-lauryl - // - alanine 6 sodium poly (itaconate acrylate) (4: 1 on a molar basis; specific viscosity of a 1 percent by weight solution in dimethylformamide at room temperature; 0.40;

Equivalent weight 65.8) 2

Sodium silicate solids (ratio

SiO ₂ : Na ₂ O = 2.4: 1) 10.25

Condensation product of 1 mole of hydrogenated tallow fatty alcohol and

4 moles of ethylene oxide 2

Sodium carboxymethyl cellulose .... 0.34

Ethylenediaminetetraacetic acid 0.18

Optical brightener 0.20

Sodium perborate tetrahydrate

(NaBO ₃ -4H ₂ O) 8.9

Various additives (inorganic salt, glycerine, unsaponified fat, etc.)

incorporated into the soap) 1.1

Moisture content 14.7

Perfumes 0.33

B e i s ρ i e 1 2

A spray-dried, granulated soap composition is produced, with the proportions in the finished product the following are:

55

Weight percent sodium soap (20% coconut

oil: 80% sebum) 52

N-Lauryl- / i-alanine sodium salt 6 Sodium tripolyphosphate (Na ₅ P ₃ O ₁₀ ) 6 Sodium silicate solids (ratio

SiO ₂ : Na ₂ O = 2.4: 1) 10.25

Sodium carboxymethyl cellulose 0.34

Ethylenediamine tetra sodium tetra-

acetate 0.18

Optical brightener 0.20

Sodium perborate tetrahydrate
(NaBO ₃ -4H ₂ O) 8.9

Weight percent

Various additives (inorganic salt, glycerine, unsaponified fat etc. which are incorporated into the soap

will be) 1.1

Moisture content 14.70

Perfumes 0.33

Example 3

A spray-dried, granulated soap composition is produced, with the proportions in the finished product the following are:

Weight percent

Sodium soap (20% coconut oil: 80% sebum) 54

3- (N, N-dimethyl-N-dodecyl) -ammonio-2-hydroxypropane-1-sulfonate 6

Sodium polyitaconate (specific viscosity of a 1 percent by weight Solution in dimethylformamide at room temperature 0.13; Equivalent weight 65) 2

Sodium silicate solids (SiO ₂ : Na ₂ O ratio = 2.4: 1) 10.25

Condensation product of 1 mole of hydrogenated tallow fatty alcohol and 4 moles of ethylene oxide 2

Sodium carboxymethyl cellulose .... 0.34

Ethylenediamine tetra sodium tetraacetate 0.18

Optical brightener 0.20

Sodium perborate tetrahydrate (NaBO ₃ -4H ₂ O) 8.9

Various additives (inorganic salt, glycerine, unsaponified fat, etc.) incorporated into the soap) 1.1

Moisture content 14.70

Perfumes 0.33

Example 4

A spray-dried, granulated soap composition is made, with the finished product the following proportions exist:

Weight percent sodium soap (20% coconut

oil: 80% sebum) 52

3- (N, N-dimethyl-N-dodecyl) -ammonio-2-hydroxypropane

1-sulfonate 3

Dodecyldimethylamine oxide 3

Sodium tripolyphosphate 4

Sodium silicate solids (ratio

SiO ₂ : Na ₂ O = 2.4: 1) 10.25

Condensation product of 1 mole of hydrogenated tallow fatty alcohol and

4 moles of ethylene oxide 2

Sodium carboxymethyl cellulose .... 0.34 ethylenediamine tetra sodium tetra-

acetate 0.18

Optical brightener 0.20

Sodium perborate tetrahydrate

(NaBO ₃ -4H ₂ O) 8.9

Various additives (inorganic salt, glycerine, unsaponified fat, etc.)

incorporated into the soap) 1.1

509 530/388

(icv \ ichtspro / cnl

Moisture wedge content 14.70

Perfuming agent 0.33

The granulated described in Examples 1 to 4 The product can be prepared by spray drying an aqueous slurry of all components, with the exception of sodium perborate and the perfume. The perfume is sprayed onto the spray-dried granulate, which is then mixed with the sodium perborate will.

When used with hard water in a household washing machine give the products of Examples 1 to 4 below the concentration at which All the hardness of the water is eliminated and the concentration of free soap is effective Washing effect is sufficient, no foam. The washing liquid is free from lime soap sludge. In the Washing machine does not leave a precipitate of lime soap. When rinsing, the water is free of lime soap sludge and also foam-free.

Similar results are obtained if, in place of the N-lauryl - /> '- alanine, the sodium salt of dodecylaminomethane carboxylic acid, N, N'-dodecylethylenediaminediacetic acid, N-methyltaurine or N-methyl-N'-sulfophenylethylenediamine are used; when the 3- (N, N-dimethyl-N-dodecyl) -ammonio-2-hydroxypropanesulfonate by 3 - (N-dodecyl-N, N-dimethylammonio) -propane-1 sulfonate is replaced or if the sodium tripolyphosphate is replaced by sodium hexametaphosphate, trisodium nitrilotriacetate or a 1: 1 mixture of these two compounds (on a weight basis).

Other illustrative examples are as follows:

Example 5

A soap composition is produced that gives a product with the following composition:

Weight percent

Sodium soap (20% coconut oil: 80% sebum) 60

Sodium salt of dodecylaminomethane carboxylic acid 10

Sodium polyitaconate (as in,

Example 3) 10

Water 17

Various accessories 3

50

Example 6

A soap composition is prepared that gives a product of the following composition:

Weight percent
Natnum soap (40% coconut

oil: 60% sebum) 60

Sodium salt of N-lauryl - / ^ - alanine 7
Monoethanol ammonium porymaleate
(specific viscosity of a
1 weight percent solution in
Dimethylformamide at room temperature 0.21; Equivalent weight 58) 14

Water 17

Various accessories ■ 2

Example 7

I-Is makes a soap composition that results in a product with the following composition:

Weight percent

Sodium soap (100% coconut oil) ..50 sodium salt of the N, N'-dodecyl

ethylenediaminediacetic acid 10

Sodium Polytitaconate Aconitate) (1: 1, on a molar basis; specific Viscosity of a 1 percent by weight solution in dimethylformamide: at room temperature 0.12;

Equivalent weight 60.8) 30

Water 9

Various accessories 1

Example 8

A soap composition is produced that gives a product with the following composition:

Sodium soap (60% coconut ^{ew 'c sprozent} oil: 40% tallow) 70

Sodium salt of N-methyltaurine .. 10

Sodium poly (ethylene maleate) (1: 1 on a molar basis; specific Viscosity of a 1 percent strength by weight solution in dimethylformamide at room temperature 1.58; Equivalent weight 72) 10

Water 8

Various accessories 2

Example 9

A soap composition is produced that gives a product with the following composition:

Sodium soap (80% coconut oil: 20% sebum) 80

Sodium salt of N-methyl-N'-sulfophenylethylenediamine 10

Sodium poly (ethylene maleate) (1: 1 on a molar basis; specific viscosity of 1 percent by weight Solution in dimethylformamide at room temperature 1.58; Equivalent weight 72) 5

Water 4

Various accessories 1

Example 10

A soap composition is produced that gives a product with the following composition:

^{Sodium soap} (20% coconut ^{weight percent}

oil: 80% sebum) 40

Sodium salt of N-lauryl-f / -alanine 15 70% potassium polymaleate: 30% polymaleic acid (1.4: 1, on a molar basis, specific viscosity of a 1 percent by weight solution in Dimethylformamide at room temperature 0.39; Equivalent weight 58) 15

16

Weight pro / enl Sodium silicate solids (ratio

SiO,: Na ₂ O = 2.4: 1) II

Water 6

^: Sodium perborate tetrahydrate

(NaBO ₃ -4H ₂ O) 10

Various accessories 3

Example 11

A soap composition is produced that gives a product with the following composition:

Weight percent sodium soap (20% coconut

oil: 80% sebum) 65

N-lauryl- / j-alanine sodium salt 10 ' ⁵

Sodium polyitaconate (specific viscosity of one weight percent Solution in dimethylformamide at room temperature 0.29;

Equivalent weight 65) 10

Nonylphcnol, which contains about 5 moles of ethylene oxide per mole of alcohol

was condensed 10

Water ; 4th

Various accessories 1 ² ^

Example 12

A soap composition is produced that gives a product with the following composition:

Weight percent

Sodium soap (20% coconut oil: 80% sebum) 60

(N-Lauryl-N, N-dimethylammonio) -

methane carboxylate 10

Sodium salt of polyitaconate

(as in example 3) 10

Water 17

Various accessories 3

40

Example 13

A soap composition is produced that gives a product with the following composition:

45

Weight percent

Sodium soap (50% coconut

oil: 50% sebum) 50

Decyldimethylamine oxide 30

Monoethanolammonium polymaleate

(as in example 6) 10

Water 9

Various accessories 1

Example 14

^F.

A liquid soap composition is produced, which gives a product with the following composition:

Weight percent sodium soap (80% coconut

oil: 20% sebum) 15

Tctradccyldimethylphosphine oxide ... 10

Sodium tripolyphosphate 5

Water 70

Example 15

A mass for bars of soap is produced, which results in a product with the following composition:

Weight percent

Sodium soap (100% coconut oil) ... 80 3-Hydroxytridecylmethylsulfoxide ... 10

Sodium hexametaphosphate 5

Water 5

Example 16

A soap mass is produced, which results in a product with the following composition:

Weight percent

Sodium soap (20% coconut oil: 80% sebum) 45

S-hydroxy ^ -decoxybutylmethyl-

sulfoxide) 22.5

Sodium salt of nitrilotriacetic acid 22.5

Water ,. 7th

Various accessories 3

Example 17

A soap mass is produced, which results in a product with the following composition:

Weight percent

Sodium soap (20% coconut oil: 80% sebum) 60

Dodecyl bis (hydroxymethyl) -

phosphine oxide 16

Sodium tripolyphosphate 8

Sodium nitrilotriacetate 8

Nonylphenol, which is about 30 mol

Alcohol was condensed 3

Water 4

Various accessories 1

As can be seen from the tables above, those compounded in special proportions result Combinations of the synthetic detergents and the salts described above superior, valuable, synergistic lime soap dispersing power.

The soap compositions according to the invention, in particular the bar-shaped products, can germicides can be added to impart antiseptic properties to the products.

Unless otherwise noted, the percentages given above are always percentages by weight.

Claims (5)

Patent claims: 1. Soap composition with improved lime soap dispersibility, consisting of a Fatty acid soap and at least one water-soluble salt of linear, polymeric phosphoric acids with more than 2 phosphorus atoms in the molecule; linear, polymeric carboxylic acids in the Acid form has a molecular weight of at least 350 and an equivalent weight between 50 and 80 and differ from a monomeric carboxylic acid with at least 2 carboxyl groups in the molecule derive and / or nitrilotriacetic acid, characterized in that it is additionally at least one synthetic detergent selected from the group of A) in its molecular structure Zwitterion or a semipolar bond having detergents and B) the group of amphoteric, synthetic detergents is selected, the weight ratio from A and / or B to the water-soluble salt (s) 1: 4 to 4: 1 and the sum of A and / or B and the water-soluble salt (s) at least 5 percent by weight, based on the Weight of the fatty acid soap. 2. Soap composition according to claim 1, characterized in that the sum of the Component A and / or B and the water-soluble salt (s) 20 to 80 percent by weight which makes fatty acid soap. 3. Soap composition according to claim 1, characterized in that the weight ratio from A and / or B to the water-soluble salt (s) «1: 2 to 2: 1. 4. Soap composition according to claim 1 in liquid form, characterized in that it consisting essentially of 10 to 30 percent by weight fatty acid soap containing 10 to 20 carbon atoms and 0.5 to 30 percent by weight of the mixture of A and / or B with the water soluble salt (s), with the remainder is a liquid carrier. 5. Soap composition according to claim 1, characterized in that it consists of 10 to 95 percent by weight a fatty acid soap with 10 to 20 carbon atoms, 5 to 100 percent by weight, based on the weight of the soap, the mixture of A and / or B with the water-soluble one or more Salt (s) and that they also 2 to 15 percent by weight, based on weight the fatty acid soap, a nonionic, alkylene oxide-containing synthetic detergent.