DE1617172A1 - Soap compositions - Google Patents

Description

DIL JUR. DIPL-CHE / Λ. WALTER BEIL LAWYERS AND NOTARIES

DR. JUR. DIPL-CHEM. H.-J. WOLFP DR. JUR. HANS CHR. AX

IECHTSANWXLTE

623 FRANKFURT AM MAIN - HIGHEST

AOaONSTKASSEjS

Our No. 12509

6th

The Procter & G-amble Company Cincinnati, Ohio, V.St.A.

Soap compositions.

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

Soap is an excellent detergent, but it has a serious disadvantage. This disadvantage is related to the tendency of soaps to have their hardness dea Metal ions that make up water, especially with calcium and magnesium ions. During this reaction, an insoluble, cheesy precipitate forms, which as Lime soap is known. This insoluble lime soap forms unwanted deposits on the inner surfaces of the washing machines. The lime soap also settles on fabrics, which are washed in hard water when soap is used as a detergent. These precipitations lead to a bad smell and color of the washed items. In addition, these precipitates show the tendency to reduce the water absorption capacity of fabrics such as

Documents ^ nrA ^ 2: _if , r _{9m3ä99iiiHtwnW9tt ν} .4. ». _18§7ι ! 09808/1194

1817172

wise towels, washed in hard water with the use of soap.

Attempts have already been made to overcome these disadvantages of the To reduce soap largely by using complexing agents which prevent the formation of lime soap prevent it from forming complexes with the metal ions in question. Other attempts aimed at detergent to replace all or part of the soap with synthetic detergents which, as such, contain the metal ions of hard water do not form insoluble compounds. In addition, synthetic detergents are used to Lime soap to disperse and prevent its deposition on the inner surfaces of the washing machine and on the washed ones Textiles. The proportion of such synthetic detergents required to effectively disperse the Lime soap is required, however, is quite large, thus making the product expensive.

An object of the present invention is to provide a new soap detergent composition. It also aims the present invention to provide a soap detergent composition which avoids the disadvantages listed above.

It has now been found that the ability of certain synthetic detergents to disperse the lime soap, can be increased significantly if the detergents in conjunction with 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.

109808/1934

According to the invention contains a soap composition with excellent dispersibility for lime soap and therefore "particularly suitable for use" in hard water about 10 ms about 95% by weight of a higher fatty acid soap and at least about 5 wt .- ^, based on the weight of the soap, of a lime soap dispersant, synergistic mixture, which consists essentially of (A) at least one water-soluble, amphoteric synthetic detergent or at least one water soluble, organic, synthetic soft soap detergent which is one in its molecular structure Zwitterion or a semipolar bond contains, or a mixture thereof and (B) at least one water-soluble borrowed Salt of a linear, polymeric carboxylic acid, which in the acid form has a * molecular weight of at least 350 and has an equivalent weight of 50 to 80 and the is derived from a monomeric carboxylic acid which contains at least 2 carboxyl groups in its molecule, or a water-soluble salt of a linear, polymeric phosphoric acid containing more than 2 phosphorus atoms in the molecule, or a water-soluble salt of nitrilotriacetic acid, or a mixture thereof. The GE-, The weight ratio of (A) to (B) in this synergistic, lime soap dispersing mixture is between about 1: 4 and about 4: 1, preferably between about 1: 2 to about 2: 1. Combinations too of the salts listed above can be used in the compositions according to the invention.

The synergistic mixture should represent at least about 5% by weight of the fatty acid soap. It can go up to about Make up 100% by weight of the soap component. Preferably it should be used in amounts of about 20 up to about 80% by weight

109808/1934

the fatty acid soap.

The compositions of the invention may also "contain up to about 20 wt. -4> of soap, a low foaming nonionic synthetic detergent.

The fatty acid soaps suitable for use in the compositions according to the invention are the sodium, potassium and alkylolammonium salts of higher fatty acids (0ηη ~ 0ρ _Ω ) Sodium or potassium tallow and coconut oil soaps, "are particularly suitable. Similarly, palm oil and palm kernel oil, as well as synthetic, for example tallow-like fats, are useful starting materials.

The amphoteric, synthetic detergents used for the use in the compositions according to the invention are suitable are synthetic detergents, which in their structure are both acidic and basic Function included. In the usual, amphoteric, synthetic detergents, the acidic reacting group is one Carboxyl, sulfuric acid, sulfonic acid or phosphoric acid group, while the basic group contains a non-quaternary nitrogen atom. The following connections can be seen as examples of suitable amphoteric, syntheti Detergents are listed:

(a) Water-soluble salts of alkylaminoalkanecarboxylic acids of the general formula:

R. NH. (CH ₂ ) _X COOH,

109808/1934

wherein χ is 1 or 2; this is a particular example Sodium salt of dodecylaminomethane carboxylic acid;

(b) water-soluble salts of N.N'-dialkylethylene diaminediacetic acid the general

N-CH ₂ - CH ₂ - ΪΓ HOOC-CH ₂ . CH ₂ -COOH

a "special example is the sodium salt of N, N ¹ -dodecyläthylendi amindi e ssigsä ure;

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

R - NH - CH ₂ - GH ₂ - SO ₅ H;

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

(d) water-soluble salts of N-alkyl-N'-sulfo phenylethylenediamines the general formula s

R - NH - CH ₂ - CH ₂ - NH -C%

a special example is the sodium salt of N-methyl-

109308/1934

N ¹ -sulfophenylethylenediamines.

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-ß-alanine.

Mixtures of amphoteric detergents are also suitable.

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

R ₁ - N ⁺ - R ₄ - X "

wherein R _{1 is} an alkyl group having 10 to 18 carbon atoms, R _{2 is} an alkyl group having 1 to 3 carbon atoms, R is an alkyl group having 1 to 3 carbon atoms, R ^ is an alkylene or hydroxyalkylene group having 1 to 4 carbon atoms and X ~ Means carboxylic acid or sulfonic acid anion. Particularly preferred compounds are salts of (N-alkyl-NN-dimethylammonioJ-metha ^ carboxylic acid, in which the alkyl group is derived from a mixture of laurine -

100808/1934

and myristic alcohols. Other suitable compounds are 3- (N-alkyl-N, N-dimethylainmonio) -2-hydroxy propane-1-sulfonate and 3- (N-alkyl-N, N-dimethylammonio) propane-1-sulfonate, wherein 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

general formula RcRgRrIi £ 0 and tertiary phos-

phinoxides of the general formula RcRgRyP ^ 0, in which

Rc is an alkyl, alkenyl or hydroxyalkyl radical with 10 to 18 carbon atoms, Rg and R ~ each an alkyl or Mean monohydroxyalkyl radical with 1 to 3 carbon atoms, for example dodecyldimethylamine oxide, dodecyl diethanolamine oxide, Decyldimethylamine oxide, letradecyl dimethylamine oxide, or dodecyl bis (hydroxymethyl) phosphine oxide, Tetradecyldimethylphosphine oxide and sulfoxides of the general formula RqRqS> 0, where Rg is an alkyl, Alkenyl, hydroxy or alkoxyalkyl radical with 10 to 18 carbon atoms and Rq is methyl or ethyl. Examples are 3-Hydroxytridecylmethylsulfoxyd or the preferred one Compound 3-Hydroxy-4-decoxybutylmethylsulfoxide.

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

Component (B) of the synergistic, lime soap dispersant Mixture as listed above is a water-soluble salt of a linear, polymeric Carboxylic acid, which in the acid form has a molecular weight of

101808/1934.

at least 350 and an equivalent weight of 50 to 80 and differing from a monomeric, with at least 2 carboxylgruppen in the molecule containing carboxylic acid derivatized; or a water-soluble courtship of a linear, polymer Phosphoric acid, which contains more than 2 phosphorus atoms in the molecule, or a water-soluble salt of nitrilo triacetic acid or a mixture thereof.

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

(a) Polymers of unsymmetrical polycarboxylic acids, e.g., polyitaconic acid, polyaconitic acid and copolymers of itaconic acid and aconitic acid;

(b) linear polymers of dicarboxylic acids in which there are no disruptive branches between the carboxyl groups present, for example, polymaleic acid, copolymers of ethylene and maleic anhydride;

(C) linear polymers of dicarboxylic acids in which there are no interfering groups between the carboxylic acid groups Branches are present, e.g. copolymers of vinyl methyl ether with maleic anhydride, copolymers of styrene and maleic anhydride, as well as car boxypolystyrene.

In all cases the polymeric carboxylic acid must have a molecular weight of at least 350 and an equivalent weight from 50 to 80 have. 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 poly-

109808/1934

mere carboxylic acid is a copolymer of a carboxylic acid monomer and a monomer without carboxyl groups, so must the quantitative proportion of the monomer without carboxyl groups be so large that the equivalent weight of the polymer Acids between 50 and 80.

The salt of the polymeric carboxylic acid 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 can be found in German patent specification no

(Patent application P 33955 IVa / '23 e cited. Special Examples of suitable salts of polymeric carboxylic acids are given in the aforementioned patent.

The precise determination of the molecular weights of polymeric compounds is extremely difficult. The received Numbers generally vary depending on the method used to determine molecular weight. It is known, for example, that stated by the producers Molecular weights of polymeric materials one Represent the average of the molecular weights of the molecules present in the polymer in question. Also be molecular weight ranges are usually given, depending on the method used to measure the molecular weight vary greatly. Of the various methods that are often used to determine the molecular weights of polymeric Compounds used are osmometric, endgroup, cryoscopic and ebullioscopic methods of determination and procedures using light scattering and ultracentrifuges. Each

109S08 / 1Q34

- ίο -

this process is currently at different stages of development. There is also for each of these Process special types of polymeric compounds for which it is best suited.

The minimum molecular weight given above out of 350 has been found empirically and is largely based on the polyelectrolytes seen when working with them Polycarboxylic acid polymers gained knowledge and experience.

Viscosity is a property that polymer chemists use more often to characterize molecular weights polymeric compounds is used. The reason for this is undoubtedly the proportionate easier and less complicated procedures for determining viscosity data. To such information clearly To do this, the test conditions under which the measurements were carried out must also be specified became. There is a known relationship between the viscosity of polymeric compounds and their relative molecular weights and since numerical values relating to this are more unambiguous and often easier to obtain than molecular weights are, the polymeric builder compounds used in the following examples are characterized by their specific Viscosity marked. In all cases, the viscosity indicator corresponds to one that is significantly 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, for example triphosphoric acid, HtP ^ O ₁₀ , tetraphosphoric acid>

105803/1934

-αϊ - "

or hexametaphosphoric acid, HgPgO ₁₈ . Salts of pyro phosphoric acid, which is linear but has only 2 phosphorus atoms in the molecule, and salts of cyclic polymeric phosphoric acid, such as irimetaphosphoric acid, are not suitable. The "preferred salts of polymeric phosphoric acids are sodium tripolyphosphate and sodium hexainetaphosphate. 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 Effect in terms of lime soap dispersing Have effect with the above-described non-soap organic detergents. Examples of such Compounds are trisodium nitrilotriacetate and tri-potassium nitrilotriacetate. Salts of other aminopolycarboxylic acids, for example ethylenediaminetetraacetic acid, have a high complexing capacity for calcium ions, however, have no synergism whatsoever with regard to the lime soap dispersing effect in the invention Context. Salts of such aminopolycarboxylic acids however, the compositions according to the invention in in small amounts for other purposes, for example to make peroxy bleaches such as sodium perborate, to stabilize, or to protect the soap against an oxidative Protect from damage during storage.

The synergistic, lime soap dispersing mixture Mixtures of salts of carboxylic acids, salts of phosphoric acid and salts of nitrilotriacetic acid can also be used

109808/1934

contain acid. Such mixtures can be mixtures within each comprehensive 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 Nxtrilotriacetaten as well as mixtures of phosphoric acid salts and trilotriacetates use. The latter binary mixtures are particularly valuable; especially a mixture of sodium tripolyphosphate with sodium nitrilotriacetate in a molar ratio of 4: 1 to 1: 4.

The water-soluble salts of the compounds used as component (B) can be the sodium, potassium, Fertilize lithium, ammonium or substituted ammonium compounds, such as iriethanolammonium and the like.

Albeit the amphoteric, zwitterionic and semi-polar synthetic detergents already have a certain ability to disperse lime soap, it becomes the same however, by the addition of any of the special salts of polymeric carboxylic acids in the specified Proportions or by adding the special salts of polymeric phosphoric acids or salts of nitrilotriacetic acid in the specified proportions still significantly increased, although the salts of the polymeric acids per se are only very slight Have lime soap dispersibility. This synergism the lime soap dispersibility is illustrated by the following studies.

That in a series of experiments I (Table 1) and in the Experimental series III (Tables 5 and 6) used sodium salt the polyitaconic acid has an equivalent weight of

109808/1934

A 1% strength by weight solution in dimethylformamide has a specific viscosity of 0.29 and a 0.06% strength by weight solution in water it is 0.07. (Both the dimethylformamide and the water were at room temperature,)

Study series I:

A series of solutions was prepared by dissolving 1 g of a mixture of the sodium salt of K-lauryl-ßalanine (LBA) with a sodium salt of polyitaconic acid (PIA) in hard water at about 54 ⁰ C (130 ⁰ P), the 0.936 g hardness builder / 3.79 1 water (14.4 grains / gallon). The various mixtures used contained 100 $>, 80 ^, 60 #, 40 #, 20 i » and 0 <$> LBA and 0 #, 20 $, 40 #, 60 $> and 10096 PIA, respectively. The pH of each solution was adjusted to 10.0.

A 19% solution of sodium soap (prepared from a mixture of 20 # coconut oil and 80 I * tallow) was run into each solution from a burette with constant stirring of the solution until a cloudy deposit appeared in the solution. The number of ml of soap solution required to produce the cloudy deposit is a measure of the lime soap dispersibility of the mixture. The results are given in Table 1 below:

Table 1 ί

PIA LBA Number of ml 'of the $ 1 soap solution for Creation of a cloudy coating

lüO 0 0

10 9 8 0b.

80 20th 60 40 40 60 20th 80 0 100

-u-

Table 1 (Port setting:

PIA LBA Number of ml of the $ 1 soap solution to produce a cloudy deposit

42.5 122 100

17.5

The table above shows an increase in the lime soap endispersion ability of the combination of LBA with PIA in comparison to the expected value based on the individual values for the lime sebum dispersibility of the two components of the mixture. Particularly noteworthy are the results that are obtained with regard to the lime soap endispergiating capacity with the proportions 60/40 and 40/60.

Examination series II:

A number of solutions were made by

2 g of a mixture of the sodium salt of N-laurylß-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 ° C containing 0.936 g hardness builder / 3f79 1 (14.4 grains / gallon) of water. The polymeric phosphoric acid salts tested were sodium tripolyphosphate (STPP) and liatric hexametaphosphate (SHMP). The salt tested was nitrilotriacetic acid

1Q98ÖB'19 34

/ I6T7172

Trisodium nitrilotriacetate (NTA).

The various mixtures used contained 100%, 80 / o, 60% 40 io, 20 $> or 0 # LBA and 0 $, 20 jo, AO ^σ / o, 60 $, 80 $ "or 100 % of the polymer Phosphate or nitrilotriacetate The pH of each solution was adjusted to 10.0.

In each solution a 1 # strength solution of Na was triumseife (obtained from a mixture of 20 $> coconut oil and tallow 80 io) left en-incoming from a burette while the solution was stirred evenly until they had a cloudy appearance . The number of ml of soap solution required to form a cloudy precipitate is a measure of the lime soap dispersibility of the mixture. The results are given in Tables 2, 3 and 4 below:

Table 2:

STPP LBA Number of ml of the 1 # soap solution for the formation of a cloudy precipitate

100 0 Table 3: 1 80 20th 35 60 40 58 40 60 65 20th 80 45 0 100 30th

SHMP LBA Number of $ 1 soap solution for the formation of a cloudy precipitate

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

100 0 80 20th 60 40 40 60 20th 80 0 10Θ

NTA LBA Number of ml of the 1 $ soap solution

for the formation of a cloudy precipitate

5.

85 130 130 100 30

The tables above show an increase in the lime dispersibility of the combination of LBA with the salt of polymeric phosphoric acid (Tables 2 and "5) or with nitrilotriacetate (Table 4) in comparison with the can be expected from the individual values for the lime content of the two components of the mixture Value. The lime soap dispersibility of NTA is at ratios of 60:40 and 40:60 are particularly noteworthy.

Investigation series III: A series of solutions were prepared by

109808/1934

by adding 1 g of a mixture of an organic detergent and a sodium salt of polyitaconic acid (PIA) in water with 0.936 g hardness constituents per 3.79 l (14.4 grain / Gallon) of water "at 54.4 ° C. The various mixtures used included $ 100, $ 80, $ 60, $ 40, $ 20 or $ 0 organic detergent and $ 0, $ 20, $ 40, $ 60, $ 80 and $ 100 PIA, respectively. The pH of each solution was set to 10.0. Two surface-active agents were investigated, namely (M-lauryl myristyl-M, lJ-dimethylammoniQ -) methane arboxylate (AMC) and IT-dodecyl-lir.I-dimethylamine oxide (DDYIA).

A $ 1 solution of a sodium elf (obtained from a mixture of $ 20 coconut oil and $ 80 tallow) was run into each solution from a burette until the solution became cloudy in appearance. The. Number of ml of the 1 $ soap solution required for the formation of a cloudy precipitate ₉ represents a measure of the lime soap dispersibility of the mixture. The results are shown in Tables 5 and 6 below.

! Table 5:

AMC PIA Number of ml of 1 # soap solution for ■ the formation of a cloudy Y & lluxm

20th

55 60 30 10

100 - ο 80 20th 60 40 40 60 20th 80 ■ 0 100

PIA Table 6: DIMA Number of ml of 1 # soap solution for 0 the formation of a cloudy precipitate 100 20th 15th 80 40- 25th 60 60 60 40 80 80 20th 100 60 0 10

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

Investigation series IV:

There was prepared a series of solutions, by reacting 2 g * 4 * ⁰ O dissolved contained a mixture of an organic detergent with sodium tripolyphosphate (STPP) in 400 ml of water at 54, the 0.936 g hardeners per 3.79 1 water. The pH was adjusted to 10.0. The various solutions that have been used here contained 100, 80 ^, 6Oj6, £ 40, 20 and 0 ^ 9t of organic surfactant with 0 i ", $ 20>, 40 #, 60 #, 80 ?! or $ 100> STPP. The detergents tested were dodecyldimethylamine oxide (DDMA.), 3- (N-dodecyl-

1934

N, lI-dimethylammonio) -2-hydroxy-l-propanesulfonate 2- (lT-alkyl -]! I, II-dlmethylainmonio) -l'-ethane carboxylate _J in which the alkyl radical is a mixture of lauryl and myristyl groups (LAEO) is; ß-Hydroxy-undecylmethylsulfoxide (HUMS). The pH of each solution was adjusted to 10.0.

In each solution, a 1% solution of a sodium soap (obtained from a mixture of 20 $ coconut oil and 80 i "tallow) with uniform stirring allowed to run in from a burette until the solution became cloudy. The number ml of the 1 ^ -igen. Soap solution, which is required to produce a cloudy precipitate, is a measure of the lime soap dispersibility of the mixture. The results are given in Tables 7 bis below:

Table 7i

DIMA STPP Number of ml of 1 # soap solution for

the formation of a cloudy precipitate

35 45 75 70 65 60 0

100 0 80 ' 20th 60 40 50 50 40 60 20th 80 0 100

109808/1934

Table 8:

STPP

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

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

LAEC STPP Number of ml of 1 # soap solution for

the formation of a cloudy precipitate

100 0 80 ' 20th 60 40 50 50 40 60 20th 80 0 100

40 65 80 80 75 45 0

STPP

100 0 80 20th 60 40

Table IQt

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

40

169808/1934

- 21 -

Table 10 (continued):

40 60 45 20th 80 20th 0 100 0

Similar studies were carried out using mixtures of organic detergents with the sodium salts of nitrilotriacetic acid (NTa), whereby the following organic detergents were investigated: 3- (N, N-Dirne thyl-N-do decyl) -ammoni o-2-hydr oxyp ropan-1 - sulfonate (DAHPS) and 3- (N, N-dimethyl-N-lauryl-myristyl) -ammonio-methanecarboxylate (AMC). The results are given in Tables 11 and 12.

Table 11:

DAHPS NTA Number of ml of the 1 # soap solution

.for the formation of a cloudy precipitate

100 0 Table 12: 25th 80 20th 120 60 40 150 40 • 60 135 20th 80 90 0 100 5

AMC HTA Number of ml of the 1 # soap solution for the formation of a good precipitate

109808 / 193.4

100 0 80 20th 60 40 40 60 20th 80 0 100

- 22 -

120 140 140

The tables above show a sharp increase the lime soap dispersibility of the combinations of the various zwitterionic or semi-polar organic, Sodium tripolyphosphate surfactants or trisodium nitrilotriacetate in comparison 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 one Lime soap dispersibility of the mixtures given in Tables 11 and 12 is particularly noteworthy.

The compositions according to the invention can be made in any shape, for example as bars, Powder, bars, liquids or pastes. The amount of soap in the compositions can of course also be used high as with the usual soap compositions and is known per se. For example, a liquid soap composition about 10 to about 30% by weight Soap along with about 0.5 to about 30 weight percent of the above described new, synergistic, lime soap dispersing mixture contain, with the remainder on IOO94 essentially a liquid carrier, e.g. water, is. Another embodiment of the present invention is a toilet cleaner piece that essentially

109108/1934

about 80 to about 95 ° Fettsäureseif i e (eg from 80 $ 20 $ tallow coconut oil) and about 5 Ms about 20 # includes a synergistic, kalkseifendispergierenden mixture of the invention.

The invention is "particularly for granulated detergent compositions, as they are used e.g. for washing processes in the household. Such compositions preferably contain from about 40 to about 80% by weight Soap, based on the weight of the total composition, and can also contain the usual additives detergents, such as alkaline builder salts (builder salts), e.g. sodium carbonate, sodium silicate, sodium sulfate, carboxymethyl cellulose, bleaching agents, e.g. peroxy compounds such as sodium perborate, optical brighteners, coloring additives, perfuming agents and the like. Such Granulated detergent compositions should contain from about 2 to about 50% by weight of the mass the synergistic, lime soap dispersing agent according to the invention Have mixture.

Another advantage of the compositions according to the invention lies in the possibility of preparing them so that solutions of such compositions in hard water only then foam vigorously until all the hardness of the water has been removed and the solution contains enough free soap, to have an effective detergency. This avoids underdosing the composition. At the Addition of high-foaming, synthetic detergents to soap to prevent lime soap from separating arises even at low concentrations of the product, at which there is not enough free soap for one Effective laundry is present, a foam build-up. The ver

109808/1934

consumers are tempted to use too little of the product and only achieves a moderate cleaning effect. This tendency is in the compositions of the invention to avoided, as they only foam strongly when there is already enough free soap for an effective one Washing is available.

The compositions according to the invention result in an effective dispersion of the during the washing process Lime soap. If the washed pieces are rinsed in hard water, the washing solution remaining in the fabric becomes diluted with a large amount of the added hard water. Under these conditions can be a certain amount Lime soap can be formed in undispersed form. According to the present invention, this tendency can be extensive prevented or completely eliminated by adding a little foaming, Alkylene oxide containing, non-ionic detergent from below described type adds. In addition, low-foaming, nonionic detergents are used to Prevent foam from forming in the rinse water.

Suitable alkylene oxide-containing, nonionic, synthetic Detergents of the type useful in the present invention are the following:

1. The polyethylene oxide condensates of alkylphenols and dialkylphenols, e.g. the condensation products of Alkylphenols, the alkyl group of which has about 6 to 12 carbon atoms contains in straight-chain or branched-chain arrangement, with ethylene oxide, the ethylene oxide in Quantities of about 5 to 30 moles of ethylene oxide per mole of alkylphenol is available. In such connections the

109808/1934

Alkyl sub s ti tu ent e.g. of polymerized propylene, diisobutylene, Be derived from oeten or honing,

2. Alkylene oxide-containing, nonionic detergents produced by condensation of ethylene oxide with the product were prepared, which is obtained in the reaction of propylene oxide with ethylenediamine. Here too is a number of compounds are suitable, the properties of which can be adjusted so that a desired GKLeichge weight between the hydrophobic and hydrophilic Koiflponen- th receives. For example, connections give satisfactory results Results,. which is about 40 to about 80 wt .-? 6 Contain polyoxyethylene and have a molecular weight between have about 5000 and about 11,000, these compounds in the reaction of Äthylenoxydgruppen with a hydrophobic bases are formed, as in turn from the reaction product of ethylenediamine with excess propylene oxide is built up and this base has a molecular weight in the range from 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, for example 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 fraction is a distilled coconut alcohol fraction with 10 to 16 carbon atoms and the following approximate distribution of chain length: 2 # - G ₁₀ , 66 £ - C ₁₂ , 23 ° h - C ₁₄ and 9 f> - C ₁ ^. Another preferred compound is the condensation product of one derived from tallow Alcohol with about 3 to about 15 moles of ethylene oxide per mole of tallow alcohol

109808/1934

ic-

get; a special example is the condensation product of 1 mole of tallow alcohol with 4 moles of ethylene oxide (TE,).

4. A known class of alkylene oxide containing, nonionic, synthetic detergents of this type is on the market under the trade name "Pluronic" available. These compounds are made by condensing ethylene oxide with a hydrophobic base, which in turn is obtained by condensation of propylene oxide with propylene glycol. The hydrophobic part the molecule, which is of course insoluble in water, has a molecular weight of about 1500-1800. The addition of polyoxyethylene residues to this hydrophobic Molecular part acts in the direction of increased water solubility of the entire molecule. The liquid character of the product is retained until the polyoxyethylene content is about 50-6 of the total weight of the Condensation product.

5 · Specific examples of the above-mentioned classes of compounds are as follows only to illustrate the type in question are listed: Nonylphenone, which is either about 5 or was condensed with about 30 moles of ethylene oxide per mole of phenol, 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 moles of ethylene oxide with one mole of tridecanol. Further illustrative examples are dodecylphenol, which with 12 mol Ethylene oxide was condensed per mole of phenol; Dinonylphenol, which condenses with 15 moles of ethylene oxide per mole of phenol became; Dodecyl mercaptan condensed with 10 moles of ethylene oxide per mole of mercaptan; Bis- (N-2-hydroxy-

109808/1934

ethyl) lauramide; Nonylphenol, which is enoxyd with 20 moles of ethyl condensed per mole of nonylphenol; Myristyl alcohol, the alcohol with 10 moles of ethylene oxide per mole of myristyl was condensed; Lauramide, which was condensed with 15 moles of ethylene oxide per mole of lauramide, and diisooctylphenol, which was condensed with 15 moles of ethylene oxide.

The preferred nonionic detergent is the condensation product from 1 mole of hydrogenated tallow fatty alcohol with 4 moles of ethylene oxide. The proportion of the little foaming nonionic detergent in the composition can constitute up to about 20% by weight of the soap content and is preferably at least about 2 to about 15% of the soap content of the composition.

The invention is illustrated by the following examples:

Example 1;

It becomes a spray-dried, granulated soap composition produced, the proportions in. finished product are the following:

Sodium soap (20 94 coconut oil

: 80% sebum) 54

Sodium salt of N-lauryl-ß-

alanins 6

109808/1934

Sodium poly (itaconate acrylate) (4: 1 on a molar basis; specific viscosity of a 1% by weight solution in dimethylformamide at room temperature: 0.40; Equivalent weight 65.8)

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

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.,

which are incorporated into the soap) 1.1

Moisture content 14.7

Perfume 0.33

Example 2;

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

109808/1934

1Ä17172

G-ew

Sodium soap (20 # coconut -

oil: 80 io sebum) 52

Sodium salt of N-lauryl-β-alanine 6 Sodium tripolyphosphate (Na ₁ -P. ^) -, _Q ) 6 Sodium silicate solids

(Ratio SiO ₂ : Ha ₃ O = 2.4: 1) 10.25 sodium carboxymethyl cellulose 0.34 ethylenediamine etranat rium -

tetraacetate 0.18

Optical brightener 0.20

Sodium perborate tetrahydrate

(KaBO, .4H ₂ O). 0.9

Various additives (inorganic 1.1

salt, glycerin, unsaponified fat, etc., which are incorporated into the soap will)

Moisture content 14.70

• Perfumes ■ 0.33 ·

Example 3:

Bs becomes a spray dried, granulated soap composition manufactured, whereby the proportions in the finished product are as follows:

Nitrium soap (20 94 coconut - 54

'6% j 80 % sebum)

3 ^ (N »N-dimethyl-IT-dodeoyl) -ammonio-2- 6 hydroypropane-1-sulfonate

109808/1934

1517172

Gi-ew .- ^ o:

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

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

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

Sodium carboxymethyl cellulose

Ethylenediamine tetra-sodium tetraacetate

Optical brightener

Sodium perborate tetrahydrate

(NaBO _3. 4H ₂ O) 8.9

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

which are 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

2 , 25 10 2 34 0, 18th ο, 20th 0,

Sodium Soap (20 96 Coconut Oil: 80 #

Sebum) 52

3- (Ν, Ν-dimethyl-N-dodecyl) -aamonio-2-hydroxypropane-1-sulfonate 3

109808/1034

Dodecyldimethylamine oxide 3

Sodium tripolyphosphate 4

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

Condensation product from 1 WoI hydrogenated Tallow alcohol and 4 moles of ethylene oxide 2

Sodium carboxymethyl cellulose 0.34 Ethylenediamine tetra sodium -

tetraacetate "0.18

Optical brightener 0.20

Natri maperboate tetrahydrate

(NaBO _5. 4H ₂ O) "8.9

Various additives (inorganic salt,

Glycerin, unsaponified fat, etc.,

which are incorporated into the soap) 1.1

Moisture content 14.70

Parfuini grounding agent 0.33

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

When used with hard water in a household washing machine, the products of the examples give to 4 below the concentration at which the total The hardness of the water is eliminated and the concentration the free soap for an effective washing effect

109808/1934

sufficient, no foam. The washing liquid is free of lime soap sludge. Remains in the washing machine no precipitation of lime soap. When rinsing, the water is free from lime soap sludge and also foam-free.

^{Similar results are obtained if the sodium salt of dodecylaminomethane carboxylic acid, N, N 1} -dodecylethylenediaminediacetic acid, N-methyltaurine or N-methyl-N'-sulfophenylethylenediamine is used in place of N-lauryl-ß-alanine; when the 3- (N, N-dimethyl-N-dodecyl) -ammonio-2-hydroxypropanesulfonate is replaced by 3- (N-dodecyl-N, N-dimethylammonio) -propane-1-sulfonate, or when 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

Sodium soap (20% coconut oil:
80% sebum) 60 Sodium salt of the dodecylamino
methane carboxylic acid 10 Sodium polyitaconate (as in Bei
game 3) 10 water 17th Various accessories 3.

109S08 / 1934

Example 6;

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

Sodium soap ($ 40 coconut

oil: 60 # sebum) 60

Sodium salt of N-lauryl-ß-

alanins 7

Monoethanolammoniump olymaleate (specific viscosity of a 1% strength by weight solution in dimethylformamide at room temperature 0.21; Equivalent weighted 58) 14

Water 17

Various accessories 2.

Example 7:

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

w.

Sodium Soap (100 # Coconut Oil)

Sodium salt of Ν, ΙΓ'-dodecyl ethylenediaminediacetic acid

Sodium poly (itaconate aconitate) (1: 1, on a molar basis; specific viscosity of a 1 wt. # solution in dimethylformamide at room temperature 0.12} equivalent weight 60.8)

Water 9

Various accessories 1

109808/1934

Example 8:

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

Sodium Soap ( $ 60> Coconut Oil:

40 i * tallow) 70

Sodium salt of N-methyltaurine 10

Sodium poly (ethylene maleate) (1: 1 on a molar basis; specific Viscosity of a 1 wt .- ^ - strength solution in dimethylformamide 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 a 1 wt .- # solution in dimethyl formamide at room temperature 1.58; Equivalent weight 72) 5

109808/1934

Weight -4> i

Water 4

Various accessories 1

Example 10;

A soap composition is made that results in a product with the following composition:

Weight

Sodium Soap ( $ 20> Coconut -

oil: 80 f> sebum) 40

Sodium salt of N-lauryl-ß-ala-

nins 15

70 $> Potassium polymal eat ': 30 <$> Polymaleic acid (1.4: 1, on a molar basis, specific viscosity of a 1% by weight solution in dimethylformamide at room temperature 0.39; equivalent weight 58)' 15

Sodium silicate solids (SiO ₂ : Na ₂ O ratio = 2.4: 1) 11

Water 6

Sodium perborate tetrahydrate

(NaBO,. 4H ₂ O) 10

Various accessories 3.

Example 11;

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

109808/1934.

1Ä17172

- 56 -

Sodium soap (20 # coconut

oil: 80 # sebum) 65

Sodium salt of N-lauryl-ß-ala-

nins 10

liatrium polyitaconate (specific viscosity of a 1 wt Solution in dimethylformamide "at room temperature 0.29; equivalent weight 65) 10

Nonylphenol, which condenses with about 5 moles of ethylene oxide per mole of alcohol became 10

Water 4

Various accessories 1.

Example 12:

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

Sodium Soap ( $ 20> Coconut Oil:

$ 80 tallow) 60

(N-Lauryl-li, U-dimethyl ammoni ο) methane carboxylate 10

Sodium salt of polyitaconate

(as in example 3) 10

Water 17

Various accessories 3.

109808/1934

Example 13:

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

Grew.-βέ:

Sodium soap (50 % coconut -

oil: 50 f> sebum) 50

Becyldimethylamine oxide 30

Monoethanolammonium polymaleate

(as in example 6) 10

Water '9

Various accessories 1.

Example, 14:

A liquid soap composition is made, which results in a product with the following composition:

ffew.-ft:

Sodium soap (80 # coconut -

oil ι 20 $> sebum). 15th

Tetradecyldimethylphosphine oxide 10 sodium tripolyphosphate 5

Water 70 *

Example 15:

Ee a mass for bars of soap is made,

109808/1934

- 38 resulting in a product with the following composition:

Weight -4> :

Sodium Soap ( $ 100> Coconut -

nut oil)

3-Hydroxytridecylmethylsul-

foxyd

Sodium hexametaphosphate water 5 -

Example 16:

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

Gfew. -ti » :

Sodium soap (20 # coconut -
oil: 80 + sebum) 45 3-hydroxy-4-decoxybutylmethyl-
sulfoxide 22.5 Sodium salt of nitrilotri
acetic acid 22.5 water 7th Various accessories 3. Example 17:

It is a soap mass produced _0, resulting in a product with the following composition:

109808/1934

i 1S17172

Sodium soap (20 % coconut -

oil: 80 io sebum)

Dodecyl bis (hydroxym ethyl) phos -

phinoxyd

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 provide a superior, valuable, synergi sti see s lime eifendi energy storage capacity.

The soap compositions according to the invention, in particular the bar-shaped products, can be germicidal Means are added to make the products anti septic To give properties.

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

109808/1934.

Claims (1)

Claims; 1. Soap composition with improved lime soap disp ergi ervennögen, characterized in that they essentially consist of (I) a fatty acid soap, and (II) at least 5 wt. -4> (based on the weight of the fatty acid soap) of a synergistic, lime soap-dispersing mixture A) at least one synthetic detergent obtained from the 1) a zwitterion in its molecular structure or a detergent containing a semi-polar bond »and 2) an amphoteric, synthetic detergent to comprehensive Group is selected, and B) at least one water-soluble salt of compounds from the 1) linear, polymeric phosphoric acids with more than 2 phosphorus atoms in the molecule; 2) linear, polymeric carboxylic acids, which in the acid form have a molecular weight of at least 350 and an equivalent weight between 50 and 80 and that of a monomeric carboxylic acid with at least 2 carboxyl groups in the Documents (Art 7 % 1 Para. Λ ; »ι. L sentence 3 of the Amendmentunaeflaa. V. ♦ · 9 · t £ M>7> 109808/1934 Molecule are derived, and 3) group comprising nitrilotriacetic acid was selected are, where the weight ratio of A) to B) is about 1: 4 to about 4: 1. 2. Soap composition with improved lime soap dispersibility according to claim ^ 1, characterized in that the synergistic, lime soap-dispersing Mixture from about 5 to about 100% by weight of the fatty acid soap matters. 3. Soap composition according to claim 1, characterized in that the synergistic, lime soap-dispersing mixture is about 20 to about 80 wt .- $ of the fatty acid soap matters. 4. Soap composition according to claim 1, characterized characterized in that the weight ratio of A) to B) is about 1; 2 to 2: 1. 5. Soap composition according to claim 1 »characterized in that it consists essentially of about 10 to about 95 wt .- ^ of a fatty acid _{soap having about 10 to about 20 carbon atoms and about 5 to about 100 wt» - $ s} based on the weight of the soap , the synergistic, lime soap dispersing mixture ". 6 * Soap preparation aach Afispra & b. X marked in liquid fora, dadtireli.,. _; that si © i® xieGsatX from about 10 Ms © ttia 30 G-ex-j .- ^ ot ^ a 10 bis eti-ja ao 1 ens toff atoms estlial tender fatty acid sif ο imd otue, 0 ₂ 3 Ms about 30 wt .- ^ of the synergistic, lime soap dispersant Mixture consists, with the remainder being a liquid carrier. 7. Soap composition according to claim 1 in bar form, characterized in that it is substantially from about 80 to about 95% by weight fatty acid soap with about 10 up to about 20 carbon atoms and about 5 to about 20% by weight of the synergistic lime soap dispersant Mixture consists. 8. Soap composition according to claim 1 in the form of a granulated cleaning agent, characterized in that that they are about 40 to about 80 wt .- ^ of a fatty acid soap having from about 10 to about 20 carbon atoms as well about 2 to about 50% by weight of the synergistic lime soap contains end-dispersing mixture. 9. Soap composition according to claim 5 »characterized in that it also contains up to about 20 wt .- $ * based on the weight of the fatty acid soap, a nonionic, alkyl enoxydhäl ti gene, synthetic detergent contains. 10. Soap composition according to claim 9 » characterized in that it contains about 2 to about 15 wt .- $, based on the weight of the fatty acid soap, of the nonionic, synthetic, alkylene oxide-containing detergent. For: Thö Procter ^) & (ramble Company Lawyer