CH639997A5 - SOAP COMPOSITION. - Google Patents

Description

The present invention relates to a soap composition with improved crack resistance. It contains anionic polymaleic acid electrolytes and is characterized by a more stable and creamy foam and by a larger foam volume than those compositions which do not contain any anionic polymaleic acid electrolytes. The products according to the invention generally have remarkable effects which make the skin supple and smooth and, in addition, have anti-inflammatory properties.

Soap compositions, and in particular bars of soap, generally contain up to about 20% water, the water being an essential component in the soap that enables the soap to be processed and shaped into bars of soap. The presence of water in soap bars creates problems with cracking in the finished soap, especially with aging. A change in the crystalline phase undoubtedly takes place during aging, and the escape of moisture contributes to the soap bars not being dimensionally stable.

It has now been found that certain anionic poly-maleic acid compounds, when added to soap compositions and made soap bars from such mixtures, give the soap bars excellent dimensional stability and excellent resistance to cracking. In addition, it has been found that many other desirable properties of the soap are beneficially influenced. It was found that the soap bars obtained according to the invention gave a creamier, longer-lasting foam and also a larger volume of foam. A clear softening or "softening" effect was also found, which was associated with a certain "smoothness" on the skin.

Numerous polymeric compounds have been added to soap, e.g. is known from US-PS 33 83 320 to use a thermoplastic resin as a matrix for soap to maintain the original dimensions of the soap bar. According to GB-PS 1288805, water-insoluble polymer particles are added to the soap in order to give it a smooth feel. From US-PS 3819525 it is known to add solid, granulated polyvinyl alcohol, the particles of which pass through mesh screens with an aperture of 0.71-0.044 mm, to the soap in order to give the soap a gentle, abrasive property for skin cleaning. U.S. Patent 3,278,444 describes polymeric sulfonates such as e.g. Polystyrene sulfonate, which is added to the soap to improve the soap's resistance to spillage. In US Pat. No. 2,938,887 it is proposed to use copolymers of an aromatic vinyl compound and a diester of an unsaturated dicarboxylic acid as dispersants for limescale deposits.

Polymaleic acid compounds are known in non-bar detergent compositions, especially as a phosphate substitute, see US Pat. No. 3,764,559. They are also said to serve to improve the maintenance of the whiteness of the laundry, see US Pat. No. 3,794,605 Soap is used as an additive to non-ionic soap mixer slurries to produce spray dried particulate products.

The object of the present invention is to create a soap composition which can be produced in bar form and which, in contrast to the soap compositions known hitherto, is distinguished by improved resistance to crack formation, a stable, creamy foam with large foam volume and with remarkable smoothing and skin-smoothing effects .

This object is achieved according to the invention by a soap composition which is characterized by a content of a water-soluble alkali, ammonium or low molecular weight amine salt of a Cs to C24 fatty acid and 0.1 to 15% by weight, based on the amount of the fatty acid salt , a mixed polymer

(1) maleic or fumaric anhydride or maleic or fumaric acid or a lower alkyl-substituted homolog thereof and / or an optionally in Ci

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639 997

C4-alkyl substituted C1-C4 alkyl partial esters of the acids mentioned or their lower alkyl-substituted homologues and

(2) a vinyl lactam of the formula

CH = CH2

wherein A forms the supplement to a 5-7-membered hetero ring and the additional ring members consist of carbon, nitrogen, oxygen and / or sulfur atoms, a vinyl ester of an aliphatic monocarboxylic acid with 2 to 6 C atoms, a Ci to C4 alkyl vinyl ether or their mixtures.

Accordingly, suitable anionic maleic acid copolymers in the soap composition according to the invention are particularly those which consist of a) maleic anhydride, maleic acid and / or their partial C 1 -C 4 -alkyl esters or e.g. Ci to C4 alkyl esters substituted with OH groups etc. and b) Ci to C4 alkyl vinyl ethers, vinyl esters of C2 to Cö monocarboxylic acids, vinyl lactams, for example vinyl pyrrolidone, vinyl morphbiolinone, vinyl oxazolidinone etc., that is to say compounds with 5 -, 6- "or 7-membered hetero rings, and mixtures thereof.

The mixed or copolymers in the form of their free acid or their anhydride described here and contained in the soap composition according to the invention should be mixed with their water-soluble salts, e.g. be equivalent to the sodium, potassium, ammonium and amine salts described above. Similarly, the maleic acid moiety also includes fumaric acid, citraconic acid and other Ci-C4 alkyl substituted maleic acid groups.

The copolymers are generally 1: 1 equimolar products, but they can also have molar ratios of maleic anhydride to comonomers in the range from about 9: 1 to 1: 9. The amount of the anionic maleic acid copolymer is in the range from 0.1 to about 15% by weight, preferably 0.5 to 10% by weight, very particularly preferably from 1 to 10% by weight, based on the dry weight of the Soap. Particularly excellent effects are obtained with a content of 1 to 5% by weight of the copolymer, based on the weight of the soap.

The soap compositions according to the invention contain a water-soluble salt of a fatty acid, for example the sodium, potassium and other alkali salts, furthermore ammonium salts and low molecular weight amine salts are suitable for the purpose according to the invention, e.g. Mono-, di- and triethanol-, pentaethoxyethanol-, triethoxymethylamine and the like. Like. The sodium soaps are preferred. The fatty acids are the Cs to C24 acids, particularly preferably the C12 to Cis acids, which can be saturated, mono- or polyunsaturated. The commercial soaps are mainly derived from tallow and / or hydrogenated tallow (tallow fatty acids and hydrogenated tallow fatty acids) and coconut oil and / or hydrogenated coconut oil (i.e. fatty acids) and their mixtures. Other common fatty acid sources are cottonseed oil, soybean oil, corn oil, olive oil, palm oil, peanut oil, fish oils, etc. Preferred soaps contain about 50 to 95% by weight of tallow fatty acids and about 5 to 50% by weight of coconut fatty acids. Soaps with about 70 to 90% by weight of tallow fatty acids and about 10 to 30% by weight of coconut fatty acids are particularly preferred. Synthetic fatty acids can also be used. These contain a considerable amount (10 to 50% by weight) of branched fatty acids. A particularly suitable soap contains 80 to 88% by weight of tallow fatty acids and about 12 to 20% by weight of coconut fatty acids.

The soap compositions according to the invention can, based on the soap according to the invention, a smaller amount, e.g. 1 to 10% by weight, up to a significant amount (e.g., about 20 to 100% by weight) of a non-soap based detergent. Examples are α-sulfonated C10 to Cîo fatty acid esters described in US Pat. No. 3,223,645, higher (Ciò to C20) alkyl ether sulfonates with 1 to 30 moles of ethylene oxide, (Ciò to C20) paraffin sulfonates, (C10- to C20-) a-olefin sulfonates, C10 to C2o fatty acid monoglyceride sulfates and alkylbenzenesulfonates, for example Decyl, dodecyl, tri-decyl, tetradecyl, pentadecyl (linear or branched) benzene sulfonates. If desired, small amounts, e.g. about 1 to 20% by weight of a nonionic detergent, preferably those derived from linear aliphatic alcohols with 9 to 18 carbon atoms and ethylene oxide (about 1 to 50 moles). Mixtures of ethylene and propylene oxide can also be used, e.g. in a molar ratio of propylene oxide: ethylene oxide from about 5: 1 to 1:10.

Other conventional and conventional additives and auxiliaries can also be added to the soap compositions according to the invention, e.g. Antioxidants in an amount of about 0.01 to 5% by weight, pigments and dyes (about 0.01 to 10% by weight), germicides, bactericides and fungicides (about 0.01 to 5% by weight), Perfumes, inorganic fillers (about 0.1 to 10% by weight), dampening solutions (about 0.1 to 10% by weight), conditioning agents (about 0.1 to 10% by weight), chelating agents (about 0 , 1 to 5 wt .-%) and the like.

The anionic maleic acid copolymers used in the composition according to the invention can be added to the soap composition in any suitable stage of soap production. The polymers of the kettle soap (usually about 60 to 70% by weight of soap and 30 to 40% by weight of water) or the soap flakes can be added with or without water to facilitate homogenization. The soap and polymers can be mixed in a conventional rolling mill, a Sigma belt mixer or a soap mixer or amalgamator, and then the mixture is preferably extruded (e.g. extruded in a vacuum) and extruded into the final bar shape. Both room temperatures and higher temperatures of about 60 to 120 ° C. can be used, the higher temperatures often facilitating solubility, flowability, mixing, processing and the like. The term “soap bar” is used here in the sense that it means any solid shape in any size and shape. For example, a distinction is made between compositions in the form of granules, particles, beads, pasta and the like.

These anionic maleic acid copolymers which can be used in the composition according to the invention are known and can be prepared by known conventional processes for the copolymerization of maleic anhydride (or its partial esters, e.g. monoalkyl esters) with the selected monomer (s). As a rule, radical polymerization (e.g. with benzoyl peroxide) is the most suitable method. Examples of certain mixed polymers which are suitable for the soap compositions according to the invention are the following, the molar ratio used being indicated in brackets:

a) vinyl pyrrolidone maleic anhydride (1: 1);

b) vinyl pyrrolidone monomethyl maleate (1: 1);

c) vinyl pyrrolidone monoethyl maleate (1: 2);

d) vinyl pyrrolidone monohydroxyethyl maleate (1: 3);

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e) vinyl acetate monomethyl maleate (1: 1);

f) '/ s-methyl ester of (a);

g) '/ j methyl ester of (a);

h) methyl vinyl ether monomethyl maleate (1: 1);

i) methyl vinyl ether-maleic anhydride (2: 3);

j) 'A methyl ester of (i);

k) '/ i-n-butyl ester of (i);

1) Isopropyl vinyl ether monoethyl maleate (1: 1).

The polymeric partial esters can also be prepared from the corresponding maleic anhydride copolymers and alcohol, e.g. 1 mole of alcohol per mole of maleic anhydride in copolymers to obtain the half ester. For example, 15.6 g of methyl vinyl ether-maleic anhydride copolymer (1: 1) can be dissolved in excess methyl alcohol (e.g. 100 ml) at room temperature to obtain the '/ 2-methyl ester.

The copolymers suitable for the purpose according to the invention are moreover characterized by average molecular weights of in particular about 50,000 to 5,000,000, preferably from about 100,000 to 1,500,000, very particularly preferably from about 150,000 to 1,000,000.

The invention is illustrated by the following examples, without being restricted thereto. Unless otherwise stated, all quantities and ratios are by weight.

example 1

18.0 g of a vinyl acetate-monomethyl maleate mixed polymer (ratio 1: 1, molecular weight 500,000) were dissolved in 84.0 g of hot water (70 ° C.). 250 g of soap flakes (sodium soap made from 85% tallow fatty acids and 15% coconut fatty acids) were added to give a viscous paste which was ground on a small three-roll mill. The shear of the rollers reduced the viscosity of the mixture, whereupon another 248 g of soap flakes were added and grinding continued. The mixture was then sent through the three rollers of a large rolling mill. The mixture was then treated without vacuum treatment, i.e. without ventilation, pressed into bars of soap. The soap bars showed a high degree of slipperiness, and when they washed their hands they formed a lot of creamy, small-pored, firm foam. The hands felt very smooth.

Example 2

Small amounts of 1 l of water were added to 2500 g of soap flakes from Example 1 in a Sigma * belt mixer provided with a heating jacket, the jacket temperature being kept at 104.4 to 110.0 ° C. with the aid of steam. A very viscous creamy paste was obtained. 120 g of powder of the copolymer from Example 1 were slowly added to this paste, the temperature rising to about 101.5 ° C. After mixing for one hour, a smooth, homogeneous, white paste was obtained. This paste was dried in a drying cabinet with circulation ventilation at 60 ° C. overnight. The product obtained was then mixed again in the Sig-ma belt mixer, ground on a three-roll mill, spread out and then air-dried for about 70 hours. The moisture content of the soap composition was 3.4%. The moisture content was then adjusted to 13.8% in an amalgamator, and 20 g of titanium dioxide and perfume were added. The mass was then ground again to obtain flakes. The flakes were vacuum extruded and extruded into excellent soap bars with an initial hardness of 85 to 90. The soap bars were pressed in the usual way using a standardized glycerin / salt solution as a separating agent. There was no sticking to the mold.

The soap bars obtained had a large foam capacity, showed a pleasant slipperiness on the skin, caused no irritation on the face and softened the skin. All of these features were rated better than the same soap without the polymer additive according to the invention.

The following results were obtained when testing for wet crack formation:

Vi hour wet

1 hour wet

Crack test index

Crack test index

Control soap bar 1

50

43

Soap bar

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Example 2

1 The control soap has the same composition and was produced in exactly the same way as the soap according to Example 2; however, it contained no polymer additive.

The Vi-Hour crack test is carried out in the following way: first, about 25 to 30% of one surface of the soap bar is scraped off. The soap bar is then immersed in water at 24 ° C. for 30 minutes and then dried at room temperature overnight. The number and strength of the cracks on the scraped surface are determined. The strength of the cracks is rated on a scale from 1 to 5, with a value of 1 for pencil or hairline cracks and a value of 5 for deep and wide cracks. The number of scales multiplied by the number of cracks gives the number given in the table above.

The 1-hour crack test is carried out similarly, except that 10% are scraped off from the opposing surfaces and the soap bar is left in water for one hour.

The hardness test is carried out with a Dietert hardness meter and gives values from 0 to 100, where 0 indicates the lowest and 100 the highest. The test uses a resilient ball to measure the indentation of the ball on the surface of the soap bar. Values of 85 are the best.

Example 3

Example 2 was repeated, but using 175 g of copolymer (5%). The finished soap bars showed an initial hardness of 88 to 93 and a final moisture content of 10%.

Example 4

Example 2 was repeated using 87.5 g of copolymer, and excellent soap bars with an extrusion hardness of 88 to 94 were obtained. In the Vi-hour crack test, the soap bar had a wet crack index of 20.

Example 5

Soap bars with 0%, 1%, 3% and 5% copolymer from Example 1 were produced. In the process, kettle soap (68% soap solids, same fatty acid composition as in the previous examples) was mixed in a closed mixer (to avoid water loss) at 121.1 ° C until it became transparent (glassy). The mass was then ground and mixed with 2.0 g of titanium dioxide and 1.5 g of perfume, then ground again and extruded.

Moisture content, hardness and crack index are summarized in the following table.

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639 997

% Polymer

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'/ z hour

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Wet crack index

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10.6

85-88

126

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89-91

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89-92

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Example 6

To a mixture of kettle soap (68% soap solids, chemically the soap fatty acids are the same as in example 1) in a reed mixer, 4% by weight, based on the soap solids, of a 1: 1 maleic anhydride-vinyl acetate copolymer (molecular weight 500,000 ) added. The temperature of the mixture was held at 112.8 to 180.6 ° C for 65 minutes. The mixture was then cooled away from the mixer, then ground twice, extruded and finally pressed into pieces. The following results were obtained:

Hardness 96-97

Flake moisture 13.0%

Soap bar moisture 7.5%

'/î hour crack index 35

Control soap comparison index (without 120 polymers)

Example 7

Example 6 was repeated using the copolymer from Example 1. A particularly good soap bar was produced. Foam behavior (duration) and foam volume were excellent. The foam structure was very dense, creamy (small bubbles), and the foam stability was excellent. The soap bars obtained were tough and had excellent impact resistance. The "wet slipperiness" is noticeable, but the soap dries very quickly without leaving a gelatinous, soft or slippery surface. The hardness of the soap bar was 94-95, the moisture content 6.2% and the 1/2 hour crack index 16. For comparison, a corresponding crack index of 120 was obtained for the control soap.

Example 8

Example 6 was repeated using 4% by weight based on the soap solids content, Gantrez S-97.

a methyl vinyl ether-maleic acid copolymer, ratio 1: 1. The soap bars all had excellent properties. The hardness was 91-92, the moisture content of the pieces 8.3%, the 1 / hour wet crack index 9.

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Example 9

Example 6 was repeated using 4% by weight, based on the soap solids, of an alternating copolymer of N-vinylpyrrolidone and maleic anhydride in a ratio of 1: 1. The manufacturing process was the same, except that the jacket temperature of the reed mixer was 115.6 to 120 ° C. The foam was excellent, there was no scab and the drying was very quick. The wet crack index was 9 and the tested bar of soap showed no end cracks.

Example 10

Example 6 was repeated using the following polymers in the amounts indicated instead of the 20 copolymers from Example 6:

a) N-vinylpyrrolidone monomethyl maleate (1: 1) 3%

b) 3% N-vinyl pyrrolidone mono- (hydroxyethyl) maleate

25 (hl)

c) ethyl vinyl ether monomethyl maleate (1: 1) 4%

d) isobutyl vinyl ether monoethyl maleate (1: 2) 4%

e) Methyl vinyl ether monomethyl maleate (1: 1) 3%

f) N-vinyloxazolidinone maleic anhydride 4%

*> (1: 1)

g) '/ 2-methyl ester of (0 4%

h) '/ 4-isobutyl ester of (0 4%

i) N-vinylmorpholinone maleic anhydride 4%

(1: 1)

r> j) '/2-Methoxytriglykol-[CHjO(CH2CH20).iH[- 4%

Esters of the copolymer from Example 6

k) '/ 4-methyl ester of the polymer from Example 6 4%

1)% methyl ester of the polymer from Example 6 4%

The present invention has been explained in more detail with regard to the preferred embodiments. It is understood that possible changes and variations, which are suggested to the person skilled in the art through the invention, also fall under the claimed subject matter of the invention.

G

Claims (9)

639 997 2nd PATENT CLAIMS 1. Soap composition, characterized by a content of a water-soluble alkali, ammonium or low molecular weight amine salt of a Cs to C24 fatty acid and 0.1 to 15% by weight, based on the amount of the fatty acid salt, of a copolymer from (a ) Maleic or fumaric anhydride or maleic or fumaric acid or a lower alkyl-substituted homologue thereof and / or a C1-C4 alkyl partial ester of the acids mentioned or their lower alkyl-substituted homologues optionally substituted in the C1-C4 alkyl group and (b) a vinyl lactam of the formula CH = CH2 wherein A forms the supplement to a 5-7-membered hetero ring and the additional ring members consist of carbon, nitrogen, oxygen and / or sulfur atoms, a vinyl ester of an aliphatic monocarboxylic acid with 2 to 6 C atoms, a Ci to C4 alkyl vinyl ether or their mixtures. 2. Soap composition according to claim 1, characterized in that the fatty acid salt is a sodium salt of a C12 to cis fatty acid. 3. Soap composition according to claim 1, characterized in that the fatty acid salt consists of a mixture of sodium salts of fatty acids consisting of 70 to 90 wt .-% tallow and / or hydrogenated tallow and 10 to 30 wt .-% coconut oil and / or Derive hydrogenated coconut oil. 4. Soap composition according to claim 1, characterized in that the copolymer is a copolymer of (a) the partial methyl ester of maleic acid and (b) vinyl acetate. 5. Soap composition according to claim 4, characterized in that the copolymer is an IA to '/ 2-PartiaI ester. 6. Soap composition according to claim 1, characterized in that the copolymer is a vinylpyrrole-don-maleic anhydride copolymer. 7. Soap composition according to claim 1, characterized in that it contains 10 to 100 wt .-%, based on the total weight of the soap, of an anionic or nonionic detergent based on non-soap. 8. Soap composition according to claim 1, characterized in that the copolymer is a vinyl acetate-maleic anhydride copolymer. 9. Soap composition according to claim 1, characterized in that the copolymer is a methyl vinyl ether-maleic acid copolymer.