CH651584A5 - Detergent composition. - Google Patents

Description

651584

2nd

PATENT CLAIMS 1. A mildly irritating detergent and cleaning agent composition, characterized in that it is an active ingredient

(a) 1 to 50% by weight of an amphoteric fatty acid complex of the formula r O 1

II

RIC-0

0.

i

H

■ Al A2

©

wherein Ri is alkyl or substituted alkyl of 6-18 carbon atoms; R2 alkyl with 8-18 carbon atoms or alkylamido of the formula

O 2 Il I

R3-C-N YH—

where R3 is alkyl of 8-18 carbon atoms,

Z is H or lower alkyl with 1-4 carbon atoms and

- 0 -Ii

Rl-C-0

0

Y is lower alkylene with 1 -4 carbon atoms,

Ai and Ai are the same or different and are from the following

Group of anionic salt parts, selected are:

5 -fCHaCHi-COOXJn -fCH2-COOX] ",

- [CH2CH0H-CH2-S03X] ",

• {CH2-CH0H-CH2-0P03X] n

10 in which X is a water-soluble cation and n is an integer of 1 or 2,

with the proviso that if only one of Ai and A2 is selected from the above anionic salt moieties, the other is lower alkyl or lower hydroxyalkyl having 1-4 carbons and

(b) 2-50% by weight of an anionic detergent selected from the group consisting of sulfosuccinates, alkyl ether carboxylates, a-sulfo fatty acids and ester car-boxylates, alkyl succinates, alkyl sarcosinates and fatty acid 20 Condensates.

2. Composition according to claim 1, characterized in that the amphoteric fatty acid complex and the anionic surfactant are present in a ratio of 1: 4 to 4: 1.

2s 3. Composition according to claim 1, characterized in that the amphoteric fatty acid complex has the formula

O H

li I /

Cllîi23 "C" 'N (CH2) 2 "N \

H

C2H4OH

CH2COOÎ

having,

where Ri is a CnH23-CisH37 mixture.

35 4. Composition according to claim 1, characterized in that the amphoteric fatty acid complex has the formula

O

II

RiC-0

0

/

c12h25-N \

, CH2CH2COONa

I ^ CH2CH2COONa

H

having,

where Ri is a CsHn-CisHn mixture.

O II

C11H23C ~ °

4s 5. Composition according to claim 1, characterized in that the amphoteric fatty acid complex has the formula

0

H ^ CK2CH2COONa

Cl4H29 ~ N

\

CH2CH2COONa

©

having.

6. Composition according to claim 1, characterized in that the amphoteric fatty acid complex makes up 5-15% by weight of the total composition.

7. The composition according to claim 1, characterized in that the anionic surfactant is an alkyl sarcosinate.

Composition according to claim 1, characterized in that the anionic surfactant is a sulfosuccinate.

9. The composition according to claim 1, characterized in that the anionic surfactant is an alkyl succinate.

10. The composition according to claim 1, characterized

55 indicates that the anionic surfactant makes up 5-40% by weight of the total composition.

eo

Detergent and cleanser compositions intended for use as personal cleansing products not only need to have good cleaning and lathering characteristics, but they must either be non-irritating to the skin and eyes or have a low irritant potential to have.

Synthetic detergents useful in such detergent and cleaning compositions,

3rd

651584

are well known and include anionic, cationic, amphoteric and nonionic detergents or surfactants. The surfactants generally show the superior foaming, cleaning and quality properties than the anionic detergents. Accordingly, most detergent and cleanser formulations intended for personal use contain anionic surfactants as one of the active ingredients. However, these surfactants tend to be very irritating to the skin and eyes in the amounts commonly used, i.e. above 10% by weight of the total composition. For this reason, detergent compositions intended for personal use and containing anionic surfactants are modified by substituting a significant amount of nonionic surfactants, which are generally mild, despite the less effective foaming and cleaning ability. Certain amphoteric surfactants have been reported to have little eye irritation potential. Although numerous detergent and cleaning agent compositions are commercially available, there is still a need for compositions in which the irritant effect is substantially eliminated without sacrificing other desired properties, such as cleaning and foaming attributes.

Various US patents describe compositions in which both amphoteric and nonionic surfactants are incorporated in the detergent compositions containing anionic surfactants. For example, U.S. Patent Nos. 2,999,069 and 3,055,836 describe shampoo compositions which contain certain mixtures of ethoxylated anionic, amphoteric and polyethoxylated nonionic surfactants. U.S. Patent No. 3,928,251 describes shampoo compositions which contain certain mixtures of anionic, nonionic and zwitterionic surfactants. Similarly, U.S. Patent No. 3,950,417 describes shampoo compositions which are said to have low eye irritation. In these compositions, nonionic and amphoteric surfactants have been added to modify the anionic surfactants. All of these compositions comprise a nonionic surfactant as an essential component as well as an anionic surfactant and, as mentioned above, these surfactants have several disadvantages. ^

It is therefore an object of the invention to provide improved detergent and cleaning agent compositions; which have a low potential for irritation to the eyes and the skin and have good foaming properties, including excellent foam stability.

Further objects of this invention are set forth in, or are obvious from, the following detailed description of this invention. The above objectives and further features and advantages of the present invention are achieved by detergent and cleaning agent compositions which contain a synergistic mixture of surface-active agents which have a low irritant effect on the eyes and on the skin and have good foaming properties. More specifically, the present invention relates to detergent and detergent compositions containing a synergistic mixture of a specific amphoteric fatty acid complex and specific anionic surfactants which have at least one carboxylic acid portion.

s The detergent and cleaning agent compositions according to the invention are now characterized in that they are active ingredients

(a) 1 to 50% by weight of an amphoteric fatty acid complex of the formula r o -

II

RjtC-0

©

15

R2-K

■ A1

I ^ A2

H

©

wherein Ri is alkyl or substituted alkyl of 6-18 carbon atoms; R2 alkyl with 8-18 carbon atoms or alkylamido of the formula

0 2

25th

P.3-C-N-

where R3 is alkyl of 8-18 carbon atoms,

Z is H or lower alkyl with 1-4 carbon atoms and

30 Y is lower alkylene with 1-4 carbon atoms,

Ai and A2 are the same or different and are selected from the following group of anionic salt parts:

- [CH2CH2-COOX] "

35 -fCH2-COOX] n,

-fCH2CH0H-CH2-S03X] n,

-tCHîCHOH-CHî-OPCbXln wherein X is a water-soluble cation, preferably Na +, 40 K +, Ca ++, Mg ++ etc., n denotes an integer of 1 or 2, with the proviso that if only one of the residues Ai and A2 is from the above anionic salt moieties, which is other lower alkyl or lower hydroxyalkyl of 1-4 carbon atoms, and 45 (b) 2-50% by weight of an anionic detergent selected from the group consisting of sulfosuccinates, alkyl ether carboxylates, a-sulfo- Fatty acids and ester carboxylates, alkyl succinates, alkyl sarcosinates and fatty acid protein condensates.

The composition according to the invention therefore contains a synergistic mixture of 1 to 50% by weight of an amphoteric fatty acid complex and 2-50% by weight of an anionic detergent, the preferred ratio being 1: 4 to 4: 1. The term "synergistic mixture" as used herein 55 refers to the mixture of two separate compounds that contain a degree of initial foam height and quality that is greater than the sum of the initial foam heights of the individual compounds.

60 The amphoteric fatty acid complexes contained in the composition of the invention are new compounds and are described and claimed in U.S. Patent Application Series 241,862, filed March 9, 1981, and may be in accordance with 65 therein described methods are prepared; the teachings of said patent applications are incorporated herein by this reference.

Representative amphoteric fatty acid complexes, which in

651 584 4

of the composition of the invention include the following:

(A)

0 II

HjL-C-0

0

O H C2H4OH

II I /

fcilH23-C-N (CH2) 2-Nx ± x IXH2COOK

H

©

wherein Ri is a CuH23-CisH37 mixture;

(b)

O

II

R ^ -C-O

O

-, 0

CH ~ CH_COONa / 2 2

c14 * rI29 ~ N \

I CH2CH2COONa H

wherein Ri is an 80% / 20% tallow-coconut fatty acid mixture;

(C)

r 0 -Ii rj_-c-0

0

0 CH3

ch2chohch2so3k

/

R2-C-N- (CH2) 2-N \.

H

CH 2CHOHCH20P03Na 2

0

wherein Ri is tallow fatty acid and R2 is a Ci iH23-Ci7H25 mixture;

(D)

'O'

II

rj ^ c-o

0

ch-chohch-so ,. ✓ 2 2 3

Cl8H37 ~ NN

i ^ ch ^ chohch-so, "H 2 J

-] ©

Mg wherein Ri is a 70% / 30% mixture of lauric and myristic acid;

(£)

9

c11h25 ^ °

0

H CH2CH2COONa "c14h29 ~ n (^

CH2CH2COONa

©

(F)

0 *

II

RIC-0

0

CH2CH2COONa

Cl2H25 ~ N \

^ CH2CH2COONa

©

The sulfosuccinates have the general formula O

where Ri is a C6Hi3-CisH37 mixture.

The amphoteric fatty acid complexes, which in the ss

Compositions of this invention are useful in an amount of 1-50% by weight of the total composition, preferably about 5-15% by weight of the total

Composition, present. R-O-C-CHCH2COOX

The specific anionic surfactants, 60 |

which have been found to be useful in the present invention are those which contain at least one carboxylic acid moiety and are selected from the group consisting of sulfosuccinates, alkyl ether car- and can be prepared by reacting maleic acid. boxylates, a-sulfo fatty acid and ester carboxylates, alkyl 65 acid with a suitable fatty alcohol, followed by the succinates, alkyl sarcosinates and fatty acid protein condensate addition of NaHSCb to the double bond.

sowed. All of these compounds are well known and can be prepared. The α-sulfo fatty acid and ester carboxylates have the following recognized procedures. general formulas

5

651584

O

II

R-CH-C-OX 'and SO3X O

II

R-CH-C-OR '

I.

SOaX

and can be made by sulfonation of the appropriate fatty acids and esters.

The alkyl ether carboxylates have the following general formula

R-0 [(CH2) 20] a-CH2C00X where a is the numbers 1-4;

and these compounds can be prepared by Williamson's ether synthesis which involves the reaction of an alkoxide with chloroacetic acid.

The alkyl succinates have the general formula

O

II

R-O-C-CH2CH2COOX

and are the reaction product of a suitable fatty alcohol with succinic acid or succinic anhydride. The alkyl sarcosinates have the general formula

O X

II I

R-C-N-CH2COOX

and are the reaction product of a suitable fatty acid with a lower substituted amine, such as glycine or N-methylglycine.

The fatty acid protein condensates have the general formula

O R 'O R "

II I II I

R-C- (NH-CH-C-NH-CH) nCOOX

and are the reaction products of a suitable fatty acid with an amino hydrolyzate.

Specific examples of suitable anionic surfactants include the following compounds:

O O

II II

(AA) CnH23-0-C-CHCH2-C-0-Na

I.

OSOsNa

O

II

(BB) C12H25-CH-C-O-N a

I.

SCbNa

O

II

(CC) C10H21-CH-C-OCH3

I.

SOsNa O O

II II

(DD) R-O-C-CH2-CH2-C-OK

wherein R is a 50/50 mixture of C12H25-C14H29, (EE) Ci3H27-0 - [(CH2) 20] 4 - CmCOONa

O CHj O CHS

II I II I

(FF) CuH23-C- (NH-CH-C-NH-CH) 5oCOONa O CH3

II I

(GG) Ci iH23-C-N-CH2COONa

The anionic surfactants useful in the compositions of the invention are present in an amount of 2-50% by weight of the total composition, preferably about 5-20% by weight of the total composition.

In order to achieve the desired results of the present invention, the amphoteric fatty acid complex and the anionic surface-active agent are present in particular in a ratio of 4: 1 to 1: 4, preferably 2: 1 to 1: 2.

Various other surfactants, such as anionic, nonionic, amphoteric, cationic, and the like, can be used in preparing the various formulations and compositions, if desired and if compatible. In addition to such other surfactants, other ingredients conventionally added to detergent and cleanser compositions for personal use can be added in smaller amounts, such as dyes, preservatives, perfumes, thickeners, opacifiers, conditioners, emollients, buffering agents and similar. The ingredients, such as colorants, preservatives and perfume, together can usually make up less than 2% by weight of the total composition.

The detergent and detergent compositions of the present invention can be in the form of liquid detergent compositions or in bar form, if desired.

Liquid detergent compositions can be prepared by mixing the amphoteric fatty acid complex and the anionic surfactant at room temperature or at slightly elevated temperatures (about 50 ° C), followed by the addition of enough deionized water to bring the composition to about 3A of its intended weight. Other ingredients such as other surfactants, various cleaning additives, fillers, carriers, perfumes, preservatives, gelling agents and the like can be added if necessary, followed by the rest of the water. The pH is then preferably adjusted to the desired range by adding strong acid, e.g. HCl, or strong base, e.g. NaOH, discontinued if necessary.

s

10th

15

20th

25th

30th

35

40

45

50

55

60

65

651584

Bar compositions according to the invention can be prepared by mixing the amphoteric fatty acid complex and the anionic surfactant in a rotary mixer with a steam jacket at temperatures within the range of 60-80 ° C. Additional surfactants, fillers, bleaches and processing oils can be added to the hot slurry if necessary. After sufficient mixing to ensure homogeneity and moisture balance, the product is usually cold rolled or tumble dried to produce flakes. Dyes and fragrances can be added to the flakes together with further water in a standard amalgamating machine in order to achieve the appropriate piece formation. After sufficient mixing, the flakes are usually ground and pressed into blocks, which are then cut into blanks, before punching them into pieces.

The detergent compositions according to the invention can be tested for eye irritation in accordance with the following modified Draize test (J.H. et al., Toilet Goods Assn. No. 17 May 1952, No. 1, Proc. Se. Sect.):

A 0.1 ml sample of a neutral composition to be tested is dropped into one eye of an albino rabbit while the other eye is used for control. Six rabbits are used for each composition. Observations are made after 1,24,48,72 and 96 hours and 7 days after the first instillation; the second and third instillation is done after 24 and 48 hours after the readings. Results can vary from essentially no change or only a slight irritation in the appearance of the rabbit's eye after seven days to severe irritation and / or complete corneal opacification. Ocular injuries are recorded for the cornea, iris and conjunctiva, with a higher number indicating greater ocular irritation, and the records are added together to give a total numerical value for each reading in the six rabbits, and of these values the Average determined. The mean value gives an indication of the potential for irritation of the composition to be tested. Based on the mean, a descriptive irritation evaluation can be given, e.g. depending on the case, none, easy, medium, serious.

The detergent compositions according to the invention provide a high foam volume and, in addition, an extraordinary foam stability, measured with an adaptation of the well-known Ross-Miles foam test principle “Oil and Soap”, September 18, 102 (1941):

s Anhydrous cosmetic lanolin is mixed with dioxane (technical quality in proportions of 2.5 g lanolin and 100 g dioxane. The lanolin is first mixed with 25 ml dioxane. This mixture is heated to a temperature of 45 ° C. on a steam bath In order to dissolve the xo lanolin in the dioxane, the remaining dioxane is then added and mixed in. This lanolin / dioxane solution, which is kept in an amber bottle, should be freshly prepared on the day of use.

15 The composition to be tested is diluted to 4 g of the composition by adding 376 ml of distilled water, and then 20 ml of the lanolin / dioxane solution described above are added with mixing. Heat is generated when the lanolin / 20 dioxane solution is added to the solution of the composition in water, and care must be taken to keep the temperature of this solution at 24-25 ° C. Both of these intermediate solutions should therefore be adjusted to a temperature of 23 ° C before mixing. The lanolin / dioxane solution should be cooled gradually to prevent the lanolin from precipitating. A final solution with a temperature of 24-25 ° C is obtained. The final solution of the composition to be tested, water, and the dioxane / 30 lanolin solution described above are then introduced into a modified Ross-Miles foam column in the usual way. All tests are run twice and the average of the two results is taken. Foam stability is determined by measuring the decay of foam height 35 after two minutes, expressed as a percentage of the original height.

Specific embodiments of the present invention are illustrated by the following examples.

40 Examples I-IX

The following compositions were prepared by mixing the surfactant components, adjusting the pH to 7.2 ± 0.2 with dilute acid or base if necessary, and adding deionized water to 100%:

% By weight

Examples

i

II

in

IV

v

VI

VII

VIII

IX

Compound B

5.0

2.5

2.5

2.5

2.5

Lauryl succinic acid

5.0

2.5

Disodium sulfococoate

5.0

2.5

Lauryl ether (4) carboxylate

5.0

2.5

Lauryl disodium sulfosuccinate

5.0

2.5

Deionized water q.s.

to 100%

Example X

The compositions made in Examples I-IX were tested for foam properties in hard water using the modified Ross Miles method above and the results are as follows:

7

651584

example

Initial foam height in mm -200 ppm hard water

I.

358

II

330

III

348

IV

330

V

330

VI

365

VII

375

VIII

368

IX

378

It can easily be seen from the above results that the compositions which contain a mixture according to the invention of the specific amphoteric fatty acid complexes and the anionic surface-active agents (Examples VÏ-IX) have a synergistic increase in the initial foam height. It can also be seen that the quality of the foam produced by the compositions according to the invention is superior to that of the other compositions in that it is denser and creamier. A foam of this nature produced is not only perceived better by the consumer, but is also capable of carrying and suspending dirt in a manner more superior to the more open, soapy foam of the compositions of Examples I-IV, and thus this dirt is easier to remove .

Example XI

A detergent stick composition was prepared by adding to a steam jacketed rotary mixer 23.7 parts by weight of stearic acid, 13.3 parts by weight of dextrin, 35.1 parts by weight of disodium a-sulfoco-coat, 14, 2 parts by weight of compound A, 0.2 part of titanium dioxide and 10.0 parts of water. The mixture was heated to a temperature of 50-60 ° C and mixed until homogeneous, and the pH was adjusted to 7.2 ± 0.2 with 50% NaOH solution. The resulting product was cooled, flaked, ground, pressed and punched into bars having the following composition:

Wt. / O / wt.

Stearic acid 23.7

Dextrin 13.3

Disodium a-sulfococoate 35.1

Compound A 14.2

TiCh 0.2

50% NaOH 5.2

Deionized water 8.3

100.0

The resulting rod foams abundantly in hard and soft water and is free from lime soap deposits and has been found to be slightly ocular irritant when tested.

Example XII

A low pH detergent bar composition was prepared according to the procedure of Example XI and had the following composition:

% By weight

Compound B 20.00

Stearic acid 15.00

Polyethylene glycol 4000 5.00

Dextrin 10.00

Talk 10.00

Disodium lauryl sulfosuccinate 35.00

Deionized water 5.00

100.00

Example XIII

A liquid cream soap product was prepared as follows: 87.5 parts by weight of Compound C and 20.0 parts by weight of lauryl succinic acid were placed in a reaction vessel equipped with a stirrer and steam, and the mixture was stirred up heated to a temperature of 45 ° C. The pH was adjusted to 7.0 ± 0.2 with dilute NaOH, followed by the addition of a portion of propylene glycol and 95 g of deionized water. The mass was cooled to a temperature of 30 ° C and 2 parts of a fragrance were added before filling into tubes. The resulting product had the following composition:

% By weight

Compound C 42.57

Lauryl succinate 9.73

Propylene glycol 0.48

Perfume 0.97

Deionized water q.s. to 100%

The product is a slightly opaque, mild, cream-like gel that easily comes out of tubes.

Example XIV

An opaque liquid soap was made and had the following composition:

% By weight

Compound D 30.0

Lauryl sarcosinate 20.0 polyethylene glycol 6000, distearate 3.0

Deionized water q.s. to 100%

The pH of the above composition was adjusted to 6.0 with dilute HCl.

Example XV

An opaque liquid soap was made and had the following composition:

% By weight

Sulfosuccinate 3.00

Compound A 2.50

Ammonium lauryl (3) ether sulfate 3.00 polyoxyethylene 80 sorbitan monolaurate 5.00

Preservative 0.10

Dyes and fragrances 0.25

Deionized water q.s. to 100%

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

651 584 8

The pH of the above composition was measured using embodiments of this invention.

Thin HCl adjusted to 6.0. shapes, arrangements and variations within the

In addition to the preferred areas of this invention described above, those skilled in the art will appreciate.

B