CA1173324A

CA1173324A - Detergent compositions

Info

Publication number: CA1173324A
Application number: CA000397730A
Authority: CA
Inventors: Diane L. Spilatro; Jacob J. Guth; Robert J. Verdicchio
Original assignee: Johnson and Johnson Baby Products Co
Current assignee: Johnson and Johnson Professional Inc
Priority date: 1981-03-09
Filing date: 1982-03-05
Publication date: 1984-08-28
Also published as: GR76364B; BR8201230A; FI820797L; NO153263B; MX156368A; AU553501B2; PH17910A; NO820730L; SE448632B; SE8201213L; CH651584A5; NO153263C; ZA821526B; DK99982A; DE3208310A1; IT1208651B; AU8119382A; JPH0252680B2; IT8247923A0; JPS57159897A

Abstract

ABSTRACT
The invention is concerned with a detergent and cleansing composition comprising a synergistic mixture of a specific amphoteric-fatty acid complex and a specific anionic surfactant containing at least one carboxylic acid moiety.
The amphoteric-fatty acid complex has the formula:

wherein Rl is alkyl or substituted alkyl containing from about 6 to 18 carbon atoms and mixtures thereof; R2 is alkyl containing from about 8 to 18 atoms and mixtures thereof or alkyl amido of the formula:

Description

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11 7332ll JBP 184 ', ~ DETERGENT COMPOSITIONS
:
Background of the Invention Detergent and cleansing compositions intended for use as personal cleansing products not only must exhibit good cleansing and foam characteristics but they must also be non-irritating or have low irritation potential to the skin and the eyes.
' ` 1 0 : Synthetic detergents which are useful in such detergent . .
and cleansing compositions are well known in the art and include anionic, cationic, amphoteric and nonionic detergents or surfactants, as they are usually referred to. The surfactants generally exhibiting the mo~e : superior properties in terms of foamingi cleaning and end result attributes are the anionic detergents. Thus, most ~t"'~' detergent and cleansing formulations intended for personal ~; use contain anionic surfactants as one of the active - ~ 20 ingredients. These surfactan~s, however, have a tendency f to be very irritating to the skin and the eyes in the levels normally utilized, i.e., above 10% by weight of the total composition. For this reason, detergent composi-tions intended for personal use containing anionic surfactants are modified by substituting a significant `~ amount of nonionic surfactants which are generally mild although of less effective foaming and cleansing ability.
; Certain amphoteric surfactants have also been reported to ~` have a low eye irritation potential. Although numerous :! 30 detergent and cleansing compositions are available commercially, there is still a need for compositions in which irritancy can be substantially eliminated without ~; sacrificing other desired properties such as cleansing and foaming attributes.

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Several U.S. patents describe compositions in which both amphoteric and nonionic surfactants are incorporated in detergent compositions containing anionic surfactants.
Thus, in U.S. Patents Nos. 2,999~069 an 3,055,836 there are described shampoo compositions comprising certain mixtures of ethoxylated anionic, amphoteric and polyethoxylated nonionic surfactants. Further, in U.S. Patqn~ No. 3,928,251 there are described shampoo compositions comprising certain mixtures of anionic, nonionic and zwitterionic surfactants. Similarly, in U.S. Patent No. 3,950,417 shampoo compositions are described for which low ocular irritancy is claimed. In ; these compositions, nonionic and amphoteric surfactants have been added to modify anionic surfactants. A11 of these compositions include a nonionic surfactant as an essential component as well as an anionic surfactant and as mentioned above, these surfactants have various negatives~
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;; ~ 20 It is, therefore, an object of this invention to provide improved detergent and cleansing compositions.
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It is a further objec~ of this invention to provide ~- improved detergent and cleansing compositions which ~ .; .
~ 1 25 exhibi~ low irritation potential to the eyes and skin.
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It is a further object of this invention to provide improved detergent and cleansing compositions which exhibit good foaming properties including excellent foam stability.

Other objects of this invention will be set forth in or be apparent from the following detailed description of the invention.

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~ ~ ~33~4 Summary of the Inven~ion :`
The foregoing objects and other features and advantages of the present invention are achieved by detergent and S cleansing compositions comprising a synergistic mixture of ~ surfactants which exhibit low eye and skin irritancy and -i~ good foam properties. More specifically, the present invention relates to detergent and cleansing compositions comprising a synergistic mixture of a specific amphoteric-fatty acid complex and specific anionic surfactants ~i containing at least one carboxylic acid moiety.
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Detailed ~escriotion of the Invention In general, this invention comprises a synergistic mixture of a specific amphoteric-fatty acid complex and a specific ~` anionic surfactant in a ratio of from about 1:4 to 4:1.
' The ~erm "synergis~ic mixture" as used herein refers to a mixture of two discrete compounds which display a degree of initial foam height and quality which is greater than the sum of the initial foam heights of the compounds taken individually.

The specific amphoteric-fatty acid complexes which have been found useful in ~he present invention are ;~ non-zwitterionic in nature and are of the formula .:~

[ R ]

~ ~ wherein Rl is alkyl or substituted alkyl containing j 35 from about 6 to 18 carbon atoms and mixtures thereof.

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, ' i ' , ' ~ l73324 R2 is alkyl containing from about 8 to 18 carbon atoms and mixtures thereof or alkyl amido of the formula ~ ~Z -I .
t R -C-N-Y~
:~ wherein R3 is aIkyl containing from about 8 to 18 carbon atoms, Z is H or lower alkyl containing from ... 1 to 4 carbon atoms, and Y is lower alkylene contain-ing from 1 to 4 carbon atoms;
.~ Al and A2 are the same or different and are selected ~: from the group of anionic salt moieties consisting , 10 of the following:
~,",;, ~cH2cH2-coox !n l ;,,.. ,, ~ H2-cOox]n ~CH2CHOH-CH2S03x]n l ~CH2 CHOH-CH2-OPo3x]n :
wherein X is a water soluble cation such as ~a , K+, Ca++, Mg+~ and the like and ~ is an integer of 1 or

2 with the proviso that if only one of Al and A2 are . selected from the anionic salt moieties above the other can be lower alkyl or lower hydroxyalkyl containing from 1 to 4 carbon atoms.
.. - ~he amphoteric-fatty acid complexes which are useful in the present invention are novel compounds described and claimed in Applicant's copending Canadian patent application Serial ~o. 397,740, filed March 5, 1982, and can be prepared in accordance with the processes ~' dsscribed therein.
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Representative amphoteric-fatty acid complexes useful in the present invention in~lude the following:

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3 3 2 ~1 , `:,. 1 1 ~ t /C2~4oa 1~
. 5 ~A~ l-C~ H23 G ~dtC~2)~
.:
` wherein Rl is a CllH~3 - S1~37 mixture.

$~ 10 11 1 r ~CH2c~2cNa 1 (B ) P~l-C-O ~14H29~N~
:~ 15 . ~ 2CH2~QoNa wherein Rl i5 ar 80%/20% tallow COCOFI t fatty acid mixture.
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20r ~ 3 / 2CHOHCH2SO ~K
( C ) ¦ Rl-C-O R2 C-N- ( C~12 ) 2 N~
~` L I CH2C~HCH20PO3Na2 . wherein Rl is tallow fatty acid and R~ is a CllH23-~17~25 mixtl~re.
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r 1l 1 r cH2cHOHC~2so3 .: 30(D~ RlC-O ~ 18H37-N Mg _ _ 1~ CH~CHOHCH2So3--wherein Rl is a ~0%/30~ mixture of lauric and ~, myristic acids.

(E) [RlC ~ [C12H25 I CH2CH2COONa ]
wherein Rl is tallow fatty acid.
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.: -6-r u 1 ~ H2COO~a l ~3 (Fl LC12H25~ ~ C14H~9-:. ~ CB2CH2COONa~

:~ 1 0 r J 1 r ~ C~2CH2COGNa ~,. tG) RlC-O C12H25-N`
_ _ I `CH2CH2COONa wherein Rl is a C6H13 - ClgN37 mi:cture.
- ~he amphoteric-fatty acid complex~s u eful in ~he composi-tions of this invention are presen~ in an amo~nt of from about 1 to 50% by weight of the total composition, prefer-ably about 5 to 15% by weight o~ the total compo ition.
-~ . The specific anionic surfac~an~s which have been found `~ ~seful in the present invention are those containing at ,. : least one carboxylic acid moiety and are selected from the .~ group consisting o~ sulfosuccinates, alkyl carboxylates, ~'. 25 ~ -sulfo ~atty acid and ester carboxylates, alkyl succi-nates, alkyl sarcosinates and fatty acid protein condensates. All of these compounds are well known in the art and can be prepared according to well-recognized processes.
: 30 . The sulfosuccinates are of the general formula '." O

~-O-C-fHCH2COOX
OSO3Na .

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and can be prepared by reacting maleic acid with a - suitable fatty alcohol followed by the addition of NaHSO3 to ~he d~uble bond.
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:` S The ~-sulfo fatty acid and ester carboxylates are of the following general formuli respectively . ' ., 11 10R-fH-C-OX' and : SO3X
:,:- O

15R-CH-C-OR' . I
,., S03X
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and can be prepared by sulfonation of the suitable fatty . acids and esters.
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: The alkyl carboxylates are of the following general : formula R-O[(CH2)2O]a-CH2COOX

~- wherein a is 1-4; and these compounds can be prepared by ;-~ the Williamson ether synthesis which involves react~ an~
alkoxide with chloroace~ic acid.

The alkyl succinates are of the general formula .. O

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,.......... - - ~: .
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'. and are the reaction product of a suitable fatty alcohol ,~ with succinic acid or succinic anhydride.
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'~` The alkyl sarcosinates are of the general formula S
~, O X
.:. R-C-N-CH2COOX

` 10 and are the reaction product of a suitable fatty acid with . a lower substituted amine such as glycine or N-methyl .. .~ .
glycine.
~; ' `~ The fatty acid protein condensates are of the general formula O R' O R"
~, 11 1 11 1 ~ R-C-(NH-C-H-C-NH-CH)n COOX
'`; 20 .~ and are the reaction products of a suitabLe fatty acid : with an amino hydrolysate.
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Specific examples of suita~le anionic surfactants include, ~ 25 :- O O
': ` 11 11 (AA) CllH23-0-C-fHCH2-C-O-Na ; 30 OSO3Na " O
(BB) C12~2s-fH-C--Na S03Na ,:
;............ 40 O
: 11 (CC) CloH~l-fH-C-OCH3 . SO3N
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3 3 ~
g . ~ I o (DD) R-0-C-CH2-CH2-C-OK
wherein R is 50/50 mixture of C12E25 - C14H29 ..
(E~) Cl3H27-o-[(cH2)2o]4 - CH2cooNa - O C~3O CH3 ",~,~ 1 11 1 ~ (FF) CllH23-C-(NH-CH-C r~H-C~)soCOONa :`'`; 15 .:~ o C~3 Il I
(GG) CllH23-C-N-CH2COONa :~ 20 The anionic surfactants useful in the compositions o~ this invention are present in an amount of from about 2 to 50~
by weight of the total composition, preferably about 5 to : 90% by weight of the total composition.
Further, to achieve the desired results of the present invention, the amphoteric-fatty acid complex and the :~ specific anionic surfactant should be in a ratio o~ from about 4:1 to 1:4, preferably ~rom about 2:1 to 1:2.
In preparing various formulations and compositions, if ~ desired and if compatible, various other surfactants can : be utilized such as other anionics, nonionics, ~` amphoterics, cationics and the like. In addition to such other surfactants, other ingredients conventionally added to detergent and cleansing compositions for personal use, such as dyes, preservatives, perfumes, thickeners, "
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, ~ opacifiers, conditioners, emollients, buffering agents and $ the like, may be added in minor amounts. Ingredients such c` as dyes, preservatives and perfumes together usually i ~ constitute less than 2% by weight of the total composition S in an amount of from about l to about 3~ by weight of the i~ total composition.
~; ' ' The detergent and cleansing compositions of the present ~~ invention may be in the form of liquid detergent compositions or detergent bar co~lpositions, as desired.
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s Liquid detergent formulations utilizing the compositions of the present invention can be prepared by admixing the ~; amphoteric-fatty acid complex and anionic surfactant at room temperature or slightly elevated temperatures (about 50C) and then sufficient deionized water is added to bring the composition to about three quarters of its intended weight. Other ingredients such as other surfactants, various detergency adjuncts, fillers, carriers, perfumes, preservatives, gelling agents and the like are added as required followed by the balance of the water. The pH is then adjusted to within the desired range by the addition of strong acid, e.g., ~ICl, or strong base ~aOH, as needed.
Detergent bar formulations utilizing the compositions of the present invention can be prepared by admixing the amphoteric-fatty acid complex and the anionic surfactant ! in a steam jacketed rotary mixer at temperatures within the range of 60-80C. Other surfactants, fillers, ; whitening agents and processing oils can be added, as needed, to the hot slurry. After adequate mixing to assure homogeneity and moisture balance the product is chill rolled or drum dried into flakes. Dyes and fragrances are added to the flakes in a standard amalgamator together with additional water to provide . .

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~.' proper bar formation. After adequate mixing the flakes are milled and plodded into logs which are then cut into blanks prior to stamping into ~ar form.
, :...-The detergent compositions of the present invention can be ~`~` tested for ocular irritation by the Eollowing modified Draize Test (J.H. et al., Toilet ~ood~ Assn. No. 17, May 1952, No. 1, Proc. Sci. Sect.).
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An O.1 ml. sample of a neutral composition under test i5 dropped into one eye of an albino rabbit, the other eye serving as a control. Six rabbits are employed for each composition. Observations are made after 1, 24, 48, 72 ~~ and 36 hours and 7 days after initial instillation; second and third instillations are made after the 24 and 48 hour - readings. Results may vary from substantially no change or only a slight irritation in the appearance o~ the rabbit's eye after 7 days to severe Lrritation and/or complete corneal opacity. Ocular lesions are scored for the cornea, iris and conjunctiva with a higher number ~`~ indicating greater ocular irritation and the scores are added to give a total numerical value for each readin~ for ~- six rabbits and averaged. The averaged score is an indication of the irritation potential of the composition ~ ~ 25 under test. Based on the averaged score, descriptive j irritation evaluation may be given, e.g., none, slight, `- moderate, severe, as the case may be.
,s Detergent compositions of the invention provide high foam " ";,! 30 volume and moreover outstanding foam stability as measured by an adaption of the well-known Ross-Miles foam test principle "Oil and Soap" 18.9-102 (1941):
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Lanolin, anhydrous, cosmetic grade is mixed with dioxane (technical grade) in the proportion of 2.5 grams lanolin and 100 grams of dioxane. The lanolin is first mixed ~ith ., ' .:

3 3 2 ~
. -12-`' 25 cc. of dioxane. This mixture is heated over a steam bath to 45C in order to dissolve the lanolin in the dioxane. The remainder of the dioxane is then added and mixed. This lanolin dioxane solution, which is stored in an amber bottle, should be prepared fresh on the day that the tests are run.

The composition to be tested is diluted by adding 376 cc.
of distilled water to 4 grams of the composition, and then by adding 20 cc. of the lanolin dioxane solution described above while mixing. Heat is produced when the lanolin dioxane solution is added to the solution of the composition in water and care must be taken in adjusting the temperature of this solution to 24-25C. Both of these intermediate solutions should therefore be adjusted to 23C before mixing. The cooling of the lanolin dioxane solution should be gradual in order to avoid precipitation of the lanolin. This will produce a final solution with a temperature of 24-25C.
The final solution of the composition to be tested, water, dioxane and lanolin described above, is then run in a modified Ross-Miles foam column in the usual way. All tests are conducted in duplicate, and the average of the two results is taken. Foam stability is determined by measuring the decay in foam height after two minutes, expressed as a percentage of the original height.
:, Specific embodiments of the present invention are illustrated by the following representative examples. It will be understood, however, that the invention is not confined to the specific limitations set forth in the individual examples, but rather to the scope of the appended claims.

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; Examples I-IX
The following compositions are prepared by admixing the surfactant components, adjusting the pH to 7.2+.2 with dilute acid or base as required and adding deionized water to 1.00%:
. .
o/O W-t/wt.
EXAMPLES
I II III IV V VI VII VIII IX
Compound B 5.0 2.5 2.5 2.5 2.5 lauryl succinnic - acid 5.0 2~5 disodium sulfo-- cocoate 5.0 2~5 lauryl ether (4) 15 carboxylate 5.0 2.5 :~ lauryl disodium , sulfosuccinate 5.0 2.5 deionized water q.s. to 100%
'', Ex mple X
The compositions prepared in Examples I-IX are tested ,.. ~ for hard water foam properties using the modified Ross-~- Miles procedure set forth hereinbefore and the results i are as follows:
~: Initial Foam Height in mm -~, 25 Example 200 ppm hard water I . 358 II

: VI 365 ~ ;' 'r~
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As can be readily seen from the results above, thecompositions containing a mixture of the speciic amphoteric - fatty acid complexes and the anionic surfactants of the present invention tExamples VI-IX) exhibit a synergistic increase in initial foam height. It is also observed that the quality of the foam generated by the compositions of the present invention is superior to that of the other compositions in that it is denser and creamier. A generated foam of this nature i5 not only perceived to be better by the consumer, but is also capable of supporting and suspending soils in a manner superior to the more open, lace-like foam of the compositions of Examples I-IV and thus these soils are more easily removed Example XI
A detergent bar composition is prepared by charging to a steam-jacketed rotary mixer 23.7 parts by weight stearic acid, 13.3 parts by weight dextrin, 35.1 parts by weight disodium -sulfococoate, 14,2 parts by weight compound A, 0.2 parts titanium dioxide and L0.0 parts water. The mixture is heated to 50-60~C and mixed until homogeneous and the pH is adjusted to 7.2+.2 with 50~ NaO~ solution.
The resulting product is chilled, rolled in flakes, 25 milled, plodded and stamped into bars having the following composition:
% wt/wt stearic acid 23.7 dextrin 13.3 disodium -sulfococoate 35.1 Compound A 14.2 TiO2 0.2 50% NaOH 5.2 deionized water 8.3 100.0 3~2~
-15~

The resulting bar foams copiously in hard and soft wa~er and free of lime soap deposits and is also found to be a slight ocular irritant when tested.

Example XII
A low pH detergent bar composition is prepared in accordance with the procedure of Example XI and has the following formulation:
% wt/wt Compound ~ 20.00 stearic acid lS. ao polyethylene glycol 4000 5.00 dextrin 10.00 talc ~o,oo lS disodium lauryl sulfosuccinate 35.00 deionized water _ 5.00 100.Qo ..
Example XI I I
: 20 A liquid cream soap product is prepared as follows: ~7.5 parts by weight of compound C and 20.0 parts by weight of lauryl succinic acid are char~ed to a vessel equipped with a stirrer and steam and are heated to 45C. The pH is adjusted to 7.0+.2 with dilute NaOH followed by the addition of 1 part of propylene glycol and 95 grams of deionized water. The mass is cooled to 30C and 2 parts of a fragrance are added prior to illing into tubes.
The resulting product has the following formulation:
; % wt/wt Compound C ~2.57 lauryl succinate 9.73 propylenc glycol 0.4a fragrance 0.97 deionized water q.s. to 100%
35 The product is a smooth opaque mild cream gel easily dispensed from tubes.

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Example XIV
An opaque liquid soap is prepared having the following formulation.
% wt/wt 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 formulation is adjusted to 6.0 with dilute HCl.

Example XV
. An opaque liquid soap is prepared having the following formulation:
.` 15 ;. ~ wt/wt sulfosuccinate 3.00 Compound A 2.50 ammonium lauryl (3) ether sulfate3.00 polyoxye~hylene 80 sorbitan monolaurate 5.00 : preservative .10 dye and fragrance .25 deionized water q.s. to 100 The pH of the above formulation is adjusted to 6.0 with dilute HCl.

In addition to the preferred embodiments described herein, other embodiments, arrangements, and variations within the spirit oE the invention and the scope of the appended claims will occur to those skilled in the art.

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Claims

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. A low irritating detergent and cleansing composition wherein the active ingredients consist essentially of (a) from about 1 to 50% by weight of an amphoteric-fatty acid complex of the formula wherein R1 is alkyl or substituted alkyl containing from about 6 to 18 carbon atoms and mixtures thereof;

R2 is alkyl containing from about 8 to 18 carbon atoms and mixtures thereof or alkyl amido of the formula wherein R3 is alkyl containing from about 8 to 18 carbon atoms, Z is H or lower alkyl containing from 1 to 4 carbon atoms; and Y is lower alkylene containing from 1 to 4 carbon atoms, A1 and A2 are the same or different and are selected from the group of anionic salt moieties consisting of the following;
?CH2CH2-COOx]n ?CH2-COOX]n, ?CH2CHOH-cH2-SO3x]n, ?CH2-CHOH-CH2-OPO3X]n wherein X is a water soluble cation and N is an integer of 1 or 2 with the proviso that if only one of A1 and A2 are selected from the anionic salt moieties above the other can be lower alkyl or lower hydroxyalkyl containing from 1 to 4 carbon atoms; and (b) from about 2 to 50% by weight of an anionic detergent selected from the group consisting of sulfosuccinates, alkyl carboxylates, .alpha. -sulfo fatty acid and ester carboxylates, alkyl succinates, alkyl sarcosinates and fatty acid protein condensates.

2. The composition of claim 1 wherein the amphoteric-fatty acid complex and the anionic surfactant are in the ratio of from about 1:4 to 4:1.

3. The composition of claim 1 wherein the amphoteric-fatty acid complex is of the formula wherein R1 is a C11H23 - C18H37 mixture.

4. The composition of claim 1 wherein the amphoteric-fatty acid complex is of the formula wherein R1 is a C6H13 - C18H37 mixture.

5. The composition of claim 1 wherein the amphoteric-fatty acid complex is of the formula

6. The composition of claim 1 wherein the amphoteric-fatty and complex is from about 5 to 15% by weight of the total composition.

7. The composition of claim 1 wherein the anionic surfactant is an alkyl sarcosinate.

8. The composition of claim 1 wherein the anionic surfactant is a sulfosuccinate.

9. The composition of claim 1 wherein the anionic surfactant is an alkyl succinate.

10. The composition of claim 1 wherein the anionic surfactant is from about 5 to 40% by weight of the total composition.