CA1179683A

CA1179683A - Detergent compounds and compositions

Info

Publication number: CA1179683A
Application number: CA000397740A
Authority: CA
Inventors: 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: 1984-12-18
Also published as: AU554101B2; FR2501200A1; FI820796L; CH648823A5; FR2501200B1; IE52291B1; MX162869B; BE892426A; IE820512L; ES8305685A1; NO155881B; DK100082A; GB2094307A; NO820731L; FI80013B; NL8200946A; GB2094307B; MX174108B; ZA821528B; SE8201214L

Abstract

ABSTRACT
The invention is concerned with new amphoteric-fatty acid complexes having the general formula:
wherein R1 is alkyl or substituted alkyl containing from about 6 to 18 carbon atoms and mixtures thereof R2 is alkyl con-taining from about 8 to 18 carbon atoms and mixtures thereof or alkyl amido of the formula:

Description

'7~6~33 1~

DETERGE~T COMPOUNDS AN~ COMPOSITIONS

Background of the Inven~ion The present invention relates to amphsteric-fatty acid complexes. More specifically, the invention relates to amphoteric-fatty acid complexes which exhibit unexpected foam properties and low ocular irritancy. The invention further relates to detergent compositions containing the novel amphoteric-fatty acid complexes in combination with other surfactants and/or detergent components.

Nonirritating detergent compositions have been known in the art and have been in use for some time. United States Patent Nos. 3,299,069 and 3,055,836 are merely two representative examples of such prior art nonirritating detergent compositions. Likewise, amphoteric compounds have been well known in the art and have been disclosed ln use with various other detergent compounds. United States Patent No. 2,528,380, discloses a ring structured amphoteric compound with a fatty acid attached to the ring nitrogen. ~one o~ the disclosure.s in the prior art disclose the amphoterlc-fatty acid complexes o~ the present invention nor the advantages provided by same.
It is an obiect of the present invention to provide novel detergent compounds.

It is another objec, of the present invention to provide novel detergent compounds which exhibit good foam properties and low ocular irritancy.

.

3~3~3 It is a further object of the present invention to provide detergent compositions which exhibit good ~oam properties and low ocular irritancy.

These and other objects of the present invention will become apparent to one skilled in the art from the detailed description given hereinafter.

Summary of the Invention This invention encompasses non-zwitterionic, amphoteric-fatty acid comp~exes of the formula [RlC~O~ [R2~1~ A ~

wherein Rl, R2, Al and A2 are as defined below.

Detailed Description of the Inventlon The present invention relates to novel non-zwitterionic, amphoteric-fatty acid complexes of the formula [RlC-O~ [R2~1~ A

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 carbon atoms and mixtures thereof or alkyl amido of the formula .
O Z
. ;. -R3-C~-N-Y

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 l-to 4 carbon atoms, Al and A2 are the same or different and are select~d from the group of anionic salt moieties consisting of the followiny:

~CH2CH2-cOox]n ~CH2-cOox~n ~CH2C~OH-CH2~sO3x~n ~CH2 CHOH-CH2~OPo3xln wherein X is a water~soluble cation such as Na+, K+, CaT~, Mg+~ and the like and n 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 containiny from 1 to 4 carbon atoms.

The non-zwitterionic, amphoteric compounds wh.ich are useful in the complexes of the present invention are of the formula:

A
R2-N\
¦ A2 H , wherein R2, A1 and A2 are as def ined above.

These compounds can be prepared in accordance with th~
teachings of the art, see for example, United States Patent NoO 2,970,160.

The fatty acid compounds which are useful in the complexes of the present invention are of the formula - O ~
~l-C-O
_ wherein Rl is as defined above. These compounds are readily available commercially from numerous sources such as the fatty acids available from Emery Industries Inc.;
Cincinnati, Ohio Procter ~ Gamble, Cincinnati, Ohio and various other: commercial suppliers.

The amphoteric-fatty acid complexes of the present invention can be prepared by admixing a suitable non-zwitterionic amphoteric and a suitable fatty acid, utilizing heat, i~ nece~sary, to facilitate the blending and adding water, if needed. The ratio of fatty acid to amphoteric can be in the range of about 0.5:1 to 1.5:1, preferably about 1;1. The pH of the resulting complex should be within the range o 6.5-8.5, pre~erably within the range of 7.0-7.5, to minimize potential irritation problems.

Specific examples of the novel amphoteric-fatty acid complexes of the present invention include:
~ ~ O H C2H40H
~A) LR1-C-O~ C11H23-C-N (CU2) 2 I~C~I2CO~K

wherein Rl is a CllH23 - ClgH37 mixture~

,, .

.i83 ., ~
~ ~ ~,cH2cH2coowa ( }3 )P~l~C-O Cl~H29~N
S _ ~¦~CE~2C~12COONa wherein Rl i5 an 80%/20% tallow coconut mixture.

~ U l~3 C~2CHOH~2S03K
~ C ~ Rl-C-O R2 C-N--( CE~2 ) 2--N~
_ _ I CH2CE~O~CH20Po3Na2 wherein Rl is tallow and R~ i~ a C11~323-C17H2s mix'~ure.
' ~9 r I 1 ~ ~ c~2c~OEcH2so3 (D) LRlC l ~18 37 1 ~ CX2CHOHCH2S03~
wherein Rl is a 70%/30% mixture of laurlc and myristic acids.

2 5 r u 1 r ( E ) LRlC-O~ C12H25-N-CH2OEI2-COO~a~
. El where in Rl is tallow .
e ~ ~cH2cH2~OoNa ~
( F ~ C12~5C- Cl4H29-N\
_CH2C~2COONa_ _ ~ (3 1~ 11 1 ~CH2CH2COONa (G )RlC-O C12~25-N
4 0 _ ¦ ~CH 2CH 2COONa where in R1 is a C6H13 ~ C18H37 mixture -~he amphoteric-fatty acid complexes of the present invention exhibit excellent surfactant properties. In particular, these complexes exhibit good foam properties and low ocular irritancy. me good foam properties are unexpected because fatty acids do not normally exhibit such properties. It has further been found within the p~ range of 7~0-7.2 that the amphoteric-~atty acids cornplexes exhibit unexpected foam synergism.

These complexes can be utilized in detergent compositions either alone or in combination with other surfactants in a range of from about 1.0 to 50.0% by weight of the total compositions.

The amphoteric surfactants which may be used in the present invention include betaines, sultaines, phosphobetaines, phosphitaines, n-alkylamino propionates, n-alkylimino dipropionates and imidazolines. The betaine and sultaine surfactants useful in this invention are described in U.S. Patent No. 3,950,417 issued April 13, 1976. The phosphobetaines and phosphitaines useful in this invention are described in U.S. Patent ~os 4,215,064 and 4,261,911. The n alkylamino propionates and n-alkylimino dipropionates are sold under the trade-name Deriphats by General MillsA The imidazolines which are useful in the compositions of this invention are described in UOS~ Patent ~o. 2,970,160.

The preferred betaine amphoteric ~urEactants include the alkylbetaines such as cocodimethylcarboxymethyl-betaine, lauryldimethylcarboxymethylbetaine, lauryl-dimethylcarboxyethylbetaine, cetyldimethylcarboxymethyl betaine, lauryl-bis-~2-hydroxyethyl~ carboxymethylbetaine, i 96~3 oleyldimethyl-qamma-carboxypropylbetaine, lauryl-bis-(2-hydr~xypropyl)-carboxyethylbetaine, and the like; the sultaines such as cocodimethylpropylsultaine, stearyldi-methylpropylsultaine, lauryl-bis-(2-hydroxyethyl) propylsultaine and the like; and the amidosultaines such as cocoamidodimethylpropylsultaine, stearylamidodimethyl-propylsultaine, laurylamido-bis-(2-hydroxyethyl) propylsultaine, and the like.

The preferred phosphobetaines include laurlc-myristic-amido-3-hydroxypropylphosphobetaine, cocamldodisodium-

3-hydroxypropylphospho~etaine, lauric-myristicamido-disodium-3-hydroxypropylphosphobetaine, lauric-myristic-amidoglyceryl-phosphobetaine, lauric-myristicamidocarboxy-disodium-3-hydroxypropylphosphobetaine, and the like. The preferred phosphitaines include cocoamidopropylmonosodium-phosphitaine, lauric-myristicamidopropylmonosodium-phosphitaine and the like.

l~he preferred n-alkylamino propionates and n-alkylimino dipropionates include those having the following structures:

R - NH2C~2CH2COO
and ~ / H2CH2COO
R NH\
CH2CH2COO ~la wherein R is from about 8 to 22 carbon atoms and mixtures thereof.

The amphoteric detergents may be present in an amount from about 2 to 10% by weight of the total composition.

It is envisioned that any anionic surfactan~ may be used in the compositions of the invention such as, for example, an alkyl sulfate of the formula R-C~2-OSO3X, an alkylether sulfate of the formula R(OCH2CH2)p-OSO X, an alkylmonoglyceryl ether sulfonate of the formula R~OCH2~CH~CH2-sO3xr OH
an alkylmonoglyceride sulfate of the formula RCOOCH2-CH-C~120S03X
OH
an alkylmonoglyceride sulfonate of the formula OH
an alkyl sulfonate of the formula and an alkylaryl sulfonate of the formula R
~ SO3X
wherein R is alkyl having from 7 to 17 carbon atoms; X is selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, and ammonium ions substituted with from 1 to 3 lower alkyls and p is an integer ~rom 1 to 6.

The anionic detergent may be present in an amount of from about 2 to 10% by weight of the total composition.
Nonionic detergents which are useful include the alkylene oxide ethers of phenolsr fatty alcohols, and alkyl mercaptans; the alkylene oxide esters of fatty acid amides; the condensation products of ethylene oxide with partial fatty acid esters, and mixtures thereof. The polyoxyalkylene chain in such agents may contain rrom 5 to 100 alkylene oxide units in which each alkylene unit has from 2 to 3 carbon atoms.

~'7~3 The nonionic surfactant may be present in an amount of from about l to 30% by weight of the tokal composition.

Cationic surfactants suitable in these compositions include mono- and bis-quaternary ammonium halides, such as stearyldimethylbenzylammonium chloride, cetyltri-methylammonium chloride, ~,N-dioctadecyl-N,N,N',~'-tetramethyl-1,5-(3-oxapentylene) di-ammonium bromide, tertiary amine salts such as cocoamidopropyldimethyl-amine hydrochloride stearylamidopropyldimethylaminecitrate' cationic polymers such as hydroxyethyl cellulose reacted with epichlorohydrin and then quaternized with trimethylamine (Polymers of this type are sold by Union Carbide under the tradename Polymer JR) and specific triesters of phosphoric acid. The specific triesters of phosphoric acid are described in Canadian Patent ~o. l,126,750 issued June 29, 1982.
The cationic surfactants should be present in an amount of from abou-t 0.5 to 3.0% by weight of the total composition.

The total amount of the active surfactant ingredients in the present invention should not be greater than about 50O!o by weight of the total composition i.n orcler to avoid ocular irritation problems, prefera'bly from about 5 to 20% by weiy'ht of the total composition with the proviso that the total amount of anionic surfactant and amphoteric surfactant should not exceed 20% by weight of the total composition. In addition, other ingredients conventionally added to surfactant compo-sitions for personal use, such as dyes, preservatives, perfumes, thickeners, opacifiers, conditioners, emol-lients, buffering agents, and the like, may be added in minor amounts. Ingredients such as dyes, preserva-tives and perfumes together usually constitute lessthan 2% by weight of the total composition and thickeners may be added to the co~position in an ~L~'7~6~33 amount of from about 1 to about 3~ by weigh~ of the total composition.

The detergent compositions of the present invention should have a pH in the range of about 6.5 to 8.5, preferably from about 7.0-7.5.

Liquid detergent compositions utilizing the complexes of the present invention can be prepared by admixing the amphoteric-fatty acid complex with the other surfactant(s) at room temperature or slishtly 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 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., HCl, or strong base NaOH, as needed.

Detergent bar compositions utilizing the complexes of the present invention can be prepared by admixing the amphoteric - fatty acid complex with the other surfactan~s) in a steam jacketed rotary mixer at temperatures within the range of 60-80C. Fillers, whitening agents and processing oils can be added, as needed, to the hot slurry. After ade~uate mixing to assure homogeneity and moisture balance the produc~ is chill rolled or drum dried înto flakes. Uyes and fragrances are added to the flakes in a standard amalgamator together with additional water to provide - proper bar formation. After adequate mixing the flakes are milled and plodded into logs which are then cut into blanks prior to s~amping into bar form.

~t7~ 3 ~11 The detergent compositions of the present inven~ion can be tested for ocular irritation by the following modif ied Draize Test (J. H~ Draize et al ., Toilet Goods Assn. No. 17 , May 1952, No. l, Proc. Sci. Sect. ) .

An 0.1 ml. sample of a neutral composition under test is dropped into one eye o~ an albino rabbit, the other eye serving as a control. Six rabbits are employed for each composition. Observations are made ater 1, 24, 48, 72 and 96 hours and 7 days after initial instillationi 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 of the rabbit's eye after 7 days to severe irritation and/or complete corneal opacity. Ocular lesions are scored for the cornea, iris and conjunctiva with a higher number indicating greater ocular irritation and ~he scores are added to give a total numerical v~lue for each reading for six rabbits and averayed. The averaged score is an indication of the irritation potential of the composition under test. 3ased on the averaged score, descriptive irritation evaluation may be given, e.g., none, slight, moderate, severe as the case may be~

Deter~ent compositions of the invention provide high foam volume and moreover outstanding oam stability as measured by an adaption oE the well-known Ross-l~iles ~oam test principle "Oil and Soap" 18.9-102 (1941) .

Lanolin, anhydrous, cosmetic grade is mixed with dioxane (technical grade) in the proportion o~ 2.5 grams lanolin and 100 grams of dioxane. The lanolin is rirst mixed with 25 cc. o 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 36~3 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.

~_~,t7~6~

~20.2 grams (.19g/moles) of a 24% active solution of an amphoteric of the ormula CllH23~C-~- ( CH2 ) 2 1~CH2COOK

are mixed with 47 grams (.24 g/moles) of premelted coconut fatty acids of the following chain length percentage distribution: C~-0.3, Cg~7.3~ C10-6-5~ C12-5-7 C14-18.g, C16-8.6, C18-7-7-The resulting product is an opaque, viscous slurry containina 34~ solids with a pH of 7.1 and is an amphoteric-fatty acid complex of the structure shown as compound G in the specification. The complex foams copiously in both soft and hard water and is a slight ocular irritant.

Exam~le II
The slurry obtained in Example I is freeze-dried by known procedures to yield abouk 95% solids. The solids are ground to a slightly tacky powder which can be utilized to form a bar soap and is a slight to moderate ocular irritant.

Example_III
Following the procedures of Example I, the amphoteric or Example I is mixed with stripped hydrogenated coconut fatty acids of the following chain length percentage distribution: C8-1, C10-1~ C12-56~ C14-24 C16~12~5 an~ Clg-5; to form an amphoteric~-fatty acid complex shown as compound A in the ~14-~pecification. ~he resultant dried powder is ~ound to be a sli~ht ocular irritan-t.
., .
Example IV
Following the procedures of Example I, 227 grams (.15 g/moles) of a 22% active solution of tetradecyl -iminodicarboxylate are dissolved in 450 grams of deionized water at a temperature of about 50-60Co 30 grams (.15 g/moles) OL the coconut fatty acid of Example I are - 10 added to form the resulting amphoteric-~atty acid complex which is a moderate irritant and is of the following structure:
1S [ U ] r CH2cH2c~ONal _ I ~ CH2CH2COONa _ H

~0 wherein Rl is a C6H13-C1gH37 mixture~

EXAM~LE V
..

300 grams ~0.07 g./moles) of an 11.1% activ~ solution of an amphoteric of the ~ormula ll H
CllH23~C~N~(CH2)2-l-CH2CHOHC~2SO3Na 30 _ H

are mixed with 14.1 grams ~0.07 g./moles) of premelted coconut fatty acids having the alkyl chain length distribution set forth in Example I. The resulting 3S product is a hazy solution containing 1~ solids, having a p~ of 7.3 and is an a~photeric-fatty acid complex of the formula:
[ r o c2~40~

I Cll}323-c-N-(cJ~2~2-N-cH2c~IoHcH2so3Na ~X~MPLE VI
360 grams (~.19 g./moles) of a 19.1~ active solution of an amphoteric of the formula r fH2cOONa 1 R~ - N
~ ~C~2COONa _ H _ wherein Rl has an alkyl chain length percent distribution as follows: Clo-2, C12-53~ C14-24~ C16-11 Clg-l~i are mixed with 40 grams (0.19 g./mo}es) of : premelted coconut fatty acids having the alkyl chain length distribution set forth in Example I. The resulting product is a hin, opaque slurry containing 27% solids havi~g a pH o~ 7~5 and is an amphoteric ~a~ty acid complex of the ~ormula.
r ~ 1 ~cH2cOoNa ~
LRl ~ ~ ~ R - N
~I CH2COONa _ ~

~1~7'~3~3 Example VII

A clear ~el hair care product is prepared as follow~; 200 grams of deionized water are charged to a vessel equipped with an agitator and steam. 50 grams of a phosphate ester hydrotrope are added and the pH is adjusted to 7Ø lS0 grams of Compound A are added and the solution is mixed until clear. 20 grams of polyethylene glycol 6000 distearate are added and heat is applied to the solution to 70C for twenty minutes. The solution is cooled to 25-30C and l.0 grams of preservative, 2.0 grams of fragrance and sufficient deionized water is added to bring the total weight to lO00 gcams.

15 The resulting product has the following compositions;

wt./wt.%
Compound A li.00 phosphate ester hydrotrope 5.00 polyethylene glycol 6000 distearate 2.00 preservative 0.10 fragrance 0.~0 deionized water q.s. to 100 Example VIII
-An opaque liquid soap is prepared having the following formulation:
wt.~wt.%
Compound A 15.00 - 30 Compound C lS.00 Cabosi' (tradename for colloidal silica, 3.50 available from Cabot Corp., Boston, Mass.) isopropanol 0.10 fragrance 0.30 deionized water q.s. to 100%

3 ~ ~ 3 The pH of the above formulation is adjusted to 6.5 with citric acid.

Example IX
5 A clear, liquid hair cleanser composition is prepared having the following formulation:

wt./wt.
Compound A 5.00 polyoxyethylene 80 sorbitan monolaurate 10.00 Deriphat~(tradename for salt of N-alXyl 5.00 beta-iminopropionic acid available from General Mills Inc.~ Kankekee, Illinois) polyethylene glycol 6000 distearate2.00 benzyl alcohol 0.10 Dowicil 200 (tradename for the cis isomer 0.10 or 1~(3-chloroalkyl)-3,5,7-triaza-1-azoniaadamantine chloride) fragrance 0.20 deionized water q.s. to lO0~

The above ~ormulation is adjusted to a pH or 7.l with 15%
HCl and has a viscosity of 413 cps. at 25C and is a slight ocular irritant. The formulation aiso exhibits good foam properties.

Example X
A detergent bar composition is prepared as follows: 50 parts of Compound A are mixed with 20 parts o~ Deriphat in a steam jacketed mixer at a temperature of 70C. After the slurry is homogeneous, lO parts of polyoxyethylene (80) sorbitan monopalmitate are added followed by the addition of lO parts each of talc and dextrin. The batch is mixed 20 minutes, cooled, milled into ribbons and pressed into detergent bars.

~.:1'7~6~3 The resulting bars have the following formulation.

~t./wt.%
Compound A 50.00 Deriphat 20.00 polyoxyethylene (80) 10.00 sorbitan monopalmitate talc lO.00 dextrin lO.00 100 . 00 and has a pH o~ 7~0. This product is a moderate irritant and exhibits excellent foaming properties.

EXAMPLE XI

In order to demonstrate the synergism of the amphoteric-fatty acid complexes of the present invention with respect to foam characteristics, compounds A and B, the amphoteric portion thereof and the coconut fatty acid portion thereof were individually tested in accordance with the modified Ross-Miles foam test set forth hereinbefore.

The results are shown in Table I below:

TABLE I
Initial foam Height (mm) -Normal Water Ha~d Water Compound % Activ and Grease 200 ppm CaCO3 amphoteric of compound A 5.0295 343 coconut fatty acid 5.0 0 0 compound A 5.0353 358 amphoteric of compound B 5.0 - 295 coconut ~atty acid 5.0 - 0 compound B 5.0 - 360 2~
In addition to the preferred embodiments described herein, other embodiments, arrangements and variations within the spirit of the invention and the scope of the appended claim will occur to those skilled in the art.

Claims

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

1. A compound 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 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.

2. The compound of claim 1 wherein R1 is a coconut fatty acid mixture.

3. The compound of claim 1 wherein R2 i5 C14H29.

4. The compound of claim 1 wherein R2 is C12H25.

5. The compound of claim 1 wherein R1 is a tallow fatty acid mixture.

6. The compound of claim 1 wherein A1 and A2 are ?CH2COOX)n.

7. The compound of claim 1 of the formula wherein R1 is a C11H23 - C18H37 mixture.

8. The compound of claim 1 of the formula wherein R1 is a C6H13 - C18H37 mixture.

9. The compound of claim 1 of the formula

10. A detergent composition wherein the active ingredients comprise from about 1 to 50% by weight of the total composition of at least one compound of the formula of claim 1.