FI80013B - TVAETTMEDELSFOERENINGAR OCH - KOMPOSITIONER. - Google Patents

Description

1 80013

The invention relates to amphoteric mixtures of fatty acid complexes and to detergent compositions containing them. More specifically, the invention relates to amphoteric fatty acid complex mixtures with surprisingly good foaming properties and low eye irritation. The invention further relates to detergent compositions comprising novel amphoteric fatty acid complexes together with other surfactants and / or detergent components.

Non-irritating detergent compositions have been known in the art and have been in use for some time.

Representative examples of such prior art non-irritating detergent compositions include those disclosed in U.S. Patent Nos. 3,299,069 and 3,055,836. Amphoteric compounds are known in the art and their use in various detergent compositions has also been described. U.S. Patent No. 2,528,380 discloses an amphoteric ring-structured compound having a fatty acid attached to a ring nitrogen atom. No previous publication has described the amphoteric fatty acid complexes of the present invention or the benefits thereof.

This invention relates to non-zwitterionic amphoteric fatty acid complex mixtures which are characterized in that the fatty acid part and the amphoteric part of the complex have the formulas 30 - _Θ _ Θ B / Ai

R.C-0 R - N

1 2 H A2

35 V- —I

having alkyl or alkenyl of about 6 to 18 carbon atoms; R 2 is alkyl of about 8 to 18 carbon atoms or alkylamido of the formula - O Z # 1 5 R 1 - C-N-Y-- - Λ - wherein R 1 is alkyl of about 8 to 18 carbon atoms; Z is H or lower alkyl of 1 to 4 carbon atoms; and Y is alkylene of 2 to 4 carbon atoms; A 1 and A 2 are the same or different and at least one is an anionic salt group (ch 2 ch 2 -coox) or t e ch 2 -coox 7 wherein X is a water-soluble cation, provided that when only one of the symbols A 1 and A 0 is an anionic the other is lower alkyl or hydroxylalkyl having 1 to 4 carbon atoms, the ratio of the fatty acid moiety to the amphoteric moiety in the complex being in the range of 0.5: 1 to 1.5: 1.

Suitable non-zwitterionic amphoteric compounds for use in the complexes of the present invention have the formula

* - H

wherein R2, A1 and A2 are as defined above. These compounds can be prepared in a manner known in the art, e.g., as described in U.S. Patent No. 2,970,160.

Fatty acid compounds suitable for use in the complexes of the present invention have the formula O ~ \ ®

II

35 R1-C-0 3 80013 wherein Rj is as defined above. These compounds are commercially available from a variety of fatty acid suppliers, including Emery Industries Inc., Cincinnati, Ohio, USA; Procter & Gamble, Cincinnati, Ohio, 5 USA, et al.

The amphoteric fatty acid complexes of the invention can be prepared by mixing together a suitable non-zwitterionic amphoteric compound and a suitable fatty acid, if necessary by heating the mixture to facilitate mixing and adding water as needed. The ratio of fatty acid to amphoteric compound may be about 0.5: 1 to 1.5: 1, preferably about 1: 1. The pH of the resulting complex should be between 6.5 and 8.5, preferably between 7.0 and 7.5, with minimal irritation.

Examples of the novel amphoteric fatty acid complexes of the present invention are as follows: O Ί0 f OH c H OH 1 ^

Il | l | / C2H4OH

(A) C1-C-O C1; 1H23-C-N- (CH2) 2-N

_ i ^ CH ^ COOK

n /

L

wherein R 2 is a mixture of C 11 H 23 -ClHH 3 O ".

25 - o Ί © Γ 1 © ί CHoCH ^ C00Na! L / 2 2

(B) R 1 -C-O C 14 H 29 N

NSsCH2CH2COONa 30 wherein R1 is an 80% / 20% mixture of tallow and coconut fatty acids.

'o 0 O ch3 Ίφ || |! I ch2chohch2so-k (C) R1C-O R2-C-N- (CH2) 2-N3-35H2CH0HCH2PO3Na2 wherein R1 is a tallow fatty acid mixture and R2 is a C1-H3 ”C17H25- mixture.

-1 © 4 80013 r ο η © r I / ch2chohch2so3 - Mg (D) R, -C-O C1 H -N / J I ^ CH2CHOCH2SO3 /

B

.... Λ% / 30% 5 wherein R 2 is a mixture of launic and myristic acids 70.

O ® ”H ® II 1 (E) Rj-C-O C12H25-N-CH2CH2-COONa 10 J L i wherein R 1 is a tallow fatty acid mixture.

f Ί Θ f ® «i CH2CH2COONa 15 (F) Ci iH23 — C“ 0 CH -n (11 23 14 29 ^ CH2CH2COONa _ L · O ΊΘ r -® | CH2CH2COONa 20 (G) R, -C-O CH? The amphoteric fatty acid complexes according to the invention have excellent surfactant properties, in particular these foams have good foaming properties and low eye irritation. the foaming properties are surprising because fatty acids generally do not have such properties, and in the pH range of 7.0 to 7.2, amphoteric fatty acid complexes have been shown to have unexpected foaming synergism.

These complexes can be used in detergent compositions either alone or in combination with other surfactants in amounts of about 1.0 to 50.0% by weight of the total composition.

5 80013

Suitable amphoteric surfactants for use in the invention include, for example, betaines, sultaines, phobobetaines, phosphitaines, n-alkylaminopropionates, n-alkyl iminodipropionates and imidazolines. Suitable betaine and sultaine surfactants are described in U.S. Patent 3,950,417, issued April 13, 1976. Phosphobetaines and phosphitaines suitable for use in the invention are described in U.S. Patent 4,215,064 and U.S. Patent Application No. 965,462. N-Alkyl-10-aminopropionates and n-alkyliminodipropionates are commercially available under the tradename Deriphat® (General Mills). Imidazolines suitable for use in the invention are described in U.S. Patent No. 2,970,160.

Preferred amphoteric betaine surfactants are alkyl betaines such as coconut dimethylcarboxyethyl betaine, lauryldimethylcarboxymethylbetaine, lauryldimethylcarboxyethylbetaxyl-ethoxymethylbimethoxy-bimethane (2-yl) -hydroxyethylbenzoxy - (2-hydroxypropyl) carboxyethyl betaine and the like; preferred sulfones include coconut dimethylpropyl sultaine, stearyldimethylpropyl sultaine, lauryl-bis- (2-hydroxyethyl) propyl sultaine and the like; and preferred amidosultamines include coconut amidodimethylpropyl sultaine, stearylamidodimethylpropyl sultaine, laurylamido-bis- (2-hydroxyethyl] propyl sultaine, and the like.

Preferred are fosfobetaiineja lauryylimyristyyliamido-3-hydroksipropyylifosfobetaiini, kookosamido 30-disodium ^ S ^ hydroksipropyylifosfobetaiini, lauriilimyris- tyyliamidodinatrium-3-hydroksipropyylifosfobetaiini, lauryylimyristyyliamidoglyseryylifosfobetaiini, lauryl myristyyliaraidokarboksidinatrium-3-hydroksipropyylifosfobetaiini the like. Preferred are fosfitaiineja kookosamido-35 propyylimononatriumfosfitaiini, lauryylimyristyyliamido - propyl monosodium phosphite and the like.

6 80013

Preferred n-alkylaminopropionates and n-alkyl iminodipropionates are as follows:?, Ch2ch2coo® fP - NH2CH2CH2COcP and R® -NH 5 alkyl, alkyl or a mixture thereof having 8 to 22 carbon atoms or a mixture thereof .

The amphoteric compounds may be present in the composition in an amount of about 2-10% by weight of the total composition.

Any anionic surfactants can be used in the compositions of the invention, such as, for example, alkyl sulfates of the formula R-C 1-4 -OSO-X, alkyl ether sulfates of the formula R (OCH 2 CH 2) -OSOX, 2 2 p ' alkyl monoglyceryl ether sulfonates of the formula r-och2-ch-ch2-so3x,

OH

20 alkyl monoglyceride sulfates of the formula rcooch2-ch-ch2oso3x,

OH

alkyl monoglyceride sulfonates of formula RC00CHoCH-CHoSO, X, 2 | 2 3

25 OH

alkyl sulfonates of formula RS03X and alkylaryl sulfonates of formula

R

@ -S ° 3X

wherein R is alkyl of 7 to 17 carbon atoms, X is an alkali metal, alkaline earth metal or ammonium ion or an ammonium ion substituted with 1 to 3 lower alkyl groups, and p is an integer from 1 to 6.

The anionic detergent compound may be present in the composition in an amount of about 2-10% by weight of the total composition.

7 80013

Suitable nonionic detergent compounds include alkylene oxide ethers of phenols, fatty alcohols and alkyl mercaptan, alkylene oxide esters of fatty acid amides, condensation products of ethylene oxide and partially esterified fatty acids, and mixtures of these compounds. The polyalkylene chain of such compounds may have 5 to 100 alkylene oxide units each having 2 to 3 carbon atoms.

The nonionic surfactant may be present in the composition in an amount of about 1-30% by weight of the total composition.

Suitable cationic surfactants for use in these compositions include, for example, mono- and bis-quaternary ammonium halides such as stearyldimethylbenzylammonium chloride, cetyl-trimethylammonium chloride, N, N-dioctadecyl-N, N, N ', N'-tetramethyl. (3-oxapentylene) diammonium bromide, tertiary amine salts such as coconut amidopropyldimethylamine hydrochloride, stearylamidopropyldimethylamine citrate; cationic polymers such as the product obtained by quaternization of the reaction product of hydroxyethylcellulose and epichlorohydrin with trimethylamine (polymers of this type sold by Union Carbide under the trade name "Polymer JR"), and certain triesters of phosphoric acid. Such phosphoric acid triesters are described in U.S. Pat. 59,838, filed July 23, 1979.

The cationic surfactant may be present in the composition in an amount of about 0.5 to 3.0% by weight of the total composition.

The total amount of surfactant contained in the composition of the invention should not exceed about 50% by weight of the composition to avoid eye irritation, preferably the surfactant is about 5-20% by weight of the composition, with the total amount of anionic and amphoteric surfactant not 35 should be greater than 20% by weight of the total composition. In addition, small amounts of other ingredients commonly used in personal care cleaners 8 80013 are used in the compositions, such as dyes, preservatives, perfumes, thickeners, opacifiers, conditioners, degreasers, buffers, etc. Ingredients such as dyes, preservatives and perfumes % by weight of the total composition, and their total amount is usually about 1 to about 3% by weight of the total composition.

The pH of the detergent compositions of the invention should be about 6.5 to 8.5, preferably about 7.0 to 7.5.

Liquid detergent compositions containing a complex of the invention can be prepared by mixing the amphoteric fatty acid complex and other surfactants at room temperature or at a slightly elevated temperature (about 50 ° C) and diluting the mixture with de-ionized water to about 3/4. intended final weight. Other ingredients such as various cleaning agents, fillers, carriers, perfumes, preservatives, gelling agents, etc. are added as needed with the remaining water to be added. The pH is then adjusted to the desired range by adding a strong acid, e.g. HCl, or a strong base, e.g.

NaOHia.

Solid detergent bodies using the complex of the invention can be prepared by mixing a 25-mile amphoteric fatty acid complex with other surfactants in a steam-jacketed rotary mixer at a temperature in the range of 60-80 ° C. Fillers, brighteners and process oils can be added to the hot pulp as needed. After sufficient mixing, the homogeneous and moisture-balanced product is rolled cold or tumble-dried into flakes. Color and fragrance are added to the flakes in a standard bleacher and a suitable amount of water to form detergent pieces. The flakes are mixed, piled and compressed into 35 bars and cut into pieces which are stamped.

The eye irritant effect of the detergent compositions of the invention can be studied by the following modified Draize test (J.H. et al., Toilet Goods Assn. No. 17, May 1952, No. 1, Proc Sci, Sect.).

9 80013 0.1 ml of the neutral sample to be examined is instilled into one eye of the albino rabbit with the other eye as a control. For each composition, 6 rabbits are used. Observations are made 1, 24, 48, 72, and 96 hours and 5 7 days after the first eye instillation, second and third eye instillations are made after 24 and 48 hours of observations. Results may range from almost unchanged or mild rabbit eye irritation after 7 days to severe irritation and / or complete corneal opacity. Corneal, lens, and conjunctival lesions are assessed, with a higher number indicating more severe eye irritation, and the scores obtained from each assessment are summed for each of the six rabbits and divided by the number of rabbits to obtain an average of 15. Mean scores indicate the irritability of the test composition. Based on the average scores, the irritancy of the composition can be reported, e.g., as irritant, mild, moderate, or severe irritant.

The compositions according to the invention give a high volume of foam and excellent foam stability, as shown by measurements carried out according to the well-known principle of the Ross-Miles foam test, "Oil and Soap" 18.9-102 (1941):

Anhydrous cosmetic grade lanolin 25 is mixed with dioxane (technical grade) in a ratio of 2.5 g lanolin + 100 g dioxane. The lanolin is first mixed with 25 ml of dioxane. The mixture is heated on a steam bath at 45 ° C to dissolve the lanolin in dioxane. The rest of the dioxane is added and stirred. This lano-30 line dioxane solution is stored in brown bottles and should always be prepared on the same day the experiment is performed.

The test composition is diluted by adding 376 ml of distilled water to 4 g of the composition and then mixing with 2 ml of the lanolin-dioxane solution prepared above. When lanolined dioxane solution is added to the aqueous solution of the composition, heat is generated and care must be taken to maintain the temperature of the solution at 10-251 ° C. Each of these stirred solutions should thus be adjusted to 23 ° C before mixing. Cooling of the lanolined dioxane solution should be performed. gradually to avoid precipitation of lanolin. This gives a final solution with a temperature of 24-25 ° C.

The final solution containing the test composition described above, water, dioxane and lanolin is then poured onto a modified Ross-Miles foam column in the usual manner. All experiments are performed in duplicate, and results are averaged over two experiments. Foam stability is determined by measuring the decrease in foam height in 2 minutes and is expressed as a percentage of the original foam height. The following examples illustrate specific embodiments of the present invention. It is to be understood, however, that these specific examples do not limit the scope of the invention.

Example I

320.2 g (0.19 mol) of formula

1? / C2H4OH

C11H23-C-N- (CH2) 2-N

^ NCH2COOK

A 24% solution of the amphoteric compound 25 according to the active ingredient is premixed with a melted coconut fatty acid mixture (47 g, 0.24 mol) having the following carbon chain distribution (%): Cg-0.3, Cg-7, 3.30 C ^ ^ q -6.5, C ^ ^ ~ ~ 50.7, 18.9, C- ^ g-8.6, C

The product obtained is a translucent viscous mass containing 34% solids and having a pH of 7.1; it is an amphoteric fatty acid complex of formula A above. This complex is rich in foam in both soft 35 and hard water, and is only slightly irritating to the eyes.

11 8001 3

Example II

The product prepared in Example I is lyophilized in a known manner to a product containing about 95% solids. The product is ground to a slightly sticky powder which can be used to prepare a unitary detergent with a low eye irritation.

Example III

Following the procedure of Example I, the amphoteric compound used therein is mixed with a mixture of hydrogenated coconut fatty acid-10 (from which the lower fatty acids have been removed) having the following chain length distribution: Cg -1, C10-1, C12-56, C12-24, C ^ g-12.5 and C ^ g-5; the amphoteric fatty acid complex represented by formula A above is obtained. The dried powder prepared proved to be very mildly irritating to the eyes.

Example IV

Following the procedure of Example I, 227 g (0.15) of a solution of tetradecyliminodicarboxylate (22% of active ingredient) are dissolved in 450 g of deionized water at about 50-60 ° C. To the solution is added 30 g (0.15 mol) of the coconut fatty acid mixture used in Example I to give a mildly irritating amphoteric fatty acid complex of the formula 25 o T © Γ 1 © ji CH_CHoC00Na

II / 2 2 ri-c-o c14h29-n J ^ ^ CH2CH2COONa 30 s where R ^ is a mixture of C8H2N-CH2H2O2.

12 80013

Example V

300 g (0.07 mol) of formula 5 / '(i)

OH C-H.OH

II 12 C11H23-C "N (CM,) 2-N-CH2CHOCH2SO3Na 10 solution (11.1% of active ingredient) and 14.1 g (0.07 mol) of a molten mixture of coconut fatty acids with a chain length of the distribution is the same as in Example I. A cloudy solution with a solids content of 15% and a pH of 7.3 is obtained, containing 15 amphoteric fatty acid complexes as follows: v Λ s 0 / 'l®

(O OH C-H.OH

I II I2 4

Rj-C-O CjL1H23-C-N (CH2) 2-N-CH2CHOCH2SO3Na

20 l J H

N /

Example VI

360 g (0.19 mol)% distribution of the chain length of the amphoteric compound of the formula 25 r -i® CH-COONa / 1R - N2 1 \ ^ CH2COONa 30: C1Q-2, C12-53, C (-24, C16-C11, C18-10) A solution containing 19.1% of active ingredient is mixed with a melted mixture of coconut fatty acids (40 g, 0.19 mol) having the same% distribution of alkyl chain length as i3 8001 3 in Example I. A thin, translucent suspension is obtained which contains 27% solids and has a pH of 7.5. The amphoteric fatty acid complex it contains is as follows: 5 r τη Ί® Γ .CH-COONa I! R, - * / R, -C-O 2 | \ 1 ^ CH2COONa 10

Example VII

A transparent gel-like hair conditioner is prepared as follows: 200 g of deionized water are placed in a vessel equipped with a stirrer and a steam jacket. 50 g of phosphate ester hydrotrope are added and the pH is adjusted to 7.0. 150 g of compound A are added and the solution is stirred until clear. 20 g of polyethylene glycol-6000-stearate are added and the solution is heated at 70 ° C for 20 minutes. The solution is cooled to 25-30 ° C and 1.0 g of preservative, 2.0 g of perfume and deionized water are added to give a total weight of 1000 g.

The composition of the prepared product is as follows: w / w% Compound A 15.00

Phosphate ester hydrotrope 5.00

Polyethylene glycol ^ eQOO -'-distearate 2.00 Preservative 0.10

Perfume 0.20 30 Deionized water ad. 100%

Example VIII

Prepare a liquid translucent "soap" using the following recipe: i4 8001 3 w / w% 5

Compound A 15.00

Compound C 15.00 "Cabosil" colloidal silicic acid, manufactured by 3.50 Cabot Corp. Boston, Mass.).

10 Isopropanol 0.10

Scent 0.30

Deionized water ad. The 100% pH is adjusted to 6.5 with citric acid.

15 Example IX

A clear, liquid hair cleanser is prepared according to the following recipe: w / w% 20 Compound A 5.00

Polyoxyethylene (80) sorbitan monolaurate 10.00 "Deriphat" (N-alkyliminopropionic acid, manufactured by General Mills Inc. Kankekee,

Illinois) 5.00 25 Polyethylene glycol ^ eOOQ- ^ distearate 2.00

Benzyl alcohol 0.10 "Dowicil 200" (1- (3-chloroalkyl) -3,5,7-triazole-1-azonia-adamantine chloride cis-isomer) 0.10 30 Fragrance 0.20

Deionized water ad 100.00% is 8001 3

Example X

The detergent composition in unit form is prepared as follows: 50 parts by weight of compound A and 20 parts by weight of "Deriphat" are heated and mixed at 70 [deg.] C. in a steam jacketed mixer.

To the resulting homogeneous mixture is added 10 parts by weight of polyoxyethylene (80) sorbitan monopalmitate and then 10 parts by weight of talc and 10 parts by weight of dextrin. The batch is mixed for 20 minutes, the mixture is cooled, rolled into strips and pressed into detergent pieces. The product obtained has the following composition: w / w%

Compound A 50.00

Deriphat 20.00 Polyoxyethylene (80) sorbitan monopalmitate 10.00

Talc 10.00

Dextrin 10.00 100.00 20 Product pH pn 7.0. The product is only slightly irritating and has excellent foaming properties.

Example XI

To demonstrate the synergism of the amphoteric fatty acid complexes of the invention, its components A (amphoteric component) and B (coconut fatty acid component) were tested separately and as a complex as described above in a modified Ross-Miles foaming experiment. The results are shown in the following Table I: 16 8001 3

Table

Active- Initial foam height (mm) Compound% by weight normal water 200 ppm + fat CaCO 2

Amphoteric Compound A of Compound A 5.0 295 343

Coconut fatty acid

Compound A 5.0 353 358

Amphoteric compound of compound B 5.0 to 295 10 Coconut fatty acid 5.0 to 0

Compound B 5.0 to 360

In addition to the preferred embodiments described above, one skilled in the art may, without departing from the spirit of the invention, perform other embodiments, arrangements, and variations.

Claims (7)

1 I R -C -C-N-Y-- wherein R 3 is alkyl of about 8 to 18 carbon atoms; Z is H or lower alkyl of 1 to 4 carbon atoms; and Y is alkylene of 2 to 4 carbon atoms; A2 and A2 are the same or different and at least one is an anionic salt group 4CH2CH2-COOX] or -ECH2 -COOX] wherein X is a water-soluble cation, provided that when only one of A2 and A2 is an anionic salt group, the other is 1- Lower alkyl or hydroxylalkyl having 4 carbon atoms, wherein the ratio of fatty acid moiety to amphoteric moiety in the complex is in the range of about 0.5: 1 to 1.5: 1. is 8001 3 A mixture useful in detergent compositions comprising a complex of fatty acids and amphoteric compounds, characterized in that the fatty acid part and the amphoteric part of the complex have the formulas _ - Θ _ Θ O Γ "7 \ io ^ / * · iU RC-0 R. -N_1 J 2 i \ AH 2 wherein Rx is alkyl or alkenyl of about 6 to 18 carbon atoms, R2 is alkyl or alkylamido of about 8 to 18 carbon atoms of formula 0z Mixture according to Claim 1, characterized in that R 1 is a mixture of coconut fatty acids. Mixture according to Claim 1, characterized in that R 2 is C x 4 H 9. Mixture according to Claim 1, characterized in that Ax and A2 are -ECH2COOX]. Mixture according to Claim 1, characterized in that the complex has the formula 10 'o \ ^ e oh ^' 3 | il | / CH2H4OH Rj-C-Q CllH23-C-N (CH2) 2-N JXCH „COOK \, .s n z \ s 15 where Rx is a mixture of Cx x 82 3 -Cx e B3 7. Mixture according to Claim 1, characterized in that the complex has the formula r -n® (j I |, / CH 2 CH 2 C 2 Na) 25 CUH23-C- ° C14H29- \ J CH „CH„ COONa * V i £. 'v Detergent composition, characterized in that it contains, as active ingredient, about 1 to 50% by weight of the total composition of at least one complex as defined in the claim. i9 8001 3