DE3208311A1 - AMPHOTIC FATTY ACID COMPLEX AND DETERGENT MIXTURES - Google Patents

Description

The invention relates to amphoteric fatty acid complexes, especially those complexes with particularly advantageous foam properties and low eye irritation. The invention also relates to detergent-containing mixtures in which the amphoteric. Fatty acid complexes in combination with other surfactants Substances and / or detergents are present.

Non-irritating compositions containing detergents are known and have been used for some time (üS-PSs 3 299 069 and 3 055 836).

Amphoterics are also known and have been described in connection with the use of various other detergents been. In US-PS 2,528,380 an amphoteric is indicated with a ring structure, where an the nitrogen atom in the ring is attached to a fatty acid. However, so far it is not from amphoteric fatty acid complexes and their advantages have been reported in accordance with the present invention.

The invention is based on the object of making new detergents available. In particular, should those compounds and mixtures containing these compounds are specified which have good foam properties and a low irritating effect on the eyes.

This task is performed by amphoteric fatty acid complexes of the general formula I.

R ₂ -N
H

(I)

-β-

dissolved, in which R _{1 is} an optionally substituted alkyl radical with about 6 to 18 carbon atoms or a mixture of such radicals, R- is an alkyl radical with about 8 to 18 carbon atoms, a mixture of such radicals or an alkylamido radical of the general formula II

0 Z

U I

R ₃ -CNY-

(II)

represents in which R _{3 is} an alkyl radical having about 8 to 18 carbon atoms, Z is a hydrogen atom or a lower alkyl radical having 1 to 4 carbon atoms and Y is a lower alkylene radical having 1 to 4 carbon atoms, and

A ₁ and A ~ are identical or different and each is an anionic salt radical of the general formula

-KIH ₂ -COOX] _n ,
-ICH ₂ CHOH-CH ₂ -So ₃ XI _n
■ fCH ₂ -CHOH-CH ₂ -OPO ₃ X] _n

represent, where X is a water-soluble cation and η is the number 1 or 2, or one of the radicals A ₁ and A _{2 is} one of the aforementioned anionic salt _{radicals and the other radical A 1} or A _{2 is} a lower alkyl or hydroxy lower alkyl radical having 1 to 4 carbons -r means material atoms.

The water-soluble cation X is preferably a sodium, potassium, calcium or magnesium ion.

- "7-

The amphoteric present in the complexes according to the invention is not a zwitterion and has the general Formula Ia

on, in the have.

R ₂ -N

(I a)

- and A_ the preceding meaning

These compounds can be made in accordance with, for example, U.S. Patent No. 2,970,160.

The fatty acid present in the complexes according to the invention has the general formula 1b

R ₁ -CO

(I b)

in which R _{1 has} the above meaning. These compounds are readily available commercially from various sources (e.g., Emery Industries Inc., Cincinnati, Ohio; Procter & Gamble, Cincinnati, Ohio).

The amphoteric fatty acid complexes according to the invention can be prepared by mixing an appropriate amphoteric and a corresponding fatty acid can be easily produced. If necessary, heat can be added, in order to facilitate the mixing and, if necessary, the appropriate addition of water. The relationship

from fatty acid to amphoteric can be about 0.5: 1 to 1/5: 1, preferably about 1: 1. Of the The pH of the complex obtained should be in the range from 6.5 to 8.5, preferably in the range from 7.0 to 7.5, in order to keep possible irritative effects of the complex low.

Specific examples of amphoteric fatty acid complexes according to the invention are given below:

15th

(A)

Il

R ₁ -CO

0 H C2H4OH

01 /

C ₁ HCN (CH ₂ J ₂ -N _n ^{11 23} I XH ₂ COOK

20th

means a mixture of groups of the structure

empire ""

~ ^C 18 ^H 37 "

25 30

(B)

Γ ° 1

Il

I Rj, -C-O

(C)

R ₁ -CO

Ci4H ₂ 9-

CH ₂ CH ₂ COONa

I XH ₂ CH ₂ COQNa H

O CH3

ί I

from sebum and coconut fatty acid

CH2CHOHCH2SO3K

ί I /

R ₂ -CN- (CH ₂ ) ₂ -N:

PCH ₂ CHOHCH ₂ OPO ₃ Na ₂ -H

RJ means a tallow fatty acid _{residue and R 2 is} a mixture of groups from the structural range -C ₁₁ H- to -C ₁ -H- ^.

I 1 ^ J 17 35

- Q—

(D)

R ₁ CO

1 ^X CH-CHOHCH-SO, -H ² 2 3

R- means a mixture of residues of dodecylic acid and Myristic acid (70:30).

(E)

RIC-O

^c 12 ^H 25 ~ ^N "" ^CH 2CH ₂ -COONa

* means a sebum fatty acid residue.

(F)

(G)

H CH ₂ CH ₂ COONa "CH ₂ CH ₂ COONa ^

CH ₂ CH ₂ COONa

i ^ CH ₂ CH ₂ COONa H

means a mixture of groups of the structural region H V> 4 β —C TI

The amphoteric fatty acid complexes according to the invention have excellent properties in terms of their interfacial activity. In particular, they show Complex good foam properties and low eye irritation. The good foam properties are therefore unexpected because they are not normally found in fatty acids. It was also found that the amphoteric fatty acid complexes in the pH range from 7.0 to 7.2 with regard to foam formation act synergistically.

The complexes according to the invention can be used in detergents containing mixtures either alone or in combination with other surfactants in a range of about 1.0 to 50.0 weight percent, each based on the total mixture.

The amphoteric surfactants that can be used in connection with the invention, are e.g. betaines, sultaines, phosphobetaines, phosphitaine, n-alkylaminopropionate, n-alkyliminodipropionate and imidazolines. Surface-active substances based on betaines and sultaines are in U.S. Patent 3,950,417. Suitable phosphobetaines and phosphitaines are disclosed in US Pat. No. 4,215,064 known. The n-alkylaminopropionate and n-alkyliminodipropionate are commercially available (Deriphats; General Mills). Suitable imidazolines are in the U.S. Patent No. 2,970,160.

Preferred betaines as amphoteric surfactants include alkyl betaines, such as Cocodimethylcarboxymethylbetäin, lauryl, Lauryldimethylcarboxyäthylbetain, cetyl dimethyl carboxymethyl betaine, lauryl bis- (2-hydroxyethyl) carboxymethyl betaine, Oleyldimethyl- 9 ^{/ M} ~ ^{car t) Ox} yP ^r ~ PPyl betaine and lauryl bis- - (2-hydroxypropyl) carboxyethyl betaine.

Preferred sultaines are cocodimethylpropylsultaine, stearyldimethylpropylsultaine and lauryl-bis (2-hydroxy-

ethyl) propylsultaine.
35

Preferred amidosultaines are cocoamidodimethylpropylsultaine, Stearylamidodimethylpropylsultaine; 5 and laurylamido bis (2-hydroxyethyl) propylsultaine.

Preferred phosphobetaines are lauric myristinamido -3-hydroxypropylphosphobetaine / cocoamidodisodium-3-hydroxypropylphosphobetaine, Lauric myristine amido disodium-3-hydroxypropy lphosphobetaine, lauric myristine amidoglycerylphosphobetaine and lauric myristine amidocarboxydisodium 3-hydroxypropylphosphobetaine.

Preferred phosphitaine are cocoamidopropyl monosodium phosphite and lauric myristinaitiidopropyl monosodium phosphitain.

Preferred n-alkylaminopropionates and n-alkyliminodipropionates are such connections with the general Formula III or IV

R -

(III)

¹ Θ

CH. ₂ Ca-COO

R - NH.

CH ₂ CH ₂ COO Na

in which R is a radical having about 8 to 22 carbon atoms "^ or a mixture of such radicals means.

The amphoteric detergents can be used in an amount of about 2 to 10% by weight, based on the total mixture,

can be used.
35

Any anionic surface-active substance can be used in the detergent-containing mixtures according to the invention, for example
an alkyl sulfate of the general formula IV

R-CH ₉ -OSO ^ X

(V)

Alkyl ether sulfate of the general formula VI

R (OCH ₂ CH ₂ ) P-OSO ₃ X:

an alkyl monoglyceryl ether sulfonate of the general formula VII

R-OCH ₂ -CH-CH ₂ -SO3X,

an alkyl monoglyceride sulfate of the general formula VIII

RCOOCH ₂ -CH-CH ₂ OSOsX

OH

(VIII),

an alkyl monoglyceride sulfonate of the general formula IX

RCOOCh ₂ CH-CH ₂ SO ₃ X OH

(ix),

an alkyl sulfonate of the general formula X

RSO ₃ X

(X)

and an alkylarylsulfonate of the general formula XI

(XI).

SO3X

In the general formulas V to XI, R is an alkyl radical having 7 to 17 carbon atoms, X is an alkali metal, alkaline earth metal , ammonium or ammonium ion substituted by 1 to 3 lower alkyl radicals, and ρ is an integer from 1 to 6.

The anionic detergent can be present in an amount of about 2 % to 10% by weight based on the total mixture.

Suitable nonionic detergents are, for example, alkylene oxide ethers of phenols, fatty alcohols and Alkyl mercaptans, alkylene oxide esters of fatty acid amides, Condensation products of ethylene oxide and partial fatty acid esters and mixtures of these Links. The polyoxyalkylene chain in such substances can contain 5 to 100 alkylene oxide units, each alkylene unit having 2 to 3 carbon atoms.

The nonionic surfactants can be in an amount of about 1 to 30 wt .-%, based on the entire mixture.

Suitable cationic surfactants in the mixtures according to the invention are mono- and bisquaternary ammonium halides, such as stearyldimethylbenzylammonium chloride, Cetyltrimethylammonium chloride and N ^ -dioctadecyl-N, H, N ', N'-tetramethyl-1,5- (3- -oxapentylene) - diammonium bromide, tertiary ammonium salts, such as cocoamidopropyldimethylamine hydrochloride and stearylamidopropyldimethylammonium citrate,

³ ^ cationic polymers, such as hydroxyethyl cellulose, the

reacted with epichlorohydrin and then quaternized with trimethylamine (Polymer JR; Union Carbides), as well as special phosphoric acid triesters.

The cationic surfactants can be used in an amount of about 0.5 to 3.0 weight percent present on the entire mixture.

The total amount of the active surface-active constituents in the mixtures according to the invention should Do not exceed 50%, based on the total mixture, in order to avoid eye irritation. Preferably the total amount of these ingredients is about 5 to 20 wt .-%, based on the total Mixture. It also applies that .the total amount of anionic and amphoteric surface-active substances 20% by weight, based on the total mixture, should not exceed.

In addition, other substances can be added, which are usually used in mixtures of substances, which are intended for use in the personal area. Such additional substances include e.g. colorants, preservatives, fragrances, thickeners, opacifiers, conditioning agents, Plasticizers and buffers, each in small amounts. Additives such as colorings, preservatives and fragrances together generally achieve a proportion of less than 2% by weight, based on the total Mixture. Thickeners can be added to the mixture in an amount of from about 1 to about 3 percent by weight

on the entire mixture. 35

The detergent-containing mixtures according to the invention should have a pH of about 6.5 "to 8.5, preferably from about 7.0 to 7.5.

Liquid detergent-containing mixtures which contain complexes according to the invention can be prepared in this way that you can use the amphoteric fatty acid complex

IQ the other surfactant or substances at room temperature or slightly elevated temperature, for example at about 50 ⁰ C, mixed with one another and then adding a sufficient amount of deionized water to set about 3/4 of the intended weight of the mixture. Then the other ingredients such as detergent auxiliaries, fillers, carriers, fragrances, preservatives and gelling agents are added in the required amounts. Finally the rest of the water is added. The desired pH is then set by adding a strong acid, for example hydrochloric acid, or a strong base, for example sodium hydroxide.

Detergent-containing mixtures in the form of sticks., The contain a complex according to the invention can be prepared by using the amphoteric fatty acid complex with the other surfactant or substances in a rotary mixer, the has a steam-powered heating jacket, at Mixed temperatures from 60 to 80 ° C. To the

Fillers, whitening agents and processing oils can be added to hot slurry as needed. After sufficient mixing until homogeneous and moisture equilibrium ³ ^ the mixture is rolled with quenching or treated in a drum dryer, with flakes

are formed. These are put in a standard amalgamator with dyes and fragrances as well c treated with further water, which ensures the production of pencils in a suitable manner. According to the appropriate Mixing, the flakes are rolled and extruded into rods, which then cut into blanks and put into pins of the desired JO th shape are pressed.

The detergent-containing mixtures according to the invention can according to the following Draize test (Toilet Goods Assn. No. 1.7 (May 1952), No. 1, Proc. Sci. Sect.)

IB tested for their eye irritation ".

A 0.1 ml sample of the neutral mixture to be tested is placed in one eye of an albino rabbit dripped while the other eye is used for comparison. Six rabbits are used for each mixture.

The treated eye is assessed 1, 24, 48, 72 and 96 hours and 7 days after the first administration. One second and third administrations are made after 24 and 48 hours. The result of the assessment of the treated eye after 7 days can range from "essentially unchanged" or "only." slight irritation "to" severe irritation "and / or" complete corneal opacity " are numbered for the cornea, iris, and conjunctiva, with a higher number being one corresponds to stronger eye irritation. The rating numbers are each for an examination of six Rabbits added to a total and averaged. The mean value is a measure of the possible irritative effect of the tested mixture. On the basis of the

°° Mean values can be used as a descriptive stimulus evaluation

specified, e.g. the irritation is "nonexistent, slight, moderate, strong".

The detergent-containing mixtures according to the invention ensure a large foam volume and above In addition, an extraordinary foam stability, as through a modification of the well-known Ross Miles foam test (Oil and Soap, 18.9-102 (1941), which is given below.

Anhydrous lanolin in a form suitable for cosmetic use is mixed with technical grade dioxane (ratio of 2.5 g lanolin: 100 g dioxane). The lanolin is first mixed with 25 ml of dioxane. This mixture is heated in a steam bath to a temperature of 45 ^° C. in order to dissolve the lanolin in the dioxane. The remaining dioxane is then mixed in * The resulting solution of lanolin in dioxane, which is kept in a brown bottle, should be freshly prepared on the same day on which the test is carried out.

The mixture to be tested is distilled by adding 376 ml. Water diluted to 4 g of the mixture and then 20 ml of the aforementioned lanolin-dioxane solution are added while stirring. In the latter case Adding is developing heat, and setting one

The temperature of the solution from 24 to 25 ° C must be done carefully. Therefore, the two solutions should be set to a temperature of 23 ^° C. before they are mixed together. The lanolin-dioxane solution should be cooled gradually to prevent precipitation of the *. Avoid lanolin. Finally, a solution with a temperature of 24 to 25 ^° C. is obtained.

-Ιδ-

This solution of the mixture to be tested, water, dioxane and lanolin is then in the usual way in given a modified Ross Miles foam column. All examinations are performed in duplicate and the two results are averaged. The foam stability is expressed as a percentage of the original with the help of the decrease in foam height after 2 minutes Height, for sure.

The examples illustrate the invention.

15 20 25 30

example 1

320.2 g (0.19 moles). a 24% active solution of an amphoter of the following formula

O H

C2H4OH | ^N CH ₂ COOK

are mixed with 47 g (0.24 mol) of premelted coconut fatty acids, which the following, in Percentage distribution of the chain lengths shows:

CgO.3;

Cg7.3; C _{1 ()} 6.5; Cj ₂ 50.7; C ₁₄ 18.9;

C ₁₈ 7.7.

The product obtained is opaque and viscous and contains 34% solids at a pH of 7.1 The amphoteric fatty acid complex has the structure given under (A) above. The complex lathers abundantly in both soft and hard water and has little eye-expressiveness.

Example 2

10

The product obtained according to Example 1 is freeze-dried in the usual manner, about 95% solids being obtained. These become one easy Grind a sticky powder that can be used to make a soap stick. It has a slight to moderate eye irritation.

Example 3

According to Example 1, the amphoteric mentioned there is mixed with hydrogenated coconut fatty acids which have the following distribution of the chain lengths given in percentages: Cg 1; C-iqI? 'C ^ ₂ SSj C ₁₄ 24; C.jg12, C ₁ QS. The amphoteric fatty acid complex obtained has the structure given above under (A). The dry powder obtained has little eye irritation.

Example 4

25 30 35

According to Example 1 227 g (0.15 mol) are dissolved to a 22% active solution of Tetradecyliminodicarboxylat in 450 g of deionized water at a temperature of about 50 to 60 ⁰ C. 30 g (0.15 mol) of the coconut fatty acids mentioned in Example 1 are added. An amphoteric fatty acid complex with a moderate eye irritation and the following structure is obtained

CH ₂ CH ₂ COONa 'CH ₂ CH ₂ COONa

R _{1 here} denotes a mixture of groups from the structural range -CgH ₁₃ to ~ ^c i8 ^H 37 *

Example 5

10 15th 20th 25th

300 g (0.07 mole) of an 11.1% active solution of an amphoter of the formula

OC ₂ H ₄ OH - - ¹

JH j
^C 11 ^H 23- ^C ~ ^N '' _{CH2) 2-N-CH2 CHOHCH ₂ SO ₃ Na

• ^H ■

are mixed with 14.1 g (0.07 mol) of premelted coconut fatty acids, which are those in Example 1 have given distribution of the alkyl chain lengths. , The product obtained is a cloudy solution with 15% solids and a pH of 7.3. The structure of the amphoteric fatty acid complex is as follows specified.

Ry- CO

O it

C2H4OH

C11H23-CN- (CH ₂₎ 2 N-CH ₂ CHOHCH ₂ SO ₃ Na

30th

Example 6

There are 360 g (0.19 mol) of a 19.1% active solution of an amphoter of the formula

- ^ CH ₂ COONa J "^ -CH ₂ COONa

are used, in which R2 has the following distribution of the alkyl chain lengths given in percentages: C ₁₀ 2; C ₁₂ 53; C ₁₄ 24; 0 ^ 11; C ^ IO.

This amount of the amphoteric is mixed with 40 grams (0.19 moles) of premelted coconut fatty acids, which have the distribution of the alkyl chain lengths given in Example 1. A thin, cloudy one is obtained Product with 27% solids and a pH of 7.5. The structure of the amphoteric fatty acid complex is given below.

Θ - ■. _CH QQ ₀ Na O ~ _Rl -co R ₂ - ^N \ ^ - - - H CH ₂ COONa

Example 7

A clear hair care product in gel form is produced in the following manner: A container equipped with a stirrer and a steam supply is charged with 200 g of deionized water. 50 g of a hydrotrope in the form of a phosphate ester are added and the pH is adjusted to 7.0. After adding 150 g of the compound given under (a) above, the solution is stirred until it is clear. Then, 20 g Polyäthylenglykoldistearat be (polyethylene glycol 6000 distearate) mixed in and the solution is heated by heat supply 20 minutes at a temperature of 70 ⁰ C. After cooling to 25 to 30 ^° C., 1.0 g of preservative, 2.0 g of fragrance and enough deionized water are added so that the total weight is 1000 g.

M t · Ιφ

-22-

The product obtained has the following composition:

Components Wt% Connection A 15.00 Phosphate ester 5.00 Polyethylene glycol distearate 2.00 Preservatives 0.10 Fragrance 0.20 Deionized water until 100 Example 8

An opaque liquid soap is made with the following composition:

Components% by weight

Connection A 15.00 Compound C 15.00 Colloidal silica (Cabosil; Cabot Corp., Boston) 3.50 Isopropanol 0.10 Fragrance 0.30 Deionized water until 100

The pH of the mixture obtained is adjusted to 6.5 with citric acid.

Be ispiel 9

A clear liquid shampoo with the following composition is made:

Components% by weight

Compound A 5.00

Polyoxyethylene sorbitan monolaurate

(Polyoxyethylene 80) 10.00

N-alkyl-P -iminopropionic acid (Deriphat, General Mills Inc., Kankekee, Illinois 5.00

Polyethylene glycol distearate (poly-

ethylene glycol 6000) 2.00

Benzyl alcohol 0.10

cis -1 (3-chloroalkyl) -3,5,7-triaza-1-azoniadamantine chloride (Dowicil 200) 0.10

Perfume '0.20

Deionized water up to

The mixture obtained is treated with 15% hydrochloric acid adjusted to a pH of 7.1 and has a viscosity of 413 mPa · s at 25 ° C. It is slightly irritating to the eyes and shows good foam properties.

Example 10

A detergent-containing stick is made in the following way: 50 parts of compound A are with Share N-alkyl-ß -iminopropionic acid in a mixer, which is provided with a steam-operated heating jacket,

³ ^ mixed at a temperature of 70 ^{0 C.} After the mixture is homogeneous, 10 parts of polyoxyethylene sorbitan monopalmitate (polyoxyethylene 80) and then 10 parts each of talc and dextrin are added. The batch is mixed for 20 minutes, cooled, formed into a tape, rolled and transferred to detergent-containing sticks by pressing.

The pens obtained have the following composition ϊ

Components Wt% Connection A 50.00 N-alkyl-ß-iminopropionic acid 20.00 Polyoxyethylene sorbitan monopalmitate (Polyoxyethylene 80) 10.00 talc 10.00 Dextrin 10.00

100.00

The pH of the pens is 7.0. The product is moderately irritating and has excellent foam properties

example

About the synergistic effect of the amphoteric fatty acid complexes according to the invention with regard to the foam properties to explain the compounds A and B, their amphoteric component and their coconut fatty acid component tested in detail according to the modified Ross Miles foam test.

The results are summarized in the table below:

Tabel

Initial foam, height (mm), activity norm;. · Water -Hard water, compound% and fat

Amphoter of the Ver
bond A 5.0 295 343 Coconut fatty acid 5.0 0 0 Connection A 5.0 353 358 Amphoter of the Ver
binding B 5.0 - - 295 Coconut fatty acid 5.0 - 0 Connection B 5.0 - 360

Claims (8)

Amphoteric fatty acid complexes and detergent-containing Mixtures P ate.nt to claims ΛAmphoteric fatty acid complexes of the general formula 1 R ₁ CO (D in the R- with an optionally substituted alkyl radical about 6 to 18 carbon atoms or a mixture of such remnants means R _{0 is} an alkyl radical with about 8 to 18 carbon atoms or a mixture of such radicals or an alkylamido radical of the general formula II O Z Il i R ₃ -CN Y- (II) represents, in which R _{3 is} an alkyl radical having about 8 to 18 carbon atoms, Z is a hydrogen atom or a lower alkyl radical having 1 to 4 carbon atoms and Y is a Nxederalkylenrest having 1 to 4 carbon atoms, and A ₁ and A2 are identical or different and are each one anionic salt residue of the formula - £ C3 ₂ -coox] _nl ■ £ CH ₂ CHOH ~ CH2 ~ SO3X] _n or represent, where X is a water-soluble cation and η is the number 1 or 2, or one of the Radicals A-) and A- are one of the aforementioned anionic Represents salt radicals and the other of the radicals A- and A- is a lower alkyl radical or hydroxy-lower alkyl radical means having 1 to 4 carbon atoms. 2. Complexes according to claim 1, characterized in that R- is a mixture of residues of coconut fatty acids or a mixture of residues of tallow fatty acids. 3. Complexes according to claim 1, characterized in that R- denotes the group ~ ^C - | 4 ^H 29 ^{o <} ^ ^er äie group ~ ^c i2 ^H 25. -Β4. Complexes according to claim 1, characterized in that A ₁ and A ₂ each represent the radical - (CH ₂ COOX) _n , in which X and η have the meaning given in claim 1. 5. Complex of the formula [■ Ri-C-O O H C ₂ HaOH • Ii ι / C ₁ , H -, - CN (CEb) 2 ~ ^N v 23 * '* jNcH ₂ COOK in which R _{1 is} a mixture of groups from the structure "C ₁₁ H ₂₃ to ·" C ₁₈ H ₃₇ . 6. Complex of the formula Il CH ₂ CR ₂ COONa ^ CH ₂ CH ₂ COONa I. H in which R _{1 is} a mixture of groups of the structural range -CcH ₄ -, to -C ₁₀ H ₀ -. 7. Complex of the formula C ₁₁ H ₂₃ CO C ₁₄ H ₂₉ -N. H CH ₂ CH ₂ COONS 8. Detergent-containing mixtures, characterized in that that they are about 1 to 50 wt .-%, based on the total mixture, of at least one compound of general formula I.