DE2416018B2 - - Google Patents

Description

The present invention relates to novel hair and skin wash compositions containing amphoteric surfactants. These surfactants are made from ethoxylated amines that are quaternized and then sulfated.

There are already many different types of amine phosphonates or sulfonates, phosphates or sulfates and related compounds are described. However, none of these compounds has an essential technical nature Found meaning.

In recent years, significant research has been carried out on phosphates for the purpose of improving the lubricating and rust and corrosion inhibiting properties of the new synthetic surface active preparations. the Most of these surface-active preparations have anionic surfactants as the active surface-active ingredient Ions. Research also continued to focus on sulfates for the purpose of improving cleaning and cleaning properties Foam properties of the new synthetic detergent preparations. Most of these synthetic Detergent preparations have anionic ions as an active cleaning ingredient. As representative of the various, to improve the surface-active cleaning agent and the foam properties in additives used in such anionic detergent preparations can include alkali metal phosphates, borates, -Carbonates, sulfates, chlorides, silicates, higher aliphatic alcohols such as lauryl alcohol, and higher Fatty acid amides and alkylolamides, such as lauroyl amide, lauroyl mono- and diaikyl amides, lauroylethanol amide and lauroyl diethanolamide. The use of the above alkali metal salts, in particular the phosphates and borates resulted in the so-called "build-up" or "heavy-duty" detergents. While some of these preparations are for use in cleaning machines of various kinds are suitable, they find limited use in areas where an essential Contact with the skin occurs because of its alkaline reaction and chemical nature. For these purposes are not "built up" or "lighter" detergents or cleaners with practical neutral pl! area preferred.

When used for shampooing, the commonly used soaps often form insoluble salts, which deposit on the hair, giving it a dull look and usually to hers

Require removal of acidic douches. Furthermore irritate

they, the eyes, tend to be at a pH of 7 or more

underneath to precipitate and foam in one pH 6-7 bad

Although the amides of these amino acids are better

to show resistance to hard water than usual soaps, they foam poorly in hard water and have poor foam stability They make the resin dull like common soaps Use as a shampoo but to a lesser extent, and fall in an aqueous medium at a pH of 4.5 out.

It has been found that the preparations according to the invention are very valuable surface-active agents included, alone or mixed with others cationic, anionic or nonionic surfactants on various of the above Areas can be used.

The preparations according to the invention contain a very valuable group of surface-active agents, which as amphoteric compounds, i.e. chemical agents that contain both cationic and anionic groups in contain a single molecule, are known and therefore have a high degree of stability and a remarkable usability in concentrated electrolytic

M see show solutions. These connections show also an unusual chemical stability under prolonged contact with alkaline systems. the Compositions according to the invention have the following advantages: They have good surface-active substances Properties such that they can be used as detergents; you can still use it as a hair shampoo used above or below a pH range of, for example, 3-10; they have the advantage of that Prevent the accumulation of electrostatic charges to the; they are well tolerated by the skin and eyes and therefore do not cause any noticeable irritation or irritation. This property makes the connections at Can be incorporated into liquid bubble baths and soaps.

These amphoterics use the sulfate esters as the anionic part and thereby deliver in addition to the Creation of a double cationic / anionic functionality, new properties such as e.g. B. Useful in as hair shampoos and soaps.

The preparations according to the invention foam better in average or hard water; she have good foam stability; they tolerate the presence of chlorine bleaches; They can be used in shampoos or cosmetics at a pH of 4.5-8.5 can be used and are better foaming agents under these conditions; they are better washing or Detergents with average or hard water; they will not do so at a pH up to 4.5 failed; they do not irritate eyes and skin, and are relatively non-toxic.

The preparations according to the invention are irritating in concentrations at which irritation becomes noticeable Eyes not; when used as a shampoo, they do not dull the hair and therefore do not require any

it special rinse; they give the hair softness and malleability after shampooing in common as well as hard water. According to the invention, surprisingly,

made that by quaternizing an ethoxylated amine and subsequent sulfation of the same, Can produce compounds that have the amine, hydroxyl, quaternary ammonium and sulfate functionalities contain.

These amphoteric surface-active compounds are compared to compounds otherwise used by Advantage and apparently show no clear isoelectric point where general surface-active and physical properties such as solubility, foaming etc. are at a minimum.

The present invention provides amphoteric chemical preparations in aqueous solutions in a acidic, neutral or alkaline pH used can be. In the former, they serve as cationic ones surfactants; in the latter as anionic surfactants.

According to the invention, new products such as shampoos, soaps, bubble baths and the like can be used. getting produced.

The aqueous hair and skin detergent compositions according to the invention are characterized in that they contain an effective amount of an amphoteric surfactant which is obtained that an aliphatic hydrocarbon amine having 6 to 22 carbon atoms with ethylene oxide condenses to form an ethoxylated amine of the formula

RN = RCH ₂ CH ₂ O) _n H] ₂

in which R stands for the aliphatic hydrocarbon radical with 6 to 22 C atoms and η denotes an integer with a value of 1 to 50, the ethoxylated amine obtained with a quaternizing agent and then the quarantined ethoxylated amine obtained with a sulfating agent in implemented in a known manner

The new preparations according to the invention can accordingly be produced from a precursor material by first adding an alkylamine having 6-22, preferably 10-18, carbon atoms in its -to Alkyl chain condensed with ethylene oxide in the presence of a base To form the quaternized component, a quaternizing agent is added, whereupon the ethoxylated amine is quaternized. Then the quaternized ethoxylated amine is formed of a Quaternary Sulphate Sulphated The sulphated amphoteric compound is usually a mixture with different amounts of monosulfate, disulfate and non-sulfated nonionic ethoxylate

The alkyl part of the amine can be saturated or so unsaturated, substituted or unsubstituted. One The pure source of the alkylamine to be used can vary in chain length from 6-22 carbon atoms; Examples of pure saturated acids used as Precursors for such an amine can be used are Capron-, Capryl-, Caprine-, Laurin-, Myristic, palmitic, stearic, arachidic and behenic acids. Include unsaturated pure fatty acid precursors those of oleic, lauroleic, and palmitoleic acid. One Substituted fatty acid suitable according to the invention is, for. B. ricinoleic acid. As a forerunner can also Mixtures of the above fatty acids, such as are commonly found in vegetable oils, animal fats and marine fats and -Oils occur to be used with success. Vegetable fatty acids suitable as precursors contain <■ "> Mixtures of different proportions of coconut oil, flaxseed oil, olive oil, palm oil, peanut oil, Tung oil and grapeseed oil. Animal and marine sources of fatty acids with saturated and unsaturated fatty acid substituents are tallow and sardine oil. According to the invention, any fatty acid or mixture of fatty acids from pure or impure sources as long as they contain 6-22 carbon atoms in the chain.

Preferred fatty acids are those in coconut oil. A typical vegetable coconut oil may contain fatty acids varying in length from 8-18 carbon atoms. These fatty acids from coconut oil can be saturated or unsaturated.

The alkylamines used according to the invention can also be derived from the esters of fatty acids. The methyl or ethyl esters of the fatty acids can easily be substituted with the polyamines polyamines be condensed with slight removal of the methanol or ethanol formed.

The fatty acid amine precursor is prepared by known processes; Reaction and reaction product are known per se and do not form part of the present invention.

Then the alkylamine thus obtained is by known methods, for. B. by reacting the amine reacted with the required number of moles of ethylene oxide to form the ethoxylated amine used in accordance with the invention. This oxyethylation is known and described, for example, in U.S. Patent 19,705,78, among others. The reaction is preferably carried out at elevated temperatures and pressures and can be caused by quaternary ammonium hydroxides, amines, acids and / or coordination compounds are catalyzed, although strongly alkaline catalysts, such as KOH or NaOH etc. due to the lower formation of by-products and more easily controllable Reaction conditions are suitable. Since the reaction is practically quantitative, the molecular ones determine Ratios of ethylene oxide and amine used, the average oxyethylene chain length of the ethoxylated amine obtained, regardless of the product of course a mixture of ethoxylated amines with different oxyethylene chain lengths Sufficient ethylene oxide is used to form an ethoxylated amine that about Contains 25-90 weight percent combined ethylene oxide. the optimal oxyethylene chain length is determined in each particular case mainly by the particular, to oxyäthylating amine, the special detergent with which it is to be mixed, the hardness of the Water in which the detergent is to be used, the desired effectiveness of the finished Product intended for special use, etc.

The amphoteric product is usually obtained by reacting appropriate proportions of ethoxylated amine in the presence of the hypophosphorous acid mentioned and a quaternizing agent such as Diethyl sulfate, the latter being present in amounts of 50-10 mol%, preferably 90-100 mol%.

The alkoxylated amine starting materials prepared by the alkoxylation of primary amines have the structure

RN = [(CH ₂ -CH ₂ O) _n H] ₂

in which R stands for an alkyl group _r o according to the above definition and η stands for an integer with a value from 1 to 50, compounds in which n = 2-20, in particular 3-10, are preferred.

After the reaction has ended, the alkoxylated amine is treated with a customary quaternizing agent to quaternize the tertiary amino group. B. dialkyl sulfates such as diethyl sulfate, diethyl sulfate, etc .; Alkyl ^su 'f ^{% acids} i ^w ' ^e methylsulphonic acid, ethylsulphonic acid etc .; Benzyl halides such as benzyl chloride, benzyl bromide, benzyl iodide, etc .; Alkyl halides, such as methyl chloride, etc. In the preparation of the quaternary alkoxylated amines used according to the invention, any customary quaternizing agent can thus be used. The hydrocarbon radical introduced in the quaternization preferably contains 1-7 carbon atoms. Then, the above quaternized preparation is preferably, but not necessarily, freed of unreacted quaternizing agent and then reacted with a sulfating agent to form a quaternized sulfate. Suitable sulfating agents include chlorosulfonic acid, sulfur trioxide, sulfamic acid and sulfuric acid oil.

According to the invention ethoxylated fatty amine and hypophosphorous acid are mixed together and heated under vacuum to about 90- 100 ⁰ C. The product is then cooled to 20-90 ° C, preferably 30 ° C, cooled; then 50-100 mol%, preferably 90-100 mol%, of a quaternizing agent are added and the mixture is heated to quaternize the ethoxylated fatty acid amine. Unreacted quaternizing agent can be removed at elevated temperature and under vacuum. Then, the remaining product is then cooled slowly, the sulfating agent in amounts of 10-200Mol-%, preferably 90-110 mol%, is at temperatures of 20- 110 ⁰ C, preferably 40-50 ⁰ C, was added thereto.

When using chlorosulfonic acid as the sulfating agent, nitrogen is released at the temperature mentioned passed through the reaction mixture until the desired level of chloride ions, preferably 0.01 - 1.0% is reached. Then the sulfate is poured into water and base, whereupon the according to the invention Product containing, surface-active solution is obtained.

The following examples illustrate methods of making typical phosphated and sulfated ones quaternized ethoxylated amphoteric compounds. Unless otherwise stated, all parts are Ratios and percentages by weight, parts by weight and wt .-% AO = ethylene oxide.

example 1

320 parts (0.5 mol) of Koskosamine + IOAO and 2 parts of 50% hypophosphorous acid were placed in a 1-1 flask equipped with a stirrer, thermometer and gas inlet. The mixture was dried under vacuum (10- 15 mm) at 90-100 ⁰ C. It was then cooled dried under dry nitrogen at 40-50 ⁰ C and 80 parts (0.52 mole) of diethyl sulfate within 2 hours at 40-50 ° C added.

The unreacted Diäthylsuifat was removed under vacuum at 85-90 ⁰ C. After cooling to 30-40 ° C., 60 parts (0.52 mol) of chlorosulfonic acid were introduced at 30-40 ° C. with the introduction of a stream of nitrogen which dispersed the droplets. The nitrogen bi fueling was 6 hours at 30-40 ⁰ C continued to a Cl ~ content of 0.5%. The sulfate acid was then poured into 150 parts of water and 51 parts of 50% sodium hydroxide solution were added to a pH of 7.3. igen yield corresponded.

Example 2

According to Example 1 were 430 parts of coconut amine + 15 EO (0.5 MoI) are used 2 parts of hypophosphorous acid and dried under vacuum at 40-50 ⁰ C, 80 parts (0.52 mole) of diethyl sulfate was added, whereupon the temperature of 40- 50 C was maintained for 2 hours of ". After distilling off unreacted volatile materials at 85-90 ⁰ C under a vacuum of 2 mm, 60 parts (0.52 mole) of chlorosulfonic acid were introduced under a stream of nitrogen to disperse the acid at 40 ° C, the nitrogen flow was continued for 6 hours then the material was poured into 150 parts of water and 50 parts of 50% sodium hydroxide, the pH was 7.3, giving 713 g of amphoteric surfactant solution with 540 g of active material, which is a 98% igen yield corresponded.

Example 3

According to Example 1, 400 parts of Talga.nin +15 Eo (0.5 mol) with 1 part of 50% hypophosphorous acid mixed and dried under vacuum. After addition of 63 parts (0.5 mol) of benzyl chloride, the mixture was 60 hours stirred at 100 ° C, cooled to 30-40 ° C and at such rate through a unit with a Liquid sulfur trioxide (sulfane) film passed so that 40 parts (0.5 mol) of sulfur trioxide were absorbed. The acid was poured into 150 parts of water, then 60 parts of 50% potassium hydroxide were added to one pH value of 7.6 added. This gave 710 parts of surface-active solution with 520 parts of active Material.

Example 4

According to Example 1, 600 parts (0.25 mol) of coconut amine + 50% and 2 parts of 50% hypophosphorous acid were dried under vacuum. At 40-50 ° C., 40 parts (0.26 mol) of diethyl sulfate were added over the course of 2 hours. After a further 2 hours at this temperature, the Reakticasmischung at 85-90 ⁰ C was stripped under vacuum and 30 parts (0.26 mole) of chlorosulfonic acid with dispersion by means of nitrogen at 40 ° C was added after 6 hours of nitrogen intake was the Cl- Content reduced to 0.07%. The crude acid was poured into 150 parts of water and 28.5 parts of 50% sodium hydroxide; 810 parts of an 80.5% strength surface-active solution with a pH of 7.5 were obtained in this way.

Example 5

According to Example 1, 315 parts of coconut amine + 5AO and 2 parts of 50% hypophosphorous acid and dried with 125 parts of diethyl sulfate The obtained quaternary material was reacted reacted with 88 parts of chlorosulfonic acid and to reduce the Cl content to 0.2% with a flushed with inert gas. The quaternized sulfate acid was dissolved in 150 parts of water and 70 parts of 50% strength Sodium hydroxide poured and provided 653 parts of a 70.8% surfactant solution with a pH of 7.6.

Example 6

A Shatnpoo formulation was made as follows manufactured:

Ilcsliindleilc wt .-% Coconut Amine Sodium Sulphate 20.0 + lOAO diethyl sulfate (F ^; eststo (T) Myristyl amine oxide 5.0 (30% ^F; eststofTgehalt) water 75.0 100.0

High quality shampoo that the ys value on is under 40 dynes / em at 0.1-0.25% concentration in water. Same properties have been shown of compounds containing 5-15 and 20 moles of ethylene oxide.

Example 7

The lime soap dispersion index ("J. Am. Oil. Chem. Soc": Vol. XXVII-88, (1950)) was used for various The above amphoterics were determined and compared with a commercially available control sample normally found in Shampoo and cosmetic products are used. The results are shown in Table 2. Ever the lower the number, the better the dispersion properties

u / as ouigu riuuum wuruu in nariem and white water on Ross Miles foaming, stability (overnight at 0 ° C), surface tension and pH value evaluated. The results of the amphoteric shampoo are shown in Table I below.

Table 1

Foam height - mm 0.25% at 30 ° C in distilled water:
160 (initially) 140 (after 5 min)

Foam height - mm 0.25% at 30 ° C in ppm CaCOj
(hard water):
175 (initially) l50 (after 5 min)

Clarity - 12 hours at 0 ⁰ C: clear and stable

ysODyncm - 0.25% solution at 25 "C: 3I, 6

Found pH: 8.0

product

Soap Dispersion Index

Coconut Amine Sodium Sulphate 2.5-5.0

+ 5 ÄO diethyl sulfate

Coconut Amine Sodium Sulphate 2.5-5.0

+ 15ÄO diethyl sulfate

Coconut Amine Sodium Sulphate 2.5-5.0

+ lOÄO-benzyl chloride

Coconut Amine Sodium Sulphate 2.5-5.0

+ 15 EO diethyl sulfate

Detergent raw material from fatty acid alkyl- 80
imidazoline-type amide sulfate

As shown above, shampoo formulations can be made that foam well in both hard and soft water, do not freeze when stored overnight at 0 ° C (ie the Kraft point is below 0 ° C); the ys (surface tension) of a 0.25% solution is 31.6 dynes / cm at 25 ° C. which is well within the acceptable range for an example up to 11

Using the amphoterics from Example 4, the following concentrates S through 11 were made with Manufactured to different degrees of ethoxylation and as liquid concentrates for bubble bath formulations evaluated.

Table 3

Liquid bubble bath concentrates

Part I

Wt% 1

8 sodium sulfate from coconut amine
+ 5 ÄO diethyl sulfate (solid)

9 like 8 with 10 ÄO (solid)

10 like 8 with 15 ÄO (solid)

11 like 8 with 20 ÄO (solid)
Coconut diethanolamine (control)
Water (control)

20.0

20.0

- - - 20.0 5.0 5.0 5.0 5.0 75.0 75.0 75.0 75.0

100.0

100.0

100.0

All of the above formulations foamed in soft and hard water and in the presence of soap and hard water well the latter is a main criterion for a high quality bubble bath The results are listed in Table 4

9 10

Table 4

Ross Miles Foam Test of Foam Bath Con / Entral Compounds I to 4 of Example 8 11

Concentrate. npm CaCOi Temp. % Ropes Foam height in mm (initially / after 5 min) i 4th Water hardness 180/155 185/165 formulation 190/165 190/170 % < I. 2 215/175 210/175 0.25 0 30th 0 170/145 175/155 185/160 205/180 0.25 200 30th 0 815/160 185/160 0.025 200 37 0.5 200 / I70 205/180 0.125 200 37 0.5 200/175 195/165

All of the above concentrates were stable after overnight freezing; even with a freeze / thaw cycle

Example 12 to 17

These compounds are also suitable and show as alkaline cleaning agents for hard surfaces Depending on the degree of their ethoxylation, excellent alkali resistance, anionic functionality and they are hydrophobic. The alkali solubility is shown in Table 5.

Table 5

Alkali solubility - 1% surface act. Medium, soluble in (x) % NaOH at -100 ° C

Example connection

% NaOH

12 Sodium sulfate of coconut amine 9.4 + 5 EO diethyl sulfate

13 Sodium Sulphate of Coconut Amine 6.6

+ 10 ÄO diethyl suirate ⁴ "

14 Sodium sulphate of coconut amine 4.9 + 15 O-diethyl sulphate

15 Sodium Sulphate of Coconut Amine 4.25

+ 20 ÄO diethyl sulfate ₄ -,

16 sodium sulfate of coconut amine 3.2 + 30 ÄO diethyl sulfate

17 Sodium sulfate of coconut amine 2,4 + 50 ÄO diethyl sulfate

V)

Example 18

According to Table 10, soaps of the Syndet soap and Syndet type can be used with dispersing, softening and antibacterial properties for lime soaps are made.

Table 6

Wt .-% μ,

1 2 3

Paraffin wax - 5-15 5-15 AmphoL surface act 5-15 20-50 20-50 65 middle

Tallow coconut oil soap
Stearic acid

Alkyldimethylbenzylammonium halide

in talc water to 60-80

0-10 0-20

0-20

0.5-1.0 -

20-60 20-60 100 100 100

Various fillers or thinners can be used in the above soap preparation to reduce costs can be used, such as B. Clay, hydrogenated tallow, powdered polyvinyl chloride resin, paraffin wax, Starch and stearic acid. Of course, these materials are only used in limited quantities, to adversely affect the properties of the soap, such as foaming power and surface slip avoid. Limited amounts, e.g. B. less than 10%, certain fillers or thinners, such as starch and stearic acid, actually improve the surface lubricity of the soap. Some fillers, like Glycerin. Polyglycerin (e.g. with a degree of polymerisation of about 6), sugar, pectin, gelatin, finely divided Silica, inhibit in limited amounts, e.g. B. less than 15%, the cracking of the soap bars if this dry out after use.

The compounds according to the invention also show the following features: No foam formation Water pressure; Foam regeneration; Foam compatibility with soap and soap foam; Release properties; Solution compatibility with very high amounts of electrolytes and / or alkalis, compatibility with quaternary germicides; germicidal, germistatic, fungicidal and fungistatic properties; Deodorising properties; and not dehydrating Properties on the skin.

The products of the invention can also be mixed with other ingredients for the following uses be mixed: hand washing compounds; disinfecting hand washing-up liquid or »light« Cleaning compounds; Pet shampoos, etc.

Claims (1)

Claim: Aqueous hair and skin detergent compositions characterized in that they contains an effective amount of an amphoteric surfactant obtained by having an aliphatic hydrocarbon amine having 6 to 22 carbon atoms Ethylene oxide condenses to form an ethoxylated amine of the formula RN = KCH ₂ CH ₂ O) _n H] ₂ in which R stands for the aliphatic hydrocarbon radical with 6 to 22 carbon atoms and π denotes an integer with a value of 1 to 50, the ethoxylated amine obtained with a quaternizing agent and then the quaternized, ethoxylated amine obtained with a sulfating agent in a manner known per se implements