DE4335782C1 - Prepn. of solid ester-quats with better emulsifying power - Google Patents

Abstract

Solid esterquats (I) are prepd. by quaternising fatty acid triethanolamine esters of formula (II) with alkylating agents, in the presence of nonionic emulsifiers comprising (a) alkyl- and/or alkenyl-oligoglycosides, (b) fatty acid-N-alkylpolyhydroxyalkylamides, (c) partial glyceride polyglycol ethers and/or (d) polyols. (In (II) R1CO = 6-22C (un)satd. acyl gp.; R2,R3 = H or R1CO and m+n+p = 0-10). Emulsions contg. 30-95 wt.% of (I) and 70-5% of the emulsifiers (a), (b), (c) and/or (d) are claimed.

Description

Field of the Invention

The invention relates to solid ester quats with improved Emulsifying power obtained by using fatty acid trietha nolamine esters in the presence of selected nonionic Emulsifiers quaternized, emulsions containing these esterquats contain as well as the use of said esterquats for Manufacture of cosmetic products.

State of the art

Damage to the hair structure is the result of frequent lead chens, permanent waves, dyeing, strong UV exposure, washing of the hair with degreasing surfactants as well as the result of a normal aging. The hair becomes brittle and loses its Shine. Furthermore, when combing the hair there is an elec Trostatic charging takes place while the hair is roughened Surface causes matting and knotting of the hair there, making combing difficult. Hair care have a combing effect  therefore attained considerable importance in the cosmetics market. Such agents can be, for example, in the form of a rinse, an aerosol foam or in the form of emulsions (Cream rinses) after shampooing in wet hair divides and either after a few minutes of exposure be rinsed or left on the hair.

As active ingredients to improve the hair structure have cationic surfactants, especially quaternary ammonium compound such as distearyldimethylammonium chloride (DSDMAC) alone or in combination with various waxes like additives, such as hydrocarbons, fatty alcohols or Fatty acid esters proven [Parf.Kosm. 56, 157 (1975)]. From The disadvantage here, however, is that the cationic surfactants mentioned have inadequate biodegradability and thus when entering surface water over time the functionality of aquatic communities can impair.

From the German patent application DE-A1 35 27 974 are darü in addition esters of betaine with fatty alcohols or fatty alcohols alcohol polyglycol ethers for use in acidic hair care well known. The betaine nests have a high eco toxicological tolerance, but are in consideration on combability, antistatic, handle and rinse behave unsatisfactorily and also not in the acidic range hydrolysis stable.

In the older German patent application DE-A1 41 38 630 the applicant has already proposed as cationic surfactants quaternized fatty acid triethanolamine ester salts, so-called  "Esterquats" to be used in acidic hair products. In the Practice has shown, however, that both the emulsifiable of these products in water, as well as their storage stability is not always fully satisfactory.

The object of the invention was therefore a Ver drive to the production of ester quats with improved emul greedability in water and higher shelf life wrap, which are used with advantage in hair care products to let.

Description of the invention

The invention relates to a method for producing solid ester quats with improved emulsifying power, in which fatty acid triethanolamine esters of the formula (I),

in which R ¹ CO represents a saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ² and R ³ independently of one another are hydrogen or R ¹ CO and n, m and p in the sense of 0 or numbers from 1 to 10, in the presence of nonionic emulsifiers selected from the group consisting of

• a) alkyl and / or alkenyl oligoglycosides,
• b) fatty acid-N-alkylpolyhydroxyalkylamides,  
• c) partial glyceride polyglycol ethers and / or
• d) polyol compounds,

quater in a manner known per se with alkylating agents kidney.

Surprisingly, it was found that the Quaternie tion of fatty acid triethanolamine esters also in the presence of can carry out said emulsifiers. That way who the solvent-free, especially alcohol-free, solid ester quats obtained, which was easy to disperse in water sen. The invention includes the knowledge that the after Inactive addition of the emulsifiers mentioned to after convention In the process, esterquats produced the emulsifying power not improved or improved only slightly. Another Advantage is that the aqueous solutions after the Esterquats obtainable according to the invention in particular are stable in storage, d. that is, homogeneous even with prolonged storage remain and have a constant viscosity. After resolution of the products according to the invention in water and pH values position, for example, hair care products with excellent application properties hold.

Esterquats and fatty acid triethanolamine esters

Esterquats are a well-known group of cationic surfactants usually by esterification of triethanolamine or triethanolamine polyglycol ethers with fatty acids and after obtained the following quaternization in organic solvents  become. Manufacture and properties of the esterquats are for example in WO 91/01 295 (Henkel) and in Über articles by O.Ponsati in C.R. Ced Congress, Barce lona, 167 (1992) and R.Puchta in C.R. CID Congress, Sitges, 59 (1993).

For the purposes of the process according to the invention, starting materials for the preparation of the esterquats are fatty acid triethanolamine esters of the formula (I), which are preferably technical mono- / di- / triester mixtures in which the degree of esterification is in the range from 1.2 to 2 , 5, in particular 1.5 to 1.9. Esters which are derived from technical C _12/18 or C _16/18 fatty acids, such as, for example, palm fatty acid, coconut fatty acid or tallow fatty acid and which can have an iodine number in the range between 0 and 40, are particularly preferred.

Emulsifiers

a) Examples of emulsifiers are alkyl and alkenyl oligoglycosides of the formula (I),

R ⁴ O [G] _p (II)

in which R ^{4 represents} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. These are known substances that can be obtained by the relevant preparative organic chemistry methods. As a representative of the extensive literature, reference is made to the documents EP-A1-0 301 298 and WO 90/3977.

The alkyl and / or alkenyl oligoglycosides can differ from Aldoses or ketoses with 5 or 6 carbon atoms derive preferably the glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or Alkenyl oligoglucosides.

The index number p in the general formula (II) gives the Degree of oligomerization (DP degree), i.e. H. the distribution of Mono- and oligoglycosides and stands for a number between two 1 and 10. While p in a given connection must always be an integer and above all the values p = 1 to 6, the value p is for a certain tes alkyl oligoglycoside an analytically determined nerious size, usually a fractional number poses. Alkyl and / or alkenyl oligo are preferred glycosides with an average degree of oligomerization p of 1.1 to 3.0 used. From an application perspective are such alkyl and / or alkenyl oligoglycosides before moves whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4.

The alkyl or alkenyl radical R ⁴ can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as those obtained in the hydrogenation of technical fatty acid remethyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Be preferred are alkyl oligoglucosides of chain length C ₈ -C ₁₀ (DP = 1 to 3), which fall as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C ₁₂ alcohol can be contaminated and alkyl oligoglu cosides based on technical C _9/11 oxo alcohols (DP = 1 to 3).

The alkyl or alkenyl radical R ⁴ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1 to 3 are preferred.

b) Another group of emulsifiers are fatty acid N- alkyl polyhydroxyalkylacides of the formula (III) in question,

in which R ⁵ CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ⁶ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands.

The fatty acid N-alkyl polyhydroxyalkylamides it is known substances, usually by re ductile amination of a reducing sugar with Am moniak, an alkylamine or an alkanolamine and after following acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride can be obtained can. Regarding the processes for their manufacture see U.S. Patents 1,985,424, 2,016,962 and 2 703 798 and the international patent application Referred to WO 92/06984. An overview of this topic from H. Kelkenberg can be found in Tens. Surf. Det. 25, 8 (1988).

The fatty acid N-alkyl poly is preferably derived droxyalkylamides of reducing sugars with 5 or 6 Carbon atoms, especially on the glucose. The preferred fatty acid N-alkyl polyhydroxyalkylamides stel len therefore represent fatty acid-N-alkylglucamides, as by the formula (IV) are represented:

Preferably used as the fatty acid N-alkylpolyhydroxyal kylamides glucamides of the formula (IV) in which R ^{6 represents} hydrogen or an amine group and R ⁵ CO represents the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Fatty acid N-alkylglucamides of the formula (IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C _12/14 coconut fatty acid or a corresponding derivative are particularly preferred. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

c) Partial glyceride polyglycol ethers can also be used as emulsifiers. These are, for example, adducts of on average 1 to 10, preferably 2 to 5, moles of ethylene oxide with fatty acid mono- or diglycerides. Typical examples are ethylene oxide adducts with technical C _12/14 or C _8/18 coconut fatty acid mono- or diglycerides.

d) Polyol compounds are also suitable as emulsifiers net, especially substances with 2 to 12 carbon atoms and 2 to 6 hydroxy groups. Typical examples are glycerin, Oligoglycerin with a degree of self-condensation of average 1.5 to 10, ethylene glycol, diethylene glycol, Triethylene glycol, propylene glycol, butylene glycol, trime thylolpropane and / or pentaerythritol and their mono- and Difatty acid esters.  

As previously explained, the essence of the invention is in producing an easily emulsifiable esterquat compound to which an emulsifier was added during production is set. Except for those already described application-related advantages, becomes elegant in this way the otherwise required use of an organic Bypassed solvent in the quaternization stage.

Usually, the ester quats according to the invention can Contain emulsifiers in such amounts that their weight part 5 to 70, preferably 10 to 30 wt .-% - based on the end product - is. For setting a desired th emulsifier content in the end product, it is necessary that calculated amount of emulsifier to the ester before quaternization to add. To calculate the required ratios is left to the person skilled in the art who is not inventive in this regard must act.

Alkylation

The alkylation of the fatty acid triethanolamine esters can begin in be carried out in a known manner. For this, the Submitted ester and with the alkylating agent - which one over certainly in equimolar amounts or a slight deficit used - stirred at elevated temperatures. After graduation the reaction can react with unreacted alkylating agent Adding a small amount of amino acid, preferably glycine, be destroyed. In this come as alkylating agents context alkyl halides, dialkyl sulfates and ethylene oxide - the latter in the presence of dialkyl phosphates - into consideration.  

The process according to the invention preferably relates to methyl quaternized ester quats in the form of their chlorides or methyl sulfate salts and ester quat salts with 1 to 5 moles of ethyl lenoxid have been quaternized.

Industrial applicability

The esters obtainable by the process according to the invention quats are easily emulsifiable in water. The emulsions are homogeneous and stable in storage and have excellent applications manure properties with regard to improvements Combability and reduction of electrostatics charging of hair.

Another object of the invention relates to emulsions, containing 30 to 95% by weight of esterquats and 5 to 70% by weight Emulsifiers selected from the group consisting of alkyl and / or alkenyl oligoglycosides, fatty acid N-alkyl polyhydroxy alkyl amides, partial glyceride polyglycol ethers and / or poly oil compounds is formed.

Another object of the invention finally relates the use of he according to the inventive method available solid ester quats for the production of cosmetic Agents, especially hair care products, in which they are in Amounts of 70 to 100, preferably 80 to 90 wt .-% - bezo on the solids content of the agents - may be included nen. In this context, hair care products are among for example hair shampoos, hair rinses, hair fixers, hair dryers understand better and the like; preferably point  the agents preferably have a pH in the range from 3 to 5 3 to 4.

The following examples are intended to be the subject of the invention explain in more detail without restricting it.

Examples I. Manufacturing examples

a) esterification. 324 g (1.2 mol) of partially hardened C _16/18 tallow fatty acid (iodine number = 40), 149 g (1 mol) of triethanolamine and 1.4 g of 50% by weight were placed in a 1 liter three-necked flask equipped with a stirrer, internal thermometer and distillation attachment. -% given hypophosphorous acid. The reaction mixture was heated at a reduced pressure of 40 mbar to a temperature of 160 ° C. over a period of 4 hours until the acid number was below 5. The crude tallow fatty acid triethanolamine ester was then cooled, the reaction mixture was depressurized and 1 liter of air was passed through with constant stirring within 15 min.

b) Quaternization. In a 500 ml three-necked flask with stirring a drip funnel and reflux condenser 70 g (0.155 mol) of the ester from a) and 7 bis 30 g of emulsifier and with stirring to 45 ° C heats (weight ratio ester quat: emulsifier = 90 10 to 70: 30). 18.9 g (0.15 mol) of dimethyl sulfate was added dropwise. After completion of the Zu The mixture was stirred for a further 2 h at 60 ° C. and unreacted strain gage by adding 0.4 g (0.005 mol) Glycine destroyed. The anhydrous ester quat / emulsifier Mixtures were he as light colored, waxy masses hold, which may then be mechanically ge were scaly.  

II. Examples of application technology

In each case 7 g of the anhydrous, solid ester quats from I) were dissolved in 93 g of water and the pH of the mixtures to 3.3 set. The emulsion formation took place under weak Stir at room temperature. In all cases, homogeneous, receive cosmetically elegant emulsions. The viscosity of the Emulsions were determined after 1, 2 and 15 d storage (Brook field RVT, spindle 2, 25 ° C, 20 rpm). The results are in Tab. 1 summarized:

Table 1

Viscosity measurements

Substances used

• a) Plantaren® APG 2000 CS UP:
  C _8/16 alkyl oligoglucoside (Henkel KGaA, Duesseldorf / FRG, DP = 1.35);
• b) Coconut glucamide:
  C _12/14 coconut fatty acid N-methylglucamide
• c) Cetiol® HE:
  Addition product of approx. 4 mol ethylene oxide onto coconut fatty acid mono / diglyceride (Henkel KGaA, Düsseldorf / FRG)
• d) Diglycerin:
  Statistical oligoglycerol mixture with approx. 43% by weight diglycerin;
• e) Dehymuls® E:
  Mixture of pentaerythritol dicoconut fatty acid ester and stearyl citrate (Henkel KGaA, Düsseldorf / FRG)

Comparative tests

For comparison, a commercially available ester quat (Dehy quart® AU 36, 90% by weight in isopropyl alcohol, from Pulcra S.A., Barcelona / ES) first freed from the solvent closing - that is, afterwards - with the emulsions mentioned mixed up. All comparative experiments showed that to form a much higher shear performance was necessary. With regard to the viscosity of the ver similar initial emulsions were achieved, however, a rapid decrease in viscosity after only a short storage name observed.

Claims (4)

1. A process for the preparation of solid ester quats with improved emulsifying power, characterized in that fatty acid triethanolamine esters of the formula (I), in which R ¹ CO is a saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ² and R ³ independently of one another are hydrogen or R ¹ CO and n, m and p in total are 0 or numbers from 1 to 10, in the presence of nonionic emulsifiers selected from the group consisting of

• a) alkyl and / or alkenyl oligoglycosides,
• b) fatty acid-N-alkylpolyhydroxyalkylamides,
• c) partial glyceride polyglycol ethers and / or
• d) polyol compounds,

quater in a manner known per se with alkylating agents kidney. 2. Emulsions containing 30 to 95 wt .-% ester quats according to An say 1 and 5 to 70 wt .-% emulsifiers selected from the Group consisting of alkyl and / or alkenyl oligoglycosides, Fatty acid N-alkyl polyhydroxyalkylamides, partial glyceride po lyglycol ethers and / or polyol compounds is formed.   3. Use of solid ester quats with improved emulsifying assets according to the method of claim 1 for the manufacture treatment of cosmetic products.