WO1996030475A1

WO1996030475A1 - Pearly lustre concentrates

Info

Publication number: WO1996030475A1
Application number: PCT/EP1996/001195
Authority: WO
Inventors: Achim Ansmann; Rolf Kawa; Gabriele Strauss
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1995-03-29
Filing date: 1996-03-20
Publication date: 1996-10-03
Also published as: DE19511569A1

Abstract

The invention concerns pearly lustre concentrates in the form of an aqueous dispersion with between 10 and 40 wt.% pearly lustre-forming components and between 15 and 55 wt.% emulsifiers which contain as pearly lustre-forming components compounds of formula (I), R1 - O - CH¿2? - CH2 - O - R?2¿, in which R1 is a C¿16? or C18 linear fatty acyl group and R?2¿ is hydrogen or an R1 group, provided that a product is present in which less than 40 % of the R2 groups stand for hydrogen and, in 30 to 60 % of the compounds in which R2 is not hydrogen, R?1 and R2¿ stand for identical fatty acyl groups, and contain as emulsifiers alkylpolyglycosides of general formula (II), RO-(Z)¿x?, in which R stands for a C6 to C22 alkyl residue, Z stands for a mono or oligosaccharide, x is a number from 1.1 to 5, or their addition products with 1 to 10 molecules of ethylene oxide and/or propylene oxide. The concentrates are characterized inter alia by a particularly brilliant pearly lustre and can contain further pearly lustre-forming agents and emulsifiers in lesser amounts.

Description

"Pearlescent concentrate"

The invention relates to a pearlescent concentrate in the form of a low-viscosity aqueous dispersion with special pearlescent components and emulsifiers.

Aqueous pearling preparations and cosmetic preparations can be given a pearlescent, aesthetically pleasing appearance by incorporating substances which, after cooling, precipitate out in the form of fine, pearlescent-looking crystals and remain dispersed in the preparations. As pearlescent substances are, for. B. the mono-, di- and optionally triesters of ethylene glycol or glycerol with C14-C22 fatty acids, oligomeric alkylene glycol esters of this type, such as PEG-3 distearate, fatty acids and monoalkanolamides of fatty acids.

It is also known to stably disperse the pearlescent agents mentioned in water or in aqueous surfactant solutions and to add the concentrated pearlescent dispersions obtained in this way to the pearlescent preparations without heating, so that this is otherwise necessary for incorporation Heating and cooling to form the pearlescent crystals is unnecessary.

Such pearlescent concentrates, which are characterized in particular by good flow and pumpability, are known from German laid-open publications DE 3843 572 and DE 41 03 551.

Although the essential development work in the field of pearlescent concentrates applies to the optimization of the dosage form, attempts are still being made to further improve the appearance of the pearlescent itself.

Surprisingly, it has now been found that when using a very special mixture of pearlescent esters with alkyl polyglycosides as emulsifiers, low-viscosity pearlescent concentrates can be formulated, the incorporation of which into the end products to a pearlescence is quite extraordinary. usual brilliance and with other excellent properties.

The use of ethylene glycol mono- and difatty acid esters as pearlescent components has long been known to the person skilled in the art, e.g. from EP-A2-0 268 992. Mixtures of a number of mono- and diesters are usually used, such as are produced under the usual reaction conditions for this esterification reaction. However, it has now been found that it has an extremely positive effect on the pearlescence in the end product, if within this ester mixture

- the content of monoesters does not exceed a certain value and

- a certain proportion of symmetrical esters, i.e. Diesters with the same fatty acid residues.

The application thus relates to a pearlescent concentrate in the form of an aqueous dispersion with 10-40% by weight of pearlescent components and 15-55% by weight of emulsifiers, characterized in that

the pearlescent components are compounds of the formula (I),

l. 0 - CH - CH ₂ - 0 - R2 (I),

in which R * is a linear fatty acyl group with 16 or 18 carbon atoms and R ^{2 is} hydrogen or a group R ¹ with the proviso that a product is present in which

- less than 40% of the groups R ^{2 are} hydrogen and

in 30 to 60% of the compounds in which R ^{2 is} not hydrogen, R ¹ and R ² stand for the same fatty acyl groups,

and as emulsifiers, alkyl polyglycosides of the general formula (II),

0- (Z) _x (II),

in which R stands for an alkyl radical with 6 to 22 carbon atoms, Z for a mono- or oligosaccharide, x for a number from 1.1 to 5, or their addition products with 1 to 10 molecules of ethylene oxide and / or propylene oxide are contained. The pearlescent-forming components according to the invention preferably contain less than 15% by weight, in particular about 10% by weight and less, of monoesters, based on the total amount of the ethylene glycol esters. Within the diesters, compounds with the same fatty acyl group are preferably present in amounts of 45-60% by weight, in particular about 50-55% by weight, based on the total amount of ethylene glycol diester.

In a preferred embodiment of the present invention, the compounds of the formula (I) are the only pearlescent components.

However, it has been shown that the exceptional pearlescence is also formed when the concentrates according to the invention contain additional pearlescent components in minor amounts, i.e. in amounts of up to 50% by weight, in particular up to 30% by weight, based on the compounds of the formula (I).

These other pearlescent compounds include, for example

linear, saturated fatty acids with 14 to 22 carbon atoms,

Mono-, di- and triesters of glycerol with linear, saturated fatty acids with 12 to 22 carbon atoms,

Monoalkanol of general formula (III),

R3 - C0 -NH - X (III),

R3 is an alkyl group with 8 to 22 C atoms, in particular with 8 to 18 C atoms, and X is a group -CH2-CH2-OH, a group -CH2-CH2-CH2-OH or a group -C (CH3 ) Represents 2-0H,

β-ketosulfones of the general formula (IV),

R5

R4 - C0 - CH - S0 ₂ - CH ₂ - R ⁶ (IV), in which R ^{4 represents} an alkyl or alkenyl group with 11 to 21 carbon atoms, R5 and R6 represent hydrogen atoms or together represent an ethylene group which forms a tetrahydrothiophene dioxide ring with the group lying between R5 and R6.

As linear fatty acids such. B. Pal itic acid, stearic acid, arachidic acid or behenic acid can be used; however, technical fatty acid cuts are also suitable which consist entirely or predominantly of fatty acids with 16 to 22 carbon atoms, e.g. B. palmitic stearic acid fractions, such as those obtained from tallow fatty acid or palm fatty acid by separating the fatty acids which are liquid at +5 ° C., or palmitic stearic acid fractions, such as are obtainable by hardening tallow fatty acid or palm fatty acid.

The esters of glycerol which can be used in the teaching according to the invention include the mono-, di- and in particular triesters with lauric acid, myristic acid, palmitic acid, stearic acid and behenic acid, and with mixtures of these fatty acids.

Preferred monoalkanolamides are the monoethanolamides. These compounds can contain a uniform alkyl radical. However, it is common in the manufacture of the alkanolamides of fatty acid mixtures from natural sources, e.g. Coconut fatty acids to go out, so that there are appropriate mixtures with respect to the alkyl radicals.

Compared to most known pearlescent agents, the β-ketosulfones of the general formula (IV) have the advantage that the pearlescence of the preparations has a higher thermal stability, i.e. that the pearlescence is maintained for several hours when the preparations are heated to above 50 ° C., sometimes even to above 70 ° C. With regard to further information on the β-ketosulfones mentioned, reference is expressly made to the content of German patent application 3508051.

Fatty acid mono- or dialkanolamides and their derivatives have recently been suspected of being involved in the formation of nitroamines. It may therefore be desirable to formulate cosmetic preparations without such alkanolamines and alkanolamine derivatives. The pearlescent concentrates according to the invention exclusively or predominantly contain alkyl polyglycosides as emulsifiers.

The alkyl polyglycosides according to formula (II) are characterized by the following parameters:

The alkyl radical R contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Examples of such alkyl radicals are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. L-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl glycosides which can be used according to the invention can contain only one specific alkyl radical R. Usually, however, these compounds are produced from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the respective working up of these compounds.

Particularly preferred are those alkyl polyglycosides in which R consists essentially of CQ and Cio alkyl groups, essentially of Cχ2 and Ci4 alkyl groups, essentially of Cg to C _j ö alkyl groups or essentially from C12 to Ciö alkyl groups consists.

Any mono- or oligosaccharides can be used as sugar building block Z. Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides are usually used. Examples of such sugars are glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose and sucrose. Preferred sugar components are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain an average of 1.1 to 5 sugar units. Alkyl glycosides with x values from 1.1 to 2 are prefers. Alkyl glycosides in which x is 1.1 to 1.4 are very particularly preferred.

The alkoxylated homologs of the alkyl polyglycosides mentioned can also be used according to the invention. These homologues can contain an average of up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit. These products also usually do not represent uniform compounds, but instead have a corresponding homolog distribution depending on the selected ethoxylation process. Such alkoxylated compounds can be obtained, for example, by using ethoxylated fatty alcohols for the synthesis of the alkyl polyglycosides. Within the framework of the teaching according to the invention, however, the use of the non-alkoxylated compounds is preferred.

In a preferred embodiment, the pearlescent concentrates according to the invention contain alkyl polyglycosides as the only emulsifiers. However, it has been shown that further emulsifiers can be present in amounts of up to 50% by weight, based on the amount of the alkyl polyglycoside of the formula (II), without significantly changing the appearance of the pearlescent luster. These emulsifiers are, in particular, further nonionic and anionic emulsifiers.

Suitable nonionic emulsifiers contain z. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms and with alkylphenols with 8 to 15 carbon atoms in the alkyl group,

Ci2-C22 fatty acid mono- and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

Sorbitan mono- and diesters of saturated and unsaturated C8-C22 fatty acids and their ethylene oxide addition products and Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil.

Mixtures of compounds from several of these classes of substances are also suitable.

Anionic emulsifiers to be used according to the invention are, in particular, alkyl sulfates and alkyl polyethylene glycol ether sulfates having 8 to 22 carbon atoms in the alkyl chain and 1 to 15, in particular 1 to 6, ethylene glycol ether groups in the molecule, which in the form of their alkali metal, magnesium, ammonium, mono-, Di- or trialkanolarnmonium salts with 2 to 3 carbon atoms are used in the alkanol group, as well as fatty alcohol (polyglycol ether) carboxylates, sulfonic succinate ono- and dialkyl esters and sulfosuccinic acid ester salts. Alkyl polyethylene glycol ether sulfates such as sodium lauryl polyglycol ether sulfate have been found to be particularly suitable.

The compounds with alkyl groups used as emulsifiers can each be uniform substances. However, it is generally preferred to use native vegetable and animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the emulsifiers which are addition products of ethylene and / or propylene oxide onto fatty alcohols, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologues which are obtained as catalysts when converting fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates. On the other hand, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred. Pearlescent concentrates which contain 20-30% by weight of pearlescent components and 20-35% by weight of emulsifiers have proven to be particularly advantageous according to the invention.

Furthermore, the pearlescent concentrates according to the invention can, if desired, contain a low molecular weight, polyhydric alcohol.

A group of preferably used low molecular weight, polyhydric alcohols contain 2-12 carbon atoms and 2-10 hydroxyl groups. Such alcohols are, for example, ethylene glycol, 1,2- and 1,3-propylene glycol, glycerin, erythritol, arabitol, adonitol, xylitol, sorbitol, mannitol, dulcitol, glucose and sucrose. The use of glycerol, 1,2-propylene glycol, 1,3-propylene glycol, sorbitol and / or glucose is particularly preferred.

The use of glycerol as a low molecular weight, polyhydric alcohol leads to pearlescent concentrates which give the end products a particularly brilliant pearlescent.

Another group of preferably used low molecular weight, polyhydric alcohols are oligomeric ethers, in particular those based on ethylene glycol, propylene glycol and glycerol. Products whose average molecular weight is below about 700 Dalton are particularly suitable. In particular, the di-, tri- and tetramers of ethylene glycol and glycerol can be used according to the invention.

According to the invention, the low molecular weight, polyhydric alcohols are preferably used in amounts of 0.1 to 25% by weight, in particular in amounts of 0.1 to 15% by weight, based on the preparation as a whole.

In addition, the pearlescent concentrates according to the invention essentially contain water.

Furthermore, buffer substances can be used in minor amounts to adjust the pH to values between 2 and 8, e.g. As citric acid and / or sodium citrate, as well as inorganic salts, for example sodium chloride, may be included as a thickener. In a first, preferred embodiment, the pearlescent concentrates according to the invention are provided with the usual preservatives known to those skilled in the art. Examples of such preservatives are formic acid, benzoic acid and pHB esters.

In a second preferred embodiment, the pearlescent concentrates are free of preservatives. In this context, preservative-free means pearlescent concentrates to which no preservatives have been added. They therefore preferably contain no preservatives or preservatives only in amounts such as those introduced with them due to the selected individual raw materials.

The pearlescent concentrates according to the invention can be pumped very well at least in a temperature range of 15-30 ° C. and over a longer period, ie. H. at least about 6 months, stable in storage.

The pearlescent concentrates according to the invention can be prepared in such a way that components (A), (B) and (C) are first heated together to a temperature which is about 1 to 30 ° C. above the melting point. In most cases this will be a temperature of around 60 to 90 ° C. The water heated to approximately the same temperature is then added to this mixture. If an ionic, water-soluble emulsifier is used as the emulsifier, it may be preferred to dissolve it in the water phase and to introduce it into the mixture together with the water. The aqueous phase can also optionally already contain the buffer substances in solution. The resulting dispersion is then kept under constant stirring to room temperature, i.e. H. cooled to about 25 ° C. The viscosity of the pearlescent concentrate is so low in most cases that the use of special stirring units such as homogenizers or other high-speed mixing devices can be dispensed with.

The pearlescent concentrates according to the invention are suitable for producing cloudy and pearlescent liquid, aqueous preparations of water-soluble surface-active substances. You can, for example, in liquid detergents and cleaning agents such as detergents, liquid mild detergents and liquid soaps, but preferably in liquid body cleaning and care products such as shampoos, liquid hand and body detergents, Shower bath preparations, bath additives (foam baths), hair rinsing agents or hair dye preparations can be incorporated.

To produce pearlescent, the pearlescent concentrates according to the invention are added to the clear aqueous preparations at 0 to 40 ° C. in an amount of 1 to 10% by weight, in particular 1.5 to 5% by weight, of the preparation and distributed therein with stirring. Depending on the preparation and the concentration in use, a metallic glossy, dense to slightly glossy, extremely dense pearlescent results.

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

B e i s p i e l e

1. Performance concentrates

Pearlescent concentrates were prepared with the compositions listed in Table 1.

Table 1: Pearlescent concentrates

Mixture no. Content [% by weight]

components

Pearlescent:

Pearlescent l ¹ 20 20 20 20 15 Pearlescent 2 ² 20 Comperlan ( ^R ) 100 ³ Cutina (R) FS 45 ⁴

Emulsifier:

Plantaren ( ^R ) H 1200 ⁵ 40 30 40 30 45 30 Dehydol (R) LS46 5 Texapon (R) N70 ⁷ 5 Cetiol (R) HEß 1

Alcohol:

Glycerin ^ 10 15

1,2-propylene glycol

Sorbitol 10

Glucose 13

Water, adjusting agent ad 100 Mixture containing

approx. 10% by weight C _j ö / is alkyl ethylene glycol monoester,

- Approx. 46% by weight Ci5 / i8 ^_A alkyl ethylene glycol diester with the same

Alkyl groups and

- About 44 wt .-% Cig / iß-alkyl ethylene glycol diesters with different

Alkyl group mixture containing

30% by weight Ciö / ig-alkyl ethylene glycol monoester,

- About 36 wt .-% Ci6 / i8-alkyl-ethylene glycol diesters with the same

Alkyl groups and

- Approx. 34% by weight Ciss / i alkyl ethylene glycol diester with different

Alkyl groups coconut fatty acid monoethanola id (approx. 95% amide; CTFA name: Cocamide MEA) (HENKEL)

Composition of the fatty acid: approx. 56% lauric acid approx. 21% myristic acid approx. 10% palmitic acid approx. 13% stearic acid and oleic acid Ci5-Ci8 ~ fatty acid (CTFA name: Palmitic Acid (and) Stearic Acid) (HENKEL) Ci2- Ci5-fatty alcohol-l, 4-glucoside (approx. 50% active substance in water; CTFA name: Lauryl Polyglycose) (HENKEL CORP.) Cχ2-Ci4-fatty alcohol + 4 ethylene oxide (HENKEL) sodium lauryl ether sulfate (approx. 72% active substance in water ; CTFA name: Sodium Laureth Sulfate) (HENKEL) polyol fatty acid ester (CTFA name: PEG-7-Glyceryl Cocoate) (HENKEL) 86% in water

Claims

Patent claims

1. pearlescent concentrate in the form of an aqueous dispersion with 10 to 40 wt .-% of pearlescent components and 15 to 55 wt .-% of emulsifiers, characterized in that

the pearlescent components are compounds of the formula (I),

R1 _ 0 - CH - CH - 0 - R ² (I),

in which R is a linear fatty acyl group with 16 or 18 carbon atoms and R ^{2 is} hydrogen or a group R ¹ with the proviso that a product is present in which

- less than 40% of the groups R ^{2 are} hydrogen and

and as emulsifiers, alkyl polyglycosides of the general formula (II),

R0- (Z) _x (II)

in which R stands for an alkyl radical with 6 to 22 carbon atoms, Z for a mono- or oligosaccharide, x for a number from 1.1 to 5, or their addition products with 1 to 10 molecules of ethylene oxide and / or propylene oxide are contained.

2. pearlescent concentrate according to claim 1, characterized in that in the formula (II) Z for glucose and x for a number between 1.1 and 2, in particular for a number between 1.1 and 1.4.

3. pearlescent concentrate according to one of claims 1 or 2, characterized gekenn¬ characterized in that further pearlescent components in amounts up to 50 wt .-%, in particular up to 30 wt .-%, based on the compounds of formula (I) are.

4. pearlescent concentrate according to one of claims 1 to 3, characterized gekenn¬ characterized in that further emulsifiers in amounts of up to 50 wt .-%, based on the amount of the alkyl polyglycoside of formula (II) are included.

5. pearlescent concentrate according to claim 4, characterized in that these further emulsifiers are anionic or nonionic.

6. pearlescent concentrate according to one of claims 1 to 5, characterized gekenn¬ characterized in that it contains 20 to 30 wt .-% of pearlescent components and 20 to 35 wt .-% of emulsifiers.

7 .. pearlescent concentrate according to one of claims 1 to 6, characterized gekenn¬ characterized in that it additionally contains a low molecular weight, polyhydric alcohol.

8. pearlescent concentrate according to claim 7, characterized in that the low molecular weight, polyhydric alcohol is contained in amounts of 0.1 to 25 wt .-%, based on the entire preparation.

9. pearlescent concentrate according to one of claims 7 or 8 characterized gekenn¬ characterized in that the low molecular weight, polyhydric alcohol contains 2 to 12 carbon atoms and 2 to 10 hydroxyl groups.

10. pearlescent concentrate according to claim 9, characterized in that the low molecular weight, polyhydric alcohol is selected from the group consisting of the substances glycerol, 1,2-propylene glycol, 1,3-propylene glycol, glucose and sorbitol.

11. pearlescent concentrate according to one of claims 7 or 8, characterized gekenn¬ characterized in that the low molecular weight, polyhydric alcohol is selected from polyethylene glycols, polypropylene glycols and polyglycerols with an average molecular weight below 700 daltons.

12. A process for the production of pearlescent concentrates according to one of claims 1 to 11, characterized in that a mixture of components (A), (B) and (C) is heated to a temperature which is 1 to 30 ° C above the melting point of the mixture, mixed with the necessary amount of water at about the same temperature and then cooled to room temperature.

13. Use of pearlescent concentrates according to one of claims 1 to 11 in an amount of 0.5 to 10 wt .-%, in particular from 1.5 to 5 wt .-%, for the production of cloudy and pearlescent liquid, aqueous preparations water-soluble surfactants.

14. A process for the preparation of cloudy and pearlescent liquid, aqueous preparations of water-soluble surface-active substances, characterized in that the clear aqueous preparations at 0 to 40 ° C pearlescent concentrates according to one of claims 1 to 11 in an amount of 0.5 to 10 % By weight, in particular from 1.5 to 5% by weight, of the preparation and distributed therein with stirring.