AU652027B2 - Pourable lustrous concentrate - Google Patents

Abstract

Lustrous concentrates containing (A) 15-40 % wt. lustrous components, (B) 5-55 % wt. emulsifiers and (C) 15-40 % wt. low-molecular polyvalent alcohols can be poured or pumped and can be stored for long periods without the addition of preserving agents.

Description

t npT DATE 07/09/92 AOJP DATE 15/10/92 APPLN. T D 17 11L 2 PCT NUMBER PCI/FP92/flfl.79 ENS (51) Internationale Paten tklassif11kation 5 (11) Internationale Ver6ffentlichungsnummer: WVO 92/13512 A61K 7/075, 7/08 Al (43) Internationales Veriiffentlichungsdatum: 20. August 1992 (20.08.92) (21) Internationales Aktenzeichen: PCT/EP92/00 179 (74) Gemeinsamer Vertreter: HENKEL KOMMANDITGE- SELLSCHAFT AUF AKTIEN; TFP/ Patentabtei lung, (22) Internationales Anmeldedatumn: 28. Januar 1992 (28.01.92) Henkelstrak~ 67, D-4000 DUsseldorf 13 (DE).

Priorititsdaten: (81) Bestimmungsstaaten: AT (europdisches Patent), AU, BE P 4103 551.8 6. Februar 1991 (06.02.91) DE (europ~isches Patent), BR, CA, CH (europiiisches Patent), DE (europdisches Patent), DK (eurc d~isches Patent), ES (europdisches Patent), FR (europdisches Pa- (71) Anmelder (for alle Bestinuzngssmtaaen ausser US): HEN- tent), GB (europiiisches Patent), GR (europaisches Pa- KEL KOM MANDITGESELLSCHAFT AUF AKTIEN tent), IT (europtiisches Patent), JP, KR, LU (europ~i- [DE/DE]; Henkelstrake 67, D-4000 Dasseldorf 13 sches Patent), MC (europ~isches Patent), NL (europaisches Patent), SE (europaisches Patent), US.

(72) Erfinder; und Erfinder/Anmelder (nur/Ofr US) KAWA, Rolf [DE/DEb; Fontanestrake 28, D-4019 Monheim 2 ANS- Verbffentlicht MANN, Achim [DE/DE]; Kirchberg 25, D-4006 Er- Mit internationalem Rech, rchenbcrichr.

krath STRAUSS, Gabriele IDE/DEl; Elbruchstrage 6, D-4000 DUsseldorf 13 (DE).

(54) Title: POURABLE LUSTROUS CONCENTRATE (54) Bezeichn-ing: FLIESSFAH IGES PERLGLANZKONZENTRAT (57) Abstract Lustrous concentrates containing 15-40 wt. lustrous components, 5-55 wt. emulsifiers and 15-40 wt. lowmolecular polyvalent alcohols can be poured or pumped and can be stored for long periods without the addition of preserving agents.

(57) Zusamnmenfassung Perlglanzkonzentrate, die 15 40 Gew.-% an perlglanizbildenden Komponenten, 5 55 Gew.-% an Emulgatoren und 15 40 an niedermolekularen, mehrwertigen Alkoholen enthalten, sind fliess- oder pumpfiihig sowie ohne Zusatz von Konservierungsmittel Uber langere Zeitrgume haltbar.

I 9* 0 016-- WO 92/13512 1 PCT/EP92/00179 Pourable Lustrous Concentrate This invention relates to a pearlescent concentrate in the form of a free-flowing or pumpable, aqueous dispersion containing 15 to 40% by weight pearlescing components.

Aqueous preparations of surfactants and cosmetic preparations can be given a pearlescent, aesthetically attractive appearance by incorporation of substances which, after cooling, precipitate in the form of fine nacreous-looking crystals and remain dispersed in the preparations. Suitable so-called pearlescers are, for example, the monoesters, diesters and optionally triesters of ethylene glycol, propylene glycol and oligomeric alkylene glycols of this type or glycerol with

C

14 22 fatty acids, fatty acids and also monoalkanolamides of fatty acids.

It is also known that the pearlescers mentioned form stable dispersions in water or in aqueous surfactant solutions and that the concentrated pearlescent dispersions obtained in this way can be added without heating to the preparations to be given a pearlescent appearance, so that there is no longer any need for the heating and cooling otherwise necessary for incorporation to form the pearlescent crystals.

Pearlescent concentrates based on the pearlescers mentioned above are known, for example, from DE-A-16 69 152, from JP-56/71021 (Chem. Abstr. 95/156360), from DE- A-34 11 328, DE-A-35 19 081 and DE-A-38 43 572.

One problem affecting the production and use of pearlescent concentrates concerns their flowability and pumpability. Flowability and pumpability are often seriously restricted, above all at high concentrations of pearlescing components, or the mixtures present can- L WO 92/13512 2 PCT/EP92/00179 not flow at all or cannot even be puiLped by conventional pumping equipment.

Accordingly, it was proposed in German patent application DE 38 43 572 to reduce the viscosity of pearlescent concentrates by addition of small quantities of low molecular weight, polyhydric alcohols and thus to establish flowability and pumpability.

In addition, known pearlescent concentrates are provided with preservatives, such as for example organic acids (formic acid, benzoic acid, salicylic acid, sorbic acid), formaldehyde, isothiazolinones, PHB esters or 1,3-dioxanes for protection against bacterial and fungal contamination.

However, preservatives are known from dermatological studies to cause a number of skin irritations and complaints. Accordingly, preservative-free personal hygiene preparations and cosmetics have very recently come increasingly onto the market. To enable products such as these to be given t:ie asethetically attractive appearance required by the consumer through the use of pearlescent concentrates, there is thus a need for pearlescent concentrates which can be formulated without preservatives. However, the absence of preservatives should not adversely affect the microbiological stability or other properties of these concentrates.

It has now been found that preservative-free pearlescent concentrates equivalent to known pearlescent concentrates in their stability and in their flowability and pumpability can be obtained by addition of relatively large quantities of low molecular weight polyhydric alcohols.

Accordingly, the procont invention rolatoc to pearlescent concentrate in the fo ree-flowing, aqueous die :ri' ich is characterized by a content Ohl I 3 According to a first embodiment of the present invention there is provided a pearlescent concentrate in the form of a free-flowing, aqueous dispersion, which comprises: 15 to 40% by weight of one or more pearlescing components, 5 to 55% by weight of one or more emulsifiers, and s 15 to 45% by weight of one or more low molecular weight, polyhydric alcohols.

According to a second embodiment of the present invention there is provided a process for the production of a concentrate as claimed in any one of claims 1 to 14, comprising the steps of mixing components and heating the mixture to a temperature 1 to above its point, mixing with the necessary quantity of water at substantially the same to temperature and subsequently cooling the resulting mixture to room temperature.

According to a third embodiment of the present invention there is provided a process for preparing a clouded and pearlescent free-flowing, aqueous preparation of one or more water-soluble surfactants comprising dispersing 0.5 to 10% by weight of a concentrate as claimed in any one of claims 1 to 15 in a clear aqueous preparation at 0 to 40 0

C.

Pearlescing components are understood to be fusible fats or waxes which crystallise out in the form of fine, pearlescing substances on cooling of their aqueous solutions or emulsions at temperatures in the range from about 30 to 90 0

C.

These fusible fats or waxes include (Al) esters corresponding to formula (I) Rl-(OCnH2n)x-OR2

(I)

in which R 1 is a linear C 1 4 22 fatty acyl group, R 2 is hydrogen or a group R 1 n 2 or 3 and x is a number of 1 to 4, (A2) monoalkanolamides corresponding to general formula (II) R3-CO-NH-X

(II)

in which R 3 is an alkyl group containing 8 to 22 and, more preferably, 8 to 18 carbon atoms and X is a -CH 2

-CH

2 -OH group, a -CH 2

-CH

2

-CH

2 -OH group or V4 [N:\LIBR]00327:KEII 3 of4 WO 92/13512 4 PCT/EP92/00179 a -C(CH 3 2 -OH group, (A3) linear, saturated C 14 22 fatty acids and (A4) B-ketosulfones corresponding to general formula

(III):

R

R

4 CO CH SO 2

CH

2

R

6

(III)

in which R 4 is a C-_ 21 alkyl or alkenyl group, R and R 6 are hydrogen atoms or together represent an ethylene group which forms a tetrahydrothiophene dioxide ring with the group between R 5 and R 6 and mono-, di- and triesters of glycerol with linear saturated C 1 22 fatty acids.

Suitable esters (Al) corresponding to the general formula R 1 (OCnH 2 n)xOR 2 are, for example, the monoesters and diesters of ethylene glycol and propylene glycol with higher fatty acids, for example with palmitic acid, stearic acid or behenic acid, or the diesters of diethylene glycol or triethylene glycol with such fatty acids.

Also suitable are mixtures of monoesters and diesters of the glycols mentioned with fatty acid mixtures, for example with hydrogenated tallow fatty acid, palm oil fatty acid or with the saturated C 14 18 fatty acid fraction of tallow fatty acid. The ethylene glycol monoester and/or diester of palmitic and/or stearic acid is particularly suitable.

Preferred monoalkanolamides (A2) are the monoethanolamides. These compounds may contain individual arkyl radicals. However, it is standard practice to produce the alkanolamides from fatty acid mixtures from natural sources, for example coconut oil fatty acids, so that corresponding mixtures are present in regard to the alkyl radicals.

_~il P s I' I-LC 'r WO 92/13512 5 PCT/EP92/00179 Suitable linear fatty acids (A3) are, for example, palmitic acid, stearic acid, arachic acid or behenic acid, although it is also possible to use technical fatty acid cuts consisting entirely or predominantly of C,_ 22 fatty acids, for example palmitic/ stearic acid fractions of the type obtained from tallow fatty acid or palm oil fatty acid by separation of the fatty acids liquid at +5"C or palmitic/stearic acid fractions of the type obtainable by hydrogenation of tallow fatty acid or palm oil fatty acid.

The B-ketosulfones (A4) of general formula (III) have the advantage over the known ethylene glycol monoesters and diesters that the pearlescence of the preparations shows higher heat stability, i.e. the preparations retain their pearlescence for several hours on heating to temperatures above 50"C and, in some cases, to temperatures above 70"C. Further information on the B-ketosulfones mentioned can be found in German patent application 35 08 051.

The esters of glycerol (A5) suitable for use in accordance with the teaching of the invention include the mono-, di- and in particular triesters with myristic acid, palmitic acid, stearic acid and behenic acid and with mixtures of these fatty acids.

Fatty alcohols containing at least 20 C atoms and, in particular, 20 to 30 C atoms may also be used as pearlescing components.

The pearlescent concentrates according to the invention may exclusively comprise representatives of 54 one of these classes of compounds and also mixtures of representatives of several of these classes of compounds.

Preferred pearlescing components are representatives of classes (Al) to (A3).

However, fatty acid mono- or dialkanolamides, I WO 92/13512 6 PCT/EP92/00179 i.e. pearlescing components of group and derivatives thereof have recently been suspected of participating in the formation of nitroamines. Accordingly, it may be desirable to formulate cosmetic preparations without such alkanclamines and alkanolamine derivatives.

For this reason, compounds of classes (Al) and (A3) can be particularly preferred pearlescing components.

Pearlescent concentrates in which at least 70% by weight and more especially at least 90% by weight of the pearlescing components consist of ethylene glycol distearate are particularly preferred.

Emulsifiers are ionic or nonionic surfaceactive compounds distinguished by a lipophilic, preferably linear, alkyl or alkenyl group and at least one 1' hydrophilic group. The hydrophilic group may be both an ionic group and also a nonionic group.

Suitable anionic emulsifiers suitable for use in accordance with the invention are, for example, alkyl sulfates and alkyl polyethylene glycol ether sulfates containing 8 to 22 C atoms in the alkyl chain and 1 to and more particularly 1 to 6 ethylene glycol ether groups in the molecule which are used in the form of their alkali, magnesium, ammonium, mono-, di- or trialkanolammonium salts containing 2 to 3 C atoms in the alkanol group. Other suitable anionic surfactants are alkanesulfonates, a-olefin sulfonates, a-sulfofatty acid methyl esters, fatty alcohol (polyglycol ether) carboxylates, sulfosuccinic acid mono- and dialkyl esters, sulfosuccinic acid ester salts, acyl isethionates, acyl taurides and acyl sarcosides containing 8 to 22 and more particularly 12 to 18 C atoms in the alkyl or acyl chain. Soaps may also be used as emulsifiers. This may be achieved, for example, by saponifying a small proportion, for example about 1 to 20% by weight, of the linear, saturated fatty acids by added alkali metal r I pd~ WO 92/13512 7 PCT/EP92/00179 hydroxide and thus converting it into an anionic emulsifier.

Preferred anionic emulsifiers are the alkyl polyethylene glycol ether sulfates such as, for example, sodium lauryl polyglycol ether sulfate.

Suitable cationic emulsifiers are quaternary ammonium surfactants, for example alkyl trimethyl ammonium chlorides and dialkyl dimethyl ammonium chlorides, for example cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chlorider distearyl dimethyl ammonium chloride, lauryl dimetlyl ammonium chloride and lauryl dimethyl benzyl ammonium chloride, cetyl pyridinium chloride and tallow alkyl tris-(oligooxyalkyl)ammonium phosphate.

Zwitterionic surfactants may also be used as the emulsifiers Zwitterionic surfactants are surfaceactive compounds which contain at least one quaternary ammonium group and at least one -COO or -SO3 group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the Nalkyl-N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium glycinate, and 2alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. The fatty acid amide derivative known by the CTFA name of cocoamidopropyl betaine is a preferred zwitterionic surfactant.

Other suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C,_ 18 alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO 3 H group and are I c Llt-- WO 92/13512 8 PCT/EP92/00179 capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids containing approximately 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylamine propionate and C 12 18 acyl sarcosine.

Finally, it is also possible to use nonionic emulsifiers which contain, for example, a polyol group, a polyalkylene glycol ether group or a combination of a polyol group and a polyglycol ether group as the hydrophilic group. Compounds such as these are, for example, (Bl) adducts of 2 to 30 mol ethylene oxide and/or 0 to mol propylene oxide with linear C 8 22 fatty alcohols, with C 1 2 22 fatty acids and with alkyl phenols containing 8 to 15 carbon atoms in the alkyl group, (B2) C 12 22 fatty acid monoesters and diesters of adducts of 1 to 30 mol ethylene oxide with glycerol, (B3) glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated C8- 22 fatty acids and ethylene oxide adducts thereof, (B4) C 8 22 alkyl mono- and -oligoglycosides and ethoxylated analogs thereof and adducts of 10 to 60 mol ethylene oxide with castor oil and hydrogenated castor oil.

Mixtures of compounds from several of these WO 92/13512 9 PCT/EP92/00179 classes are also suitable.

The adducts of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids, alkyl phenols, glycerol monoesters and diesters and sorbitan monoesters and diesters of fatty acids or with castor oil are known commercially available products. They are homolog mixtures of which the average degree of alkoxylation corresponds to the ratio between the quantities of ethylene oxide and/or propylene oxide and substrate with which the addition reaction is carried out.

C

12 22 fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE-PS 20 24 051 as refatting agents for cosmetic preparations. C 8 22 alkyl mono- and -oligoglycosides, their production and their use as surfactants are known, for example, from US-A 3,839,318, US-A 3,707,535, US-A 3,547,828, DE-A 19 43 689, DE-A 20 36 472 and DE-A 30 01 064 and from EP-A 77 167. They are prepared in particular by reaction of glucose or oligosaccharides with primary C 8 22 alcohols. So far as the glycoside residue is concerned, both monoglycosides, in which a cyclic sugar residue is attached to the fatty alcohol by a glycoside bond, and also oligomeric glycosides having a degree of oligomerization of up to, preferably, about 8 are suitable. Degrees of oligomerization of 1.4 and lower can be particularly preferred. The degree of oligomerization is a statistical mean value on which a homolog distribution typical of such technical products is based.

The compounds of group (Bl) are particularly preferred nonionic emulsifiers for the purposes of the invention.

The compounds containing alkyl groups used as surfactants may be individual substances. However, it is generally preferred to use native vegetable and WO 92/13512 10 PCT/EP92/00179 animal starting materials in the production of these compounds, so that mixtures having different alkyl chain lengths depending on the particular starting material used are obtained.

The surfactants which are adducts of ethylene and/or propylene oxide with fatty alcohols may be both products with a "normal" homolog distribution and products with a "narrow" homolog distribution. Products Iwith a "normal" homolog distribution are understood to be mixtures of homologs which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. By contrast, narrow homolog distributions are obtained when, for example, hydrotalcites, alkline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of so-called "narrow-range" products can be preferred.

According to the teaching of the invention, the pearlescent concentrates may contain representatives of one or more of the surfactant classes mentioned.

Since pearlescent concentrates are mainly added to formulations containing anionic surfactants, anionic emulsifiers are preferred emulsifiers In addition, the pearlescent concentrates according to the invention, which contain only nonionic, zwitterionic and/or ampholytic surfactants, have proved to be particularly universally usable and to be particularly compatible with water-containing preparations of water-soluble surfactants of any type and any ionicity.

Accordingly, the use of surfactants from these classes is also preferred.

The presence of low molecular weight polyhydric alcohols is crucial to the flowability or pumpability of the pearlescent concentrates according to the invention L_ WO 92/135122 PCT/EP92/00179 and also to their resistance to bacterial and fungal contamination.

Preferred low molecular weight polyhydric alcohols contain 2 to 6 carbon atoms and 2 to 6 hydroxyl groups. Alcohols such as these are, for example, ethylene glycol, 1,2- and 1,3-propylene glycol, glycerol, di- and triethylene glycol, erythritol, arabitol, adonitol, xylitol, sorbitol, mannitol and dulcitol. It is particularly preferred to use glycerol, 1,2-propylene glycol, 1,3-propylene glycol and/or sorbitol.

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

In addition to the components mentioned above, the pearlescent concentrates according to the inv.ition essentially contain water.

In addition, the concentrates may contain small quantities of buffers to adjust the pH to values in the range from 2 to 8, for example citric acid and/or ;-dium citrate, and also inorganic salts, for example sodium chloride, as thickener.

Although the pearlescent concentrates are normally free from preservatives, small quantities of commercially available preservatives introduced for example through certain starting materials may be present in exceptional cases.

The pearlescent concentrates according to the invention are pumpable at least over a temperature range of 5 to 40°C and remain stable in storage for prolonged periods, i.e. for at least about 3 months.

The pearlescent concentrates according to the invention are preferably prepared by initially heating components and together to a temperature approximately 1 to 30"C above the melting point. In

J

WO 92/13512 12 PCT/EP92/00179 most cases, this will be a temperature in the range from about 60 to 90'C. The water heated to substantially the same temperature is then added to this mixture. Where an ionic water-soluble surfactant is used as the emulsifier, it may be preferred to dissolve it in the aqueous phase and to introduce it together with the water into the mixture. The aqueous phase may even already contain the buffer substances in dissolved form.

The dispersion formed is then cooled with continuous stirring to room temperature, i.e. to around 25°C. In most cases, the viscosity of the pearlescent concentrate is so low that there is no need to use special stirring units, such as homogenizers or other high-speed mixers.

The pearlescent concentrates according to the invention are suitable for the production of clouded and pearlescent, liquid aqueous preparations of water-soluble surfactants. They may be incorporated, for example, in liquid detergents, such as dishwashing detergents, liquid light-duty detergents and liquid soaps but are preferably incorporated in liquid personal hygiene and body-care preparations, such as for example shampoos, liquid hand and body soaps, shower bath preparations, bath additives (foam baths), hair rinses or hair dyes.

To produce pearlescence, the pearlescent concentrates according to the invention are added to the clear aqueous preparations at 0 to 40°C in a quantity of 1 to by weight and more especially in a quantity of to 5% by weight of the preparation and are dispersed therein with stirring. A metallic, dense to slightly lustrous, extremely dense pearlescence is obtained, depending on the preparation and the concentration used.

The following Examples are intended to illustrate the invention without limiting it in any way.

e -i 'i I WO 92/13512 PCT/EP92/00179 Examples 1. Pearlescent concentrates Pearlescent concentrates having the compositions shown in Table 1 were prepared. The components shown in the form of trade names are the following substances: 1 Ethylene glycol distearate (at least 90% diester)

(HENKEL)

2 Coconut oil fatty acid monoethanolamide

(CTFA

name: Cocamide MEA (approx. 95% amide)) (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 3 Palmitic/stearic acid mixture (approx. 1:1) SFatty alcohol polyglycol ether (CTFA name: (approx. 74% C 12

/I

4 fatty alcohol))

(HENKEL)

5 Sodium lauryl ether sulfate (CTFA name: Sodium Laureth Sulfate (approx. 72% active substance))

(HENKEL)

6 C 12 4 fatty alcohol 4 ethylene oxide (HENKEL) 7 Aqueous solution of a fatty acid amide derivative of betaine structure having the formula

R-CONH-(CH

2 3

-N+(CH

3 )z-CH 2 -COO (CTFA name Cocamidopropyl Betaine (approx. 30% active substance, approx. 5% NaCl)) (HENKEL) a. h ~I I WO 92/13512 14 PCT/EP92/0a.79 8 C 12 14 fatty alcohol 3 ethylene oxide (HENKEL) 9 Polyol fatty acid ester (CTFA name: PEG-7-Glyceryl Cocoate) (HENKEL) 86% Water P WO 92/13512 WO 9213512PCT/EP92/00179 Table I: Free-flowing Pearlescent concentrates Content by weight) Mixture No.

Components Pearlescer (A) of which Cutina ()AGS1 Comperlan ()1002 Fatty acid 16/18~ Emulsifier (B) of which Dehydol ()1001 Texapon ()N705 Dehydo l(R LS4' Dehyton K-7 Dehydol ()LS38 CetiolR) HE' Alcohol (C) of which glycerol 1 0 1,2-propylene glycol 1,3-propylene glycol sorbitol 1 2 3 4 5 6 7 8 9 23 30 25 25 25 23 25 23 20 20 25 25 25 25 20 25 20 3 5 3 3 20 22 26 17 17 19 22 18.5 22 10 2 5 2 -2 20 21 20 20 11 11 5 11 6 6 9 7.5 5 20 20 30 30 20 30 20 30 40 Water Buffer ad 100 WO 92/13512 16 PCT/EP92/00179 Application Examples 1) Shower bath Parts by weight Texapon(R)N25 11 Dehyton(R)K 7 Lamepon(R)S 12 Pearlescent concentrate 1 3 Water ad 100 The viscosity of the shower bath was then adjusted to 4,000 mPas by addition of sodium chloride.

11 Sodium lauryl ether sulfate (CTFA name: Sodium Laureth Sulfate (approx. 28% active substance in water) (HENKEL) 12 Protein hydrolyzate fatty acid condensate potassium salt (CTFA name: Potassium Coco-Hydrolyzed Animal Collagen) (HENKEL) 2) Mild shampoo Parts by weight Texapon(R)ASV13 14 Texapon(RSB 314 Dehyton(R)G 1 5 14 Nutrilan(R)I 5016 Pearlescent concentrate 2 2 Water ad 100 The viscosity was then adjusted to 5,000 mPas by addition of sodium chloride and Arlypon'R)F (narrow-range ethoxylated fatty alcohol) (HENKEL)).

I- WO 92/13512 17 PCT/EP92/00179 13 A mixture of special fatty alcohol ether sulfates (CTFA name: Sodium Laureth Sulfate (and) Magnesium Laureth Sulfate (and) Sodium Laureth 8-Sulfate (and) Magnesium Laureth 8-sulfate (and) Sodium Oleth Sulfate (and) Magnesium Oleth Sulfate (approx. active substance in water)) (HENKEL) 14 Sulfosuccinic acid semiester based on an alkyl polyglycol ether, di Na salt (CTFA name: disodium laureth sulfosuccinate (approx. 40% active substance in water)) (HENKEL) Amphoteric fatty acid amide derivative (N-hydroxyethyl-N-cocoalkylamidoethyl glycinate, Na salt) (CTFA name: Cocoamphodiacetate (approx. 30% active substance in water)) (HENKEL) 16 Partial protein hydrolyzate of degraded bovine collagen (CTFA name: Hydrolyzed Animal Protein)

(HENKEL)

3) Foam bath Parts by weight Texapon(R)N 4017 Dehyton(R)K Dehyton(R)G Cetiol(R)HE Pearlescent concentrate 3 Water ad 100 The viscosity was then adjusted to 6,000 mPas by addition of sodium chloride.

17 Sodium lauryl ether sulfate (CTFA name: Sodium Laureth Sulfate (approx. 28% active substance in water)) (HENKEL) 4

Claims (23)

1. A pearlescent concentrate in the form of a free-flowing, aqueous dispersion, which comprises: 15 to 40% by weight of one or more pearlescing components, s 5 to 55% by weight of one or more emulsifiers, and 15 to 44s by weight of one or more low molecular weight, polyhydric alcohols.

2. A concentrate as claimed in claim 1, which comprises: 20 to 30% by weight of one or more pearlescing components, 10 to 35% by weight of one or more emulsifiers, and 20 to 40% by weight of one or more low molecular weight, polyhydric alcohols.

3. A concentrate as claimed in claim 1 or claim 2, wherein said pearlescing component is (Al) an ester corresponding to formula (I) R 1 -(OC n H2 n x -OR 2 (I) is in which R 1 is a linear C 14 22 fatty acyl group, R 2 is hydrogen or a group R 1 n 2 or 3 and x is a number of 1 to 4, (A2) a monoalkanolamide corresponding to general formula (II) R 3 -CO-NH-X (II) in which R 3 is an alkyl group containing 8 to 22 and X is a -CH 2 -CH 2 -OH group, a -CH 2 CH 2 -CH 2 -OH group or a -C(CH 3 2 -OH group, (A3) a linear, saturated C 1 6 22 fatty acid, or a mixture of any two or more thereof.

4. A concentrate as claimed in claim 3, wherein said R 3 alkyl group has 8 to 18 carbon atoms.

5. A concentrate as claimed in claim 3 or claim 4, wherein at least 70% by weight of the pearlescing components comprises ethylene glycol distearate.

6. A concentrate as claimed in claim 3 or claim 4, wherein at least 90% by weight of the pearlescing components comprises ethylene glycol distearate.

7. A concentrate as claimed in any one of claims 1 to 6, wherein said emulsifiers are nonionic, ampholytic and/or zwitterionic emulsifiers.

8. A concentrate as claimed in any one of claims 1 to 6, wherein said emulsifiers are nonionic surfactants.

9. A concentrate as claimed in claim 8, wherein said surfactants comprise any one or more of: (B1) adducts of 2 to 30 mol ethylene oxide and/or 0 to 5 mol propylene oxide with linear C8- 22 fatty alcohols, with C 12 22 fatty acids and with alkyl phenols containing 8 to carbon atoms in the alkyl group, (B2) C 12 22 fatty acid monoesters and diesters of adducts of 1 to 30 mol ethylene oxide with glycerol, [N:\LIBR]00327:KEH 18 of 4 L. -i c~ 19 (B3) glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated C8- 22 fatty acids and ethylene oxide adducts thereof, (B4) C 8 22 alkyl mono- and -oligoglycosides and ethoxylated analogs thereof, and adducts of 10 to 60 mol ethylene oxide with castor oil and hydrogenated caster oil.

A concentrate as claimed in claim 7, wherein said zwitterionic emulsifiers are bentaines.

11. A concentrate as claimed in any one of claims 1 to 6, wherein said emulsifiers are anionic emulsifiers.

12. A concentrate as claimed in any one of claims 1 to 11, wherein said polyhydric alcohols have 2 to 6 carbon atoms and 2 to 6 hydroxyl groups.

13. A concentrate as claimed in claim 12, wherein said polyhydric alcohol is glycerol, 1,2-propylene glycol, 1,3-propylene glycol, sorbitol or a mixture of any two or more thereof.

14. A concentrate as claimed in claim 13, wherein said polyhydric alcohol is glycerol. is

15. A pearlescent concentrate in the form of a free-flowing, aqueous dispersion, substantially as hereinbefore described with reference to any one of the Examples.

16. A process for the production of a concentrate as claimed in any one of claims 1 to 14, comprising the steps of mixing components and heating the mixture to a temperature 1 to 30 0 C above its point, mixing with the necessary quantity of water at substantially the same temperature and subsequently cooling the resulting mixture to room temperature.

17, A process for preparing a pearlescent concentrate in the form of a free-flowing, aqueous dispersion, substantially as hereinbefore described with reference to any one of the Examples.

18. A process for preparing a clouded and pearlescent free-flowing, aqueous preparation of one or more water-soluble surfactants comprising dispersing 0.5 to 10% by weight of a concentrate as claimed in any one of claims 1 to 15 in a clear aqueous preparation at 0 to 40 0 C. i

19. A process as claimed in claim 18, wherein 1.5 to 5% by weight of said concentrate is dispersed.

20. A process for the production of a clouded and pearlescent free-flowing, aqueous preparation of one or more water-soluble surfactants, substantially as hereinbefore described with reference to any one of the Application Examples.

21. An aqueous preparation prepared by the process of any one of claims 18 to

22. A free-flowing aqueous preparation of one or more water-soluble surfactants, substantially as hereinbefore described with reference to any one of the Application Examples. [N:\LIBR]00327:KEH 19 of 4 I L'~ Dated 9 June, 1994 Henkel Kom manditgesellschaft auf Aktien Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON [N:\LIBR]00327:KEH 20 of 4 INTERNATIONAL SEARCH REPORT International Application No PCT/EP 92/00179 I. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, Indicate all) 6 According to International Patent Classification (IPC) or to both National Classification and IPC Int. Cl. 5 7/075, 7/08 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System Classification Symbols Int.C1. 5 A 61 K Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched III. DOCUMENTS CONSIDERED TO BE RELEVANT' Category I Citation of Document, "1 with indication, where appropriate, of the relevant passages 12 Relevant to Claim No. 13 X EP,A2, 0376083 (HENKEL KOMMANDITGESELLSCHAFT AUF 1-7, 9- AKTIEN), 4 July 1990 13 see cliams 1-6,9-12 A EP,A2, 0300379 (HENKEL KOMMANDITGESELLSCHAFT AUF 1-13 AKTIEN) 25 January 1989 see the whole document A EP,A2, 0205922 (HENKEL KOMMANDITGESELLSCHAFT AUF 1-13 AKTIEN) 30 December 1986 see the whole document SSpecial categories of cited documents: r0 later document published after the International filing date document defining the generalstate ofthe art which is not or priority date and not in conflict with the application but considered to be of particular relevance cited to understand the principle or theory underlying the invention earlier document but published on or after the international document of particular relevance; the claimed invention filing date cannot be considered rJvel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another of particular relevance;the claimed nvention Citation or other special reason (as specified) document of particular relevance; the claimed invention citation or other special reason las specified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the international filing date but in the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Search Report 21 April 1992 (21.04.92) 8 May 1992 (08.05.92) International Searching Authority Signature of Authorized Officer European Patent Office Form PCTIISAI210 Isecond sheet) (January 1985) II ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO.PCT/EP 92/00179 55623 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 28/02/92 The European Patent office is in no way liable for theseparticulars which are merely given for the purpose of information. Patent document Publication Patent family Publication cited in search report date member(s) date EP-A2- 0376083 04/07/90 AU-D- 4666589 01/08/90 CA-A- 2006248 23/06/90 DE-A- 3843572 28/06/90 EP-A- 0449904 09/10/91 WO-A- 90/07323 12/07/90 EP-A2- 0300379 25/01/89 DE-A- 3724547 02/02/89 JP-A- 1051138 27/02/89 EP-A2- 0205922 30/12/86 CA-A- 1265721 13/02/90 DE-A- 3519080 04/12/86 JP-A- 61277607 08/12/86 US-A- 4777038 11/10/88 For more details about this annex: see Official Journal of the European patent Office, No. 12/82 EPO F'RM P0479 II I I I INTERNATIONALER RECHERCHENBERICHT Internationales Aktenzelchen PCT/EP 92/00179 1. KLASSIFIKATION DES ANMELDUNGSGENSTANDS (bei mehreren Klass ifikationssymbolen sind shle anzugeben) Nach der Internationaten Paten tkt assifi kation (IPC) Oder nach der nationalen Klasssilikation mid der IPC A 61 K'7/075, 7/08 11. RECHERCHIERTE SACHGEBIETE Rechprcnierter Mindestpriitstoft7 Khassifikationssyslem Klass ifi kationssym bole I nI. CI A 61 K Recherctiierte nicht zumn Mindestpr~tstott gehdrende Verbtfentlichungen, soweit diese unter die recherchierten Sachgebiete talhena Ill. EINSCHLAGIGE VER6FFENTLICHUNGEN' Art Kennzeichnung der Verdlhentlichung 1 soweit ertorderhich unter Angabe der matgeblichen Teile' 2 Betr. Anspruch Nrt

2 3 X EP, A2, 0376083 (HENKEL KOMMANDITGESELLSCHAFT AUF 1-7,9- AKTIEN) 4 Juli 1990, 13 siehe AnsprUche 1-6,9-12 A EP, A2, 0300379 (HENKEL KOMMANDITGESELLSICHAFT AUF 1-13 AKTIEN) 25 Januar 1989, siehe Dokument insgesamt A -EP, A2, 0205922 (HENKEL K0MMANDITGESE, ,.SCHAFT AUF 1-13 AKTIEN) 30 Dezember 1986, siehe Dokument insgesamt Besondere Kategorien von angegebenen Verlittenthichiungen A' Verbhhentichung, die den ahigemeinen Stand der Technik Spfitere Verdffentlichung, die nach dem internationahen An- detiniert, aber nicht als besonders bedeutsam anzusehen ist meldedatum Oder dem Priorit~tsdatum vercjhtentlicht worden ist und mit der Animeldung nicht kollidiert. sondern nur zumn 51teres Dokument, das jedoch erst am Oder nach dem interna- Verstincinis des der Ertindung zugrundehiegenden Prinzips tionahen Anmeldedatum verhittentlicht warden ist Oder der ihir zugrundeliegenden Theorie angegeben ist Verhiffentlichung, die geeignet ist. einen PrioritStsanspruch Verbffentlichurig von besonderer Bedeutung, die beanspruch- zweifelhatt erscheinen zu hassen, Oder durch die das Verhil- te Ertindung kann nicht als neu Oder auf erthnderischer T~tig- lentlichungsdatum einer anderen im Recherchenbericht ge- keit beruhend betrachlet werden nannten Veritffentlichung belegit werden soil Oder die aus ein- emn anderen besonderen Grund angegeben ist (wie ausgethihrt) verbffentlichung von besonderer Bedeutung, die beanspruch- o Veoftntlihun, di sih at ele mndhihe ftenarug, e Erfindung kann nicht als aut erfinderischer Titigkeit be- '0 ene entzung, eine Auss at einger ndceOfeManbahmn ruhend betrachiet werden, wenn die Vertftfentlichung mit ei etz nieAstlugOeradr anhe iner Oder mehireren anderen Verhittentlichungen dieser Kate- bezititgorie in Verbindung gebracht wird und diese Verbindung tir 'P Verdttentlichung, die vor dem internationalen Anmeldeda- einen Factimann naheliegend ist tumn, abet nach dem beanspruchten Priorititsdatumn verot tent- Verhittentlichung, die Mitg lied derselben Patentfamilie ist ticht worden ist IV. BESCHEINIGUNG Datum des Abschiusses der internationalen Recherche Absendedatum des internationalen Rechenchenberichts 21. April 1992 8M Y19 Internationale Recherche nbe hbhrde Unterschrift des bevoltmichtigten Bedi );-ep EuropaAies Patentamnt T~ L Formbhatt PCT/ISA/210 (Blatt 2) (Januar 1985) 1-i ANHANG ZUM OiBER DIE INI INTERNATIONALEN RECHERCHENBERICHT ERNATIONALE PATENTANMVELDUNG N R.PCT/EP 92/00179 SA 55623 In diesem Anhang sind die Mitglieder der Patenttamilien der inn obengenannten internationalen Recherchenbericht angefiihrtel Patentdakumente angegeben.am2/ /9 Die Angaben Oiber die Familienmitglieder entsprechen dem Stand der Datei des Europ~ischen Palentamts a2/29 Diese Angaben dienen cur zur Unterrichtung und erfolgen ohne Gew~hr. Im Recherchenberih t Datum der Mitglied(er) der Datum der angefiihrtes Patentdoku ment I Verbffen tlichu ng Patentfamilie Verdffentmlichung EP-A2- 0376083 04/07/90 AU-ID- 4666589 01/08/90 CA-A- 2006248 23/06/90 IDE-A- 3843572 28/06/90 EP-A- 0449904 09/10/91 WO-A- 90/07323 12/07/90 EP-A2- 0300379 25/01/89 IDE-A- 3724547 02/02/89 JP-A- 1051138 27/02/89 EP-A2- 0205922 30/12/86 CA-A- 1265721 13/02/9j IDE-A- 3519080 04/12/86 JP-A- 61277607 08/12/86 US-A- 4777038 11/10/88 FUr n~here Einzetheiten zu diesemn Anhang :siehe Amtsblatt des Europ~ischen Patentamts, Nr.12/82 EPO FORM P0473 A