WO2011006657A1

WO2011006657A1 - Liquid or gel-like composition comprising microencapsulated colorant granules

Info

Publication number: WO2011006657A1
Application number: PCT/EP2010/004311
Authority: WO
Inventors: Angela Lachmann; Harald Oswald; Sambit Roy; Sharmad Chandratre; Matthias Loeffler; Carsten Cohrs
Original assignee: Clariant International Ltd
Priority date: 2009-07-17
Filing date: 2010-07-15
Publication date: 2011-01-20
Also published as: EP2277982B1; US8680032B2; JP5669836B2; EP2454354A1; KR101706408B1; BR112012001088A2; EP2454355A1; KR20120052313A; US20120178662A1; EP2277982A1; CN102449130A; JP2012533528A; JP5743229B2; WO2011006658A1; US20120183479A1; ES2378495T3; JP2012533637A

Abstract

The invention relates to liquid or gel-like compositions comprising microencapsulated colorant granules consisting of a core (A) and a shell (B), whereby the core (A) has a diameter of between 1 and 1000 micrometer and comprises a) a colorant (I), b) microcrystalline cellulose, c) a polyol; and whereby the shell (B) has a thickness of between 1 to 500 micrometer and comprises d) a polymer selected from the group consisting of polycarboxylic acids, vinyl polymers, styrene- (meth)acrylic copolymers, cellulose and cellulose derivatives.

Description

Liquid or gel-like composition comprising microencapsulated colorant granules Description The present application relates to liquid or gel-like compositions comprising microencapsulated colorant granules.

Dyes have been included in detergent products either to provide product aesthetics, coloring of wash water or to increase perceived cleaning of white fabrics. Furthermore attempts have been made to incorporate particles comprising a dye into cleansing compositions which change color during use in order to indicate that sufficient time has elapsed and that a sufficient treatment with the cleansing composition has been achieved. The choice of dye and the way to incorporate it in a composition should be carefully monitored to avoid spotting or staining of fabrics, skin, hair or hard surfaces after the treatment and/or to avoid the migration or the bleeding of the dye across the composition which may lead to a rather unattractive composition. WO 2008/132616 discloses a composition comprising at least one thermo chromic dye, changing the color of the cleansing composition when the composition reaches a temperature of from about 21 ⁰C to about 40 ⁰C. These color changing cleansing compositions are limited to thermo chromic dyes but do not indicate when a sufficient treatment with the cleansing compositions has been achieved.

Therefore, it was an object of the present invention to provide liquid or gel-like compositions such as cleansing products or personal care products which comprise an indicator for determining how long washing processes or applications should continue with the product in order to achieve a satisfying result. More particularly, a need currently exists for cleansing compositions that change color during use in order to indicate that a sufficient treatment with the cleansing compositions has been achieved. Surprisingly it has now been found that this object is solved using pigments, which are converted to particular microencapsulated colorant granules. These pigments are suited to induce color to liquid or gel-like compositions during their application and in particular to the foam built-up during the washing process.

The present invention relates to liquid or gel-like compositions comprising one or more microencapsulated colorant granules consisting of a core (A) and a shell (B), whereby the core (A) has a diameter of between 1 and 1000 micrometer, preferably between 10 and 500 micrometer, more preferably between 100 and 400 micrometer, even more preferably between 200 and 300 micrometer, and comprises

a) a colorant (I),

b) microcrystalline cellulose,

c) a polyol;

and whereby the shell (B) has a thickness of between 1 to 500 micrometer, preferably between 10 and 400 micrometer, more preferably between 50 and 300 micrometer, even more preferably between 100 and 300 micrometer, and comprises

d) a polymer selected from the group consisting of polycarboxylic acids, copolymers of polycarboxylic acids, vinyl polymers, cellulose and cellulose derivatives.

Within the meaning of the present invention the term "liquid" means liquid at ambient conditions, i.e. at a temperature of 20 °C and a pressure of 1 atm

(= 1.013^■ 10⁵ Pa or 1013 hPa). Preferably, the liquid compositions according to the present invention have a viscosity of from 1 to 10 000 mPa^• s. The viscosity is measured using the inventive liquid composition as such under the following conditions:

for measuring the viscosity in the range of from 1 to 250 mPa^■ s:

temperature: 20 ⁰C; apparatus: Brookfield RV 1 ; Spindle No. 1 ; 20 r.p.m. (rounds per minutes); for measuring the viscosity in the range of from > 250 to 500 mPa^■ s: temperature: 20 ⁰C; apparatus: Brookfield RV 2; Spindle No. 2; 20 r.p.m. (rounds per minutes);

for measuring the viscosity in the range of from > 500 to 5000 mPa^• s:

temperature: 20 ⁰C; apparatus: Brookfield RV 3; Spindle No. 3; 20 r.p.m. (rounds per minutes);

for measuring the viscosity in the range of from > 5000 to 10000 mPa^• s:

temperature: 20 ⁰C; apparatus: Brookfield RV 4; Spindle No. 4; 20 r.p.m. (rounds per minutes).

Within the meaning of the present invention the term "gel-like" means gel-like at ambient conditions, i.e. at a temperature of 20 ⁰C and a pressure of 1 atm

(= 1.013^■ 10⁵ Pa or 1013 hPa). Preferably, the gel-like compositions according to the present invention have a viscosity of from > 10 000 to 200 000 mPa^■ s and particularly preferably of from 20 000 to 150 000 mPa^■ s. The viscosity is measured using the inventive gel-like composition as such under the following conditions: temperature: 20 ⁰C; apparatus: Brookfield Viscosimeter RV; Spindle No. 7; 20 r.p.m. (rounds per minutes). In one preferred embodiment of the invention the inventive compositions are liquid. In another preferred embodiment of the invention the inventive compositions are gel-like.

In a preferred embodiment of the invention, a white pigment (e), such as titanium dioxide (C.I. Pigment White 6), barium sulfate or zinc oxide, is incorporated into the shell. In this case the color of the core colorant (I) is hidden and the foam is to change from white to the color of colorant (I).

In a further preferred embodiment of the invention, the shell contains a colorant (II) (f) which color is different from the color of colorant (I). In this case, it is expedient to apply colorant (II) as a top-coat onto the shell containing components (d) and (e). Then, the color of the foam is to change from the color of colorant (II) to the color of colorant (I). It is preferred that the color of colorant (II) is equal or at least similar to the color of the cleansing base, so that the microencapsulated colorant granules are invisible or at least hardly visible in the inventive compositions. In any embodiment of the invention, the core and the shell may contain some water not exceeding an amount for sustaining granular form, e.g. 0 to 50 %, preferably 1 to 30 %, more preferably 5 to 20 %, by weight, based on the total weight of the granules. In a preferred embodiment of the invention, the microencapsulated colorant granules contained in the inventive compositions contain

a) 5 to 60 % by weight, preferably 10 to 40% by weight, of colorant (I), b) 10 to 40 % by weight, preferably 15 to 30 % by weight, of microcrystalline cellulose,

c) 10 to 40 % by weight, preferably 15 to 30 % by weight, of polyol,

d) 0.1 to 20 % by weight, preferably 1 to 10 % by weight, of the polymer, relating to the total weight of the granules.

The amount of the white pigment (e) if any, may vary between 0 and 50 %, preferably between 0.1 and 30 %, by weight, relating to the total weight of the microencapsulated colorant granules.

The amount of colorant (II) (T), if any, may vary between 0 and 25 %, preferably between 0.1 and 20 % by weight, relating to the total weight of the

microencapsulated colorant granules.

In a further preferred embodiment of the invention, the microencapsulated colorant granules contained in the inventive compositions contain

c) 10 to 40 % by weight, preferably 15 to 30 % by weight, of polyol, d) 0.1 to 20 % by weight, preferably 1 to 10 % by weight, of the polymer, e) 0.1 to 30 % by weight, preferably 1 to 20 % by weight, of white pigment; and 1 to 30 %, preferably 5 to 20 %, by weight of water,

relating to the total weight of the granules.

c) 10 to 40 % by weight, preferably 15 to 30 % by weight, of polyol,

d) 0.1 to 20 % by weight, preferably 1 to 10 % by weight, of the polymer, e) 0.1 to 30 % by weight, preferably 1 to 20 % by weight, of white pigment; f) 0.1 to 20 % by weight, preferably 1 to 15 % by weight, of colorant (II); and 1 to 30 %, preferably 5 to 20 %, by weight of water,

relating to the total weight of the granules.

The inventive compositions may be colored or upon application may result in a coloring (in case the compositions were colorless before their application) or may result in a color change of the composition itself. A similar coloring or color change may occur with respect to the foam resulting from the application of the inventive compositions. The coloring or color change of the inventive compositions and/or foam occurs independently of the temperature of the inventive compositions so that there is no need to use thermo chromic dyes as colorants. Therefore, it is preferred that colorant (I) and colorant (II) are not thermo chromic.

All color pigments from the group consisting of inorganic pigments, organic pigments and effect pigments come into consideration for use as colorant (I) and (II). By definition, pigments - in contradistinction to dyes - are virtually insoluble in the application medium. Preferred organic pigments are monoazo, disazo, laked azo, β-naphthol, Naphthol AS, benzimidazolone, disazo condensation, azo metal complex pigments and polycyclic pigments such as, for example, phthalocyanine, quinacridone, perylene, perinone, thioindigo, anthanthrone, anthraquinone, flavanthrone, indanthrone, isoviolanthrone, pyranthrone, dioxazine, quinophthalone, isoindolinone, isoindoline and diketopyrrolopyrrole pigments.

Of the organic pigments mentioned, particularly suitable ones are in a very fine state of subdivision wherein preferably at least 95% by weight and more preferably at least 99% by weight of the pigment particles have a particle size < 500 nm.

Advantageously, the pigment particles have a d₅o value between 50 and 500 nm, preferably between 70 and 350 nm. As an illustrative selection of particularly preferred organic pigments there may be mentioned monoazo and disazo pigments, more particularly the Colour Index pigments Pigment Yellow 1 , Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 16, Pigment Yellow 17, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 81 , Pigment Yellow 83, Pigment Yellow 87, Pigment Yellow 97, Pigment Yellow 111 , Pigment Yellow 126, Pigment Yellow 127, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 174, Pigment Yellow 176, Pigment Yellow 191 , Pigment Yellow 213, Pigment

Yellow 214, Pigment Yellow 219, Pigment Red 38, Pigment Red 144, Pigment Red 214, Pigment Red 242, Pigment Red 262, Pigment Red 266, Pigment Red 269, Pigment Red 274, Pigment Orange 13, Pigment Orange 34 or Pigment Brown 41 ; β-naphthol and Naphthol AS pigments, more particularly the Colour Index pigments Pigment Red 2, Pigment Red 3, Pigment Red 4, Pigment Red 5, Pigment Red 9, Pigment Red 12, Pigment Red 14, Pigment Red 53:1 , Pigment Red 112, Pigment Red 146, Pigment Red 147, Pigment Red 170, Pigment Red 184, Pigment Red 187, Pigment Red 188, Pigment Red 210, Pigment Red 247, Pigment Red 253, Pigment Red 256, Pigment Orange 5, Pigment Orange 38 or Pigment Brown 1; laked azo and metal complex pigments, more particularly the Colour Index pigments Pigment Red 48:2, Pigment Red 48:3, Pigment Red 48:4, Pigment Red 57:1 , Pigment Red 257, Pigment Orange 68 or Pigment Orange 70; benzimidazoline pigments, more particularly the Colour Index pigments Pigment Yellow 120, Pigment Yellow 151 , Pigment Yellow 154, Pigment Yellow 175, Pigment Yellow 180, Pigment Yellow 181 , Pigment Yellow 194, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208, Pigment Violet 32, Pigment Orange 36, Pigment Orange 62, Pigment Orange 72, Pigment Blue 80 or Pigment Brown 25; isoindolinone and isoindoline pigments, more particularly the Colour Index pigments Pigment Yellow 139 or Pigment Yellow 173; phthalocyanine pigments, more particularly the Colour Index pigments Pigment Blue 15, Pigment Blue 15:1 , Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Green 7 or Pigment Green 36; anthanthrone, anthraquinone, quinacridone, dioxazine, indanthrone, perylene, perinone and thioindigo pigments, more particularly the Colour Index pigments Pigment Yellow 196, Pigment Red 122, Pigment Red 149, Pigment Red 168, Pigment Red 177, Pigment Red 179, Pigment Red 181 , Pigment Red 207, Pigment Red 209, Pigment Red 263, Pigment Blue 60, Pigment Violet 19, Pigment Violet 23 or Pigment Orange 43; triarylcarbonium pigments, more particularly the Colour Index pigments Pigment Red 169, Pigment Blue 56 or Pigment Blue 61 ; diketopyrrolopyrrole pigments, more particularly the Colour Index pigments Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272, Pigment Orange 71 , Pigment Orange 73, Pigment Orange 81. Preferred inorganic pigments are for example titanium dioxides, zinc sulfides, zinc oxides, iron oxides, magnetites, manganese iron oxides, chromium oxides, ultramarine, nickel or chromium antimony titanium oxides, manganese titanium rutiles, cobalt oxides, mixed oxides of cobalt and of aluminum, rutile mixed phase pigments, sulfides of the rare earths, spinels of cobalt with nickel and zinc, spinels based on iron and chromium with copper zinc and also manganese, bismuth vanadates and also blend pigments, more particularly the Colour Index pigments Pigment Yellow 184, Pigment Yellow 53, Pigment Yellow 42, Pigment Yellow Brown 24, Pigment Red 101 , Pigment Blue 28, Pigment Blue 36, Pigment

Green 50, Pigment Green 17. Preference is also given to mixtures of inorganic pigments and also mixtures of organic pigments with inorganic pigments. Colorant (I) and colorant (II) can be used for example as powder pigment, as presscake, as dispersion, as solid pigment preparation or as liquid pigment formulation in the manufacture of the microencapsulated colorant granules.

Preference is given to aqueous glycol-containing pigment dispersions or formulations.

More preferably, colorant (I) and colorant (II) are selected from colorants allowed for cosmetic use and from colorants allowed for detergents.

Even more preferably colorant (I) and colorant (II) are selected from the group consisting of C.I. Pigment Black 7 (C.I. 77266), C.I. Pigment Blue 15 (C.I. 74160), C.I. Pigment Blue 15:1 (C.I. 74160), C.I. Pigment Blue 15:3 (C.I. 74160),

C.I. Pigment Blue 15:6 (C.I. 74160), C.I. Pigment Blue 80 (C.I. 77007),

C.I. Pigment Red 4 (C.I. 12085), C.I. Pigment Red 5 (C.I. 12490), C.I. Pigment Red 112 (C.I. 12370), C.I. Pigment Red 122 (C.I. 73915),

C.I. Pigment Red 181 (C.I. 73360), C.I. Pigment Red 254 (C.I. 56110),

C.I. Vat Red 1 , C.I. Pigment Green 7 (C.I. 74260), C.I. Pigment Green 36

(C.I. 74265), C.I. Pigment Violet 23 (C.I. 51319), C.I. Pigment Yellow 1

(C.I. 11680), C.I. Pigment Yellow 3 (C.I. 11710) and C.I. Pigment Yellow 122 (C.I. 21090).

Preferred polyols (c) are glycerine, glycols, polyglycols, pentaerythrite, sugar alcohols, especially mannitol, sorbitol, xylitol, maltitol, lactitol, lactose and monosaccharides, especially lactose. Microcrystalline cellulose (E460i) and powdered cellulose (E460ii) are

commercially available as inactive fillers, thickeners or stabilizers in processed foods and pharmaceuticals. While microcrystalline cellulose is used in the core as component b), powdered cellulose can be used in the shell as component d). Instead of or in addition to powdered cellulose, cellulose derivatives can be used, such as ethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl cellulose.

Preferred polycarboxylic acids used as component d) are polyacrylic acid, polymethacrylic acid, acrylate-methacrylate copolymers, such as methacrylic acid- ethylacrylate copolymers, poly(ethylacrylate-methylmethacrylate- hydroxyethylmethacrylate), styrene-(meth)acrylates, and maleic acid copolymers, such as acrylic acid-maleic acid copolymers.

Preferred vinyl polymers used as component d) are polyvinyl acetates and vinyl (meth)acrylic copolymers.

In a preferred embodiment of the invention the polymer used as component d) and contained in the one or more microencapsulated colorant granules is selected from the group consisting of polyacrylic acid, polymethacrylic acid, copolymers of polyacrylic and polymethacrylic acid, styrene-(meth)acrylates, maleic acid copolymers, polyvinylacetates, vinyl acrylic copolymers, vinyl methacrylic copolymers, cellulose, ethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, and hydroxyethyl cellulose. The molecular weight of polymers (d) is preferably between 500 and

500 000 g/mol, more preferably between 1 000 and 300 000 g/mol.

In a preferred embodiment of the invention the inventive compositions comprise microencapsulated colorant granules as characterized before, wherein the particle size distribution of the granules is between 100 and 1500 μm, more preferred between 200 and 1000 μm, most preferred between 300 and 600 μm. The microencapsulated colorant granules contained in the inventive compositions can preferably be prepared by a process with the following steps:

• admixing and homogenizing water, microcrystalline cellulose, the polyol and the colorant (I) to form a homogeneous mass;

• extruding the homogeneous mass followed by granulation and optional drying, to form microbeads as the core of the microencapsulated colorant granules; • coating the microbeads with the components d) and optionally e) and

optionally f).

For example, colorant (I) in powderous form is homogenized with microcrystalline cellulose, the polyol and water in a planetary mixer until a homogeneous gel-like mass is obtained. This mass is then subjected to a screw extruder to get small noodles which are further charged into a spherodizer to get microbeads. These microbeads are treated as core. For coating, the core microbeads are subjected to a fluidized bed processing unit, wherein a solution or suspension of components (d) and optionally (e) and optionally (f) in water is sprayed onto the microbeads.

In one embodiment, a suspension of white pigment (e) and polymer (d) in water is sprayed onto the microbeads.

In another embodiment, in a first spraying operation, a suspension of white pigment (e) and polymer (d) in water is sprayed onto the microbeads, followed by a second spraying operation, wherein a suspension of colorant (II) and polymer (d) in water is sprayed onto the microbeads to get a colored coating.

The preferred processing temperature during spraying is between 20 and 80 ⁰C, especially between 30 and 60 ⁰C. The coated microbeads obtained are dried to obtain microencapsulated colorant granules.

The microencapsulated colorant granules can be incorporated in colorless or colored liquid or gel-like cleansing compositions suitable for cleaning hard surfaces, washing clothes and dishes, and softening fabrics thereby producing inventive compositions. These inventive liquid or gel-like compositions can be employed for household, institutional and/or industrial applications. The

microencapsulated colorant granules can furthermore be incorporated in colorless or colored liquid or gel-like personal cleansing compositions or personal care products thereby also producing inventive compositions. During the application, particularly during the washing process, the shell decomposes and the fine colorant particles are released into the inventive compositions and/or disperse into the foam resulting from the inventive compositions inducing a coloring or color change of the inventive composition and/or the foam.

Preferred inventive compositions are compositions suitable for cleaning hard surfaces such as general or all-purpose cleaners, window cleaners, sanitary cleaners, disinfectants or vehicle cleaners, compositions suitable for washing clothes such as detergents or high density liquids (HDL), dish washing

compositions such as hand dishwash compositions, compositions suitable for softening fabrics or any other suitable cleaning products.

Further preferred inventive compositions are personal cleansing compositions such as personal cleansing compositions for skin, hair and teeth, e.g. shower baths, body washes, shampoos, hand soaps, facial soaps or facial cleansing compositions, baby washes or toothpastes or personal care products such as body lotions or sunscreens. Further preferred inventive compositions are pet detergents or washes. In general, the microencapsulated colorant granules are present in the inventive compositions in an amount of from 0.1 to 10 % by weight, preferably in an amount of from 0.2 to 7 % by weight, more preferably in an amount of from 0.5 to 5 % by weight, relative to the total weight of the inventive composition.

The compositions according to the invention, in particular the inventive cleansing compositions, personal cleansing compositions and personal care compositions may contain components which are common in the respective art, such as nonionic, anionic, cationic, and amphoteric surfactants, dispersing agents such as suspending agents, emollients, preservatives, fragrances, pH modifiers, antimicrobial agents, colorants, water, and non-aqueous solvents.

In a preferred embodiment of the invention the inventive compositions comprise at least 40 % by weight of water, relative to the total weight of the inventive composition. Preferably, these inventive compositions comprise not more than

99 % by weight of water, relative to the total weight of the inventive composition. In a more preferred embodiment of the invention the inventive compositions comprise of from 50 to 98 % by weight and more preferably of from 55 to 97 % by weight of water, relative to the total weight of the inventive composition.

The amount of surfactants contained in the inventive compositions can vary greatly depending upon various factors. In some embodiments of the invention, the inventive compositions may contain surfactants in an amount of from 1 to 60 % by weight and preferably of from 5 to 40 % by weight, relative to the total weight of the inventive composition.

The inventive compositions may also contain various emollients. In fact, some of the above described surfactants may be considered emollients. Particular emollients that may be used include ethoxylated and propoxylated alcohols, such as cetyl alcohols and ethoxylated lanolin. In some instances, the inventive compositions may also include one or more non-aqueous solvents. Although not required, non-aqueous solvents can sometimes aid in dissolving certain components, e.g. preservatives or antimicrobial agents. Examples of some suitable non-aqueous solvents include, but are not limited to:

glycerine; glycols, such as propylene glycol, butylene glycol, triethylene glycol, hexylene glycol, polyethylene glycols, ethoxydiglycol, and dipropyleneglycol;

alcohols, such as ethanol, n-propanol, and isopropanol; triglycerides; ethyl acetate; acetone; triacetin; and combinations thereof. Preferred solvent

combinations include a glycol, particularly hexylene and/or propylene glycol, and one or more lower alcohols, particularly isopropanol, n-propanol, and/or ethanol.

The inventive compositions may also contain various preservatives to increase the shelf life of the composition. Preferably, the preservative is present in an amount of from 0.001 to 5 % by weight, more preferably of from 0.001 to about 1 % by weight, and even more preferably, of from 0.1 to 0.15 % by weight, relative to the total weight of the inventive composition.

If necessary, various pH modifiers may be utilized in the inventive compositions to achieve the desired pH level. For instance, some examples of basic pH modifiers that may be used in the inventive compositions include, but are not limited to ammonia, mono-, di-, and tri-alkylamines, mono-, di-, and tri-alkanolamines, alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal silicates, mineral acids, carboxylic acids, and polymeric acids.

In a preferred embodiment of the invention the inventive compositions possess a pH value of from 1 to 12, preferably of from 2 to 10 and more preferably of from 2.5 to 8.5. In a further preferred embodiment of the invention the inventive compositions comprise one or more dispersing agents. As dispersing agent any known dispersing agent may be used. For example, the dispersing agent may be a clay, a starch including starch derivatives, a modified cellulose, a natural gum, a wax, a fatty acid, a fatty alcohol, a multifunctional alcohol, a colloidal or a fumed particle, a fatty acid ester, a polyoxyethylene glycol ether, or a mixture thereof.

However, in one preferred embodiment of the invention the inventive compositions comprise one or more polymers containing one or more structure units derived from acryloyldimethyltaurine and/or salts thereof (acryloyldimethyltaurates) as dispersing agent/s.

Preferred polymers containing one or more structure units derived from

acryloyldimethyltaurine and/or salts thereof are polymers containing

a) one or more structure units derived from acryloyldimethyl taurine and/or salts thereof, preferably derived from 2-acrylamido-2-methyl-propan- sulfonic acid and/or salts thereof,

b) one or more structure units derived from b1) or b2)

b1) open-chain N-vinyl amides and/or cyclic N-vinyl amides having a ring size of from 3 to 9, preferably N-vinyl pyrrolidon,

b2) 2-Carboxyethylacrylic acid and/or salts thereof, and, if desired,

additionally one or more unsaturated monocarboxylic acids and/or salts thereof, preferably acrylic acid, and

c) optionally one or more cross-linkers, i.e. monomers with two or more

olefinic double bonds and preferably one or more cross-linkers.

Such polymers are commercially available from Clariant (e.g. Aristoflex^® AVC and Aristoflex^® TAC)

In a further preferred embodiment of the invention the inventive compositions comprise one or more polymers containing structure units derived from

terephthalic acid and/or salts or esters thereof as dispersing agent/s. Preferred polymers containing structure units derived from terephthalic acid and/or salts or esters thereof are polymers containing

a) one or more structure units derived from terephthalic acid and/or salts or esters thereof,

b) one or more structure units derived from compounds comprising two or more hydroxyl (HO-) groups, preferably derived from diols b1) and/or b2) b1) polyethylene glycols, preferably polyethylene glycols with a weight average molecular weight of from 200 to 8000 g/mol,

b2) ethylene glycol and/or propylene glycol,

c) optionally one or more structure units derived from sulfonated aromatic

dicarboxylic acids and/or salts or esters thereof, preferably derived from sulfoisophthalic acid and/or salts or esters thereof, and

d) optionally one or more structure units derived from compounds comprising one hydroxyl (HO-) group and selected from the group consisting of sulfonated mono- or polyethylene glycols and alkyl mono- or polyethylene glycols.

Such polymers are commercially available from Clariant (e.g. Texcare^® SRN 100, Texcare^® SRN 170, Texcare^® SRN 240, Texcare^® SRN 300, Texcare^® SRN 325 or Texcare^® SRA 300).

The dispersing agent may be present in the inventive compositions in an amount sufficient to prevent the microencapsulated colorant granules from settling. The dispersing agent may be present in the inventive compositions in an amount of from 0.1 to 15 % by weight, preferably of from 0.1 to 10 % by weight and more preferably of from 0.5 to 3 % by weight, relative to the total weight of the inventive composition.

The inventive compositions possess the advantage that they may change color upon application. Therefore, the inventive compositions preferably are color changing compositions. In a further preferred embodiment of the invention the inventive compositions are personal care or cleansing compositions.

In the following examples "parts" refer to parts by weight and percentages refer to weight percent (wt.-%) if not expressly stated otherwise.

EXAMPLES

A) Preparation of microencapsulated colorant granules

Example A1): Microencapsulated colorant granules (colorant (I))

33 parts of powdered C.I. Pigment Red 181 were homogenized with 33 parts of microcrystalline cellulose and 33 parts of lactose and 30 parts of water in a planetary mixer until a homogeneous gel-like mass was obtained. This mass was subjected to a screw extruder to get small noodles which were further charged into a spherodizer to get microbeads of about 200 to 300 micrometer in diameter. The microbeads were subjected to a fluidized bed processing unit. A dispersion of 5 parts of methacrylic acid-ethylacrylate copolymer (1 :1 ; mw approximately 250 000 g/mol) in 5 parts of water was sprayed with the microbeads at a temperature of about 50 ⁰C to get a colorless polyacrylate coating onto the beads. The final beads were removed from the fluidized bed unit and dried. Example A2): Microencapsulated colorant granules (colorant (I) + TiOa)

33 parts of powdered C.I. Pigment Blue 15:1 were homogenized with 33 parts of microcrystalline cellulose and 33 parts of xylitol and 30 parts of water in a planetary mixer until a homogeneous gel-like mass was obtained. This mass was subjected to a screw extruder to get small noodles which were further charged into a spherodizer to get microbeads of about 200 to 250 micrometer in diameter. These microbeads were treated as core. The microbeads were subjected to a fluidized bed processing unit. A dispersion of 15 parts of titanium dioxide in 5 parts of water and 5 parts of sodium polyacrylate (Mowilith^® DM 6400) was sprayed with the microbeads at a temperature of about 50 °C to get a Tiθ₂-polyacrylate coating onto the beads. The final beads were removed from the fluidized bed unit and dried to give microencapsulated colorant granules of about 400 to 450 micrometer in diameter.

Example A3): Microencapsulated colorant granules (colorant (I) + TiO₂ + colorant (II))

33 parts of powdered C.I. Pigment Green 7 were homogenized with 33 parts of microcrystalline cellulose and 33 parts of sorbitol and 30 parts of water in a planetary mixer until a homogeneous gel-like mass was obtained. This mass was subjected to a screw extruder to get small noodles which were further charged into a spherodizer to get microbeads of about 200 to 250 micrometer in diameter. These microbeads were treated as core.

The microbeads were subjected to a fluidized bed processing unit. A dispersion of 15 parts of titanium dioxide in 5 parts of water and 5 parts of sodium polyacrylate (Mowilith^® DM 6400) was sprayed with the microbeads at a temperature of about 50 °C to get a TiO₂-polyacrylate coating onto the beads.

Further, a suspension of 15 parts of C.I. Pigment Red 5, 5 parts of water and 5 parts of sodium polyacrylate (Mowilith^® DM 6400) was sprayed with the coated microbeads at a temperature of about 50 ⁰C to get a red-colored coating on these beads.

The final beads were removed from the fluidized bed unit and dried to give microencapsulated colorant granules of about 400 to 450 micrometer in diameter. B) Application Examples

Example B1): All-Purpose Cleaner

Composition:

A Genapol^® C070 1.5 wt-%

Cio/Ci₈-Fatty alcohol with 7 moles of

ethylene oxide (100 % a.m.)

B Praepagen^® HY 1.4 wt-%

Ci₂/C-|₄-Alkyl dimethyl hydroxyethyl ammonium

chloride (40 % a.m., aqueous)

C Sodium Tripolyphosphate 1.0 wt-%

D Water ad 100 wt-%

E Perfume qs

F Example A2 1.0 wt-% G Preservant qs

H Carbopol^® (BF Goodrich) 0.5 wt-%

Polyacrylate

Preparation:

I. Mix C and D at room temperature

II. Add A to I and mix

III. Add B to Il and mix

IV. Add E, F, G and H to III and mix

EXAMPLE B2): All-Purpose Cleaner

Composition:

A Genamin^® T120 3.2 wt-%

Ethoxylated alkyl amine (100 % a.m.)

B Praepagen^® HY 2.0 wt-%

C₁₂/Ci₄-Alkyl dimethyl hydroxyethyl ammonium

chloride (40 % a.m., aqueous) C Water ad 100 wt-%

D Perfume qs

E Example A3 1.5 wt-%

F Preservant qs

G Carbopol^® (BF Goodrich) 0.5 wt-%

Polyacrylate

Preparation:

I. Mix A and C at room temperature

II. Add B to I and mix

III. Add D, E, F and G to Il and mix

EXAMPLE B3): All-Purpose Cleaner

Composition:

A Praepagen^® HY 30.0 wt-%

C₁₂/Ci₄-Alkyl dimethyl hydroxyethyl ammonium

chloride (40 % a.m., aqueous)

B oleyl alcohol with 10 moles of ethylene oxide (100 %) 25.0 wt-%

C water ad 100 wt-%

D Example A2 1.0 wt-%

E Carbopol^® (BF Goodrich) 1.0 wt-%

Polyacrylate Preparation:

I. Mix A and C at room temperature

II. Heat B at 34 to 40 ⁰C

III. add Il to I

IV. heat III and homogenize at 80 to 85 ⁰C with stirring

V. cool to room temperature

Vl. add D and E to V and mix Example B4): Laundry detergent

Composition:

A Hostapur SAS (60 wt-%, aqueous, Clariant) 9.00 wt-%

Secondary C1₂-₁₆ alkane sulfonate, Na-salt

GENAPOL^® LRO liquid (30 wt-%, aqueous, Clariant) 10.00 wt-%

Sodium laureth sulphate

Genapol^® DU 080 (100 wt-%, Clariant) 2.00 wt-%

C₁₁- Oxoalkoholpolyglykolether mit 8 EO

Sodiumtripolyphosphate 14.00 wt-%

B Water ad 100 wt-%

C Praepagen^® HY 2.00 wt-%

Ci₂/C-|₄-Alkyl dimethyl hydroxyethyl ammonium

chloride (40 % a.m., aqueous)

Texcare^® SRN 170 (Clariant) 2.00 wt-%

Non-ionic polyester of propylene terephthalate

Cellulase 0.25 wt-%

D KCI 2.00 wt-%

E Perfume qs

Example A2 1.00 wt-%

Preservant qs

Preparation:

I. Mix A and B at room temperature

II. Add C to I and mix

III. Add D to Il and mix

IV. Add E to III an mix Example B5): Shower Bath

Composition

A GENAPOL^® LRO liquid (30 wt-%, aqueous, Clariant) 40.0 wt-%

Sodium laureth sulfate

B Fragrance 0.3 wt-%

C Water ad 100 wt-%

Example A1 1.5 wt-%

Preservative q.s.

GENAGEN^® LDA (30 wt-%, aqueous, Clariant) 6.0 wt-%

Disodium lauroamphodiacetate

Citric acid q.s.

D Aristoflex^® TAC (Clariant) 1.0 wt-%

Ammonium Acryloyl Dimethyltaurate/Carboxyethyl

Acrylate Crosspolymer

Preparation:

I. Stir B into A.

II. Add components from C successively to I.

III. Adjust pH to 5.5.

IV. Adjust the viscosity by stirring D into II.

Example B6): Antidandruff Shampoo

A OCTOPI ROX^® (Clariant) 0.5 wt-% Piroctone olamine

B Water 10.0 wt-%

C GENAPOL^® LRO liquid (30 wt-%, aqueous, Clariant) 30.0 wt-% Sodium laureth sulfate

D Belsil^® DMC 6032 (Wacker Chemie) 1.5 wt-% Dimethicone copolyol acetate

Fragrance 0.3 wt-%

E ALLANTOIN^® D (Clariant) 0.3 wt-% F Water ad 100 wt-%

G Example A3 0.5 wt-%

Panthenol (Hoffmann La Roche) 1.0 wt-%

GENAGEN^® CAB (30 wt-%, aqueous, Clariant) 8.0 wt-%

Cocamidopropylbetaine

H Aristoflex^® TAC (Clariant) 1.0 wt-%

Ammonium Acryloyl Dimethyltaurate/Carboxyethyl

Acrylate Crosspolymer Preparation:

I. Mix A with B.

II. Stir C into I until a clear solution is obtained.

III. Add components from D successively to II.

IV. Stir E into F with heating and then stir mixture into

V. Add components from G successively to IV.

VI. Adjust pH if appropriate.

VII. Adjust the viscosity by stirring H into V or Vl.

Example B7): OΛ/V Skin Milk with Keratolytic Effect, Surfactant-Free Composition

A Texcare^® SRN 170 (Clariant) 1.0 wt-% Non-ionic polyester of propylene terephthalate

Mineral oil 4.0 wt-% Almond oil 4.0 wt-%

Cetiol^® SN (Henkel) 8.0 wt-% Cetearyl isononanoate

B Aristoflex^® AVC (Clariant) 0.3 wt-%

Ammonium acryloyldimethyltaurate/VP copolymer

C Water ad 100 wt-%

Example A2 1.0 wt-%

Citric acid 0.3 wt-% Malic acid 0.4 wt-%

Glycolic acid 0.7 wt-%

Lactic acid 0.7 wt-%

D Fragrances 0.3 wt-%

Preparation:

I. Mix A and B.

II. Mix the components C.

Ill Add Il to I.

IV. Stir D into III.

V. Homogenize emulsion, pH 3.5.

Example B8) Sunscreen

Composition

A Crodamol^® AB 4.0 wt-%

C₁₂-₁₅ Alkyl Benzoate

Water ad 100 wt-%

Neo Heliopan^® AV 7.5 wt-% Ethylhexyl Methoxycinnamate

SilCare^® Silicone 41 M80 (Clariant) 5.0 wt-%

C2₄-28 Alkyl Dimethicone

B Neo Heliopan^® BB 3.0 wt-%

Benzophenone-3

C Aristoflex^® AVC (Clariant) 1.0 wt-%

Ammonium acryloyldimethyltaurate/VP Copolymer

D Example A1 1.0 wt-%

Preparation:

I. Heat A to about 80 ⁰C.

II. Dissolve B in I

III cool Il to 25 ⁰C without stirring IV. add C to III under gentle stirring

V. add D to IV under gentle stirring

Claims

Patent claims

1. Liquid or gel-like composition comprising one or more microencapsulated colorant granules consisting of a core (A) and a shell (B), whereby the core (A) has a diameter of between 1 and 1000 micrometer and comprises

a) a colorant (I),

b) microcrystalline cellulose,

c) a polyol;

and whereby the shell (B) has a thickness of between 1 to 500 micrometer and comprises

2. Liquid or gel-like composition as claimed in claim 1, characterized in that the one or more microencapsulated colorant granules further contain a white pigment (e) in the shell (B).

3. Liquid or gel-like composition as claimed in claim 1 or 2, characterized in that the one or more microencapsulated colorant granules further contain (f) a colorant (II) in the shell (B).

4. Liquid or gel-like composition as claimed in one or more of claims 1 to 3, characterized in that the one or more microencapsulated colorant granules contain a) 5 to 60 % by weight of colorant (I),

b) 10 to 40 % by weight of microcrystalline cellulose,

c) 10 to 40 % by weight of polyol,

d) 0.1 to 20 % by weight of the polymer,

relating to the total weight of the granules.

5. Liquid or gel-like composition as claimed in one or more of claims 1 to 4, characterized in that the one or more microencapsulated colorant granules contain a) 5 to 60 % by weight of colorant (I),

b) 10 to 40 % by weight of microcrystalline cellulose,

c) 10 to 40 % by weight of polyol,

d) 0.1 to 20 % by weight of the polymer,

e) 0.1 to 30 % by weight of white pigment; and 1 to 30 % by weight of water, relating to the total weight of the granules.

6. Liquid or gel-like composition as claimed in one or more of claims 1 to 5, characterized in that the one or more microencapsulated colorant granules contain a) 5 to 60 % by weight of colorant (I),

b) 10 to 40 % by weight of microcrystalline cellulose,

c) 10 to 40 % by weight of polyol,

d) 0.1 to 20 % by weight of the polymer,

e) 0.1 to 30 % by weight of white pigment;

f) 0.1 to 20 % by weight of colorant (II); and 1 to 30 % by weight of water, relating to the total weight of the granules.

7. Liquid or gel-like composition as claimed in one or more of claims 1 to 6, characterized in that colorant (I) and colorant (II) contained in the one or more microencapsulated colorant granules are selected from colorants allowed for cosmetic use and from colorants allowed for detergents.

8. Liquid or gel-like composition as claimed in one or more of claims 1 to 7, characterized in that colorant (I) and colorant (II) contained in the one or more microencapsulated colorant granules are selected from the group consisting of C.I. Pigment Black 7 (C.I. 77266), C.I. Pigment Blue 15 (C.I. 74160), C.I. Pigment Blue 15:1 (C.I. 74160), C.I. Pigment Blue 15:3 (C.I. 74160),

C.I. Pigment Blue 15:6 (C.I. 74160), C.I. Pigment Blue 80 (C.I.77007),

C.I. Pigment Red 181 (C.I. 73360), C.I. Pigment Red 254 (C.I. 56110), C.I. Vat Red 1 , C.I. Pigment Green 7 (C.I. 74260), C.I. Pigment Green 36

(C.I. 74265), C.I. Pigment Violet 23 (C.I. 51319), C.I. Pigment Yellow 1

9. Liquid or gel-like composition as claimed in one or more of claims 1 to 8, characterized in that the polyol (c) contained in the one or more

microencapsulated colorant granules is selected from the group consisting of glycerine, glycols, polyglycols, pentaerythrite, sugar alcohols, especially mannitol, sorbitol, xylitol, maltitol, lactitol, lactose and monosaccharides, especially lactose.

10. Liquid or gel-like composition as claimed in one or more of claims 1 to 9, characterized in that the polymer contained in the one or more microencapsulated colorant granules is selected from the group consisting of polyacrylic acid, polymethacrylic acid, copolymers of polyacrylic and polymethacrylic acid, styrene- (meth)acrylates, maleic acid copolymers, polyvinylacetates, vinyl acrylic

copolymers, vinyl methacrylic copolymers, cellulose, ethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, and hydroxyethyl cellulose.

11. Liquid or gel-like composition as claimed in one or more of claims 1 to 10, characterized in that it comprises the one or more microencapsulated colorant granules in an amount of from 0.1 to 10% by weight, .relative to the total weight of the composition.

12. Liquid or gel-like composition as claimed in one or more of claims 1 to 11 , characterized in that it comprises at least 40 % by weight of water, relative to the total weight of the composition.

13. Liquid or gel-like composition as claimed in one or more of claims 1 to 12, characterized in that it comprises one or more dispersing agents.

14. Liquid or gel-like composition as claimed in one or more of claims 1 to 13, characterized in that it comprises one or more polymers containing one or more structure units derived from acryloyldimethyltaurine and/or salts thereof.

15. Liquid or gel-like composition as claimed in one or more of claims 1 to 14, characterized in that it comprises one or more polymers containing structure units derived from terephthalic acid and/or salts or esters thereof.

16. Liquid or gel-like composition as claimed in one or more of claims 1 to 15, characterized in that it is a color changing composition.

17. Liquid or gel-like composition as claimed in one or more of claims 1 to 16, characterized in that it is a personal care or cleansing composition.