WO2007090759A1

WO2007090759A1 - Copolymers and their use as rheology modifier

Info

Publication number: WO2007090759A1
Application number: PCT/EP2007/050864
Authority: WO
Inventors: Rachel Clare Weston; Howard Roger Dungworth; Andrew Taylor; Eleanor Bernice Ridley
Original assignee: Ciba Holding Inc.
Priority date: 2006-02-07
Filing date: 2007-01-30
Publication date: 2007-08-16

Abstract

This invention relates to multi-associative polymers, their production and their use as rheology modifiers for water-and/or oil-based compositions, especially for water-and/or oil-based personal care products.

Description

Copolymers and their use as rheology modifier

This invention relates to multi-associative polymers, their production and their use as rheology modifiers for water-and/or oil-based compositions, especially for water-and/or oil-based personal care products. Rheology modifiers are used generally to adjust or modify the rheological properties of formulations. Such properties include, without limitation, viscosity, flow rate, stability to viscosity change over time, and the ability to suspend particles in such formulations.

Thickeners are used extensively in personal care compositions such as cosmetic and pharmaceutical formulations, to affect the aesthetics, product application and suspension and de- livery of the active raw materials.

It is standard practice to include viscosifying (co-)polymers in personal care product composition in order to achieve optimum rheology characteristics. Various polymer types have been proposed for the purpose of increasing the viscosity of personal care compositions.

The aim of the present invention was to find a polymer, which has advantages over the prior art in important characteristics, such as good rheology properties but also good properties relating to the transparency of the formulations.

Associative thickeners are well known. They comprise hydrophilic, water-soluble polymers with hydrophobic terminal groups or side chains. The hydrophobic terminal groups may be aliphatic or aromatic hydrocarbons and they are water insoluble. They can be joined to the hydrophilic polymer backbone by means of a hydrophilic spacer so that they remain flexible. Their structure is similar to that of surfactants. Interaction between the hydrophobic groups or side chains is what is considered to provide for very high viscosity. There are various types of associative thickeners but those that are of particular interest in connection with the present invention are the hydrophobic alkali-soluble emulsions in which the hydrophilic polymer backbone comprises an alkali soluble polyacrylate derived from monomers such as alkyl acrylates for example ethyl acrylate and methyl acrylate and acrylic acid and/or methacrylic acid. The hydrophobic side chains are attached to the polymer backbone by, for example, a polyoxyethylene oxide spacer. The thickening effect can be adjusted by altering the ratios of the monomers. All this is well known. Examples of associative thickeners used as paint thickeners, printing pastes and the like are disclosed in European Patent Specification

0 216 479. Other associative thickeners are described in detail in European Patent Specifications 0 013 836 and 0 011 806. These can be used in the present invention subject to their being modified in accordance with the definition of the invention as set out above. The novel and improved copolymer dispersions of the present invention are those obtained by aqueous emulsion copolymerisation of monomers defined below.

The present invention relates to a copolymer comprising

(1 ) at least two different monomers of formula (I),

R¹ H₂C=C-D- A_mB_nAp- R (Q

wherein

R' is hydrogen, C_rC₄alkyl Or -CH₂-COOH,

A is propyleneoxy or butyleneoxy,

B is ethyleneoxy, O

I l D is ^{~ C~}°^~ Or -NH- Or -CH₂- O -, n is zero or an integer from 1 to 100, m and p are each zero or an integer less than n and R is a hydrophobic group of 8 to 30 carbon atoms, and

(2) at least one acid functional monomer, and (3) at least one hydrophobic monomers, and.

(4) optionally at least one polyethylenically unsaturated monomer. Preferred monomers of group (1 ) are monomers of formula (I), wherein

R' is hydrogen or methyl, A is propyleneoxy or butyleneoxy,

B is ethyleneoxy, n is an integer 5 to 80, m and p are each zero or an integer less than n and R is a hydrophobic group of 12 - 24 carbon atoms. More preferred monomers of group (1 ) are ceteareth-10 methacrylate, ceteareth-20 methacrylate, ceteareth-25 methacrylate, palmeth-10 methacrylate, palmeth-20 methacry- late, palmeth-25 methacrylate, beheneth-10 methacrylate, beheneth 20 methacrylate, be- heneth 25 methacrylate, ceteth-10 methacrylate, ceteth-20 methacrylate, ceteth-25 methacrylate, laureth-25 methacrylate, steareth-10 methacrylate, steareth-20 methacrylate, steareth-25 methacrylate, steareth-50 acrylate, steareth-10 allyl ether and steareth-20 allyl ether.

Preferred monomers of group (2) are methacrylic acid, acrylic acid or a mixture there.

Preferred monomers of group (3) are hydrophobic monomers, which are vinyl, generally acrylic, monomers and may be a blend of monomers. The monomers are generally water insoluble but a proportion of these monomers may be a water soluble monomer such as acrylamide. By water insoluble monomer in the context of the present specification we mean monomer that is soluble in water to a degree of up to 5% at room temperature. Suitable monomers are styrene and alkyl and/or halo-substituted styrenes, (meth)acrylonitrile, vinyl alkanoates (especially the acetate), vinyl and vinylidene halides (especially the chloride), N- alkyl (meth)acrylamides, hydroxy alkyl and alkoxy alkyl (meth)acrylates and alkyl (meth)- acrylates. Preferred monomers are styrene, 2-hydroxy ethyl acrylate, acrylonitrile, vinyl chloride and vinyl acetate and the alkyl (meth)acrylates. Preferably at least 50% by weight of hydrophobic monomer, and most preferably 100%, is alkyl (meth)acrylate. In all these monomers any alkyl groups may contain 1 to 8 carbon atoms but particularly preferred monomers are CrC₄ alkyl (meth)acrylates such as methyl methacrylate, butyl acrylate, ethyl acrylate or methyl acrylate.

Preferred monomers of group (4) are polyethylenically unsaturated monomer such as 1 ,4- butanediol diacrylate, allyl methacrylate, pentaerythritol triacrylate and diallyl phthalate. These monomers are used in a small amount.

A preferred embodiment of the present invention relates to a copolymer comprising (1 ) at least two different monomers of formula (I), wherein

R' is hydrogen or methyl,

A is propyleneoxy or butyleneoxy,

B is ethyleneoxy, n is an integer 5 to 80, m and p are each zero or an integer less than n and

R is a hydrophobic group of 12 - 24 carbon atoms, and - A -

(2) methacrylic acid, and/or acrylic acid, and

(3) at least one hydrophobic monomers, which is vinyl or acrylic, and

(4) optionally, at least one polyethylenically unsaturated monomer such as 1 ,4-butanediol diacrylate, allyl methacrylate, pentaerythritol triacrylate and/or diallyl phthalate. A more preferred embodiment of the present invention relates to a copolymer comprising

(1) at least two different monomers selected from the group consisting of ceteareth-10 methacrylate, ceteareth-20 methacrylate, ceteareth-25 methacrylate, palmeth-10 methacrylate, palmeth-20 methacrylate, palmeth-25 methacrylate, be- heneth-10 methacrylate, beheneth 20 methacrylate, beheneth 25 methacrylate, ceteth- 10 methacrylate, ceteth-20 methacrylate, ceteth-25 methacrylate, laureth-25 methacrylate, steareth-10 methacrylate, steareth-20 methacrylate, steareth-25 methacrylate, steareth-50 acrylate, steareth-10 allyl ether and steareth-20 allyl ether, and

(2) methacrylic acid, and/or acrylic acid, and (3) at least one hydrophobic monomers, which is selected from the group consisting of styrene and alkyl and/or halo-substituted styrenes, (meth)acrylonitrile, vinyl alkanoates (especially the acetate), vinyl and vinylidene halides (especially the chloride), N-alkyl (meth)acrylamides, hydroxy alkyl and alkoxy alkyl (meth)acrylates and alkyl (meth)acrylates, and (4) optionally, at least one polyethylenically unsaturated monomer such as 1 ,4-butanediol diacrylate, allyl methacrylate, pentaerythritol triacrylate and/or diallyl phthalate.

The emulsion copolymer dispersions obtained have solids contents of from 20 - 50% by weight and the copolymer dispersion has a weight average molecular weight of about 50,000 to several million. A chain transfer agent may be used to obtain molecular weights in the lower part of the range. On the other hand, use of 0.05% to 1 % of monomer of group (4), based on total monomers, serves to provide molecular weights at the higher part of the range.

The polymer consists of the following proportions of the first three components (groups):

0.5 - 50 weight-percent (wt-%) based on the total weight of the polymer, of at least two dif- ferent monomers of group (1 ), preferably 5 - 25 wt-% and more preferably 10 - 20 wt-%;

20 - 70 wt-% of at least one monomer of group (2), preferably 20 - 50 wt-% and more preferably 30 - 45 wt-%; 10 - 70 wt-% of at least one monomer of group (3), preferably 20 - 60 wt-% and more preferably 40 - 60 wt-%;

The weight percentages (wt-%) are based on the total weight of the copolymer. The sum of the wt-% of all the components is always 100. Therefore an especially preferred embodiment of the present invention related to a copolymer comprising

(1 ) 0.5 - 50 wt-%, preferably 5 - 25 wt-% more preferably 10 - 20 wt-%, based on the total weight of the copolymer, of at least two different monomers of formula (I), wherein R' is hydrogen, C_rC₄alkyl or -CH₂-COOH,

A is propyleneoxy or butyleneoxy,

B is ethyleneoxy, O

I l

D is ^{~ C~}°^~ Or -NH- Or -CH₂- O -, n is zero or an integer from 1 to 100, m and p are each zero or an integer less than n and

R is a hydrophobic group of 8 to 30 carbon atoms, and

(2) 20 - 70 wt-%, preferably 20 - 50 wt-%, more preferably 30 - 45 wt-%, based on the total weight of the copolymer, of at least one acid functional monomer, and

(3) 10 - 70 wt-%, preferably 20 - 60 wt-%, more preferably 40 - 60 wt-% -%, based on the total weight of the copolymer, of at least one hydrophobic monomers, and.

(4) optionally at least one polyethylenically unsaturated monomer.

The component (4) is preferably present in the copolymer in an amount of 50 - 2000 ppm, preferably 50 - 1500 ppm, based on the total weight of the copolymer.

A preferred embodiment of the present invention relates to a copolymer comprising (1 ) 0.5 - 50 wt-%, preferably 5 - 25 wt-% more preferably 10 - 20 wt-%, based on the total weight of the copolymer, of at least two different monomers of formula (I), wherein

R' is hydrogen or methyl, A is propyleneoxy or butyleneoxy, B is ethyleneoxy, n is an integer 5 to 80, m and p are each zero or an integer less than n and R is a hydrophobic group of 12 - 24 carbon atoms, and

(2) 20 - 70 wt-%, preferably 20 - 50 wt-%, more preferably 30 - 45 wt-%, based on the total weight of the copolymer, of methacrylic acid, and/or acrylic acid, and

(3) 10 - 70 wt-%, preferably 20 - 60 wt-%, more preferably 40 - 60 wt-%, based on the total weight of the copolymer, of at least one hydrophobic monomers, which is vinyl or acrylic, and

(4) optionally, 50 - 2000 ppm, preferably 50 - 1500 ppm, based on the total weight of the copolymer, of at least one polyethylenically unsaturated monomer such as 1 ,4-buta- nediol diacrylate, allyl methacrylate, pentaerythritol triacrylate and/or diallyl phthalate.

A more preferred embodiment of the present invention relates to a copolymer comprising (1 ) 0.5 - 50 wt-%, preferably 5 - 25 wt-% more preferably 10 - 20 wt-%, based on the total weight of the copolymer, of at least two different monomers selected from the group consisting of ceteareth-10 methacrylate, ceteareth-20 methacrylate, ceteareth-25 methacrylate, palmeth-10 methacrylate, palmeth-20 methacrylate, palmeth-25 methacrylate, be- heneth-10 methacrylate, beheneth 20 methacrylate, beheneth 25 methacrylate, ceteth-

10 methacrylate, ceteth-20 methacrylate, ceteth-25 methacrylate, laureth-25 methacrylate, steareth-10 methacrylate, steareth-20 methacrylate, steareth-25 methacrylate, steareth-50 acrylate, steareth-10 allyl ether and steareth-20 allyl ether, and (2) 20 - 70 wt-%, preferably 20 - 50 wt-%, more preferably 30 - 45 wt-%, based on the total weight of the copolymer, of methacrylic acid, and/or acrylic acid, and

(3) 10 - 70 wt-%, preferably 20 - 60 wt-%, more preferably 40 - 60 wt-% -%, based on the total weight of the copolymer, of at least one hydrophobic monomers, which is selected from the group consisting of styrene and alkyl and/or halo-substituted styrenes, (meth)acrylonitrile, vinyl alkanoates

(especially the acetate), vinyl and vinylidene halides (especially the chloride), N-alkyl (meth)acrylamides, hydroxy alkyl and alkoxy alkyl (meth)acrylates and alkyl (meth)acrylates, and

Preferred thickeners for use in the invention are alkali soluble or swellable aqueous emulsions of methyl acrylate/ethyl acrylate/acrylic acid/methacrylic acid/ beheneth-25 methacrylate/ ceteareth-25 methacrylate.

Usually, at least 0.01 wt-%, based on the total weight of the formulation, of the inventive co- polymer are used in a formulation. Preferably, 0.05 - 20 wt-%, more preferably, 0.1 - 15 wt-%.

In use the thickener of the invention is included in conventional personal care formulations. The dosage of the thickener of the invention in the formulations is adapted for the required viscosity being obtained. The target viscosity will to some extent be chosen having regard to the formulation and end use.

When used the formulation is preferably neutral to mildly alkaline, of the order of pH 6 to 10, preferably 6.5 to 7.5. Where necessary the pH can be adjusted for example by the addition of an alkali such as sodium hydroxide or ammonium hydroxide.

The new copolymer can be used in water- and/or oil-based compositions, preferably in wa- ter- and/or oil-based personal care products.

Furthermore the new copolymer can also be used in the field of thickening printing pastes and paints. The new polymer can be used in analogy to the formulation as described for example in European Patent Application 161 038.

A further preferred embodiment of the present invention is the use of the copolymers for wa- ter- and/or oil-based compositions, preferably for water- and/or oil-based personal care products.

The thickener-rheology modifier system of this invention is useful in personal care compositions and more particularly in hair care and skin care compositions. These compositions will generally comprise at least one cosmetically-functional agent used in an amount effective to impart desired cosmetic properties to the personal care composition. The term "cosmetically- functional agent", as used herein, means any material, compound or composition applied to the hair or skin for cosmetic application thereof. Exemplary agents include emollients, hu- mectants, lubricants, UV-light inhibitors, preservatives, pigments, dyes, colorants, alpha-hy- droxy acids, aesthetic enhancers such as starch, perfumes and fragrances, film formers (water proofing agent), antiseptics, antifungal, antimicrobial and other medicaments, solvents, surfactants, natural or synthetic polymers, hair conditioning agents and hair fixatives. Such cosmetically-functional agents include mineral oils, glycerol, beeswax, lanolin, acety- lated lanolin, stearic acid, palmitic acid, cetyl alcohol, sodium salts of olefin sulphonates, various proteins, polymeric sugars, conditioning agents such as polyquaternium and hair fixatives such as polyvinyl pyrrolidone) and N-vinyl formamide or polyvinyl formamide.

The cosmetically-functional agent may be present in the personal care composition in an amount of up to 60 wt-% (the wt-% based on the total weight of the personal care composi- tion).

Personal care compositions are for example shampoos, bath and shower additives, hair-care products, wax/fat compositions, liquid soaps, lotions, gels, cremes, deodorants, stick preparations, powders, ointments, other aqueous or alcoholic or aqueous/alcoholic solutions, for example cleaning solutions for the skin, moist cleaning sheets and oils. Personal care compositions include a very wide range of products. Suitable products are, for example, especially the following: skin-care products, for example skin washing and cleansing products in the form of bars of soap or liquid soaps, syndets or washing pastes, bath products, for example liquid (foam baths, milks, shower products) or solid bath products, such as bath pearls and bath salts; skin-care products, such as skin emulsions, multiple emulsions or skin oils; decorative body-care products, for example face make-ups in the form of day or powder creams, face powders (lose and compressed), rouge or cream make-ups, eye- care products, for example eye shadow products, mascara, eyeliners, eye creams or eye-fix creams; lip-care products, for example lipstick, lip gloss, lip liner, nail-care products, such as nail varnish, nail varnish remover, nail hardeners or cuticle removers; feminine hygiene products, such as feminine hygiene washing lotions or sprays; foot-care products, for example foot baths, foot powders, food creams or foot balms, special deodorants and antiperspirants or products for scrubbing off callouses; sunscreens, such as sun milks, lotions, creams, oils, sunblockers or tropicals, pre-sun products or after-sun products; suntanning products, for example self-tanning creams; depigmenting products, for example products for bleaching or lightening skin; insect repellents, for example insect oils, lotions, sprays or sticks; deodorants, for example deodorant sprays, non-aerosol sprays, deodorant gels, sticks or roll-ons; antiperspirants, for example antiperspirant sticks, creams or roll-ons; products for cleansing and treating impure skin, for example syndets (solid or liquid), peeling or scrubbing products or peeling masks; chemical depilatory products, for example depilatory powders, liquid depilatory prod- ucts, creamy or pasty depilatory products, depilatory gels or aerosol foams; shaving products, for example shaving soap, foaming shaving creams, non-foaming shaving creams, shaving foams and gels, preshaving products for dry shaving, aftershaves or aftershave lotions; scents, for example perfumes (Eau de Cologne, Eau de Toilette, Eau de Parfum, Par- fum de Toilette, perfume), perfume oils or perfume creams; products for oral and dental hygiene as well as for dentures, for example toothpastes, tooth gels, tooth powders, mouth-wash concentrates, anti-plaque mouth-washes, denture cleaning products or denture adhesion products; cosmetic formulations for hair treatment, for example hair washes in the form of shampoos, hair conditioners, hair-care products, for example pretreatment products, hair tonics, hair styling creams and gels, pomades, hair rinses, deep conditioning treatments, intensive hair care treatments, hair setting products, for example waving agents for perms (hot wave, mild wave, cold wave), hair straightening products, liquid hair fixatives, hair foams, hair sprays, bleaching agents, for example hydrogen per- oxide solutions, bleaching shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semitemporary or permanent hair dyes, products containing self-oxidizing dyes, or natural hair dyes, such as henna or camomile.

The personal care compositions listed above can be in a very wide range of forms of presentation, for example - in the form of liquid formulations as an oil/water (O/W) emulsion, in the form of a gel, in the form of an oil, cream, milk or lotion, in the form of a powder, lacquer, pellets or make-up, in the form of a stick, in the form of a spray (spray with propellant or pumping spray) or an aerosol, - in the form of a foam, or in the form of a paste.

The oral hygiene composition may comprise an additional antibacterial enhancing agent, for example an anionic polymeric polycarboxylate, a dehydrated polyphosphate salt, a compound which provides a source of fluoride ions, a polishing material, including siliceous mate- rial or sodium bicarbonate, an orally acceptable vehicle, including a water-phase with hu- mectants, thickeners, surface-active agents and a flavoring or sweetening material.

The oil phase (oil-component) can be chosen from the following substance groups without limiting the kind of lipophilic ingredient to those substances:

Fatty alcohols: Guerbet alcohols based on fatty alcohols having from 6 to 18, preferably from 8 to 10 carbon atoms including cetyl alcohol, stearyl alcohol, cetearyl alcohol, oleyl alcohol, octyldodecanol, benzoate of C₁₂-C₁5 alcohols, acetylated lanolin alcohol, etc.

Esters of fatty acids: esters of linear C₆-C₂₄ fatty acids with linear C₃-C₂₄ alcohols, esters of branched C₆-Ci₃carboxylic acids with linear C₆-C₂₄ fatty alcohols, esters of linear C₆-C₂₄ fatty acids with branched alcohols, especially 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C₆-C₂₂ fatty alcohols, especially dioctyl malates, esters of linear and/or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, for example caproic acid, caprylic acid, 2-ethylhexa- noic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, lino- lenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and technical-grade mixtures thereof (obtained, for example, in the pressure removal of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerisation of unsaturated fatty acids) with alcohols, for example, isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linoyl alcohol, linolenyl alcohol, elaeostearyl alcohol, ara- chidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical-grade mixtures thereof (obtained, for example, in the high-pressure hydrogenation of technical-grade methyl esters based on fats and oils or aldehydes from Roelen's oxo-syn- thesis and as monomer fractions in the dimerisation of unsaturated fatty alcohols).

Examples of such ester oils are isopropylmyristate, isopropylpalmitate, isopropylstearate, isopropyl isostearate, isopropyloleate, n-butylstearate, n-hexyllaurate, n-decyloleate, isooc- tylstearate, iso-nonylstearate, isononyl isononanoate, 2-ethylhexylpalmitate, 2-hexyllaurate, 2-hexyldecylstearate, 2-octyldodecylpalmitate, oleyloleate, oleylerucate, erucyloleate, eru- cylerucate, cetearyl octanoate, cetyl palmitate, cetyl stearate, cetyl oleate, cetyl behenate, cetyl acetate, myristyl myristate, myristyl behenate, myristyl oleate, myristyl stearate, myristyl palmitate, myristyl lactate, propylene glycol dicaprylate/caprate, stearyl heptanoate, diisostearyl malate, octyl hydroxystearate, etc..

Further oil components that can be used are dicarboxylic acid esters, such as diethylhexyl 2,6-naphthalate, di-n-butyl adipate, di(2-ethylhexyl)-adipate, di(2-ethylhexyl)-succinate and diisotridecyl acelate, and also diol esters, such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di(2-ethylhexanoate), propylene glycol diisostearate, pro- pylene glycol dipelargonate, butanediol diisostearate and neopentyl glycol dicaprylate. Esters of C6-C₂₄ fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, saturated and/or unsaturated, especially benzoic acid, esters of C₂-Ci₂dicarboxylic acids with linear or branched alcohols having from 1 to 22 carbon atoms or polyols having from 2 to 10 carbon atoms and from 2 to 6 hydroxy groups. Natural or synthetic triglycerides including glyceryl esters and derivatives, such as di- or triglycerides, based on Cβ-Ciβ fatty acids, modified by reaction with other alcohols (caprylic/capric triglyceride, wheat germ glycerides, etc.). Fatty acid esters of polyglycerol (polyglyceryl-n) such as polyglyceryl-4 caprate, polyglyceryl-2 isostearate, etc. or castor oil (Ricinus Communis), hydrogenated vegetable oil, sweet almond oil, wheat germ oil, sesame oil, hydrogenated cottonseed oil, coconut oil, avocado oil, corn oil, hydrogenated castor oil, shea butter, cocoa butter, soybean oil, mink oil, sunflower oil, safflower oil, macadamia nut oil, olive oil, hydrogenated tallow, apricot kernel oil, hazelnut oil, borago oil, etc..

Waxes including esters of long-chain acids and alcohols as well as compounds having wax- like properties, e.g. carnauba wax (Copernicia Cerifera), beeswax (white or yellow), lanolin wax, candellila wax (Euphorbia Cerifera), ozokerite, japan wax, paraffin wax, microcrystalline wax, ceresin, cetearyl esters wax, synthetic beeswax, etc.. Also, hydrophilic waxes such as cetearyl alcohol or partial glycerides.

Pearlescent waxes: ikylene glycol esters, especially ethylene glycol distearate; fatty acid al- kanolamides, especially coco fatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polyvalent, unsubstituted or hydroxy-substituted carboxylic acids with fatty alcohols having from 6 to 22 carbon atoms, especially long-chained esters of tartaric acid; fatty substances, for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially laurone and distearyl ether; fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having from 12 to 22 carbon atoms with fatty alcohols having from 12 to 22 carbon atoms and/or polyols having from 2 to 15 carbon atoms and from 2 to 10 hydroxy groups, and mixtures thereof.

Hydrocarbon oils: mineral oil (light or heavy), petrolatum (yellow or white), microcrystalline wax, paraffinic and isoparaffinic compounds, hydrogenated isoparaffinic molecules as polydecenes, and polybutene, hydrogenated polyisobutene, squalane, isohexadecane, isododecane and others from plant and animal kingdom.

Silicones or siloxanes (organosubstituted polysiloxanes): dimethylpolysiloxanes, methyl- phenylpolysiloxanes, cyclic silicones, and also amino-, fatty acid-, alcohol-, polyether-, ep- oxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds, which at room temperature may be in either liquid or resinous form. Linear polysiloxanes: dimethicone such as Dow Corning^® 200 fluid, Mirasil^® DM (Rhodia), dimethiconol. Cyclic silicone fluids: cyclopen- tasiloxanes volatiles such as Dow Corning^® 345 fluid, Silbione^® grade, Abil^® grade. Phenyl- trimethicone; Dow corning® 556 fluid. Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units with hydrogenated silicates. A detailed survey by Todd et al. of suitable volatile silicones may in addition be found in Cosm. Toil. 91, 27 (1976).

It is also suitable to use nonvolatile organopolysiloxane compounds as described for example in WO 94/21 224. Such compounds improve the disentangling, softness and hold proper- ties. Preferably, organopolysiloxane compounds are nonvolatile organopolysiloxane chosen from polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins or organomodified polysiloxanes, with the exception of polysiloxanes carrying polyethylene- oxy and/or polypropyleneoxy, or carboxylate or bisulphite, groups.

The organopolysiloxanes are nonvolatile organopolysiloxane oils or organosiloxane gum or resin organic solutions or alternatively emulsions or microemulsions containing these organopolysiloxanes.

Examplesof such nonvolatile organopolysiloxane compounds are polyalkylsiloxanes, mainly linear polydimethylsiloxanes: either, containing end trimethylsilyl groups, such as, for example, and without implied limitation, Silbione oils of the 70047 series marketed by Rhone- Poulenc, 47 V 500,000 oil from Rhόne-Poulenc or certain Viscasil^® from General Electric, or containing end trihydroxysilyl groups, such as the oils of the 48 V series from Rhone- Poulenc.

Mention may also be made, in this class of polyalkylsiloxanes, of polyalkylsiloxanes sold by the Company Goldschmidt under the names Abilwax^® 9800 and Abilwax^® 9801 , which are polyalkyl(CrC₂o)siloxanes.

Mention may be made, among the polyalkylarylsiloxanes, of linear and/or branched polydi- methylphenylsiloxanes or polydimethyldiphenylsiloxanes, with a viscosity of 10^"5 to 5 x 10^"2 Im²S^"1 at 25°C, such as, for example: Rhodorsil^® 763 oil from Rhone -Poulenc, silicone oils of the 70641 series from Rhone - Poulenc, such as Silicone 70641 V 30 and 70641 V 200 oils from Rhone -Poulenc, the product DC 556 Cosmetic Grad Fluid from Dow Corning, silicones of the PK series from Bayer, such as PK20, silicones of the PN and PH series from Bayer, such as PN 1000 and PH 1000, certain oils of the SF series from General Electric, such as SF 1250, SF 1265, SF 1 154 and SF 1023, 618 V 25000 oil from Rhone-Poulenc.

The silicone gums in accordance with the present invention are polydiorganosiloxanes with a high molecular mass of between 200,000 and 1 ,000,000, used alone or as a mixture in a solvent chosen from polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, methylene chloride, pentane, dodecane, tridecane, tetradecane or their mix- tures.

Mention is made, for example, of the following compounds: polydimethylsiloxane, optionally hydroxylated at the chain end, poly[(dimethylsiloxane)/(methylvinylsiloxane)], poly[(dimethylsiloxane)/(diphenylsiloxane)], poly[(dimethylsiloxane)/(phenylmethylsiloxane)], poly[(dimethylsiloxane)/(diphenylsiloxane)/(methylvinylsiloxane)].

Mention may be made, for example, without implied limitation, of the following mixtures:

1 ) the mixtures formed from a polydimethylsiloxane hydroxylated at the chain end

(Dimethiconol according to the CTFA nomenclature) and from a cyclic polydimethylsilox- ane (Cyclomethicone according to the CTFA nomenclature), such as the product Q2

1401 sold by the Company Dow Corning; 2) the mixtures formed from a polydimethylsiloxane gum with a cyclic silicone, such as the product SF 1214 Silicone Fluid from General Electric, which is an SE 30 gum with a MW of 500,000 dissolved in SF 1202 Silicone Fluid (decamethylcyclopentasiloxane);

3) the mixtures of two PDMS of different viscosities, in particular of a PDMS gum and of a PDMS oil, such as the products SF 1236 and CF 1241 from the Company General Electric. The product SF 1236 is the mixture of an SE 30 gum defined hereinabove, with a viscosity of 20 mV¹, and of an SF 96 oil, with a viscosity of 5.10^"6 mV (15% of SE 30 gum and 85% of SF 96 oil).

The product CF 1241 is the mixture of an SE 30 gum (33%) and of a PDMS (67%) with a viscosity of 10^"3 mV .

The organopolysiloxane resins which can be used in accordance with the invention are crosslinked siloxane systems containing the units: R₂Si0_2/2, RSiO_3/2 and SiO₄/₂, in which R represents a hydrocarbon group having 1 to 6 carbon atoms or a phenyl group. The particularly preferred products among these are those in which R denotes a lower alkyl radical or a phenyl radical.

Mention may be made, among these resins, of the product sold under the name Dow Corning 593 or of those sold under the names Silicone Fluid SS 4230 and SS 4267 by the Company General Electric and which are "dimethyl/trimethylpolysiloxane".

The organomodified silicones in accordance with the present invention are silicones as de- fined above containing, in their general structure, one or a number of organofunctional groups directly attached to the siloxane chain or attached via a hydrocarbon radical.

Mention is made, for example, of the silicones containing: a) fluorinated groups such as trifluoroalkyls, such as, for example, those sold by the Company General Electric under the names "FF 150 Fluorosilicone Fluid" or by the Company Shin Etsu under the names X-22-819, X-22-820, X-22-821 and X-22-822; b) hydroxyacylamino groups, such as those described in European Patent Application

342 834 and in particular the silicone sold by the Company Dow Corning under the name Q2-8413; c) thiol groups, as in the silicones X 2-8360 from Dow Corning or GP 72A and GP 71 from Genesee; d) substituted or unsubstituted amino groups, as in GP4 Silicone Fluid from Geneses, GP 7100 from Genesee, Q2 8220 from Dow Corning, AFL 40 from Union Carbide or the silicone known as "Amodimethicone" in the CTFA dictionary; e) hydroxylated groups, such as the polyorganosiloxanes containing hydroxyalkyl and in particular gamma-hydroxypropyl functional groups, described in French Patent Application 85 16334; f) alkoxylated groups, as in Silicone copolymer F 755 from SWS Silicones and the products Abilwax^® 2428, Abilwax^® 2434 and Abilwax^® 2440 from the Company Goldschmidt; g) acyloxyalkyl groups, such as, for example, the polyorganopolysiloxanes described in French Patent Application 88 17433, and in particular gamma-stearoyloxypropyl groups; h) quaternaryammonium groups, as in the products X2 81 08 and X2 81 09 or the product Abil^® K 3270 from the Company Goldschmidt; i) amphoteric or betaine groups, such as in the product sold by the Company Goldschmidt under the name Abil^® B 9950.

The polyorganosiloxanes are present in composition, preferably personal care composition, in a proportion up to 50% by weight, based on the total weight of the composition. Preferably the polyorganosiloxanes are present from 0.2 to 50% by weight, more preferably between 1 and 30% by weight, based on the total weight of the composition.

Fluorinated or perfluorinated oils: perfluorhexane, dimethylcyclohexane, ethylcyclopentane (Flutec^® grades), polyperfluoro- methylisopropyl ether (Fomblin^® grades).

The oil components can be used in an amount of up to 99 wt-%. In an O/W-formulation the oil component is preferably present in an amount of from 5 wt-% to 50 wt-% and more preferably from 10 wt-% to 35 wt-%, based on the total weight of the personal care composition.

Emulsifiers:

Any conventionally usable emulsifier can be used for the personal care compositions. Emul- sifier systems may comprise for example:

Carboxylic acids and their salts: alcalin soap of sodium, potassium and ammonium, metallic soap of calcium or magnesium, organic basis soap such as lauric, palmitic, stearic and oleic acid;

Alkyl phosphates or phosphoric acid esters: acid phosphate, diethanolamine phosphate, po- tassium cetyl phosphate; Ethoxylated Carboxylic Acids or Polyethyleneglycol esters (PEG-n acylates). Linear fatty alcohols having from 8 to 22 carbon atoms, branched from 2 to 30 mol of ethylene oxide and/or from 0 to 5 mol propylene oxide with fatty acids having from 12 to 22 carbon atoms and with alkylphenols having from 8 to 15 carbon atoms in the alkyl group. Fatty alcohol Po- lyglycolether such as laureth-n, ceteareth-n, steareth-n, oleth-n. Fatty acid polyglycolether such as PEG-n stearate, PEG-n oleate, PEG-n cocoate;

Monoglycerides and Polyol esters. C₁₂-C₂₂ fatty acid mono- and di-esters of addition products of from 1 to 30 mol of ethylene oxide with polyols;

Fatty acid and polyglycerol ester such as Monostearate glycerol, diisostearoyl polyglyceryl-3- diisostearates, polyglyceryl-3-diisostearates, triglyceryl diisostearates, polyglyceryl-2-ses- quiisostearates or polyglyceryl dimerates. Mixtures of compounds from a plurality of those substance classes are also suitable. Fatty acid polyglycolesters such as monostearate di- ethylene glycol, fatty acid and polyethylene glycol esters, fatty acid and saccharose esters such as sucro esters, glycerol and saccharose esters such as sucro glycerides; Sorbitol and sorbitan: Sorbitan mono- and di-esters of saturated and unsaturated fatty acids having from 6 to 22 carbon atoms and ethylene oxide addition products;

Polysorbate-n series, sorbitan esters such as sesquiisostearate, sorbitan, PEG-(6)- isostearate sorbitan, PEG-(10)-sorbitan laurate, PEG-17-dioleate sorbitan;

Glucose derivatives: C8-C₂₂alkyl-mono and oligo-glycosides and ethoxylated analogues with glucose being preferred as the sugar component. O/W emulsifiers such as methyl gluceth-20 sesquistearate, sorbitan stearate/sucrose cocoate, methyl glucose sesquistearate, cetearyl alcohol/cetearyl glucoside. VWO emulsifiers such as methyl glucose dioleate/ methyl glucose isostearate;

Sulphates and sulphonated derivatives: dialkylsulphosuccinat.es (DOSS: dioctyl succinate), alkyl lauryl sulphonate, linear sulphonated parafins, sulphonated tetrapropylene sulphonate, sodium lauryl sulphates, ammonium and ethanolamine lauryl sulphates, lauryl ether sulphates, sodium laureth sulphates, sulphosuccinates, acetyl isothionates, alkanolamide sulphates such as taurines, methyl taurines, imidazole sulphates;

Amine derivatives: amine salts, ethoxylated amines such as oxide amine, with chains con- taining a heterocycle such as alkyl imidazolines, pyridine derivatives, isoquinoteines, cetyl pyridinium chlorure, cetyl pyridinium bromure, quaternary ammonium such as cetyltrimethyl- bromure ammonium bromure (CTBA), stearylalkonium; Amide derivatives: alkanolamides such as acylamide DEA, ethoxylated amides, such as PEG-n acylamide, oxydeamide;

Polysiloxane/polyalkyl/polyether copolymers and derivatives: dimethicone, copolyols, silicone polyethylene oxide copolymer, silicone glycol copolymer; Propoxylated or POE-n ethers (Meroxapols), polaxamers or poly(oxyethylene)m-block- poly(oxypropylene)n-block(oxyethylene);

Zwitterionic surfactants that carry at least one quaternary ammonium group and at least one carboxylate and/or sulphonate group in the molecule. Zwitterionic surfactants that are especially suitable are the so-called betaines, such as N-alkyl-N,N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammo- nium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl- 3-carboxymethyl-3-hydroxyethylimidazolines each having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethyl-carboxy-methylglycinate, N-al- kylbetaine, N-alkylaminobetaines; Alkylimidazolines, alkylopeptides, lipoaminoacides.

Self emulsifying bases (K.F. DePoIo - A short textbook of cosmetology, Chapter 8, Table 8- 7, pp. 250-251):

Non ionic bases such as PEG-6 beeswax (and) PEG-6 stearate (and) polyglyceryl -2 isostearate [Apifac], glyceryl stearate (and) PEG-100 stearate. [Arlacel 165], PEG-5 glyceryl stearate [arlatone 983 S], sorbitan oleate (and) polyglyceryl-3 ricinoleate. [Arlacel 1689], sor- bitan stearate and sucrose cocoate [arlatone 2121], glyceryl stearate and laureth-23 [Cera- synth 945], cetearyl alcohol and ceteth-20 [Cetomacrogol Wax], cetearyl alcohol and poly- sorbate 60 and PEG-150 and stearate-20[Polawax GP 200, Polawax NF], cetearyl alcohol and cetearyl polyglucoside [Emulgade PL 1618], cetearyl alcohol and ceteareth-20 [Emul- gade 1000NI, Cosmowax], cetearyl alcohol and PEG-40 castor oil [Emulgade F Special], cetearyl alcohol and PEG-40 Castor Oil and sodium cetearyl sulphate [Emulgade F], stearyl alcohol and steareth-7 and steareth-10 [Emulgator E 2155], cetearyl alcohol and steareth-7 and steareth-10 [Emulsifying wax U. S. N. F], glyceryl stearate and PEG-75 stearate [Gelot 64], propylene glycol ceteth-3 Acetate .[Hetester PCS], propylene glycol isoceth-3 acetate [Hetester PHA], cetearyl alcohol and ceteth-12 and oleth-12 [Lanbritol Wax N 21], PEG -6 stearate and PEG-32 stearate [Tefose 1500], PEG-6 stearate and ceteth-20 and steareth-20 [Tefose 2000], PEG-6 stearate and ceteth-20 and glyceryl stearate and steareth-20 [Tefose 2561], glyceryl stearate and ceteareth-20 [Teginacid H, C, X]. Anionic alkaline bases such as PEG-2 stearate SE, glyceryl stearate SE [Monelgine, Cutina KD], propylene glycol stearate [Tegin P].

Anionic acid bases such as cetearyl alcohol and sodium cetearyl sulphate [Lanette N, Cutina LE, Crodacol GP], cetearyl alcohol and sodium lauryl sulphate [Lanette W], trilaneth-4 phos- phate and glycol stearate and PEG-2 stearate [Sedefos 75], glyceryl stearate and sodium lauryl sulphate [Teginacid Special].

Cationic acid bases such as cetearyl alcohol and cetrimonium bromide.

The emulsifiers may be used in an amount of, for example, from 1 wt-% to 30 wt-%, especially from 4 wt-% to 20 wt-% and preferably from 5 wt-% to 10 wt-%, based on the total weight of the composition.

When formulated in O/W emulsions, the preferably amount of such emulsifier system could represent 5 wt-% to 20 wt-% of the oil phase.

Adjuvants and additives:

The personal care compositions, for example creams, gels, lotions, alcoholic and aque- ous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments, may in addition contain, as further adjuvants and additives, mild surfactants, super-fatting agents, consistency regulators, additional thickeners, polymers, stabilizers, biogenic active ingredients, deodorizing active ingredients, anti-dandruff agents, film formers, swelling agents, further UV light-protective factors, antioxidants, hydrotropic agents, pre- servatives, insect repellents, self-tanning agents, solubilizers, perfume oils, colourants, bacteria-inhibiting agents and the like.

The adjuvants and additives may optionally be present in the personal care composition in an amount of, for example, from 0.1 wt-% to 25 wt-% based on the total weight of the composition. Super-fatting agents:

Substances suitable for use as super-fatting agents are, for example, lanolin and lecithin and also polyethoxylated or acrylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter simultaneously acting as foam stabilizers. Surfactants:

Examples of suitable mild surfactants, that is to say surfactants especially well tolerated by the skin, include carboxylic acids and salts, alkyl sulphates, alkyl ether sulphates, alkylsul- phonates, alkylarylsulphonates, olefin sulphonates, sulphosuccinates, acyl isothionates, al- kanolamide sulphates, taurines, methyl taurines, taurates, isethionates, sarcosinates, imidazole sulphates, alkyl phosphates, alkylamido alkyl amines, alkyl substituted amino acids, ac- etylated amino acids and peptides, alkylamines, alkylimidazolines, alkoxylated amines, alkyl ampho(di)acetates, alkyl ampho(di)propionates amido betaines, alkyl betaines, alkyl sul- phobetaines, alkanolamides, amine oxides, glycerides, ethoxylated glycerides, polyglyceryl esters, Sorbitan esters, carbohydrate esters, ethoxylated carboxylic acids, phosphoric acid trimesters, ethoxylated alcohols, ethoxylated/ propoxylated polysiloxanes, ethoxylated polypropylene oxide ethers, alkyl glycosides, fatty alcohol polyglycol ether sulphates, monoglyc- eride sulphates, mono- and/or di-alkyl sulphosuccinates, fatty acid taurides, fatty acid gluta- mates, α-olefin sulphonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides and/or protein fatty acid condensation products, the latter preferably being based on wheat proteins.

Consistency regulators / Additional Thickeners and Rheology modifiers: As additional thickeners and rheology modifiers, there come into consideration the groups of silicium dioxide, magnesium silicates, aluminium silicates, polysaccharides or derivatives thereof for example hyaluronic acid, xanthan gum, guar-guar, agar-agar, alginates, Car- raghenan, gellan, pectines, or modified cellulose such as hydroxycellulose, hydroxypropyl- methylcellulose. In addition polyacrylates or homopolymer of reticulated acrylic acids and polyacrylamides, e.g. the Carbopol® range (e.g. CARBOPOL types 980, 981 , 1382, ETD 2001 , ETD2020, Ultrez 10; INCI: Carbomer) or Salcare range such as Salcare SC80 (Steareth-10 AIIyI Ether/ Acrylates Copolymer), Salcare SC81 (Acrylate copolymers, Salcare SC91 and Salcare AST (Sodium Acrylate Copolymer/PPG-1 trideceth-6), Sepigel 305 (polyacrylamide/laureth-7), Simulgel NS and Simulgel EG (hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer), Stabilen 30 (acrylate/vinyl isodecanoate crosspolymer), Pemulen TR- 1 (acrylate/Cio-C3o alkyl acrylate crosspolymer), Luvigel EM (sodium acrylate copolymer), Aculyn 28 (acrylate/beheneth-25 methacrylate copolymer), etc.

Polymers:

Suitable cationic polymers are, for example, cationic cellulose derivatives, for example a quaternized hydroxymethyl cellulose obtainable under the name Polymer JR 400^® from

Amerchol, cationic starches, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone/vinyl imidazole polymers, for example Luviquat^® (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides, for example lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat^®L/Grϋnau), quaternised wheat polypeptides, polyethyleneimine, cationic silicone polymers, for example amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Car- taretin^®/Clariant), copolymers of acrylic acid with dimethyldiallylammonium chloride (Mer- quat^® 550/Chemviron), polyaminopolyamides, as described, for example, in FR-A-2 252 840, and the cross-linked water-soluble polymers thereof, cationic chitin derivatives, for example of quaternised chitosan, optionally distributed as microcrystals; condensation products of di- haloalkyls, for example dibromobutane, with bisdialkylamines, for example bisdimethylamino- 1 ,3-propane, cationic guar gum, for example Jaguar^® C-17, Jaguar^® C-16 from Celanese, quaternised ammonium salt polymers, for example Mirapol^® A-15, Mirapol^® AD-1 , Mirapol^® AZ-1 from Miranol. As anionic, zwitterionic, amphoteric and non-ionic polymers there come into consideration, for example, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and esters thereof, uncrosslinked polyacrylic acids and polyacrylic acids cross linked with polyols, acrylamidepropyltrimethylammonium chlo- ride/acrylate copolymers, octyl acrylamide/methyl methacrylate/tert-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, vinylpyrrolidone/dimethyl-aminoethyl methacrylate/vinyl caprolactam terpolymers and also optionally derivatised cellulose ethers and silicones. Furthermore the polymers as described in European Patent Specification 1 093 796 (pages 3 - 8, paragraphs 17 - 68) may be used. Biogenic active ingredients:

Biogenic active ingredients are to be understood as meaning, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes. Deodorizing active ingredients:

As deodorizing active ingredients there come into consideration, for example, antiperspi- rants, for example aluminium chlorohydrates (see J. Soc. Cosm. Chem. 24, 281 (1973)). Under the trade mark Locron^® of Clariant, there is available commercially, for example, an aluminium chlorohydrate corresponding to formula AI₂(OH)₅CI x 2.5 H₂O, the use of which is es- pecially preferred (see J. Pharm. Pharmacol. 26, 531 (1975)). Besides the chlorohydrates, it is also possible to use aluminium hydroxyacetates and acidic aluminium/zirconium salts. Esterase inhibitors may be added as further deodorizing active ingredients. Such inhibitors are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and especially triethyl citrate (Hydagen^® CAT, Henkel KGaA, Dϋsseldorf/GER), which inhibit enzyme activity and hence reduce odour formation. Further substances that come into consideration as esterase inhibitors are sterol sulphates or phosphates, for example lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulphate or phosphate, dicarboxylic acids and esters thereof, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester and hydroxycarboxylic acids and esters thereof, for example citric acid, malic acid, tartaric acid or tartaric acid diethyl ester. Antibacterial active ingredients that influence the germ flora and kill or inhibit the growth of sweat-decomposing bacteria can likewise be present in the preparations (especially in stick preparations). Examples include chitosan, phenoxyethanol and chlorhexidine gluconate. 5-chloro-2-(2,4-di- chlorophenoxy)-phenol (Irgasan^®, Ciba Specialty Chemicals Inc.) has also proved especially effective.

Anti-dandruff agents:

As anti-dandruff agents there may be used, for example, climbazole, octopirox and zinc py- rithione. Customary film formers include, for example, chitosan, microcrystalline chitosan, quaternised chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers of quaternary cellulose derivatives containing a high proportion of acrylic acid, collagen, hyaluronic acid and salts thereof and similar compounds.

Antioxidants:

The personal care product can optionally contain one or more antioxidants. Any common an- tioxidant can be used.

Typical examples of such antioxidants are 4,4'-di-α-cumyl-diphenylamine, mono- and dialky- lated tert-butyl/tert-octyl-diphenylamines, n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinna- mate, Tetradibutyl pentaerythrityl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5- di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzyl- phosphonate, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate thiodiethylene bis(3,5- di-tert-butyl-4-hydroxyhydro-cinnamate), 1 ,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)benzene, 3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinna- mate), 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 1 ,3,5-tris(2,6-di- methyl-4-tert-butyl-3-hydroxybenzyl) isocyanurate, 1 ,1 ,3-tris(2-methyl-4-hydroxy-5-tert-butyl- phenyl)butane, 1 ,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl] isocyanurate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene bis(3,5-di-tert- butyl-4-hydroxyhydrocinnamate), 1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-tri- azine, N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydro-cinnamamide), calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylene bis[3,3-di(3-tert-butyl-4-hy- droxyphenyl)butyrate], octyl S.S-di-tert-butyM-hydroxybenzylmercaptoacetate, bis(3,5-di-tert- butyl-4-hydroxyhydrocinnamoyl)-hydrazide, N,N'-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocin- namoyloxy)-ethyl]oxamide, and N,N-dialkylhydroxylamine prepared from di(hydrogenated tallow)amine by direct oxidation. Further suitable antioxidants areamino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (e.g. anserine), carotinoids, carotenes (e.g. β-carotene, β-carotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglycose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyl, oleyl, linoleyl, cholesteryl and glyceryl esters thereof) and also salts thereof, di- lauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and also sulphoximine compounds (e.g. buthionine sulphoximines, homocysteine sulphoximine, buthionine sul- phones, penta-, hexa-, hepta-thionine sulphoximine), also (metal) chelating agents (e.g. α- hydroxy fatty acids, palmitic acid phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g. linolenic acid, Ii- noleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (e.g. vitamin A palmitate) and also coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiaretic acid, trihydroxybutyrophe- none, uric acid and derivatives thereof, mannose and derivatives thereof, superoxide dismu- tase, N-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]-sulphanilic acid (and salts thereof, for example the disodium salts), zinc and derivatives thereof (e.g. ZnO, ZnSO₄), selenium and derivatives thereof (e.g. selenium methionine), stilbene and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of HALS (="Hindered Amine Light Stabilizers") compounds may also be mentioned.

The amount of antioxidants present is usually from 0.001 wt-% to 25 wt-%, preferably from 0.01 wt-% to 3 wt-%, based on the weight of the personal care product. Hydrotropic agents: To improve the flow behaviour it is also possible to employ hydrotropic agents, for example ethoxylated or non ethoxylated mono-alcohols, diols or polyols with a low number of C-atoms or their ethers (e.g. ethanol, isopropanol, 1 ,2-dipropanediol, propyleneglycol, glycerol, ethylene glycol, ethylene glycol monoethylether, ethylene glycol monobutylether, propylene gly- col monomethylether, propylene glycol monoethylether, propylene glycol monobutylether, di- ethylene glycol monomethylether; diethylene glycol monoethylether, diethylene glycol monobutylether and similar products). The polyols that come into consideration for that purpose have preferably from 2 to 15 carbon atoms and at least two hydroxy groups. The polyols may also contain further functional groups, especially amino groups, and/or may be modified with nitrogen. Typical examples are as follows: glycerol, alkylene glycols, for example ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and also polyethylene glycols having an average molecular weight of from 100 to 1000 Dalton; technical oli- goglycerol mixtures having an intrinsic degree of condensation of from 1.5 to 10, for example technical diglycerol mixtures having a diglycerol content of from 40 wt-% to 50 wt-%; methylol compounds, such as, especially, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol; lower alkyl-glucosides, especially those having from 1 to 8 carbon atoms in the alkyl radical, for example methyl and butyl glucoside; sugar alcohols having from 5 to 12 carbon atoms, for example sorbitol or mannitol; sugars having from 5 to 12 carbon atoms, for example glucose or saccharose; amino sugars, for example glucamine; dialcohol amines, such as diethanolamine or 2-amino-1 ,3-propanediol.

Preservatives and Bacteria-inhibiting agents:

Suitable preservatives include, for example, methyl-, ethyl-, propyl-, butyl- parabens, ben- zalkonium chloride, 2-bromo-2-nitro-propane-1 ,3-diol, dehydroacetic acid, diazolidinyl urea, 2-dichloro-benzyl alcohol, DMDM hydantoin, formaldehyde solution, methyldibromoglutani- trile, phenoxyethanol, sodium hydroxymethylglycinate, imidazolidinyl urea and triclosan and further substance classes listed in the following reference: K. F. DePoIo - A short textbook of cosmetology, Chapter 7, Table 7-2, 7-3, 7-4 and 7-5, pp. 210-219.

Bacteria-inhibiting agents:

Typical examples of bacteria-inhibiting agents are preservatives that have a specific action against gram-positive bacteria, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexi- dine (1 ,6-di(4-chlorophenyl-biguanido)hexane) or TCC (3,4,4'-trichlorocarbanilide). A large number of aromatic substances and ethereal oils also have antimicrobial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, mint oil and thyme oil. A natural deodorizing agent of interest is the terpene alcohol farnesol (3,7,11- trimethyl-2,6,10-dodecatrien-1-ol), which is present in lime blossom oil. Glycerol monolaurate has also proved to be a bacteriostatic agent. The amount of the additional bacteria-inhibiting agents present is usually from 0.1 wt-% to 2 wt-%, based on the solids content of the preparations.

Perfume oils: There may be mentioned as perfume oils mixtures of natural and/or synthetic aromatic substances. Natural aromatic substances are, for example, extracts from blossom (lilies, lavender, roses, jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli, petit- grain), from fruit (aniseed, coriander, carraway, juniper), from fruit peel (bergamot, lemons, oranges), from roots (mace, angelica, celery, cardamom, costus, iris, calmus), from wood (pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses (tarragon, lemon grass, sage, thyme), from needles and twigs (spruce, pine, Scots pine, mountain pine), from resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials also come into consideration, for example civet and cas- toreum. Typical synthetic aromatic substances are, for example, products of the ester, ether, aldehyde, ketone, alcohol or hydrocarbon type. Aromatic substance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes in- elude, for example, the linear alkanals having from 8 to 18 hydrocarbon atoms, citral, citron- ellal, citronellyl oxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeo- nal; the ketones include, for example, the ionones, α,α-isomethylionone and methyl cedryl ketone; the alcohols include, for example, anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenyl ethyl alcohol and terpinol; and the hydrocarbons include mainly the terpenes and balsams. It is preferable, however, to use mixtures of various aromatic substances that together produce an attractive scent. Ethereal oils of relatively low volatility, which are chiefly used as aroma components, are also suitable as perfume oils, e.g. sage oil, camomile oil, clove oil, melissa oil, oil of cinnamon leaves, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil and lavandin oil. Preference is given to the use of bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenyl ethyl alcohol, α,α-hexyl cinna- maldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, boisambrene forte, am- broxan, indole, hedione, sandelice, lemon oil, tangerine oil, orange oil, allyl amyl glycolate, cyclovertal, lavandin oil, muscatel sage oil, α-damascone, bourbon geranium oil, cyclohexyl salicylate, vertofix coeur, iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat alone or in admixture with one another.

Colourants:

There may be used as colourants the substances that are suitable and permitted for cos- metic purposes, as compiled, for example, in the publication "Kosmetische Farbemittel" of the Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Wein- heim, 1984, pages 81 to 106. The colourants are usually used in concentrations of from 0.001 wt-% to 0.1 wt-%, based on the total mixture.

Other adjuvants: It is furthermore possible for the personal care composition to contain, as adjuvants, anti- foams, such as silicones, structurants, such as maleic acid, solubilisers, such as ethylene glycol, propylene glycol, glycerol or diethylene glycol, opacifiers, such as latex, styrene/PVP or styrene/acrylamide copolymers, complexing agents, such as EDTA, NTA, alaninediacetic acid or phosphonic acids, propellants, such as propane/butane mixtures, N₂O, dimethyl ether, CO₂, N₂ or air, so-called coupler and developer components as oxidation dye precursors, reducing agents, such as thioglycolic acid and derivatives thereof, thiolactic acid, cys- teamine, thiomalic acid or mercaptoethanesulphonic acid, or oxidizing agents, such as hydrogen peroxide, potassium bromate or sodium bromate.

There come into consideration as insect repellents, for example, N,N-diethyl-m-toluamide, 1 ,2-pentanediol or insect repellent 3535; suitable self-tanning agents are, for example, dihy- droxyacetone and/or erythrulose or dihydroxy acetone and/or dihydroxy acetone precursors as described in WO 01/85124 and/or erythrulose.

Ultraviolet Light Absorbers:

Ultraviolet Light Absorbers (UV absorbers) are employed in cosmetics to protect the product from chemical or physical deterioration induced by ultraviolet light. Sunscreen agents are OTC drug ingredients, which protect the skin from ultraviolet light. UV absorbers, like sunscreen agents, have the ability to convert incident ultraviolet radiation into less damaging infrared radiation (heat). Suitable UV absorbers are, for example:

Aetaminosalol, allantoin PABA, benzalphthalide, benzophenone, benzophenone-1 , -2,-3, -4, -5, -6, -7, -8, -9, -10, -1 1 , or -12, benzotriazolyl dodecyl p-cresol, 3-benzylidene camphor, benzylidenecamphor hydrolyzed collagen sulphonamide, benzylidene camphor sulphonic acid, benzyl salicylate, bis-ethylhexyloxyphenol methoxyphenyl triazine, bornelone, bumetri- zole, butyl methoxydibenzoylmethane, butyl PABA, callophyllum inophyllum seed oil, ca- mellia sinensis leaf extract, carotenoids, ceria silica, ceria/silica talcum, cinoxate, DEA- methoxycinnamate, dibenzoxazoyl naphthalene, di-t-butyl hydroxybenzylidene camphor, diethylhexyl butamido triazone, diethylhexyl 2,6-naphthalate, digalloyl trioleate, diisopropyl methyl cinnamate, 1 -(3, 4-dimethoxyphenyl)-4,4-dimethyl-1 ,3-pentanediene, dimethyl PABA ethyl cetearyldimonium tosylate, dimorpholinopyridazinone, diphenyl carbomethoxy acetoxy naphthopyran, disodium bisethylphenyl triaminotriazine stilbenedisulphonate, disodium distyrylbiphenyl disulphonate, disodium phenyl dibenzimidazole tetrasulphonate, drometrizole, drometrizole trisiloxane, esculin, ethyl dihydroxypropyl PABA, ethyl diisopro- pylcinnamate, ethylhexyl dimethoxybenzylidene dioxoimidazolidine propionate, ethylhexyl dimethyl PABA, ethylhexyl ferulate, ethylhexyl methoxycinnamate, ethylhexyl salicylate, ethylhexyl triazone, ethyl methoxycinnamate, ethyl PABA, ethyl urocanate, etocrylene, ferulic acid, 4-(2-beta-glucopyranosiloxy) propoxy-2-hydroxybenzophenone, glyceryl ethylhexanoate dimethoxycinnamate, glyceryl PABA, glycol salicylate, hexanediol salicylate, homosalate, hydrolyzed lupine protein, isoamyl p-methoxycinnamate, isopentyl trimethoxycinnamate trisiloxane, isopropylbenzyl salicylate, isopropyl dibenzoylmethane, isopropyl methoxycinnamate, menthyl anthranilate, menthyl salicylate, 4-methylbenzylidene camphor, methylene bis-benzotriazolyl tetramethylbutylphenol, octocrylene, octrizole, PABA, PEG-25 PABA, pentyl dimethyl PABA, phenylbenzimidazole sulphonic acid, pinus pinaster bark extract, polyacrylamidomethyl benzylidene camphor, polysilicone-15, potassium methoxycinnamate, potassium phenylbenzimidazole sulphonate, red petrolatum, sodium benzotriazolyl butylphenol sulphonate, sodium isoferulate, sodium phenylbenzimidazole sulphonate, sodium urocanate, spirulina platensis powder, TEA-phenylbenzimidazole sulphonate, TEA-salicylate, terephthalylidene dicamphor sulphonic acid, tetrabutyl phenyl hydroxybenzoate, titanium dioxide, tocotrienols, triPABA panthenol, urocanic acid, VA/crotonates/methacryloxybenzophenone-1 copolymer and Vitis Vinifera (Grape) seed extract.

Polymeric beads or hollow spheres as SPF enhancers:

The combination of the UV-absorbers described above, with SPF enhancers, such as non- active ingredients like Styrene/acrylate copolymer, silica beads, spheroidal magnesium sili- cate, spherical polyamide powder such as n-lactam polymer (Orgasol^® range, EIf Atochem) cross linked Polymethylmethacrylate (PMMA; Micopearl M305 Seppic), can maximize better the UV protection of the sun products. Holosphere additives (Sunspheres^® ISP, Silica Shells Kobo.) deflect radiation and the effective path length of the photon is therefore increased. (EP0893119). Some beads, as mentioned previously, provide a soft feel during spreading. Moreover, the optical activity of such beads, e.g. Micropearl M305, cans modulate skin shine by eliminating reflection phenomena and indirectly may scatter the UV light.

When formulated in O/W emulsions, the preferably amount of such SPF enhancers should represent 1 wt-% to 10 wt-% of the total amount of the personal care composition. A typical O/W- based personal care composition comprises:

0.5 - 10 wt-% of at least one of the inventive copolymer

2 - 25 wt-% of at least one oil-component,

0 - 25 wt-% of at least one adjuvant and/or additive, water up to 100 wt-%. A typical oil-based personal care composition comprises

0.5 - 10 wt-% of at least one of the inventive copolymer

50 - 99 wt-% of at least one oil-component,

0 - 25 wt-% of at least one adjuvant and/or additive.

A soap has, for example, the following composition: 0.1 to 5% wt-% of at least one inventive copolymer

0.3 to 1 % wt-% of titanium dioxide

1 to 10% wt-% of stearic acid to 100 wt-% of soap base, for example the sodium salts of tallow fatty and coconut fatty acid or glycerols. A shampoo has, for example, the following composition:

0.1 to 5% wt-% of at least one inventive copolymer

12.0% wt-% of sodium laureth-2-sulphate,

4.0% wt-% of cocamidopropylbetaine,

3.0% wt-% of NaCI and water to 100 wt-%.

A deodorant has, for example, the following composition:

0.1 to 5% of at least one inventive copolymer

40% by weight of ethanol, 0.3% by weight of perfume oil and water to 100%.

The new polymers are also useful in thickening of printing paste and paints. The new polymers are obtainable by conventional polymerisation processes. The following examples are set forth merely to exemplify the invention and are not intended to limit the metes and bounds of the invention, which is set forth by the claims appended hereto.

Parts and percentages are by weight. The temperatures are stated in degrees Celsius. Examples

Synthesis of the copolymer

These examples illustrate the preparation the copolymer.

Example A:

Monomer

Methyl acrylate 57.421 parts Methacrylic acid 26.974 parts

Acrylic acid 5.225 parts

Polyethoxylated behenyl methacrylate (i.e. Sipomer BEM^®) 10.370 parts

Pentaerythritol triacrylate 0.010 parts

Ceteareth methacrylate (i.e. Plex 6954) 11.455 parts Aqueous

Water 79.765 parts

Sodium alkyl ether sulphate (i.e. Disponil FES993) 8.780 parts

Vessel

Water 92.112 parts Sodium alkyl ether sulphate (i.e. Disponil FES77) 7.424 parts

Fatty alcohol alkoxylate (i.e Sympatens AL/090) 0.371 parts

Ammonium persulphate 0.093 parts

Initiator

Water 99.510 parts Ammonium persulphate 0.490 parts A vessel phase is prepared by mixing 92.112 parts water, 7.424 parts Disponil FES77, 0.371 parts Sympatens AL/090 into a 5 I pot, without the ammonium persulphate initiator, and heated to 80°C in a water bath.

The monomer phase is prepared by mixing 57.421 parts methyl acrylate, 26.974 parts methyl methacrylate, 5.225 parts acrylic acid, 1.0370 parts beheneth-25 methacrylate and 0.010 parts pentaerythritol triacrylate and 11.455 parts Plex 6954.

The aqueous phase is prepared by mixing 79.765 parts water, 8.780 parts Disponil FES993.

An initiator phase is prepared by mixing 99.510 parts water and 0.490 parts ammonium persulphate. The monomer pre-emulsion is formed by homogenisation of the monomer phase into the aqueous phase by Silverson high shear mixer for 5 mins.

Once the vessel is at 80°C the vessel initiator charge is added and the pre-emulsion feed started. The monomer pre-emulsion and initiator are added over 3 hours. The polymer is held for 30 minutes before the post addition of initiator is added. The vessel is held for 2 hours at 80°C before cooling to <40°C.

Examples B - T (Table 1 )

The following copolymers are produced in analogy of Example A, wherein the educts are replaced accordingly.

MA = methyl acrylate EA = ethyl acrylate

MAA = methyl methacrylate

AA = acrylic acid

PLEX = ceteareth-25 methacrylate

BEM = beheneth-25 methacrylate SEM = steareth-25 methacrylate

Rionic S10 = Steareth 10 allyl ether

StMa = stearyl methacrylate

PETA = pentaerythritol triacrylate

DAP = diallyl phthalate 2, i ra

Formulation Examples: Personal Care Formulations

Example 1 : Shampoo Formulation

The use of polymers of the present invention in typical surfactant based personal care products can be demonstrated by preparation of the formulation below:

The formulation example 1 can also prepared with the copolymers B - T as defined in Table 1. The overall properties of these formulations are similar.

Example 2: Shower Gel Form ula tion

This formulation contains a combination of an anionic surfactant and non-ionic foam booster that is advantageously thickened with a copolymer of the present invention.

The formulation example 2 can also prepared with the copolymers B - T as defined in Table 1. The overall properties of these formulations are similar. Example 3: Foaming facial wash

This personal care formulation demonstrates the use of polymers of the present invention in milder surfactant products.

The formulation example 3 can also prepared with the copolymers B - T as defined in Table 1. The overall properties of these formulations are similar.

Example 4: Conditioning Antibacterial Facial Wash

This formulation uses a combination of the copolymer of the present invention and a liquid dispersion thickener to provide a stable smooth flowing opaque surfactant based formulation.

Method:

Add Part B in order into a clean, dry beaker and warm to 40°C. Dissolve Part A into part B with stirring at 40°C. Allow to cool, add part C with continued stirring. Add ingredients under part D in turn, stirring between additions. Add part E, stir with increased speed until a smooth formulation is formed.

The formulation example 4 can also prepared with the copolymers B - T as defined in

Table 1. The overall properties of these formulations are similar. Example 5: Light Nourishing Cream for Mature Skins

Copolymers of the present invention can be used as polymeric stabilizers and aqueous phase rheology modifiers in a wide variety of skin and hair care products, such as this light moisturiser.

Method:

Heat part A and B separately to 75°C. Add part A to part B under stirring and then homogenize for 30 sec at 1 1000 rpm. At 65°C add part C, and then adjust the pH to around

6.50 with part D. Add part E and F below 40°C with stirring.

The formulation example 5 can also prepared with the copolymers B - T as defined in

Table 1. The overall properties of these formulations are similar. Example 6: Sun Protection Gel (estimated in vivo SPF 26)

This formulation shows the application of copolymers of the present invention in emulsions containing UVA and UVB absorbers.

Method:

Blend part B and heat to 75-80°C. Neutralize with part C to pH > 6.5, until the phase is completely clear. Heat part A to 75°C. Add part B to part A under stirring. Homogenize with an Ultra Turrax at 1 1 000 rpm. Cool down to 40°C and incorporate each ingredient of part D.

Adjust the pH with part E to 7.0. Add fragrance.

The formulation Example 6 can also prepared with the copolymers B - T as defined in

Table 1. The overall properties of these formulations are similar. Example 7: Lye Relaxer

This formulation demonstrates the use of copolymers of the present invention in high pH systems. They can also be used in no-lye relaxers, depilatories and hair colour developers. In addition these polymers can be used in household applications such as oven cleaners.

Method:

In an appropriate vessel, premix Part A and heat oil phase to 78C. In a separate vessel, premix Part B, and heat water phase to 8OC with moderate stirring. Combine parts A and B at 78-80°C and mix for 10 minutes. Cool to 45°C. Premix Phase C and add to batch at 45°C.

Mix for 15 minutes. Add remaining ingredients under Part D with mixing in between, mix for

20 minutes until homogenous. Continue cooling to 25C and homogenize.

The formulation example 7 can also prepared with the copolymers B - T as defined in

Table 1. The overall properties of these formulations are similar. Example 8: Temporary Hair Colour Gel

The copolymers of the present invention can also be used in combination with temporary hair colour to produce smooth colour gels.

Method:

Add Part A to main vessel. Add Part B singularly to main vessel. Add Part C and add to main vessel mix until gel has formed. Premix Part D and mix until thoroughly dissolved.

Add part E and Premix D and mix until smooth and homogeneous.

The formulation example 8 can also prepared with the copolymers B - T as defined in

Table 1. The overall properties of these formulations are similar.

Example 9: Styling Gel

This formulation is a clear viscous gel containing a typical hair setting resin and offers good rheological characteristics.

Method:

To a clean beaker add Part A and mix. Premix Part B and set aside. Add Part C singularly, mixing well after each addition. Premix Part D and add to batch. Add Part E. Slowly add Part

B and mix well.

The formulation example 9 can also prepared with the copolymers B - T as defined in

Table 1. The overall properties of these formulations are similar. Example 10: Glitter Gel

This formulation demonstrates that copolymers of the present invention have suspension characteristics, and can be used in a wide variety of personal care applications such as exfoliating scrubs as well as decorative cosmetics. There are also applications in household products such as those containing abrasive particles.

Method:

Combine parts A and B separately on clean, dry vessels. Pour part B into part A under stirring.

Add part C into A/B. Stir slowly and adjust the pH with part D to around pH 6.5

The formulation example 10 can also prepared with the copolymers B - T as defined in

Table 1. The overall properties of these formulations are similar.

Formulation Examples - Household Products Example 11: Hand Dishwasher Liquid

Copolymers of the present invention can be used to prepare household formulations such as a liquid dishwash. This product could also contain suspended beads of, for example, antibacterial actives, which would disperse in use.

The formulation shows good overall properties.

The formulation example 11 can also prepared with the copolymers B - T as defined in Table 1. The overall properties of these formulations are similar. Example 12: All-purpose cleaner

A further example of household product formulations is in household cleaners, where the copolymer is used at low levels to provide good spray characteristics and cling to vertical surfaces.

The formulation shows good overall properties.

The formulation example 12 can also prepared with the copolymers B - T as defined in table

1. The overall properties of these formulations are similar. Formulation Examples: Printing Paste Formulations

Example 13 : A typical print paste stock formulation thickened with Polymer of Example A

A typical print paste stock recipe would be :

The formulation shows good overall properties.

The formulation example 13 can also prepared with the copolymers B - T as defined in table

1. The overall properties of these formulations are similar.

Claims

1. A copolymer comprising

(1) at least two different monomers of formula (I),

R¹ H₂C=C-D- A_mB_nA_p- R (D

wherein

R' is hydrogen, C_rC₄alkyl Or -CH₂-COOH, A is propyleneoxy or butyleneoxy,

B is ethyleneoxy, O

I l

D is ^{~ C~}°^~ Or -NH- Or -CH₂- O -, n is zero or an integer from 1 to 100, m and p are each zero or an integer less than n and R is a hydrophobic group of 8 to 30 carbon atoms, and

(2) at least one acid functional monomer, and

(3) at least one hydrophobic monomers, and. (4) optionally at least one polyethylenically unsaturated monomer.

2. A copolymer according to claim 1 comprising

(1 ) at least two different monomers of formula (I), wherein

R' is hydrogen or methyl, A is propyleneoxy or butyleneoxy,

R is a hydrophobic group of 12 - 24 carbon atoms, and (2) methacrylic acid, and acrylic acid or acrylic acid, and (3) at least one hydrophobic monomers, which is vinyl or acrylic, and

(4) optionally, at least one polyethylenically unsaturated monomer such as 1 ,4-buta- nediol diacrylate, allyl methacrylate, pentaerythritol triacrylate and diallyl phthalate or diallyl phthalate.

3. A copolymer according to claim 1 comprising

(1) at least two different monomers selected from the group consisting of ceteareth-10 methacrylate, ceteareth-20 methacrylate, ceteareth-25 methacrylate, palmeth-10 methacrylate, palmeth-20 methacrylate, palmeth-25 methacrylate, beheneth-10 methacrylate, beheneth 20 methacrylate, beheneth 25 methacrylate, ceteth-10 methacrylate, ceteth-20 methacrylate, ceteth-25 methacrylate, laureth-25 methacrylate, steareth-10 methacrylate, steareth-20 methacrylate, steareth-25 methacrylate, steareth-50 acrylate, steareth-10 allyl ether and steareth-20 allyl ether, and

(2) methacrylic acid, and acrylic acid or acrylic acid, and (3) at least one hydrophobic monomers, which is selected from the group consisting of styrene and alkyl and halo-substituted styrenes or halo-substituted styrenes, (meth)acrylonitrile, vinyl alkanoates (especially the acetate), vinyl and vinylidene halides (especially the chloride), N-alkyl (meth)acrylamides, hydroxy alkyl and alkoxy alkyl (meth)acrylates and alkyl (meth)acrylates, and (4) optionally, at least one polyethylenically unsaturated monomer such as 1 ,4-buta- nediol diacrylate, allyl methacrylate, pentaerythritol triacrylate and diallyl phthalate or diallyl phthalate.

4. A copolymer according to claim 1 , wherein the copolymer has a solids contents of from 20 - 50% by weight and the copolymer dispersion has a weight average molecular weight of about 50,000 to several million

5. A copolymer according to claim 1 comprising

0.5 - 50 wt-%, based on the total weight of the polymer, of at least two different monomers of group (1 ).

6. A copolymer according to claim 1 comprising 20 - 70 wt-%, based on the total weight of the polymer, of at least one monomer of group (2).

7. A copolymer according to claim 1 comprising 10 - 70 wt-%, based on the total weight of the polymer, of at least one monomer of group (3).

8. A copolymer according to claim 1 comprising

50 - 2000 ppm, based on the total weight of the copolymer, of at least one monomer of group (4).

9. Use of the copolymer according to claim 1 as thickener in water and oil based or in oil based compositions.

10. Use according to claim 9, wherein the water and oil or the oil based compositions are personal care compositions.

11. Use according to claim 10, wherein the personal care are shampoos, bath and shower additives, haircare products, wax/fat compositions, liquid soaps, lotions, gels, cremes, deodorants, stick preparations, powders, ointments, cleaning solutions for the skin, moist cleaning sheets and oils.

12. Use according to claim 9, wherein the water and oil or the oil based compositions are printing pastes or paints.