WATER-SOLUBLE AND/OR WATER-SWELLABLE HYBRID POLYMER

Abstract

The present invention relates to a water-soluble and/or water-swellable hybrid polymer, to a composition comprising the hybrid polymer, as well as to the use of the hybrid polymer as a thickening agent, structurant, and/or rheology modifier.

Description

The present invention relates to a water-soluble and/or water-swellable hybrid polymer, to a composition comprising the hybrid polymer, as well as to the use of the hybrid polymer as a thickening agent, structurant, and/or rheology modifier.

Cleansing and caring for the skin, scalp, and hair is very important for general hygiene, e.g. for removal of unwanted materials such as sebum, oils, dirt, makeup, or for moisturization, colouring or protection. Many cosmetic products require a certain minimum viscosity in order to achieve ease of application to the substrate and/or retention on the substrate to be treated. Many cosmetic products comprise viscosity-increasing or rheology-influencing agents. These are often referred to as thickening agents, thickeners or gelling agents. Thickening agents used in cosmetics or personal hygiene products include viscous liquids such as polyethylene glycol, synthetic polymers such as polyacrylic acid and vegetable gums. In the 1990s, innovative thickeners based on 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and their salts were introduced into the market (EP0816403 and WO98/00094). In both homopolymer and copolymer form (e.g. Aristoflex® AVC from Clariant), such thickeners are superior in many respects to the corresponding polycarboxylates (Carbopols).

Many materials employed in cosmetics are traditionally derived from crude oil. Environmental, economic and sustainability questions are restricting the use of products derived from this limited resource: synthetic surfactants, for example, have been blamed for environmental incidents, particularly vis-à-vis aquatic problems in rivers and lakes. Therefore, there is a desire to identify more sustainable and biodegradeable, yet gentle and effective materials. Indeed, consumers are very interested in “natural” products including products with a high percentage of “natural” compounds and/or compounds that are derived from renewable materials. Consumers perceive compounds derived from natural materials to be gentler and more environmentally friendly.

Compounds derived from natural materials have various other benefits, including increased biodegradability and also more sustainable availability because they are not based on a limited resource. Compounds derived from plant-based resources are particularly useful since the source compound can simply be regrown. Consumers are also particularly comfortable with using compounds derived from well-known plants, especially those that are considered staple products.

US20040228809A1, for example, discloses an aerosol or pump foam product for treating hair, said product comprising a composition for foam production and said composition comprising inter alia at least one cationic cellulose derivative and at least one chitosan. Cellulose and chitosan are both natural polymers (or derivatives thereof) and they are also both polysaccharides. Indeed, chitosan is derived from chitin, which is what the shells of crustaceans are made from.

However, some natural polymers or derivatives thereof have some performance drawbacks, such as leaving residues and/or having poor solubility in an aqueous formulation environment. Attempts have been made to combine 2-acrylamido-2-methyl-1-propane sulfonic acid monomers with polysaccharides—for example: Srivastava et al, Modification of natural polymer via free radical graft copolymerisation of 2-acrylamido-2-methyl-1-propane sulfonic acid in aqueous media and study of swelling and metal ion sorption behaviour, Journal of Applied Polymer Science (2009), 114(3), 1426-1434; Srivastava et al, Graft copolymerisation of 2-acrylamido-2-methyl-1-propane sulphonic acid onto xanthan gum by ascorbic/bromate redox pair, PMSE Preprints (2004), 90, 698-699; Adhikary et al, Synthesis, characterization, and application of amylopectin-graft-poly(AM-co-AMPS), Journal of Applied Polymer Science (2012), 126(S1). However, these disclosures do not provide final polymers that have acceptable performance. Furthermore, the polymers provided are not in a form that is sufficiently useful.

WO2018/108663, WO2018/108664, WO2018/108665, and WO2018/108667 disclose water-soluble and/or water-swellable hybrid polymers comprising a polysaccharide polymer and a synthetic polymer.

There is an ongoing need for polymeric thickening agents that can provide the excellent performance of modern polymers with the increased biodegradability as well as the more sustainable availability of natural-based polymers.

The present invention relates to a water-soluble and/or water-swellable hybrid polymer comprising

• • (i) from 30 wt.-% to 99 wt.-% water-soluble and/or water-swellable polysaccharide polymer, wherein the polysaccharide polymer is an uncharged polysaccharide polymer;
  • (ii) from 1 wt.-% to 70 wt.-% synthetic polymer comprising
    • (a) from 90 mol-% to 99.9 mol-%, preferably 95 mol-% to 99.5 mol-% of repeating units according to Formula (1)

• • • • wherein
      • R¹ and R² are independently selected from H, methyl or ethyl;
      • A is a linear or branched C₁-C₁₂-alkyl group; and
      • Q⁺ is H⁺, NH₄⁺, an organic ammonium ion [NHR⁵R⁶R⁷]⁺ wherein R⁵, R⁶, and R⁷ independently of one another is hydrogen, a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched, mono- or poly-unsaturated alkenyl group having 2 to 22 carbon atoms, a C₆-C₂₂ alkylamidopropyl group, a linear mono-hydroxyalkyl group having 2 to 10 carbon atoms or a linear or branched dihydroxyalkyl group having 3 to 15 carbon atoms, and wherein at least one of the radicals R⁵, R⁶, and R⁷ is not hydrogen, or Q⁺ is Li⁺, Na⁺, K⁺, ½ Ca⁺⁺, ½ Mg⁺⁺, ½ Zn⁺⁺, ⅓ Al⁺⁺⁺ or combinations thereof;
    • (b) from 0.01 mol-% to 10 mol-%, preferably to 5 mol-%, more preferably to 3 mol-% of crosslinking or branching units, wherein the crosslinking or branching units result from the incorporation of a monomer comprising at least two olefinically unsaturated double bonds;
  • wherein the components (i) and (ii) are polymerised by radical precipitation polymerisation in a polar solvent.

The hybrid polymers of the present invention show excellent performance as thickening agents. Advantageously, they are biodegradable and sustainable. The hybrid polymers of the present invention have an increased renewable carbon index (RCI), as they are based on polysaccharide polymers.

Definitions and General

In this document, including in all embodiments of all aspects of the present invention, the following definitions apply unless specifically stated otherwise. All percentages are by weight (w/w) of the total composition. “wt.-%” means percentage by weight. All ratios are weight ratios. References to ‘parts’ is a ratio by weight. “QS” or “QSP” means sufficient quantity for 100% or for 100 g. +/− indicates the standard deviation. All ranges are inclusive and combinable. The number of significant digits conveys neither a limitation on the indicated amounts nor on the accuracy of the measurements. All measurements are understood to be made at 23° C. and at ambient conditions, where “ambient conditions” means at 1 atmosphere (atm) of pressure and at 50% relative humidity. “Relative humidity” refers to the ratio (stated as a percent) of the moisture content of air compared to the saturated moisture level at the same temperature and pressure. Relative humidity can be measured with a hygrometer, in particular with a probe hygrometer from VWR® International. Embodiments and aspects described herein may comprise or be combinable with elements, features or components of other embodiments and/or aspects despite not being expressly exemplified in combination, unless an incompatibility is stated.

“Molecular weight” or “M.Wt.” or “MW” and grammatical equivalents mean the weight average molecular weight unless otherwise specifically specified.

Number Average Molecular Weight: M_n

The number average molecular weight is the statistical average molecular weight of all the polymer chains in the sample, and is defined by:

$M_n=\frac{\sum N_i{M}_i}{\sum N_i}$

where M_i is the molecular weight of a chain and Ni is the number of chains of that molecular weight. M_n can be predicted by polymerisation mechanisms and is measured by methods that determine the number of molecules in a sample of a given weight; for example, colligative methods such as end-group assay. If M_n is quoted for a molecular weight distribution, there are equal numbers of molecules on either side of M_n in the distribution.

Weight Average Molecular Weight: MW

The weight average molecular weight is defined by:

$M_w=\frac{\sum N_i{M}_i^2}{\sum N_i{M}_i}$

Compared to M_n, M_W takes into account the molecular weight of a chain in determining contributions to the molecular weight average. The more massive the chain, the more the chain contributes to MW.

The polydispersity index PDI is used as a measure of the broadness of a molecular weight distribution of a polymer, and is defined by:

$\mathrm{PDI}=\frac{M_w}{M_n}$

The larger the PDI, the broader the molecular weight distribution. A monodisperse polymer where all the chain lengths are equal has an M_w/M_n=1.

“Viscosity” is measured at 25° C. in centipoise (cP) using an RV Brookfield viscometer with 10-90% torque at 20 RPM, unless otherwise stated.

“Water-soluble” refers to any material that is sufficiently soluble in water to form a clear solution to the naked eye at a concentration of 0.1% by weight of the material in water at 25° C. The term “water-insoluble” refers to any material that is not “water-soluble”.

“Substantially free from” or “substantially free of” means less than 1%, or less than 0.8%, or less than 0.5%, or less than 0.3%, or about 0%, by total weight of the composition or formulation.

“Hair” means mammalian keratin fibres including scalp hair, facial hair and body hair. It includes such hair still being attached to a living subject and also hair that has been removed therefrom such as hair swatches and hair on a doll/mannequin. In at least one embodiment, “hair” means human hair. “Hair shaft” or “hair fibre” means an individual hair strand and may be used interchangeably with the term “hair.”

“Cosmetically acceptable” means that the compositions, formulations or components described are suitable for use in contact with human keratinous tissue without undue toxicity, incompatibility, instability, allergic response, and the like. All compositions and formulations described herein which have the purpose of being directly applied to keratinous tissue are limited to those being cosmetically acceptable.

“Derivatives” includes but is not limited to amide, ether, ester, amino, carboxyl, acetyl, acid, salt and/or alcohol derivatives of a given compound. In at least one embodiment, “derivatives thereof” means the amide, ether, ester, amino, carboxyl, acetyl, acid, salt and/or alcohol derivatives thereof.

“Monomer” means a discrete, non-polymerised chemical moiety capable of undergoing polymerisation in the presence of an initiator or any suitable reaction that creates a macromolecule, e.g. such as radical polymerisation, polycondensation, polyaddition, anionic or cationic polymerisation, ring opening polymerisation or coordination insertion polymerisation. “Unit” means a monomer that has already been polymerised, i.e. is part of a polymer.

“Polymer” means a chemical formed from the polymerisation of two or more monomers. The term “polymer” shall include all materials made by the polymerisation of monomers as well as natural polymers. Polymers made from only one type of monomer are called homopolymers. Herein, a polymer comprises at least two monomers. Polymers made from two or more different types of monomers are called copolymers. The distribution of the different monomers can be random, alternating or block-wise (i.e. block copolymer). The term “polymer” used herein includes any type of polymer including homopolymers and copolymers.

“Kit” means a package comprising a plurality of components. “Kit” may be referred to as “kit-of-parts”. An example of a kit is, for example, a first composition and a separately packaged second composition and optionally application instructions.

Explanation of and Benefits Provided by the Invention

It has been found that hybrid polymers can be synthesised that combine the advantages of modern, synthetic polymers with those of natural or natural-derived polymers. Furthermore, such hybrid polymers can be synthesised in a one-step process, rather than a process requiring multiple synthesis and/or purification steps. Indeed, the hybrid polymers herein described are polymerised by radical precipitation polymerisation in a polar solvent. This polymerisation method results in the production of the hybrid polymer in a convenient form—powder form. Such solid form has the advantage that it is more economical to ship in view of the low weight and high concentration of active material (hybrid polymer), and lack of solvent. Furthermore, being in powder form reduces the risks associated with shipping and/or storing the product in liquid form—in terms of the product degrading in view of the molecules being able to move and react with other molecules such as the container walls and/or microbes being able to survive in the liquid and consume, grow in and/or contaminate the product.

The herein described one-step process providing powder form is achieved in view of the fact that precipitation polymerisation is used, i.e. the product of the reaction is produced as an insoluble precipitate—the product precipitates from the reaction mixture. The precipitant thus is no longer soluble in the reaction mixture and thus has no influence on the rheology and viscosity of the reaction mixture.

Conventional radical graft polymerisation results in a highly viscous gel. This has the disadvantage that once a certain viscosity level is reached, it is no longer possible to stir the reaction mixture in order to ensure even distribution of reactants and temperature. In most cases the reaction must be stopped relatively early and thus only a low yield of hybrid polymer can be produced. Furthermore, the reaction product is soluble and thus in solution with solvent. For example, it is not acceptable for formulators using the hybrid polymer in e.g. end-applications to supply them with a 50% solution of hybrid polymer. As a result, with conventional radical graft polymerisation, further processing steps are required in order to remove the solvent from the product and thus increase the concentration level of hybrid polymer versus solvent—indeed it is preferred to remove as much solvent as possible. During the drying process of highly viscous gels, insoluble surface/film-forming coatings and/or non-homogenous clumps may be formed that have a high residual water content. It is not possible to completely exclude and/or remove water from such hybrid polymer produced in this way.

The present invention relates to a water-soluble and/or water-swellable hybrid polymer.

Hybrid Polymer

The water-soluble and/or water-swellable hybrid polymer may herein simply be referred to as ‘hybrid polymer’, for brevity. The hybrid polymer comprises (i) from 30 wt.-% to 99 wt.-% polysaccharide polymer and (ii) from 1 wt.-% to 70 wt.-% synthetic polymer. Preferably, the hybrid polymer comprises (i) from 30 wt.-% to 95 wt.-% polysaccharide polymer and (ii) from 5 wt.-% to 70 wt.-% synthetic polymer.

In at least one embodiment, the hybrid polymer comprises

• • (i) from 30 wt.-% to 90 wt.-%, or from 30 wt.-% to 85 wt.-%, or from 30 wt.-% to 80 wt.-%, or from 30 wt.-% to 75 wt.-%, or from 30 wt.-% to 70 wt.-%, or from 35 wt.-% to 65 wt.-%, or from 40 wt.-% to 60 wt.-%, or from 45 wt.-% to 55 wt.-% polysaccharide polymer, by total weight of the hybrid polymer;
  • (ii) from 10 wt.-% to 70 wt.-%, or from 15 wt.-% to 70 wt.-%, or from 20 wt.-% to 70 wt.-%, or from 25 wt.-% to 70 wt.-%, or from 30 wt.-% to 70 wt.-%, or from 35 wt.-% to 65 wt.-%, or from 40 wt.-% to 60 wt.-%, or from 45 wt.-% to 55 wt.-% synthetic polymer, by total weight of the hybrid polymer.

In a preferred embodiment, the hybrid polymer comprises at least 40 wt.-%, preferably at least 50 wt.-%, more preferably at least 60 wt.-%, even more preferably at least 65 wt.-%, or at least 70 wt.-% polysaccharide polymer, by total weight of the hybrid polymer.

In a preferred embodiment, the hybrid polymer comprises at most 60 wt.-%, preferably at most 50 wt.-%, more preferably at most 40 wt.-%, more preferably at most 30 wt.-%, more preferably at most 25 wt.-%, even more preferably at most 20 wt.-%, even more preferably at most 15 wt.-%, particularly preferably at most 10 wt.-% synthetic polymer, by total weight of the hybrid polymer.

In a preferred embodiment, the hybrid polymer comprises

• • (i) from 40 wt.-% to 95 wt.-%, preferably from 50 wt.-% to 90 wt.-%, more preferably from 60 wt.-% to 85 wt.-%, more preferably from 60 wt.-% to 80 wt.-%, even more preferably from 60 wt.-% to 75 wt.-%, particularly preferably from 60 wt.-% to 70 wt.-%, or from 65 wt.-% to 75 wt.-% polysaccharide polymer, by total weight of the hybrid polymer;
  • (ii) from 5 wt.-% to 60 wt.-%, preferably from 10 wt.-% to 50 wt.-%, more preferably from 15 wt.-% to 40 wt.-%, more preferably from 20 wt.-% to 40 wt.-%, even more preferably from 25 wt.-% to 40 wt.-%, particularly preferably from 30 wt.-% to 40 wt.-%, or from 25 wt.-% to 35 wt.-% synthetic polymer, by total weight of the hybrid polymer.

In another preferred embodiment, the hybrid polymer comprises

• • (i) from 50 wt.-% to 95 wt.-%, preferably from 60 wt.-% to 95 wt.-%, more preferably from 70 wt.-% to 95 wt.-%, even more preferably from 80 wt.-% to 95 wt.-% polysaccharide polymer, by total weight of the hybrid polymer;
  • (ii) from 5 wt.-% to 50 wt.-%, preferably from 5 wt.-% to 40 wt.-%, more preferably from 5 wt.-% to 30 wt.-%, even more preferably from 5 wt.-% to 20 wt.-% synthetic polymer, by total weight of the hybrid polymer.

For example, the hybrid polymer has a weight ratio of polysaccharide polymer to synthetic polymer of 30:70; or 40:60; or 50:50; or 60:40; or 70:30; or 80:20; or 90:10; or 95:5; or 99:1; or any other ratio between 30:70 and 99:1.

In at least one embodiment, the hybrid polymer is substantially free of species that release ammonia when the hybrid polymer is used, e.g. employed in alkaline cosmetic compositions.

In at least one embodiment, the structure of the hybrid polymer is such that the polysaccharide polymer is a backbone onto which the synthetic polymer is grafted.

Synthetic Polymer

The hybrid polymer comprises a synthetic polymer. “Synthetic polymer” herein means any polymer that is not a naturally-occurring polymer nor a derivative of a naturally-occurring polymer.

The synthetic polymer comprises from 90 mol-% to 99.9 mol-% units (a) and from 0.01 mol-% to 10 mol-% units (b). Preferably, the synthetic polymer comprises from 95 mol-% to 99.9 mol-% units (a). Preferably, the synthetic polymer comprises from 0.01 mol-% to 5 mol-% units (b), more preferably from 0.01 mol-% to 3 mol-% units (b). In at least one embodiment, the synthetic polymer comprises units (a) and units (b) such that the sum thereof is at least 99 mol-%. In at least one embodiment, the synthetic polymer consists of units (a) and units (b).

Units (a)

The synthetic polymer comprises repeating units according to Formula (1)

• • wherein
  • R¹ and R² are independently selected from H, methyl or ethyl;
  • A is a linear or branched C₁-C₁₂-alkyl group; and
  • Q⁺ is H⁺, NH₄⁺, an organic ammonium ion conforming to [NHR⁵R⁶R⁷]⁺ wherein R⁵, R⁶, and R⁷ independently of one another is hydrogen, a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched, mono- or poly-unsaturated alkenyl group having 2 to 22 carbon atoms, a C₆-C₂₂ alkylamidopropyl group, a linear mono-hydroxyalkyl group having 2 to 10 carbon atoms or a linear or branched dihydroxyalkyl group having 3 to 15 carbon atoms, and wherein at least one of the radicals R⁵, R⁶, and R⁷ is not hydrogen, or Q⁺ is Li⁺, Na⁺, K⁺, ½ Ca⁺⁺, ½ Mg⁺⁺, ½ Zn⁺⁺, ⅓ Al⁺⁺⁺ or combinations thereof.

Preferably, Q⁺ is H⁺, NH₄⁺, Na⁺, or K⁺. More preferably, Q⁺ is H⁺, NH₄⁺, Na⁺. Particularly preferably, Q⁺ is NH₄⁺ or Na⁺.

In at least one embodiment, the synthetic polymer comprises at least one repeating unit (a) according to Formula (1) wherein R¹ and R² are independently selected from H, methyl or ethyl; A is a linear or branched C₁-C₁₂-alkyl group; and Q⁺ is H⁺, Li⁺, Na⁺, K⁺, ½ Ca⁺⁺, ½ Mg⁺⁺, ½ Zn⁺⁺, ⅓ Al⁺⁺⁺ or combinations thereof, preferably wherein Q⁺ is Na⁺.

In at least one embodiment, Q⁺ is NH₄⁺. In at least one embodiment, Q⁺ is selected from the group monoalkylammonium, dialkylammonium, trialkylammonium and/or tetraalkylammonium salts, in which the alkyl substituents of the amines may independently of one another be (C₁ to C₂₂)-alkyl radicals or (C₂ to C₁₀)-hydroxyalkyl radicals.

NH₄⁺ is preferred because it is more soluble in the favored solvent used in the polymer synthesis. Na⁺ is preferred because of reduced likelihood of unpreferred gases being produced during synthesis and also due to economic advantages.

In at least one embodiment, the synthetic polymer comprises at least one repeating unit according to Formula (1). In at least one embodiment, the synthetic polymer comprises two or more different repeating units according to Formula (1), such as repeating units according to Formula (1) having different Q⁺ counterions.

In at least one embodiment, the repeating units according to Formula (1) result from the incorporation of a monomer selected from the group consisting of acryloyldimethyltaurates, acryloyl-1,1-dimethyl-2-methyltaurates, acryloyltaurates, acryloyl-N-methyltaurates, and combinations thereof. Preferably the repeating units according to Formula (1) result from the incorporation of acryloyldimethyltaurate.

In at least one embodiment, the repeating units according to Formula (1) have a degree of neutralisation of between 0 mol-% and 100 mol-%. In at least one embodiment, the repeating units according to Formula (1) have a degree of neutralisation of from 50.0 to 100 mol-%, preferably from 80 mol-% to 100 mol-%, more preferably from 90.0 to 100 mol-%, even more preferably from 95.0 to 100 mol-%. Particular preference is given to a degree of neutralisation of more than 80 mol-%, more preferably more than 90 mol-%, even more preferably more than 95 mol-%.

In at least one embodiment, the synthetic polymer comprises from 95 mol-% to 99.9 mol-%, or at least 95.5 mol-%, or at least 96 mol-%, or at least 96.5 mol-%, or at least 97 mol-%, or at least 97.5 mol-%, or at least 98 mol-%, or at least 98.5 mol-%, or at least 99 mol-%, or at least 99.5 mol-% of repeating units according to Formula (1).

Units (b)

The synthetic polymer comprises crosslinking or branching units, wherein the crosslinking or branching units result from the incorporation of a monomer comprising at least two olefinically unsaturated double bonds. The synthetic polymer comprises from 0.01 mol-% to 10 mol-%, preferably from 0.01 mol-% to 5 mol-%, more preferably from 0.01 mol-% to 3 mol-% of crosslinking or branching units.

In at least one embodiment, the crosslinking or branching units comprise at least one oxygen, nitrogen, sulfur or phosphorus atom. In at least one embodiment, the crosslinking or branching units result from monomers having a molecular weight of less than 500 g/mol. In at least one embodiment, the units (b) are bifunctional or trifunctional crosslinking agents.

In at least one embodiment, the synthetic polymer comprises at least one crosslinking or branching unit. In at least one embodiment, the synthetic polymer comprises two or more different crosslinking or branching units.

In at least one embodiment, the crosslinking or branching units result from the incorporation of a monomer according to Formula (2):

• • wherein
  • R¹ is independently selected from H, methyl or ethyl; and
  • R² is a linear or branched alkylene group having 1 to 6 carbon atoms, or is a linear or branched, mono- or polyunsaturated alkenylene group having 2 to 6 carbon atoms.

In at least one embodiment, the crosslinking or branching units result from the incorporation of a monomer according to Formula (3)

• • wherein
  • R¹ is independently selected from H, methyl or ethyl; and
  • R² is H, or is a linear or branched alkyl group having 1 to 6 carbon atoms, or is a linear or branched, mono- or polyunsaturated alkylene group having 2 to 6 carbon atoms;
  • D, E, and F are independently methyleneoxy (—CH₂O—), ethyleneoxy (—CH₂—CH₂—O—), propyleneoxy (—CH(CH₃)—CH₂—O—), a linear or branched alkylene group having 1 to 6 carbon atoms, a linear or branched, singularly or multiply unsaturated alkenylene group having 2 to 6 carbon atoms, a linear mono-hydroxyalkylene group having 2 to 6 carbon atoms or a linear or branched dihydroxyalkylene group having 3 to 6 carbon atoms; and
  • o, p, and q each independently are an integer from 1 to 50.

In at least one embodiment, the crosslinking or branching units result from the incorporation of a crosslinker selected from the group consisting of methylenebisacrylamide; methylenebismethacrylamide; esters of unsaturated monocarboxylic and polycarboxylic acids with polyols, preferably di-acrylates and tri-acrylates and -methacrylates (e.g. glycerol propoxylate triacrylate [GPTA]), more preferably butanediol and ethylene glycol diacrylate and -methacrylate, trimethylolpropane triacrylate (TMPTA) and trimethylolpropane trimethacrylate (TMPTMA); allyl compounds, preferably allyl (meth)acrylate, triallyl cyanurate, diallyl maleate, polyallyl esters, tetraallyloxyethane, triallylamine, tetraallylethylenediamine; allyl esters of phosphoric acid; and/or vinylphosphonic acid derivatives. In at least one embodiment, the crosslinking or branching units result from the incorporation of trimethylolpropane triacrylate (TMPTA).

Particularly preferred as crosslinkers for the synthetic polymers of the invention are glycerol propoxylate triacrylate (GPTA), trimethylolpropane triacrylate (TMPTA), pentaerythritol diacrylate mono stearate (PEAS), hexanediol diacrylate (HDDA), and hexanediol dimethacrylate (HDDMA). Especially preferred is glycerol propoxylate triacrylate (GPTA).

Units (c)

In at least one embodiment, the synthetic polymer comprises at least one neutral repeating structural unit (c).

In at least one embodiment, the synthetic polymer comprises (c) from 1.0 mol-% to 9.99 mol-%, preferably from 2.0 mol-% to 9.99 mol-% of neutral repeating structural units. In at least one embodiment, the synthetic polymer comprises at least one neutral repeating structural unit selected from the group consisting of N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, vinylacetate, N,N-dimethylacrylamide, N-isopropylacrylamide, acrylamide, methylacrylate, behenylpolyethoxy-(25)-methacrylate, laurylpoly-ethoxy-(7)-methacrylate, cetylpolyethoxy-(10)-methacrylate, stearylpoly-ethoxy-(8)-methacrylate, methoxypoly-ethoxy-(12)-methacrylate, and combinations thereof.

Units (d)

In at least one embodiment, the synthetic polymer comprises at least one anionic repeating structural unit (d).

In at least one embodiment, the synthetic polymer comprises from 1.0 mol-% to 9.99 mol-%, preferably from 2.0 mol-% to 9.99 mol-% of anionic repeating structural units, wherein the anionic repeating structural units result from the incorporation of a monomer comprising at least one carboxylate anion, and wherein the anionic repeating structural units are different from units (a).

In at least one embodiment, the anionic repeating structural unit results from the incorporation of monomers according to formula (A):

• • wherein
  • R¹ and R³ are H, methyl or ethyl, or C(O)O⁻ Z+;
  • X, Y are selected from a covalent bond, O, CH₂, C(O)O, OC(O), C(O)NR³ or NR³C(O);
  • M are selected from a covalent bond, —[C(O)O—CH₂—CH₂]_n—, a linear or branched alkylene group with 1 to 6 carbon atoms, a linear or branched, mono- or polyunsaturated alkenylene group with 2 to 6 carbon atoms, a linear mono-hydroxyalkylene group with 2 to 6 carbon atoms or a linear or branched di-hydroxyalkylene group with 3 to 6 carbon atoms;
  • n is an integer from 1-5 and
  • Z⁺ is H⁺, NH₄⁺, an organic ammonium ion [HNR⁵R⁶R⁷]⁺
    • wherein R⁵, R⁶ and R⁷ are independently hydrogen, a linear or branched alkyl group with 1 to 22 carbon atoms, a linear or branched, mono- or polyunsaturated alkenyl group with 2 to 22 carbon atoms, a C₆ to C₂₂ alkylamidopropyl group, a linear mono-hydroxyalkyl group with 2 to 10 carbon atoms or a linear or branched di-hydroxyalkyl group with 3 to 10 carbon atoms, and wherein at least one of R⁵, R⁶ and R⁷ is not hydrogen, or Z⁺ is Li⁺, Na⁺, K⁺, ½ Ca⁺⁺, ½ Mg⁺⁺, ½ Zn⁺⁺, ⅓ Al⁺⁺⁺ or combinations thereof. In at least one embodiment, Z⁺ is H⁺, NH₄⁺, Li⁺, Na⁺, K⁺, ½ Ca⁺⁺, ½ Mg⁺⁺, ½ Zn⁺⁺, or ⅓ Al⁺⁺⁺ preferably H⁺, NH₄⁺, Li⁺, Na⁺ or K⁺.

In at least one embodiment, the anionic repeating structural unit results from the incorporation of monomers according to formula (A) wherein X is a covalent bond or is CH₂.

In at least one embodiment, the anionic repeating structural unit results from the incorporation of monomers according to formula (A) wherein Y is a covalent bond, CH₂, C(O)O, or C(O)NR³. In at least one embodiment, the anionic repeating structural unit results from the incorporation of monomers according to formula (A) wherein M is a covalent bond, —[C(O)O—CH₂—CH₂]_n—, a linear or branched alkylene group with 1 to 6 carbon atoms. In at least one embodiment, the anionic repeating structural unit results from the incorporation of monomers according to formula (A) wherein R¹ is H, methyl or ethyl; X is a covalent bond or is CH₂; Y is a covalent bond, CH₂, C(O)O, or C(O)NR³; R³ is H, methyl or ethyl; M is a covalent bond,

• • —[C(O)O—CH₂—CH₂]_n—, a linear or branched alkylene group with 1 to 6 carbon atoms; Z⁺ is H⁺, NH₄⁺, Li⁺, Na⁺, K⁺, ½ Ca⁺⁺, ½ Mg⁺⁺, ½ Zn⁺⁺, or ⅓ Al⁺⁺⁺ or combinations thereof.

In at least one embodiment, the synthetic polymer comprises at least one anionic repeating structural unit selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, carboxyethylacrylate, carboxyethylacrylate oligomers, 2-propylacrylic acid 2-ethylacrylic acid, and their respective alkali or alkaline earth metal salts.

Optional Units (e)

In at least one embodiment, the synthetic polymer comprises at least one optional unit (e). In at least one embodiment, the optional unit results from the incorporation of a monomer selected from the group consisting of unsaturated carboxylic acids and their anhydrides and salts, and also their esters with aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic alcohols having a carbon number of from 1 to 22. In at least one embodiment, the optional unit results from the incorporation of at least one monomer selected from the group consisting of functionalised (meth)acrylic acid esters, acrylic or methacrylic acid amides, polyglycol acrylic or methacrylic acid esters, polyglycol acrylic or methacrylic acid amides, dipropyleneglycolacrylic or methacrylic acid esters, dipropylenglycolacrylic or methacrylic acid amides, ethoxylated fatty alcohol acrylates or -methacrylates, propoxyl ated fatty alcohol acrylates or linear or cyclic N-vinylamides or N-methylvinyl amides.

In at least one embodiment, the optional unit results from the incorporation of a monomer selected from the group consisting of N-vinylformamide, N-vinylacetamide, N methyl-N-vinylformamide, N-methyl-N-vinylacetamide, N-vinyl-2-pyrrolidone (NVP), N vinylcaprolactam, vinylacetate, methylvinylether, ethylvinylether, methylallylether, ethylmethallylether, styrol, acetoxystyrol, methylmethallylether, ethylallylether, tert-butylacrylamide, N,N-diethylacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-dipropylacrylamide, N-isopropylacrylamide, N-propylacrylamide, acrylamide, methacrylamide, methylacrylate, methymethylacrylate, tert-butylacrylate, tert-butylmethacrylate, n-butylacrylate, n-butylmethacrylate, laurylacrylate, laurylmethacrylate, behenylacrylate, behenylmethacrylate, cetylacrylate, cetylmethacrylate, stearylacrylate, stearylmethacrylate, tridecylacrylate, tridecylmethacrylate, polyethoxy-(5)-methacrylate, polyethoxy-(5)-acrylate, polyethoxy-(10)-methacrylate, polyethoxy-(10)-acrylate, behenylpolyethoxy-(7)-methacrylate, behenylpolyethoxy-(7)-acrylate, behenylpolyethoxy-(8)-methacrylate, behenylpoly-ethoxy-(8)-acrylate, behenylpolyethoxy-(12)-methacrylate, behenylpoly-ethoxy-(12)-acrylate, behenylpolyethoxy-(16)-methacrylate, behenylpolyethoxy-(16)-acrylate, behenylpolyethoxy-(25)-methacrylate, behenylpolyethoxy-(25)-acrylate, laurylpoly-ethoxy-(7)-methacrylate, laurylpolyethoxy-(7)-acrylate, laurylpolyethoxy-(8)-methacrylate, laurylpolyethoxy-(8)-acrylate, laurylpolyethoxy-(12)-methacrylate, laurylpolyethoxy-(12)-acrylate, laurylpolyethoxy-(16)-methacrylate, laurylpolyethoxy-(16)-acrylate, laurylpolyethoxy-(22)-methacrylate, laurylpolyethoxy-(22)-acrylate, laurylpolyethoxy-(23)-methacrylate, laurylpolyethoxy-(23)-acrylate, cetylpolyethoxy-(2)-methacrylate, cetylpolyethoxy-(2)-acrylate, cetylpolyethoxy-(7)-methacrylate, cetylpolyethoxy-(7)-acrylate, cetylpolyethoxy-(10)-methacrylate, cetylpolyethoxy-(10)-acrylate, cetylpolyethoxy-(12)-methacrylate, cetylpolyethoxy-(12)-acrylate cetylpoly-ethoxy-(16)-methacrylate, cetylpolyethoxy-(16)-acrylate cetylpolyethoxy-(20)-methacrylate, cetylpolyethoxy-(20)-acrylate, cetylpolyethoxy-(25)-methacrylate, cetylpolyethoxy-(25)-acrylate, cetylpolyethoxy-(25)-methacrylate, cetylpolyethoxy-(25)-acrylate, stearylpolyethoxy-(7)-methacrylate, stearylpolyethoxy-(7)-acrylate, stearylpoly-ethoxy-(8)-methacrylate, stearylpolyethoxy-(8)-acrylate, stearylpolyethoxy-(12)-methacrylate, stearylpolyethoxy-(12)-acrylate, stearylpolyethoxy-(16)-methacrylate, stearylpolyethoxy-(16)-acrylate, stearylpolyethoxy-(22)-methacrylate, stearylpoly-ethoxy-(22)-acrylate, stearylpolyethoxy-(23)-methacrylate, stearylpolyethoxy-(23)-acrylate, stearylpolyethoxy-(25)-methacrylate, stearylpolyethoxy-(25)-acrylate, tridecylpolyethoxy-(7)-methacrylate, tridecylpolyethoxy-(7)-acrylate, tridecylpolythoxy-(10)-methacrylate, tridecylpolyethoxy-(10)-acrylate, tridecylpolyethoxy-(12)-methacrylate, tridecylpolyethoxy-(12)-acrylate, tridecylpolyethoxy-(16)-methacrylate, tridecylpolyethoxy-(16)-acrylate, tridecylpolyethoxy-(22)-methacrylate, tridecylpoly-ethoxy-(22)-acrylate, tridecylpolyethoxy-(23)-methacrylate, tridecylpolyethoxy-(23)-acrylate, tridecylpoly-ethoxy-(25)-methacrylate, tridecylpolyethoxy-(25)-acrylate, methoxypolyethoxy-(7)-methacrylate, methoxy-polyethoxy-(7)-acrylate, methoxypoly-ethoxy-(12)-methacrylate, methoxypolyethoxy-(12)-acrylate, methoxypolyethoxy-(16)-methacrylate, methoxypolyethoxy-(16)-acrylate, methoxypolyethoxy-(25)-methacrylate, methoxy-polyethoxy-(25)-acrylate, acrylic acid, ammonium acrylate, sodium acrylate, potassium acrylate, lithium acrylate, zinc acrylate, calcium acrylate, magnesium acrylate, zirconium acrylate, methacrylic acid, ammonium methacrylate, sodium methacrylate, potassium methacrylate, lithium methacrylate, calcium methacrylate, magnesium methacrylatee, zirconium methacrylate, zinc methacrylate, 2-carboxyethylacrylate, ammonium 2-carboxyethylacrylate, sodium 2-carboxyethylacrylate, potassium 2-carboxyethylacrylate, lithium 2 carboxyethylacrylate, zinc 2-carboxyethylacrylate, calcium 2-carboxyethylacrylate, magnesium 2-carboxyethylacrylate, zirconium 2-carboxyethylacrylate, 2-carboxyethylacrylate-oligomere, ammonium 2-carboxyethylacrylate-oligomers, sodium 2-carboxyethylacrylate-oligomers, potassium 2-carboxyethylacrylate-oligomers, lithium 2 carboxyethylacrylate-oligomers, zinc 2-carboxyethylacrylate-oligomers, calcium 2-carboxyethylacrylate-oligomers, magnesium 2-carboxyethylacrylate-oligomers, zirconium 2-carboxyethylacrylate-oligomers, itaconic acid, sodium itaconate, potassium itaconate, lithium itaconate, calcium itaconate, magnesium itaconate, zirconium itaconate, zinc itaconate,2-ethylacryl acid, ammonium 2-ethylacrylate, sodium 2-ethylacrylate, potassium 2-ethylacrylate, lithium 2-ethylacrylate, calcium 2-ethylacrylate, magnesium 2-ethylacrylate, zirconium 2-ethylacrylate, zinc 2-ethylacrylate, 2-propylacryl acid, ammonium 2-propylacrylate, sodium 2-propylacrylate, potassium 2-propylacrylate, lithium 2-propylacrylate, calcium 2-propylacrylate, magnesium 2-propylacrylate, magnesium 2-propylacrylate, zirconium 2-propylacrylate, zinc 2-propylacrylate, and combinations thereof.

In a preferred embodiment, the optional unit results from the incorporation of a monomer selected from the group consisting of N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylacetamide, N-vinyl-2-pyrrolidone (NVP), N,N-diethylacrylamide, acrylamide, methacrylamide, methylacrylate, methylmethylacrylate, tert-butylacrylate, acrylic acid, methacrylic acid, 2-carboxyethylacrylate, 2-carboxyethylacrylate oligomers, itaconic acid, and combinations thereof.

In at least one embodiment, the optional unit results from the incorporation of a monomer selected from the group consisting of acrylic acid, methacrylic acid, styrenesulfonic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, and senecic acid. In at least one embodiment, the optional unit results from monomers selected from the group consisting of open-chain N-vinyl amides, preferably N-vinylformamide (VIFA), N-vinylmethylformamide, N-vinylmethylacetamide (VIMA) and N-vinylacetamides; cyclic N-vinyl amides (N-vinyl lactams) with a ring size of 3 to 9, preferably N-vinylpyrrolidones (NVP) and N-vinylcaprolactam; amides of acrylic and methacrylic acid, preferably acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, and N,N-diisopropylacrylamide; alkoxylated acrylamides and methacrylamides, preferably hydroxyethyl methacrylate, hydroxymethylmethacrylamide; hydroxyethylmethacryl amide, hydroxypropylmethacrylamide, and mono[2-(methacryloyloxy)ethyl]succinate; N,N-dimethylaminomethacrylate; diethylaminomethylmethacrylate; acrylamideo- and methacrylamideoglycolic acid; 2- and 4-vinylpyridine; vinyl acetate; glycidyl methacrylate; styrene; acrylonitrile; vinyl chloride; stearyl acrylate; lauryl methacrylate; vinylidene chloride; tetrafluoroethylene; and combinations thereof.

Polysaccharide Polymer

The hybrid polymer comprises polysaccharide polymer. The polysaccharide polymer is water-soluble and/or water-swellable. In at least one embodiment, the polysaccharide polymer absorbs water and/or forms a gel or gum when immersed in water. In at least one embodiment, the polysaccharide polymer is a natural gum or mucilage. Natural gums are useful because they are generally soluble in water due to the presence of an excessive number of —OH moieties which form hydrogen bonds with water molecules. In at least one embodiment, the polysaccharide polymer is a natural gum derived from a plant.

The polysaccharide polymer is an uncharged polysaccharide polymer. The term “uncharged polysaccharide polymer” is well known to a person skilled in the art.

In at least one embodiment, the polysaccharide polymer is selected from the group consisting of tara gum, guar gum, locust bean gum, cassia tora gum, fenugreek gum, cellulose, starch, glucomannan, Tamarindus Indica Seed Gum, sclerotium gum, dextran, dextrin, and combinations thereof, preferably from the group consisting of tara gum, guar gum, glucomannan, and combinations thereof.

In at least one embodiment, the polysaccharide polymer is selected from the group consisting of tara gum, guar gum, locust bean gum, cassia tora gum, fenugreek gum, cellulose, starch, glucomannan, and combinations thereof, preferably from the group consisting of tara gum, guar gum, glucomannan, and combinations thereof.

In at least one embodiment, the polysaccharide polymer is selected from the group consisting of tara gum, guar gum, locust bean gum, cassia tora gum, fenugreek gum, cellulose, starch, and combinations thereof, preferably from the group consisting of tara gum, guar gum, and combinations thereof.

In at least one embodiment, the polysaccharide polymer comprises mannose and/or galactose units, preferably the polysaccharide polymer is a galactomannan. Galactomannans are polysaccharides consisting of a mannose backbone with galactose side groups (more specifically, a (1-4)-linked beta-D-mannopyranose backbone with branchpoints from their 6-positions linked to alpha-D-galactose, i.e. 1-6-linked alpha-D-galactopyranose).

In at least one embodiment, the polysaccharide polymer is selected from the group consisting of tara gum, guar gum, locust bean gum, cassia tora gum, fenugreek gum, glucomannan, Tamarindus Indica Seed Gum, sclerotium gum, dextran, dextrin, and combinations thereof, preferably from the group consisting of tara gum, guar gum, glucomannan, and combinations thereof.

In at least one embodiment, the polysaccharide polymer is selected from the group consisting of tara gum, guar gum, locust bean gum, cassia tora gum, fenugreek gum, glucomannan, and combinations thereof, preferably from the group consisting of tara gum, guar gum, glucomannan, and combinations thereof.

In at least one embodiment, the polysaccharide polymer is selected from the group consisting of tara gum, guar gum, locust bean gum, cassia tora gum, fenugreek gum, and combinations thereof, preferably from the group consisting of tara gum, guar gum, and combinations thereof.

In a particularly preferred embodiment, the polysaccharide polymer comprises tara gum, preferably is tara gum.

In a particularly preferred embodiment, the polysaccharide polymer comprises guar gum, preferably is guar gum.

In a particularly preferred embodiment, the polysaccharide polymer comprises glucomannan, preferably is glucomannan.

Purified versions of the above polysaccharides may also be used.

Chemically modified versions of the above polysaccharides may also be used.

“Modified polysaccharide” means that the polysaccharide polymer was subjected to one or more suitable physical, enzymatic or chemical process(es) to be converted into a modified form of the polysaccharide polymer. Examples of such processes include:

• • acidic treatment of polysaccharide polymer by the reaction with acids (e.g. hydrochloric acid, phosphoric acid, or sulphuric acid)
  • alkaline treatment of polysaccharide polymer by the reaction with bases (e.g. sodium hydroxide or potassium hydroxide)
  • bleached polysaccharide polymer by the reaction with peracetic acid, hydrogene peroxide, sodium hypochlorite, sulfur dioxide, sulphites, potassium permanganate or ammonium persulfate
  • enzymatic modified form of the polysaccharide polymer by the treatment with enzymes
  • oxidised polysaccharide polymer by oxidation (e.g. with sodium hypochlorite)
  • acetylated polysaccharide polymer by esterification with e.g. anhydrides
  • hydroxypropyl polysaccharide by reaction with propylene oxide
  • hydroxyethyl polysaccharide by reaction with ethylene oxide

In at least one embodiment, the polysaccharide polymer is a guar gum or a guar gum derivative. In at least one embodiment, the guar gum derivative is selected from the group consisting of hydroxypropyl guar gum, carboxymethyl guar gum, carboxymethyl hydroxypropyl guar gum, and quaternary ammonium guar gum.

Fenugreek gum is, as its name suggests, derived from fenugreek and is a galactomannan where the ratio of mannose:galactose is approximately 1:1. Tara gum is a galactomannan and comes from the small tree or thorny shrub having the latin name Caesalpinia spinosa. The ratio of mannose:galactose in tara gum is approximately 3:1. Locust bean gum is a galactomannan vegetable gum extracted from the seeds of the carob tree. Locust bean gum consists mainly of high-molecular-weight hydrocolloidal polysaccharides composed of galactose and mannose units combined through glycosidic linkages. Guar gum is a polysaccharide composed of the sugars galactose and mannose: the backbone is a linear chain of β 1,4-linked mannose residues to which galactose residues are 1,6-linked at every second mannose, forming short side-branches. Guar gum is primarily the ground endosperm of guar beans. Glucomannan is a polysaccharide composed of the sugars glucose and mannose.

In at least one embodiment, the polysaccharide polymer is substantially free of starch, amylose, amylopectin, glycogen, cellulose, and derivatives thereof. Cellulose derivatives include for example cellulose ethers, carboxymethylcellulose, hydroxyethylcellulose. Such polysaccharides are either neither water-soluble nor water-swellable, and/or result in hybrid polymers that are not desirable from a performance perspective.

In a preferred embodiment, a 1% gel of the hybrid polymer of the invention in deionized water has a mesh size of from 10 nm to 80 nm, preferably from 10 nm to 50 nm, more preferably from 15 nm to 50 nm, even more preferably from 20 nm to 50 nm, particularly preferably from 30 nm to 40 nm. In a preferred embodiment, a 1% gel of the hybrid polymer of the invention in deionized water has a mesh size of from 10 nm to 40 nm, preferably from 15 nm to 40 nm.

The % as used in this context refers to wt.-%.

A mesh size within these ranges is advantageous because it forms a stable polymer gel.

The mesh size as used herein is calculated as follows:

$\mathrm{mesh}\mathrm{size}\left[\mathrm{nm}\right]=\sqrt[3]{\mathrm{kT}/G_{\mathrm{initial}}^{\prime }}$

• • wherein:
  • G′_initial is the network stability G′_initial;
  • k is the Boltzmann constant; and
  • T is the measurement temperature:

	k	Boltzmann constant	1.380649E−23	J/K
	T	Measurement temperature	293.15	K.
	G′initial	Network stability G′initial		Pa

The network stability G′_intial as used herein is determined using a hybrid rheometer. More specifically, a DHR-3 of TA Instruments is used. DHR refers to Discovery Hybrid Rheometer.

In a preferred embodiment, a 1% gel of the hybrid polymer of the invention in deionized water has a tan delta (elasticity loss factor) of from 0.2 to 0.9, preferably from 0.3 to 0.7, more preferably from 0.3 to 0.6, particularly preferably from 0.4 to 0.6. The % as used in this context refers to wt.-%.

A tan delta within these ranges is advantageous because it shows a viscoelastic behavior.

The tan delta as used herein is determined using a hybrid rheometer. More specifically, a DHR-3 of TA Instruments is used. DHR refers to Discovery Hybrid Rheometer.

In a preferred embodiment, a 1% gel of the hybrid polymer of the invention in deionized water has a yield point of from 1 Pa to 15 Pa, preferably from 2 Pa to 12 Pa, more preferably from 2 Pa to 9 Pa, even more preferably from 2 Pa to 8 Pa, even more preferably from 3 Pa to 7 Pa, particularly preferably from 3 Pa to 6 Pa. The % as used in this context refers to wt.-%.

A yield point within these ranges is advantageous because it fits to the desired rheology-modifying properties.

The yield point as used herein is determined using a hybrid rheometer. More specifically, a DHR-3 of TA Instruments is used. DHR refers to Discovery Hybrid Rheometer.

In a preferred embodiment, a 1% gel of the hybrid polymer of the invention in deionized water has a mesh size as described above or a tan delta as described above or a yield point as described above.

In a preferred embodiment, a 1% gel of the hybrid polymer of the invention in deionized water has a mesh size as described above or a tan delta as described above.

In a preferred embodiment, a 1% gel of the hybrid polymer of the invention in deionized water has a mesh size as described above or a yield point as described above.

In a preferred embodiment, a 1% gel of the hybrid polymer of the invention in deionized water has a tan delta as described above or a yield point as described above.

In a preferred embodiment, a 1% gel of the hybrid polymer of the invention in deionized water has a mesh size as described above and a tan delta as described above.

In a preferred embodiment, a 1% gel of the hybrid polymer of the invention in deionized water has a mesh size as described above and a yield point as described above.

In a preferred embodiment, a 1% gel of the hybrid polymer of the invention in deionized water has a tan delta as described above and a yield point as described above.

In a particularly preferred embodiment, a 1% gel of the hybrid polymer of the invention in deionized water has a mesh size as described above and a tan delta as described above and a yield point as described above.

In a preferred embodiment, the hybrid polymer of the invention has a biodegradability of at least 30%, preferably at least 60%, particularly preferably at least 80%, determined according to OECD Method 301 B.

In a preferred embodiment, the hybrid polymer of the invention is readily biodegradable, which means that the hybrid polymer has a biodegradability of at least 60%, determined according to OECD Method 301 B.

In another embodiment, the hybrid polymer of the invention is inherently biodegradable (OECD 302).

Example embodiments of hybrid polymers where the polysaccharide polymer is glucomannan are given in the following Table:

		Synthetic
			Monomer
Example	Glucomannan	Polymer	[ATBS/	Crosslinker
embodiment	[wt.-%]	[wt.-%]	mol-%]	[Name/mol-%]
E1	69.5	30.5	98.7	TMPTA	1.3
E2	69.5	30.5	99.1	GPTA	0.9
E3	80	20	98.1	TMPTA	1.9
E4	80	20	98.7	GPTA	1.3
E5	90	10	96.1	TMPTA	3.9

Such hybrid polymers can, for example, be prepared according to the methods described in the Examples section.

Polymerisation

The hybrid polymer components (i) and (ii) are polymerised by radical precipitation polymerisation in a solvent. Radical precipitation polymerisation has the advantage over other synthesis methods in that it results in a more useful level of polymer branching. In at least one embodiment, the polymerisation is grafting radical precipitation polymerisation.

In at least one embodiment, the radical precipitation polymerisation is carried out in a polar solvent mixture comprising:

• • I) water and
  • II) a further compound.

In at least one embodiment the compound II) is polar and organic.

In at least one embodiment the compound II) is selected from polar alcohols and ketones. In at least one embodiment the compound II) is one or more polar alcohols and one or more ketones.

In a preferred embodiment, the compound II) is selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, dimethyl ketone, diethyl ketone, pentan-2-one, butanone, tetrahydro pyrane, tetrahydro furane, 2-methyl-tetrahydro furane, 1,3-dioxane, 1,4-dioxane, preferably 2-propanol, 2-methyl-2-propanol, dimethyl ketone, tetrahydro furane, 2-methyl-tetrahydro furane, more preferably 2-methyl-2-propanol and dimethyl ketone. In a particularly preferred embodiment, the compound II) is 2-methyl-2-propanol.

In a preferred embodiment, the solvent mixture contains from 0.5 to 10 wt.-%, preferably from 1 to 8 wt.-% and more preferably from 2 to 5 wt.-% water.

In a preferred embodiment, the solvent mixture contains from 90 to 99.5 wt.-%, preferably from 92 to 99 wt.-% and more preferably from 95 to 98 wt.-% 2-methyl-2-propanol.

In a preferred embodiment, the solvent mixture contains water and 2-methyl-2-propanol. In a preferred embodiment, the solvent mixture contains from 0.5 to 10 wt.-%, preferably from 1 to 8 wt.-% and more preferably from 2 to 5 wt.-% water, and from 90 to 99.5 wt.-%, preferably from 92 to 99 wt.-% and more preferably from 95 to 98 wt.-% 2-methyl-2-propanol.

In a preferred embodiment, the solvent mixture contains from 0.5 to 10 wt.-% water, from 1 to 98.5 wt.-% 2-methyl-2-propanol and from 1 to 98.5 wt.-% dimethyl ketone, preferably from 0.5 to 7.5 wt.-% water, from 5 to 94.5 wt.-% 2-methyl-2-propanol and from 5 to 94.5 wt.-% dimethyl ketone.

In at least one embodiment, the monomers resulting in units (a) and/or (b) are neutralised with a base prior to the polymerisation, and/or the hybrid polymer after polymerisation is neutralised with a base. In at least one embodiment, the base is selected from bases comprising an ion selected the group consisting of Li⁺, Na⁺, K⁺, Ca⁺⁺, Mg⁺⁺, Zn⁺⁺, Al⁺⁺⁺ and combinations thereof; preferably wherein the base is selected from hydroxides, carbonates and hydrogen carbonates comprising an ion selected the group consisting of Li⁺, Na⁺, K⁺, Ca⁺⁺, Mg⁺⁺, Zn⁺⁺, Al⁺⁺⁺ and combinations thereof.

The present invention also relates to a composition. The composition comprises:

• • (i) a hybrid polymer according to the present invention;
  • (ii) a carrier.

In a preferred embodiment, the composition comprises from 0.1 to 10 wt.-%, preferably from 0.1 to 2.5 wt.-%, more preferably from 0.1 to 1.0 wt.-%, also more preferably from 0.5 to 2.5 wt.-%, even more preferably from 0.5 to 1.0 wt.-% of the hybrid polymer according to the present invention, by total weight of the composition.

In at least one embodiment, the composition is a cosmetic composition. In at least one embodiment, the cosmetic composition is selected from the group consisting of shampoo, body wash, facial cleanser, cleansing masks, bubble bath, intimate wash, bath oil, cleansing milk, micellar water, make-up remover, cleansing wipes, perfume, liquid soaps, shaving soaps, shaving foams, cleansing foams, day creams, night creams, anti-ageing creams, body milks, body lotions, face serums, eye creams, sunscreen sprays, sun care milks, sun care creams, sun care gels, after-shave lotions, pre-shaving creams, depilatory creams, whitening creams, self-tanning creams, anti-acne gels, mascaras, foundations, primers, concealers, bb creams, eyeliners, highlighters, lip stains, hand sanitizers, nail varnish removers, conditioners, hair styling gels, hair styling creams, hair shine serums, scalp treatments, hair colourants, split end fluids, deodorants, antiperspirants, baby creams, insect repellent sprays, hand creams, foot creams, exfoliators, scrubs, and cellulite treatments.

Carrier

A carrier is useful for providing the compounds used in present invention in liquid form. In at least one embodiment, the carrier is a cosmetically acceptable carrier. In at least one embodiment, the composition comprises at least 10 wt.-% water. Water is useful for economic reasons but also because it is highly cosmetically acceptable. Optionally the composition comprises water-miscible or water-soluble solvents such as lower alkyl alcohols. In at least one embodiment, the composition comprises C₁-C₅ alkyl monohydric alcohols, preferably C₂-C₃ alkyl alcohols. The alcohols which may be present are in particular lower monohydric or polyhydric alcohols having 1 to 4 carbon atoms customarily used for cosmetic purposes, such as preferably ethanol and isopropanol.

In at least one embodiment, the composition comprises a water-soluble polyhydric alcohol. In at least one embodiment, the water-soluble polyhydric alcohols are polyhydric alcohols having two or more hydroxyl groups in the molecule. In at least one embodiment, the water-soluble polyhydric alcohol is selected from the group consisting of: dihydric alcohols such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol; trihydric alcohols such as glycerine, trimethylol propane, 1,2,6-hexanetriol and the like; tetrahydric alcohols such as penthaerythritol; pentahydric alcohols such as xylytol, etc.; hexahydric alcohols such as sorbitol, mannitol; polyhydric alcohol polymers such as diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerine, polyethylene glycol, triglycerine, tetraglycerine, polyglycerine; dihydric alcohol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether; dihydric alcohol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether; dihydric alcohol ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diadipate, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate; glycerine monoalkyl ethers such as xyl alcohol, selachyl alcohol, batyl alcohol; sugar alcohols such as sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, starch sugar, maltose, xylytose, starch sugar reduced alcohol, glysolid, tetrahydrofurfuryl alcohol, POE tetrahydrofurfuryl alcohol, POP butyl ether, POP POE butyl ether, tripolyoxypropylene glycerine ether, POP glycerine ether, POP glycerine ether phosphoric acid, POP POE pentanerythritol ether, and mixtures thereof.

In a preferred embodiment, the composition comprises a cosmetically acceptable carrier selected from the group consisting of water, glycols, ethanol, and combinations thereof.

In a preferred embodiment, the composition comprises an aqueous, alcoholic or aqueous-alcoholic carrier, and wherein the aqueous, alcoholic or aqueous-alcoholic carrier comprises water, ethanol, propanol, isopropanol, 1,2-propylene glycol, 1,3-propylene glycol, isobutanol, butanol, butyl glycol, butyl diglycol, glycerol, or a mixture thereof; preferably wherein the aqueous, alcoholic or aqueous-alcoholic solvent comprises water, ethanol, propanol, isopropanol, 1,2-propylene glycol, 1,3-propylene glycol, glycerol, or mixtures thereof; more preferably wherein the aqueous, alcoholic or aqueous-alcoholic carrier comprises water, isopropanol, 1,2-propylene glycol, 1,3-propylene glycol, or mixtures thereof; even more preferably wherein the aqueous, alcoholic or aqueous-alcoholic carrier consists of water or consists of a mixture of water and an alcohol wherein the alcohol is selected from the group consisting of isopropanol, 1,2-propylene glycol and 1,3-propylene glycol.

Natural carriers can also be used. In at least one embodiment, the composition comprises a carrier selected from the group consisting of plant oil, honey, plant-derived sugar compositions, and mixtures thereof.

Viscosity

In at least one embodiment, the composition has a viscosity of from 0 mPas to 200,000 mPas, or from 1 mPas to 200,000 mPas, or from 50,000 mPas to 200,000 mPas, or from 50,000 mPas to 100,000 mPas. In at least one embodiment, the composition has a viscosity of from 0.1 mPas to 50,000 mPas, or from 1 mPas to 20,000 mPas, or from 1 mPas to 10,000 mPas, or from 1 mPas to 5,000 mPas, or from 5 mPas to 3,500 mPas. The viscosity measurement conditions are defined in the definitions section above. Viscosity may be important for anti-drip reasons. Dripping can be inconvenient for the user. Furthermore, more viscous compositions can be useful for measured dispensing. In at least one embodiment, the composition has a viscosity of from 0 mPas to 1,000 mPas, or from 1 mPas to 1,000 mPas. This viscosity range is advantageous when the composition is in the form of a facial cleanser in view of the need for distribution on skin and ability to rinse off.

In at least one embodiment, the composition further comprises a viscosity-modifying substance. The viscosity-modifying substance is preferably a thickening polymer. In at least one embodiment, the thickening polymer selected from the group consisting of: copolymers of at least one first monomer type, which is chosen from acrylic acid and methacrylic acid, and at least one second monomer type, which is chosen from esters of acrylic acid and ethoxylated fatty alcohol; crosslinked polyacrylic acid; crosslinked copolymers of at least one first monomer type, which is chosen from acrylic acid and methacrylic acid, and at least one second monomer type, which is chosen from esters of acrylic acid with C₁₀- to C₃₀-alcohols; copolymers of at least one first monomer type, which is chosen from acrylic acid and methacrylic acid, and at least one second monomer type, which is chosen from esters of itaconic acid and ethoxylated fatty alcohol; copolymers of at least one first monomer type, which is chosen from acrylic acid and methacrylic acid, at least one second monomer type, which is chosen from esters of itaconic acid and ethoxylated C₁₀- to C₃₀-alcohol and a third monomer type, chosen from C₁- to C₄-aminoalkyl acrylates; copolymers of two or more monomers chosen from acrylic acid, methacrylic acid, acrylic esters and methacrylic esters; homopolymers of acryloyldimethyltaurate; crosslinked homopolymers of acryloyldimethyltaurate; copolymers of vinylpyrrolidone and salts of acryloyldimethyltaurate; copolymers of salts of acryloyldimethyltaurate and monomers chosen from esters of methacrylic acid and ethoxylated fatty alcohols; copolymers of salts of acryloyldimethyltaurate, methacrylic acid and monomers chosen from and alkylated acrylamid; salts of acryloyldimethyltaurate and N-vinylpyrrolidone; salts of acryloyldimethyltaurate, methacrylic acid and monomers chosen from esters of methacrylic acid; hydroxyethylcellulose; hydroxypropylcellulose; hydroxypropylguar; glyceryl polyacrylate; glyceryl polymethacrylate; copolymers of at least one C₂—, C₃— or C₄-alkylene and styrene; polyurethanes; hydroxypropyl starch phosphate; polyacrylamide; copolymer of maleic anhydride and methyl vinyl ether crosslinked with decadiene; carob seed flour; guar gum; xanthan; dehydroxanthan; carrageenan; karaya gum; hydrolyzed corn starch; copolymers of polyethylene oxide, fatty alcohols and saturated methylenediphenyl diisocyanate (e.g. PEG-150/stearyl alcohol/SMDI copolymer); and mixtures thereof.

pH

In at least one embodiment, the composition has a pH value of from 2.0 to 12.0, preferably from 3.0 to 9.0, more preferably from 4.5 to 8. By varying the pH value, a composition can be made available that is suitable for different applications.

In at least one embodiment, the composition comprises an alkalizing agent or pH adjusting agent. In at least one embodiment, ammonia or caustic soda is suitable, but water-soluble, physiologically tolerable salts of organic and inorganic bases can also be considered. In at least one embodiment, the pH adjusting agent is selected from ammonium hydrogen carbonate, ammonia, monoethanolamine, ammonium carbonate. In at least one embodiment, the alkalizing agents is selected from the group consisting of 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, tris(hydroxyl-methyl)-aminomethane, 2-amino-1-butanole, tris-(2-hydroxypropyl)-amine, 2,2-iminobisethanol, lysine, iminourea (guanidine carbonate), tetrahydro-1,4-oxazine, 2-amino-5-guanidin-valeric acid, 2-aminoethansulfonic acid, diethanolamine, triethanolamine, N-methyl ethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, glucamine, sodium hydroxide, potassium hydroxide, lithium hydroxide and magnesium oxide, and mixtures thereof.

To establish an acidic pH value, and acid can be included. In at least one embodiment, the composition comprises an acid selected from the group consisting of hydrochloric acid, phosphoric acid, acetic acid, formic acid, sulfuric acid, hydrochloric acid, citric acid, and mixtures thereof. Citric acid is most preferred in that it has high consumer acceptance. In at least one embodiment, the acidic pH is adjusted with a buffer such as a phosphate buffer, a TRIS buffer or a citric buffer. The buffers may be used alone or in combination with an acid.

Form

In at least one embodiment, the composition is in liquid form. In an alternative embodiment, the composition is in solid form. Optionally, the composition is in powdered or granulated form. This is advantageous in that it is not needed to ship liquid, which is typically heavy over long distances, and thus has economic and environmental benefits. A solid form can be achieved by spray drying the composition, the employment of a rotary evaporator, by drying on trays at temperature above the boiling point of the solvent, in vacuum, by drying in the reactor, in vertical or horizontal powder dryers, by atmospheric, pressure or vacuum filtration with subsequent drying of the wet filtrate. The composition can be converted into liquid form after it has been shipped e.g. by adding water.

Surfactants

In at least one embodiment, the composition comprises a surfactant or surfactant system. In at least one embodiment, the surfactant or surfactant system comprises a surfactant selected from the group consisting of anionic surfactants, cationic surfactants, non-ionic surfactants, zwitterionic surfactants and/or amphoteric surfactants.

In at least one embodiment, the composition comprises a total amount of surfactant of from 0.01 wt.-% to 70 wt.-%, from 0.1 wt.-% to 40%, from 1 wt.-% to 30%, from 2 wt.-% to 20 wt.-%.

In at least one embodiment, the composition comprises an anionic surfactant. In at least one embodiment, the anionic surfactant is selected from the group consisting of (C₁₀-C₂₀)-alkyl and alkylene carboxylates, alkyl ether carboxylates, fatty alcohol sulfates, fatty alcohol ether sulfates, alkylamide sulfates and sulfonates, fatty acid alkylamide polyglycol ether sulfates, alkanesulfonates and hydroxyalkanesulfonates, olefinsulfonates, acyl esters of isethionates, α-sulfo fatty acid esters, alkylbenzenesulfonates, alkylphenol glycol ether sulfonates, sulfosuccinates, sulfosuccinic monoesters and diesters, fatty alcohol ether phosphates, protein/fatty acid condensation products, alkyl monoglyceride sulfates and sulfonates, alkylglyceride ether sulfonates, fatty acid methyltaurides, fatty acid sarcosinates, sulforicinoleates, acylglutamates, and mixtures thereof. The anionic surfactants (and their mixtures) can be used in the form of their water-soluble or water-dispersible salts, examples being the sodium, potassium, magnesium, ammonium, mono-, di-, and triethanolammonium, and analogous alkylammonium salts. In at least one embodiment, the anionic surfactant is the salt of an anionic surfactant comprising 12 to 14 carbon atoms. In at least one embodiment, the anionic surfactant is selected from the group consisting of sodium lauryl sulfate, sodium laureth sulfate, sodium tridecyl sulfate, sodium trideceth sulfate, sodium myristyl sulfate, sodium myreth sulfate, and mixtures thereof.

In at least one embodiment, the composition comprises an acylglycinate surfactant. In at least one embodiment, the acylglycinate surfactant conforms to the formula (Y):

• • wherein
  • R^1a is a linear or branched, saturated alkanoyl group having 6 to 30, preferably 8 to 22, particularly preferably 8 to 18, carbon atoms or is a linear or branched, mono- or polyunsaturated alkenoyl group having 6 to 30, preferably 8 to 22 and particularly preferably 12 to 18 carbon atoms, and
  • Q_a⁺ is a cation. In at least one embodiment, Q_a⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, Mg⁺⁺, Ca⁺⁺, Al⁺⁺⁺, NH₄⁺, a monoalkylammmonium ion, a dialkylammonium ion, a trialkylammonium ion and a tetraalkylammonium ion, or combinations thereof. Optionally R^1a is, independently from one another, selected from (C₁-C₂₂)-alkyl radicals or (C₂-C₁₀)-hydroxyalkyl radicals. In at least one embodiment, the acylglycinate surfactant is selected from sodium cocoylglycinate and potassium cocoylglycinate. In at least one embodiment, the acylglycinate surfactant is selected from those conforming to formula (Y), wherein R is C₁₂ alkyl or C₁₄ alkyl. In at least one embodiment, the acylglycinate surfactant is selected from those conforming to formula (Y), wherein R is C₁₆ alkyl or C₁₈ alkyl.

In at least one embodiment, the composition comprises a glutamate surfactant corresponding to formula (Z) or a salt thereof:

• • wherein
  • R′ is HOOC—CH₂—CH₂— or M⁺⁻ OOC—CH₂—CH₂— wherein M⁺ is a cation; and wherein R is a linear or branched, saturated alkanoyl group having 6 to 30, preferably 8 to 22, more preferably 8 to 18, carbon atoms or is a linear or branched, mono- or polyunsaturated alkenoyl group having 6 to 30, preferably 8 to 22 and more preferably 12 to 18 carbon atoms. In at least one embodiment, M⁺ is a metal cation. In at least one embodiment, M⁺ is selected from the group consisting of Li⁺, Na⁺, K⁺, Mg⁺⁺, Ca⁺⁺, Al⁺⁺⁺, NH₄⁺, a monoalkylammmonium ion, a dialkylammonium ion, a trialkylammonium ion and a tetraalkylammonium ion, or combinations thereof. In at least one embodiment, the glutamate surfactant is selected from sodium cocoyl glutamate and potassium cocoyl glutamate. In at least one embodiment, the glutamate surfactant is selected from those conforming to formula (Z), wherein R is C₁₂ alkyl or C₁₄ alkyl. In at least one embodiment, the glutamate surfactant is selected from those conforming to formula (Z), wherein R is C₁₆ alkyl or C₁₈ alkyl.

In at least one embodiment, the composition comprises from 0.01 wt.-% to 30 wt.-%, or 1 wt.-% to 25 wt.-%, preferably from 5 wt.-% to 20 wt.-%, more preferably from 12 wt.-% to 18 wt.-% anionic surfactant.

In at least one embodiment, the composition comprises a non-ionic surfactant.

In at least one embodiment, the non-ionic surfactant has an HLB (Hydrophilic Lipophilic Balance) of greater than 12. Optionally, the non-ionic surfactant is selected from the group consisting of ethoxylated or ethoxylated/propoxylated fatty alcohols with a fatty chain comprising from 12 to 22 carbon atoms, ethoxylated sterols, such as stearyl- or lauryl alcohol (EO-7), PEG-16 soya sterol or PEG-10 soya sterol, polyoxyethylene polyoxypropylene block polymers (poloxamers), and mixtures thereof.

In at least one embodiment, the non-ionic surfactant is selected from the group consisting of ethoxylated fatty alcohols, fatty acids, fatty acid glycerides or alkylphenols, in particular addition products of from 2 to 30 mol of ethylene oxide and/or 1 to 5 mol of propylene oxide onto C₈- to C₂₂-fatty alcohols, onto C₁₂- to C₂₂-fatty acids or onto alkyl phenols having 8 to 15 carbon atoms in the alkyl group, C₁₂- to C₂₂-fatty acid mono- and diesters of addition products of from 1 to 30 mol of ethylene oxide onto glycerol, addition products of from 5 to 60 mol of ethylene oxide onto castor oil or onto hydrogenated castor oil, fatty acid sugar esters, in particular esters of sucrose and one or two C₈- to C₂₂-fatty acids, INCI: Sucrose Cocoate, Sucrose Dilaurate, Sucrose Distearate, Sucrose Laurate, Sucrose Myristate, Sucrose Oleate, Sucrose Palmitate, Sucrose Ricinoleate, Sucrose Stearate, esters of sorbitan and one, two or three C₈- to C₂₂-fatty acids and a degree of ethoxylation of from 4 to 20, polyglyceryl fatty acid esters, in particular of one, two or more C₈- to C₂₂-fatty acids and polyglycerol having preferably 2 to 20 glyceryl units, alkyl glucosides, alkyl oligoglucosides and alkyl polyglucosides having C₈ to C₂₂-alkyl groups, e.g. decylglucoside or laurylglucoside, and mixtures thereof.

In at least one embodiment, the non-ionic surfactant is selected from the group consisting of fatty alcohol ethoxylates (alkylpolyethylene glycols), alkylphenol polyethylene glycols, alkylmercaptan polyethylene glycols, fatty amine ethoxylates (alkylaminopolyethylene glycols), fatty acid ethoxylates (acylpolyethylene glycols), polypropylene glycol ethoxylates (Pluronics®), fatty acid alkylol amides, (fatty acid amide polyethylene glycols), N-alkyl-, N-alkoxypolyhydroxy-fatty acid amide, sucrose esters, sorbitol esters, polyglycol ethers, and mixtures thereof.

In at least one embodiment, the composition comprises a fatty N-methyl-N-glucamide surfactant. In at least one embodiment, the fatty N-methyl-N-glucamide surfactant conforms to the formula (X):

• • wherein
  • R is a linear or branched alkyl or alkenyl group having from 3 to 30 carbon atoms. In at least one embodiment, R is an alkyl group having from 3 to 30 carbon atoms.

In at least one embodiment, R is a saturated aliphatic hydrocarbon group which can be linear or branched and can have from 3 to 20 carbon atoms in the hydrocarbon chain, preferably linear or branched. Branched means that a lower alkyl group such as methyl, ethyl or propyl is present as substituent on a linear alkyl chain. In at least one embodiment, R is selected from the group consisting of 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl and 1-octadecyl. Suitable fatty N-methyl-N-glucamide surfactants are described in WO2013/178700 and EP0550637, which are incorporated herein by reference. In at least one embodiment, the N-methyl-N-glucamide surfactant is selected from those conforming to formula (X), wherein R is C₁₂ alkyl or C₁₄ alkyl. In at least one embodiment, the N-methyl-N-glucamide surfactant is selected from those conforming to formula (X), wherein R is C₁₆ alkyl or C₁₈ alkyl. N-methyl-N-glucamide surfactants are available from Clariant under their GlucoTain® brand.

In at least one embodiment, the composition comprises from 1 wt.-% to 20 wt.-%, more preferably from 2 wt.-% to 10 wt.-%, even more preferably from 3 wt.-% to 7 wt.-% non-ionic surfactant.

In at least one embodiment, the amphoteric surfactants are selected from the group consisting of N—(C₁₂-C₈)-alkyl-β-aminopropionates and N—(C₁₂-C₁₈)-alkyl-β-iminodipropionates as alkali metal salts and mono-, di-, and trialkylammonium salts; N-acylaminoalkyl-N,N-dimethylacetobetaine, preferably N—(C₈-C₁₈)-acylaminopropyl-N,N-dimethylacetobetaine, (C₁₂-C₈)-alkyl-dimethylsulfopropylbetaine, amphosurfactants based on imidazoline (trade name: Miranol®, Steinapon®), preferably the sodium salt of 1-(β-carboxymethyloxyethyl)-1-(carboxymethyl)-2-laurylimidazolinium; amine oxide, e.g., (C₁₂-C₁₈)-alkyl-dimethylamine oxide, fatty acid amidoalkyldimethylamine oxide, and mixtures thereof.

In at least one embodiment, the composition comprises a betaine surfactant. Optionally, the betaine surfactant is selected from C₈- to C₁₈-alkylbetaines. In at least one embodiment, the betaine surfactant is selected from the group consisting of cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethylalphacarboxyethylbetaine, cetyldimethylcarboxymethylbetaine, oleyldimethylgammacarboxypropylbetaine and laurylbis(2-hydroxypropyl)alphacarboxyethylbetaine and combinations thereof. Optionally, the betaine surfactant is selected from C₈- to C₁₈-sulfobetaines. In at least one embodiment, the betaine surfactant is selected from the group consisting of cocodimethylsulfopropylbetaine, stearyldimethylsulfopropylbetaine, lauryldimethyl-sulfoethylbetaine, laurylbis(2-hydroxyethyl)sulfopropylbetaine, and combinations thereof. Optionally, the betaine surfactant is selected from carboxyl derivatives of imidazole, the C₈- to C₁₈-alkyldimethylammonium acetates, the C₈- to C₁₈-alkyldimethylcarbonylmethylammonium salts, and the C₈- to C₈-fatty acid alkylamidobetaines, and mixtures thereof. Optionally, the C₈- to C₁₈-fatty acid alkylamidobetaine is selected from coconut fatty acid amidopropylbetaine, N-coconut fatty acid amidoethyl-N-[2-(carboxymethoxy)ethyl]glycerol (CTFA name: Cocoamphocarboxyglycinate), and mixtures thereof.

In at least one embodiment, the composition comprises from 0.5 wt.-% to 20 wt.-%, preferably from 1 wt.-% to 10 wt.-% amphoteric surfactant.

In at least one embodiment, the composition comprises a surfactant system. In at least one embodiment, the surfactant system comprises at least one surfactant selected from the group consisting of lauryl sulfate, laureth sulfate, cocoamidopropylbetaine, sodium cocoylglutamate, lauroamphoacetate, and mixtures thereof. In at least one embodiment, the surfactant system comprises sodium laureth sulphate, sodium lauryl sulphate, and optionally cocamidopropyl betaine. In at least one embodiment, the surfactant system comprises sodium laureth sulphate, Potassium Cocyl Glutamate, and cocamidopropyl betaine.

Conditioning Agent

In at least one embodiment, the composition comprises a conditioning agent. In at least one embodiment, the conditioning agent is a water insoluble, water dispersible, non-volatile, liquid that forms emulsified, liquid particles. In at least one embodiment, the conditioning agent is a silicone (e.g., silicone oil, cationic silicone, silicone gum, high refractive silicone, and silicone resin), an organic conditioning oil (e.g., hydrocarbon oils, polyolefins, and fatty esters), or combinations thereof.

In at least one embodiment, the conditioning agent is a silicone, and wherein the composition comprises from 0.01 wt.-% to 10 wt.-%, or from 0.1 wt.-% to 5 wt.-% silicone conditioning agent, by total weight of the composition. Suitable silicone conditioning agents, and optional suspending agents for the silicone, are described in U.S. Pat. No. 5,104,646. In at least one embodiment, the composition comprises a silicone gum selected from the group consisting of polydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane) copolymer, poly(dimethylsiloxane) (diphenylsiloxane) (methylvinylsiloxane) copolymer, and mixtures thereof.

In at least one embodiment, the composition comprises a terminal aminosilicone. “Terminal aminosilicone” as defined herein means silicone comprising one or more amino groups at one or both ends of the silicone backbone. In at least one embodiment, the composition is substantially free of any silicone compound comprising pendant amino groups. In an embodiment, the composition is substantially free of any silicone compound other than terminal aminosilicones. In at least one embodiment, the amino group at least one terminus of the silicone backbone of the terminal aminosilicone is selected from the group consisting of primary amines, secondary amines and tertiary amines. In at least one embodiment, the composition comprises a terminal aminosilicone conforming to Formula (S):

(R^F)_aG_3-a-Si—(—OSiG₂)_n—O-SiG_3-a(R^F)_a  (S)

• • wherein
  • G is hydrogen, phenyl, hydroxy, or C₁-C₈ alkyl, preferably methyl;
  • a is an integer having a value from 1 to 3, preferably 1;
  • b is 0, 1 or 2, preferably 1;
  • n is a number from 0 to 1,999;
  • R^F is a monovalent radical conforming to the general formula C_qH_2qL, wherein q is an integer having a value from 2 to 8 and
  • L is selected from the following groups: —N(R^T)CH₂—CH₂—N(R^T)₂; —N(R^T)₂;
  • —N(R^T)₃A⁻; —N(R^T)CH₂—CH₂—NR^TH₂A⁻; wherein R^T is hydrogen, phenyl, benzyl, or a saturated hydrocarbon radical, preferably an alkyl radical from having from 1 to 20 carbon atoms; A⁻ is a halide ion.

In at least one embodiment, the terminal aminosilicone corresponding to Formula (S) has a=1, q=3, G=methyl, n is from 1000 to 2500, alternatively from 1500 to 1700; and L is —N(CH₃)₂. A suitable terminal aminosilicone corresponding to Formula (S) has a=O, G=methyl, n is from 100 to 1500, or from 200 to 800, and L is selected from the following groups: —N(R^T)CH₂—CH₂—N(R^T)₂; —N(R^T)₂; —N(R^T)₃A⁻; —N(R^T)CH₂—CH₂—NR^TH₂A⁻; wherein R^T is selected from hydrogen, phenyl, benzyl, or a saturated hydrocarbon radical, preferably an alkyl radical from having from 1 to 20 carbon atoms; A⁻ is a halide ion, alternatively L is —NH₂. In at least one embodiment, the terminal aminosilicone is selected from the group consisting of bis-aminomethyl dimethicone, bisaminoethyl dimethicone, bis-aminopropyl dimethicone, bis-aminobutyl dimethicone, and mixtures thereof. In at least one embodiment, the viscosity of the terminal aminosilicone is from 1,000 to 30,000 mPas, or from 5,000 to 20,000 mPas measured at 25° C.

In at least one embodiment, the composition comprises from 0.1 wt.-% to 20 wt.-%, or from 0.5 wt.-% to 10 wt.-%, or from 1 wt.-% to 6 wt.-% terminal aminosilicone, by total weight of the composition.

In at least one embodiment, the composition comprises a high melting point fatty compound. The high melting point fatty compound has a melting point of 25° C. or higher. In at least one embodiment, the high melting point fatty compound is selected from the group consisting of a fatty alcohol, fatty acid, fatty alcohol derivative, fatty acid derivative, and mixtures thereof. Non-limiting examples of the high melting point compounds are found in International Cosmetic Ingredient Dictionary, Fifth Edition, 1993, and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992. The composition may comprise from 0.1 wt.-% to 40 wt.-%, or from 1 wt.-% to 30 wt.-%, or from 1.5 wt.-% to 16 wt.-%, or from 1.5 wt.-% to 8 wt.-% of a high melting point fatty compound, by total weight of the composition. This is advantageous in view of providing improved conditioning benefits such as slippery feel during the application to wet hair, softness and moisturized feel on dry hair. In at least one embodiment, the fatty alcohol is selected from the group consisting of: cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof. In at least one embodiment, the composition comprises a linear fatty alcohol, wherein the linear fatty alcohol is also comprised in a lamellar gel matrix. The lamellar gel matrix is suitable for providing various conditioning benefits such as slippery feel during the application to wet hair and softness and moisturized feel on dry hair. The linear fatty alcohol may comprise from 8 to 24 carbon atoms. In at least one embodiment, the linear fatty alcohol is selected from the group consisting of: cetyl alcohol, stearyl alcohol, and mixtures thereof. In an embodiment, the weight ratio of total linear fatty alcohol to terminal aminosilicone is from 0.5:1 to 10:1, or from 1:1 to 5:1, or from 2.4:1 to 2.7:1. In at least one embodiment, the lamellar gel matrix comprises a cationic surfactant and a high melting point fatty compound. In view of providing the lamellar gel matrix, the cationic surfactant and the high melting point fatty compound are contained at a level such that the weight ratio of the cationic surfactant to the high melting point fatty compound is in the range of from 1:1 to 1:10, or from 1:1 to 1:6.

In at least one embodiment, the composition comprises a cationic surfactant. In at least one embodiment, the composition comprises from 0.05 wt.-% to 3.0 wt.-%, or from 0.075 wt.-% to 2.0 wt.-%, or from 0.1 wt.-% to 1.0 wt.-%, of cationic surfactant by total weight of the composition. In at least one embodiment, the cationic surfactant is comprised in a lamellar gel matrix. In other words, the composition comprises a lamellar gel matrix and the lamellar gel matrix comprises the cationic surfactant. In an embodiment, cationic surfactant is according to Formula (C):

• • wherein
  • at least one of R⁷¹, R⁷², R⁷³ and R⁷⁴ is selected from an aliphatic group of from 8 to 30 carbon atoms, an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl, or an alkylaryl group having up to 22 carbon atoms;
  • the remainder of R⁷¹, R⁷², R⁷³ and R⁷⁴ are independently selected from the group consisting of an aliphatic group consisting of from 1 to 22 carbon atoms, and an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to 22 carbon atoms;
  • X is selected from the group consisting of: halogen, acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfonate, sulfate, alkylsulfate, alkyl sulfonate radicals, and combinations thereof.

In at least one embodiment, the cationic surfactant is selected from the group consisting of behenyl trimethyl ammonium chloride, methyl sulfate or ethyl sulfate, and stearyl trimethyl ammonium chloride, methyl sulfate or ethyl sulfate. It is believed that a longer alkyl group provides improved smoothness and soft feeling on wet and dry hair, compared to cationic surfactants with a shorter alkyl group. It is also believed that such cationic surfactants can provide reduced irritation, compared to those having a shorter alkyl group.

In at least one embodiment, the cationic surfactant is a di-long alkyl quatemized ammonium salt selected from the group consisting of: dialkyl (14-18) dimethyl ammonium chloride, ditallow alkyl dimethyl ammonium chloride, dihydrogenated tallow alkyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride, and mixtures thereof.

In at least one embodiment, the cationic surfactant is a tertiary amido amine having an alkyl group of from 12 to 22 carbons. The tertiary amido amine may be selected from the group consisting of stearamidopropyldimethyl-, stearamidopropyldiethyl-, stearamidoethyldiethyl-, stearamidoethyldimethyl-, palmitamidopropyldimethyl-, palmitamidopropyldiethyl-, palmitamidoethyldiethyl-, palmitamidoethyldimethyl-, behenamidopropyldimethyl-, behenamidopropyldiethyl-, behenamidoethyldiethyl-, behenamidoethyldimethyl-, arachidamidopropy Idimethy 1-, arachidamidopropyldiethyl-, arachidamidoethyldiethyl-, and arachidamidoethyldimethyl-amine, diethylaminoethylstearamide, and mixtures thereof. A tertiary amido amine may be used in combination with an acid. The acid is typically used as a salt-forming anion. In an embodiment, the acid is selected from the group consisting of lactic acid, malic acid, hydrochloric acid, 1-glumatic acid, acetic acid, citric acid, and mixtures thereof.

In at least one embodiment, the cationic surfactant is selected from the group consisting of cetyltrimonium chloride (CTAC), stearyltrimonium chloride (STAC), behentrimonium methosulfate, stearoylamidopropyldimethyl amine (SAPDMA), distearyldimethylammonium chloride, and mixtures thereof.

Hairstyling Polymers

In at least one embodiment, the composition further comprises a hairstyling polymer. In at least one embodiment, the hairstyling polymer is selected from the group consisting of: amphoteric hairstyling polymers, zwitterionic hairstyling polymers, anionic hairstyling polymers, non-ionic hairstyling polymers, cationic hairstyling polymers, and mixtures thereof. In at least one embodiment, the composition comprises from 0.01 wt.-% to 20 wt.-%, or from 0.01 wt.-% to 16 wt.-%, or from 0.01 wt.-% to 10 wt.-%, or from 1 wt.-% to 8 wt.-%, or from 2 wt.-% to 6 wt.-% of hairstyling polymer.

In at least one embodiment, the hairstyling polymer is a water-compatible hairstyling polymer, alternatively a water-soluble hairstyling polymer. In at least one embodiment, the composition is substantially free of a water-incompatible hairstyling polymer. An example of a water-incompatible hairstyling polymer includes an Acrylates/t-Butylacrylamide Copolymer which is a copolymer of tert-butyl acrylamide and one or more monomers of acrylic acid, methacrylic acid, or one of their simple esters (e.g. Ultrahold® 8 from BASF). Balance® CR from Akzo Nobel, which is an acrylates copolymer of two or more monomers of (meth)acrylic acid or one of their simple esters, is water-compatible. The octylacrylamide/acrylate/butylaminoethyl methacrylate copolymer Amphomer® is also water-compatible. In at least one embodiment, the hairstyling polymer is a latex hairstyling polymer.

The composition may comprise a cationic hairstyling polymer. In at least one embodiment, the cationic hairstyling polymers is selected from group consisting of those with primary, secondary, tertiary or quaternary amino groups. In at least one embodiment, the cationic hairstyling polymer has a cationic charge density, and wherein the cationic charge density is from 1 to 7 meq/g. In at least one embodiment, the cationic hairstyling polymer comprises quaternary amino groups. In at least one embodiment, the cationic hairstyling polymer is a homo- or copolymer where the quaternary nitrogen groups are contained either in the polymer chain or as substituents on one or more of the monomers. The ammonium group-containing monomers can be copolymerised with non-cationic monomers. In at least one embodiment, the cationic hairstyling polymer comprises cationic monomers where the cationic monomers are unsaturated compounds that can undergo radical polymerisation, and which bear at least one cationic group. In at least one embodiment, the cationic monomers are selected from the group consisting of: ammonium-substituted vinyl monomers such as, for example, trialkylmethacryloxyalkylammonium, trialkylacryloxyalkylammonium, dialkyldiallylammonium and quaternary vinylammonium monomers with cyclic, cationic nitrogen-containing groups such as pyridinium, imidazolium or quaternary pyrrolidones, e.g. alkylvinylimidazolium, alkylvinylpyridinium, or alkylvinylpyrrolidone salts. The alkyl groups of these monomers may be lower alkyl groups such, as for example, C₁- to C₇-alkyl groups, and may also be are C₁- to C₃-alkyl groups.

In at least one embodiment, cationic hairstyling polymer comprises ammonium group-containing monomers being copolymerised with non-cationic monomers. The non-cationic monomers may be selected from the group consisting of: acrylamide, methacrylamide, alkyl-and dialkylacrylamide, alkyl- and dialkylmethacrylamide, alkyl acrylate, alkyl methacrylate, vinylcaprolactone, vinylcaprolactam, vinylpyrrolidone, vinyl esters, for example vinyl acetate, vinyl alcohol, propylene glycol or ethylene glycol, and mixture thereof. The alkyl groups of these monomers may be C₁- to C₇-alkyl groups and may be C₁- to C₃-alkyl groups. In at least one embodiment, cationic hairstyling polymer comprises at least one quaternary amino group. Suitable polymers with at least one quaternary amino group include, for example, those described in the CTFA Cosmetic Ingredient Dictionary under the designations ‘polyquaternium’ such as methylvinylimidazolium chloride/vinylpyrrolidone copolymer (polyquaternium-16) or quaternized vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer (polyquaternium-11; Gafquat® 755N-PW from ISP) as well as quaternary silicone polymers or silicone oligomers such as, for example, silicone polymers with quaternary end groups (quatemium-80).

In at least one embodiment, the hairstyling polymer is a cationic hairstyling polymer being of synthetic origin. In at least one embodiment, the cationic hairstyling polymers of synthetic origin are selected from the group consisting of: poly(dimethyldiallylammonium chloride); copolymers from acrylamide and dimethyldiallylammonium chloride; quaternary ammonium polymers, formed by the reaction of diethyl sulfate with a copolymer from vinylpyrrolidone and dimethylaminoethyl methacrylate, especially vinylpyrrolidone/dimethylaminoethyl methacrylate methosulfate copolymer (e.g. Gafquat© 755 N; Gafquat® 734); quaternary ammonium polymers from methylvinylimidazolium chloride and vinylpyrrolidone (e.g. Luviquat® HM 550 from BASF; Luviquat® Hold from BASF; polyquaternium-46 [vinylcaprolactam {VCap}, vinylpyrrolidone {VP} and quaternized vinylimidazole {QVI}] from BASF; Luviquat® FC 905 from BASF [polyquaternium-16]); Luviquat Supreme® from BASF (polyquaternium-68, quaternised copolymer of vinyl pyrrolidone, methacrylamides, vinyl imidazole and quaternized vinyl imidazole); polyquaternium-35; polyquaternium-57; polymers from trimethylammonium ethyl methacrylate chloride; terpolymers from dimethyldiallylammonium chloride, sodium acrylate and acrylamide (e.g. Merquat® Plus 3300); copolymers from vinylpyrrolidone, dimethylaminopropyl methacrylamide, and methacryloylaminopropyllauryldimethylammonium chloride; terpolymers from vinylpyrrolidone, dimethylaminoethyl methacrylate, and vinylcaprolactam (e.g. Gaffix® VC 713); vinylpyrrolidone/methacrylamidopropyltrimethylammonium chloride copolymers (e.g. Gafquat® HS 100); copolymers from vinylpyrrolidone and dimethylaminoethyl methacrylate; copolymers from vinylpyrrolidone, vinylcaprolactam, and dimethylaminopropylacrylamide; poly- or oligoesters formed from at least one first type of monomer that is selected from hydroxyacids substituted with at least one quaternary ammonium group; dimethylpolysiloxane substituted with quaternary ammonium groups in the terminal positions; and mixtures thereof.

In at least one embodiment, the hairstyling polymer is a cationic hairstyling polymer being of natural origin. In at least one embodiment, the cationic hairstyling polymers being of natural origin are selected from the group consisting of: cationic derivatives of polysaccharides, for example, cationic cellulose derivatives, starch, guar, and mixtures thereof. Cationic derivatives of polysaccharides may be represented by the general formula (D):

G-O—B—N⁺—R^a—R^b—R^cX⁻  (D)

• • wherein
  • G is an anhydroglucose residue, for example, starch or cellulose anhydroglucoses;
  • B is a divalent bonding group, for example, alkylene, oxyalkylene, polyoxyalkylene or hydroxyalkylene;
  • R^a, R^b and R^c are independently from one another, alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl or alkoxyaryl, any of which can have up to 22 carbon atoms, wherein the total number of carbon atoms in R^a, R^b and R^c is may be a maximum of 20.

In at least one embodiment, the hairstyling polymer is a cationic cellulose derivative being selected from the group consisting of: those that have at least one quaternary ammonium group, e.g. a copolymer made of hydroxyethyl cellulose and diallyldimethyl ammonium chloride (polyquaternium-4), or the reaction product made of hydroxyethyl cellulose and an epoxide substituted with a trialkyl ammonium group (polyquaternium-10), wherein the alkyl groups can have 1 to 20 carbon atoms, or wherein the alkyl group is methyl. In at least one embodiment, the hairstyling polymer is a cationic cellulose derivative having a molecular weight of from 100,000 Da to 600,000 Da, or from 200,000 Da to 400,000 Da. In at least one embodiment, the cationic cellulose derivative has a nitrogen content, wherein the nitrogen content is from 0.5 wt.-% to 4 wt.-%, or from about 1.5 wt.-% to 3 wt.-%. In at least one embodiment, the hairstyling polymer is a cationic cellulose derivative being polyquaternium-4. Polyquaternium-4 is sold under the trade names Celquat® HIOO and Celquat® L200, of which Celquat® L200 is especially preferred.

In at least one embodiment, the hairstyling polymer is a cationic latex hairstyling polymer. In at least one embodiment, the cationic hairstyling polymer is selected from the group consisting of: polyquaternium-4, polyquaternium-11, polyquaternium-16, polyquaternium-68, mixtures thereof, and mixtures of polyquaternium-68 with a non-ionic hairstyling polymer. In at least one embodiment, the hairstyling polymer is selected from the group consisting of: polyquaternium-4, polyquaternium-11, polyquaternium-68, and mixtures thereof. In at least one embodiment, the composition comprises a chitosan, a chitosan salt or a chitosan derivative. In at least one embodiment, the composition comprises less than 0.1 wt.-% by weight chitosan, chitosan salts and chitosan derivatives. In another embodiment, the composition is substantially free from chitosan, chitosan salts and chitosan derivatives. In at least one embodiment, the composition comprises a hairstyling polymer selected from the group consisting of: polyquaternium-4, polyquaternium-11, polyquaternium-16, polyquaternium-68, mixtures thereof; or from the group consisting of: polyquaternium-4, polyquaternium-68, and mixtures thereof. In at least one embodiment, the composition comprises a hairstyling polymer selected from the group consisting of: polyquaternium-4, polyquaternium-11, polyquaternium-68, mixtures thereof; or from the group consisting of: polyquaternium-4, polyquaternium-68, and mixtures thereof.

In at least one embodiment, the composition comprises less than 0.5 wt.-% of a cationic hairstyling polymer by total weight of the composition.

In at least one embodiment, the composition comprises an amphoteric or zwitterionic hairstyling polymer. In at least one embodiment, the amphoteric or zwitterionic hairstyling polymer is selected from the group consisting of: copolymers formed from alkylacrylamide, alkylaminoalkyl methacrylate, and two or more monomers from acrylic acid and methacrylic acid as well as, if necessary, their esters, especially copolymers from octylacrylamide, acrylic acid, butylaminoethyl methacrylate, methyl methacrylate and hydroxypropyl methacrylate (octylacrylamide/acrylate/butylaminoethyl methacrylate copolymer, for example Amphomer® from Akzo Nobel); copolymers, that are formed from at least one of a first type of monomer that possesses quaternary amino groups and at least one of a second type of monomer that possesses acid groups; copolymers from fatty alcohol acrylates, alkylamine oxide methacrylate and at least one monomer selected from acrylic acid and methacrylic acid as well as, if necessary, acrylic acid esters and methacrylic acid esters, especially copolymers from lauryl acrylate, stearyl acrylate, ethylamine oxide methacrylate and at least one monomer selected from acrylic acid and methacrylic acid as well as, if necessary, their esters; copolymers from methacryloyl ethyl betaine and at least one monomer selected from methacrylic acid and methacrylic acid esters; copolymers from acrylic acid, methyl acrylate and methacrylamidopropyltrimethylammonium chloride (polyquaternium-47); copolymers from acrylamidopropyltrimethylammonium chloride and acrylates or copolymers from acrylamide, acrylamidopropyltrimethylammonium chloride, 2-amidopropylacrylamide sulfonate and dimethylaminopropylamine (polyquaternium-43); oligomers or polymers, producible from quaternary crotonoylbetaines or quaternary crotonoylbetaine esters. In at least one embodiment, the composition comprises an amphoteric or zwitterionic latex hairstyling polymer. In at least one embodiment, the hairstyling polymer is selected from the group consisting of: polyquaternium-47, octylacrylamide/acrylate/butylaminoethyl methacrylate copolymers, and mixtures thereof.

The hairstyling composition may comprise an anionic hairstyling polymer. In at least one embodiment, the anionic hairstyling polymer is selected from the group consisting of: acrylates copolymers of two or more monomers of (meth)acrylic acid or one of their simple esters (e.g. Balance® CR from Akzo Nobel); acrylates/hydroxyesters acrylates copolymers including those being copolymers of butyl acrylate, methyl methacrylate, methacrylic acid, ethyl acrylate and hydroxyethyl methacrylate (e.g. Acudyne™ 1000 from Dow Personal Care); terpolymers of acrylic acid, ethyl acrylate, and N-tert-butylacrylamide; crosslinked or uncrosslinked vinyl acetate/crotonic acid copolymers; terpolymers of tert-butylacrylate, ethyl acrylate and methacrylic acid; sodium polystyrenesulfonate; copolymers of vinyl acetate, crotonic acid and vinyl propionate; copolymers of vinyl acetate, crotonic acid and vinyl neodecanoate; aminomethylpropanol/acrylate copolymers; copolymers of vinylpyrrolidone and at least one further monomer selected from among acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters; copolymers of methyl vinyl ether and maleic acid monoalkyl esters; aminomethylpropanol salts of copolymers of allyl methacrylate and at least one further monomer selected from among acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters; crosslinked copolymers of ethyl acrylate and methacrylic acid; copolymers of vinyl acetate, mono-n-butyl maleate and isobornyl acrylate; copolymers of two or more monomers selected from among acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters, copolymers of octylacrylamide and at least one monomer selected from among acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters; polyesters of diglycol, cyclohexanedimethanol, isophthalic acid and sulfoisophthalic acid; polyurethanes; and copolymers of polyurethane and acrylates. e.g. polyurethane-14/AMP-acrylates polymer blend (e.g. DynamX® from Akzo Nobel). Suitable polyester polymers include polyester-5 polymers, for example AQ® 48 Ultra Polymer, (diglycol/CHDM/isophthalates/SIP copolymer [a copolymer of diethylene glycol, 1,4-cyclohexanedimethanol and the simple esters of isophthalic acid and sulfoisophthalic acid]), AQ® 55 S, and AQ® 38 S, all from Eastman Chemical Company. Also suitable is a polyvinylmethacrylic acid/maleic acid copolymer (Omnirez® 2000 from ISP). Anionic latex hairstyling polymers are also suitable. In at least one embodiment, the anionic hairstyling polymer is selected from the group consisting of: polyurethane-1 (e.g. Luviset® P.U.R. from BASF), polyurethane-14/AMP-acrylates copolymer blend (e.g. DynamX® from Akzo Nobel), acrylates copolymers of two or more monomers of (meth)acrylic acid or one of their simple esters (e.g. Balance® CR from Akzo Nobel), and mixtures thereof. In at least one embodiment, the anionic hairstyling polymer is polyurethane-1.

The composition may comprise a non-ionic hairstyling polymer. In at least one embodiment, the composition comprises a non-ionic hairstyling polymer, wherein are non-ionic hairstyling polymer is a homo- or copolymer that is formed from at least one of the following monomers: vinylpyrrolidone, vinylcaprolactam, vinyl esters such as, for example, vinyl acetate, vinyl alcohol, acrylamide, methacrylamide, alkyl- and dialkylacrylamide, alkyl- and dialkylmethacrylamide, alkyl acrylate, alkyl methacrylate, propylene glycol or ethylene glycol, where the alkyl groups in these monomers may be C₁- to C₇-alkyl groups or C₁- to C₃-alkyl groups. In at least one embodiment, the composition comprises a homopolymer selected from the group consisting of: vinylcaprolactam, vinylpyrrolidone, N-vinylformamide and mixtures thereof. In at least one embodiment, the non-ionic hairstyling polymer is selected from the group consisting of: copolymers of vinylpyrrolidone and vinyl acetate, terpolymers of vinylpyrrolidone, vinyl acetate and vinyl propionate, polyacrylamides; polyvinyl alcohols as well as polyethylene glycol/polypropylene glycol copolymers; and mixtures thereof. In at least one embodiment, the non-ionic hairstyling polymer is selected from the group consisting of: polyvinylpyrrolidone/dimethylaminopropylaminoacrylates copolymer (Aquaflex® SF 40 from ISP); isobutylene ethylmaleinimide/hydroxy ethylmaleinimide copolymer (Aquaflex® FX 64 from ISP); vinylcaprolactam/polyvinylpyrrolidone/dimethylaminoethyl methacrylate copolymer (Advantage® from ISP); and mixtures thereof. Non-ionic latex hairstyling polymers are also suitable. In at least one embodiment, the non-ionic hairstyling polymer is selected from the group consisting of: polyvinylpyrrolidone (K90, 85, 80, 60, 30), polyvinylpyrrolidone/vinyl acetate copolymers (PVP/VA 64), terpolymers of vinylpyrrolidone, methacrylamide and vinylimidazole (e.g. Luviset® Clear from BASF), and mixtures thereof. In at least one embodiment, the non-ionic hairstyling polymer is selected from the group consisting of: PVP K 60, 30, and PVP/VA 37/64. In at least one embodiment, the non-ionic hairstyling polymer is selected from the group consisting of: PVP K60 and PVP/VA 37/64.

In at least one embodiment, the composition comprises an anionic latex hairstyling polymer. In at least one embodiment, the anionic latex hairstyling polymer is a urethane-based polymer, for example polyurethane-34 (Baycusan® from Bayer). Polyurethane-34 is described in EP2105127A1. In at least one embodiment, the hairstyling polymer is the latex hairstyling polymer polyurethane-34.

In at least one embodiment, the anionic hairstyling polymer and/or cationic hairstyling polymer is present in neutralized or partially neutralized form. In at least one embodiment, the composition comprises a neutralising agent, and wherein the neutralising agent is selected from the group consisting of: potassium hydroxide, sodium hydroxide, triisopropanolamine (TIPA), 2-aminobutanol, 2-aminomethyl propanol (AMP), aminoethylpropandiol, dimethyl stearamine (Armeen 18 D), sodium silicate, tetrahydroxypropyl ethylenediamine (Neutrol® TE), ammonia (NH₃), triethanolamine, trimethylamine (Tris Amino Ultra), aminomethylpropandiol (AMPD) and mixtures thereof. In at least one embodiment, the neutralising agent is 2-aminomethyl propanol.

Auxiliaries

In at least one embodiment, the composition comprises additives common in cosmetology, pharmacy, and dermatology, which are hereinafter called auxiliaries. In at least one embodiment, the auxiliary is selected from the group consisting of oily substances, emulsifiers, coemulsifiers, cationic polymers, film formers, superfatting agents, stabilizers, active biogenic substances, glycerol, preservatives, pearlizing agents, dyes and fragrances, solvents, opacifiers, functional acids, and also protein derivatives such as gelatin, collagen hydrolysates, natural or synthetic-based polypeptides, egg yolk, lecithin, lanolin and lanolin derivatives, fatty alcohols, silicones, deodorants, substances with a keratolytic and keratoplastic action, enzymes, and/or carriers/solvents.

In at least one embodiment, the composition comprises water soluble vitamins and their derivatives, water soluble amino acids and their salts and/or derivatives, viscosity modifiers, dyes, nonvolatile solvents or diluents (water soluble and insoluble), pearlescent aids, thickeners, foam boosters, additional surfactants or nonionic co-surfactants, pediculocides, pH adjusting agents, perfumes, preservatives, chelants, proteins, skin active agents, sunscreens, UV absorbers, vitamins, niacinamide, caffeine, minoxidil, and combinations thereof. In at least one embodiment, the composition comprises from 0 wt.-% to 5 wt.-% vitamins and amino acids, by total weight of the composition. The composition may also comprise pigment materials such as inorganic, nitroso, monoazo, disazo, carotenoid, triphenyl methane, triaryl methane, xanthene, quinoline, oxazine, azine, anthraquinone, indigoid, thionindigoid, quinacridone, phthalocianine, botanical, natural colors, including: water soluble components such as those having C.I. Names. The composition may comprise from 0 wt.-% to 5 wt.-% pigment materials. The composition may comprise from 0 wt.-% to 5 wt.-% antimicrobial agents.

In at least one embodiment, the composition comprises an oily substance, which is any fatty substance which is liquid at room temperature (25° C.). In at least one embodiment, the composition comprises oily substance selected from the group consisting of silicone oils, volatile or nonvolatile, linear, branched or cyclic, optionally with organic modification; phenylsilicones; silicone resins and silicone gums; mineral oils such as paraffin oil or vaseline oil; oils of animal origin such as perhydrosqualene, lanolin; oils of plant origin such as liquid triglycerides, e.g., sunflower oil, corn oil, soybean oil, rice oil, jojoba oil, babusscu oil, pumpkin oil, grapeseed oil, sesame oil, walnut oil, apricot oil, macadamia oil, avocado oil, sweet almond oil, lady's-smock oil, castor oil, triglycerides of caprylic/capric acids, olive oil, peanut oil, rapeseed oil, argan oil, abyssinian oil, and coconut oil; synthetic oils such as purcellin oil, isoparaffins, linear and/or branched fatty alcohols and fatty acid esters, preferably guerbet alcohols having 6 to 18, preferably 8 to 10, carbon atoms; esters of linear (C₆-C₁₃) fatty acids with linear (C₆-C₂₀) fatty alcohols; esters of branched (C₆-C₁₃) carboxylic acids with linear (C₆-C₂₀) fatty alcohols, esters of linear (C₆-C₁₈) fatty acids with branched alcohols, especially 2-ethylhexanol; esters of linear and/or branched fatty acids with polyhydric alcohols (such as dimerdiol or trimerdiol, for example) and/or guerbet alcohols; triglycerides based on (C₆-C₁₀) fatty acids; esters such as dioctyl adipate, diisopropyl dimer dilinoleate; propylene glycols/dicaprylate or waxes such as beeswax, paraffin wax or microwaxes, alone or in combination with hydrophilic waxes, such as cetylstearyl alcohol, for example; fluorinated and perfluorinated oils; fluorinated silicone oils; mixtures of the aforementioned compounds.

In at least one embodiment, the composition comprises a non-ionic coemulsifier. In at least one embodiment, the non-ionic coemulsifier is selected from adducts of from 0 to 30 mol of ethylene oxide and/or from 0 to 5 mol of propylene oxide with linear fatty alcohols having 8 to 22 carbon atoms, with fatty acids having 12 to 22 carbon atoms, with alkylphenols having 8 to 15 carbon atoms in the alkyl group, and with sorbitan or sorbitol esters; (C₁₂-C₁₈) fatty acid monoesters and diesters of adducts of from 0 to 30 mol of ethylene oxide with glycerol; glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and, where appropriate, their ethylene oxide adducts; adducts of from 15 to 60 mol of ethylene oxide with castor oil and/or hydrogenated castor oil; polyol esters and especially polyglycerol esters, such as polyglyceryl polyricinoleate and polyglyceryl poly-12-hydroxystearate, for example. Likewise suitable are mixtures of compounds from one or more of these classes of substance. Examples of suitable ionogenic coemulsifiers include anionic emulsifiers, such as mono-, di- or tri-phosphoric esters, but also cationic emulsifiers such as mono-, di-, and tri-alkyl quats and their polymeric derivatives.

In at least one embodiment, the composition comprises a cationic polymer. Suitable cationic polymers include those known under the INCI designation “Polyquaternium”, especially Polyquaternium-31, Polyquaternium-16, Polyquaternium-24, Polyquaternium-7, Polyquaternium-22, Polyquaternium-39, Polyquaternium-28, Polyquaternium-2, Polyquaternium-10, Polyquaternium-11, and also Polyquaternium 37 & mineral oil & PPG trideceth (Salcare SC95), PVP-dimethylaminoethyl methacrylate copolymer, guar-hydroxypropyltriammonium chlorides, and also calcium alginate and ammonium alginate. It is additionally possible to employ cationic cellulose derivatives; cationic starch; copolymers of diallylammonium salts and acrylamides; quaternized vinylpyrrolidone/vinylimidazole polymers; condensation products of polyglycols and amines; quaternized collagen polypeptides; quaternized wheat polypeptides; polyethyleneimines; cationic silicone polymers, such as amidomethicones, for example; copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine; polyaminopolyamide and cationic chitin derivatives, such as chitosan, for example.

In at least one embodiment, the composition comprises a superfatting agent. As superfatting agents it is possible to use substances such as, for example, polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, monoglycerides, and fatty acid alkanol amides, the latter serving simultaneously as foam stabilizers. Moisturizers available include for example isopropyl palmitate, glycerol and/or sorbitol.

In at least one embodiment, the composition comprises a stabiliser. As stabiliser it is possible to use metal salts of fatty acids, such as magnesium, aluminum and/or zinc stearate, for example.

In at least one embodiment, the composition comprises a care additive. The compositions can be blended with conventional ceramides, pseudoceramides, fatty acid N-alkylpolyhydroxyalkyl amides, cholesterol, cholesterol fatty acid esters, fatty acids, triglycerides, cerebrosides, phospholipids, panthenol and similar substances as a care additive.

In at least one embodiment, the composition comprises a preservative or preservative system. Examples of suitable preservatives include benzyl alcohol, piroctone olamine, phenoxyethanol, parabens, pentanediol, benzoic acid/sodium benzoate, sorbic acid/potassium sorbate, and other organic acids used to provide antimicrobial protection. Preservation boosting ingredients include anisic acid, lactic acid, sorbitan caprylate, ethylhexylglycerin, caprylyl glycol, octanediol, and similar substances. In at least one embodiment, the composition comprises 0.01 to 5 wt.-%, particularly preferably from 0.05 wt.-% to 1 wt.-% of at least one preservative. Suitable preservatives are the substances listed in the International Cosmetic Ingredient Dictionary and Handbook, 9th Edition with the function “preservatives”. In at least one embodiment, the preservative is selected from the group consisting of phenoxyethanol, benzyl paraben, butyl paraben, ethyl paraben, isobutyl paraben, isopropyl paraben, methyl paraben, propyl paraben, iodopropynyl butylcarbamate, methyldibromoglutaronitrile, DMDM hydantoin and combinations thereof. In at least one embodiment, the composition comprises a preservative selected from the group consisting of cetyltrimethyl ammoniumchloride, cetylpyridinium chloride, benzethonium chloride, diisobutylethoxyethyldimethyl benzylammoniumchloride, sodium N-lauryl sarcosinate, sodium-N-palmethylsarcosinate, Lauroylsarcosine, N-myristoylglycine, potassium-N-laurylsarcosine, trimethylammoniumchloride, sodium aluminium chlorohydroxylactate, triethylcitrate, tricetylmethylammoniumchloride, 2,4,4′-trichloro-2′-hydroxydiphenylether (Triclosan), phenoxyethanol, 1,5-pentandiol, 1,6-hexandiol, 3,4,4′-trichlorocarbanilide (Triclocarban), diaminoalkylamide, L-lysine hexadecylamide, heavy metal citrate salts, salicylate, piroctose, zinc salts, pyrithione and its heavy metal salts, zinc pyrithione, zinc phenol sulfate, farnesol, ketoconazol, oxiconazol, bifonazole, butoconazole, cloconazole, clotrimazole, econazole, enilconazole, fenticonazole, isoconazole, miconazole, sulconazole, tioconazole, fluconazole, itraconazole, terconazole, naftifine, terbinafine, selenium disulfide, Octopirox®, methylchloroisothiazolinone, methylisothiazolinone, methyldibromo glutaronitrile, AgCl, chloroxylenol, sodium salts of diethylhexylsulfosuccinate, sodiumbenzoate, phenoxyethanol, benzylalkohol, phenoxyisopropanol, paraben, such as butyl-, ethyl-, methyl-und propylparaben, and their salts, pentandiol, 1,2-octanediol, ethylhexylglycerin, benzylalcohol, sorbic acid, benzoic acid, lactic acid, imidazolidinyl urea, diazolidinyl urea, dimethylol dimethyl hydantoin (DMDMH), sodium salts of hydroxymethyl glycinate, hydroxyethylglycine of sorbic acid and combinations thereof. In at least one embodiment, the preservative is selected from the group consisting of phenoxyethanol, benzyl paraben, butyl paraben, ethyl paraben, isobutyl paraben, isopropyl paraben, methyl paraben, propyl paraben, iodopropynyl butylcarbamate, methyldibromoglutaronitrile, DMDM hydantoin and combinations thereof. In at least one embodiment, the composition is substantially free of parabens.

In at least one embodiment, the composition comprises an anti-fungal substance. In at least one embodiment, the anti-fungal substance is selected from the group consisting of ketoconazole, oxiconazole, bifonazole, butoconazole, cloconazole, clotrimazole, econazole, enilconazole, fenticonazole, isoconazole, miconazole, sulconazole, tioconazole, fluconazole, itraconazole, terconazole, naftifine and terbinafine, zinc pyrithione, octopirox, and combinations thereof. In at least one embodiment, the composition comprises a total amount of anti-fungal substance in the composition of from 0.1 wt.-% to 1 wt.-%. In at least one embodiment, the composition comprises a pyridinethione anti-dandruff particulates, for example 1-hydroxy-2-pyridinethione salts, are highly preferred particulate anti-dandruff agents. The concentration of pyridinethione antidandruff particulate may ranges from 0.1% to 4%, by weight of the composition, preferably from 0.1% to 3%, more preferably from 0.3% to 2%. Preferred pyridinethione salts include those formed from heavy metals such as zinc, tin, cadmium, magnesium, aluminum and zirconium, preferably zinc, more preferably the zinc salt of 1-hydroxy-2-pyridinethione (known as “zinc pyridinethione” or “ZPT”), more preferably 1-hydroxy-2-pyridinethione salts in platelet particle form. Salts formed from other cations, such as sodium, may also be suitable. Pyridinethione anti-dandruff agents are described, for example, in U.S. Pat. Nos. 2,809,971; 3,236,733; 3,753,196; 3,761,418; 4,345,080; 4,323,683; 4,379,753; and 4,470,982. It is contemplated that when ZPT is used as the anti-dandruff particulate in the compositions herein, that the growth or regrowth of hair may be stimulated or regulated, or both, or that hair loss may be reduced or inhibited, or that hair may appear thicker or fuller.

Functional acids are acidic substances used to impart a clinical functionality to the skin or hair upon application. Suitable functional acids include alpha hydroxy acids, beta-hydroxy acids, lactic acid, retinoic acid, and similar substances.

In at least one embodiment, the composition comprises an astringent. In at least one embodiment, the astringent is selected from the group consisting of magnesium oxide, aluminium oxide, titanium dioxide, zirconium dioxide, zinc oxide, oxide hydrates, aluminium oxide hydrate (boehmite) and hydroxide, chlorohydrates of calcium, magnesium, aluminium, titanium, zirconium or zinc. In at least one embodiment, the composition comprises from 0.001 wt.-% to 10 wt.-%, or from 0.01 wt.-% to 9 wt.-%, or from 0.05 wt.-% to 8 wt.-%, or from 0.1 wt.-% to 5 wt.-% astringent.

In at least one embodiment, the composition comprises a deodorizing agent. In at least one embodiment, the deodorizing agent is selected from the group consisting of allantoin, bisabolol, and combinations thereof. In at least one embodiment, the composition comprises from 0.001 wt.-% to 10 wt.-%, or from 0.01 wt.-% to 9 wt.-%, or from 0.05 wt.-% to 8 wt.-%, or from 0.1 wt.-% to 5 wt.-% deodorizing agent.

In at least one embodiment, the composition comprises a sun protection agent and/or UV filter. Suitable sun protection agents and UV filters are disclosed in WO2013017262A1 (published on 7^th Feb. 2013), from page 32, line 11 to the end of page 33. In at least one embodiment, the sun protection agent and/or UV filter is selected from the group consisting of 4-amino benzoic acid, 3-(4′-trimethylammonium)-benzylide-boran-2-one-methylsulfate, camphor benzalkonium methosulfate, 3,3,5-trimethyl-cyclohexylsalicylate, 2-hydroxy-4-methoxybenzophenone, 2-phenylbenzimidazole-5-sulfonic acid and potassium-, sodium-und triethanolamine salts thereof, 3,3′-(1,4-phenylene dimethine)-bis-(7,7-dimethyl-2-oxobicyclo[2.2.1]-heptane-1-methane sulfonic acid) and its salts, 1-(4-tert.-butylphenyl)-3-(4-methoxyphenyl)propan-1,3-dion, 3-(4′-sulfo)-benzylidene-bornane-2-one its salts, 2-cyan-3,3-diphenyl-acrylic acid-(2-ethylhexylester), polymers of N-[2(and 4)-(2-oxoborn-3-ylidenmethyl)benzyl]-acrylamide, 4-methoxy-cinnamic acid-2-ethyl-hexylester, ethoxylated ethyl-4-amino-benzoate, 4-methoxy-cinnamic acid-isoamylester, 2,4,6-tris-[p-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, 2-(2H-benzotriazole-2-yl)-4-methyl-6-(2-methyl-3-(1,3,3,3-tetramethyl-1-(trimethylsilyloxy)-disiloxanyl)-propyl)phenol, 4,4′-[(6-[4-((1,1-dimethylethyl)-amino-carbonyl)phenylamino]-1,3,5-triazin-2,4-yl)diimino]bis-(benzoic acid-2-ethylhexylester), 3-benzophenone, 4-benzophenone (acic), 3(4′-methylbenzyliden)-D,L-camphor, 3-benzylidene-camphor, salicylic acid-2-ethylhexylester, 4-dimethyl aminobenzic acid-2-ethylhexylester, hydroxy-4-methoxy-benzophenone-5 sulfonic acid and the sodium salt thereof, 4-isopropyl benzylsalicylate, N,N,N-trimethyl-4-(2-oxoborn-3-ylidenemethyl) anilium methyl sulfate, homosalate (INN), oxybenzone (INN), 2-phenylbenzimidazole-5-sulfonic acid and its sodium, potassium, and triethanolamine salts, octylmethoxy cinnamic acid, isopentyl-4-methoxy cinnamic acid, isoamyl-β-methoxy cinnamic acid, 2,4,6-trianilino-(p-carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine (octyl triazone) phenol, 2,2(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3-(1,3,3,3-tetramethyl-1-(trimethylsilyl)oxy)-disiloxanyl)propyl (drometrizole trisiloxane) benzic acid, 4,4-((6-(((1,1-dimethylethyl)amino)carbonyl)phenyl)amino)-1,3,5-triazine-2,4-diyl)diimino)bis,bis(2-ethylhexyl)ester) benzoic acid, 4,4-((6-(((1,1-dimethylethyl)amino)-carbonyl)phenyl)amino)-1,3,5-triazine-2,4-diyl)diimino)bis,bis(2-ethylhexyl)ester), 3-(4′-methylbenzylidene)-D,L-camphor (4-methylbenzylidene camphor), benzylidene-camphor-sulfonic acid, octocrylene, polyacrylamidomethyl-benzylidene-camphor, 2-ethylhexyl salicylate (octyl salicylate), 4-dimethyl-aminobenzoeacidethyl-2-hexylester (octyl dimethyl PABA), PEG-25 PABA, 2 hydroxy-4-methoxybenzo-phenone-5-sulfonic acid (5-benzophenone) and the sodium salt thereof, 2,2′-methylene-bis-6-(2H-benzotriazol-2-yl)-4-(tetramethyl-butyl)-1,1,3,3-phenol, the sodium salt of 2-2′-bis-(1,4-phenylene)1H-benzimidazole-4,6-disulfonic acid, (1,3,5)-triazine-2,4-bis((4-(2-ethyl-hexyloxy)-2-hydroxy)-phenyl)-6-(4-methoxyphenyl), 2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate, glyceryl octanoate, di-β-methoxy cinnamic acid, p-amino-benzoic acid and its ester, 4-tert-butyl-4′-methoxydibenzoylmethane, 4-(2-β-glucopyranoxy)propoxy-2-hydroxybenzophenone, octyl salicylate, methyl-2,5-diisopropyl cinnamic acid, cinoxate, dihydroxy-dimethoxybenzophenone, disodium salts of 2,2′-dihydroxy-4,4′-dimethoxy-5,5′-disulfobenzophenone, dihydroxybenzophenone, 1,3,4-dimethoxyphenyl-4,4-dimethyl-1,3-pentanedione, 2-ethylhexyl-dimethoxybenzyliden-dioxoimidazolidinpropionate, methylene-bis-benztriazolyl tetramethylbutylphenol, phenyldibenzimidazoltetrasulfonate, bis-ethylhexyloxyphenol-methoxyphenol-triazine, tetrahydroxybenzophenone, terephthalylidendicamphor-sulfonic acid, 2,4,6-tris[4,2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, methyl-bis(trimethylsiloxy)silyl-isopentyl trimethoxy cinnamic acid, amyl-p-dimethylaminobenzoate, amyl-p-dimethylamino benzoate, 2-ethylhexyl-p-dimethylaminobenzoate, isopropyl-p-methoxy cinnamic acid/diisopropyl cinnamic acid ester, 2-ethylhexyl-p-methoxy cinnamic acid, 2-hydroxy-4-methoxy benzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and the trihydrate, 2-hydroxy-4-methoxybenzophenone-5-sulfonate sodium salt, phenyl-benzimidazole sulfonic acid, and combinations thereof. In at least one embodiment, the composition comprises from 0.001 wt.-% to 10 wt.-%, preferably from 0.05 wt.-% to 5 wt.-%, even more preferably from 0.1 wt.-% to 3 wt.-%, most preferably from 0.05 wt.-% to 1 wt.-% sun protection agent and/or UV filter. In at least one embodiment, the composition comprises a photoprotective substance in an amount of from 0.01 to 10 wt.-%, or from 0.1 to 5 wt.-%, particularly preferably from 0.2 to 2 wt.-%. The photoprotective substances include, in particular, all of the photoprotective substances specified in EP 1 084 696, which is incorporated herein by reference. In a preferred embodiment, the photoprotective substance is selected from the group consisting of 2-ethylhexyl 4-methoxycinnamate, methyl methoxycinnamate, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, polyethoxylated p-aminobenzoates, and combinations thereof.

In at least one embodiment, the composition comprises an anti-oxidant. In at least one embodiment, the anti-oxidant is selected from the group consisting of amino acids, peptides, sugars, imidazoles, carotinoids, carotenes, chlorogenic acid, lipoic acid, thiols, thiol glycosyl esters, thiol N-acetyl esters, thiol methyl esters, thiol ethyl esters, thiol propyl esters, thiol amyl esters, thiol butyl esters, thiol lauryl esters, thiol palmitoyl esters, thiol oleyl esters, thiol linoleyl esters, thiol cholesteryl esters, thiol glyceryl esters, dilaurylthiodipropionate, distearylthiodipropionate, thiodipropionic acid, metal chelators, hydroxy acids, fatty acids, folic acids, vitamin C, tocopherol, vitamin A, stilbenes, derivatives and combinations thereof. In at least one embodiment, the anti-oxidant is selected from the group consisting of glycine, histidine, tyrosine, tryptophan, urocaninic acid, D,L-carnosine, D-carnosine, L-carnosine, beta-carotene, alpha-carotene, lycopene, dihydrolipoic acid, aurothioglucose, propylthiouracil, thioredoxine, glutathione, cysteine, cystine, cystamine, buthioninsulfoximine, homocysteinsulfoximine, buthioninsulfone, penta-, hexa-, heptathioninsulfoximine, hydroxyfatty acids, palmitic acid, phytinic acid, lactoferrin, citric acid, lactic acid, malic acid, humic acid, bile acid, bilirubin, biliverdin, EDTA, EGTA, linoleic acid, linolenic acid, oleic acid, butylhydroxyanisol, trihydroxybutyrophenone, ubichinon, ubichinol, ascorbylpalmitate, Mg-ascorbylphosphate, ascorbylacetate, vitamin E acetate, vitamin A palmitate, carnosine, mannose, ZnO, ZnSO₄, selenium methionine, stilbenes, superoxide dismutase, and combinations thereof. In at least one embodiment, the antioxidant is selected from the group consisting of vitamin A, vitamin A derivatives, vitamin E, vitamin E derivatives, and combinations thereof. In at least one embodiment, the composition comprises from 0.001 wt.-% to 10 wt.-%, preferably from 0.05 wt.-% to 5 wt.-%, even more preferably from 0.1 wt.-% to 3 wt.-%, most preferably from 0.05 wt.-% to 1 wt.-% antioxidant.

In at least one embodiment, the composition comprises a dye or pigment. In at least one embodiment, the composition comprises at least one pigment. Suitable dyes and pigments are disclosed in WO2013017262A1 in the table spanning pages 36 to 43. These may be colored pigments which impart color effects to the product mass or to hair, or they may be luster effect pigments which impart luster effects to the product mass or to the hair. The color or luster effects on the hair are preferably temporary, i.e. they last until the next hair wash and can be removed again by washing the hair with customary shampoos. In at least one embodiment, the composition comprises a total amount of from 0.01 wt.-% to 25 wt.-%, preferably from 5 wt.-% to 15 wt.-% pigment. In at least one embodiment, the particle size of the pigment is from 1 micron to 200 micron, preferably from 3 micron to 150 micron, more preferably 10 micron to 100 micron. The pigments are colorants which are virtually insoluble in the application medium, and may be inorganic or organic. Inorganic-organic mixed pigments are also possible. Preference is given to inorganic pigments. The advantage of inorganic pigments is their excellent resistance to light, weather and temperature. The inorganic pigments may be of natural origin. In at least one embodiment, the inorganic pigment is selected from the group consisting of chalk, ochre, umber, green earth, burnt sienna, graphite, and combinations thereof. The pigments may be white pigments, such as, for example, titanium dioxide or zinc oxide, black pigments, such as, for example, iron oxide black, colored pigments, such as, for example, ultramarine or iron oxide red, lustre pigments, metal effect pigments, pearlescent pigments, and fluorescent or phosphorescent pigments, where preferably at least one pigment is a colored, nonwhite pigment. In at least one embodiment, the pigment is selected from the group consisting of metal oxides, hydroxides and oxide hydrates, mixed phase pigments, sulfur-containing silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and molybdates, and the metals themselves (bronze pigments), and combinations thereof. In at least one embodiment, the pigment is selected from the group consisting of titanium dioxide (Cl 77891), black iron oxide (Cl 77499), yellow iron oxide (Cl 77492), red and brown iron oxide (Cl 77491), manganese violet (Cl 77742), ultramarine (sodium aluminum sulfosilicates, Cl 77007, Pigment Blue 29), chromium oxide hydrate (Cl 77289), Prussian blue (ferric ferrocyanide, Cl 77510), carmine (cochineal), and combinations thereof. In at least one embodiment, the pigment is selected from the group consisting of pearlescent and colored pigments based on mica which are coated with a metal oxide or a metal oxychloride, such as titanium dioxide or bismuth oxychloride, and optionally further color-imparting substances, such as iron oxides, Prussian blue, ultramarine, carmine etc. and where the color can be determined by varying the layer thickness. Such pigments are sold, for example, under the trade names Rona®, Colorona©, Dichrona® and Timiron® by Merck, Germany. In at least one embodiment, the pigment is selected from the group consisting of organic pigments such as sepia, gamboge, bone charcoal, Cassel brown, indigo, chlorophyll and other plant pigments. In at least one embodiment, the pigment is selected from the group consisting of synthetic organic pigments such as azo pigments, anthraquinoids, indigoids, dioxazine, quinacridone, phthalocyanine, isoindolinone, perylene and perinone, metal complex, alkali blue and diketopyrrolopyrrole pigments.

In at least one embodiment, the composition comprises from 0.01 wt.-% to 10 wt.-%, preferably from 0.05 wt.-% to 5 wt.-%, of at least one particulate substance. Suitable substances are, for example, substances which are solid at room temperature (25° C.) and are in the form of particles. In at least one embodiment, the particulate substance is selected from the group consisting of silica, silicates, aluminates, clay earths, mica, insoluble salts, in particular insoluble inorganic metal salts, metal oxides, e.g. titanium dioxide, minerals and insoluble polymer particles are suitable. The particles are present in the composition in undissolved, preferably stably dispersed form, and, following application to the keratin substrate and evaporation of the solvent, can deposit on the substrate in solid form. A stable dispersion can be achieved by providing the composition with a yield point which is large enough to prevent the solid particles from sinking. An adequate yield point can be established using suitable gel formers in a suitable amount. In at least one embodiment, the particulate substance is selected from the group consisting of silica (silica gel, silicon dioxide) and metal salts, in particular inorganic metal salts, where silica is particularly preferred. Metal salts are, for example, alkali metal or alkaline earth metal halides, such as sodium chloride or potassium chloride; alkali metal or alkaline earth metal sulfates, such as sodium sulfate or magnesium sulfate.

In at least one embodiment, the composition comprises a direct dye. Preferred among the direct dyes are the following compounds, alone or in combination with one another: Hydroxyethyl-2-nitro-β-toluidine, 2-hydroxyethylpicramic acid, 4-nitrophenylaminourea, tri(4-amino-3-methylphenyl)carbenium chloride (Basic Violet 2), 1,4-di-amino-9,10-anthracenedione (Disperse Violet 1), 1-(2-hydroxy-ethyl)amino-2-nitro-4-[di(2-hydroxyethyl)amino]benzene (HC Blue No. 2), 4-[ethyl-(2-hydroxyethyl)amino]-1-[(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Blue No. 12), 1-amino-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Red No. 13), 4-amino-1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitrophenol, 1-amino-5-chloro-4-[(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 10), 5-chloro-1,4-[di(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 11), 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitro-1-trifluoromethylbenzene (HC Yellow No. 13), 8-amino-2-bromo-5-hydroxy-4-imino-6-{[3-(trimethylammonio)-phenyl]amino}-1(4H)-naphthalenone chloride (C.I. 56059; Basic Blue No. 99), 1-[(4-aminophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (C.I. 12250; Basic Brown No. 16), 1-[(4-amino-2-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (Basic Brown No. 17), 2-hydroxy-1-[(2-methoxyphenyl)azo]-7-(trimethylammonio)naphthalene chloride (C.I. 12245; Basic Red No. 76), 3-methyl-1-phenyl-4-{[3-(trimethylammonio)phenyl]azo}pyrazol-5-one chloride (C.I. 12719; Basic Yellow No. 57) and 2,6-diamino-3-[(pyridin-3-yl)azo]pyridine as well as the salts thereof. Particularly preferred among the aforesaid direct dyes are the following compounds, alone or in combination with one another: hydroxyethyl-2-nitro-β-toluidine, 2-hydroxyethylpicramic acid, 4-nitrophenylaminourea, tri(4-amino-3-methylphenyl)carbenium chloride (Basic Violet 2), 1,4-di-amino-9,10-anthracenedione (Disperse Violet 1), 1-(2-hydroxy-ethyl)amino-2-nitro-4-[di(2-hydro-xyethyl)amino]benzene (HC Blue No. 2), 4-[ethyl-(2-hydroxyethyl)amino]-1-[(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Blue No. 12), 1-amino-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Red No. 13), 4-amino-1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitrophenol, 1-amino-5-chloro-4-[(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 10), 5-chloro-1,4-[di(2,3-dihydroxypropyl)-amino]-2-nitrobenzene (HC Red No. 11), 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitro-1-trifluoromethylbenzene (HC Yellow No. 13), 8-amino-2-bromo-5-hydroxy-4-imino-6-{[3-(trimethylammonio)-phenyl]amino}-1(4H)-naphthalenone chloride (C.I. 56059; Basic Blue No. 99), 1-[(4-aminophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (C.I. 12250; Basic Brown No. 16), 1-[(4-amino-2-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (Basic Brown No. 17), 2-hydroxy-1-[(2-methoxyphenyl)azo]-7-(trimethylammonio)naphthalene chloride (C.I. 12245; Basic Red No. 76), 3-methyl-1-phenyl-4-{[3-(trimethylammonio)phenyl]azo}pyrazol-5-one chloride (C.I. 12719; Basic Yellow No. 57) and 2,6-diamino-3-[(pyridin-3-yl)azo]pyridine as well as the salts thereof. In at least one embodiment, the total quantity of direct dyes in the composition amounts to 0.01 to 15 wt.-%, preferably 0.1 to 10 wt.-%, most preferred 0.5 to 8 wt.-%.

The present invention also relates to the use of the hybrid polymer according to the present invention as a thickening agent, structurant, and/or rheology modifier.

In at least one embodiment, the hybrid polymer is used in a cosmetic composition.

The present invention also relates to a kit comprising the composition according to the present invention and a formulation selected from the group consisting of hair conditioning formulations, hair styling formulations, intensive conditioning formulations, skin moisturizing formulations, and combinations thereof.

The present invention also relates to a container comprising a package comprising a receptacle comprising the composition according to the present invention and wherein the package comprises a closure for containing the composition in the receptacle.

The present invention also relates to a method for cleansing hair and/or skin comprising applying the composition according to the present invention onto hair and/or skin.

The present invention also relates to the use of the composition according to the present invention as a cosmetic agent.

The present invention also relates to a polymerisation process for synthesising a water-soluble and/or water-swellable hybrid polymer comprising:

• • (i) from 30 wt.-% to 99 wt.-% water-soluble and/or water-swellable polysaccharide polymer as defined herein;
  • (ii) from 1 wt.-% to 70 wt.-% synthetic polymer as defined herein;
  • characterised in that the components (i) and (ii) are polymerised by radical precipitation polymerisation in a solvent. Preferably the polymerisation is grafting radical precipitation polymerisation.

In at least one embodiment, the monomers resulting in units in the synthetic polymer are neutralised with a base prior to the polymerisation, and/or the hybrid polymer after polymerisation is neutralised with a base.

In at least one embodiment, the monomers resulting in units (a) and/or (b) are neutralised with a base prior to the polymerisation, and/or the hybrid polymer after polymerisation is neutralised with a base.

In at least one embodiment, the base is selected from bases comprising a cation selected from the group consisting of NH₄⁺, Li⁺, Na⁺, K⁺, Ca⁺⁺, Mg⁺⁺, Zn⁺⁺, Al⁺⁺⁺, Zr⁺⁺⁺⁺ and mixtures thereof; preferably the base is selected from hydroxides, carbonates and hydrogen carbonates comprising a cation selected from the group consisting of NH₄⁺, Li⁺, Na⁺, K⁺, Ca⁺⁺, Mg⁺⁺, Zn⁺⁺, Al⁺⁺⁺ and mixtures thereof. In at least one embodiment, the base is selected from the group consisting of gaseous ammonia, ammonium hydrogen carbonate, ammonium carbonate, ammonium hydroxide, sodium hydrogen carbonate, sodium carbonate, sodium hydroxide, potassium hydrogen carbonate, potassium carbonate, potassium hydroxide, lithium hydrogen carbonate, lithium carbonate, lithium hydroxide, calcium hydrogen carbonate, calcium carbonate, calcium hydroxide, preferably sodium hydrogen carbonate, sodium carbonate, sodium hydroxide, potassium hydrogen carbonate, potassium carbonate, potassium hydroxide, even more preferably sodium hydrogen carbonate, sodium carbonate, sodium hydroxide, most preferably sodium hydrogen carbonate and sodium carbonate.

In at least one embodiment, the solvent is an organic or inorganic solvent having a highly inert behaviour in free-radical polymerisation reactions and which advantageously allows the formation of medium or high molecular weights, or mixtures of such solvents. The choice of chemistry and level of solvent is important in view of ensuring the dispersion and dissolving of the units making up the hybrid polymer in the reaction mixture. Furthermore, the hybrid polymer as it is synthesised should not result in the build-up of clumps and/or adhesions in the reaction mixture or on the equipment. It is advantageous that no significant agglomerates and adhesions build up within the stirring equipment because of the risk of damage and extension cleaning requirements. In at least one embodiment, the solvent has a boiling point of from 20° C. to 110° C., or from 40° C. to 95° C., or from 50° C. to 90° C. In at least one embodiment, the solvent is a polar solvent. In at least one embodiment, the solvent is selected from the group consisting of water, lower alcohols, and mixtures of water and lower alcohols. In at least one embodiment, the solvent is selected from the group consisting of methanol, ethanol, propanol, acetone, iso-, sec- and t-butanol, hydrocarbons having 1 to 30 carbon atoms, and mixtures and emulsions thereof. In at least one embodiment, the solvent is a mixture of water and a solvent selected from the group consisting of methanol, ethanol, propanol, acetone, iso-, sec- and t-butanol, hydrocarbons having 1 to 30 carbon atoms. In at least one embodiment, the solvent is selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, dimethyl ketone, diethyl ketone, tetrahydropyran, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, 1,4-dioxane, preferably ethanol, 1-propanol, 2-propanol, 2-methylpropan-2-ol, 1-butanol, 2-butanol, dimethyl ketone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, even more preferably 2-propanol, 2-methylpropan-2-ol, dimethyl ketone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, most preferably 2-methylpropan-2-ol and dimethyl ketone. In at least one embodiment, the solvent is a mixture of water and a solvent is selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, dimethylketone, diethylketone, tetrahydropyran, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, 1,4-dioxane, preferably ethanol, 1-propanol, 2-propanol, 2-methylpropan-2-ol, 1-butanol, 2-butanol, dimethylketone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, even more preferably 2-propanol, 2-methylpropan-2-ol, dimethylketone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, most preferably 2-methylpropan-2-ol and dimethyl ketone. In at least one embodiment, the solvent mixture comprises from 0.1 wt.-% to 30 wt.-% water, or from 0.5 wt.-% to 25 wt.-% water, or from 1 wt.-% to 20 wt.-% water, preferably from 0.5 wt.-% to 15 wt.-% water. It is advantageous to ensure that the level of water in the solvent is 30 wt.-% or below in view of reduced likelihood of clumping during the polymerisation process. Such build-up of clumps can put the stirring mechanism under undesirable strain. In at least one embodiment, the solvent mixture comprises from 1 wt.-% to 99.5 wt.-% preferably from 5 wt.-% to 95 wt.-%, more preferably from 10 wt.-% to 90 wt.-% 2-methylpropan-2-ol. In at least one embodiment, the solvent mixture is 2-methylpropan-2-ol and dimethyl ketone. In at least one embodiment, the solvent mixture comprises from 0.5 to 10 wt.-% water, from 1 wt.-% to 98.5 wt.-% 2 methylpropan-2-ol and from 1 wt.-% to 98.5 wt.-% dimethyl ketone, preferably from 0.5 wt.-% to 7.5 wt.-% water, from 5 wt.-% to 94.5 wt.-% 2-methylpropan-2-ol and from 5 wt.-% to 94.5 wt.-% dimethyl ketone, most preferably from 1 wt.-% to 5 wt.-% water, from 7.5 wt.-% to 91.5 wt.-% 2-methylpropan-2-ol and from 7.5 wt.-% to 91.5 wt.-% dimethyl ketone.

In at least one embodiment, the radical precipitation polymerisation is carried out in a polar solvent mixture comprising:

• • I) water and
  • II) a further compound.

In at least one embodiment the compound II) is polar and organic.

In at least one embodiment the compound II) is selected from polar alcohols and ketones. In at least one embodiment the compound II) is one or more polar alcohols and one or more ketones.

In a preferred embodiment, the compound II) is selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, dimethyl ketone, diethyl ketone, pentan-2-one, butanone, tetrahydro pyrane, tetrahydro furane, 2-methyl-tetrahydro furane, 1,3-dioxane, 1,4-dioxane, preferably 2-propanol, 2-methyl-2-propanol, dimethyl ketone, tetrahydro furane, 2-methyl-tetrahydro furane, more preferably 2-methyl-2-propanol and dimethyl ketone. In a particularly preferred embodiment, the compound II) is 2-methyl-2-propanol.

In a preferred embodiment, the solvent mixture contains from 0.5 to 10 wt.-%, preferably from 1 to 8 wt.-% and more preferably from 2 to 5 wt.-% water.

In a preferred embodiment, the solvent mixture contains from 90 to 99.5 wt.-%, preferably from 92 to 99 wt.-% and more preferably from 95 to 98 wt.-% 2-methyl-2-propanol.

In a preferred embodiment, the solvent mixture contains from 0.5 to 10 wt.-% water, from 1 to 98.5 wt.-% 2-methyl-2-propanol and from 1 to 98.5 wt.-% dimethyl ketone, preferably from 0.5 to 7.5 wt.-% water, from 5 to 94.5 wt.-% 2-methyl-2-propanol and from 5 to 94.5 wt.-% dimethyl ketone.

In at least one embodiment, the polymerisation takes place at a temperature of from 0° C. to 150° C., or from 10° C. to 100° C., or from 20° C. to 90° C., or from 30° C. to 80° C., or from 30° C. to 70° C., or from 40° C. to 60° C., or from 50° C. to 70° C.

In at least one embodiment, the polymerisation takes place at either atmospheric pressure or under elevated or reduced pressure. In at least one embodiment, the polymerisation may also be performed under an inert gas atmosphere, preferably under nitrogen gas.

In at least one embodiment, the polymerisation is carried out in the presence of an initiator. The initiator is used for initiating the polymerisation. In at least one embodiment, the initiator is selected from high-energy electromagnetic rays, mechanical energy, a chemical initiator, or combinations thereof. In at least one embodiment, the initiator is a radical-producing initiator. In at least one embodiment, the initiator is selected from the group consisting of organic peroxides, persulfates, azo initiators, and mixtures thereof. In at least one embodiment, the initiator is an organic peroxide selected from the group consisting of benzoyl peroxide, tert-butyl hydroperoxide, di-tert-butyl hydroperoxide, triphenylmethyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dilauroyl peroxide (DLP), and mixtures thereof.

In a particularly preferred embodiment, the polymerisation is carried out in the presence of dimethyl 2,2′-azobis(2-methylpropionate), 2,2-azobis(2,4-dimethylvaleronitril) or dilauroyl peroxide (DLP). In a particularly preferred embodiment, the polymerisation is carried out in the presence of dimethyl 2,2′-azobis(2-methylpropionate) or 2,2-azobis(2,4-dimethylvaleronitril). In a particularly preferred embodiment, the polymerisation is carried out in the presence of dilauroyl peroxide (DLP).

In at least one embodiment, the initiator is an azo initiator selected from the group consisting of azo-bis-isobutyronitrile (AIBN), 2,2′-azobis(4-methoxy-2.4-dimethyl valeronitrile), 2,2′-azobis(2,4-dimethyl valeronitrile), dimethyl 2,2′-azobis(2-methylpropionate), 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane-1-carbonitrile), 2,2′-azobis[n-(2-propenyl)-2-methyl-propionamide], azobisamideopropyl hydrochloride (ABAH), and mixtures thereof. In at least one embodiment, the initiator is an azo initiator selected from the group consisting of azo-bis-isobutyronitrile (AIBN) and azobisamideopropyl hydrochloride (ABAH).

In at least one embodiment, the initiator is a persulfate selected from the group consisting of potassium peroxidisulfate, potassium peroxidisulfate, ammonium peroxidisulfate, potassium peroxi mono sulfat, sodium peroximonosulfate, ammonium peroximonosulfate, and mixtures thereof. Organic persulfates are also useful.

In at least one embodiment, the initiator is selected from the group consisting of inorganic peroxy compounds, such as (NH₄)₂S₂O₈, K₂S₂O₈ or H₂O2, for example, where appropriate in combination with reducing agents (e.g., sodium hydrogensulfite, ascorbic acid, iron(II) sulfate) or redox systems comprising as reducing component an aliphatic or aromatic sulfonic acid (e.g., benzenesulfonic acid, toluenesulfonic acid, etc.).

In at least one embodiment, the initiator is a mixture of a redox initiator and an azo initiator. This has the advantage that a redox initiator system generates significant amount of —O* radicals on polysaccharide backbone and azo initiator will deliver enough active synthetic polymer chains. The combination of a redox initiator and an azo initiator will increase the amount of grafted synthetic polymer chains on polysaccharide backbone.

In at least one embodiment, the initiator is a mixture of ammonium peroxidisulfate and sodium sulfite, potassium peroxidisulfate and sodium sulfite, ammonium peroxidisulfate and ascorbic acid, sodium peroxidisulfate and ascorbic acid, ammonium peroxidisulfate and N,N,N′,N′-tetramethylene diamine, potassium peroxidisulfate and N,N,N′,N′-tetramethylene diamine, ammonium peroximonosulfate and N,N,N′,N′-tetramethylene diamine, ammonium peroximonosulfate and ascorbic acid, ammonium peroximonosulfate and thiourea, ammonium peroximonosulfate and malonic acid, ammonium peroximonosulfate and glycolic acid, ammoniumperoxi-monosulfate and malic acid, 2-hydroxy-2-sulfonatoacetic acid and sodium sulfite, 2-hydroxy-2-sulfonatoacetic acid and ammonium peroximonosulfat, 2-hydroxy-2-sulfonatoacetic acid and N,N,N′,N′-tetramethylendiamin, tert.-butylhydroperoxide and N,N,N′,N′-tetramethylendiamin, 2-hydroxy-2-sulfonatoacetic acid and tert.-butylhydroperoxide, blends of sodium sulfite, 2-hydroxy-2-sulfonatoacetic acid disodium salt, 2-hydroxy-2-sulfinatoacetic acid disodium salt with tert.-butylhydroperoxide, Bruggolite® E28, TP 1651, NHS, FF6 M or FF7 with organic peroxides, for example tert.-butylhydroxy peroxide or lauroylperoxide.

In at least one embodiment, the polymerisation comprises the step of treating the water-soluble and/or water-swellable polysaccharide polymer with water prior to polymerisation. This water treatment step preferably results in a homogenous distribution of water molecules in the polysaccharide polymer.

In at least one embodiment, the polymerisation comprises the step of recovering the hybrid polymer after polymerisation.

EXAMPLES

General Synthesis Example

The water-soluble and/or water-swellable hybrid polymer comprises (i) water soluble and/or water-swellable polysaccharide polymer; and (ii) synthetic polymer. Components (i) and (ii) are polymerised by radical precipitation polymerisation in a solvent. Preferably the polymerisation is grafting radical precipitation polymerisation.

Firstly, to the water-soluble and/or water-swellable polysaccharide polymer (component [i]) a defined amount of water is added, which is then combined with the monomers used for the synthetic polymer (component [ii]) that have been dispersed or dissolved in solvent.

The solvent is preferably a solvent mixture of 2-methylpropan-2-ol and water where the level of water in the solvent mixture is below 30 wt.-% by total weight of the solvent mixture. The polymerisation reaction is started for example by a radical-releasing initiator combined with a redox-initiator system.

The synthetic polymer is preferably thus polymerised at the same time as the hybrid polymer is synthesized. The polymerisation reaction is preferably carried out between 30° C. and 70° C. and over a timeframe of at least 30 minutes. The hybrid polymer is produced in the solvent mixture as a white, slightly yellowish precipitate. The hybrid polymer is recovered from the solvent via evaporation or drying means (e.g. vacuum drying) and/or via vacuum or pressurized filtration and subsequent drying. The vaporized solvent can be condensed, recovered, and can be used for further polymerisations.

In some cases, the monomer(s) resulting in the structural units for the synthetic polymer is/are neutralized prior to the start of synthesis. In this case, the acidic groups of the monomers are at least partly transferred by a base in its corresponding salts. However, the neutralization of the acidic groups on the synthetic polymer can also be carried out after the radical precipitation polymerisation.

Example 1 (Method 1)

In a 1-Liter glass lab reactor equipped with a reflux condenser, sub surface gas inlet tubing, inner temperature sensor and pH probe and overhead agitator 243.7 g dry 2-methylpropan-2-ol and 6.2 g deionized water was dosed. 27.4 g ATBS was added and neutralized to a pH of 6.5 to 7.5 by injection of gaseous ammonia. The temperature was kept below 40° C. Then 62.6 g of tara gum and 0.5 g trimethylolpropane triacrylate (TMPTA) were added to the reaction mixture. At agitation of 200 rpm nitrogen was injected subsurface for 0.5 h with a rate of 1.7 standard liter per minute (SLM). During this time the temperature of the reaction mixture was raised and stabilized to 65° C. with help of a water bath. At 65° C. the pH was re-adjusted to a pH of 6.5 to 7.5. Then the reaction was initiated by addition of 0.15 g tert.-butyl hydroperoxide and continuously dosing of a mixture containing 0.52 g Brüggolit® FF6M (8% in water). After 30 min the reaction was heated up to 70° C. and 0.78 g dimethyl 2,2′-azobis(2-methylpropionate) (V601) was added and stirred over approximately 120 min.

The hybrid polymer is produced in the solvent mixture as a white, voluminous precipitate.

The hybrid polymer is recovered from the solvent via vacuum filtration and drying in vacuum oven (50 mbar, 80° C.).

Example 2 (Method 2)

In a 1-Liter glass lab reactor equipped with a reflux condenser, sub surface gas inlet tubing, inner temperature sensor and pH probe and overhead agitator 243.7 g dry 2-methylpropan-2-01 and 6.2 g deionized water was dosed. 18 g ATBS was added and neutralized to a pH of 6.5 to 7.5 by injection of gaseous ammonia above the surface. The temperature was kept below 40° C. Then 72 g of tara gum and 0.75 g trimethylolpropane triacrylate (TMPTA) were dissolved/dispersed in the reaction mixture. At agitation of 200 rpm nitrogen was injected with a rate of 2 SLM subsurface for 0.5 h. During this time the temperature of the reaction mixture was raised and stabilized to 65° C. with help of a water bath. At 65° C. the pH was re-adjusted to a pH of 6.5 to 7.5. Then the reaction was initiated by addition of 0.15 g tert.-butyl hydroperoxide and continuously dosing of a mixture containing 0.52 g Brüggolit® FF6M (8% in water). After 30 min the reaction was heated up to 70° C. and 0.82 g 2,2-azobis(2,4-dimethylvaleronitril) (V-65) was added and stirred over approximately 120 min.

The hybrid polymer is produced in the solvent mixture as a white, voluminous precipitate.

The hybrid polymer is recovered from the solvent via pressurized filtration and drying in vacuum oven (50 mbar, 80° C.).

Example 3 (Method 3)

In a 1-Liter glass lab reactor equipped with a reflux condenser, sub surface gas inlet tubing, inner temperature sensor and pH probe and overhead agitator 243.3 g dry 2-methylpropan-2-ol and 7.0 g deionized water was dosed. 18 g ATBS was added and neutralized to a pH of 6.5 to 7.5 by injection of gaseous ammonia above the surface. The temperature was kept below 40° C. Then 72 g of tara gum and 0.5 g propoxylated glycerol triacrylate (GPTA) were dissolved/dispersed in the reaction mixture. At agitation of 200 rpm nitrogen was injected with a rate of 1.8 SLM subsurface for 0.5 h. During this time the temperature of the reaction mixture was raised and stabilized to 55° C. with help of a water bath. At 55° C. the pH was re-adjusted to a pH of 6.5 to 7.5. Then the reaction was initiated by addition of 0.15 g tert-butyl hydroperoxide and continuously dosing of a mixture containing 0.52 g Brüggolit® FF7 (8% in water). After 30 min the reaction was heated up to 80° C. and 0.82 g 2,2-azobis(2,4-dimethylvaleronitril) (V-65) was added and stirred over approximately 240 min.

The hybrid polymer is produced in the solvent mixture as a white, voluminous precipitate.

The hybrid polymer is recovered from the solvent via filtration and drying in vacuum oven (50 mbar, 80° C.).

Example 4 (Method 4)

In a 1-Liter glass lab reactor equipped with a reflux condenser, sub surface gas inlet tubing, inner temperature sensor and pH probe and overhead agitator 388.4 g dry 2-methylpropan-2-01 and 11.6 g deionized water was dosed. 28.7 g ATBS was added and neutralized to a pH of 6.5 to 7.5 by injection of gaseous ammonia above the surface. The temperature was kept below 40° C. Then 115 g of guar gum and 0.8 g propoxylated glycerol triacrylate (GPTA) were dissolved/dispersed in the reaction mixture. At agitation of 200 rpm nitrogen was injected with a rate of 2 SLM subsurface for 0.5 h. During this time the temperature of the reaction mixture was raised and stabilized to 55° C. with help of a water bath. At 55° C. the pH was re-adjusted to a pH of 6.5 to 7.5. Then the reaction was initiated by addition of 0.25 g tert-butyl hydroperoxide and continuously dosing of a mixture containing 0.83 g Brüggolit® FF7 (8% in water). After 30 min the reaction was heated up to 80° C. and 1.3 g 2,2-azobis(2,4-dimethylvaleronitril) (V-65) was added and stirred over approximately 240 min.

The hybrid polymer is produced in the solvent mixture as a white, voluminous precipitate.

The hybrid polymer is recovered from the solvent by drying in vacuum oven (50 mbar, 80° C.).

Example 5 (Method 5)

In a 1-Liter glass lab reactor equipped with a reflux condenser, sub surface gas inlet tubing, inner temperature sensor and pH probe and overhead agitator 388.8 g dry 2-methylpropan-2-01 and 11.2 g deionized water was dosed. NaHCO₃ was equimolar charged in tert-butanol and 18 g AMPS was slowly dosed to achieve a final pH of 6.5 to 7.5. The temperature was kept below 40° C. Then 72 g of tara gum and 0.5 g propoxylated glycerol triacrylate (GPTA) were dissolved/dispersed in the reaction mixture. At agitation of 200 rpm nitrogen was injected subsurface for 0.5 h with a rate of 1.5 SLM. During this time the temperature of the reaction mixture was raised and stabilized to 55° C. with help of a water bath. At 55° C. the pH was re-adjusted to a pH of 6.5 to 7.5. Then the reaction was initiated by addition of 0.15 g tert-butyl hydroperoxide and continuously dosing of a mixture containing 0.52 g Brüggolit® FF7 (8% in water). After 30 min the reaction was heated up to 80° C. and 0.82 g 2,2-azobis(2,4-dimethylvaleronitril) (V-65) was added and stirred over approximately 240 min.

The hybrid polymer is produced in the solvent mixture as a white, voluminous precipitate.

The hybrid polymer is recovered from the solvent via vacuum filtration and drying in vacuum oven (50 mbar, 80° C.).

Example 6 (Method 6)

In a glass lab reactor equipped with a reflux condenser, sub surface gas inlet tubing, inner temperature sensor and pH probe and overhead agitator 390 g dry 2-methylpropan-2-ol and 10 g deionized water was dosed. 43.1 g ATBS was added and neutralized to a pH of 6.5 to 7.5 by injection of gaseous ammonia above the surface. The temperature was kept below 40° C. Then 100.5 g of tara gum, 0.8 g trimethylolpropantriacrylate (TMPTA) were added to the reaction mixture. At agitation of 200 rpm nitrogen was injected with a rate of 1.7 SLM subsurface for 0.5 h. During this time the temperature of the reaction mixture was stabilized at 40° C. with help of a water bath. At 40° C. the pH was re-adjusted to a pH of 6.5 to 7.5. Then the reaction was initiated by addition of 0.25 g tert-butyl hydroperoxide, 2.16 g DLP and continuously dosing of a mixture containing 0.83 g Brüggolit® FF7 (8% in water) for 2.5 h. Then the reaction mixture was heated up to 60° C. for 1 h and refluxed under stirring for further 4 h.

The hybrid polymer is produced in the solvent mixture as a white, voluminous precipitate.

The hybrid polymer is recovered from the solvent by drying in vacuum (150 mbar, 80° C., 10 h).

According to the general procedure (general synthesis example above) and Methods 1-6 above all other hybrid polymer examples in Table 1 and Table 1 a were synthesized by correspondingly adjusting the composition and/or the amount of solvent, water, polysaccharide polymer, monomer, crosslinker and/or initiator system.

TABLE 1
Hybrid polymers
						Synthetic
				Poly-		Mono-			Initiator System
				saccharide	Poly-	mer	Cross-		Reducing	Radical
		Sol-		Polymer	mer	[ATBS/	linker	t-	agent	Inititaor
Ex-		vent	Water	[Name/	[wt.-	mol-	[Name/	BHP	[Name/	[Name/
ample	Method	[g]	[g]	wt.-%]	%]	%]	mol-%]	[g]	g]	gl
7	2	243.3	6.2	Guar	80.0	20.0	98.1	TMPTA	1.9	0.15	FF6M	0.52	V-601	0.78
				Gum
8	2	243.2	6.2	Guar	90.0	10.0	96.2	TMPTA	3.9	0.15	FF6M	0.52	V-601	0.78
				Gum
9	2	243.8	6.3	Tara	80.0	20.0	98.1	TMPTA	1.9	0.15	FF6M	0.52	V-601	0.78
				Gum
10	2	243.9	6.3	Tara	90.0	10.0	96.2	TMPTA	3.8	0.15	FF6M	0.52	V-601	0.78
				Gum
11	1	244.6	6.3	Tara	69.5	30.5	98.7	TMPTA	1.3	0.15	FF6M	0.52	V-65	0.82
				Gum
12	2	243.2	6.2	Tara	80.0	20.0	98.6	GPTA	1.4	0.15	FF6M	0.52	V-65	0.82
				Gum
13	2	243.8	6.3	Tara	80.0	20.0	98.3	GPTA	1.4	0.15	FF6M	0.52	V-65	0.82
				Gum
14	2	243.4	6.2	Tara	80.0	20.0	98.0	GPTA	2.0	0.15	FF6M	0.52	V-65	0.82
				Gum
15	3	245.3	6.3	Tara	80.0	20.0	98.6	GPTA	1.4	0.15	FF7	0.52	V-65	0.82
				Gum
16	1	243.6	6.2	Tara	69.5	30.5	99.1	GPTA	0.9	0.15	FF6M	0.52	V-65	0.82
				Gum
17	3	388.8	11.2	Tara	80.0	20.0	98.7	GPTA	1.3	0.25	FF6M	0.83	V-65	1.31
				Gum
18	3	388.8	11.2	Tara	80.0	20.0	98.6	GPTA	1.4	0.25	FF7	0.83	V-65	1.31
				Gum
19	4	388.4	11.6	Guar	70.0	30.0	98.7	TMPTA	1.3	0.25	FF7	0.83	V-65	1.31
				Gum
20	4	388.4	11.6	Guar	70.0	30.0	99.1	GPTA	0.9	0.25	FF7	0.83	V-65	1.31
				Gum
21	4	388.4	11.6	Guar	80.0	20.0	98.2	TMPTA	1.9	0.25	FF7	0.83	V-65	1.31
				Gum
22	4	388.4	11.6	Guar	80.0	20.0	98.6	GPTA	1.4	0.25	FF7	0.83	V-65	1.31
				Gum
23	5	388.8	11.2	Tara	69.5	30.5	99.1	GPTA	0.9	0.25	FF7	0.83	V-65	1.31
				Gum
24	5	388.8	11.2	Tara	80.0	20.0	98.7	GPTA	1.3	0.25	FF7	0.83	V-65	1.31
				Gum
25	5	388.8	11.2	Guar	69.5	30.5	99.1	GPTA	0.9	0.25	FF7	0.83	V-65	1.31
				Gum
26	5	388.8	11.2	Guar	80.0	20.0	98.7	GPTA	1.3	0.25	FF7	0.83	V-65	1.31
				Gum
27	6	390	10	Tara	68.0	32.0	98.3	TMPTA	1.3	0.25	FF7	0.83	DLP	2.16
				Gum
28	2	244.0	6.3	Tara	70	30	98.7	TMPTA	1.3	0.15	FF6M	0.52	V-601	0.79
				Gum
29	3	250	6	Tara	80	20	98.6	GPTA	1.4	0.15	FF6M	0.52	V65	0.82
				Gum
30	3	250.3	6	Tara	80	20	98.6	GPTA	1.4	0.15	FF7	0.52	V65	0.82
				Gum
31	1	244.0	6.3	Guar	69.5	30.5	98.7	TMPTA	1.3	0.15	FF6M	0.52	V-601	0.78
				Gum
32	6	1592	38.8	Tara	68.6	31.4	98.2	TMPTA	1.3	0.98	FF7	0.52	DLP	8.36
				Gum
61	6	400	9.6	Gluco-	70	30	98.3	TMPTA	1.3	0.26	FF7	0.83	DLP	2.16
				mannan

TABLE 1a
Hybrid polymers with additional monomers based on Tara Gum
						Synthetic Graft
							Mono-	Mono-
				Poly-		mer	mer	Cross-
				saccharide		1	2	linker	Initiator System
				Polymer	Poly-	Name	Name	Name		Reducing	Radical
Ex-		Sol-		[Name/	mer	[mol-	[mol-	[mol-	t-BHP	agent	Inititaor
ample	Method	vent	Water	wt.-%]	[wt.-%]	%]	%	%]	[g]	[Name]	[g]	[Name]	[g]
63	6	389.2	10.8	Tara	70	30	ATBS	NVP	TMPTA	0.25	FF7	0.83	DLP	1.50
				Gum			93.60	4.50	1.90
64	6	389.2	10.8	Tara	70	30	ATBS	NVP	TMPTA	0.25	FF7	0.83	DPL	1.50
				Gum			90.10	8.00	1.90
65	6	389.2	10.8	Tara	70	30	ATBS	MAEOBe	PEG-	0.25	FF7	0.83	DLP	1.50
				Gum			97.81	1.51	DMA
									550
									0.68
66	6	389.2	10.8	Tara	70	30	ATBS	MAEOBe	PEG-	0.25	FF7	0.83	DLP	1.50
				Gum					DMA
									750
							96.50	3.00	0.50
67	6	389.2	10.8	Tara	70	30	ATBS	CEA	GPTA	0.25	FF7	0.83	DLP	1.50
				Gum			93.23	5.98	0.79
68	1	386.4	13.6	Tara	70	30	ATBS	CEA	GPTA	0.25	FF7	0.83	V 601	1.21
				Gum			97.74	1.47	0.79
69	5	389.2	10.8	Tara	70	30	ATBS	AA	GPTA	0.25	FF7	0.83	DLP	1.50
				Gum			94.85	4.50	0.65
70	6	389.2	10.8	Tara	70	30	ATBS	AA	TMPTA	0.25	FF7	0.83	DLP	1.50
				Gum			90.48	9.00	0.52
71	5	389.2	10.8	Tara	70	30	ATBS	AA	TMPTA	0.25	FF7	0.83	DLP	1.50
				Gum			90.48	9.00	0.52
72	5	374.4	25.6	Tara	70	30	ATBS	AA	GPTA	0.25	FF7	0.83	DLP	1.50
				Gum			94.98	4.50	0.52
73	6	380	20	Tara	70	30	ATBS	MAEOBe	TMPTA	0.25	FF7	0.83	DLP	1.50
				Gum			97.88	1.60	0.52
74	5	400		Tara	70	30	ATBS	AA	TMPTA	0.25	FF7	0.83	DLP	1.50
				Gum			90.48	9.00	0.52

Key:

• • ATBS: 2-acrylamido-2-methylpropane sulfonic acid
  • DLP: dilauroyl peroxide
  • GPTA: propoxylated glycerol triacrylate
  • TMPTA: trimethylolpropane triacrylate
  • FF6M or Bruggolite® FF6M: blend comprising 45-55% 2-hydroxy-2-sulfinatoacetic acid di sodium salt, up to 25% 2-hydroxy-2-sulfonatoacetic acid di sodium salt and up to 40% sodium sulfite by the company Brüggemann
  • FF7 or Bruggolite® FF7: blend comprising minimum 30% 2-hydroxy-2-sulfinatoacetic acid di sodium salt, minimum 35% 2-hydroxy-2-sulfonatoacetic acid di sodium salt and up to 5% sodium sulfite by the company Brüggemann
  • t-BHP: tert-butyl hydroperoxide as 70% solution in water
  • V601: dimethyl 2,2′-azobis(2-methylpropionate)
  • V65: 2,2-azobis(2,4-dimethylvaleronitril)
  • AA: Acrylic Acid
  • CEA: 2-Carboxyethylacrylate
  • NVP: N-Vinylpyrrolidinon
  • PEG-DMA-550: Poylethyleneglycol dimethacrylate with a polyethyleneoxy block with a Mw of approximately 550 g/mol
  • PEG-DAM-750: Poylethyleneglycol dimethacrylate with a polyethyleneoxy block with a Mw of approximately 750 g/mol
  • MAEOBe: Behenylpolyethoxy (25) methacrylate—with 25 mol equivalent of ethylenoxide

Rheological Characterization of the Hybrid Polymers

To determine the rheological properties a hybrid polymer exhibits in water, a 1% gel of the hybrid polymer in deionized water was prepared. The % as used in this context refers to wt.-%.

Instrumentation and Procedure

The rheological characterization of aqueous gels formed from biohybrid polymers was performed using an oscillatory rheometer equipped with a cone and plate geometry and appropriate temperature control. The cone angle should be low (≤4°) and the diameter should be chosen in a way that the resulting torque is reasonable within the instrument's range. A TA Instruments DHR-3 with 40/1 cone geometry (diameter 40 mm, cone angle 1°) on an APS (Advanced Peltier System) with lower plate of same diameter was used. All materials in contact with the sample are made from stainless steel.

The instrument was set to measurement temperature (20° C.) and the geometry gap was zeroed before the sample was loaded.

The measurement procedure consists of several steps, which are shown in the Table below.

Sufficient sample volume is loaded with a spoon or spatula to the lower plate. The geometry is brought to the trimming position, typically some ten micrometers higher than measurement position. The sample is trimmed with a spatula and excess volume is removed. Now the instrument's procedure is started, and all following steps are processed automatically. This ensures a correct timing and reproducible and comparable repetitions.

TABLE
Steps
Steps	Parameters	Remark
1	Conditioning	T = 20° C.	Set temperature for all
	Sample		following steps
2	Time Sweep	t = 60 s; γ = 0.05%; ω =	Fixed parameter set
3	Oscillation	10 rad/s γ = 0.1%-1%	End strain must not
	Amplitude		exceed LVR!
4	Step (Transient)	Creep: t = 10 s; σ = 0.1 Pa	3× creep&recovery;
	Repeated Creep	Recovery: t = 20 s	σ < γy
5	Oscillation	γ = 0.1%- 200%	End strain must exceed
	Amplitude		LVR!
6	Flow Ramp	tequil. = 20 s; tmeas. = 180 s;	stress ramp; end stress
		γ =0-20 Pa	must exceed yield point
LVR = linear viscoelastic region

Step 1: sets temperature for all following steps. It has no time impact.

Step 2: Time Sweep, is an oscillatory experiment with set strain and frequency. Plot of storage and loss module show strength of network. Increasing values show structure build up, e.g. recovery from sample loading and squeezing to measurement position. If values are constant from beginning, recovery doesn't occur or is already finished.

Step 3: Amplitude Sweep, detects network strength G′_initial and G″_initial and tan δ_initial (also referred to as tan delta_initial or tan delta; this is also the tan delta referred to in the claims). G′_initial is determined as the plateau value of the Amplitude Sweep. Must not exceed LVR (linear viscoelastic region). Otherwise following creep test would be influenced.

Step 4: Repeated Creep, 3 Repetitions of Creep and Recovery. Typically, recovery time is twice as long as creep time. Creep stress must not exceed yield point. Otherwise deformations are too high, shear flow will occur, and recovery will not take place.

Step 5: Amplitude Sweep, detects network strength and tan δ₂ (also referred to as tan delta₂) after Creep. Must exceed LVR (linear viscoelastic region), to detect its complete range.

Step 6: Flow Ramp, stress ramp to detect yield point. Start value is zero, end value must be higher than yield point. For analysis, viscosity vs. stress is plotted and peak maximum in viscosity gives the yield stress.

The mesh size is calculated as follows:

$\mathrm{mesh}\mathrm{size}\left[\mathrm{nm}\right]=\sqrt[3]{\mathrm{kT}/G_{\mathrm{initial}}^{\prime }}$

• • wherein:
  • G′_initial is the network stability G′_initial, which is determined as described above;
  • k is the Boltzmann constant; and
  • T is the measurement temperature:

	k	Boltzmann constant	1.380649E−23	J/K
	T	Measurement temperature	293.15	K
	G′initial	Network stability G′initial	Pa

The tan delta is the ratio of the network stability G″ to the network stability G′:

$\tan \delta =G^{″}/G^{\prime }$

The tan delta_initial is the ratio of the network stability G″_initial to the network stability G′_initial

$\tan {\delta }_{\mathrm{initial}}=G_{\mathrm{initial}}^{″}/G_{\mathrm{initial}}^{\prime }$

The results of the rheological characterization of the hybrid polymers are given in Table 2.

TABLE 2
Rheological characterization
		Mesh	Network	Network		Yield
		size	stability	stability	tan	Point
Example	Polymer*	[nm]	G′initial [Pa]	G″initial [Pa]	deltainitial	[Pa]
33	Hybrid	29	158.27	74.00	0.47	3
	polymer of
	Example 31
34	Hybrid	43	52.21	29.30	0.56	0.24
	polymer of
	Example 7
35	Hybrid	50	32.32	22.92	0.70	1.63
	polymer of
	Example 8
36	Hybrid	37	77.95	47.5	0.61	3
	polymer of
	Example 28
37	Hybrid	44	46.35	37.8	0.81	1.6
	polymer of
	Example 9
38	Hybrid	62	17.25	17.4	1.01	0.9
	polymer of
	Example 10
39	Hybrid	30	148.45	75.7	0.51	3.2
	polymer of
	Example 11
40	Hybrid	36	89.8	48.5	0.54	2.7
	polymer of
	Example 12
41	Hybrid	39	67.6	47.3	0.7	0.44
	polymer of
	Example 13
42	Hybrid	36	85.91	50.34	0.59	3.8
	polymer of
	Example 14
43	Hybrid	41	58.3	32.4	0.56	2.5
	polymer of
	Example 15
44	Hybrid	41	58.5	27.8	0.47	3.9
	polymer of
	Example 16
45	Hybrid	39	69.18	36.54	0.52	5.74
	polymer of
	Example 29
46	Hybrid	41	60.61	31.67	0.52	5.85
	polymer of
	Example 30
47	Hybrid	41	59.11	31.63	0.53	4.73
	polymer of
	Example 17
48	Hybrid	40	64.65	32.64	0.5	5.18
	polymer of
	Example 18
49	100 wt.-%	61	17.8	17.8	1	1
	tara gum
	(comparative
	example)
50	100 wt.-%	52	28.02	18.37	0.66	2.0
	guar gum
	(comparative
	example)
51	Hybrid	25	245.95	96.1	0.39	3.41
	polymer of
	Example 19
52	Hybrid	43	50.16	18.84	0.36	3.6
	polymer of
	Example 20
53	Hybrid	36	88.88	49.37	0.55	4
	polymer of
	Example 21
54	Hybrid	44	48.44	20.99	0.43	2.5
	polymer of
	Example 22
55	Hybrid	26	223	109	0.5	3.5
	polymer of
	Example 32
56	Hybrid	22	357	166	0.45	4.2
	polymer of
	Example 27
62	Hybrid	19	630	216	0.35	7.0
	polymer of
	Example 61
*In the column “Polymer” of Table 2, reference is made to various hybrid polymers. Each hybrid polymer is defined by a reference to a certain Example. These Examples refer to the Examples given in Table 1.

As shown in Table 2, the hybrid polymers have excellent rheological properties.

Determination of the biodegradability of the hybrid polymers

The biodegradability of the hybrid polymers was determined according to OECD Method 301 B. The results are given in Table 3.

TABLE 3
Biodegradability
			Biodegradability
	Example	Polymer*	[%]
	57	Hybrid polymer of Example 28	84.5
	58	Hybrid polymer of Example 9	64.0
	59	Hybrid polymer of Example 10	80.5
	60	100 wt.-% tara gum (comparative	86.3
		example)
*In the column “Polymer” of Table 3, reference is made to various hybrid polymers. Each hybrid polymer is defined by a reference to a certain Example. These Examples refer to the Examples given in Table 1.

As shown in Table 3, the hybrid polymers are readily biodegradable according to OECD Method 301 B.

Example Compositions

The following Example Compositions comprise Hybrid H, which is the hybrid polymer of the present invention, in particular any of the hybrid polymers of Examples 7 to 32.

Example Composition 1: After Sun Cream Gel
	A	Mineral Oil	3.00%
		Isopropyl Palmitate	3.00%
		Cetearyl Isononanoate	3.00%
		Jojoba Oil	3.00%
		Walnut Oil	3.00%
		Tocopheryl Acetate	1.00%
	B	Hybrid H	1.20%
	C	Water	ad 100%
		Glycerin	3.00%
		Allantoin (Clariant)	0.20%
		Nipaguard ® POM (Clariant)	1.00%
		Phenoxyethanol, Methylparaben, Piroctone
		Olamine
		Panthenol	1.00%
	D	Collagen nativ 1%	3.00%
		Ethanol	1.50%
Procedure:
I Mix A, then add B.
II Mix C.
III Stir II into I.
IV Add D to III.
V Finally homogenize the emulsion.

Example Composition 2: Sun Milk SPF 15
A	Ethylhexyl Stearate	7.00%
	Decyl Oleate	5.00%
	Plantasens ® Natural Emulsifier HE 20	3.00%
	(Clariant)
	Cetearyl Glucoside (and) Sorbitan Olivate
	Dimethicone	2.00%
	Octocrylene	7.00%
	Butyl Methoxydibenzoylmethane	2.50%
	Ethylhexyl Salicylate	4.50%
B	Water	Ad 100%
	Glycerin	3.00%
C	Hybrid H	1.00%
D	Nipaguard ® POM (Clariant)	1.00%
	Phenoxyethanol (and) Piroctone Olamine (and)
	Methylparaben
E	Citric Acid	q.s.
Procedure:
I Mix the components of A and melt at approx. 80° C.
II Mix the components of B and stir until homogenous, heat up to 80° C.
III Add C to I.
IV Add III to II and homogenize with a high shear mixer at 19.000 rpm for 2 min.
V Cool down to room temperature while stirring (200 rpm).
VI Add D to V and stir at 200 rpm until homogenous.
VII Finally adjust the pH with E to 6.5.

Example Composition 3: Liquid Soap
A	Water	Ad 100%
	Glycerin	3.00%
	1,2-Propanediol	2.00%
	Hybrid H	3.00%
B	Genapol ® LRO liquid (Clariant)	20.00%
	Sodium Laureth Sulfate
	Genagen ® CAB 818 (Clariant)	4.00%
	Cocamidopropyl Betaine
	GlucoTain ® Clear (Clariant)	2.00%
	Capryloyl/Caproyl Methyl Glucamide
C	Nipaguard ™ DMDMH (Clariant)	0.40%
	DMDM Hydantoin
	Fragrance	0.20%
	Sodium Cloride	0.50%
D	Citric Acid	0.10%
Procedure:
I Mix ingredients of phase A.
II Mix phase B and add to I.
III Add phase C in the given order.
IV Stir until homogeneous.
V Adjust pH to 5.5.

Example Composition 4: Effect Shower Gel
	A	Genapol ® LRO liquid (Clariant)	30.00%
		Sodium Laureth Sulfate
		Genagen ® CAB 818 (Clariant)	6.00%
		Cocamidopropyl Betaine
		Hostapon ® KCG (Clariant)	5.00%
		Sodium Cocoyl Glutamate
	B	Water	Ad 100%
	C	Hybrid H	1.40%
	D	Nipaguard DMDMH (Clariant)	0.50%
		DMDM Hydantoin
		Cirebelle 104 Blue	1.00%
		Synthetic Wax
Procedure:
I Mix the components of A and B until complete dissolved.
II Add C and stir until the solution is free of lumps.
III Add D to II.
IV Finally adjust the pH if necessary.

Example Composition 5: Facial Cleanser
	A	Water	Ad 100%
		Hybrid H	1.80%
	B	Genapol ® LRO paste (Clariant)	4.50%
		Sodium Laureth Sulfate
		Medialan ® LD (Clariant)	13.50%
		Sodium Lauroyl Sarcosinate
		Genagen ® CAB 818 (Clariant)	3.00%
		Cocamidopropyl Betaine
	C	Citric Acid	q.s.
	D	Benzoic Acid	0.50%
Procedure:
I Add Polymer to water and stir until homogeneous.
II Add the ingredients of phase B to I in the given order.
III Adjust pH to 4.0 with phase C.
IV Add D.

Example Composition 6: Mascara
A	Hydroxyethylcellulose	0.50%
	Hybrid H	0.50%
	1,2-Propyleneglycol	1.00%
	Magnesium Aluminium Silicate	1.00%
	Triethanolamine 99%	1.50%
	Water	Ad 100%
B	Stearic Acid	3.00%
	SilCare ® Silicone 41M15 (Clariant)	1.00%
	Caprylyl Methicone
	SilCare ® Silicone 31M50 (Clariant)	2.00%
	Caprylyl Trimethicone
	Tego ® Care 450	4.00%
	Polyglyceryl-3 Methylglucose Distearate
	Polybutene.	2.00%
	Beeswax	2.50%
	Plantasens ® Olive Wax S51 (Clariant)	2.50%
	Hydrogenated Olive Oil
	Microcrystalline Wax	3.50%
C	Iron Oxides	10.0%
D	Phenonip ™ ME (Clariant)	1.00%
	Phenoxyethanol, Methylparaben, Ethylparaben
E	Baycusan ® C 1004	2.00%
	Polyurethane-35
Procedure:
I Mix ingredients of phase A. Then heat to 80° C. while stirring.
II Mix ingredients of phase B and heat to 80° C.
III Add C to B and homogenize.
IV Add A to III while homogenizing (4 min, 20000 rpm), stir vigorously until 35-40° C.
V Add D and stir until homogeneous.
VI Add E and stir until homogeneous then stir until room temperature.

Example Composition 7: BB Cream SPF 15
A	Water	Ad 100%
	Glycerin	2.00%
	Hybrid H	1.00%
B	Hostaphat ® KW 340 D (Clariant)	3.00%
	Triceteareth-4 Phosphate
	Cetearyl Alcohol	2.00%
	Octocrylene	7.00%
	Butyl Methoxydibenzoylmethane	2.50%
	Ethylhexyl Salicylate	4.50%
	Plantasens ® Olive LD (Clariant)	2.00%
	Hydrogenated Ethylhexyl Olivate (and)
	Hydrogenated Olive Oil Unsaponifiables
	12-15 Alkyl Benzoate	8.00%
	Plantasens ® Olive Squalane (Clariant)	2.00%
	Squalane
	Plantasens ® Shea Butter (Clariant)	1.00%
	Butyrospermum Parkii (Shea) Butter
	XIAMETER ® PMX-200 Silicone Fluid 200 CS	2.00%
	Dimethicone
C	Chroma-Lite ® Black	0.05%
	Mica (and) Bismuth Oxychloride (and)
	Iron Oxides
	Chroma-Lite ® Red	0.20%
	Mica (and) Bismuth Oxychloride (and)
	Iron Oxides
	Chroma-Lite ® Yellow	0.60%
	Mica (and) Bismuth Oxychloride (and)
	Iron Oxides
	Titanium Dioxide	5.00%
	Butylene Glycol	4.00%
D	Plantasens ® Natural Vitamin E (Clariant)	1.00%
	Tocopherol
	Panthenol	0.50%
	Gatuline ® Age Defense 2	1.00%
	Aqua (and) Juglans Regia (Walnut) Seed Extract
	Sodium Hyaluronate	0.40%
	Orgasol ® 4000 EXD NAT COS Caresse	1.00%
	Nylon-6/12
	Fragrance	0.20%
	Nipaguard ® POB (Clariant)	0.80%
	Phenoxyethanol (and) Piroctone Olamine (and)
	Benzoic Acid
E	Citric Acid	q.s.
Procedure:
I Mix ingredients of phase A until dissolved. Then heat to 80° C.
II Mix ingredients of phase B and heat to 80° C.
III Premix phase C then add to B and homogenize gently by using Ultra-Turrax.
IV Pour III into I and homogenize gently by using Ultra-Turrax. Then stir until 35° C.
V Add phase D in the given order and stir until homogeneous.
VI Adjust the pH to 5.5 to 6.0 with phase E.

Example Composition 8: O/W Foundation
A	Water	Ad 100%
	Hybrid H	1.00%
	Magnesium Aluminium Silicate	1.00%
B	Plantasens ® Natural Emulsifier HP10 (Clariant)	4.50%
	Sucrose Polystearate, Cetearyl Alcohol,
	Olea Europaea (Olive) Oil Unsaponifiables
	SilCare ® Silicone 31M50 (Clariant)	2.00%
	Caprylyl Trimethicone
	XIAMETER ® PMX-200 Silicone Fluid 100 CS	2.00%
	Dimethicone
	Caprylic/Capric Triglyceride	5.00%
	Plantasens ® Olive Wax S51 (Clariant)	1.50%
	Hydrogenated Vegetable Oil
C	Chroma-Lite ® Black	0.10%
	Mica (and) Bismuth Oxychloride (and)
	Iron Oxides
	Chroma-Lite ® Red	0.40%
	Mica (and) Bismuth Oxychloride (and)
	Iron Oxides
	Chroma-Lite ® Yellow	1.20%
	Mica (and) Bismuth Oxychloride (and)
	Iron Oxides
	Titanium Dioxide	7.00%
	Dicaprylyl Carbonate	4.00%
	Butylene Glycol	3.00%
D	Plantasens ® Natural Vitamin E (Clariant)	1.00%
	Tocopherol
	Orgasol ® 4000 EXD NAT COS Caresse	1.00%
	Nylon-6/12
	Fragrance	0.20%
	Nipaguard ® POB (Clariant)	0.80%
	Phenoxyethanol (and) Piroctone Olamine (and)
	Benzoic Acid
E	Citric Acid	q.s.
Procedure:
I Mix ingredients of phase A and homogenize gently by using Ultra-Turrax, then stir and heat to 70° C.
II Mix ingredients of phase B and heat to 70° C.
III Premix phase C then add to B and homogenize gently by using Ultra-Turrax.
IV Pour III into I and homogenize gently by using Ultra-Turrax. Then stir until 35° C.
V Add phase D and stir until homogeneous.
VI Adjust the pH to 5.5 to 6.0 with phase E.

Example Composition 9: Liquid Highlighter
A	Water	Ad 100%
	Bentonite	1.00%
B	Hybrid H	1.00%
C	Liquiwax ™ PolyIPL	2.00%
	Stearyl/PPG-3 Myristyl Ether Dimer Dilinoleate
	Plantasens ® Olive Wax S51 (Clariant)	2.00%
	Hydrogenated Olive Oil
	Stearic Acid	1.20%
	Isostearic Acid	0.90%
D	Water	5.00%
	Sodium Hydroxide	0.12%
E	Orgasol ® 4000 EXD NAT COS Caresse	1.50%
	Nylon-6/12
	Timiron ® Super Gold	2.50%
	Mica, Titanium Dioxide
	Xirona ® Indian Summer	2.50%
	Silica (and) Iron Oxides
F	Panthenol	0.50%
	Cyclopentasiloxane	7.50%
	Phenonip ™ ME (Clariant)	1.00%
	Phenoxyethanol, Methylparaben, Ethylparaben
	Tocopheryl Acetate	1.00%
Procedure:
I Phase A: disperse Bentonite in water.
II Add B to I and mix until dissolved, then heat to 80° C.
III Melt C at 80° C.
IV Add III to II while homogenizing (2 min, 20000 rpm).
V Premix D, add to IV and stir until homogeneous.
VI Add E to V and stir until cool (35° C.).
V Add F and stir until room temperature.

Example Composition 10: Lipstain
A	Water	Ad 100%
	Glycerin	30.00%
	Hybrid H	3.00%
B	FD&C Red No.40	0.15%
	CI16035
C	Emulsogen ® HCO 040 (Clariant)	0.50%
	PEG-40 Hydrogenated Castor Oil
	Phenonip ™ ME (Clariant)	1.00%
	Phenoxyethanol, Methylparaben, Ethylparaben
	Flavour	0.20%
Procedure:
I Mix the components of A and stir until dissolved.
II Add B and stir until the solution is homogeneous.
III Add C and stir until dissolved.
IV Finally adjust the pH to 6.5 to 7.0, if necessary.

Example Composition 11: Eyeliner Gel
A	Water	Ad 100%
	Glycerin	1.00%
	Hybrid H	2.00%
B	Phenonip ™ ME (Clariant)	1.00%
	Phenoxyethanol, Methylparaben, Ethylparaben
C	PVP	1.50%
D	Water	10.00%
	Timiron ® Super Gold	12.00%
	Mica, CI77891, Titanium Dioxide
Procedure:
I Mix the components of A and stir until dissolved.
II Add B and stir until the solution is homogeneous.
III Premix C separately, then add to II and stir until dissolved.
IV Add D while stirring.
V Finally adjust pH to 7.5.

Example Composition 12: After Shave Balm
A	Hostaphat ® KL 340 D (Clariant)	2.00%
	Trilaureth-4 Phosphate
	Octopirox ® (Clariant)	0.05%
	Piroctone Olamine
B	Plantasens ® Abyssinian Oil (Clariant)	2.00%
	Crambe Abyssinica Seed Oil
	Isopropyl Isostearate	3.00%
	Plantasens ® Inca Inchi Serum (Clariant)	1.00%
	Plukenetia Volubilis Seed Oil (and) Phytosterols
	(and) Olea Europaea (Olive) Oil Unsaponifi-
	ables (and) Beeswax
C	Water	Ad 100%
	Polyglykol 400 (Clariant)	3.00%
	PEG-8
	Allantoin	0.30%
D	Hybrid H	1.50%
E	Dimethicone	1.00%
F	Citric Acid	q.s.
G	Phenonip ™ ME (Clariant)	1.00%
	Phenoxyethanol, Methylparaben, Ethylparaben
Procedure:
I Mix and dissolve the components of A.
II Add B into I.
III Mix and dissolve the components of C.
IV Add D into II.
V Add III to IV and stir at about 200 rpm for one hour.
VI Add E to V and stir for 30 min.
VII Adjust the pH with F to 5.5.
VIII Add G to VI and stir.
IX Finally homogenize.

Example Composition 13: Sprayable Body Milk
A	Hostaphat ® KL 340 D (Clariant)	1.00%
	Trilaureth-4 Phosphate
	Mineral Oil	8.00%
	Isopropyl Palmitate	3.00%
	Cetearyl Alcohol	0.50%
	Caprylic/ Capric Triglyceride	2.00%
	Glyceryl Stearate	0.50%
	SilCare ® Silicone 41M15 (Clariant)	1.00%
	Caprylyl Methicone
B	Hybrid H	1.00%
C	Water	ad 100%
	Glycerin	5.00%
D	Ethanol	5.00%
	Tocopheryl Acetate	1.00%
E	Nipaguard ® POM (Clariant)	1.00%
	Phenoxyethanol, Methylparaben, Piroctone
	Olamine
Procedure:
I Melt A at 60° C., then add B.
II Heat C to 60° C.
III Stir II into I, and stir until cool.
IV Add the components of D one after another to III at 35° C.
V Add E and then finally homogenize the emulsion.

Example Composition 14: Body Lotion for Men
	A	Caprylic/Capric Triglyceride	3.50%
		Plantasens ® Olive LD (Clariant)	3.00%
		Hydrogenated Ethylhexyl Olivate (and)
		Hydrogenated Olive Oil Unsaponifiables
		Myristyl Myristate	2.50%
		Cetearyl Alcohol	2.00%
		Octyldodecanol	1.00%
		Glyceryl Stearate Citrate	1.50%
	B	Hybrid H	1.20%
	C	Water	ad 100%
		Glycerin	5.00%
	D	Ethanol	3.00%
		Tocopheryl Acetate	1.00%
		Aloe Barbadensis Leaf Juice	1.00%
		Nipaguard ® POM (Clariant)	1.00%
		Phenoxyethanol, Methylparaben,
		Piroctone Olamine
		Fragrance	0.20%
	E	Sodium Hydroxide	q.s.
	Procedure:
	I Melt the components of A at approx. 70° C.
	II Mix the components of C and heat to approx. 70° C.
	III Add B to I when completely melted.
	IV Add C to III.
	V At 35° C. add the components of D to IV.
	VI Adjust the pH with E to 6.0 to 6.5.

Example Composition 15: Anti-Ageing Cream Gel
A	Caprylic/Capric Triglyceride	5.00%
	Dicaprylyl Ether	5.00%
	Cetearyl Alcohol	2.00%
	Nipaguard ® POB (Clariant)	0.80%
	Phenoxyethanol (and) Piroctone Olamine (and)
	Benzoic Acid
B	Ubiquinone	0.10%
C	Aristoflex ® HMB (Clariant)	0.40%
	Ammonium Acryoyldimethyltaurate/Beheneth-25
	Methacrylate Crosspolymer
	Hybrid H	0.40%
D	Sodium Hyaluronate	0.30%
E	Water	Ad 100%
F	Tocopheryl Acetate	0.30%
	Fragrance	0.30%
Procedure:
I Mix the components of A and melt at 60° C.
II Add B and solve while shaking lightly.
III Add C.
IV Solve D in E and add to III.
V Add F to IV at 35° C.

Example Composition 16: Light Day Cream
A	Water	Ad 100%
	Hybrid H	0.75%
	Glycerin	3.00%
B	Plantasens ® Natural Emulsifier HE20 (Clariant)	1.20%
	Cetearyl Glucoside, Sorbitan Olivate
	Aristoflex ® AVC (Clariant)	0.10%
	Ammonium Acryloyldimethyltaurate/VP
	Copolymer
	Plantasens ® Abyssinian Oil (Clariant)	3.00%
	Crambe Abyssinica Seed Oil
	Octyldodecanol	5.00%
	Isodecyl Neopentanoate	3.00%
C	Plantasens ® Natural Vitamin E (Clariant)	0.50%
	Tocopherol
	Nipaguard ® SCP (Clariant)	1.00%
	Phenoxyethanol (and) Sorbitan Caprylate
	Fragrance	0.30%
D	Citric Acid	q.s.
Procedure:
I Mix ingredients of phase A, stir for 5 minutes and homogenize during 1 min using Ultra-Turrax.
II Add B and heat to 75° C.
III At Temperature, homogenize gently during 1 min using Ultra-Turrax.
IV Cool down under stirring.
V Below 40° C. add C and stir.
VI Adjust pH with D to 5.5.

Example Composition 17: Caring Night Cream
A	Water	Ad 100%
	Glycerin	2.00%
	Hybrid H	1.00%
B	Hostaphat ® KW 340 D (Clariant)	2.00%
	Triceteareth-4 Phosphate
	Plantasens ® Oat Serum (Clariant)	3.00%
	Avena Sativa (Oat) Kernel Oil (and) Phytosterols
	(and) Olea Europaea (Olive) Oil Unsaponifiables
	(and) Beeswax
	Plantasens ® Shea Butter (Clariant)	7.00%
	Butyrospermum Parkii (Shea) Butter
	Isopropyl Palmitate	5.00%
	Macadamia Integrifolia Seed Oil	4.00%
	Cera Alba (Beeswax)	3.00%
C	Nipaguard ® SCP (Clariant)	1.00%
	Phenoxyethanol (and) Sorbitan Caprylate
	Fragrance	0.30%
D	Sodium Hydroxide	0.10%
Procedure:
I Mix ingredients of phase A and heat to 75° C.
II Mix ingredients of phase B and heat to 75° C.
III At Temperature, pour phase B into phase A and homogenize gently by using Ultra-Turrax.
IV Cool down under stirring.
V Below 40° C. add C and stir.
VI Adjust pH with D to 5.5.

Example Composition 18: Sprayable Hair Styling Gel
	A	Hybrid H	0.90%
	B	Water	Ad 100%
	C	Genapol ® LA-230 (Clariant)	4.00%
		Laureth-23
		Diaformer ® Z-632N (Clariant)	4.50%
		Acrylates/Stearyl Acrylate/Ethylamine Oxide
		Methacrylate Copolymer
		Dipropylene Glycol	1.00%
		Polyglykol 400	0.50%
		PEG-8
		Nipaguard ™ DMDMH (Clariant)	0.50%
		DMDM Hydantoin
		Panthenol	0.50%
	D	Emulsogen ® HCO 040 (Clariant)	0.50%
		PEG-40 Hydrogenated Castor Oil
		Fragrance	0.30%
	Procedure:
	I Add A to B while stirring. Stir until a smooth gel is formed.
	II Add the components of C one after the other to I and stir until dissolved.
	III Mix the components of D and add to II while stirring.

Example Composition 19: Conditioning Shampoo
A	Water	Ad 100%
	Hybrid H	1.10%
B	Genapol ® LRO liquid (Clariant)	30.00%
	Sodium Laureth Sulfate
C	Genagen ® CAB 818 (Clariant)	6.00%
	Cocamidopropyl Betaine
	XIAMETER ® PMX-200 Silicone Fluid 50 CS	0.25%
	Dimethicone
D	Water	10.00%
	Jaguar ® C-162	0.20%
	Hydroxypropyl Guar (and) Hydroxypropyl Guar
	Hydroxypropyltrimonium Chloride
E	Citric Acid	q.s.
F	Water	4.00%
G	Sodium Benzoate	0.45%
	Sodium Chloride	0.50%
VII	Add phase G and stir until dissolved.
Procedure:
I Mix the ingredients of phase A and stir until dissolved.
II Add phase B and stir until homogeneous.
III Premix phase C and add to II while stirring.
IV Premix pahse D and add to II while stirring.
V Adjust pH with E to 5.5 to 6.0.
VI Premix phase F and add to V, stir until dissolved.

Methods of use:

Example Composition 19 is applied to wet hair. Tap water is employed to create a lather and spread the composition throughout the hair and scalp. The composition is immediately rinsed from the hair. The hair may further be conditioned.

Example Composition 20: Nail Varnish Remover Gel
	A	Water	Ad 100%
		Ethanol	27.00%
		Polyglykol ® 400 (Clariant)	3.00%
		PEG-8
		Glycerin	3.00%
		Aristoflex ® TAC (Clariant)
		Ammonium Acryloyldimethyltaurate/
		Carboxyethyl Acrylate Crosspolymer
		Hybrid H	1.00%
	B	Ethyl Acetate	30.00%
	Procedure:
	I Add the components of A one after another and stir until homogenous.
	II Add B into A and stir until completely dissolved.
	III Add C to II.

Example Composition 21: Whitening Gel
	A	Genapol ® T 250 (Clariant)	2.00%
		Ceteareth-25
		Genapol ® DAT 100 (Clariant)	1.10%
		PEG-150 Polyglyceryl-2 Tristearate
	B	Water	Ad 100%
	C	Ascorbic Acid 2- Glucoside	3.00%
	D	Sodium Hydroxide	q.s.
	E	Hybrid H	1.50%
		Nipaguard ™ DMDMH (Clariant)	2.00%
		DMDM Hydantoin
	Procedure:
	I Combine the ingredients of phase A and B while stirring and heating to 60° C.
	II Cool to room temperature and add C.
	III Adjust pH with D to 6.0.
	IV Add E while stirring, continue stirring until homogeneous.

Example Composition 22: O/W Self Tanning Cream
	A	Hostaphat ® CC 100 (Clariant)	1.00%
		Cetyl Phosphate
		Glyceryl Stearate	0.50%
		Cetearyl Alcohol	0.50%
		Mineral Oil	8.00%
		Isopropyl Palmitate	7.00%
		Tocopheryl Acetate	1.00%
		SilCare ® Silicone 41M15 (Clariant)	1.00%
		Caprylyl Methicone
	B	Hybrid H	2.00%
	C	Water	ad 100%
		Hostapon ® KCG (Clariant)	0.50%
		Sodium Cocoyl Glutamate
		Glycerin	5.00%
	D	Fragrance	0.20%
		Phenonip ™ ME (Clariant)	1.00%
		Phenoxyethanol, Methylparaben,
		Ethylparaben
	E	Dihydroxyacetone	5.00%
		Water	8.00%
		Sodium Hydroxide	q.s.
	Procedure:
	I Melt A at 85° C.
	II Stir B in A.
	III Premix phase C and add to II, then stir until 30-35° C.
	IV Add D to III.
	V Dissolve Dihydroxyacetone in water and add E to IV.
	VI Adjust pH to 4.0, if necessary

Example Composition 23: Make Up Remover
	A	Water	ad 100%
		Glycerin	3.00%
		Hybrid H	0.80%
	B	Hostaphat ® KL 340 D (Clariant)	3.00%
		Trilaureth-4 Phosphate
		Cetearyl Alcohol	1.50%
		Plantasens ® Olive LD (Clariant)	2.00%
		Hydrogenated Ethylhexyl Olivate (and)
		Hydrogenated Olive Oil Unsaponifiables
		Isostearyl Isostearate	4.00%
		Isohexadecane	4.00%
	C	Sodium Hydroxide	q.s.
	D	Nipaguard ® SCP (Clariant)	1.00%
		Phenoxyethanol (and) Sorbitan Caprylate
		Fragrance	0.20%
	Procedure:
	I Mix phase A and stir until dissolved then heat to 80° C.
	II Combine ingredients of phase B separately and heat until 80° C.
	III Pour II into I and homogenize gently by using Ultra-Turrax. Then cool to room temperature while stirring.
	IV Adjust pH with C to 5.5.
	V Add D and stir until homogeneous.

Example Composition 24: Insect Repellent Lotion
	A	Diethyl Toluamide	10.00%
		DEET
		Hostaphat ® KL 340 D (Clariant)	1.00%
		Trilaureth-4 Phosphate
		Isohexadecan	5.00%
		C12-15 Alkyl Benzoate	5.00%
		Cyclopentasiloxane	2.00%
	B	Hybrid H	1.00%
	C	Water	Ad 100%
		Ethanol	10.00%
	D	Fragrance	0.30%
		Nipaguard ® POB (Clariant)	0.80%
		Phenoxyethanol (and) Piroctone
		Olamine (and) Benzoic Acid
	Procedure:
	I Mix the components of A.
	II Stir the components of B into I.
	III Then add C and stir well.
	IV Finally add D and homogenize the emulsion.

Example Composition 25: Emulsifier-free Cream Gel
	A	Caprylic/Capric Triglyceride	3.00%
		Glycine Soya (Soybean) Oil	1.00%
		Isopropyl Palmitate	3.60%
	B	Glycerin	1.00%
		Water	Ad 100%
	C	Hybrid H	1.50%
	D	Fragrance	0.30%
		Nipaguard ® POB (Clariant)	0.80%
		Phenoxyethanol (and) Piroctone
		Olamine (and) Benzoic Acid
	E	Sodium hydroxide	q.s.
	Procedure:
	I Mix the components of A.
	II Mix the components of B.
	III Add C to A.
	IV Add II to III and stir until komogeneous.
	V Add D to IV and stir for 10 min.
	VI Adjust pH with E to 5.5.-6.0

Example Composition 26: Sulfate-free Shampoo
A	Hybrid H	0.5%
	Water	20.0%
	Glycerin	1.0%
B	Hostapon ® SG (Clariant)	23.0%
	Sodium Cocoyl Glycinate
	Hostapon ® CGN (Clariant)	9.5%
	Sodium Cocoyl Glutamate
C	Lactic Acid	q.s.
D	Genagen ™ KB (Clariant)	15.0%
	Coco-Betaine
	Water	Ad. 100%
	Perlogen ® SF 3000 (Clariant)	5.0%
	Aqua (and) Glycol Distearate (and)
	Laureth-4 (and) Cocamidopropyl Betaine
E	Velsan ® SC (Clariant)	1.0%
	Sorbitan Caprylate
	Genamin ® PQ 43 (Clariant)	1.0%
	Polyquaternium-43
	Nipaguard ® CG 43 (Clariant)	0.1%
	Methylchloroisothiazolinone (and)
	Methylisothiazolinone
	Fragrance	q.s.
Procedure:
I Mix the components of A.
II Add the components of B to I under stirring.
III Adjust pH of II to 6.5.
IV Add the components of D to III under stirring.
V Add components of E one by one to IV under stirring.

Example Composition 27: Hair conditioner
A	Water	Ad. 100%
	Glycerin	3.0%
	Disodium EDTA	0.1%
B	Hybrid H	0.5%
C	Cetyl alcohol	8.0%
	Genamin ® KDMP (Clariant)	2.0%
	Behentrimonium Chloride
	Plantasens ® Olive Squalene (Clariant)	2.0%
	Squalene
D	Genamin ® CTAC (Clariant)	4.0%
	Cetrimonium Chloride
	Plantasens ® Olive LD (Clariant)	2.0%
	Hydrogenated Ehtylhexyl Olivate (and)
	Hydrogenated Olive Oil Unsaponifiables
E	Velsan ® SC (Clariant)	1.0%
	Sorbitan Caprylate
	Phenoxetol ™ (Clariant)	0.5%
	Phenoxyethanol
	Fragrance	q.s.
Procedure:
I Mix the components of A.
II Add B to I under stirring and heat to 65° C.
III Add the components of C to II under stirring at 65° C.
IV Add the components of D to III one by one under stirring and stir for 15 min at 65° C.
V Cool down to 30° C. and add components of E one by one to IV under stirring.

Claims

1-18. (canceled)

19. A water-soluble and/or water-swellable hybrid polymer comprising (i) from 30 wt.-% to 99 wt.-% water-soluble and/or water-swellable polysaccharide polymer, wherein the polysaccharide polymer is an uncharged polysaccharide polymer; and(ii) from 1 wt.-% to 70 wt.-% synthetic polymer comprising (a) from 90 mol-% to 99.9 mol-% of repeating units according to Formula (1)

20. The hybrid polymer according to claim 19, wherein a 1% gel of the hybrid polymer in deionized water has a mesh size of from 10 nm to 80 nm.

21. The hybrid polymer according to claim 19, wherein a 1% gel of the hybrid polymer in deionized water has a tan delta of from 0.2 to 0.9.

22. The hybrid polymer according to claim 19, wherein a 1% gel of the hybrid polymer in deionized water has a yield point of from 1 Pa to 15 Pa.

23. The hybrid polymer according to claim 19, wherein the hybrid polymer has a biodegradability of at least 30%, as determined according to OECD Method 301 B.

24. The hybrid polymer according to claim 19, wherein the hybrid polymer comprises (i) from 40 wt.-% to 95 wt.-% polysaccharide polymer; and(ii) from 5 wt.-% to 60 wt.-% synthetic polymer.

25. The hybrid polymer according to claim 19, wherein the polysaccharide polymer is selected from the group consisting of tara gum, guar gum, locust bean gum, cassia tora gum, fenugreek gum, glucomannan, Tamarindus Indica Seed Gum, sclerotium gum, dextran, dextrin, and combinations thereof.

26. The hybrid polymer according to claim 19, wherein the monomers resulting in units (a) and/or (b) are neutralised with a base prior to the polymerisation, and/or the hybrid polymer after polymerisation is neutralised with a base.

27. The hybrid polymer according to claim 26, wherein the base is selected from bases comprising an ion selected from the group consisting of Li+, Na+, K+, Ca++, Mg++, Zn++, Al+++ and combinations thereof.

28. The hybrid polymer according to claim 19, wherein the repeating units according to Formula (1) result from the incorporation of a monomer selected from the group consisting of acryloyldimethyltaurates, acryloyl-1,1-dimethyl-2-methyltaurates, acryloyltaurates, acryloyl-N-methyltaurates, and combinations thereof.

29. The hybrid polymer according to claim 19, wherein the crosslinking or branching units result from the incorporation of a monomer according to Formula (2)

30. The hybrid polymer according to claim 19, wherein the crosslinking or branching units result from the incorporation of a monomer according to Formula (3)

31. The hybrid polymer according to claim 19, wherein the crosslinking or branching units result from the incorporation of a crosslinker selected from the group consisting of methylenebisacrylamide; methylenebismethacrylamide; esters of unsaturated monocarboxylic and polycarboxylic acids with polyols, preferably di-acrylates and tri-acrylates and -methacrylates (e.g. glycerol propoxylate triacrylate [GPTA]), more preferably butanediol and ethylene glycol diacrylate and -methacrylate, trimethylolpropane triacrylate (TMPTA) and trimethylolpropane trimethacrylate (TMPTMA); allyl compounds, preferably allyl (meth)acrylate, triallyl cyanurate, diallyl maleate, polyallyl esters, tetraallyloxyethane, triallylamine, tetraallylethylenediamine; allyl esters of phosphoric acid; and vinylphosphonic acid derivatives.

32. The hybrid polymer according to claim 19, wherein the structure of the hybrid polymer is such that the polysaccharide polymer is a backbone onto which the synthetic polymer is grafted.

33. The hybrid polymer according to claim 19, wherein the radical precipitation polymerisation is carried out in a polar solvent mixture comprising: I) water and II) a further compound.

34. A composition comprising: (i) a hybrid polymer as defined in claim 19; and(ii) a carrier.

35. The composition according to claim 34, wherein the composition is selected from the group consisting of shampoo, body wash, facial cleanser, face mask, bubble bath, intimate wash, bath oil, cleansing milk, micellar water, make-up remover, cleansing wipes, hair mask, perfume, liquid soap, shaving soap, shaving foam, cleansing foam, day cream, anti-ageing cream, body milk, body lotion, body mousse, face serum, eye cream, sunscreen lotion, sun cream, face cream, after-shave lotion, pre-shaving cream, depilatory cream, skin-whitening gel, self-tanning cream, anti-acne gel, mascara, foundation, primer, concealer, blush, bronzer, blemish balm (bb) cream, eyeliner, night cream, eye brow gel, highlighter, lip stain, hand sanitizer, hair oil, nail varnish remover, conditioner, hair styling gel, hair styling cream, anti-frizz serum, scalp treatment, hair colorant, split end fluid, deodorant, antiperspirant, baby cream, insect repellent, hand cream, sunscreen gel, foot cream, exfoliator, body scrub, cellulite treatment, bar soap, cuticle cream, lip balm, hair treatment, eye shadow, bath additive, body mist, eau de toilette, mouthwash, toothpaste, lubricating gel, moisturizer, serum, toner, aqua sorbet, cream gel, styling mousse, dry shampoo, lip stick, lip gloss, hydro-alcoholic gel, body oil, shower milk, illuminator, lip crayon, hair spray, combing cream, and sunblock.