Water soluble polymers and their use in cosmetic and pharmaceutic products

0001The present invention relates to water-soluble polymers produced by copolymerization of macromonomers and their use in cosmetic and pharmaceutical compositions.

0002In recent years, water-soluble polymers have become increasingly important in industry and science. In terms of quantity, polyelectrolytes make up a very large part of the total annual production of water-soluble polymers. They are used as flocculants in paper processing, the detergent industry, textile processing, as protective colloids or in their cross-linked variants as thickeners, to name just a few areas of application.

0003Thickeners, especially the "superabsorbents" based on polyacrylic acid, have been an integral part of the hygiene sector since their development in the 1970s. Newer thickeners, such as the crosslinked polyacrylamidopropylene methyl sulfonic acid (or its salts), are notable for their markedly improved pH stability and better processability.

0004In order to simplify cosmetic preparations, in recent years there has been an increasing search for raw materials that combine several properties in one formulation component. Pure "thickeners" are being replaced by new substances which, for example, still have emulsifier properties in their property profile and thus make it unnecessary to add separate emulsifiers in formulations. The synthesis of the polymers described below offers the ideal instrument for this. The interesting combination of a polyelectrolyte (eg poly-AMPS) with non-polar parts of the molecule offers the possibility of varying the hydrophilic-hydrophobic balance of a polymer, as has only been observed in a few cases in synthetic polymer chemistry.

0005The temperature behavior of the polymers is an important property. Generally, polymers show high viscosity at low temperatures and low viscosity at high temperatures. Often, however, polymers are desired that have a thickening effect above certain temperatures, but remain pumpable and processable in solution at low temperatures.

0006<patcit id="pcit0001" dnum="EP0583814A"><text>EP-A-0 583 814</text></patcit> and <patcit id="pcit0002" dnum="EP0629649A"><text>EP-A-0 629 649</text></patcit> disclose polymers based on acrylic acid as the main chain and polyethylene and / or polypropylene glycols as side chains. These polymers show a thickening with increasing temperatures.

0007All attempts to produce such polymers on an industrial scale have so far been unsuccessful. In addition, the use of main chain polymers containing acrylic acid was necessary for the realization of the concept of thermo-thickening polymer solutions in water. One of the most serious problems with this class of polymer is precipitation due to instabilities to divalent ions.

0008In the present invention, a new class of polymers and a process for their preparation are now described. This process based on radical copolymerization, in particular precipitation polymerization, makes it possible to produce a large number of new polymers with different thermal solution behavior on an industrial scale without great preparative effort.

0009Surprisingly, it has been found that polymers which meet the requirements mentioned can also be prepared by means of macromonomer synthesis. The consequence of this is that the specification of acrylic acid as one of the main chain monomers required according to the prior art is omitted.

0010The invention relates to water-soluble polymers which can be prepared by free-radical copolymerization of<ol id="ol0001"><li>A) one or more macromonomers of the formula (1)         R¹-Y- (R²-O)_x-R³     (1) where R¹ an acrylic or methacrylic residue; R² (C.₂-C₄) Alkylene; x is an integer between 1 and 500; Y = O, S, PH or NH; and R³ a saturated or unsaturated linear or branched aliphatic or cycloaliphatic (C₆-C₃₀) Mean hydrocarbon residue, and</li><li>B) one or more olefinically unsaturated comonomers which contain oxygen, nitrogen, sulfur, phosphorus, chlorine and / or fluorine.</li></ol>

0011<patcit id="pcit0003" dnum="US5837789A"><text>US 5,837,789</text></patcit> discloses superabsorbent crosslinked polymers for aqueous liquids which are composed of partially neutralized monomers with monoethylenically unsaturated acidic groups, optionally further monomers and polymers which can be copolymerized therewith, and which are suitable, if appropriate, as grafting bases. According to the<patcit id="pcit0004" dnum="US5837789A"><text>US 5,837,789</text></patcit> superabsorbent polymers are water-insoluble.

0012<patcit id="pcit0005" dnum="EP0850894A"><text>EP 0 850 894</text></patcit> describes as cement additives copolymers containing unsaturated polyalkylene glycol ether-based monomers (I), maleic acid-based monomers (II) and other monomers (III) which can be copolymerized with these monomers. In the polyalkylene glycol ether-based monomers (I), the polyalkylene glycol group is bonded to the unsaturated part of the molecule via an ether bond.

0013<patcit id="pcit0006" dnum="US5395907A"><text>US 5,395,907</text></patcit> discloses a water-soluble or water-dispersible pressure sensitive adhesive containing a copolymer of a water-soluble base monomer and a water-soluble macromer. The macromer contains alkyleneoxy groups with 2 to 6 carbon atoms, to which hydrogen is -H or C_1-5-Alkyl groups are bound. <patcit id="pcit0007" dnum="GB1167524A"><text>GB 1,167,524</text></patcit> describes a process for the production of water- or alkali-soluble or swellable copolymers. By way of example, the preparation of copolymers of polyethylene glycol monomethacrylate monononylphenyl ether with maleic anhydride and methyl vinyl ether or with styrene and maleic anhydride or with acrylamide is disclosed.

0014R² particularly preferably represents an ethylene or propylene radical. x particularly preferably stands for a number between 3 and 50, particularly preferably for a number between 7 and 30. With R³ are aliphatic or cycloaliphatic hydrocarbons, which can be saturated or unsaturated. R³ particularly preferably stands for a (C₆-C₂₂) Hydrocarbon residue, particularly preferred for a (C₁₂-C₁₈) Hydrocarbon residue.

0015The macromonomers are generally prepared by the reaction of reactive derivatives of (meth) acrylic acid with compounds containing hydroxyl groups, in particular alkoxylated alkyl radicals. Ring-opening addition to (meth) acrylic acid glycidyl ester is also possible.

0016Suitable olefinically unsaturated comonomers B) are preferably olefinically unsaturated acids and their salts with mono- and divalent counterions, particularly preferably styrene sulfonic acid, acrylamidopropylmethylene sulfonic acid (AMPS), vinyl sulfonic acid, vinyl phosphonic acid, allylsulfonic acid, methallylsulfonic acid, acrylic acid, (meth) acrylic acid, maleic acid or Maleic anhydride and its salts; Esters of acrylic and (meth) acrylic acid with aliphatic, aromatic or cyclo-aliphatic alcohols with a carbon number of 1 to 22; Esters of acrylic and (meth) acrylic acid with alkyl ethoxylates, open-chain and cyclic N-vinyl amides (N-vinyl lactams) with a ring size of 4 to 9 atoms, particularly preferably N-vinyl formamide (NVF), N-vinyl methyl formamide, N-vinyl methylacetamide (VIMA), N-vinyl acetamide, N-vinyl pyrrolidone (NVP) and N-vinyl caprolactam; Amides of acrylic and methacrylic acid, particularly preferably acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, alkoxylated acrylic and methacrylamides, such as, for example MAPTAC and APTAC; 2-vinyl pyridine; 4-vinyl pyridine; Vinyl acetate; Glycidyl methacrylate; Acrylonitrile; Vinyl chloride; Vinylidene chloride; Tetrafluoroethylene and / or DADMAC.

0017Suitable counterions for the salts of the olefinically unsaturated acids are preferably lithium, sodium, potassium, magnesium, calcium, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, the alkyl substituents of the ammonium ions being independent of one another (C₁-C₂₂) -Alkylreste, which can be occupied by 0 to 3 hydroxyalkyl groups, the alkyl chain length in a range of C₂ to C₁₀ can vary. One to three times ethoxylated ammonium compounds with different degrees of ethoxylation are also suitable. Sodium and ammonium are particularly preferred as counterions. The degree of neutralization of the olefinically unsaturated acids is preferably between 70 and 100 mol%.

0018Water-soluble polymers which can be prepared by free-radical copolymerization of are particularly preferred<ol id="ol0002" compact="compact"><li>A) one or more macromonomers selected from the group of the esters of (meth) acrylic acid with alkyl ethoxylates, the 5 to 80 EO units and (C₁₀-C₂₂) Alkyl residues, and</li><li>B) one or more olefinically unsaturated comonomers selected from the group consisting of acrylamidopropylmethylene sulfonic acid (AMPS), sodium and ammonium salts of acrylamidopropylmethylene sulfonic acid (AMPS), acrylamide, N-vinylformamide, N-vinylmethylacetamide and / or sodium methallylsulfonate.</li></ol>

0019Particularly suitable macromonomers A) are esters of (meth) acrylic acid<ul id="ul0001" list-style="none" compact="compact"><li>(C.₁₀-C₁₈) Fatty alcohol polyglycol ether with 8 EO units (Genapol^® C-080)</li><li>C.₁₁-Oxoalcohol polyglycol ether with 8 EO units (Genapol^® UD-080)</li><li>(C.₁₂-C₁₄) Fatty alcohol polyglycol ether with 7 EO units (Genapol^® LA-070)</li><li>(C.₁₂-C₁₄) Fatty alcohol polyglycol ether with 11 EO units (Genapol^® LA-110)</li><li>(C.₁₆-C₁₈) Fatty alcohol polyglycol ether with 8 EO units (Genapol^® T-080)</li><li>(C.₁₆-C₁₈) Fatty alcohol polyglycol ether with 15 EO units (Genapol^® T-1 50)</li><li>(C.₁₆-C₁₈) Fatty alcohol polyglycol ether with 11 EO units (Genapol^® T-110)</li><li>(C.₁₆-C₁₈) Fatty alcohol polyglycol ether with 20 EO units (Genapol^® T-200)</li><li>(C.₁₆-C₁₈) Fatty alcohol polyglycol ether with 25 EO units (Genapol^® T-250)</li><li>(C.₁₈-C₂₂) Fatty alcohol polyglycol ether with 25 EO units</li></ul>and / or iso- (C₁₆-C₁₈) Fatty alcohol polyglycol ethers with 25 EO units and as olefinically unsaturated comonomers B) are particularly suitable the sodium and ammonium salts of acrylamidopropylmethylene sulfonic acid (AMPS). With the Genapol^®-Types are products from Clariant.

0020The molar proportions of the macromonomers A) and the comonomers B) in the polymer can vary between 0.1 and 99.9 mol%. In a preferred embodiment (highly hydrophobically modified polymers), the proportion of macromonomers A) is 50.1 to 99.9 mol%, preferably 70 to 95 mol%, particularly preferably 80 to 90 mol%. In a further preferred embodiment (low-hydrophobically modified polymers), the proportion of macromonomers A) is 0.1 to 50 mol%, preferably 5 to 25 mol%, particularly preferably 10 to 20 mol%.

0021The monomer distribution of the macromonomers A) and comonomers B) in the polymers can be, for example, alternating, block-like (also multiblock) or statistical (also gradient). The polymers generally have a number average molecular weight of 1000 to 20,000,000 g / mol, preferably 20,000 to 5,000,000, particularly preferably 100,000 to 1,500,000 g / mol.

0022In a preferred embodiment, the polymers according to the invention are crosslinked, ie they contain at least one crosslinker with at least two double bonds which is polymerized into the polymer. Suitable crosslinkers are, in particular, methylenebisacryl and methacrylamide, esters of unsaturated mono- or polycarboxylic acids with polyols, for example diacrylates or triacrylates, for example butanediol and ethylene glycol diacrylate or methacrylate and trimethylolpropane triacrylate, allyl compounds such as, for example, allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl ester, polyallyl ester, tetraallyloxyethane, triallylamine, tetraallyl ethylenediamine, allyl ester of phosphoric acid and / or vinylphosphonic acid derivatives.

0023A preferred embodiment of the invention are those polymers which consist of a water-soluble polymer skeleton and macromonomers A) with heat-sensitive side chains which have an LCST behavior in water, and whose aqueous solution has a viscosity which rises above a certain threshold temperature with increasing temperature increases or remains approximately constant.

0024Another preferred embodiment of the invention are those polymers whose aqueous solution has a viscosity which is low below a first threshold temperature, rises to a maximum above this first threshold temperature and rises again as the temperature rises above a second threshold temperature. It is preferred that the viscosity of the polymer solutions below the first threshold temperature is 5 to 50%, in particular 10 to 30%, of the maximum viscosity at the second threshold temperature.

0025Also a preferred embodiment of the invention are those polymers whose aqueous solutions have a high viscosity and no thermoassociative behavior even at room temperature. The viscosities of the 1% strength aqueous solutions are preferably 20,000 mPas to 100,000 mPas, in particular 60,000 mPas to 70,000 mPas. Such polymers show a high thickening performance, good emulsifying properties and good dispersion properties in aqueous, aqueous-alcoholic and aqueous-surfactant solution or in emulsions even at room temperature. Preparations containing such polymers also show good transparency and high electrolyte stability.

0026The polymers according to the invention are produced by radical copolymerization, such as, for example, precipitation polymerization, emulsion polymerization, solution polymerization or suspension polymerization. Precipitation polymerization is particularly suitable, particularly preferably precipitation polymerization in tert-butanol.

0027With the aid of precipitation polymerization in tert-butanol, a particle size distribution of the polymers which is particularly favorable for the use of the polymers can be achieved. The size distribution of the polymer particles can be determined, for example, by laser diffraction or sieve analysis. The following particle size distribution, as determined by sieve analysis for an AMPS copolymer, is representative of a favorable size distribution: 60.2% less than 423 micrometers, 52.0% less than 212 micrometers, 26.6% less than 106 micrometers, 2.6% smaller than 45 micrometers and 26.6% larger than 850 micrometers.

0028The polymerization reaction can be carried out in the temperature range between 0 and 150.degree. C., preferably between 10 and 100.degree. C., both under normal pressure and under elevated or reduced pressure. As usual, the polymerization can also be carried out in a protective gas atmosphere, preferably under nitrogen.

0029High-energy electromagnetic radiation or the usual chemical polymerization initiators can be used to initiate the polymerization, for example organic peroxides, such as benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, azo compounds, such as azobisisobutyronitrile, azobisdimethylvaleronitrile, as well as inorganic₄)₂S₂O₈, K₂S₂O₈ or H₂O₂, optionally in combination with reducing agents, such as sodium bisulfite and iron (II) sulfate, or redox systems which have an aliphatic or aromatic sulfonic acid as reducing component, such as benzenesulfonic acid, toluenesulfonic acid or derivatives of these acids, such as Mannich adducts of sulfinic acid, aldehydes and amino compounds , contain.

0030The polymers according to the invention are suitable as thickeners and dispersants for aqueous preparations, aqueous-alcoholic and aqueous-surfactant preparations and as emulsifiers, suspending agents with a thickening effect and consistency adjuster for emulsions and suspensions. Mixtures of the polymers can also be used. The polymers are particularly suitable for use in cosmetic and pharmaceutical compositions. It is important that the polymers can be used without the use of an additional co-emulsifier and / or without the use of an additional consistency agent. The use of co-emulsifiers and consistency enhancers is therefore not mandatory, but possible.

0031The invention thus also relates to aqueous preparations, aqueous-alcoholic preparations, aqueous-surfactant preparations, emulsions and suspensions containing the polymers according to the invention. The preparations, emulsions and suspensions are preferably cosmetic and pharmaceutical agents, such as shampoos, shower baths, shower gels, foam baths, gels, lotions, creams and ointments.

0032The preparations, emulsions and suspensions according to the invention contain, based on the finished formulation, preferably 0.05 to 10% by weight, particularly preferably 0.1 to 5% by weight, particularly preferably 0.5 to 3% by weight, on polymers according to the invention.

0033The polymers according to the invention can be used as thickeners for agents on an aqueous or aqueous-alcoholic basis, for example hair gels. Furthermore, the polymers according to the invention are suitable as thickeners, dispersants and consistency agents for aqueous surfactant preparations, for example shampoos, shower baths, shower gels, foam baths and the like. The thickening effect of the polymers according to the invention in aqueous surfactants is enhanced by an association of the polymer side chains and the surfactants and can be controlled by the choice of the side chains of the polymers and by the choice of the surfactants. The suspending or The dispersing and stabilizing effect of the polymers according to the invention in aqueous surfactants is caused by the association of the polymer side chains and the liquid components insoluble in aqueous surfactants, for example silicone oils, or the insoluble components, for example zinc pyrethione.

0034As further auxiliaries and additives, the agents according to the invention can contain all customary anionic, cationic, zwitterionic, non-ionic and amphoteric surfactants, as well as other additives commonly used in cosmetics, such as, for example Superfatting agents, stabilizers, biogenic agents, glycerin, preservatives, pearlescent agents, colors and fragrances, solvents, opacifiers, other thickeners and dispersants, also protein derivatives such as gelatin, collagen hydrolyzates, polypeptides on a natural and synthetic basis, egg yolk, lecithin, lanolin and lanolin derivatives, fatty alcohol , Silicones, deodorants, substances with keratolytic and keratoplastic effects, Contain enzymes and carrier substances. In addition, agents having an antimicrobial action can be added to the agents according to the invention

0035The total amount of the surfactants used in the agents according to the invention can, based on the finished agent, be between 5 and 70% by weight, preferably between 10 and 40% by weight, particularly preferably between 12 and 35% by weight. The following may be mentioned as anionic detergent substances: (C₁₀-C₂₀) -Alkyl and alkylene carboxylates, alkyl ether carboxylates, fatty alcohol sulfates, fatty alcohol ether sulfates, alkylamide sulfates and sulfonates, Fettsäurealkylamidpolyglykolethersulfate, 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, alkyl glyceride ether sulfonates, fatty acid methyl taurides, fatty acid sarcosinates, sulforicinoleates, acyl glutamates. These compounds and their mixtures are used in the form of their water-soluble or water-dispersible salts, for example the sodium, potassium, magnesium, ammonium, mono-, di- and triethanolammonium and analogous alkylammonium salts.

0036The proportion by weight of the anionic surfactants in the agents according to the invention is preferably in the range from 7 to 30% by weight, particularly preferably 10 to 25% by weight, particularly preferably 12 to 22% by weight.

0037Suitable cationic surfactants are, for example, quaternary ammonium salts such as di- (C₁₀-C₂₄) -Alkyl-dimethylammonium chloride or bromide, preferably di- (C₁₂-C₁₈) Alkyl dimethyl ammonium chloride or bromide; (C.₁₀-C₂₄) Alkyl dimethyl ethyl ammonium chloride or bromide; (C.₁₀-C₂₄) Alkyltrimethylammonium chloride or bromide, preferably cetyltrimethylammonium chloride or bromide and (C₂₀-C₂₂) Alkyl trimethyl ammonium chloride or bromide; (C.₁₀-C₂₄) -Alkyl-dimethylbenzylammonium chloride or bromide, preferably (C₁₂-C₁₈) Alkyl dimethylbenzylammonium chloride; N- (C₁₀-C₁₈) Alkyl pyridinium chloride or bromide, preferably N- (C₁₂-C₁₆) Alkyl pyridinium chloride or bromide; N- (C₁₀-C₁₈) Alkyl isoquinolinium chloride, bromide or monoalkyl sulfate; N- (C₁₂-C₁₈) -Alkyl-polyolaminoformylmethylpyridinium chloride; N- (C₁₂-C₁₈) -Alkyl-N-methyl-morpholinium chloride, bromide or monoalkyl sulfate; N- (C₁₂-C₁₈) Alkyl N-ethyl morpholinium chloride, bromide or monoalkyl sulfate; (C.₁₆-C₁₈) Alkyl pentaoxethyl ammonium chloride; Diisobutylphenoxyethoxyethyldimethylbenzylammonium chloride; Salts of N, N-diethylaminoethylstearylamide and oleylamide with hydrochloric acid, acetic acid, lactic acid, citric acid, phosphoric acid; N-acylaminoethyl-N, N-diethyl-N-methylammonium chloride, bromide or monoalkyl sulfate and N-acylaminoethyl-N, N-diethyl-N-benzylammonium chloride, bromide or monoalkyl sulfate, with acyl preferably for Stearyl or oleyl.

0038The proportion by weight of the cationic surfactants in the agents according to the invention is preferably in the range from 1 to 10% by weight, particularly preferably 2 to 7% by weight, particularly preferably 3 to 5% by weight.

0039Examples of suitable nonionic surfactants which can be used as washing-active substances are: fatty alcohol ethoxylates (alkyl polyethylene glycols); Alkylphenol polyethylene glycols; Alkyl mercaptan polyethylene glycols; Fatty amine ethoxylates (alkylamino polyethylene glycols); Fatty acid ethoxylates (acyl polyethylene glycols); Polypropylene glycol ethoxylates (Pluronics^®); Fatty acid alkylolamides (fatty acid amide polyethylene glycols); N-alkyl, N-alkoxypolyhydroxy fatty acid amides, sucrose esters; Sorbitol ester and polyglycol ether.

0040The proportion by weight of the nonionic surfactants in the agents according to the invention is preferably in the range from 1 to 20% by weight, particularly preferably 2 to 10% by weight, particularly preferably 3 to 7% by weight.

0041Preferred amphoteric surfactants are: N- (C₁₂-C₁₈) -Alkyl-β-aminopropionate and N- (C₁₂-C₁₈) -Alkyl-β-iminodipropionate as alkali and mono-, di- and trialkylammonium salts; N-acylaminoalkyl-N, N-dimethyl-acetobetaine, preferably N- (C₈-C₁₈) -Acylaminopropyl-N, N-dimethylacetobetaine; (C.₁₂-C₁₈) Alkyl dimethyl sulfopropyl betaine; Amphoteric surfactants based on imidazoline (trade name: Miranol^®, Steinapon^®), preferably the sodium salt of 1 - (β-carboxymethyloxyethyl) -1 - (carboxymethyl) -2-lauryl-imidazolinium; Amine oxides, e.g. (C₁₂-C₁₈) -Alkyldimethylamine oxide, fatty acid amidoalkyl-dimethylamine oxide.

0042The proportion by weight of the amphoteric surfactants in the agents according to the invention is preferably in the range from 0.5 to 20% by weight, particularly preferably 1 to 10% by weight.

0043Furthermore, foam-reinforcing co-surfactants from the group alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines, amine oxides and fatty acid alkanolamides or polyhydroxyamides can be used in the agents according to the invention.

0044Preferred surfactants in the agents according to the invention are lauryl sulfate, laureth sulfate, cocoamidopropyl betaine, sodium cocoyl glutamate, disodium laureth sulfosuccinate and coconut fatty acid diethanolamide. The preparations according to the invention can also contain other additives customary in cosmetics, such as superfatting agents, stabilizers, biogenic active ingredients, glycerol, preservatives, pearlescent agents, colors and fragrances, solvents, opacifiers, thickeners and dispersants, and also protein derivatives such as gelatin, collagen hydrolyzates, polypeptides on a natural and synthetic basis , Egg yolk, lecithin, lanolin and lanolin derivatives, fatty alcohols, silicones, Contain deodorants, substances with keratolytic and keratoplastic effects, enzymes and carrier substances. In addition, agents having an antimicrobial action can be added to the agents according to the invention. Substances such as, for example, polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers. Typical examples of fats are glycerides; beeswax, paraffin wax or microwaxes, among others, are suitable as waxes, optionally in combination with hydrophilic waxes, for example cetylstearyl alcohol.

0045Metal salts of fatty acids such as magnesium, aluminum and / or zinc stearate can be used as stabilizers. Biogenic active substances are understood to mean, for example, plant extracts and vitamin complexes. Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid. Suitable pearlizing agents are, for example, glycol distearic acid esters, such as ethylene glycol distearate, but also fatty acid monoglycol esters. The dyes which can be used are those which are suitable and approved for cosmetic purposes.

0046Other suitable thickeners are sodium, potassium, ammonium chloride, sodium sulfate, fatty acid alkylolamides, cellulose derivatives, for example hydroxyethyl cellulose, guar gum, polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl guar gum, starch and starch derivatives, and natural gums, carboxyvinyl polymers, for example Carbopol 934, -940 941, -956, -980, -981, -1342, -1382, ethylene glycol esters of fatty acids with 14 to 22, particularly preferably 16 to 22 carbon atoms, especially mono- and di-ethylene glycol stearate. Also preferred are stearin monoethanolamide, stearin diethanolamide, stearin isopropanolamide, stearin monoethanolamide stearate, stearyl stearate, cetyl palmitate, glyceryl stearate, stearamide diethanolamide distearate, stearamide monoethanolamide stearate, N, N-dihydrocarbyl (C₁₂-C₂₂) - especially (C₁₆-C₁₈) - amidobenzoic acid and its soluble salts, N, N-di (C₁₆-C₁₈) amidobenzoic acid and its derivatives. The dispersants are used, based on the finished composition, in concentrations of preferably 0.5 to 10% by weight, particularly preferably 0.5 to 5% by weight, particularly preferably 1 to 4% by weight. The desired viscosity of the agents can be adjusted by adding water and / or organic solvents or by adding a combination of organic solvents and thickeners. In principle, all monohydric or polyhydric alcohols are suitable as organic solvents. Alcohols with 1 to 4 carbon atoms such as ethanol, propanol, isopropanol, n-butanol, i-butanol, t-butanol, glycerol and mixtures of the alcohols mentioned are preferably used. Other preferred alcohols are polyethylene glycols with a molecular weight below 2000. In particular, use of polyethylene glycol with a relative molecular weight between 200 and 600 and in amounts of up to 45% by weight and of polyethylene glycol with a relative molecular weight between 400 and 600 in amounts of 5 to 25% by weight is preferred. Other suitable solvents are, for example, triacetin (glycerol triacetate) and 1-methoxy-2-propanol.

0047Suitable carrier materials are vegetable oils, natural and hardened oils, waxes, fats, water, alcohols, polyols, glycerol, glycerides, liquid paraffins, liquid fatty alcohols, sterols, polyethylene glycols, cellulose and cellulose derivatives.

0048Ketoconazole, oxiconazole, bifonazole, butoconazole, cloconazole, clotrimazole, econazole, enilconazole, fenticonazole, isoconazole, miconazole, sulconazole, tioconazole, fluconazole, itraconazole naftine, terifazine, terifazine can be used as fungicidal active ingredients.

0049Silicones, polyalkylsiloxanes, polyalkylarylsiloxanes, polyethersiloxane copolymers, as in <patcit id="pcit0008" dnum="US5104645A"><text>US 5,104,645</text></patcit> and the writings cited therein, improve the nourishing effect of the agents according to the invention. The agents according to the invention can be mixed with conventional ceramides, pseudoceramides, fatty acid-N-alkylpolyhydroxyalkylamides, cholesterol, cholesterol fatty acid esters, fatty acids, triglycerides, cerebrosides, phospholipids and similar substances.

0050The polymers according to the invention can be used as emulsifiers, stabilizers and / or consistency enhancers in emulsions. Crosslinked polymers are particularly suitable for this. The emulsions can be either water-in-oil emulsions or oil-in-water emulsions. The emulsifying, stabilizing and / or consistency effect of the polymers according to the invention in emulsions is caused or enhanced by an association of the polymer side chains with one another, and by an interaction of the polymer side chains with the hydrophobic oil components.

0051The non-aqueous proportion of the emulsions, which largely consists of the emulsifier, the thickener and the oil body, is usually 5 to 95%, preferably 15 to 75% by weight. It follows that the emulsions can contain 5 to 95% by weight and preferably 25 to 85% by weight of water, depending on whether lotions with a comparatively low viscosity or creams and ointments with a high viscosity are to be produced.

0052The emulsions can be used as skin care products, such as day creams, night creams, skin care creams, nutritional creams, body lotions, ointments and the like, and as further auxiliaries and additives, oil bodies, co-emulsifiers, superfatting agents, fats, waxes, stabilizers, biogenic active substances, glycerol, Contain preservatives, colors and fragrances.

0053Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear (C.₆-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 dimer diol or trimer diol) and / or Guerbet alcohols, triglycerides based (C₆-C₁₀) Fatty acids, vegetable oils, branched primary alcohols, substituted cyclohexanes, Guerbet carbonates, dialkyl ethers and / or aliphatic or aromatic hydrocarbons. The proportion of the oil bodies in the non-aqueous proportion of the emulsions can make up 5 to 95 and preferably 15 to 75% by weight.

0054Suitable nonionic co-emulsifiers are, inter alia, addition products of 0 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms, with alkylphenols with 8 to 15 carbon atoms in the alkyl group and on sorbitan or sorbitol esters; (C.₁₂-C₁₈) Fatty acid monoesters and diesters of adducts of 0 to 30 moles 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, if appropriate, their ethylene oxide addition products; Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil; Polyol and especially polyglycerol esters, such as polyglycerol polyricinoleate and polyglycerol poly-12-hydroxystearate. Mixtures of compounds from several of these classes of substances are also suitable.

0055Suitable ionogenic co-emulsifiers are, for example, anionic emulsifiers, such as mono-, di- or tri-phosphoric acid esters, but also cationic emulsifiers such as mono-, di- and tri-alkyl quats and their polymeric derivatives. In order to adjust the rheological properties of aqueous or solvent-based emulsions or suspensions, a large number of different systems are specified in the specialist literature. Cellulose ethers and other cellulose derivatives (e.g. Carboxymethyl cellulose, hydroxyethyl cellulose), gelatin, starch and starch derivatives, sodium alginates, fatty acid polyethylene glycol esters, agar-agar, tragacanth or dextrins. Various materials are used as synthetic polymers, such as Polyvinyl alcohols, polyacrylamides, polyvinylamides, polysulfonic acids, polyacrylic acid, polyacrylic acid esters, polyvinyl pyrrolidone, polyvinyl methyl ether, polyethylene oxides, copolymers of maleic anhydride and vinyl methyl ether, as well as various mixtures and copolymers of the above compounds, including their various salts and esters. These polymers can optionally be cross-linked or uncross-linked. The emulsions can be prepared in a known manner, ie for example by hot, hot / cold or PIT emulsification.

0056The polymers according to the invention can also be used for the formulation of crop protection agents. In this area of ​​application, there has been a rethink in the development of new drug formulations in recent years. The focus was not on research for new active substances, but on the search for auxiliary reagents to enhance the effects of known active substances on the plant surface. The addition of these so-called adjuvants enables the amount of active ingredient used to be reduced while maintaining the effectiveness of the overall formulation in comparison with formulations free of adjuvants. Non-polar modified water-soluble polyelectrolytes on the one hand enable an increase in the viscosity of the active substance solution present - which leads to a slower "beading off" of the leaf surfaces and thus to a longer exposure time to the leaf - and on the other hand the non-polar side residues result in increased adsorption on the likewise non-polar leaf surfaces.

0057The following examples and applications are intended to explain the invention in more detail, but without restricting it thereto.

Examples and applications

1) Representation of the macromonomers

a) Variant 1: methacrylic acid glycidyl ester

0058600 g of Genapol T-250 are placed in a one liter three-necked flask with stirrer, internal thermometer and reflux condenser and 75 g of methacrylic acid glycidyl ester are added. The reaction mixture is then heated to 100 ° C. for 2 hours and the excess methacrylate is distilled off in vacuo. The resulting macromonomer can be used in the polymerization without further purification.

b) Variant 2: free meth / acrylic acid

0059500 g of Genapol UD-070 are placed in a one liter three-necked flask equipped with a stirrer, internal thermometer and reflux condenser, and 100 g of meth- / acrylic acid and p-toluenesulfonic acid as catalyst are added. The reaction mixture is then boiled under reflux for 2 hours and the excess acid and the water of reaction formed are distilled off in vacuo. The resulting macromonomer can be used in the polymerization without further purification.

c) Variant 3: halogen derivatives of meth / acrylic acid

0060500 g of Genapol UD-070 with a primary amino end group are placed in a one liter three-necked flask with stirrer, internal thermometer and reflux condenser, and 110 g of meth- / acrylic acid chloride and 50 g of sodium carbonate are added. The reaction mixture is then boiled under reflux for 2 hours. The cessation of CO₂-Development indicates the end of the modification reaction. The excess acid chloride is distilled off in vacuo. The resulting macromonomer with a meth / acrylamide end group can be used in the polymerization without further purification.

d) Variant 4: esters of meth / acrylic acid

0061500 g of Genapol LA-090 are placed in a one liter three-necked flask equipped with a stirrer, internal thermometer and reflux condenser, and 100 g of methyl methacrylate and 20 g of titanium tetraisopropylate are added. The reaction mixture is then boiled under reflux for 2 hours. After the alcohol formed has been distilled off, the remaining ester is distilled off in vacuo. The resulting macromonomer with a meth / acrylic acid end group can be used in the polymerization without further purification.

2) polymerization

0062General polymerization instructions for the preparation of the side chain polymers according to the invention by the precipitation process in t-butanol

0063500 ml of t-butanol are placed in a 2-liter Quickfit flask with reflux condenser, gas inlet, internal thermometer and stirrer and the calculated amount of AMPS is added. Then by NH₃-Introduction neutralized and the LCST side arms produced as under 1) (several different species also possible) are added to the reaction mixture. If further comonomers are required, these can be added to the reaction mixture after neutralization. After inerting the mixture with N₂ or argon is added as an initiator at an internal temperature of 60 ° C and initiating the polymerization reaction. The finished polymer precipitates after a few minutes. The mixture is heated to reflux for two hours and the polymer is then freed from the solvent via a suction filter and dried in vacuo. This regulation is generally applicable to all polymerization reactions described below.

Side chain polymers with thickening properties

Example 1: Reaction according to general polymerization instructions

0064<tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="73mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><thead><row><entry valign="top">Reactant</entry><entry valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>Macromonomer variant 1 - Genapol type^®T-250</entry><entry>20</entry></row><row><entry>NH₃-neutralized AMPS</entry><entry>100</entry></row><row><entry>t-butanol</entry><entry>300</entry></row><row><entry>AIBN (initiator)</entry><entry>1</entry></row></tbody></tgroup></table></tables>

Example 2: Reaction according to general polymerization instructions

0065<tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="73mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><thead><row><entry valign="top">Reactant</entry><entry valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>Macromonomer variant 3 - type Genapol^® UD-80</entry><entry>30</entry></row><row><entry>NH₃-neutralized AMPS</entry><entry>90</entry></row><row><entry>t-butanol</entry><entry>300</entry></row><row><entry>AIBN (initiator)</entry><entry>1</entry></row></tbody></tgroup></table></tables>

Example 3: Reaction according to general polymerization instructions

0066<tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="73mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><thead><row><entry valign="top">Reactant</entry><entry valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>Macromonomer variant 3 - type Genapol^® T-250</entry><entry>30</entry></row><row><entry>NH₃-neutralized AMPS</entry><entry>90</entry></row><row><entry>Methylenebisacrylamide (crosslinker)</entry><entry>1.5</entry></row><row><entry>t-butanol</entry><entry>300</entry></row><row><entry>AIBN (initiator)</entry><entry>1</entry></row></tbody></tgroup></table></tables>

Example 4: Reaction according to general polymerization instructions

0067<tables id="tabl0004" num="0004"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="72mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><thead><row><entry valign="top">Reactant</entry><entry valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>Macromonomer variant 1 - Genapol type^®L-070</entry><entry>20</entry></row><row><entry>Na neutralized AMPS</entry><entry>75</entry></row><row><entry>Acrylamide</entry><entry>50</entry></row><row><entry>t-butanol</entry><entry>300</entry></row><row><entry>AIBN (initiator)</entry><entry>1</entry></row></tbody></tgroup></table></tables>

Example 5: Reaction according to general polymerization instructions

0068<tables id="tabl0005" num="0005"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="75mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><thead><row><entry valign="top">Reactant</entry><entry valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>Macromonomer variant 4 - Genapol type^®UD-080</entry><entry>15</entry></row><row><entry>Macromonomer variant 1 - Genapol type^®T-250</entry><entry>15</entry></row><row><entry>NH₃-neutralized AMPS</entry><entry>100</entry></row><row><entry>t-butanol</entry><entry>300</entry></row><row><entry>AIBN (initiator)</entry><entry>1</entry></row></tbody></tgroup></table></tables>

Example 6: Reaction according to general polymerization instructions

0069<tables id="tabl0006" num="0006"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="75mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><thead><row><entry valign="top">Reactant</entry><entry valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>Macromonomer variant 1 - Genapol type^®LA-110</entry><entry>20</entry></row><row><entry>NH₃-neutralized AMPS</entry><entry>100</entry></row><row><entry>t-butanol</entry><entry>300</entry></row><row><entry>AIBN (initiator)</entry><entry>1</entry></row></tbody></tgroup></table></tables>

Example 7: Reaction according to general polymerization instructions

0070<tables id="tabl0007" num="0007"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="73mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><thead><row><entry valign="top">Reactant</entry><entry valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>Macromonomer variant 1 - Genapol type^®T-080</entry><entry>20</entry></row><row><entry>NH₃-neutralized AMPS</entry><entry>100</entry></row><row><entry>t-butanol</entry><entry>300</entry></row><row><entry>AIBN (initiator)</entry><entry>1</entry></row></tbody></tgroup></table></tables>

Example 8: Reaction according to general polymerization instructions

0071<tables id="tabl0008" num="0008"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="73mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><thead><row><entry valign="top">Reactant</entry><entry valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>Macromonomer variant 1 - Genapol type^®T-150</entry><entry>25</entry></row><row><entry>NH₃-neutralized AMPS</entry><entry>100</entry></row><row><entry>AT THE</entry><entry>10</entry></row><row><entry>t-butanol</entry><entry>350</entry></row><row><entry>AIBN (initiator)</entry><entry>1</entry></row></tbody></tgroup></table></tables>

Example 9: Reaction according to general polymerization instructions

0072<tables id="tabl0009" num="0009"><table frame="all"><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="75mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="20mm" /><colspec colnum="4" colname="col4" colwidth="20mm" /><thead><row><entry align="center" valign="top" /><entry align="center" valign="top">9,1</entry><entry align="center" valign="top">9,2</entry><entry align="center" valign="top">9,3</entry></row><row><entry valign="top">Reactant</entry><entry align="center" valign="top">Quantity (g)</entry><entry align="center" valign="top">Quantity (g)</entry><entry align="center" valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>Macromonomer variant 1 - Genapol type^®LA-110</entry><entry align="center">10</entry><entry align="center">20</entry><entry align="center">10</entry></row><row><entry>Macromonomer variant 1 - Genapol type^®T-150</entry><entry align="center">12,5</entry><entry align="center">12,5</entry><entry align="center">25</entry></row><row><entry>NH₃-neutralized AMPS</entry><entry align="center">100</entry><entry align="center">100</entry><entry align="center">100</entry></row><row><entry>AT THE</entry><entry align="center">10</entry><entry align="center">10</entry><entry align="center">10</entry></row><row><entry>t-butanol</entry><entry align="center">350</entry><entry align="center">350</entry><entry align="center">350</entry></row><row><entry>AIBN (initiator)</entry><entry align="center">1</entry><entry align="center">1</entry><entry align="center">1</entry></row></tbody></tgroup></table></tables>

Example 10: Polymer blend

0073<tables id="tabl0010" num="0010"><table frame="all"><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="19mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="20mm" /><colspec colnum="4" colname="col4" colwidth="20mm" /><thead><row><entry valign="top" /><entry align="center" valign="top">10.1</entry><entry align="center" valign="top">10.2</entry><entry align="center" valign="top">10.3</entry></row><row><entry valign="top">polymer</entry><entry align="center" valign="top">Quantity (g)</entry><entry align="center" valign="top">Quantity (g)</entry><entry align="center" valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>example 1</entry><entry align="center">10</entry><entry align="center">20</entry><entry align="center">10</entry></row><row><entry>Example 3</entry><entry align="center">10</entry><entry align="center">10</entry><entry align="center">20</entry></row></tbody></tgroup></table></tables>

Example 11: Reaction according to general polymerization instructions but at 45 ° C starting temperature

0074<tables id="tabl0011" num="0011"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="129mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><thead><row><entry valign="top">Reactant</entry><entry valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>Macromonomer variant 1 - type (C₁₈-C₂₂) Fatty alcohol polyglycol ether with 25 EO units</entry><entry>25</entry></row><row><entry>NH₃-neutralized AMPS</entry><entry>100</entry></row><row><entry>t-butanol</entry><entry>300</entry></row><row><entry>Azobisdimethylvaleronitrile (initiator)</entry><entry>1</entry></row></tbody></tgroup></table></tables>

Example 12: Reaction according to general polymerization instructions, but at 45 ° C starting temperature

0075<tables id="tabl0012" num="0012"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="75mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><thead><row><entry valign="top">Reactant</entry><entry valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>Macromonomer variant 1 - Genapol type^®UD-080</entry><entry>20</entry></row><row><entry>NH₃-neutralized AMPS</entry><entry>100</entry></row><row><entry>t-butanol</entry><entry>300</entry></row><row><entry>Azobisdimethylvaleronitrile (initiator)</entry><entry>1</entry></row></tbody></tgroup></table></tables>

Example 13: Reaction according to general polymerization instructions

0076<tables id="tabl0013" num="0013"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="73mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><thead><row><entry valign="top">Reactant</entry><entry valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>Macromonomer variant 1 - Genapol type^®T-200</entry><entry>15</entry></row><row><entry>NH₃-neutralized AMPS</entry><entry>100</entry></row><row><entry>t-butanol</entry><entry>300</entry></row><row><entry>AIBN (initiator)</entry><entry>1</entry></row></tbody></tgroup></table></tables>

Example 14: Reaction according to general polymerization instructions

0077<tables id="tabl0014" num="0014"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="45mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><thead><row><entry valign="top">Reactant</entry><entry align="center" valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>Genapol^®T-250 methacrylate</entry><entry align="center">97</entry></row><row><entry>NH₃-neutralized AMPS</entry><entry align="center">3</entry></row><row><entry>t-butanol</entry><entry align="center">300</entry></row><row><entry>TMPTA</entry><entry align="center">1,8</entry></row><row><entry>Dilauroyl peroxide (initiator)</entry><entry align="center">1</entry></row></tbody></tgroup></table></tables>

Example 15 (comparison): Reaction according to general polymerization instructions

0078<tables id="tabl0015" num="0015"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="41mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><thead><row><entry valign="top">Reactant</entry><entry valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>MPEG 750 methacrylate</entry><entry>80</entry></row><row><entry>NH₃-neutralized AMPS</entry><entry>20</entry></row><row><entry>t-butanol</entry><entry>300</entry></row><row><entry>TMPTA</entry><entry>1.8</entry></row><row><entry>AIBN (initiator)</entry><entry>1</entry></row></tbody></tgroup><tgroup cols="2" rowsep="0"><colspec colnum="1" colname="col1" colwidth="41mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><tbody><row><entry namest="col1" nameend="col2" align="justify">Viscosity 1.0% (H₂Dist.) 55,000 mPas (Brookfield spindle 7) Viscosity 0.5% (H₂Dist.) 19,000 mPas (Brookfield spindle 7)</entry></row></tbody></tgroup></table></tables>

Example 16: Reaction according to general polymerization instructions

0079<tables id="tabl0016" num="0016"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="45mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><thead><row><entry valign="top">Reactant</entry><entry align="center" valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>Genapol^®T-250 methacrylate</entry><entry align="center">97</entry></row><row><entry>NH₃-neutralized AMPS</entry><entry align="center">3</entry></row><row><entry>t-butanol</entry><entry align="center">300</entry></row><row><entry>Dilauroyl peroxide (initiator)</entry><entry align="center">1</entry></row></tbody></tgroup></table></tables>

Example 17 (comparison): Reaction according to general polymerization instructions

0080<tables id="tabl0017" num="0017"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="41mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><thead><row><entry valign="top">Reactant</entry><entry align="center" valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>MPEG-750 methacrylate</entry><entry align="center">20</entry></row><row><entry>NH₃-neutralized AMPS</entry><entry align="center">80</entry></row><row><entry>t-butanol</entry><entry align="center">300</entry></row><row><entry>ABAH (initiator)</entry><entry align="center">1</entry></row></tbody></tgroup><tgroup cols="2" rowsep="0"><colspec colnum="1" colname="col1" colwidth="41mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><tbody><row><entry namest="col1" nameend="col2" align="justify">Viscosity 1.0% (H₂Dist.) 1,500 mPas (Brookfield spindle 5) Viscosity 0.5% (H₂O dest.) 400 mPas (Brookfield spindle 5)</entry></row></tbody></tgroup></table></tables>

Comparative Example 1:

0081Comparative Example 1 shows that the temperature at which viscosification sets in and the strength of the effect can be influenced (Figure 1). The polymers used are based on Examples 6, 7 and 8. In addition, a polymer is made from<patcit id="pcit0009" dnum="EP0583814B"><text>EP-B-0 583 814</text></patcit> adjusted. These are pAMPS / 1,2-POE5 from example 1.3. Figure 1 shows the viscosity of the polymers in aqueous solution. In Figure 1 it can be seen that the maxima of the viscosification can be found at different temperatures: for example 6 at 120 ° C, for example 7 at 140 ° C and for example 8 at over 200 ° C. pAMPS / 1.2-POE5 has its maximum temperature at 200 ° C. The application concentrations are also significantly lower than for pAMPS / 1.2-POE5 (Figure 1).<img file="EP1069142B1_D0001.tif" />

0082Furthermore, it can be clearly seen that the polymers according to the invention have a basic viscosity even at room temperature due to the hydrophobic interaction of the alkyl residues of the side chains. pAMPS / 1.2-POE5 does not develop such a basic viscosity. Furthermore, the polymers according to the invention are distinguished in that the width of the thermoassociating effect can be controlled.

0083The two examples below show the influence of mixtures of different side arms in one polymer (Example 18) and the influence of mixtures of different polymers (Example 19).

Example 18:

0084This example shows the development of viscosity at different temperatures for the polymers from Example 9. Different side arms are used in one polymer (Figure 2).<img file="EP1069142B1_D0002.tif" />

Example 19:

0085Figure 3 shows how the viscosity behavior changes depending on the temperature. Examples 10.1 to 10.3 are different mixing ratios of the polymers from Example 6 and Example 7. The width and strength of the thermoassociating effect can be adjusted via the mixing ratio.<img file="EP1069142B1_D0003.tif" />

Examples of oil emulsions

0086The test emulsions are stored at 40 ° C, 45 ° C and 50 ° C for a period of 90 days. 3 different oil mixtures are used in each case. The oil mixtures are composed as follows:<tables id="tabl0018" num="0018"><table frame="none"><tgroup cols="4" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="29mm" /><colspec colnum="2" colname="col2" colwidth="12mm" /><colspec colnum="3" colname="col3" colwidth="45mm" /><colspec colnum="4" colname="col4" colwidth="19mm" /><thead><row><entry valign="top">Mixture I:</entry><entry valign="top" /><entry valign="top">Mixture II:</entry><entry valign="top" /></row></thead><tbody><row><entry>Paraffin oil nv</entry><entry>50 %</entry><entry>Cetiol V</entry><entry>25 %</entry></row><row><entry>Isopropyl palmitate</entry><entry>30 %</entry><entry>Squalane</entry><entry>25 %</entry></row><row><entry>Soybean oil</entry><entry>20 %</entry><entry>Myritol 318 isopropyl palmitate</entry><entry>25 % 25 %</entry></row></tbody></tgroup></table></tables><tables id="tabl0019" num="0019"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="24mm" /><colspec colnum="2" colname="col2" colwidth="12mm" /><thead><row><entry valign="top">Mixture III:</entry><entry valign="top" /></row></thead><tbody><row><entry>Soybean oil</entry><entry>50 %</entry></row><row><entry>almond oil</entry><entry>20 %</entry></row><row><entry>Avocado oil</entry><entry>20 %</entry></row><row><entry>Jojoba oil</entry><entry>1 0 %</entry></row></tbody></tgroup></table></tables>

Assessment key:

0087<ul id="ul0002" list-style="none" compact="compact"><li>0 = no emulsifier effect</li><li>1 = separated in 2 or 3 phases</li><li>3rd = Creaming + oil or water + creaming, homogeneous emulsion in between</li><li>4th = Water separation, no creaming, no oil separation</li><li>5 = Oil separation, no creaming, no water separation</li><li>6 = Creaming</li><li>7 = weakly recognizable creaming</li><li>8th = practically fine</li><li>9 = completely homogeneous emulsion</li></ul>

Emulsifying index:

0088<ul id="ul0003" list-style="none" compact="compact"><li>4.1 - 5.0 = very good</li><li>3.1 - 4.0 = good</li><li>2.1 - 3.0 = medium</li><li>1.1 - 2.0 = bad</li><li>0 - 1.0 = very bad</li></ul>

Test emulsions with uncrosslinked polymers according to the invention

0089<tables id="tabl0020" num="0020"><table frame="all"><tgroup cols="13"><colspec colnum="1" colname="col1" colwidth="32mm" /><colspec colnum="2" colname="col2" colwidth="15mm" /><colspec colnum="3" colname="col3" colwidth="15mm" /><colspec colnum="4" colname="col4" colwidth="15mm" /><colspec colnum="5" colname="col5" colwidth="15mm" /><colspec colnum="6" colname="col6" colwidth="15mm" /><colspec colnum="7" colname="col7" colwidth="15mm" /><colspec colnum="8" colname="col8" colwidth="16mm" /><colspec colnum="9" colname="col9" colwidth="16mm" /><colspec colnum="10" colname="col10" colwidth="16mm" /><colspec colnum="11" colname="col11" colwidth="16mm" /><colspec colnum="12" colname="col12" colwidth="16mm" /><colspec colnum="13" colname="col13" colwidth="16mm" /><thead><row><entry valign="top">composition</entry><entry valign="top">20</entry><entry valign="top">21</entry><entry valign="top">22</entry><entry valign="top">23</entry><entry valign="top">24</entry><entry valign="top">25</entry><entry valign="top">26</entry><entry valign="top">27</entry><entry valign="top">28</entry><entry valign="top">29</entry><entry valign="top">30</entry><entry valign="top">31</entry></row></thead><tbody><row><entry>Polymer It. Ex. 2</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>1,0</entry><entry>-</entry><entry>-</entry><entry>1,0</entry><entry>-</entry><entry>-</entry><entry>0,5</entry><entry>-</entry><entry>-</entry></row><row><entry>Polymer It. Ex. 1</entry><entry>-</entry><entry>1,0</entry><entry>1,0</entry><entry>-</entry><entry>-</entry><entry>1,0</entry><entry>-</entry><entry>-</entry><entry>1,0</entry><entry>-</entry><entry>-</entry><entry>0,5</entry></row><row><entry>Polymer It. Ex. 6</entry><entry>1,0</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>1,0</entry><entry>-</entry><entry>-</entry><entry>1,0</entry><entry>-</entry><entry>-</entry><entry>0,5</entry><entry>-</entry></row><row><entry>Oil mixture I</entry><entry>19,0</entry><entry>19,0</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry></row><row><entry>Oil mixture II</entry><entry>-</entry><entry>-</entry><entry>19,0</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry></row><row><entry>Oil mixture III</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>19,0</entry><entry>19,0</entry><entry>19,0</entry><entry>27,0</entry><entry>27,0</entry><entry>27,0</entry><entry>27,0</entry><entry>27,0</entry><entry>27,0</entry></row><row><entry>Carbopol 980</entry><entry>0,3</entry><entry>0,3</entry><entry>0,3</entry><entry>0,3</entry><entry>0,3</entry><entry>0,3</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry></row><row><entry>Sodium hydroxide solution 10%</entry><entry>1,2</entry><entry>1,2</entry><entry>1,2</entry><entry>1,2</entry><entry>1,2</entry><entry>1,2</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry></row><row><entry>water</entry><entry>Ad 100</entry><entry>Ad 100</entry><entry>Ad 100</entry><entry>Ad 100</entry><entry>Ad 100</entry><entry>Ad 100</entry><entry>Ad 100</entry><entry>Ad 100</entry><entry>Ad 100</entry><entry>Ad 100</entry><entry>Ad 100</entry><entry>Ad 100</entry></row><row><entry>Emulsifying index</entry><entry>3,9</entry><entry>4,0</entry><entry>4,0</entry><entry>3,9</entry><entry>3,8</entry><entry>3,7</entry><entry>2,8</entry><entry>2,5</entry><entry>2,8</entry><entry>2,8</entry><entry>2,6</entry><entry>2,7</entry></row><row><entry>Emulsifying effect</entry><entry>Well</entry><entry>Well</entry><entry>Well</entry><entry>Well</entry><entry>Well</entry><entry>Well</entry><entry>moderate</entry><entry>moderate</entry><entry>moderate</entry><entry>moderate</entry><entry>moderate</entry><entry>moderate</entry></row></tbody></tgroup></table></tables>

0090The stability test shows that the uncrosslinked polymers according to the invention in combination with an additional consistency enhancer deliver stable emulsions.

Test emulsions with crosslinked polymers according to the invention

0091<tables id="tabl0021" num="0021"><table frame="all"><tgroup cols="10"><colspec colnum="1" colname="col1" colwidth="32mm" /><colspec colnum="2" colname="col2" colwidth="14mm" /><colspec colnum="3" colname="col3" colwidth="14mm" /><colspec colnum="4" colname="col4" colwidth="16mm" /><colspec colnum="5" colname="col5" colwidth="16mm" /><colspec colnum="6" colname="col6" colwidth="16mm" /><colspec colnum="7" colname="col7" colwidth="16mm" /><colspec colnum="8" colname="col8" colwidth="16mm" /><colspec colnum="9" colname="col9" colwidth="16mm" /><colspec colnum="10" colname="col10" colwidth="16mm" /><thead><row><entry valign="top">composition</entry><entry valign="top">32</entry><entry valign="top">33</entry><entry valign="top">34</entry><entry valign="top">35</entry><entry valign="top">36</entry><entry valign="top">37</entry><entry valign="top">38</entry><entry valign="top">39</entry><entry valign="top">40</entry></row></thead><tbody><row><entry>Polymer It. Ex. 3</entry><entry>1</entry><entry>1</entry><entry>1</entry><entry>1</entry><entry>1</entry><entry>1</entry><entry>0,75</entry><entry>0,75</entry><entry>0,75</entry></row><row><entry>Oil mixture I</entry><entry>27</entry><entry /><entry /><entry>27</entry><entry /><entry /><entry>27</entry><entry /><entry /></row><row><entry>Oil mixture II</entry><entry /><entry>27</entry><entry /><entry /><entry>27</entry><entry /><entry /><entry>27</entry><entry /></row><row><entry>Oil mixture III</entry><entry /><entry /><entry>27</entry><entry /><entry /><entry>27</entry><entry /><entry /><entry>27</entry></row><row><entry>Carbopol 980</entry><entry>0,3</entry><entry>0,3</entry><entry>0,3</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry></row><row><entry>Sodium hydroxide solution 10%</entry><entry>1,2</entry><entry>1,2</entry><entry>1,2</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry></row><row><entry>water</entry><entry>Ad 100</entry><entry>Ad 100</entry><entry>Ad 100</entry><entry>Ad 100</entry><entry>Ad 100</entry><entry>Ad 100</entry><entry>Ad 100</entry><entry>Ad 100</entry><entry>Ad 100</entry></row><row><entry>Emulsifying index</entry><entry>4,7</entry><entry>4,8</entry><entry>4,7</entry><entry>4,6</entry><entry>4,4</entry><entry>4,5</entry><entry>4,5</entry><entry>4,6</entry><entry>4,6</entry></row><row><entry>Emulsifying effect</entry><entry>Very good</entry><entry>Very good</entry><entry>Very good</entry><entry>Very good</entry><entry>Very good</entry><entry>Very good</entry><entry>Very good</entry><entry>Very good</entry><entry>Very good</entry></row></tbody></tgroup></table></tables>

0092The stability test shows that the crosslinked polymers according to the invention act simultaneously as a consistency agent and as an emulsifier with very good emulsifying properties. Stable emulsions are obtained without an additional co-emulsifier and without an additional consistency agent.

Formulation examples, all figures in% by weight

Example 41: O / W - skin milk

Composition:

0093<tables id="tabl0022" num="0022"><table frame="none"><tgroup cols="3" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="10mm" /><colspec colnum="2" colname="col2" colwidth="48mm" /><colspec colnum="3" colname="col3" colwidth="19mm" /><tbody><row><entry>A</entry><entry>^®Polymer It. Ex. 2</entry><entry>0.50 %</entry></row><row><entry /><entry>Mineral oil, low viscosity</entry><entry>5.00 %</entry></row><row><entry /><entry>^®Miglyol 812 (Dynamite Nobel)</entry><entry>4.00 %</entry></row><row><entry /><entry>Capryl / Caprin triglycerides</entry><entry /></row><row><entry /><entry>Isopropyl palmitate</entry><entry>6.00 %</entry></row><row><entry /><entry>Soybean oil</entry><entry>3.00 %</entry></row><row><entry /><entry>Jojoba oil</entry><entry>2.00 %</entry></row><row><entry>B</entry><entry>^®Aristoflex AVC (Clariant)</entry><entry>30 %</entry></row><row><entry /><entry>AMPS / VIFA copolymer</entry><entry /></row><row><entry>C.</entry><entry>^®Hostapon KCG (Clariant)</entry><entry>1.00 %</entry></row><row><entry /><entry>Sodium cocoyl glutamate</entry><entry /></row><row><entry /><entry>water</entry><entry>ad 100%</entry></row><row><entry /><entry>Glycerin</entry><entry>3.00 %</entry></row><row><entry /><entry>Sodium hydroxide (10% in water)</entry><entry>1.20 %</entry></row><row><entry>D</entry><entry>Fragrances</entry><entry>0.30 %</entry></row></tbody></tgroup></table></tables>

Manufacturing

0094<ul id="ul0004" list-style="none" compact="compact"><li>Stir IB into A, add C and stir well.</li><li>II Stir D into I.</li><li>III homogenize emulsion</li></ul>

Example 42: O / W - skin milk

composition

0095<tables id="tabl0023" num="0023"><table frame="none"><tgroup cols="3" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="10mm" /><colspec colnum="2" colname="col2" colwidth="42mm" /><colspec colnum="3" colname="col3" colwidth="19mm" /><tbody><row><entry>A</entry><entry>Polymer It. Ex. 1</entry><entry>0.50 %</entry></row><row><entry /><entry>Isopropyl palmitate</entry><entry>4,00 %</entry></row><row><entry /><entry>Almond oil 5.00%</entry><entry>4.00 %</entry></row><row><entry /><entry>Wheat germ oil</entry><entry>1.00 %</entry></row><row><entry /><entry>^®Cetion SN (Henkel)</entry><entry>8,00 %</entry></row><row><entry /><entry>Cetearyl isononanoate</entry><entry /></row><row><entry /><entry /><entry /></row><row><entry>B</entry><entry>^®Aristoflex AVC (Clariant)</entry><entry>0.30 %</entry></row><row><entry /><entry>AMPS / VIFA copolymer</entry><entry /></row><row><entry>C.</entry><entry>water</entry><entry>ad 100%</entry></row><row><entry>D</entry><entry>Fragrances</entry><entry>0.30 %</entry></row></tbody></tgroup></table></tables>

Manufacturing

0096<ul id="ul0005" list-style="none" compact="compact"><li>Mix IA and B, then add C.</li><li>II D add to I.</li><li>III homogenize emulsion</li></ul>

Example 43: O / W after-sun milk

Composition:

0097<tables id="tabl0024" num="0024"><table frame="none"><tgroup cols="3" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="10mm" /><colspec colnum="2" colname="col2" colwidth="67mm" /><colspec colnum="3" colname="col3" colwidth="16mm" /><tbody><row><entry>A</entry><entry>Polymer It. Ex. 1</entry><entry>1,00%</entry></row><row><entry /><entry>Isopropyl palmitate</entry><entry>5,00 %</entry></row><row><entry /><entry>^®Cetion SN (Henkel)</entry><entry>4,00 %</entry></row><row><entry /><entry>Cetearyl isononanoate</entry><entry /></row><row><entry /><entry>Soybean oil</entry><entry>4,00 %</entry></row><row><entry /><entry>^®Miglyol 812 (Dynamite Nobel)</entry><entry>3,00 %</entry></row><row><entry /><entry>Capryl / Caprin triglycerides</entry><entry /></row><row><entry /><entry>Jojoba oil</entry><entry>3,00 %</entry></row><row><entry /><entry>Wheat germ oil</entry><entry>1,00 %</entry></row><row><entry>D</entry><entry>^®AQUAMOLLIN BC Plv. (Clariant)</entry><entry>0,10 %</entry></row><row><entry /><entry>Ethylenediamine Tetraacetic Acid Sodium Salt</entry><entry /></row><row><entry /><entry>Citric acid (10%)</entry><entry>0,30 %</entry></row><row><entry /><entry>water</entry><entry>68,80 %</entry></row><row><entry /><entry>Glycerin</entry><entry>3,00 %</entry></row><row><entry /><entry>ALLANTOIN (Clariant)</entry><entry>0,20 %</entry></row><row><entry /><entry>Preservative</entry><entry>qs</entry></row><row><entry>E</entry><entry>Ethanol</entry><entry>1 ,50 %</entry></row><row><entry /><entry>Perfume oil</entry><entry>0,30 %</entry></row></tbody></tgroup></table></tables>

Manufacturing

0098<ul id="ul0006" list-style="none" compact="compact"><li>I Mix the components of A homogeneously</li><li>II Stir CD into I at approx. 35 °.</li><li>III Homogenize the emulsion.</li></ul>

Examples of water in oil formulations

Example 44: Reaction according to general polymerization instructions

0099<tables id="tabl0025" num="0025"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="45mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><thead><row><entry valign="top">Reactant</entry><entry valign="top">Quantity (g)</entry></row></thead><tbody><row><entry>Genapol^®T-250 methacrylate</entry><entry>90</entry></row><row><entry>NH₃-neutralized AMPS</entry><entry>10</entry></row><row><entry>TMPTA</entry><entry>1,5</entry></row><row><entry>t-butanol</entry><entry>300</entry></row><row><entry>Dilauroyl peroxide (initiator)</entry><entry>1</entry></row></tbody></tgroup></table></tables>

Example 45: W / O cream

composition

0100<tables id="tabl0026" num="0026"><table frame="none"><tgroup cols="3" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="10mm" /><colspec colnum="2" colname="col2" colwidth="52mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><tbody><row><entry>A</entry><entry>^®HOSTACERIN DGI (Clariant)</entry><entry>4.00 %</entry></row><row><entry /><entry>Polyglyceryl-2 sesquiisostearate</entry><entry /></row><row><entry /><entry>Beeswax</entry><entry>2.00 %</entry></row><row><entry /><entry>Polymer It. Ex. 18</entry><entry>1,5 %</entry></row><row><entry /><entry>Mineral oil, low viscosity</entry><entry>5.00 %</entry></row><row><entry /><entry>vaseline</entry><entry>10.00 %</entry></row><row><entry /><entry>^®Cetiol V (Henkel KGaA)</entry><entry>5.00 %</entry></row><row><entry /><entry>Decyl Oleate</entry><entry /></row><row><entry>B</entry><entry>1,2-propylene glycol</entry><entry>3.00 %</entry></row><row><entry /><entry>water</entry><entry>69,10 %</entry></row><row><entry /><entry>Preservative</entry><entry>qs</entry></row><row><entry>C.</entry><entry>Fragrance</entry><entry>0.40 %</entry></row></tbody></tgroup></table></tables>

Manufacturing

0101<ul id="ul0007" list-style="none" compact="compact"><li>Melt at 80 ° C</li><li>II B heat to 80 ° C.</li><li>III Stir II into I.</li><li>IV Stir until cool.</li><li>V At 35 ° C add C to IV.</li></ul>

Examples of surfactant formulations

Example 46: body wash

composition

0102<tables id="tabl0027" num="0027"><table frame="none"><tgroup cols="3" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="10mm" /><colspec colnum="2" colname="col2" colwidth="50mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><tbody><row><entry>A</entry><entry>^®GENAPOL LRO liquid (Clariant)</entry><entry>40.00 %</entry></row><row><entry /><entry>Sodium Laureth sulfate</entry><entry /></row><row><entry>B</entry><entry>Fragrance</entry><entry>0.30 %</entry></row><row><entry>C.</entry><entry>water</entry><entry>52.70 %</entry></row><row><entry /><entry>Dyestuff</entry><entry>qs</entry></row><row><entry /><entry>Preservative</entry><entry>qs</entry></row><row><entry /><entry>^®GENAGEN LDA (Clariant)</entry><entry>6.00 %</entry></row><row><entry /><entry>Disodium lauroamphodiacetate</entry><entry /></row><row><entry /><entry>Citric acid</entry><entry>qs</entry></row><row><entry>D</entry><entry>Polymer It. Ex. 6</entry><entry>1.00 %</entry></row></tbody></tgroup></table></tables>

Manufacturing

0103<ul id="ul0008" list-style="none" compact="compact"><li>Stir IB into A.</li><li>II Add components from C successively to I.</li><li>III Set pH to 5.5</li><li>IV Adjust the viscosity by stirring D into II</li></ul>

Example 47: Baby Shampoo

composition

0104<tables id="tabl0028" num="0028"><table frame="none"><tgroup cols="3" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="10mm" /><colspec colnum="2" colname="col2" colwidth="51mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><tbody><row><entry>A</entry><entry>water</entry><entry>60.70 %</entry></row><row><entry /><entry>^®GENAPOL ZRO liquid (Clariant)</entry><entry>25.00 %</entry></row><row><entry /><entry>Sodium Laureth Sulfate</entry><entry /></row><row><entry /><entry>^®HOSTAPON CLG (Clariant)</entry><entry>8.00 %</entry></row><row><entry /><entry>Sodium lauroyl glutamate</entry><entry /></row><row><entry /><entry>^®GENAPOL SBE (Clariant)</entry><entry>5.00 %</entry></row><row><entry /><entry>Disodium Laureth Sulfosuccinate</entry><entry /></row><row><entry /><entry>Fragrance</entry><entry>0.30 %</entry></row><row><entry /><entry>Dyestuff solution</entry><entry>qs</entry></row><row><entry /><entry>Preservative</entry><entry>qs</entry></row><row><entry>B</entry><entry>Polymer It. Example 4</entry><entry>1,00 %</entry></row></tbody></tgroup></table></tables>

Manufacturing

0105<ul id="ul0009" list-style="none" compact="compact"><li>Solve IB in A.</li><li>II adjust pH if necessary</li></ul>

Example 48: Anti-dandruff shampoo, clear

composition

0106<tables id="tabl0029" num="0029"><table frame="none"><tgroup cols="3" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="10mm" /><colspec colnum="2" colname="col2" colwidth="55mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><tbody><row><entry>A</entry><entry>^®OCTOPIROX (Clariant)</entry><entry>0.50 %</entry></row><row><entry /><entry>Piroctone olamine</entry><entry /></row><row><entry>B</entry><entry>water</entry><entry>10.00 %</entry></row><row><entry>C.</entry><entry>^®GENAPOL LRO LIQUID (Clariant)</entry><entry>30.00 %</entry></row><row><entry /><entry>Sodium Laureth Sulfate</entry><entry /></row><row><entry>D</entry><entry>^®Belsil DMC 6032 (Wacker Chemie)</entry><entry>1.50 %</entry></row><row><entry /><entry>Dimethicone Copolyol Acetate</entry><entry /></row><row><entry /><entry>Fragrance</entry><entry>0.30 %</entry></row><row><entry>E</entry><entry>^®ALLANTOIN (Clariant)</entry><entry>0.30 %</entry></row><row><entry>F</entry><entry>water</entry><entry>46.40 %</entry></row><row><entry>G</entry><entry>Dyestuff solution</entry><entry>qs</entry></row><row><entry /><entry>Panthenol (Hoffmann La Roche)</entry><entry>1.00 %</entry></row><row><entry /><entry>^®GENAGEN CAB (Clariant)</entry><entry>8.00 %</entry></row><row><entry /><entry>Cocamidopropyl betaines</entry><entry /></row><row><entry>H</entry><entry>Polymer It. Example 7</entry><entry>1.10 %</entry></row></tbody></tgroup></table></tables>

Manufacturing

0107<ul id="ul0010" list-style="none" compact="compact"><li>Mix IA with B.</li><li>II Stir C in I until clear solution</li><li>III Add components from D to I one after the other</li><li>IV Stir in F while heating and then stir in I.</li><li>V Add components from G to I one after the other</li><li>VI adjust pH if necessary</li><li>VII Adjust the viscosity by stirring H into I.</li></ul>

Example 49: Anti-dandruff shampoo, pearlescent

composition

0108<tables id="tabl0030" num="0030"><table frame="none"><tgroup cols="3" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="10mm" /><colspec colnum="2" colname="col2" colwidth="71mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><tbody><row><entry>A</entry><entry>water</entry><entry>38.7 %</entry></row><row><entry>B</entry><entry>^®HOSTAPON SCI-65 (Clariant)</entry><entry>3.00 %</entry></row><row><entry /><entry>Sodium Cocoyl Isethionate</entry><entry /></row><row><entry>C.</entry><entry>^®GENAPOL LRO liquid (Clariant)</entry><entry>35.00 %</entry></row><row><entry /><entry>Sodium Laureth Sulfate</entry><entry /></row><row><entry /><entry>^®HOSTAPON KCG (Clariant)</entry><entry>5.00 %</entry></row><row><entry /><entry>Sodium cocoyl glutamate</entry><entry /></row><row><entry /><entry>^®Belsil DMC 6032 (Wacker)</entry><entry>1.00 %</entry></row><row><entry /><entry>Dimethicone Copolyol Acetate</entry><entry /></row><row><entry /><entry>Fragrance</entry><entry>0.30 %</entry></row><row><entry /><entry>^®GENAGEN CAB (Clariant)</entry><entry>9.00 %</entry></row><row><entry /><entry>^®Cocamidopropyl betaines</entry><entry /></row><row><entry /><entry>GENAPOL TSM (Clariant)</entry><entry>4.00 %</entry></row><row><entry /><entry>PEG-3 Distearate (and) Sodium Laureth Sulfate</entry><entry /></row><row><entry /><entry>Merquat 550</entry><entry>0.50 %</entry></row><row><entry /><entry>Polyquatium-7</entry><entry /></row><row><entry /><entry>Zinc Omadine FPS (Olin)</entry><entry /></row><row><entry /><entry>Zinc Pyrithione (48%)</entry><entry>2.50 %</entry></row><row><entry /><entry>Polymer according to Ex. 9.1</entry><entry>1.00 %</entry></row><row><entry /><entry>Dyestuff solution</entry><entry>qs</entry></row><row><entry /><entry>Preservative</entry><entry>qs</entry></row></tbody></tgroup></table></tables>

Manufacturing

0109<ul id="ul0011" list-style="none" compact="compact"><li>I Loosen at A at 80 ° CB</li><li>II After cooling to approx. 35 ° C, add components C one after the other</li></ul>

Examples of gels

Example 50: Hair gel with conditioning properties

composition

0110<tables id="tabl0031" num="0031"><table frame="none"><tgroup cols="3" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="10mm" /><colspec colnum="2" colname="col2" colwidth="51mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><tbody><row><entry>A</entry><entry>water</entry><entry>92.00 %</entry></row><row><entry /><entry>Panthenol</entry><entry>1.50 %</entry></row><row><entry /><entry>UVAsorb S5</entry><entry>0.05 %</entry></row><row><entry /><entry>Benzophenone-4</entry><entry /></row><row><entry /><entry>Dyestuff solution</entry><entry>qs</entry></row><row><entry /><entry>Preservative</entry><entry>qs</entry></row><row><entry>B</entry><entry>^®Emulsogen HCO 040 (Clariant)</entry><entry>0.50 %</entry></row><row><entry /><entry>PEG-40 Hydrogenated Castor Oil</entry><entry /></row><row><entry /><entry>perfume</entry><entry>qs</entry></row><row><entry>C.</entry><entry>Polymer according to example 3</entry><entry>2.00 %</entry></row><row><entry>D</entry><entry>Gafquat 755N (ISP)</entry><entry>2.50 %</entry></row><row><entry /><entry>Polyquaternium-11</entry><entry /></row></tbody></tgroup></table></tables>

Manufacturing

0111<ul id="ul0012" list-style="none" compact="compact"><li>I Mix components A.</li><li>II Mix components B and add to I.</li><li>III Give C to D to I.</li></ul>

Example 51: Hair gel with strong hold

composition

0112<tables id="tabl0032" num="0032"><table frame="none"><tgroup cols="3" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="10mm" /><colspec colnum="2" colname="col2" colwidth="51mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><tbody><row><entry>A</entry><entry>water</entry><entry>91.50 %</entry></row><row><entry /><entry>PVP K-30 (ISP)</entry><entry>4.00 %</entry></row><row><entry /><entry>PVP</entry><entry /></row><row><entry /><entry>Panthenol</entry><entry>0.50 %</entry></row><row><entry /><entry>UVAsorb S5</entry><entry>0.05 %</entry></row><row><entry /><entry>Benzophenone-4</entry><entry /></row><row><entry /><entry>Dyestuff solution</entry><entry>qs</entry></row><row><entry /><entry>Preservative</entry><entry>qs</entry></row><row><entry>B</entry><entry>Abil B 8851 (Goldschmidt)</entry><entry>1.00 %</entry></row><row><entry /><entry>Dimethicone copolyol</entry><entry /></row><row><entry /><entry>^®Emulsogen HCO 040 (Clariant)</entry><entry>0.50 %</entry></row><row><entry /><entry>PEG-40 Hydrogenated Castor Oil</entry><entry /></row><row><entry /><entry>perfume</entry><entry>qs</entry></row><row><entry>C.</entry><entry>Polymer according to example 3</entry><entry>2.50 %</entry></row></tbody></tgroup></table></tables>

Manufacturing

0113<ul id="ul0013" list-style="none" compact="compact"><li>I Mix components A.</li><li>II Put components B in I.</li><li>III Put components C in I.</li></ul>