DE4401708A1 - Polymer concentrate and use - Google Patents

Abstract

Aqueous concentrates of cationic, zwitterionic or amphoteric polymers containing at least 25 wt % of polymers and with a viscosity of under 3000 mPas measured by the Brookfield method at 20 DEG C which are suitable for hair and skin treatment, can be included in ordinary hair treatment agents with excellent results.

Description

The invention relates to aqueous polymer concentrates with an improved hand availability and their use.

Water-soluble polymeric compounds are indispensable today part of an ever increasing number of products. So questions arise to provide these connections and their incorporation into the Pro products increasingly important.

These polymers are usually on the market today in powder form or offered in the form of aqueous solutions. However, both forms of offer are not to be regarded as optimal.

As a rule, powders can not be so precise and with simple co dosing like liquid dosage forms. This is especially after partial if the exact adherence to the quantities is of decisive importance is for the properties of the end product. The opening continues dissolving powders generally takes significantly longer than mixing two of liquid phases, especially when problems such as lumps occur during the solution process formation, formation of gels etc. occur.

In contrast, the liquid supply forms only contain the polymers in highly diluted form (20 wt .-% and less), which means the transport quantities increased unnecessarily. More concentrated solutions, for example that for the Polymers known in cosmetics, on the other hand, are generally high viscous so that they are difficult or impossible to pump; even if they  are barely pumpable, they often cause considerable problems during incorporation into the end products.

There is therefore a strong need for water-soluble polymers with properties necessary for the application concerned, which are described in Formable form of highly concentrated low-viscosity aqueous solutions and are easy to incorporate into the end products.

An important area of application for water-soluble polymers is hay cosmetic products for the treatment of skin and hair. In particular Polymers are used in hair treatment products to create an Aviva effect and to give the hair hold and fullness.

The invention therefore relates to aqueous concentrates for hair and Skin treatment suitable cationic, zwitterionic or amphoteric Polymers, characterized in that the polymer content is at least 25% by weight and the viscosity of the concentrate, measured according to Brookfield at 20 ° C, is less than 3000 mPa · s.

All viscosity data given in the text refer to 20 ° C, measured Brookfield using a spindle 3 at 20 rpm.

The polymer concentrates according to the invention can be cationic, zwit Contain terionic, amphoteric and nonionic polymers. It is preferred that the polymer concentrates ent only polymers of one of these types hold. However, it is also possible for representatives of several of these polymers types are included.

Cationic polymers are those high molecular weight compounds that have a larger number of cationic groups, especially quaternary ammonium groups pen, included. Cationic polymers can also be made from only one (cationic) monomer type, as well as copolymers from mind at least one "cationic" monomer type and at least one "non-ionic a "type of monomer. In the latter case, at least 5%, in particular at least 10% of which are of the cationic type.  

For the purposes of the invention, amphoteric polymers are understood to mean polymers those that have both free amino groups and free ones in the molecule Contain -COOH-, -SO₃H- or phosphate groups and for the formation of internal Salts are capable.

Zwitterionic polymers are understood to mean those polymers the both cationic and anionic groups or easily into them convertible groups included.

Cationic groups are, for example, groups that have at least one ammo contain nium or phosphonium unit; Examples of an easy in a cationic group are primary, secondary and convertible units especially tertiary amino groups. Ammonium groups are preferred cat ionic groups.

Examples of anionic groups are carbon, sulfone and phos phosphoric acid groups in free form or in salt form. The carbon acid groups and their alkali, alkaline earth, aluminum and ammonium salts are preferred anionic groups.

Konzen has particularly advantageous properties in the sense of the invention occurred with zwitterionic polymers.

Such zwitterionic polymers can be constructed from monomers that contain both cationic and anionic groups. The polymers in this case can consist of a single type of monomer. But it is also possible, copolymers of the monomers mentioned and others not to use ionic monomers. Such nonionic monomers can for example vinyl-based esters and amides, such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxypropyl methacrylate and Be acrylamide. These copolymers preferably contain at least 20%, in particular at least 50%, of ionic monomers.

Zwitterionic polymers preferred in the context of the invention are made of at least 2 ionic monomers, one cationic and one anionic Monomer, built up. Cationic and anionic monomers can  in a molar ratio of 1: 1. However, it is preferred to use a monomer type, especially the cationic monomers, to be used in excess. Cationic and anionic monomers in a ratio of 95: 5 are preferred up to 50:50, in particular from 80:20 to 55:45. Can continue the polymers nonionic monomers of the above type in amounts up to 50 mol%, in particular up to 20 mol%, contain.

Preferred according to the invention are those described in DE-A-39 29 973 zwitterionic polymers, which essentially consist of

• (α) Monomers with quaternary ammonium groups of the general formula (I), R¹-CH = CR²-CO-Z- (C _n H2 _n ) -N (⁺) R³R⁴R⁵ A (⁻) (I) in the R¹ and R² independently stand for hydrogen or a methyl group and R³, R⁴ and R⁵ independently of one another for alkyl groups with 1 to 4 carbon atoms, Z an NH group or an oxygen atom, n an integer from 2 to 5 and A (⁻) the anion is an organic or inorganic acid,
  and
• (β) monomeric carboxylic acids of the general formula (II), R⁶-CH = CR⁷-COOH (II) in which R⁶ and R⁷ independently of one another are hydrogen or methyl group are pen, or alkali, alkaline earth, aluminum or ammonium salts of these acids.

Suitable starting monomers for the monomers (α) are e.g. B. Dimethylamino ethyl acrylamide, dimethylaminoethyl methacrylamide, dimethylaminopropylacryl amide, dimethylaminopropyl methacrylamide and diethylaniinoethylacrylamide, when Z represents an NH group or dimethylaminoethyl acrylate, dimethyl aminoethyl methacrylate and diethylaminoethyl acrylate when Z is oxygen atom is.  

Regarding the production of the monomers mentioned and the quaternization the tertiary amino groups are those listed in DE-A-39 29 973 References literature.

Advantageously, those monomers of formula (I) are used which Represent derivatives of acrylamide or methacrylamide. Still before are added such monomers as counterions or halide, methoxysulfate or Contain ethoxysulfate ions. Such mono are also preferred mers of formula (I) in which R³, R⁴ and R⁵ are methyl groups.

The methacrylamidopropyl trimethylammonium chloride is a very special one preferred monomer of formula (I).

Monomeric carboxylic acids (β) are acrylic acid, methacrylic acid, crotonic acid and 2-methyl-crotonic acid. Acrylic or methacrylic acid, in particular, are preferred special acrylic acid used. Preferred salts used for this car bonic acids are lithium, sodium, potassium, magnesium, calcium and Aluminum salt. The sodium salt is particularly preferred. Can continue the ammonium salts are used in which the ammonium ion is one to three alkyl groups with 1-4 carbon atoms or hydroxyalkyl groups with Can have 2-4 carbon atoms as substituents. Salts with unsubstituted ized ammonium ions and triethanolammonium ions are preferred.

Regarding the production of these zwitterionic polymers is express Lich referred to the disclosure of DE-A-39 29 973.

Among the concentrates according to the invention are those with a polymer hold of 35% and more particularly preferred.

Furthermore, concentrates are preferred which have a viscosity lower than 1000 mPa · s, measured according to Brookfield at 20 ° C.

The aqueous concentrates according to the invention usually only contain Water and the dissolved polymer. In individual cases, however, it can be advantageous be to add other components to the concentrate.  

Surfactants are particularly suitable as further components. Because of her Compatibility with end products of any ionogenicity are particularly important special nonionic surfactants preferred. Examples of such non-iono Gene surfactants are ethoxylated fatty alcohols, polyethylene glycols, partial glycerides, sorbitan esters, castor oil-ethylene oxide adducts and in particular Fatty alcohol polyglycosides.

Subject of the application is also the use of the fiction moderate concentrates for the production of cosmetic products.

Such cosmetic preparations are, for example, hair treatment agents, Skin treatment agents, shower preparations, bath preparations and sunscreen with tel.

The concentrates according to the invention have proven to be particularly advantageous for proven the manufacture of hair treatment agents. Such hair hand agents are, for example, shampoos, conditioners, conditioners, Hair treatments, hair fixers, hair dryer lotions, hair lotions, colorants and duration corrugating agent. The corresponding hair treatment agents contain in addition to Polymers and water are all common cosmetic stocks for these products parts. Depending on the type of agent, these can be, for example:

• - Anionic surfactants, such as fatty alkyl sulfates and ether sulf fate,
• cationic surfactants, such as quaternary ammonium compounds,
• zwitterionic surfactants, such as betaines,
• - ampholytic surfactants,
• - Non-ionic surfactants, such as alkyl polyglycosides, poly ethylene glycols, partial glycerides, sorbitan esters, castor oil ethylene oxide adducts and ethoxylated fatty alcohols,
• Structurants such as glucose, gluconic acid and maleic acid,
• - Hair conditioning compounds such as phospholipids, for example Soy lecithin, egg lecithin and cephaline, sterols and sterol derivatives such as for example that sold under the name Generol® 122 Soyasterol and silicone oils,  
• animal and vegetable protein hydrolyzates, especially elastin, Collagen, keratin, milk protein, soy protein, almond protein and Wheat protein hydrolyzates, their condensation products with fatty acids, e.g. B. soy protein fatty acid condensate, collagen hydrolyzate fatty acid kon densat, protein hydrolyzate-abietic acid condensate, its salts, e.g. B. Ka lium or TEA salts, as well as quaternized protein hydrolyzates,
• - perfume oils, dimethyl isosorbide and cyclodextrins,
• - Solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol,
• - dyes,
• - Anti-dandruff agents such as Piroctone Olamine, Zink Omadine and Undecy lens acid-fatty acid condensate,
• - other substances for adjusting the pH value,
• - Active ingredients such as panthenol, allantoin, pyrrolidone carboxylic acids and their Salts, plant extracts and vitamins,
• - light stabilizers,
• - consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,
• - Fats and waxes such as walrus, beeswax, montan wax, paraffins and Fatty alcohols,
• - fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA and phosphonic acids,
• - Swelling and penetration substances such as glycerin, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and pri mary, secondary and tertiary phosphates,
• Opacifiers such as latex,
• - pearlescent agents such as ethylene glycol mono- and distearate,
• - Blowing agents such as propane-butane mixtures, N₂O, dimethyl ether, CO₂ and Air as well
• - antioxidants
• - direct dyes
• - So-called coupler and developer components as an oxidation dye intermediate products,
• - Reducing agents such. B. thioglycolic acid and its derivatives, thio lactic acid, cysteamine, thio malic acid and α-mercaptoethanesulfonic acid, and  
• - Oxidizing agents such as hydrogen peroxide, potassium bromate and sodium bro mat.

The concentrates according to the invention are used to produce these products preferably used in such amounts that the polymer concentration in the end product between 0.05 and 10% by weight, in particular between 0.1 and 2 % By weight, based on the total end product.

The following examples are intended to explain the invention in more detail.  

Examples 1. Preparation of a polymer from methacrylamidopropyltrimethyl ammonium chloride and acrylic acid in a molar ratio of 65:35

In a reactor with stirring system, heating, cooling, reflux condenser, 2 zu Barrels, nitrogen connection and temperature measuring device were 253.5 g of water submitted.

In the first feed vessel, the monomer feed consisting of 562 g of a 50% aqueous methacrylamidopropyltrimethylammonium chloride solution (Röhm; 1.36 mol), 53 g acrylic acid (BASF; 0.74 mol) and 86 g 33% aq caustic soda, in the order listed for the components provides, the sodium hydroxide solution was added in portions with stirring.

The starter solution was dissolved by dissolving 3 g of azobiscyanpentanoic acid (V 501; VAK0) in a mixture of 40 g water and 2.6 g 33% sodium hydroxide solution (with stirring, approx. 30 min).

After the water in the reaction vessel was heated to 80 ° C, 7% of the monomer feed and then 50% of the starter solution. After 15 minutes, the rest were then carried out in parallel in the course of 90 minutes Liche monomer feed and the remaining starter solution added dropwise, wherein the reaction temperature by slight cooling to about 80 ° C constant ge was holding. After the feed had ended, the mixture was stirred for a further 60 minutes Stirred at 80 ° C; then the reaction solution was at 60 ° C and then cooled to 40 ° C under nitrogen.

The reaction solution can then, also under nitrogen, in suitable Containers are filled for distribution or further storage.

The product was in the form of a clear, slightly yellow colored solution that had a pH of 7.0 ± 0.5. The dry residue contributed 37.2 ± 0.3 wt%. The viscosity of this solution was 1.0 ± 0.5 Pas · s  (measured according to Brookfield at 20 ° C with a rotary viscometer Syn chro Lectric; Spindle 3, 20 rpm).

2. Examples of use

The amounts in the following examples are% by weight.

2.1 volume hair shampoo

2.2 hair shampoo

2.3 Hair conditioner

2.4 Conditioning shampoo

2.5 Conditioning shampoo

2.6 Conditioning shampoo

2.7 Conditioning shampoo

2.8 Conditioning shampoo

2.9. hair conditioner

2.10 hair conditioner

2.11. hair conditioner

2.12. hair conditioner

Claims (10)

1. Aqueous concentrate of suitable for hair and skin treatment cat ionic, zwitterionic or amphoteric polymers, characterized in that the polymer content is at least 25 wt .-% and the viscosity of the concentrate, measured according to Brookfield at 20 ° C, smaller than 3000 mPa · s. 2. Aqueous concentrate according to claim 1, characterized in that the Polymers is a zwitterionic polymer. 3. Aqueous concentrate according to claim 2, characterized in that it contains a zwitterionic polymer which is composed essentially of

• A) Monomers with quaternary ammonium groups of the general formula (I), R¹-CH = CR²-CO-Z- (C _n H _2n ) -N (⁺) R³R⁴R⁵ A (⁻) (I) in which R¹ and R² are independent of each other for hydrogen or a methyl group and R³, R⁴ and R⁵ independently of one another for alkyl groups with 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer from 2 to 5 and A (⁻) is the anion of one is organic or inorganic acid and
• B) monomeric carboxylic acids of the general formula (II), R⁶-CH = CR⁷-COOH (II) in which R⁶ and R⁷ are independently hydrogen or methyl groups, or the alkali metal, alkaline earth metal, aluminum or ammonium salts of these acids.

4. Aqueous concentrate according to claim 3, characterized in that the zwitterionic polymers from monomers of type (A) and monomers of type (B) in a molar ratio of 50:50 to 95: 5, in particular from 55: 45 to 80: 20. 5. Aqueous concentrate according to one of claims 3 or 4, characterized records that the monomer of type (A) methacrylamidopropyl-trime thyl-ammonium chloride and the monomer of type (B) acrylic acid or Is salt of acrylic acid. 6. Aqueous concentrate according to one of claims 1 to 5, characterized records that the content of polymers is at least 35 wt .-%. 7. Aqueous concentrate according to one of claims 1 to 6, characterized records that the viscosity of the concentrate, measured according to Brook field at 20 ° C, is less than 1000 mPa · s. 8. Use of an aqueous concentrate according to one of claims 1 to 7 for the production of cosmetic products. 9. Use according to claim 8, characterized in that the cosmetics product is a hair treatment product. 10. Use according to claim 8 or 9, characterized in that the aqueous polymer concentrate is used in such an amount that the polymer concentration in the end product 0.05 to 10 wt .-%, in particular whose 0.1 to 2 wt .-%, based on the entire product, contributes.