NO792000L - STABLE Aqueous SOLUTION OF VINYL COPY POLYMERIZATES CONTAINING CATIONIC GROUPS AND ANION ANTICIDES OR ANIONIC POLYELECTOLYLTS - Google Patents

Description

The present invention relates to aqueous solutions of cationic vinyl copolymers containing anionic surfactants or anionic polyelectrolytes. Usual-

such solutions are unstable because insoluble salts or complexes of the aforementioned cationic and anionic components are formed. Thus, water-soluble polymers of quaternized aminoalkyl esters of acrylic or methacrylic acid precipitate due to anionic surfactants or due to polyacrylic

acid or its alkali salts. Despite this, there is often a need to produce aqueous solutions, with compatible components with the opposite charge because both components are needed at the same time due to the specific functions, or because one component is already present in aqueous solution and only difficult or even cannot be removed at all until the second component is added.

An example of the simultaneous need for incompatible counter-ionic ingredients is hair cosmetics. These should contain both anionic surfactants as hair washing agent and also cationic vinyl polymers as hair fixing agents and hair conditioners.

To prepare aqueous solutions of this type,

becomes, according to NL-AS 7 607 314, a mixture of anionic, non-ionic and amphoteric surfactants combined with a nitrogen-containing amphoteric polyelectrolyte containing aminoalkyl groups and small amounts of carboxyl groups. The use of anionic surfactants instead of that of three different types of composite surfactant mix-

However, ing is generally preferred.

Stable aqueous solutions of anionic polyelectrolytes and vinyl copolymers with units of unsaturated carboxylic acids on one side and units with primary, secondary or

tertiary amino groups on the other hand, according to US-PB

3,950,296 is produced at special pH values. When approaching the isoelectric point, insoluble precipitates occur.

It was the task of the present invention to enable the production of stable aqueous solutions which contain dissolved vinyl copolymers of a cationic character next to each other, and such ionic or ionizable dissolved compounds which have a precipitating effect on an aqueous solution of poly(methacryloxyethyl-trimethylammonium chloride), without to stabilize

the strength and durability depend on the choice of very special components or compliance with a narrow pH range. Poly(methacryloxyethyl-trimethylammonium chloride) with an average molecular weight of 100,000. was selected because of the easy technical availability as a reference substance for determining the inflammability.

The thus incompatible ionic resp. ionizable substances are also incompatible with other cationic polyelectrolytes. Vinyl copolymers with a cationic character are understood to mean those where the stoichiometric proportion of cationic groups, i.e. amino or ammonium groups, clearly dominates over anionic groups,

i.e. carboxyl or carboxylate groups.

A solution to the given task can be found in the aqueous solutions according to the requirements. Decisive for durability is the content of quaternary ammonium groups in vinyl copolymer (2).

There is not in all cases an unlimited compatible

heat between the otherwise incompatible ionic compounds, however,

in any case an improved compatibility is reached compared

with purely cationic polyelectrolytes. Improved compatibility

can e.g. appear at particular temperatures, concentrations or pH values. There are other cases where the

compatibility problems for cationic polyelectrolytes with counterionic compounds occur only under certain unfavorable conditions. In these cases too, the area of incompatibility can be narrowed according to the invention.

The solutions according to the invention contain the components mentioned in the main claim under points (2) and (3) in dissolved form. Alongside these, depending on the need and desired application, they may contain other dissolved or non-dissolved components.

Vinyl copolymer seed ( 2)

The vinyl copolymer that makes up component (2) is built up of vinyl monomers, i.e. monomers with a radically polymerizable or at least mixture polymerizable carbon double bond in the form of a vinyl group, a vinylidene group or a vinylene group. The vinyl copolymers according to the invention can be built up exclusively from the monomer units (A) and (B) and in any case contain more than 10 basic mol% of these units.

The cationic groups do not have to be present entirely in the form of quaternary ammonium groups. They can even be present predominantly in the form of primary, secondary or tertiary amino groups or primary, secondary or tertiary ammonium groups derived from them by salt formation with an acid, so that only the quaternary ammonium group makes up at least 5 basic mol% of the monomer units in the vinyl copolymer mixture (2). Preferably make up

this proportion 5-25 basis mol%. The cationic character of the vinyl copolymer is maintained as long as the anionic units (B)

with carboxyl or carboxylate groups are stoichiometrically inferior to the cationic units (A) and (C).

In preferred cases, the stoichiometric excess of cationic groups in relation to anionic groups amounts to 5-20 basic mol%. The proportion of non-ionic monomer units (D) is preferably below 50 basic mol%.

The units of type (C) are derived from vinyl monomers with a primary, secondary or tertiary amino group, whereby the latter

is preferred because of the good polymerizability. A preferred group is the amirioalkylesters and the aminoalkylamides

of acrylic and methacrylic acid, such as, for example, dimethylaminoethyl acrylate and methacrylate, diethylaminoethyl acrylate and methacrylate, butylaminoethyl acrylate and methacrylate, piperidinoethyl, morpholinoethyl and piperazinoethyl esters of acrylic and methacrylic acid, N-dimethylaminomethylacrylamide and -methacrylamide and N-dimethylaminopropylacrylamide and -methacrylamide. Other useful monomers with amino groups are vinylpyridine, vinylimidazole and vinylimidazolidine. The corresponding ammonium salts are obtained from these monomers by reaction with an organic or an inorganic acid such as hydrochloric acid, sulfuric acid, acetic acid or chloroacetic acid.

The units (A) with quaternary ammonium groups originate from monomers which in turn originate from the above-mentioned tertiary amino group-containing monomers by quaternization, preferably with methyl chloride, benzyl chloride or dimethyl sulfate.

The anionic units (B) originate from maleic acid, fumaric acid, itaconic acid, crotonic acid and preferably from acrylic or methacrylic acid. Equally suitable are the water-soluble salts of these acids, especially alkali and. the ammonium salts..

The monomer units (D) also present in the copolymer are non-ionic or ionizable. These can originate from water-soluble monomers, e.g. from acrylic and methacrylamide, vinyl pyrrolidone, hydroxyalkyl esters of α,γ-unsaturated polymerizable mono- or dicarboxylic acids, especially da. those with 2-4 carbon atoms in the hydroxyalkyl residue, as well as from the hypothetical monomeric vinyl alcohol. The monomer units (D) can also originate from water-insoluble comonomers to such an extent that the water solubility of the polymer is maintained. Such compounds include alkyl esters (especially of C^_^-alcohols) and nitriles of a,B-unsaturated carboxylic acids, vinyl esters of a<y>fatty acids, vinyl halides, vinyl aromatics, a-olefins and/or dienes.

Such vinyl copolymers are particularly suitable for hair cosmetic preparations where the stoichiometric ratio between the cationic groups (A) and (C) and the anionic groups (B) is close to 1:1, especially in the range between 1:1 and 1.5:1. Typical compositions contain roughly equal proportions of the units (B) and (C) and a relatively small proportion of the units (A).

For the production of the water-soluble polymers, there are a large number of methods according to which the vinyl copolymers (2) used according to the invention can also be produced. Next to the polymerization of relatively diluted aqueous monomer solutions under the influence of water-soluble radical generators, above all such methods have gained importance in which highly concentrated aqueous monomer solutions are polymerized by means of water-soluble radical generators or ultraviolet light. This results in hard polymers which can be treated as solids and which, before use, are dissolved in water in the desired concentrations. The polymerization is carried out according to BE-PS 695 342 in foil bags, according to DE-PS 1 770 588 in open containers, according to DE-OS 2 545 290 on an endless belt, according to DE-OS 2 009 218 as bead polymerization in a non-aqueous phase, and according to DE-OS 2 322 883 as suspension polymerization in oil to form a resistant and water-soluble organosol. The molecular weight of the vinyl copolymer seed (2) can lie between 10.00 and one million. Preferably, they are produced in the presence of regulators and have molecular weights between 1,000 and 50,000.

The ionic or ionizable compound ( 3)

The compounds according to this group form, with purely cationic polyelectrolytes such as poly(methacryloxyethyl-trimethylammonium chloride), water-insoluble salts or complexes which precipitate out of aqueous solutions. The precipitating effect can appear in the form of a flaking, a flocculation or the formation of larger and insoluble aggregates, e.g. as a bottom-deposited pro-. skill. Sometimes this precipitation only occurs at certain temperatures, concentrations or pH values. The precipitating effect is based on the anionic component in the compound (3). The compound (3) is either one of anions or cations built up and in aqueous solution a partially or completely dissociating compound, or it turns into a dissociated compound in aqueous solution such as e.g. polycarboxylic acids which on dissociation form protons and polycarboxylate anions. The anions present in the aqueous solution then have a precipitating effect on purely cationic polyelectrolytes when

either contain more charges or are bound to a large hydrophobic residue, i.e. constitute anionic surfactants. As anionic surfactants, the solution can contain common soaps as well as all common surfactants of the sulfate and sulfonate type. Examples of such are the alkali salts of aromatic sulphonic acids, sulphated oils, sulphates of fatty alcohols and sulphated oxyalkylation products of phenols, alkylated phenols, fatty alcohols and fatty acid amides.

Water-soluble high molecular weight compounds with carboxyl or carboxylate groups which are compatible with purely cationic polymers, but not with the cationic type vinyl polymers (2) according to the invention, are in particular polyacrylic acid, partially seeded polyacrylonitrile or polyacrylamide, polymethacrylic acid, mixed polymers of maleic acid with ethylene or styrene and carboxymethylcellulose, above all such compounds with molecular weights above 1000. The same applies to the water-soluble salts, especially the alkali salts and ammonium salts of these compounds.

For example, polyacrylic acid and poly(dimethylaminoethyl methacrylate) are incompatible in aqueous solution. In contrast to this, concentrated aqueous solutions (30<y>ect-% solids) of polyacrylic acid and et. mixed polymer with a cationic character consisting of

37 mol% dimethylaminoethyl methacrylate

6 mol% methacryloxyethyl trimethylammonium chloride

27 mol-% methacrylic acid and

20 mol% hydroxypropyl acrylate.

These solutions are completely compatible and clear at a stoichiometric ratio between the cationic groups in the mixed polymer and the carboxyl groups in the polyacrylic acid within the range of 2:1 to over 7:1. Dilute solutions (1% by weight solids) are at least compatible and clear for the aforementioned ionic ratio at values above 4:1.

The concentration for the inventive solutions of oppositely charged compounds (2) and (3) can go. right up to the saturation limit. Above a solids content of 80% by weight, there is generally no longer a liquid system. In the area of high concentrations for the vinyl copolymer seed (2), the solutions are highly viscous. Of particular technical interest is the concentration range of 0.5-15% by weight for each of compounds (2) and (3), because compatibility problems here play the greatest role. If the total concentration falls below 1% by weight, the compatibility phenomena slowly disappear so that there is no need for the application of the invention in this area.

Enhanced compatibility problems tend to occur when a cationic polyelectrolyte is confronted with anionic compounds (3) in excess of stoichiometric amounts. The invention therefore has increased significance for aqueous solutions where the ionic or ionizable compounds (3), calculated in ionic charge equivalents, exist stoichiometrically in greater quantity than amino-

and the ammonium groups in the vinyl copolymer (2).

Example 1

Storage-resistant hair shampoos are composed of:-.

a) 10 parts by weight (ci2~C14)-n-alkylpolyethylene glycol ether sulfate sodium salt b) 5 parts by weight vinyl copolymer A to F with a cationic character.

For comparison, instead of the vinyl copolymer seed, the same amount of the cationic poly(methacry1-oxyethyl-trimethylammonium chloride) (M = 100,000) was used.

The polymers A to F

Composition in molande:

Example 2

An aqueous solution of the following components was prepared:

5 parts by weight of a mixed polymer of

45% by weight of methacryloxyethyl-trimethylammonium chloride

5% by weight methacrylic acid

5% by weight of dimethylaminoethyl methacrylate

45% by weight 2-hydroxypropyl acrylate

10 parts by weight of (ci2~C14)-n-alkyl polyethylene glycol ether sulfate sodium salt

85 parts by weight, water.

The solution is clear and permanent.

Example 3

An aqueous solution of the following components was prepared: 5 parts by weight of a mixed polymer of 10% by weight methacryloxyethyltrimethylammonium chloride

10% by weight methacrylic acid

10% by weight dimethylaminoethyl methacrylate

70% by weight 2-hydroxypropyl acrylate

10 parts by weight of (C12-C14)-n-alkyl polyethylene glycol ether sulfate sodium salt

85 parts by weight of water.

The solution is clear and permanent.

Claims (5)

1. Aqueous solution, of 1) 20 to 99% by weight water 2) 0.5 to 79% by weight of a water-soluble cationic vinyl copolymer made up of A) units of monomers with a quaternary ammonium salt group, B) units of a cc,$-unsaturated carboxylic acid or water-soluble salts thereof, C) optionally units of monomers with an amino or primary, secondary or tertiary ammonium group D) optionally units of at least one further non-ionic comonomer that can be mixed with the monomers (A), (B) and (C), wherein (A) constitutes at least 5 mol%, (A) and (C) together more than 20 mol%, (B) at least -5 mol%, but less than the sum of (A) and (C) and (D) less than 75 mol% of the units in the vinyl copolymer seed. 3) 0.5 to 79% by weight of at least one water-soluble ionic or ionizable compound with a precipitating effect on an aqueous solution of poly(methacryloxyethyl-trimethylammonium chloride). 2. Aqueous solution according to claim 1, characterized in that the ionic or ionizable compound (3), calculated in ionic charge equivalents, stoichiometrically present in a greater amount than the amino and ammonium groups in the vinyl copolymer seed (2). 3. Aqueous solution according to claims 1 and 2, characterized in that the ionic or ionizable compound (3) is an anionic surfactant, a polycarboxylic acid or an anionic polyelectrolyte. 4. Aqueous solution according to claim 3, characterized in that the ionic compound - (3) is an anionic surfactant. 5. Hair washing and conditioning agent, containing an aqueous solution according to claims 1-4.