WO1998003567A1

WO1998003567A1 - Process for preparing water-dispersible polymer blends

Info

Publication number: WO1998003567A1
Application number: PCT/EP1997/003754
Authority: WO
Inventors: Wolfgang Müller; Gerald Wildburg; Stefan Stein; Axel Sanner
Original assignee: Basf Aktiengesellschaft
Priority date: 1996-07-23
Filing date: 1997-07-14
Publication date: 1998-01-29
Also published as: EP0914359A1; CN1226261A; JP2000514814A; KR20000067991A; CA2260822A1; AU3543697A; BR9710524A; DE19629452A1

Abstract

The invention concerns a process for preparing water-dispersible polymer blends comprising a polyamide and a second polymer by polymerizing an aqueous dispersion or solution consisting of a polyamide, one or a plurality of ethylenically unsaturated monomers, a polymerization initiator and optionally an emulsifier.

Description

Process for the production of water-dispersible polymer blends

description

The present invention relates to water-dispersible polymer blends made of polyamide and polymers with ethylenically unsaturated monomers, their production and use.

US Pat. No. 4,946,932 describes the preparation of water-dispersed polymer blends from polyesters or polyester amides and polymers from ethylenically unsaturated monomers which are produced via free-radical polymerization. These blends are used in paints, adhesives or other coatings. A disadvantage of these blends is that they do not form clear polymer films. Another disadvantage is that the polyester or polyesteramide component is subject to hydrolysis and is therefore restricted in its manufacture and use.

US Pat. No. 5,277,978 describes the use of sulfate- and sulfonate-containing polyester as a protective colloid for stable polymer dispersions. It is recommended there to use only amounts of 0.5-10% of the protective colloid, based on the ethylenically unsaturated monomer. A warning is given against the use of an excessive amount of protective colloid, since this could have a negative influence on the properties of the dispersion.

Clear, transparent films are obtained. As is known from US 4,946,932, cloudy films are obtained when larger amounts of polyester are used.

EP 0687 459 describes cosmetic compositions containing aqueous dispersions of polyesters with ethylenically unsaturated monomers. The aqueous dispersions thus obtained can be used to obtain homogeneous and transparent films, but only if plasticizers are additionally added. In addition, these dispersions have the disadvantage that they are hydrolysis unstable due to the polyester.

The object was therefore to produce water-dispersible polymer blends which are suitable for use in coatings, cosmetic and pharmaceutical compositions, adhesives, for textile and leather finishing and as paper coatings and have the following properties: 1) Formation of transparent, clear films without the addition of plasticizers

2) Filming at RT without adding plasticizer

3) Use of hydrolysis-stable polymers

This object has been achieved by a process for the preparation of water-dispersible polymer blends from a polyamide and a second polymer by poly erizing an aqueous dispersion or solution from a polyamide, one or more ethylenically unsaturated monomers, a polymerization initiator and, if appropriate, an emulsifier.

Practically all common water-dispersible and water-soluble polyamides are suitable as polyamides for the production of the water-dispersible polymer blends. Those which are produced from:

al) 0 to 99 mol% of a monoaminocarboxylic acid with 2 to 12 carbon atoms or its lactam a2) 0.5 to 50 mol% of at least one diamine with 2 to

18 carbon atoms, a3) 0 to 49 mol% of a sulfonate group-bearing dicarboxylic acid with 4 to 12 carbon atoms, and a4) 0.5 to 49 mol% of a dicarboxylic acid with 2 to 16 carbon atoms.

Suitable monomers a1) are the monoaminocarboxylic acids or their lactams known for the production of polyamides, such as, for example, ω-aminoundecanoic acid, ε-caprolactam, laurinlacta, capryllactam or enantholactam.

Suitable monomers a2) are in particular optionally substituted aliphatic, cycloaliphatic or aromatic diamines. Suitable diamines are, for example, alkylenediamines or cycloalkyldiamines, such as 1,2-diaminocyclohexane, 1,5-pentanediamine, 4,4'-diaminodicyclohexylmethane, 2,2 '- (4,4'-diaminodicyclohexyl) propane, 3, 3 '-Dimethyl-4, 4' -diaminodicyclohexylmethane or, preferably, hexamethylenediamine. Piperazine, 2, 2,4-trimethylhexamethylene diamine are also suitable.

2-butyl-2-ethyl-l, 5-pentanediamine or 4,7-dioxadecane-l, 10-diamine, 2-methylpentamethylene diamine and isophorone diamine.

Suitable monomers a3) carrying sulfonate groups are those

Consideration in which the sulfonate group is present as a salt, e.g. B. as a salt of an alkali metal, such as lithium, sodium or potassium, or an ammonium group which may be substituted with one to four aliphatic or aromatic groups. Suitable monomers bearing sulfonate groups are salts of aliphatic or aromatic dicarboxylic acids, such as, for example, sulfosuccinic acid or 5-sulfopropoxyisophthalic acid. The sodium salt of 5-sulfo-isophthalic acid is preferably used.

Suitable monomers a4) are, for example, aliphatic dicarboxylic acids, such as sebacic acid, azelaic acid, dodecanedicarboxylic acid or preferably adipic acid or sebacic acid. Suitable aromatic dicarboxylic acids are, for example, isophthalic acid or terephthalic acid, which can also be substituted, such as, for example, 3-tert-butyl-isophthalic acid, and further 3,3'- or 4,4'-diphenyldicarboxylic acid, 3,3'- or 4,4 ' -Diphenylmethane-dicarboxylic acid, 3,3'- or 4,4'-diphenylsulfone-dicarboxylic acid, 1,4- or 2,6-naphthalenedicarboxylic acid or 2-phenoxyterephthalic acid.

From the monomer groups al) to a4), both individual monomers and mixtures of monomers within a group can be used.

Particularly suitable ethylenically unsaturated monomers for the second polymer of the water-dispersible polymer blend are monoethylenically unsaturated monomers such as olefins with up to 4 carbon atoms, e.g. Ethylene, vinylaromatic monomers with up to 10 carbon atoms such as styrene, α-methylstyrene, ortho-chlorostyrene or vinyltoluenes, vinyl and vinylidene halides such as vinyl and vinylidene chloride, esters from vinyl alcohol and monocarboxylic acids having 1 to 18 carbon atoms such as Vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, esters of preferably 3 to

Α, β-monoethylenically unsaturated mono- and dicarboxylic acids containing 6 carbon atoms, such as in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid with alkanols generally having 1 to 12, preferably 1 to 8 and in particular 1 to 4 carbon atoms, such as especially acrylic acid and methacrylic acid, methyl, ethyl, n-butyl, isobutyl and -2-ethylhexyl esters, dimethyl maleate or n-butyl maleate, nitriles of the α, β-monoethylenically unsaturated carboxylic acids mentioned, such as Acrylonitrile or methacrylonitrile and C ₄ to Cg-conjugated dienes, such as 1,3-butadiene and isoprene, into consideration. Monomers which differ from the monomers mentioned and which, when polymerized, usually give rise to water-soluble homopolymers, are normally only used as modifying monomers in amounts, based on the total amount of the monomers used, of less than 50% by weight, generally 0 to 15, preferably 1 to 10% by weight, with copolymerized. Examples of such monomers are α, β-mono- which have 3 to 6 C atoms. ethylenically unsaturated mono- and dicarboxylic acids and their amides, such as, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, acrylamide and methacrylamide, furthermore vinyl sulfonic acids and their water-soluble salts, vinylphosphonic acid, their salts and esters with alcohols with up to 4 C. -Atoms and N-vinylpyrrolidone and 2-hydroxyethyl acrylate, 3-hydroxypropyl-1 - acrylate or dimethylaminoethyl acrylate.

In addition, either alone or in combination with one or more vinyl, acrylic or methacrylic monomers, silicone-containing monomers and macromonomers and fluorine-containing monomers such as, for example, perfluorooctyl methacrylate or 1, 1, 1, 3, 3, 3-hexafluoroisopropyl methacrylate can be used.

Crosslinking monomers are used in amounts of 0 to 15, preferably 0.5 to 10% by weight, in particular 1 to 6% by weight, based on the total amount of the monomers used, which are only used during the drying of the polymer enter into the crosslinking reaction, the crosslinking reaction being effected by annealing and, if appropriate, by adding catalysts, such as, for example proton-releasing substances such as maleic acid, diammonium hydrogen phosphate or ammonium nitrate can be forced. Examples of such monomers are N-alkylolamides of 3 to 10 carbon atoms, α, β-monoethylenically unsaturated carboxylic acids, among which N-methylolacrylamide and N-methylolmethacrylamide are preferred. More than crosslinking monomers are kolsäure the Acrylamidogly- and methacrylamidoglycolic acid and their ethers, esters or ether-esters with alcohols such as alkanols having up to 12 carbon atoms, for example Acrylamidomethoxyessigsäure, Acrylamidohydro- xyessigsäuremethylester, Acrylamidomethoxyessigsäuremethylester, Methacrylamidomethoxyessigsäure, Methacryla idohydroxyessigsäure- methylester, Methacrylamidomethoxyessigsäuremethylester that corresponding butyl and butoxy derivatives, butyl acrylamidobutoxyacetate and butyl methacrylamidobutoxyacetate. The ammonium salts of the (meth) acrylamido acids mentioned are also suitable.

The free radical aqueous graft polymerization can optionally be carried out in the presence of regulators. Suitable regulators are, for example, mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercapto-propionic acid, butyl mercaptan and dodecyl mercaptan. Allyl compounds such as allyl alcohol are also suitable as regulators.

Customary additives can be added to the polymer dispersions. They are usually added after the end of the polymerization. Crosslinking non-polymerisable ones are mentioned Substances that can usually be present in amounts of 0.1 to 5% by weight. Contains the polymer free carboxyl groups, suitable compounds are ^"which such groups can cross-link such as basic compounds, carbonates of polyvalent metals such as zinc oxide, calcium oxide or the respective hydroxides, acetates or carboxylic or the corresponding mixed salts. Furthermore, compounds which gegebenenf existing lls Cross-linking hydroxyl groups, such as di- and polyfunctional inorganic acids and acid derivatives, for example phosphorus oxychloride, alkali metal trimethosphates, alkali polyphosphates or alkali metal traborate, di- and polyfunctional organic acids, for example adipic acid, citric acid, 1, 2, 3, 4-butanetetracarboxylic acid, all cis - 1, 2, 3, 4 -cyclopentantetracarboxylic acid, derivatives of di- and polyfunctional organic acids, such as anhydrides or mixed anhydrides, for example diacetyladipic acid, acetylcitric acid anhydride, acid chlorides, for example cyanuric acid chloride, imidazolides and guanidine derivatives, and also di- and polyfunctional isocyanates Hexamethylene diisocyanate, 2, 4-diisocyanate toluene, di- and polyfunctional alkylating agents, for example epichlorohydrin, ß, ß '-dichloroethyl ether, diepoxides, various aldehydes or aldehyde derivatives such as formaldehyde, acetaldehyde, acrolein, 2, 5-dimethoxytetrahialdehyde or . Condensation products based on formaldehyde, glyoxal, melamine, phenol and / or urea are also suitable. Here formaldehyde and the formaldehyde-containing crosslinking systems are less suitable due to toxicological concerns.

Suitable polymerization initiators for the production of the water-dispersible polymer blends according to the invention are all those which are capable of triggering a radical aqueous emulsion polymerization. It can be both peroxides, for example alkali metal peroxydisulfates, ammonium peroxydisulfate or H ₂ O, and azo compounds.

Combined systems which are composed of at least one organic reducing agent and at least one peroxide and / or hydroperoxide, for example tert. -Butylhydroperoxid and the sodium metal salt of hydroxymethanesulfinic acid or hydrogen peroxide and ascorbic acid. Combined systems which also contain a small amount of a metal compound which is soluble in the polymerization medium and whose metallic component can occur in several valence stages are also suitable, for example ascorbic acid / iron (II) sulfate / hydrogen peroxide, the sodium metal salt often being used instead of ascorbic acid hydroxymethanesulfinic acid, sodium sulfite, sodium hydrogen sulfite or sodium metalibisulfite and, instead of hydrogen peroxide, tert-butyl hydroperoxide or alkali metal peroxidisulfates and / or ammonium peroxidisulfates are used. In As a rule, the amount of free-radical initiator systems used is 0.1 to 2% by weight, based on the total amount of the monomers to be polymerized. _A mmonium- and / or alkali metal peroxodisulfates are particularly preferably used alone or as part of combined systems as initiators.

Other suitable initiators are oil-soluble initiators such as organic peroxides, for example tertiary-butylperoxy-2-ethylhexanoate, percarbonates or diazo compounds.

The process according to the invention can be carried out with or without an emulsifier. In principle, the protective colloids and emulsifiers of an anionic, cationic or nonionic type normally used as dispersants come into consideration as accompanying surface-active substances. A detailed description of suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 411 to 420. Surfactants are preferred exclusively as accompanying substances Emulsifiers are used, the molecular weights of which, in contrast to the protective colloids, are usually below 2000. Of course, if mixtures of surface-active substances are used, the individual components must be compatible with one another, which can be checked with a few preliminary tests if in doubt. Anionic and nonionic emulsifiers are preferably used as accompanying surfactants. Common accompanying emulsifiers are, for example, ethoxylated fatty alcohols (degree of ethoxylation (EO): 3 to 50, alkyl radical: Cβ to C _3ß ), ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C ₄ - to Cg), ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: Cχ - to Ciβ), ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C ₄ - to C ₉ ), alkali metal salts of dialkyl esters of sulfosuccinic acid as well as alkali and ammonium salts of alkyl sulfates (alkyl radical: Cβ- to Cχ ₂ ), of alkyl sulfonic acids (alkyl radical: C ₁₂ - to Ciβ) of alkyl diphenyl oxide sulfonic acids (alkyl radical: C_ ₂ - to Ciβ) ^and ^of alkylarylsulfonic acids (alkyl radical: Cg - to Ciβ) and the corresponding acids. Further suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208. The surface-active substances are generally used in amounts of 0 to 5. preferably 0.1 to 1% by weight, based on the amount of the monomers to be polymerized, is also used. The process according to the invention is preferably used for the production of polymer blends which contain more than 10% by weight of polyamide, in particular more than 40% by weight, based on the total weight of polymer. 5

The invention further relates to the water-dispersible polymer blends which can be produced using the process according to the invention described above. Particularly suitable polymer blends are those which contain a polyamide content of 10 10% by weight, based on the total weight of polymer.

These polymer blends are suitable for a large number of applications, for example as adhesives, in paper production and finishing, as film formers for cosmetic applications,

15 in particular for applications on skin and nails, for pharmaceutical formulations, for textile manufacture and finishing, for leather finishing, as clear coats and pigmented paints to protect metals, mineral materials such as masonry, concrete, fiber-containing or organic materials such as

20 wood, cardboard, textiles, tar cardboard, and plastics.

An advantage of the polymer blends according to the invention can be seen in the fact that clear films are formed with different polymers even with a high polyamide content. Clear films can be widely

25 mixing ratios of polycondensate and radical polymer can be obtained. Such compositions have the advantage that otherwise incompatible polymers can be combined in their properties. This makes it possible to fine-tune the properties of the aqueous dispersions. Thus, in

30 water redispersible films can be obtained. The same is true

Production of water-resistant films possible. Furthermore, pigment-compatible dispersions can be obtained by suitable combinations of polyamides with ethylenically unsaturated monomers. Solvent-resistant (e.g. THF-resistant

35 stent) films can be obtained.

Another advantage can be seen in the good film formation without addition of plasticizer at room temperature, even if polyamides with glass transition temperatures far above the filming temperature 40 are used.

The polymer blends obtainable by the process according to the invention are finely divided hybrid dispersions with an average particle size of generally less than 150 nm. 45 The invention is further illustrated by the following examples.

Example 1:

Manufacture of a polyamide

The following monomer mixture was placed in 1300 ml of water in a 10-1 laboratory autoclave:

645 g of sodium 5-sulfoisophthalic acid, 598 g of isophthalic acid, 1116 g of 50% strength hexamethylenediamine solution, 190 g of 2, 2, 4-trimethylhexamethylene diamine, 787 g of AH salt. The autoclave was heated to 200 ° C. in the course of 3 h, during which the steam formed was distilled off. The temperature was kept unchanged for another hour. The temperature was then raised to 280 ° C. within 1 h. The mixture was then condensed in a stream of nitrogen for 2 h. The melt was then drawn out via a nozzle, cooled in an air bed and granulated.

The polyamide formed had a viscosity number (VZ) of 45 determined based on DIN 53 246 (0.5% solution of the copolyamide in 96% HS0) and a glass transition temperature of 143 ° C.

Example 2:

Manufacture of a polyamide

As described in Example 1, a polyamide was made from 840 g sodium 5-sulfoisophthalic acid, 521 g isophthalic acid, 1458 g

50% hexamethylenediamine solution, 710 g ε-caprolactam and 1200 ml water.

The glass transition temperature of the polyamide was 149 ° C.

Example 3:

Production of a polymer blend

140 g of the polyamide from Example 1 were dispersed in 850 g of water at 80 ° C. with stirring. A mixture of 54 g of methyl methacrylate and 6 g of butanediol bisacrylate was then added dropwise over the course of one hour while stirring. The resulting mixture was then stirred at 80 ° C. for one hour before 1 ml of t-butylperoxy-2-ethylhexanoate (Trigonox 21 S from Akzo) was added as a radical starter. Then 6 h with transfer of Polymerized nitrogen. The resulting dispersion was filtered through a nylon filter after cooling.

Examples 4 and 5:

Manufacture of polymer blends

Examples 4 and 5 were prepared by the same procedure described for Example 3.

Example 6

Production of a polymer blend

A mixture of 619.3 g of water, 40 g of polyamide from Example 2, 2.67 g of sodium lauryl sulfate (15% solution) and 1.6 g of a 25% sodium hydroxide solution was heated to 85 ° C. and at 5% by weight of feed 1, 10% by weight of feed 2 and 10% by weight of feed 3. The mixture was polymerized at 85 ° C. for 15 minutes and the metering of the remaining amounts of feeds 1, 2 and 3 was then started. The addition was carried out continuously over 2 hours (feed 1) and 2.5 hours (feed 2 and 3). The mixture was then polymerized at 85 ° C for 1 hour.

Feed 1: 200 g of butyl acrylate

200 g methyl methacrylate

Feed 2: 99.1 g of water

4 g sodium peroxodisulfate

Feed 3: 100 g of water

14.4g sodium hydroxide (25%) Example 7

Production of a polymer blend

5 A mixture of 889.1 g of water, 60 g of polyamide from Example 2, 2 g of sodium lauryl sulfate (15% solution) and 1.2 g of a 25% sodium hydroxide solution was heated to 85 ° C. and with 5% by weight of feed 1.10% by weight of feed 2 and 10% by weight of feed 3 are added. The mixture was polymerized at 85 ° C. for 15 minutes and the metering of the remaining amounts of feeds 1, 2 and 3 was then started. The addition was carried out continuously over 2 hours (feed 1) and 2.5 hours (feed 2 and 3). The mixture was then polymerized at 85 ° C for 1 hour.

15 feed 1: 150 g of butyl acrylate

150 g methyl methacrylate

Feed 2: 99.1 g of water

3 g sodium peroxodisulfate

20th

Feed 3: 100 g of water

10.8g sodium hydroxide (25%)

Example 8

25

Production of a polymer blend

A mixture of 984.5 g of water, 112 g of polyamide from Example 2, 1.87 g of sodium lauryl sulfate (15% solution) and 1.12 g of one

30% 25% sodium hydroxide solution was heated to 85 ° C. and 5% by weight of feed 1, 10% by weight of feed 2 and 10% by weight of feed 3 were added. The mixture was polymerized at 85 ° C. for 15 minutes and the metering of the remaining amounts of feeds 1, 2 and 3 was then started. The addition took place continuously over 2 hours

35 (feed 1) and 2.5 hours (feed 2 and 3). The mixture was then polymerized at 85 ° C for 1 hour.

Feed 1: 140 g of butyl acrylate

140 g methyl methacrylate

40

Feed 2: 99.1 g of water

2.8 g sodium peroxodisulfate

Feed 3: 100 g of water 45 10.1 g of sodium hydroxide (25%) Example 9 ^' ' *

Production of a polymer blend

A mixture of 1006.3 g of water, 200 g of polyamide from Example 2, 1.33 g of sodium lauryl sulfate (15% solution) and 0.8 g of a 25% sodium hydroxide solution was heated to 85 ° C. and at 5% by weight of feed 1, 10% by weight of feed 2 and 10% by weight of feed 3. The mixture was polymerized at 85 ° C. for 15 minutes and the metering of the remaining amounts of feeds 1, 2 and 3 was then started. The addition was carried out continuously over 2 hours (feed 1) and 2.5 hours (feed 2 and 3). The mixture was then polymerized at 85 ° C for 1 hour.

Feed 1: 100 g of butyl acrylate

100 g methyl methacrylate

Feed 2: 99.1 g of water

2 g sodium peroxodisulfate

Feed 3: 100 g of water

7.2 g of sodium hydroxide (25%) Example 10

Production of a polymer blend

A mixture of 1606.3 g of water, 400 g of polyamide from Example 2, 1.33 g of sodium lauryl sulfate (15% solution) and 0.8 g of a 25% sodium hydroxide solution was heated to 85 ° C. and at 5% by weight of feed 1, 10% by weight of feed 2 and 10% by weight of feed 3. The mixture was polymerized at 85 ° C. for 15 minutes and the metering of the remaining amounts of feeds 1, 2 and 3 was then started. The addition was carried out continuously over 2 hours (feed 1) and 2.5 hours (feed 2 and 3). The mixture was then polymerized at 85 ° C for 1 hour.

Feed 1: 100 g of butyl acrylate

100 g methyl methacrylate

Feed 2: 99.1 g of water

2 g sodium peroxodisulf t

Feed 3: 100 g of water

7.2 g sodium hydroxide (25%) Example 11

Production of a polymer blend

5 A mixture of 1151.8 g of water, 40 g of polyamide from Example 2, 2.67 g of sodium lauryl sulfate (15% solution) and 1.60 g of a 25% sodium hydroxide solution was heated to 85 ° C. and 5 wt. % of feed 1, 10% by weight of feed 2 and 10% by weight of feed 3. Polymerization was carried out for 15 minutes at 85 ° C. and 10 the metering of the remaining amounts of feeds 1, 2 and 3 was then started. The addition was carried out continuously over 2 hours (feed 1) and 2.5 hours (feed 2 and 3). The mixture was then polymerized at 85 ° C for 1 hour.

15 feed 1: 200 g of butyl acrylate

180 g methyl methacrylate 20 g methacrylic acid

Feed 2: 99.1 g of water and 20 g of sodium peroxodisulfate

Feed 3: 100 g of water

14.4 g sodium hydroxide (25%) Example 12 25

Production of a polymer blend

A mixture of 1016.3 g of water, 200 g of polyamide from Example 2, 1.33 g of sodium lauryl sulfate (15% solution) and 0.8 g of one

30 25% sodium hydroxide solution was heated to 85 ° C and with 5

% By weight of feed 1, 10% by weight of feed 2 and 10% by weight of feed 3 were added. The mixture was polymerized at 85 ° C. for 15 minutes and the metering of the remaining amounts of feeds 1, 2 and 3 was then started. The addition took place continuously over 2 hours

Feed 1: 100 g of butyl acrylate

90 g methyl methacrylate 40 10 g methacrylic acid

Feed 2: 99.1 g of water

2 g sodium peroxodisulfate

45 Feed 3: 100 g of water

7.2 g sodium hydroxide (25%) Example 13

Production of a polymer blend

A mixture of 1131.8 g of water, 40 g of polyamide from Example 2, 2.67 g of sodium lauryl sulfate (15% solution) and 1.60 g of a 25% sodium hydroxide solution was heated to 85 ° C. and with 5 wt .-% of feed 1, 10% by weight of feed 2 and 10% by weight of feed 3. The mixture was polymerized at 85 ° C. for 15 minutes and the metering of the remaining amounts of feeds 1, 2 and 3 was then started. The addition was carried out continuously over 2 hours (feed 1) and 2.5 hours (feed 2 and 3). The mixture was then polymerized at 85 ° C for 1 hour.

Feed 1: 400 g methacrylate

Feed 2: 99.1 g of water

4 g sodium peroxodisulfate

Feed 3: 100 g of water

14.4g sodium hydroxide (25%)

Example 14

Production of a polymer blend

A mixture of 1006.3 g of water, 200 g of polyamide from Example 2, 1.33 g of sodium lauryl sulfate (15% solution) and 0.80 g of a 25% sodium hydroxide solution was heated to 85 ° C. and with 5 wt .-% of feed 1, 10% by weight of feed 2 and 10% by weight of feed 3. The mixture was polymerized at 85 ° C. for 15 minutes and the metering of the remaining amounts of feeds 1, 2 and 3 was then started. The addition takes place continuously over 2 hours (feed 1) and 2.5 hours (feed 2 and 3). The mixture was then polymerized at 85 ° C for 1 hour.

Feed 1: 200 g methacrylate

Feed 2: 99.1 g water 2 g sodium peroxodisulfate

Feed 3: 100 g of water

7.2 g sodium hydroxide (25%) Example 15

Production of a polymer blend

Feed 1: 400 g vinyl acetate

Feed 2: 99.1 g of water

4 g sodium peroxodisulfate

Feed 3 100 g of water

14.4g sodium hydroxide (25%)

Example 16

Production of a polymer blend

A mixture of 1006.3 g of water, 200 g of polyamide from Example 2, 1.33 g of sodium lauryl sulfate (15% solution) and 0.80 g of a 25% sodium hydroxide solution was heated to 85 ° C. and with 5 wt .-% of feed 1, 10% by weight of feed 2 and 10% by weight of feed 3. The mixture was polymerized at 85 ° C. for 15 minutes and the metering of the remaining amounts of feeds 1, 2 and 3 was then started. The addition was carried out continuously over 2 hours (feed 1) and 2.5 hours (feed 2 and 3). The mixture was then polymerized at 85 ° C for 1 hour.

Feed 1: 200 g vinyl acetate

Feed 2: 99.1 g water 2 g sodium peroxodisulfate

Feed 3: 100 g of water

7.2 g sodium hydroxide (25%) Compilation of the results from the examples:

*) Solids content of the dispersion according to DIN 53 189

Example 17

Use of the polymer blend as an adhesive for aluminum paper lamination

20 g of water and 3 g of thickener (30% by weight aqueous solution of a copolymer based on acrylic acid and acrylamide emulsified in an aliphatic petroleum fraction) are stirred into 100 g of aqueous polymer dispersion, for example from Examples 7, 11 or 12. 2 g / m ² (dry) of this laminating adhesive is applied to the matt side of a 0.015 mm thick, one-sided matt aluminum foil. Buxine paper (80 g / m ² ) is rolled up onto the wet adhesive bed and the substrate obtainable in this way is dried at 50 ° C. for 3 minutes. It is then cut to a format of 200 mm x 30 mm. The test takes place after 24 hours.

Aluminum-paper composites with good strengths were found.

Example 18

Use of the polymer blend as a binder for nonwovens

A polymer prepared according to Examples 6 to 10 with 96% by weight of ethyl acrylate and 4% by weight of acrylamidoglycolic acid, solids content 45%, is used as the binder. The nonwovens are consolidated with the polymers by known methods (Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 23, 1983, pp. 738 to 742). After the nonwoven treatment, drying and tempering of the nonwoven fabric obtained is carried out.

Nonwovens with good usage properties are obtained.

Example 19 10

Use as a hair fixer

(Percentages in% by weight)

15 Formulation formulation 1

25% of an aqueous dispersion from Example 4 0.2% perfume oil, dye and preservative 74.8% water 20 were mixed.

Formulation formulation 2

25 15% of the aqueous dispersion from Example 5

1.5% of a copolymer of 60% by weight N-vinylpyrrolidone and 40% by weight vinyl acetate

0.2% perfume oil, dye and preservative

83.3% water 30 was mixed.

The formulations thus obtained show a good strengthening effect 35

Example 20

Use as nail polish (percentages in% by weight) 40

75% of the dispersion from Example 6 were mixed with 1% color pigment and 24% water.

Glossy, well adhering films are obtained. 45 Example 21

Binder for a paper coating slip

Containing 60 wt .-% paper coating slip

80 g China Clay 5PS (kaolin) 20 g Omyalite 90 (chalk)

0.2 g Polysalz ® S (low molecular weight polyacrylic acid, dispersant for kaolin and chalk) 11.5 g aqueous dispersion (calculated dry) according to Examples 6 to 10 with 55% by weight n-butyl acrylate, 43% by weight methyl methacrylate and 2% by weight .-% acrylic acid, solids content 50% 0.6 g Blankophor® PSG-fl. (optical brightener) and 0.3 g Sterocoll® D (calculated dry), (aqueous dispersion of an acrylic ester polymer rich in acrylic acid, thickener) water

A paper coating slip with good coating properties is obtained.

Claims

claims

1. A process for producing water-dispersible polymer blends from a polyamide and a second polymer by polymerizing an aqueous dispersion or solution from a polyamide, one or more ethylenically unsaturated monomers, a polymerization initiator and, if appropriate, an emulsifier.

2. The method according to claim 1, characterized in that the polymer blend contains more than 10 wt .-% polyamide.

3. The method according to claim 1, characterized in that the polyamide

al) 0 to 99 mol% of a monoaminocarboxylic acid with 2 to 12

C atoms or their lactam a2) 0.5 to 50 mol% of at least one diamine with 2 to 18 C atoms, a3) 0 to 49 mol% of a dicarboxylic acid with 4 to 12 C atoms carrying sulfonate groups, and a4 ) 0.5 to 49 mol% of a dicarboxylic acid having 2 to 16 carbon atoms.

4. The method according to claim 1, characterized in that the second polymer is composed of the monomers n-butyl acrylate, methyl methacrylate, or methacrylic acid or mixtures thereof.

5. Water-dispersible polymer blends obtainable by a process according to claims 1 to 4.

6. Use of a polymer blend according to claim 5 for paper coating.

7. Use of a polymer blend according to claim 5 for cosmetic formulations.

8. Use of a polymer blend according to claim 7, characterized in that the polymer blend is used for a hair care product.

9. Use of a polymer blend according to claim 7, characterized in that the polymer blend is used for a nail polish.

10. Use of a polymer blend according to claim 5 as an adhesive.

11. Use of a polymer blend according to claim 5 as a binder for nonwovens.