DE2710033B2 - Coating and impregnating compound - Google Patents

Description

The invention relates to coating or impregnating compositions which contain a vinyl addition polymer and be agreed to contain cyclic esters of acrylic acid and / or methacrylic acid.

When using aqueous dispersions of emulsion polymers, the particles of which are insoluble in water, the effectiveness of the dispersion with regard to the formation of a film after the application of the polymer dispersion to a surface to be painted depends on the glass transition temperature of the dispersed polymer and on the temperature at which one This is particularly clear from US Pat. No. 2,795,564, which describes the applicability of many acrylic polymers for the preparation of water-based paints or more mono-ethylenically unsaturated monomers (with a group HjC = CX) have an apparent glass transition temperature, which depends on the components and the proportion of such components in the polymer. It is stated that some monomers of this type s, such as methyl methacrylate, where styrene, vinyl acetate, vinyl chloride and acrylonitrile are similar in this respect, tend to produce homopolymers which have relatively high glass transition values, the glass transition temperature described in this US Pat Symbol T). In homopolymerization, the monomers indicated above give hard polymers, ie polymers with a glass transition temperature or a 7> value of more than 20 ° C. On the other hand, numerous monoethylenically unsaturated monomers are mentioned in this US Pat. This characterization relates to polymers with glass transition temperatures jn or 7> values of 20 ° C or less.

It is also mentioned in the said US-PS that by copolymerization of various hard and / or soft monomers in predetermined proportions of a copolymer with a predetermined glass transition temperature or a predetermined 7> value which can be obtained from -40 ° C to 150 ° C or above fluctuates. Coatings made from aqueous dispersions of the various polymers can be used be such that an application of the coating compositions or of water-based paints Such polymers are carried out at normal temperature or even lower temperatures can, with good film-forming qualities are obtained if the Γζ-value of each single set Polymers is not above the ambient temperatures at which the coating is carried out will. For example, in general, water-based paint coatings that comprise a polymer with a 7> value of around 15 ° C Can be applied at room temperature and produce a good film formation by simply drying the applied film in the ambient atmosphere. On the other hand, contains the coating composition as theirs the primary film-forming component is an emulsion polymer having a 7 * / value greater than room temperature, for example about 35 ° C or above, then the film obtained from such a paint can be elevated temperatures, for example 35 ° C or about it, while drying require to

ensure that the polymer particles converge or fuse with one another to a sufficient extent to form a continuous film. Some polymers can have a glass transition temperature that is significantly above room temperature, for example 30 to 35 ° C, and are still able to form a continuous film at normal room temperatures due to an affinity for water (hydrophilicity) of a specific polymerize unit in the dispersed polymer ι ο particles. An example of such a monomeric component is vinyl acetate. The hydrophilicity of a polymer, as a result of the fact that it contains a substantial amount of vinyl acetate (or other equivalent hydrophilic monomer), promotes the coalescence of the polymer particles into a continuous film at temperatures below that of the Tr value of such a polymer, as can be determined by a standard test

The manufacture of paints on water balls using polymers with low 7> values, soft enables the maintenance of normal room temperatures without the use of a plasticizer, results in the formation of films, which in many cases are very hard and tough after drying. On the other hand, the use of polymers with high glass transition temperatures generally requires which are significantly above room temperature, for example above 35 ° C, generally that The presence of a permanent or volatile plasticizer (the plasticized polymer has a lower 7> value) or maintaining a high drying temperature, thus good continuous Films on the to be coated «!: surfaces are generated.

It has now been found that the incorporation of dicyclopentenyl acrylate and / or dicyclopentenyl methacrylate in aqueous coating compositions, such as water-based paints, made from water-soluble addition polymers or from aqueous dispersions of water-insoluble addition polymer particles are produced, such as are obtainable, for example, by emulsion polymerization, such masses a heretofore can give unachievable versatility without great effort and expense.

The symbol DCPA is used below for dicyclopentenyl acrylate and the symbol DCPMA for the corresponding methacrylate. DCP (M) A turns off General term used under which a mixture of these two materials or one of these Materials is to be understood

Dicyclopentyl-imethJ-acrylate has the following formula, it is assumed:

R O

CH ₂ = CCO

CH,

CH

(D

bO

wherein R is H or -CH ₃ . The (meth) acryloxy substituent can either be in the 5- or 6-position, the commercial product being a mixture of the two isomers. DCP (M) A can be prepared by adding methacrylic acid to one of the double bonds of dicyclopentadiene. According to the invention, a coating or impregnation is used kidney compound on the basis of aqueous dispersions or solutions of vinyl addition polymers and monomeric acrylic or methacrylic acid esters created, which is characterized in that the aqueous Dispersions or solutions as monomeric acrylic or methacrylic acid esters 1 to 200% by weight, based on the Weight of the vinyl addition polymer, dicyclopentenyl acrylate and / or dicyclopentenyl methacrylate and contain a desiccant.

It has been found that the addition of a DCP (M) A to coating compositions based on vinyl addition polymers of monoethylenically unsaturated monomers, in particular those with a terminal group H ₂ C-CcC, is extremely beneficial in terms of facilitating the coating and the film-forming effect during drying at normal room temperatures, in addition, the cured film has a greater hardness and toughness as a result of the reactive air-curing properties of the DCP (M) A which is conventionally used to accelerate the oxidation of drying oils is added to accelerate the hardening of the coating film during drying. The amount of DCP (M) A in the coating composition can be selected within a wide range, depending on the used mass, its components and i In particular the film-forming polymer contained therein and its apparent glass transition temperature.

When adding to an emulsion polymer dispersion, the DCP (M) A plays a role which is extremely advantageous It can serve as a leveling agent since it acts as a plasticizer for the dispersed polymer particles If the dispersed polymer has a 7> value, which is above room temperature, for example at 35 ° C, so that coating compositions such as Water-based paints that are made from the polymer dispersion are not continuous Form a film when drying under ambient conditions, then as much DCP (M) A can be in the polymer dispersion or in the coating composition, which a contains such polymer dispersion, are mixed in that the 7> value and the effective film-forming temperature are reduced to such an extent that the Masses capable of forming continuous films at ambient temperature. At the same time the product is hard and non-blocking when air-drying the films due to the autoxidizable nature of the mass.

If DCP (M) A is based on an aqueous dispersion of an emulsion polymer with coatings such a low Tr value that film formation would be done at room temperature without DCP (M) A added, then the films that obtained from the DCP (M) A-containing polymer composition, cured upon air curing of the DCP (M) A and tough.

According to one embodiment of the invention, the vinyl addition polymer is dispersed in the form of water-insoluble particles and has an apparent Freezing temperature from -40 to + 150 ° C and preferably from 15 to 100 ° C, in particular from 15 ° C or underneath, on.

The coating compositions preferably contain one or more drying agents. The used Desiccant is any polyvalent metal-containing complex or salt that is present.

that catalyzes the oxidative hardening of drying oils or drying oil-modified alkyl resins. Examples of drying agents are various salts of polyvalent metals, such as calcium, copper, zinc, manganese, lead, cobalt, iron and zirconium, which are present as cations. Simple inorganic salts are suitable, for example the halides, in particular chlorides, nitrates or sulfates. Salts of organic acids, such as acetylacetonates, acetates, propionates and butyrates, are also suitable. The drying agents can also consist of complex reaction products of metal oxides, acetates or borates and vegetable oils. Suitable drying agents are also salts of naphthenic acids or of (Cg-C3o) -tiphatic acids. Examples of the aliphatic component or fatty acid component or the anion of the salt acting as a drying agent are the components of naphthenic acids, resin acids, ie rosin acids, tail oil fatty acids, linseed oil fatty acids, 2-ethylcaproic acid, lauric acid, palmitic acid, myristic acid, linolenic acid, oleic acid, linolenic acid Cerotic acid, montaic acid and abietic acid. Preferred salts which act as drying agents are those of cobalt and manganese, such as cobalt octoate, cobalt naphthenate and manganese octoate and naphthenate. Mixtures of various drying agents can also be used. The drying agents mentioned in "Encyclopedia of Chemical Technology", Kirk-Othmer, Volume 5, published by Interscience Encyclopedia, Inc, New York (1950) on pages 195-205 can be used.

The amount of desiccant can be very low. It is generally based on the Metal content in an amount of 0.0005 to 2%, based on the weight of component (b), which DCP (M) A contains, used The drying agent can be added to the mass before storage, provided that such an addition is made in the absence of oxygen. A volatile one can also be used Add stabilizing agent to the mass in order to inhibit the oxidizing effect of the drying agent or to avoid. The mass is then kept in sealed containers to prevent volatilization of the inhibitor. Da: Stabilizer can be used in small amounts from 0.1 to 2 % By weight based on the weight of the component (b) containing the DCP (M) A can be used. That Stabilizing agent is generally a volatile ketone oxime or aldehyde oxime. Specific examples are methyl ethyl ketone oxime, methyl butyl ketone oxime, 5-methyl-3-heptane oxime, cyclohexanone oxime and butyraldehyde oxime. The addition of such inhibitors is essential if a long stability and useful life of the aqueous compositions, the dispersed polymer, DCP (M) A and desiccants contain, are desired.

The coating compositions can, of course, contain other materials such as that discussed above Patent specification is indicated, for example pigments, dispersants, sequestering agents, defoaming agents Humectants, thickeners, bactericides, fungicides, odor modifiers as well other resinous materials in dispersed forms. The various pigments and other materials mentioned in the known patent specification, can be used.

In general, the amount of component (b) containing CCP (M) A in the coating composition is used, about 1 to 200% by weight and preferably 5 to 150% by weight, based on the Weight of the vinyl addition polymer that is the main film-forming component make up the coating mass. The vinyl addition polymer in the inventive Composition can consist of any of the polymers described in US Pat. No. 2,795,564.

ίο For example, the polymer can heal a «JJ-unsaturated carboxylic acid, such as acrylic acid or Methacrylic acid, units of an ester of acrylic acid with a (Ci - Cie) alkanol and / or an ester of Methacrylic acid with a Cs-Cie-alkanol as well Have units of a (Ci - Q) -alkyl methacrylate.

It should be noted that the acrylic polymers described in US Pat. No. 2,795,564, the above mentioned are not the only types of vinyl addition polymers that can be produced by incorporation of DCP (M) A together with a desiccant can be modified and improved. In the the copolymer systems described in the cited patent, the curing component is a low one Methacrylate such as methyl methacrylate, similar Cfpolymersysteme in which the hard lower methacrylate partially or completely by curing monomers such as styrene, vinyl toluene, acrylonitrile, methacrylonitrile, Vinyl chloride, vinylidene chloride or vinyl acetate can also be replaced by the admixture can be improved by DCP (M) A and a drying agent. Copolymers made from such monomers with at least one Cj-Cie-alkyl acrylate and / or a (C * -C] s) -alkyl methacrylate can be used will. However, preferred copolymers are those comprising units of methyl methacrylate and at least one (Ci - CtJ-alkyl acrylate, optionally with units of acrylonitrile.

It has been found that the OCP [M) A can also be used in conjunction with aqueous coating systems based on natural latices or synthetic latices made from butadiene. Chloroprene, styrene / butadiene copolymers, acrylonitrile / butadiene / styrene copolymers as well as related synthetic rubber systems with low 7> values are suitable, films obtained from these dispersions are also suitable in terms of hardness by the addition of DCP (M ) A improved together with a desiccant

The use of DCP (M) A makes it possible

to produce hard and tough coating films from coating compositions that contain a polymer with a low 7> contain value that is usually a soft Film Forms These benefits can be seen without using a plasticizer, or at least with one Achieve reduced volume of a permanent plasticizer in the masses.

The incorporation of DCP (M) A into the coating compositions is not limited to such compositions the film-forming component essentially off

bo water-insoluble dispersed particles of a polymer or copolymers or contains such a polymer. The DCP (M) A can also aqueous solutions of vinyl addition polymers are added, in which the solubility of the Polymers essentially have true solubility due to the low molecular weight of the polymer is, which contains hydrophilic groups.Furthermore, the addition can be made to solutions of such polymers,

which are characterized by the formation of colloidal solutions.

The soluble polymers can reduce their solubility due to a high content of hydrophilic groups, such as acidic mers, which can be in acidic form or in salt form. Examples of such Acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, citraconic acid and aconitic acid. The salts can be salts of ammonia, amines, such as dimethylaminoethanol or triethylamine as well as 2-amino-2-methyl-1-propanol, or of alkali metals, especially sodium, potassium or Lithium, act. In addition to polymers that contain large amounts of acidic units, such as units of polyacrylic acid or contain polymethacrylates, or copolymers, such as copolymers of 15% methacrylic acid and 85% butyl methacrylate, one can also Use copolymers having a large amount of amide group-containing units, for example Acrylamide or methacrylamide units, or polymers that contain a large amount of amine units have, for example honey polymers of Oxazolidinyläthyliicrylat, or copolymers of the latter amine-containing polymer with up to 20% by weight Methyl acrylate. The water solubility can also be traced back to polymerized mers, the hydroxyl groups contain, for example hydroxyethyl acrylate or methacrylate, 2-hydroxypropyl acrylate or 3-hydroxypropyl acrylate. The water solubility may also be the result of the copolymerization of two or more Be types of the mentioned hydrophylizing monomers. In these cases the DCP (M) A serves together with a drying agent for modifying the properties of the finished coating film.

The use of the DCP (M) A in the coating compounds serves various functions or purposes. In Aqueous solutions of water-soluble polymers is used to facilitate the adjustment of the viscosity Overlaying makes it easy, without the necessity of adding excessive water to the solution or to be diluted with another water-miscible volatile solvent. The DCP (M) A then becomes part of the binder component during air drying and contributes to the solvent resistance, Water resistance, alkali resistance, to the gloss, hardness and toughness of the hardened Coating films. In coating compositions based on aqueous dispersions of water-insoluble Polymer particles, such as those obtained, for example, by emulsion polymerization, serve this purpose DCP (M) A as a leveling agent, hardener, agent to increase the toughness and agent to control the Viscosity In all cases, the DCP (M) A becomes during the air curing of the coating compositions, which the vinyl polymer, DCP (M) A and the desiccant contain part of the binder in the final hardened Coating films. The addition of volatile organic solvents to the coating compositions can therefore avoided, so that environmental pollution, toxicity and the risk of flammability be avoided.

The non-volatile reactive component can consist essentially of DCP (M) A, which also is preferably the case, if necessary, it can jcuccii äüCii from emer iviiscuung from at least one larger amount (more than 50 to 100% by weight, for example 51 to 99% by weight) DCP (M) A and off a smaller amount (less than 50 to 0

% by weight) of another non-volatile reactive ethylenically unsaturated monomeric material consisting of (1) a (Ci - C ^ aliphatic ester of acrylic acid and / or methacrylic acid, for example (Cio-Cm) -alkyl and (Cio-CwJ- Alkenyl acrylates and methacrylates, (2) a vinyl ester of a (Cio —Cm) aliphatic acid and (3) reactive dialkyl esters of maleic acid, fumaric acid or itaconic acid in which the alkyl group contains 1 to 8 carbon atoms to water, solvents, abrasion and blocking resistance of the compositions of the invention also a non-volatile reactive polyethylenically unsaturated material in a small amount of up? \\ 25% by weight, preferably 2 to 15% by weight based on the weight of the binder containing , for example a

Glycol or Polvol (meth) acrylate.
for example

Ethylene glycol di (meth) acrylate,

1,4-butanediol di (meth) acrylate,

1,6-hexanediol di (meth) acrylate,

l ^ -Butylene glycol Kmeth / acrylate,

Neopentyl glycol di (meth) acrylate.

Pentaerythritol and tetra (meth) acrylate,

Trim'ithy! Olpropane tri (meth) acrylate and

Allyl (rr> eth) -acry! Ate.

Examples of the esters (1) described above are

Decyl acrylate, isodecyl acrylate, undecyl acrylate,

Lauryl acrylate, cetylacrylate,

Pentadecyl acrylate, flexadecyl acrylate,

Octadecyl acrylate,

the corresponding methacrylates and the unsaturated analogs, such as

Oleyl acrylate or methacrylate,

Linoleyl (meth) acrylate and

Linolenyl (meth) acrylate.
Examples of (2) are vinyl decanoate. Vinyl laurate,

Vinyl oleate, vinyl palmitate,

Vinyl myristate and vinyl stearate.
Examples of the diesters (3) are

Dimethyl maleate, fumarate and itaconate,

Diethyl maleate, fumarate and itaconate as well as

Dibutyl maleate, fumarate and itaconate.
Some preferred embodiments of the invention are illustrated in more detail by the following examples. Unless otherwise stated, all parts and percentages relate to weight. Unless stated otherwise, the temperature data are in "Celsius".

example 1

Coating compounds on the base
of hard latex polymers and DCPMA

Polymer A is an aqueous latex polymer having the following monomer composition: 433 parts of ethyl acrylate, 55 parts of methyl methacrylate _r 5 and 1.0 part methacrylic acid. The latex is neutralized with ammonium hydroxide and has a pH of 9.5. It is also characterized by a solids content of 46 ^%, an average particle diameter of 0.11 μ and a ti value of 32 ° C.

The polymer B is an aqueous latex polymer with the following monomer composition: 46 parts of butyl acrylate, 53 parts of methyl methacrylate and 1 part of methacrylic acid. The latex is neutral with ammonia

sated and has a pH of 9.5. It is also characterized by a solids content of 46.5%, a mean particle diameter of 0.15 µ and a 7> value of 22 ° C.

A series of coating compounds is made from each of the polymers A and B by adding DCPMA with stirring and subsequent addition of 0.1 part of cobalt (II) as acetylacetonate and 0.25 parts Cyclohexanone oxime per 100 parts of latex solids

10

and DCPMA. Other coating compositions are made from polymers A and B in the same way produced, the volatile flow control agent 2,2,4-trimethylpentanediol-1,3-monoisobutyrate with stirring is admitted. The various coating compositions are first tested for their film-forming ability, i.e. H. their minimum film formation temperature (MFT) tested according to ASTM method D-2354. The results can be seen from Table I.

Table I. Parts of DCPMA or 2,2,4-trimethylpentanediol MFT (C) toughness Polymer !, 3 monoisobutyrate /! 00 parts Lalex solids visually 37 no 38 Il Λ 20 DCPMA 4th <1 40 DCPMA <1 9 20 2,2,4-trimethylpentanediol-1,3-monoiso 5 butyrate 19th no 14th 2-4 B. 15 DCPMA <1 <1 40 DCPMA <1 2 15 2,2,4-trimethylpentanediol 1,3-monoiso- <ι butvrat

Coatings are then applied to aluminum test panels in such a way that the film thickness is in dry State is 33 μ. After drying for a period of 4 weeks at ambient conditions the film properties are determined, which are summarized in Table II below.

Table II
Polymer

Parts of DCPMA or 2,2,4-trimethylpentanediol
1,3-monoisobutyrate / 100 parts latex solids Button
Hardness, number pencil
hardness Impression
availability *) (KHN) no no movie puiverföimige deposit 20 DCPMA 7.1 H no 40 DCPMA 10.1 2H no 20 2,2,4-trimethylpentanediol-1,3-monoiso-
butyrate 0.5 HB moderate no 1.1 - moderate 15 DCPMA 1.6 F. easy 40 DCPMA 4.0 F. track 15 2,2,4-trimethyl] pentanediol-1,3-monoiso-
butyrate 0.5 F. moderate

*) A box is placed on a film under a pressure of 0.14 kg / cm ² for a period of 2 hours. It is examined to what extent the cheesecloth fibers have left an impression in the film.

Example 2

Coating compounds based on soft latex polymers and DCPMA

The polymer C is an aqueous latex copolymer with the following monomer composition: 53 parts Bütylacryiai, 46 parts Meihyhnethacrylai and 1 part Methacrylic acid. The latex is neutralized with ammonium hydroxide and has a pH of 9.1. He draws furthermore by a solids content of 464%, a

mean particle diameter of 0.1 μ, a 7> value of 15 ° C and an MFT value of 12 ° C.

The polymer D is an aqueous latex copolymer with the following monomer composition: 70 parts of butyl acrylate, 29 parts of methyl methacrylate and 1 part of methacrylic acid. The latex is neutralized with ammonium hydroxide and has a pH of 9.0. It is also characterized by a solids content of 46.5%, an average particle diameter of 0.1 μ, a 7} value of -7 ° C and an MFT value of <0 ° C.

The polymers C and D are converted into coating compositions by adding DCPMA with stirring and subsequent addition of 0.1 part of cobalt (H) in the form of the acetate and 0.25 part of cyclohexanone oxime per 100 parts made from latex solids and DCPMA.

The coatings are placed on steel test panels in a

in such an amount that the thickness of the finished Films is 38 μ after drying. After drying at ambient conditions for a The coating properties are determined over a period of at least 2 weeks. The results go from Table III.

Table III Parts of DCPMA Relative Button Pencil hardness wet Rusting of steel Poly per 100 parts Stickiness hardness 6B meres Lalexfest stole Number (KHN) dry 5B 0 no 0.34 2 B - strong ' C. 40 no 0.50 HB - none 0 sticky 0.20 5B - strong D. 40 sticky 0.23 5B - moderate 80 easy gluing 0.35 3B track 120 very easy 0.65 2 B none Adhere

Example 3 Pigmented latex paint containing DCPMA

Pigment dispersions are prepared by grinding the following ingredients in a Cowles dissolver for 15 minutes at 1650 meters per minute.

material Parts by weight Dispersants (Tamol731.25%) 10.8 Defoamer (Nopco NDW) 2.0 Propylene glycol 59.8 Rutile TiO ₂ 270.0

The following materials are added to the above dispersions with stirring:

material painting painting painting medium A medium B medium C Propylene glycol 69 32.2 water - 30.0 30.0 Latex polymer B according to Example 1 376 313.4 267.7 (46.5%) DCPMA - 28.8 49.4 Cyclohexanone oxime - 0.43 0.44 Cobalt (II) acetylacetonate - 0.76 0.77 2,2,4-trimethylpentanediol-1,3-mono- 26th 0 0 isobutyrate Hydroxyethyl cellulose 49.1 71.6 80 (2.5% in water) water 38.7 86.9

All paints have a pigment concentration of 28 μm in the dry film thickness tion of 30 Yohjmen-%, a pH value. about 65 1 back. during a period of 2 weeks bsi

9.1 and a cancellation viscosity of approximately & 0 to 85 Cancer units on. The paints are applied to steel test panels in such an amount that the

Environmental conditions are used to determine the coating properties, which are shown in Table IV below summarized are:

Table IV 27 10 033 painting 14th painting 13th medium B medium C 2.1 3.5 Knoop hardness, number (KHN) painting HB HB Pencil hardness medium A 5.53 5.53 Continuous impact strength (m-kg) 1.4 track no Indentability (60 C / B. 0.14 kg / cm ² / 3O minutes 5.53 little easy Face to face blocking easy (60 C70,14 kg / ^cm2 / 60 minutes) strong

Claims (9)

Patent claims: 1. Coating or impregnation compound based on aqueous dispersions or solutions of s Vinyl addition polymers and monomeric acrylic or methacrylic acid esters !!, characterized in that the aqueous dispersions or Solutions as monomeric acrylic or methacrylic acid esters 1 to 200 parts by weight, based on the ι ο Weight of the vinyl addition polymer, dicyclopentenyl acrylate and / or dicyclopentenyl methacrylate, as well as a desiccant. 2. Composition according to claim 1, characterized in that the monomers of more than 50 to 100% by weight of dicyclopentenyl acrylate and / or methacrylate and less than 50 to 0% by weight of one or more of the following ingredients: 1) an Oo - C ^ aliphatic ester of acrylic acid and / or methacrylic acid, 2) a vinyl ester of a C ₁₀ -Cal aliphatic acid, 3) a dialkyl ester of maleic acid, fumaric acid or itaconic acid, the alkyl groups being 1 contain up to 8 carbon atoms. 3. Composition according to one of claims 1 to 2, characterized in that it is a volatile Contains aldehyde oxime or ketone oxime as stabilizers 4. Composition according to one of claims 1 to 3, characterized in that the vinyl addition polymer units of at least one «^ -unsaturated carboxylic acid, units of at least one ester of acrylic acid with a Ci-Cie-alkanol and / or an ester of methacrylic acid with a C5 - Cu-alkanol and units of at least one Ci-G ₁ -alkyl methacrylate 5. Composition according to claim 4, characterized in that the vinyl addition polymer is a copolymer containing units of at least methyl methacrylate acrylonitrile, vinyl chloride, vinyl acetate, styrene or vinyl toluene and units of at least one Ci-Cia-alkyl acrylate and one (C ₄ -Ci ₈ ) Alkyl methacrylate. 6. Composition according to claim 5, characterized in that the vinyl addition polymer is a copolymer, the units of methyl methacrylate and contains at least one (Ci - O) -alkyl acrylate. 7. Composition according to claim 6, characterized in that the vinyl addition polymer also w Contains units of acrylonitrile. 8. Composition according to one of claims 1 to 3, characterized in that dar- vinyl addition polymers in the aqueous. Phase is resolved and Contains units with hydrophilic groups which consist of v> hydroxyl, carboxyl, amide and / or amine. 9. Composition according to one of the preceding claims, characterized in that the drying agent is a salt or a complex of a polyvalent metal and 0.0005 to 2 wt .-%, m) calculated as the amount of metal that makes up monomers.