FI61038B - FRAMEWORK FOR THE SUPPLY OF PLASTIC DISTRIBUTORS AND DISPERSERS - Google Patents

Description

γβι m «advertisementPublish, Sun 61038 JOiA M (11> utläggnincsskrift 0, U0 ° C Patent granted 10 05 1932

Patent Oaddelat ^ (51) K ».ik? /Int.ci.3 C 08 P 218/10, 220/18, C 09 D 3/74 FINLAND — FINLAND (21) PK * nttih» k * iwi * -pti * «Tti *» ei «» in * 7622U7 (22) Hakamitpilvi - AmOknlngvdtg 05.08.76 ^ (23) Alkupllvi - Giltlghatsdag 05.08.76 (41) Tullut Julklteksl - Blivlt offantllg 09.02.77

Pktantti · and the Registrar Board .... ...

_,, (44) Date of departure and hearing. -

Patent and regiaterstyralsan Antdkan utlagd och utl.skriftan publlcarad 29.01.82 (32) (33) (31) Requested atuolkaut — Begird prlorltet 08. 08.75 26.06.76 Federal Republic of Germany-Förbunds-republiken Tyskland (DE) P 2535372.k, p 2628760.5 (71) Hoechst Aktiengesellschaft, 6230 Frankfurt / Main 80, Federal Republic of Germany Förbundsrepubliken Tyskland (DE) (72) Helmut Braun, Hofheim / Taunus, Helmut Rinno, Lorsbach / Taunus,

Werner Stelzel, Bad Soden / Taunus, Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (7 * 0 Oy Kolster Ab (5 * 0 Method for preparing plastic dispersions for dispersion paints - Förfarande för framställning av plastdispersioner användbara i dispersing

Difficulties in wet bonding dispersion dyes to smooth, non-absorbent substrates have long limited their use to certain dispersion dyes. Low pigmented dispersion dyes, and again those that dry to glossy or silky matt, will adhere poorly to smooth, non-absorbent substrates if the paint layer is rewetted after drying. Particularly poor is adhesion to fresh paint layers that have not been aged.

Slightly pigmented dispersion dyes are selected when the paint layer needs to be washed. Due to the high binder content, these colors form a uniform, washable film. Thus, the pigment content of glossy and silk carpet dispersion dyes is less than 40% by volume and generally about 10-25%. In addition, they contain higher amounts of organic 2,61038 solvents, about 3-15%, to improve gloss, brushability and leveling time, as well as film-forming agents. Gloss, spreadability and leveling time are affected, for example, by polyhydric, water-miscible alcohols containing up to 6 carbon atoms, in particular ethylene and propylene glycol or their ethers from monomethyl ether to monobutyl ether. To improve film formation, limited use of water-soluble solvents such as monoglycol ethers of carboxylic acids and especially esters of carboxylic acids with glycols or monoalkyl ethers of oligoglycols. Butyl diglycol acetate is one of the most prolific members of this group. The combination of low pigmentation and high solvent content has a particularly detrimental effect on the wet adhesion of the dispersion paint layers.

Inadequate wet adhesion results in the layers classified as washable per se no longer possessing this property if applied to smooth, non-absorbent substrates, such as old alkyd resin or oil paint surfaces. In damp rooms, such as kitchens or bathrooms, and in many work areas where water condensation must be taken into account, new coats of paint can come off the substrate if sufficient wet adhesion is not provided. In addition, the lack of wet adhesion makes painting work difficult. For example, if a stone foot and the wall or walls above it and the ceiling are painted different colors, the first brush may be stained to a second color due to inaccurate brush control. In principle, these stains can be removed with a damp cloth. However, a lack of wet adhesion can then easily damage the first brush or remove it completely.

For these reasons, many experiments have been performed to modify plastic dispersions so that the dispersion paints made therefrom acquire the desired wet adhesion property. For example, it is known from DE 1 595 501 to prepare plastic dispersions by polymerizing suitable monomers in an aqueous emulsion, incorporating 0.2 to 15% by weight of comonomers, based on the total amount of monomers, of oxirane-containing compounds in the copolymer at room temperature and Suitable oxirane compounds are in particular glycidyl esters of acrylic or methacrylic acid, but also allyl glycidyl ether or vinyl glycidyl ether.

3 61038 The use of plastic dispersions of this kind gives dispersion dyes which already have a relatively good wet adhesion. However, for many uses, this wet adhesion is not yet sufficient.

It has now been found that the method according to the invention gives dispersions in which the wet adhesion of the paints and varnishes prepared to the absorbent substrate is particularly good. In the process according to the invention, a monomer mixture consisting of the following components is polymerized in an aqueous system: A) 20-80% by weight, preferably 40-60% by weight, based on the total amount of monomers, of curable monomers methyl methacrylate, styrene and / or vinyltoluene, B) 20-80% by weight %, preferably 40-60% by weight, of an emollient monomer based on the total amount of monomers, an acrylic acid ester having a linear or branched alkyl group having 2 to 8 carbon atoms in the alcohol group, or a conjugated diene containing 4 to 8 carbon atoms and optionally substituted by halogen, C) 0.1-5% by weight of acrylic acid, methacrylic acid, acrylamide and / or methacrylamide, the process being characterized in that the polymerization additionally uses D) 0.5-10% by weight of an acetic acid ester of the formula O 0 RR 'ch3-c-ch2-cxc = ch where X = -O-, -O-CH2' or -O-CH2-CH2-O-C- and R = H or CH2 and 0 R '= H or CH 2, or a weapon of hydroxypropyl acrylate or methacrylate tetikkahappoesteriä.

The plasticizers mentioned in B) are, for example, ethyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate or butadiene, isoprene or chloroprene.

The monomers mentioned in D) are, for example, acetylacetic acid vinyl ester, acetic acid allyl ester or acetic acid ester of β-hydroxyethyl acrylate or methacrylate or acetic acid ester of hydroxypropyl acrylate or methacrylate. Preferably 1-5% by weight of acetic acid ester is used, which is preferably acetic acid allyl ester.

4,61038

In dispersions prepared in an acidic range, it is often advantageous to adjust the pH to between 7.5 and 10 with ammonia or suitable amines, for example water-soluble tertiary amines, in order to improve storage stability and facilitate color preparation.

Plastic dispersions are very complex systems. The preparation of the high-grade dispersions according to the invention requires the use of experience based on emulsion polymerization, including those not specifically mentioned in this connection. Ignoring the rules known to those skilled in the art for emulsion polymerization can adversely affect important properties, such as the water resistance of dispersion films or brushed films. Thus, the dispersions must not substantially exceed the conventionally used amounts of ionic emulsifiers up to 3% and preferably up to 2% or up to 6% and preferably up to 4% of non-ionic emulsifiers.

As nonionic emulsifiers, for example, alkyl polyol glycol ethers such as lauryl, oleyl or stearyl alcohol or ethoxylation products of alcohol mixtures such as coconut fatty alcohol are used; alkylphenol polyglycol ethers such as ethoxylation products of octyl or nonylphenol, diisopropylphenol, triisopropylphenol or di- or tri-tert-butylphenol; or polypropylene oxide ethoxylation products.

Suitable ionic emulsifiers are primarily anionic emulsifiers. In this case, ammonium salts of alkyl, aryl or alkylaryl sulfonates, sulphates, phosphates, phosphonates or other compounds containing anionic end groups can be used, in which case the oligo- or polyethylene oxide units can also be located between the hydrocarbon residue and the anionic group. Typical examples are sodium lauryl sulphate, sodium octylphenol glycol ether sulphate, sodium dodecylbenzene sulphonate, sodium lauryl diglycol sulphate, ammonium tri-tert-butylphenol penta or octaglycol sulphate.

If desired, natural substances such as acacia, starch, alginates or modified natural products such as methyl, ethyl, hydroxyalkyl or carboxymethylcellulose or synthetic substances such as polyvinyl alcohol, polyvinylpyrrolidone or the like are used as the protective colloid. Preferably, modified cellulose derivatives and synthetic protective colloids can be used.

However, the addition of these protective colloids is only limited to those known to those skilled in the art when using the disclosed monomer systems. The amounts used are often small, 0.001-1%, and their suitability and method of addition must be tested on a case-by-case basis. If the use of protective colloids is necessary, the method described in, for example, DE 1 570 312 can be used.

Oil and / or preferably water-soluble radical generators or oxidation-reduction systems are used to initiate and continue the polymerization. Suitable are, for example, hydrogen peroxide, potassium or ammonium peroxide disulphate, dibenzoyl peroxide, lauryl peroxide, tri-tert-butyl peroxide, bis-azo-diisobutyronitrile alone or with reducing ingredients, for example sodium bisulphite ascorbic acid or glucose, glucose, glucose with the active compounds.

A particular advantage of the dispersions prepared according to the invention is that they are suitable for the preparation of glossy dispersion paints which have good wet adhesion to non-absorbent substrates and also have good saponification resistance.

Example 1

First prepare a monomer emulsion having the following composition: 310 parts by weight of water 6 parts by weight of sodium salt of lauryl alcohol di-glycol ether sulfate 12 parts by weight of methacrylic acid 6 parts by weight of acrylic acid 300 parts by weight of butyl acrylate 300 parts by weight of acetone 12 parts by weight allyl ester

The ingredients are mixed in a high speed mixer until a stable emulsion is formed. In a 2-liter three-necked flask located in a heat bath equipped with a stirrer, reflux condenser, dropping funnel and thermometer, a mixture containing 6 61038 303 parts by weight of water is heated to 3 parts by weight of lauryl alcohol di-glycol ether sulphate etherate sodium sulphate etherate C and a solution containing 0.45 parts by weight of ammonium peroxydisulphate in 15 parts by weight of water is added. The dosing of the remainder of the monomer mixture is then started and the polymerization is completed. The total dosing time is 2 hours, the polymerization temperature and the post-heating time are between 81-83 ° C. At the end of the monomer dosing, 0.15 parts by weight of ammonium peroxydisulphate in 5 parts by weight of water are added, further heated for 60 minutes and then cooled. The pH is then adjusted to 9.5 with 15 ml of 25% ammonia; the solids content is about 50 percent.

Example 2

The procedure is as strictly as described in Example 1, except that no acetic acid allyl ester is used in the polymerization.

Example 3

First prepare the following monomer emulsion: 310 parts by weight of water 9 parts by weight of ammonium tri-tert-butylphenol glycol ether sulphate containing 8 parts of ethylene oxide 12 parts by weight of methacrylic acid 6 parts by weight of acrylic acid 300 parts by weight of methylhexyl acylate part of acetic acid allyl ester

The mixture is stirred in a high speed mixer until a stable emulsion is formed. In the apparatus of Example 1, a mixture containing 306 parts by weight of water, 3 parts by weight of ammonium tri-tert-butylphenol polyglycol ether sulfate containing about 8 parts by weight of ethylene oxide units is heated to 81 ° C and a solution containing 0.45 parts by weight of ammonium peroxy di-sulphate in 15 parts by weight of water. The dosing of the remainder of the monomer emulsion is then started and the polymerization is completed. The total dosing time is 2 hours, the polymerization temperature and the temperature during post-heating are between 81-83 ° C.

7 61038

At the end of the monomer addition, 0.15 part by weight of ammonium peroxydisulphate in 5 parts of water is added, heated for 1 hour and cooled. The pH is then adjusted to 9.3 with 15 ml of 25% ammonia, the solids content being about 50%. Example 4

The procedure is as strictly as described in Example 3, except that no acetic acid allyl ester is used in the polymerization. Example 5

The following monomer mixture is prepared: 380 parts by weight of water 6 parts by weight of ammonium tri-tert-butylphenol polyglycol ether sulphate containing about 8 parts by weight of ethylene oxide 12 parts by weight of methacrylic acid 6 parts by weight of acrylic acid 12 parts by weight of acrylamide 450 parts by weight of acrylamide 450 part by weight of vinyl toluene 18 parts by weight of acetic acid allyl ester The mixture is stirred with a high-speed mixer until a stable emulsion is formed. In the apparatus of Example 1, a mixture containing 390 parts by weight of water containing 3 parts by weight of ammonium tri-tert-butylphenol glycol ether sulfate containing about 8 parts by weight of ethylene oxide glycol ether sulfate containing about 30 parts by weight of about 30 ethylene oxide units of nonylphenol polyglycol ether C and a solution containing 0.45 parts by weight of ammonium peroxy diisulphate in 15 parts by weight of water is added. The dosing of the remainder of the monomer emulsion is then started and the polymerization is completed. The total dosing time is 2 hours, the polymerization temperature and the temperature during the post-heating time are between 81-83 ° C. At the end of the monomer addition, 0.15 part by weight of ammonium peroxydisulphate in 5 parts by weight of water is added, heated for 60 minutes and cooled. The pH is then adjusted to 9.5 with 15 ml of 25% ammonia. The solids content is about 45 percent.

8 61038

Example 6

The procedure is as detailed as in Example 5, except that acetylacetic acid allyl ester is not used in the polymerization.

To prepare dispersion dyes with good wet adhesion, the dispersion is mixed with the pigment slurry. Pigment slurries, also called pigment doughs or pigment pastes, which are suitable for the production of low-pigmented dispersion dyes and in particular gloss dyes, consist, for example, of titanium dioxide uniformly slurried in water.

They regularly contain protective colloids such as cellulose derivatives and dispersants, for example salts of poly (meth) acrylic acid or sodium polyphosphate. Conventional ingredients in the pigment slurry further include antimicrobial preservatives, antifoams, pH stabilizers and fillers. Particularly suitable titanium dioxide pigments are rutile and anatase. In glossy dyes, it is important that the average particle diameter of the pigment particles is close to the lower limit of the wavelength of light, i.e. about 0.4-0.2 micrometers. In addition, special high surface area silicate pigments, for example, can be used in the production of low-pigmented, matt dyes. Matte colors rich in binder give paint surfaces that are easy to clean. The pigment paste may, of course, also contain colored pigments, but the desired color tone can also be adjusted by tinting the dispersion color containing the white pigment.

The pigment slurry can be prepared by known methods, for example by dispersing the pigment in a mixing device or also in ball and sand mills. When used in gloss paints, the pigment slurry must not contain significant amounts of pigment deposits, as they adversely affect the gloss.

Excipients, for example plasticizers, anti-rust agents, alkyd resins, thickeners or drying oils, can be added either to the dispersion or to the finished dispersion paint. Plasticizers are then not the solvents initially mentioned as film-forming agents, which have only a temporary effect, but compounds such as dibutyl phthalate, which lower the film-forming temperature and remain in the polymer for long periods of time. To study wet adhesion, gloss dyes were prepared according to the following preparation instructions.

9 61 O 3 8

Preparation instructions I

1. 41.0 parts by weight of water

15.6 parts by weight of a 3% aqueous solution of Xylose H 2 O.

Calgon N (solid) 0.4 parts by weight

Dispersant PA 30 3.0 parts by weight

Ammonia, 25% 1.0 part by weight Preservative 2.0 parts by weight

Defoamer 3.0 parts by weight

Titanium dioxide, grain size 0.2-0.4 micrometers 175.0 parts by weight of 1,2-propylene glycol 10.0 parts by weight are dispersed and then the 2nd dispersion (dry matter content 50%) was used 710.0 parts by weight and, if the pH is not above about 7, 2.0 parts by weight of 25% ammonia are added.

A mixture containing: 3. butyl diglycol acetate 10 parts by weight of 1,2-propylene glycol 27.0 parts by weight is then slowly added with stirring.

In step 1, said liquid or soluble ingredients, except 1,2-propylene glycol, are placed in a mixing vessel in that order, and the pigment is dispersed therein with a solvent. Finally, 1,2-propylene glycol is added. This pigment paste is prepared in a relatively large amount so as to guarantee the same conditions in mixtures with different dispersions, e.g. with regard to the dispersion of the pigment.

Preparation instructions II

Preparation II differs from Preparation I in an otherwise different composition of the solvent composition to be added to the finished dye (method step 3 in dye preparation) and then adding dye to a mixture containing 36.5 parts by weight of 1,2-propylene glycol, 13.5 parts by weight of butyl diglycol acetate and 20 parts by weight , 2,4-trimethylpentanediol-1,3-monoisobutyrate-1 (trade name: Texanol).

Preparation instructions III

Preparation III also differs from both of the above instructions in terms of the composition of the solvent mixture otherwise added to the finished dye, in which case the dye is added to a mixture containing 51.1 parts by weight of 1,2-propylene glycol, 18.9 parts by weight of butyl diglycol acetate and 20 parts by weight. part of 2,2,4-trimethylpentanediol-1,3-monoisobutyrate-1 (trade name; Texanol).

For the preparation of the individual colors, a corresponding proportion of the pigment paste was taken and mixed into a dispersion about one day old using a slow-rotating mixer using the methods mentioned in the preparation instructions above. The solvents mentioned in 3. were then added. After complete mixing, the colors were screened.

These gloss paints were applied after a standstill period of 1 day to glass sheets and steel sheets pre-sprayed with air-drying, glossy alkyd resin varnish, which was aged 24 hours after drying at 100 ° C. A membrane puller with a gap of 200 micrometers was used. After a 24 hour drying time, the gloss dyes were tested for wet adhesion according to both of the following procedures.

1) Abrasion test

A mechanical abrasive machine, for example disclosed in German patent publication DE 2 262 956, which resembles a Gardner-Washability and Abrasion device, but with a path length of about 1.20 m, is placed with prefabricated glass sheets so that the brushed dispersion paint film is perpendicular to the brushes. Thanks to the length of the path, about 15 colors can be examined simultaneously in one experiment. Use pig brushes moistened with distilled water at the beginning of the experiment. During the test, distilled water is also added to the path of the brushes so that the trace of the brush is always covered by the water film. When the wet adhesion is unsatisfactory, the dispersion arm detaches from the substrate after a few movements of the brush and tears at the wet-dry film interface. The farther the brushes move before the film comes off, the better the wet adhesion. Optimal wet adhesion is achieved when, after 5000 brushing movements (1 brushing movement is a reciprocating movement), the film of the moistened brushing jar has not yet come off.

2) Condensation test In this case, use a rectangular thermostat half-filled with water at 50 ° C and fitted with a fan in the gas space above the surface of the water. The pre-treated steel plates are placed in the opening above - the test surface of the 61038 to be tested downwards - and thus close the opening. The thermostat is located in a room at 23 ° C. Due to the temperature difference, water vapor condenses on the lower surface of the plates and affects the glossy color films. After each exposure time of 15 minutes, the plates are removed and inspected.

Unsatisfactory wet adhesion occurs with the formation of bubbles between the dispersion paint and the alkyd resin varnish and the easy detachability of the film, for example using a thimble. With good wet adhesion, the film is still bubble-free after 6 hours and cannot be removed. The test results are shown in Table I.

Table I

Summary of test results

Example Preparation instructions Abrasion test Resistance to condensation

No No double brush strokes in the experiment number 1 I> 5000> 6 hours 2+ I 110 <15 minutes 3 I> 5000> 6 hours II> 5000> 6 hours III> 5000> 6 hours 4+ I 70 15 minutes 5 I> 5000> 6 hours 6+ I 50 <15 minutes +) non-inventive comparative test Example 7 A color solution containing: 3090 g of distilled water 80.5 g of sodium dodecylbenzenesulphonate 15 g of potassium persulphate 3 g of sodium hydroxide (solid) is placed in a 16-liter pressure cooker equipped with a plate mixer

The solution and the entire apparatus are purged with nitrogen and the other procedural steps are also performed in an inert gas atmosphere.

A mixture containing 1200 g of butadiene, 1560 g of styrene and 90 g of acetic acid allyl ester is pumped from the precursor into a pressure vessel.

The mixer is started (approx. 300 rpm) and heating is started.

At a temperature of 70 ° C (internal pressure of about 10 bar) is polymerized for 2 1/2 hours and then a solution containing 40 g of sodium dodecylbenzenesulphonate and 750 g of distilled water is added by pumping.

After a further 2 hours of polymerization at 70 [deg.] C., a solution containing 15 g of potassium persulfate in 250 g of distilled water is added and then a mixture containing 180 g of styrene and 60 g of acrylic acid is metered in over a period of about 15 minutes.

The post-reaction time is 3 hours (also at 70 ° C). Finally, the vessel is cooled, aerated and the product is filtered.

The solids content is about 42%. The amount of coagulate is small.

Example 8

The procedure is as in Example 7, except that the total amount of styrene (1740 g) is replaced by vinyl toluene.

Example 9

The procedure is as described in Example 7, except that half of the amount of styrene (780 g in the pre-vessel and 90 g in the post-dose) is replaced by vinyl toluene.

Non-inventive comparative example

The procedure is as described in Example 7, except that acetic acid allyl ester is not used and the amount of water in the dispersion dye solution is reduced by 90 grams to 3000 grams.

To prepare a dispersion dye with good wet adhesion, the dispersion is mixed with the pigment slurry. Pigment slurries, also called pigment doughs or pigment pastes, which are suitable for use in low pigmented dispersion dyes, and in particular gloss dyes, consist, for example, of titanium dioxide uniformly slurried in water.

They regularly contain protective colloids such as cellulose derivatives, for example hydroxyethylcellulose, and dispersants, for example salts of poly (meth) acrylic acid or sodium polyphosphate. Conventional pigment slurry ingredients further include antimicrobial preservatives, defoamers, pH stabilizers and fillers. In glossy dyes, it is important that the average particle diameter of the pigment is close to the lower limit of the wavelength of light, i.e. about 0.4-0.2 micrometers. In addition, special high-surface area silicate pigments, for example, can be used in the production of low-pigmented matt dyes. Matt paints with a high content of 13 61 0 38 binders give paint surfaces that are easy to clean. In addition, the pigment paste may contain naturally colored pigments, but the desired color tone can also be achieved by tinting a dispersion color containing a white pigment.

The pigment slurry can be prepared by known methods, for example by dispersing the pigment in a mixing device or also in a ball or sand mill. When used in gloss paints, the pigment sludge must not contain significant amounts of pigment deposits, as these have a detrimental effect on gloss.

Excipients, for example plasticizers, crosslinking agents, buffers, thickeners, thixotroping agents, anti-rust agents, alkyd resins or drying oils can be added to either the dispersion or the finished dispersion paint. The plasticizers are then not the solvents known at the beginning, known as film-forming agents, which have only a temporary effect, but compounds, such as dibutyl phthalate, which lower the film-forming temperature and remain in the polymer for long periods.

To study wet adhesion, gloss dyes were prepared according to the following manufacturing instructions.

1. 41.0 parts by weight of water

O

15.6 parts by weight of a 3 **% aqueous solution of Tylose H 20

Calcon N (solid) 0.4 parts by weight

Dispersant PA 30 3.0 parts by weight

Ammonia, 25% 1.0 part by weight Preservative 2.0 parts by weight

Defoamer 3.0 parts by weight

Titanium dioxide, grain size 0.2-0.4 micrometers 175.0 parts by weight of 1,2-propylene glycol 10.0 parts by weight were dispersed and then the 2nd dispersion (dry matter content 42%) was used 843.0 parts by weight and, if the pH was not above 7, 2.0 parts by weight of 25% ammonia were added.

Finally, a mixture containing was added slowly with stirring

Butyl diglycol acetate 10.0 parts by weight 1,2-propylene glycol 27.0 parts by weight.

In step 1, said liquid or soluble ingredients, 61038 except 1,2-propylene glycol, were placed in a mixing vessel in that order and then the pigment was dispersed with stirring. Finally, 1,2-propylene glycol was added. This pigment paste was prepared in a rather large amount so that when mixed with different dispersions to be tested, the same conditions can be guaranteed, for example with regard to the dispersion of the pigment.

For the preparation of individual colors, an appropriate proportion of the pigment paste was taken and mixed with a dispersion about 1 day old according to the procedures mentioned in the above-mentioned instructions using a slow-rotating mixer. After complete mixing, the colors were screened. After a standstill period of 1 day, these gloss dyes were applied to glass sheets and steel sheets pre-sprayed with air-drying, pigmented, glossy alkyd resin varnish which had been aged for 24 hours at 100 ° C after drying. Film-drawn ice with a gap of 200 micrometers was used. After a drying time of 24 hours, these Glossy Inks were formulated for wet adhesion by both of the following methods.

1) Abrasion test

In a mechanical abrasive machine, for example in German patent publication DE 2 262 956, which resembles a Gardner-Washability and Abrasion device but has a path length of about 1.20 m, prefabricated glass sheets are placed so that the brushed dispersion paint film is perpendicular to the direction of travel of the brushes. the length allows about 15 colors to be examined simultaneously in one experiment. Use pig bristle brushes moistened with distilled water at the beginning of the experiment. During the test, distilled water is also added to the path of the brushes so that the trace of the brush is always covered by the water film. When the wet adhesion is unsatisfactory, the dispersion paint detaches from the substrate after a few brush movements and tears at the wet-dry film interface. The farther the brushes move before the film comes off, the better the wet adhesion. Optimal wet adhesion is achieved when, after 5000 brushing movements (1 brushing movement is a reciprocating movement), the film has not yet come off the moistened brushing ice.

2) Condensation test In this case, a rectangular thermostat 61038 15 w is half-filled with water at 50 ° C and a fan is installed in the gas space above the upper surface of the water. In the opening above, the pre-treated steel plates are placed - the surface to be tested downwards - and thus close the opening. The thermostat is located in a room maintained at 23 ° C. As a result of the temperature difference, water vapor condenses on the underside of the plates and affects the glossy color films. The plate is removed after an exposure time of 15 minutes each time and inspected. Unsatisfactory wet adhesion occurs with the formation of bubbles between the dispersion paint and the alkyd resin varnish and the easy peelability of the film, for example using a thimble. With good wet adhesion, the film is still bubble-free after 4 hours and does not come off.

The test results are shown in Table II.

Table II

Summary of Test Results Example Abrasion test

Well double brush pulls Resistance in condensation test number 1> 3000> 4 hours 2> 3000> 4 hours 3> 3000> 4 hours 4+ 170 <15 minutes +) non-inventive comparative example

Example 10

Example 1 is repeated using 2- (acetoacetyloxy) ethyl methacrylate instead of acetic acid allyl ester.

Example 11

Example 3 is repeated using 2- (acetoacetyloxy) propyl crotonate instead of acetylacetic acid allyl ester.

Example 12

Example 5 is repeated, replacing 18 parts of acetic acid allyl ester with 12 parts of 2- (acetoacetyloxy) propyl acrylate.

Example 13

Example 1 is repeated in which 12 parts of acetic acid allyl ester are replaced by 18 parts of 2- (acetoacetyloxy) propyl methacrylate and the amount of water in the monomer emulsion is 316 parts.

Example 14

Example 3 is repeated using 2- (acetoacetyloxy) ethyl crotonate instead of the acetylacetic acid allyl ester. Example 15

Example 5 is repeated using 2- (acetoacetyloxy) ethyl acrylate instead of acetic acid allyl ester. Test results

According to the above preparation instructions, gloss dyes were prepared from the dispersions obtained in Examples 10-15. The test results are shown in Table III,

Table III

Example Preparation instructions Abrasion test Durability

No No condensation number of double brush strokes in the test 10 I> 5000> hours III> 5000> hours 11 II> 5000> hours 12 I> 5000> hours II> 5000> hours 13 III> 5000> hours 14 I> 5000> hours 15 I> 5000> hours

Claims (3)

17 61 038 A process for the preparation of aqueous plastic dispersions suitable for the preparation of paints with good wet adhesion, in which the following monomers are copolymerized: A) 20-80% by weight, preferably 40-60% by weight, based on the total amount of monomers, -80% by weight, preferably 40-60% by weight, based on the total number of monomers, of an emollient monomer which is an acrylic acid ester having a linear or branched alkyl having 2 to 8 carbon atoms in the alcohol group, or a conjugated diene containing 4 to 8 carbon atoms, and optionally substituted by halogen, C) 0.1-5% by weight of acrylic acid, methacrylic acid, acrylamide and / or methacrylamide, characterized in that D) 0.5-10% by weight of an acetic acid ester of the formula OORR 'ch3-c- ch2-cxc = ch 0 tr where X is -O-, -O-Cl · ^ - or -O-Cl 2 -Cl 2 -O-C and R is H or CH 2 and R 'is H or CH 2, or an acetic acid ester of hydroxypropyl acrylate or methacrylate. Process according to Claim 1, characterized in that 1 to 5% by weight of acetic acid ester is used in the polymerization. Process according to Claim 1 or 2, characterized in that acetic acid allyl ester is used as the acetic acid ester.