DK146477B - APPLICATION OF ARTIFICIAL DISTRIBUTIONS AS A BINDING AGENT IN LOW PIGMENTED COATING COLORS - Google Patents

Description

(19) DENMARK (cf |)

§ (12) SUBMISSION WRITING on 146477 B

PATENT DIRECTORATE. AND THE TRADE BRAND

(21) Patent Application No .: 3561/76 (51) Int.CI.3: C09D 5/00 (22) Filing Date: augβ Aug 1976 C 09 D 3/727 (41) Aim. available: 09 Feb 1977 (44) Submitted: 17 Oct 1983 (86) International Application No: - (30) Priority: 08 Aug 1975 DE 2535373 (71) Applicant: 'HOECHST AKTIENGESELLSCHAFT; 6230 Frankfurt / Maln 80, DE.

(72) Inventor: Helmut * Brown; DE, Helmut 'Rinno; DE, Werner 'Stelzel; THE.

(74) Plenipotentiary: The engineering firm Budde, Schou & Co (54) Use of plastic dispersions as a binder in low pigmented smear colors

The problem of dispersion dye wet adhesion on smooth, non-absorbent substrates has for a long time limited the use of certain dispersion dyes. Low pigmented dispersion paints, and among them again especially those which dry up to shiny or silky matte films, are poorly adhered to smooth, non-sugary substrates when the smears are moistened again after drying. Particularly bad is the wet adhesion of fresh smears that are not yet aged.

£ Low pigmented dispersion paints are selected in those cases where the smear should be washable. Due to the high binder content in these colors, a closed, washable film is formed.

^ Shiny or silky matte dispersion paints also have a pigment volume concentration of less than 40% and usually of approx. 10 - 25%.

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For enhancing gloss, flowability and "open time" (the time when a freshly applied film is still wet on the surface, ie a closed film has not yet formed) and as a film consolidation agent (agent which helps to firm the film after smears), they additionally contain larger amounts of organic solvents, approx. between 3 and 20%. Gloss, flowability and open time are affected e.g. using polyhydric water miscible alcohols with up to 6 carbon atoms, in particular ethylene and propylene glycol or monomethyl, monoethyl or monobutyl ethers thereof. To improve the film consolidation, limited water-soluble solvents such as the monoglycol ethers of carboxylic acids and especially esters of are used. carboxylic acids with monoalkyl ethers of glycols or oligoglycols. Butyldiglycol acetate is one of the most widespread representatives of this group. The combination of low pigmentation and higher solvent content has a particularly negative effect on the wet adhesion of the dispersion dye smears.

Defective wet adhesion means that the smears intended to be washable are no longer in possession of this property when applied to smooth, non-absorbent substrates, e.g. on old alkyd resin or oil paint smears.

In damp rooms, such as kitchens or bathrooms and many industrial premises where condensation water is to be formed, the new wipe can detach from the substrate when insufficient wet adhesion is provided. Finally, a defective wet stitching makes the ironing work difficult. For example, The plinth and the top half or wall and ceiling are done in different colors, it may happen that the first coat is soiled with a different color due to inaccurate brushing. In principle, these dirt can be removed with a damp cloth or sponge. However, in the case of defective wet stitching, the first wipe is easily damaged or pushed off completely.

For these reasons, attempts have not been made to modify plastic dispersions such that the dispersion dyes produced with these dispersion colors have the desired wet adhesion. Numerous monomers containing special functional groups (eg, certain cycloureides, oxazolidines, azomethines or aziridines) have been proposed as comonomers in the emulsion polymerization to improve dispersion dye wet adhesion on non-absorbent substrates.

To improve wet adhesion, it is also suggested by embedded amino groups in the polymer chains of emulsion polymers, by using comonomers with special reactive groups, e.g. oxirane groups or groups with nucleophilic substitutable halogen atoms, in the emulsion polymerization and only after the polymerization is completed introduce the amino groups into the polymer unit by reaction with ammonia or amines.

However, dispersion smears containing such amino group-containing polymers as binder frequently have a tendency to yellowing symptoms. Furthermore, wet adhesion is often only slightly improved. At low pigmentation, many of these colors give smears that are sufficiently adhered to a smooth, non-absorbent surface, but if organic solvents are added to these colors, smears produced therefrom have far from any wet adhesion.

German Patent Specification No. 1,495,706 discloses synthetic dispersions in which the polymerization fraction contains monomers containing keto groups, via which a crosslinking with e.g. dicarboxylic acid bis-hydrazides are possible. These dispersions are used e.g. within the textile refinement for the production of purification-resistant plains or in the ironing technique for the production of solvent-resistant dyes.

It has now been found that low pigmented, high wet adhesive solvent-containing smears appear when using as a binder, plastic dispersions made by polymerization of olefinically unsaturated monomers, including a keto group-containing compound, in aqueous medium containing gaseous emulsion containing gum and protective colloids having a solids content of 20-70% and containing in the polymerization portion a polymerizable acetic acid ester as a comonomer.

Accordingly, the invention relates to the use of plastic dispersions thus prepared as binders in low pigmented, high wet adhesive stripping paints, the use of which is (a) used in the preparation of the plastic dispersion as a copolymerizable acetate the proportion of acetic acetic ester is 0.5-10% by weight of all monomers, (b) the pigment volume concentration is 7-30% of the smear color, and (c) the solvent is an organic solvent whose amount is 3-20% by weight of the smear color.

The acetic acetic esters contained as comonomers in the plastic dispersions to be used according to the invention are preferably acetic acetic acid vinyl or allyl esters or diesters of the general formula 4-O-R-CH = CC-O-AC-CH 2 -C-CH 3 where R is H or CH 2, and A is - (C 1 -C 4 - or - (C 1 -C 4 - O-, where 1 - n - 4, and 1 - m · έ: 3). Based on the total weight of all monomers, the proportion of acetate acetic acid is 0.5-10% by weight, preferably 1-5% by weight.

Instead of a single dispersion, mixtures of different dispersions may be used, however, at least one of which must contain the polymer-bound acetate acetic ester, namely in such an amount that the acetic acetic ester is present in the above amounts, based on the total weight of all the mixture contained monomers.

In the sense of the invention, low pigmented dispersion colors are dispersion colors whose pigment volume concentration is between .7 and 30%, preferably between 10 and 20%.

In the present invention, organic solvents are glycols and derivatives thereof, e.g. ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, oligoglycols such as di- or triglycol, glycol or oligoglycol ethers such as methyl, ethyl, propyls or butyl mono-, di- or tri-glycol ethers, mono-, di or triglycol esters such as mono-, di- or tri-glyco1-acetate, propionate or butyrate and (oligo-) glycol-half-ether-half-esters such as methyl, ethyl, propyl or butyl mono-, di- or tri-glycol acetate, propionate or butyrate. Also, mixtures of such compounds must be organic solvents within the meaning of the invention. The organic solvents are added to the color in an amount of from 3 to 20% by weight, preferably 5 to 15% by weight, based on the total weight of the color.

The aqueous plastic dispersions have a solids content of between 20 and 70%, preferably between 40 and 60%. Incidentally, the aqueous plastic dispersions are customarily prepared by methods known to those skilled in the art.

The choice of the other monomers is not critical. In speech, all monomers used in plastic dispersions are commonly used, which can be combined in a sensible way with each other according to the demands made in practice. Suitable for example. vinyl esters of organic carboxylic acids whose carbon backbone contains 1-30, preferably 1-20, carbon atoms, e.g. vinyl acetate, vinyl propionate, iso-nonanoic acid vinyl ester and vinyl esters of branched-chain monocarboxylic acids of up to 20 carbon atoms, esters of acrylic acid or methacrylic acid having 1 to 30, preferably 1-20, carbon atoms in the alcohol group, 5 146477 such as ethyl acrylate, isopropyl acrylate, ethyl hexyl acrylate, methyl methacrylate, butyl methacrylate, aromatic or aliphatic α, β-unsaturated hydrocarbons such as ethylene, propylene, styrene, vinyl toluene, vinyl halides such as vinyl chloride, unsaturated nitriles, such as acrylonitrile or diesters of maleic acid, diesters of maleic acid, diesters of maleic acid, diesters of maleic acid, diesters of maleic acid. dibutyl fumarate, α, β-unsaturated carboxylic acid such as acrylic acid, methacrylic acid or crotonic acid and derivatives thereof such as acrylamide or methacrylamide.

In selecting the appropriate monomer or monomer combinations, the generally accepted views for the preparation of smear dispersions must be taken into account. In particular, care must be taken that polymers are formed which, under the established drying conditions for the color, form a film and the choice of the monomers for the production of copolymers must be made so that, according to the position of the polymerization parameters, formation of copolymers with the keto group-containing monomers can be expected. . Listed below are some suitable monomer combinations: ethyl acrylate / methyl methacrylate / (meth-) acrylic acid / acetic acid allyl ester, isopropyl acrylate / methyl methacrylate / (meth-) acrylic acid / acetacetic acid acrylic acid ester, butyl acrylate / methyl acrylic acid / methylmethacrylate / (meth) acrylic acid / acetacetic acid allyl ester, 2-ethylhexylacrylate / methylmethacrylate / (meth) acrylic acid / acetacetic acid acrylic acid ester, ethyl acrylate / styrene / methylmethacrylate / (methyl) acrylic acid / acetacetic acid / / ((meth) acrylic acid / acetic acid acetic acid ester, 2-ethylhexyl acrylate / styrene / (meth-) acrylic acid / acetic acid acrylic ester, vinyl acetate / butyl acrylate / acetic acid acyl acetate / vinyl acetate / acetic acid / acetic acid / acetic acid / acetate , vinyl acetate / 2-ethylhexanoic acid vinyl ester / acetacetic acid allyl ester, vinyl acetate / versatin 10 acid vinyl ester / Acetic Acid Allyl Ester, Vinyl Acetate / Ethylene / Acetic Acid Allyl Ester and Vinyl Acetate / Ethylene / Vinyl Chloride / Acetic Acid Allyl Ester.

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Plastic dispersions are extremely complex systems. The preparation of dispersions suitable for the invention. targets, assuming the experience of the field of emulsion polymerization, even though not specifically described herein. Ignoring the rules known to one of ordinary skill in the art of emulsion polymerization can therefore affect important properties, e.g. the water resistance, in an unfavorable direction. Therefore, based on the polymer content, the dispersions should not exceed the commonly used amounts of up to 3%, preferably up to 2%, ionic emulsifiers or up to 6%, preferably up to 4%, non-ionic emulsifiers.

As nonionic emulsifiers, e.g. alkyl polyglycol ethers, e.g. the ethoxylation products of lauryl, oleyl or stearyl alcohol or of mixtures such as coconut fatty alcohol, alkylphenol polyglycol ethers, such as the ethoxylation products of octyl or nonylphenol, diisopropylphenol, triisopropylphenol or of di- or tri-tertylene or tert-butylphenol

Speaking as ionic emulsifiers comes primarily anionic emulsifiers. These may be the alkali metal or ammonium salts of alkyl, aryl or alkyl aryl sulfonates, sulfates, phosphates, phosphonates or compounds with other anionic end groups, as there may also be oligo or polyethylene oxide units between the hydrocarbon group and the anionic group. Typical examples are sodium lauryl sulfate, sodium octylphenol glycol ether sulfate, sodium dodecylbenzenesulfonate, sodium lauryl diglycol sulfate, ammonium tri-tert.butylphenol penta or octaglycol sulfate.

As protective colloids, natural substances such as gum arabic, starch, alginates or modified natural substances such as methyl, ethyl, hydroxyalkyl or carboxymethyl cellulose, or synthetic compounds such as polyvinyl alcohol, polyvinylpyrrolidone, or mixtures of such compounds are optionally used. Preferably, modified cellulose derivatives and synthetic protective colloids may be used.

To initiate and carry on the polymerization, oil and / or preferably water-soluble radical formers or redox systems are used. Suitable are e.g. hydrogen peroxide, potassium or ammonium peroxide disulfate, dibenzoyl peroxide, lauryl peroxide, tert-butyl peroxide, bis-azodiisobutyronitrile, alone or together with reducing components, e.g. sodium bisulfite, rongalite, glucose, ascorbic acid and other compounds having a reducing effect.

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In the present application of the specified plastic dispersions in high wet stripping strokes, the dispersions are mixed with a pigment slurry. Such pigment slurries, also called pigment doughs or pigment pastes, which are suitable for use in low pigmented dispersion colors and especially gloss colors, consist e.g. of titanium dioxide uniformly dispersed in water. They usually contain protective colloids such as cellulose derivatives, e.g. hydroxyethyl cellulose, and dispersants, e.g. salts of poly (meth) acrylic acid or sodium polyphosphate. Furthermore, common ingredients in the pigment slurry are antimicrobial preservatives, antifoam agents, pH stabilizers and fillers. Particularly suitable titanium dioxide pigments are rutile and anatase. For gloss colors, it is important that the average particle diameter of the pigment is close to the lower limit of the light wavelength, ie. know from approx. 0.4 to 0.2 µ. For the manufacture of low pigmented matte colors, for example, while using special surface-rich silicate pigments. Binder-medium matte colors provide smudges that are easy to clean. The pigment paste may, of course, also contain colored pigments, but the desired tint can be adjusted just as well by fading the dispersion color with white pigment.

The pigment slurry can be prepared by the known methods, e.g. by dispersing the pigment in a dissolver or on ball or sand mills or by rolling mills. For use in gloss colors, the pigment slurry must not contain significant amounts of pigment aggregates because these adversely affect the gloss.

For either the dispersion or the finished dispersion color, adjuvants, e.g. plasticizers, cross-linking agents, buffering agents, thickeners, thixotropic agents, antifouling agents, alkyd resins or drying oils. In this case, plasticizers are not the solvents initially referred to as film consolidation agents with only temporary effect, but compounds such as dibutyl phthalate which lower the film formation temperature and remain in the polymer for a long time.

The examples described below serve to illustrate the invention.

Example 1 In a 2 liter three-necked flask, which is in a hot bath, equipped with a stirrer, reflux, drip funnel and thermometer, stir with stirring a dispersion float consisting of 146477 8603 parts by weight 18 parts by weight polyvinyl alcohol with a degree of hydrolysis of 88 mole percent. and a viscosity of the 4% aqueous solution at 20 ° C of 18 cP 0/9 parts by weight of sodium vinyl sulfonate 6 parts by weight of sodium dodecylbenzenesulfonate 0.72 parts by weight Nal

1.67 parts by weight · 12 I ^ O

1.5 parts by weight of ammonium peroxide disulfate and 60 parts by weight of vinyl acetate, thereby initiating polymerization. When the temperature has risen to 70 ° C, the dosing of a mixture starting from 540 parts by weight of vinyl acetate and 18 parts by weight of acetic acetic acid allyl ester is started. The total dosing time is approx. 3 hours.

After completion of the monomer addition, reheat at the polymerization temperature (70 ° C) for an additional 2 hours with continued stirring and then cool the mixture.

Example 2 (Comparative Example)

Proceed in exactly the same manner as described in Example 1, but no acetic acetic acid allyl ester is added.

Example 3 In an apparatus such as that described in Example 1, a dispersion float consisting of 607 parts by weight of water 18 parts by weight of oleyl polyglycol ether is heated by approx. Ethylene oxide units 0.2 parts by weight of sodium dodecylbenzenesulfonate 12; parts by weight of hydroxyethyl cellulose with an average degree of polymerization of approx. 400 (mol. Wt. About 100,000) 1/5 parts by weight of sodium acetate 2.5 parts by weight of ammonium peroxide disulfate and 60 parts by weight of a monomer mixture taken from a mixture of 450 parts by weight of vinyl acetate, 150 parts by weight of iso-nonanoic acid vinyl ester and 12 parts by weight of acetic acid allyl ester, to 70 ° C, and at this temperature, the remaining monomer mixture (552 parts by weight) is dosed over 3 hours. After dosing, 0.5 parts by weight of ammonium peroxide disulfate is added in 15 parts by weight of water and then heated for 2 hours. Adhesive content is at approx. 50%.

Example 4 (Comparative Example)

Proceed in exactly the same manner as described in Example 3, but no acetic acetic acid allyl ester is added.

Example 5 In an apparatus such as that described in Example 1, a dispersion float consisting of 618 parts by weight of water 18 parts by weight of nonylphenol polyglycol ether is heated by approx. 30 parts of ethylene oxide 1.5 parts by weight of sodium acetate 12 parts by weight of hydroxyethyl cellulose with an average polymer in degree of approx. 400 (molar weight approx. 100,000) 2.5 parts by weight of ammonium peroxide disulfate 62 parts by weight (10%) of a monomer mixture consisting of 480 parts by weight of vinyl acetate, 120 parts by weight of dibutyl malinate and 18 parts by weight of acetic acid allyl ester to 70 ° C and the remaining monomer mixture dosed over 3 hours. . After dosing, 0.5 parts by weight of ammonium peroxide disulfate is added in 15 parts by weight of water and then heated for 2 hours. The solids content is at approx. 50%.

Example 6 (Comparative Example)

Proceed in exactly the same manner as described in Example 5, but no acetic acetic acid allyl ester is added.

Example 7 In an apparatus such as that described in Example 1, a dispersion float consisting of 146477 10 636 parts by weight of water 18 parts by weight of nonylphenol polyglycol ether is heated by approx. 30 ethylene oxide units

12 parts by weight of polyvinyl alcohol with the degree of hydrolysis 88 mole percent and a viscosity of the 4% aqueous solution at 20 ° C at 18 cP

0.9 parts by weight sodium vinyl sulfonate 1.5 parts by weight sodium acetate 2.5 parts by weight ammonium peroxide disulfate 48 parts by weight vinyl acetate 12 parts by weight versatin-10-acid vinyl ester and 1.2 parts by weight of acetic acid aryl ester at 70 ° C, and at this temperature a mixture is dispensed from 432 parts by weight of vinyl acetate, 108 parts by weight. -10-acid vinyl ester and 18 parts by weight of acetic acid allyl ester over 3 hours. After dosing, 0.5 parts by weight of ammonium peroxide disulfate is added in 15 parts by weight of water and then heated for 2 hours. The solids content is at approx. 50%.

Example 8 (Comparative Example)

Proceed in exactly the same manner as described in Example 7, but no acetic acetic acid allyl ester is added.

Example 9

First, a monomer emulsion of the following composition is prepared: 308 parts by weight of water 6 parts by weight of ammonium tri-tert.butylphenol polyglycol ether sulfate with approx. 8 parts ethylene oxide 12 parts by weight methacrylic acid 6 parts by weight acrylic acid 300 parts by weight 2-ethylhexyl acrylate 300 parts by weight methyl methacrylate and 12 parts by weight acetic acetic acid allylic ester are stirred with a fast stirrer until a stable emulsion is obtained.

In an apparatus such as that described in Example 1, a mixture of water parts 3 parts by weight of ammonium tri-tert.butylphenol polyglycol ether sulfate is heated from ca. 8 ethylene oxide units and 60 parts by weight of monomer emulsion to 81 ° C and a solution from 0.45 parts by weight of ammonium peroxy sulfate in 15 parts by weight of water are added. Next, the dosing of the remaining monomer emulsion is started and the polymerization is completed.

The total dosing time is 2 hours and the polymerization temperature and the temperature during the post-heating time are between 81 and 83 ° C. After completion of the monomer dose, 0.15 parts by weight of ammonium peroxide disulfate is added in 5 parts by weight of water, which is further heated for 60 minutes and then cooled. The solids content is approx. 50%.

Example 10 (Comparative Example)

Proceed in exactly the same manner as described in Example 9, but no acetic acetic acid allyl ester is added.

Example 11

First, a monomer emulsion of the following composition is prepared: 310 parts by weight of water 6 parts by weight of sodium salt of lauryl alcohol containing 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 styrene and 18 parts by weight of acetic acid aryl acetic ester is stirred with a fast stirring emulsion until a stable stirring is obtained.

In an apparatus such as that described in Example 1, a mixture is heated from 303 parts by weight of water 3 parts by weight of sodium salt of lauryl alcohol containing glycol ether sulfate and 62 parts by weight of the monomer emulsion to 81 ° C, and a solution of 0.45 parts by weight of ammonium peroxide disulfate in 15 parts by weight of water is added. Next, the dosing of the remaining monomer emulsion is started and the polymerization is completed.

The total dosing time is 2 hours, and the polymerization temperature and the temperature during the post-heating time are between 81 and 146 ° C. Upon completion of the monomer dosage, 0.15 parts by weight of aerosonic peroxide disulfate is added in 5 parts by weight of water, which is further heated for 60 minutes and then cooled. The adhesive content is approx. 50%.

Example 12 (Comparative Example)

Proceed in exactly the same manner as described in Example 11, but no acetic acetic acid allyl ester is added.

For testing the wet adhesion, gloss colors are prepared according to the recipe below.

1. Water 41.0 parts by weight 3% aqueous solution of 15.6 parts by weight "Tylose H 20" ® "Calgon N" ® (solid) 0.4 parts by weight

Dispersant PA 30 3.0 parts by weight

Ammonia, 25% 1.0 weight percent

Preservative 2.0 parts by weight

Anti-foaming agent 3.0 parts by weight

Titanium dioxide 175.0 parts by weight of grain size 0.2 - 0.4 μ 1.2- Propylene glycol 10.0 parts by weight is dispersed and then the second dispersion (at 50% solids - 710.0 parts by weight content) to which 2.0 parts by weight 25% is added ammonia if the pH does not exceed approx. 7th

With stirring, a mixture of 3. Butyldiglycol acetate 10.0 parts by weight 1.2- Propylene glycol 27.0 parts by weight is then slowly added.

The liquid or soluble constituents listed below, with the exception of the 1,2-propylene glycol, are first placed in a stirrer in the order in which the pigment is dispersed with a dissolver. Next, 1,2-propylene glycol is added. Of this pigment paste, a greater amount is produced to ensure the same conditions, e.g. with respect to the pigment dispersion, for the mixture with the various dispersions to be tested.

For the preparation of the individual colors, a corresponding proportion is extracted from the pigment paste, which in the method mentioned in the above recipe is mixed with the approx. 1 day old dispersions under a slow stirrer. Next, the solvents mentioned in 3. are added. Once finished, the colors are sieved.

After one day's stand, these gloss colors are applied to glass plates and to steel plates on which is already sprayed an air-drying, pigmented, glossy alkyd resin varnish which has been aged at 100 ° C for 24 hours after drying. A film applicator with a gap height of 200 µ is used. After 24 hours drying time for the gloss colors, these are tested for wet adhesion by the two methods described below.

1) Wear Testing On such a mechanical wear machine, such as. is described in German Publication No. 2,262,956, which is similar to Gardner's washable and abrasive machine, though with an approx.

1.20 m long running distance, the prepared glass sheets are placed in such a way that the applied dispersion color films are perpendicular to the brush direction of travel. Due to the length of the run, approx. 15 colors are examined simultaneously in one test run. A pig hairbrush is used, which is moistened with distilled water at the beginning of the test. During the test, distilled water is also dripped onto the running distance of the brush, so that the brush path is constantly covered with a water film. In case of insufficient wet adhesion, after a few brushing steps, the dispersion color is pushed away from the base of the brush and goes off at the boundary between moist and dry film. The wet adhesion is the better the longer the brush runs before the film is pushed off. Optimal wet adhesion exists when the film after 3000 brushing operations (1 brushing is a back and forth) has not yet been pushed off in the dampened brush web.

2) Condensation experiments

Here is used a right-angle thermostat, which is half filled with water at a temperature of 50 ° C, and in whose gas space above the water surface a fan is mounted. The top opening is coated with the prepared steel sheets - with the test surface facing down - and thereby closed. The thermostat is in a room maintained at 23 ° C.

At the temperature difference, water vapor condenses on the underside of the plates and affects the glossy color films. After 15 minutes in each case, the plates are picked up and evaluated.

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Insufficient wet adhesion appears in the formation of blisters between the dispersion color and the alkyd resin lacquer and in the film's easy peelability, e.g. with your fingertip. With good wet adhesion, the film is still blister-free and does not peel even after 4 hours. The test results are given in Table I.

Table I

Example Rubbing test Resistance at No._ number of double brush strokes condensation test 1> 3000> 4 hours 2+ 30 10 minutes 3> 3000> 4 hours 4+ 250 10 minutes 5 ^ 3000> 4 hours 6+ 120 15 minutes 7> 3000> 4 hours 8+ 50 <15 minutes 9> 3000> 4 hours 10+ 70 415 minutes 11> 3000> 4 hours 12+ 110 <^ 15 minutes 4.

comparative examples, not according to the invention.

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Example 13

Example 1 is repeated, however, using 2- (acetoacetyl) oxyethyl acrylate instead of acetic acetic acid allyl ester.

Example 14

Example 1 is repeated, however, using 2- (acetoacetyl) oxyethyl methacrylate instead of acetic acetic acid allyl ester.

Example 15

Example 1 is repeated, however, using 2- (acetoacetyl) ~ -oxypropylcrotonate instead of acetic acetic acid allyl ester.

Example 16

Example 1 is repeated, however, using 2- (acetoacetyl-oxy-propyl acrylate) instead of acetic acetic acid allyl ester.

Example 17

Example 1 is repeated, however, using 2- (acetoacetyl]) oxy-propyl methacrylate instead of acetic acetic acid allyl ester.

Example 18

Example 1 is repeated, however, using 18 parts by weight of 2- (acetoacetyl) oxyethylcrotonate instead of 18 parts by weight of acetoacetyl allyl ester and using 613 parts by weight of water.

Test Results.

In the manner set forth in Example 12, gloss colors prepared from Examples 13-18 are prepared and tested as in Example 12. The results of the tests are shown in Table II.

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Table II

Example Trimming test, Resistance at No._number of double brush stroke condensation test 13> 3000> * 4 hours 14> 3000 ^ 4 hours 15> 3000> 4 hours 16> 3000> 4 hours 17> 3000> 4 hours 18> 3000> 4 hours