Finely divided aqueous multistage polymer dispersion, method for the production thereof, and use thereof as a binder

Abstract

The present invention provides very finely divided polymer dispersions obtainable by at least one two-stage emulsion polymerization, wherein 1) an acid-rich first polymer P1 is prepared by a radical polymerization from a 1.sup.st composition comprising A) at least one monomer selected from the group of (cyclo)alkyl (meth)acrylates, vinylaromatics having up to 20 carbon atoms, a radically polymerizable compound selected from the group of ethylenically unsaturated nitriles having up to 20 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl halides having up to 10 carbon atoms, and vinyl ethers of alcohols containing 1 to 10 carbon atoms B) at least one ,-ethylenically unsaturated carboxylic acid C) at least one crosslinking monomer with a keto or aldehyde group D) optionally at least one adhesion promoter E) optionally tert-butyl acrylate F) optionally further monomers M in the presence of a chain link transfer agent, 2) the polymer P1 prepared under 1) is admixed with a base, 3) a hydrophobic polymer P2 is prepared by radical polymerization, in the presence of the polymer P1 treated under 2), from a 2.sup.nd composition comprising A) at least one monomer selected from the group of (cyclo)alkyl (meth)acrylates, vinylaromatics having up to 20 carbon atoms, a radically polymerizable compound selected from the group of ethylenically unsaturated nitriles having up to 20 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl halides having up to 10 carbon atoms, and vinyl ethers of alcohols containing 1 to 10 carbon atoms B) optionally at least one ,-ethylenically unsaturated carboxylic acid C) at least one crosslinking monomer with a keto or aldehyde group D) optionally at least one adhesion promoter, and also E) optionally further monomers M, 4) and by optional addition, subsequent to the polymerization of P1 and P2, of a water-soluble at least trifunctional alkoxylated polyamine, more particularly an ethoxylated and/or propoxylated triamine.

Claims

1. A polymer dispersion, obtained by at least one two-stage emulsion polymerization process comprising: 1) preparing an acid-rich first polymer P1 by a first stage radical emulsion polymerization from a 1.sup.st composition comprising: A) at least one monomer selected from the group consisting of a (cyclo)alkyl (meth)acrylate, a vinylaromatic having up to 20 carbon atoms, a radically polymerizable compound selected from the group consisting of an ethylenically unsaturated nitrile having up to 20 carbon atoms, a vinyl ester of a carboxylic acid containing up to 20 carbon atoms, a vinyl halide having up to 10 carbon atoms, and a vinyl ether of an alcohol containing 1 to 10 carbon atoms, B) at least one ,-ethylenically unsaturated carboxylic acid, C) at least one crosslinking monomer with a keto or aldehyde group, D) optionally at least one adhesion promoter, E) optionally tert-butyl acrylate, and F) optionally a further monomer M in the presence of a chain link transfer agent; 2) mixing the polymer P1 with a base; 3) preparing a hydrophobic polymer P2 by a second stage radical emulsion polymerization, in the presence of the polymer P1 obtained from 2), from a 2.sup.nd composition comprising A) at least one monomer selected from the group consisting of a (cyclo)alkyl (meth)acrylate, a vinylaromatic having up to 20 carbon atoms, a radically polymerizable compound selected from the group consisting of an ethylenically unsaturated nitrile having up to 20 carbon atoms, a vinyl ester of a carboxylic acid containing up to 20 carbon atoms, a vinyl halide having up to 10 carbon atoms, and a vinyl ether of an alcohol containing 1 to 10 carbon atoms, B) optionally at least one ,-ethylenically unsaturated carboxylic acid, C) at least one crosslinking monomer with a keto or aldehyde group, D) optionally at least one adhesion promoter, and E) optionally a further monomer M; and 4) subsequent to the polymerization of P1 and P2, adding a water-soluble at least trifunctional polyamine.

2. The polymer dispersion according to claim 1, wherein the water-soluble trifunctional polyamine is an ethoxy/propoxylated triamine, and a molar ratio of the ethoxy/propoxylated triamine to the keto- and/or aldehyde-functional monomer C), is 1:1 to 1:9.

3. The polymer dispersion according to claim 1, wherein a weight-average molecular weight of the polymerized monomers of the first stage polymerization is between 2 and 35 kDa, and a weight-average molecular weight of polymerized monomers of the second stage polymerization is greater than 50 kDa.

4. The polymer dispersion according to claim 1, wherein a weight ratio of the acid-rich polymer P1 to the hydrophobic polymer P2 ranges from 20/80 to 50/50.

5. The polymer dispersion according to claim 1, wherein the monomers of the first stage polymerization are selected such that the P1 has a glass transition temperature of greater than 50 C.

6. The polymer dispersion according to claim 1, wherein the monomers of the second stage polymerization are selected such that the polymer P2 has a glass transition temperature of at least 50 C. lower than that of the polymer P1.

7. The polymer dispersion according to claim 1, wherein the 1st composition comprises A) 33-93 wt % of at least one (cyclo)alkyl (meth)acrylate having a homopolymer Tg of greater than 50 C., and 0 to 60 wt % of a (cyclo)alkyl (meth)acrylate having a homopolymer Tg of less than 0 C., B) 5-15 wt % of at least one ,-ethylenically unsaturated carboxylic acid, C) 2-15 wt % of at least one crosslinking monomer with a keto or aldehyde group, D) 0-4 wt % of at least one adhesion promoter, E) 0-25 wt % of tert-butyl acrylate, and F) 0-10 wt % of monomer M, relative to 100 wt % of the monomers to be polymerized in the 1.sup.st composition.

8. The polymer dispersion according to claim 1, wherein the 2.sup.nd composition comprises A) 0-55 wt % of at least one (cyclo)alkyl (meth)acrylate and/or vinylaromatic monomer having a homopolymer Tg of greater than 50 C., and 44 to 99 wt % of a (cyclo)alkyl (meth)acrylate having a homopolymer Tg of less than 0 C., B) 0-2 wt % of at least one ,-ethylenically unsaturated carboxylic acid, C) 1-10 wt % of at least one crosslinking monomer with a keto or aldehyde group, D) 0-2 wt % of at least one adhesion promoter, E) 0-10 wt % of monomer M, relative to 100 wt % of the monomers to be polymerized in the 2.sup.nd composition.

9. The polymer dispersion according to claim 1, wherein tert-butyl acrylate is contained as a further monomer E) in the first stage polymerization in an amount of 1.5-2.5 wt %, based on a total weight of the 1.sup.st stage monomers used for the polymerization.

10. The polymer dispersion according to claim 1, wherein a particle size of the polymer P1 and/or of the polymer P2 is in a range of from 1 nm to 100 nm.

11. A method for producing the polymer dispersion according to claim 1, the method comprising: 1) preparing an acid-rich first polymer P1 from the 1.sup.st composition; 2) admixing the polymer P1 with a base; 3) preparing a hydrophobic polymer P2 from the 2.sup.nd composition in the presence of the polymer P1 obtained from 2); and 4) subsequent to the polymerization of P1 and P2, optionally adding a water-soluble at least trifunctional alkoxylated polyamine.

12. A coating material in the form of an aqueous composition, the coating material comprising i) at least one polymer dispersion according to claim 1, ii) optionally at least one (in)organic filler and/or an (in)organic pigment, iii) optionally an additive, and iv) water.

13. A coating composition, comprising the polymer dispersion according to claim 1.

14. A paint or a varnish, comprising the polymer dispersion according to claim 1.

15. The polymer dispersion according to claim 1, wherein a content of the ,-ethylenically unsaturated carboxylic acid in the first, acid-rich stage is from 5 to 15 wt % and a content of the ,-ethylenically unsaturated carboxylic acids in the second stage is from 0 to 2 wt %, based on the total monomers of the respective stages.

16. A polymer dispersion, obtained by at least one two-stage emulsion polymerization process comprising: 1) preparing an acid-rich first polymer P1 by a first stage radical emulsion polymerization from a 1.sup.st composition comprising: A) at least one monomer selected from the group consisting of a (cyclo)alkyl (meth)acrylate, a vinylaromatic having up to 20 carbon atoms, a radically polymerizable compound selected from the group consisting of an ethylenically unsaturated nitrile having up to 20 carbon atoms, a vinyl ester of a carboxylic acid containing up to 20 carbon atoms, a vinyl halide having up to 10 carbon atoms, and a vinyl ether of an alcohol containing 1 to 10 carbon atoms, B) at least one ,-ethylenically unsaturated carboxylic acid, C) at least one crosslinking monomer with a keto or aldehyde group, D) optionally at least one adhesion promoter, E) optionally tert-butyl acrylate, and F) optionally a further monomer M in the presence of a chain link transfer agent; 2) mixing the polymer P1 with a base; 2) preparing a hydrophobic polymer P2 by a second stage radical emulsion polymerization, in the presence of the polymer P1 obtained from 2), from a 2.sup.nd composition comprising A) at least one monomer selected from the group consisting of a (cyclo)alkyl (meth)acrylate, a vinylaromatic having up to 20 carbon atoms, a radically polymerizable compound selected from the group consisting of an ethylenically unsaturated nitrile having up to 20 carbon atoms, a vinyl ester of a carboxylic acid containing up to 20 carbon atoms, a vinyl halide having up to 10 carbon atoms, and a vinyl ether of an alcohol containing 1 to 10 carbon atoms, B) optionally at least one ,-ethylenically unsaturated carboxylic acid, C) at least one crosslinking monomer with a keto or aldehyde group, D) optionally at least one adhesion promoter, and E) optionally a further monomer M; and 4) subsequent to the polymerization of P1 and P2, optionally adding a water-soluble at least trifunctional polyamine and wherein a weight-average molecular weight of the polymerized monomers of the first stage polymerization is between 2 and 35 kDa, and a weight-average molecular weight of polymerized monomers of the second stage polymerization is greater than 50 kDa.

Description

(1) Further advantages and advantageous embodiments of the subjects of the invention are illustrated by FIG. 1 and elucidated in the description hereinafter. It should be borne in mind here that the drawing is merely descriptive in nature and is not intended to restrict the invention in any form whatsoever. In the drawing:

(2) FIG. 1 shows drawdowns onto glass of the formulation according to the invention after two-day drying at RT and two-hour contact with water.

(3) FIG. 1 shows four different coatings comprising the formulation of the invention on glass plate, to which, after drying at room temperature (RT) in the lower region, DI water (fully demineralized water) was placed. The formulations comprise a polymer dispersion with crosslinking monomer only in the first stage (CE 1A and 1C), and also this monomer in both stages (IE 1A and 1C, inventive). It can be seen that the coatings based on the polymer dispersions of the invention show no instances of destruction or damage of the surfaces.

(4) The invention is elucidated in more detail by the examples hereinafter.

INVENTIVE EXAMPLE 1 (IE1)

(5) A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25 C. (room temperature) under a nitrogen atmosphere with

(6) TABLE-US-00002 722.1 g of deionized water and 30.8 g of 15 wt % aqueous solution of sodium lauryl sulfate

(7) and this initial charge was heated to 80 C. with stirring. When this temperature had been reached, the entire feed 1 was added and stirring took place for 2 minutes. Thereafter feed 2 was commenced and was metered in over the course of 45 minutes. After the end of feed 2, polymerization was continued for 10 minutes, then feed 3 was added and stirred in for 10 minutes. The weight-average molecular weight of the polymer in a sample taken at this point in time was around 8.6 kDa. Subsequently feed 4a was commenced and was metered in 45 minutes. After that, immediately feed 4b and, in parallel with it, feed 5 were commenced and were metered in 45 minutes.

(8) Feed 1 (homogeneous solution of):

(9) TABLE-US-00003 55.8 g of deionized water and 4.2 g of sodium peroxodisulfate

(10) Feed 2 (homogeneous mixture of):

(11) TABLE-US-00004 369.5 g of deionized water 20.5 g of a 15 wt % aqueous solution of sodium lauryl sulfate 53.2 g of methacrylic acid 19.0 g of a 25 wt % solution of ureidomethacrylate in methyl methacrylate 331.7 g of methyl methacrylate 24.5 g of n-butyl acrylate 47.6 g of acetoacetoxyethyl methacrylate 21.9 g of 2-ethylhexyl thioglycolate

(12) Feed 3:

(13) TABLE-US-00005 42.1 g of a 25 wt % ammonia solution

(14) Feed 4a (homogeneous mixture of):

(15) TABLE-US-00006 181.8 g of deionized water 17.7 g of a 15 wt % aqueous solution of sodium lauryl sulfate 311.9 g of n-butyl acrylate 123.2 g of styrene 23.8 g of acetoacetoxyethyl methacrylate 6.3 g of allyl glycidyl ether

(16) Feed 4b (homogeneous mixture of):

(17) TABLE-US-00007 181.8 g of deionized water 17.7 g of a 15 wt % aqueous solution of sodium lauryl sulfate 311.9 g of n-butyl acrylate 123.2 g of styrene 23.8 g of acetoacetoxyethyl methacrylate

(18) Feed 5 (homogeneous solution of):

(19) TABLE-US-00008 9.3 g of deionized water and 0.7 g of sodium peroxodisulfate

(20) After the end of feeds 4b and 5, the polymerization mixture was left to react further at 80 C. for 30 minutes; then 117 g of deionized water were added and stirring was carried out at 80 C. for 60 minutes more.

(21) Subsequently a further 105 g of deionized water were added and the aqueous polymer dispersion obtained was cooled to room temperature. Lastly, the dispersion was filtered through a 125 m filter.

(22) The resulting 3307 g of the aqueous polymer dispersion had a solids content of 43.3 wt % and a pH of 7.4. The MFFT was 0 C. The weight-average molecular weight of the polymer of the dispersion was around 800 kDa. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 36 nm.

INVENTIVE EXAMPLE 1A (IE 1A)

(23) 500.0 g of inventive example 1 were introduced and with stirring

(24) 60.2 g of a 25 wt % aqueous solution of Jeffamin T403 (from Huntsman) were added. Stirring was continued for 10 minutes, after which the dispersion was filtered through a 125 m filter.

(25) Solids content of the mixture was 41.3 wt %, pH was 9.5.

INVENTIVE EXAMPLE 1B (IE 1B)

(26) 500.0 g of inventive example 1 were introduced and with stirring

(27) 40.5 g of a 25 wt % aqueous solution of Jeffamin T403 were added. Stirring was continued for 10 minutes, after which the dispersion was filtered through a 125 m filter. Solids content of the mixture was 42.3 wt %, pH was 8.7.

INVENTIVE EXAMPLE 1C (IE 1C)

(28) 500.0 g of inventive example 1 were introduced and with stirring

(29) 20.7 g of a 25 wt % aqueous solution of Jeffamin T403 were added. Stirring was continued for 10 minutes, after which the dispersion was filtered through a 125 m filter. Solids content of the mixture was 42.7 wt %, pH was 7.9.

INVENTIVE EXAMPLE 2 (IE2)

(30) A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25 C. (room temperature) under a nitrogen atmosphere with

(31) 728.0 g of deionized water and

(32) 30.8 g of 15 wt % aqueous solution of sodium lauryl sulfate

(33) and this initial charge was heated to 80 C. with stirring. When this temperature had been reached, the entire feed 1 was added and stirring took place for 2 minutes. Thereafter feed 2 was commenced and was metered in over the course of 45 minutes. After the end of feed 2, polymerization was continued for 10 minutes, then feed 3 was added and stirred in for 10 minutes. Subsequently feed 4a was commenced and was metered in 45 minutes. After that, immediately feed 4b and, in parallel with it, feed 5 were commenced and were metered in 45 minutes.

(34) Feed 1 (homogeneous solution of):

(35) TABLE-US-00009 55.8 g of deionized water and 4.2 g of sodium peroxodisulfate

(36) Feed 2 (homogeneous mixture of):

(37) TABLE-US-00010 369.5 g of deionized water 20.5 g of a 15 wt % aqueous solution of sodium lauryl sulfate 53.2 g of methacrylic acid 350.7 g of methyl methacrylate 24.5 g of n-butyl acrylate 47.6 g of acetoacetoxyethyl methacrylate 21.9 g of 2-ethylhexyl thioglycolate

(38) Feed 3:

(39) TABLE-US-00011 31.6 g of a 25 wt % ammonia solution

(40) Feed 4a (homogeneous mixture of):

(41) TABLE-US-00012 163.8 g of deionized water 17.7 g of a 15 wt % aqueous solution of sodium lauryl sulfate 310.1 g of n-butyl acrylate 121.8 g of styrene 23.8 g of acetoacetoxyethyl methacrylate 6.3 g of allyl glycidyl ether

(42) Feed 4b (homogeneous mixture of):

(43) TABLE-US-00013 197.8 g of deionized water 17.7 g of a 15 wt % aqueous solution of sodium lauryl sulfate 313.6 g of n-butyl acrylate 124.6 g of styrene 23.8 g of acetoacetoxyethyl methacrylate

(44) Feed 5 (homogeneous solution of):

(45) TABLE-US-00014 9.3 g of deionized water and 0.7 g of sodium peroxodisulfate

(46) After the end of feeds 4b and 5, the polymerization mixture was left to react further at 80 C. for 30 minutes; then 117 g of deionized water were added and stirring was carried out at 80 C. for 60 minutes more.

(47) Subsequently a further 105 g of deionized water were added and the aqueous polymer dispersion obtained was cooled to room temperature. Lastly, the dispersion was filtered through a 125 m filter.

(48) The resulting 3291 g of the aqueous polymer dispersion had a solids content of 43.5 wt % and a pH of 7.3. The MFFT was 0 C. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 40 nm.

INVENTIVE EXAMPLE 2A (IE 2A)

(49) 500.0 g of inventive example 2 were introduced and with stirring

(50) 39.5 g of a 25 wt % aqueous solution of Jeffamin T403 were added. Stirring was continued for 10 minutes, after which the dispersion was filtered through a 125 m filter. Solids content of the mixture was 42.2 wt %, pH was 8.7.

COMPARATIVE EXAMPLE 1 (CE1)

(51) A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25 C. (room temperature) under a nitrogen atmosphere with

(52) TABLE-US-00015 722.1 g of deionized water and 30.8 g of 15 wt % aqueous solution of sodium lauryl sulfate

(53) and this initial charge was heated to 80 C. with stirring. When this temperature had been reached, the entire feed 1 was added and stirring took place for 2 minutes. Thereafter feed 2 was commenced and was metered in over the course of 45 minutes. After the end of feed 2, polymerization was continued for 10 minutes, then feed 3 was added and stirred in for 10 minutes. The weight-average molecular weight of the polymer in a sample taken at this point in time was around 8.8 kDa. Subsequently feed 4a was commenced and was metered in 45 minutes. After that, immediately feed 4b and, in parallel with it, feed 5 were commenced and were metered in 45 minutes.

(54) Feed 1 (homogeneous solution of):

(55) TABLE-US-00016 55.8 g of deionized water and 4.2 g of sodium peroxodisulfate

(56) Feed 2 (homogeneous mixture of):

(57) TABLE-US-00017 369.5 g of deionized water 20.5 g of a 15 wt % aqueous solution of sodium lauryl sulfate 53.2 g of methacrylic acid 19.0 g of a 25 wt % solution of ureidomethacrylate in methyl methacrylate 306.2 g of methyl methacrylate 2.4 g of n-butyl acrylate 95.2 g of acetoacetoxyethyl methacrylate 21.9 g of 2-ethylhexyl thioglycolate

(58) Feed 3:

(59) TABLE-US-00018 42.1 g of a 25 wt % ammonia solution

(60) Feed 4a (homogeneous mixture of):

(61) TABLE-US-00019 181.8 g of deionized water 17.7 g of a 15 wt % aqueous solution of sodium lauryl sulfate 323.4 g of n-butyl acrylate 135.5 g of styrene 6.3 g of allyl glycidyl ether

(62) Feed 4b (homogeneous mixture of):

(63) TABLE-US-00020 181.8 g of deionized water 17.7 g of a 15 wt % aqueous solution of sodium lauryl sulfate 322.7 g of n-butyl acrylate 136.2 g of styrene

(64) Feed 5 (homogeneous solution of):

(65) TABLE-US-00021 9.3 g of deionized water and 0.7 g of sodium peroxodisulfate

(66) After the end of feeds 4b and 5, the polymerization mixture was left to react further at 80 C. for 30 minutes; then 117 g of deionized water were added and stirring was carried out at 80 C. for 60 minutes more.

(67) Subsequently a further 105 g of deionized water were added and the aqueous polymer dispersion obtained was cooled to room temperature. Lastly, the dispersion was filtered through a 125 m filter.

(68) The resulting 3307 g of the aqueous polymer dispersion had a solids content of 43.5 wt % and a pH of 7.3. The MFFT was 0 C. The weight-average molecular weight of the polymer of the dispersion was around 810 kDa. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 38 nm.

COMPARATIVE EXAMPLE 1A (CE 1A)

(69) 500.0 g of comparative example 1 were introduced and with stirring

(70) 60.2 g of a 25 wt % aqueous solution of Jeffamin T403 were added. Stirring was continued for 10 minutes, after which the dispersion was filtered through a 125 m filter. Solids content of the mixture was 41.6 wt %, pH was 9.3.

COMPARATIVE EXAMPLE 1B (CE 1B)

(71) 500.0 g of comparative example 1 were introduced and with stirring

(72) 40.5 g of a 25 wt % aqueous solution of Jeffamin T403 were added. Stirring was continued for 10 minutes, after which the dispersion was filtered through a 125 m filter. Solids content of the mixture was 42.0 wt %, pH was 8.5.

COMPARATIVE EXAMPLE 1C (CE 1C)

(73) 500.0 g of comparative example 1 were introduced and with stirring

(74) 20.7 g of a 25 wt % aqueous solution of Jeffamin T403 were added. Stirring was continued for 10 minutes, after which the dispersion was filtered through a 125 m filter. Solids content of the mixture was 43.1 wt %, pH was 7.8.

COMPARATIVE EXAMPLE 2 (CE2)

(75) A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25 C. (room temperature) under a nitrogen atmosphere with

(76) TABLE-US-00022 722.1 g of deionized water and 30.8 g of 15 wt % aqueous solution of sodium lauryl sulfate

(77) and this initial charge was heated to 80 C. with stirring. When this temperature had been reached, the entire feed 1 was added and stirring took place for 2 minutes. Thereafter feed 2 was commenced and was metered in over the course of 45 minutes. After the end of feed 2, polymerization was continued for 10 minutes, then feed 3 was added and stirred in for 10 minutes. Subsequently feed 4 was commenced and was metered in 90 minutes. When the first half of feed 4 had been metered, feed 5 was commenced and was metered in parallel to the remaining feed 4 in 45 minutes.

(78) Feed 1 (homogeneous solution of):

(79) TABLE-US-00023 55.8 g of deionized water and 4.2 g of sodium peroxodisulfate

(80) Feed 2 (homogeneous mixture of):

(81) TABLE-US-00024 369.5 g of deionized water 20.5 g of a 15 wt % aqueous solution of sodium lauryl sulfate 53.2 g of methacrylic acid 350.7 g of methyl methacrylate 24.5 g of n-butyl acrylate 47.6 g of acetoacetoxyethyl methacrylate 21.9 g of 2-ethylhexyl thioglycolate

(82) Feed 3:

(83) TABLE-US-00025 42.1 g of a 25 wt % ammonia solution

(84) Feed 4 (homogeneous mixture of):

(85) TABLE-US-00026 361.6 g of deionized water 35.5 g of a 15 wt % aqueous solution of sodium lauryl sulfate 627.2 g of n-butyl acrylate 249.2 g of styrene 47.6 g of acetoacetoxyethyl methacrylate

(86) Feed 5 (homogeneous solution of):

(87) TABLE-US-00027 9.3 g of deionized water and 0.7 g of sodium peroxodisulfate

(88) After the end of feeds 4 and 5, the polymerization mixture was left to react further at 80 C. for 30 minutes; then 117 g of deionized water were added and stirring was carried out at 80 C. for 60 minutes more.

(89) Subsequently a further 105 g of deionized water were added and the aqueous polymer dispersion obtained was cooled to room temperature. Lastly, the dispersion was filtered through a 125 m filter.

(90) The resulting 3296 g of the aqueous polymer dispersion had a solids content of 43.3 wt % and a pH of 7.3. The MFFT was 0 C. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 40 nm.

COMPARATIVE EXAMPLE 2A (CE 2A)

(91) 500.0 g of comparative example 2 were introduced and with stirring

(92) 39.5 g of a 25 wt % aqueous solution of Jeffamin T403 were added. Stirring was continued for 10 minutes, after which the dispersion was filtered through a 125 m filter. Solids content of the mixture was 41.8 wt %, pH was 9.3.

INVENTIVE EXAMPLE 3 (IE3)

(93) A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25 C. (room temperature) under a nitrogen atmosphere with

(94) TABLE-US-00028 722.1 g of deionized water and 30.8 g of 15 wt % aqueous solution of sodium lauryl sulfate

(95) and this initial charge was heated to 80 C. with stirring. When this temperature had been reached, the entire feed 1 was added and stirring took place for 2 minutes. Thereafter feed 2 was commenced and was metered in over the course of 45 minutes. After the end of feed 2, polymerization was continued for 10 minutes, then feed 3 was added and stirred in for 10 minutes. The weight-average molecular weight of the polymer in a sample taken at this point in time was around 7.8 kDa. Subsequently feed 4 was commenced and was metered in 90 minutes. When the first half of the 4 had been metered, feed 5 was commenced and was metered in parallel to the remaining feed 4 in 45 minutes.

(96) Feed 1 (homogeneous solution of):

(97) TABLE-US-00029 55.8 g of deionized water and 4.2 g of sodium peroxodisulfate

(98) Feed 2 (homogeneous mixture of):

(99) TABLE-US-00030 283.2 g of deionized water 20.5 g of a 15 wt % aqueous solution of sodium lauryl sulfate 47.6 g of methacrylic acid 38.1 g of a 25 wt % solution of ureidomethacrylate in methyl methacrylate 239.1 g of methyl methacrylate 103.6 g of tert-butyl acrylate 47.6 g of acetoacetoxyethyl methacrylate 22.0 g of 2-ethylhexyl thioglycolate

(100) Feed 3:

(101) TABLE-US-00031 37.6 g of a 25 wt % ammonia solution

(102) Feed 4 (homogeneous mixture of):

(103) TABLE-US-00032 339.2 g of deionized water 35.5 g of a 15 wt % aqueous solution of sodium lauryl sulfate 639.8 g of n-butyl acrylate 260.4 g of styrene 23.8 g of acetoacetoxyethyl methacrylate

(104) Feed 5 homogeneous solution of):

(105) TABLE-US-00033 9.3 g of deionized water and 0.7 g of sodium peroxodisulfate

(106) After the end of feeds 4 and 5, the polymerization mixture was left to react further at 80 C. for 30 minutes; then 117 g of deionized water were added and stirring was carried out at 80 C. for 60 minutes more.

(107) Subsequently a further 69 g of deionized water were added and the aqueous polymer dispersion obtained was cooled to room temperature. Lastly, the dispersion was filtered through a 125 m filter.

(108) The resulting 3146.9 g of the aqueous polymer dispersion had a solids content of 43.5 wt % and a pH of 7.6. The MFFT was 0 C. The weight-average molecular weight of the polymer in the dispersion was around 720 kDa. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 45 nm.

INVENTIVE EXAMPLE 4 (IE4)

(109) A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25 C. (room temperature) under a nitrogen atmosphere with

(110) TABLE-US-00034 722.1 g of deionized water and 30.8 g of 15 wt % aqueous solution of sodium lauryl sulfate

(111) and this initial charge was heated to 80 C. with stirring. When this temperature had been reached, the entire feed 1 was added and stirring took place for 2 minutes. Thereafter feed 2 was commenced and was metered in over the course of 45 minutes. After the end of feed 2, polymerization was continued for 10 minutes, then feed 3 was added and stirred in for 10 minutes. The weight-average molecular weight of the polymer in a sample taken at this point in time was around 7.7 kDa. Subsequently feed 4 was commenced and was metered in 90 minutes. When the first half of feed 4 had been metered, feed 5 was commenced and was metered in parallel to the remaining feed 4 in 45 minutes.

(112) Feed 1 (homogeneous solution of):

(113) TABLE-US-00035 55.8 g of deionized water and 4.2 g of sodium peroxodisulfate

(114) Feed 2 (homogeneous mixture of):

(115) TABLE-US-00036 283.2 g of deionized water 20.5 g of a 15 wt % aqueous solution of sodium lauryl sulfate 47.6 g of methacrylic acid 38.1 g of a 25 wt % solution of ureidomethacrylate in methyl methacrylate 239.1 g of methyl methacrylate 103.6 g of tert-butyl acrylate 47.6 g of acetoacetoxyethyl methacrylate 22.0 g of 2-ethylhexyl thioglycolate

(116) Feed 3:

(117) TABLE-US-00037 37.6 g of a 25 wt % ammonia solution

(118) Feed 4 (homogeneous mixture of):

(119) TABLE-US-00038 339.2 g of deionized water 35.5 g of a 15 wt % aqueous solution of sodium lauryl sulfate 656.6 g of n-butyl acrylate 243.6 g of styrene 23.8 g of acetoacetoxyethyl methacrylate

(120) Feed 5 (homogeneous solution of):

(121) TABLE-US-00039 9.3 g of deionized water and 0.7 g of sodium peroxodisulfate

(122) After the end of feeds 4 and 5, the polymerization mixture was left to react further at 80 C. for 30 minutes; then 117 g of deionized water were added and stirring was carried out at 80 C. for 60 minutes more.

(123) Subsequently a further 69 g of deionized water were added and the aqueous polymer dispersion obtained was cooled to room temperature. Lastly, the dispersion was filtered through a 125 m filter.

(124) The resulting 3146.9 g of the aqueous polymer dispersion had a solids content of 45.0 wt % and a pH of 7.5. The MFFT was 0 C. The weight-average molecular weight of the polymer in the dispersion was around 730 kDa. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 45 nm.

INVENTIVE EXAMPLE 5 (IE5)

(125) A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25 C. (room temperature) under a nitrogen atmosphere with

(126) TABLE-US-00040 726.6 g of deionized water and 30.8 g of 15 wt % aqueous solution of sodium lauryl sulfate

(127) and this initial charge was heated to 80 C. with stirring. When this temperature had been reached, the entire feed 1 was added and stirring took place for 2 minutes. Thereafter feed 2 was commenced and was metered in over the course of 45 minutes. After the end of feed 2, polymerization was continued for 10 minutes, then feed 3 was added and stirred in for 10 minutes. Subsequently feed 4 was commenced and was metered in 90 minutes. When the first half of feed 4 had been metered, feed 5 was commenced and was metered in parallel to the remaining feed 4 in 45 minutes.

(128) Feed 1 (homogeneous solution of):

(129) TABLE-US-00041 55.8 g of deionized water and 4.2 g of sodium peroxodisulfate

(130) Feed 2 (homogeneous mixture of):

(131) TABLE-US-00042 369.5 g of deionized water 20.5 g of a 15 wt % aqueous solution of sodium lauryl sulfate 47.6 g of methacrylic acid 282.8 g of methyl methacrylate 98.0 g of tert-butyl acrylate 47.6 g of acetoacetoxyethyl methacrylate 21.9 g of 2-ethylhexyl thioglycolate

(132) Feed 3:

(133) TABLE-US-00043 37.6 g of a 25 wt % ammonia solution

(134) Feed 4 (homogeneous mixture of):

(135) TABLE-US-00044 361.6 g of deionized water 35.5 g of a 15 wt % aqueous solution of sodium lauryl sulfate 627.2 g of n-butyl acrylate 249.2 g of styrene 47.6 g of acetoacetoxyethyl methacrylate

(136) Feed 5 (homogeneous solution of):

(137) TABLE-US-00045 9.3 g of deionized water and 0.7 g of sodium peroxodisulfate

(138) After the end of feeds 4 and 5, the polymerization mixture was left to react further at 80 C. for 30 minutes; then 117 g of deionized water were added and stirring was carried out at 80 C. for 60 minutes more.

(139) Subsequently a further 105 g of deionized water were added and the aqueous polymer dispersion obtained was cooled to room temperature. Lastly, the dispersion was filtered through a 125 m filter.

(140) The resulting 3296 g of the aqueous polymer dispersion had a solids content of 43.5 wt % and a pH of 7.6. The MFFT was 0 C. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 45 nm.

INVENTIVE EXAMPLE 5A (IE 5A)

(141) 500.0 g of inventive example 5 were introduced and with stirring

(142) 39.5 g of a 25 wt % aqueous solution of Jeffamin T403 were added. Stirring was continued for 10 minutes, after which the dispersion was filtered through a 125 m filter. Solids content of the mixture was 42.3 wt %, pH was 9.5.

COMPARATIVE EXAMPLE 3 (CE3)

(143) A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25 C. (room temperature) under a nitrogen atmosphere with

(144) TABLE-US-00046 722.1 g of deionized water and 30.8 g of 15 wt % aqueous solution of sodium lauryl sulfate

(145) and this initial charge was heated to 80 C. with stirring. When this temperature had been reached, the entire feed 1 was added and stirring took place for 2 minutes. Thereafter feed 2 was commenced and was metered in over the course of 45 minutes. After the end of feed 2, polymerization was continued for 10 minutes, then feed 3 was added and stirred in for 10 minutes. The weight-average molecular weight of the polymer in a sample taken at this point in time was around 7.4 kDa. Subsequently feed 4 was commenced and was metered in 90 minutes. When the first half of feed 4 had been metered in, feed 5 was commenced and metered in parallel to the rest of feed 4 over 45 minutes.

(146) Feed 1 (homogeneous solution of):

(147) TABLE-US-00047 55.8 g of deionized water and 4.2 g of sodium peroxodisulfate

(148) Feed 2 (homogeneous mixture of):

(149) TABLE-US-00048 283.2 g of deionized water 20.5 g of a 15 wt % aqueous solution of sodium lauryl sulfate 47.6 g of methacrylic acid 38.1 g of a 25 wt % solution of ureidomethacrylate in methyl methacrylate 318.2 g of methyl methacrylate 24.5 g of n-butyl acrylate 47.6 g of acetoacetoxyethyl methacrylate 22.0 g of 2-ethylhexyl thioglycolate

(150) Feed 3:

(151) TABLE-US-00049 37.6 g of a 25 wt % ammonia solution

(152) Feed 4 (homogeneous mixture of):

(153) TABLE-US-00050 339.2 g of deionized water 35.5 g of a 15 wt % aqueous solution of sodium lauryl sulfate 639.8 g of n-butyl acrylate 260.4 g of styrene 23.8 g of acetoacetoxyethyl methacrylate

(154) Feed 5 (homogeneous solution of):

(155) TABLE-US-00051 9.3 g of deionized water and 0.7 g of sodium peroxodisulfate

(156) After the end of feeds 4 and 5, the polymerization mixture was left to react further at 80 C. for 30 minutes; then 117 g of deionized water were added and stirring was carried out at 80 C. for 60 minutes more.

(157) Subsequently a further 69 g of deionized water were added and the aqueous polymer dispersion obtained was cooled to room temperature. Lastly, the dispersion was filtered through a 125 m filter.

(158) The resulting 3146.9 g of the aqueous polymer dispersion had a solids content of 45.0 wt % and a pH of 7.5. The MFFT was 0 C. The weight-average molecular weight of the polymer of the dispersion was around 690 kDa. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 42 nm.

INVENTIVE EXAMPLE 6 (IE6)

(159) A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25 C. (room temperature) under a nitrogen atmosphere with

(160) TABLE-US-00052 722.1 g of deionized water and 30.8 g of 15 wt % aqueous solution of sodium lauryl sulfate

(161) and this initial charge was heated to 80 C. with stirring. When this temperature had been reached, the entire feed 1 was added and stirring took place for 2 minutes. Thereafter feed 2 was commenced and was metered in over the course of 45 minutes. After the end of feed 2, polymerization was continued for 10 minutes, then feed 3 was added and stirred in for 10 minutes. Subsequently feed 4 was commenced and was metered in 90 minutes. When the first half of feed 4 had been metered, feed 5 was commenced and was metered in parallel to the remaining feed 4 in 45 minutes.

(162) Feed 1 (homogeneous solution of):

(163) TABLE-US-00053 55.8 g of deionized water and 4.2 g of sodium peroxodisulfate

(164) Feed 2 (homogeneous mixture of):

(165) TABLE-US-00054 373.7 g of deionized water 20.5 g of a 15 wt % aqueous solution of sodium lauryl sulfate 47.6 g of methacrylic acid 359.8 g of methyl methacrylate 21.0 g of n-butyl acrylate 47.6 g of acetoacetoxyethyl methacrylate 21.9 g of 2-ethylhexyl thioglycolate

(166) Feed 3:

(167) TABLE-US-00055 37.6 g of a 25 wt % ammonia solution

(168) Feed 4 (homogeneous mixture of):

(169) TABLE-US-00056 361.9 g of deionized water 35.5 g of a 15 wt % aqueous solution of sodium lauryl sulfate 627.2 g of n-butyl acrylate 249.2 g of styrene 47.6 g of acetoacetoxyethyl methacrylate

(170) Feed 5 (homogeneous solution of):

(171) TABLE-US-00057 9.3 g of deionized water and 0.7 g of sodium peroxodisulfate

(172) After the end of feeds 4 and 5, the polymerization mixture was left to react further at 80 C. for 30 minutes; then 117 g of deionized water were added and stirring was carried out at 80 C. for 60 minutes more.

(173) Subsequently a further 105 g of deionized water were added and the aqueous polymer dispersion obtained was cooled to room temperature. Lastly, the dispersion was filtered through a 125 m filter.

(174) The resulting 3295.7 g of the aqueous polymer dispersion had a solids content of 43.6 wt % and a pH of 7.6. The MFFT was 0 C. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 37 nm.

INVENTIVE EXAMPLE 6A (IE 6A)

(175) 500.0 g of inventive example 6 were introduced and with stirring

(176) 39.5 g of a 25 wt % aqueous solution of Jeffamin T403 were added. Stirring was continued for 10 minutes, after which the dispersion was filtered through a 125 m filter. Solids content of the mixture was 42.0 wt %, pH was 9.5.

COMPARATIVE EXAMPLE 6B (CE 6B)

(177) 500.0 g of inventive example 6 were introduced and with stirring

(178) 7.8 g of a 50 wt % aqueous solution of hexamethylenediamine were added. Stirring was continued for 10 minutes, after which the dispersion was filtered through a 125 m filter.

(179) Solids content of the mixture was 43.7 wt %, pH was 9.8.

(180) Measurement Methods

(181) Molecular Weight

(182) In this text, the weight-average molecular weight Mw, unless otherwise indicated, is determined via a size exclusion chromatography (SEC) with tetrahydrofuran+0.1 wt % trifluoroacetic acid as eluent at a flow rate of 1 ml/min and a column temperature of 35 C. The sample is diluted in the eluent to a concentration of 2 mg/ml and 100 l of this is injected after the sample solution has been filtered through a 0.2 m filter (Sartorius Minisart SRP 25) in order to remove any possible gel fraction. As the columns, three columns with an internal diameter of 7.5 mm were combined as follows: 5 cm precolumn (Plgel 10 Guard precolumn), followed by two 30 cm separating columns (each Plgel 10 Mixed B). Detection took place using a differential refractometer of type Agilent 1100, UV photometer of type Agilent 1100 VWD, PSS SLD7000-BI-MwA (UV/254 nm/Agilent). Calibration was carried out using narrow-range polystyrene standards from Polymer Laboratories with molecular weights of M=580 to M=7,500,000, and also hexylbenzene (M=162). The values outside the elution range were extrapolated.

(183) The filtration which precedes the determination of molecular weight removes any possible gel fraction of the polymer, and so the values reported relate to the sol fraction.

(184) Solids Content

(185) Solids content (SC) was determined generally by drying a defined amount of the aqueous polymer dispersion (around 1 g) to constant weight in a drying cabinet at 140 C., in an aluminum crucible having an internal diameter of around 5 cm. Two separate measurements were conducted. The values reported in the examples represent the average of each of the two results.

(186) Minimum Film-Forming Temperature

(187) The minimum film-forming temperature (MFFT) was determined with Ullmanns Enzyklopdie der technischen Chemie, 4.sup.th ed., Vo. 19, Verlag Chemie, Weinheim (1980), p. 17. The measuring apparatus used was a film-forming plate from Coesfeld (a metal plate to which a temperature gradient is applied). Filming took place at a wet film thickness of 1 mm. The minimum film-forming temperature reported is the temperature at which the film begins to develop cracking.

(188) Particle Size

(189) The particle size of the polymer of the invention was determined by means of hydrodynamic chromatography (HDC).

(190) Glass Transition Temperature

(191) Unless otherwise indicated, the glass transition temperature Tg was determined by means of the Fox equation.

(192) Water Resistance of the Coating

(193) A formulation of the respective polymer dispersion, as defined in table 1, is drawn down onto glass with a wet thickness of 300 m. It is subsequently dried for X days at RT (standard conditions). Then DI water is placed on the coating and a waiting time is observed. The assessment was delivered in school grades from 0 to 5 after Y hours. Grade 0=no damage, grade 5=complete failure.

(194) TABLE-US-00058 Water Water resistance resistance Inventive X Y (school Comparative (school examples (days) (hours) grade) examples grade) IE 1 2 5 3 CE 1 5 IE 1A 2 5 0 CE 1A 5 IE 1B 2 5 1 CE 1B 5 IE 1C 2 5 2.5 CE 1C 5 IE 2A 1 1 3 CE 2A 5 IE 3 1 3 1 CE 3 4 IE 4 1 3 1 IE 5 1 1 1 IE 5A 1 1 0 IE 6A 3 1 0 CE 6B 4.5

(195) Inventive example 1 shows the effect on the water resistance of the coating when the crosslinking monomer is used in both stages; the series A-C shows the effect of the propoxylated triamine added in differing amount.

(196) Inventive example 2 shows the effect on the water resistance of the coating when a monomer M bearing epoxide groups is used in the 2.sup.nd stage.

(197) Inventive examples 3, 4, and 5 show the effect on the water resistance of the coating when tert-butyl acrylate is used in stage 1; furthermore, inventive example 5A shows the additional improvement from adding the propoxylated triamine.

(198) Inventive example 6A and comparative example 6B show the comparison between use of a propoxylated triamine and of an aliphatic diamine.

(199) TABLE-US-00059 TABLE 1 Formulation of an opaque coating Concentration Weight fraction Component Definition Manufacturer (wt %) (ppt) DI - water 01 80 EnviroGem AD01 Wetting agent Air Products 1 FoamStar ST 2454 Defoamer BASF SE 2 Dispex CX 4231 Pigment dispersant BASF SE 30 7.5 Ammonia, concentrated Neutralizing agent 25 2 Tiona 595 TiO.sub.2 pigment Cristal 230 Rheovis PU 1340 Polyurethane thickener BASF SE 30 17 Emulsion polymer 45 600 FoamStar SI 2210 Defoamer BASF SE 2 DI - water 02 58.5 Total 1000