FINELY DIVIDED AQUEOUS EMULSION POLYMERS AND USE THEREOF FOR HYDROPHOBIC COATINGS

Abstract

The present invention relates to a polymer dispersion obtainable by at least one two-stage emulsion polymerization, by 1) preparing a polymer A by a radical polymerization from a 1st composition comprising A) at least one monomer, B) at least one anionic copolymerizable emulsifier, 2) admixing the polymer A prepared at 1) with a base, 3) in the presence of the polymer A treated at 2), preparing a polymer B by radical polymerization from a 2nd composition comprising A) at least one monomer, B) at least one anionic copolymerizable emulsifier. The present invention also relates to a process for preparing the polymer dispersion of the invention, to coating materials in the form of an aqueous composition comprising the polymer dispersion of the invention, and to the use of the polymer dispersion of the invention for coating compositions or paints and varnishes.

Claims

1-17. (canceled)

18: A polymer dispersion obtained by at least one, two-stage emulsion polymerization, which comprises: 1) preparing a polymer A by a radical polymerization from a first composition comprising A) at least one monomer, B) at least one anionic copolymerizable emulsifier, 2) admixing the polymer A prepared at 1) with a base, wherein the weight-average molecular weight of the polymers of the polymerization of the first stage is between 5 and 25 kDa and the monomers of the polymerization of the first stage are selected such that the glass transition temperature calculated for a polymer prepared from the monomers of the first stage is, being situated in the range from 70° C. to 125° C. 3) in the presence of the polymer A treated at 2), preparing a polymer B by radical polymerization from a second composition comprising A) at least one monomer, B) at least one anionic copolymerizable emulsifier wherein the weight-average molecular weight of the polymers of the polymerization of the first stage is between 5 and 25 kDa and the monomers of the polymerization of the first stage are selected such that the glass transition temperature calculated for a polymer prepared from the monomers of the first stage is, being situated in the range from 70° C. to 125° C.

19: The polymer dispersion according to claim 18, wherein a polymer A is prepared in aqueous medium by a radical emulsion polymerization.

20: The polymer dispersion according to claim 18, wherein the polymer dispersion further comprises a crosslinking additive.

21: The polymer dispersion according to claim 18, wherein the polymer A is in dispersion in water.

22: The polymer dispersion according to claim 18, wherein the first composition comprises A1) at least one (cyclo)alkyl (meth)acrylate, A2) at least one α,β-ethylenically unsaturated carboxylic acid, A3) at least one compound selected from the group consisting of 2-(2-oxoimidazolidin-1-yl)ethyl (meth)acrylate, 2-ureidoethyl (meth)acrylate (UMA), acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2-(acetoacetoxy)ethyl methacrylate, diacetoneacrylamide (DAAM), diacetonemethacrylamide, or mixtures thereof, and A4) at least one chain transfer agent, and B) at least one anionic copolymerizable emulsifier.

23: The polymer dispersion according to claim 18, wherein the second composition comprises A1) at least one (cyclo)alkyl (meth)acrylate and/or a vinylaromatic, and B) at least one anionic copolymerizable emulsifier.

24: The polymer dispersion according to claim 18, wherein the at least one anionic copolymerizable emulsifier is selected from the group consisting of (1) a compound of formula (I) ##STR00015##  where R1 is H, alkyl, cycloalkyl, aralkyl, aryl, or alkoxyaryl, R2, R2′ is H or R2 and R2′ are O, R3 is H or alkyl, R4 is H or OH, X is SO.sub.3.sup.−, HPO.sub.4.sup.−, PO.sub.4.sup.2−, or COO.sup.−, m is 0 or 1, and n is an integer between 0 and 1000; (2) a compound of formula (II) ##STR00016##  where X is SO.sub.3.sup.−, PO.sub.4.sup.2−, or SO.sub.4.sup.−, and R is H, alkyl, cycloalkyl, aralkyl, aryl or alkoxyaryl; (3) a compound of formula (III) ##STR00017##  where R1 is H, alkyl, cycloalkyl, aralkyl, aryl or alkoxyaryl, X is SO.sub.4.sup.−, SO.sub.3.sup.−, HPO.sub.4−, PO.sub.4.sup.2−, or COO.sup.−, and n is an integer between 0 and 1000; (4) a compound of the formula (IV) ##STR00018##  where R1 is H, alkyl, cycloalkyl, aralkyl, aryl, or alkoxyaryl, Y is SO.sub.3.sup.−, PHO.sub.3.sup.−, or PO.sub.3.sup.2−, and n is an integer between 0 and 1000; or mixtures of the compounds of the formulae (I) to (IV).

25: The polymer dispersion according to claim 18, wherein the particle size of the polymer A and/or of the polymer B is in a range from 1 nm to 100 nm.

26: The polymer dispersion according to claim 18, wherein the first composition comprises A1) 40-94 wt % of at least one (cyclo)alkyl (meth)acrylate, A2) 1-15 wt % of at least one α,β-ethylenically unsaturated carboxylic acid, A3) 5-45 wt % of at least one compound selected from the group consisting of 2-(2-oxoimidazolidin-1-yl)ethyl (meth)acrylate, 2-ureidoethyl (meth)acrylate (UMA), acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2-(acetoacetoxy)ethyl methacrylate, diacetoneacrylamide (DAAM), diacetonemethacrylamide, or mixtures thereof, the amount figures of Al) to A3) being based in each case on 100 wt % of the monomers to be polymerized in the first composition.

27: The polymer dispersion according to claim 18, wherein the first composition comprises A1) 40-93.9 wt % of at least one (cyclo)alkyl (meth)acrylate, A2) 1-15 wt % of at least one α,β-ethylenically unsaturated carboxylic acid, A3) 5-20 wt % of at least one compound selected from the group consisting of 2-(2-oxoimidazolidin-1-yl)ethyl (meth)acrylate, 2-ureidoethyl (meth)acrylate (UMA), acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2-(acetoacetoxy)ethyl methacrylate, diacetoneacrylamide (DAAM), diacetonemethacrylamide, or mixtures thereof, A4) 0-5 wt % of at least one chain transfer agent, and B) 0.05-5 wt % of at least one anionic copolymerizable emulsifier, the amount figures of A1) to B) being based in each case on 100 wt % of the monomers to be polymerized in the first composition.

28: The polymer dispersion according to claim 18, wherein the polymer dispersion is free from nonpolymerizable emulsifiers.

29: A process for preparing a polymer dispersion according to claim 18, the process comprising: carrying out at least one, two-stage emulsion polymerization comprising: 1) preparing a polymer A by a radical polymerization from a first composition comprising A) at least one monomer, B) at least one anionic copolymerizable emulsifier, 2) admixing the polymer A prepared at 1) with a base, wherein the weight-average molecular weight of the polymers of the polymerization of the first stage is between 5 and 25 kDa and the monomers of the polymerization of the first stage are selected such that the glass transition temperature calculated for a polymer prepared from the monomers of the first stage is, being situated in the range from 70° C. to 125° C. 3) in the presence of the polymer A treated at 2), preparing a polymer B by radical polymerization from a second composition comprising A) at least one hydrophilic and/or hydrophobic monomer, B) at least one anionic copolymerizable emulsifier, wherein the weight-average molecular weight of the polymers of the polymerization of the first stage is between 5 and 25 kDa and the monomers of the polymerization of the first stage are selected such that the glass transition temperature calculated for a polymer prepared from the monomers of the first stage is, being situated in the range from 70° C. to 125° C.

30: A process for preparing a polymer dispersion according to claim 18, comprising: carrying out at least one, two-stage emulsion polymerization, comprising: 1) preparing a polymer A in dispersion in water, in aqueous medium, by a radical polymerization from a first composition, the first composition comprising: A1) at least one (cyclo)alkyl (meth)acrylate, A2) at least one α,β-ethylenically unsaturated carboxylic acid, A3) at least one compound selected from the group consisting of 2-(2-oxoimidazolidin-1-yl)ethyl (meth)acrylate, 2-ureidoethyl (meth)acrylate (UMA), acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2-(acetoacetoxy)ethyl methacrylate, diacetoneacrylamide (DAAM), diacetonemethacrylamide, or mixtures thereof, and A4) at least one chain transfer agent, and B) at least one anionic copolymerizable emulsifier, 2) admixing the polymer A prepared at 1) with a base, 3) in the presence of the polymer A treated at 2), preparing a polymer B by radical polymerization from a second composition, the second composition comprising A1) at least one (cyclo) (meth)acrylate and B) at least one anionic copolymerizable emulsifier.

31: A process for preparing a polymer dispersion according to claim 30, wherein the at least one anionic copolymerizable emulsifier is selected from the group consisting of (1) a compound of formula (I) ##STR00019##  where R1 is H, alkyl, cycloalkyl, aralkyl, aryl, or alkoxyaryl, R2, R2′ is H or R2 and R2′ are O, R3 is H or alkyl, R4 is H or OH, X is SO.sub.3.sup.−, HPO.sub.4.sup.−, PO.sub.4.sup.2−, or COO.sup.−, m is 0 or 1, and n is an integer between 0 and 1000; (2) a compound of formula (II) ##STR00020##  where X is SO.sub.3.sup.−, PO.sub.4.sup.2−, or SO.sub.4.sup.−, and R is H, alkyl, cycloalkyl, aralkyl, aryl or alkoxyaryl; (3) a compound of formula (III) ##STR00021##  where R1 is H, alkyl, cycloalkyl, aralkyl, aryl or alkoxyaryl, X is SO.sub.4.sup.−, SO.sub.3.sup.−, HPO.sub.4.sup.−, PO.sub.4.sup.2−, or COO.sup.−, and n is an integer between 0 and 1000; (4) a compound of the formula (IV) ##STR00022##  where R1 is H, alkyl, cycloalkyl, aralkyl, aryl, or alkoxyaryl, Y is SO.sub.3.sup.−, PHO.sub.3.sup.−, or PO.sub.3.sup.2−, and n is an integer between 0 and 1000; or mixtures of the compounds of the formulae (I) to (IV).

32: A coating material in the form of an aqueous composition, comprising: i) at least one polymer dispersion according to claim 18, ii) optionally at least one (in)organic filler and/or (in)organic pigment, iii) optionally an additive, iv) water.

Description

[0295] 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:

[0296] FIG. 1 shows wet drawdowns onto a Leneta film of the formulation according to the invention.

[0297] FIG. 1 shows five different wet drawdowns onto a Leneta film of the formulation according to the invention, comprising acrylate thickeners and the polymer dispersions 1E1 to 1E3 of the invention, in comparison to binders from WO 2012/130712-A1 (CE1 and CE2). It can be seen that the formulations based on the polymer dispersions of the invention exhibit wet transparency.

[0298] The invention is elucidated in more detail by the examples hereinafter.

INVENTIVE EXAMPLE 1 (IE1)

[0299] A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25° C. (room temperature) under a nitrogen atmosphere with

[0300] 732.6 g of deionized water and

[0301] 18.5 g of Adeka Reasoap SR-1025 (25 wt % aqueous solution)

[0302] 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. When 50% of this feed had been metered in, over 45 minutes, the feed was stopped, and feed 5 was added and stirred in for 10 minutes. Then the remainder of feed 4 and, in parallel therewith, feed 6 were metered in over the course of 45 minutes.

[0303] Feed 1 (homogeneous solution of):

[0304] 55.8 g of deionized water and

[0305] 4.2 g of sodium peroxodisulfate

[0306] Feed 2 (homogeneous mixture of):

[0307] 196.1 g of deionized water

[0308] 6.2 g of Adeka Reasoap SR-1025 (25 wt % aqueous solution)

[0309] 45.5 g of methacrylic acid

[0310] 18.2 g of a 25 wt % strength solution of ureidoethyl methacrylate in methyl methacrylate

[0311] 300.3 g of methyl methacrylate

[0312] 45.5 g of n-butyl acrylate

[0313] 227.5 g of a 20 wt % strength aqueous solution of diacetoneacrylamide, and

[0314] 22.8 g of 2-ethylhexyl thioglycolate

[0315] Feed 3:

[0316] 27.0 g of a 25 wt % strength ammonia solution

[0317] Feed 4 (homogeneous mixture of):

[0318] 396.1 g of deionized water

[0319] 10.6 g of Adeka Reasoap SR-1025 (25 wt % aqueous solution)

[0320] 280.0 g of n-butyl acrylate

[0321] 343.0 g of methyl methacrylate, and

[0322] 322.0 g of 2-ethylhexyl acrylate

[0323] Feed 5:

[0324] 9.0 g of a 25 wt % strength ammonia solution

[0325] Feed 6 (homogeneous solution of):

[0326] 9.3 g of deionized water and

[0327] 0.7 g of sodium peroxodisulfate

[0328] After the end of feeds 4 and 6, the polymerization mixture was left to react further at 80° C. for 30 minutes; then 167.2 g of deionized water were added and stirring was carried out at 80° C. for 90 minutes more.

[0329] The aqueous polymer dispersion obtained was then cooled to room temperature. At room temperature, 189.6 g of a 12 wt % strength aqueous solution of adipic dihydrazide were added. Lastly, the dispersion was filtered through a 125 μm filter.

[0330] The resulting 3430.4 g of the aqueous polymer dispersion had a solids content of 42.6 wt %, the MFFT was ≦0° C. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 41 nm (measured by means of HDC).

INVENTIVE EXAMPLE 2 (IE2)

[0331] A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25° C. (room temperature) under a nitrogen atmosphere with

[0332] 732.6 g of deionized water and

[0333] 18.5 g of Adeka Reasoap SR-1025 (25 wt % aqueous solution)

[0334] 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. When 50% of this feed had been metered in, over 45 minutes, the feed was stopped, and feed 5 was added and stirred in for 10 minutes. Then the remainder of feed 4 and, in parallel therewith, feed 6 were metered in over the course of 45 minutes.

[0335] Feed 1 (homogeneous solution of):

[0336] 55.8 g of deionized water and

[0337] 4.2 g of sodium peroxodisulfate

[0338] Feed 2 (homogeneous mixture of):

[0339] 196.1 g of deionized water

[0340] 6.2 g of Adeka Reasoap SR-1025 (25 wt % aqueous solution)

[0341] 45.5 g of methacrylic acid

[0342] 18.2 g of a 25 wt % strength solution of ureidoethyl methacrylate in methyl methacrylate

[0343] 300.3 g of methyl methacrylate

[0344] 45.5 g of n-butyl acrylate

[0345] 227.5 g of a 20 wt % strength aqueous solution of diacetoneacrylamide, and

[0346] 21.0 g of 2-ethylhexyl thioglycolate

[0347] Feed 3:

[0348] 27.0 g of a 25 wt % strength ammonia solution

[0349] Feed 4 (homogeneous mixture of):

[0350] 396.1 g of deionized water

[0351] 10.6 g of Adeka Reasoap SR-1025 (25 wt % aqueous solution)

[0352] 280.0 g of n-butyl acrylate

[0353] 7.0 g of allyl methacrylate

[0354] 336.0 g of methyl methacrylate, and

[0355] 322.0 g of 2-ethylhexyl acrylate

[0356] Feed 5:

[0357] 9.0 g of a 25 wt % strength ammonia solution

[0358] Feed 6 (homogeneous solution of):

[0359] 9.3 g of deionized water and

[0360] 0.7 g of sodium peroxodisulfate

[0361] After the end of feeds 4 and 6, the polymerization mixture was left to react further at 80° C. for 30 minutes; then 167.2 g of deionized water were added and stirring was carried out at 80° C. for 90 minutes more.

[0362] The aqueous polymer dispersion obtained was then cooled to room temperature. At room temperature, 189.6 g of a 12 wt % strength aqueous solution of adipic dihydrazide were added. Lastly, the dispersion was filtered through a 125 μm filter.

[0363] The resulting 3425.9 g of the aqueous polymer dispersion had a solids content of 42.5 wt %, the MFFT was ≦0° C. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 40 nm (measured by means of HDC).

INVENTIVE EXAMPLE 3 (IE3)

[0364] A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25° C. (room temperature) under a nitrogen atmosphere with

[0365] 732.6 g of deionized water and

[0366] 18.5 g of Adeka Reasoap SR-1025 (25 wt % aqueous solution)

[0367] 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. When 50% of this feed had been metered in, over 45 minutes, the feed was stopped, and feed 5 was added and stirred in for 10 minutes. Then the remainder of feed 4 and, in parallel therewith, feed 6 were metered in over the course of 45 minutes.

[0368] Feed 1 (homogeneous solution of):

[0369] 55.8 g of deionized water and

[0370] 4.2 g of sodium peroxodisulfate

[0371] Feed 2 (homogeneous mixture of):

[0372] 196.1 g of deionized water

[0373] 6.2 g of Adeka Reasoap SR-1025 (25 wt % aqueous solution)

[0374] 45.5 g of methacrylic acid

[0375] 28.0 g of a 25 wt % strength solution of ureidoethyl methacrylate in methyl methacrylate

[0376] 290.5 g of methyl methacrylate

[0377] 45.5 g of n-butyl acrylate

[0378] 227.5 g of a 20 wt % strength aqueous solution of diacetoneacrylamide, and

[0379] 21.0 g of 2-ethylhexyl thioglycolate

[0380] Feed 3:

[0381] 27.0 g of a 25 wt % strength ammonia solution

[0382] Feed 4 (homogeneous mixture of):

[0383] 396.1 g of deionized water

[0384] 10.6 g of Adeka Reasoap SR-1025 (25 wt % aqueous solution)

[0385] 280.0 g of n-butyl acrylate

[0386] 343.0 g of methyl methacrylate, and

[0387] 322.0 g of 2-ethylhexyl acrylate

[0388] Feed 5:

[0389] 9.0 g of a 25 wt % strength ammonia solution

[0390] Feed 6 (homogeneous solution of):

[0391] 9.3 g of deionized water and

[0392] 0.7 g of sodium peroxodisulfate

[0393] After the end of feeds 4 and 6, the polymerization mixture was left to react further at 80° C. for 30 minutes; then 167.2 g of deionized water were added and stirring was carried out at 80° C. for 90 minutes more.

[0394] The aqueous polymer dispersion obtained was then cooled to room temperature. At room temperature, 189.6 g of a 12 wt % strength aqueous solution of adipic dihydrazide were added. Lastly, the dispersion was filtered through a 125 μm filter.

[0395] The resulting 3425.9 g of the aqueous polymer dispersion had a solids content of 42.5 wt %, the MFFT was ≦0° C. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 40 nm (measured by means of HDC).

COMPARATIVE EXAMPLE 1 (CE1)

[0396] A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25° C. (room temperature) under a nitrogen atmosphere with

[0397] 289.6 g of deionized water and

[0398] 32.0 g of a 15 wt % strength aqueous solution of sodium lauryl sulfate

[0399] 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 40 minutes. After the end of feed 2, polymerization was continued for 10 minutes, then 0.8 g of a 25 wt % strength aqueous solution of ammonia was added and was stirred in for 10 minutes. Subsequently feed 3 was commenced and was metered in continuously at constant flow rate over the course of 90 minutes. 45 minutes after the start of feed 3, 0.8 g of a 25 wt % strength ammonia solution was added.

[0400] Feed 1 (homogeneous solution of):

[0401] 31.9 g of deionized water and

[0402] 2.4 g of sodium peroxodisulfate

[0403] Feed 2 (homogeneous mixture of):

[0404] 60.1 g of deionized water

[0405] 4.0 g of a 15 wt % strength aqueous solution of sodium lauryl sulfate

[0406] 7.2 g of methacrylic acid

[0407] 54.0 g of a 15 wt % strength aqueous solution of methacrylamide

[0408] 18.0 g of styrene

[0409] 101.6 g of methyl methacrylate

[0410] 21.0 g of n-butyl acrylate

[0411] 9.7 g of a 25 wt % strength solution of ureido ethyl methacrylate in methyl methacrylate

[0412] 72.0 g of a 20 wt % strength aqueous solution of diacetoneacrylamide, and

[0413] 2.9 g of 2-ethylhexyl thioglycolate

[0414] Feed 3 (homogeneous mixture of):

[0415] 175.3 g of deionized water

[0416] 8.0 g of a 15 wt % strength aqueous solution of sodium lauryl sulfate

[0417] 288.0 g of n-butyl acrylate

[0418] 60.0 g of n-butyl methacrylate, and

[0419] 72.0 g of methyl methacrylate

[0420] After the end of feed 3, the polymerization mixture was allowed to continue reacting at 80° C. for 90 minutes. Then 2.5 g of a 25 wt % strength ammonia solution were added and were stirred in for 15 minutes.

[0421] The aqueous polymer dispersion obtained was then cooled to room temperature. At a temperature below 40° C., 60 g of a 12 wt % strength aqueous solution of adipic dihydrazide were added. Lastly, the dispersion was filtered through a 125 μm filter.

[0422] The resulting 1373.8 g of the aqueous polymer dispersion had a solids content of 43.6 wt %, the MFFT was ≦0° C. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 67 nm.

COMPARATIVE EXAMPLE 2 (CE2)

[0423] A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25° C. (room temperature) under a nitrogen atmosphere with

[0424] 701.3 g of deionized water and

[0425] 30.8 g of a 15 wt % strength aqueous solution of sodium lauryl sulfate

[0426] 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 40 minutes. After the end of feed 2, polymerization was continued for 10 minutes, then 1.9 g of a 25 wt % strength aqueous solution of ammonia were added and were stirred in for 10 minutes. Subsequently feed 3 was commenced and was metered in continuously at constant flow rate over the course of 90 minutes. 45 minutes after the start of feed 3, 1.9 g of a 25 wt % strength ammonia solution were added, and feed 4 was commenced and was metered in continuously with a constant flow rate in parallel with the remainder of feed 3.

[0427] Feed 1 (homogeneous solution of):

[0428] 65.1 g of deionized water and

[0429] 4.9 g of sodium peroxodisulfate

[0430] Feed 2 (homogeneous mixture of):

[0431] 140.1 g of deionized water

[0432] 9.3 g of a 15 wt % strength aqueous solution of sodium lauryl sulfate

[0433] 16.8 g of methacrylic acid

[0434] 126.0 g of a 15 wt % strength aqueous solution of methacrylamide

[0435] 42.0 g of styrene

[0436] 237.2 g of methyl methacrylate

[0437] 49.0 g of n-butyl acrylate

[0438] 22.5 g of a 25 wt % strength solution of ureido ethyl methacrylate in methyl methacrylate

[0439] 168.0 g of a 20 wt % strength aqueous solution of diacetoneacrylamide, and

[0440] 11.2 g of 2-ethylhexyl thioglycolate

[0441] Feed 3 (homogeneous mixture of):

[0442] 404.0 g of deionized water

[0443] 9.3 g of a 15 wt % strength aqueous solution of sodium lauryl sulfate

[0444] 315.0 g of n-butyl acrylate

[0445] 266.0 g of 2-ethylhexyl acrylate

[0446] 140.0 g of n-butyl methacrylate, and

[0447] 259.0 g of methyl methacrylate

[0448] Feed 4 (homogeneous solution of):

[0449] 9.3 g of deionized water and

[0450] 0.7 g of sodium peroxodisulfate

[0451] After the end of feeds 3 and 4, the polymerization mixture was allowed to continue reacting at 80° C. for 90 minutes. Then 5.9 g of a 25 wt % strength ammonia solution were added and were stirred in for 15 minutes.

[0452] The aqueous polymer dispersion obtained was then cooled to room temperature. At a temperature below 40° C., 140 g of a 12 wt % strength aqueous solution of adipic dihydrazide were added. Lastly, the dispersion was filtered through a 125 μm filter.

[0453] The resulting 3177.2 g of the aqueous polymer dispersion had a solids content of 42.8 wt %, the

[0454] MFFT was ≦0° C. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 77 nm.

COMPARATIVE EXAMPLE 3 (CE3)

[0455] A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25° C. (room temperature) under a nitrogen atmosphere with

[0456] 721.0 g of deionized water and

[0457] 30.8 g of a 15 wt % strength aqueous solution of sodium lauryl sulfate

[0458] 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. When 50% of this feed had been metered in, over 45 minutes, the feed was stopped, and feed 5 was added and stirred in for 10 minutes. Then the remainder of feed 4 and, in parallel therewith, feed 6 were metered in over the course of 45 minutes.

[0459] Feed 1 (homogeneous solution of):

[0460] 55.8 g of deionized water and

[0461] 4.2 g of sodium peroxodisulfate

[0462] Feed 2 (homogeneous mixture of):

[0463] 191.4 g of deionized water

[0464] 10.3 g of a 15 wt % strength aqueous solution of sodium lauryl sulfate

[0465] 45.5 g of methacrylic acid

[0466] 18.2 g of a 25 wt % strength solution of ureidoethyl methacrylate in methyl methacrylate

[0467] 300.3 g of methyl methacrylate

[0468] 45.5 g of n-butyl acrylate

[0469] 227.5 g of a 20 wt % strength aqueous solution of diacetoneacrylamide, and

[0470] 22.8 g of 2-ethylhexyl thioglycolate

[0471] Feed 3:

[0472] 27.0 g of a 25 wt % strength ammonia solution

[0473] Feed 4 (homogeneous mixture of):

[0474] 388.9 g of deionized water

[0475] 17.7 g of a 15 wt % strength aqueous solution of sodium lauryl sulfate

[0476] 280.0 g of n-butyl acrylate

[0477] 343.0 g of methyl methacrylate, and

[0478] 322.0 g of 2-ethylhexyl acrylate

[0479] Feed 5:

[0480] 9.0 g of a 25 wt % strength ammonia solution

[0481] Feed 6 (homogeneous solution of):

[0482] 9.3 g of deionized water and

[0483] 0.7 g of sodium peroxodisulfate

[0484] After the end of feeds 4 and 6, the polymerization mixture was left to react further at 80° C. for 30 minutes; then 167.2 g of deionized water were added and stirring was carried out at 80° C. for 90 minutes more.

[0485] The aqueous polymer dispersion obtained was then cooled to room temperature. At room temperature, 189.6 g of a 12 wt % strength aqueous solution of adipic dihydrazide were added. Lastly, the dispersion was filtered through a 125 μm filter.

[0486] The resulting 3427.7 g of the aqueous polymer dispersion had a solids content of 42.6 wt %, the MFFT was ≦0° C. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 39 nm (measured by means of HDC).

COMPARATIVE EXAMPLE 4 (CE4)

[0487] A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25° C. (room temperature) under a nitrogen atmosphere with

[0488] 728.0 g of deionized water and

[0489] 23.1 g of a 20 wt % strength aqueous solution of isotridecanol ethoxylate.sup.1)

[0490] 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. When 50% of this feed had been metered in, over 45 minutes, the feed was stopped, and feed 5 was added and stirred in for 10 minutes. Then the remainder of feed 4 and, in parallel therewith, feed 6 were metered in over the course of 45 minutes.

[0491] Feed 1 (homogeneous solution of):

[0492] 55.8 g of deionized water and

[0493] 4.2 g of sodium peroxodisulfate

[0494] Feed 2 (homogeneous mixture of):

[0495] 194.6 g of deionized water

[0496] 7.7 g of a 20 wt % strength aqueous solution of isotridecanol ethoxylate.sup.1)

[0497] 45.5 g of methacrylic acid

[0498] 18.2 g of a 25 wt % strength solution of ureidoethyl methacrylate in methyl methacrylate

[0499] 300.3 g of methyl methacrylate

[0500] 45.5 g of n-butyl acrylate

[0501] 227.5 g of a 20 wt % strength aqueous solution of diacetoneacrylamide, and

[0502] 22.8 g of 2-ethylhexyl thioglycolate

[0503] Feed 3:

[0504] 27.0 g of a 25 wt % strength ammonia solution

[0505] Feed 4 (homogeneous mixture of):

[0506] 393.3 g of deionized water

[0507] 13.3 g of a 20 wt % strength aqueous solution of isotridecanol ethoxylate.sup.1)

[0508] 280.0 g of n-butyl acrylate

[0509] 343.0 g of methyl methacrylate, and

[0510] 322.0 g of 2-ethylhexyl acrylate

[0511] Feed 5:

[0512] 9.0 g of a 25 wt % strength ammonia solution

[0513] Feed 6 (homogeneous solution of):

[0514] 9.3 g of deionized water and

[0515] 0.7 g of sodium peroxodisulfate

[0516] After the end of feeds 4 and 6, the polymerization mixture was left to react further at 80° C. for 30 minutes; then 167.2 g of deionized water were added and stirring was carried out at 80° C. for 90 minutes more.

[0517] The aqueous polymer dispersion obtained was then cooled to room temperature. At room temperature, 189.6 g of a 12 wt % strength aqueous solution of adipic dihydrazide were added. Lastly, the dispersion was filtered through a 125 μm filter.

[0518] The resulting 3427.6 g of the aqueous polymer dispersion had a solids content of 42.6 wt %, the MFFT was ≦0° C. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 43 nm (measured by means of HDC).

[0519] 1) Such as Lutensol TO 82 from BASF SE

[0520] Formulations

[0521] Both stains and paints were formulated. [0522] Wet transparency was assessed on stains: drawn down with a wet film thickness of 300 μm onto Leneta film. Rating with school grades: 1=very good, transparent, 5=very poor, opaque. [0523] Whitening: drawn down onto a glass plate with a wet film thickness of 300 μm is a film of the stain under test. Measurement may then take place after a drying time of 3 days at RT. The glass plates are placed into a glass beaker filled with about 400 ml of DI H2O, and assessed visually after 45 minutes. Evaluation: 0=no whitening, 1=a trace of whitening, 2=slight whitening, 3=moderate whitening, 4=severe whitening, 5=total whitening. [0524] Water absorption: Apply the paint under test to a Teflon-coated substrate. The slot size for application is to be selected so as to form a film with a dry thickness of approximately 400 μm. After the film has dried, it is detached from the substrate and stored in free suspension or lying on a rack at room temperature for at least 3 days. Punch out 3 test specimens in each case, measuring 50×40 mm, and store them again at RT for at least 4 days, determine their weight using an analytical balance, and place between steel mesh baskets so that the film is neither lying on the base nor is able to float, and is wetted by water from all sides. After 24 hours of storage in the water chest filled with deionized water, remove test specimens, dry them off, and immediately reweigh them on the analytical balance. Evaluation: Water absorption=[(final WA mass−initial mass)/initial mass]×100%. [0525] Capillary water absorption both on dried stains and paints: [0526] Test instrument: Erichsen film drawer 400 μm 10 cm wide. [0527] Test materials: pine block (30×10×2 cm), 150 ml beaker. [0528] Procedure: The paint under test is drawn down onto the pine block using the Erichsen film drawer. After drying for at least one day, the block is cut up into three equal-sized sections (approximately 10×10×2 cm) and dried for a total of 7 days. After the drying time, the test specimens are weighed (0 value). Thereafter the coated side of the test specimen is [0529] pressed onto the opening of the filled beakers and turned. Now the uncoated side should be pointing downward, and the water in the beaker should be in contact with the coated side of the test specimen. After 3 days of water contact time, remove the test specimens (beaker away and dry off) and re-weigh the test specimens. [0530] Pendulum hardness: Films with a wet thickness of 300 μm were drawn onto glass and dried at room temperature for 7 days. The hardness was determined according to EN ISO 1522 (December 2006).
Formulation of stain 1
Formulation of stain 2
Formulation of the paint
Results of the experiments

TABLE-US-00001 IE1 IE2 IE3 CE1 CE2 CE3 CE4 Stain 1 Wet transparency 1 1 1 4 5 (school grade) Capillary water 280 275 275 318 233 absorption (g/m.sup.2 × 3 d) Pendulum 52 52 52 41 43 hardness (s) Stain 2 Wet transparency 1 2 4 (school grade) Whitening after 1 h 2 2-3 3-4 (school grade) Water absorption 16.0 18.3 17.7 (24 h) (%) Pendulum 49 52 46 hardness (s) Paint Capillary water 203 198 198 250 210 absorption (g/m.sup.2 × 3 d) Pendulum 57 50 59 42 48 hardness (s)

INVENTIVE EXAMPLE 4 (IE4)

[0531] A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25°C. (room temperature) under a nitrogen atmosphere with

[0532] 732.6 g of deionized water and

[0533] 18.5 g of Adeka Reasoap SR-1025 (25 wt % aqueous solution)

[0534] 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. When 50% of this feed had been metered in, over 45 minutes, the feed was stopped, and feed 5 was added and stirred in for 10 minutes. Then the remainder of feed 4 and, in parallel therewith, feed 6 were metered in over the course of 45 minutes.

[0535] Feed 1 (homogeneous solution of):

[0536] 55.8 g of deionized water and

[0537] 4.2 g of sodium peroxodisulfate

[0538] Feed 2 (homogeneous mixture of):

[0539] 196.1 g of deionized water

[0540] 6.2 g of Adeka Reasoap SR-1025 (25 wt % aqueous solution)

[0541] 45.5 g of methacrylic acid

[0542] 18.2 g of a 25 wt % strength solution of ureidoethyl methacrylate in methyl methacrylate

[0543] 300.3 g of methyl methacrylate

[0544] 45.5 g of n-butyl acrylate

[0545] 227.5 g of a 20 wt % strength aqueous solution of diacetoneacrylamide, and

[0546] 21.0 g of 2-ethylhexyl thioglycolate

[0547] Feed 3:

[0548] 27.0 g of a 25 wt % strength ammonia solution

[0549] Feed 4 (homogeneous mixture of):

[0550] 396.1 g of deionized water

[0551] 10.6 g of Adeka Reasoap SR-1025 (25 wt % aqueous solution)

[0552] 658.0 g of n-butyl acrylate

[0553] 280.0 g of methyl methacrylate, and

[0554] 7.0 g of allyl methacrylate

[0555] Feed 5:

[0556] 9.0 g of a 25 wt % strength ammonia solution

[0557] Feed 6 (homogeneous solution of):

[0558] 9.3 g of deionized water and

[0559] 0.7 g of sodium peroxodisulfate

[0560] After the end of feeds 4 and 6, the polymerization mixture was left to react further at 80° C. for 30 minutes; then 167.2 g of deionized water were added and stirring was carried out at 80° C. for 90 minutes more.

[0561] The aqueous polymer dispersion obtained was then cooled to room temperature. At room temperature, 189.6 g of a 12 wt % strength aqueous solution of adipic dihydrazide were added. Lastly, the dispersion was filtered through a 125 μm filter.

[0562] The resulting 3425.9 g of the aqueous polymer dispersion had a solids content of 42.3 wt %, the MFFT was ≦0° C. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 42 nm (measured by means of HDC).

COMPARATIVE EXAMPLE 5

Adeka Reasoap Only in Initial Charge and Feed 2

[0563] A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25° C. (room temperature) under a nitrogen atmosphere with

[0564] 732.6 g of deionized water and

[0565] 18.5 g of Adeka Reasoap SR-1025 (25 wt % aqueous solution)

[0566] 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. When 50% of this feed had been metered in, over 45 minutes, the feed was stopped, and feed 5 was added and stirred in for 10 minutes. Then the remainder of feed 4 and, in parallel therewith, feed 6 were metered in over the course of 45 minutes.

[0567] Feed 1 (homogeneous solution of):

[0568] 55.8 g of deionized water and

[0569] 4.2 g of sodium peroxodisulfate

[0570] Feed 2 (homogeneous mixture of):

[0571] 196.1 g of deionized water

[0572] 6.2 g of Adeka Reasoap SR-1025 (25 wt % aqueous solution)

[0573] 45.5 g of methacrylic acid

[0574] 18.2 g of a 25 wt % strength solution of ureidoethyl methacrylate in methyl methacrylate

[0575] 300.3 g of methyl methacrylate

[0576] 45.5 g of n-butyl acrylate

[0577] 227.5 g of a 20 wt % strength aqueous solution of diacetoneacrylamide, and

[0578] 21.0 g of 2-ethylhexyl thioglycolate

[0579] Feed 3:

[0580] 27.0 g of a 25 wt % strength ammonia solution

[0581] Feed 4 (homogeneous mixture of):

[0582] 387.0 g of deionized water

[0583] 17.7 g of a 15 wt % aqueous solution of sodium lauryl sulfate

[0584] 658.0 g of n-butyl acrylate

[0585] 280.0 g of methyl methacrylate, and

[0586] 7.0 g of allyl methacrylate

[0587] Feed 5:

[0588] 9.0 g of a 25 wt % strength ammonia solution

[0589] Feed 6 (homogeneous solution of):

[0590] 9.3 g of deionized water and

[0591] 0.7 g of sodium peroxodisulfate

[0592] After the end of feeds 4 and 6, the polymerization mixture was left to react further at 80° C. for 30 minutes; then 167.2 g of deionized water were added and stirring was carried out at 80° C. for 90 minutes more.

[0593] The aqueous polymer dispersion obtained was then cooled to room temperature. At room temperature, 189.6 g of a 12 wt % strength aqueous solution of adipic dihydrazide were added. Lastly, the dispersion was filtered through a 125 μm filter.

[0594] The resulting 3425.8 g of the aqueous polymer dispersion had a solids content of 42.5 wt %, the MFFT was ≦0° C. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 47 nm (measured by means of HDC).

COMPARATIVE EXAMPLE 6

Adeka Reasoap Only in Feed 4 (CE6)

[0595] A polymerization vessel equipped with metering devices and temperature regulation was charged at 20 to 25° C. (room temperature) under a nitrogen atmosphere with

[0596] 719.6 g of deionized water and

[0597] 30.8 g of a 15 wt % aqueous solution of sodium lauryl sulfate

[0598] 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. When 50% of this feed had been metered in, over 45 minutes, the feed was stopped, and feed 5 was added and stirred in for 10 minutes. Then the remainder of feed 4 and, in parallel therewith, feed 6 were metered in over the course of 45 minutes.

[0599] Feed 1 (homogeneous solution of):

[0600] 55.8 g of deionized water and

[0601] 4.2 g of sodium peroxodisulfate

[0602] Feed 2 (homogeneous mixture of):

[0603] 192.1 g of deionized water

[0604] 10.3 g of a 15 wt % aqueous solution of sodium lauryl sulfate

[0605] 45.5 g of methacrylic acid

[0606] 18.2 g of a 25 wt % strength solution of ureidoethyl methacrylate in methyl methacrylate

[0607] 300.3 g of methyl methacrylate

[0608] 45.5 g of n-butyl acrylate

[0609] 227.5 g of a 20 wt % strength aqueous solution of diacetoneacrylamide, and

[0610] 21.0 g of 2-ethylhexyl thioglycolate

[0611] Feed 3:

[0612] 27.0 g of a 25 wt % strength ammonia solution

[0613] Feed 4 (homogeneous mixture of):

[0614] 396.1 g of deionized water

[0615] 10.6 g of Adeka Reasoap SR-1025 (25 wt % aqueous solution)

[0616] 658.0 g of n-butyl acrylate

[0617] 280.0 g of methyl methacrylate, and

[0618] 7.0 g of allyl methacrylate

[0619] Feed 5:

[0620] 9.0 g of a 25 wt % strength ammonia solution

[0621] Feed 6 (homogeneous solution of):

[0622] 9.3 g of deionized water and

[0623] 0.7 g of sodium peroxodisulfate

[0624] After the end of feeds 4 and 6, the polymerization mixture was left to react further at 80° C. for 30 minutes; then 167.2 g of deionized water were added and stirring was carried out at 80° C. for 90 minutes more.

[0625] The aqueous polymer dispersion obtained was then cooled to room temperature. At room temperature, 189.6 g of a 12 wt % strength aqueous solution of adipic dihydrazide were added. Lastly, the dispersion was filtered through a 125 μm filter.

[0626] The resulting 3425.3 g of the aqueous polymer dispersion had a solids content of 42.4 wt %, the MFFT was ≦0° C. On dilution with deionized water, the aqueous polymer dispersion has a weight-average particle diameter of 46 nm (measured by means of HDC).

Formulation of the Stain

Results of the Experiments

[0627]

TABLE-US-00002 IE4 CE5 CE6 Stain Whitening after 1 h 3 3-4 3-4 (school grade) Capillary water absorption 86 99 118 (g/m.sup.2 × 3 d) Pendulum hardness (s) 38 38 35