Aqueous multi-stage copolymer compositions for use in leather topcoats

Abstract

The present invention provides aqueous composition comprising a multi-stage acrylic emulsion polymer having a first stage polymer of from 0.5 to 4 wt. %, based on the total weight of monomers used to make the first stage polymer, of a copolymerized carboxylic acid or salt group containing monomer, and having 10 to 30 wt. %, on total solids of the multi-stage acrylic emulsion polymer, of a second stage polymer of from 3 to 15 wt. % of a copolymerized hydroxyl group containing monomer, the first stage polymer having a glass transition temperature (Tg) by dynamic mechanical analysis (DMA) of less than 10 C. and the second stage polymer having a Tg (DMA) of greater than 80 C.; and (ii) from 25 to 75 wt. %, based on the total solids weight of the multi-stage acrylic polymer, of a polyurethane.

Claims

1. An aqueous composition comprising: (i) from 10 to 50 wt. %, based on the total solids weight of the composition, of a multi-stage acrylic emulsion polymer having 70 to 90 wt. %, based on the total solids weight of the polymer, of a first stage polymer of from 0.5 to 3 wt. %, based on the total weight of monomers used to make the first stage polymer, of a copolymerized carboxylic acid or salt group containing monomer, and having 10 to 30 wt. %, based on the total solids weight of the multi-stage acrylic emulsion polymer, of a second stage polymer of from 3 to 15 wt. %, based on the total weight of monomers used to make the second stage polymer, of a copolymerized hydroxyl group containing monomer, the first stage polymer having a glass transition temperature (Tg) by dynamic mechanical analysis (DMA) of less than 10 C. and the second stage polymer having a Tg (DMA) of greater than 80 C.; and (ii) from 25 to 75 wt. %, based on the total solids weight of the multi-stage acrylic polymer, of a polyurethane having a polymeric Tg determined by differential scanning calorimetry (DSC), scanning from a temperature of 90 C. to 150 C. at a heating rate of 20 C./min, of 20 to 70 C.

2. The aqueous composition as claimed in claim 1, wherein the (i) multi-stage acrylic emulsion polymer comprises as the first stage polymer a polymer of from 1 to 3 wt. %, based on the total weight of monomers used to make the first stage polymer, of a copolymerized carboxylic acid or salt group containing monomer.

3. The aqueous composition as claimed in claim 1, wherein the (i) multi-stage acrylic emulsion polymer comprises as the second stage polymer a polymer of from 3 to 12 wt. %, based on the total weight of monomers used to make the second stage polymer, of a copolymerized hydroxyl group containing monomer.

4. The aqueous composition as claimed in claim 1, wherein the (i) multi-stage acrylic emulsion polymer comprises copolymerized hydroxyethyl methacrylate as the copolymerized hydroxyl group containing monomer.

5. The aqueous composition as claimed in claim 1, wherein the second stage polymer of the (i) multi-stage acrylic emulsion polymer has a Tg (DMA) of greater than 100 C.

6. The aqueous composition as claimed in claim 1, wherein the first stage polymer of the (i) multi-stage acrylic emulsion polymer is substantially free of copolymerized hydroxyl group containing monomers and of copolymerized diethylenically or polyethylenically unsaturated vinyl monomers.

7. The aqueous composition as claimed in claim 1, wherein the second stage polymer of the (i) multi-stage acrylic emulsion polymer is substantially free of copolymerized carboxylic acid or salt group containing monomers and is substantially free of copolymerized diethylenically or polyethylenically unsaturated vinyl monomers.

8. The aqueous composition as claimed in claim 1, wherein the first stage polymer of the (i) multi-stage acrylic emulsion polymer has a Tg (DMA) that is at least 100 C. less than the Tg (DMA) of the second stage polymer.

9. The aqueous composition as claimed in claim 1, wherein at least one polyurethane in the (ii) polyurethane dispersion comprises a condensate of one or more polyester polyol or polyether polyol or polycarbonate polyol with a diisocyanate or a polyisocyanate.

10. The aqueous composition as claimed in claim 1, further comprising (iii) from 1 to 50 wt. % of a polyorganosiloxane composition, based on the total solids weight of the aqueous composition, the polyorganosiloxane composition having a polyorganosiloxane with a weight average particle size of from 1.0 to 10 m.

11. A coated article comprising leather upholstery having thereon a coating of the aqueous compositions as in claim 1.

12. The aqueous composition as claimed in claim 1, further comprising from 1 to 40 wt. %, based on the total solids weight of the composition, of one or more crosslinker comprising a polyisocyanate, a polyaziridine, or aminoplast resin.

13. The aqueous composition as claimed in claim 1, further comprising 5 to 20 wt. %, based on the total solids weight of the composition, of one or more multi-stage acrylic copolymeric dullers.

14. The aqueous composition as claimed in claim 13, further comprising an additional inorganic or organic duller.

Description

EXAMPLES

(1) In the following examples, unless otherwise indicated, all units of temperature are room temperature and all units of pressure are standard pressure (1 atm or 760 mBar).

(2) In the following examples, the abbreviations have the following meanings:

(3) EA=ethyl acrylate; BA=butyl acrylate; AN=acrylonitrile; AA=acrylic acid; EHA=2-ethylhexyl acrylate; AAEM=2-acetoacetylethyl methacrylate; ALMA=allyl methacrylate; DVB=divinyl benzene; HEMA=2-hydroxyethyl methacrylate; MAA=methacrylic acid; MMA=methyl methacrylate; BMA=butyl methacrylate; t-BA=tert-butyl acrylate; STY=styrene.

(4) In the following Examples, the following materials were used:

(5) Polyurethane Dispersion 1 (PUD 1): Primal Binder U-91 (The Dow Chemical Co., Midland, Mich.) is a polyurethane made using a polyester polyol having a Tg of 52.9 C. and a particle size of 61.4 nm as measured by Bi-90.

(6) Polyurethane Dispersion 2 (PUD 2): Hauthaway 2501 (C.L. Hauthaway and Sons Company, Lynn, Mass.), a pud made using a polycarbonate polyol and having a Tg of 35.4 C. (product literature) and a particle size of 92.7 nm as measured by Bi-90

(7) Polyurethane Dispersion 3 (PUD 3): Hauthaway 2357 (C.L. Hauthaway and Sons), a pud made using a polyether polyol and having a Tg of 43.1 C. (product literature) and a particle size of 42.6 nm as measured by Bi-90;

(8) Polyurethane Dispersion 4: BAYDERM bottom CTR aqueous polyurethane dispersion (Lanxess GmbH, Leverkusen, DE, (Lanxess));

(9) Polyurethane Dispersion 5: BAYDERM bottom PR aqueous polyurethane dispersion (The Dow Chemical Company, Midland, Mich., (Dow));

(10) Polysiloxane 1: A feel additive comprising polydimethylsiloxane as a 60 wt. % aqueous dispersion having a weight average particle size (Mastersizer) of about 3 to 5 m and a dynamic viscosity of about 30,000 Pa.Math.s (neat, 0.01 Hz at 25 C.).

(11) Polysiloxane 2: A feel additive comprising a polydimethylsiloxane as a 60 wt. % aqueous dispersion, having a weight average particle size (Mastersizer) of 2.5 to 4.5 m and a median dynamic viscosity of about 45,000 Pa.Math.s (neat, 0.01 Hz at 25 C.).

(12) Polysiloxane 3: A feel additive comprising, a polydimethylsiloxane as a 45 wt. % aqueous dispersion having a weight average particle size (Mastersizer) of from 0.2 to 0.6 m and dynamic viscosity of about 400,000 Pa.Math.s (neat, 0.01 Hz at 25 C.).

(13) Intermediate 1: Silica duller preparation for leather topcoat.

(14) Intermediate 2 or Acrylic Duller: Acrylic emulsion polymer duller bead made using a multiple stage emulsion polymerization particle composition of 80% (96 BA/4 ALMA)//20% (96 MMA/4 EA), particle size 4 um (DCP) and solid content of 32%.

(15) Crosslinker 1: AQUADERM XL-DI 2 Aliphatic polyisocyanate crosslinker, (Lanxess);

(16) Crosslinker 2: AQUADERM XL-80 Aliphatic polyisocyanate crosslinker, (Lanxess);

(17) Flow Agent: Aquaderm Fluid H polydimethylsiloxane Flow agent (Lanxess);

(18) HYDRHOLAC UD-4 polymer bound duller (Dow);

(19) Black Pigment dispersion 1: EUDERM BLACK BN carbon black Pigment dispersion (Lanxess);

(20) Black Pigment Dispersion 2: EUDERM X-Black B carbon black pigment dispersion 2 (Lanxess);

(21) HEUR (Hydrophobically modified Ethylene Oxide Urethane) rheology Modifier: Acrysol RM-1020 rheology modifier (Dow);

(22) Soft anti-tack agent and filler: .sup.1EUDERM Nappa Soft S2 casein and triglyceride aqueous preparation (Lanxess);

(23) Matting agent: EUDERM Duller SN-2 silicic acid aqueous preparation (Lanxess);

(24) Acrylic Emulsion Polymer Binder: PRIMAL SB 300 Acrylic Emulsion polymer (Dow).

(25) In all of the test methods, below, unless otherwise indicated, leather was finished in one of two ways: Leather was embossed on the indicated basecoat using a crushed goat plate at 100 C./300 bar pressure for 10 seconds. The leather was staked (placed on a stake) 2 times prior to applying top coat. Alternatively, leather was smooth finished over basecoat using a Model N Finiflex smooth roll (Koch Tanning Machinery Co., Waukesha, Wis.) at a temperature of 120 C.

(26) Standard Test Methods

(27) Cold Flex: Cold flex testing was conducted on smooth finished leather that was top coated with the indicated composition and allowed to cure for 3 days. A six station, low temperature flexometer (Giuliani corporation, model G6FN, Torino Italy) was used for this determination. Conditions employed were 10 C. for 30,000 flexing cycles and testing was conducted on leather that was cut into 3.84 cm (1.5)6.4 cm (2.5) pieces. The leather was evaluated for damage to the topcoat after flexing and visually assessed by stereoscope and rated using a visual rating scale of 1-5 which represents substantial topcoat cracking to no topcoat damage. A higher rating represents improved performance. Generally an acceptable result is 3 or higher.

(28) Flexibility Determination:

(29) A 3.8 cm6.5 cm swatch of leather finished with the indicated composition using a was positioned on a Bally Flexometer device (model 2397, Otto Specht Company, Stuttgart, DE). The leather was flexed for 100,000 cycles at ambient temperature. After flexing, the leather was visually evaluated for cracking and generation of white crazing in the flexing area. For the evaluation the sample was examined under a 10 sterio-scope. The results are recorded and rated using a visual rating scale of 1-5 which represents substantial topcoat cracking to no topcoat damage. A higher rating represents improved performance but generally an acceptable result is 3 or higher.

(30) Color Determination:

(31) Color of the leather finished with the indicated composition was determined using a color spectrophotometer (X-Rite 8400 Sphere spectrophotometer, X-Rite Incorporated, Grand Rapids, Mich.). CIE L*a*b* values were determined using a D65 light source at a 10 degree standard observer (gloss excluded).

(32) Wet Rub Fastness:

(33) Wet rub fastness was determined on finished leather that was top coated with the indicated composition and allowed to cure for 24 hours prior to testing. A three station Veslic Tester (Schap Corporation, Spring Lake, Mich.) equipped with Veslic pads (Ar N 701 pads, Swissatest corporation, St Gallen, CH) that were soaked with 1 gram of water was used for testing leather that was cut into 12.8 cm (5)2.56 cm (1) pieces. One kilogram of weight was applied to the pad and 2000 rub cycles were applied to the leather. The pads were visually evaluated for pigment transfer and assessed by using a grey scale rating of 1 to 5 which represents substantial to no pigment transferred from the leather to the pad. A higher rating represents improved performance. Generally an acceptable rating is 4 or higher.

(34) Soft-Feel Assessment:

(35) Finished leather articles were manually handled to determine the degree of softness to touch. A relative rating of 1-5 was assessed on the degree of softness provided. A rating of 1 represents leather that has a relative hard surface feeling and a rating of 5 represents leather that has a relatively very soft feeling at the surface. An acceptable rating is 3 or higher.

(36) Gakushin Method:

(37) To measure abrasion resistance of a leather topcoat, the conventional method described in Improvements in Gakushin Wear Testing Through Laboratory Automation (Journal of the American Leather Chemists Association, Volume 108, Issue 6, (2013), pp. 200-209) was employed. In this method, a higher value represents improved abrasion performance.

(38) Synthesis: Synthesis of Acrylic Multi-Stage Polymer Emulsion Polymer 1

(39) First Stage:

(40) 1025 g of deionized water was added into 5 L round bottom flask (reactor) fitted with a stirrer, condenser, temperature probe and a nitrogen flush.

(41) Reactor and added water were degassed for 30 min. A monomer emulsion was prepared in a separate jar by addition of 203.4 g deionized water, 31.6 g sodium lauryl sulfate (28% solution), 31.8 g of sodium salt of branched alkylbenzene sulfonic acid (22% solution), 411 g of butyl acrylate, 411 g of 2-ethylhexyl acrylate, and 16.8 g of acrylic acid. At 40 C., 25% of the monomer emulsion was pumped into the reactor followed by charging each of 7 mg of FeSO.sub.4.7H.sub.2O in 10 g deionized water, 0.2 g of ammonium persulfate in 15 g of deionized water and 0.4 g of sodium hydrosulfite in 15 g of deionized water. Polymerization was allowed to proceed for 10 minutes of exotherm. After polymerization was complete, the rest of the monomer emulsion was pumped into the reactor at 48 C. and the pump lines were rinsed with 80 g of deionized water followed by addition of 0.6 g of ammonium persulfate in 15 g of deionized water and 1.1 g of sodium hydrosulfite in 25 g of deionized water. Polymerization was allowed to proceed for 10 minutes of exotherm. After polymerization was complete, 0.5 g of t-butyl hydroperoxide in 15 g of deionized water and 0.4 g of sodium formaldehyde sulfoxylate in 15 g of deionized water were charged separately to the reactor.

(42) Second Stage:

(43) At 64 C., 191.5 g of methyl methacrylate and 18.2 g of 2-hydroxyethyl methacrylate were mixed and pumped to the reactor containing the first stage polymer; the pump lines lines were rinsed with 25 g of deionized water, then 1.0 g of t-butyl hydroperoxide in 35 g of deionized water and 0.8 g of sodium formaldehyde sulfoxylate in 25 g of deionized water were separately charged to the reactor. Polymerization was allowed to proceed for 5 minutes of exotherm. After polymerization was complete, residual monomers were reacted by pumping separately 1.6 g of t-butyl hydroperoxide in 50 g of deionized water and 1.4 g of Bruggolite FF6 (disodium salts of 2-hydroxy-2-sulfinatoacetic acid and 2-hydroxy-2-sulfonatoacetic acid 70% w/w and sodium sulfite 30% w/w, Brggemann Chemical U.S., Inc., Newtown Square, Pa.) in 50 g of deionized water to the reactor over a 30 minute period.

(44) After the reactor was allowed to cool to 35 C., the emulsion polymer was neutralized by pumping a mixture of 76.3 g of deionized water, 10.7 g sodium lauryl sulfate (28% solution), and 11.1 g of triethyl amine into the reactor over 45 minutes. A final dilution of 60 g of deionized water was added to the reactor.

(45) The resulting emulsion polymer was filtered over a 45 micron screen and the filtrate was analyzed to give a total solids of 37.1 wt. %, a pH of 7.8 and a weight average particle size of 111.1 nm (BI-90).

(46) Synthesis of Comparative Emulsion Polymer 2A:

(47) The emulsion polymer 2 was synthesized as disclosed in Example 1, above, except monomer amounts were adjusted according to the ratios described in Table 3A, below.

(48) Synthesis of Emulsion Polymer Comparatives 1 and 2:

(49) The emulsion polymers Comparatives 1 and 2 were synthesized as disclosed in Example 1, above, except monomer amounts were adjusted according to the ratios described in Table 3A, below.

(50) Synthesis of Emulsion Polymer Comparative 3:

(51) The emulsion polymer was prepared according to description in Example of European Patent no. EP1274794B1, to Biver et al., to give a multi-stage emulsion polymer of 28 MMA/55.9 BA/0.81 Butanediol Acrylate/0.43 diallyl maleate//13.8 MMA/1.01 MAA in which the latter stage is the outer stage.

(52) Formulations for making coatings were formed from the indicated compositions, as follows:

(53) A basecoat formulation for treating leather was prepared by sequentially adding the materials listed in Table 1, below, and mixed using a lab top, three blade mixer. The basecoat formulation was applied to the indicated leather substrate by spray application to a final add-on of 4-5 dry grams/square foot (40 to 55 g/m.sup.2).

(54) TABLE-US-00001 TABLE 1 Basecoat Formulation Material grams Water 204 Soft anti-tack agent and filler 136 Matting agent 260 Acrylic Emulsion Polymer Binder 340 Polyurethane dispersion 4 170 Polyurethane dispersion 5 425 Black Pigment dispersion 2 255 HEUR Rheology Modifier 6 Total 1797.7

(55) A silica duller dispersion was prepared using a high shear dispersator by adding in order the materials listed in Table 2, below. Silica was added slowly over about 1.5 hours to obtain the dispersion.

(56) TABLE-US-00002 TABLE 2 Intermediate 1: Silica Duller Preparation For Leather Topcoat Grind preparation Material Grams Water 1516.2 .sup.8 Polymeric dispersant 130.3 .sup.9Amino silane 9.5 .sup.10Inorganic silica duller 202.1 .sup.11Defoamer 1.5 .sup.12Nonionic surfactant 65.4 .sup.11Defoamer 1.5 water 77.4 HEUR Rheology Modifier 12.9 total grind 2016.8 .sup.8 TAMOL 731a dispersant (Dow); .sup.9Dynasylan 1505 (Evonik Industries); .sup.10ACEMATT TS-100 (Evonik Industries); .sup.11Surfynol 104BC (Air Products); .sup.12Tergitol 15-S-5 (Dow);

(57) TABLE-US-00003 TABLE 3A Acrylic Polymer Compositions for Topcoats Tg.sup.1 BA EHA AA HEMA HEMA MMA ( C.) Emulsion 1.sup.st Stage 2.sup.nd Stage 1.sup.st Stage; Polymer (80% of total) (20% of Total) 2.sup.nd Stage 1 49.00 49.00 2.00 8.68 91.32 43.1; 117.3 Compar- 96.50 3.50 100.00 31.9; ative 1 124.5 Compar- 45.75 45.75 3.50 5.00 100.00 37.1; ative 2A 122.3 Compar- 49.00 49.00 2.00 17.36 82.64 46.9; ative 2 113.4 Compar- 4.6; ative 3 137.9 .sup.1DMA.

(58) TABLE-US-00004 TABLE 3B Topcoat Formulations (amounts shown in grams) Formulation Comp Comp. Comp. Comp. Example 1A Example 1 Example 2 Example 3 3A 4A 5A Emulsion 1 1 1 1 Comp 3 Comp 3 Comp 3 Polymer Water 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Intermediate 1 40.7 40.7 40.7 40.7 40.7 40.7 40.7 Acrylic Duller 23.0 23.0 23.0 23.0 23.0 23.0 23.0 Flow Agent 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Polysiloxane 2 14.0 14.0 14.0 14.0 14.0 14.0 14.0 Black Pigment 1 1.0 1.0 1.0 1.0 1.0 1.0 dispersion 1 HEUR rheology 0.8 0.8 0.8 0.8 0.8 0.8 0.8 modifier Extra water 11.7 13.7 9.2 14.1 13.4 8.8 13.7 Emulsion polymer 66.7 33.3 33.3 33.3 33.7 33.7 33.7 Polyurethane 31.5 31.5 Dispersion 1 Polyurethane 36.1 36.1 Dispersion 3 Polyurethane 31.2 31.2 Dispersion 2 HEUR rheology 2.1 1.3 1.3 1.2 1.3 1.2 1.2 modifier Crosslinker 1 20.0 20 20 20 20 20 20 Total 202.0 201.3 201.3 201.2 201.3 201.2 201.2

(59) TABLE-US-00005 TABLE 3C More Topcoat Formulations (amounts shown in grams) Formulation Example Comp 6A Comp 4 Comp 7A Comp 5 Emulsion Polymer Comp 1 Comp 2A Comp 2 Comp 2A Water 36.6 36.6 36.6 73.3 Flow Agent 2.4 2.4 2.4 4.9 Black Pigment 7.3 7.3 7.3 14.7 dispersion 2 HYDRHOLAC UD-4 104.9 104.9 104.9 210.2 Emulsion Polymer 48.8 48.8 48.8 97.8 Polysiloxane 1 17.1 17.1 17.1 34.2 HEUR rheology modifier 3 2.2 2.2 4.4 Amount premix 180 180 180 420 transferred Crosslinker 2 20 20 20 46.7

(60) TABLE-US-00006 TABLE 3D Topcoat Formulations with Duller Beads (amounts shown in grams) Formulation Example 1 Comp. 8A Comp. 9A Emulsion Polymer 1 1 1 Water 20.0 24.8 24.8 Intermediate 1 40.7 40.7 40.7 Intermediate 2 acrylic Duller 23.0 23.0 23.0 Flow Agent 2.0 2.0 2.0 Polysiloxane 2 14.0 Polysiloxane 3 (comparative) 18.7 Black Pigment dispersion 1 1.0 1.0 1.0 HEUR rheology modifier 0.8 0.8 0.8 Extra water 13.7 Emulsion Polymer 33.3 33.3 33.3 Polyurethane Dispersion 1 31.5 31.5 31.5 HEUR rheology modifier 1.3 1.2 1.2 Crosslinker 1 20 20 20 Total 201.3 178.2 197.0

(61) TABLE-US-00007 TABLE 3E Topcoat Formulations with Dullers and Siloxanes (amounts shown in grams) Comp form. Formulation Example 1 10A 6 Emulsion polymer 1 1 1 Water 20.0 24.8 24.8 Intermediate 1 40.7 40.7 40.7 Intermediate 2 acrylic Duller 23.0 11.5 Flow Agent 2.0 2.0 2.0 Polysiloxane 2 14.0 7.0 7.0 Black Pigment dispersion 1 1.0 1.0 1.0 HEUR rheology modifier 0.8 0.8 0.8 Extra water 13.7 Emulsion Polymer 33.3 33.3 33.3 Polyurethane Dispersion 1 31.5 31.5 31.5 HEUR rheology modifier 1.3 1.2 1.2 Crosslinker 1 20 20 20 Total 201.3 162.3 173.8

(62) Topcoat formulations were prepared by sequentially adding the materials listed in Tables 3B-3E, above, to a container and mixing using a lab top, three blade mixer. After mixing, the topcoats were filtered through a 125 m paint strainer and sprayed over the basecoat described in Table 1, above. The final add-on for topcoat was 16.1-26.9 dry grams per square meter of leather. Performance of the topcoat formulations is presented in Tables 4A to 4D, below.

(63) TABLE-US-00008 TABLE 4A Results Formulation Comp. Comp Comp. Comp. Example 1A 1 2 3 3A 4A 5A Wet rub fastness 2.5 5 4 4.5 5 1 2 Cold flex 2 4 2 4 1 2 1

(64) Table 4A, above, shows that a combination of the inventive Emulsion Polymer 1 with polyurethane dispersions in Examples 1 to 3 provide significantly improved wet rub fastness performance than comparative Example 1A that contains no polyurethane dispersion. Also a combination of the inventive Emulsion Polymer 1 with polyurethane dispersions in Examples 1 to 3 provide a better overall balance of wet rub fastness and cold flex performance than comparative Emulsion Polymer 3 combined with polyurethane dispersions in Comparative Examples 3A, 4A and 5A.

(65) TABLE-US-00009 TABLE 4B Results Formulation Example Comp 6A 4 Comp 7A Comp 5 Cold Flex 1 4 2.5 1

(66) Table 4B, above, shows that the inventive combination of the inventive multi-stage acrylic emulsion polymer Emulsion Polymer 1 with a polyurethane dispersion provides in Example 4 significantly improved cold flex performance when comparative to formulations of Comparative Emulsion Polymers 1 or 2 combined with a polyurethane dispersion in Comparative Examples 6A and 7A. Thus, by reducing the copolymerized carboxylic acid monomer level from 3.5 wt. % to 2.0 wt. % in the first stage polymer and including 8.7 wt. % of copolymerized hydroxyl functional monomer in the second stage, as in Emulsion Polymer 1, the cold flex is optimized along with the early flex while maintaining the wear resistance of the topcoat. See Example 1 and compare comp Ex. 6A and 7A. Further, when including 17.4% of the hydroxyl functional monomer in the second stage of Comparative Emulsion Polymer 2_in Comparative Example 7A, one does not observe cold flex. Not shown in any Table, one also does not observe wet rub advantages when using Comparative Emulation Polymer 2. Emulsion Polymer 2A having more than 3 wt. % of copolymerized ethylenically unsaturated carboxylic acid or salt group containing monomer exhibits less desirable cold flex than compositions comprising multi-stage acrylic emulsion polymers made from the preferred amount of less than 3 wt. % of copolymerized ethylenically unsaturated carboxylic acid or salt group containing monomer, such as Emulsion Polymer 1.

(67) TABLE-US-00010 TABLE 4C Results Formulation Example 1 Comp. 8A Comp. 9A Wet rub fastness 5 1 4 Gakushin (conventional) 6667 4733

(68) Table 4C, above, shows that formulations containing a combination of the inventive multi-stage acrylic emulsion polymer Emulsion Polymer 1 with a polyurethane dispersion and 4.2% polyorganosiloxane composition of particle size 3 to 4 um in Example 1 provides dramatically better wet rub performance and Gakushin wear performance than a formulation containing Emulsion Polymer 1 containing 4.5% of a polyorganosiloxane composition of a weight average particle size >1 um.

(69) TABLE-US-00011 TABLE 4D Results Formulation Example 1 Comp. 10A 6 Soft-feel 5 2 4

(70) Table 4D, above, shows that formulations containing a combination of the inventive multi-stage acrylic emulsion polymer Emulsion Polymer 1 with a polyurethane dispersion and from 2.1 to 3.7 wt. % of acrylic duller bead particles and 2.2 to 4.2 wt. % polysiloxane composition having a weight average particle size 3 to 4 m, as in Examples 1 and 6 provides dramatically better soft-feel than a comparative Example 10A that contains the same Emulsion Polymer 1 but has no acrylic duller bead.