POLYMER DISPERSION FOR DURABLE COATING, AND THE COATING COMPRISING THE SAME

Abstract

The present invention provides a coating composition comprising a polymer binder and from 1% to 40% by dry weight based on total dry weight of the coating composition, titanium dioxide particles, wherein the polymer binder comprises, as polymerized units, by dry weight based on total dry weight of the polymer binder, from 50% to 99%, ethylenically unsaturated nonionic monomers, and from 1% to 5%, a vinyl functionalized benzotriazole.

Claims

1. A coating composition comprising a polymer binder, and from 1% to 40% by dry weight based on total dry weight of the coating composition, titanium dioxide particles, wherein the polymer binder comprises, as polymerized units, by dry weight based on total dry weight of the polymer binder, from 50% to 99%, ethylenically unsaturated nonionic monomers, and from 1% to 5%, a vinyl functionalized benzotriazole having the following Structure (I): ##STR00006## wherein n is an integer of from 6 to 40; wherein R.sub.1 is a vinyl-containing group selected from methyl acrylate, methacrylamide, acrylate, acrylamide, vinyl ether, and allyl ether; wherein R.sub.2 is selected from C.sub.1-4 alkylene and C.sub.1-5 alkylenylcarboxy; wherein X.sub.1, X.sub.2, X.sub.3 or X.sub.4 is each independently selected from H, C.sub.1-10 alkyl, OH and OCH.sub.3; and wherein Y.sub.1, Y.sub.2, Y.sub.3 or Y.sub.4 is each independently selected from H, OH and OCH.sub.3.

2. The coating composition according to claim 1 wherein the polymer binder further comprises, as polymerized units, from 0.1% to 20% by dry weight based on total dry weight of the polymer binder, an ethylenically unsaturated monomer carrying at least one functional group selected from carboxyl, carboxylic anhydride, hydroxyl, amide, amino, ureido, acetoacetate, sulphonate, phosphonate, and any combinations thereof.

3. The coating composition according to claim 1 wherein the vinyl functionalized benzotriazole is a 2-(2-hydroxy-3-tertbutyl-5-methacrylethyloxylate ethylphenyl)-2H-benzotriazole having the following Structure (II): ##STR00007## wherein n is an integer of from 6 to 20.

4. The coating composition according to claim 1 wherein the vinyl functionalized benzotriazole is a 2-(2-hydroxy-3-tertbutyl-5-methacrylethyloxylate ethylenylcarboxy phenyl)-2H-benzotriazole having the following Structure (III): ##STR00008## wherein n is an integer of from 6 to 20.

5. The coating composition according to claim 1 wherein the vinyl functionalized benzotriazole having the Structure (I) is from 2% to 4% by dry weight based on total dry weight of the polymer binder.

6. The coating composition according to claim 1 wherein the vinyl functionalized benzotriazole having the Structure (I) has an R.sub.1 of being methyl acrylate or acrylate.

7. The coating composition according to claim 1 wherein the vinyl functionalized benzotriazole having the Structure (I) has an R.sub.2 being ethylene or ethylenylcarboxy.

8. The coating composition according to claim 1 wherein the vinyl functionalized benzotriazole having the Structure (I) has any of X.sub.1, X.sub.2, X.sub.3 and X.sub.4 being H, OH or t-butyl.

9. The coating composition according to claim 1 wherein the vinyl functionalized benzotriazole having the Structure (I) has any of Y.sub.1, Y.sub.2, Y.sub.3 and Y.sub.4 being H or OH.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0006] The Polymer Binder

[0007] The polymer binder comprises, as polymerized units, by dry weight based on total dry weight of the polymer binder, from 50% to 99%, preferably from 60% to 98%, and more preferably from 70% to 97%, ethylenically unsaturated nonionic monomers.

[0008] The ethylenically unsaturated nonionic monomers are ,-ethylenically unsaturated monomers without bearing an ionic charge between pH=1-14. Suitable examples of the ethylenically unsaturated nonionic monomers include (meth)acrylic ester monomers, i.e., methacrylic ester or acrylic ester monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, methyl methacrylate, butyl methacrylate, isodecyl methacrylate, lauryl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate; (meth)acrylonitrile; styrene and substituted styrene such as -methyl styrene, and vinyl toluene; butadiene; ethylene; propylene; -olefin such as 1-decene; vinyl ester such as vinyl acetate, vinyl butyrate, and vinyl versatate; and other vinyl monomers such as vinyl chloride and vinylidene chloride. Preferably, the ,-ethylenically unsaturated nonionic monomers are ethyl acrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, and any combinations thereof.

[0009] Optionally, the polymer binder further comprises, as polymerized units, from 0.1% to 20%, preferably from 0.5% to 10%, and more preferably from 1% to 5%, by dry weight based on total dry weight of the polymer binder, an ethylenically unsaturated monomer carrying at least one functional group selected from carboxyl, carboxylic anhydride, hydroxyl, amide, amino, ureido, acetoacetate, sulphonate, phosphonate, and any combinations thereof. Suitable examples of these monomers are ethylenically unsaturated carboxylic or dicarboxylic acid such as acrylic or methacrylic acid, itaconic acid, and maleic acid; ethylenically unsaturated amide such as (meth)acrylamide; ethylenically unsaturated N-alkylolamide such as N-methylol(meth)acrylamide and 2-hydroxyethyl(meth)acrylamide; hydroxyalkyl ester of the carboxylic or dicarboxylic acid, such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; amino-functional monomers such as N,N-dimethylaminoethyl methacrylate; ureido-functional monomers such as methacrylamidoethyl-2-imidazolidinone; monomers bearing acetoacetate-functional groups such as acetoacetoxyethyl methacrylate; and any combinations thereof.

[0010] The polymer binder of the present invention further comprises, as polymerized units, from 1% to 5%, preferably from 1.5% to 4.5%, and more preferably from 2% to 4%, by dry weight based on total dry weight of the polymer binder, a vinyl functionalized benzotriazole having the following Structure (I):

##STR00002##

[0011] wherein n is an integer of from 6 to 40, preferably from 6 to 30, and more preferably from 6 to 20;

[0012] wherein R.sub.1 is a vinyl-containing group selected from methyl acrylate, methacrylamide, acrylate, acrylamide, vinyl ether, and allyl ether; preferably R.sub.1 is methyl acrylate, methacrylamide, acrylate or acrylamide; and more preferably R.sub.1 is methyl acrylate or acrylate;

[0013] wherein R.sub.2 is selected from C.sub.1-4 alkylene and C.sub.1-5 alkylenylcarboxy, and is preferably ethylene or ethylenylcarboxy;

[0014] wherein X.sub.1, X.sub.2, X.sub.3 or X.sub.4 is each independently selected from H, C.sub.1-10 alkyl, OH and OCH.sub.3; and is preferably H, OH or t-butyl; and

[0015] wherein Y.sub.1, Y.sub.2, Y.sub.3 or Y.sub.4 is each independently selected from H, OH and OCH.sub.3; and is preferably H or OH.

[0016] The vinyl functionalized benzotriazole of the present invention preferably is 2-(2-hydroxy-3-tertbutyl-5-methacrylethyloxylate ethylphenyl)-2H-benzotriazole having the following Structure (II):

##STR00003##

[0017] wherein n is an integer of from 6 to 20;

[0018] or is 2-(2-hydroxy-3-tertbutyl-5-methacrylethyloxylate ethylenylcarboxy phenyl)-2H-benzotriazole having the following Structure (III):

##STR00004##

[0019] wherein n is an integer of from 6 to 20.

[0020] The Coating Composition

[0021] The coating composition of the present invention comprises the polymer binder, and from 1% to 40%, preferably from 3% to 30%, and more preferably from 5% to 20%, by dry weight based on total dry weight of the coating composition, titanium dioxide particles.

[0022] Any titanium dioxide particles can be used in the coating composition of the present invention. Commercially available titanium dioxide particles include TI-PURE R-706 and TI-PURE R-902+ from DuPont, TIONA 595 from Millennium Inorganic Chemicals, TIOXIDE TR92 from Huntsman Corporation, LOMON R-996 and LOMON LR-997 from LOMON Corporation, BILLION BLR-688 and BILLION BLR-699 from Henan Billions Chemical Co., Ltd., DOGUIDE SR-237 from Shandong Doguide Group Co., Ltd., NTR-606 from Ningbo Xinfu Titanium Dioxide Co., Ltd., and R-2195 and R-2295 from Dawn Group. Preferably, the titanium dioxide particles are selected from TI-PURE R-706 and TI-PURE R-902+ available from DuPont.

[0023] The coating composition may further comprise other pigments or extenders.

[0024] As used herein, the term pigment refers to a particulate inorganic material which is capable of materially contributing to the opacity or hiding capability of a coating. Pigments typically have a refractive index of greater than 1.8 and include zinc oxide, zinc sulfide, barium sulfate, and barium carbonate. For the purpose of clarity, titanium dioxide particles of the present invention are not pigment of the present invention.

[0025] The term extender refers to a particulate inorganic materials having a refractive index of less than or equal to 1.8 and greater than 1.3 and include calcium carbonate, aluminium oxide (Al.sub.2O.sub.3), clay, calcium sulfate, aluminosilicate, silicate, zeolite, mica, diatomaceous earth, solid or hollow glass, and ceramic bead.

[0026] The coating composition may further contain at least one conventional coating additives such as coalescing agents, cosolvents, surfactants, buffers, neutralizers, thickeners, non-thickening rheology modifiers, dispersants, humectants, wetting agents, mildewcides, biocides, plasticizers, antifoaming agents, defoaming agents, anti-skinning agents, colorants, flowing agents, crosslinkers, and anti-oxidants.

[0027] Preparation of the Coating Composition

[0028] The preparation of the coating composition can be well-known methods of the art and involves the process of admixing appropriate coating ingredients in the indicated proportions to provide coating as well as the final dry coating film with the desired properties.

[0029] Application of the Coating Composition

[0030] The coating composition may be applied by conventional application methods such as brushing, roller application, and spraying methods such as air-atomized spray, air-assisted spray, airless spray, high volume low pressure spray, and air-assisted airless spray.

[0031] Suitable substrates for coating application include concrete, cement board, medium-density fiberboard (MDF) and particle board, gypsum board, wood, stone, metal, plastics, wall paper and textile, etc. Preferably, all the substrates are pre-primed by waterborne or solvent-borne primers.

Examples

I. Raw Materials

[0032]

TABLE-US-00001 Abbreviation Chemical BA butyl acrylate MMA methyl methacrylate (M)AA (methyl)acrylic acid SLS sodium lauryl sulfate EDTA ethylene diamine tetraacetic acid IAA isoascorbic acid t-BHP tert-butyl hydroperoxide APS ammonium persulfate AM acrylamide

TABLE-US-00002 Chemical Supplier OROTAN 731A dispersant The Dow Chemical Company TRITON CF-10 wetting agent The Dow Chemical Company TRITON X-405 wetting agent The Dow Chemical Company ACRYSOL SCT-275 rheology The Dow Chemical Company modifier ACRYSOL RM-2020 rheology The Dow Chemical Company modifier TRITON CF-10 wetting agent The Dow Chemical Company TI-PURE R-706 TiO.sub.2 DuPont Company COASOL coalescent The Dow Chemical Company TEXANOL coalescent Eastman Chemical Company ROCIMA 361 biocide The Dow Chemical Company BYK 022 defoamer BYK Additives & Instruments KATHON LXE biocide The Dow Chemical Company ROPAQUE Ultra E opaque polymer The Dow Chemical Company PRIMAL AC-261P binder The Dow Chemical Company

II. Test Procedures

[0033] 1. Gloss Retention Test for TiO.sub.2-Containing Coatings and Clear Coatings

[0034] Drawdown of coating compositions was made with a 150 m Bird Film Applicator on an aluminum sheet (for TiO.sub.2-containing coatings) or a 40% PVC coating (for clear coatings) (40% PVC coating formulation was described in Table 1). Coatings were allowed to dry for one week in a Constant Temperature Room (CTR) under 25 C. and the surface gloss of the dry coating at 60 degree geometry was determined by a BYK-Gardner Micro-TRI-Gloss 20/60/85 Gloss Meter, and was recorded as A1. Coatings were then put into a QUV Accelerated Weathering Tester from Q-Lab Corporation for 1800 hours (for clear coatings) and 1100 hours (for TiO.sub.2-containing coatings), then taken out, and allowed to cool down and dry. The surface gloss of the dry coatings at 60 degree geometry was determined by the same Gloss Meter, and was recorded as A2. Gloss retention for each coating was calculated by the formula A2/A1100% and recorded in Table 3.

TABLE-US-00003 TABLE 1 40% PVC coating formulation* Materials (g) Grind Water 110 propylene glycol 26.00 KATHON LXE biocide 0.80 BYK 022 defoamer 0.20 OROTAN 731A dispersant 5.00 TI-PURE R-706 TiO.sub.2 190 Let-down PRIMAL AC-261P binder 354 ROPAQUE Ultra E opaque polymer 112 TEXANOL coalescent 21.06 TRITON X-405 wetting agent 2.00 ACRYSOL RM-2020 rheology modifier 8.27 Total 829.33 *The Grind ingredients were mixed using a high speed Cowles disperser. The Let-down ingredients were added using a conventional lab mixer.

III. Experimental Examples

[0035] 1. Preparation for Polymer Binders

[0036] 1) Comparative Polymer Binder 1

[0037] A monomer emulsion was prepared by mixing 855.1 g BA, 993.1 g MMA, 18.87 g AA, 18.6 g 50% AM solution, 22.59 g 28% SLS solution, and 475 g deionized (DI) water and emulsified with stirring. 22.59 g 28% SLS solution and 706 g DI water were then charged to a five-liter multi-neck flask fitted with mechanical stirring. The contents of the flask were heated to 90 C. under a nitrogen atmosphere. To the stirred flask, 5.61 g sodium carbonate in 21.7 g DI water, 56.4 g of the monomer emulsion, 7.71 g APS in 23.9 g DI water were added. The remaining monomer emulsion, 0.96 g APS in 412 g DI water were then added gradually over 65 minutes to the flask. Reactor temperature was maintained at 88 C. Then, 30 g DI water was used to rinse the emulsion feed line to the reactor. Thereafter, the reaction mixture was stirred at reaction temperature for one more hour and then cooled to room temperature. The final pH value was adjusted to 8.5 using NH.sub.4OH (25% active). Comparative Polymer Binder 1 has a solid of 50.27% and a particle size of 132 nm.

[0038] 2) Comparative Polymer Binder 2

[0039] Comparative Polymer Binder 2 was prepared by a similar procedure according to that for preparing Comparative Polymer Binder 1, but using a different monomer emulsion. The monomer emulsion for Comparative Polymer Binder 2 was prepared by mixing 855.1 g BA, 983.7 g MMA, 18.87 g AA, 18.6 g 50% AM solution, 9.4 g UV absorber monomer B, 22.59 g 28% SLS solution and 475 g DI water with stirring. Comparative Polymer Binder 2 has a solid of 49.98% and a particle size of 137 nm.

[0040] 3) Comparative Polymer Binder 3

[0041] Comparative Polymer Binder 3 was prepared by a similar procedure according to that for preparing Comparative Polymer Binder 1, but using a different monomer emulsion. The monomer emulsion was prepared by mixing 855.1 g BA, 983.7 g MMA, 18.87 g AA, 18.6 g 50% AM solution, 9.4 g UV absorber monomer A, 22.59 g 28% SLS solution and 475 g DI water with stirring. Comparative Polymer Binder 3 has a solid of 49.93% and a particle size of 137 nm.

[0042] 4) Comparative Polymer Binder 4

[0043] Comparative Polymer Binder 4 was prepared by a similar procedure according to that for preparing Comparative Polymer Binder 1, but using a different monomer emulsion. The monomer emulsion was prepared by mixing 855.1 g BA, 964.9 g MMA, 18.87 g AA, 18.6 g 50% AM solution, 28.2 g UV absorber monomer B, 22.59 g 28% SLS solution and 475 g DI water with stirring. Comparative Polymer Binder 4 has a solid of 49.92% and a particle size of 136 nm.

[0044] 5) Polymer Binder 5

[0045] Polymer Binder 5 was prepared by a similar procedure according to that for preparing Comparative Polymer Binder 1, but using a different monomer emulsion. The monomer emulsion was prepared by mixing 855.1 g BA, 964.9 g MMA, 18.87 g AA, 18.6 g 50% AM solution, 28.2 g UV absorber monomer A, 22.59 g 28% SLS solution and 475 g DI water with stirring. Polymer Binder 5 has a solid of 50.12% and a particle size of 136 nm.

[0046] 6) Polymer Binder 6

[0047] Polymer Binder 6 was prepared by a similar procedure according to that for preparing Comparative Polymer Binder 1, but using a different monomer emulsion. The monomer emulsion was prepared by mixing 855.1 g BA, 964.9 g MMA, 18.87 g AA, 18.6 g 50% AM solution, 18.8 UV absorber monomer A, 22.59 g 28% SLS solution and 475 g DI water with stirring. Polymer Binder 6 has a solid of 49.85% and a particle size of 130 nm.

[0048] 7) Polymer Binder 7

[0049] Polymer Binder 7 was prepared by a similar procedure according to that for preparing Comparative Polymer Binder 1, but using a different monomer emulsion. The monomer emulsion was prepared by mixing 855.1 g BA, 964.9 g MMA, 18.87 g AA, 18.6 g 50% AM solution, 56.4 g UV absorber monomer A, 22.59 g 28% SLS solution and 475 g DI water with stirring. Polymer Binder 7 has a solid of 49.91% and a particle size of 136 nm.

[0050] 2. Preparation for Coating Compositions

[0051] 1) Preparation for Clear Coatings

[0052] 100 g Polymer Binder and 5 g TEXANOL coalescent were mixed and agitated for 24 hours to prepare the clear coatings.

[0053] 2) Preparation for 18 PVC Titanium Dioxide-Containing Coatings

[0054] 18 PVC titanium dioxide-containing coatings were prepared according to the procedure of Table 2. The Grind ingredients were mixed using a high speed Cowles disperser. The Let-down ingredients were added using a conventional lab mixer.

TABLE-US-00004 TABLE 2 18 PVC titanium dioxide-containing coating formulation Materials (g) Grind Water 5.75 Propylene Glycol anti freezing agent 5.50 KATHON LXE biocide 0.20 TRITON CF-10 wetting agent 0.50 BYK 022 defoamer 0.11 OROTAN 731A dispersant 1.50 TI-PURE R-706 TiO.sub.2 50.75 Let-down Polymer Binder 142.50 TEXANOL coalescent 3.25 TRITON X-405 wetting agent 0.50 ROCIMA 361 biocide 1.75 Water 34.75 ACRYSOL RM-2020 NPR rheology modifier 3.75 ACRYSOL SCT-275 rheology modifier 0.75 Total 251.56

IV. Results

[0055] Comparative Polymer Binders 1 to 4 and Polymer Binders 5 to 7 were each made into a clear coating and a 18 PVC TiO.sub.2-containing coating for gloss retention test.

TABLE-US-00005 TABLE 3 Gloss retention with different UV absorber Gloss retention for coatings 18 PVC UV TiO.sub.2- absorber Clear containing Polymer Binders monomer * Coatings Coatings Comparative 9.09% 51.42% Polymer Binder 1 Comparative 0.5% B 36.36% 54.28% Polymer Binder 2 Comparative 0.5% A 89.78% 52.86% Polymer Binder 3 Comparative 1.5% B 48.86% 54.28% Polymer Binder 4 Polymer Binder 5 1.5% A 89.77% 68.6% Polymer Binder 6 1% A 88.64% 60% Polymer Binder 7 3% A 89.77% 77% * by dry weight based on total dry weight of the Polymer Binder.

[0056] UV absorber monomer A is 2-(2-hydroxy-3-tertbutyl-5-methacrylethyloxylate ethylenylcarboxy phenyl)-2H-benzotriazole having the Structure (III) with n being 6, while UV absorber monomer B is 2-(2-hydroxy-5-methacryl ethylphenyl)-2H-benzotriazole having the following Structure (IV) comprising no repeating unit of CH.sub.2CH.sub.2O,

##STR00005##

[0057] The primary difference between UV absorber monomer A and UV absorber monomer B is that UV absorber monomer A comprised 6 CH.sub.2CH.sub.2O repeating unit (n=6), while UV absorber monomer B comprised no CH.sub.2CH.sub.2O repeating unit. UV absorber monomer A is the vinyl functionalized benzotriazole of the present invention, while UV absorber monomer B is not.

[0058] As shown in Table 3, Comparative Polymer Binders 2 to 4 polymerizing either UV absorber monomer, compared to Comparative Polymer Binder 1 which did not polymerize any UV absorbers, had improved gloss retentions for clear coatings, but barely improved gloss retentions for 18 PVC TiO.sub.2-containing coatings. Comparative Polymer Binder 3 (polymerized UV absorber monomer A) had an even better gloss retention in the clear coating compared to Comparative Polymer Binders 2 and 4 (polymerized UV absorber monomer B).

[0059] Polymer Binders 5 to 7 polymerizing higher level UV absorber monomer A (at least 1% by dry weight based on total dry weight of the polymer binder) provided significantly improved gloss retentions to both clear coatings, and 18 PVC TiO.sub.2-containing coatings as well. It could be concluded that not only the particular UV absorber, but also the loading level played important roles to the gloss retention of TiO.sub.2-containing coatings.