Low gloss polyester coating powder compositions

Abstract: Low gloss in a coating derived from a polyester/triglycidyl isocyanurate coating powder is achieved by including in the coating powder 2-10 phr ethylene acrylic acid copolymer, 0.2-1.0 phr of a compound selected from 2-mercapto benzothiazole, metal salts of 2-mercapto benzothiazole, such as zinc 2-mercapto benzothiazole, and up to 10 phr polyolefin wax.

Description: The present invention is directed to polyester coating powder compositions, particularly those polyester powder coating compositions cured with triglycidyl isocyanurate (TGIC), formulated to have low gloss. A well-known type of coating powder is based on acid-functional polyester resin and TGIC as a curative. Such a coating powder is found, for example, in US-A-5,321,000, 5,326,832 and 4,379,895. Polyester coating powders are particularly advantageous in some outdoor applications, such as coating lawn furniture or window frames, because polyester coatings exhibit good UV-stability. Coatings formed from polyester coating powder compositions tend to have relatively high gloss. For reasons of aesthetic preference, it would be desirable to have coating powders which provide low gloss. Gloss reduction of polyester coating powders has been attempted previously, the approaches generally being adding high levels of pigments and/or waxes. 60° Gardner Haze-Gloss units approaching 25 have been achieved by such high loading methods. However, higher amounts of filler and/or wax result in unacceptable blocking of the powder and/or orange peel of the coating, limiting the amount of gloss reduction which might be attained. The present invention consists in a coating powder composition comprising a polyester resin and triglycidyl isocyanurate, characterised in that the composition further comprises: a) from 2 to 10 parts per hundred parts of resin by weight of an un-neutralised copolymer consisting essentially of 80 to 95 wt% ethylene and 5 to 20 wt% acrylic and/or methacrylic acid; b) from 0.2 to 1.0 parts per hundred parts of resin by weight of a compound selected from 2-mercapto benzothiazole, metal salts of 2-mercapto benzothiazole and mixtures thereof; and c) from 0 to 10 parts per hundred parts of resin by weight polyolefin wax. The coating powder preferably contains 2 to 10 phr of polyolefin wax. Herein, unless otherwise noted, the resin of the coating powder is considered to be the polyester and TGIC. Levels of other components are given as parts per hundred resin, by weight (phr). Percentages, unless otherwise noted, are weight percentages. In coating powders of this type, the polyester is typically present at between 90 and 95 wt% of the total of polyester plus TGIC; and TGIC is present at beetween 5 and 10 wt% of the total of polyester plus TGIC. Polyesters of the type generally used in coating powders are useful in the practice of the present invention. Molecular weights (number average) (M n ) of the polyesters generally range from 2000 to 7000, preferably between 3000 and 3500. Acid numbers typically range between 30 and 60, preferably between 30 and 35. Glass transition temperatures are typically in the range of between 40°C and 80°C. To be curable by TGIC, the polyesters have acid functionalities of at least 2, up to 3.5, but preferably in the range of between 2.1 and 2.5. Polyesters are formed in conventional manner from carboxylic acids (or their anhydrides) having acid functionalities of 2 or greater and polyols having hydroxyl functionality of 2 or greater. Examples of suitable multi-functional carboxylic acids include benzene-1,2,4-tricarboxylic acid, phthalic acid, tetrahydraphthalic acid, hexahydrophthalic acid, endobicyclo-2,2,1-5-heptyne-2,3-dicarboxylic acid, tetrachlorophthalic acid, cyclohexanedioic acid, succinic acid, isophthalic acid, terephthalic acid, azelaic acid, maleic acid, trimesic acid, 3,6-dichlorophthalic acid, tetrachlorophthalic acid, adipic acid, sebacic acid, and like carboxylic acids, Examples of suitable multi-functional alcohols include glycerin, trimethylolpropane, trimethylolethane, trishydroxyethylisocyanurate, pentaerythritol, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,3-, 1,2- and 1,4-butanediols, heptanediol, hexanediol, octanediol, 2,2-'bis (4-cyclohexanol) propane, neopentyl glycol, 2,2,3-trimethylpentane-1,3-diol, 1,4-dimethylolcyclohexane, 2,2,4-trimethylpentane diol, etc. To obtain carboxyl-functional polyesters of desired molecular weight, the monomer mixture used to form the polyester has an appropriate excess of carboxyl functionality to hydroxyl functionality. The copolymer used in the present invention as one of the gloss reducing agents is formed of between 80 and 95 wt% ethylene monomer and between 5 and 20 wt% acrylic acid and/or methacrylic acid, preferably acrylic acid. The melt index (MI 2 ) as measured by ASTM D-1238 is between 10 and 30, preferably in the region of about 20. 2-mercapto benzothiazole and metal salts are presently used for vulcanizing rubber. Examples of suitable compounds for use in the present invention include, but are not limited to zinc 2-mercapto benzothiazole, 2-mercapto benzothiazole and mixtures thereof. Zinc 2-mercapto benzothiazole is the currently preferred additive. The polyolefin waxes are substantially saturated aliphatic hydrocarbons (alkanes). Polyolefin waxes useful in the invention include paraffins derived from petroleum and low molecular weight, e.g., less than 10,000, polyethylenes. For use in the present invention, the polyolefin wax should have a melting point of between 90°C and 120°C. Optionally, the coating powder may include a cure catalyst, such as methyl triphenyl phosphonium bromide (MTPB), tetra n-butyl phosphonium bromide (TPB), di-butyltin oxide, and tetrabutyl titanate. The coating composition may be filled or unfilled. Filling is possible up to about 50 to 60 phr with fillers and pigments such as carbon black, titanium dioxide, silica, etc. The thermosetting resin coating particulates are produced in the usual manner. The components are blended, and then are melt-compounded with heating above the melting point of the resin for a short time, e.g., 30-90 sec., so that no significant curing occurs. The molten compound is extruded, and after extrusion, the composition is rapidly cooled. The composition is then ground and, as necessary, the particulates sorted according to size. For electrostatic coating application, the particulates are generally in the 5-100 micron size range with a major portion generally being in the 20-40 micron size range. Larger particulates are useful for fluidized bed coating operations. The invention will now be described in greater detail by way of specific examples, examples 1, 3, 10, 13 and 14 are comparative examples. EXAMPLES 1-15 A slow reacting (A) and a fast reacting (B) carboxylic acid terminated polyester were prepared from the following monomer mixes and had the following properties Monomer A (wt%) B (wt%) Neopentyl glycol 27.57 35.30 Trimethylol propane 1.19 Terephthalic acid 65.09 52.72 Isophthalic acid 6.15 7.78 Adipic acid 3.22 Ethylene glycol 0.68 Ethyl triphenyl phosphonium bromide (cure catalyst) 0.20 The polyesters had the following specific properties A B Acid number 33 33 Molecular weight (number average) 3300 4200 Glass transition temperature (°C) 53 60 Sample preparation involved blending the carboxyl terminated polyester resin or resins, TGIC (curing agent), flow additives, pigments and the waxes in the amounts shown in tables 1 & 2. The sample was then extruded at 93°C (200°F) to facilitate melt blending. The extruded material was mixed with dry flow additive and then ground into powder. The powder (particles less than 105 µm in size) was electrostatically sprayed onto a grounded Q-panel. The panel was cured in an oven at 204°C (400°F) for 10 minutes. Gel time and hot plate melt flow were tested on the powder and direct impact, pencil hardness, flexibility, MEK resistance and gloss were tested on panels with a coating thickness of 46 to 56 µm (1.8 - 2.2 mils). The properties for the samples given in Tables 1, 3, 5, and 7 are listed in Tables 2, 4, 6, and 8. SAMPLES IN PARTS PER HUNDRED (PHR) OF DIFFERENT EXPERIMENTS SAMPLE NUMBER #1 #2 #3 Slow Reacting Carboxylic Acid Terminated Polyester 46.5 46.5 46.5 Fast Reacting Carboxylic Acid Terminated Polyester 46.5 46.5 46.5 TGIC 7.0 7.0 7.0 Flow Additives 2.2 2.2 2.2 TiO 2 40 40 40 Carbon Black 0 0 0 EAA Copolymer 0 0 8 Polyolefin Wax with zinc 2-mercapto benzothiazole 0 8 0 PROPERTIES OF SAMPLES DESCRIBED IN TABLE 1 SAMPLE NUMBER #1 #2 #3 Gel Time (secs) 132 62 125 HPMF (mm) 80 63 70 Direct Impact (in-lbs) joules (160) 18 (160) 18 (160) 18 Pencil Hardness (mar/scourge) H/2H H/2H H/2H Flexibility (3/16" or 4·8mm rod) Pass Pass pass MEK Resistance 5 4 - 5 5 Gloss (20°/60°) 81/95 5/24 6/42 Sample #1 is a sample without any wax and 40 phr of TiO 2 . The coating from this sample resulted in a high 60° gloss of 95. When 8 phr of each of DT 3329 and EAA copolymer was added in two different samples (#2 and #3) the gloss achieved was 24 and 42, respectively. In all the three samples described in Table 1, it was attempted to use the reactivity difference between two resins to reduce the gloss. Without addition of wax no significant reduction in gloss was noticed. SAMPLES OF DIFFERENT EXPERIMENTS SAMPLE NUMBER #4 #5 #6 Slow Cure Carboxylic Acid Terminated Polyester 46.5 0 46.5 Fast Cure Carboxylic Acid Terminated Polyester 46.5 93.0 46.5 TGIC 7.0 7.0 7.0 Flow Additives 2.2 2.2 2.2 TiO 2 40 40 0 Carbon Black 0 0 2 EAA Copolymer 4 4 2 Polyolefin Wax with zinc 2-mercapto benzothiazole 4 4 4 PROPERTIES OF SAMPLES DESCRIBED IN TABLE 3 SAMPLE NUMBER #4 #5 #6 Gel Time (secs) 75 75 120 HPMF (mm) 65 60 73 Direct Impact (in-lbs) joules (160) 18 (160) 18 (160) 18 Pencil Hardness (mar/scourge) H/2H H/2H H/2H Flexibility (3/16" or 4·8 mm rod) Pass Pass Pass MEK Resistance 4 4 4 Gloss (20°/60°) 0/15 0/15 5/27 In sample #4, 4 phr of each DT 3329 and EAA copolymer was used and synergistically the gloss dropped to 15 units. This is well below the gloss achieved with 8 phr of the individual waxes (sample #2 and #3). This gloss level was achieved even in the absence of slow reacting carboxyl polyester (sample #5). Sample #6 has reduced amounts of the waxes (2 phr of EAA copolymer and 4 phr of DT 3329) and the gloss increased to 27. SAMPLES OF DIFFERENT EXPERIMENTS SAMPLE NUMBER #7 #8 #9 Slow cure Carboxylic Acid Terminated Polyester 46.5 46.5 46.5 Fast Cure Carboxylic Acid Terminated Polyester 46.5 46.5 46.5 TGIC 7 7 7 Flow Additives 2.2 2.2 2.2 TiO 2 40 40 40 Carbon Black 0 0 0 Ethylene-Acrylic Acid Copolymer 4 7 4 Polyolefin Wax with zinc 2-mercapto benzothiazole 8 8 4 Barium Sulfate 0 0 60 PROPERTIES OF SAMPLES DESCRIBED IN TABLE 5 SAMPLE NUMBER #7 #8 #9 Gel Time (secs) 70 64 106 HPMF (mm) 57 71 30 Direct Impact (in-lbs) joules (160) 18 (160) 18 (120) 13·6 Pencil Hardness (mar/scourge) F/H F/H F/H Flexibility (3/16" or 4·8 mm rod) Pass Pass Fail MEK Resistance 4 - 5 4 5 Gloss (20°/60°) 0/13 0/11 0/14 In samples #7 and #8 by increasing the amounts of the waxes, the gloss was reduced between 13 and 11 units without sacrificing any properties. In sample (#9), 4 phr each of DT 3329 and EAA copolymer was combined with 60 phr of barium sulfate and the HPMF was reduced drastically without any reduction in gloss. SAMPLES OF DIFFERENT EXPERIMENTS SAMPLE NUMBER #10 #11 232-93-5 Slow cure Carboxylic Acid Terminated Polyester 46.5 46.5 46.5 Fast Cure Carboxylic Acid Terminated Polyester 46.5 46.5 46.5 TGIC 7 7 7 Flow Additives 2.2 2.2 2.2 TiO 2 0 0 0 Carbon Black 2 2 2 Ethylene-Acrylic Acid Copolymer 0 4 4 Polyolefin Wax with zinc 2-mercapto benzothiazole 0 4 4 Barium Sulfate 0 0 60 PROPERTIES OF SAMPLES DESCRIBED IN TABLE 7 SAMPLE NUMBER #10 #11 #12 Gel Time (secs) 134 51 52 HPMF (mm) 118 121 57 Direct Impact (in-lbs) joules (160) 18 (160) 18 (160) 18 Pencil Hardness (mar/scourge) B/F F/H HB/F Flexibility (3/16" 4·8 mm rod) Pass Pass Pass MEK Resistance 4 5 4 - 5 Gloss (20°/60°) 88/95 5/22 0/16 Samples described in Tables 7 and 8 contain 2 phr of carbon black instead of 40 phr TiO 2 as pigments. Without any wax the gloss achieved was 95 units. Sample #11 containing 4 parts each of DT 3329 and EAA copolymer resulted in gloss of 22 units. This is higher than what was achieved in formulations containing TiO 2 . This is due to increased HPMF when 40 phr of TiO 2 was replaced with 2 phr of carbon black. In sample #12 the HPMF was reduced by the addition of 60 phr of barium sulfate and the gloss was reduced to 16. Table 9 shows formulations with EAA copolymer and polyolefin wax without zinc 2-mercapto benzothiazole (#13) and EAA copolymer and zinc 2-mercapto benzothiazole (#14). Lower gloss that resulted from the synergy between DT 3329 and EAA copolymer (#15) could not be achieved. SAMPLES AND GLOSS LEVELS Notebook NUMBER #13 #14 #15 EAA Copolymer 4 4 6.4 DT 3329 4 Polyolefin Wax 4 Zinc 2-mercapto benzothiazole 1.6 Gloss (60°) 14 45 45

Claims: A coating powder composition comprising a polyester resin and triglycidyl isocyanurate, characterised in that the composition further comprises: a) from 2 to 10 parts per hundred parts of resin by weight of an un-neutralised copolymer consisting essentially of 80 to 95 wt% ethylene and 5 to 20 wt% acrylic and/or methacrylic acid; b) from 0.2 to 1.0 parts per hundred parts of resin by weight of a compound selected from 2-mercapto benzothiazole, metal salts of 2-mercapto benzothiazole and mixtures thereof; and c) from 0 to 10 parts per hundred parts of resin by weight polyolefin wax. A coating powder composition according to claim 1 wherein said benzothiazole compound is zinc 2-mercapto benzothiazole. A coating powder composition according to claim 1 or claim 2 which contains 2 or more parts per hundred parts of resin by weight of the polyolefin wax (c).

Inventors: DEIBERT E SUSANNE, MUTHIAH JENO, DEIBERT, E. SUSANNE, MUTHIAH, JENO
Applicants: MORTON INT INC, MORTON INTERNATIONAL, INC.
Application year: 1997
Main classification: C09D167
IPC codes: C09D167