Granted Patent B2

US 12,435,238 · App. 17/250,989 · Granted Oct 7, 2025

Inventors: Jianhui Zhou (Kingsport, TN); Stacey James Marsh (Church Hill, TN)

Assignee: Eastman Chemical Company

C09D167/02C08G63/199C09D7/20

Abstract

Claims (52)

1. A coating composition comprising:

A. 40 to 70 weight percent, based on the total weight of (A) and (C), of at least one curable, aliphatic polyester, comprising residues of:

i. a hydroxyl component, said hydroxyl component comprising the residues of:

a. from 31 to 45 mole %, based on the total moles of (a) and (b), of 2,2,4,4-tetraalkylcyclobutane-1,3-diol; and

b. from 55 to 69 mole %, based on the total moles of (a) and (b), of other diols and polyols;

ii. a diacid component, said diacid component comprising the residues of at least one aliphatic dicarboxylic acid comprising:

C. 95 to 100 mole %, based on the total moles of the diacids (c) and (d), of an alicyclic dicarboxylic acid; and

d. 0 to 5 mole %, based on the total moles of the diacids (c) and (d), of an acyclic aliphatic diacid;

wherein the at least one curable, aliphatic polyester has a hydroxyl number of 255 to 350 mgKOH/g of polyester, a Tg of 16 to 45 degree C., and an acid number of 0 to 15 mgKOH/g;

B. from 30 to 60 weight percent, based on the total weight of (A) and (B), of a crosslinker;

C. from 35 to 60 weight percent, based on the total weight of the coating composition, of a solvent other than water;

wherein when said coating composition is cured, a cured coating is formed having: (1) a tree sap resistance of greater than 70 degree C. as determined in accordance with the temperature-gradient oven method according to DIN EN ISO 2812-5:2007-05; (2) a gloss retention, based on a simulated carwash test using a sheen wet abrasion scrub tester machine with brush ID 42472 and tested according to DIN EN ISO 20566, of greater than 75%; and (3) a fracture resistance greater than 20 mN when tested using a nano scratch tester with 2 μm indenter per ASTM D7187-15.

2. The composition of claim 1 wherein said 2,2,4,4-tetraalkylcyclobutane-1,3-diol is represented by the general structure:

wherein R1, R2, R3, and R4 each independently represent a lower alkyl radical having 1 to 8 carbon atoms.

3. The composition of claim 2 wherein said 2,2,4,4-tetraalkylcyclobutane-1,3-diol is selected from the group consisting of 2,2,4,4-tetramethylcyclobutane-1,3-diol, 2,2,4,4-tetraethylcyclobutane-1,3-diol, 2,2,4,4-tetra-n-propylcyclobutane-1,3-diol, 2,2,4,4-tetra-n-butylcyclobutane-1,3-diol, 2,2,4,4-tetra-n-pentylcyclobutane-1,3-diol, 2,2,4,4-tetra-n-hexylcyclobutane-1,3-diol, 2,2,4,4-tetra-n-heptylcyclobutane-1,3-diol, 2,2,4,4-tetra-n-octylcyclobutane-1,3-diol, 2,2-dimethyl-4,4-diethylcyclobutane-1,3-diol, 2-ethyl-2,4,4-trimethylcyclobutane-1,3-diol, 2,4-dimethyl-2,4-diethyl-cyclobutane-1,3-diol, 2,4-dimethyl-2,4-di-n-propylcyclobutane-1,3-diol, 2,4-n-dibutyl-2,4-diethylcyclobutane-1,3-diol, 2,4-dimethyl-2,4-diisobutylcyclobutane-1,3-diol, and 2,4-diethyl-2,4-diisoamylcyclobutane-1,3-diol.

4. The composition of claim 2 wherein said 2,2,4,4-tetraalkylcyclobutane-1,3-diol is 2,2,4,4-tetramethylcyclobutane-1,3-diol.

5. The composition of claim 1 wherein said other diols and polyols comprise: (b) (1) a diol selected from the group consisting of 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, hydroxypivalyl hydroxypivalate, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and mixtures thereof, and (b) (2) a polyol selected from the group consisting of 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, glycerin, pentaerythritol, erythritol, threitol, di-pentaerythritol, sorbitol, and mixtures thereof.

6. The composition of claim 1 wherein said alicyclic diacid ii (c) is selected from the group consisting of 1,4 cyclohexanedicarboxylic acid, 1,3 cyclohexanedicarboxylic acid, hexahydrophthalic anhydride (HHPA), methyl hexahydrophthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic acid, 2,3-norbornanedicarboxylic acid, 2,3-norbornanedicarboxylic acid anhydride, and mixtures thereof.

7. The composition of claim 1 wherein said acyclic diacid ii (d) is selected from the group consisting of succinic acid, adipic acid, maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, dodecanedioic acid, sebacic acid, azelaic acid and mixtures thereof.

8. The composition of claim 1 wherein said crosslinker is selected from the group consisting of toluene diisocyanate, diphenylmethane 4,4′-diisocyanate, isocyanurates of 4,4′-diisocyanate, methylenebis-4,4′-isocyanatocyclohexane, isophorone diisocyanate, isocyanurates of isophorone diisocyanate, 1,6-hexamethylene diisocyanate, isocyanurates of 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, p-phenylene diisocyanate, triphenylmethane 4,4′,4″-triisocyanate, tetramethyl xylene diisocyanate, metaxylene diisocyanate, and polyisocyanates.

9. The composition of claim 8 further comprising a crosslinking catalyst selected from the group consisting of triethylene diamine, N-methyl morpholine, N-ethyl morpholine, diethyl ethanolamine, 1-methyl-4-dimethylamino ethyl piperazine, 3-methoxy-N-dimethyl propyl amine, N-dimethyl-N′-methyl isopropyl propylene diamine, N,N-diethyl-3-diethyl amino propylamine, N,N-dimethyl benzyl amine, dicyclohexylmethylamine, 2,4,6-tris dimethylaminomethylphenol, N, N-dimethyl cyclohexylamine, triethylamine, tri-n-butylamine, 1,8-diaza-bichloro[5,40]-undecene-7 N-methyl diethanolamine, N,N-dimethyl ethanolamine, N, N-diethyl cyclohexylamine, N, N,N′N′-tetramethyl-ethylene diamine, 1,4-diaza-bicyclo-[2,2,2]-octane N-methyl-N-dimethylaminoethyl-piperazine, bis-(N,N-diethylaminoethyl)-adipate, N,N-diethylbenzylamine, pentamethyldiethylene triamine, N,N,N′, N′-tetramethyl-1,3-butanediamine, 1,2-dimethylimidazole, 2-methylimidazole, stannous chloride, dibutyl tin di-2-ethyl hexoate, stannous octoate, dibutyl tin dilaurate, trimethyl tin hydroxide, dimethyl tin dichloride, dibutyl tin diacetate, dibutyl tin oxide, tributyl tin acetate, tetramethyl tin, dimethyl dioctyl tin, tin ethyl hexoate, tin laurate, dibutyl tin maleate, dioctyl tin diacetate, zinc octoate, phenyl mercuric propionate, lead octoate, lead naphthenate, and copper naphthenate.

10. The coating composition of claim 1 wherein said crosslinker is melamine crosslinker.

11. The composition of claim 10 further comprising a crosslinking catalyst selected from the group consisting of p-toluenesulfonic acid, dodecylbenzene sulfonic, dinonylnaphthalene sulfonic acid, and dinonylnaphthalene disulfonic acid.

12. A coating composition consisting essentially of:

I. a polyester component comprising:

A. 40 to 70 weight percent, based on the total weight of (A) and (C), of at least one curable, aliphatic polyester, comprising residues of:

i. a hydroxyl component, said hydroxyl component comprising the residues of:

a. from 31 to 45 mole %, based on the total moles of (a) and (b), of 2,2,4,4-tetraalkylcyclobutane-1,3-diol; and

b. from 55 to 69 mole %, based on the total moles of (a) and (b), of other diols and polyols;

ii. a diacid component, said diacid component comprising the residues of at least one aliphatic dicarboxylic acid comprising:

C. 95 to 100 mole %, based on the total moles of the diacids (c) and (d), of an alicyclic dicarboxylic acid;

d. and 0 to 5 mole %, based on the total moles of the diacids (c) and (d), of an acyclic aliphatic diacid;

wherein the at least one curable, aliphatic polyester has a hydroxyl number of 120 to 350 mgKOH/g of polyester, a Tg of 16 to 45 degree C., and an acid number of 0 to 15 mgKOH/g;

B. from 30 to 60 weight percent, based on the total weight of (A) and (B), of a crosslinker comprising an isocyanate or melamine crosslinker;

C. from 35 to 60 weight percent, based on the total weight of the coating composition, of a solvent other than water; and

II. a hydroxyl functional thermosetting acrylic resin component

wherein when said coating composition is cured, a cured coating is formed having: (1) a tree sap resistance of greater than 70 degree C. as determined in accordance with the temperature-gradient oven method according to DIN EN ISO 2812-5:2007-05; (2) a gloss retention, based on a simulated carwash test using a sheen wet abrasion scrub tester machine with brush ID 42472 and tested according to DIN EN ISO 20566, of greater than 75%; and (3) a fracture resistance greater than 20 mN when tested using a nano scratch tester with 2 μm indenter per ASTM D7187-15.

13. The coating composition of claim 12 wherein the weight percent of said polyester component is from 15 to 100 weight percent and the weight percent of said hydroxyl functional thermosetting acrylic resin component is from greater than 0 to 85 weight percent based on the total weight percent of polyester component and hydroxyl functional thermosetting acrylic resin in the coating composition.

14. The coating composition of claim 12 wherein the weight percent of said polyester component is from 30 to 100 weight percent and the weight percent of said hydroxyl functional thermosetting acrylic resin component is from greater than 0 to 70 weight percent based on the total weight percent of polyester component and hydroxyl functional thermosetting acrylic resin in the coating composition.

15. The coating composition of claim 12 , wherein the coating composition further comprises additives selected from the group consisting of UV inhibitors, UV absorbers, UV light stabilizers, colorants, pigments, pigment wetting and dispersing agents, surfactants, anti-foaming agents, anti-skinning agents, anti-flooding agents, anti-floating agents, fungicides, mildewcides, corrosion inhibitors, thickening agents, coalescents, viscosity agents, suspension agents, abrasion resistant particles, antioxidants, thixotropic agents, fillers, leveling agents, wetting agents, flow control agents, defoamers, flattening agents, rheology control agents, anti-settling agents, anti-sag agents, slip agents, and mixtures thereof.

16. A coating composition comprising:

I. a polyester component comprising:

A. 40 to 70 weight percent, based on the total weight of (A) and (C), of at least one curable, aliphatic polyester, comprising residues of:

i. a hydroxyl component, said hydroxyl component comprising the residues of:

a. from 31 to 45 mole %, based on the total moles of (a) and (b), of 2,2,4,4-tetramethyl-1,3-cyclobutanediol; and

b. from 55 to 69 mole %, based on the total moles of (a) and (b), of trimethylolpropane;

ii. a diacid component consisting essentially of the residues of hexahydrophthalic anhydride; and

wherein the curable polyester has a hydroxyl number of 255 to 350 mgKOH/g of polyester, and an acid number of 0 to 15 mgKOH/g;

B. from 30 to 60 weight percent, based on the total weight of (A) and (B), of a crosslinker comprising an isocyanate;

C. from 35 to 60 weight percent, based on the total weight of the coating composition, of a solvent other than water; and

II. a hydroxyl functional thermosetting acrylic resin component;

wherein when said coating composition is cured, a cured coating is formed having: (1) a tree sap resistance of greater than 70 degree C. as determined in accordance with the temperature-gradient oven method according to DIN EN ISO 2812-5:2007-05; (2) a gloss retention, based on a simulated carwash test using a sheen wet abrasion scrub tester machine with brush ID 42472 and tested according to DIN EN ISO 20566, of greater than 75%; and (3) a fracture resistance greater than 20 mN when tested using a nano scratch tester with 2 μm indenter per ASTM D7187-15.

Continuity (2)

References Cited (36)