Graphic art films comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol

Abstract

Described are graphic art films comprising polyester compositions comprising polyesters which comprise (a) a dicarboxylicacidcomponent having terephthalic acid residues; optionally, aromatic dicarboxylic acid residues or aliphatic dicarboxylic acid residues or ester residues thereof; 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and 1,4-cyclohexanedimethanol residues.

1 . A graphic art film comprising at least one polyester composition comprising at least one polyester, which comprises:
 (a) a dicarboxylic acid component comprising:
 i) 70 to 100 mole % of terephthalic acid residues; 
 ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and 
 iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and 
   (b) a glycol component comprising:
 i) 15 to 50 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and 
 ii) 50 to 85 mole % of 1,4-cyclohexanedimethanol residues, 
   wherein the total mole % of the dicarboxylic acid component is 100 mole %, the total mole % of the glycol component is 100 mole %; and   wherein the inherent viscosity of the polyester is from 0.50 to 0.75 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C.;   wherein the polyester has a Tg of from 100 to 150° C.;   wherein said polyester has a notched Izod impact strength of at least 7.5 ft-lb/inch at 23° C. according to ASTM D256 with a 10-mil notch in a ⅛-inch thick bar;   wherein the melt viscosity of said polyester is less than 10,000 poise as measured at 1 radian/second on a rotary melt rheometer at 290° C.; and   wherein said polyester composition contains no polycarbonate.   
     
     
         2 . The graphic art film of  claim 1 , wherein the inherent viscosity of the polyester is from 0.50 to 0.68 dL/g. 
     
     
         3 . The graphic art film of  claim 1 , wherein the inherent viscosity of the polyester is from 0.60 to 0.75 dL/g. 
     
     
         4 . The graphic art film of  claim 1 , wherein the polyester has a Tg of 105 to 140° C. 
     
     
         5 . The graphic art film of  claim 1 , wherein the polyester has a Tg of 100 to 120° C. 
     
     
         6 . The graphic art film of  claim 1 , wherein the polyester has a Tg of 120 to 140° C. 
     
     
         7 . The graphic art film of  claim 1 , wherein the glycol component of the polyester comprises 15 to 25 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 75 to 85 mole % 1,4-cyclohexanedimethanol residues. 
     
     
         8 . The graphic art film of  claim 1 , wherein the glycol component of the polyester comprises 20 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 80 mole % 1,4-cyclohexanedimethanol residues. 
     
     
         9 . The graphic art film of  claim 6 , wherein the glycol component of the polyester comprises 30 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 70 mole % 1,4-cyclohexanedimethanol residues. 
     
     
         10 . The graphic art film of  claim 1 , wherein the glycol component of the polyester comprises 20 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 65 to 80 mole % 1,4-cyclohexanedimethanol residues. 
     
     
         11 . The graphic art film of  claim 1 , wherein the dicarboxylic acid component comprises 80 to 100 mole % of terephthalic acid residues. 
     
     
         12 . The graphic art film of  claim 1 , wherein the dicarboxylic acid component comprises 90 to 100 mole % of terephthalic acid residues. 
     
     
         13 . The graphic art film of  claim 1 , wherein the dicarboxylic acid component comprises 95 to 100 mole % of terephthalic acid residues. 
     
     
         14 . The graphic art film of  claim 1 , wherein the polyester comprises from 0.1 to 25 mole % of 1,3-propanediol residues, 1,4-butanediol residues, or a mixture thereof. 
     
     
         15 . The graphic art film of  claim 1 , wherein the polyester comprises from 0.1 to 10 mole % of 1,3-propanediol residues, 1,4-butanediol residues, or a mixture thereof. 
     
     
         16 . The graphic art film of  claim 1 , wherein the polyester comprises from 0.01 to 15 mole % of ethylene glycol residues. 
     
     
         17 . The graphic art film of  claim 1 , wherein the 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues are a mixture comprising greater than 50 mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and less than 50 mole % of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. 
     
     
         18 . The graphic art film of  claim 1 , wherein the 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues are a mixture comprising greater than 55 mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and less than 45 mole % of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. 
     
     
         19 . The graphic art film of  claim 1 , wherein the 2,2,4,4-tetramethyl-1,3-cyclobutanediol are a mixture comprising greater than 50 mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol and less than 50 mole % of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, and wherein the dicarboxylic acid component comprises 80 to 100 mole % of terephthalic acid residues. 
     
     
         20 . The graphic art film of  claim 1 , wherein the polyester composition comprises at least one polymer chosen from poly(etherimides), polyphenylene oxides, poly(phenylene oxide)/polystyrene blends, polystyrene resins, polyphenylene sulfides, polyphenylene sulfide/sulfones, polysulfones; polysulfone ethers, poly(ether-ketones), polyamides, polystyrene, polystyrene copolymers, styrene acrylonitrile copolymers, acrylonitrile butadiene styrene copolymers, poly(methylmethacrylate), or acrylic copolymers. 
     
     
         21 . The graphic art film of  claim 1 , wherein the polyester comprises residues at least one branching agent an amount of 0.01 to 10 mole % based on the total mole % of the diol residues or diacid residues present in the polyester. 
     
     
         22 . The graphic art film of  claim 1 , wherein the melt viscosity of the polyester is less than 6,000 poise as measured at 1 radian/second on a rotary melt rheometer at 290° C. 
     
     
         23 . The graphic art film of  claim 1 , wherein the polyester has a crystallization half-time of greater than 100 minutes at 170° C. 
     
     
         24 . The graphic art film of  claim 1 , wherein the polyester has a crystallization half-time of greater than 1,000 minutes at 170° C. 
     
     
         25 . The graphic art film of  claim 1 , wherein the polyester composition has a density of less than 1.3 g/ml at 23° C. 
     
     
         26 . The graphic art film of  claim 1 , wherein the polyester composition comprises at least one thermal stabilizer or a reaction product thereof. 
     
     
         27 . The graphic art film of  claim 1 , wherein the yellowness index of the polyester according to ASTM D-1925 is less than 50. 
     
     
         28 . The graphic art film of  claim 1 , wherein the polyester has a notched Izod impact strength of at least 10 ft-lbs/in at 23° C. according to ASTM D256 with a 10-mil notch in a ⅛-inch thick bar. 
     
     
         29 . The graphic art film of  claim 1 , wherein the polyester has a notched Izod impact strength of at least 10 ft-lbs/in at 23° C. according to ASTM D256 with a 10-mil notch in a ¼-inch thick bar. 
     
     
         30 . The graphic art film of  claim 1 , wherein the polyester comprises the residue of at least one catalyst comprising a tin compound or a reaction product thereof. 
     
     
         31 . The graphic art film of  claim 1 , wherein the graphic art film is thermoformed. 
     
     
         32 . The graphic art film of  claim 1 , further comprising at least one ink chosen from a thermally-cured ink or an ultra-violet cured ink. 
     
     
         33 . The graphic art film of  claim 1 , wherein the graphic art film is chosen from: nameplates; membrane switch overlays; point-of-purchase displays; flat and in-mold decorative panels on washing machines; flat touch panels on refrigerators; flat panel on ovens; decorative interior trim for automobiles; instrument clusters for automobiles; cell phone covers; heating and ventilation control displays; automotive console panels; automotive gear shift panels; control displays and warning signals for automotive instrument panels; facings, dials and displays on household appliances; facings, dials, and displays on washing machines; facings, dials, and displays on dishwashers; keypads for electronic devices; keypads for mobile phones, personal digital assistants, and remote controls; displays for electronic devices; panels and housings for phones; logos on electronic devices; or logos for hand-held phones. 
     
     
         34 . The graphic art film of  claim 1 , wherein the graphic art film is formed by extrusion. 
     
     
         35 . The graphic art film of  claim 1 , wherein the graphic art film is produced by calendering. 
     
     
         36 . The graphic art film of  claim 1 , wherein the graphic art film is produced by compression molding. 
     
     
         37 . The graphic art film of  claim 1 , wherein the graphic art film is produced by solution casting. 
     
     
         38 . An in-mold decorated article comprising the graphic art film of  claim 1 . 
     
     
         39 . An embossed article comprising the graphic art film of  claim 1 . 
     
     
         40 . A hard-coated article comprising the graphic art film of  claim 1 . 
     
     
         41 . The graphic art film of  claim 1 , wherein the graphic art film is textured. 
     
     
         42 . A graphic art film comprising at least one polyester composition comprising at least one polyester, which comprises:
 (a) a dicarboxylic acid component comprising:
 i) 70 to 100 mole % of terephthalic acid residues; 
 ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and 
 iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and 
   (b) a glycol component comprising:
 i) 20 to 40 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and 
 ii) 60 to 80 mole % of 1,4-cyclohexanedimethanol residues, 
   wherein the total mole % of the dicarboxylic acid component is 100 mole %, the total mole % of the glycol component is 100 mole %;   wherein the inherent viscosity of the polyester is from 0.50 to 0.75 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C.;   wherein the polyester has a Tg of from 100 to 140° C.;   wherein said polyester has a notched Izod impact strength of at least 7.5 ft-lb/inch at 23° C. according to ASTM D256 with a 10-mil notch in a ⅛-inch thick bar;   wherein the melt viscosity of said polyester is less than 10,000 poise as measured at 1 radian/second on a rotary melt rheometer at 290° C.; and   wherein said polyester composition contains no polycarbonate.   
     
     
         43 . The graphic art film of  claim 42 , wherein the inherent viscosity of the polyester is from 0.50 to 0.68 dL/g. 
     
     
         44 . The graphic art film of  claim 42 , wherein the inherent viscosity of the polyester is from 0.60 to 0.75 dL/g. 
     
     
         45 . The graphic art film of  claim 42 , wherein the polyester has a Tg of 105 to 130° C. 
     
     
         46 . The graphic art film of  claim 42 , wherein the polyester has a Tg of 100 to 120° C. 
     
     
         47 . The graphic art film of  claim 42 , wherein the polyester has a Tg of 120 to 140° C. 
     
     
         48 . The graphic art film of  claim 42 , wherein the graphic art film is thermoformed. 
     
     
         49 . The graphic art film of  claim 42 , further comprising at least one ink chosen from a thermally-cured ink or an ultra-violet cured ink. 
     
     
         50 . The graphic art film of  claim 42 , wherein the graphic art film is chosen from: nameplates; membrane switch overlays; point-of-purchase displays; flat and in-mold decorative panels on washing machines; flat touch panels on refrigerators; flat panel on ovens; decorative interior trim for automobiles; instrument clusters for automobiles; cell phone covers; heating and ventilation control displays; automotive console panels; automotive gear shift panels; control displays and warning signals for automotive instrument panels; facings, dials and displays on household appliances; facings, dials, and displays on washing machines; facings, dials, and displays on dishwashers; keypads for electronic devices; keypads for mobile phones, personal digital assistants, and remote controls; displays for electronic devices; panels and housings for phones; logos on electronic devices; or logos for hand-held phones. 
     
     
         51 . An in-mold decorated article comprising the graphic art film of  claim 42 . 
     
     
         52 . An embossed article comprising the graphic art film of  claim 42 . 
     
     
         53 . A hard-coated article comprising the graphic art film of  claim 42 . 
     
     
         54 . The graphic art film of  claim 42 , wherein the graphic art film is textured. 
     
     
         55 . A graphic art film comprising at least one polyester composition comprising at least one polyester, which comprises:
 (a) a dicarboxylic acid component comprising:
 i) 70 to 100 mole % of terephthalic acid residues; 
 ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and 
 iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and 
   (b) a glycol component comprising:
 i) 30 to 40 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and 
 ii) 60 to 70 mole % of 1,4-cyclohexanedimethanol residues, 
   wherein the total mole % of the dicarboxylic acid component is 100 mole %, the total mole % of the glycol component is 100 mole %;   wherein the inherent viscosity of the polyester is from 0.60 to 0.75 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C.; and   wherein the polyester has a Tg of from 100 to 140° C.;   wherein said polyester has a notched Izod impact strength of at least 7.5 ft-lb/inch at 23° C. according to ASTM D256 with a 10-mil notch in a ⅛-inch thick bar;   wherein the melt viscosity of said polyester is less than 10,000 poise as measured at 1 radian/second on a rotary melt rheometer at 290° C.; and   wherein said polyester composition contains no polycarbonate.   
     
     
         56 . An in-mold decorated article comprising the graphic art film of  claim 55 . 
     
     
         57 . An embossed article comprising the graphic art film of  claim 55 . 
     
     
         58 . A hard-coated article comprising the graphic art film of  claim 55 . 
     
     
         59 . The graphic art film of  claim 55 , wherein the graphic art film is textured. 
     
     
         60 . A graphic art film comprising at least one polyester composition comprising at least one polyester, which comprises:
 (a) a dicarboxylic acid component comprising:
 i) 70 to 100 mole % of terephthalic acid residues; 
 ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and 
 iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and 
   (b) a glycol component comprising:
 i) 15 to 50 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and 
 ii) 50 to 85 mole % of 1,4-cyclohexanedimethanol residues, 
   wherein the total mole % of the dicarboxylic acid component is 100 mole %, the total mole % of the glycol component is 100 mole %; and   (c) residues of at least one branching agent;   wherein the inherent viscosity of the polyester is from 0.50 to 0.75 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C.; and   wherein the polyester has a Tg of from 100 to 140° C.;   wherein said polyester has a notched Izod impact strength of at least 7.5 ft-lb/inch at 23° C. according to ASTM D256 with a 10-mil notch in a ⅛-inch thick bar;   wherein the melt viscosity of said polyester is less than 10,000 poise as measured at 1 radian/second on a rotary melt rheometer at 290° C.; and   wherein said polyester composition contains no polycarbonate.   
     
     
         61 . An in-mold decorated article comprising the graphic art film of  claim 60 . 
     
     
         62 . An embossed article comprising the graphic art film of  claim 60 . 
     
     
         63 . A hard-coated article comprising the graphic art film of  claim 60 . 
     
     
         64 . The graphic art film of  claim 60 , wherein the graphic art film is textured. 
     
     
         65 . The container of  claim 42  or  55  wherein the wherein the melt viscosity of the polyester is less than 6,000 poise as measured at 1 radian/second (rad/sec) on a rotary melt rheometer at 290° C. 
     
     
         66 . The container of  claim 1 ,  42 ,  55  or  60 , wherein the polyester has a b* value of from −10 to less than 10 and a L* value from 50 to 90 according to the L*, a* and b* color system of the CIE (International Commission on Illumination. 
     
     
         67 . The container of  claim 42 ,  55  or  60 , wherein the polyester comprises residues from at least one branching agent in the amount of 0.01 to 5 mole % based on the total mole percentage of the diacid residues or diol residues. 
     
     
         68 . The container of  claim 42 ,  55  or  60 , wherein said polyester comprises residues from at least one branching agent in an amount of 0.1 to 0.7 mole % based on the total mole percentage of the diacid residues or diol residues. 
     
     
         69 . The container of  claim 42 ,  55  or  60 , wherein said polyester comprises residues from at least one branching agent selected from trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, or 3-hydroxyglutaric acid. 
     
     
         70 . The container of  claim 60 , wherein said polyester comprises residues from trimellitic anhydride. 
     
     
         71 . The container of  claim 1  or  55 , wherein the polyester comprises a thermal stabilizer which is a phosphorus compound chosen from at least one of phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonous acid, or an ester or salt thereof. 
     
     
         72 . The container of  claim 42 ,  55  or  60  wherein the polyester has a notched Izod impact strength of at least 10 ft-lbs/in at 23° C. according to ASTM D256 with a 10-mil notch in a ⅛-inch thick bar.