US20110189415A1 - Graphic art films comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol - Google Patents

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

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US20110189415A1
US20110189415A1 US13017352 US201113017352A US2011189415A1 US 20110189415 A1 US20110189415 A1 US 20110189415A1 US 13017352 US13017352 US 13017352 US 201113017352 A US201113017352 A US 201113017352A US 2011189415 A1 US2011189415 A1 US 2011189415A1
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Prior art keywords
mole
polyester
graphic art
art film
tetramethyl
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Abandoned
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US13017352
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Emmett Dudley Crawford
Douglas Stephens McWilliams
David Scott Porter
Gary Wayne Connell
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Eastman Chemical Co
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Eastman Chemical Co
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    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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    • C08G63/16Dicarboxylic acids and dihydroxy compounds
    • C08G63/18Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181Acids containing aromatic rings
    • C08G63/183Terephthalic acids
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    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24058Structurally defined web or sheet [e.g., overall dimension, etc.] including grain, strips, or filamentary elements in respective layers or components in angular relation
    • Y10T428/24074Strand or strand-portions
    • Y10T428/24091Strand or strand-portions with additional layer[s]
    • Y10T428/24099On each side of strands or strand-portions
    • Y10T428/24107On each side of strands or strand-portions including mechanically interengaged strands, strand-portions or strand-like strips
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24479Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31507Of polycarbonate
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31652Of asbestos
    • Y10T428/31663As siloxane, silicone or silane
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31786Of polyester [e.g., alkyd, etc.]

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.

Description

    CROSS-REFERENCES TO RELATED APPLICATIONS
  • This application is a continuation of U.S. application Ser. No. 11/390,563 filed on Mar. 28, 2006, which claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application Ser. No. 60/691,567 filed on Jun. 17, 2005, U.S. Provisional Application Ser. No. 60/731,454 filed on Oct. 28, 2005, U.S. Provisional Application Ser. No. 60/731,389, filed on Oct. 28, 2005, U.S. Provisional Application Ser. No. 60/739,058, filed on Nov. 22, 2005, and U.S. Provisional Application Ser. No. 60/738,869, filed on Nov. 22, 2005, U.S. Provisional Application Ser. No. 60/750,692 filed on Dec. 15, 2005, U.S. Provisional Application Ser. No. 60/750,693, filed on Dec. 15, 2005, U.S. Provisional Application Ser. No. 60/750,682, filed on Dec. 15, 2005, and U.S. Provisional Application Ser. No. 60/750,547, filed on Dec. 15, 2005, all of which are hereby incorporated by this reference in their entireties.
  • FIELD OF THE INVENTION
  • The present invention generally relates to graphic art films comprising a polyester compositions made from terephthalic acid, or an ester thereof, or mixtures thereof, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 1,4-cyclohexanedimethanol, having a certain combination of two or more of high impact strengths, high glass transition temperature (Tg), toughness, certain inherent viscosities, low ductile-to-brittle transition temperatures, good color and clarity, low densities, chemical resistance, hydrolytic stability, and long crystallization half-times, which allow them to be easily formed into articles. For example, the graphic art films of the present invention can have a combination of two or more of the following properties: thermoformability, toughness, clarity, chemical resistance, Tg, and flexibility.
  • BACKGROUND OF THE INVENTION
  • Graphic art films can be produced with a variety of plastic materials by a variety of processes (melt extrusion, solvent casting, compression molding, etc.). Polycarbonates are widely used in a variety of molding and extrusion applications. Films or sheets formed from the polycarbonates must be dried prior to thermoforming. If the films and/or sheets are not pre-dried prior to thermoforming, thermoformed articles formed from the polycarbonates can be characterized by the presence of blisters that are unacceptable from an appearance standpoint.
  • Poly(1,4-cyclohexylenedimethylene) terephthalate (PCT), a polyester based solely on terephthalic acid or an ester thereof and 1,4-cyclohexanedimethanol, is known in the art and is commercially available. This polyester crystallizes rapidly upon cooling from the melt, making it very difficult to form amorphous articles by methods known in the art such as extrusion, injection molding, and the like. In order to slow down the crystallization rate of PCT, copolyesters can be prepared containing additional dicarboxylic acids or glycols such as isophthalic acid or ethylene glycol. These ethylene glycol- or isophthalic acid-modified PCTs are also known in the art and are commercially available.
  • One common copolyester used to produce films, sheeting, and molded articles is made from terephthalic acid, 1,4-cyclohexanedimethanol, and ethylene glycol. While these copolyesters are useful in many end-use applications, they exhibit deficiencies in properties such as glass transition temperature and impact strength when sufficient modifying ethylene glycol is included in the formulation to provide for long crystallization half-times. For example, copolyesters made from terephthalic acid, 1,4-cyclohexanedimethanol, and ethylene glycol with sufficiently long crystallization half-times can provide amorphous products that exhibit what is believed to be undesirably higher ductile-to-brittle transition temperatures and lower glass transition temperatures than the compositions revealed herein.
  • The polycarbonate of 4,4′-isopropylidenediphenol (bisphenol A polycarbonate) has been used as an alternative for polyesters known in the art and is a well known engineering molding plastic. Bisphenol A polycarbonate is a clear, high-performance plastic having good physical properties such as dimensional stability, high heat resistance, and good impact strength. Although bisphenol-A polycarbonate has many good physical properties, its relatively high melt viscosity leads to poor melt processability and the polycarbonate exhibits poor chemical resistance. It is also difficult to thermoform.
  • Polymers containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol have also been generally described in the art. Generally, however, these polymers exhibit high inherent viscosities, high melt viscosities and/or high Tgs (glass transition temperatures) such that the equipment used in industry can be insufficient to manufacture or post polymerization process these materials.
  • Thus, there is a need in the art for graphic art films comprising at least one polymer having a combination of two or more properties, chosen from at least one of the following: toughness, high glass transition temperatures, high impact strength, hydrolytic stability, chemical resistance, long crystallization half-times, low ductile to brittle transition temperatures, good color, and clarity, lower density and/or thermoformability of polyesters while retaining processability on the standard equipment used in the industry.
  • SUMMARY OF THE INVENTION
  • It is believed that certain graphic art films comprising polyester compositions formed from terephthalic acid, an ester thereof, or mixtures thereof, 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol with certain monomer compositions, inherent viscosities and/or glass transition temperatures are superior to polyesters known in the art and to polycarbonate with respect to one or more of high impact strengths, hydrolytic stability, toughness, chemical resistance, good color and clarity, long crystallization half-times, low ductile to brittle transition temperatures, lower specific gravity, and thermoformability. These compositions are believed to be similar to polycarbonate in heat resistance and are still processable on the standard industry equipment.
  • In one aspect, the invention relates to 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) 10 to 99 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
      • ii) 1 to 90 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 0.1 to 1.2 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 200° C.
  • In another aspect, the invention relates to 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 70 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
      • ii) 30 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 0.35 to 1.2 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 160° C.
  • In another aspect, the invention relates to 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 %; and
  • 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 120° C.
  • In another aspect, the invention relates to 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) 40 to 55 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
      • ii) 45 to 60 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 0.60 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 120 to 140° C.
  • In another aspect, the invention relates to 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 90 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
      • ii) 10 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 0.1 to 1.2 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 200° C.
  • In another aspect, the invention relates to 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 70 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
      • ii) 30 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 0.35 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 150° C.
  • In another aspect, the invention relates to 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) 25 to 50 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
      • ii) 50 to 75 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 0.35 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 150° C.
  • In another aspect, the invention relates to a graphic art film comprising at least one polyester composition comprising at least one polyester, which comprises:
  • (I) 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) 10 to 99 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
        • ii) 1 to 90 mole % of 1,4-cyclohexanedimethanol residues, and
  • (II) residues of at least one branching agent;
  • 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 0.1 to 1.2 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 200° C.
  • In another aspect, the invention relates to a graphic art film comprising at least one polyester composition comprising at least one polyester, which comprises:
  • (I) 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) 10 to 99 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and
        • ii) 1 to 90 mole % of 1,4-cyclohexanedimethanol residues, and
  • (II) at least one thermal stabilizer or reaction products thereof;
  • 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 0.1 to 1.2 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 200° C.
  • In one aspect, the polyester composition contains at least one polycarbonate.
  • In one aspect, the polyester composition contains no polycarbonate.
  • In one aspect, the polyesters useful in the invention contain less than 15 mole % ethylene glycol residues, such as, for example, 0.01 to less than 15 mole % ethylene glycol residues.
  • In one aspect, the polyesters useful in the invention contain no ethylene glycol residues.
  • In one aspect the polyester compositions useful in the invention contain at least one thermal stabilizer and/or reaction products thereof.
  • In one aspect, the polyesters useful in the invention contain no branching agent, or alternatively, at least one branching agent is added either prior to or during polymerization of the polyester.
  • In one aspect, the polyesters useful in the invention contain at least one branching agent without regard to the method or sequence in which it is added.
  • In one aspect, the polyesters useful in the invention are made from no 1,3-propanediol, or, 1,4-butanediol, either singly or in combination. In other aspects, 1,3-propanediol or 1,4-butanediol, either singly or in combination, may be used in the making of the polyesters useful in this invention.
  • In one aspect of the invention, the mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol useful in certain polyesters useful in the invention is greater than 50 mole % or greater than 55 mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol or greater than 70 mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol; wherein the total mole percentage of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to a total of 100 mole %.
  • In one aspect of the invention, the mole % of the isomers of 2,2,4,4-tetramethyl-1,3-cyclobutanediol useful in certain polyesters useful in the invention is from 30 to 70 mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol or from 30 to 70 mole % of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, or from 40 to 60 mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol or from 40 to 60 mole % of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, wherein the total mole percentage of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to a total of 100 mole %.
  • In one aspect, the polyester compositions are useful in graphic art film(s) including but not limited to extruded and/or molded articles including, but not limited to, extruded, calendered, and/or molded articles including but not limited to, extruded articles, cast extrusion articles, thermoformed articles, profile extrusion articles, extrusion molded articles, extrusion blow molded articles, and extrusion stretch blow molded articles.
  • Also, in one aspect, use of the polyester compositions of the invention minimizes and/or eliminates the drying step prior to melt processing or thermoforming.
  • In one aspect, certain polyesters useful in the invention can be amorphous or semicrystalline. In one aspect, certain polyesters useful in the invention can have a relatively low crystallinity. Certain polyesters useful in the invention can thus have a substantially amorphous morphology, meaning that the polyesters comprise substantially unordered regions of polymer.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a graph showing the effect of comonomer on the fastest crystallization half-times of modified PCT copolyesters.
  • FIG. 2 is a graph showing the effect of comonomer on the brittle-to-ductile transition temperature (Tbd) in a notched Izod impact strength test (ASTM D256, ⅛-in thick, 10-mil notch).
  • FIG. 3 is a graph showing the effect of 2,2,4,4-tetramethyl-1,3-cyclobutanediol composition on the glass transition temperature (Tg) of the copolyester.
  • DETAILED DESCRIPTION OF THE INVENTION
  • The present invention may be understood more readily by reference to the following detailed description of certain embodiments of the invention and the working examples.
  • In accordance with the purpose(s) of this invention, certain embodiments of the invention are described in the Summary of the Invention and are further described herein below. Also, other embodiments of the invention are described herein.
  • It is believed that the polyester(s) and/or polyester composition(s) which are included in the graphic art film(s) of the invention described herein can have a unique combination of two or more physical properties such as high impact strengths, moderate to high glass transition temperatures, chemical resistance, hydrolytic stability, toughness, low ductile-to-brittle transition temperatures, good color and clarity, low densities, long crystallization half-times, and good processability thereby easily permitting them to be formed into articles. In some of the embodiments of the invention, the polyesters have a unique combination of the properties of good impact strength, heat resistance, chemical resistance, density and/or the combination of the properties of good impact strength, heat resistance, and processability and/or the combination of two or more of the described properties, that have never before been believed to be present in graphic art film(s) comprising the polyester compositions which comprise the polyester(s) as disclosed herein.
  • “Graphic art film,” as used herein, is a film having a thermally-curable ink (e.g., heat-curable ink or air-curable ink) or radiation-curable ink (e.g., ultra-violet-curable ink) printed thereon or therein. “Curable” refers to capable of undergoing polymerization and/or crosslinking. In addition to the ink, the graphic art film may optionally also include varnishes, coatings, laminates, and adhesives.
  • Exemplary thermally or air-cured inks involve pigment(s) dispersed in one or more standard carrier resins. The pigment can be 4B Toner (PR57), 2B Toner (PR48), Lake Red C (PR53), lithol red (PR49), iron oxide (PR101), Permanent Red R (PR4), Permanent Red 2G (PO5), pyrazolone orange (PO13), diaryl yellows (PY12, 13, 14), monoazo yellows (PY3,5,98), phthalocyanine green (PG7), phthalocyanine Blue, β form (PB15), ultramarine (PB62), permanent violet (PV23), titanium dioxide (PW6), carbon black (furnace/channel) (PB7), PMTA pink, green, blue, violet (PR81, PG1, PB1, PV3,), copper ferrocyanide dye complexes (PR169, PG45, PB62, PV27), or the like. (Parenthetical identifications in the foregoing refer to the generic color index prepared by the Society of Dyers and Colourists.) Such pigments and combinations thereof can be used to obtain various colors including, but not limited to, white, black, blue, violet, red, green, yellow, cyan, magenta, or orange.
  • Other exemplary inks, including radiation-cured inks are disclosed in U.S. Pat. No. 5,382,292, where the disclosure of such inks are incorporated herein by reference.
  • Examples of typical carrier resins used in standard inks include those which have nitrocellulose, amide, urethane, epoxide, acrylate, and/or ester functionalities. Standard carrier resins include one or more of nitrocellulose, polyamide, polyurethane, ethyl cellulose, cellulose acetate propionate, (meth)acrylates, poly(vinyl butyral), poly(vinyl acetate), poly(vinyl chloride), and the like. Such resins can be blended, with widely used blends including nitrocellulose/polyamide and nitrocellulose/polyurethane.
  • Ink resin(s) normally can be solvated or dispersed in one or more solvents. Typical solvents employed include, but are not limited to, water, alcohols (e.g., ethanol, 1-propanol, isopropanol, etc.), acetates (e.g., n-propyl acetate), aliphatic hydrocarbons, aromatic hydrocarbons (e.g., toluene), and ketones. Such solvents typically can be incorporated in amounts sufficient to provide inks having viscosities, as measured on a #2 Zahn cup as known in the art, of at least 15 seconds, such as at least 20 seconds, at least 25 seconds, or from 25 to 35 seconds.
  • In one embodiment, the polyester have sufficient Tg values to allow thermoformability, and to allow ease of printing.
  • In one embodiment, the graphic art film has at least one property chosen from thermoformability, toughness, clarity, chemical resistance, Tg, and flexibility.
  • Graphic art films can be used in a variety of applications, such as, for example, in-mold decorated articles, embossed articles, hard-coated articles. The graphic art film can be smooth or textured.
  • Exemplary graphic art films include, but are not limited to, nameplates; membrane switch overlays (e.g., for an appliance); point-of-purchase displays; flat or in-mold decorative panels on washing machines; flat touch panels on refrigerators (e.g., capacitive touch pad arrays); flat panel on ovens; decorative interior trim for automobiles (e.g., a polyester laminate; instrument clusters for automobiles; cell phone covers; heating and ventilation control displays; automotive console panels; automotive gear shift panels; control displays or warning signals for automotive instrument panels; facings, dials or displays on household appliances; facings, dials or displays on washing machines; facings, dials or displays on dishwashers; keypads for electronic devices; keypads for mobile phones, personal digital assistants (PDAs, or hand-held computers) or remote controls; displays for electronic devices; displays for hand-held electronic devices such as phones and PDAs; panels and housings for mobile or standard phones; logos on electronic devices; and logos for hand-held phones.
  • The term “polyester”, as used herein, is intended to include “copolyesters” and is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional carboxylic acids and/or multifunctional carboxylic acids with one or more difunctional hydroxyl compounds and/or multifunctional hydroxyl compounds. Typically the difunctional carboxylic acid can be a dicarboxylic acid and the difunctional hydroxyl compound can be a dihydric alcohol such as, for example, glycols. Furthermore, as used in this application, the term “diacid” or “dicarboxylic acid” includes multifunctional acids, such as branching agents. The term “glycol” as used in this application includes, but is not limited to, diols, glycols, and/or multifunctional hydroxyl compounds. Alternatively, the difunctional carboxylic acid may be a hydroxy carboxylic acid such as, for example, p-hydroxybenzoic acid, and the difunctional hydroxyl compound may be an aromatic nucleus bearing 2 hydroxyl substituents such as, for example, hydroquinone. The term “residue”, as used herein, means any organic structure incorporated into a polymer through a polycondensation and/or an esterification reaction from the corresponding monomer. The term “repeating unit”, as used herein, means an organic structure having a dicarboxylic acid residue and a diol residue bonded through a carbonyloxy group. Thus, for example, the dicarboxylic acid residues may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof. As used herein, therefore, the term dicarboxylic acid is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a reaction process with a diol to make polyester. As used herein, the term “terephthalic acid” is intended to include terephthalic acid itself and residues thereof as well as any derivative of terephthalic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof or residues thereof useful in a reaction process with a diol to make polyester.
  • In one embodiment, terephthalic acid may be used as the starting material. In another embodiment, dimethyl terephthalate may be used as the starting material. In another embodiment, mixtures of terephthalic acid and dimethyl terephthalate may be used as the starting material and/or as an intermediate material.
  • The polyesters used in the present invention typically can be prepared from dicarboxylic acids and diols which react in substantially equal proportions and are incorporated into the polyester polymer as their corresponding residues. The polyesters of the present invention, therefore, can contain substantially equal molar proportions of acid residues (100 mole %) and diol (and/or multifunctional hydroxyl compounds) residues (100 mole %) such that the total moles of repeating units is equal to 100 mole %. The mole percentages provided in the present disclosure, therefore, may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units. For example, a polyester containing 30 mole % isophthalic acid, based on the total acid residues, means the polyester contains 30 mole % isophthalic acid residues out of a total of 100 mole % acid residues. Thus, there are 30 moles of isophthalic acid residues among every 100 moles of acid residues. In another example, a polyester containing 30 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, based on the total diol residues, means the polyester contains 30 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues out of a total of 100 mole % diol residues. Thus, there are 30 moles of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues among every 100 moles of diol residues.
  • In other aspects of the invention, the Tg of the polyesters useful in the graphic art film(s) of the invention can be at least one of the following ranges: 100 to 200° C.; 100 to 190° C.; 100 to 180° C.; 100 to 170° C.; 100 to 160° C.; 100 to 155° C.; 100 to 150° C.; 100 to 145° C.; 100 to 140° C.; 100 to 138° C.; 100 to 135° C.; 100 to 130° C.; 100 to 125° C.; 100 to 120° C.; 100 to 115° C.; 100 to 110° C.; 105 to 200° C.; 105 to 190° C.; 105 to 180° C.; 105 to 170° C.; 105 to 160° C.; 105 to 155° C.; 105 to 150° C.; 105 to 145° C.; 105 to 140° C.; 105 to 138° C.; 105 to 135° C.; 105 to 130° C.; 105 to 125° C.; 105 to 120° C.; 105 to 115° C.; 105 to 110° C.; greater than 105 to 125° C.; greater than 105 to 120° C.; greater than 105 to 115° C.; greater than 105 to 110° C.; 110 to 200° C.; 110 to 190° C.; 110 to 180° C.; 110 to 170° C.; 110 to 160° C.; 110 to 155° C.; 110 to 150° C.; 110 to 145° C.; 110 to 140° C.; 110 to 138° C.; 110 to 135° C.; 110 to 130° C.; 110 to 125° C.; 110 to 120° C.; 110 to 115° C.; 115 to 200° C.; 115 to 190° C.; 115 to 180° C.; 115 to 170° C.; 115 to 160° C.; 115 to 155° C.; 115 to 150° C.; 115 to 145° C.; 115 to 140° C.; 115 to 138° C.; 115 to 135° C.; 110 to 130° C.; 115 to 125° C.; 115 to 120° C.; 120 to 200° C.; 120 to 190° C.; 120 to 180° C.; 120 to 170° C.; 120 to 160° C.; 120 to 155° C.; 120 to 150° C.; 120 to 145° C.; 120 to 140° C.; 120 to 138° C.; 120 to 135° C.; 120 to 130° C.; 125 to 200° C.; 125 to 190° C.; 125 to 180° C.; 125 to 170° C.; 125 to 160° C.; 125 to 155° C.; 125 to 150° C.; 125 to 145° C.; 125 to 140° C.; 125 to 138° C.; 125 to 135° C.; 127 to 200° C.; 127 to 190° C.; 127 to 180° C.; 127 to 170° C.; 127 to 160° C.; 127 to 150° C.; 127 to 145° C.; 127 to 140° C.; 127 to 138° C.; 127 to 135° C.; 130 to 200° C.; 130 to 190° C.; 130 to 180° C.; 130 to 170° C.; 130 to 160° C.; 130 to 155° C.; 130 to 150° C.; 130 to 145° C.; 130 to 140° C.; 130 to 138° C.; 130 to 135° C.; 135 to 200° C.; 135 to 190° C.; 135 to 180° C.; 135 to 170° C.; 135 to 160° C.; 135 to 155° C.; 135 to 150° C.; 135 to 145° C.; 135 to 140° C.; 140 to 200° C.; 140 to 190° C.; 140 to 180° C.; 140 to 170° C.; 140 to 160° C.; 140 to 155° C.; 140 to 150° C.; 140 to 145° C.; 148 to 200° C.; 148 to 190° C.; 148 to 180° C.; 148 to 170° C.; 148 to 160° C.; 148 to 155° C.; 148 to 150° C.; 150 to 200° C.; 150 to 190° C.; 150 to 180° C.; 150 to 170° C.; 150 to 160; 155 to 190° C.; 155 to 180° C.; 155 to 170° C.; and 155 to 165° C.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 10 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 90 mole % 1,4-cyclohexanedimethanol; 10 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 90 mole % 1,4-cyclohexanedimethanol; 10 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 90 mole % 1,4-cyclohexanedimethanol; 10 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 90 mole % 1,4-cyclohexanedimethanol; 10 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 90 mole % 1,4-cyclohexanedimethanol, 10 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 90 mole % 1,4-cyclohexanedimethanol; 10 to 70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 90 mole % 1,4-cyclohexanedimethanol; 10 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 90 mole % 1,4-cyclohexanedimethanol; 10 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 90 mole % 1,4-cyclohexanedimethanol; 10 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 90 mole % 1,4-cyclohexanedimethanol; 10 to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 90 mole % 1,4-cyclohexanedimethanol; 10 to less than 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 to 90 mole % 1,4-cyclohexanedimethanol; 10 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 90 mole % 1,4-cyclohexanedimethanol; 10 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 90 mole % 1,4-cyclohexanedimethanol; 10 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 90 mole % 1,4-cyclohexanedimethanol; 10 to less than 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 65 up to 90 mole % 1,4-cyclohexanedimethanol; 10 to 30 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 90 mole % 1,4-cyclohexanedimethanol; 10 to 25 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 75 to 90 mole % 1,4-cyclohexanedimethanol; 11 to 25 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 89 mole % 1,4-cyclohexanedimethanol; 12 to 25 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 88 mole % 1,4-cyclohexanedimethanol; and 13 to 25 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 87 mole % 1,4-cyclohexanedimethanol;
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 14 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 86 mole % 1,4-cyclohexanedimethanol; 14 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 86 mole % 1,4-cyclohexanedimethanol; 14 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 86 mole % 1,4-cyclohexanedimethanol; 14 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 86 mole % 1,4-cyclohexanedimethanol; 14 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 86 mole % 1,4-cyclohexanedimethanol, 14 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 86 mole % 1,4-cyclohexanedimethanol; 14 to 70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 86 mole % 1,4-cyclohexanedimethanol; 14 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 86 mole % 1,4-cyclohexanedimethanol; 14 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 86 mole % 1,4-cyclohexanedimethanol; 14 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 86 mole % 1,4-cyclohexanedimethanol; and 14 to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 86 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 14 to less than 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 up to 86 mole % 1,4-cyclohexanedimethanol; 14 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 86 mole % 1,4-cyclohexanedimethanol; 14 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 86 mole % 1,4-cyclohexanedimethanol; 14 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 86 mole % 1,4-cyclohexanedimethanol; 14 to 30 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 86 mole % 1,4-cyclohexanedimethanol; and 14 to 25 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 86 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 15 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 85 mole % 1,4-cyclohexanedimethanol; 15 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 85 mole % 1,4-cyclohexanedimethanol; 15 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 85 mole % 1,4-cyclohexanedimethanol; 15 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 85 mole % 1,4-cyclohexanedimethanol; 15 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 85 mole % 1,4-cyclohexanedimethanol, 15 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 85 mole % 1,4-cyclohexanedimethanol; 15 to 70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 85 mole % 1,4-cyclohexanedimethanol; 15 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 85 mole % 1,4-cyclohexanedimethanol; 15 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 85 mole % 1,4-cyclohexanedimethanol; 15 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 85 mole % 1,4-cyclohexanedimethanol; and 15 to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 85 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 15 to less than 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 up to 85 mole % 1,4-cyclohexanedimethanol; 15 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 85 mole % 1,4-cyclohexanedimethanol; 15 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 85 mole % 1,4-cyclohexanedimethanol; 15 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 85 mole % 1,4-cyclohexanedimethanol; 15 to 30 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 85 mole % 1,4-cyclohexanedimethanol; 15 to 25 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 85 mole % 1,4-cyclohexanedimethanol; 15 to 20 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 80 mole % 1,4-cyclohexanedimethanol; and 17 to 23 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 77 to 83 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 20 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 80 mole % 1,4-cyclohexanedimethanol; 20 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 80 mole % 1,4-cyclohexanedimethanol; 20 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 80 mole % 1,4-cyclohexanedimethanol; 20 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 80 mole % 1,4-cyclohexanedimethanol; 20 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 80 mole % 1,4-cyclohexanedimethanol, 20 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 80 mole % 1,4-cyclohexanedimethanol; 20 to 70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 80 mole % 1,4-cyclohexanedimethanol; 20 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 80 mole % 1,4-cyclohexanedimethanol; 20 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 80 mole % 1,4-cyclohexanedimethanol; 20 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 80 mole % 1,4-cyclohexanedimethanol; 20 to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 80 mole % 1,4-cyclohexanedimethanol; 20 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 80 mole % 1,4-cyclohexanedimethanol; 20 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 80 mole % 1,4-cyclohexanedimethanol; 20 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 80 mole % 1,4-cyclohexanedimethanol; 20 to 30 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 80 mole % 1,4-cyclohexanedimethanol; and 20 to 25 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 80 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 25 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 75 mole % 1,4-cyclohexanedimethanol; 25 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 75 mole % 1,4-cyclohexanedimethanol; 25 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 75 mole % 1,4-cyclohexanedimethanol; 25 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 75 mole % 1,4-cyclohexanedimethanol; 25 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 75 mole % 1,4-cyclohexanedimethanol, 25 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 75 mole % 1,4-cyclohexanedimethanol; 25 to 70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 75 mole % 1,4-cyclohexanedimethanol; 25 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 75 mole % 1,4-cyclohexanedimethanol; 25 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 75 mole % 1,4-cyclohexanedimethanol; 25 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 75 mole % 1,4-cyclohexanedimethanol; 25 to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 75 mole % 1,4-cyclohexanedimethanol; 25 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 75 mole % 1,4-cyclohexanedimethanol; 25 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 75 mole % 1,4-cyclohexanedimethanol; 25 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 75 mole % 1,4-cyclohexanedimethanol; and 25 to 30 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 75 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 30 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 70 mole % 1,4-cyclohexanedimethanol; 30 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 70 mole % 1,4-cyclohexanedimethanol; 30 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 70 mole % 1,4-cyclohexanedimethanol; 30 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 70 mole % 1,4-cyclohexanedimethanol; 30 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 70 mole % 1,4-cyclohexanedimethanol, 30 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 70 mole % 1,4-cyclohexanedimethanol; 30 to 70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 70 mole % 1,4-cyclohexanedimethanol; 30 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 70 mole % 1,4-cyclohexanedimethanol; 30 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 70 mole % 1,4-cyclohexanedimethanol; 30 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 70 mole % 1,4-cyclohexanedimethanol; 30 to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 70 mole % 1,4-cyclohexanedimethanol; 30 to less than 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 to 70 mole % 1,4-cyclohexanedimethanol; 30 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 70 mole % 1,4-cyclohexanedimethanol; 30 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 70 mole % 1,4-cyclohexanedimethanol; 30 to 35 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 70 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 35 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 65 mole % 1,4-cyclohexanedimethanol; 35 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 65 mole % 1,4-cyclohexanedimethanol; 35 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 65 mole % 1,4-cyclohexanedimethanol; 35 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 65 mole % 1,4-cyclohexanedimethanol; 35 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 65 mole % 1,4-cyclohexanedimethanol, 35 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 65 mole % 1,4-cyclohexanedimethanol; 35 to 70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 65 mole % 1,4-cyclohexanedimethanol; 35 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 65 mole % 1,4-cyclohexanedimethanol; 35 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 65 mole % 1,4-cyclohexanedimethanol; 35 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 65 mole % 1,4-cyclohexanedimethanol; 35 to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 65 mole % 1,4-cyclohexanedimethanol; 35 to less than 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 to 65 mole % 1,4-cyclohexanedimethanol; 35 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 65 mole % 1,4-cyclohexanedimethanol; 35 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 65 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 37 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 63 mole % 1,4-cyclohexanedimethanol; 37 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 63 mole % 1,4-cyclohexanedimethanol; 37 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 63 mole % 1,4-cyclohexanedimethanol; 37 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 63 mole % 1,4-cyclohexanedimethanol; 37 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 63 mole % 1,4-cyclohexanedimethanol, 37 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 63 mole % 1,4-cyclohexanedimethanol; 37 to 70 mole 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 63 mole % 1,4-cyclohexanedimethanol; 37 to 63 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 37 to 63 mole % 1,4-cyclohexanedimethanol; 37 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 63 mole % 1,4-cyclohexanedimethanol; 37 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 63 mole % 1,4-cyclohexanedimethanol; 37 to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 63 mole % 1,4-cyclohexanedimethanol; 37 to less than 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 to 63 mole % 1,4-cyclohexanedimethanol; 37 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 63 mole % 1,4-cyclohexanedimethanol; 37 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 63 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 40 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 60 mole % 1,4-cyclohexanedimethanol; 40 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 60 mole % 1,4-cyclohexanedimethanol; 40 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 60 mole % 1,4-cyclohexanedimethanol; 40 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 60 mole % 1,4-cyclohexanedimethanol; 40 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 60 mole % 1,4-cyclohexanedimethanol, 40 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 60 mole % 1,4-cyclohexanedimethanol; 40 to 70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 60 mole % 1,4-cyclohexanedimethanol; 40 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 60 mole % 1,4-cyclohexanedimethanol; 40 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 60 mole % 1,4-cyclohexanedimethanol; 40 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 60 mole % 1,4-cyclohexanedimethanol; 40 to less than 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 to 60 mole % 1,4-cyclohexanedimethanol; 40 to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 60 mole % 1,4-cyclohexanedimethanol; and 40 to 45 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 60 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 45 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 55 mole % 1,4-cyclohexanedimethanol; 45 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 55 mole % 1,4-cyclohexanedimethanol; 45 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 55 mole % 1,4-cyclohexanedimethanol; 45 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 55 mole % 1,4-cyclohexanedimethanol; 45 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 55 mole % 1,4-cyclohexanedimethanol, 45 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 55 mole % 1,4-cyclohexanedimethanol; 45 to 70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 55 mole % 1,4-cyclohexanedimethanol; 45 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 55 mole % 1,4-cyclohexanedimethanol; 45 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 55 mole % 1,4-cyclohexanedimethanol; greater than 45 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to less than 55 mole % 1,4-cyclohexanedimethanol; 45 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 55 mole % 1,4-cyclohexanedimethanol; and 45 to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 55 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: greater than 50 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to less than 50 mole % 1,4-cyclohexanedimethanol; greater than 50 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to less than 50 mole % 1,4-cyclohexanedimethanol; greater than 50 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to less than 50 mole % 1,4-cyclohexanedimethanol; greater than 50 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to less than 50 mole % 1,4-cyclohexanedimethanol; greater than 50 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to less than 50 mole % 1,4-cyclohexanedimethanol, greater than 50 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to less than 50 mole % 1,4-cyclohexanedimethanol; greater than 50 to 70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to less than 50 mole % 1,4-cyclohexanedimethanol; greater than 50 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to less than 50 mole % 1,4-cyclohexanedimethanol; greater than 50 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to less than 50 mole % 1,4-cyclohexanedimethanol; and greater than 50 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to less than 50 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 50 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 50 mole % 1,4-cyclohexanedimethanol; 50 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 50 mole % 1,4-cyclohexanedimethanol; 50 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 50 mole % 1,4-cyclohexanedimethanol; 50 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 50 mole % 1,4-cyclohexanedimethanol; 50 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 50 mole % 1,4-cyclohexanedimethanol, 50 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 50 mole % 1,4-cyclohexanedimethanol; 50 to 70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 50 mole % 1,4-cyclohexanedimethanol; 50 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 50 mole % 1,4-cyclohexanedimethanol; 50 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 50 mole % 1,4-cyclohexanedimethanol; and 50 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 50 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 55 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 45 mole % 1,4-cyclohexanedimethanol; 55 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 45 mole % 1,4-cyclohexanedimethanol; 55 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 45 mole % 1,4-cyclohexanedimethanol; 55 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 45 mole % 1,4-cyclohexanedimethanol; 55 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 45 mole % 1,4-cyclohexanedimethanol, 55 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 45 mole % 1,4-cyclohexanedimethanol; 55 to 70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 45 mole % 1,4-cyclohexanedimethanol; 55 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 45 mole % 1,4-cyclohexanedimethanol; and 55 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 45 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 60 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 40 mole % 1,4-cyclohexanedimethanol; 60 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 40 mole % 1,4-cyclohexanedimethanol; 60 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 40 mole % 1,4-cyclohexanedimethanol; 60 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 40 mole % 1,4-cyclohexanedimethanol; 60 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 40 mole % 1,4-cyclohexanedimethanol, 60 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 40 mole % 1,4-cyclohexanedimethanol; and 60 to 70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 40 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the invention include but are not limited to at least one of the following combinations of ranges: 65 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 35 mole % 1,4-cyclohexanedimethanol; 65 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 35 mole % 1,4-cyclohexanedimethanol; 65 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 35 mole % 1,4-cyclohexanedimethanol; 65 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 35 mole % 1,4-cyclohexanedimethanol; 65 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 35 mole % 1,4-cyclohexanedimethanol, 65 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 35 mole % 1,4-cyclohexanedimethanol; and 65 to 70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 40 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 70 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 30 mole % 1,4-cyclohexanedimethanol; 70 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 30 mole % 1,4-cyclohexanedimethanol; 70 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 30 mole % 1,4-cyclohexanedimethanol; 70 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 30 mole % 1,4-cyclohexanedimethanol; 70 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 30 mole % 1,4-cyclohexanedimethanol, and 70 to 75 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 30 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 75 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 25 mole % 1,4-cyclohexanedimethanol; 75 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 25 mole % 1,4-cyclohexanedimethanol; 75 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 25 mole % 1,4-cyclohexanedimethanol; 75 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 25 mole % 1,4-cyclohexanedimethanol, and 75 to 80 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 25 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: 80 to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 20 mole % 1,4-cyclohexanedimethanol; 80 to 95 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 20 mole % 1,4-cyclohexanedimethanol; 80 to 90 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 20 mole % 1,4-cyclohexanedimethanol, and 80 to 85 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 20 mole % 1,4-cyclohexanedimethanol.
  • In other aspects of the invention, the glycol component for the polyesters useful in the graphic art film(s) of the invention include but are not limited to at least one of the following combinations of ranges: greater than 45 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to less than 55 mole % 1,4-cyclohexanedimethanol; greater than 45 to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to less than 55 mole % 1,4-cyclohexanedimethanol; 46 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 54 mole % 1,4-cyclohexanedimethanol; and 46 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 54 mole % 1,4-cyclohexanedimethanol.
  • In addition to the diols set forth above, the polyesters useful in the polyester compositions of the graphic art film(s) of the invention may also be made from 1,3-propanediol, 1,4-butanediol, or mixtures thereof. It is contemplated that compositions of the invention made from 1,3-propanediol, 1,4-butanediol, or mixtures thereof can possess at least one of the Tg ranges described herein, at least one of the inherent viscosity ranges described herein, and/or at least one of the glycol or diacid ranges described herein. In addition or in the alternative, the polyesters made from 1,3-propanediol or 1,4-butanediol or mixtures thereof may also be made from 1,4-cyclohexanedmethanol in at least one of the following amounts: from 0.1 to 99 mole %; from 0.1 to 90 mole %; from 0.1 to 80 mole %; from 0.1 to 70 mole %; from 0.1 to 60 mole %; from 0.1 to 50 mole %; from 0.1 to 40 mole %; from 0.1 to 35 mole %; from 0.1 to 30 mole %; from 0.1 to 25 mole %; from 0.1 to 20 mole %; from 0.1 to 15 mole %; from 0.1 to 10 mole %; from 0.1 to 5 mole %; from 1 to 99 mole %; from 1 to 90 mole %, from 1 to 80 mole %; from 1 to 70 mole %; from 1 to 60 mole %; from 1 to 50 mole %; from 1 to 40 mole %; from 1 to 35 mole %; from 1 to 30 mole %; from 1 to 25 mole %; from 1 to 20 mole %; from 1 to 15 mole %; from 1 to 10 mole %; from 1 to 5 mole %; from 5 to 99 mole %, from 5 to 90 mole %, from 5 to 80 mole %; 5 to 70 mole %; from 5 to 60 mole %; from 5 to 50 mole %; from 5 to 40 mole %; from 5 to 35 mole %; from 5 to 30 mole %; from 5 to 25 mole %; from 5 to 20 mole %; and from 5 to 15 mole %; from 5 to 10 mole %; from 10 to 99 mole %; from 10 to 90 mole %; from 10 to 80 mole %; from 10 to 70 mole %; from 10 to 60 mole %; from 10 to 50 mole %; from 10 to 40 mole %; from 10 to 35 mole %; from 10 to 30 mole %; from 10 to 25 mole %; from 10 to 20 mole %; from 10 to 15 mole %; from 20 to 99 mole %; from 20 to 90 mole %; from 20 to 80 mole %; from 20 to 70 mole %; from 20 to 60 mole %; from 20 to 50 mole %; from 20 to 40 mole %; from 20 to 35 mole %; from 20 to 30 mole %; and from 20 to 25 mole %.
  • For certain embodiments of the invention, the polyesters useful in the invention may exhibit at least one of the following inherent viscosities as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C., 0.10 to 1.2 dL/g; 0.10 to 1.1 dL/g; 0.10 to 1 dL/g; 0.10 to less than 1 dL/g; 0.10 to 0.98 dL/g; 0.10 to 0.95 dL/g; 0.10 to 0.90 dL/g; 0.10 to 0.85 dL/g; 0.10 to 0.80 dL/g; 0.10 to 0.75 dL/g; 0.10 to less than 0.75 dL/g; 0.10 to 0.72 dL/g; 0.10 to 0.70 dL/g; 0.10 to less than 0.70 dL/g; 0.10 to 0.68 dL/g; 0.10 to less than 0.68 dL/g; 0.10 to 0.65 dL/g; 0.20 to 1.2 dL/g; 0.20 to 1.1 dL/g; 0.20 to 1 dL/g; 0.20 to less than 1 dL/g; 0.20 to 0.98 dL/g; 0.20 to 0.95 dL/g; 0.20 to 0.90 dL/g; 0.20 to 0.85 dL/g; 0.20 to 0.80 dL/g; 0.20 to 0.75 dL/g; 0.20 to less than 0.75 dL/g; 0.20 to 0.72 dL/g; 0.20 to 0.70 dL/g; 0.20 to less than 0.70 dL/g; 0.20 to 0.68 dL/g; 0.20 to less than 0.68 dL/g; 0.20 to 0.65 dL/g; 0.35 to 1.2 dL/g; 0.35 to 1.1 dL/g; 0.35 to 1 dL/g; 0.35 to less than 1 dL/g; 0.35 to 0.98 dL/g; 0.35 to 0.95 dL/g; 0.35 to 0.90 dL/g; 0.35 to 0.85 dL/g; 0.35 to 0.80 dL/g; 0.35 to 0.75 dL/g; 0.35 to less than 0.75 dL/g; 0.35 to 0.72 dL/g; 0.35 to 0.70 dL/g; 0.35 to less than 0.70 dL/g; 0.35 to 0.68 dL/g; 0.35 to less than 0.68 dL/g; 0.35 to 0.65 dL/g; 0.40 to 1.2 dL/g; 0.40 to 1.1 dL/g; 0.40 to 1 dL/g; 0.40 to less than 1 dL/g; 0.40 to 0.98 dL/g; 0.40 to 0.95 dL/g; 0.40 to 0.90 dL/g; 0.40 to 0.85 dL/g; 0.40 to 0.80 dL/g; 0.40 to 0.75 dL/g; 0.40 to less than 0.75 dL/g; 0.40 to 0.72 dL/g; 0.40 to 0.70 dL/g; 0.40 to less than 0.70 dL/g; 0.40 to 0.68 dL/g; 0.40 to less than 0.68 dL/g; 0.40 to 0.65 dL/g; greater than 0.42 to 1.2 dL/g; greater than 0.42 to 1.1 dL/g; greater than 0.42 to 1 dL/g; greater than 0.42 to less than 1 dL/g; greater than 0.42 to 0.98 dL/g; greater than 0.42 to 0.95 dL/g; greater than 0.42 to 0.90 dL/g; greater than 0.42 to 0.85 dL/g; greater than 0.42 to 0.80 dL/g; greater than 0.42 to 0.75 dL/g; greater than 0.42 to less than 0.75 dL/g; greater than 0.42 to 0.72 dL/g; greater than 0.42 to less than 0.70 dL/g; greater than 0.42 to 0.68 dL/g; greater than 0.42 to less than 0.68 dL/g; and greater than 0.42 to 0.65 dL/g.
  • For certain embodiments of the invention, the polyesters useful in the invention may exhibit at least one of the following inherent viscosities as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C.: 0.45 to 1.2 dL/g; 0.45 to 1.1 dL/g; 0.45 to 1 dL/g; 0.45 to 0.98 dL/g; 0.45 to 0.95 dL/g; 0.45 to 0.90 dL/g; 0.45 to 0.85 dL/g; 0.45 to 0.80 dL/g; 0.45 to 0.75 dL/g; 0.45 to less than 0.75 dL/g; 0.45 to 0.72 dL/g; 0.45 to 0.70 dL/g; 0.45 to less than 0.70 dL/g; 0.45 to 0.68 dL/g; 0.45 to less than 0.68 dL/g; 0.45 to 0.65 dL/g; 0.50 to 1.2 dL/g; 0.50 to 1.1 dL/g; 0.50 to 1 dL/g; 0.50 to less than 1 dL/g; 0.50 to 0.98 dL/g; 0.50 to 0.95 dL/g; 0.50 to 0.90 dL/g; 0.50 to 0.85 dL/g; 0.50 to 0.80 dL/g; 0.50 to 0.75 dL/g; 0.50 to less than 0.75 dL/g; 0.50 to 0.72 dL/g; 0.50 to 0.70 dL/g; 0.50 to less than 0.70 dL/g; 0.50 to 0.68 dL/g; 0.50 to less than 0.68 dL/g; 0.50 to 0.65 dL/g; 0.55 to 1.2 dL/g; 0.55 to 1.1 dL/g; 0.55 to 1 dL/g; 0.55 to less than 1 dL/g; 0.55 to 0.98 dL/g; 0.55 to 0.95 dL/g; 0.55 to 0.90 dL/g; 0.55 to 0.85 dL/g; 0.55 to 0.80 dL/g; 0.55 to 0.75 dL/g; 0.55 to less than 0.75 dL/g; 0.55 to 0.72 dL/g; 0.55 to 0.70 dL/g; 0.55 to less than 0.70 dL/g; 0.55 to 0.68 dL/g; 0.55 to less than 0.68 dL/g; 0.55 to 0.65 dL/g; 0.58 to 1.2 dL/g; 0.58 to 1.1 dL/g; 0.58 to 1 dL/g; 0.58 to less than 1 dL/g; 0.58 to 0.98 dL/g; 0.58 to 0.95 dL/g; 0.58 to 0.90 dL/g; 0.58 to 0.85 dL/g; 0.58 to 0.80 dL/g; 0.58 to 0.75 dL/g; 0.58 to less than 0.75 dL/g; 0.58 to 0.72 dL/g; 0.58 to 0.70 dL/g; 0.58 to less than 0.70 dL/g; 0.58 to 0.68 dL/g; 0.58 to less than 0.68 dL/g; 0.58 to 0.65 dL/g; 0.60 to 1.2 dL/g; 0.60 to 1.1 dL/g; 0.60 to 1 dL/g; 0.60 to less than 1 dL/g; 0.60 to 0.98 dL/g; 0.60 to 0.95 dL/g; 0.60 to 0.90 dL/g; 0.60 to 0.85 dL/g; 0.60 to 0.80 dL/g; 0.60 to 0.75 dL/g; 0.60 to less than 0.75 dL/g; 0.60 to 0.72 dL/g; 0.60 to 0.70 dL/g; 0.60 to less than 0.70 dL/g; 0.60 to 0.68 dL/g; 0.60 to less than 0.68 dL/g; 0.60 to 0.65 dL/g; 0.65 to 1.2 dL/g; 0.65 to 1.1 dL/g; 0.65 to 1 dL/g; 0.65 to less than 1 dL/g; 0.65 to 0.98 dL/g; 0.65 to 0.95 dL/g; 0.65 to 0.90 dL/g; 0.65 to 0.85 dL/g; 0.65 to 0.80 dL/g; 0.65 to 0.75 dL/g; 0.65 to less than 0.75 dL/g; 0.65 to 0.72 dL/g; 0.65 to 0.70 dL/g; 0.65 to less than 0.70 dL/g; 0.68 to 1.2 dL/g; 0.68 to 1.1 dL/g; 0.68 to 1 dL/g; 0.68 to less than 1 dL/g; 0.68 to 0.98 dL/g; 0.68 to 0.95 dL/g; 0.68 to 0.90 dL/g; 0.68 to 0.85 dL/g; 0.68 to 0.80 dL/g; 0.68 to 0.75 dL/g; 0.68 to less than 0.75 dL/g; 0.68 to 0.72 dL/g; greater than 0.76 dL/g to 1.2 dL/g; greater than 0.76 dL/g to 1.1 dL/g; greater than 0.76 dL/g to 1 dL/g; greater than 0.76 dL/g to less than 1 dL/g; greater than 0.76 dL/g to 0.98 dL/g; greater than 0.76 dL/g to 0.95 dL/g; greater than 0.76 dL/g to 0.90 dL/g; greater than 0.80 dL/g to 1.2 dL/g; greater than 0.80 dL/g to 1.1 dL/g; greater than 0.80 dL/g to 1 dL/g; greater than 0.80 dL/g to less than 1 dL/g; greater than 0.80 dL/g to 1.2 dL/g; greater than 0.80 dL/g to 0.98 dL/g; greater than 0.80 dL/g to 0.95 dL/g; greater than 0.80 dL/g to 0.90 dL/g.
  • It is contemplated that compositions useful in the graphic art film(s) of the invention can possess at least one of the inherent viscosity ranges described herein and at least one of the monomer ranges for the compositions described herein unless otherwise stated. It is also contemplated that compositions useful in the graphic art film(s) of the invention can posses at least one of the Tg ranges described herein and at least one of the monomer ranges for the compositions described herein unless otherwise stated. It is also contemplated that compositions useful in the graphic art film(s) of the invention can posses at least one of the Tg ranges described herein, at least one of the inherent viscosity ranges described herein, and at least one of the monomer ranges for the compositions described herein unless otherwise stated.
  • For the desired polyester, the molar ratio of cis/trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol can vary from the pure form of each or mixtures thereof. In certain embodiments, the molar percentages for cis and/or trans 2,2,4,4,-tetramethyl-1,3-cyclobutanediol are greater than 50 mole % cis and less than 50 mole % trans; or greater than 55 mole % cis and less than 45 mole % trans; or 30 to 70 mole % cis and 70 to 30% trans; or 40 to 60 mole % cis and 60 to 40 mole % trans; or 50 to 70 mole % trans and 50 to 30% cis or 50 to 70 mole % cis and 50 to 30% trans; or 60 to 70 mole % cis and 30 to 40 mole % trans; or greater than 70 mole cis and less than 30 mole % trans; wherein the total sum of the mole percentages for cis- and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to 100 mole %. The molar ratio of cis/trans 1,4-cyclohexandimethanol can vary within the range of 50/50 to 0/100, such as between 40/60 to 20/80.
  • In certain embodiments, terephthalic acid or an ester thereof, such as, for example, dimethyl terephthalate, or a mixture of terephthalic acid and an ester thereof, makes up most or all of the dicarboxylic acid component used to form the polyesters useful in the invention. In certain embodiments, terephthalic acid residues can make up a portion or all of the dicarboxylic acid component used to form the present polyester at a concentration of at least 70 mole %, such as at least 80 mole %, at least 90 mole %, at least 95 mole %, at least 99 mole %, or 100 mole %. In certain embodiments, higher amounts of terephthalic acid can be used in order to produce a higher impact strength polyester. In one embodiment, dimethyl terephthalate is part or all of the dicarboxylic acid component used to make the polyesters useful in the present invention. For the purposes of this disclosure, the terms “terephthalic acid” and “dimethyl terephthalate” are used interchangeably herein. In all embodiments, ranges of from 70 to 100 mole %; or 80 to 100 mole %; or 90 to 100 mole %; or 99 to 100 mole %; or 100 mole % terephthalic acid and/or dimethyl terephthalate and/or mixtures thereof may be used.
  • In addition to terephthalic acid, the dicarboxylic acid component of the polyester useful in the invention can comprise up to 30 mole %, up to 20 mole %, up to 10 mole %, up to 5 mole %, or up to 1 mole % of one or more modifying aromatic dicarboxylic acids. Yet another embodiment contains 0 mole % modifying aromatic dicarboxylic acids. Thus, if present, it is contemplated that the amount of one or more modifying aromatic dicarboxylic acids can range from any of these preceding endpoint values including, for example, from 0.01 to 30 mole %, 0.01 to 20 mole %, from 0.01 to 10 mole %, from 0.01 to 5 mole % and from 0.01 to 1 mole. In one embodiment, modifying aromatic dicarboxylic acids that may be used in the present invention include but are not limited to those having up to 20 carbon atoms, and which can be linear, para-oriented, or symmetrical. Examples of modifying aromatic dicarboxylic acids which may be used in this invention include, but are not limited to, isophthalic acid, 4,4′-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid, and trans-4,4′-stilbenedicarboxylic acid, and esters thereof. In one embodiment, the modifying aromatic dicarboxylic acid is isophthalic acid.
  • The carboxylic acid component of the polyesters useful in the invention can be further modified with up to 10 mole %, such as up to 5 mole % or up to 1 mole % of one or more aliphatic dicarboxylic acids containing 2-16 carbon atoms, such as, for example, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and dodecanedioic dicarboxylic acids. Certain embodiments can also comprise 0.01 or more mole %, such as 0.1 or more mole %, 1 or more mole %, 5 or more mole %, or 10 or more mole % of one or more modifying aliphatic dicarboxylic acids. Yet another embodiment contains 0 mole % modifying aliphatic dicarboxylic acids. Thus, if present, it is contemplated that the amount of one or more modifying aliphatic dicarboxylic acids can range from any of these preceding endpoint values including, for example, from 0.01 to 10 mole % and from 0.1 to 10 mole %. The total mole % of the dicarboxylic acid component is 100 mole %.
  • Esters of terephthalic acid and the other modifying dicarboxylic acids or their corresponding esters and/or salts may be used instead of the dicarboxylic acids. Suitable examples of dicarboxylic acid esters include, but are not limited to, the dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the esters are chosen from at least one of the following: methyl, ethyl, propyl, isopropyl, and phenyl esters.
  • The 1,4-cyclohexanedimethanol may be cis, trans, or a mixture thereof, for example a cis/trans ratio of 60:40 to 40:60. In another embodiment, the trans-1,4-cyclohexanedimethanol can be present in an amount of 60 to 80 mole %.
  • The glycol component of the polyester portion of the polyester composition useful in the invention can contain 25 mole % or less of one or more modifying glycols which are not 2,2,4,4-tetramethyl-1,3-cyclobutanediol or 1,4-cyclohexanedimethanol; in one embodiment, the polyesters useful in the invention may contain less than 15 mole % of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 10 mole % or less of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 5 mole % or less of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 3 mole % or less of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 0 mole % modifying glycols. Certain embodiments can also contain 0.01 or more mole %, such as 0.1 or more mole %, 1 or more mole %, 5 or more mole %, or 10 or more mole % of one or more modifying glycols. Thus, if present, it is contemplated that the amount of one or more modifying glycols can range from any of these preceding endpoint values including, for example, from 0.01 to 15 mole % and from 0.1 to 10 mole %.
  • Modifying glycols useful in the polyesters useful in the invention refer to diols other than 2,2,4,4,-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol and may contain 2 to 16 carbon atoms. Examples of suitable modifying glycols include, but are not limited to, ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol or mixtures thereof. In one embodiment, the modifying glycol is ethylene glycol. In another embodiment, the modifying glycols are 1,3-propanediol and/or 1,4-butanediol. In another embodiment, ethylene glycol is excluded as a modifying diol. In another embodiment, 1,3-propanediol and 1,4-butanediol are excluded as modifying diols. In another embodiment, 2,2-dimethyl-1,3-propanediol is excluded as a modifying diol.
  • The polyesters and/or the polycarbonates useful in the polyesters compositions of the invention can comprise from 0 to 10 mole percent, for example, from 0.01 to 5 mole percent, from 0.01 to 1 mole percent, from 0.05 to 5 mole percent, from 0.05 to 1 mole percent, or from 0.1 to 0.7 mole percent, based the total mole percentages of either the diol or diacid residues; respectively, of one or more residues of a branching monomer, also referred to herein as a branching agent, having 3 or more carboxyl substituents, hydroxyl substituents, or a combination thereof. In certain embodiments, the branching monomer or agent may be added prior to and/or during and/or after the polymerization of the polyester. The polyester(s) useful in the invention can thus be linear or branched. The polycarbonate can also be linear or branched. In certain embodiments, the branching monomer or agent may be added prior to and/or during and/or after the polymerization of the polycarbonate.
  • Examples of branching monomers include, but are not limited to, multifunctional acids or multifunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid and the like. In one embodiment, the branching monomer residues can comprise 0.1 to 0.7 mole percent of one or more residues chosen from at least one of the following: trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1,2,6-hexanetriol, pentaerythritol, trimethylolethane, and/or trimesic acid. The branching monomer may be added to the polyester reaction mixture or blended with the polyester in the form of a concentrate as described, for example, in U.S. Pat. Nos. 5,654,347 and 5,696,176, whose disclosure regarding branching monomers is incorporated herein by reference.
  • The glass transition temperature (Tg) of the polyesters useful in the invention was determined using a TA DSC 2920 from Thermal Analyst Instrument at a scan rate of 20° C./min.
  • Because of the long crystallization half-times (e.g., greater than 5 minutes) at 170° C. exhibited by certain polyesters useful in the present invention, it is possible to produce calendered graphic art film(s), compression molded graphic art film(s), and solution casted graphic art film(s). The polyesters of the invention can be amorphous or semicrystalline. In one aspect, certain polyesters useful in the invention can have relatively low crystallinity. Certain polyesters useful in the invention can thus have a substantially amorphous morphology, meaning that the polyesters comprise substantially unordered regions of polymer.
  • In one embodiment, an “amorphous” polyester can have a crystallization half-time of greater than 5 minutes at 170° C. or greater than 10 minutes at 170° C. or greater than 50 minutes at 170° C. or greater than 100 minutes at 170° C. In one embodiment, of the invention, the crystallization half-times are greater than 1,000 minutes at 170° C. In another embodiment of the invention, the crystallization half-times of the polyesters useful in the invention are greater than 10,000 minutes at 170° C. The crystallization half time of the polyester, as used herein, may be measured using methods well-known to persons of skill in the art. For example, the crystallization half time of the polyester, t1/2) can be determined by measuring the light transmission of a sample via a laser and photo detector as a function of time on a temperature controlled hot stage. This measurement can be done by exposing the polymers to a temperature, Tmax, and then cooling it to the desired temperature. The sample can then be held at the desired temperature by a hot stage while transmission measurements are made as a function of time. Initially, the sample can be visually clear with high light transmission and becomes opaque as the sample crystallizes. The crystallization half-time is the time at which the light transmission is halfway between the initial transmission and the final transmission. Tmax is defined as the temperature required to melt the crystalline domains of the sample (if crystalline domains are present). The sample can be heated to Tmax to condition the sample prior to crystallization half time measurement. The absolute Tmax temperature is different for each composition. For example PCT can be heated to some temperature greater than 290° C. to melt the crystalline domains.
  • As shown in Table 1 and FIG. 1 of the Examples, 2,2,4,4-tetramethyl-1,3-cyclobutanediol is more effective than other comonomers such ethylene glycol and isophthalic acid at increasing the crystallization half-time, i.e., the time required for a polymer to reach half of its maximum crystallinity. By decreasing the crystallization rate of PCT, i.e. increasing the crystallization half-time, amorphous articles based on modified PCT may be fabricated by methods known in the art such as extrusion, injection molding, and the like. As shown in Table 1, these materials can exhibit higher glass transition temperatures and lower densities than other modified PCT copolyesters.
  • The polyesters can exhibit an improvement in toughness combined with processability for some of the embodiments of the invention. For example, it is unexpected that lowering the inherent viscosity slightly of the polyesters useful in the invention results in a more processable melt viscosity while retaining good physical properties of the polyesters such as toughness and heat resistance.
  • Increasing the content of 1,4-cyclohexanedimethanol in a copolyester based on terephthalic acid, ethylene glycol, and 1,4-cyclohexanedimethanol can improve toughness, which can be determined by the brittle-to-ductile transition temperature in a notched Izod impact strength test as measured by ASTM D256. This toughness improvement, by lowering of the brittle-to-ductile transition temperature with 1,4-cyclohexanedimethanol, is believed to occur due to the flexibility and conformational behavior of 1,4-cyclohexanedimethanol in the copolyester. Incorporating 2,2,4,4-tetramethyl-1,3-cyclobutanediol into PCT is believed to improve toughness, by lowering the brittle-to-ductile transition temperature, as shown in Table 2 and FIG. 2 of the Examples. This is unexpected given the rigidity of 2,2,4,4-tetramethyl-1,3-cyclobutanediol.
  • In one embodiment, the melt viscosity of the polyester(s) useful in the invention is less than 30,000 poise as measured a 1 radian/second on a rotary melt rheometer at 290° C. In another embodiment, the melt viscosity of the polyester(s) useful in the invention is less than 20,000 poise as measured a 1 radian/second on a rotary melt rheometer at 290° C.
  • In one embodiment, the melt viscosity of the polyester(s) useful in the invention is less than 15,000 poise as measured at 1 radian/second (rad/sec) on a rotary melt rheometer at 290° C. In one embodiment, the melt viscosity of the polyester(s) useful in the invention is less than 10,000 poise as measured at 1 radian/second (rad/sec) on a rotary melt rheometer at 290° C. In another embodiment, the melt viscosity of the polyester(s) useful in the invention is less than 6,000 poise as measured at 1 radian/second on a rotary melt rheometer at 290° C. Viscosity at rad/sec is related to processability. Typical polymers have viscosities of less than 10,000 poise as measured at 1 radian/second when measured at their processing temperature. Polyesters are typically not processed above 290° C. Polycarbonate is typically processed at 290° C. The viscosity at 1 rad/sec of a typical 12 melt flow rate polycarbonate is 7000 poise at 290° C.
  • In one embodiment, certain polyesters useful in this invention are visually clear. The term “visually clear” is defined herein as an appreciable absence of cloudiness, haziness, and/or muddiness, when inspected visually. When the polyesters are blended with polycarbonate, including bisphenol A polycarbonates, the blends can be visually clear in one aspect of the invention.
  • The present polyesters possess one or more of the following properties. In other embodiments, the polyesters useful in the invention may have a yellowness index (ASTM D-1925) of less than 50, such as less than 20.
  • In one embodiment, polyesters of this invention exhibit superior notched toughness in thick sections. Notched Izod impact strength, as described in ASTM D256, is a common method of measuring toughness. When tested by the Izod method, polymers can exhibit either a complete break failure mode, where the test specimen breaks into two distinct parts, or a partial or no break failure mode, where the test specimen remains as one part. The complete break failure mode is associated with low energy failure. The partial and no break failure modes are associated with high energy failure. A typical thickness used to measure Izod toughness is ⅛″. At this thickness, very few polymers are believed to exhibit a partial or no break failure mode, polycarbonate being one notable example. When the thickness of the test specimen is increased to ¼″, however, no commercial amorphous materials exhibit a partial or no break failure mode. In one embodiment, compositions of the present example exhibit a no break failure mode when tested in Izod using a ¼″ thick specimen.
  • The polyesters useful in the invention can possess one or more of the following properties. In one embodiment, the polyesters useful in the invention exhibit a notched Izod impact strength of at least 150 J/m (3 ft-lb/in) at 23° C. with a 10-mil notch in a 3.2 mm (⅛-inch) thick bar determined according to ASTM D256; in one embodiment, the polyesters useful in the invention exhibit a notched Izod impact strength of at least (400 J/m) 7.5 ft-lb/in at 23° C. with a 10-mil notch in a 3.2 mm (⅛-inch) thick bar determined according to ASTM D256; in one embodiment, the polyesters useful in the invention exhibit a notched Izod impact strength of at least 1000 J/m (18 ft-lb/in) at 23° C. with a 10-mil notch in a 3.2 mm (⅛-inch) thick bar determined according to ASTM D256. In one embodiment, the polyesters useful in the invention exhibit a notched Izod impact strength of at least 150 J/m (3 ft-lb/in) at 23° C. with a 10-mil notch in a 6.4 mm (¼-inch) thick bar determined according to ASTM D256; in one embodiment, the polyesters useful in the invention exhibit a notched Izod impact strength of at least (400 J/m) 7.5 ft-lb/in at 23° C. with a 10-mil notch in a 6.4 mm (¼-inch) thick bar determined according to ASTM D256; in one embodiment, the polyesters useful in the invention exhibit a notched Izod impact strength of at least 1000 J/m (18 ft-lb/in) at 23° C. with a 10-mil notch in a 6.4 mm (¼-inch) thick bar determined according to ASTM D256.
  • In another embodiment, certain polyesters useful in the invention can exhibit an increase in notched Izod impact strength when measured at 0° C. of at least 3% or at least 5% or at least 10% or at least 15% as compared to the notched Izod impact strength when measured at −5° C. with a 10-mil notch in a ⅛-inch thick bar determined according to ASTM D256. In addition, certain other polyesters useful in the invention can also exhibit a retention of notched Izod impact strength within plus or minus 5% when measured at 0° C. through 30° C. with a 10-mil notch in a ⅛-inch thick bar determined according to ASTM D256.
  • In yet another embodiment, certain polyesters useful in the invention can exhibit a retention in notched Izod impact strength with a loss of no more than 70% when measured at 23° C. with a 10-mil notch in a ¼-inch thick bar determined according to ASTM D256 as compared to notched Izod impact strength for the same polyester when measured at the same temperature with a 10-mil notch in a ⅛-inch thick bar determined according to ASTM D256.
  • In one embodiment, the polyesters useful in the invention and/or the polyester compositions of the invention, with or without toners, can have color values L*, a* and b*, which can be determined using a Hunter Lab Ultrascan Spectra Colorimeter manufactured by Hunter Associates Lab Inc., Reston, Va. The color determinations are averages of values measured on either pellets of the polyesters or plaques or other items injection molded or extruded from them They are determined by the L*a*b* color system of the CIE (International Commission on Illumination) (translated), wherein L* represents the lightness coordinate, a* represents the red/green coordinate, and b* represents the yellow/blue coordinate. In certain embodiments, the b* values for the polyesters useful in the invention can be from −10 to less than 10 and the L* values can be from 50 to 90. In other embodiments, the b* values for the polyesters useful in the invention can be present in one of the following ranges: −10 to 9; −10 to 8; −10 to 7; −10 to 6; −10 to 5; −10 to 4; −10 to 3; −10 to 2; from −5 to 9; −5 to 8; −5 to 7; −5 to 6; −5 to 5; −5 to 4; −5 to 3; −5 to 2; 0 to 9; 0 to 8; 0 to 7; 0 to 6; 0 to 5; 0 to 4; 0 to 3; 0 to 2; 1 to 10; 1 to 9; 1 to 8; 1 to 7; 1 to 6; 1 to 5; 1 to 4; 1 to 3; and 1 to 2. In other embodiments, the L* value for the polyesters useful in the invention can be present in one of the following ranges: 50 to 60; 50 to 70; 50 to 80; 50 to 90; 60 to 70; 60 to 80; 60 to 90; 70 to 80; 79 to 90.
  • In one embodiment, the polyesters useful in the invention exhibit a ductile-to-brittle transition temperature of less than 0° C. based on a 10-mil notch in a ⅛-inch thick bar as defined by ASTM D256.
  • In one embodiment, the polyesters useful in the invention can exhibit at least one of the following densities: a density of less than 1.3 g/ml at 23° C.; a density of less than 1.2 g/ml at 23° C.; a density of less than 1.18 g/ml at 23° C.; a density of 0.80 to 1.3 g/ml at 23° C.; a density of 0.80 to 1.2 g/ml at 23° C.; a density of 0.80 to less than 1.2 g/ml at 23° C.; a density of 1.0 to 1.3 g/ml at 23° C.; a density of 1.0 to 1.2 g/ml at 23° C.; a density of 1.0 to 1.1 g/ml at 23° C.; a density of 1.13 to 1.3 g/ml at 23° C.; a density of 1.13 to 1.2 g/ml at 23° C.
  • In some embodiments, use of the polyester compositions useful in the invention minimizes and/or eliminates the drying step prior to melt processing and/or thermoforming.
  • The polyester portion of the polyester compositions useful in the invention can be made by processes known from the literature such as, for example, by processes in homogenous solution, by transesterification processes in the melt, and by two phase interfacial processes. Suitable methods include, but are not limited to, the steps of reacting one or more dicarboxylic acids with one or more glycols at a temperature of 100° C. to 315° C. at a pressure of 0.1 to 760 mm Hg for a time sufficient to form a polyester. See U.S. Pat. No. 3,772,405 for methods of producing polyesters, the disclosure regarding such methods is hereby incorporated herein by reference.
  • In another aspect, the invention relates to graphic art film(s) comprising a polyester produced by a process comprising:
  • (I) heating a mixture comprising the monomers useful in any of the polyesters in the invention in the presence of a catalyst at a temperature of 150 to 240° C. for a time sufficient to produce an initial polyester;
  • (II) heating the initial polyester of step (I) at a temperature of 240 to 320° C. for 1 to 4 hours; and
  • (III) removing any unreacted glycols.
  • Suitable catalysts for use in this process include, but are not limited to, organo-zinc or tin compounds. The use of this type of catalyst is well known in the art. Examples of catalysts useful in the present invention include, but are not limited to, zinc acetate, butyltin tris-2-ethylhexanoate, dibutyltin diacetate, and dibutyltin oxide. Other catalysts may include, but are not limited to, those based on titanium, zinc, manganese, lithium, germanium, and cobalt. Catalyst amounts can range from 10 ppm to 20,000 ppm or 10 to 10,000 ppm, or 10 to 5000 ppm or 10 to 1000 ppm or 10 to 500 ppm, or 10 to 300 ppm or 10 to 250 based on the catalyst metal and based on the weight of the final polymer. The process can be carried out in either a batch or continuous process.
  • Typically, step (I) can be carried out until 50% by weight or more of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol has been reacted. Step (I) may be carried out under pressure, ranging from atmospheric pressure to 100 psig. The term “reaction product” as used in connection with any of the catalysts useful in the invention refers to any product of a polycondensation or esterification reaction with the catalyst and any of the monomers used in making the polyester as well as the product of a polycondensation or esterification reaction between the catalyst and any other type of additive.
  • Typically, Step (II) and Step (III) can be conducted at the same time. These steps can be carried out by methods known in the art such as by placing the reaction mixture under a pressure ranging from 0.002 psig to below atmospheric pressure, or by blowing hot nitrogen gas over the mixture.
  • The invention further relates to a polyester product made by the process described above.
  • The invention further relates to a polymer blend. The blend comprises:
  • (a) 5 to 95 wt % of at least one of the polyesters described above; and
  • (b) 5 to 95 wt % of at least one polymeric component.
  • Suitable examples of polymeric components include, but are not limited to, nylon, polyesters different from those described herein, polyamides such as ZYTEL® from DuPont; polystyrene, polystyrene copolymers, styrene acrylonitrile copolymers, acrylonitrile butadiene styrene copolymers, poly(methylmethacrylate), acrylic copolymers, poly(ether-imides) such as ULTEM® (a poly(ether-imide) from General Electric); polyphenylene oxides such as poly(2,6-dimethylphenylene oxide) or poly(phenylene oxide)/polystyrene blends such as NORYL 1000® (a blend of poly(2,6-dimethylphenylene oxide) and polystyrene resins from General Electric); polyphenylene sulfides; polyphenylene sulfide/sulfones; poly(ester-carbonates); polycarbonates such as LEXAN® (a polycarbonate from General Electric); polysulfones; polysulfone ethers; and poly(ether-ketones) of aromatic dihydroxy compounds; or mixtures of any of the other foregoing polymers. The blends can be prepared by conventional processing techniques known in the art, such as melt blending or solution blending. In one embodiment, the polycarbonate is not present in the polyester composition. If polycarbonate is used in a blend in the polyester compositions useful in the invention, the blends can be visually clear. However, the polyester compositions useful in the invention also contemplate the exclusion of polycarbonate as well as the inclusion of polycarbonate.
  • Polycarbonates useful in the invention may be prepared according to known procedures, for example, by reacting the dihydroxyaromatic compound with a carbonate precursor such as phosgene, a haloformate or a carbonate ester, a molecular weight regulator, an acid acceptor and a catalyst. Methods for preparing polycarbonates are known in the art and are described, for example, in U.S. Pat. No. 4,452,933, where the disclosure regarding the preparation of polycarbonates is hereby incorporated by reference herein.
  • Examples of suitable carbonate precursors include, but are not limited to, carbonyl bromide, carbonyl chloride, or mixtures thereof; diphenyl carbonate; a di(halophenyl)carbonate, e.g., di(trichlorophenyl)carbonate, di(tribromophenyl)carbonate, and the like; di(alkylphenyl)carbonate, e.g., di(tolyl)carbonate; di(naphthyl)carbonate; di(chloronaphthyl)carbonate, or mixtures thereof; and bis-haloformates of dihydric phenols.
  • Examples of suitable molecular weight regulators include, but are not limited to, phenol, cyclohexanol, methanol, alkylated phenols, such as octylphenol, para-tertiary-butyl-phenol, and the like. In one embodiment, the molecular weight regulator is phenol or an alkylated phenol.
  • The acid acceptor may be either an organic or an inorganic acid acceptor. A suitable organic acid acceptor can be a tertiary amine and includes, but is not limited to, such materials as pyridine, triethylamine, dimethylaniline, tributylamine, and the like. The inorganic acid acceptor can be either a hydroxide, a carbonate, a bicarbonate, or a phosphate of an alkali or alkaline earth metal.
  • The catalysts that can be used include, but are not limited to, those that typically aid the polymerization of the monomer with phosgene. Suitable catalysts include, but are not limited to, tertiary amines such as triethylamine, tripropylamine, N,N-dimethylaniline, quaternary ammonium compounds such as, for example, tetraethylammonium bromide, cetyl triethyl ammonium bromide, tetra-n-heptylammonium iodide, tetra-n-propyl ammonium bromide, tetramethyl ammonium chloride, tetra-methyl ammonium hydroxide, tetra-n-butyl ammonium iodide, benzyltrimethyl ammonium chloride and quaternary phosphonium compounds such as, for example, n-butyltriphenyl phosphonium bromide and methyltriphenyl phosphonium bromide.
  • The polycarbonates useful in the polyester compositions of the invention also may be copolyestercarbonates such as those described in U.S. Pat. Nos. 3,169,121; 3,207,814; 4,194,038; 4,156,069; 4,430,484, 4,465,820, and 4,981,898, the disclosure regarding copolyestercarbonates from each of the U.S. patents is incorporated by reference herein.
  • Copolyestercarbonates useful in this invention can be available commercially and/or can be prepared by known methods in the art. For example, they can be typically obtained by the reaction of at least one dihydroxyaromatic compound with a mixture of phosgene and at least one dicarboxylic acid chloride, especially isophthaloyl chloride, terephthaloyl chloride, or both.
  • In addition, the polyester compositions and the polymer blend compositions useful in the graphic art film(s) of this invention may also contain from 0.01 to 25% by weight of the overall composition common additives such as colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers, including but not limited to, UV stabilizers, thermal stabilizers and/or reaction products thereof, fillers, and impact modifiers. For example, UV additives can be incorporated into the graphic art film(s) through addition to the bulk, through application of a hard coat, or through the coextrusion of a cap layer. Examples of typical commercially available impact modifiers well known in the art and useful in this invention include, but are not limited to, ethylene/propylene terpolymers; functionalized polyolefins, such as those containing methyl acrylate and/or glycidyl methacrylate; styrene-based block copolymeric impact modifiers, and various acrylic core/shell type impact modifiers. Residues of such additives are also contemplated as part of the polyester composition.
  • The polyesters of the invention can comprise at least one chain extender. Suitable chain extenders include, but are not limited to, multifunctional (including, but not limited to, bifunctional) isocyanates, multifunctional epoxides, including for example, epoxylated novolacs, and phenoxy resins. In certain embodiments, chain extenders may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, chain extenders can be incorporated by compounding or by addition during conversion processes such as injection molding or extrusion. The amount of chain extender used can vary depending on the specific monomer composition used and the physical properties desired but is generally about 0.1 percent by weight to about 10 percent by weight, preferably about 0.1 to about 5 percent by weight, based on the total weigh of the polyester.
  • Thermal stabilizers are compounds that stabilize polyesters during polyester manufacture and/or post polymerization, including, but not limited to, phosphorous compounds, including, but not limited to, phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonous acid, and various esters and salts thereof. The esters can be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ethers, aryl, and substituted aryl. In one embodiment, the number of ester groups present in the particular phosphorous compound can vary from zero up to the maximum allowable based on the number of hydroxyl groups present on the thermal stabilizer used. The term “thermal stabilizer” is intended to include the reaction product(s) thereof. The term “reaction product” as used in connection with the thermal stabilizers of the invention refers to any product of a polycondensation or esterification reaction between the thermal stabilizer and any of the monomers used in making the polyester as well as the product of a polycondensation or esterification reaction between the catalyst and any other type of additive. These can be present in the polyester compositions useful in the invention.
  • Reinforcing materials may be useful in the compositions of this invention. The reinforcing materials may include, but are not limited to, carbon filaments, silicates, mica, clay, talc, titanium dioxide, Wollastonite, glass flakes, glass beads and fibers, and polymeric fibers and combinations thereof. In one embodiment, the reinforcing materials are glass, such as, fibrous glass filaments, mixtures of glass and talc, glass and mica, and glass and polymeric fibers.
  • Graphic art films can be made from films and/or sheets, where films and/or sheets useful in the present invention can be of any thickness which would be apparent to one of ordinary skill in the art. In one embodiment, the films and/or sheets of the invention have a thickness of no more than 40 mils, such as, for example, less than 30 mils, less than 20 mils, less than 10 mils, less than 5 mils, and 1 mil. In one embodiment, the films and/or sheets of the invention have a thickness of no less than 5 mils, such as no less than 10 mils, and no less than 20 mils.
  • The invention further relates to the film(s) and/or sheet(s) comprising the polyester compositions of the invention. The methods of forming the polyesters into film(s) and/or sheet(s) are well known in the art. Examples of film(s) and/or sheet(s) of the invention including but not limited to melt extruded film(s) and/or sheet(s), calendered film(s) and/or sheet(s), compression molded film(s) and/or sheet(s), and solution casted film(s) and/or sheet(s). Methods of making film and/or sheet include but are not limited to extrusion, calendering, compression molding, and solution casting.
  • The invention further relates to graphic art film(s) described herein. These graphic art film(s) include, but are not limited to, calendered graphic art film(s), compression molded graphic art film(s), and solution casted graphic art film(s). Methods of making graphic art film(s) include, but are not limited to, calendering, compression molding, and solution casting.
  • For the purposes of this disclosure, the term “wt” means “weight”.
  • The following examples further illustrate how the graphic art film(s) of the invention can be made and evaluated, and are intended to be purely exemplary of the invention and are not intended to limit the scope thereof. Unless indicated otherwise, parts are parts by weight, temperature is in degrees C. or is at room temperature, and pressure is at or near atmospheric.
  • EXAMPLES Measurement Methods
  • The inherent viscosity of the polyesters was determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C.
  • Unless stated otherwise, the glass transition temperature (Tg) was determined using a TA DSC 2920 instrument from Thermal Analyst Instruments at a scan rate of 20° C./min according to ASTM D3418.
  • The glycol content and the cis/trans ratio of the compositions were determined by proton nuclear magnetic resonance (NMR) spectroscopy. All NMR spectra were recorded on a JEOL Eclipse Plus 600 MHz nuclear magnetic resonance spectrometer using either chloroform-trifluoroacetic acid (70-30 volume/volume) for polymers or, for oligomeric samples, 60/40 (wt/wt) phenol/tetrachloroethane with deuterated chloroform added for lock. Peak assignments for 2,2,4,4-tetramethyl-1,3-cyclobutanediol resonances were made by comparison to model mono- and dibenzoate esters of 2,2,4,4-tetramethyl-1,3-cyclobutanediol. These model compounds closely approximate the resonance positions found in the polymers and oligomers.
  • The crystallization half-time, t1/2, was determined by measuring the light transmission of a sample via a laser and photo detector as a function of time on a temperature controlled hot stage. This measurement was done by exposing the polymers to a temperature, Tmax, and then cooling it to the desired temperature. The sample was then held at the desired temperature by a hot stage while transmission measurements were made as a function of time. Initially, the sample was visually clear with high light transmission and became opaque as the sample crystallized. The crystallization half-time was recorded as the time at which the light transmission was halfway between the initial transmission and the final transmission. Tmax is defined as the temperature required to melt the crystalline domains of the sample (if crystalline domains are present). The Tmax reported in the examples below represents the temperature at which each sample was heated to condition the sample prior to crystallization half time measurement. The Tmax temperature is dependant on composition and is typically different for each polyester. For example, PCT may need to be heated to some temperature greater than 290° C. to melt the crystalline domains.
  • Density was determined using a gradient density column at 23° C.
  • The melt viscosity reported herein was measured by using a Rheometrics Dynamic Analyzer (RDA II). The melt viscosity was measured as a function of shear rate, at frequencies ranging from 1 to 400 rad/sec, at the temperatures reported. The zero shear melt viscosity (η0) is the melt viscosity at zero shear rate estimated by extrapolating the data by known models in the art. This step is automatically performed by the Rheometrics Dynamic Analyzer (RDA II) software.
  • The polymers were dried at a temperature ranging from 80 to 100° C. in a vacuum oven for 24 hours and injection molded on a Boy 22S molding machine to give ⅛×½×5-inch and ¼×½×5-inch flexure bars. These bars were cut to a length of 2.5 inch and notched down the ½ inch width with a 10-mil notch in accordance with ASTM D256. The average Izod impact strength at 23° C. was determined from measurements on 5 specimens.
  • In addition, 5 specimens were tested at various temperatures using 5° C. increments in order to determine the brittle-to-ductile transition temperature. The brittle-to-ductile transition temperature is defined as the temperature at which 50% of the specimens fail in a brittle manner as denoted by ASTM D256.
  • Color values reported herein were determined using a Hunter Lab Ultrascan Spectra Colorimeter manufactured by Hunter Associates Lab Inc., Reston, Va. The color determinations were averages of values measured on either pellets of the polyesters or plaques or other items injection molded or extruded from them. They were determined by the L*a*b* color system of the CIE (International Commission on Illumination) (translated), wherein L* represents the lightness coordinate, a* represents the red/green coordinate, and b* represents the yellow/blue coordinate.
  • In addition, 10-mil films were compression molded using a Carver press at 240° C.
  • Unless otherwise specified, the cis/trans ratio of the 1,4 cyclohexanedimethanol used in the following examples was approximately 30/70, and could range from 35/65 to 25/75. Unless otherwise specified, the cis/trans ratio of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol used in the following examples was approximately 50/50.
  • The following abbreviations apply throughout the working examples and figures:
  • TPA Terephthalic acid
    DMT Dimethyl terephthalate
    TMCD 2,2,4,4-tetramethyl-1,3-cyclobutanediol
    CHDM 1,4-cyclohexanedimethanol
    IV Inherent viscosity
    ηo Zero shear melt viscosity
    Tg Glass transition temperature
    Tbd Brittle-to-ductile transition temperature
    Tmax Conditioning temperature for
    crystallization half time measurements
  • Example 1
  • This example illustrates that 2,2,4,4-tetramethyl-1,3-cyclobutanediol is more effective at reducing the crystallization rate of PCT than ethylene glycol or isophthalic acid. In addition, this example illustrates the benefits of 2,2,4,4-tetramethyl-1,3-cyclobutanediol on the glass transition temperature and density.
  • A variety of copolyesters were prepared as described below. These copolyesters were all made with 200 ppm dibutyl tin oxide as the catalyst in order to minimize the effect of catalyst type and concentration on nucleation during crystallization studies. The cis/trans ratio of the 1,4-cyclohexanedimethanol was 31/69 while the cis/trans ratio of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol is reported in Table 1.
  • For purposes of this example, the samples had sufficiently similar inherent viscosities thereby effectively eliminating this as a variable in the crystallization rate measurements.
  • Crystallization half-time measurements from the melt were made at temperatures from 140 to 200° C. at 10° C. increments and are reported in Table 1. The fastest crystallization half-time for each sample was taken as the minimum value of crystallization half-time as a function of temperature, typically occurring around 170 to 180° C. The fastest crystallization half-times for the samples are plotted in FIG. 1 as a function of mole % comonomer modification to PCT.
  • The data shows that 2,2,4,4-tetramethyl-1,3-cyclobutanediol is more effective than ethylene glycol and isophthalic acid at decreasing the crystallization rate (i.e., increasing the crystallization half-time). In addition, 2,2,4,4-tetramethyl-1,3-cyclobutanediol increases Tg and lowers density.
  • TABLE 1
    Crystallization Half-times (min)
    at at at at at at at
    Comonomer IV Density Tg Tmax 140° C. 150° C. 160° C. 170° C. 180° C. 190° C. 200° C.
    Example (mol %)1 (dl/g) (g/ml) (° C.) (° C.) (min) (min) (min) (min) (min) (min) (min)
    1A 20.2% A2 0.630 1.198 87.5 290 2.7 2.1 1.3 1.2 0.9 1.1 1.5
    1B 19.8% B 0.713 1.219 87.7 290 2.3 2.5 1.7 1.4 1.3 1.4 1.7
    1C 20.0% C 0.731 1.188 100.5 290 >180 >60 35.0 23.3 21.7 23.3 25.2
    1D 40.2% A2 0.674 1.198 81.2 260 18.7 20.0 21.3 25.0 34.0 59.9 96.1
    1E 34.5% B 0.644 1.234 82.1 260 8.5 8.2 7.3 7.3 8.3 10.0 11.4
    1F 40.1% C 0.653 1.172 122.0 260 >10 days >5 days >5 days 19204 >5 days >5 days >5 days
    1G 14.3% D 0.6463 1.188 103.0 290 55.0 28.8 11.6 6.8 4.8 5.0 5.5
    1H 15.0% E 0.7284 1.189 99.0 290 25.4 17.1 8.1 5.9 4.3 2.7 5.1
    1The balance of the diol component of the polyesters in Table 1 is 1,4-cyclohexanedimethanol; and the balance of the dicarboxylic acid component of the polyesters in Table 1 is dimethyl terephthalate; if the dicarboxylic acid is not described, it is 100 mole % dimethyl terephthalate.
    2100 mole % 1,4-cyclohexanedimethanol.
    3A film was pressed from the ground polyester of Example 1G at 240° C. The resulting film had an inherent viscosity value of 0.575 dL/g.
    4A film was pressed from the ground polyester of Example 1H at 240° C. The resulting film had an inherent viscosity value of 0.0.652 dL/g.
    where:
    A is Isophthalic Acid
    B is Ethylene Glycol
    C is 2,2,4,4-Tetramethyl-1,3-cyclobutanediol (approx. 50/50 cis/trans)
    D is 2,2,4,4-Tetramethyl-1,3-cyclobutanediol (98/2 cis/trans)
    E is 2,2,4,4-Tetramethyl-1,3-cyclobutanediol (5/95 cis/trans)
  • As shown in Table 1 and FIG. 1, 2,2,4,4-tetramethyl-1,3-cyclobutanediol is more effective than other comonomers, such ethylene glycol and isophthalic acid, at increasing the crystallization half-time, i.e., the time required for a polymer to reach half of its maximum crystallinity. By decreasing the crystallization rate of PCT (increasing the crystallization half-time), amorphous articles based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol-modified PCT as described herein may be fabricated by methods known in the art. As shown in Table 1, these materials can exhibit higher glass transition temperatures and lower densities than other modified PCT copolyesters.
  • Preparation of the polyesters shown on Table 1 is described below.
  • Example 1A
  • This example illustrates the preparation of a copolyester with a target composition of 80 mol % dimethyl terephthalate residues, 20 mol % dimethyl isophthalate residues, and 100 mol % 1,4-cyclohexanedimethanol residues (28/72 cis/trans).
  • A mixture of 56.63 g of dimethyl terephthalate, 55.2 g of 1,4-cyclohexanedimethanol, 14.16 g of dimethyl isophthalate, and 0.0419 g of dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. The flask was placed in a Wood's metal bath already heated to 210° C. The stirring speed was set to 200 RPM throughout the experiment. The contents of the flask were heated at 210° C. for 5 minutes and then the temperature was gradually increased to 290° C. over 30 minutes. The reaction mixture was held at 290° C. for 60 minutes and then vacuum was gradually applied over the next 5 minutes until the pressure inside the flask reached 100 mm of Hg. The pressure inside the flask was further reduced to 0.3 mm of Hg over the next 5 minutes. A pressure of 0.3 mm of Hg was maintained for a total time of 90 minutes to remove excess unreacted diols. A high melt viscosity, visually clear and colorless polymer was obtained with a glass transition temperature of 87.5° C. and an inherent viscosity of 0.63 dl/g. NMR analysis showed that the polymer was composed of 100 mol % 1,4-cyclohexanedimethanol residues and 20.2 mol % dimethyl isophthalate residues.
  • Example 1B
  • This example illustrates the preparation of a copolyester with a target composition of 100 mol % dimethyl terephthalate residues, 20 mol % ethylene glycol residues, and 80 mol % 1,4-cyclohexanedimethanol residues (32/68 cis/trans).
  • A mixture of 77.68 g of dimethyl terephthalate, 50.77 g of 1,4-cyclohexanedimethanol, 27.81 g of ethylene glycol, and 0.0433 g of dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. The flask was placed in a Wood's metal bath already heated to 200° C. The stirring speed was set to 200 RPM throughout the experiment. The contents of the flask were heated at 200° C. for 60 minutes and then the temperature was gradually increased to 210° C. over 5 minutes. The reaction mixture was held at 210° C. for 120 minutes and then heated up to 280° C. in 30 minutes. Once at 280° C., vacuum was gradually applied over the next 5 minutes until the pressure inside the flask reached 100 mm of Hg. The pressure inside the flask was further reduced to 0.3 mm of Hg over the next 10 minutes. A pressure of 0.3 mm of Hg was maintained for a total time of 90 minutes to remove excess unreacted diols. A high melt viscosity, visually clear and colorless polymer was obtained with a glass transition temperature of 87.7° C. and an inherent viscosity of 0.71 dl/g. NMR analysis showed that the polymer was composed of 19.8 mol % ethylene glycol residues.
  • Example 1C
  • This example illustrates the preparation of a copolyester with a target composition of 100 mol % dimethyl terephthalate residues, 20 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and 80 mol % 1,4-cyclohexanedimethanol residues (31/69 cis/trans).
  • A mixture of 77.68 g of dimethyl terephthalate, 48.46 g of 1,4-cyclohexanedimethanol, 17.86 g of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 0.046 g of dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. This polyester was prepared in a manner similar to that described in Example 1A. A high melt viscosity, visually clear and colorless polymer was obtained with a glass transition temperature of 100.5° C. and an inherent viscosity of 0.73 dl/g. NMR analysis showed that the polymer was composed of 80.5 mol % 1,4-cyclohexanedimethanol residues and 19.5 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.
  • Example 1D
  • This example illustrates the preparation of a copolyester with a target composition of 100 mol % dimethyl terephthalate residues, 40 mol % dimethyl isophthalate residues, and 100 mol % 1,4-cyclohexanedimethanol residues (28/72 cis/trans).
  • A mixture of 42.83 g of dimethyl terephthalate, 55.26 g of 1,4-cyclohexanedimethanol, 28.45 g of dimethyl isophthalate, and 0.0419 g of dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. The flask was placed in a Wood's metal bath already heated to 210° C. The stirring speed was set to 200 RPM throughout the experiment. The contents of the flask were heated at 210° C. for 5 minutes and then the temperature was gradually increased to 290° C. over 30 minutes. The reaction mixture was held at 290° C. for 60 minutes and then vacuum was gradually applied over the next 5 minutes until the pressure inside the flask reached 100 mm of Hg. The pressure inside the flask was further reduced to 0.3 mm of Hg over the next 5 minutes. A pressure of 0.3 mm of Hg was maintained for a total time of 90 minutes to remove excess unreacted diols. A high melt viscosity, visually clear and colorless polymer was obtained with a glass transition temperature of 81.2° C. and an inherent viscosity of 0.67 dl/g. NMR analysis showed that the polymer was composed of 100 mol % 1,4-cyclohexanedimethanol residues and 40.2 mol % dimethyl isophthalate residues.
  • Example 1E
  • This example illustrates the preparation of a copolyester with a target composition of 100 mol % dimethyl terephthalate residues, 40 mol % ethylene glycol residues, and 60 mol % 1,4-cyclohexanedimethanol residues (31/69 cis/trans).
  • A mixture of 81.3 g of dimethyl terephthalate, 42.85 g of 1,4-cyclohexanedimethanol, 34.44 g of ethylene glycol, and 0.0419 g of dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. The flask was placed in a Wood's metal bath already heated to 200° C. The stirring speed was set to 200 RPM throughout the experiment. The contents of the flask were heated at 200° C. for 60 minutes and then the temperature was gradually increased to 210° C. over 5 minutes. The reaction mixture was held at 210° C. for 120 minutes and then heated up to 280° C. in 30 minutes. Once at 280° C., vacuum was gradually applied over the next 5 minutes until the pressure inside the flask reached 100 mm of Hg. The pressure inside the flask was further reduced to 0.3 mm of Hg over the next 10 minutes. A pressure of 0.3 mm of Hg was maintained for a total time of 90 minutes to remove excess unreacted diols. A high melt viscosity, visually clear and colorless polymer was obtained with a glass transition temperature of 82.1° C. and an inherent viscosity of 0.64 dl/g. NMR analysis showed that the polymer was composed of 34.5 mol % ethylene glycol residues.
  • Example 1F
  • This example illustrates the preparation of a copolyester with a target composition of 100 mol % dimethyl terephthalate residues, 40 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and 60 mol % 1,4-cyclohexanedimethanol residues (31/69 cis/trans).
  • A mixture of 77.4 g of dimethyl terephthalate, 36.9 g of 1,4-cyclohexanedimethanol, 32.5 g of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 0.046 g of dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. The flask was placed in a Wood's metal bath already heated to 210° C. The stirring speed was set to 200 RPM throughout the experiment. The contents of the flask were heated at 210° C. for 3 minutes and then the temperature was gradually increased to 260° C. over 30 minutes. The reaction mixture was held at 260° C. for 120 minutes and then heated up to 290° C. in 30 minutes. Once at 290° C., vacuum was gradually applied over the next 5 minutes until the pressure inside the flask reached 100 mm of Hg. The pressure inside the flask was further reduced to 0.3 mm of Hg over the next 5 minutes. A pressure of 0.3 mm of Hg was maintained for a total time of 90 minutes to remove excess unreacted diols. A high melt viscosity, visually clear and colorless polymer was obtained with a glass transition temperature of 122° C. and an inherent viscosity of 0.65 dl/g. NMR analysis showed that the polymer was composed of 59.9 mol % 1,4-cyclohexanedimethanol residues and 40.1 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.
  • Example 1G
  • This example illustrates the preparation of a copolyester with a target composition of 100 mol % dimethyl terephthalate residues, 20 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues (98/2 cis/trans), and 80 mol % 1,4-cyclohexanedimethanol residues (31/69 cis/trans).
  • A mixture of 77.68 g of dimethyl terephthalate, 48.46 g of 1,4-cyclohexanedimethanol, 20.77 g of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 0.046 g of dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. The flask was placed in a Wood's metal bath already heated to 210° C. The stirring speed was set to 200 RPM throughout the experiment. The contents of the flask were heated at 210° C. for 3 minutes and then the temperature was gradually increased to 260° C. over 30 minutes. The reaction mixture was held at 260° C. for 120 minutes and then heated up to 290° C. in 30 minutes. Once at 290° C., vacuum was gradually applied over the next 5 minutes until the pressure inside the flask reached 100 mm of Hg and the stirring speed was also reduced to 100 RPM. The pressure inside the flask was further reduced to 0.3 mm of Hg over the next 5 minutes and the stirring speed was reduced to 50 RPM. A pressure of 0.3 mm of Hg was maintained for a total time of 60 minutes to remove excess unreacted diols. A high melt viscosity, visually clear and colorless polymer was obtained with a glass transition temperature of 103° C. and an inherent viscosity of 0.65 dl/g. NMR analysis showed that the polymer was composed of 85.7 mol % 1,4-cyclohexanedimethanol residues and 14.3 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.
  • Example 1H
  • This example illustrates the preparation of a copolyester with a target composition of 100 mol % dimethyl terephthalate residues, 20 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues (5/95 cis/trans), and 80 mol % 1,4-cyclohexanedimethanol residues (31/69 cis/trans).
  • A mixture of 77.68 g of dimethyl terephthalate, 48.46 g of 1,4-cyclohexanedimethanol, 20.77 g of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 0.046 g of dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. The flask was placed in a Wood's metal bath already heated to 210° C. The stirring speed was set to 200 RPM at the beginning of the experiment. The contents of the flask were heated at 210° C. for 3 minutes and then the temperature was gradually increased to 260° C. over 30 minutes. The reaction mixture was held at 260° C. for 120 minutes and then heated up to 290° C. in 30 minutes. Once at 290° C., vacuum was gradually applied over the next 5 minutes with a set point of 100 mm of Hg and the stirring speed was also reduced to 100 RPM. The pressure inside the flask was further reduced to a set point of 0.3 mm of Hg over the next 5 minutes and the stirring speed was reduced to 50 RPM. This pressure was maintained for a total time of 60 minutes to remove excess unreacted diols. It was noted that the vacuum system failed to reach the set point mentioned above, but produced enough vacuum to produce a high melt viscosity, visually clear and colorless polymer with a glass transition temperature of 99° C. and an inherent viscosity of 0.73 dl/g. NMR analysis showed that the polymer was composed of 85 mol % 1,4-cyclohexanedimethanol residues and 15 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.
  • Example 2
  • This example illustrates that 2,2,4,4-tetramethyl-1,3-cyclobutanediol improves the toughness of PCT-based copolyesters (polyesters containing terephthalic acid and 1,4-cyclohexanedimethanol).
  • Copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol were prepared as described below. The cis/trans ratio of the 1,4-cyclohexanedimethanol was approximately 31/69 for all samples. Copolyesters based on ethylene glycol and 1,4-cyclohexanedimethanol were commercial polyesters. The copolyester of Example 2A (Eastar PCTG 5445) was obtained from Eastman Chemical Co. The copolyester of Example 2B was obtained from Eastman Chemical Co. under the trade name Spectar. Example 2C and Example 2D were prepared on a pilot plant scale (each a 15-lb batch) following an adaptation of the procedure described in Example 1A and having the inherent viscosities and glass transition temperatures described in Table 2 below. Example 2C was prepared with a target tin amount of 300 ppm (Dibutyltin Oxide). The final product contained 295 ppm tin. The color values for the polyester of Example 2C were L*=77.11; a*=−1.50; and b*=5.79. Example 2D was prepared with a target tin amount of 300 ppm (Dibutyltin Oxide). The final product contained 307 ppm tin. The color values for the polyester of Example 2D were L*=66.72; a*=−1.22; and b*=16.28.
  • Materials were injection molded into bars and subsequently notched for Izod testing. The notched Izod impact strengths were obtained as a function of temperature and are also reported in Table 2.
  • For a given sample, the Izod impact strength undergoes a major transition in a short temperature span. For instance, the Izod impact strength of a copolyester based on 38 mol % ethylene glycol undergoes this transition between 15 and 20° C. This transition temperature is associated with a change in failure mode; brittle/low energy failures at lower temperatures and ductile/high energy failures at higher temperatures. The transition temperature is denoted as the brittle-to-ductile transition temperature, Tbd, and is a measure of toughness. Tbd is reported in Table 2 and plotted against mol % comonomer in FIG. 2.
  • The data shows that adding 2,2,4,4-tetramethyl-1,3-cyclobutanediol to PCT lowers Tbd and improves the toughness, as compared to ethylene glycol, which increases Tbd of PCT.
  • TABLE 2
    Notched Izod Impact Energy (ft-lb/in)
    Comonomer IV Tg Tbd at at at at at at at at at at
    Example (mol %)1 (dl/g) (° C.) (° C.) at −20° C. −15° C. −10° C. −5° C. 0° C. 5° C. 10° C. 15° C. 20° C. 25° C. 30° C.
    2A 38.0% B 0.68 86 18 NA NA NA 1.5 NA NA 1.5 1.5 32 32 NA
    2B 69.0% B 0.69 82 26 NA NA NA NA NA NA 2.1 NA 2.4 13.7 28.7
    2C 22.0% C 0.66 106 −5 1.5 NA 12 23 23 NA 23 NA NA NA NA
    2D 42.8% C 0.60 133 −12 2.5 2.5 11 NA 14 NA NA NA NA NA NA
    1The balance of the glycol component of the polyesters in the Table is 1,4-cyclohexanedimethanol. All polymers were prepared from 100 mole % dimethyl terephthalate.
    NA = Not available.
    where:
    B is Ethylene glycol
    C is 2,2,4,4-Tetramethyl-1,3-cyclobutanediol (50/50 cis/trans)
  • Example 3
  • This example illustrates that 2,2,4,4-tetramethyl-1,3-cyclobutanediol can improve the toughness of PCT-based copolyesters(polyesters containing terephthalic acid and 1,4-cyclohexanedimethanol). Polyesters prepared in this example comprise from 15 to 25 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.
  • Copolyesters based on dimethyl terephthalate, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 1,4-cyclohexanedimethanol were prepared as described below, having the composition and properties shown on Table 3. The balance up to 100 mol % of the diol component of the polyesters in Table 3 was 1,4-cyclohexanedimethanol (31/69 cis/trans).
  • Materials were injection molded into both 3.2 mm and 6.4 mm thick bars and subsequently notched for Izod impact testing. The notched Izod impact strengths were obtained at 23° C. and are reported in Table 3. Density, Tg, and crystallization halftime were measured on the molded bars. Melt viscosity was measured on pellets at 290° C.
  • TABLE 3
    Compilation of various properties for certain polyesters useful in the invention
    Notched Notched
    Izod of Izod of
    3.2 mm 6.4 mm Melt
    thick thick Crystallization Viscosity
    Pellet Molded bars at bars at Specific Halftime from at 1 rad/sec
    TMCD % cis IV Bar IV 23° C. 23° C. Gravity Tg melt at 170° C. at 290° C.
    Example mole % TMCD (dl/g) (dl/g) (J/m) (J/m) (g/mL) (° C.) (min) (Poise)
    A 15 48.8 0.736 0.707 1069 878 1.184 104 15 5649
    B 18 NA 0.728 0.715 980 1039 1.183 108 22 6621
    C 20 NA 0.706 0.696 1006 1130 1.182 106 52 6321
    D 22 NA 0.732 0.703 959 988 1.178 108 63 7161
    E 21 NA 0.715 0.692 932 482 1.179 110 56 6162
    F 24 NA 0.708 0.677 976 812 1.180 109 58 6282
    G 23 NA 0.650 0.610 647 270 1.182 107 46 3172
    H 23 47.9 0.590 0.549 769 274 1.181 106 47 1736
    I 23 48.1 0.531 0.516 696 352 1.182 105 19 1292
    NA = Not available
  • Example 3A
  • 21.24 lb (49.71 gram-mol) dimethyl terephthalate, 14.34 lb (45.21 gram-mol) 1,4-cyclohexanedimethanol, and 4.58 lb (14.44 gram-mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together in the presence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). The reaction was carried out under a nitrogen gas purge in an 18-gallon stainless steel pressure vessel fitted with a condensing column, a vacuum system, and a HELICONE-type agitator. With the agitator running at 25 RPM, the reaction mixture temperature was increased to 250° C. and the pressure was increased to 20 psig. The reaction mixture was held for 2 hours at 250° C. and at a pressure of 20 psig. The pressure was then decreased to 0 psig at a rate of 3 psig/minute. The temperature of the reaction mixture was then increased to 270° C. and the pressure was decreased to 90 mm of Hg. After a 1 hour hold time at 270° C. and 90 mm of Hg, the agitator speed was decreased to 15 RPM, the reaction mixture temperature was increased to 290° C., and the pressure was decreased to <1 mm of Hg. The reaction mixture was held at 290° C. and at a pressure of <1 mm of Hg until the power draw to the agitator no longer increased (70 minutes). The pressure of the pressure vessel was then increased to 1 atmosphere using nitrogen gas. The molten polymer was then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass a 6-mm screen. The polymer had an inherent viscosity of 0.736 dL/g and a Tg of 104° C. NMR analysis showed that the polymer was composed of 85.4 mol % 1,4-cyclohexane-dimethanol residues and 14.6 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The polymer had color values of: L*=78.20, a*=−1.62, and b*=6.23.
  • Example 3B to Example 3D
  • The polyesters described in Example 3B to Example 3D were prepared following a procedure similar to the one described for Example 3A. The composition and properties of these polyesters are shown in Table 3.
  • Example 3E
  • 21.24 lb (49.71 gram-mol) dimethyl terephthalate, 12.61 lb (39.77 gram-mol) 1,4-cyclohexanedimethanol, and 6.30 lb (19.88 gram-mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together in the presence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). The reaction was carried out under a nitrogen gas purge in an 18-gallon stainless steel pressure vessel fitted with a condensing column, a vacuum system, and a HELICONE-type agitator. With the agitator running at 25 RPM, the reaction mixture temperature was increased to 250° C. and the pressure was increased to 20 psig. The reaction mixture was held for 2 hours at 250° C. and 20 psig pressure. The pressure was then decreased to 0 psig at a rate of 3 psig/minute. The temperature of the reaction mixture was then increased to 270° C. and the pressure was decreased to 90 mm of Hg. After a 1 hour hold time at 270° C. and 90 mm of Hg, the agitator speed was decreased to 15 RPM, the reaction mixture temperature was increased to 290° C., and the pressure was decreased to <1 mm of Hg. The reaction mixture was held at 290° C. and at a pressure of <1 mm of Hg for 60 minutes. The pressure of the pressure vessel was then increased to 1 atmosphere using nitrogen gas. The molten polymer was then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass a 6-mm screen. The polymer had an inherent viscosity of 0.715 dL/g and a Tg of 110° C. X-ray analysis showed that the polyester had 223 ppm tin. NMR analysis showed that the polymer was composed of 78.6 mol % 1,4-cyclohexane-dimethanol residues and 21.4 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The polymer had color values of: L*=76.45, a*=−1.65, and b*=6.47.
  • Example 3F
  • The polyester described in Example 3F was prepared following a procedure similar to the one described for Example 3A. The composition and properties of this polyester are shown in Table 3.
  • Example 3H
  • 21.24 lb (49.71 gram-mol) dimethyl terephthalate, 12.61 lb (39.77 gram-mol) 1,4-cyclohexanedimethanol, and 6.30 lb (19.88 gram-mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together in the presence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). The reaction was carried out under a nitrogen gas purge in an 18-gallon stainless steel pressure vessel fitted with a condensing column, a vacuum system, and a HELICONE-type agitator. With the agitator running at 25 RPM, the reaction mixture temperature was increased to 250° C. and the pressure was increased to 20 psig. The reaction mixture was held for 2 hours at 250° C. and 20 psig pressure. The pressure was then decreased to 0 psig at a rate of 3 psig/minute. The temperature of the reaction mixture was then increased to 270° C. and the pressure was decreased to 90 mm of Hg. After a 1 hour hold time at 270° C. and 90 mm of Hg, the agitator speed was decreased to 15 RPM, the reaction mixture temperature was increased to 290° C., and the pressure was decreased to <1 mm of Hg. The reaction mixture was held at 290° C. and at a pressure of <1 mm of Hg for 12 minutes. The pressure of the pressure vessel was then increased to 1 atmosphere using nitrogen gas. The molten polymer was then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass a 6-mm screen. The polymer had an inherent viscosity of 0.590 dL/g and a Tg of 106° C. NMR analysis showed that the polymer was composed of 77.1 mol % 1,4-cyclohexane-dimethanol residues and 22.9 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The polymer had color values of: L*=83.27, a*=−1.34, and b*=5.08.
  • Example 3I
  • 21.24 lb (49.71 gram-mol) dimethyl terephthalate, 12.61 lb (39.77 gram-mol) 1,4-cyclohexanedimethanol, and 6.30 lb (19.88 gram-mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together in the presence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). The reaction was carried out under a nitrogen gas purge in an 18-gallon stainless steel pressure vessel fitted with a condensing column, a vacuum system, and a HELICONE-type agitator. With the agitator running at 25 RPM, the reaction mixture temperature was increased to 250° C. and the pressure was increased to 20 psig. The reaction mixture was held for 2 hours at 250° C. and 20 psig pressure. The pressure was then decreased to 0 psig at a rate of 3 psig/minute. The temperature of the reaction mixture was then increased to 270° C. and the pressure was decreased to 90 mm of Hg. After a 1 hour hold time at 270° C. and 90 mm of Hg, the agitator speed was decreased to 15 RPM, the reaction mixture temperature was increased to 290° C., and the pressure was decreased to 4 mm of Hg. The reaction mixture was held at 290° C. and at a pressure of 4 mm of Hg for 30 minutes. The pressure of the pressure vessel was then increased to 1 atmosphere using nitrogen gas. The molten polymer was then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass a 6-mm screen. The polymer had an inherent viscosity of 0.531 dL/g and a Tg of 105° C. NMR analysis showed that the polymer was composed of 76.9 mol % 1,4-cyclohexane-dimethanol residues and 23.1 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The polymer had color values of: L*=80.42, a*=−1.28, and b*=5.13.
  • Example 4
  • This example illustrates that 2,2,4,4-tetramethyl-1,3-cyclobutanediol can improve the toughness of PCT-based copolyesters(polyesters containing terephthalic acid and 1,4-cyclohexanedimethanol). Polyesters prepared in this example fall comprise more than 25 to less than 40 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.
  • Copolyesters based on dimethyl terephthalate, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 1,4-cyclohexanedimethanol (31/69 cis/trans) were prepared as described below, having the composition and properties shown on Table 4. The balance up to 100 mol % of the diol component of the polyesters in Table 4 was 1,4-cyclohexanedimethanol (31/69 cis/trans).
  • Materials were injection molded into both 3.2 mm and 6.4 mm thick bars and subsequently notched for Izod impact testing. The notched Izod impact strengths were obtained at 23° C. and are reported in Table 4. Density, Tg, and crystallization halftime were measured on the molded bars. Melt viscosity was measured on pellets at 290° C.
  • TABLE 4
    Compilation of various properties for certain polyesters useful in the invention
    Notched Notched
    Izod of Izod of
    3.2 mm 6.4 mm Melt
    thick thick Crystallization Viscosity
    Pellet Molded bars at bars at Specific Halftime from at 1 rad/sec
    TMCD % cis IV Bar IV 23° C. 23° C. Gravity Tg melt at 170° C. at 290° C.
    Example mole % TMCD (dl/g) (dl/g) (J/m) (J/m) (g/mL) (° C.) (min) (Poise)
    A 27 47.8 0.714 0.678 877 878 1.178 113 280 8312
    B 31 NA 0.667 0.641 807 789 1.174 116 600 6592
    NA = Not available
  • Example 4A
  • 21.24 lb (49.71 gram-mol) dimethyl terephthalate, 11.82 lb (37.28 gram-mol) 1,4-cyclohexanedimethanol, and 6.90 lb (21.77 gram-mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together in the presence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). The reaction was carried out under a nitrogen gas purge in an 18-gallon stainless steel pressure vessel fitted with a condensing column, a vacuum system, and a HELICONE-type agitator. With the agitator running at 25 RPM, the reaction mixture temperature was increased to 250° C. and the pressure was increased to 20 psig. The reaction mixture was held for 2 hours at 250° C. and 20 psig pressure. The pressure was then decreased to 0 psig at a rate of 3 psig/minute. The temperature of the reaction mixture was then increased to 270° C. and the pressure was decreased to 90 mm of Hg. After a 1 hour hold time at 270° C. and 90 mm of Hg, the agitator speed was decreased to 15 RPM, the reaction mixture temperature was increased to 290° C., and the pressure was decreased to <1 mm of Hg. The reaction mixture was held at 290° C. and at a pressure of <1 mm of Hg until the power draw to the agitator no longer increased (50 minutes). The pressure of the pressure vessel was then increased to 1 atmosphere using nitrogen gas. The molten polymer was then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass a 6-mm screen. The polymer had an inherent viscosity of 0.714 dL/g and a Tg of 113° C. NMR analysis showed that the polymer was composed of 73.3 mol % 1,4-cyclohexane-dimethanol residues and 26.7 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.
  • Example 4B
  • The polyester of Example 4B was prepared following a procedure similar to the one described for Example 4A. The composition and properties of this polyester are shown in Table 4.
  • Example 5
  • This example illustrates that 2,2,4,4-tetramethyl-1,3-cyclobutanediol can improve the toughness of PCT-based copolyesters(polyesters containing terephthalic acid and 1,4-cyclohexanedimethanol). Polyesters prepared in this example comprise 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues in an amount of 40 mol % or greater.
  • Copolyesters based on dimethyl terephthalate, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 1,4-cyclohexanedimethanol were prepared as described below, having the composition and properties shown on Table 5. The balance up to 100 mol % of the diol component of the polyesters in Table 5 was 1,4-cyclohexanedimethanol (31/69 cis/trans).
  • Materials were injection molded into both 3.2 mm and 6.4 mm thick bars and subsequently notched for Izod impact testing. The notched Izod impact strengths were obtained at 23° C. and are reported in Table 5. Density, Tg, and crystallization halftime were measured on the molded bars. Melt viscosity was measured on pellets at 290° C.
  • TABLE 5
    Compilation of various properties for certain polyesters useful in the invention
    Notched Notched
    Izod of Izod of
    3.2 mm 6.4 mm Melt
    thick thick Crystallization Viscosity
    Pellet Molded bars at bars at Specific Halftime from at 1 rad/sec
    TMCD % cis IV Bar IV 23° C. 23° C. Gravity Tg melt at 170° C. at 290° C.
    Example mole % TMCD (dl/g) (dl/g) (J/m) (J/m) (g/mL) (° C.) (min) (Poise)
    A 44 46.2 0.657 0.626 727 734 1.172 119 NA 9751
    B 45 NA 0.626 0.580 748 237 1.167 123 NA 8051
    C 45 NA 0.582 0.550 671 262 1.167 125 19782 5835
    D 45 NA 0.541 0.493 424 175 1.167 123 NA 3275
    E 59 46.6 0.604 0.576 456 311 1.156 139 NA 16537
    F 45 47.2 0.475 0.450 128 30 1.169 121 NA 1614
    NA = Not available
  • Example 5A
  • 21.24 lb (49.71 gram-mol) dimethyl terephthalate, 8.84 lb (27.88 gram-mol) 1,4-cyclohexanedimethanol, and 10.08 lb (31.77 gram-mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together in the presence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). The reaction was carried out under a nitrogen gas purge in an 18-gallon stainless steel pressure vessel fitted with a condensing column, a vacuum system, and a HELICONE-type agitator. With the agitator running at 25 RPM, the reaction mixture temperature was increased to 250° C. and the pressure was increased to 20 psig. The reaction mixture was held for 2 hours at 250° C. and 20 psig pressure. The pressure was then decreased to 0 psig at a rate of 3 psig/minute. Then the agitator speed was decreased to 15 RPM, the temperature of the reaction mixture was then increased to 290° C. and the pressure was decreased to 2 mm of Hg. The reaction mixture was held at 290° C. and at a pressure of 2 mm of Hg until the power draw to the agitator no longer increased (80 minutes). The pressure of the pressure vessel was then increased to 1 atmosphere using nitrogen gas. The molten polymer was then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass a 6-mm screen. The polymer had an inherent viscosity of 0.657 dL/g and a Tg of 119° C. NMR analysis showed that the polymer was composed of 56.3 mol % 1,4-cyclohexane-dimethanol residues and 43.7 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The polymer had color values of: L*=75.04, a*-1.82, and b*=6.72.
  • Example 5B to Example 5D
  • The polyesters described in Example 5B to Example 5D were prepared following a procedure similar to the one described for Example 5A. The composition and properties of these polyesters are shown in Table 5.
  • Example 5E
  • 21.24 lb (49.71 gram-mol) dimethyl terephthalate, 6.43 lb (20.28 gram-mol 1,4-cyclohexanedimethanol, and 12.49 lb (39.37 gram-mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together in the presence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). The reaction was carried out under a nitrogen gas purge in an 18-gallon stainless steel pressure vessel fitted with a condensing column, a vacuum system, and a HELICONE-type agitator. With the agitator running at 25 RPM, the reaction mixture temperature was increased to 250° C. and the pressure was increased to 20 psig. The reaction mixture was held for 2 hours at 250° C. and 20 psig pressure. The pressure was then decreased to 0 psig at a rate of 3 psig/minute. Then the agitator speed was decreased to 15 RPM, the temperature of the reaction mixture was then increased to 290° C. and the pressure was decreased to 2 mm of Hg. The reaction mixture was held at 290° C. and at a pressure of <1 mm of Hg until the power draw to the agitator no longer increased (50 minutes). The pressure of the pressure vessel was then increased to 1 atmosphere using nitrogen gas. The molten polymer was then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass a 6-mm screen. The polymer had an inherent viscosity of 0.604 dL/g and a Tg of 139° C. NMR analysis showed that the polymer was composed of 40.8 mol % 1,4-cyclohexanedimethanol residues and 59.2 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The polymer had color values of: L*=80.48, a*=−1.30, and b*=6.82.
  • Example 5F
  • 21.24 lb (49.71 gram-mol) dimethyl terephthalate, 8.84 lb (27.88 gram-mol) 1,4-cyclohexanedimethanol, and 10.08 lb (31.77 gram-mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together in the presence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). The reaction was carried out under a nitrogen gas purge in an 18-gallon stainless steel pressure vessel fitted with a condensing column, a vacuum system, and a HELICONE-type agitator. With the agitator running at 25 RPM, the reaction mixture temperature was increased to 250° C. and the pressure was increased to 20 psig. The reaction mixture was held for 2 hours at 250° C. and 20 psig pressure. The pressure was then decreased to 0 psig at a rate of 3 psig/minute. The temperature of the reaction mixture was then increased to 270° C. and the pressure was decreased to 90 mm of Hg. After a 1 hour hold time at 270° C. and 90 mm of Hg, the agitator speed was decreased to 15 RPM and the pressure was decreased to 4 mm of Hg. When the reaction mixture temperature was 270° C. and the pressure was 4 mm of Hg, the pressure of the pressure vessel was immediately increased to 1 atmosphere using nitrogen gas. The molten polymer was then extruded from the pressure vessel. The cooled, extruded polymer was ground to pass a 6-mm screen. The polymer had an inherent viscosity of 0.475 dL/g and a Tg of 121° C. NMR analysis showed that the polymer was composed of 55.5 mol % 1,4-cyclohexane-dimethanol residues and 44.5 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The polymer had color values of: L*=85.63, a*=−0.88, and b*=4.34.
  • Example 6—Comparative Example
  • This example shows data for comparative materials in Table 6. The PC was Makrolon 2608 from Bayer, with a nominal composition of 100 mole % bisphenol A residues and 100 mole % diphenyl carbonate residues. Makrolon 2608 has a nominal melt flow rate of 20 grams/10 minutes measured at 30° C. using a 1.2 kg weight. The PET was Eastar 9921 from Eastman Chemical Company, with a nominal composition of 100 mole % terephthalic acid, 3.5 mole % cyclohexanedimethanol (CHDM) and 96.5 mole % ethylene glycol. The PETG was Eastar 6763 from Eastman Chemical Company, with a nominal composition of 100 mole % terephthalic acid, 31 mole % cyclohexanedimethanol (CHDM) and 69 mole % ethylene glycol. The PCTG was Eastar DN001 from Eastman Chemical Company, with a nominal composition of 100 mole % terephthalic acid, 62 mole % cyclohexanedimethanol (CHDM) and 38 mole % ethylene glycol. The PCTA was Eastar AN001 from Eastman Chemical Company, with a nominal composition of 65 mole % terephthalic acid, 35 mole % isophthalic acid and 100 mole % cyclohexanedimethanol (CHDM). The Polysulfone was Udel 1700 from Solvay, with a nominal composition of 100 mole % bisphenol A residues and 100 mole % 4,4-dichlorosulfonyl sulfone residues. Udel 1700 has a nominal melt flow rate of 6.5 grams/10 minutes measured at 343 C using a 2.16 kg weight. The SAN was Lustran 31 from Lanxess, with a nominal composition of 76 weight % styrene and 24 weight % acrylonitrile. Lustran 31 has a nominal melt flow rate of 7.5 grams/10 minutes measured at 23° C. using a 3.8 kg weight. The examples of the invention show improved toughness in 6.4 mm thickness bars compared to all of the other resins.
  • TABLE 6
    Compilation of various properties for certain commercial polymers
    Notched Notched
    Izod of Izod of
    3.2 mm 6.4 mm
    thick thick Crystallization
    Pellet Molded bars at bars at Specific Halftime from
    Polymer IV Bar IV 23° C. 23° C. Gravity Tg melt
    Example name (dl/g) (dl/g) (J/m) (J/m) (g/mL) (° C.) (min)
    A PC  12 MFR NA 929  108  1.20 146 NA
    B PCTG 0.73 0.696 NB 70 1.23 87 30 at 170° C.
    C PCTA 0.72 0.702 98 59 1.20 87 15 at 150° C.
    D PETG 0.75 0.692 83 59 1.27 80 2500 at 130° C. 
    E PET 0.76 0.726 45 48 1.33 78 1.5 at 170° C. 
    F SAN 7.5 MFR NA 21 NA 1.07 ~110 NA
    G PSU 6.5 MFR NA 69 NA 1.24 ~190 NA
    NA = Not available
  • Example 7
  • This example illustrates the effect of the amount of 2,2,4,4-tetramethyl-1,3-cyclobutanediol used for the preparation of the polyesters of the invention on the glass transition temperature of the polyesters. Polyesters prepared in this example comprise from 15 to 25 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.
  • Example 7A to Example 7F
  • Dimethyl terephthalate, 1,4-cyclohexanedimethanol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol were weighed into a 500-ml single neck round bottom flask. NMR analysis on the 2,2,4,4-tetramethyl-1,3-cyclobutanediol starting material showed a cis/trans ratio of 53/47. The polyesters of this example were prepared with a 1.2/1 glycol/acid ratio with the entire excess coming from the 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Enough dibutyltin oxide catalyst was added to give 300 ppm tin in the final polymer. The flask was under a 0.2 SCFC nitrogen purge with vacuum reduction capability. The flask was immersed in a Belmont metal bath at 200° C. and stirred at 200 RPM after the reactants had melted. After about 2.5 hours, the temperature was raised to 210° C. and these conditions were held for an additional 2 hours. The temperature was raised to 285° C. (in approximately 25 minutes) and the pressure was reduced to 0.3 mm of Hg over a period of 5 minutes. The stirring was reduced as the viscosity increased, with 15 RPM being the minimum stirring used. The total polymerization time was varied to attain the target inherent viscosities. After the polymerization was complete, the Belmont metal bath was lowered and the polymer was allowed to cool to below its glass transition temperature. After about 30 minutes, the flask was reimmersed in the Belmont metal bath (the temperature had been increased to 295° C. during this 30 minute wait) and the polymer mass was heated until it pulled away from the glass flask. The polymer mass was stirred at mid level in the flask until the polymer had cooled. The polymer was removed from the flask and ground to pass a 3 mm screen. Variations to this procedure were made to produce the copolyesters described below with a targeted composition of 20 mol %.
  • Inherent viscosities were measured as described in the “Measurement Methods” section above. The compositions of the polyesters were determined by 1H NMR as explained before in the Measurement Methods section. The glass transition temperatures were determined by DSC, using the second heat after quench at a rate of 20° C./min.
  • Example 7G to Example 7P
  • These polyesters were prepared by carrying out the ester exchange and polycondensation reactions in separate stages. The ester exchange experiments were conducted in a continuous temperature rise (CTR) reactor. The CTR was a 3000 ml glass reactor equipped with a single shaft impeller blade agitator, covered with an electric heating mantle and fitted with a heated packed reflux condenser column. The reactor was charged with 777 g (4 moles) of dimethyl terephthalate, 230 g (1.6 moles) of 2,2,4,4-tetramethyl-1,3,-cyclobutanediol, 460.8 g (3.2 moles) of cyclohexane dimethanol and 1.12 g of butyltin tris-2-ethylhexanoate (such that there will be 200 ppm tin metal in the final polymer). The heating mantle was set manually to 100% output. The set points and data collection were facilitated by a Camile process control system. Once the reactants were melted, stirring was initiated and slowly increased to 250 rpm. The temperature of the reactor gradually increased with run time. The weight of methanol collected was recorded via balance. The reaction was stopped when methanol evolution stopped or at a pre-selected lower temperature of 260° C. The oligomer was discharged with a nitrogen purge and cooled to room temperature. The oligomer was frozen with liquid nitrogen and broken into pieces small enough to be weighed into a 500 ml round bottom flask.
  • In the polycondensation reactions, a 500 ml round bottom flask was charged with approximately 150 g of the oligomer prepared above. The flask was equipped with a stainless steel stirrer and polymer head. The glassware was set up on a half mole polymer rig and the Camile sequence was initiated. The stirrer was positioned one full turn from the flask bottom once the oligomer melted. The temperature/pressure/stir rate sequence controlled by the Camile software for each example is reported in the following tables.
  • Camile Sequence for Example 7G and Example 7H
  • Stage Time (min) Temp (° C.) Vacuum (torr) Stir (rpm)
    1 5 245 760 0
    2 5 245 760 50
    3 30 265 760 50
    4 3 265 90 50
    5 110 290 90 50
    6 5 290 6 25
    7 110 290 6 25
  • Camile Sequence for Example 7M to Example 7P
  • Stage Time (min) Temp (° C.) Vacuum (torr) Stir (rpm)
    1 5 245 760 0
    2 5 245 760 50
    3 30 265 760 50
    4 3 265 90 50
    5 110 290 90 50
    6 5 290 3 25
    7 110 290 3 25
  • Camile Sequence for Example 7J and Example 7K
  • Stage Time (min) Temp (° C.) Vacuum (torr) Stir (rpm)
    1 5 245 760 0
    2 5 245 760 50
    3 30 265 760 50
    4 3 265 90 50
    5 110 290 90 50
    6 5 290 2 25
    7 110 290 2 25
  • Camile Sequence for Example 7I and Example 7L
  • Stage Time (min) Temp (° C.) Vacuum (torr) Stir (rpm)
    1 5 245 760 0
    2 5 245 760 50
    3 30 265 760 50
    4 3 265 90 50
    5 110 290 90 50
    6 5 290 1 25
    7 110 290 1 25
  • The resulting polymers were recovered from the flask, chopped using a hydraulic chopper, and ground to a 6 mm screen size. Samples of each ground polymer were submitted for inherent viscosity in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C., catalyst level (Sn) by x-ray fluorescence, and color (L*, a*, b*) by transmission spectroscopy. Polymer composition was obtained by 1H NMR. Samples were submitted for thermal stability and melt viscosity testing using a Rheometrics Mechanical Spectrometer (RMS-800).
  • The table below shows the experimental data for the polyesters of this example. The data shows that an increase in the level of 2,2,4,4-tetramethyl-1,3-cyclobutanediol raises the glass transition temperature in an almost linear fashion, for a constant inherent viscosity. FIG. 3 also shows the dependence of Tg on composition and inherent viscosity.
  • TABLE 7
    Glass transition temperature as a function of inherent viscosity and
    composition
    ηo at ηo at ηo at
    Exam- mol % % cis IV Tg 260° C. 275° C. 290° C.
    ple TMCD TMCD (dL/g) (° C.) (Poise) (Poise) (Poise)
    A 20 51.4 0.72 109 11356 19503 5527
    B 19.1 51.4 0.60 106 6891 3937 2051
    C 19 53.2 0.64 107 8072 4745 2686
    D 18.8 54.4 0.70 108 14937 8774 4610
    E 17.8 52.4 0.50 103 3563 1225 883
    F 17.5 51.9 0.75 107 21160 10877 5256
    G 22.8 53.5 0.69 109 NA NA NA
    H 22.7 52.2 0.68 108 NA NA NA
    I 23.4 52.4 0.73 111 NA NA NA
    J 23.3 52.9 0.71 111 NA NA NA
    K 23.3 52.4 0.74 112 NA NA NA
    L 23.2 52.5 0.74 112 NA NA NA
    M 23.1 52.5 0.71 111 NA NA NA
    N 22.8 52.4 0.73 112 NA NA NA
    O 22.7 53 0.69 112 NA NA NA
    P 22.7 52 0.70 111 NA NA NA
    NA = Not available
  • Example 8
  • This example illustrates the effect of the amount of 2,2,4,4-tetramethyl-1,3-cyclobutanediol used for the preparation of the polyesters of the invention on the glass transition temperature of the polyesters. Polyesters prepared in this example fall comprise more than 25 to less than 40 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.
  • Dimethyl terephthalate, 1,4-cyclohexanedimethanol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol were weighed into a 500-ml single neck round bottom flask. NMR analysis on the 2,2,4,4-tetramethyl-1,3-cyclobutanediol starting material showed a cis/trans ratio of 53/47. The polyesters of this example were prepared with a 1.2/1 glycol/acid ratio with the entire excess coming from the 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Enough dibutyltin oxide catalyst was added to give 300 ppm tin in the final polymer. The flask was under a 0.2 SCFC nitrogen purge with vacuum reduction capability. The flask was immersed in a Belmont metal bath at 200° C. and stirred at 200 RPM after the reactants had melted. After about 2.5 hours, the temperature was raised to 210° C. and these conditions were held for an additional 2 hours. The temperature was raised to 285° C. (in approximately 25 minutes) and the pressure was reduced to 0.3 mm of Hg over a period of 5 minutes. The stirring was reduced as the viscosity increased, with 15 RPM being the minimum stirring used. The total polymerization time was varied to attain the target inherent viscosities. After the polymerization was complete, the Belmont metal bath was lowered and the polymer was allowed to cool to below its glass transition temperature. After about 30 minutes, the flask was reimmersed in the Belmont metal bath (the temperature had been increased to 295° C. during this 30 minute wait) and the polymer mass was heated until it pulled away from the glass flask. The polymer mass was stirred at mid level in the flask until the polymer had cooled. The polymer was removed from the flask and ground to pass a 3 mm screen. Variations to this procedure were made to produce the copolyesters described below with a targeted composition of 32 mol %.
  • Inherent viscosities were measured as described in the “Measurement Methods” section above. The compositions of the polyesters were determined by 1H NMR as explained before in the Measurement Methods section. The glass transition temperatures were determined by DSC, using the second heat after quench at a rate of 20° C./min.
  • The table below shows the experimental data for the polyesters of this example. FIG. 3 also shows the dependence of Tg on composition and inherent viscosity. The data shows that an increase in the level of 2,2,4,4-tetramethyl-1,3-cyclobutanediol raises the glass transition temperature in an almost linear fashion, for a constant inherent viscosity.
  • TABLE 8
    Glass transition temperature as a function of inherent viscosity and
    composition
    ηo at ηo at ηo at
    Exam- mol % % cis IV Tg 260° C. 275° C. 290° C.
    ple TMCD TMCD (dL/g) (° C.) (Poise) (Poise) (Poise)
    A 32.2 51.9 0.71 118 29685 16074 8522
    B 31.6 51.5 0.55 112 5195 2899 2088
    C 31.5 50.8 0.62 112 8192 4133 2258
    D 30.7 50.7 0.54 111 4345 2434 1154
    E 30.3 51.2 0.61 111 7929 4383 2261
    F 30.0 51.4 0.74 117 31476 17864 8630
    G 29.0 51.5 0.67 112 16322 8787 4355
    H 31.1 51.4 0.35 102 NA NA NA
    NA = Not available
  • Example 9
  • This example illustrates the effect of the amount of 2,2,4,4-tetramethyl-1,3-cyclobutanediol used for the preparation of the polyesters of the invention on the glass transition temperature of the polyesters. Polyesters prepared in this example comprise 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues in an amount of 40 mol % or greater.
  • Examples A TO AC
  • These polyesters were prepared by carrying out the ester exchange and polycondensation reactions in separate stages. The ester exchange experiments were conducted in a continuous temperature rise (CTR) reactor. The CTR was a 3000 ml glass reactor equipped with a single shaft impeller blade agitator, covered with an electric heating mantle and fitted with a heated packed reflux condenser column. The reactor was charged with 777 g of dimethyl terephthalate, 375 g of 2,2,4,4-tetramethyl-1,3,-cyclobutanediol, 317 g of cyclohexane dimethanol and 1.12 g of butyltin tris-2-ethylhexanoate (such that there will be 200 ppm tin metal in the final polymer). The heating mantle was set manually to 100% output. The set points and data collection were facilitated by a Camile process control system. Once the reactants were melted, stirring was initiated and slowly increased to 250 rpm. The temperature of the reactor gradually increased with run time. The weight of methanol collected was recorded via balance. The reaction was stopped when methanol evolution stopped or at a pre-selected lower temperature of 260° C. The oligomer was discharged with a nitrogen purge and cooled to room temperature. The oligomer was frozen with liquid nitrogen and broken into pieces small enough to be weighed into a 500 ml round bottom flask.
  • In the polycondensation reactions, a 500 ml round bottom flask was charged with 150 g of the oligomer prepared above. The flask was equipped with a stainless steel stirrer and polymer head. The glassware was set up on a half mole polymer rig and the Camile sequence was initiated. The stirrer was positioned one full turn from the flask bottom once the oligomer melted. The temperature/pressure/stir rate sequence controlled by the Camile software for these examples is reported in the following table, unless otherwise specified below.
  • Camile Sequence for Polycondensation Reactions
  • Stage Time (min) Temp (° C.) Vacuum (torr) Stir (rpm)
    1 5 245 760 0
    2 5 245 760 50
    3 30 265 760 50
    4 3 265 90 50
    5 110 290 90 50
    6 5 290 6 25
    7 110 290 6 25
  • Camile Sequence for Examples A, C, R, Y, AB, AC
  • Stage Time (min) Temp (° C.) Vacuum (torr) Stir (rpm)
    1 5 245 760 0
    2 5 245 760 50
    3 30 265 760 50
    4 3 265 90 50
    5 110 290 90 50
    6 5 290 6 25
    7 110 290 6 25
  • For Examples B, D, F, the same sequence in the preceding table was used, except the time was 80 min in Stage 7. For Examples G and J, the same sequence in the preceding table was used, except the time was 50 min in Stage 7. For Example L, the same sequence in the preceding table was used, except the time was 140 min in Stage 7.
  • Camile Sequence for Example E
  • Stage Time (min) Temp (° C.) Vacuum (torr) Stir (rpm)
    1 5 245 760 0
    2 5 245 760 50
    3 30 265 760 50
    4 3 265 90 50
    5 110 300 90 50
    6 5 300 7 25
    7 110 300 7 25
  • For Example I, the same sequence in the preceding table was used, except the vacuum was 8 torr in Stages 6 and 7. For Example O, the same sequence in the preceding table was used, except the vacuum was 6 torr in Stages 6 and 7. For Example P, the same sequence in the preceding table was used, except the vacuum was 4 torr in Stages 6 and 7. For Example Q, the same sequence in the preceding table was used, except the vacuum was 5 torr in Stages 6 and 7.
  • Camile Sequence for Example H
  • Stage Time (min) Temp (° C.) Vacuum (torr) Stir (rpm)
    1 5 245 760 0
    2 5 245 760 50
    3 30 265 760 50
    4 3 265 90 50
    5 110 280 90 50
    6 5 280 5 25
    7 110 280 5 25
  • For Example U and AA, the same sequence in the preceding table was used, except the vacuum was 6 torr in Stages 6 and 7. For Example V and X, the same sequence in the preceding table was used, except the vacuum was 6 torr and stir rate was 15 rpm in Stages 6 and 7. For Example Z, the same sequence in the preceding table was used, except the stir rate was 15 rpm in Stages 6 and 7.
  • Camile Sequence for Example K
  • Stage Time (min) Temp (° C.) Vacuum (torr) Stir (rpm)
    1 5 245 760 0
    2 5 245 760 50
    3 30 265 760 50
    4 3 265 90 50
    5 110 300 90 50
    6 5 300 6 15
    7 110 300 6 15
  • For Example M, the same sequence in the preceding table was used, except the vacuum was 8 torr in Stages 6 and 7. For Example N, the same sequence in the preceding table was used, except the vacuum was 7 torr in Stages 6 and 7.
  • Camile Sequence for Examples S and T
  • Stage Time (min) Temp (° C.) Vacuum (torr) Stir (rpm)
    1 5 245 760 0
    2 5 245 760 50
    3 30 265 760 50
    4 5 290 6 25
    5 110 290 6 25
  • The resulting polymers were recovered from the flask, chopped using a hydraulic chopper, and ground to a 6 mm screen size. Samples of each ground polymer were submitted for inherent viscosity in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C., catalyst level (Sn) by x-ray fluorescence, and color (L*, a*, b*) by transmission spectroscopy. Polymer composition was obtained by 1H NMR. Samples were submitted for thermal stability and melt viscosity testing using a Rheometrics Mechanical Spectrometer (RMS-800).
  • Examples AD to AK and AT
  • The polyesters of these examples were prepared as described above for Examples A to AC, except that the target tin amount in the final polymer was 150 ppm for examples AD to AK and AT. The following tables describe the temperature/pressure/stir rate sequences controlled by the Camile software for these examples.
  • Camile Sequence for Examples AD, AF, and AH
  • Stage Time (min) Temp (° C.) Vacuum (torr) Stir (rpm)
    1 5 245 760 0
    2 5 245 760 50
    3 30 265 760 50
    4 3 265 400 50
    5 110 290 400 50
    6 5 290 8 50
    7 110 295 8 50
  • For Example AD, the stirrer was turned to 25 rpm with 95 min left in Stage 7.
  • Camile Sequence for Example AE
  • Stage Time (min) Temp (° C.) Vacuum (torr) Stir (rpm)
    1 10 245 760 0
    2 5 245 760 50
    3 30 283 760 50
    4 3 283 175 50
    5 5 283 5 50
    6 5 283 1.2 50
    7 71 285 1.2 50
  • For Example AK, the same sequence in the preceding table was used, except the time was 75 min in Stage 7.
  • Camile Sequence for Example AG
  • Stage Time (min) Temp (° C.) Vacuum (torr) Stir (rpm)
    1 10 245 760 0
    2 5 245 760 50
    3 30 285 760 50
    4 3 285 175 50
    5 5 285 5 50
    6 5 285 4 50
    7 220 290 4 50
  • Camile Sequence for Example AI
  • Stage Time (min) Temp (° C.) Vacuum (torr) Stir (rpm)
    1 5 245 760 0
    2 5 245 760 50
    3 30 265 760 50
    4 3 265 90 50
    5 110 285 90 50
    6 5 285 6 50
    7 70 290 6 50
  • Camile Sequence for Example AJ
  • Stage Time (min) Temp (° C.) Vacuum (torr) Stir (rpm)
    1 5 245 760 0
    2 5 245 760 50
    3 30 265 760 50
    4 3 265 90 50
    5 110 290 90 50
    6 5 290 6 25
    7 110 295 6 25
  • Examples AL to AS
  • Dimethyl terephthalate, 1,4-cyclohexanedimethanol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol were weighed into a 500-ml single neck round bottom flask. The polyesters of this example were prepared with a 1.2/1 glycol/acid ratio with the entire excess coming from the 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Enough dibutyltin oxide catalyst was added to give 300 ppm tin in the final polymer. The flask was under a 0.2 SCFC nitrogen purge with vacuum reduction capability. The flask was immersed in a Belmont metal bath at 200° C. and stirred at 200 RPM after the reactants had melted. After about 2.5 hours, the temperature was raised to 210° C. and these conditions were held for an additional 2 hours. The temperature was raised to 285° C. (in approximately 25 minutes) and the pressure was reduced to 0.3 mm of Hg over a period of 5 minutes. The stirring was reduced as the viscosity increased, with 15 RPM being the minimum stirring used. The total polymerization time was varied to attain the target inherent viscosities. After the polymerization was complete, the Belmont metal bath was lowered and the polymer was allowed to cool to below its glass transition temperature. After about 30 minutes, the flask was reimmersed in the Belmont metal bath (the temperature had been increased to 295° C. during this 30 minute wait) and the polymer mass was heated until it pulled away from the glass flask. The polymer mass was stirred at mid level in the flask until the polymer had cooled. The polymer was removed from the flask and ground to pass a 3 mm screen. Variations to this procedure were made to produce the copolyesters described below with a targeted composition of 45 mol %.
  • Inherent viscosities were measured as described in the “Measurement Methods” section above. The compositions of the polyesters were determined by 1H NMR as explained before in the Measurement Methods section. The glass transition temperatures were determined by DSC, using the second heat after quench at a rate of 20° C./min.
  • The table below shows the experimental data for the polyesters of this example. The data shows that an increase in the level of 2,2,4,4-tetramethyl-1,3-cyclobutanediol raises the glass transition temperature in an almost linear fashion, for a constant inherent viscosity. FIG. 3 also shows the dependence of Tg on composition and inherent viscosity.
  • TABLE 9
    Glass transition temperature as a function of inherent viscosity and
    composition
    ηo at ηo at ηo at
    Exam- mol % % cis IV Tg 260° C. 275° C. 290° C.
    ple TMCD TMCD (dL/g) (° C.) (Poise) (Poise) (Poise)
    A 43.9 72.1 0.46 131 NA NA NA
    B 44.2 36.4 0.49 118 NA NA NA
    C 44 71.7 0.49 128 NA NA NA
    D 44.3 36.3 0.51 119 NA NA NA
    E 46.1 46.8 0.51 125 NA NA NA
    F 43.6 72.1 0.52 128 NA NA NA
    G 43.6 72.3 0.54 127 NA NA NA
    H 46.4 46.4 0.54 127 NA NA NA
    I 45.7 47.1 0.55 125 NA NA NA
    J 44.4 35.6 0.55 118 NA NA NA
    K 45.2 46.8 0.56 124 NA NA NA
    L 43.8 72.2 0.56 129 NA NA NA
    M 45.8 46.4 0.56 124 NA NA NA
    N 45.1 47.0 0.57 125 NA NA NA
    O 45.2 46.8 0.57 124 NA NA NA
    P 45 46.7 0.57 125 NA NA NA
    Q 45.1 47.1 0.58 127 NA NA NA
    R 44.7 35.4 0.59 123 NA NA NA
    S 46.1 46.4 0.60 127 NA NA NA
    T 45.7 46.8 0.60 129 NA NA NA
    U 46 46.3 0.62 128 NA NA NA
    V 45.9 46.3 0.62 128 NA NA NA
    X 45.8 46.1 0.63 128 NA NA NA
    Y 45.6 50.7 0.63 128 NA NA NA
    Z 46.2 46.8 0.65 129 NA NA NA
    AA 45.9 46.2 0.66 128 NA NA NA
    AB 45.2 46.4 0.66 128 NA NA NA
    AC 45.1 46.5 0.68 129 NA NA NA
    AD 46.3 52.4 0.52 NA NA NA NA
    AE 45.7 50.9 0.54 NA NA NA NA
    AF 46.3 52.6 0.56 NA NA NA NA
    AG 46 50.6 0.56 NA NA NA NA
    AH 46.5 51.8 0.57 NA NA NA NA
    AI 45.6 51.2 0.58 NA NA NA NA
    AJ 46 51.9 0.58 NA NA NA NA
    AK 45.5 51.2 0.59 NA NA NA NA
    AL 45.8 50.1 0.624 125 NA NA 7696
    AM 45.7 49.4 0.619 128 NA NA 7209
    AN 46.2 49.3 0.548 124 NA NA 2348
    AP 45.9 49.5 0.72 128 76600 40260 19110
    AQ 46.0 50 0.71 131 68310 32480 17817
    AR 46.1 49.6 0.383 117 NA NA 387
    AS 45.6 50.5 0.325 108 NA NA NA
    AT 47.2 NA 0.48 NA NA NA NA
    NA = Not available
  • Example 10
  • This example illustrates the effect of the predominance of the type of 2,2,4,4-tetramethyl-1,3-cyclobutanediol isomer (cis or trans) on the glass transition temperature of the polyester.
  • Dimethyl terephthalate, 1,4-cyclohexanedimethanol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol were weighed into a 500-ml single neck round bottom flask. The polyesters of this example were prepared with a 1.2/1 glycol/acid ratio with the entire excess coming from the 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Enough dibutyltin oxide catalyst was added to give 300 ppm tin in the final polymer. The flask was under a 0.2 SCFC nitrogen purge with vacuum reduction capability. The flask was immersed in a Belmont metal bath at 200° C. and stirred at 200 RPM after the reactants had melted. After about 2.5 hours, the temperature was raised to 210° C. and these conditions were held for an additional 2 hours. The temperature was raised to 285° C. (in approximately 25 minutes) and the pressure was reduced to 0.3 mm of Hg over a period of 5 minutes. The stirring was reduced as the viscosity increased, with 15 RPM being the minimum stirring used. The total polymerization time was varied to attain the target inherent viscosities. After the polymerization was complete, the Belmont metal bath was lowered and the polymer was allowed to cool to below its glass transition temperature. After about 30 minutes, the flask was reimmersed in the Belmont metal bath (the temperature had been increased to 295° C. during this 30 minute wait) and the polymer mass was heated until it pulled away from the glass flask. The polymer mass was stirred at mid level in the flask until the polymer had cooled. The polymer was removed from the flask and ground to pass a 3 mm screen. Variations to this procedure were made to produce the copolyesters described below with a targeted composition of 45 mol %.
  • Inherent viscosities were measured as described in the “Measurement Methods” section above. The compositions of the polyesters were determined by 1H NMR as explained before in the Measurement Methods section. The glass transition temperatures were determined by DSC, using the second heat after quench at a rate of 20° C./min.
  • The table below shows the experimental data for the polyesters of this Example. The data shows that cis 2,2,4,4-tetramethyl-1,3-cyclobutanediol is approximately twice as effective as trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol at increasing the glass transition temperature for a constant inherent viscosity.
  • TABLE 10
    Effect of 2,2,4,4-tetramethyl-1,3-cyclobutanediol cis/trans composition on Tg
    ηo □at ηo at
    mol % ηo at 260° C. 275° C. 290° C. % cis
    Example TMCD IV (dL/g) Tg (° C.) (Poise) (Poise) (Poise) TMCD
    A 45.8 0.71 119 N.A. N.A. N.A. 4.1
    B 43.2 0.72 122 N.A. N.A. N.A. 22.0
    C 46.8 0.57 119 26306 16941 6601 22.8
    D 43.0 0.67 125 55060 36747 14410 23.8
    E 43.8 0.72 127 101000 62750 25330 24.5
    F 45.9 0.533 119 11474 6864 2806 26.4
    G 45.0 0.35 107 N.A. N.A. N.A. 27.2
    H 41.2 0.38 106 1214 757 N.A. 29.0
    I 44.7 0.59 123 N.A. N.A. N.A. 35.4
    J 44.4 0.55 118 N.A. N.A. N.A. 35.6
    K 44.3 0.51 119 N.A. N.A. N.A. 36.3
    L 44.0 0.49 128 N.A. N.A. N.A. 71.7
    M 43.6 0.52 128 N.A. N.A. N.A. 72.1
    N 43.6 0.54 127 N.A. N.A. N.A. 72.3
    O 41.5 0.58 133 15419 10253 4252 88.7
    P 43.8 0.57 135 16219 10226 4235 89.6
    Q 41.0 0.33 120 521 351 2261 90.4
    R 43.0 0.56 134 N.A. N.A. N.A. 90.6
    S 43.0 0.49 132 7055 4620 2120 90.6
    T 43.1 0.55 134 12970 8443 3531 91.2
    U 45.9 0.52 137 N.A. N.A. N.A. 98.1
    NA = not available
  • Example 11
  • This example illustrates the preparation of a copolyester containing 100 mol % dimethyl terephthalate residues, 55 mol % 1,4-cyclohexanedimethanol residues, and 45 mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.
  • A mixture of 97.10 g (0.5 mol) dimethyl terephthalate, 52.46 g (0.36 mol) 1,4-cyclohexanedimethanol, 34.07 g (0.24 mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 0.0863 g (300 ppm) dibutyl tin oxide was placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. The flask was placed in a Wood's metal bath already heated to 200° C. The contents of the flask were heated at 200° C. for 1 hour and then the temperature was increased to 210° C. The reaction mixture was held at 210° C. for 2 hours and then heated up to 290° C. in 30 minutes. Once at 290° C., a vacuum of 0.01 psig was gradually applied over the next 3 to 5 minutes. Full vacuum (0.01 psig) was maintained for a total time of about 45 minutes to remove excess unreacted diols. A high melt viscosity, visually clear and colorless polymer was obtained with a glass transition temperature of 125° C. and an inherent viscosity of 0.64 dl/g.
  • Example 12—Comparative Example
  • This example illustrates that a polyester based on 100% 2,2,4,4-tetramethyl-1,3-cyclobutanediol has a slow crystallization half-time.
  • A polyester based solely on terephthalic acid and 2,2,4,4-tetramethyl-1,3-cyclobutanediol was prepared in a method similar to the method described in Example 1A with the properties shown on Table 11. This polyester was made with 300 ppm dibutyl tin oxide. The trans/cis ratio of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol was 65/35.
  • Films were pressed from the ground polymer at 320° C. Crystallization half-time measurements from the melt were made at temperatures from 220 to 250° C. at 10° C. increments and are reported in Table 11. The fastest crystallization half-time for the sample was taken as the minimum value of crystallization half-time as a function of temperature. The fastest crystallization half-time of this polyester is around 1300 minutes. This value contrasts with the fact that the polyester (PCT) based solely on terephthalic acid and 1,4-cyclohexanedimethanol (no comonomer modification) has an extremely short crystallization half-time (<1 min) as shown in FIG. 1.
  • TABLE 11
    Crystallization Half-times (min)
    at at at at
    Comonomer IV Tg Tmax 220° C. 230° C. 240° C. 250° C.
    (mol %) (dl/g) (° C.) (° C.) (min) (min) (min) (min)
    100 mol % F 0.63 170.0 330 3291 3066 1303 1888
    where: F is 2,2,4,4-Tetramethyl-1,3-cyclobutanediol (65/35 Trans/Cis)
  • Example 13
  • Sheets comprising a polyester that had been prepared with a target composition of 100 mole % terephthalic acid residues, 80 mole % 1,4-cyclohexanedimethanol residues, and 20 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues were produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 177 mil and then various sheets were sheared to size. Inherent viscosity and glass transition temperature were measured on one sheet. The sheet inherent viscosity was measured to be 0.69 dl/g. The glass transition temperature of the sheet was measured to be 106° C. Sheets were then conditioned at 50% relative humidity and 60° C. for 2 weeks. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example G). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 106° C. can be thermoformed under the conditions shown below, as evidenced by these sheets having at least 95% draw and no blistering, without predrying the sheets prior to thermoforming.
  • Thermoforming Conditions Part Quality
    Sheet Part
    Heat Time Temperature Volume Blisters
    Example (s) (° C.) (mL) Draw (%) (N, L, H)
    A 86 145 501 64 N
    B 100 150 500 63 N
    C 118 156 672 85 N
    D 135 163 736 94 N
    E 143 166 760 97 N
    F 150 168 740 94 L
    G 159 172 787 100 L
  • Example 14
  • Sheets comprising a polyester that had been prepared with a target composition of 100 mole % terephthalic acid residues, 80 mole % 1,4-cyclohexanedimethanol residues, and 20 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues were produced using a 3.5 inch single screw. A sheet was extruded continuously, gauged to a thickness of 177 mil and then various sheets were sheared to size. Inherent viscosity and glass transition temperature were measured on one sheet. The sheet inherent viscosity was measured to be 0.69 dl/g. The glass transition temperature of the sheet was measured to be 106° C. Sheets were then conditioned at 100% relative humidity and 25° C. for 2 weeks. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 60/40/40% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example G). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 106° C. can be thermoformed under the conditions shown below, as evidenced by the production of sheets having at least 95% draw and no blistering, without predrying the sheets prior to thermoforming.
  • Thermoforming Conditions Part Quality
    Sheet Part
    Heat Time Temperature Volume Blisters
    Example (s) (° C.) (mL) Draw (%) (N, L, H)
    A 141 154 394 53 N
    B 163 157 606 82 N
    C 185 160 702 95 N
    D 195 161 698 95 N
    E 215 163 699 95 L
    F 230 168 705 96 L
    G 274 174 737 100 H
    H 275 181 726 99 H
  • Example 15—Comparative Example
  • Sheets consisting of Kelvx 201 were produced using a 3.5 inch single screw extruder. Kelvx is a blend consisting of 69.85% PCTG (Eastar from Eastman Chemical Co. having 100 mole % terephthalic acid residues, 62 mole % 1,4-cyclohexanedimethanol residues, and 38 mole % ethylene glycol residues); 30% PC (bisphenol A polycarbonate); and 0.15% Weston 619 (stabilizer sold by Crompton Corporation). A sheet was extruded continuously, gauged to a thickness of 177 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 100° C. Sheets were then conditioned at 50% relative humidity and 60° C. for 2 weeks. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example E). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 100° C. can be thermoformed under the conditions shown below, as evidenced by the production of sheets having at least 95% draw and no blistering, without predrying the sheets prior to thermoforming.
  • Thermoforming Conditions Part Quality
    Sheet Part
    Heat Time Temperature Volume Blisters
    Example (s) (° C.) (mL) Draw (%) (N, L, H)
    A 90 146 582 75 N
    B 101 150 644 83 N
    C 111 154 763 98 N
    D 126 159 733 95 N
    E 126 159 775 100 N
    F 141 165 757 98 N
    G 148 168 760 98 L
  • Example 16—Comparative Example
  • Sheets consisting of Kelvx 201 were produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 177 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 100° C. Sheets were then conditioned at 100% relative humidity and 25° C. for 2 weeks. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 60/40/40% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example H). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 100° C. can be thermoformed under the conditions shown below, as evidenced by the production of sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
  • Thermoforming Conditions Part Quality
    Sheet Part
    Heat Time Temperature Volume Blisters
    Example (s) (° C.) (mL) Draw (%) (N, L, H)
    A 110 143 185 25 N
    B 145 149 529 70 N
    C 170 154 721 95 N
    D 175 156 725 96 N
    E 185 157 728 96 N
    F 206 160 743 98 L
    G 253 NR 742 98 H
    H 261 166 756 100 H
    NR = Not recorded
  • Example 17—Comparative Example
  • Sheets consisting of PCTG 25976 (100 mole % terephthalic acid residues, 62 mole % 1,4-cyclohexanedimethanol residues, and 38 mole % ethylene glycol residues) were produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 87° C. Sheets were then conditioned at 50% relative humidity and 60° C. for 4 weeks. The moisture level was measured to be 0.17 wt %. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example A). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 87° C. can be thermoformed under the conditions shown below, as evidenced by the production of sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
  • Thermoforming Conditions Part Quality
    Sheet Part
    Heat Time Temperature Volume Blisters
    Example (s) (° C.) (mL) Draw (%) (N, L, H)
    A 102 183 816 100 N
    B 92 171 811 99 N
    C 77 160 805 99 N
    D 68 149 804 99 N
    E 55 143 790 97 N
    F 57 138 697 85 N
  • Example 18—Comparative Example
  • A miscible blend consisting of 20 wt % Teijin L-1250 polycarbonate (a bisphenol-A polycarbonate), 79.85 wt % PCTG 25976, and 0.15 wt % Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 94° C. Sheets were then conditioned at 50% relative humidity and 60° C. for 4 weeks. The moisture level was measured to be 0.25 wt %. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example A). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 94° C. can be thermoformed under the conditions shown below, as evidenced by the production of sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
  • Thermoforming Conditions Part Quality
    Sheet Part
    Heat Time Temperature Volume Blisters
    Example (s) (° C.) (mL) Draw (%) (N, L, H)
    A 92 184 844 100 H
    B 86 171 838 99 N
    C 73 160 834 99 N
    D 58 143 787 93 N
    E 55 143 665 79 N
  • Example 19—Comparative Example
  • A miscible blend consisting of 30 wt % Teijin L-1250 polycarbonate, 69.85 wt % PCTG 25976, and 0.15 wt % Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 99° C. Sheets were then conditioned at 50% relative humidity and 60° C. for 4 weeks. The moisture level was measured to be 0.25 wt %. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example A). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 99° C. can be thermoformed under the conditions shown below, as evidenced by the production of sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
  • Thermoforming Conditions Part Quality
    Sheet Part
    Heat Time Temperature Volume Blisters
    Example (s) (° C.) (mL) Draw (%) (N, L, H)
    A 128 194 854 100 H
    B 98 182 831 97 L
    C 79 160 821 96 N
    D 71 149 819 96 N
    E 55 145 785 92 N
    F 46 143 0 0 NA
    G 36 132 0 0 NA
    NA = not applicable. A value of zero indicates that the sheet was not formed because it did not pull into the mold (likely because it was too cold).
  • Example 20—Comparative Example
  • A miscible blend consisting of 40 wt % Teijin L-1250 polycarbonate, 59.85 wt % PCTG 25976, and 0.15 wt % Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 105° C. Sheets were then conditioned at 50% relative humidity and 60° C. for 4 weeks. The moisture level was measured to be 0.265 wt %. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Examples 8A to 8E). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 105° C. can be thermoformed under the conditions shown below, as evidenced by the production of sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
  • Thermoforming Conditions Part Quality
    Sheet Part
    Heat Time Temperature Volume Blisters
    Example (s) (° C.) (mL) Draw (%) (N, L, H)
    A 111 191 828 100 H
    B 104 182 828 100 H
    C 99 179 827 100 N
    D 97 177 827 100 N
    E 78 160 826 100 N
    F 68 149 759 92 N
    G 65 143 606 73 N
  • Example 21—Comparative Example
  • A miscible blend consisting of 50 wt % Teijin L-1250 polycarbonate, 49.85 wt % PCTG 25976, and 0.15 wt % Weston 619 was produced using a 1.25 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 111° C. Sheets were then conditioned at 50% relative humidity and 60° C. for 4 weeks. The moisture level was measured to be 0.225 wt %. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Examples A to D). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 111° C. can be thermoformed under the conditions shown below, as evidenced by the production of sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
  • Thermoforming Conditions Part Quality
    Sheet Part
    Heat Time Temperature Volume Blisters
    Example (s) (° C.) (mL) Draw (%) (N, L, H)
    A 118 192 815 100 H
    B 99 182 815 100 H
    C 97 177 814 100 L
    D 87 171 813 100 N
    E 80 160 802 98 N
    F 64 154 739 91 N
    G 60 149 0 0 NA
    NA = not applicable. A value of zero indicates that the sheet was not formed because it did not pull into the mold (likely because it was too cold).
  • Example 22—Comparative Example
  • A miscible blend consisting of 60 wt % Teijin L-1250 polycarbonate, 39.85 wt % PCTG 25976, and 0.15 wt % Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 117° C. Sheets were then conditioned at 50% relative humidity and 60° C. for 4 weeks. The moisture level was measured to be 0.215 wt %. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example A). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 117° C. cannot be thermoformed under the conditions shown below, as evidenced by the inability to produce sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
  • Thermoforming Conditions Part Quality
    Sheet Part
    Heat Time Temperature Volume Blisters
    Example (s) (° C.) (mL) Draw (%) (N, L, H)
    A 114 196 813 100 H
    B 100 182 804 99 H
    C 99 177 801 98 L
    D 92 171 784 96 L
    E 82 168 727 89 L
    F 87 166 597 73 N
  • Example 23—Comparative Example
  • A miscible blend consisting of 65 wt % Teijin L-1250 polycarbonate, 34.85 wt % PCTG 25976, and 0.15 wt % Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 120° C. Sheets were then conditioned at 50% relative humidity and 60° C. for 4 weeks. The moisture level was measured to be 0.23 wt %. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example A). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 120° C. cannot be thermoformed under the conditions shown below, as evidenced by the inability to produce sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
  • Thermoforming Conditions Part Quality
    Sheet Part
    Heat Time Temperature Volume Blisters
    Example (s) (° C.) (mL) Draw (%) (N, L, H)
    A 120 197 825 100 H
    B 101 177 820 99 H
    C 95 174 781 95 L
    D 85 171 727 88 L
    E 83 166 558 68 L
  • Example 24—Comparative Example
  • A miscible blend consisting of 70 wt % Teijin L-1250 polycarbonate, 29.85 wt % PCTG 25976, and 0.15 wt % Weston 619 was produced using a 1.25 inch single screw extruder. Sheets consisting of the blend were then produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 123° C. Sheets were then conditioned at 50% relative humidity and 60° C. for 4 weeks. The moisture level was measured to be 0.205 wt %. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw, and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Examples A and B). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 123° C. cannot be thermoformed under the conditions shown below, as evidenced by the inability to produce sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
  • Thermoforming Conditions Part Quality
    Sheet Part
    Heat Time Temperature Volume Blisters
    Example (s) (° C.) (mL) Draw (%) (N, L, H)
    A 126 198 826 100 H
    B 111 188 822 100 H
    C 97 177 787 95 L
    D 74 166 161 19 L
    E 58 154 0 0 NA
    F 48 149 0 0 NA
    NA = not applicable. A value of zero indicates that the sheet was not formed because it did not pull into the mold (likely because it was too cold).
  • Example 25—Comparative Example
  • Sheets consisting of Teijin L-1250 polycarbonate were produced using a 3.5 inch single screw extruder. A sheet was extruded continuously, gauged to a thickness of 118 mil and then various sheets were sheared to size. The glass transition temperature was measured on one sheet and was 149° C. Sheets were then conditioned at 50% relative humidity and 60° C. for 4 weeks. The moisture level was measured to be 0.16 wt %. Sheets were subsequently thermoformed into a female mold having a draw ratio of 2.5:1 using a Brown thermoforming machine. The thermoforming oven heaters were set to 70/60/60% output using top heat only. Sheets were left in the oven for various amounts of time in order to determine the effect of sheet temperature on the part quality as shown in the table below. Part quality was determined by measuring the volume of the thermoformed part, calculating the draw and visually inspecting the thermoformed part. The draw was calculated as the part volume divided by the maximum part volume achieved in this set of experiments (Example A). The thermoformed part was visually inspected for any blisters and the degree of blistering rated as none (N), low (L), or high (H). The results below demonstrate that these thermoplastic sheets with a glass transition temperature of 149° C. cannot be thermoformed under the conditions shown below, as evidenced by the inability to produce sheets having greater than 95% draw and no blistering, without predrying the sheets prior to thermoforming.
  • Thermoforming Conditions Part Quality
    Sheet Part
    Heat Time Temperature Volume Blisters
    Example (s) (° C.) (mL) Draw (%) (N, L, H)
    A 152 216 820 100 H
    B 123 193 805 98 H
    C 113 191 179 22 H
    D 106 188 0 0 H
    E 95 182 0 0 NA
    F 90 171 0 0 NA
    NA = not applicable. A value of zero indicates that the sheet was not formed because it did not pull into the mold (likely because it was too cold).
  • It can be clearly seen from a comparison of the data in the above relevant working examples that the polyesters of the present invention offer a definite advantage over the commercially available polyesters with regard to glass transition temperature, density, slow crystallization rate, melt viscosity, and toughness.
  • The invention has been described in detail with reference to the embodiments disclosed herein, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims (72)

  1. 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. 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. 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. 4. The graphic art film of claim 1, wherein the polyester has a Tg of 105 to 140° C.
  5. 5. The graphic art film of claim 1, wherein the polyester has a Tg of 100 to 120° C.
  6. 6. The graphic art film of claim 1, wherein the polyester has a Tg of 120 to 140° C.
  7. 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. 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. 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. 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. 11. The graphic art film of claim 1, wherein the dicarboxylic acid component comprises 80 to 100 mole % of terephthalic acid residues.
  12. 12. The graphic art film of claim 1, wherein the dicarboxylic acid component comprises 90 to 100 mole % of terephthalic acid residues.
  13. 13. The graphic art film of claim 1, wherein the dicarboxylic acid component comprises 95 to 100 mole % of terephthalic acid residues.
  14. 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. 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. 16. The graphic art film of claim 1, wherein the polyester comprises from 0.01 to 15 mole % of ethylene glycol residues.
  17. 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. 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. 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. 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. 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. 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. 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. 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. 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. 26. The graphic art film of claim 1, wherein the polyester composition comprises at least one thermal stabilizer or a reaction product thereof.
  27. 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. 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. 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. 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. 31. The graphic art film of claim 1, wherein the graphic art film is thermoformed.
  32. 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. 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. 34. The graphic art film of claim 1, wherein the graphic art film is formed by extrusion.
  35. 35. The graphic art film of claim 1, wherein the graphic art film is produced by calendering.
  36. 36. The graphic art film of claim 1, wherein the graphic art film is produced by compression molding.
  37. 37. The graphic art film of claim 1, wherein the graphic art film is produced by solution casting.
  38. 38. An in-mold decorated article comprising the graphic art film of claim 1.
  39. 39. An embossed article comprising the graphic art film of claim 1.
  40. 40. A hard-coated article comprising the graphic art film of claim 1.
  41. 41. The graphic art film of claim 1, wherein the graphic art film is textured.
  42. 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. 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. 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. 45. The graphic art film of claim 42, wherein the polyester has a Tg of 105 to 130° C.
  46. 46. The graphic art film of claim 42, wherein the polyester has a Tg of 100 to 120° C.
  47. 47. The graphic art film of claim 42, wherein the polyester has a Tg of 120 to 140° C.
  48. 48. The graphic art film of claim 42, wherein the graphic art film is thermoformed.
  49. 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. 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. 51. An in-mold decorated article comprising the graphic art film of claim 42.
  52. 52. An embossed article comprising the graphic art film of claim 42.
  53. 53. A hard-coated article comprising the graphic art film of claim 42.
  54. 54. The graphic art film of claim 42, wherein the graphic art film is textured.
  55. 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. 56. An in-mold decorated article comprising the graphic art film of claim 55.
  57. 57. An embossed article comprising the graphic art film of claim 55.
  58. 58. A hard-coated article comprising the graphic art film of claim 55.
  59. 59. The graphic art film of claim 55, wherein the graphic art film is textured.
  60. 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. 61. An in-mold decorated article comprising the graphic art film of claim 60.
  62. 62. An embossed article comprising the graphic art film of claim 60.
  63. 63. A hard-coated article comprising the graphic art film of claim 60.
  64. 64. The graphic art film of claim 60, wherein the graphic art film is textured.
  65. 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. 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. 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. 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. 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. 70. The container of claim 60, wherein said polyester comprises residues from trimellitic anhydride.
  71. 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. 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.
US13017352 2005-06-17 2011-01-31 Graphic art films comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol Abandoned US20110189415A1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
US69156705 true 2005-06-17 2005-06-17
US73145405 true 2005-10-28 2005-10-28
US73138905 true 2005-10-28 2005-10-28
US73886905 true 2005-11-22 2005-11-22
US73905805 true 2005-11-22 2005-11-22
US75054705 true 2005-12-15 2005-12-15
US75069305 true 2005-12-15 2005-12-15
US75068205 true 2005-12-15 2005-12-15
US75069205 true 2005-12-15 2005-12-15
US11390563 US7902320B2 (en) 2005-06-17 2006-03-28 Graphic art films comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US13017352 US20110189415A1 (en) 2005-06-17 2011-01-31 Graphic art films comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol

Applications Claiming Priority (1)

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US13017352 US20110189415A1 (en) 2005-06-17 2011-01-31 Graphic art films comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol

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US11390563 Continuation US7902320B2 (en) 2005-06-17 2006-03-28 Graphic art films comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol

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US20110189415A1 true true US20110189415A1 (en) 2011-08-04

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Family Applications (59)

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US11390826 Active 2028-01-04 US7906610B2 (en) 2005-06-17 2006-03-28 Food service products comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11391505 Active 2027-04-12 US7838620B2 (en) 2005-06-17 2006-03-28 Thermoformed sheet(s) comprising polyester compositions which comprise cyclobutanediol
US11390794 Active 2027-04-05 US8119761B2 (en) 2005-06-17 2006-03-28 Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom
US11391063 Expired - Fee Related US7576171B2 (en) 2005-06-17 2006-03-28 Pacifiers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390883 Active 2027-06-10 US7834129B2 (en) 2005-06-17 2006-03-28 Restaurant smallware comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390629 Active 2026-04-12 US7803439B2 (en) 2005-06-17 2006-03-28 Blood therapy containers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11391659 Abandoned US20060287496A1 (en) 2005-06-17 2006-03-28 Polyester compositions comprising minimal amounts of cyclobutanediol
US11391156 Active 2027-05-24 US7812112B2 (en) 2005-06-17 2006-03-28 Outdoor signs comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390882 Abandoned US20060287486A1 (en) 2005-06-17 2006-03-28 Optical media comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390858 Active 2028-01-13 US7951900B2 (en) 2005-06-17 2006-03-28 Dialysis filter housings comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11391571 Abandoned US20060287494A1 (en) 2005-06-17 2006-03-28 Polyester compositions containing high amounts of cyclobutanediol and articles made therefrom
US11390811 Expired - Fee Related US7868128B2 (en) 2005-06-17 2006-03-28 Skylights and windows comprising polyester compositions formed from 2,2,4,4,-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390793 Abandoned US20060286389A1 (en) 2005-06-17 2006-03-28 Protein-resistant articles comprising cyclobutanediol
US11390864 Expired - Fee Related US7812111B2 (en) 2005-06-17 2006-03-28 LCD films comprising polyester compositions formed from 2,2,4,4-tetramethy1-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390672 Abandoned US20060287479A1 (en) 2005-06-17 2006-03-28 Polyester compositions containing cyclobutanediol and articles made therefrom
US11391485 Active 2027-06-01 US7842776B2 (en) 2005-06-17 2006-03-28 Appliance parts comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390630 Expired - Fee Related US7807774B2 (en) 2005-06-17 2006-03-28 Vending machines comprising polyester compositions formed from 2,2,4,4,-tetramethyl-1,3,-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390847 Abandoned US20060287484A1 (en) 2005-06-17 2006-03-28 Opththalmic devices comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390752 Active 2027-04-10 US8063173B2 (en) 2005-06-17 2006-03-28 Polyester compositions containing low amounts of cyclobutanediol and articles made therefrom
US11390631 Active 2027-06-15 US7855267B2 (en) 2005-06-17 2006-03-28 Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature
US11390671 Active 2027-04-29 US8063172B2 (en) 2005-06-17 2006-03-28 Film(s) and/or sheet(s) made using polyester compositions containing low amounts of cyclobutanediol
US11390722 Expired - Fee Related US7893187B2 (en) 2005-06-17 2006-03-28 Glass laminates comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390827 Active 2027-12-18 US7893188B2 (en) 2005-06-17 2006-03-28 Baby bottles comprising polyester compositions which comprise cyclobutanediol
US11391495 Expired - Fee Related US7807775B2 (en) 2005-06-17 2006-03-28 Point of purchase displays comprising polyester compositions formed from 2,2,4,4-tetramethyl-1, 3,-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390836 Abandoned US20060286330A1 (en) 2005-06-17 2006-03-28 Sterilization containers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390654 Abandoned US20060287477A1 (en) 2005-06-17 2006-03-28 Greenhouses comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4- cyclohexanedimethanol
US11391576 Active 2028-02-19 US7803441B2 (en) 2005-06-17 2006-03-28 Intravenous components comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390655 Expired - Fee Related US8067525B2 (en) 2005-06-17 2006-03-28 Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and high glass transition temperature
US11390853 Abandoned US20070270569A1 (en) 2005-06-17 2006-03-28 Film(s) and/or sheet(s) made from polyester compositions containing cyclobutanediol and articles made therefrom
US11391565 Active 2027-05-06 US7781562B2 (en) 2005-06-17 2006-03-28 Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US11391125 Abandoned US20070010650A1 (en) 2005-06-17 2006-03-28 Tough amorphous polyester compositions
US11390814 Abandoned US20060286327A1 (en) 2005-06-17 2006-03-28 Retort containers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390751 Active 2026-04-16 US7803440B2 (en) 2005-06-17 2006-03-28 Bottles comprising polyester compositions which comprise cyclobutanediol
US11391137 Active 2027-05-17 US7985827B2 (en) 2005-06-17 2006-03-28 Polyester compositions which comprise cyclobutanediol having certain cis/trans ratios
US11390750 Abandoned US20060287480A1 (en) 2005-06-17 2006-03-28 Outdoor shelters comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390955 Active 2027-05-25 US7915376B2 (en) 2005-06-17 2006-03-28 Containers comprising polyester compositions which comprise cyclobutanediol
US11390865 Abandoned US20060287485A1 (en) 2005-06-17 2006-03-28 Sound barriers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390563 Expired - Fee Related US7902320B2 (en) 2005-06-17 2006-03-28 Graphic art films comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11391642 Active 2026-08-22 US7510768B2 (en) 2005-06-17 2006-03-28 Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US12091572 Abandoned US20090093573A1 (en) 2005-03-02 2006-10-27 Polyester Compositions Which Comprise Cyclobutanediol and at Least One Phosphorus Compound
US12091568 Abandoned US20090093574A1 (en) 2005-03-02 2006-10-27 Polyester Compositions Containing Cyclobutanediol Having High Glass Transition Temperature and Articles Made Therefrom
US12361779 Active US7740941B2 (en) 2005-06-17 2009-01-29 Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US12479893 Abandoned US20100092705A1 (en) 2005-06-17 2009-06-08 Bottles comprising polyester compositions which comprise cyclobutanediol
US12724492 Abandoned US20100174030A1 (en) 2005-06-17 2010-03-16 Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US12724480 Active US7906212B2 (en) 2005-06-17 2010-03-16 Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US12784193 Active 2026-04-07 US8101705B2 (en) 2005-06-17 2010-05-20 Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US12900060 Expired - Fee Related US8133967B2 (en) 2005-06-17 2010-10-07 Restaurant smallware comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US12943217 Active US8119762B2 (en) 2005-06-17 2010-11-10 Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature
US13007838 Active 2028-05-27 US9169348B2 (en) 2005-06-17 2011-01-17 Baby bottles comprising polyester compositions which comprise cyclobutanediol
US13016147 Active 2026-09-12 US8354491B2 (en) 2005-06-17 2011-01-28 Containers comprising polyester compositions which comprise cyclobutanediol
US13017352 Abandoned US20110189415A1 (en) 2005-06-17 2011-01-31 Graphic art films comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US13162870 Active US9181387B2 (en) 2005-06-17 2011-06-17 Polyester compositions which comprise cyclobutanediol having certain cis/trans ratios
US13215511 Active US8507638B2 (en) 2005-06-17 2011-08-23 Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US13348677 Active US8415450B2 (en) 2005-06-17 2012-01-12 Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom
US13709097 Active 2026-04-29 US9175134B2 (en) 2005-06-17 2012-12-10 Containers comprising polyester compositions which comprise cyclobutanediol
US13776038 Active US9181388B2 (en) 2005-06-17 2013-02-25 Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom
US14865714 Active US9534079B2 (en) 2005-06-17 2015-09-25 Containers comprising polyester compositions which comprise cyclobutanediol
US14865705 Active US9765181B2 (en) 2005-06-17 2015-09-25 Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom
US14865681 Abandoned US20160009857A1 (en) 2005-06-17 2015-09-25 Baby bottles comprising polyester compositions which comprise cyclobutanediol

Family Applications Before (50)

Application Number Title Priority Date Filing Date
US11390826 Active 2028-01-04 US7906610B2 (en) 2005-06-17 2006-03-28 Food service products comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11391505 Active 2027-04-12 US7838620B2 (en) 2005-06-17 2006-03-28 Thermoformed sheet(s) comprising polyester compositions which comprise cyclobutanediol
US11390794 Active 2027-04-05 US8119761B2 (en) 2005-06-17 2006-03-28 Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom
US11391063 Expired - Fee Related US7576171B2 (en) 2005-06-17 2006-03-28 Pacifiers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390883 Active 2027-06-10 US7834129B2 (en) 2005-06-17 2006-03-28 Restaurant smallware comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390629 Active 2026-04-12 US7803439B2 (en) 2005-06-17 2006-03-28 Blood therapy containers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11391659 Abandoned US20060287496A1 (en) 2005-06-17 2006-03-28 Polyester compositions comprising minimal amounts of cyclobutanediol
US11391156 Active 2027-05-24 US7812112B2 (en) 2005-06-17 2006-03-28 Outdoor signs comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390882 Abandoned US20060287486A1 (en) 2005-06-17 2006-03-28 Optical media comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390858 Active 2028-01-13 US7951900B2 (en) 2005-06-17 2006-03-28 Dialysis filter housings comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11391571 Abandoned US20060287494A1 (en) 2005-06-17 2006-03-28 Polyester compositions containing high amounts of cyclobutanediol and articles made therefrom
US11390811 Expired - Fee Related US7868128B2 (en) 2005-06-17 2006-03-28 Skylights and windows comprising polyester compositions formed from 2,2,4,4,-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390793 Abandoned US20060286389A1 (en) 2005-06-17 2006-03-28 Protein-resistant articles comprising cyclobutanediol
US11390864 Expired - Fee Related US7812111B2 (en) 2005-06-17 2006-03-28 LCD films comprising polyester compositions formed from 2,2,4,4-tetramethy1-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390672 Abandoned US20060287479A1 (en) 2005-06-17 2006-03-28 Polyester compositions containing cyclobutanediol and articles made therefrom
US11391485 Active 2027-06-01 US7842776B2 (en) 2005-06-17 2006-03-28 Appliance parts comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390630 Expired - Fee Related US7807774B2 (en) 2005-06-17 2006-03-28 Vending machines comprising polyester compositions formed from 2,2,4,4,-tetramethyl-1,3,-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390847 Abandoned US20060287484A1 (en) 2005-06-17 2006-03-28 Opththalmic devices comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390752 Active 2027-04-10 US8063173B2 (en) 2005-06-17 2006-03-28 Polyester compositions containing low amounts of cyclobutanediol and articles made therefrom
US11390631 Active 2027-06-15 US7855267B2 (en) 2005-06-17 2006-03-28 Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature
US11390671 Active 2027-04-29 US8063172B2 (en) 2005-06-17 2006-03-28 Film(s) and/or sheet(s) made using polyester compositions containing low amounts of cyclobutanediol
US11390722 Expired - Fee Related US7893187B2 (en) 2005-06-17 2006-03-28 Glass laminates comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390827 Active 2027-12-18 US7893188B2 (en) 2005-06-17 2006-03-28 Baby bottles comprising polyester compositions which comprise cyclobutanediol
US11391495 Expired - Fee Related US7807775B2 (en) 2005-06-17 2006-03-28 Point of purchase displays comprising polyester compositions formed from 2,2,4,4-tetramethyl-1, 3,-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390836 Abandoned US20060286330A1 (en) 2005-06-17 2006-03-28 Sterilization containers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390654 Abandoned US20060287477A1 (en) 2005-06-17 2006-03-28 Greenhouses comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4- cyclohexanedimethanol
US11391576 Active 2028-02-19 US7803441B2 (en) 2005-06-17 2006-03-28 Intravenous components comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390655 Expired - Fee Related US8067525B2 (en) 2005-06-17 2006-03-28 Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and high glass transition temperature
US11390853 Abandoned US20070270569A1 (en) 2005-06-17 2006-03-28 Film(s) and/or sheet(s) made from polyester compositions containing cyclobutanediol and articles made therefrom
US11391565 Active 2027-05-06 US7781562B2 (en) 2005-06-17 2006-03-28 Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US11391125 Abandoned US20070010650A1 (en) 2005-06-17 2006-03-28 Tough amorphous polyester compositions
US11390814 Abandoned US20060286327A1 (en) 2005-06-17 2006-03-28 Retort containers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390751 Active 2026-04-16 US7803440B2 (en) 2005-06-17 2006-03-28 Bottles comprising polyester compositions which comprise cyclobutanediol
US11391137 Active 2027-05-17 US7985827B2 (en) 2005-06-17 2006-03-28 Polyester compositions which comprise cyclobutanediol having certain cis/trans ratios
US11390750 Abandoned US20060287480A1 (en) 2005-06-17 2006-03-28 Outdoor shelters comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390955 Active 2027-05-25 US7915376B2 (en) 2005-06-17 2006-03-28 Containers comprising polyester compositions which comprise cyclobutanediol
US11390865 Abandoned US20060287485A1 (en) 2005-06-17 2006-03-28 Sound barriers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11390563 Expired - Fee Related US7902320B2 (en) 2005-06-17 2006-03-28 Graphic art films comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US11391642 Active 2026-08-22 US7510768B2 (en) 2005-06-17 2006-03-28 Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US12091572 Abandoned US20090093573A1 (en) 2005-03-02 2006-10-27 Polyester Compositions Which Comprise Cyclobutanediol and at Least One Phosphorus Compound
US12091568 Abandoned US20090093574A1 (en) 2005-03-02 2006-10-27 Polyester Compositions Containing Cyclobutanediol Having High Glass Transition Temperature and Articles Made Therefrom
US12361779 Active US7740941B2 (en) 2005-06-17 2009-01-29 Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US12479893 Abandoned US20100092705A1 (en) 2005-06-17 2009-06-08 Bottles comprising polyester compositions which comprise cyclobutanediol
US12724492 Abandoned US20100174030A1 (en) 2005-06-17 2010-03-16 Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US12724480 Active US7906212B2 (en) 2005-06-17 2010-03-16 Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US12784193 Active 2026-04-07 US8101705B2 (en) 2005-06-17 2010-05-20 Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US12900060 Expired - Fee Related US8133967B2 (en) 2005-06-17 2010-10-07 Restaurant smallware comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US12943217 Active US8119762B2 (en) 2005-06-17 2010-11-10 Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature
US13007838 Active 2028-05-27 US9169348B2 (en) 2005-06-17 2011-01-17 Baby bottles comprising polyester compositions which comprise cyclobutanediol
US13016147 Active 2026-09-12 US8354491B2 (en) 2005-06-17 2011-01-28 Containers comprising polyester compositions which comprise cyclobutanediol

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Application Number Title Priority Date Filing Date
US13162870 Active US9181387B2 (en) 2005-06-17 2011-06-17 Polyester compositions which comprise cyclobutanediol having certain cis/trans ratios
US13215511 Active US8507638B2 (en) 2005-06-17 2011-08-23 Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US13348677 Active US8415450B2 (en) 2005-06-17 2012-01-12 Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom
US13709097 Active 2026-04-29 US9175134B2 (en) 2005-06-17 2012-12-10 Containers comprising polyester compositions which comprise cyclobutanediol
US13776038 Active US9181388B2 (en) 2005-06-17 2013-02-25 Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom
US14865714 Active US9534079B2 (en) 2005-06-17 2015-09-25 Containers comprising polyester compositions which comprise cyclobutanediol
US14865705 Active US9765181B2 (en) 2005-06-17 2015-09-25 Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom
US14865681 Abandoned US20160009857A1 (en) 2005-06-17 2015-09-25 Baby bottles comprising polyester compositions which comprise cyclobutanediol

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US (59) US7906610B2 (en)
EP (49) EP1891137B1 (en)
JP (38) JP2008544121A (en)
KR (14) KR101249595B1 (en)
CN (1) CN103755930A (en)
DE (19) DE602006007346D1 (en)
ES (1) ES2341482T3 (en)
WO (39) WO2007001535A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100249293A1 (en) * 2009-03-27 2010-09-30 Eastman Chemical Company Polyester blends
US9273206B2 (en) 2012-07-09 2016-03-01 Eastman Chemical Company Ternary blends of terephthalate or isophthalate polyesters containing EG, CHDM and TMCD
US9598533B2 (en) 2005-11-22 2017-03-21 Eastman Chemical Company Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US9765203B2 (en) 2006-03-28 2017-09-19 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof
US9982125B2 (en) 2012-02-16 2018-05-29 Eastman Chemical Company Clear semi-crystalline articles with improved heat resistance

Families Citing this family (155)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007053549A1 (en) * 2005-10-28 2007-05-10 Eastman Chemical Company Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
WO2007053548A3 (en) * 2005-10-28 2007-06-21 Benjamin Fredrick Barton Polyester compositions comprising minimal amounts of cyclobutanediol
US8586701B2 (en) 2005-10-28 2013-11-19 Eastman Chemical Company Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7704605B2 (en) * 2006-03-28 2010-04-27 Eastman Chemical Company Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US20130072628A1 (en) * 2005-06-17 2013-03-21 Eastman Chemical Company Coating compositions containing cyclobutanediol
US7906610B2 (en) * 2005-06-17 2011-03-15 Eastman Chemical Company Food service products comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
WO2008140705A8 (en) * 2007-05-10 2009-09-11 Eastman Chemical Company Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US8083094B2 (en) 2006-08-10 2011-12-27 Capitol Vial Inc. Container and cap assembly
US20110089187A1 (en) * 2006-08-10 2011-04-21 Capitol Vial Inc. Shatterproof Container And Cap Assembly
US20080053752A1 (en) * 2006-09-06 2008-03-06 Peter Miller System and method for securing a window in a panel
US20080085390A1 (en) 2006-10-04 2008-04-10 Ryan Thomas Neill Encapsulation of electrically energized articles
US8287991B2 (en) * 2006-10-04 2012-10-16 Eastman Chemical Company Using branched polymers to control the dimensional stability of articles in the lamination process
US8080191B2 (en) * 2006-10-20 2011-12-20 Pepsico, Inc. Extrudable polyethylene terephthalate blend
WO2008088336A1 (en) * 2007-01-18 2008-07-24 Sabic Innovative Plastics Ip B.V. COATED ARTICLES OF MANUFACTURE MADE OF HIGH Tg POLYMER BLENDS
EP2126623B1 (en) * 2007-03-08 2014-05-14 OKIA Optical Co. Ltd. Eyeglasses and eyeglass frames comprising glycol modified copolyesters
JP5346443B2 (en) 2007-04-16 2013-11-20 ローム株式会社 The semiconductor light emitting device and a manufacturing method thereof
US8514545B2 (en) * 2007-04-20 2013-08-20 Ink-Logix, Llc In-molded capacitive switch
US8198979B2 (en) 2007-04-20 2012-06-12 Ink-Logix, Llc In-molded resistive and shielding elements
US7748137B2 (en) * 2007-07-15 2010-07-06 Yin Wang Wood-drying solar greenhouse
US20090023885A1 (en) * 2007-07-16 2009-01-22 Texas State University - San Marcos Treatment method for imparting high impact resistance in certain cbdo copolymers
US7772362B2 (en) * 2007-07-16 2010-08-10 Texas State University Treatment method for imparting self-healing and shape memory properties to certain CBDO copolymers
CN101434744B (en) * 2007-11-14 2013-12-18 财团法人工业技术研究院 Mixture and encapsulating material
US8501287B2 (en) * 2007-11-21 2013-08-06 Eastman Chemical Company Plastic baby bottles, other blow molded articles, and processes for their manufacture
KR20100087171A (en) * 2007-11-21 2010-08-03 이스트만 케미칼 컴파니 Plastic baby bottles, other blow molded articles, and processes for their manufacture
GB0800459D0 (en) * 2008-01-11 2008-02-20 Innovata Biomed Ltd Improvements in or relating to inhalers
DE202008005269U1 (en) * 2008-02-28 2008-08-21 Mapa Gmbh Gummi- Und Plastikwerke Soother with fixed on a mouth shield teat part
US8404755B2 (en) * 2008-04-18 2013-03-26 Pepsico, Inc. Polyester composition and method for preparing articles by extrusion blow molding
US7901780B2 (en) * 2008-06-25 2011-03-08 Solutia Inc. Polymer interlayers comprising blends of plasticized poly(vinyl butyral) and poly(cyclohexanedimethylene terephthalate-co-ethylene terephthalate) copolyester
US8198371B2 (en) * 2008-06-27 2012-06-12 Eastman Chemical Company Blends of polyesters and ABS copolymers
US7960007B2 (en) * 2008-07-11 2011-06-14 Teknor Apex Company Retortable liners and containers
US8110265B2 (en) 2008-12-09 2012-02-07 The Coca-Cola Company Pet container and compositions having enhanced mechanical properties and gas barrier properties
US20100143546A1 (en) 2008-12-09 2010-06-10 The Coca-Cola Company Container and composition for enhanced gas barrier properties
US8895654B2 (en) * 2008-12-18 2014-11-25 Eastman Chemical Company Polyester compositions which comprise spiro-glycol, cyclohexanedimethanol, and terephthalic acid
US20100168328A1 (en) * 2008-12-30 2010-07-01 Ganesh Kannan Process for the manufacture of polycyclohexane dimethylene terephthalate copolymers from polyethylene terephthalate, and compositions and articles thereof
US9161888B2 (en) 2009-01-13 2015-10-20 Michelle Lamar Pacifier apparatus
US8324316B2 (en) * 2009-02-06 2012-12-04 Eastman Chemical Company Unsaturated polyester resin compositions containing 2,2,2,4-tetramethyl-1,3-cyclobutanediol and articles made therefrom
US9029461B2 (en) 2009-02-06 2015-05-12 Eastman Chemical Company Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol
US9029460B2 (en) 2009-02-06 2015-05-12 Stacey James Marsh Coating compositions containing acrylic and aliphatic polyester blends
US20100210775A1 (en) 2009-02-13 2010-08-19 Eastman Chemical Company Reinforced polyester compositions having improved toughness
KR101546564B1 (en) 2009-04-01 2015-08-21 이스트만 케미칼 컴파니 Improved process for the production of polyesters
US9008321B2 (en) 2009-06-08 2015-04-14 Nokia Corporation Audio processing
JP5586177B2 (en) * 2009-06-23 2014-09-10 三菱樹脂株式会社 Laminated sheet, and a metal plate coated with a multilayer sheet
ES2355220B2 (en) * 2009-08-17 2011-09-19 Sp Kloner Ecotec, S.L. Structural profile members for producing household utensils and process for those profiles.
KR20110028696A (en) * 2009-09-14 2011-03-22 에스케이케미칼주식회사 Polyester resin copolymerized with isosorbide and 1,4- cyclohexane dimethanol and preparing method thereof
US8586652B2 (en) * 2009-10-09 2013-11-19 Eastman Chemical Company Polyester compositions for molding clear parts
CN102597051B (en) * 2009-10-19 2014-12-17 伊士曼化工公司 Radio-frequency sealable polymer and articles thereof
US20110104342A1 (en) * 2009-11-03 2011-05-05 Kevin David Glaser Chlorine-Free Packaging Sheet with Tear-Resistance Properties
US8574694B2 (en) 2009-11-03 2013-11-05 Curwood, Inc. Packaging sheet with improved cutting properties
JP4888853B2 (en) 2009-11-12 2012-02-29 学校法人慶應義塾 Improve visibility method for a liquid crystal display device, and a liquid crystal display device using the same
EP2521526A2 (en) * 2009-11-20 2012-11-14 Dentsply International Inc. Dental materials using 2,2,4,4-tetramethyl-1,3-cyclobutanediol
FR2957152B1 (en) * 2010-03-04 2012-08-03 Christian Dalloz Sunoptics New composite material has optical use and its production process
JP5653061B2 (en) * 2010-04-09 2015-01-14 株式会社ジェイエスピー Building or civil engineering extruded thermoplastic resin foam
US8283800B2 (en) 2010-05-27 2012-10-09 Ford Global Technologies, Llc Vehicle control system with proximity switch and method thereof
US9776903B2 (en) 2010-06-17 2017-10-03 Johns Manville Apparatus, systems and methods for processing molten glass
US9096452B2 (en) 2010-06-17 2015-08-04 Johns Manville Methods and systems for destabilizing foam in equipment downstream of a submerged combustion melter
US8973400B2 (en) 2010-06-17 2015-03-10 Johns Manville Methods of using a submerged combustion melter to produce glass products
US8997525B2 (en) 2010-06-17 2015-04-07 Johns Manville Systems and methods for making foamed glass using submerged combustion
USRE46462E1 (en) 2011-10-07 2017-07-04 Johns Manville Apparatus, systems and methods for conditioning molten glass
US8991215B2 (en) 2010-06-17 2015-03-31 Johns Manville Methods and systems for controlling bubble size and bubble decay rate in foamed glass produced by a submerged combustion melter
US8769992B2 (en) 2010-06-17 2014-07-08 Johns Manville Panel-cooled submerged combustion melter geometry and methods of making molten glass
US8973405B2 (en) 2010-06-17 2015-03-10 Johns Manville Apparatus, systems and methods for reducing foaming downstream of a submerged combustion melter producing molten glass
US9021838B2 (en) 2010-06-17 2015-05-05 Johns Manville Systems and methods for glass manufacturing
US8686072B2 (en) 2010-06-29 2014-04-01 Sabic Innovative Plastics Ip B.V. Flame resistant polyester compositions, method of manufacture, and articles therof
US8604105B2 (en) 2010-09-03 2013-12-10 Eastman Chemical Company Flame retardant copolyester compositions
US8650914B2 (en) 2010-09-23 2014-02-18 Johns Manville Methods and apparatus for recycling glass products using submerged combustion
US20130260069A1 (en) * 2010-12-06 2013-10-03 Colgate-Palmolive Company Laminate Tube Having a Resilent Copolymer Coating
US20120184687A1 (en) 2011-01-17 2012-07-19 Eastman Chemical Company Clear Binary Blends of Aliphatic-Aromatic Polyesters and Copolyestercarbonates
DE102011009820A1 (en) * 2011-01-31 2011-10-13 Mitsubishi Polyester Film Gmbh Biaxially stretched foil, useful e.g. for electrical insulation, comprises black pigment, diol component made of 1,4-cyclohexane dimethanol, and dicarboxylic acid component made of benzene dicarboxylic acid or naphthalene dicarboxylic acid
EP2673326B1 (en) 2011-02-07 2018-01-10 Valspar Sourcing, Inc. Coating compositions for containers and other articles and methods of coating
EP2677001A4 (en) 2011-02-18 2016-10-19 Midori Anzen Co Ltd Transparent resin composition having good chemical resistance, durability and stability under natural environmental conditions, harsher natural environmental conditions, and similar or harsher usage conditions, and product using same
US9421308B2 (en) 2011-02-22 2016-08-23 Polyone Corporation Polyester compounds suitable for hydroclaving
US9090769B2 (en) 2011-04-05 2015-07-28 Ticona Llc Molded articles having a swirl-like or marble-like appearance and compositions for producing same
US20120305575A1 (en) * 2011-06-01 2012-12-06 Eastman Chemical Company High strength bottle
US8975903B2 (en) 2011-06-09 2015-03-10 Ford Global Technologies, Llc Proximity switch having learned sensitivity and method therefor
US8928336B2 (en) 2011-06-09 2015-01-06 Ford Global Technologies, Llc Proximity switch having sensitivity control and method therefor
JP2013001089A (en) * 2011-06-21 2013-01-07 Nippon Kararingu Kk Card sheet
JP2013001090A (en) * 2011-06-21 2013-01-07 Nippon Kararingu Kk Card sheet
KR20140036263A (en) * 2011-06-21 2014-03-25 니혼 칼라링 가부시끼가이샤 Sheet for card
US9150006B2 (en) 2011-06-23 2015-10-06 Eastman Chemical Company Lamination process optimization utilizing neopentyl glycol-modified polyesters
EP2546282A1 (en) * 2011-07-14 2013-01-16 Basf Se Thermoplastic moulding material
US10004286B2 (en) 2011-08-08 2018-06-26 Ford Global Technologies, Llc Glove having conductive ink and method of interacting with proximity sensor
WO2013034950A8 (en) * 2011-09-08 2013-12-05 Société Anonyme Des Eaux Minerales D'evian "S.A.E.M.E" Method for producing a bio-pet polymer
US9857502B2 (en) 2011-09-09 2018-01-02 Lg Innotek Co., Ltd. Method of fabricating film of substrate and film, backlight unit and liquid crystal display using the same
US9143126B2 (en) 2011-09-22 2015-09-22 Ford Global Technologies, Llc Proximity switch having lockout control for controlling movable panel
US8875544B2 (en) 2011-10-07 2014-11-04 Johns Manville Burner apparatus, submerged combustion melters including the burner, and methods of use
EP2578412B1 (en) * 2011-10-07 2014-06-25 3M Innovative Properties Company Printable film
US8707740B2 (en) 2011-10-07 2014-04-29 Johns Manville Submerged combustion glass manufacturing systems and methods
US20130095270A1 (en) * 2011-10-14 2013-04-18 Eastman Chemical Company Polyester compositions containing furandicarboxylic acid or an ester thereof, cyclobutanediol and cyclohexanedimethanol
US20140221599A1 (en) * 2011-10-28 2014-08-07 Nissin Dental Products Inc. Molded body for dental use
US10093796B2 (en) 2011-11-01 2018-10-09 Midori Anzen Co., Ltd. Resin composition and molded body
US8994228B2 (en) 2011-11-03 2015-03-31 Ford Global Technologies, Llc Proximity switch having wrong touch feedback
JP5899235B2 (en) * 2011-11-04 2016-04-06 旭化成メディカル株式会社 Blood treatment separation membrane, and blood processor incorporating the membrane
US8878438B2 (en) 2011-11-04 2014-11-04 Ford Global Technologies, Llc Lamp and proximity switch assembly and method
CN102676591A (en) * 2012-01-12 2012-09-19 河南科技大学 Method for preparing polyester containing 3-hydroxy glutaric acid unit
US8669314B2 (en) 2012-02-03 2014-03-11 Sabic Innovative Plastics Ip B.V. Hydrolytic stability in polycarbonate compositions
KR101417250B1 (en) * 2012-02-20 2014-07-08 (주)엘지하우시스 High temperature resistant multilayer resistant opitical multilater film and its manufacturing method
ES2638388T3 (en) 2012-02-28 2017-10-20 Sabic Global Technologies B.V. Processes and compositions for cleaning mixing devices to improve the production of polycarbonate
US9065447B2 (en) 2012-04-11 2015-06-23 Ford Global Technologies, Llc Proximity switch assembly and method having adaptive time delay
US8933708B2 (en) 2012-04-11 2015-01-13 Ford Global Technologies, Llc Proximity switch assembly and activation method with exploration mode
US9219472B2 (en) 2012-04-11 2015-12-22 Ford Global Technologies, Llc Proximity switch assembly and activation method using rate monitoring
US9197206B2 (en) 2012-04-11 2015-11-24 Ford Global Technologies, Llc Proximity switch having differential contact surface
US9559688B2 (en) 2012-04-11 2017-01-31 Ford Global Technologies, Llc Proximity switch assembly having pliable surface and depression
US9944237B2 (en) 2012-04-11 2018-04-17 Ford Global Technologies, Llc Proximity switch assembly with signal drift rejection and method
US9531379B2 (en) 2012-04-11 2016-12-27 Ford Global Technologies, Llc Proximity switch assembly having groove between adjacent proximity sensors
US9660644B2 (en) 2012-04-11 2017-05-23 Ford Global Technologies, Llc Proximity switch assembly and activation method
US9568527B2 (en) 2012-04-11 2017-02-14 Ford Global Technologies, Llc Proximity switch assembly and activation method having virtual button mode
US9520875B2 (en) 2012-04-11 2016-12-13 Ford Global Technologies, Llc Pliable proximity switch assembly and activation method
US9287864B2 (en) 2012-04-11 2016-03-15 Ford Global Technologies, Llc Proximity switch assembly and calibration method therefor
US9831870B2 (en) 2012-04-11 2017-11-28 Ford Global Technologies, Llc Proximity switch assembly and method of tuning same
US9184745B2 (en) 2012-04-11 2015-11-10 Ford Global Technologies, Llc Proximity switch assembly and method of sensing user input based on signal rate of change
US9136840B2 (en) 2012-05-17 2015-09-15 Ford Global Technologies, Llc Proximity switch assembly having dynamic tuned threshold
US9080763B2 (en) 2012-05-17 2015-07-14 GE Lighting Solutions, LLC Edge lit luminaires for windows
US8981602B2 (en) 2012-05-29 2015-03-17 Ford Global Technologies, Llc Proximity switch assembly having non-switch contact and method
US9337832B2 (en) 2012-06-06 2016-05-10 Ford Global Technologies, Llc Proximity switch and method of adjusting sensitivity therefor
US9641172B2 (en) 2012-06-27 2017-05-02 Ford Global Technologies, Llc Proximity switch assembly having varying size electrode fingers
US9032760B2 (en) 2012-07-03 2015-05-19 Johns Manville Process of using a submerged combustion melter to produce hollow glass fiber or solid glass fiber having entrained bubbles, and burners and systems to make such fibers
WO2014025407A1 (en) 2012-08-09 2014-02-13 Valspar Sourcing, Inc. Polycarbonates
CN104582671B (en) 2012-08-09 2018-06-29 威士伯采购公司 Dental materials and preparation
CN104541210A (en) 2012-08-09 2015-04-22 威士伯采购公司 Developer for thermally responsive record materials
US9102597B2 (en) 2012-09-05 2015-08-11 Sabic Global Technologies B.V. Indane bisphenols, polymers derived therefrom, and methods of use thereof
US8922340B2 (en) 2012-09-11 2014-12-30 Ford Global Technologies, Llc Proximity switch based door latch release
US9533905B2 (en) 2012-10-03 2017-01-03 Johns Manville Submerged combustion melters having an extended treatment zone and methods of producing molten glass
EP2907851B1 (en) * 2012-10-15 2017-05-03 Asahi Kasei Kabushiki Kaisha Thermoplastic resin composition and molded product thereof
US9127122B2 (en) 2012-10-23 2015-09-08 Eastman Chemical Company Copolyesters containing neopentyl glycol and 2,2,4,4-tetraalkyl 1,3-cyclobutanediol
US8623483B1 (en) 2012-10-23 2014-01-07 Eastman Chemical Company Copolyesters containing neopentyl glycol and 2,2,4,4-tetraalkyl 1,3-cyclobutanediol
US8796575B2 (en) 2012-10-31 2014-08-05 Ford Global Technologies, Llc Proximity switch assembly having ground layer
US9227865B2 (en) 2012-11-29 2016-01-05 Johns Manville Methods and systems for making well-fined glass using submerged combustion
US9296894B2 (en) 2013-03-13 2016-03-29 Sabic Global Technologies B.V. Reinforced polyestercarbonate, polycarbonate-polydiorganosiloxane, poly(butylene-terephthalate) blend, and article comprising same
US9311204B2 (en) 2013-03-13 2016-04-12 Ford Global Technologies, Llc Proximity interface development system having replicator and method
US9777922B2 (en) 2013-05-22 2017-10-03 Johns Mansville Submerged combustion burners and melters, and methods of use
WO2014193388A1 (en) 2013-05-30 2014-12-04 Johns Manville Submerged combustion glass melting systems and methods of use
US20140370218A1 (en) 2013-06-14 2014-12-18 Eastman Chemical Company Foamed articles with deep undercuts
WO2015069662A1 (en) * 2013-11-06 2015-05-14 The Board Of Trustees Of The Leland Stanford Junior University Methods for modifying a hydrophobic polymer surface and devices thereof
WO2015078966A1 (en) * 2013-11-29 2015-06-04 Ppg Industries Ohio, Inc. Coating composition
JP5630795B1 (en) 2014-03-24 2014-11-26 有限会社金栄堂 A method of designing a colored lens
CN104017365B (en) * 2014-05-19 2016-05-11 安徽省康利亚实业有限公司 A rail vehicle with a high strength cable and preparation method
US9238609B2 (en) 2014-05-23 2016-01-19 Sabic Global Technologies B.V. Dicarboxylic acid monomers and methods of making and using the same
JP2015028177A (en) * 2014-09-22 2015-02-12 イーストマン ケミカル カンパニー Improved method for producing polyester
US10038443B2 (en) 2014-10-20 2018-07-31 Ford Global Technologies, Llc Directional proximity switch assembly
US9487619B2 (en) 2014-10-27 2016-11-08 Eastman Chemical Company Carboxyl functional curable polyesters containing tetra-alkyl cyclobutanediol
US9650539B2 (en) 2014-10-27 2017-05-16 Eastman Chemical Company Thermosetting compositions based on unsaturated polyesters and phenolic resins
US9598602B2 (en) 2014-11-13 2017-03-21 Eastman Chemical Company Thermosetting compositions based on phenolic resins and curable poleyester resins made with diketene or beta-ketoacetate containing compounds
US9654103B2 (en) 2015-03-18 2017-05-16 Ford Global Technologies, Llc Proximity switch assembly having haptic feedback and method
CN107548352A (en) 2015-04-28 2018-01-05 沙特基础工业全球技术有限公司 Multi-layer materials and articles made therefrom and methods of making
US9548733B2 (en) 2015-05-20 2017-01-17 Ford Global Technologies, Llc Proximity sensor assembly having interleaved electrode configuration
US9751792B2 (en) 2015-08-12 2017-09-05 Johns Manville Post-manufacturing processes for submerged combustion burner
US10041666B2 (en) 2015-08-27 2018-08-07 Johns Manville Burner panels including dry-tip burners, submerged combustion melters, and methods
US9815726B2 (en) 2015-09-03 2017-11-14 Johns Manville Apparatus, systems, and methods for pre-heating feedstock to a melter using melter exhaust
US9982884B2 (en) 2015-09-15 2018-05-29 Johns Manville Methods of melting feedstock using a submerged combustion melter
US10081563B2 (en) 2015-09-23 2018-09-25 Johns Manville Systems and methods for mechanically binding loose scrap
CN108368223A (en) * 2015-12-22 2018-08-03 埃克森美孚化学专利公司 Terephthalate - co - biphenylcarboxylic acid polyesters
US9988553B2 (en) 2016-02-22 2018-06-05 Eastman Chemical Company Thermosetting coating compositions
US10011737B2 (en) 2016-03-23 2018-07-03 Eastman Chemical Company Curable polyester polyols and their use in thermosetting soft feel coating formulations
JP6256721B2 (en) * 2016-03-28 2018-01-10 東洋紡株式会社 The polarizer protective film, a polarizing plate, a liquid crystal display device using the same
CN106188553A (en) * 2016-08-11 2016-12-07 苏州柯创电子材料有限公司 Copolyester electronic insulating pad and manufacture method thereof

Citations (96)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2202046A (en) * 1936-07-13 1940-05-28 Celanese Corp Process for thermal dehydration of lower fatty acids
US2278537A (en) * 1937-10-19 1942-04-07 Celanese Corp Manufacture of aliphatic compounds
US2936324A (en) * 1958-04-14 1960-05-10 Eastman Kodak Co Preparation of 2, 2, 4, 4-tetraalkylcyclobutane-1, 3-diols
US3030335A (en) * 1959-01-02 1962-04-17 Gen Electric Aromatic polycarbonate reaction products
US3075952A (en) * 1959-01-21 1963-01-29 Eastman Kodak Co Solid phase process for linear superpolyesters
US3091600A (en) * 1961-01-05 1963-05-28 Eastman Kodak Co Linear aromatic acid copolyesters modified with dimer glycols having 36 carbons
US3169121A (en) * 1957-08-22 1965-02-09 Gen Electric Carbonate-carboxylate copolyesters of dihydric phenols and difunctional carboxylic acids
US3227764A (en) * 1960-12-30 1966-01-04 Eastman Kodak Co Separation of cis and trans isomers of tetraalkyl - 1,3 - cyclobutanediols and novel compound obtained thereby
US3236899A (en) * 1961-02-23 1966-02-22 Eastman Kodak Co Treatment of 2, 2, 4, 4-tetraalkyl-1, 3-cyclobutanediols
US3249652A (en) * 1962-10-24 1966-05-03 Du Pont Segmented copolyester of 2, 2, 4, 4-tetramethyl-1, 3-cyclobutylene terephthalate andethylene terephthalate
US3312741A (en) * 1963-04-29 1967-04-04 Eastman Kodak Co 2, 2-dialkyl-3-alkoxy cyclobutanone derivatives
US3313777A (en) * 1959-12-18 1967-04-11 Eastman Kodak Co Linear polyesters and polyester-amides from 2, 2, 4, 4-tetraalkyl-1, 3-cyclobutanediols
US3317466A (en) * 1961-09-14 1967-05-02 Eastman Kodak Co Three-dimensional polycyclic bisphenol polycarbonates and polyesters
US3366689A (en) * 1965-03-31 1968-01-30 Daikin Ind Ltd Process for manufacturing ketenes
UST873016I4 (en) * 1969-11-28 1970-04-28 Defensive publication
US3799953A (en) * 1972-09-01 1974-03-26 Bayer Ag 1,4-bis(4,'4''-dihydroxy-triphenylmethyl)benzene
US4001184A (en) * 1975-03-31 1977-01-04 General Electric Company Process for preparing a branched polycarbonate
US4010145A (en) * 1975-05-12 1977-03-01 Eastman Kodak Company Process and catalyst inhibitor systems for preparing synthetic linear polyesters
US4084889A (en) * 1976-07-28 1978-04-18 Vischer Optics, Inc. Eyeglass frame
US4156069A (en) * 1976-04-02 1979-05-22 Allied Chemical Corporation Bisphenol-A/terephthalate/carbonate melt processable copolymers
US4185009A (en) * 1975-01-03 1980-01-22 Bayer Aktiengesellschaft Branched, high-molecular weight thermoplastic polycarbonates
US4188314A (en) * 1976-12-14 1980-02-12 General Electric Company Shaped article obtained from a carbonate-polyester composition
US4194038A (en) * 1979-01-25 1980-03-18 Allied Chemical Corporation Poly(ester-carbonates) from dicarboxylic acid chlorides
US4263364A (en) * 1979-12-14 1981-04-21 Eastman Kodak Company Stampable reinforced thermoplastic polyester sheets
US4367186A (en) * 1978-09-27 1983-01-04 Bayer Aktiengesellschaft Process for the preparation of modified polycarbonate molding compositions
US4379802A (en) * 1982-04-21 1983-04-12 Eastman Kodak Company Stampable reinforced thermoplastic polyester sheet with improved surface finish
US4384106A (en) * 1982-03-09 1983-05-17 Owens-Illinois, Inc. Copolyesters
US4424140A (en) * 1982-06-03 1984-01-03 Union Carbide Corporation Stabilization of polycondensation catalysts
US4426512A (en) * 1983-06-09 1984-01-17 Eastman Kodak Company Polyester containers having improved gas barrier properties
US4427614A (en) * 1980-04-30 1984-01-24 Imperial Chemical Industries Plc 3-Hydroxybutyric acid polymers
US4430484A (en) * 1981-01-14 1984-02-07 General Electric Company Polyester-carbonate resin blends
US4431793A (en) * 1982-06-09 1984-02-14 General Electric Company Aromatic polycarbonate end capped with branched chain alkyl acyl halide or acid
US4578295A (en) * 1984-07-16 1986-03-25 Owens-Illinois, Inc. High barrier polymer blend and articles prepared therefrom
US4578437A (en) * 1983-08-01 1986-03-25 Eastman Kodak Company Copolyester/polyester blends having reduced carbon dioxide permeability
US4642959A (en) * 1983-11-29 1987-02-17 Swiech Jr Tom E Vending machine panels
US4738880A (en) * 1985-03-18 1988-04-19 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Aromatic polyester film having silicone resin layer and liquid crystal display panel made thereof
US4816308A (en) * 1986-12-27 1989-03-28 Mitsubishi Gas Chemical Company, Inc. Multilayered container
US4826903A (en) * 1988-02-22 1989-05-02 Eastman Kodak Company Condensation polymer containing the residue of an acyloxystyrl compound and shaped articles produced therefrom
US4892922A (en) * 1987-11-30 1990-01-09 Eastman Kodak Company Polyester polymer containing the residue of a benzopyran colorant compound and shaped articles produced therefrom
US4892923A (en) * 1988-02-22 1990-01-09 Eastman Kodak Company Polyester compositions containing the residue of a naphthopyran compound and shaped articles produced therefrom
US4981898A (en) * 1987-12-31 1991-01-01 General Electric Company Polycarbonate-polyester blends
US4985342A (en) * 1987-11-09 1991-01-15 Toray Silicone Company, Ltd. Polysiloxane pattern-forming material with SiO4/2 units and pattern formation method using same
US5017680A (en) * 1990-07-03 1991-05-21 Eastman Kodak Company Process and catalyst-inhibitor systems for preparing poly(ethylene terephthalate)
US5017679A (en) * 1989-08-30 1991-05-21 Eastman Kodak Company Polyesters terminated with carboxycyclohexanecarboxylate groups
US5104450A (en) * 1990-09-26 1992-04-14 Eastman Kodak Company Formulations of cellulose esters with arylene-bis(diaryl phosphate)s
US5183863A (en) * 1991-05-31 1993-02-02 Toyo Boseki Kabushiki Kaisha Viscoelastic resin composition for vibration-damping material
US5191038A (en) * 1989-06-01 1993-03-02 General Electric Company Preparation of branched polycarbonate composition from cyclic aromatic polycarbonate oligomer, polyhydric phenol and polycarbonate
US5207967A (en) * 1992-03-02 1993-05-04 Eastman Kodak Company Multicomponent polyester/polycarbonate blends with improved impact strength and processability
US5288764A (en) * 1993-01-29 1994-02-22 Amoco Corporation Increased throughput in foaming and other melt fabrication of polyester
US5288715A (en) * 1990-09-26 1994-02-22 Eastman Kodak Company Light sensitive silver halide element with cellulose ester film base
US5292783A (en) * 1990-11-30 1994-03-08 Eastman Kodak Company Aliphatic-aromatic copolyesters and cellulose ester/polymer blends
US5378796A (en) * 1994-02-09 1995-01-03 Eastman Chemical Company Process for preparing copolyesters
US5382292A (en) * 1993-07-28 1995-01-17 Eastman Kodak Company Edge guide lubricating fluid delivery apparatus
US5384377A (en) * 1993-09-03 1995-01-24 Eastman Chemical Company Toners for polyesters
US5480926A (en) * 1995-04-28 1996-01-02 Eastman Chemical Company Blends of ultraviolet absorbers and polyesters
US5486562A (en) * 1990-07-12 1996-01-23 General Electric Company Modifications of poly(alkylene cyclohexanedicarboxylate) blends
US5489665A (en) * 1991-05-08 1996-02-06 Daicel Chemical Industries, Ltd. Process for producing polycarbonate
US5494992A (en) * 1993-01-29 1996-02-27 Daicel Chemical Industries, Ltd. (Co)polycarbonate and process for producing the same
US5498688A (en) * 1993-04-16 1996-03-12 Daicel Chemical Industries, Ltd. Two-step process for the preparation of a (co)polycarbonate by transesterification
US5498668A (en) * 1994-10-31 1996-03-12 Eastman Chemical Company Blends of certain polyesters with acrylics
US5506014A (en) * 1995-09-01 1996-04-09 Eastman Chemical Company Pet copolyesters containing succinic and naphthalenedicarboxylic acid moieties having improved barrier properties
US5591530A (en) * 1992-10-01 1997-01-07 Minnesota Mining And Manufacturing Company Flexible optically uniform sign face substrate
US5705575A (en) * 1995-05-31 1998-01-06 Shell Oil Company Copolyester composition
US5859116A (en) * 1997-01-21 1999-01-12 Eastman Chemical Company Clarity and adjustable shrinkage of shrink films using miscible polyester blends
US5863622A (en) * 1996-12-05 1999-01-26 Hoechst Celanese Corporation Polarizer laminates comprising coextruded liquid crystal polymer moieties and integral thermoplastic cover layers
US6011124A (en) * 1996-12-28 2000-01-04 Eastman Chemical Company Blends of bisphenol a polycarbonate and polyesters
US6012597A (en) * 1998-03-18 2000-01-11 Mitsubishi Plastics, Inc. Polyester bottle with a handle and method of manufacturing the same
US6022603A (en) * 1996-04-05 2000-02-08 Teijin Limited Ethylene terephthalate/ethylene-2,6-naphthalene-dicarboxylate copolymers for bottles
US6025061A (en) * 1998-04-23 2000-02-15 Hna Holdings, Inc. Sheets formed from polyesters including isosorbide
US6030671A (en) * 1998-01-09 2000-02-29 Msc Specialty Films, Inc. Low emissivity window films
US6037424A (en) * 1996-12-28 2000-03-14 Eastman Chemical Company Clear blends of polycarbonates and polyesters
US6043322A (en) * 1996-12-28 2000-03-28 Eastman Chemical Company Clear polycarbonate and polyester blends
US6044996A (en) * 1995-10-19 2000-04-04 Amcor Limited Hot fill container
US6183848B1 (en) * 1999-06-03 2001-02-06 Eastman Chemical Company Low melt viscosity amorphous copolyesters with enhanced glass transition temperatures having improved gas barrier properties
US6191209B1 (en) * 1999-06-30 2001-02-20 Ciba Specialty Chemicals Corporation Polyester compositions of low residual aldehyde content
US6211309B1 (en) * 1998-06-29 2001-04-03 Basf Corporation Water-dispersable materials
US6221556B1 (en) * 1999-03-05 2001-04-24 General Electric Company Article for optical data storage device
US6342304B1 (en) * 1990-11-30 2002-01-29 Eastman Chemical Company Aliphatic aromatic copolyesters
US6352783B1 (en) * 1999-12-13 2002-03-05 Eastman Kodak Company Copolyester containing 4,4'-biphenyldicarboxylic acid, 1,4-cyclohexanedimethanol and an ultraviolet light absorbing compound and articles made therefrom
US6354986B1 (en) * 2000-02-16 2002-03-12 Gambro, Inc. Reverse-flow chamber purging during centrifugal separation
US6359070B1 (en) * 1998-04-23 2002-03-19 E. I. Du Pont Nemours And Company Polyesters including isosorbide as a comonomer blended with other thermoplastic polymers
US6504002B1 (en) * 2001-12-21 2003-01-07 General Electric Company Process for the production of branched melt polycarbonate by late addition of fries-inducing catalyst
US20030032737A1 (en) * 1999-06-30 2003-02-13 Stephen Andrews Polyester compositions of low residual aldehyde content
US20030060546A1 (en) * 2001-04-11 2003-03-27 Moskala Eric Jon Films prepared from plasticized polyesters
US20030077546A1 (en) * 2001-04-27 2003-04-24 Eastman Kodak Company Photographic elements coated on transparent support with reflective protective overcoat
US20030075516A1 (en) * 1998-01-23 2003-04-24 Pall Corporation Biological fluid treatment system
US20040022526A1 (en) * 2000-03-28 2004-02-05 Yoshiki Kuno Hard disk apparatus, medium, and collection of information
US20040063864A1 (en) * 2002-03-27 2004-04-01 Adams Valerie Sue Polyester/polycarbonate blends with reduced yellowness
US20050008885A1 (en) * 2003-07-11 2005-01-13 Blakely Dale Milton Addition of UV absorbers to PET process for maximum yield
US6846508B1 (en) * 1998-05-06 2005-01-25 Dow Corning France, S.A. Method for adhering substrates using adhesive devices containing silicone gels
US6846440B2 (en) * 1998-03-17 2005-01-25 Eastman Chemical Company Polyester resin compositions for calendering
US20050072060A1 (en) * 2003-09-23 2005-04-07 Moncho Fernando R. Shelter
US20060004151A1 (en) * 2004-06-30 2006-01-05 General Electric Company Copolymers containing indan moieties and blends thereof
US7169880B2 (en) * 2003-12-04 2007-01-30 Eastman Chemical Company Shaped articles from cycloaliphatic polyester compositions
US7354628B2 (en) * 2002-07-24 2008-04-08 Covidien Ag Medical device lubricant comprising radiation curable silicon material
US7482397B2 (en) * 2003-01-13 2009-01-27 Eastman Chemical Company Polycarbonate compositions

Family Cites Families (348)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US360547A (en) * 1887-04-05 Shelving
US873016A (en) 1907-12-10 James Burnham Pneumatic and solid tire for vehicle-wheels.
US516994A (en) * 1894-03-20 Game apparatus
US589404A (en) 1897-09-07 bettini
US300906A (en) * 1884-06-24 William d
US644833A (en) * 1898-11-18 1900-03-06 Sims Hydraulic Engine Company Impact water-motor.
US696854A (en) * 1900-06-06 1902-04-01 Wesley R Cain Lamplighter and match-extinguisher.
US729775A (en) * 1902-06-03 1903-06-02 Arthur E Krause Method of removing oil or oily matter from water.
US858012A (en) * 1906-10-17 1907-06-25 C J De Boor Smoke-consuming furnace.
US1187437A (en) * 1914-08-27 1916-06-13 david r Lucas Ladder-bracket.
NL16356C (en) 1924-07-22
GB478326A (en) * 1936-07-17 1938-01-17 Henry Dreyfus Improvements in the manufacture of ketene, acetic anhydride or a homologue thereof
US2720507A (en) 1952-10-03 1955-10-11 Eastman Kodak Co Organo-metallic tin catalysts for preparation of polyesters
NL104015C (en) 1953-10-16
US2806064A (en) 1954-02-23 1957-09-10 Celanese Corp Production of anhydrous ketenes
DE1007996B (en) 1955-03-26 1957-05-09 Bayer Ag A process for preparing thermoplastics
US3153008A (en) 1955-07-05 1964-10-13 Gen Electric Aromatic carbonate resins and preparation thereof
BE592181A (en) 1955-12-22
US2991273A (en) 1956-07-07 1961-07-04 Bayer Ag Process for manufacture of vacuum moulded parts of high molecular weight thermoplastic polycarbonates
US3148172A (en) 1956-07-19 1964-09-08 Gen Electric Polycarbonates of dihydroxyaryl ethers
US2999846A (en) 1956-11-30 1961-09-12 Schnell Hermann High molecular weight thermoplastic aromatic sulfoxy polycarbonates
US2999835A (en) 1959-01-02 1961-09-12 Gen Electric Resinous mixture comprising organo-polysiloxane and polymer of a carbonate of a dihydric phenol, and products containing same
GB993121A (en) 1959-01-21 1965-05-26 Eastman Kodak Co Linear superpolyester production
FR1291273A (en) 1959-01-21 1962-04-20 Eastman Kodak Co Novel process for the preparation of a linear product obtained superpolyester and
US3075852A (en) * 1959-08-12 1963-01-29 Matthew J Bonora Fingerprinting
US3201474A (en) 1959-09-24 1965-08-17 Eastman Kodak Co Process of manufacturing dialkyl ketenes
FR83790E (en) 1959-12-18 1964-10-09 Kodak Pathe Novel polymers derived from 2, 2, 4, 4-tetraalkyl-1, 3-cyclobutanediols and their industrial applications
FR1278284A (en) 1959-12-18 1961-12-08 Kodak Pathe Novel polymers derived from 2, 2, 4, 4-tetraalkyl-1, 3-cyclobutanediols and their industrial applications
BE615850Q (en) 1960-12-16 1962-07-16 Eastman Kodak Co Novel polymers derived from 2,2,4,4-tetraalkyl-1,3-cyclobutanediols and their industrial applications
US3000906A (en) * 1960-02-05 1961-09-19 Eastman Kodak Co Purification of pivalolactone
US3062852A (en) * 1960-03-30 1962-11-06 Eastman Kodak Co Esters of 2, 2, 4, 4-tetraalkylcyclobutane-1, 3-diols
US3207814A (en) 1961-01-03 1965-09-21 Gen Electric Carbonate-polyester copolymer resinous compositions
GB1002372A (en) 1961-04-25 1965-08-25 Chisso Corp Process for continuously hydrogenating higher aldehydes in liquid phase
US3360547A (en) 1961-05-01 1967-12-26 Eastman Kodak Co Polyesters of tetraalkylcyclobutanediol
US3259469A (en) 1961-07-26 1966-07-05 Eastman Kodak Co Apparatus for manufacturing ketenes
US3218372A (en) 1961-08-18 1965-11-16 Kunoshima Kagaku Kogyo Kabushi Molding material and molded articles
US3287390A (en) 1961-08-21 1966-11-22 Mcneilab Inc 2, 2, 4, 4-tetramethylcyclobutyl compounds
US3254047A (en) * 1961-09-14 1966-05-31 Eastman Kodak Co Additives for increasing modulus of elasticity of polycarbonate films
US3190928A (en) * 1961-09-27 1965-06-22 Eastman Kodak Co Preparation of tetraalkylcyclo-butanediols
US3236999A (en) * 1962-10-01 1966-02-22 North American Aviation Inc Computer having floating point division
DE1520178A1 (en) 1963-02-09 1969-12-04 Kalle Ag A process for the production of polyethylene terephthalate
US3317465A (en) * 1963-06-26 1967-05-02 Robertson Co H H Combination catalyst-inhibitor for betahydroxy carboxylic esters
US3288854A (en) 1963-07-05 1966-11-29 Eastman Kodak Co Addition of dialkylketenes to alkoxyacetylenes
US3329722A (en) 1964-01-10 1967-07-04 Englehard Ind Inc Production of 3-hydroxy-2, 2, 4, 4-tetraalkyl-cyclobutanones
DE1997729U (en) 1964-05-04 1968-12-05 Eastman Kodak Co Apparatus for the production of ketene by pyrolyzing to ketenes cleavable compounds
FR1434658A (en) 1964-05-13 1966-04-08 Eastman Kodak Co to new insulating layer electrical conductors
GB1090241A (en) 1964-05-13 1967-11-08 Kodak Ltd Polyester insulating layers
FR1456345A (en) 1964-12-07 1966-10-21 Eastman Kodak Co New polyester preparation process and products obtained
US3544514A (en) * 1965-01-15 1970-12-01 Bayer Ag Process for the production of thermoplastic polycarbonates
FR1432471A (en) 1965-05-12 1966-03-18 Eastman Kodak Co A process for preparing cyclic diols by catalytic hydrogenation of the corresponding ketones
US3484339A (en) 1966-05-02 1969-12-16 Eastman Kodak Co Blends of polyesters containing free carboxyl groups and laminate thereof
JPS541040B1 (en) 1967-02-17 1979-01-19
US3541059A (en) 1967-04-19 1970-11-17 Calgon C0Rp Novel reaction products of glycidyl esters and alkali metal sulfite or bisulfite,and polymers thereof
US3502620A (en) * 1967-05-11 1970-03-24 Eastman Kodak Co Branched polyesters containing terminal carboxyl groups
US3456177A (en) * 1967-05-29 1969-07-15 Web Press Eng Inc Operational amplifier and regenerative motor control incorporating an operational amplifier
US3504002A (en) * 1967-08-29 1970-03-31 Du Pont Selected 6-difluoromethylene steroids of the pregnane series
US3546008A (en) 1968-01-03 1970-12-08 Eastman Kodak Co Sizing compositions and fibrous articles sized therewith
US3546177A (en) 1968-03-07 1970-12-08 Eastman Kodak Co Polyesters containing sterically hindered trialkyl phosphates
GB1251834A (en) * 1968-04-02 1971-11-03
GB1278284A (en) 1969-08-16 1972-06-21 Norman Wood Improvements in or relating to the manufacture of resonators of stringed musical instruments
US3629202A (en) 1969-09-12 1971-12-21 Eastman Kodak Co Treating polyesters with organic acids for improved stability
UST875010I4 (en) * 1969-11-20 1970-06-09 Defensive publication
US3734874A (en) 1970-02-27 1973-05-22 Eastman Kodak Co Polyesters and polyesteramides containing ether groups and sulfonate groups in the form of a metallic salt
JPS4920078B1 (en) 1970-09-26 1974-05-22
BE774720A (en) 1970-11-02 1972-02-14 Fiber Industries Inc Polyester thermo-stabilized and method for making
BE794938A (en) 1972-02-02 1973-08-02 Eastman Kodak Co New copolyesters METHOD OF PREPARATION AND applications
US3915913A (en) 1972-08-15 1975-10-28 Eastman Kodak Co Hot melt polymer blends
US3845884A (en) 1973-06-05 1974-11-05 Hall & Myers Bottle with an inverted portion support and sealing ring
US3907754A (en) 1974-06-19 1975-09-23 Eastman Kodak Co Process and catalyst-inhibitor system for preparing synthetic linear polyester
DE2431072C3 (en) 1974-06-28 1980-04-30 Bayer Ag, 5090 Leverkusen
US4056504A (en) 1974-08-16 1977-11-01 Bayer Aktiengesellschaft Polycarbonate molding compositions
US3962189A (en) 1974-11-01 1976-06-08 Eastman Kodak Company Process and catalyst-inhibitor systems for preparing synthetic linear polyesters
US4136089A (en) 1975-02-22 1979-01-23 Bayer Aktiengesellschaft Molded articles of crystalline poly (ethylene/alkylene) terephthalates which crystallize rapidly
US4111846A (en) 1977-05-06 1978-09-05 W. R. Grace & Co. Hydrosol and catalyst preparation
US4046933A (en) * 1975-09-16 1977-09-06 Ppg Industries, Inc. Laminated window structure and its method of fabrication
JPS6137091B2 (en) * 1976-01-09 1986-08-22 Mitsui Petrochemical Ind
US4125572A (en) 1976-12-14 1978-11-14 General Electric Company Thermoplastic molding composition
US4391954A (en) 1976-12-14 1983-07-05 General Electric Company Thermoplastic molding composition
US4123436A (en) 1976-12-16 1978-10-31 General Electric Company Polycarbonate composition plasticized with esters
DE2715932C2 (en) 1977-04-09 1989-03-23 Bayer Ag, 5090 Leverkusen, De
US4160383A (en) * 1977-12-27 1979-07-10 Will Ross Inc. Unitary sample-vent-valve assembly
DE2811982A1 (en) 1978-03-18 1979-09-27 Huels Chemische Werke Ag A process for preparing high molecular weight poly (ethylene terephthalate)
US4233196A (en) 1979-04-30 1980-11-11 Eastman Kodak Company Polyester and polyesteramide compositions
DE2921868C2 (en) 1979-05-30 1988-08-25 Obser, Karl, 8000 Muenchen, De
US4238593B1 (en) 1979-06-12 1994-03-22 Goodyear Tire & Rubber Method for production of a high molecular weight polyester prepared from a prepolymer polyester having an optional carboxyl content
JPS6113488B2 (en) 1979-12-21 1986-04-14 Daicel Chem
US4264751B1 (en) 1980-03-12 1992-01-28 Goodyear Tire & Rubber
DE3164692D1 (en) 1980-04-30 1984-08-16 Dainippon Ink & Chemicals Ultraviolet-transmissible composition
JPH038021B2 (en) * 1981-11-13 1991-02-05 Ricoh Kk
US4356299A (en) 1982-02-04 1982-10-26 Rohm And Haas Company Catalyst system for a polyethylene terephthalate polycondensation
US4786692A (en) 1982-12-20 1988-11-22 General Electric Company High strength, reduced heat distortion temperature thermoplastic composition
US4469861A (en) * 1982-12-27 1984-09-04 General Electric Company Polycarbonate composition from branched chain dihydric phenol
US4465820A (en) 1983-06-03 1984-08-14 General Electric Company Copolyestercarbonates
US4452933A (en) * 1983-06-09 1984-06-05 General Electric Company Stabilized polyester-polycarbonate blends and stabilization process therefor
US4480086A (en) 1983-09-09 1984-10-30 Eastman Kodak Company Radiation-resistant copolyesters
US4525504A (en) * 1983-10-24 1985-06-25 Eastman Kodak Company Stabilized polyester compositions suitable for outdoor applications
US4939186A (en) 1984-02-10 1990-07-03 General Electric Company Enhancing color stability to sterilizing radiation of polymer compositions
US4587437A (en) 1984-03-19 1986-05-06 Rockwell International Corporation Coupling/decoupling capacitor multiplier
JPS6199954A (en) * 1984-10-18 1986-05-19 Toray Ind Inc Optical recording medium
US5239020A (en) * 1985-08-21 1993-08-24 Eastman Kodak Company Polyester/polycarbonate blends
EP0273144A3 (en) 1986-12-15 1990-03-21 General Electric Company Cross-linked branched polycarbonate composition
GB8705712D0 (en) 1987-03-11 1987-04-15 Du Pont Canada Lid for food trays
US4733880A (en) * 1987-03-17 1988-03-29 Wilhelm Iii Donald Ridable arm exercise bicycle
US4749773A (en) 1987-07-27 1988-06-07 Eastman Kodak Company Condensation polymers containing methine ultraviolet radiation-absorbing residues and shaped articles produced therefrom
US5326821A (en) 1987-10-28 1994-07-05 Unitika Ltd. Resin composition for powder coatings
US4982342A (en) * 1987-11-05 1991-01-01 Kabushiki Kaisha Toyota Chuo Kenkyusho Image processor system having multifunction look-up table units
US4882412A (en) 1987-11-30 1989-11-21 Eastman Kodak Company Polyester polymer containing the residue of the UV absorbing benzopyran compound and shaped articles produced therefrom
US4846359A (en) 1987-12-18 1989-07-11 The Procter & Gamble Company Multi-layered plastic bottle having integrally formed handle and method of making
JP2873823B2 (en) * 1988-02-15 1999-03-24 大日本印刷株式会社 The packaging bag
GB2216919B (en) 1988-04-08 1991-11-13 Stc Plc Kiosk housing for telephone equipment
GB8817061D0 (en) * 1988-07-18 1988-08-24 Protein Tech Int Functional protein product from vegetable protein materials
US4976057A (en) 1988-07-21 1990-12-11 Bianchi Dennis R Simulated neon sign
JPH0779833B2 (en) * 1988-08-10 1995-08-30 川澄化学工業株式会社 Resistant γ-irradiation of the body fluid treatment device
US4845188A (en) * 1988-08-19 1989-07-04 Eastman Kodak Company Condensation polymers containing methine ultraviolet radiation-absorbing residues and shaped articles produced therefrom
US5000991B2 (en) 1988-12-01 2000-07-11 Sekisui Plastics Process for producing polyester resin foam and polyester resin foam sheet
US4946932A (en) 1988-12-05 1990-08-07 Eastman Kodak Company Water-dispersible polyester blends
DE3926719A1 (en) 1988-12-23 1990-07-05 Bayer Ag Polycarbonates from alkylcyclohexylidenbisphenolen
US4937134A (en) 1989-04-17 1990-06-26 The Dow Chemical Company Elastomeric optical interference films
US5326584A (en) 1989-04-24 1994-07-05 Drexel University Biocompatible, surface modified materials and method of making the same
JPH02305816A (en) * 1989-05-18 1990-12-19 Kuraray Co Ltd Oxygen-permeable molding
JPH03207743A (en) 1990-01-09 1991-09-11 Mitsubishi Rayon Co Ltd Methacrylic resin molded material having excellent transmittance and diffusibility of light
US6288161B1 (en) 1990-01-31 2001-09-11 Pechiney Emballage Flexible Europe Barrier compositions and articles made therefrom
CA2035149A1 (en) 1990-02-06 1991-08-07 Charles E. Lundy Blends of polycarbonates and aliphatic polyesters
US5224958A (en) 1990-05-04 1993-07-06 The Research Foundation Of State University Of New York Silicone elastomer line prosthetic devices and methods of manufacture
DE4036359A1 (en) 1990-11-15 1992-05-21 Hoechst Ag A process for reducing the discoloration of a plastic molding composition at the processing temperature
US6495656B1 (en) 1990-11-30 2002-12-17 Eastman Chemical Company Copolyesters and fibrous materials formed therefrom
US5118760A (en) 1990-12-26 1992-06-02 Eastman Kodak Company Impact resistant polymer blends
US5142088A (en) 1991-01-28 1992-08-25 General Electric Company Preparation of branched polycarbonates and chloroformates, and intermediates therefor
US5310787A (en) 1991-06-04 1994-05-10 Du Pont-Mitsui Polychemicals Co., Ltd. Polyester packaging material
EP0544008B1 (en) 1991-06-17 1996-03-27 Seiko Epson Corporation Phase difference elemental film, phase difference plate and liquid crystal display using same
US5254610A (en) * 1991-08-02 1993-10-19 Eastman Kodak Company Polyester/polycarbonate blends containing phosphites
US5169994A (en) 1991-08-20 1992-12-08 Eastman Kodak Company Process for the manufacture of 2,2,4,4-tetramethycyclobutanediol
US5256761A (en) 1991-09-23 1993-10-26 Eastman Kodak Company Polyester coatings containing covalently-bound mesogenic monomers
DE69216343T2 (en) * 1991-10-04 1997-07-31 Oki Electric Ind Co Ltd A thermoreversible recording material, and thermoreversible recording method using this material
US5217128A (en) 1991-10-28 1993-06-08 Johnson Enterprises, Inc. Thermoplastic bottle with reinforcing ribs
FR2682956B1 (en) 1991-10-29 1994-01-07 Rhone Poulenc Chimie water-soluble polyester preparation process and / or water-dispersible and use of these polyesters for sizing textile son.
JP2797804B2 (en) 1992-01-09 1998-09-17 日本電気株式会社 Backlight and a liquid crystal display device
BE1006297A3 (en) 1992-10-26 1994-07-12 Axxis Nv Plastic sheet, process for the production thereof and shape parts containing the plate.
US5258556A (en) 1993-02-01 1993-11-02 Eastman Kodak Company Process for the manufacture of 2,2,4,4-tetramethylcyclobutanediol
US5372879A (en) 1993-02-22 1994-12-13 Teijin Limited Biaxially oriented polyester film
US5463011A (en) * 1993-06-28 1995-10-31 Zeneca Limited Acid derivatives
WO1995005413A1 (en) 1993-08-12 1995-02-23 Eastman Chemical Company Water-dispersible acrylic-modified polyester resins used in coatings and process for their preparation
US5474735A (en) 1993-09-24 1995-12-12 Continental Pet Technologies, Inc. Pulse blow method for forming container with enhanced thermal stability
US5354791A (en) 1993-10-19 1994-10-11 General Electric Company Epoxy-functional polyester, polycarbonate with metal phosphate
US5413870A (en) 1994-01-03 1995-05-09 Flood; Christopher J. Decorative bathroom panel including embedded fabric
US5475144A (en) 1994-06-08 1995-12-12 The University Of Delaware Catalyst and process for synthesis of ketenes from carboxylic acids
DE4425143A1 (en) * 1994-07-15 1996-01-18 Basf Ag Substituted pyrimidine compounds and their use
US5543488A (en) 1994-07-29 1996-08-06 Eastman Chemical Company Water-dispersible adhesive composition and process
DE69529032D1 (en) 1994-08-25 2003-01-16 Nippon Kokan Kk Copolyester polymer blending and packaging material from
US5442036A (en) 1994-09-06 1995-08-15 Eastman Chemical Company Branched copolyesters especially suitable for extrusion blow molding
US6162890A (en) 1994-10-24 2000-12-19 Eastman Chemical Company Water-dispersible block copolyesters useful as low-odor adhesive raw materials
DE69532875T2 (en) 1994-10-24 2004-08-19 Eastman Chemical Co., Kingsport Water-block copolyester
EP0714764A3 (en) 1994-12-02 1997-03-05 Gen Electric Improved impact resistant laminate
US5534609A (en) 1995-02-03 1996-07-09 Osi Specialties, Inc. Polysiloxane compositions
CA2171584A1 (en) 1995-04-11 1996-10-12 James P. Mason Compositions having low birefringence
US5650453A (en) 1995-04-28 1997-07-22 General Electric Company UV curable epoxysilicone blend compositions
JP3153437B2 (en) * 1995-05-11 2001-04-09 電気化学工業株式会社 Polyester-based multi-layer sheet and the container and its manufacturing method
JP4025890B2 (en) * 1995-06-22 2007-12-26 スリーエム カンパニー Encapsulated lens retroreflective sheeting
US5646237A (en) 1995-08-15 1997-07-08 Eastman Chemical Company Water-dispersible copolyester-ether compositions
JP3200338B2 (en) 1995-08-30 2001-08-20 帝人株式会社 The method of producing an aromatic polycarbonate
US5624987A (en) * 1995-09-15 1997-04-29 Brink; Andrew E. Polyalkylene ethers as plasticizers and flow aids in poly(1,4-cyclohexanedimethylene terephthalate) resins
US5868704A (en) 1995-09-18 1999-02-09 W. L. Gore & Associates, Inc. Balloon catheter device
US5633340A (en) * 1995-09-21 1997-05-27 Eastman Chemical Company Polyester molding compositions
US5696176A (en) 1995-09-22 1997-12-09 Eastman Chemical Company Foamable polyester compositions having a low level of unreacted branching agent
US5552512A (en) 1995-10-06 1996-09-03 Eastman Chemical Company Thermoplastic copolyesters having improved gas barrier properties
JPH09135896A (en) * 1995-11-17 1997-05-27 Shimadzu Corp Artificial organ module
US5608031A (en) 1995-11-30 1997-03-04 Eastman Chemical Company Polyesters modified with 1,4-cyclohexaned imethanol having high clarity prepared utilizing an antimony containing catalyst/stabilizer system
US5643666A (en) 1995-12-20 1997-07-01 Eastman Chemical Company Solid surfaces which are prepared from copolyesters laminated onto a high resolution image
US5688874A (en) 1995-12-22 1997-11-18 Eastman Chemical Company Process for preparing blends of poly(ethylene terephthalate) and poly(ethylene 2,6-naphthalenedicarboxylate)
US5656715A (en) 1996-06-26 1997-08-12 Eastman Chemical Company Copolyesters based on 1,4-cyclohexanedimethanol having improved stability
US5977347A (en) 1996-07-30 1999-11-02 Daicel Chemical Industries, Ltd. Cellulose acetate propionate
US5814679A (en) 1996-10-18 1998-09-29 General Electric Company Premium release photo-curable silicone compositions
US5783307A (en) 1996-11-04 1998-07-21 Eastman Chemical Company UV stabilized multi-layer structures with detectable UV protective layers and a method of detection
US5955565A (en) 1996-12-28 1999-09-21 Eastman Chemical Company Polyesters from terephthalic acid, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and ethylene glycol
US6005059A (en) 1996-12-28 1999-12-21 Eastman Chemical Company Clear polycarbonate and polyester blends
US5942585A (en) * 1996-12-28 1999-08-24 Eastman Chemical Company Polycarbonate and polyester blends
US5989663A (en) 1996-12-30 1999-11-23 Eastman Chemical Company Blow-molding polyesters from terephthalic acid, 2, 2, 4, 4-tetramethyl-1,3-cyclobutanediol, and ethylene glycol