USOO6635350B2 (12) United States Patent (10) Patent No.: US 6,635,350 B2 Connor et al. (45) Date of Patent: Oct. 21, 2003 (54) POLYMERIC 1,5- OR 18-DISUBSTITUTED 5,882,358 A * 3/1999 Smith et al. ................... 8/527 ANTHRAQUINONE-DERIVATIVE 6,447,591 B1 * 9/2002 Titterington et al...... 106/31.29 COLORANTS AND ARTICLES COMPRISING SUCH COLORANTS * cited by examiner (75) Inventors: Daniel M. Connor, Inman, SC (US); John W. Miley, Jr., Campobello, SC Primary Examiner Ramsey Zacharia (US) (74) Attorney, Agent, or Firm Terry T. Moyer; William S. (73) Assignee: Milliken & Company, Spartanburg, SC Parks (US) (57) ABSTRACT (*) Notice: Subject to any disclaimer, the term of this Red colorants comprising a chromophore having at least one patent is extended or adjusted under 35 poly(oxyalkylene) chain attached to the 1-position, as well U.S.C. 154(b) by 137 days. as at least one poly(oxyalkylene) chain attached to either. the (21) Appl. No.: 09/981,279 5-position or the 8-position of an anthraquinone backbone are provided. Such colorants exhibit excellent base stability, (22) Filed: Oct. 16, 2001 effective colorations, excellent low extraction rates, and high (65) Prior Publication Data lightfastness levels, particularly when incorporated within US 2003/0096118 A1 May 22, 2003 certain media and/or on the Surface of certain Substrates, (51) Int. Cl." ........................... B32B 9/00; CO7C 50/18; pits S. isol) sh CO7C 50/24; CO7C 50/26; CO9B 1/16 increase C solu IIIly in CCL SOTWCS O resins ereby (52) U.S. Cl. .................... 428/411.1; 106/493; 552/208; permitting the introduction of Such excellent coloring chro 552/238; 552/255; 552/258 mophores within diverse media and/or diverse Substrates as (58) Field of Search .......................... 106/493; 552/208, well as provides a liquid colorant which facilitates handling. 552/238, 255, 258; 428/411.1 Compositions and articles comprising Such colorants are (56) References Cited provided as well as methods for producing Such inventive colorants are also provided. U.S. PATENT DOCUMENTS 4,999,418 A 3/1991 Krutaka et al. ............. 528/272 10 Claims, No Drawings US 6,635,350 B2 1 2 POLYMERIC 1,5- OR 1,8-DISUBSTITUTED provide decorative, aesthetic, and other like effects. ANTHRAQUINONE-DERIVATIVE However, the chromophores present within Such dyes, COLORANTS AND ARTICLES COMPRISING pigments, and the like, are highly desired for the hues and SUCH COLORANTS shades they provide within the ultimate thermoplastic articles themselves. Facilitating the introduction of Such chromophores within Such formulations is thus a highly FIELD OF THE INVENTION desired target within the colored thermoplastic industry, whether it be in terms of handling, extraction, cleaning, or This invention relates to red colorants comprising a chromophore having at least one poly(oxyalkylene) chain the like. attached to the 1-position, as well as at least one poly Attempts to meet this desire have included the introduc (oxyalkylene) chain attached to either the 8-position or the tion of certain Standard types of polymeric colorants within 5-position of an anthraquinone backbone. Such colorants plastics (be they thermoplastic-or thermoset-types). These exhibit excellent thermal stability, effective colorations, colorants are primarily poly(oxyalkylenated) compounds, excellent low extraction rates, and high lightfastneSS levels, Such as triphenylmethanes, methines, and the like (i.e., those 15 found within U.S. Pat. No. 4.992,204, to Kluger et al.). particularly when incorporated within certain media and/or Some of these colorants exhibit certain problems during on the Surface of certain Substrates, particularly polyesters. incorporation into thermosets and thermoplastics. In ther The poly(oxyalkylene) chains also increase the Solubility in moplastic compositions Such as polyesters, many of these different Solvents or resins thereby permitting the introduc previously disclosed compositions are not stable at the tion of Such excellent coloring chromophores within diverse polyester processing temperatures. As a result, the colora media and/or on diverse Substrates as well as provides a tions provided by Such polymeric colorants may be reduced liquid colorant which facilitates handling. Compositions and in Strength or changed in Shade under Such circumstances. articles comprising Such colorants are provided as well as Other types of colorants have been discussed within the methods for producing Such inventive colorants. prior art, Such as azOS and bisaZOS, but the Specific colora DISCUSSION OF THE PRIOR ART 25 tions provided by Such compounds are limited to certain hues and their utilization within polyesters is Suspect from a All U.S. patents cited within this specification are hereby number of perspectives (Such as thermal Stability, and the incorporated by reference. like). There is thus a desire to introduce new types of There continues to be a need to provide Versatile colorants colorants comprising different types of chromophores for the within various applications Such that the coloring agent itself purpose of providing new, effective, versatile colorants for exhibits excellent colorations (particularly at low color Such myriad end-uses as noted above and that exhibit loadings due to inherently high absorption), high thermal excellent colorations, extraction, thermal Stability, mixing stability, effective lightfastness, low extraction (or drastic with other coloring agents, and low toxicity, at least. reduction in possibility of removal therefrom via extraction One approach to obtain the desired coloration has been to by Solvents or like Sources), ease in handling, ability to mix 35 use difunctional dyes that possess the necessary pendant thoroughly with other coloring agents and thus to provide groups to allow them to be copolymerized into a thermo effective different hues and tints within or on target plastic like polyester. This approach is exemplified by U.S. Substrates, and acceptable toxicity levels. There has been a Pat. No. 4,999,418 to Krutak et al. Though such a method need to provide improved colorants meeting this criteria for provides effectively colored thermoplastics with good per certain thermoplastic media, Such as polyesters, Such that the 40 formance Such as excellent extraction (due to the copoly colorants themselves exhibit excellent compatibility therein merized nature of the dyes), good lightfastness, low toxicity, (for instance in terms of dispersion and the other character and the like, there are many drawbacks to Such technology. istics desired for Such plastics as noted above). In particular, Primarily, such drawbacks include the necessity for Such characteristics for polyesters are desired for colorants extremely thermally stable chromophores because the colo that impart, for example, though not necessarily, a red Shade. 45 rant must Survive in the reactor for extended periods of time Other hues are available as well for Such a desired, high in addition to the heat history afforded by the molding of the performing polyester plastic colorant, including Violet, as finished article (e.g., Such thermal stability requirements one example, dependent on the presence of certain coupling greatly limit the Selection of hues and often provides for or modifying moieties present on the chromophore back more expensive colorant molecules). Another drawback is bone itself. It is believed and, as noted above, has been 50 the necessity of dedicating a high cost polyester production determined, that Such desirable polyester plastic colorations vessel to color due to the inherent contamination of the with the characteristics noted above are possible through the vessel by the colorant (which invariably limits flexibility in addition of certain pendant groups to the chromophore manufacturing of resins). Furthermore, another drawback is backbone which do not act as couplers or color modifiers the necessity of the end user or article manufacturer to Store Such as, for example poly(oxyalkylene) groups and thus 55 large amounts of colored resins of different shades which any chromophore (and resultant hue or tint) may be utilized limits the flexibility and adds cost to the end user. The with the desired anthraquinone chromophore itself. colorants disclosed, for example within U.S. Pat. No. 4,499, Previous coloring agents for Such end-uses have included 418, are inherently powdered or like Solid in nature and thus pigments, dyes, or dyestuffs, with each having its own are not Suitable for direct addition to the molten plastic drawback, be it an extraction problem from the finished 60 during any injection molding Step, as one example. Such article, a handling problem during manufacturing due to powdered coloring agents are developed Solely for actual Solid dust particles, a Staining problem, due to the difficulty polymerization within the target resin prior to any molding, asSociated with cleaning Such coloring agents from manu injection, and other like proceSS Step. Drawbacks, thus, to facturing machinery after colored plastic production, and these powdered types include undesirable dusting, contami other like issues. As a result, there is a clear desire to provide 65 nation and Staining of equipment, clogging (during feeding easier to handle, leSS eXtractable, easy-to-clean, etc., color into the molten resin, for example), and poor control of ing agents for introduction within thermoplastic articles to metering during coloring of the target resin within and/or at US 6,635,350 B2 3 4 the molding