Organic compounds -- part of the class 532-570 series – Organic compounds – Polycyclo ring system containing anthracene configured ring...
Reexamination Certificate
2001-10-19
2004-03-30
Seidleck, James J. (Department: 1711)
Organic compounds -- part of the class 532-570 series
Organic compounds
Polycyclo ring system containing anthracene configured ring...
C552S238000, C552S003000, C552S003000, C552S003000, C552S003000, C552S003000, C552S100000, C552S104000, C552S109000, C552S109000, C552S109000, C430S517000, C430S521000, C430S533000, C528S271000, C528S272000, C528S274000, C528S288000, C528S291000, C008S489000, C008S512000
Reexamination Certificate
active
06713641
ABSTRACT:
FIELD OF THE INVENTION
The present invention pertains to certain novel blue, diol anthra-quinone blue colorant compounds having excellent thermal stability and which can be reacted into or copolymerized with polyester thus providing a blue-colored polyesters useful for manufacturing a variety of shaped articles such as photographic film base, particularly roentgenographic (X-ray) film. This invention also pertains to certain novel blue anthraquinone colorant compounds which contain two ethylenically-unsaturated (vinyl), photo-polymerizable radicals which may be derived from the aforesaid diol anthraquinone compounds. The anthraquinone colorant compounds containing two ethylenically-unsaturated may be reacted into or copolymerized (or cured) with ethylenically-unsaturated monomers to produce colored vinyl polymers.
BACKGROUND
X-ray film typically contains a blue colorant to facilitate the perception of the photographic image. The blue-tinted film bases serve to prevent the disadvantages with roentgenographic materials in which a photographic emulsion is provided on both surfaces of the film support and wherein a filter desensitization action results in that the photographic images have a yellow fog or haze, thus interfering with the image definition. It is desirable that the blue colorant (or toner) has a minimum light absorbance in the short wavelength region in the visible light absorption spectrum, particularly in the 400-450 nm range so that no additional yellow color be introduced into the film. Blue colorants for X-ray film also should be thermally stable, soluble in the polyester, resistant to sublimation and stable to conditions that may be encountered during storage, such as high humidity. The colorant must have no adverse effect upon the gelatin-silver halide emulsion coated onto the blue-colored film base.
It is known to use various blue anthraquinone colorant compounds to impart the necessary blue hue to the polyester, e.g., poly(ethylene terephthalate), particularly 1,4-bis(2′,6′-dialkylanilino)anthraquinone compounds as well as blue anthraquinone dyes containing hydroxy and arylamino groups. See, for example, the anthraquinone compounds disclosed in U.S. Pat. Nos. 3,488,195; 3,849,139; 3,918,976; and 3,933,502. In the prior art, the tinted poly(ethylene terephthalate) (PET) is colored by the so-called dope dyeing method which involves drying PET pellets, mixing the colorant with the PET, followed by heating the mixture, extruding, stretching and heat-treating the melt and forming it into film. Without the drying step, the starting polyester will undergo hydrolysis upon heat-melting, which results in polymer degradation which produces film having inferior and inadequate properties. The colorant compounds must possess sufficient heat stability to withstand molding or extrusion temperatures as high as 270° C.-300° C. For color control, it also is desirable to prepare a masterbatch by blending PET pellets or chips with the colorant using a dry blending method followed by kneading and melt extruding to produce a colored concentrate composition, e.g., a colorant concentration of about 1%. The masterbatch then is mixed with additional uncolored PET pellets and melt blended and extruded to produce a polyester, typically in the form of pellets, having a total colorant content of about 100-400 parts per million be weight (ppmw).
In the coloring process described above, it is necessary, of course, to use a colorant that can be readily dispersed and dissolved in a polyester to achieve uniformity during the extrusion process, since the film support must have a high degree of transparency and be completely free of optical imperfections. Problems associated with the above-described process include sublimation and volatility problems encountered during the extruding and heat stretching steps, resulting in loss of colorant and contamination of equipment and surrounding areas. Also, when a masterbatch is required to achieve uniformity, the step added by formation of the masterbatch increases the costs to the overall coloration process. In either case, the required handling of dry powder colorant is hazardous and results in unavoidable contamination problems. Furthermore, uniformity problems are encountered unless melt blending and extruding times are extended to ensure adequate mixing and solubilization of the colorant.
It also is known to color polyesters such as PET by adding the colorants during the polyester preparation step, e.g., as described in U.S. Pat. No. 3,488,195, column 2, lines 43-45. Such addition of a colorant during polyester synthesis occasions longer periods of time at high temperature causing more pronounced problems of colorant volatility resulting in loss of dye by sublimation. Also, colorants having higher thermal stability are needed. Furthermore, the blue anthraquinone dyes having aromatic hydroxy groups and arylamino groups change shades usually toward green under polyester manufacturing conditions, presumably as a result of metalization, rendering the resulting colored polyester unsuitable for use in manufacturing X-ray film.
U.S. Pat. No. 5,372,864 discloses certain 1,4-bis(2′,6′-dialkylanilino)-anthraquinone colorant compounds substituted with sulfonamide groups which contain polyester-reactive groups and which have been copolymerized into polyesters at low levels. Efforts to utilize the disclosed reddish-blue colorants of Formula I U.S. Pat. No. 5,372,864 to color polyesters by copolymerization during polyester manufacture have provided colored polyesters wherein the blue colorant is too hypsochromic, i.e., too red, in color to be suitable as toners or colorants for X-ray film and require the addition of second colorant compound such as a cyan phthalocyanine, e.g., as described in U.S. Pat. No. 5,744,294. WO 92/13921 discloses various functionalized chromophores, including anthraquinone colorant compounds and the copolymerization of the functionalized chromophores into polyesters to prepare color concentrates. The color concentrates are used as colorants for a variety of thermoplastic polymeric materials including polyesters. However, WO 92/13921 does not describe any anthraquinone colorant compound which is suitable for the tinting or coloration of X-ray film. Similarly, Solvent Blue 45 having the formula:
has been proposed as a colorant for X-ray film. However, Solvent Blue 45 also is too red and greener blue dyes are recommended for shading to produce a more neutral blue colorant system. See, for example, Japanese patent documents JP 55-038825 A2 and JP 62-061065 B4. The addition of a second dye, of course, greatly contributes to the difficulty of color control.
As stated above, the present invention also pertains to certain novel blue anthraquinone colorant compounds which contain at least two ethylenically-unsaturated, photopolymerizable radicals which may be reacted into or copolymerized (or cured) with ethylenically-unsaturated monomers to produce colored vinyl polymers. It is known (J.S.D.C., April 1977, pp 114-125) to produce colored polymeric materials by combining a reactive polymer such as terepolymers having epoxy groups or polyacryloyl chloride with anthraquinone dyes containing nucleophilic reactive groups such as amino or hydroxy groups; to graft acryloylaminoanthraquinone dyes to the backbone of vinyl or divinyl polymers; and to polymerize anthraquinone dyes containing certain olefinic groups to produce polymeric dyes/pigments. U.S. Pat. No. 4,115,056 describes the preparation of blue, substituted 1,4-diaminoanthraquinone dyes containing one acryloyloxy group and the use of the dyes in coloring various fibers, especially polyamide fibers. U.S. Pat. No. 4,943,617 discloses liquid crystalline copolymers containing certain blue, substituted 1,5-diamino-4,8-dihydroxy-anthraquinone dyes containing an olefinic group copolymerized therein to provide liquid crystal copolymers having high dichromism. U.S. Pat. No. 5,055,602 describes the preparation of certain substituted 1,4-diamino-anthraquinone dyes containing polym
Cyr Michael John
Pearson Jason Clay
Rhodes Gerry Foust
Weaver Max Allen
Wells Sara Stanley
Blake Michael J.
Eastman Chemical Company
Graves, Jr. Bernard J.
McClendon Sanza L.
Seidleck James J.
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