US 20110124837Al (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0124837 A1 Hong et al. (43) Pub. Date: May 26, 2011 (54) POLYMERIC VIOLET ANTHRAQUINONE (52) US. Cl. ....................................... .. 528/226; 528/220 COLORANT COMPOSITIONS AND METHODS FOR PRODUCING THE SAME (57) ABSTRACT (76) Inventors: Xiaoyong Michael Hong, Greer, This invention relates to polymeric violet anthraquinone SC (US); Robert L. Mahaffey, colorants having at least one poly(oxyalkylene) chain Spartanburg, SC (U S) attached to an anthraquinone structure. Such colorants exhibit bright violet shade, excellent compatibility With organic (21) Appl. No.: 12/624,646 media or aqueous systems, good lightfastness, and excellent thermal stability. The Water soluble poly(oxyalkylene) sub (22) Filed: Nov. 24, 2009 stituted polymeric violet anthraquinone colorants also pos sess high Water solubility, high color strength, non-staining Publication Classi?cation properties, and high pH stability. The processes and methods (51) Int. Cl. for making such polymeric violet anthraquinone colorants C08G 16/00 (2006.01) and their use for coloring consumer products are also pro C08G 75/00 (2006.01) vided. US 2011/0124837 A1 May 26, 2011 POLYMERIC VIOLET ANTHRAQUINONE creams or pastes. Similar to the acid dyes described above, COLORANT COMPOSITIONS AND these compositions cause staining to the substances to Which METHODS FOR PRODUCING THE SAME they are applied. In this instance, it is desirable to use staining anthraquinone colorants for dyeing human hair. Thus, the FIELD OF THE INVENTION colorants taught by Kaiser et al. are not polymeric in nature, and they are not non-staining. Additionally, the colorants [0001] This invention relates to compositions of polymeric taught by Kaiser et al. preferably contain tWo nitrogen-con violet anthraquinone colorants, to processes for making the taining primary groups on the anthraquinone radical. compositions, and also to the use of the compositions thus [0006] US. Pat. Nos. 1,881,752 and 2,014,810 to Lodge et prepared for coloring consumer products. The colorants are al., US. Pat. No. 2,117,569 to Peter and US. Pat. No. 2,580, generally characterized as being Water soluble, non-staining 190 to Peter et al. described several anthraquinone dyestuffs, and pH stable. including anthraquinone violet dyes. US. Pat. No. 3,689,510 to Kolliker et al. describes a class of Water soluble BACKGROUND OF THE INVENTION anthraquinone dyes With an iO4COOR group in at least one [3-position. These dyes may be used for dyeing synthetic [0002] Anthraquinone dyes have been Widely used to dye polyester ?bers and exhibit good fastness to light and subli fabrics, such as cotton, polyester, acrylic, Wool, cellulose mation. US. Pat. No. 3,715,373 to AndreWs disclosed a pro acetate, nylon, and the like, due to their excellent light fast cess to prepare 1,4-diamino-2-alkoxy or phenoxy ness, uniform leveling, dye bath stability, and shade bril anthraquinone dyestuffs from an acyl-substituted 1,4-di liancy. Anthraquinones are also Well knoWn for use as color amino-2-haloanthraquinone in a inert solvent. David O. ing agents for providing coloration to oils, drugs, cosmetic UkponmWan and et al. in J. Chem. Eng. Data 1984, Vol. 29, pp. 482-483 and 1987, Vol. 32, pp 282-284, synthesiZed a products, paper, rubber, printing inks, plastics, coatings, series of 1-amino-4-(arylamino)anthraquinone 2-ether and leather, Waxes, and detergents. These types of anthraquinone 1,4-Bis(arylamino)-2-(aryloxy)anthraquinone dyes used for dyes may be classi?ed as acid dyes, disperse dyes, vat dyes, dyeing synthetic polymer ?bers. HoWever, these references metalliZable dyes, direct dyes, solvent dyes, basic dyes, reac teach the manufacture of small molecule anthraquinone dyes. tive dyes, and the like. Thus, no teaching or fair suggestion of polymeric versions of [0003] Many violet anthraquinone dyes are knoWn. Com such dyestuffs is knoWn, nor is it taught or fairly suggested mercially available examples of violet anthraquinone dyes that these colorants could be used for coloring consumer include Acid Violet 39, Acid Violet 41, Acid Violet 42, Acid products. Violet 43, AcidVlolet 48,AcidViolet 5 1, AcidViolet 34, Acid [0007] Great Britain Patent No. 859,283 teaches Water Violet 47, Acid Violet 109, Acid Violet 126, Basic Violet 24, soluble anthraquinone dyestuffs useful for dyeing ?bers, BasicViolet 25, DisperseViolet 1, DisperseViolet 4, Disperse leather and paper. The Water solubility is introduced by sul Violet 26, Disperse Violet 27, Disperse V1olet 28, Disperse fonic acid, sulfuric, or carboxylic acid groups on the Violet 57, Solvent Violet 11, Solvent Violet 13, Solvent Violet anthraquinone dye molecule. These are small molecules 14, Solvent Violet 26, Solvent Violet 28, Solvent Violet 31, Which contain triaZine units and ionic groups to make them Solvent V1olet 36, Solvent Violet 37, Solvent Violet 38, Sol Water soluble. These dyes are also generally blue in nature. ventViolet 48, SolventViolet 59, SolventViolet 60, Vat Violet [0008] Other anthraquinone colorants, such as 1,4-disub 13, Vat V1olet 15, Vat Violet 16. HoWever, these violet stituted aliphatic aminoanthraquinones, are disclosed in US. anthraquinone dyes are not polymeric in nature, and they tend Pat. No. 4,846,846 to Rekers et al. Wherein anthraquinones to exhibit stability, gelling and precipitation challenges When Were prepared from a mixture of quiniZarin, leucoquiniZarin, and amine in Water folloWed by various puri?cation proce incorporated into other formulations, such as detergent for dures. The preferred amines are sec-alkyl primary amines mulations and other consumer cleaning products. Further With terminal reactive groups, such as 40H, iNHZ, or more, the Water soluble violet anthraquinone dyes, such as iSH, on the end of the amine moiety. These anthraquinone acid violet dyes, are knoWn to cause staining to textile sub colorants are used to color polyurethane resins, particularly strates (such as fabrics), skin, and other surfaces. Thus, they foams. are not suitable for use in applications Where non-staining [0009] US. Pat. No. 4,137,243 to Farmer discloses poly colorants are desired, such as in Washable markers and paints meric anthraquinone colorants With terminal amino groups and in cleaning formulations such as laundry detergents and from leucoquiniZarin and polymeric diamines. The leucoqui fabric softeners. niZarin can be generated in-situ by reduction of quiniZarin [0004] Furthermore, these anthraquinone violet dyes are With sodium hydrosul?te. The polymeric aminoan generally provided in poWder form Which is often dif?cult to thraquinone colorants prepared according to the above patent handle. While these dyes may be made into liquid form by processes tend to contain high levels of impurities, such that dissolving the dye in Water or organic liquid, the solubility of further puri?cation is needed to obtain higher purity such liquid dyes is loW and the resulting liquid dye solutions anthraquinone colorants. Puri?cation of loW melting or liquid tend to have very loW color strength. Color strength, or color Water-soluble anthraquinone colorants usually involves time value, is determined using a modi?ed version of AATCC Test consuming extraction and Washing procedures that often Method 182-2000 Wherein the color value is determined and require organic solvents, Which generally are not environ calculated on the absorbance of a 1 gram per liter through a mentally friendly. Additionally, these solvents are typically one centimeter cell length of the colorant, in the appropriate not suitable for use in many consumer product applications solvent, by UV-vis spectroscopy. and complete removal is required. The organic solvents are [0005] Attempts by others to make violet anthraquinone often expensive and generate additional Waste during produc colorants include US. Pat. No. 3,192,117 to Kaiser et al., tion of the anthraquinone colorants. Furthermore, some of the Which provides some examples of violet anthraquinone com impurities in these anthraquinone colorants are often dif?cult positions useful as hair dyes. These colorants exhibit good to ?lter and generally cause dull color, shade shift, and stain dyeing ability When they are incorporated into the dyeing ing. US 2011/0124837 A1 May 26, 2011 [0010] Us. Pat. Nos. 4,224,228 and 4,244,691 to Adam Wherein: disclose Water soluble anthraquinone dyes in the form of free [0016] Al is selected from the group consisting of hydro acid having one or more iSO3H group on the anthraquinone gen, alkyl, hydroxyalkyl, polyoxyalkylene, and aryl; conjugated system. These anthraquinone dyes are used for [0017] X is a linking group andis selected from the group dyeing or printing textile materials, such as natural and syn consisting of oxygen and sulfur; thetic polyamide ?bers, and exhibit good dye uptake and [0018] A2 is selected from the group consisting of alkyl fastness to Wet-processing. Optionally, these anthraquinone or aryl having no polymer chains; a polyoxyalkylene dyes have ?ber-reactive groups, such as acryloyl, vinylsulfo moiety or an aryl linked polyoxyalkylene moiety With nyl, chloroacetyl, ?uorotriaZinyl radicals, and bromoacryloyl greater than three repeating units and terminated With a hydroxyl or alkyl or aryl; and an aryl group further groups. substituted by Y-A3 Wherein the aryl group is selected [0011] Us. Pat. No. 6,022,944 to Weaver et al. discloses from phenylene or a substituted phenylene moiety; Y is colored anthraquinone or condensed anthraquinone com a linking group and is selected from the group consisting pounds With one or more sulfonamido linkages and poly of oxygen, nitrogen, sulfonyl, sulfonamido, and car (oxyalkylene) moieties. These colorants exhibit improved boxyl; Water dispersibility and compatibility With other organic [0019] A3 is a polyoxyalkylene moiety terminated With a compounds. HoWever, the process to make these colorants hydroxyl or alkyl or aryl group; involves adding one or more iSOZCI groups on the conju [0020] A4 is selected from the group consisting of hydro gated rings, Which is dif?cult and involves hard-to-handle gen; an aryl group that is optionally substituted With reagents.