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 (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. are also Well knoWn for use as color amino-2-haloanthraquinone in a inert . 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 , 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. alkyl, polyoxyalkylene, or sulfonate moieties, or com [0012] Us. Pat. No. 6,593,483 to Xia describes a poly binations thereof; an alkyl group that is optionally sub meric blue anthraquinone colorant, Wherein a poly(oxyalky stituted With polyoxyalkylene, hydroxyl, alkoxyl, car lene) chain is attached to the 1-position, or/ and the 4-position boxylic acid or ester, sulfonate, or sulfate groups; and a through aromatic amino group(s) on an anthraquinone back cyclohexyl group that is optionally substituted With one bone. U.S. Pat. No. 6,635,350 to Connor et al. discloses a or more alkyl or polyoxyalkylene groups; and polymeric red anthraquinone colorant, Where at least one [0021] A5-A8 are independently selected from the group poly(oxyalkylene) chain is attached to the 1-position, as Well consisting of hydrogen, halogen, nitro, amino, alky as at least one poly(oxyalkylene) chain is attached to either lamino, arylamino moieties, and combinations thereof. the 5-position or the 8-position of an anthraquinone back [0022] Also provided herein is a polymeric violet bone. anthraquinone colorant comprising a compound represented [0013] Thus, there is a need for a polymeric violet by structure (IV): anthraquinone colorant that exhibits excellent light and pH stability, that is compatible With other materials, and that is suitable for use in coloring various consumer products. The (IV) A colorant is also desirably non-staining and Water soluble With A8 0 HN/ 1 bright shades. [0014] Accordingly, one object of this invention is to pro A7 0 _A2 vide a polymeric violet anthraquinone colorant, preferably a 1,4-diamino-2-polyalkyleneoxy violet anthraquinone colo rant, that exhibits bright shades, high pH stability, good light A6 fastness and compatibility With other materials. Another object of this invention is to provide methods to make such A5 0 HN anthraquinone colorants. A further object of this invention is \A4 to use these inventive colorants for coloration of consumer products, such as liquid and solid laundry detergents and Wherein: liquid fabric softeners. [0023] Al is selected from the group consisting of hydro gen, alkyl, hydroxyalkyl, polyoxyalkylene, and aryl; SUMMARY OF THE INVENTION [0024] A2 is selected from the group consisting of alkyl or aryl having no polymer chains; a polyoxyalkylene [0015] Provided herein is a polymeric violet anthraquinone moiety or an aryl linked polyoxyalkylene moiety With colorant comprising a compound represented by structure (I): greater than three repeating units and terminated With a hydroxyl or alkyl or aryl; and an aryl group further substituted by Y-A3 Wherein the aryl group is selected from phenylene or a substituted phenylene moiety; Y is (1) a linking group and is selected from the group consisting of oxygen, nitrogen, sulfonyl, sulfonamido, and car boxyl; [0025] A3 is a polyoxyalkylene moiety terminated With a hydroxyl or alkyl or aryl group; [0026] A4 is selected from the group consisting of hydro gen; an aryl group that is optionally substituted With alkyl, polyoxyalkylene, or sulfonate moieties, or com binations thereof; an alkyl group that is optionally sub stituted With polyoxyalkylene, hydroxyl, alkoxyl, car boxylic acid or ester, sulfonate, or sulfate groups; and a US 2011/0124837 A1 May 26, 2011

cyclohexyl group that is optionally substituted With one [0034] Additionally provided herein is a method for mak or more alkyl or polyoxyalkylene groups; and ing a polymeric violet anthraquinone colorant comprising the [0027] AS-A8 are independently selected from the group sequential steps of: (a) reacting bromamine acid With a poly consisting of hydrogen, halogen, nitro, amino, alky oxyalkylene substituted primary aromatic or aliphatic amine lamino, arylamino moieties, and combinations thereof. in the presence of a copper-containing catalyst compound to [0028] Further provided herein is a polymeric violet form l-amino-4-arylamino-2-anthraquinone sulfonic acid, anthraquinone colorant, Wherein the colorant comprises a and (b) reacting the anthraquinone of step “a” With an alcohol, compound represented by structure (IV-B): a polymeric alcohol, a thiol, or a polymeric thiol and With a base to form l-amino-2-polyalkyleneoxy-4-arylamino-an thraquinone, methyl ether. (IV-B) A DESCRIPTION OF THE INVENTION A8 0 HN/ 1 [0035] All Us. and foreign patents and Us. patent appli A7 O—A2 cations disclosed in this speci?cation are hereby incorporated by reference in their entirety. [0036] The terms “polyalkyleneoxy” and “poly(oxyalky As R1 lene),” as used interchangeably herein, generally refer to molecular structures containing the folloWing repeating A5 0 HN R2 units: 4CH2CH2Oi, iCH2CH2CH2Oi, 4CH2CH2CH2CH2Oi, 4CH2CH(CH3)Oi, 4CH2CH2CH(CH3)Oi, and any combinations thereof. R5 R3 Furthermore, the polyoxyalkylene constituent may be R4 selected from the group consisting of one or more monomers selected from a C2_2O alkyleneoxy group, a glycidol group, a glycidyl group, or mixtures thereof. Wherein: [0037] The term “alkyl,” as used herein, is intended to [0029] Al is selected from the group consisting of hydro encompass any straight or branched alkyl moiety having from gen, alkyl, hydroxyalkyl, polyoxyalkylene, and aryl; 1 to 30 carbon atoms. [0030] A2 is selected from the group consisting of alkyl [0038] The term “anthraquinone,” as used herein, generally or aryl having no polymer chains; a polyoxyalkylene refers to the folloWing general chemical structure and num moiety, or an aryl linked polyoxyalkylene moiety, ter bering sequence: minated With a hydroxyl or alkyl or aryl; and an aryl group further substituted by Y-A3 Wherein the aryl group is selected from phenylene or a substituted phenylene moiety; Y is a linking group and is selected from the group consisting of oxygen, nitrogen, sulfonyl, sulfona mido, and carboxyl; [0031] A3 is a polyoxyalkylene moiety terminated With a hydroxyl or alkyl or aryl group; [0032] R1, R2, R3, R4, and R5 are independently selected from the group consisting of hydrogen, Cl-C2O alkyl, Cl-C2O alkoxy, and Q-E, Wherein Q is a linking group selected from the group consisting of N, O, S, S02, S03, [0039] The term “violet,” as used herein, is generally CO2, SO2N, alkyl, and alkoxy, and E is a polymer chain intended to refer to compounds that exhibit a maximum and end group that conforms to the structure of general absorbance in the visible spectrum in the Wavelength range of formula (VI), as shoWn beloW: about 550 nanometers to about 610 nanometers. [0040] The polymeric violet anthraquinone colorant of the [polyoxyalkyene constituent] ZR’ (VI) present invention may be represented by general structure (I): Wherein Z is l or 2; Wherein the polyoxyalkylene constituent is selected from the group consisting of one or more monomers selected from a (I) A C2_2O alkyleneoxy group, a glycidol group, a glycidyl group, A8 0 HN/ 1 or mixtures thereof; Wherein R' is an end group selected from the group consisting A7 X _A2 of hydrogen, Cl_2O alkyl, Cl_2O alkylester, halo, hydroxyl, thio, cyano, sulfonyl, sulfo, sulfato, aryl, nitro, carboxyl, Cl_2O alkoxy, amino, Cl_2O alkylamino, acrylamino, Cl_2O A6 alkylthio, C L20 alkylsulfonyl, C L20 alkylphenyl, phosphonyl, Cl_2O alkylphosphonyl, Cl_2O alkoxycarbonyl, and phe A5 0 HN nylthio; \A4 Wherein at least one of R1, R2, R3, R4, R5 is Q-E; and [0033] AS-A8 are independently selected from the group Wherein: consisting of hydrogen, halogen, nitro, amino, alky [0041] Al is selected from the group consisting of hydro lamino, arylamino moieties, and combinations thereof. gen, alkyl, hydroxyalkyl, polyoxyalkylene, and aryl; US 2011/0124837 A1 May 26, 201 l

[0042] X is a linking group and is selected from the group consisting of oxygen and sulfur; (II-A) [0043] A2 is selected from the group consisting of alkyl A or aryl having no polymer chains; a polyoxyalkylene o HN/ l moiety or an aryl linked polyoxyalkylene moiety With o—A2 greater than three repeating units and terminated With a hydroxyl or alkyl or aryl; and an aryl group further substituted by Y-A3 Wherein the aryl group is selected B1 from phenylene or a substituted phenylene moiety; Y is a linking group and is selected from the group consisting 0 HN B2 of oxygen, nitrogen, sulfonyl, sulfonamido, and car boxyl; [0044] A3 is a polyoxyalkylene moiety terminated With a B5 B3 hydroxyl or alkyl or aryl group; B4 [0045] A4 is selected from the group consisting of hydro gen; an aryl group that is optionally substituted With [0052] Wherein: alkyl, polyoxyalkylene, or sulfonate moieties, or com [0053] Al is selected from the group consisting of hydro binations thereof; an alkyl group that is optionally sub gen, alkyl, hydroxyalkyl, polyoxyalkylene, and aryl; stituted With polyoxyalkylene, hydroxyl, alkoxyl, car [0054] A2 is selected from the group consisting of alkyl boxylic acid or ester, sulfonate, or sulfate groups; and a or aryl having no polymer chains; a polyoxyalkylene cyclohexyl group that is optionally substituted With one moiety, or an aryl linked polyoxyalkylene moiety, With or more alkyl or polyoxyalkylene groups; and greater than three repeating units and terminated With a [0046] AS-A8 are independently selected from the group hydroxyl or alkyl or aryl; and an aryl group further consisting of hydrogen, halogen, nitro, amino, alky substituted by Y-A3 Wherein the aryl group is selected from phenylene or a substituted phenylene moiety; Y is lamino, arylamino moieties, and combinations thereof. a linking group and is selected from the group consisting [0047] Additional embodiments of the polymeric violet of oxygen, nitrogen, sulfonyl, sulfonamido, and car anthraquinone colorant of the present invention are repre boxyl; A3 is a polyoxyalkylene moiety terminated With a sented by the general structures shoWn below: hydroxyl or alkyl or aryl group; and [0055] B l-B5 are independently selected from the group consisting hydrogen, methyl, and sulfonate moieties, (11) and combinations thereof. A o HN/ l

O _ A2 (111)

O HN \A4

[0048] Wherein: [0049] Al is selected from the group consisting of hydro gen, alkyl, hydroxyalkyl, polyoxyalkylene, and aryl; [0050] A2 is selected from the group consisting of alkyl or aryl having no polymer chains; a polyoxyalkylene wherein: moiety, or an aryl linked polyoxyalkylene moiety, With [0056] Al is selected from the group consisting of hydro greater than three repeating units and terminated With a gen, alkyl, hydroxyalkyl, polyoxyalkylene, and aryl; hydroxyl or alkyl or aryl; and an aryl group further [0057] X is a linking group and is selected from the group substituted by Y-A3 Wherein the aryl group is selected consisting of oxygen and sulfur; and from phenylene or a substituted phenylene moiety; Y is [0058] A2 is selected from the group consisting of alkyl a linking group and is selected from the group consisting or aryl having no polymer chains; a polyoxyalkylene of oxygen, nitrogen, sulfonyl, sulfonamido, and car moiety, or an aryl linked polyoxyalkylene moiety, With boxyl; A3 is a polyoxyalkylene moiety terminated With a greater than three repeating units and terminated With a hydroxyl or alkyl or aryl; and an aryl group further hydroxyl or alkyl or aryl group; and substituted by Y-A3 Wherein the aryl group is selected [0051] A4 is an aryl group that is optionally substituted from phenylene or a substituted phenylene moiety; Y is With alkyl, polyoxyalkylene, or sulfonate moieties, or a linking group and is selected from the group consisting combinations thereof. of oxygen, nitrogen, sulfonyl, sulfonamido, and car US 2011/0124837 A1 May 26, 2011

boxyl; and A3 is a polyoxyalkylene moiety terminated ing greater than three repeating units and terminated With a hydroxyl or alkyl or aryl group. With a hydroxyl or alkyl or aryl; and an aryl group further substituted by Y-A3 Wherein the aryl group is selected from phenylene or a substituted phenylene moiety; Y is (IV) a linking group and is selected from the group consisting A of oxygen, nitrogen, sulfonyl, sulfonamido, and car A8 0 HN/ 1 boxyl; A7 O_A2 [0066] A3 is a polyoxyalkylene moiety terminated With a hydroxyl or alkyl or aryl group; [0067] R1, R2, R3, R4, and R5 are independently selected A6 from the group consisting of hydrogen, Cl-C2O alkyl, Cl-C2O alkoxy, and Q-E, Wherein Q is a linking group A5 0 HN selected from the group consisting of N, O, S, S02, S03, \A4 CO2, SO2N, alkyl, and alkoxy, and E is a polymer chain and end group that conforms to the structure of general wherein: formula (V I), as shoWn beloW: [0059] Al is selected from the group consisting of hydro gen, alkyl, hydroxyalkyl, polyoxyalkylene, and aryl; [polyoxyalkyene constituentLR' (VI) [0060] A2 is selected from the group consisting of alkyl Wherein Z is 1 or 2; or aryl having no polymer chains; a polyoxyalkylene Wherein the polyoxyalkylene constituent is selected from the moiety or an aryl linked polyoxyalkylene moiety With group consisting of one or more monomers selected from a greater than three repeating units and terminated With a C2_2O alkyleneoxy group, a glycidol group, a glycidyl group, hydroxyl or alkyl or aryl; and an aryl group further or mixtures thereof; substituted by Y-A3 Wherein the aryl group is selected Wherein R' is an end group selected from the group consisting from phenylene or a substituted phenylene moiety; Y is of hydrogen, Cl_2O alkyl, Cl_2O alkylester, halo, hydroxyl, a linking group and is selected from the group consisting thio, cyano, sulfonyl, sulfo, sulfato, aryl, nitro, carboxyl, of oxygen, nitrogen, sulfonyl, sulfonamido, and car Cl_2O alkoxy, amino, Cl_2O alkylamino, acrylamino, Cl_2O boxyl; alkylthio, C L20 alkylsulfonyl, C L20 alkylphenyl, phosphonyl, [0061] A3 is a polyoxyalkylene moiety terminated With a Cl_2O alkylphosphonyl, Cl_2O alkoxycarbonyl, and phe hydroxyl or alkyl or aryl group; nylthio; [0062] A4 is selected from the group consisting of hydro Wherein at least one of R1, R2, R3, R4, R5 is Q-E; and gen; an aryl group that is optionally substituted With alkyl, polyoxyalkylene, or sulfonate moieties, or com [0068] AS-A8 are independently selected from the group binations thereof; an alkyl group that is optionally sub consisting of hydrogen, halogen, nitro, amino, alky stituted With polyoxyalkylene, hydroxyl, alkoxyl, car lamino, arylamino moieties, and combinations thereof. boxylic acid or ester, sulfonate, or sulfate groups; and a [0069] Preferably, Q is oxygen, E is a polyoxyalkylene cyclohexyl group that is optionally substituted With one moiety consisting of ethylene oxide and propylene oxide or more alkyl or polyoxyalkylene groups; and monomers, and Z is 1. [0063] AS-A8 are independently selected from the group consisting of hydrogen, halogen, nitro, amino, alky (IV-B) lamino, arylamino moieties, and combinations thereof. A A8 0 HN/ 1

(IV-A) A7 0 _A2 A A8 0 HN/ 1

A7 O—A2 A5 Rl A5 0 HN R2

As R1 A5 0 HN R2 R5 R3 R4 R5 R3 Wherein: R4 [0070] Al is selected from the group consisting of hydro gen, alkyl, hydroxyalkyl, polyoxyalkylene, and aryl; Wherein: [0071] A2 is selected from the group consisting of alkyl [0064] Al is selected from the group consisting of hydro or aryl having no polymer chains; a polyoxyalkylene gen, alkyl, hydroxyalkyl, polyoxyalkylene, and aryl; moiety, or an aryl linked polyoxyalkylene moiety, ter [0065] A2 is selected from the group consisting of alkyl minated With a hydroxyl or alkyl or aryl; and an aryl or aryl having no polymer chains; a polyoxyalkylene group further substituted by Y-A3 Wherein the aryl group moiety, or an aryl linked polyoxyalkylene moiety, hav is selected from phenylene or a substituted phenylene US 2011/0124837 A1 May 26, 2011

moiety; Y is a linking group and is selected from the [0081] Dl-D5 are the same or different and are selected group consisting of oxygen, nitrogen, sulfonyl, sulfona from the group consisting of hydrogen, Cl-C2O alkyl, mido, and carboxyl; Cl-C2O alkoxy, and Q-E, Wherein Q is a linking group [0072] A3 is a polyoxyalkylene moiety terminated With a selected from the group consisting of N, O, S, S02, S03, hydroxyl or alkyl or aryl group; CO2, SO2N, alkyl, and alkoxy, and E is a polymer chain [0073] R1, R2, R3, R4, and R5 are independently selected and end group that conforms to the structure of general from the group consisting of hydrogen, Cl-C2O alkyl, formula (VI), as shoWn beloW: Cl-C2O alkoxy, and Q-E, Wherein Q is a linking group [polyoxyalkyene constituentLR' (VI) selected from the group consisting of N, O, S, S02, S03, CO2, SO2N, alkyl, and alkoxy, and E is a polymer chain Wherein Z is 1 or 2; and end group that conforms to the structure of general Wherein the polyoxyalkylene constituent is selected from the formula (VI), as shoWn beloW: group consisting of one or more monomers selected from a C2_2O alkyleneoxy group, a glycidol group, a glycidyl group, [polyoxyalkyene constituentLR' (VI) or mixtures thereof; Wherein Z is 1 or 2; Wherein R' is an end group selected from the group consisting Wherein the polyoxyalkylene constituent is selected from the of hydrogen, Cl_2O alkyl, Cl_2O alkylester, halo, hydroxyl, group consisting of one or more monomers selected from a thio, cyano, sulfonyl, sulfo, sulfato, aryl, nitro, carboxyl, C2_2O alkyleneoxy group, a glycidol group, a glycidyl group, Cl_2O alkoxy, amino, Cl_2O alkylamino, acrylamino, Cl_2O or mixtures thereof; alkylthio, C L20 alkylsulfonyl, C L20 alkylphenyl, phosphonyl, Wherein R' is an end group selected from the group consisting Cl_2O alkylphosphonyl, Cl_2O alkoxycarbonyl, and phe of hydrogen, Cl_2O alkyl, Cl_2O alkylester, halo, hydroxyl, nylthio; thio, cyano, sulfonyl, sulfo, sulfato, aryl, nitro, carboxyl, Wherein at least one of D1, D2, D3, D4, D5 is Q-E; and Cl_2O alkoxy, amino, Cl_2O alkylamino, acrylamino, Cl_2O Wherein AS-A8 are independently selected from the group alkylthio, C L20 alkylsulfonyl, C L20 alkylphenyl, phosphonyl, consisting of hydrogen, halogen, nitro, amino, alkylamino, Cl_2O alkylphosphonyl, Cl_2O alkoxycarbonyl, and phe arylamino moieties, and combinations thereof. nylthio; [0082] Preferably, Q is oxygen, E is a polyoxyalkylene Wherein at least one of R1, R2, R3, R4, R5 is Q-E; and moiety consisting of ethylene oxide and propylene oxide [0074] AS-A8 are independently selected from the group monomers, and Z is 1. consisting of hydrogen, halogen, nitro, amino, alky [0083] The inventive polymeric violet anthraquinone colo lamino, arylamino moieties, and combinations thereof. rants are generally synthesiZed according to the procedures [0075] Preferably, Q is oxygen, E is a polyoxyalkylene described herein. HoWever, the rate of the reaction may be moiety consisting of ethylene oxide and propylene oxide affected, for example, by the temperature, the speci?c raW monomers, and Z is 1. materials, and the agitation rate employed. The progress of the reaction may be monitored by visible spectroscopy, Thin Layer Chromatography (TLC), and/ or High Performance Liquid Chromatography (HPLC). A (V) [0084] Synthesis of the inventive colorants can be achieved A8 0 HN/ 1 by several routes as illustrated by the folloWing methods. All A7 O—A2 four methods beloW have in common the substitution of a leaving group at the 2 position of the anthraquinone moiety by a nucleophile. In order to generate the color desired, it is necessary to have a substituted amino group at the 4 position A5 D1 of the anthraquinone moiety. This may be achieved by react A5 0 HN D2 ing bromamine acid With a suitable arylamine as in Method 1 or With a polyoxyalkylene-substituted arylamine as in Method 2, or using an anthraquinone With a preformed D5 D3 4-amino group as in Methods 3 and 4. [0085] As discussed herein, polymeric alcohol compounds D4 may be used to make the inventive polymeric violet anthraquinone colorants of the present invention. Polymeric [0076] Wherein: alcohol compounds include any polymer With one or more hydroxyl group Which can be used to react With the suitable [0077] Al is selected from the group consisting of hydro anthraquinone compounds to make the inventive polymeric gen, alkyl, hydroxyalkyl, polyoxyalkylene, and aryl; violet anthraquinone colorants. Polymeric alcohols include, [0078] A2 is a C l-C2O alkyl, phenyl or substituted phenyl, but are not limited to, polyethylene glycols, polyethylene a polyoxyalkylene moiety terminated With a hydroxyl or glycol monoethers, polyethylene glycol monoesters, alkyl or aryl or an aryl group further substituted by Y-A3, polypropylene glycols and their monoesters and monoethers, Wherein the aryl group is selected from phenylene or a star-shaped or multi-armed poly(ethylene oxide)s, copoly substituted phenylene moiety; mers of ethylene glycol and propylene glycol, polyglycidols, [0079] Y is a linking group and is selected from the group polyglycidyl ethers, polyvinyl alcohols, polyacrylate and consisting of oxygen, nitrogen, sulfonyl, sulfonamido, polymethylacrylate homopolymers or copolymers With and carboxyl; hydroxyl group (s), hydroxyl terminated polybutadiene, poly [0080] A3 is a polyoxyalkylene moiety terminated With a ether polyols, polyester polyols, hydroxyl terminated poly hydroxyl or alkyl or aryl ether; dimethylsiloxane, hydroxyl terminated polyamines like US 2011/0124837 A1 May 26, 2011

ethoxylated polyethylenimine, polyethylene mono-alcohols, base, Which results in displacement of the sulfonic acid group polyethylene-block-poly(ethylene glycol)s, polyoxyethylene to yield the 2-alkoxy derivative, a violet chromophore. This alkyl ethers, and polytetrahydrofurans. Preferably, the poly reaction is shoWn beloW:

O N 2 0 NH2 ArNHZ : i i .SO3H @ii?O Br o HN \Ar Bromamine Acid : i0 iNH2 .O(CH2CH2O)XR

o HN \Ar meric alcohols are polymers having ethylene glycol, propy [0090] (R:CH3) 1-amino-2-polyalkyleneoXy-4-ary lcnc glycol, or glycidyl other as repeating units. lamino-anthraquinonc, methyl other [0086] Commercially available examples of polymeric [0091] The polyoxyalkylene substituted primary aromatic alcohols include alcohol ethoxylates from Air Products amines used in this method may be represented by general including Tomadol® 45-13, Tomadol® 25-7, Tomadol® 1-9, structure (V11): Tomadol® 23-5, Tomadol® 91-6 and Tomadol® 45-7; poly ethylene glycols from DoW including CarboWaX® PEG 200, CarboWaX® PEG 300 and CarboWaX® PEG 400; methoxy (v11) polyethylene glycols (MPEGs) from DoW including Carbo R1 R2 WaxTM MPEG 350 and CarboWaxTM MPEG 550; alkoxylated polyols from Perstorp including Polyol 3165, Polyol 4800, Polyol R2490 and Polyol R6405. [0087] Polymeric phenols refer generally to any polymer With phenol or substituted phenol moieties as the end group. R5 R4 The general structure of such polymer is HO-Ph-R', Wherein R' is the polymer chain and Ph is a ring or a substi tuted benZene ring. Mercaptan terminated polymers gener Wherein R1, R2, R3, R4, R5 are the same or different and are ally refer to any polymer having an iSH as the end group. selected from the group consisting of hydrogen, Cl_2O alkyl, C L20 alkoxy, halogen, nitro, amino, carboxylic acid, carboxy Method 1 lic acid ester, carboxamide, sulfonic acid, sulfonamide and sulfonic acid esters. The ?rst step of this method, the bro [0088] One method for making the polymeric violet mamine acid reaction With the polyoxyalkylene substituted anthraquinone colorant of the present invention involves a primary aromatic or aliphatic amine, typically employs a tWo step reaction. The ?rst step consists of reacting bro copper catalyst as mentioned above. Examples of this catalyst mamine acid With a polyoxyalkylene substituted primary aro include CuCl, CuCl2, Cu poWder, or CuSO4. A solvent, such matic or aliphatic amine catalyZed by metallic copper, cupric as alcohol (such as methanol, ethanol, propylene glycol, or (Cu (11)), or cuprous (Cu (1)) ions, also knoWn as an Ullmann glycerol), dimethylformamide (DMF), dimethylsulfoxide condensation reaction, and as further described on page 501 (DMSO), and the like, may optionally be utiliZed. A mild base to 502 of “March’s Advanced Organic Chemistry: Reactions, may be used, such as sodium carbonate, sodium bicarbonate, Mechanisms, and Structure” by Michael B. Smith and Jerry and the like. The typical reaction temperature is betWeen 60° March, 5th Edition, 2001 and the references contained C. and 150° C. therein. The resulting anthraquinone intermediate is [0092] The second step of this method consists of heating 1-amino-4-arylamino-2-anthraquinone sulfonic acid. the 1-amino-4-arylamino-2-anthraquinonesulfonic acid and [0089] The second step consists of reacting the 1-amino-4 an OH or SH terminated polymer With a base to 50° C. to 250° arylamino-2-anthraquinone sulfonic acid With an alcohol, a C. in a reactor With optional solvent. Preferably, the reaction polymeric alcohol, a thiol, or a polymeric thiol and With a temperature is from 50° C. to 150° C. More preferably, the US 2011/0124837 A1 May 26, 2011

reaction temperature is from 70° C. to 1200 C. A strong base [0094] The polyoxyalkylene substituted primary aromatic is typically needed for this reaction. Alkali hydroxides can be amines With polyoxyalkylene chains have general structure used, such as sodium hydroxide, potassium hydroxide, or (VIII), as described in US. Pat. No. 6,593,482, and as shoWn lithium hydroxide. Alkali alkoxides also may be used, such as beloW: sodium methoxide, sodium butoxide, or potassium isopro (VIII) poxide. Other useful bases include, but are not limited to, R1 R2 sodium hydride, sodium amide, sodium bis(trimethylsilyl) amide, tetramethylammonium hydroxide (TMAH), benZylt rimethylammonium hydroxide (BTMAH), lithium diisopro pylamide, sodium trimethylsilanolate. Solvent for this reaction may be Water, alcohols, ethers, , dimethylsul foxide (DMSO), dimethylforrnamide (DMF), and the like. The use of a solvent is optional. Solvent may be used to help Wherein R1, R2, R3, R4, R5 are the same or different and are dissolve the reactants/products or reduce the viscosity of the selected from the group consisting of hydrogen, C 1 -C20 alkyl, reaction mixtures. C l-C2O alkoxy, and Q-E, Wherein Q is a linking group selected from the group consisting of N, O, S, S02, S03, CO2, SO2N, alkyl, and alkoxy, and E is a polymer chain and end group that Method 2 conforms to the structure of general structure formula (IX), as shoWn beloW: [0093] Another method of synthesizing the polymeric vio let anthraquinone colorant involves reacting a polyoxyalky [polyoxyalkyene constituentLR' (1X) lene substituted primary aromatic or aliphatic amine With Wherein Z is 1 or 2; bromamine acid, folloWed by treatment of the anthraquinone Wherein polyoxyalkylene constituent is selected from the intermediate obtained With an alcohol or glycol compound group consisting of one or more monomers selected from a and a base. This method is illustrated beloW: C2_2O alkyleneoxy group, a glycidol group, a glycidyl group, or mixtures thereof; Wherein R' is an end group selected from the group consisting of hydrogen, C L20 alkyl, C L20 alkylester, halo, hydroxyl, thio, cyano, sulfonyl, sulfo, sulfato, aryl, nitro, carboxyl, C 1,20 alkoxy, amino, C 1,20 alkylamino, acrylamino, C 1,20 alkylthio, C L20 alkylsulfonyl, C L20 alkylphenyl, phosphonyl, C L20 alkylphosphonyl, C L20 alkoxycarbonyl, and phe nylthio; and Wherein at least one of R1, R2, R3, R4, R5 is Q-E. [0095] Preferably, Q is oxygen, E is a combination of eth Brornamine Acid ylene oxide and propylene oxide, and Z is 1. [0096] The alcohol reactant used in the second step to replace the sulfonic acid moiety on the anthraquinone may be an alcohol, such as methanol, ethanol, propylene glycol, glyc erol, a polyol, the monoether of a polyol, or the like. Phenol or substituted phenols also may be used. The base and reaction ROH, Base conditions used are the same as those described in Method 1. —> Method 3

[0097] One can directly treat an anthraquinone acid blue compound having a sulfonic acid moiety in the 2 position, e.g. 1-amino-4-arylamino-2-anthraquinone sulfonic acid or l-arnino-4- (4' -polyalkyleneoxy phenylarnino)— monosodium salt, such as Acid Blue 145, With a polymeric 2-sulfonic acid-anthraquinone alcohol and a base compound as shoWn by the reaction below: NH; 0 NH2 OR SO3H

HO(CH2CH2O)XR —> HN Base @ii? 0 HN | \ / / CH l-amino-Z-alkoxy-4- (4' —polyalkylene NaO3S 3 oxy phenylamino) anthraquinone Acid Blue 145 US 2011/0124837 A1 May 26, 2011

Wherein Al is selected from NH2, OH, or hydrogen; X is -continued selected from O, S, CH2, OPh or OPhO groups; E conforms to 0 NH; the general formula: O(CH2CH2O)XR [polyoxyalkyene constituentLR'; Wherein Z is 1 or 2; Wherein polyoxyalkylene constituent is selected from the group consisting of one or more monomers selected from a 0 HN C2_2O alkyleneoxy group, a glycidol group, a glycidyl group, | \ or mixtures thereof; and Wherein R' is an end group selected from the group consisting / / CH of hydrogen, Cl_2O alkyl, Cl_2O alkylester, halo, hydroxyl, NaO3S 3 thio, cyano, sulfonyl, sulfo, sulfato, aryl, nitro, carboxyl, (R I CH3), 1—a.rnino—2—polyalkyleneoxy—4 Cl_2O alkoxy, amino, Cl_2O alkylamino, acrylamino, Cl_2O —(sulfonated—4'—methyl amino) alkylthio, C L20 alkylsulfonyl, C L20 alkylphenyl, phosphonyl, anthraquinone, methyl ether Cl_2O alkylphosphonyl, Cl_2O alkoxycarbonyl, and phe nylthio. [0102] Examples of violet polymeric anthraquinone colo [0098] The reaction conditions are those described in Step rants made according to according to one or more of the 2 of Method 1. methods described herein are shoWn beloW and have general [0099] Examples of suitable acid blue dyes Which may be structures @(I), @(II) or @(III): used to make the inventive polymeric violet colorants of the present invention include Color Index Acid Blue 23, Acid Blue 25, Acid Blue 41, Acid Blue 53, Acid Blue 62, Acid Blue 68, Acid Blue 69, Acid Blue 111, Acid Blue 124, Acid Blue 127, Acid Blue 129, Acid Blue 138, Acid Blue 150, Acid Blue 230, Acid Blue 277, and Acid Blue 344. Also, reactive blue dyes may be used to make the inventive polymeric violet colorants if there is an iSO3H moiety on the [3 position of the anthraquinone backbone. The following are examples of such suitable reactive blue dyes: Reactive Blue 2, Reactive Blue 4, Reactive Blue 5, Reactive Blue 19, Reactive Blue 27, Reac tive Blue 29, Reactive Blue 36, Reactive Blue 49, Reactive Blue 50, Reactive Blue 69, Reactive Blue 74, Reactive Blue 94, and Reactive Blue 166. Method 4 [0100] One also can use 1-amino-4-arylamino-2-haloan thraquinone to make the inventive polymeric anthraquinone. In this instance, the 2-position of the anthraquinone is substi tuted by a halogen, such as ?uorine, chlorine, bromine, and iodine. Preferably, the halogen is chlorine or bromine. The compound, 1 -amino-4 -arylamino -2 -haloanthraquinone, reacts With a polymeric alkali metal alkoxide or phenoxide at a temperature range of about 800 C. to about 2000 C. in a non-aqueous medium to give the product illustrated in For mula IV. Examples of such halogen substituted anthraquinone colorants include acid blue, disperse blue and solvent blue dyes. Speci?c examples of such dyes include Acid Blue 78, Acid Blue 81 , Acid Blue 96, Disperse Blue 56, Disperse Blue 81, and Solvent Blue 12. [0101] Additionally, a violet polymeric anthraquinone Wherein the average n:3 to 100; and colorant having general structure (X) may be made according Wherein R' is an end group selected from the group consisting to one or more of the methods described herein: of hydrogen, Cl_2O alkyl, Cl_2O alkylester, halo, hydroxyl, thio, cyano, sulfonyl, sulfo, sulfato, aryl, nitro, carboxyl, Cl_2O alkoxy, amino, Cl_2O alkylamino, acrylamino, Cl_2O (X) alkylthio, C L20 alkylsulfonyl, C L20 alkylphenyl, phosphonyl, Cl_2O alkylphosphonyl, Cl_2O alkoxycarbonyl, and phe nylthio. [0103] In general, the inventive polymeric violet anthraquinone colorants have excellent compatibility With the target formulations to Which they are added. Furthermore, the polymeric violet anthraquinone colorants may be tailored to be miscible With the intended systems. The inventive poly meric violet anthraquinone colorants have excellent colora tions, loW extraction, thermal stability, and lightfastness US 2011/0124837 A1 May 26, 2011

Within target thermoplastic and/ or thermoset articles. The invention, are disclosed in US. Pat. Nos. 4,640,690; 4,732, violet polymeric colorants contain poly(oxyalkylene) groups 570; and 4,812,141 to Baumgartner et al. that are easy to process, Which mix Well Within target plastics, [0108] Examples of speci?c thermoset formulations, Which and Which provide excellent colorations Within the target may be suitable for use With the anthraquinone of the present ?nished articles. invention, are disclosed in commonly assigned US. Pat. Nos. [0104] The inventive polymeric violet anthraquinone colo 4,284,729 to Cross et al. and 4,846,846 to Rekers et al. In general, polyurethane foam is produced through the cata rants as described herein are preferably Water soluble. More lyZed polymerization of the reaction products of polyols and speci?cally, the colorants are preferably Water soluble at con isocyanates. BloWing agents present Within the polymeriza centrations Which provide su?icient coloration for a desired tion step typically provide the necessary foam-making capa end-use application. Furthermore, the polymeric violet bility. Such a reaction is Well knoWn throughout the polyure anthraquinone colorants of the present invention are prefer thane industry and has been practiced for many years. ably Water fugitive (i.e. Washable from substrates With Water) [0109] It is also contemplated to be Within the scope of this on all kinds of substrates, such as, for example, human skin, invention that a large variety of colors and shades may be textile substrates, coated surfaces (such as, for example, obtained by blending the inventive polymeric violet painted surfaces), ceramic surfaces, etc. Also, the inventive anthraquinone colorant With one or more additional Water polymeric violet anthraquinone colorants are generally liquid soluble colorants. Blending of the colorants may be readily or semi-solid at ambient conditions. “Semi-solid” generally accomplished, for example, When combining colorants hav means the colorant is a highly viscous liquid, or may even be ing substantially identical solubility characteristics. Several paste-like, and its melting temperature, if it has any, is typi exemplary classes of colorants include the Reactint® and cally beloW about 60° C. Liquitint® colorants (available from Milliken Chemical of [0105] There are several advantages to polymeric violet Spartanburg, SC.) These colorants are generally Water anthraquinone colorants made according to these methods. soluble, or dispersible, at room temperature and may be suit First, these colorants are generally more soluble in Water than ably blended With the anthraquinone colorant of the present other colorants. They are generally pH stable and non-stain invention to achieve improved colors and shades. ing, Which alloWs for their use in many consumer products, such as laundry detergents and other cleaning products. Addi EXAMPLES tionally, these colorants have a Wider range of compatibility [0110] The folloWing examples are provided for illustra With other materials. This alloWs for ease of incorporation of tion purposes and should not be considered as limiting the the colorants into these other materials. Thus, the polymeric scope of the invention. violet anthraquinone colorants represent a useful advance [0111] All color values and absorbance values Were mea over the prior art. sured using a Beckman DU 650 spectrophotometer. Gener [0106] Additionally, the polymeric violet anthraquinone ally, the higher the color value, the stronger the colorant. All colorants of the present invention generally possess many values and percentages are provided based on 100 percent desirable and advantageous properties for use in various con solids, unless otherWise indicated. sumer products. The colorants generally have good alkali fastness. They can typically be used in high pH formulations, Example 1 such as Wherein the pH is betWeen about 8 and about 13, [0112] A mixture Was prepared containing 9.17 grams of Without having stability problems. Such pH ranges are often Acid Blue 129, 2.4 grams of 50% sodium hydroxide solution found in poWder detergents, heavy-duty liquid detergents, and 30.0 grams of poly(ethylene glycol) mono methyl ether hard surface cleaners, etc. Additionally, these anthraquinone (having molecular Weight:550). The mixture Was heated to colorants may exhibit desirable color brightness due to ?uo 1000 C. for 3 hours. TLC analysis Was used to con?rm that all rescence of the anthraquinone chromophore. As such, these of the Acid Blue 129 had reacted. 10 mL of Water Was then anthraquinone colorants may be used to color various per added, and the reaction mixture Was neutraliZed to pH 7 With sonal care, home care, and fabric care products. For example, muriatic acid. The resulting product Was a liquid polymeric the colorants may be used to color soap bars, liquid soaps, violet anthraquinone colorant With an absorption maximum fabric softeners, car Washing formulations, glass cleaners, in methanol at 584 nm. The structure of the resulting product toilet cleaners, shampoos, and the like. Examples of speci?c is shoWn below: laundry detergent formulations (both granular and liquid), Which may be suitable for use With the anthraquinone of the 0 NH2 present invention, are disclosed in commonly assigned US. Pat. No. 5,770,552 to Bruhnke. Examples of speci?c fabric O(CH2CH2O)nCH3 softener formulations, Which may be suitable for use With the anthraquinone of the present invention, are disclosed in US. Pat. No. 5,770,557 to Bruhnke. CH3 [0107] The polymeric violet anthraquinone colorants can 0 HN also be used in industrial formulations, such as heavy-duty industrial cleaners and detergents and fertilizers. Addition ally, it is contemplated that the colorants of the current inven H3C CH3 tion may be ideal for use in coloring thermoplastic materials l—a.rnino—2—polyalkyleneoxy-4— (2 ,4,6 , (such as, for example, polyole?n and polyester) and thermo trimethyl phenylamino) anthraquinone set materials (such as, for example, polyurethane foam). Examples of speci?c thermoplastic formulations, Which may Average n I 12 be suitable for use With the anthraquinone of the present US 2011/0124837 A1 May 26, 2011

Example 2 [0116] The polymeric violet anthraquinone colorant Was [0113] Example 1 Was repeated, except that the 50% subsequently incorporated into a Wax based candle formula sodium hydroxide solution Was replaced With 3.0 grams of tion at 0.3% Weight loading. The colored candle exhibited an sodium tert-butoxide poWder. A liquid polymeric violet excellent uniform violet shade. anthraquinone colorant having the same name, structure, and absorption value as shoWn in Example 1 Was obtained. Example 5 Example 3 [0117] A mixture of0.8 grams ofNaOH pellet, 7.5 grams of [0114] A mixture Was prepared that contained 8.3 grams of glycerol 15 E0 and 1.0 grams of Acid Blue 25 Was charged Acid Blue 25, 2.4 grams of 50% aqueous sodium hydroxide into a 3-neck ?ask equipped With agitator, temperature probe solution and 30.0 grams of poly(ethylene glycol) mono methyl ether (molecular Weight:550). The mixture Was and condenser. The reaction mixture Was heated to 1 100 C. for heated to 100° C. for 3 hours. TLC analysis Was used to 2 hours. TLC analysis con?rmed that all of the Acid Blue 25 con?rm that all of the Acid Blue 25 Was reacted. 20 mL of Was consumed. The reaction mixture contained the liquid Water Was then added, and the reaction mixture Was neutral violet polymeric anthraquinone colorant having a maximum iZed to pH 7 With hydrochloric acid. The resulting product absorption in methanol of 572 nm. Was a liquid polymeric violet anthraquinone colorant With absorption maximum in methanol at 588 nm. The structure of the resulting product is shoWn below: 0 NH2

0 NH2 “ETD l—amino-2-po1yalkylenoxy-4-phenylamino anthraquinone x+y+z:15onaverage

l-alnino—2—polyalkyleneoxy—4— phenylamino anthraquinone Example 6 Average n I 12 [0118] 13.7 grams of Aniline PEG 10 E0, 8.1 grams of bromamine acid sodium salt, 5.0 grams of sodium bicarbon Example 4 ate, 0.1 grams of cuprous chloride Were charged into 50 grams of Water in a reaction ?ask equipped With stirrer, temperature [0115] A mixture of 524 grams of Tomadol® 25-7 (from Air Products), 36 grams of sodium tert-butoxide (from probe, and a condenser. The reaction mixture Was heated to BASF) and 116 grams ofAcid Blue 129 Was heated to 1000 C. re?ux and stirred overnight. The reaction mixture turned blue. While stirring in a reaction ?ask for 3 hours. TLC analysis Was After evaporation and removing salts by ?ltering the metha used to con?rm that all of the Acid Blue 129 Was reacted. 660 nol solution, a crude product having an absorption maximum grams of the reaction mixture Was collected. The reaction in methanol of 624 nm Was obtained. mixture contained a liquid polymeric violet anthraquinone [0119] 4.0 grams of the product from above Was mixed With colorant having a maximum absorption in methanol of 584 30 grams of methanol and 10 grams of 50% caustic solution. nm. The mixture Was heated to 780 C. for 3 hours and a liquid polymeric violet anthraquinone colorant Was obtained. The colorant exhibited a maximum absorption of 587 nm in methanol. This reaction and the structure thus obtained are shoWn beloW:

SO3Na

l—a.rnino-2—alkoxy—polyethyleneoxy-4 (2,4,6,-trimethylphenyla.rnino) anthraquinone Average n I 7 US 2011/0124837 A1 May 26, 2011

-continued TABLE 1 0 NH2 pH Stability of Fxamnle 1 ocH3 Delta E value after 10 days at Buffer Solution 50° C. oven

pH 2.0 buffer 0.896 pH 4.0 buffer 1.018 pH 6.0 buffer 0.340 pH 8.0 buffer 0.346 pH 12.45 buffer 5.178

[0123] The test results illustrate that the inventive poly l—arnino—2—methoxy—4—[4-polyethylenoxy-anilyl] meric violet anthraquinone colorants exhibit good pH stabil anthraquinone ity.

Average n I 10 Test 2: pH Stability of Example 6 [0124] This test is provided to illustrate the pH stability of the polymeric violet anthraquinone colorant of Example 6. [0125] The same procedure utiliZed in Test 1 Was folloWed Example 7 for testing the polymeric anthraquinone violet colorant of Example 6, except that the colorant Was evaluated after tWo [0120] 4.0 grams of PEG 200, 4.2 grams ofAcid Blue 25 Weeks and after 4 Weeks. Test results are provided in Table 2. and 20 gram of 50% caustic Were charged into a three neck TABLE 2 reaction ?ask equipped With condenser, temperature control, thermometer and agitator. The mixture Was heated to 100° C. pH Stability of Fxamnle 6 for 2 hours. TLC analysis Was used to con?rm that the blue Delta E after 2 Weeks at Delta E after 4 Weeks at colorant Was no longer present. The reaction mixture Was then Buffer Solution 50° C. 50° C. neutraliZed With a 10% sulfuric acid solution. The reaction mixture contained the liquid polymeric violet anthraquinone pH 2.0 buffer 2.082 3.386 colorant exhibited a maximum absorption of 569 nm in Water. pH 12.45 buffer 2.398 4.321 The liquid polymer violet anthraquinone colorant had the following structure: Test 3: Stain Testing of Example 1 [0126] This test is provided to illustrate the non-staining feature of the polymeric violet anthraquinone of Example 1. [0127] 30 ppm of the polymeric violet anthraquinone colo rant of Example 1 Was added to a standard liquid laundry detergent. 127 ppm of the polymeric violet anthraquinone colorant of Example 1 Was added to a fabric softener formu lation. Each colorant-containing formulation Was evaluated for staining on several different fabric sWatches comprised of different ?ber types. The stain evaluation Was performed by visual observation according to the rating system for AATCC Grey Scale No. 2 “Grey Scale For Staining.” A rating of “5” l—arnino—2-polyethyleneoxy-4-phenylarnino—anthraquinone indicates no staining Was observed. A rating of “1” indicates high degree of staining Was present. [0128] Test results are provided in Table 3. Average n I 5 TABLE 3

Stain Testing of Example 1 Test 1: pH Stability of Example 1 AATCC Stain AATCC Stain Rating in Rating in Laundry Fabric [0121] This test is provided to illustrate the pH stability of Sample Detergent Softener the polymeric violet anthraquinone colorant of Example 1. Spun Diacetate 5 5 [0122] 100 ppm of the polymeric violet colorant from Bleached Cotton 5 3/4 Example 1 Was added to various pH buffer solutions. The Nylon 6,6 (Polyalnide) 5 5 colored buffer solutions Were put into a 500 C. oven for 10 Dacron 54 (Polyester) 5 5 days and the shade of the ?nal colored solutions Was com Orlon 75 (Acrylic) 5 5 W001 5 5 pared With the initial solutions using a spectrometer Gretag Terry Cotton 5 3/4 MacbethTM Color-Eye 7000A spectrophotometer. Test results are provided in Table 1. US 2011/0124837 A1 May 26, 2011

[0129] These and other modi?cations and variations to the Wherein: present invention may be practiced by those of ordinary skill Al is selected from the group consisting of hydrogen, alkyl, in the art, Without departing from the spirit and scope of the hydroxyalkyl, polyoxyalkylene, and aryl; present invention. Furthermore, those of ordinary skill in the A2 is selected from the group consisting of alkyl or aryl art Will appreciate that the foregoing description is by Way of having no polymer chains; a polyoxyalkylene moiety, or an aryl linked polyoxyalkylene moiety, With greater than example only, and is not intended to limit the scope of the three repeating units and terminated With a hydroxyl or invention described in the appended claims. alkyl or aryl; and an aryl group further substituted by We claim: Y-A3 Wherein the aryl group is selected from phenylene 1. A polymeric violet anthraquinone colorant comprising a or a substituted phenylene moiety; Y is a linking group compound represented by structure (I): and is selected from the group consisting of oxygen, nitrogen, sulfonyl, sulfonamido, and carboxyl; A3 is a (1) polyoxyalkylene moiety terminated With a hydroxyl or A1 alkyl or aryl group; and A8 0 HN/ A4 is an aryl group that is optionally substituted With alkyl, polyoxyalkylene, or sulfonate moieties, or combina A7 X—A2 tions thereof. 3. The colorant of claim 2, Wherein the colorant comprises a compound represented by structure (ll-A): A6 (II-A) A5 0 HN A1 \ A4 0 HN/ Wherein: O _ A2 Al is selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, polyoxyalkylene, and aryl; X is a linking group and is selected from the group con B1 sisting of oxygen and sulfur; A2 is selected from the group consisting of alkyl or aryl 0 HN B2 having no polymer chains; a polyoxyalkylene moiety or an aryl linked polyoxyalkylene moiety With greater than three repeating units and terminated With a hydroxyl or alkyl or aryl; and an aryl group further substituted by B4 Y-A3 Wherein the aryl group is selected from phenylene or a substituted phenylene moiety; Y is a linking group Wherein: and is selected from the group consisting of oxygen, Al is selected from the group consisting of hydrogen, alkyl, nitrogen, sulfonyl, sulfonamido, and carboxyl; hydroxyalkyl, polyoxyalkylene, and aryl; A3 is a polyoxyalkylene moiety terminated With a hydroxyl A2 is selected from the group consisting of alkyl or aryl having no polymer chains; a polyoxyalkylene moiety, or or alkyl or aryl group; an aryl linked polyoxyalkylene moiety, With greater than A4 is selected from the group consisting of hydrogen; an three repeating units and terminated With a hydroxyl or aryl group that is optionally substituted With alkyl, poly alkyl or aryl; and an aryl group further substituted by oxyalkylene, or sulfonate moieties, or combinations Y-A3 Wherein the aryl group is selected from phenylene thereof; an alkyl group that is optionally substituted With or a substituted phenylene moiety; Y is a linking group polyoxyalkylene, hydroxyl, alkoxyl, carboxylic acid or and is selected from the group consisting of oxygen, ester, sulfonate, or sulfate groups; and a cyclohexyl nitrogen, sulfonyl, sulfonamido, and carboxyl; A3 is a group that is optionally substituted With one or more polyoxyalkylene moiety terminated With a hydroxyl or alkyl or polyoxyalkylene groups; and alkyl or aryl group; and B l-B5 are independently selected from the group consist AS-A8 are independently selected from the group consist ing hydrogen, methyl, and sulfonate moieties, and com ing of hydrogen, halogen, nitro, amino, alkylamino, ary binations thereof. lamino moieties, and combinations thereof. 4. The colorant of claim 3, Wherein the colorant comprises 2. The colorant of claim 1, Wherein the colorant comprises a compound represented by structure (111): a compound represented by structure (11):

(III) (H) US 2011/0124837 A1 May 26, 2011

wherein: 6. The colorant of claim 5, Wherein the colorant comprises Al is selected from the group consisting of hydrogen, alkyl, a compound represented by Structure (IV-A): hydroxyalkyl, polyoxyalkylene, and aryl; X is a linking group and is selected from the group con (IV-A) sisting of oxygen and sulfur; and A1 A8 0 HN/ A2 is selected from the group consisting of alkyl or aryl having no polymer chains; a polyoxyalkylene moiety, or A7 o—A2 an aryl linked polyoxyalkylene moiety, With greater than three repeating units and terminated With a hydroxyl or alkyl or aryl; and an aryl group further substituted by A5 Rl Y-A3 Wherein the aryl group is selected from phenylene A5 0 HN R2 or a substituted phenylene moiety; Y is a linking group and is selected from the group consisting of oxygen, nitrogen, sulfonyl, sulfonamido, and carboxyl; andA3 is R5 R3 a polyoxyalkylene moiety terminated With a hydroxyl or alkyl or aryl group. 5. A polymeric violet anthraquinone colorant comprising a compound represented by structure (IV): Wherein: Al is selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, polyoxyalkylene, and aryl; A2 is selected from the group consisting of alkyl or aryl (IV) A1 having no polymer chains; a polyoxyalkylene moiety, or A8 0 HN/ an aryl linked polyoxyalkylene moiety, having greater than three repeating units and terminated With a A7 O—A2 hydroxyl or alkyl or aryl; and an aryl group further substituted by Y-A3 Wherein the aryl group is selected from phenylene or a substituted phenylene moiety; Y is A6 a linking group and is selected from the group consisting of oxygen, nitrogen, sulfonyl, sulfonamido, and car A5 0 HN \ A4 boxyl; A3 is a polyoxyalkylene moiety terminated With a hydroxyl or alkyl or aryl group; R1, R2, R3, R4, and R5 are independently selected from the Wherein: group consisting of hydrogen, Cl_2O alkyl, Cl-C2O Al is selected from the group consisting of hydrogen, alkyl, alkoxy, and Q-E, Wherein Q is a linking group selected hydroxyalkyl, polyoxyalkylene, and aryl; from the group consisting of N, O, S, S02, S03, CO2, SOZN, alkyl, and alkoxy, and E is a polymer chain and A2 is selected from the group consisting of alkyl or aryl end group that conforms to the structure of general for having no polymer chains; a polyoxyalkylene moiety or mula (V I), as shoWn beloW: an aryl linked polyoxyalkylene moiety With greater than three repeating units and terminated With a hydroxyl or [polyoxyalkyene constituentLR' (VI) alkyl or aryl; and an aryl group further substituted by Wherein Z is 1 or 2; Y-A3 Wherein the aryl group is selected from phenylene Wherein the polyoxyalkylene constituent is selected from the or a substituted phenylene moiety; Y is a linking group group consisting of one or more monomers selected from a and is selected from the group consisting of oxygen, C2_2O alkyleneoxy group, a glycidol group, a glycidyl group, nitrogen, sulfonyl, sulfonamido, and carboxyl; or mixtures thereof; A3 is a polyoxyalkylene moiety terminated With a hydroxyl Wherein R' is an end group selected from the group consisting or alkyl or aryl group; of hydrogen, Cl_2O alkyl, Cl_2O alkylester, halo, hydroxyl, thio, cyano, sulfonyl, sulfo, sulfato, aryl, nitro, carboxyl, A4 is selected from the group consisting of hydrogen; an Cl_2O alkoxy, amino, Cl_2O alkylamino, acrylamino, Cl_2O aryl group that is optionally substituted With alkyl, poly alkylthio, C L20 alkylsulfonyl, C L20 alkylphenyl, phosphonyl, oxyalkylene, or sulfonate moieties, or combinations Cl_2O alkylphosphonyl, Cl_2O alkoxycarbonyl, and phe thereof; an alkyl group that is optionally substituted With nylthio; polyoxyalkylene, hydroxyl, alkoxyl, carboxylic acid or Wherein at least one of R1, R2, R3, R4, R5 is Q-E; and ester, sulfonate, or sulfate groups; and a cyclohexyl AS-A8 are independently selected from the group consist group that is optionally substituted With one or more ing of hydrogen, halogen, nitro, amino, alkylamino, ary alkyl or polyoxyalkylene groups; and lamino moieties, and combinations thereof. AS-A8 are independently selected from the group consist 7. The colorant of claim 6, Wherein Q is oxygen, E is a ing of hydrogen, halogen, nitro, amino, alkylamino, ary polyoxyalkylene moiety consisting of ethylene oxide and lamino moieties, and combinations thereof. propylene oxide monomers, and Z is 1. US 2011/0124837 A1 May 26, 2011 15

8. A polymeric Violet anthraquinone colorant, wherein the 10. The method for making the polymeric Violet colorant comprises a compound represented by structure (IV anthraquinone colorant of claim 1, comprising the sequential B): steps of: (a) reacting bromamine acid With a polyoxyalkylene sub stituted primary aromatic or aliphatic amine to form an (IV-B) anthraquinone intermediate, and A1 (b) reacting the anthraquinone of step “a” With an alcohol, A8 0 HN/ a polymeric alcohol, a thiol, or a polymeric thiol and A7 0 _ A2 With a base to form a polymeric Violet anthraquinone colorant. 11. The method of claim 10, Wherein the polyoxyalkylene A6 R1 substituted primary aromatic amine is represented by general structure (V11): A5 0 HN R2

(V11) R5 R3 R4

Wherein: Al is selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, polyoxyalkylene, and aryl; A2 is selected from the group consisting of alkyl or aryl Wherein R1, R2, R3, R4, R5 are the same or different and are having no polymer chains; a polyoxyalkylene moiety, or selected from the group consisting of hydrogen, C 1 -C20 alkyl, an aryl linked polyoxyalkylene moiety, terminated With Cl-C2O alkoxy, halogen, nitro, amino, carboxylic acid, car a hydroxyl or alkyl or aryl; and an aryl group further boxylic acid ester, carboxamide, sulfonic acid, sulfonamide substituted by Y-A3 Wherein the aryl group is selected and sulfonic acid esters. from phenylene or a substituted phenylene moiety; Y is 12. The method of claim 10, Wherein the polyoxyalkylene a linking group and is selected from the group consisting substituted primary aromatic amine is represented by general of oxygen, nitrogen, sulfonyl, sulfonamido, and car structure (V111): boxyl; A3 is a polyoxyalkylene moiety terminated With a hydroxyl or alkyl or aryl group; (V111) R1, R2, R3, R4, and R5 are independently selected from the group consisting of hydrogen, Cl-C2O alkyl, Cl-C2O alkoxy, and Q-E, Wherein Q is a linking group selected from the group consisting of N, O, S, S02, S03, CO2, SOZN, alkyl, and alkoxy, and E is a polymer chain and end group that conforms to the structure of general for mula (VI), as shoWn beloW: [polyoxyalkyene constituentLR' (VI) Wherein R1, R2, R3, R4, R5 are the same or different and are selected from the group consisting of hydrogen, C l-C2O Wherein Z is 1 or 2; alkyl, Cl-C2O alkoxy, and Q-E, Wherein Q is a linking Wherein the polyoxyalkylene constituent is selected from the group selected from the group consisting of N, O, S, group consisting of one or more monomers selected from a S02, S03, CO2, SO2N, alkyl, and alkoxy, and E is a C2_2O alkyleneoxy group, a glycidol group, a glycidyl group, polymer chain and end group that conforms to the struc or mixtures thereof; ture of general structure formula (IX), as shoWn beloW: Wherein R' is an end group selected from the group consisting [polyoxyalkyene constituentLR' (1X) of hydrogen, Cl_2O alkyl, Cl_2O alkylester, halo, hydroxyl, Wherein Z is 1 or 2; thio, cyano, sulfonyl, sulfo, sulfato, aryl, nitro, carboxyl, Wherein polyoxyalkylene constituent is selected from the Cl_2O alkoxy, amino, Cl_2O alkylamino, acrylamino, Cl_2O group consisting of one or more monomers selected alkylthio, C L20 alkylsulfonyl, C L20 alkylphenyl, phosphonyl, Cl_2O alkylphosphonyl, Cl_2O alkoxycarbonyl, and phe from a C2_2O alkyleneoxy group, a glycidol group, a nylthio; glycidyl group, or mixtures thereof; Wherein R' is an end group selected from the group con Wherein at least one of R1, R2, R3, R4, R5 is Q-E; and sisting of hydrogen, Cl_2O alkyl, Cl_2O alkylester, halo, AS-A8 are independently selected from the group consist hydroxyl, thio, cyano, sulfonyl, sulfo, sulfato, aryl, nitro, ing of hydrogen, halogen, nitro, amino, alkylamino, ary carboxyl, Cl_2O alkoxy, amino, Cl_2O alkylamino, acry lamino moieties, and combinations thereof. lamino, Cl_2O alkylthio, Cl_2O alkylsulfonyl, Cl_2O alky 9. The colorant of claim 8, Wherein Q is oxygen, E is a lphenyl, phosphonyl, Cl_2O alkylphosphonyl, Cl_2O polyoxyalkylene moiety consisting of ethylene oxide and alkoxycarbonyl, and phenylthio; and propylene oxide monomers, and Z is 1. Wherein at least one of R1, R2, R3, R4, R5 is Q-E. US 2011/0124837 A1 May 26, 2011

13. The method of claim 12, wherein Q is oxygen, E is a (a) providing l-amino-4-arylamino-2-haloanthraquinone combination of ethylene oxide and propylene oxide, and Z is having a halogen in the “2” position, and l. (b) reacting the haloanthraquinone compound of step a 14. The method of claim 10, Wherein step “a” is carried out With a polymeric alkali metal alkoxide or phenoxide to in the presence of a copper-containing catalyst. form a polymeric violet anthraquinone colorant. 15. The method of claim 14, Wherein the copper-containing catalyst is selected from CuCl, CuCl2, copper poWder, and 26. The method of claim 25, Wherein the halogen is CuSO4. selected from the group consisting of ?uorine, chlorine, bro 16. The method of claim 10, Wherein the reaction of step mine, and iodine. “a” further includes a solvent. 27. A method for making a polymeric violet anthraquinone 17. The method of claim 16, Wherein the solvent is selected colorant comprising the sequential steps of: from the group consisting of alcohol, dimethylformamide (a) reacting bromamine acid With a polyoxyalkylene sub (DMF), and dimethylsulfoxide (DMSO). stituted primary aromatic or aliphatic amine in the pres 18. The method of claim 10, Wherein the reaction of step ence of a copper-containing catalyst compound to form “a” further includes a base. l-amino-4-arylamino-2-anthraquinone sulfonic acid, 19. The method of claim 10, Wherein the reaction of step and “a” is carried out at a temperature betWeen 60° C. and 150° C. 20. The method of claim 10, Wherein the reaction of step (b) reacting the anthraquinone of step a With an alcohol, “b” further includes a solvent. a polymeric alcohol, a thiol, or a polymeric thiol and 21. The method of claim 20, Wherein the solvent is selected With a base to form l-amino-2-polyalkyleneoxy-4-ary from the group consisting of Water, alcohol, ether, toluene, lamino-anthraquinone, methyl ether. dimethylsulfoxide (DMSO), and dimethylformamide 28. The method of claim 27, Wherein the polyoxyalkylene (DMF). substituted primary aromatic amine is represented by general 22. The method of claim 10, Wherein the base of step “b” is structure (V11): selected from the group consisting of alkali hydroxides, alkali alkoxides, sodium hydride, sodium amide, sodium bis(trim ethylsilyl)amide, tetramethylammonium hydroxide (V11) (TMAH), benZyltrimethylammonium hydroxide (BTMAH), R1 R2 lithium diisopropylamide, and sodium trimethylsilanolate. 23. The method of claim 10, Wherein the reaction of step “b” is carried out at a temperature betWeen 50° C. and 250° C. 24. A method for making the polymeric violet anthraquinone colorant of claim 1 comprising the sequential steps of: (a) providing an anthraquinone acid blue compound hav ing a sulfonic acid moiety in the “2” position, and Wherein R1, R2, R3, R4, R5 are the same or different and are (b) reacting the anthraquinone acid blue compound of step selected from the group consisting of hydrogen, C 1 -C20 alkyl, “a” With a polymeric alcohol and a base to form a poly Cl-C2O alkoxy, halogen, nitro, amino, carboxylic acid, car meric violet anthraquinone colorant. boxylic acid ester, carboxamide, sulfonic acid, sulfonamide 25. A method for making the polymeric violet and sulfonic acid esters. anthraquinone colorant of claim 1 comprising the sequential steps of: * * * * *